Nuclear Magnetic Resonance: Volume 28 [1 ed.] 9781847553843, 9780854043224

Citation preview

Nuclear Magnetic Resonance Volume 28

A Specialist Periodical Report

Nuclear Magnetic Resonance Volume 28 A Review of the Literature Published between June 1997 and May 1998 Senior Reporter G. A. Webb, Department of Chemistry, University of Surrey, Guildford, UK Rep0rters

1. Barsukov, University of Leicester, UK A. C. de Dios, University of lllinois at Chicago, USA F? C. Driscoll, University College, London, UK H . Fukui, Kitami Institute of Technology, Japan C. J. Jameson, University of lllinois at Chicago, USA K. Kamienska-Trela, Polish Academy of Sciences, Warszawa, Poland A. Khan, University of Lund, Sweden H. Kogelberg, Imperial College School of Medicine, Harrow, UK S. M . Kristensen, University of Copenhagen, Denmark H . Kurosu, Nara Women's University, Nara City, Japan R. Ludwig, Universitgt Dortmund, Germany M. J. W. Prior, University of Nottingham, UK W . Schilf, Polish Academy of Sciences, Warszawa, Poland R. R. Sharp, University of Michigan, Ann Arbor, Michigan, USA M. E. Smith, University of Kent, Canterbury, UK T. Watanabe, Tokyo University of Fisheries, Tokyo, Japan J. Wojcik, Polish Academy of Sciences, Warszawa, Poland M. Yamaguchi, Kao Corporation, Tochigi, Japan T. Yamanobe, University of Gunma, Japan

RSaC

ROYAL SOClEpl OF CHEMISTRY

ISBN 0-85404-322-5 ISSN 0305-9804 Copyright Cf2 The Royal Society of Chemistry 1999 All rights reserved Apurt from any fair dealing for the purposes of research or private study, or criticism or review us permitted under the terms of the UK Copyright, Designs and Putents Act, 1988, this publication muy not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprogruphic reproduction only in uccordmce with the terms of the licences issued by the Copyright Licencing Agency in the UK, or in uccordance with the terms of the licences issued by the appropriute Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royul Society of Chemistry ut the address printed on this puge.

Published by The Royal Society of Chemistry Thomas Graham House, Science Park, Milton Road, Cambridge CB4 OWF, UK

For further information see our web site at www.rsc.org Typeset by Computape (Pickering) Ltd, Pickering, North Yorkshire, UK Printed by Athenaeum Press Ltd, Gateshead, Tyne and Wear, UK

Preface

Volume 28 of the Specialist Periodical Reports on NMR comprises the usual combination of annual and biennial reports which taken together attempt to provide a comprehensive coverage of the NMR literature appearing between June 1997 and May 1998. The volume of published work involving NMR techniques continues to burgeon and, in some areas, threatens to become something of a behemoth. Thus my sincere thanks are due to all members of the reporting team for their determined efforts to provide accounts which are devoid of some of the more nugatory aspects of the literature while remaining highly readable. It is my very great pleasure to welcome Dr I . Barsukov, who covers Multiple Resonance, and Dr A. C. de Dios who joins Professor C. J. Jameson in reporting on Theoretical and Physical Aspects of Nuclear Shielding to the reporting team and to thank Dr H. Kogelberg, who is retiring, for her contribution on Conformational Analysis. Finally I wish to show my appreciation of the continuous efforts of the RSC production team with whom I have had the pleasure of working on this series for a number of years. University of Surrey Guild ford October 1998

G. A. Webb

V

Contents

Chapter 1

Chapter 2

Chapter 3

NMR Books and Reviews By W. Schilf

1

1 Books

1

2 Regular Review Series

1

3 Edited Books and Symposia

5

4 Reviews in Periodicals

15

5 Reviews and Books in Foreign Languages

32

Theoretical and Physical Aspects of Nuclear Shielding By C.J. Jumeson und A. C.de Dios

42

I Theoretical Aspects of Nuclear Shielding 1.1 General Theory 1.2 Ab Initio Calculations

42 42 49

2 Physical Aspects of Nuclear Shielding 2.1 Anisotropy of the Shielding Tensor 2.2 Shielding Surfaces and Rovibrational Averaging 2.3 Isotope Shifts 2.4 Intermolecular Effects on Nuclear Shielding

55 55 59 62

3 References

71

Applications of Nuclear Shielding By ?I.% Yumuguchi

77

1 Introduction

77

2 Various Chemical and Physical Influences to Nuclear Shieldings

77

~

~~~

Nuclear Magnetic Resonance, Volume 28 @:I The Royal Society of Chemistry, 1999

vii

64

Contents

viii

2.1

2.2

2.3 2.4

2.5 2.6 2.7

2.8 2.9 2.10

Computer Assisted Structural Assignment 2.1.1 Spectrum Simulation, Computer Assisted Assignments, and Related Techniques 2.1.2 Nuclear Shielding Calculations Stereochemical Nuclear Shielding Non-Equivalence 2.2.1 Chirality Determination by Mosher's and Related Methods 2.2.2 Other Stereochemistry Determination Isotope Effects Substituen t Effects 2.4.1 Proton Substituent Effects 2.4.2 Carbon and Heteroatom Substituent Effects Intramolecular Hydrogen Bonding Effects and Related Effects Bond Anisotropy, Ring Current Effects and Aromaticity Intermolecular Hydrogen Bonding Effects, Inclusion Phenomena and Related Effects 2.7.1 Proton and Heteronuclear Shifts 2.7.2 Cyclodextrins (CDs) 2.7.3 Other Molecular Recognition Shift Reagent Miscellaneous Topics Reviews

3 Shieldings of Particular Nuclear Species 3.1 Group 1 ('H, 2H, 3H, 6,7Li,23Na,87Rb, 133Cs) 3.1.1 Hydrogen ( I H) 3.1.2 Deuterium ( 2H) 3.1.3 Tritium ( 3H) 3.1.4 Lithium (637Li) 3.1.5 Sodium (23Na) 3.1.6 Rubidium (87Rb) 3.1.7 Cesium ( 133Cs) 3.2 Group 2 (9Be, 43Ca) 3.2.1 Beryllium (9Be) 3.2.2 Calcium (43Ca) 3.3 Group 3 and Lanthanoids (89Y, '39La, 171Yb) 3.3.1 Yttrium ( 8 9 ~ ) 3.3.2 Lanthanum ( 139La) 3.3.3 Ytterbium ( 17'Yb) 3.4 Group 4 (47349Ti) 3.5 Group 5 (51V, 93Nb) 3.5.1 Vanadium (51V) 3.5.2 Niobium (93Nb) 3.6 Group 6 (95M0, '83W) 3.6.1 Molybdenum (95M0)

77 77 78 79 79 80 81 81 81 81 82 82 83 83 83 84 85 86 86 86 86 86 87 87 88 88 88 89 89 89 90 90

90 90 90 90 90 90 91 91 91

Contents

3.6.2 Tungsten ( Is3W) 3.7 Group 7 ( 55Mn,99Tc) 3.7.1 Manganese (55Mn) 3.7.2 Technetium (99Tc) 3.8 Group 8 (99Ru, 1870s) 3.8.1 Ruthenium (99Ru) 3.8.2 Osmium ( Is7Os) 3.9 Group 9 ( 59C0, Io3Rh) 3.9.1 CObd'lt (59cO) 3.9.2 Rhodium ( '03Rh) 3.10 Group 10 (195Pt) 3.11 Group 11 ('09Ag) 3.12 Group 12 ('I3Cd, 199Hg) 3.12.1 Cadmium ( I3Cd) 3.12.2 Mercury ( 199Hg) 3.13 Group 13 ('IB, 27Al,69'71Gd,2037205T1) 3.13.1 Boron ("B) 3.13.2 Aluminium (27Al) 3.13.3 Gallium (69371Ga) 3.13.4 Thallium (2037205Tl) 3.14 Group 14 ( I3C,29Si,73Ge, Il9Sn, 207Pb) 3.14.1 Carbon ( I3C) 3.14.2 Silicon (29Si) 3.14.3 Tin ( '17,119Sn) 3.14.4 Lead (207Pb) 3.15 Group 15 ( l4*I5N,31P) 3.15.1 Nigrogen ( 14315N) 3.15.2 Phosphorus ( 31P) 3. I6 Group 16 ( I7O, 77Se, 125Te) 3.16.1 Oxygen ( I7O) 3.16.2 Selenium (77Se) 3.16.3 Tellurium ( '25Te) 3.17 Group 17 (I9F) 3.18 Group 18 (3He, 1297131Xe) 3.18.1 Helium ( 3He) 3.18.2 Xenon ( 129*131Xe)

Chapter 4

92 92 92 92 92 92 93 93 93 93 93 95 95 95 95 96 96 96 97 97 97 97 98 98 100 100 100 101 102 102 102 103 103 104 104 104

4 References

105

Theoretical Aspects of Spin-Spin Couplings By H . Fukui

124

1 Introduction

124

2 Multiconfigurational Self-Consistent Field Calculations 2.1 MCSCF Linear Response Theory

124 124

Contents

X

2.2

Chapter 5

MCSCF Calculation of Indirect Nuclear Spin-Spin Couplings

128

3 Nuclear Motion Effects

133

4 Isotope Effects

137

5 Relativistic Effects

140

6 New Operators for the Fermi-Contact Interaction

142

7 Dependence on Conformation and Bond Character 7.1 Conformation Dependence of Spin-Spin Couplings 7.2 Spin-Spin Couplings and Bond Character

145 145 146

8 References

147

Applications of Spin-Spin Couplings By K. Kamieriska-Trela and J. Wcijcik

151

1 Introduction

151

2 Methods

152

3 One-Bond Couplings to Hydrogen

154

4 One-Bond Couplings Not Involving Hydrogen

158

5 Two-Bond Couplings to Hydrogen

168

6 Two-Bond Couplings Not Involving Hydrogen

171

7 Three-Bond Hydrogen-Hydrogen Couplings

173

8 Three-Bond Couplings Between Hydrogen and Heteronuclei 182 9 Three-Bond Couplings Not Involving Hydrogen

186

10 Couplings Over More Than Three Bonds and Through-Space 188

Chapter 6

11 References

190

Nuclear Spin Relaxation in Liquids and Gases By R. Ludwig

208

1 Introduction

208

Contents

Chapter 7

xi

2 General, Physical and Experimental Aspects of Nuclear Spin Relaxation 2.1 General Aspects 2.2 Experimental Aspects 2.3 Relaxation in Coupled Spin Systems 2.4 Dipolar Couplings and Distance Information 2.5 Exchange Spectroscopy 2.6 Quadrupolar Interactions 2.7 Slow Motions in Glasses 2.8 Models for Molecular Dynamics

210 210 21 1 213 214 215 216 217 218

3 Selected Applications of Nuclear Spin Relaxation 3.1 Pure Liquids 3.2 Non-Electrolyte Solutions 3.3 Transition Metal Complexes

219 219 220 22 1

4 Nuclear Spin Relaxation in Gases

222

5 Self-Diffusion in Liquids 5.1 Experimental and Theoretical Aspects 5.2 Selected Examples

224 224 224

6 References

225

Solid State NMR By M . E. Smith

232

1 Introduction

232

2 Technique Development 2.1 Theoretical 2.2 Experimental

233 233 233

3 Carbonaceous Materials 3.1 Coals, Pitches and Oil Shales 3.2 Fullerenes, Diamonds and Other Carbons

236 236 237

4 Organic Materials

238 238 240 242

4.1 General 4.2 Organometallics 4.3 Bio-organic 4.4 Liquid Crystals, Membranes, Bilayers, Cell Walls and Woods 5 Organic-Inorganic Materials 5.1 General

244 246 246

Conrents

5.2 Polysiloxanes 5.3 Soils and Humic Substances

Chapter 8

247 247

6 Inorganic Materials 6.1 General 6.2 Silicates and Aluminosilicates 6.3 Microporous and Mesoporous Materials 6.3.1 Silicate-based Systems 6.3.2 Other Structural Studies 6.3.3 In-Situ and Surface Reactions 6.4 Glasses 6.5 Ceramics

249 249 250 252 252 254 254 256 256

7 Miscellaneous 7.1 General 7.2 Dynamics and Intercalates

258 258 259

8 References

259

Multiple Pulse NMR By I. Barsukov

293

1 Introduction

293

2 Variation of the Radiofrequency Pulse 2.1 Selective Excitation Pulses 2.2 Composite and Decoupling Pulses 2.3 Solvent Suppression

293 293 294 294

3 Homonuclear Correlation Spectroscopy

294

4 Dipolar Coupling, Chemical Exchange and Relaxation 4.1 Dipolar Coupling and Chemical Exchange 4.2 Relaxation Time Measurements 4.3 Translational Diffusion Experiments

295 295 296 298

5 Inverse Proton Detected Correlation Spectroscopy 5.1 General 5.2 Isotope Filtered Experiments 5.3 Isotope Edited Experiments 5.4 Scalar Coupling Constants Measurements 5.4.1 Quantitative J-Correlation 5.4.2 E-COSY 5.4.3 Spin-State Selective Experiments 5.5 Heteronuclear Double Resonance Experiments

299 299 299 300 300 30 1 30 1 30 1 302

...

Contents

xi11

5.6 Heteronuclear Triple Resonance Experiments

Chapter 9

303

6 References

304

NMR of Natural Macromolecules By P. C. Driscoll and S. M . Kristensen

309

1 Introduction

309

2 Solution Structure Determination 2. I General Points 2.2 Landmark Protein Structures 2.3 Other Protein Structures 2.4 Large Proteins 2.5 Protein-Protein Complexes 2.6 Protein-Small Molecule Complexes 2.7 Calcium-Binding Proteins 2.8 Glycoprotein Structure and Dynamics 2.9 RNA Structure 2.10 DNA Structure 2.1 1 Nucleic Acid Aptamers 2.12 Protein-RNA Interactions 2.13 Protein-DNA Interactions

3 10 3 10 3 10 312 3 14 3 14 315 315 315 316 317 320 32 1 323

3 Technical Developments 3.1 Residual Dipolar Couplings 3.2 Enhanced Molecular Alignment 3.3 Aspects of Deuterium Incorporation 3.4 Spin-Spin Couplings 3.5 Resolution in NOESY Spectra

326 326 327 328 329 330

4 SAR-by-NMR

333

5 Computational Methods

333

6 Protein Folding 6.1 Protein Folding Pathways 6.2 Partly Folded States 6.3 Random Coils

336 336 337 338

7 Protein Hydration

339

8 Acidity Constants

34 1

9 Nuclear Relaxation in Biological Macromolecules 9. I Back bone Dynamics

342 342

Contents

xiv

9.2 9.3 9.4 9.5 9.6 9.7

Amino-Acid Side Chain Dynamics Aspects of Dipole/CSA and Dipole-Dipole Cross-Correlation Rotational Diffusion Anisotropy Aspects of Model-Free Analysis I5N, I3C and 2H Relaxation Applications Related Topics

343 344 346 147 348 351

10 Miscellaneous Topics

352

1 1 References

353

Chapter 10 Synthetic Macromolecules By H . Kurosu und T. Yumanobe

364

1 Introduction

364

2 Liquid Crystals

364

3 Primary Structure

365

4 Characterization of the Synthetic Macromolecules in the Solid State 4.1 Solid State I3CNMR Studies for Synthetic Macromolecules 4.2 Solid State Multi-Nuclear NMR Studies for Synthetic Macromolecules 4.3 Dynamics of the Synthetic Macromolecules in the Solid State 4.4 Gels and Crosslinked Macromolecules

375 375 376 377 379

5 Studies for Polymer Blend and Diffusion of the Synthetic Macromolecules

380

6 Characterization of the Synthetic Macromolecules in the Solution State

382

7 References

382

Chapter 11 Conformational Analysis By H . Kogelberg

395

1 Introduction

395

2 Methods

395

Contents

xv

3 Small Organic Molecules 3.1 Small Peptides and Peptide Analogues 3.2 Nucleotide Analogues 3.3 Heterocycles 3.4 Aromatic Compounds 3.5 Hosts, Guests and Host Guest Interactions 3.6 Acyclic Compounds 3.7 Mono-, Bi- and Tri-Cyclic Compounds

396 397 399 400 402 402 403 403

4 Nucleic Acids 4.1 Dynamics

404 404

5 Proteins and Peptides 5.1 Dynamics 5.2 Protein Engineering 5.3 Folding 5.4 Ligand Binding

404 406 407 407 408

6 Carbohydrates

409

7 Membrane Environments

41 1

8 Inorganic and Organometallic Compounds 8.1 Transition Metal Complexes 8.2 Main Group Metal Complexes

412 412 413

9 References

414

Chapter 12 Nuclear Magnetic Resonance Spectroscopy of Living Systems By M. J. W. Prior

432

1 Reviews and New Methodology 1.1 General Applications 1.2 Spectral Editing, Localisation and Instrumentation 1.3 lntracellular Ions, Metabolites and pH

432 432 432 433

2 Cells 2.1 Bacteria 2.2 Blood 2.3 Mammalian 2.4 Plant 2.5 Reproductive 2.6 Tumour 2.7 Yeast and Fungi

434 434 435 436 437 437 437 438

3 Plants and Algae

439

Contents

xvi

4 Tissue Studies 4.1 Brain and Spinal Cord 4.2 Eye 4.3 Heart 4.4 Kidney 4.5 Liver 4.6 Muscle 4.7 Tumour 4.8 Vascular 4.9 Whole Animal

440 440 443 443 450 450 45 1 452 453 453

5 Clinical Studies 5.1 Reviews

454 454 454 457 457 458 458 458

5.2 5.3 5.4 5.5 5.6 5.7

Brain Liver Muscle Tumour Adipose Tissue Skin

6 References Chapter 13 Nuclear Magnetic Resonance Imaging By T. Watanabe

459 468

1 Introduction

468

2 General Aspects and Reviews

468

3 Instruments

469

4 Pulse Sequences

470

5 Data Processing

470

6 Solid State NMR Imaging

47 1

7 Other Nuclei

472

8 Diffusion, Flow, and Velocity Image 8.1 Pulse Sequence and Model Experimental 8.2 Diffusion, Flow, Velocity and Mass Transport 8.3 Rapid NMR Rheometry

472 472 473 474

9 Solvent Assisted Imaging and Porosity

474

xvii

Conten IS

10 Water and Hydration

475

11 Polymers (Gel, Drug Release System, Rubber, Resin)

476

12 Food and Food Processing

477

13 Plants and Seeds

478

14 In Vivo and Ex Vivo Imaging

479

15 References

480

Chapter 14 NMR of Paramagnetic Species By R. R. Sharp

485

1 Introduction

485

2 Theory 2.1 Effect of Zero Field Splitting Interactions on Nuclear Spin Relaxation 2.2 Paramagnetic Effects on Multiple Quantum Coherences

485

3 Porphyrins 3.1 Electronic Properties of Porphyrins 3.2 Rotational Isomers of the Axial Ligands 3.3 Carbon-Ni(I1) Bonds 3.4 Polymeric Porphyrin Complexes 3.5 Unusual Spin States in Porphyrins 3.6 Trans-Porphyrin Bridging Substituents 3.7 Ally1 and Vinyl Axial Ligation 3.8 Lanthanide Porphyrinates

487 487 488 489 489 490 49 1 49 1 492

4 Lanthanides 4.1 Structure and Dynamics 4.1.1 In Vivo pH Probe 4,1.2 Low Denticity Complexes 4.2 Lanthanide Shift Reagents 4.2.1 Chiral Shift Reagents 4.2.2 Biological Applications of Shift Reagents 4.2.3 23NaShift Reagents 4.3 Polynuclear Lanthanide Complexes

492 493 495 495 496 496 497 497 498

5 MRI Contrast Agents 5.1 Optimizing Proton Relaxivity 5.2 Organ-Specific Contrast Agents

498 498 500

485 486

xviii

Contents

6 Kinetics of Electron Transfer Reactions 6.1 Intramolecular Electron Transfer 6.2 Electron Transfer Proteins

50 1 502 502

7 CIDNP 7.1 Validity of Kaptein’s Rules 7.2 Magnetic Field Effects 7.2.1 High Magnetic Fields 7.2.2 Pulsed Magnetic Fields 7.3 Time-Resolved CIDNP 7.4 Biochemical Applications

503 503 504 505 506 506 507

8 D-Block Ions 8.1 Polynuclear Metal Centers 8.2 Spin-State Equilibria 8.3 Solution Structure and Dynamics 8.4 Analysis of Hyperfine Shifts

508 508 510 510 51 1

9 New Experimental Techniques 9.1 Tissue Studies in Plants 9.2 Adsorbed Paramagnetic ions 9.3 New Solid-state NMR Techniques 9.4 NMR of Paramagnetic Metalloproteins 9.4.1 Solution Structures of Paramagnetic Proteins 9.5 Novel Practical Applications

51 1 51 1 512 513 514 514 515

10 References Chapter 15 NMR of Liquid Crystals and Micellar Solutions By A . Khan

515

522

1 introduction

522

2 Reviews

523

3 Models and Methods

524

4 Lyotropic Polymorphism 4.1 Phase Diagrams and Phase Structures

525 525

5 isotropic Micellar Solution Phases 5.1 Normal Micelles 5.2 Mixed Micelles and Solubilisation 5.3 Reversed Micelles and Microemulsions

529 529 53 1 53 1

6 Lyotropic Mesophases

533

xix

Contents

6.1 Alkyl Chains and Headgroups in Liquid Crystalline Phases 6.2 Alkyl Chains and Headgroups in Vesicles

533 536

7 Surfactant-Proteinand Surfactant-PolymerSystems 7.1 Surfactant-ProteinSystems 7.2 Surfactant-PolymerSystems

538 538 540

8 Water and Counterions

540

9 Thermotropic Mesomorphism 9.1 Relaxation Studies 9.2 Bandshape-Order Parameters

542 542 543

10 Synthesis and Properties of Amphiphilic Materials

546

1 1 References

546

Author Index

557

Symbols and Abbreviations

These lists contain the symbols and abbreviations most frequently used in this volume, but they are not expected to be exhaustive. Some specialized notation is only defined in the relevant chapter. An attempt has been made to standardize usage throughout the volume as far as is feasible, but it must be borne in mind that the original research literature certainly is not standardized in this way, and some difficulties may arise from this fact. Trivial use of subscripts etc. is not always mentioned in the symbols listed below. Some of the other symbols used in the text, e.g. for physical constants such as h or T , or for the thermodynamic quantities such as H or S , are not included in the list since they are considered to follow completely accepted usage.

Symbols hyperline (electron-nucleus) interaction constant (i) hyperfine (electron-nucleus) interaction constant (ii) parameter relating to electric field effects on nuclear shielding (i) magnetic induction field (magnetic flux density) (ii) parameter relating to electric field effects on nuclear shielding static magnetic field of NMR or ESR spectrometer r.f. magnetic fields associated with V I ,y spin-rotation coupling constant of nucleus X (used sometimes in tensor form): c2 + 2~:). components of C parallel and perpendicular to a molecular symmetry axis (i) self-diffusion coefficient (ii) zero-field splitting constant rotational diffusion tensor components of D parallel and perpendicular to a molecular symmetry axis internal diffusion coefficient overall isotropic diffusion coefficient electric field eigenvalue of *(or a contribution to 2) nuclear o r electronic g-factor magnetic field gradient element of matrix representation of 2 Hamiltonian operator-subscripts indicate its nature nuclear spin operator for nucleus i components of I, (i) ionization potential (ii) moment of inertia nuclear spin-spin coupling constant through n bonds (in Hz). Further information may be given by subscripts or in brackets. Brackets are used for indicating the species of nuclei coupled, e.g. J( "C, H) or additionally, the coupling path, e g . J(P0CF) reduced splitting observed in a double resonance experiment rotational quantum number reduced nuclear spin--spin coupling constant (see the notes concerning " J )

='/3(~i

'

xx

Symbols and Abbreviations

xxi

eigenvalue off;, (magnetic component quantum number) equilibrium macroscopic magnetization of a spin system in the presence of

BO

t

T

P "fx

6X

AJ An A6 A" AC7 : ,1

AX

components of macroscopic magnetization the number of average mol. wt. valence p orbital of atom A fractional population (or rotamers etc.) element of bond-order, charge-density matrix electric field gradient (i) nuclear quadrupole moment (ii) quality factor for an r.f. coil valence s-orbital of atom A electron density in SA at nuclear A (i) singlet state (ii) electron (or, occasionally, nuclear spin) cf: I (iii) ordering parameter for oriented systems (iv) overlap integral between molecular orbitals elapsed time (i) temperature (ii) triplet state coalescence temperature for an N M R spectrum the glass transition temperature (of a polymer) spin-lattice relaxation time of the X nuclei (further subscripts refer to the relaxation mechanism) spin-spin relaxation time of the X nucleus (further subscripts refer to the relaxation mechanism) inhomogeneity contribution to dephasing time for M , ?r M y total dephasing time for M , or M y ; (T;)-' = 75' + ( T 2 ) - ' decay time following 900 120 ppm shift. Similarly, the same model fails to account for the entire gas-to-liquid shifts in CH3F and CHF3.199 On the other hand, similar to interpreting '29Xe chemical shifts in zeolites, understanding solvent or medium effects will require incorporation of dynamic averaging. A significant development in this area is the application of the quantum cluster equilibrium (QCE) theory to calculating chemical shieldings in the liquid phase, particularly for associated liquids.200 203 This particular approach begins with construction of clusters starting from the monomer up to a hexamer. Each cluster is geometry optimized via an ab initio method and the shielding is calculated a t the optimized geometry for each of the clusters. Using standard statistical thermodynamics and employing energies (vibrational frequencies, etc.) obtained from a& initio calculations, partition functions are calculated and the distribution of molecules among the various clusters can be obtained. This distribution is then used for determining population-weighted NMR shieldings. This scheme has been applied to N-methyl f ~ r m a m i d e , ~ammonia,2007201 '~ and N-methyl acetamide.202Since the averaging is not limited to NMR shieldings, the QCE method is also able to provide population-weighted geometries, quadrupole coupling constants, asymmetry parameters, specific heats, ClausiusClapeyron pressure dependence, and vibrational frequencies in the liquid phase. Agreement is achieved not only with values at one given temperature but, more importantly, the predicted temperature dependence of these parameters nicely parallels the observed trends. The success in reproducing the temperature dependence is an indication that most of the temperature dependence is in the changes in the distributions of the molecules among various clusters. Predicting chemical shieldings in solids is still a formidable challenge. The basic question involves the choice of a suitable fragment that is large enough to reproduce observed trends but with a size that is still manageable with present computational resources. The size of a model greatly depends on the identity of the atom to which the nucleus of interest belongs. Cations are smaller in size and are less polarizable thereby requiring only its nearest neighbors. On the other hand, anions or elements of high electronegativity will demand a larger fragment that includes not only the nearest neighbors but also the second nearest neighbors. Tosse11204has recently studied the effect of second nearest neighbors to the I5N NMR shielding in crystalline a- and P-Si3N4.The effects arising from second nearest neighbors on the I5N shielding can be as large as 80 ppm. The

2: Theoretical and Physical Aspects of Nuclear Shielding

71

shielding calculated with the largest fragment, SigNgH21, is still 50 ppm more shielded than the experimental shielding in P-Si3N4, indicating that the above fragment is still inadequate. Although experimental values are not available for boron nitride, Gastreich and Marian205 have addressed the question of how distant from an I5N nucleus are the atoms that need to be included in order to reproduce its shielding in solid nitrides. As in Tossel's study, this work shows that the second nearest neighbors are also necessary. On the computational front, the problem of shieldings in solids may have been alleviated by a new parallelization scheme introduced by Wolinski et al.' Thus, instead of having just one processor d o the computational task, a parallel set of computers is used to calculate integrals in vectorized batches. With this advancement, the shielding can be calculated for a system containing 120 atoms and 1500 basis functions in about 5 days using six Pentium processors.

3 1 2 3 4 5 6 7 8 9 10

II 12 13 14 15

16 17 18 19 20 21 22 23 24 25

References K. Wolinski, R. Haacke, J. F. Hinton, P. Pulay, J. Comput. Chem., 1997,18, 816. A. D. Becke, Can. J. Chem., 1996,74,995.

K. Capelle and E. K. U. Gross, Phys. Rev. Lett., 1997, 78, 1872. F. Salsbury Jr. and R. A. Harris, Chem. Phys. Left., 1997,279,247. C. J. Grayce and R. A. Harris, J. Phys. Chem., 1995,99,2724. G . Vignale and M. Rasolt, Phys. Rev. Lett., 1987,59, 2360. G. Vignale and M. Rasolt, Phys. Rev. B, 1989,37, 10685. A. M. Lee, N. C. Handy, and S. M. Colwell, J. Chem. Phys., 1995,103, 10095. V. G. Malkin, 0. L. Malkina, and D. R. Salahub, Chem. Phys. Lett., 1993,204,80. B. Farid, Philos. Mug. B, 1997,76, 145. G. Schreckenbach and T. Ziegler, J. Phys. Chem., 1995,99,606. G . Rauhut, S. Puryear, K. Wolinski, P. Pulay, J. Phys. Chem., 1996,100,6310. J. R. Cheeseman, G. W. Trucks, T. A. Keith, M. J. Frisch, J. Chem. Phys., 1996, 104,5497. As implemented in DGauss, Version 4. I, Oxford Molecular, Oxford, 1998. V. G. Malkin, 0. L. Malkina, M. E. Casida, and D. R. Salahub, J. Am. Chem. Soc., 1994,116, 5898. G. Schreckenbach, T. Ziegler, Theor. Chem. Acc., 1998,99,7 1. M. Kaupp, V. G. Malkin, and 0. L. Malkina, Encyclopedia of Computational Chemistry, Ed. P. v. R. Schleyer, Wiley, New York, 1998. M. Kaupp, 0. L. Malkina, and V. G. Malkin, J. Chem. Phys., 1997,106,9201. M. Kaupp, V. G. Malkin, 0. L. Malkina, and D. R. Salahub, J. Am. Chem. SOC., 1995,117, 1851. M. Kaupp, V. G. Malkin, 0. L. Malkina, and D. R. Salahub, J. Am. Chem. Suc., 1995,117,8492. M. Kaupp, V. G. Malkin, 0. L. Malkina, and D. R. Salahub, Chem. Phys. Lett., 1995,235, 382. G. Schreckenbach and T. Ziegler, Intl. J. Quantum Chem., 1997,61,899. Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem., 1996,100, 3359. G . Schreckenbach, T. Ziegler, Intl. J. Quuntum Chem., 1996,60,753. Y. Ruiz-Morales, G. Schreckenbach, T. Ziegler, J. Phys. Chem., 1997, 101,4121.

72

Nucleur Mugnetic Resonunee

26

C. C. Ballard, M. Hada, H. Kaneko, and H. Nakatsuji, Chem. Phys. Lett., 1996, 254,170. V. G. Malkin, 0. L. Malkina, D. R. Salahub, Chem. Phys. Lett., 1996,261, 335. M. Kaupp, 0.L. Malkina, V. G. Malkin, Chem. Phys. Lett., 1997,265, 55. M. Kaupp, 0. L. Malkina, V. G. Malkin, and P. Pyykko, Chem. Eur. J., 1998,4, 118. M. Kaupp and 0. L. Malkina, J. Chem. Phys., 1998,108,3648. C. J. Jameson and H. S. Gutowsky, J. Chem. Phys., 1969,51,2790. C. J. Jameson, J. Am. Chem. Soc., 1969, 91,6232. H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett., 1995,233,95. H. Nakatsuji, M. Hada, T. Tejima, T. Nakajima, and M. Sugimoto, Chem. Phys. Lett., 1996,249, 284. H. Nakatsuji, T. Nakajima, M. Hada, H. Takashima, and S. Tanaka, Chem. Phys. Lett., 1995,247,418. H. Takashima, M. Hada, and H. Nakatsuji, Chem. Phys. Lett., 1995,235, 13. H. Kaneko, M. Hada, T. Nakajima, H. Nakatsuji, Chem. Phys. Lett., 1996,261, 1 . H. Nakatsuji, M. Hada, H. Kaneko, and C. C. Ballard, Chem. Phys. Lett., 1996, 255, 195. M. Hada, H. Kaneko, €1. Nakatsuji, Chem. Phys. Lett., 1996,261, 7. H. Nakatsuji, Z. M. Hu, T. Nakajima, Chem. Phys. Lett., 1997, 275,429. S. Berger, W. Bock, G. Frenking, V. Jonas, and F. Mueller, J. Am. Chem. Suc., 1995, 117,3820. Y. Ishikawa, T. Nakajima, M. Hada, and H. Nakatsuji, Chem. Phys. Lett., 1998, 283, 1 19. M. B. Ferraro, T. E. Herr, P. Lazzeretti, M. Malagoli, and R. Zanasi, J. Chem. Phys., 1993,98, 4030. P. Lazzeretti, M. Malagoli, R. Zanasi, M. B. Ferraro, and M. C. Caputo, J. Chem. Phys., 1995, 103, 1852. P. Lazzeretti, J. Mol. Struct. (THEOCHEM), 1995,336, 1. M. B. Ferraro, M. C. Caputo, M. P. B. Varela, and P. Lazzeretti, Intl. J. Quantum Chem., 1998,66,31. R. Zanasi, P. Lazzeretti, P. W. Fowler, Chem. Phys. Lett., 1997,278,251. P. Lazzeretti, R. Zanasi, Intl. J. Quantum Chem., 1996,60,249. P. Lazzeretti, M. Malagoli, and R. Zanasi, Chem. Phys. Lett., 1994,220,299. R. Zanasi and P. W. Fowler, Chem. Phys. Lett., 1995, 238,270. P. W. Fowler, P. Lazzeretti, R. Zanasi, Chem. Phys. Lett., 1990, 165, 79. P. W. Fowler, P. Lazzeretti, M. Malagoli, R. Zanasi, Chem. Phys. Lett., 1991, 179, 174. P. W. Fowler, P. Lazzeretti, M. Malagoli, R. Zanasi, J. Phys. Chem., 1991,95, 6404. C. S. Yannoni, R. D. Johnson, G. Meijer, D. S. Bethune, and J. R. Salem, J. Phys. Chem., 1991,95,9. J. Cioslowski, Chem. Phys. Lett., 1994,227,361. M. Buhl and W. Thiel, Chem. Phys. Lett., 1995,233,585. J. Gauss and J. F. Stanton, J. Mol. Struct. (THEOCHEM), 1997,398,73. J. A. Bohmann, F. Weinhold, and T. C. Farrar, J. Chem. Phys., 1997, 107, 1173. C. J. Jameson and A. K. Jameson, Chem. Phys. Lett., 1987, 135,254. M. Buhl, Chem. Phys. Lett., 1997,267, 251. J. Lounila, J. Vaara, Y. Hiltunen, A. Pulkkinen, J. Jokisaari, M. Alakorpela, K. J. Ruud,oChem.Phys., 1997, 107, 1350. P. 0. Astrand, K. V. Mikkelsen, P. Jorgensen, K. Ruud, and T. Helgaker, J. Chem. Phys., 1998, 108,2528.

27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62

2: Theoretical and Physical Aspects of Nuclear Shielding

63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101

I02 103

73

M. Buhl, W. Thiel, U. Fleischer, and W. Kutzelnigg, J. Phys. Chem., 1995,99,4000. T. Higashioji, M. Hada, M. Sugimoto, and H. Nakatsuji, Chem. Phys., 1996, 203, 159. J. Jokisaari, P. Lazzeretti, and P. Pyykko, Chem. Phys., 1988,123,339. G. Magyarfalvi and P. Pulay, Chem. Phys. Lett., 1994,225,280. M. Buhl, J. Gauss, and J. F. Stanton, Chem. Phys. Lett., 1995,241,248. G. Schreckenbach, Y . Ruiz-Morales, and T. Ziegler, J. Chem. fhys., 1996,104,8605. G. Malli and C. Froese, Zntl. J. Quantum Chem., 1967, lS, 95. T. D. Gierke and W. H. Flygare, J. Am. Chem. Soc., 1972,94,7277. Q. Chen, D. L. Freeman, J. D. Odom, and P. D. Ellis, Poster Abstracts, 36th Experimental NMR Conference, Boston, 1995, p. 333. W. H. Pan and J. P. Fackler, J. Am. Chem. Soc., 1978, 100,5783. N. Godbout and E. Oldfield, J. Am. Chem. SOC.,1997, 119,8065. R. Bramley, M. Brorson, A. M. Sargeson, and C. E. Schaffer, J. Am. Chem. Soc., 1985,107,2780. M. Buhl, Chem. Phys. Lett., in press. M. Buhl, Orgunomet., 1997,16,261. J. C. C. Chan, S. C. F. Auyeung, P. J. Wilson, G. A. Webb, J. Mol. Struct. (THEOCHEM), 1996,365, 125. J. C. C. Chan, S. C. F. Auyeung, J. Mol. Struct. (THEOCHEM), 1997,393,93. A. Bagno, J. Mul. Struct. (THEOCHEM), 1997,418,243. R. E. Wasylishen, C. Connor, and J. 0. Friedrich, Can. J. Chem., 1984,62,981. D. B. Chesnut, L. D. Quin, S. B. Wild, Heteroatom Chem., 1997,8,451. D. B. Chesnut, Chem. Phys., 1997,224, 133. D. B. Chesnut, Chem. fhys. Lett., 1995,246,235. D. B. Chesnut and E. F. C. Byrd, Chem. fhys., 1996,213, 153. D. Sykes, J. D. Kubicki, and T. C. Farrar, J. fhys. Chem., 1997,101,2715. T. Xu, D. H. Barich, P. D. Torres, J. B. Nicholas, and J. F. Haw, J. Am. Chem. Soc., 1997,119,396. T. Xu, D. H. Barich, P. D. Torres, and J. F. Haw, J. Am. Chem. Soc., 1997,119,406. M. Hricovini, 0. L. Malkina, F. Bizik, L. T. Nagy, and V. G. Malkin, J. Phyx Chem., 1997,101,9756. F. Liu, C. G. Phung, D. W. Alderman, D. M. Grant, J. Am. Chem. Soc., 1996, 118, 10629. H. Dahn, P. A. Carrupt, Mugn. Reson. Chem., 1997,3S, 577. J. C. Facelli, J. fhys. Chem. B, 1998,102, 2111. T. C. Stringfellow and T. C. Farrar, Spectrochim. Acta, 1997,53, 2425. D. B. Chesnut, Chem. Phys., 1997,214,73. H. Fukui, T. Baba, H. Matsuda, and K. Miura, J. Chem. Phys., 1994,100,6608. H. Fukui, K. Miura, and H. Matsuda, J. Chem. Phys., 1992, %, 2039. J. Gaussand J. F. Stanton, J. Chem. Phys., 1995,103,3561. J. Gauss and J. F. Stanton, J. Chem. Phys., 1996,104,2574. D. B. Chesnut, Chem. Phys., 1998,231, 1 . J. Kaski, P. Lantto, J. Vaara, and J. Jokisaari, J. Am. Chem. Soc., 1998,120, 3993. T. Helgaker, M. Jaszunski, and K. Ruud, Mol. fhys., 1997,91, 881. J. Jaballas and T. Onak, J. Organomet. Chem., 1998,550, 101. M. Hofmann, M. A. Fox, R. Greatrex, R. E. Williams, and P. v. R. Schleyer, J. Organomet. Chem., 1998,550,331. M. A. Fox, R. Greatrex, A. Nikrahi, P. T. Brain, M. J. Picton, D. W. H. Rankin, H. E. Robertson, M. Biihl, L. Li, and R. A. Beaudet, Inorg. Chem., 1998,37,2166.

74 104 105

I06 107 108 109 110

Ill 112 1 I3 1 I4 115 1 I6 I17 118 1 I9 120 121 122 I23 124 125 126 127 128 I29 130

131 I32 I33 134

I35

Nucleur Magnetic Resonance

M. B. Ezhova, H. M. Zhang. J. A. Maguire, and N. S. Hosmane, J. Organomet. Chem., 1998,550,409. S . J. Cranson, M. A. Fox, R. Greatrex, and N. N. Greenwood, J. Organomet. Chem., 1998,550,207. B. Wrackmeyer, B. Schwarze, W. Milius, R. Boese, 0. G. Parchment, and G. A. Webb, J. Orgunomet. Chem., 1998,552,247. P. J. Wilson, B. J. Howlin, and G. A. Webb, J. Mol. Struct., 1996,385, 185. P. J. Ortiz, E. M. Evleth, and L. A. Montero, J. Mol. Struct. ( T H E O C H E M ) , 1998, 432, 121. G. Cuevas, E. Juaristi, and A. Vela, J. Mol. Struct. ( T H E O C H E M ) , 1997,418,231, G . K. S. Prakash, Q. J. Wang, G. Rasul, and G. A. Olah, J. Orgunomet. Chem., 1998,550, 119. M. Biihl, A. Curioni, and W. Andreoni, Chem. Phys. Lett., 1997,274, 231. J. M. Schulman and R. L. Disch, J. Comput. Chem.. 1998, 19, 189. P. Hodgkinson and L. Emsley, J. Chem. Phys., 1997,107,4808. K. Schmidt-Rohr, J. Mugn. Reson., 1998, 131, 209. T. M. de Swiet, M. Tomaselli, and A. Pines, Chem. Phys. Lett., 1998,285, 59. J. Z. Hu, D. W. Alderman, R. J. Pugmire, and D. M. Grant, J. Magn. Reson., 1997, 126, 120. D.-K. Lee and A. Ramamoorthy, J. M a p . Reson., 1998, 133, 204. N. Tjandra and A. Bax, J. Am. Chem. Soc., 1997,119,9576. A. E. Walling, R. E. Pargas, A. C. de Dios, J. Phys. Chem., 1997,101,7299. A. C . de Dios, D. D. Laws and E. Oldfield, J. Am. Chem. Soc., 1994,116, 7784. A. C. de Dim and E. Oldfield, J. Am. Chem. Soc., 1994,116,5307. R. )I. Havlin, I-1. B. Le, D. D. Laws, A. C. de Dios, and E. Oldfield, J. Am. Chem. Soc., 1997, 119, 11951. J. Heller, D. D. Laws, M. Tomaselli, D. S. King, D. E. Wemmer, A. Pines, R. H. Havlin, and E. Oldfield, J. Am. Chem. Soc., 1997, 119,7827. K. Eichele, J. C. C. Chan, R. E. Wasylishen, and J. F. Britten, J. Phys. Chem., 1997, 101,5423. K. Eichele, R. E. Wasylishen, K. Maitra, J. H. Nelson, and J. F. Britten, Inorg. Chem., 1997,36,3539. C. J. Jameson, A. C. de Dios and A. K. Jameson, Chem. Phys. Lett., 1990,167,575. S . Kroeker, K. Eichele, R. E. Wasylishen, and J. F. Britten, J. Phys. Chem., 1997, 101,3727. S. Dick, U. GoDner, A. Weiss, C. Robl, G. Grossmann, G. Ohms, and M. Muller, J. Solid State Chem., 1997, 132,47. R. Salzmann, M. Wojdelski, M. Mcrnahon, R. H. Havlin, and E. Oldfield, J. Am. Chem. Soc., 1998,120, 1349. M. S. Solum, K. L. Altmann, M. Strohmeier, D. A. Berges, Y. L. Zhang, J. C. Facelli, R. J. Pugmire, and D. M. Grant, J. Am. Chem. Soc., 1997,119,9804. M. Strohmeier, A. M. Orendt, J. C. Facelli, M. S. Solum, R. J. Pugrnire, R. W. Parry, and D. M. Grant, J. Am. Chem. Soc., 1997,119,7114. T. Asakura, Y. Yamazaki, K. W. Seng, and M. Demura, J. Mol. Struct., 1998,446,179. A. Shoji, T. Ozaki, T. Fujito, K. Deguchi, I. Ando, and J. Magoshi, J. Mol. Struct., 1998,441,251. R. Salzmann, M. Kaupp, M. T. Mcmahon, and E. Oldfield, J. Am. Chem. Soc., 1998,120,477I . R. Havlin, M. Mcmahon, R. Srinivasan, H. B. Le, and E. Oldfield, J. Phys. Chem., 1997,101,8908.

2: Theoretical und Physical Aspects of Nuclear Shielding 136 137 138 139 140 141 142 I43 144 145

146 147 148 149 150

151 152 153 154 155 156 157 158

159 1 60 161 162 163 164

165 166 167 168 169 170 171 172 173 174

75

A. M. Orendt, J. Z. Hu, Y. J. Jiang, J. C. Facelli, W. Wang, R. J. Pugmire, C. H. Ye, and D. M. Grant, J. Phys. Chem., 1997,101,9169. J. G. Pearson, H. B. Le, L. K. Sanders, N. Godbout, R.H. Havlin, and E. Oldfield, J. Am. Chem. Soc., 1997,119, 11941. H. M. Sulzbach, G. Vacek, P. R. Schreiner, J. M. Glabraith, P. v. R. Schleyer, H. F. Schaffer, J. Comput. Chem., 1997,l8, 126. A. C. Wang and A. Bax, J. Am. Chem. Suc., 1996,118,2483. J.-S. Hu and A. Bax, J. Am. Chem. Suc., 1997,119,6360. N. Tjandra and S. Grzesiek, J. Am. Chem. Soc., 1996, 118, 6264. H. B. Le, J. G. Pearson, A. C. de Dios and E. Oldfield, J. Am. Chem. Suc., 1995,117, 3800. T. Head-Gordon, M. Head-Gordon, M. J. Frisch, C. L. Brooks, and J. A. Pople, J. Am. Chem. Suc., 1991,113, 5989. S. Spera and A. Bax, J. Am. Chem. Soc., 1991,113, 5490. D. D. Laws, H. Le, A. C. de Dios, R. H. Havlin, and E. Oldfield, J. Am. Chem. Soc., 1995,117,9542. J. Gauss and D. Sundholm, Mol. Phys., 1997,91,449. D. Sundholm and J. Gauss, Mol. Phys., 1997,92, 1007. A. Dransfeld and D. B. Chesnut, Chem. Phys., 1998,234,69. C. J. Jameson and A. C. de Dios, J. Chem. Phys., 1993,98,2208. C . J. Jameson, J. Am. Chem. Soc., 1987, 109,2586. C. J. Jameson, A. C. de Dios and A. K. Jameson, J. Chem. Phys., 1991,95,1069. W. T. Raynes and N. Panteli, Mol. Phys., 1983,48,439. D. Sundholm, J. Gauss and A. Schafer, J. Chem. Phys., 1996, 105, 11051. C. J. Jameson and H. J. Osten, J. Chem. Phys., 1984,81,2556. C. J. Jameson, and A. K. Jameson, J. Chem. Phys., 1986,85,5484. C. J. Jameson, A. K. Jameson, and D. Oppusunggu, J. Chem. Phys., 1986,85,5480. C . J. Jameson and H. J. Osten, J. Chem. Phys., 1984,81,4293. C . J. Jameson and H. J. Osten, J. Chem. Phys., 1984,81,4300; 1985,83,915. D. B. Chesnut and D. W. Wright, J. Cumput. Chem., 1991,12,546. W. T. Raynes, N. M. Sergeyev, P. Sandor, and M. Grayson, Mugn. Reson. Chem., 1997,35, 141. N. M. Sergeyev, N. D. Sergeyeva, Y. A. Strelenko, and W. T. Raynes, Chem. Phys. Lett., 1997,277, 142. L. J. Hasbrouck and J. M. Risley, Tetrahedron Lett., 1998,39,4191. K. Wolinski, J. Chem. Phys., 1997,106,6061. C . E. Johnson and F. A. Bovey, J. Chem. Phys., 1958,29, 1012 . C. J. Jameson and A. D. Buckingham, J. Chem. Phys., 1980,73,5684. P. v. R. Schleyer, H. J. Jiao, N. J. R. v. Hommes, V. G. Malkin, and 0. L. Malkina, J. Am. Chem. Soc., 1997,119, 12669. M. Bilde and A. E. Hansen, Mol. Phys., 1997,92, 237. M. Buhl, Chem. Eur. J., 1998,4,734. I. Alkorta and J. Elguero, New J. Chem., 1998,381. D. A. Case, J. Biomul. NMR, 1995,6, 341. A. C. de Dios and C. J. Jameson, J. Chem. Phys., 1997,107,4253. M. Buhl, S. Patchkovskii, and W. Thiel, Chem. Phys. Lett., 1997,275, 14. C. J. Jameson, H. M. Lim, and A. K. Jameson, Solid State Nucl. Mugn. Resun., 1997,9, 277. C . J. Jameson, A. K. Jameson, R. E. Gerald, and H. M. Lim, J. Phys. Chem. B, 1997,101,8418.

76 175 176 177 178 I79 180 181 I82 I83 184 185 186 187 188 I89 190 191 192 193 194 195 I96 197 198 199 200 20 1 202 203 204 205

Nuclear Mugnetic Resonunce

C. J. Jameson, A. K. Jameson, and H. M. Lim, J. Chem. Phys., 1997,107,4364. C. J. Jameson and H. M. Lim, J. Chem. Phys., 1997,107,4373. J. H. Kantola, J. Vaara, T. T. Rantala, and J. Jokisaari, J. Chem. Phys., 1997, 107, 6470. A. K. Jameson, C. J. Jameson, A. C. de Dios, E. Oldfield, R. E. Gerald 11, and G. L. Turner, Solicl Stute Nucl. Mugn. Reson., 1995,4, I . C. J. Jameson and A. C. de Dios, J. Chem. Phys., I992,97,417. C. J. Jameson, A. K. Jameson, B. I. Baello and H. M. Lim, J. Chem. Phys., 1994, 100,5965. C . J. Jameson, A. K. Jameson, H. M. Lim, and B. I. Baello, J. Chem. Phys., 1994, loo, 5977. S. M. Cybulski and D. M. Bishop, Mol. Phys., 1998,93,739. F. Yang, G. N. Phillips Jr., J. Mol. Biol., 1996,256, 762. I . Gerothanassis, P. J. Barrie, M. Momentau, G. E. Hawkes, J. Am. Chem. Soc., 1994,116, 1 1944. A. C. de Dios and E. M. Earle, J. Phys. Chem., 1997,101,8132. M. T. Mcmahon, A. C. de Dios, N. Godbout, R. Salzmann, D. D. Laws, H. B. Le, R. H. Havlin, and E. Oldfield, J. Am. Chem. Soc., 1998, 120,4784. P. J. Wilson, B. J. Howlin, and G. A. Webb, J. Mol. Struct., 1997,405, 139. F. M. Geiger, J. M. Hicks, and A. C. de Dios, J. Phys. Chem., 1998,102, 1514. C. Maerker, P. v. R. Schleyer, K. R.Liedl, T. K. Ha, M. Quack, and M. A. Suhm, J. Comput. Chem., 1997,18, 1695. K. Jackowski and A. Barszczewicz, J. Mol. Struct. (THEOCHEM), 1998,431,47. G. Zheng, L. M. Wang, J. Z. Hu, X. D. Zhang, L. F. Shen, C. H. Ye, and G. A. Webb, Magn. Reson. Chem., 1997,35,606. J. Vaara, K. Ruud, 0. Vahtras, H. Agren, and J. Jokisaari, J. Chem. Phys., 1998, 109,1212. J. Vaara, J. Kaski, J. Jokisaari, and P. Diehl, J. Phys. Chem., 1997,101,9185. C . J. Jameson, A. K. Jameson, D. Oppusunggu, S. Wille, P. M. Burrell, and J. Mason, J. Chem. Phys., 1981,74,81. E. Diez, J. San Fabian, I. P. Gerothanassis, A. L. Esteban, J.-L. M. Abboud, R. H. Contreras, and D. G. de Kowalewski, J. Magn. Reson., 1997, 124,8. M. Witanowski, Z. Biedrzycka, W. Sicinska, Z. Grabowski, J. Mugn. Reson., 1998, 131,54. S. Miertus, E. Scrocco and J. Tomasi, Chem. Phys., 1981,55, 117. M. A. Vincent, I. J. Palmer, and I. H. Hillier, J. Mol. Struct. (THEOCHEM), 1997, 394, 1. P. 0. Astrand, K. V. Mikkelsen, K. Ruud, and T. Helgaker, J. Phys. Chem., 1996, 100,19771. R. Ludwig, F. Weinhold, and T. C. Farrar, Ber. Bunsenges. Phys. Chem., 1998, 102, 197. R. Ludwig, F. Weinhold, and T. C. Farrar, Ber. Bunsenges. Phys. Chem., 1998, 102, 205. R. Ludwig, F. Weinhold, and T. C. Farrar, J. Phys. Chem., 1997,101,8861. R. Ludwig, F. Weinhold, and T. C. Farrar, J . Chem. Phys., 1997, 107,499. J. A. Tossell, J. Magn. Reson., 1997,127,49. M. Gastreich and C. M. Marian, J. Comput. Chem., 1998, 19, 716.

J

Applications of Nuclear Shielding BY M. YAMAGUCHI

1

Introduction

The format of this report remains similar as in the previous years. Various chemical and physical influences to nuclear shieldings are considered in the first section. The shieldings of particular nuclear species are described in the following section according to their position in the Periodic Table. Since there are huge numbers of articles on NMR spectroscopy during the period of this review, the coverage of this report is restricted to widely available and common journals, which are published in English, due to space limitation.

2

Various Chemical and Physical Influences to Nuclear Shieldings

2.1 Computer Assisted Structural Assignment - 2.1.1 Spectrum Simulation, Computer Assisted Assignments, and Related Techniques - A sequential assignment protocol for proteins was developed using heteronuclear 3D NMR.' A model for the prediction of the proton chemical shifts in substituted alkanes (CHARGE4) was extended to include a variety of bromo- and iodo-alkanes.* A computer program, named ORB, was developed to predict 'H, I3C, and 15N NMR chemical shifts of previously unassigned protein^.^ An automated NMR assignment software package, CAPRI, was used in a procedure for amino acids r e ~ o g n i t i o nA . ~ neural network based determination was developed for amino acid class and secondary structure of 15N labeled proteins.' A spin system assignment tool was described for the automated assignment of high-resolution three-dimensional protein NMR spectm6 A computer program, SHIFTY, was developed to accurately and automatically predict the ' H and I3C chemical shifts of unassigned proteins on the basis of sequence h o m o l ~ g u e sA . ~novel graphical method was given for the determination of the complex NMR shift and equilibrium constant for a hetero-association accompanying self-associations.' The I3C NMR chemical shift of sp3 carbon atoms situated in the a position relative to the double bond in acyclic alkenes was estimated with multilayer feed forward artificial neural networks and multilayer regression.' A new method for three-dimensional spectrum prediction, CSERCH-STEREO, was reported permitting incorporation of stereochemical features to improve the quality of the obtained chemical shift values. l o Nuclear Magnetic Resonance, Volume 28 @> The Royal Society of Chemistry, 1999

77

78

Nuclear Mugnet ic Resonunce

2.1.2 Nticlear Shielding Calculations - Shielding tensors of the protons inside and outside the aromatic 1,%dihydro-[ 141-annulene ring, and of the corresponding protons in a closely similar open chain, were computed ab initio using the LORG method. Accurate (root-mean-square error -3 ppm) predictions of I3C chemical shifts were achieved for many of the common structural types of organic molecules through empirical scaling of shieldings calculated from GIAO theory with a small basis set and with geometries obtained from molecular mechanics methods.I 2 The semi-empirical bond polarization theory was applied to the calculation of I3C chemical shift tensors. l 3 13CNMR chemical shift calculations were reported for azepines and diazepines (ab initio and DFT cal~ulation),'~ for CH3F, CH3CI and CH3Br (SCF-CHF/LORG procedure and moderately large basis sets),15 and for diamond, chemical-vapor-deposited diamond, and diamondlike amorphous carbon. l 6 'H and I3C NMR chemical shift calculations were reported for solid acetylene (the couples Hartree-Fock (CHF) p r o c e d ~ r e ) , 'for ~ mercurimethanes and organomercury hydrides (DFT calculations, comparing quasirelativistic and nonrelativistic effective-core potentials)," for a select group of cyclopropyl systems (ab initio/gauge-independent A 0 procedure), l 9 for 1,3-diheterocyclohexanes (DFT procedure),20 and for substituted benzylic mono- and dications (DFT/IGLO procedure).2' The GIAO approach was used within the coupled Hartree-Fock approximation to compute the 'H, I3C,and 15N NMR shielding constants in two tautomeric forms of both the histamine molecule and its protonated form.22 'H, 13C, 15N NMR and ab initio/IGLO/GIAO-MP2 calculations were used to study mono-, di-, tri-, and tetraprotonated g ~ a n i d i n eThe . ~ ~ dependence of the 13C, "N, and 'H isotropic NMR chemical shifts on amine substitution of aromatic ring systems were examined both experimentally and by DFTIGIAO methods.24 Temperature dependence 'H, I4N, and I7O NMR chemical shifts and quadrupole coupling constants for the amide hydrogen, the nitrogen, and the carbonyl oxygen nuclei in neat, liquid N-methylacetamide were calculated by ab initio methods and compared with experimental measurement^.^^ Triple-zeta basis sets with two polarization functions were used to calculate the electronic properties of ten mesoionic compounds and the 13C and I5N chemical shifts were calculated using the GIAI-CHF procedure.26 GIAO calculated 'H, I3C, I7O NMR chemical shifts as obtained at various computational levels were reported for the three parent compounds phenol, benzaldehyde, and salicylaldehyde, and for 13 different benzoyl and the 13 corresponding 2-hydroxybenzoyl compounds.27 170 and I3C NMR chemical shifts of a series of oxonium and carboxonium ions and their corresponding protonated dications were investigated by ab initio/IGLO/ GIAO-MP2 methods.*' 6Li and 13Cnuclear magnetic shielding constants of 3-Nmethylamino-N-methylpyrrolidine lithium amide and its complex with methyllithium were calculated using ab initio/DFT procedure and compared with the experimen taI resu~ t s.29 I'B NMR chemical shifts and structures of the 12-vertex oxa- and thia-nidododecaborate, and B13H132-were studied by DFT/GIAO method.30 I'B and I7O

''

3: Applications of Nuclear Shielding

79

NMR parameters were calculated for B203 and alkali borate glasses using ab initio self-consistent field MO theory.31 A good correlation was found between DFT calculations of carbonyl I7O NMR chemical shifts for substituted trifluoromethyl aryl ketones and those observed in CC14 solution.32The experimental values of the I7O NMR chemical shifts in the carbonyl group were compared with ab initio values.33 NMR chemical shift calculations at the SOS-DFPT/PW9 1/[7s6p2d/5s4pld/3s]// B3LYP/6-31G(d) level of theory were used to study the trimethylsilylium cation.34 Ab initio quantum mechanical calculations of 3'P NMR chemical shift shieldings were performed at the MP2 level of theory on the neutral and singly charged 7-phosphabicyclo[2.2.llheptane, -heptene, and -heptadiene neutral, cationic, and anionic molecules using a P:tz2p/C:tzp/H:dz locally dense basis set.35 Chemical shieldings of the S nucleus were calculated with the GIAO method for a wide range of organic and inorganic S compounds, using the 6-31 l++G(2d,2p) basis set.36 Substituent effects on 33S NMR parameters in 3-XC6H4S03Na ( X = N 0 2 , NH3+, CF3, SO3-, OH, H, CH3, NH2, and 0 - ) were studied t h e ~ r e t i c a l l yGradient-correlated .~~ levels of DFT, medium-sized basis sets, and optimized geometries, were used to calculate "V NMR chemical shifts and reactivities of oxovanadium(V) corn pound^.^^ 59C0 NMR chemical shift calculations were reported for [ C O ( N H ~ ) ~ ] [CC~O~(, N H ~ ) ~ C O ~and ] B ~C, ~ ( a c a c )for ~,~~ [CO(NH~)~X]'~+")+ (X= NO-, SCN-, SS032', Cl-, OCO;-, ONO-, N3-, H20, NOz-) c o r n p l e x e ~hexacoordinated ,~~ diamagnetic cobalt(II1) complexes (DFTIGLO and DFT-GIAO proced~re).~' DFT method was used to predict the isotropic 59C0 NMR chemical shifts and shielding tensor elements of some Co(II1) complexes.42 The 93Nb and 47Ti NMR chemical shifts of niobium hexahalides and titanium tetrahalides were studied by the ab initio UHF/finite perturbation method including the spin-orbit i n t e r a ~ t i o nCalculations .~~ of '25Te NMR chemical shifts were reported for a number of organic, inorganic, and organometallic Te-containing complexes using GIAO and DFT.44 Interaction energies and NMR chemical shifts of noble gases (He, Ne, Ar, Kr and Xe) in c 6 0 were calculated at the counterpoise-correlated MP2/6-3 1G** level (using a DZP basis for Kr and Xe).45 The intermolecular nuclear magnetic shielding surfaces for '29Xe in the systems Xe-CO2, Xe-N2, and Xe-CO using a gage-invariant ab initio method at the coupled Hartree-Fock level with GIAO procedure.46 The reliability of 'H NMR chemical shift calculations for DNA was assessed by comparing the experimental and calculated chemical shifts of a reasonably large number of independently determined DNA structure^.^^ Using the protein crystal structure the chemical shift dispersions of binase a-CH protons were calculated for protein in native state and in a compact denatured 2.2 Stereochemical Nuclear Shielding Non-Equivalence - 2.2.I Chirality Determination by Mosher's and Related Methods - The Mosher's MTPA esters method or related modified method was applied to determine the absolute configuration of corchoionosides A, B, and C, histamine release inhibitors from the leaves of Vietnamese Corchorus olitorius L. ( T i l i a ~ e a e )incarvilline ,~~ and a new alkaloid, hydroxyincarvilline from Incarvillea ~inensis,~' 4-deoxyannomontacin and (2,4-

80

Nuclear Mugnetic Resonance

cis and trans)-annomontacinone from Goniothalamus g i g a n t e ~ s , ~ several ' longchain catechols from Plectranthus sylvestris (Labiatae),52 the fragments composing the phytotoxin p h ~ m a l i d e some , ~ ~ hydroxy-fatty acids produced by the insect genus L a ~ c i f e r (-)-galbonolide ,~~ A,55 coriacyclodienin and coriacycloenin from Annona ~ o r i a c e a ,stephaoxocanidine ~~ from Stephania ~ e p h a r a n t h a , ~ ~ aplyolides A-E, from the skin of the marine mollusk Aplysia d e ~ i l a n nor,~~ zoanthamine, a promising candidate of an osteoporotic 12-hydroxybullatacins A and B from Rollinia mucosa,60 some new diterpenoids from the alga Dictyota dichotoma,61C-3 of synthetic panaxytriol,62 (2,4-cis and trans)-gigantecinone and 4-deoxygigantecin from Goniothalamus g i g a n t e ~ s nodulisporic ,~~ Acid A from a Nodulisporium S P . , ~fluoromethylated secondary alcohols,65 some Marine Metabolites from Cystoseira ~ p p . several , ~ ~ antimycobacterial polyynes from Devil's Club (Oplopanax horridus; A r a l i a ~ e a e ) ,the ~ ~ polyacetylenic constituents of Ginseng Radix Rubrd,68 cis-2-hydroxycyclohexanamineand corresponding ethers by asymmetric reductive a m i n a t i ~ n 5-substituted ,~~ cyclohexenones via nucleophile addition to (all!oxyarene)chromium tricarbonyl comp l e ~ e s , ~petrocortynes ' and petrosiacetyimes from a sponge of the genus Petr~sia,~ isosaraine' 1 and isosaraine-2 from the Mediterranean sponge Reniera , ~ ~ new triquinane-type sesquiterpe~ a r a i a, ~group ~ of d i p y r a n o c o ~ m a r i n ssome noids from Macrocystidia cucumis (basidi~mycetes),~~ novel ent-vibsane- and dolabellane-type diterpenoids from the liverwort Odontoschisma d e n ~ d a t u m , ~ ~ cladocoran A and B from the Mediterranean coral Cladocora c e ~ p i t o s a . ~ ~ (S)-phenylglycine methyl ester was applied to elucidate the absolute configuration by ' H NMR of a series of aliphatic carboxylic acids, Ph(CH2),CHRC02H (n = 1-6; R = Me, Et).77 'H NMR spectra of an a-chiral carboxylic acid esters with (R)- and (S)-ethyl 2-(9-anthryl)-2-hydroxyacetate gave the absolute configuration a ~ s i g n m e n tThe . ~ ~ factors governing the efficiency of arylmethoxyacetic acids for the determination of the absolute configuration of alcohols by NMR, were identified and their influence was studied.79 Menthyldichlorophosphate, ROP(:O)C12 (R = menthyl) reacted readily with a variety of chiral and meso-vicinal and 1,3-diols to yield phosphate esters that exhibit diastereomeric differences in the 31PNMR spectra." Esters of 1-( 1 -(naphthyl)ethylurea derivatives of some amino acids were examined as chiral NMR resolving shift reagents.8' 2.2.2 Other Stereochemistry Determination Chiral recognition by 'H NMR for epoxides in the presence of a chiral dirhodium complex, (R)-Rh2(MTPA)4.82 Proton-decoupled 13C NMR in a lyotropic chiral nematic solvent was studied as an analytical tool for the measurement of the enantiomeric excess.83The NMR spectroscopic interactions of ephedrine and N-methylephedrine with three pcyclodextrins were studied to discriminate ~hirality.'~ Chiral recognition of aamino acid derivatives by charged p-cyclodextrins was studied by 'H NMR." Heptakis(2,3-di-O-acetylated)-p-cyclodextrinwas tested for its utilizability to check the enantiomeric purity of the chiral protonated phenethylamines, such as selegiline, amphetamine and norephedrine, by N MR.86 Recognition of the helicity of 1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid by linear oligosaccharides was studied by H NM R and capillary zone electroph~resis.~~ ~

'

3: Applications of Nuclear Shielding

81

2.3 Isotope Effects - Deuterium isotope effects in 13C NMR spectra of transazobenzene," of cis- and trans-~tilbene,~~ of amides," of deuterated [2.2]metacyclophanes:' of o-hydroxyacyl aromatics,92 of en am in one^,^^ and of the enolenaminone tautomerism of a-heterocyclic ketones94were reported. Deuterium isotope effects on H and 13C chemical shifts of intramolecularly hydrogen bonded perylenequinones were r e p ~ r t e d . ~Secondary ' isotope effects on 13C chemical shifts were measured in a series quinolinols, quinaldinic acid Noxides and quinoline-2-carboxyamide N - ~ x i d e .Primary ~~ and secondary deuterium isotope effects on 'H and I3C chemical shifts were measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure.97 Exchange of amide protons with 2H gave isotope effects on 13CNMR chemical shifts for carbon atoms near the site of sub~titution.~' Threedimensional, triple resonance NM R techniques were described for measurement of two-bond (intraresidual) and three-bond (sequential) amide deuterium isotope effects on 13Cachemical shifts.99 2H, 13C, 15N, "0 isotope effects on acid-base equilibria were determined by 13C NMR. loo Long-range intrinsic and equilibrium deuterium isotope effects on 19Fchemical shifts were reported.'" An experimental study of isotope effects on NMR parameters for "B(2/1 H), I3C(2/lH), 15N(2/lH), 3'P(2/l H), 95M0(13/12C), and 199Hg(l3/12C) in the solid-state was reported.'02 Solid-state I5N NMR and theoretical studies of primary and secondary geometric deuterium isotope effects were measured on low-barrier NHN-hydrogen bonds. Io3

'

2.4 Substituent Effects - 2.4.2 Proton Substituent Effects - Analysis of the N MR shifts of unsaturated carbon atoms in monounsaturated linear-chain esters and acids ruled out any explanation in terms of an 'electric field effect', but was semiquantitatively consistent with a 's-inductive' mechanism.'04 Substituent induced I H chemical shifts of 3-substituted camphors was reported."' Substituent effects in 'H and 13C NMR chemical shifts were analysed for 11 orthosubstituted thiocyanatobenzenes,Io6 for some azobenzenes and N-benzylideneanilines,Io7 for some 2- and 3-thiophenecarboxanilides(meta- or parasubstituted in the phenyl ring),"' for seventeen (E)-benzaldoximes and three acetophenone oximes, both carrying substituted p-amino group^,'^' and for substituted furans. ' l o 2.4.2 Carbon and Heteroatom Substituent Effects - Substituent effects in I3C NMR were reported for para-substituted benzylideneacetones with long distance electronic effects'' and for four p-substituted a-phenylcinnamic and six 3- and six 4-pyridylacrylic acids.I12 The substituent effects of a solid-state I3C NMR chemical shift in the principal values in methoxynaphthalenes were studied. l 3 Nitrogen NMR chemical shifts of 2-amino-5-nitro-6-methylpyridine derivatives were measured to study substituent induced effects of alkyl, aryl, nitro, and nitroso substituents on the amino nitrogen.' l4 Natural abundance 170NMR spectra of 4-substituted N-chlorobenzamides were obtained in acetonitrile at 75°C and compared with those for similarly substituted benzamides to show substituent effects.Il5

82

Nuclear Magnetic Resonance

The ability of the monoatomic 0-spacers SiMe2, CMe2 and CH2 to mediate substituent effects in 4- and 4,4'-substituted dimethyldiphenylsilanes 2,2diphenylpropanes and diphenylmethanes, respectively, was studied by 29Si and I3C NMR.Il6 I3C and Il9Sn NMR were used to study 3-substituted(X)bicyclo[l . l . l]pent-1-yltrimethylstannanes to show through-space transmission of polar substituent effects.' l 7 The IH, I3C, 170NMR spectra for para- and meta-substituted 4-arylaminopent-3-en-2-ones (acyclic enaminones) and 3-arylaminocyclohex-2-en-1-ones (cyclic enaminones) were reported to investigate substituent effects and intramolecular hydrogen The 'H, 13Cand 15N NMR spectra of a series of 5-alkylthio-3-aryl-2-cyano-5-dialkylaminopenta-2,4-dienenitriles with different amino and aryl substituents were recorded to correlate with electronic effects of the substituents on the donor side of the butadiene system and also the para-Ph substit~ents."~ The 'H, I3C and 19F NMR spectra of 3'- and 4'-substituted 3and 4'-substituted 3- and 4-fluorobenzanilides and thiobenzanilides were measured to show the 19F substituent-induced shifts, transmission of substituent effects through the thiocarboxamide group. I2O The 13C chemical shifts of nine 2-X-substituted phenetol derivatives were measured together with the I3Cchemical shifts of the corresponding X-monosubstituted benzenes to study the ethoxy group conformational effect on I3C chemical shifts.12'

2.5 Intramolecular Hydrogen Bonding Effects and Related Effects - 'H NMR and some spectroscopic or theoretical methods were used to study intramolecular hydrogen bonding in some P-diketones having a substituent at the a position,122 123 the 7c-conjugated in 1, I'-Bis[N-formyl-N'-p-chlorophenylthiourea]ferrocene, . . .O=C--C=C-OH. . .P-diketone enol in triamides Me2NCO(CH2),CH2CONH(CH2),CONHMe (n,m = 1 ,l; 2,l; 1,3; 2,2; 3,3), diamine Me2NCO(CH2)4CONHMe, and related compounds,125 in 2-hydroxybenzaldimine compounds.'26 Three N-oxides of Schiff bases (nitrones) with intramolecular hydrogen bonds were studied by FT-IR and 'H and I3C NMR.'27 Several oxamide derivatives were studied by 'H, I3C, I5N and variable temperature NMR to show three-center intramolecular hydrogen bondings.128Five (2hydroxyalky1)phosphoryl compounds (Rl2P(0)CH2CH(OH)R2; R' = MeO, R2 = Ph; R' = R 2 = Ph; R ' = Ph, R 2 = But; R1 = Me, R 2 =Ph; R' = Me, R2=Bu-') were studied using x-ray crystallography, IR, and NMR to show substituent effect on the nature of the hydrogen bonding.'29 Two types of aminopolyin aqueous phosphonates, (CH~)2.p(CH2P03)pN(CH2)mN(CH2P03)p~(CH~)~-p~ solution were investigated by means of potentiometry and 31PNMR to show protonation behavior and intramolecular interactions. I3O 2.6 Bond Anisotropy, Ring Current Effects and Aromaticity - The structure, aromaticity, and magnetic properties of o-benzyne and 1 I related model compounds were studied theoretically. 1 3 ' The unsubstituted 1,2,5-trithiepin was synthesized and its 'H and 13C NMR spectra were analysed as a l07c-electron heteroaromatic system.132An [11][13]-

3: Applicutions of Nuclear Shielding

83

fulvalene derivative, 13-(4,9-methanocycloundeca-2,4,6,8,lO-pen taeny1idene)-4,9dimethylcyclotrideca- 1,3,9,11-tetraene-5,7-diyne, was synthesized and ring current effects arising from 1On- and 14n-electron systems were not detected by 'H and 13CNMR.'33 The ring currents in the sterically congested and highly nonplanar porphyrin complexes were studied using a double-dipole model of the porphyrin ring ' ~ ~ benz~carbaporphyrin'~~ were prepared current effect. 134 A ~ u l i p o r p h i l i n and and their NMR and UV-vis spectra were discussed to study the borderline porphyrinoid aromaticity. The tropicity of the catalytic partial hydrogenation products of the 5,lOdimethyl-6,8-bisdehydro[1 3lannulenone were discussed on the basis of H NMR.'37 The bridged [ 14lannulene dimethyldihydropyrene was used as the aromatic ring current probe in [ 14lannulene fused organometallics. 138 The first example of an iso[ 17]annulenopyrrole, trans-N-cyclohexyl-2',5', 1Ob, 1Oc-tetramethylpyrrolo[3,4-e]- 1Ob, 1Oc-dihydropyrene, was synthesized and its diatropicity was studied. 139 [ 18lAnnulen derivatives, anti,anti-8,17-epithio- 1,6:10,15-bismethano[ 18]annulene-7,18-dione and its dicationic species were prepared and their electronic structures studied by X-ray crystallography and ' H and 13C NMR.I4'

'

2.7 Intermolecular Hydrogen Bonding Effects, Inclusion Phenomena and Related Effects - 2.7. I Proton and Heteronudear Shifts - The acid-amide intermolecular hydrogen bonding of a 2,2-dimethylbutynoic acid dimer with a pyridinone terminus was studied in crystals by X-ray crystallography, in chloroform solutions by ' H NMR, vapor phase osmometry, and in the gas phase by FABMS.I4' Chemical shift measurements and discussion of specific splitting of some signals in 'H NMR spectra of amides and alkylureas in guanidine-HCI solutions were reported. 142 Ethanol self-association was studied by NMR in binary aqueous mixtures and in mixtures containing urea as a third c ~ m p o n e n t .The ' ~ ~'H NMR chemical shift was measured for water from 25 to 600°C and from 1 to 400 bar to study the hydrogen bonds in supercritical water. '41 2.7.2 Cyclodextrins (CDs) - The a-CD inclusion complex with poly(&caprolactone),145 with ionene-6, I0 dibromide and 1,10-bis(trimethy1ammonium) decane d i i ~ d i d e ,with ' ~ ~ 4-fluorophen01,'~~ were studied by NMR. The complexation properties of a-CD and a water-soluble sulfonated calixarene, with dimeric viologen guests were investigated by 'H NMR and ~ o l t a m m e t r y .The ' ~ ~ addition of alkali salts of chaotropic anions to an a-CD solution in D20 caused marked downfield shifts in the 'H NMR signal of the C(5)-H located in the interior of the a-CD cavity.'49 'H NMR spectra of a-CD and p-nitrotoluene with laserpolarized '29Xe was reported. 150 The p-CD inclusion complex with acenaphthene, 5 1 diclofenac (sodium salt of 2-[(2,6-dichlorophenyl)amino]benzeneaceticacid),'52 with g l i ~ l a z i d e , 'with ~ ~ 1naphthalenesulfonate,'54 with 1,8-dimethyInaphthalene, 155 with sodium alkyl ~ u l f o n a t e ,with ' ~ ~ c i p r o f l ~ x a c i n ,with ' ~ ~ the semisynthetic sweetener, neohesper-

'

Nuclear Magnetic Resonance

84

'"

idin dihydrochalcone, with tetrahelicene dicarboxylic acid, with poly(4sodium styrenesulfonate),'60 with ring A of cholesterol'6' were studied by 'H NMR and some spectroscopic analyses. A detailed structural study of the inclusion compounds of some substituted phenols with (3-CD was carried out by UV-vis, fluorescence, ' H and solid-state 13CNMR and potentiometric investigations.'62 The p-CD, heptakis(2,3-di-O-acetyl)p-CD,and heptakis(6-0-acetyl)pC D with ephedrine and N-methylephedrine were studied by UV spectroscopy and NMR. 6A-Amino-6A-deoxy-P-CD and 3A-amino-3A-deoxy-(2AS,3A,S)p-CD inclusion complex with 3-nitrophenyl esters of 2-phenylpropanoic acid and ibuprofen were studied by 'H NMR. 164 The hydroxypropyl-P-CD, dimethyl-PC D and p-CD inclusion complexes with ~lofibrate,'~'and with tretinoin,'66 with sulfaguanidine, sulfafurazole, sulfaproxyline and sulfathiazole, were studied by H NMR and some spectroscopic analyses. The hydroxypropyl-P-CD inclusion complex with haloperidol was studied by ' H NMR.16' The partially methylated p-CD inclusion complex with gliclazide was studied by phase solubility and ' H NMR. 169 Two p-CD derivatives inclusion complexes with haloperidol were studied by SDC and ' H NMR.I7' Several water soluble p-CD derivatives inclusion complexes with spironolactone were studied by ' H NMR.17' The hydroxypropyl-P-CD inclusion complex with methocarbamol was studied by H NMR, DSC, and IR.'72 The p- and dimethyl-P-CD inclusion complexes with papaverine were studied by DSC and X-ray diffractometry, C D spectroscopy, and ' H NMR.'73 A solid complex of c60 with y-CD was studied by ' H NMR and 13CCP/MAS NMR.'74 The y-CD inclusion complex with some poly(alky1 vinyl ether) were studied by IR, ' H NMR, 13C NMR, X-ray diffractometry, and thermal and elemental analyses. 175 The a- and p-CD inclusion complex with 2,6- and 2,9-substituted bicyclo[3.3.llnonanes were studied by H NMR.'76 a-, p-, and Hydroxypropyl-aC D inclusion complexes with water-soluble polyester, synthesized from dimethyl octane- 1,8-dicarboxyIate and polyethylene glycol were studied by surface tension measurements, H NMR, and titration microcalorimetry. 177 The a-and y-CD inclusion complexes with diheptanoylphosphatidylcholinewere studied by 'H NMR.'78 4 Cyclodextrins (parent p- and y-CDs and hydroxypropylated p- and yCDs) with spironolactone in aqueous solution and in the solid state were investigated by 13C CPlMAS NMR, powder X-ray diffractometry and thermal a n a 1 y ~ e s . IThe ~ ~ preparation and 'H NMR and XPS studies of self-assembled monolayers from preformed inclusion complexes of CDs and thiols on Au electrodes was described. The interactions of guest moieties attached as side chains on a polymer chain with a-, p-, y-CDs were studied by NMR."' The a-, p-, y-CD inclusion complexes with aliphatic polyesters were studied by FTIR, 'H NMR, I3C CP/ MAS NMR, and X-ray diffraction.'82

'

'

2.7.3 Other Molecular Recognition - The binding properties of the 1,3-bridged calix[5]crowns towards a number of quaternary ammonium, phosphonium, and iminium ions were investigated by ' H NMR in CDC13 solution.'83 'H NMR was

3: Applications of Nucleur Shielding

85

used to study the complexation reaction between lithium ion and 12-crown-4, 15crown-5 and 18-crown-6 in a number of binary acetonitrile-nitrobenzene mi~tures.''~The orthogonal dimer structure of m-xylene type dithioureas in solution and solid state was elucidated on the basis of 'H NMR, vapor pressure osmometry and X-ray crystallography. Complexation of macrocyclic azoniacyclophane CP44 with fluorinated phenyl compounds was studied by 'H NMR.'86 The interaction of xenon with cryptophane-A in 1,1,2,2Cyclohexanetetrachloroethane-d2 was investigated by '29Xe and 'H NMR. d l l was used to probe the interior environments and ring inversion dynamics of two self-assembling molecular capsules. '88 Shift Reagent - Three new formulations of TmDOTP" (DOTP8'= 1,4,7,10tetraazacyclododecane- 1,4,7,11-tetrakis(meth ylenephosphonate)) were prepared as 23Na NMR frequency shift reagent to study ion-pairing interactions with C ~ ( e n ) ~ ~ ' .The conformational analysis of some lactones was performed by the lanthanide induced shift (LIS) technique, using Yb(f0d)3.'~' A general approach was introduced for resolving signal overlap in the NMR spectra of proteins by the differential shifts induced upon the addition of a stable paramagnetic lanthanide complex. 19' (S)-a-Methoxyphenyl- and (S)-a-methoxy-2-naphthylaceticacids were used as NMR chiral shift reagents for the stereochemical analysis of chiral alkyl s ~ l f o x i d e s .(S)-a-Methoxyphenylacetic '~~ acid was used as an NMR shift reagent to predict the absolute configuration of some sulfoxide-containing sugars. 193 'H ' ~ ~a n t i ~ y r i n ewere ' ~ ~ studied in CDCl3 solution at NMR spectra of ~ i t i o l o n eand ambient temperatures with the achiral lanthanide shift reagent and with the chiral lanthanide shift reagent. Two chiral crown ethers with lanthanide tetrakis(Pdiketonate) and silver P-diketonate were used as chiral NMR shift reagents for amino acid esters, amines and amino alcohols.'96 Chiral carboxylic acids such as N-(R)- 1-(1-naphthyl)ethylaminocarbonyl-L-tert-leucine, N-(R)- 1-(1-naphthyl)ethylaminocarbonyl-L-valine and N-(3,5-dinitrobenzoyl)-~-leucinewere solubilized in CHC13 by the addition of NEt3 and the resulting ion pairs were useful chiral resolving agents for sulfoxides, amines and alcohols.'97 The well known drugs (S)-Ibuprofen and (S)-Naproxen were used as NMR shift reagents for the stereochemistry analysis of alkylsulfoxides.'98 Enantiomeric composition of ibuprofen in bulk drug was determined by ' H NMR with a chiral lanthanide chelate. 199 0-Nitromandelic acid, easily prepared from either enantiomer of mandelic acid, was used as a chiral solvating agent for the determination of enantiomeric purity of several diamine derivatives and other compounds.200 Chiral tetrakis europate anions are used to spectroscopically resolve racemic mixtures of chiral alkylmethylphenylsulfonium ions using 'H NMR.20' Optically active 2,3'-dihydroxy- 1,l '-binaphthyl derivatives were used as chiral shift reagents in the chiral recognition of cyclic N-Me amino alcohols and non-cyclic compounds (ephedrine, pseudoephedrine). 202 Tris[tetrachlorobenzene-1,2-bis (oxa1ato)lphosphate anion (TRISPHAT) was an efficient NMR chiral shift The chlorocobalreagent for cationic tris(bis-imine)ruthenium(I I) ~ornplexes.~'~ t(II1) complex of apap-tetramethylchiroporphyrin,CoCl(TMCP), was prepared

2.8

86

Nuclear Magnetic Resonance

as a potential enantioselective host or chiral NMR shift reagent for optically active a m i n e ~ . ~ New ' ~ chiral hosts for carboxylic acids were synthesized and their capacity for discrimination of enentiotopic nuclei and binding properties were explored by NMR.205

2.9 Miscellaneous Topics - IlJPAC 1997 recommendations were given for parameters and symbols for use in NMR.206The intrinsic accuracy of the NMR derived biological structure models in solution was discussed.207 The 'H (300 MHz) and 13C(75 MHz) NMR chemical shifts for >30 common impurities, such as laboratory solvents, stabilizers, greases and water, were reported in seven deutera ted NM R solvents.208 The influence of magic angle spinning on sample temperature was discussed.209 The calibration of temperature in a magic-angle spinning probe with lead nitrate was The temperature dependence of the 'H, 13C, and I4N isotropic chemical shifts of isocyanomethane, CH3NC was measured.2' The 6Li CP/MAS NMR spectra of several commonly available lithium-containing solids were obtained and lithium acetate hydrate was recommended for the 6Li CP/MAS experiment setting

'

2.10 Reviews - A review was given on solution NMR beyond 25 kDa,*I3 on NMR applications to fatty acids and triacylgly~erols,~'~ on NMR of molecules in the gas on NMR of metal hydrogen on the authentication and quality assessment of virgin olive oil using 'H and 13C NMR,2'7 on the recent progress in surface NMR-electrochemistry,2's on high-pressure NMR including apparatus, studies of model membranes, and two-dimensional NMR at high on the use of NMR to probe the structure of interfacial water of organized assemblies, such as aqueous micelles, reverse micelles, and water-inoil microemulsions,220 on the applications of NMR and molecular modeling to the study of protein-carbohydrate interactions.221Some review articles were given on polymer science fields using NMR methods for elucidating structure and dynamics of polymers,222for structures and dynamics of polymer gel systems,223 for crosslinked polymers,224 for the conformational connection between the microstructure of polymers and their N MR spectra.225

3

Shieldings of Particular Nuclear Species

During the period of this review, the NMR spectra of most elements have at least received some chemical, biological, or physical investigation. Due to the space limitation, structure determination and related studies of natural products or macromolecules will be excluded for the most popular nuclei ('H, I3C, l4*I5N, I9F, and 3'P).

3.1 Group 1 ('H, 'H, 3H, 697Li,23Na, 87Rb,133Cs) - 3.2.2 Hydrogen - ('H) - A review was given on H NMR studies of the structure of neuropeptide Y and its analogs.226

3: Applications of Nuclear Shielding

87

Temperature coefficients were measured using by 2D NMR methods for the amide and C"H proton chemical shifts in two globular proteins, bovine pancreatic trypsin inhibitor and hen egg-white l y ~ o z y m e . ~ ~ ~ Temperature-dependent gas-phase H NMR spectra of seven thiocarbonylsubstituted N, N-dimet hyl thioamides (YSCN(CH3)2) were reported.228 The formation of alkali metal ion complexes with the crown ethers, 18-crown-6, benzo18-crown-6, and dibenzo-18-crown-6 was studied by 'H NMR and a b initio theoretical calculations.229 'H NMR based on the CRAMPS technique was used to identify and monitor the protons of surface Al-OH groups and 'physisorbed' water associated with a high-surface-area (230 m2/g) pseudo-boehmite material following dehydration in the 1 10- I 100"C temperature range.23oInfluence of 'H NMR chemical shift anisotropy on magic-angle spinning spectra of hydrate crystals was reported.23' 3.1.2 Deuterium ('H) - 2H NMR was used to study the distribution of 2H atoms in brain lactate in rats after i.p. injection of 2H20.232 2H NMR of choline-deuterolabeled 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC-a-d2 and POPC-fbd2) was used to detect and quantify domain formation induced in cationic lipid-containing bilayers upon the addition of anionic polyele~trolytes.~~~ The 2H double-quantum-filtered NMR spectrum of isolated rat sciatic nerve, equilibrated with deuterated saline, was composed of three quadrupolar-split water signals.234Three kinds of 2H-labeled Bombyx mori silk fibroin fibers were prepared and their structural characterization were performed by solid-state 2H NMR.235 13C NMR at 125.76 MHz with 'H and 2H decoupling, 2H NMR at 76.77 MHz with 'H decoupling, and 'H NMR at 500.14 MHz with 2H decoupling were employed as analytical tools to study the comple: mixtures of deuterated ethanes resulting from the catalytic H-D exchange of normal ethane with gas-phase deuterium in the presence of a platinum The carbon, nitrogen and hydrogen stable-isotope contents of nicotine extracted from tobacco leaves were determined by Isotope Ratio Mass Spectrometry (overall 2H, I3C and 15N contents) and by the SNIF NMR method.237The SNIF NMR method was also applied for adulterated bitter almond and cinnamon oils using benzaldehyde as a molecular probe,238for glycerol samples extracted from plant lipids, obtained in the fermentation of sugars, or from commercial sources,239and for the determination of the authenticity of Brazilian orange juice (Citrus ~inensis).~~' 'H and 2H NMR were used to study the saturated, monounsaturated, and polyunsaturated fatty acids from fish lipids.24' Solid-state deuterium NMR was used to study the dynamics of organic molecules in the as-synthesized high-silica tectosilicate n 0 n a s i 1 . ~ ~ ~

3.1.3 Tritium ( j H ) - 3H NMR was used to characterize 3,5-[3H6]dimethoxy-4hydroxyacetophenone, an inducing compound of the vir Gene in Agrobacterium t ~ m e f a c i e n s the , ~ ~ complex ~ formed by [4-3H]benzenesulfonamide and human carbonic anhydrase I,244 and 25,26,26,26,27,27,27-heptafluoro15-ketosterols labeled at C-23 with 2H or 3H.245

88

Nuclear Magnetic Resonance

3.1.4 Lithium (6,7Li) - 6Li and I5N NMR were used to study lithium diisopropylamide (f'Li]LDA and [6Li, "NILDA) in toluene/pentane solutions containing a variety of mono- and polydentate l i g a n d ~ to , ~ study ~ ~ solution structures of a chiral bidentate lithium amide in relation to the solvent-dependent enantioselectivities in deprotonation reaction,247 to study [6Li]LiPMP (LiPMP = lithium- 2,2,4,6,6-~entamethylpiperidide)and [6Li, I5N]LiPMP in hydrocarbon solution to reveal a mixture of four isomeric cyclic tetramers and one isomeric t ~ i m e r , and ~ ~ *to study the solution structures of a chiral tridentate lithium amide in relation to enantioselective deprotonation of 4-tertbutylcyclohexanone.249 The reaction mixture of [6Li]lithium (2-methoxy-(R)- 1phenylethyl)((S)-phenylethy1)amide and cyclohexane oxide in DEE was studied by 'H and 6Li NMR.250 New dihydro-1,3,5-dithiazineand two dimeric dihydro1,3,5-dithiazines were synthesized and 'H, 13C, "B, and 7Li NMR were used to study the reactions of these dithiazines with BHiSMe2, BHiTHF, and MeI.25' (Aminomethy1)lithium compounds, LiCH2NRR'xTHF (NRR' = NMe2 (x = 0), NPhMe (x = 2), NPh2 (x = 1.9,N C ~ H I O (x = 0, N C ~ H I=Opiperidino), and NC7H14 (NC7H14 = 2,6-dimethylpiperidino))were prepared and characterized by X-ray crystallography and 'H, 13C, and 7Li NMR252 'H, 7Li, and 23Na NMR spectra and relaxations were measured with Li and Na salts of poly(acry1ic acid) and of poly(Me methacrylate)-block-poly(acry1ic acid) micelles at 300 K in D20 at concentrations 0.5-0.005% w t . / ~ tInterac.~~~ tions of Li 2-(2-methoxyethoxy)ethoxide with the model dimer di-tert-butyl 2lithio-2,4,4-trimethylglutarate and living poly(tert-butyl methacrylate) oligoand of living oligomers of tert-butyl methacrylate with a lithium counterion and of the model living dimer di-tert-butyl 2-lithio-2,4,4-trimethylglutarate with LiC1255were studied using 'H, I3C, 7Li, 6Li, 1D and 2D, NMR and a b initio SCF 3-21G and MNDO quantum chemical calculations. The reactions of Bu3SnCH2SR with BuLi in n-hexane (R = Me, t-Bu) and in nhexane/THF gave the solvate-free compounds, LiCH2SR (R = Me, t-Bu, Ph) and the products were characterized by microanalyses, and 'H, I3C, and 7Li NMR.256 'H and 7Li NMR were used to study the self-assembly clusters (Li12S606N12) containing diazasulfite anions.257 The solid-state structure of the TMEDA complex of fluorenyllithium was studied by the 6Li-'3C REDOR NMR.258 Lithium intercalated SnS2 compounds were studied with 6,7Liand I I9Sn solid-state NMR.259The temperature dependence of the 7Li NMR in a LiKS04 single crystal grown by slow evaporation was studied.2606Li and 7Li solid-state NMR were used to study the structure and dynamics in LiNb03-WO3 solid solutions.261

3.2.5 Sodium ('"a) - A review was given on 23Na NMR for strides of sodium ions in ordered systems.262 The ternary Na2RbC60 fulleride was studied by variable-temperature solid-state 13Cand 23Na NMR.263 3.1.6 Rubidium (87Rb) - Heterogeneous mesoporous stable basic catalysts were prepared by wet or solid-state impregnation of MCM-41 with cesium acetate and lanthanum nitrate followed by thermal decomposition and the new stable heterogeneous basic catalyst was studied by 23Naand 87RbMAS NMR.264

3: Applications of Nuclear Shielding

89

The reactions of Rb salts with N-(arylazoalkenoy1)azacoronands (RCOCC1:CMeN:NC6H2-OH-2-C12-3,4 where HR = 1-aza- 15-crown-5, 1-aza- 18-crown-6, 1aza-2 1-crown-7) were investigated using 87Rb and 13C solid-state NMR.265The two distinct sites in Rb2CrO4 were characterized in terms of their 87Rb quadrupole coupling and chemical shielding anisotropy interactions employing 87Rb single crystal N M R . ~ ~ ~ 3.2.7 Cesium ('"Cs) - 133CsNMR was used to study endothelial Na+-K+ATPase activity without the use of an exogenous shift reagent.267 'H and '33Cs NMR were used to study the nucleoside, 5'-(t-butyl-dimethylsilyl)-2',3'-0isopropylidene isoG, to give a self-assembled ionophore with remarkable Cs+/K+ selectivity.268The kinetics and mechanism of the cesium cation complexation by 5,11,17,23-tetra-p-tert-butyl-25,26,27,28-tetramethoxycalix[4]arene were studied in a 1:1 (vol./vol.) mixture of deuterated chloroform and deuterated acetonitrile using 'H and 133CsNMR, and 2D-EXSY 133CsNMR.269 133Cs+was used as an NMR active K+ analog to study quantification of ion transport in perfused rat heart and inhibition of ion transport in septic rat heart.270'27' Heterogeneous mesoporous stable basic catalysts were prepared by wet or solid-state impregnation of MCM-4 1 with cesium acetate and lanthanum nitrate followed by thermal decomposition and these MCM-41 catalysts were studied by 23Na, 133CsNMR.272 Single-crystal NMR was used to characterize the 133Cs chemical shift and electric field gradient tensors in C S C D ( S C N ) ~'33Cs . ~ ~ ~NMR and 2-dimensional EXSY NMR and 51V NMR spectra were recorded of Cs2S207 and of the catalytically important C S ~ S ~ O ~ -mixtures V ~ O ~ in the temperature range 20-550 "C,covering both the solid and liquid region.274'H MAS, 27Al,and '33Cs NMR were used to investigate the host-guest interactions of oxidic nanoparticles in a Y-type zeolite prepared by exchange with cesium cations followed by impregnation with cesium hydroxide and calcination.275 In situ synchrotron X-ray powder diffraction and 1 3 k s and 23Na MAS NMR were used to investigate the cation migration and ordering in samples of cesium-exchanged zeolite NaY as a function of temperature and cesium cation-exchange level and during dehydration.276

3.2 Group 2 (9Be,43Ca) - 3.2.1 Beryllium f9Be) - 9Be NMR was used to characterize beryllium(I1) solvates [BeS,(H20)4-,]2' (n = 0-4, S = N,N-dimethyl~ ~ ~hydrolysis of formamide and 1,1,3,3-tetramethylurea) in a c e t ~ n i t r i l e .The beryllium(I1) in the systems Be(II)-H20 and Be(I1)-DMS0:water (80:20, w:w) were studied at 25°C by 9Be NMR and voltammetric analyses.278 [Be3(poH)3(H20)6]3' was prepared, isolated as a solvated picrate salt, and characterized by X-ray crystallography and 9Be NMR.279 Several sterically encumbered beryllium compounds were synthesized and characterized by X-ray crystallography and 'H, 9Be, and I3C NMR.*" A range of sodalite framework structures containing Be with general formula M8[BeZ04]& (M = CD, Zn, 2 = Si, Ge, and X = S , Se or Te) were synthesized and the structures of these materials were studied by neutron diffraction, powder X-ray diffraction, and 9Be, 27Al,and 29Si MAS N M R . ~ ~ '

90

Nucleur Magnetic Resonance

3.2.2 Calcium ("Ca) - 43Ca MAS NMR spectra were collected for 12 solid phases including silicates, carbonates and sulfates.282 '39La, I7'Yb) - 3.3.1 Yttrium (" Y) - The 3.3 Group 3 and Lanthanoids ( LnC13/RLi reagent system commonly used with Ln = Ce for organic alkylation reactions was studied with Ln = Y to make use of the "Y in NMR analyses.283 The reaction of Y tris[bis(trimethylsilyl)methanide] with bis(trimethylsily1)phosphine in aromatic hydrocarbons yielded dimeric Y tris[bis(trimethylsilyl)phosphide] and the structure was deduced from 3'P and 8gY NMR and X-ray cry~tallography.~'~ The chemical shift, the range of chemical shift anisotropy, and the spin-lattice relaxation times (TI) in Y2O3, Y3A15012, and Y202S were measured by solid-state "Y MAS and static NMR.285 3.3.2 Lanthanum ('j9La) - Tris(ally1)lanthanum complexes with various donor hgands, La(q3-C3H5)iL (L = DME, TMED, 2HMPT) were prepared and characterized by elemental analyses, 'H, I3C, and '39La NMR, and X-ray crystallography.286 3.3.3 Ytterbium ("' Yb) - (COT*)Ln(DAD)(THF) (Ln = Sm, Yb; COT* = 1,4(Me3Si&H6; DAD = 1,4-diazadienes) were prepared and studied by H and I7lYb NMR.287 Several lanthanide(I1) and lanthanide(II1) complexes [Ln(LL')2X(THF),] (LL' = q3-RN:C(But)CHR, R = SiMe3; X = C1, n = 1 and L n = C e o r N d ; o r X = i o d o , n = l and Ln=Sm;orX=iodo, n = O a n d L n = Y b ) , [Srn(LL')z(THF)] and [Yb(LL')2] were synthesized and characterized by elemental analyses, mass spectroscopy, and 'H, 13C,29Si, 17'Yb, and 19F NMR.288A series of nine Yb(I1) bis(cyclopentadieny1) complexes were studied by 17'Yb CP/MAS NMR.289

c7y4%)

3.4 Group 4 - The new compounds, Ti(q-C5Me5)Me2E (E=CbFS, OC6F5) and T ~ ( ~ - C S M ~ S ) M ~ ( O were C ~ prepared F ~ ) ~ and characterized by a variety of techniques, including 47,49TiNMR.290 47749Ti NMR spectra of powdered samples of the three common phases of titania, Ti02 were reported.291 3.5 Group 5 (51V, 93Nb)- 3.5.2 Vanadium (" V ) - The action of vanadate on intact human erythrocytes was studied by 'H spin echo and 5'V NMR as a model for the behavior of vanadium(V) complexes in experimental diabetes.292 The potential biological activity of vanadium analogs of AMP, ADT, ATP, 2',3'CAMP, and 3',5'-CAMP stimulated the full speciation study of the vanadateadenosine and vanadate-adenosine-imidazolesystems in aqueous solution using a combination of potentiometry and 51V NMR.293 A potentiometric and 51V, I3C and 'H NMR studies of the aqueous H+-vanadate(V)-L-prolyl-L-alaninekalanyl-glycine systems were reported.294 Aqueous interactions of vanadate and peroxovanadate with dithiothreitol, (CH2SHCHOHCHOHCH2SH), were studied by 5'V NMR.295 Correlation between "V NMR chemical shift and reactivity of oxovana-

3: Applicutions of Nuclear Shielding

91

dium(V) catalysts for ethylene polymerization was studied.296 Vanadate-inserted layered double hydroxides were prepared and 5'V NMR was used to investigate the grafting process.297The speciation of V doped into anatase particles of 50-90 diameter was studied by a variety of techniques including solid state 5'V NMR, EPR, XPS and Raman ~ p e c t r o s c o p i e s . ~ ~ ~ 51V NMR was used to study the reactions of vanadate with N,N-dimethylhydroxyamine in aqueous to study the reactions of hydrogen peroxide to vanadium (V) precursors in aqueous acidic solutions leading to the formation of a cationic monoperoxo species [VO(02)]' and an anionic diperoxo complex [VO(O2)2]-, depending on the pH and on the excess of H202,300to study the aqueous reactions of hydroxylamine and N-methylhydroxylamine with ana ad ate,^" to study the oxovanadium(V) complex VO( L) structure and its solid-state p-0x0-bridged linear chain polymeric structure together with IR.302 H and 51V NMR were used to study the oxidation reaction of vanadium(V)dit hiolate complex to vanadium(V)-q ,q2-disulfenate, 303 to characterize the dioxovanadium(V) complexes V02(bpg) (Hbpg = N,N-bis(2-pyridylmethyl)glycine), [V02(pmida)]- (H2pmida = N-(2-pyridylmethyl)iminodiacetic acid), and [V02(ada)]- (Hzada = N-(2-aminomethyl)iminodiacetic acid),304to characterize a cubane-type cluster (Et4N)[VFe&(Etzdtc)4] (Et~dtc-= diethyldithioarba am ate),^'^ and to study the brown colored VVO(Asal)(Hpd) and VVO(Asal)(Hzpt) (H2Asal = salicylaldimine of glycine (A = g), 1-alanine (A = a), 1-valine (A = v), or I-phenylalanine (A = P ) ) . ~ ' ~Some paramagnetic V(II1) complexes Tp*VC12(L) (Tp* = hydrotri(3,5-dimethyl-l -pyrazolyl)borate) were prepared and characterized by 'H, 13C, and "V NMR.307 A new vanadium(V) complex, diammonium (nitrilot riacet a to)dioxovanadate(V) (N H4)2 [VOzNTA], was synthesized and characterized by X-ray crystallography and 13C and "V NMR.308 Interaction of N-hydroxyacetamide with vanadate in aqueous solution was studied in 0.15 mol dm-3 NaCl medium by potentiometry, spectrophotometry, and "V and I7O NMR.3w 3.5.2 Niobium ('jNb) - 'H, I3C, and 93Nb NMR, Raman, IR, and electronic spectroscopy were used to identify the substitution products formed in the solvolysis of NbCIS and TaC15 by MeOD.310 3.6 Group 6 (95M0, lS3W) - 3.6.1 Molybdenum ('5M0)- A review was given on 95M0 NMR s t ~ d i e s . ~ " L-Mannonic acid312and D-gluconic acid313were found to form complexes both with tungsten(V1) and molybdenum(V1) in aqueous solution by using 'H, 13C, 170,95M0, '83W NMR (1D and 2D). Polynuclear Mo-Cu-Se compounds containing thiolate ligands, [ E ~ ~ N ] ~ [ M o C U ~ S ~ ~ ( R(R2 ~ N=CEt2, S ~ ) CSHIO, ~] (PhCH2)z) and [ E ~ ~ N ] ~ [ M o C U ~ S ~ ~ ( Mwere ~ ~ Nsynthesized C S ~ ) ~ ] , and studied by X-ray crystallography, IR, and ' H and 95M0 NMR.314 95M0 NMR was used to study five diamagnetic Mo(V) heterometallic trinuclear incomplete cubane-like and to study [ M o ~ ( O ~ C C ~ H ~ R - ~ ) ~ (R=NMe2, CF3).3'6 95M0 NMR, IR, and X-ray crystallography were used to ~ to characterize several Mo( W)study a trinuclear linear M o S ~ C U~ornplex,~"

92

Nucleur Magnetic Resonunce

Cu-S cluster compounds,318 and to study adducts with M o 0 2 - tetrahedra coordinated to Cr(II1) or Co(II1) c o m p l e ~ e s . [Mo(C0)3L3] ~'~ (L = 1,3,5-triaza-7phosphaadamantane or 4-ethyl-2,6,7-trioxa-l-phosphabicyclo-[2.2.2]-octane) were synthesized and characterized by X-ray crystallography, IR, H, 31Pand 95M0NMR.320

'

3.6.2 Tungsten (18'W) - 183WNMR was used to study the polyoxometalates substituted by noble metal cations (Bu4N),[XWI 1M(OH2)039](M = Pd(I1) or Ir(1V); X = B , n = 7 ; X = S i or Ge, n = 6 ; X = P , n = 5 ) and to study the (BU4N)JPzW 17M(OH2)061] (M = Pd(II), Ru(III), reaction of tungsten metal powder with hydrogen peroxide together with Raman and TOF-MASS,323 and to characterize twelve new Dawson-type tungstophosphate heteropoly complexes a2-MaH#"W 18-,,Tin062]XH20and a1,2,3-M,Hb[P2W18-n(Ti02)n062-n]~H20 (M = K+, NEt4+ or NBu4+; N = 1, a + b = 8; n = 3, a + b = 12) together with IR, UV, polarography, cyclic voltammetry, and XPS.324 183W and 31P NMR were used to study organophosphoryl derivatives of trivacant tungstophosphates of general formula c~-A-[PW~O~~(RPO) to~ ] ~ characterize -,~~~ lanthanide complexes of p o l y o ~ o m e t a l a t e s , ~ ~to ~ study some lanthanide complexes of heteropolyt~ngstates,~~~ and to characterize unstable polyoxo polyoxometalate, [P2W,2(Nb02)6056]12-.328 Donor-stabilized bis(sily1ene)tungsten complexes CpW(CO)2{(SiMe2)-. .Do. - a(SiMe2)) (Cp = q-C5H5; Do = Net2, OMe) were synthesized and studied by X-ray crystallography and 29Si and 183WNMR.329 A-P- Na7SiW9Nb3O40and Na5[(q5-C5Mes)RhSi W9Nb30401 were synthesized and characterized by 'H, 13C, and IS3WNMR.330

3.7 Group 7 (55Mn,*Tc) - 3.7.I Manganese ("Mn) - Silyl derivatives of the mixed sandwiches cyclopentadienyl manganese benzene and cyclopentadienyl manganese biphenyl, CpMn(C6H6) and CpMn(C6H5-Ph), were prepared and characterized by IH,13C, 29Si, and 55Mn NMR.331Reaction products of iron, cobalt, nickel, and manganese carbonyl complexes with distibinomethane, Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm), were characterized by elemental analyses, IR and 'H, I3C, 55Mn, and 59C0 NMR, and FAB mass spectrometry.332 3.7.2 Technetium (99Tc) - Lewis-acid properties of technetium(V1 I) dioxide trifluoride, Tc02F3 were studied by 19F, 1 7 0 , and 99Tc NMR, Raman, DFT calculations of Tc02F3, M+Tc02F4- [M = Li, Cs, N(CH3)4], and T c O ~ F ~ C H ~ Cand N , X-ray crystallography of LifTc02F4-.333 A range of complexes with general formula [MO(X)(CN)4]"- of W(IV), Mo(IV), Re(V), Tc(V), and Os(V1) were prepared and characterized by 13C, 15N, 170, and 99Tc NMR, utilizing 13C-and "N-enriched cyano complexes.334

3.8 Group 8 (99Ru,'*'a )3.8.1 Ruthenium ( Y y R ~- )The 99Ru NMR spectra of tris-polypyridine ruthenium(I I) complexes were studied in acetonitrile solut i ~ n . ~ ~ ~

3: Applicutions of Nucleur Shielding

93

3.8.2 Osmium (la70s) - 1870s, 31P and I7O NMR were used to study carbonylated and alkylated (p-cymene)OsI(L)PR3 complexes.336

3.9 Group 9 c9C0,Io3Rh) - 3.9.I Cobalt ('9C0) - 59C0NMR spectra of small Co particles in a Si02 matrix were measured.33759C0 NMR was used to study several series of co-evaporated Col-,Fe, thin-film alloys prepared by MBE on MgO (OOI), GaAs (loo), and GaAs (1 10) substrates at deposition temperatures between 175 and 500 0.338 59C0NMR was used to study a crystal of tris(2,4-pentanedionate-O,O')Co(III) as a function of crystal orientation in an applied magnetic field of 9.40 T,339to study diamagnetic complexes with general structure Co(Por)L2 (Por = tetraphenylporphyrin, tetramethoxyphenylporphyrin,and octaethylporphyrin; L = imidazole, methylimidazole, pyridine, and is~quinoline),~~' to study the preparative conditions and stability of ci~-[Co(N02)4(NH~)~] - , which had been a missing link in the ammine-nitro Co(II1) series,34'and to study the microdynamic motions of the clusters A[M(CO~(CO)I~)-(A = H, NEt4; M = Fe, Ru) and HFeC03(C0)9 [P(OCH3)3]3,342and to study interactions of tripositive cobalt(II1) complex ions in various solvents together with the electronic absorption spectra.343Solid and liquid phase 59C0NMR were used to study cobalamins and their derivative^.^^ Methylcobalt(II1) compounds with solely classical ligands were prepared and characterized by 'H, 13C, and 59C0 NMR, absorption spectroscopy, and X-ray ~ r y s t a l l o g r a p h y .Interactions ~~~ between micelles and tripositive ions of metal complexes such as [M(en)3]3' (M = Co or Cr, en = ethylendiamine), [M(chxn)3I3' (chxn = (R,R)-1,2-~yclohexanediamine),and [M(phen)3I3' (phen = 1,lO-phenanthroline), were studied using 59C0 NMR and paramagnetic Cr(II1)-induced 13C NMR relaxations of the surf act ant^.^^^ O

3.9.2 Rhodium (Io3Rh) -- Fifty-four carboxylate and thiolate complexes of Rh including [Rh(02CR)(PPh3)3] (R = CH3, CF3), [Rh2(SC6F5)2(PPh3)4] and derivatives were studied by 2-dimensional inverse '03Rh-3'P correlated NMR (HMQC).347Solution studies of a trinuclear rhodium(II1) aqua ion was studied using lo3Rh NMR, UV/VIS spectroscopy, charge per Rh determination and elution behavior to show this oligomer can exist in several structural forms.348 The structure of [Rh(NCBPh3)(H)(SnPh3)(PPh&] was determined by X-ray crystallography, and its pyridine-containing derivatives were studied by H, "N, 3'P, Io3Rh,'I9Sn NMR.349

3.10 Group 10 (I9%) - 195PtNMR of organometallic compounds was reviewed.350 'H, I3C, 195PtNMR were used to identify the products and the binding sites of platinum(I1) and palladium(I1) complex ions with peptides, His-Ala and His-GlyAla.351 First observation of '95Pt NMR in commercial graphite-supported platinum electrodes in an electrochemical environment was reported.352 '95Pt NMR was used to study several halotrimethylplatinum(1V)complexes of chiral 2,6-bis[4-(S)-methylo~azolin-2-yl]pyridine,~~~ to study the single crystal 44

94

Nuclear Magnetic Resonance

atom core Ni38Pt6 in the metal cluster compound, [HNi38Pt6(C0)48]5-,354 to study heterobimetallic complexes containing the Pt-Pd-Y core with qualitative extended Hueckel-fragment MO calculations,355to study the first homoleptic imino ether complex [Pt(NHC(OEt)Et)4](CF3!303)2 together with X-ray crystallography, IR,356to characterize new axial-dichloro platinum(IV) cisplatin analogs, [Pt( 1,4DACH)trans-ClzLL] (1,4-DACH = cis-l,4-diaminocyclohexane and LL = 1,l-cyclobutanedicarboxylato (CBDCA), oxalato, malonato, methylmalonato or tartronato) with 1,4DACH as a carrier ligand together with elemental analyses, 1~.357

'H and 195Pt NMR were used to study the aqueous reactions of K[Pt(Ph2SO)C13] with nitriles in different conditions of pH,358 to study the protsnation mediated interconversion of mono- (S) versus bidentate (S,O) cooidination of Pt(I1) by N-acyl-N',N'-dialkylthio~reas,~~~ to study and characterize the reactions of [M(p0(H20)2)~' (M = Pt or Pd; PO = 2-(pyridin-2-y1)-2oxazoline) with the model nucleobases 1-methylthymine and l - m e t h y l ~ r a c i lto ,~~~ study the pH- and time-dependent reactions of [Pt(en)(H20)2I2' (en = H2NCH2CH2NH2) with the histidylmethionine dipeptides cycle(-his-met-), his-Hmet and m e t - H h i ~ , ~and ~ ' to study the reactions of [PtCl(en)(tmtu)]NO3 and [PtCl(dach)(tmtu)]N03 (en = 1,2-ethanediamine, dach = racemic trans-l,2cyclohexanediamine, tmtu = 1,1,3,3-tetramethylthiourea) and [ { Pt(en)C1}2{pC2H4(NMeCSNMe2)2-S,S'}](N03)2 and [{ Pt(en)C1} { p-C6H 12(NMeCSNMe2)2S,S'}](NO&OSEtOH with 5'-GMP and r(GpG) and their chemistry in aqueous 31Pand '95Pt NMR were used to study several novel Pd(II), Pt(I1) and Pt(1V) dimers containing 1,2-bis(diphenylphosphino)acetylene (dppa) as bridging ligand364 and to characterize the crystalline complex [Pt(PPh3)2(PhSOCH:CHSOPh)].365 Platinum(I1) complexes of para-substituted 4- phenylthiosemicarbazides, RPhNHCSNHNH2 (R = H, CH3, Br, F and NO2) were prepared and characterized by IR and I5N and 195PtNMR.366 'H, I3C, and '95Pt NMR were used to characterize platinum(I1) complexes of 3,3'-disub~tituted-2,3'-bipyridines,~~~ to characterize square planar Pd(I1) and Pt(I1) complexes involving tetradentate diphosphadithia ligands, ML(PF6)2, M = Pd, Pt; L = Ph2P(CH2)2S(CH2)2PPh2,Ph2P(CH2)2S(CH2)3S(CH2)2PPh2,or P~~P(CH~)~S(O-C~H~)S(CH~)~PP~~,~~* to study the interaction of PtC142- with the new azaparacyclophane 2,5,8,11-tetraaza[ 1 2 ] p a r a ~ y c l o p h a n e to , ~ ~charac~ terize a new class of mono- and dinuclear platinum(I1) complexes, [PtCl(diamine)(L)]N03 and [ { PtCl(diamine)} 2(L-L)](N03)2 (L = monofunctional thiourea derivative; L-L = bifunctional thiourea derivative),370and to study five- and sixmembered platinum(I1) and palladium(1) metallacycles from the alcoholysis of di- and triazaphosphole complexes.371 The reaction products 1-alkynylplatinum(II) complexes with trialkylboranes were characterized by "B, 13C, 31P, and 195Pt NMR.372 [(Dppe)Pt{pSCH(CH2CH2)2NMe}2PtIMe3] was synthesized and characterized by X-ray diffraction and 1-dimensional and 2-dimensional variable temperature H, 13C, 3 ' P and 195PtNMR.373Platinum(I1) phosphine complexes of dicarboxylates and ammonia were prepared and characterized by 3'P, "N, 195Pt,and 'H NMR.374 Oxidative addition of the silicon-halogen bonds of halosilanes R3Si-X (X= C1,

95

3: Applications of Nuclear Shielding

Br, I) to platinum(0) complexes PtL, (L = tertiary phosphine) yielded transR3SiPtXL2 species and the resulting silylplatinum species were studied by H, 13C,29Si,31P,and 195PtNMR.375

'

3.11 Group 11 ('09Ag) - The formation of the first example of a rectangular [2 X 3]G grid by mixed-ligand recognition was reported and the product was determined in solution by 'H, I3C, and Io9Ag NMR, and in the solid state by Xray crystallography of a solvated form.376 Perfluoroalkylsilver(1) compounds were prepared and studied by 19F and Io9Ag NMR.377Silver 1,5-pentanedithiolate Ag2[S(CH2)5S]was prepared and characterized by solid-state reflectance UVvisible, X-ray diffraction, 13C and Io9Ag CPMAS NMR compared to corresponding spectra for two crystallographically characterized homoleptic Ag thiolates, the cluster [Ags{p2-S(CH&NMe2} 3{p2- S(CH2)3NHMe2}3](C104)2 and the infinite strand A ~ S C E ~ Z C H ~ . ~ ~ ~ 3.12 Group 12 ('I3CD, lwHg) - 3.12.1 Cadmium ('13CD) - 'I3CD NMR was used to study the enzymic reaction of histidinol dehydrogenase (HDH) stimulated by about maximally 75% on the addition of CD2+ ion to the reaction mixture "3CD-substituted HDH in the presence of excess CD2+,379to study a large variety of ~~-HB(3-Phpz)~CD(acetate) ad duct^,^^' to study eleven symmetric and asymmetric novel piperazine-containing open-chain ligands with 13CDto distinguish between the structures of the different complexation sites on a nearly quantitative and to study a new CD thiolate, [CICD8{ SCH(CH2CH2)2N(H)Me}16](c104)1 I 6[SCH(CH2CH2)2N(H)Mej32H20 together with X-ray crystallography and XPS.382CD(I1) complexes containing a bidentate phosphine ligand, 2,2-dimethyl-2-sila-1,3-bis(diphenyIphosphino)propane, were studied by vibrational and 31P and 'I3CD NMR and by X-ray c r y ~ t a l l o g r a p h yThree . ~ ~ ~ monomeric CD(I1) phenoxide complexes were prepared and characterized by 'H, 13C,and '13CD NMR.384

'

3.22.2 Mercury ( I Y 9 H g ) - The blue copper proteins rusticyanin (Thiobacillus ferrooxidans) and azurin (Pseudomonas aeruginosa) were studied after Hg( I I) substitution into the blue copper site by 2D 'H-'99Hg NMR.385 Methylmercury (CH3-Hg(II)) interactions with multilamellar vesicles of dimyristoyl- and dipalmytoyl-phosphatidylcholine, -phosphatidic acid, -phosphatidylglycerol, -phosphatidylserine and -phosphatidylethanolamine were investigated from the metal viewpoint by solution 199Hg NMR and from the membrane side by diphenylhexatriene fluorescence polarization and solid-state 31PNMR.386 'H, I3C, and 199Hg NMR were used to characterize complexes of the cyanomercury cation with various polypyrazolylborato l i g a n d ~and ~ ~to~ study mercuraindacycles, to characterize the reaction products of indium([) halides with 1,8-naphthalenediylbis(mercury(II) halides),388to characterize the reaction products of phenylmercury(I1) acetate with a series of alkyl, aryl and heterocyclic thiosemicarbazones in and to study dichlorobis(acetophenone thiosemicarbazone)mercury(II) formed from phenylmercury(I1) chloride and acetophenone t h i o s e m i c a r b a ~ o n e . Pyridinephenylmercury(I1) ~~~ compounds,

96

Nuclear Magnetic Resonance

[Hg(PhPy)(S2PPh2)] and [Hg2(S2PPh2)4], were studied by IR, Raman and 'H, 31P and 199HgNMR.39' A series of mercury(I1) complexes containing the bidentate phosphine ligand, Ph2PCH2Si(CH3)2CH2PPh2, were prepared and studied by IR, Raman, and 'H, I3C, 31P, and 199HgNMR.392 Solid-state 199HgMAS NMR spectra were recorded for HgX2 (X = CN, Cl) and [Hg(X)OAc] (X = Me, Ph, CN, Cl, SCN), and mercury(I1) thiocyanate complexes and related compounds.3933394 3.13 Group 13 ("B, 27AI,6997'Ga,2039205Tl) - 3.23. I Boron ("B) - "B and 'H N MR parameters were measured for the unique polyhedral azaborane species using single- and double-resonance experiments and two-dimensional shift correlation methods.395 Parent tricarbollides [nido-7,8,9-C3B8H 'I-, nido-7,8,9C3B8H12, [nido-7,8, 10-C3B8HlI]-, and their derivatives were prepared and characterized by X-ray crystallography, 'H, 13C, and I l B NMR with IGLO NMR chemical shift calculations.396The planar boron-containing purin analogs, 1-hydroxy- 1H-2,3,1-benzoxazaborine, 1,2-dihydro- I -hydroxy-2,3,1 -benzodiazaborine, and related 2,3,1-benzodiheteraborines, were studied using isotope enriched compounds by 'H, I3C, "B, and I5N NMR.397 Mono-1-alkynyltin compounds (Me3Sn-CCR'; R' = H, Me, Ph, SnMe3) with various dialkyl(Nazoly1)borane.s (azolyl= pyrrolyl, 2,5-dimethylpyrrolyl, indolyl, carbazolyl) gave organometallic-substituted alkenes and all products were characterized by H, "B, 13Cand 19Sn NMR.398

'

'

3.13.2 Aluminum (27A/) - 27Al NMR was used to study aluminum transport

across yeast cells using Dy(N03)33 as a shift reagent399and to study the internal detoxification mechanism for A1 in an Al-accumulating plant, hydrangea (Hydrangea macropylla), focusing on A1 forms present in the cells.400The novel tetranuclear diethylaluminum aryloxide carboxylate adduct [Et2A1]4[(p02C)C6H4-2-p-0]2 was prepared and characterized by elemental analyses, H and 27Al NMR, IR, and X-ray cry~tallography.~~' In the fluorine-assisted selective alkylation reactions to fluorinated epoxides and carbonyl compounds, the pentacoordinate complex formation of Me3Al with fluoro epoxides was characterized by low-temperature I3Cand 27AlNMR.402'H, I3C, and 27Al NMR were used to study the interaction of an unsaturated alcohol, 10-undecen- 1-01, with A1 compounds AlEt3 and M A 0 (30% toluene solution) at room temperature and elevated temperature^,^'^ to characterize the four intramolecularly coordinated azidoalanes R2Al(N3) and RAI'Bu(N3) (R = (CH2)3NMe2, 2(Me2NCH2)C6H4),404and to characterize coordination of alane and aluminum alkyls to the N-donor atom of side chain functionalized cyclopentadienyliron and nickel complexes.405 27Al NMR was applied to study the multi-coordination properties of longchain polyphosphate anions with A13' ions.406 Accurate values for the 27Al chemical shielding anisotropy were reported for sapphire ( ~ t - A 1 2 0 3 )The . ~ ~ ~influence of surface area, paramagnetic impurities, and spinning speed on the 27AI MAS NMR visibility in a number of y- and qA1203 samples was investigated.408 The novel metal-incorporated aluminophosphates MAPO- 1 1, MAPO-36, CoAPO-36,ZAPO-36, MAPO-39, MAPO-43

'

3: Applications of Nuclear Shielding

97

and MAPO-50 were prepared and studied by 27Al and 31PMAS NMR.409 The framework structure of As-synthesized AIP04-14 was investigated with a combination of different one-dimensional 27Al and 3'P solid-state NMR and 27Al/31P double resonance method^.^" 13C,27AI,and 31PMAS NMR were used to study the structural changes occurring upon isomorphous substitution of Si into the alumino-phosphate f r a m e ~ o r k . ~27Al, " 'H, 170and 13C NMR were used to investigate the structure of the methylaluminoxane (MAO) cocatalyst of Kaminsky-Sinn catalyst^.^'^ 3.13.3 Gallium (69*71Ga)- Adducts Ph3PGa13 and Ph3AsGaI3, obtained by adding the ligands to EtzOGaI3, were studied by 7'Ga NMR, IR/Raman spectroscopy and X-ray ~rystallography.~'~ A new brucite-like layered Mg/Ga &mH2O was synthesized and double hydroxide [M~o.~I~G~o.**~(OH)~](C~~)O. characterized by X-ray diffraction, diffuse reflectance, IR, 'H and 71Ga MAS NMR.4'4 71Ga and 31P solid-state static and MAS NMR were used to study two new Ga phosphonates Ga(OH)(03PC2H4C02H)H20 and Ga3(0H)3(03PC2H4C02);2H20.4'5 Single-crystal 7'Ga NMR was used to study the chemical shift and quadrupole coupling tensors of the garnet Y3Ga5012.4'6 MFI-type Ga-silicate was synthesized and characterized by 71GaMAS NMR.4'7 Air-equilibrated cloverite containing normal and deuterated water was studied by 'H, 31P,and 7'Ga NMR with magic angle spinning.418 3.13.4 Thallium (203,205T1) - 205TlNMR was used to probe the solution structure and dynamics of thallium-containing metal cornple~es,4'~ to study the hydrolysis of Tl(1) at 25°C,420 to study the properties of T1 nuclei in porphyrin c o m p l e x e ~ . ~ ~The ' tris[3-trifluoromethyI]-5-(2-thieny)pyrazolyl]hydroborato thallium complex, Tl[TpCF33Tn]was prepared and characterized by X-ray crystallography and 19F and 203Tl NMR.422 Ligand exchange reactions of thallium(II1) cyano complexes, T1(CN)n3-", were systematically studied in aqueous solution containing 4 M ionic medium ([C104-Itot = 4 M, [Na+Itot= 1 M, [Li+]tot+[H+]t,t=3 M}, at 25"C, using 205Tl and 13C NMR.423 Pyridoxal thiosemicarbazonate monohydrate of dimethylthallium(II1) was prepared and characterized by X-ray crystallography and IR in solid-state and by 'H, A3C,and 205Tl NMR in DMSO solution.424 The seleno- and tellurothallate(1) anions T12Ch;- (Ch = Se and or/Te) and the T l ~ S e 2anion ~isotopically enriched in 77Se were obtained and characterized by 77Se, 203Tl, and 205Tl NMR, Raman spectroscopy, and X-ray ~ r y s t a l l o g r a p h y . ~ ~ ~ 3.14 Group 14 (l3C', 29Si,73Ge,l19Sn, *wPb) - 3.24.2 Carbon (13C) - The preparation of enantiomeric [1-'3C]ketoorifens (KPs) and their acylglucuronides

was reported for the N M R spectroscopic studies on the stereoselective pharmacokinetics and reactivities of KP acylglucuronides."26 Mesityl-2,6-dimethyldilyl dication was prepared and characterized by 'H and 13C NMR and the data compared with DFT/IGLO calculations.427The principal elements of the I3C NMR chemical shift tensors were studied for metal-olefin complexes, [Ag(cod)z]BF4, [CuCl(cod)]2, PtClz(cod), [RhCl(cod)]2, and

98

Nuclear Magnetic Resonance

K[PtC13(C2H4)] with theoretical calculations using density functional methods.428 I3C NMR chemical shifts of ethylenic carbons in polyunsaturated fatty acids and related compounds were reported.429 I3C NMR full assignment was given for methyl and methylene region of regioregular p~lypropylenes.~~' 3.14.2 Silicon ("Si) - The 29Si NMR spectra of trimethylsilyl and tertbutyldimethylsilyl derivatives of selected diols were measured.43' 29Si NMR spectra of trimethylsilyl derivatives of 26 simple alcohols were measured under standardized conditions.432Deca- and dodecasilsesquioxane cages were prepared and studied by 29Si NMR.43329Si and 7Li NMR were used to study lithium2-{ 2,4,6bridged bis(sily1 anion) of 9,10-dimethy1-9,1O-di~ilaanthracene.~~~ Tris[bis(trimethylsilyl)methyl]phenyl}-2-silanaphthalene was prepared and characterized by X-ray crystallography, Raman, UV-vis, and 'H, I3C, and 29Si NMR.435 The 29Si chemical shift tensors were determined for three stable silylenes by slow-spinning solid-state N MR.436 3.14.3 Tin ( f f 7 * f f y S n-) Il9Sn NMR was used to study several sugar-tin derivatives437 and the interaction of tin(1V) with the anticancer antibiotic doxorubicin in N,N-dimethylformamide solution.438 Some meta- and orthosubstituted tetra- and triaryltin compounds were prepared and studied by X-ray crystallography and 13C and lI9Sn NMR.439'H, I3C, and Il9Sn NMR were used to study tris( 1-butyl)stannyl D-glucuronate in hexadeuteriodimethyl sulfoxide, tetradeuteriomethanol and deuteriochloroform,uo to characterize various 0-(3triorganostanny1)propyl carbohydrate derivatives,u' to study estertin compounds, (Me02CCH2CH2)2SnX2[X, = 12, Br2; Cl and Br; or (NCS)2],u2 to 3-(2characterize two water-soluble organotin compounds, methoxyethoxy)propyltin trichloride and bis(3-(2-methoxyethoxy)propyl)tin d i c h l ~ r i d eand , ~ ~to characterize stable six-coordinate tin(1V) and organotin(1V) derivatives R2SnQ*2 (R = Me, Et, Bun, But) (HQ* = l-phenyl-3-methy1-4trichloro-acetyl-pyrazol-5-one).~ Pentaalkyl-6-triorganostannyl-2,3,4,5-tetrdcarba-nido-hexaboranes were prepared and studied by 'H, I'B, I3C and 'I9Sn NMR.u5 The reactions of encapsulation of iron(I1) by template crosslinking of tris-dioximates with tin(1V) bromide and fluoride were studied and the resulting clathrochelate tin-containing iron(1I) dioximates were confirmed by elemental analyses, IR, 'H, I3C, I9F, and Il9Sn NMR and Il9Sn Moessbauer spectra.446 Diorganotin(IV) and diorganosilicon( IV) derivatives of the types R2MCl(TSCZ) and R2M(TSCZ)2 (TSCZ=anion of a thiosemicarbazone ligand; R = Ph, Me; M = Sn, Si) were synthesized and characterized by elemental analyses, molecular weight determinations and conductivity measurements, IR, and 'H, I3C, 29Siand lI9Sn NMR.u7 Molecular structure of a penta-coordinate organotin compound with a three-dentate ligand derived from the lithiation of 2-methylbenzoxazole was characterized by X-ray crystallography and 'H, "B, I3C, I5N and Il9Sn NMR.&' N-Triorganostannyl (R$n)-substituted pyrroles and indoles [R = Me, Et, tBu], N-(trimethylstanny1)carbazole, N-trimethylstannyl-2,5-dimethylpyrrole,the corresponding Si and Pb

3: Applications of Nucleur Shidiing

99

derivatives and N-trimethylstannyL-2-methylindole were prepared and studied by 'H, I3C, "N, 29Si, II9Sn and 207Pb NMR.449 The coordination behavior of a-trichlorostannyl alcohols, HO(CH2),SnC13 (n = 3- 5), was studied by solidstate 13Cand Il7Sn NMR, by 'H, 13C, '19Sn, and I7O as well as gradient-assisted 2-dimensional 'H-I I9Sn HMQC and 'I9Sn EXSY NMR spectroscopy in CD2C12 and acetone-d6 solutions, X-ray crystallography, and AM 1 quantum mechanical calculations.450 Hexamethyl-l,2,3-tristanna[3]ferrocenophanewas prepared and characterized by X-ray crystallography and 'H, 13C, 77Se, I 19Sn, '25Te NMR.451 Novel organo-substituted 2,5-dihydro- 1-azonia- and 1-phosphonia-2-stanna-5boratoles were prepared and characterized by 'H, "B, I3C, I4N, 29Si, 31Pand 'I9Sn NMR.452 Il9Sn and 19F solid-state NMR were used to study organotin fluorides, Bu3SnF and Mes3SnF (Mes = m e ~ i t y l ) Nucleophilic .~~~ addition reactions of cyclopentadienide anions (Cp-) to bis(cyclopentadienyl)tin( 11) and -Pb(II) gave complexes containing paddle-wheel [(q5-Cp)3E]-(Cp = C5H5; E = Sn, Pb) anions and 13C and Il9Sn solid-state MAS NMR and a b initio calculations were used to study the structure of the products.454 A series of tri- and diorganotin steroidcarboxylates were synthesized and characterized by 1D and 2D 'H, I3C, 'I7Sn and 'H-13C HMQC and HMBC NMR and 'I9Sn MAS NMR.455 Two chiral organostannics, the tetraalkyl ((-)-menthyl)Me3Sn and the hydride ((-)-menthyl)Me2SnH, were synthesized and their reactions with the surface of partially dehydroxylated Si02 were followed by analysis of evolved gases, IR, and 13C and 'I9Sn MAS NMR spectroscopic characterizations of the grafted organometallic^.^^^ A series of organotin complexes with pyrrole-2-carboxaldehyde2hydroxybenzoylhydrazone and pyrrole-2-carboxaldehyde2-picolinoylhydrazone was investigated by IR, 'H, and I19Sn NMR.457 Trinuclear Sn compounds, (Ph2XSnCH&SnXPh (X = Ph; X = F; X = C1) and (PhC12SnCH2)2SnC12 and tetranuclear Sn compounds (Ph2XSnCH2SnXPh)2CH2 (X = Ph; X = F; X = C1) were prepared and studied by variable temperature Il9Sn and I9F NMR.458The reactions of SnX2 (X = C1, Br) with tri(n-octy1)phosphine oxide in benzene under aerobic conditions yielded the oxidative addition products SnX4(TOP0)2and the structures in solution were determined by 31Pand 'I9Sn NMR.459 'H, I3C, and I9Sn NMR were used to study the structure of 1,4-bis(diiodophenylstannyl)butane, 12PhSnCH2CH2CH2CH2SnPh12,460 to characterize four di-n-butyltin(1V) complexes were prepared with sulfanylacetic, 2-~ulfanylpropionic,sulfanylsuccinic and 2,3-disulfanylsuccinic acid,46' to study [p2-,q2-alkynylhexacarbonylcobaltlorganotin complexes, (C12-,q2-HC2SnR3)C02(co)6(R = Et, tBu), R2Sn[(p2,q2-C2H)Co2(C0)& (R = Me, Et, tBu, Ph), Me4-nSn[(~2-,r12-C2Me)C0*(C0)8]n (n = 1, 2, 3), and M~CCS~[(JL~-,~~-C~M~)CO~(CO)~],~~~ to characterize some new diorgdnochlorotin( I V) complexes R~C~S~(C~C~O-S~CNCH~CH~XCH~ (X = CH2, CHMe, NMe, 0; R = Me, B u ) , ~to~ characterize ~ dibutylbis(2,4dihydroxybenz~ato)tin(IV),~~ to characterize mono-organotin(1V) and tin(IV) derivatives of 2-mercaptopyridine and 2-mer~aptopyrirnidine;~~ to study tin(I1) citrates, SnM(C6H407) (M = Sn or Zn) and SnMM'(C6H407) (M = M' = Na, K or NH4; M = NMe4, M'= H) and related monotin(I1) salts of 1,5-di-Me and 1,5-diBu citrate,466 and to study a series of dibutyltin(1V) complexes of Schiff bases

I 00

Nuclear Magnetic Resonance

derived from 2-aminophenol and benzaldehyde, anisaldehyde, 2-furfural, acetophenone, benzyl Me ketone, benzil, salicylaldehyde, 2-hydroxy- 1-naphthaldehyde and 2-hydro~yacetophenone.~~~ New iodide heterobimetallic isopropoxides [12Sn{Al(OPri)4}2], [12Sn{Ti(OPri)5)2],[12Sn{Nb(OPri)6}2],and [13Sn{Zr(OPf)5 (PriOH)}] were prepared and characterized by X-ray crystallography and 'H, ~ }prepared ( ~ ~ P Pand ~~)~ 13C, 27Al, and 'I9Sn NMR.468 { ( B U S ~ ) ~ ~ ~ ~ ~ ( O H )was characterization by 'H, 13C, II9Sn, and 31P NMR and 2D gradient-assisted 'H-"9Sn HMQC, 'H-13C HMQC, 'H ROESY, and 3'P-'H HOESY NMR.469 The '19Sn MAS NMR spectra of the three Sn sulfides SnS, SnS2 and Sn2S3were discussed with respect to results from X-ray structure analyses.470 A new thiostannate, (C12H25NH3)4[Sn2S6]2H20was synthesized and characterized by X-ray crystallography, 13C and "9Sn CP/MAS NMR, IR, absorption spectroscopy, and thermal analyses.47' The reaction of the trinuclear tin cluster [(Me2Sn)2(Me2SnO)(OCH3)(HONZO)(ONZO)] (HONZOH = o-H0N:CHC6H4-OH, salicylaldoxime) with proton-donating n u ~ l e o p h i l e sor~ with ~ ~ ammonium was investigated using 'H-'19Sn HMQC and l19Sn MAS NMR and X-ray crystallography. 3.14.4 Lead ("'Pb) - 207Pb NMR was used to investigate the nature of aryllead(1V) tricarboxylate species in solution474and to study aromatic lead(1V) ~ ~ ~207Pb NMR compounds, (C6H5)3PbR (R = alkyl, alkenyl, a l k ~ n y l ) .The spectra were measured in solution, for a series of compounds modeling the 'H, 13C,and 207Pb interaction of lead(I1) with the humic substances of the s0i1.4~~ NM R were used to characterize several six-membered heterocyclic organolead c o m p o u n d ~ , 4to~ ~study lead(1V) carboxylates containing acetate, benzoate and cinnamate l i g a n d ~and , ~ ~to~study the reactions between Ti(OR)4 (R = Et, Pf) or [Zr(OPri)4(PriOH)]2and various lead oxide precursors in different experimental conditions and to characterize isolated various mixed-metal species.479Tri(tertbuty1)plumbyl derivatives of Group 14 elements were prepared by the reaction of tBugPb2 with an excess of Lithium and characterized by 'H, 13C, 29Si, '19Sn and 207Pb NMR.480 N-Boryl-substituted bis(amin0)stannylenes and -plumbylenes were prepared and characterized by 'H, I3C, 14N, 29Si, 'I9Sn, and *07PbNMR.481 MAS and static 207PbNMR were used to resolve and assign different lead sites in crystalline lead oxides and lead silicates to their isotropic chemical shifts.482

3.15 Group 15 (14*15N,31P) - 3.15.1 Nitrogen

( ' I P f 5 N )- 13Cand I5N NMR were used to study the interaction of KSe13C"N with gold(1)-captoril (Aucap), in aqueous solution I3C and "N NMR483and to examine whole cells and cell wall fractions of Staphylococcus aureus labeled by various combinations of [ 1-'3C]glycine, [ '5N]glycine, ~-[6-'~C]lysine, ~-[6-'~N]lysine, D-[ 1-'3C]alanine, and D-[' 5~alanine.484 High-precision 14N NM R measurements of solvent-induced shielding variations were reported for some nitrobenzene for some isoamides and their N-protonated for three oxime systems in a variety of s0lvents,4~~ and for the iminium ions Me2N+=C(H)Cl, Me2N+=C(H)Ph, and Et2N+=CH2in aprotic solvents.48815N NMR was used to study an unsymmetrical derivative of

3: Applications of Nuclear Shielding

101

1,8-bis(dimethylarnino)-4-picrylnaphthalene. Determination of 15N chemical shifts and long range connectivities of several alkaloids was presented.489 6Li and 15N NMR were used to study [15N,'5N]-N,N,N',N'-tetramethylethylenediamine and its solvation of [6Li]-BuLi in toluene-d8 solvent at - 1 10 0.490 The structure of the amide bonds of gluconamide was elucidated and compared to acetanilide by the combined application of I3C and "N double- and triple-resonance solid-state NMR.49' Diisocyanomethane, H2C(NfC-)2, was prepared and characterized by IR in gas phase, 'H, 13C, and I4N NMR, and X-ray ~ r y s t a l l o g r a p h y'H, . ~ ~13C, ~ and 15N NMR were used to study the one-electron oxidation and reduction to study the products of 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxy1,493 con formational equilibria of some 2-( 3'-hydroxyphenyl)-4-aryl-3H- 1,5-benzoazepines,494 to study the equilibria of 6- and 8-substituted tetrazolo[ 1,5-a]pyridines,495to study 4-nitro- 1,8-bk(dimethylamino)naphthalene and its protonated form,496,497and to study the structure and purity of pr0piolamide.4~~ "N, 6Li, and 13C NMR were used to investigate CuCN-derived butyl cuprates, BuC U ( C ' ~ N ) ~and L ~ B u ~ C U ~ L ~ L ~ Five C I ~derivatives N . ~ ~ ~ of mesoionic 1,2,3,4thiatriazolo-5-aminide and its salts were synthesized and the structures of the compounds were examined by 'H, 13C, 14N, and I5N NMR."' The partial highresolution phase diagram of the NH4+ pentadecafluorooctanoate (APFO)/H20 system (weight fraction of APFO 0.350-0.630) was established using 14N NMR to determine the liquid crystalline phase transition temperature^.^^' I5N solidstate NMR was used to study a range of Pt ammine complexes.502Using dynamic solid-state I5N CP/MAS NMR, the kinetics of the degenerate intermolecular triple proton and deuteron transfer in the cyclic trimers of "N-labeled polycrystalline 3,5-dimethylpyrazole were studied in a wide temperature range.503The I5N chemical shift tensor principal values in a series of "N-enriched heterocycles were reported.504The magnitudes and orientations of the principal elements of the ' H NMR chemical shift, 'H--I5Ndipolar coupling, and I5N chemical shift interaction tensors in "N"'-tryptophan and "N"-histidine nitrogen sites were determined by the analyses of three-dimensional powder patterns obtained from "N-labeled powder samples of the amino acids. 505 Nanostructured mesoporus silicates displaying hexagonally arranged channels, templated using a liquid crystal mesophase, were investigated using 2H and 15N NMR.506The principal values of both the I3C and I5N chemical shift tensors were reported for the Zn, Ni, and Mg 5,10,15,20-tetraphenylporphyrincomplexes. 507 3.25.2 Phosphorus (3'P) - The relations of 31Pchemical shift with the degree of the substitution, the different kind of substituting group, reaction activation energy, and electronegativity and of the coupling constants with the degree of the substitution were studied.508The analyses of 31Pand I5N NMR data of a series of 40 iminophosphines R-P:N-R' revealed that the E/Z stereochemistry of the P:N double bond can be predicted on the basis of a simultaneous comparison of ~ first stable arsaphosphaallene, ArP:C:AsAr the values of d3'P and ' ' J P N . ~ ' The (Ar = 2,4,6-tri-tert-butylphenyl), was synthesized and characterized by 'H, I3C, and "P NMR and X-ray ~rystallography.~'' The powder sample of CD3(P04)2, given a known single-crystal X-ray struc-

I02

Nucleur Magnetic Resonance

ture, was studied by two-dimensional 3'P double-quantum single-quantum MAS correlation experiments to distinguish specific P sites of such orthophosphates and to show "P and 'I3CD shielding tensor^.^" The complex formation and NMR behavior of a,o-alkylenediamine-N,N,N',N'-tetramethylenetetraphosphonate with cobalt(II1) were investigated by 31PNMR.512 3.16 Group 16 ('70, 77Se, '"Te) - 3.16.I Oxygen f f ' 0 ) - Natural abundance I7O N MR spectra of 4 1, 2,2-diacylenamines (enamino diketones and enamino

diesters), recorded in acetonitrile solution, were reported.513The 170NMR spectra for P,y or y,6 unsaturated alcohols were I7O solution NMR was used to investigate the classical two-step procedure for the preparation of sol-gel derived SiO2-TiOz or SiOz-ZrO2 I7O NMR was used to study siliceous zeolite f a ~ j a s i t e , ~and ' ~ to study athiirene- 1-oxide and related s ~ l f o x i d e s .A ~ 'variable-temperature ~ and -pressure, multiple-field I7O NMR study was performed on (carboxymethyl)(iminobis (ethylenenitrio1o)tetraacetate (dtpa)-type gadolinium(II1) complexes in order to study water exchange and rotational dynamics5I8 and on the water-soluble ionic aryl Pt species [Pt {C6H3(CH2NMe2)-2,6}(OH2)]+to study fast water The I7O and 'H NMR chemical shifts of H20 [6(170H2),6('H20)] in aqueous solutions of various strong inorganic electrolytes were measured and used to determine the 6(170) and 6('H) chemical shifts of hydroxide ion and some of its a q u a - c o m p l e ~ e s .IR, ~ ~ ~I3C NMR, and natural abundance 1 7 0 NMR spectra were measured for a series of eleven glycidyl ethers.521Six crystalline titanodiphenylsiloxanes were synthesized and characterized by 29Si and 170NMR, IR, and time-of-flight mass spectroscopy.522'H, I3C, and 1 7 0 NMR were used to study 2substituted enaminones RCOCMe:CHNHCMe3 (R = Me, Et, Ph) and PhCOCPh:CHNHCMe3523 and to characterize a tetranuclear niobium 0x0 acetate complex, Nb404(OA~)4(0Pri)8.524 High resolution solid-state 1 7 0 MQMAS NMR spectra of I70-enriched compounds were observed.525 3.16.2 Selenium (77Se) - 77Se NMR was used to characterize [K(2.2.2crypt and)l2[(p-0){ p-02Si(CH3)2} 2(GeSe)2] and [K(2.2.2-cryptand)]2[Sb2Se6],526

to study selenothioic acid S-alkyl esters,527to study polychalcogenadisilabicyclo [ k . l . m ] a l k a n e ~ , to ~ ~ ~study [NEt4]2[As2Se6], [enH][AsSe6j2.2.2-cryptand (enand to H = monoprotonated en), [Net4][Asseg], and [(en)21n(SeAs(Se)Se2)]en,529 study organometallic selenolates, [CpW(C0)3SeC(0)NMe2] and { [CpW(C0)3]2Se4}.530 Variable-temperature 77Se NMR was used to show the existence of rotamers of the complexes [CpCr(CO)2]2Se and [CpCr(C0)2]~Se2.~~' 'H, I3C, and 77SeNMR were used to characterize the novel alkyl(pentamethy1cyclopentadieny1)selenium derivative, Se(C5Me5)Me and a mixture of the polyselenides Se,(C5MeS)2 (n = 2, 3 and 4),532 to characterize diyne-bridged metal clusters, [(C0)6Fe2Se2{p-HC:C(CCR)}M] (R = Me and nBu; M = Cp2Mo2(C0)4, C02(C0)6, R u ~ ( C O and ) ~ ~O S ~ ( C O ) ~to~ study ) , ~ ~an ~ unusual annulation of a Fischer carbene complex anchored on a Fe2(CO)&Se)2 core [Fe2(C0)6Se2{ p(CO)3Cr(q5-C5H(CH2Ph)(Ph)(OEt))}],534 and to study optically active boroxazolidine, borathiazolidine and boraselenazolidine and their N-borane adducts from

3: Applications of Nucleur Shielding

103

the corresponding 2-imino-heteroa~olidines.~~~ 'H, 31P,and 77SeNMR were used to characterize phosphaalkyne-bridged cluster Fe4Se2(p-Se2PCBut)(C0)11 536 and to characterize monohydride complexes of W(1V) containing bulky selenolate ligands, [WH(SeR)3(L)(PMe2Ph)] (R = C6H3Pr-i2-2,6 or C6HzMe3-2,4,6; L = PMe2Ph, pyridine and N-methylirnidaz~le).~~~ The I3C, 15N and 77Se NMR data were reported for some seleno and diseleno azines and related comp o u n d ~ Mono. ~ ~ ~ and di-selenoether complexes of tin(1V) halides, Sn&L2 (X = Cl, L2 = MeSe(CHz),SeMe, PhSe(CHz),SePh (n = 2 or 3), C6H4(SeMe)2-0 or 2 Me2Se; X = Br, L2 = MeSe(CH*),SeMe (n = 2 or 3), C6H4(SeMe)2-oor 2 Me2Se) were prepared and characterized by a combination of variable-temperature H, I9Sn and 77Se NMR, IR, microanalyses, and X-ray ~ r y s t a l l o g r a p h yPhoto.~~~ isomerization of ethyl 2-(3-acylselenoureido)thiophene-3-carboxylatesand their benzo analogs was studied by FTIR, 'H, I3C, I5N, 77SeNMR.540Thermolysis of Fe3(C0)9(p3-Se)(p3-E)(E = S, Te) with Cp2Mo2(C0)6 gave the new mixed-metal, mixed trichalcogenide clusters and the products were characterized by IR, 'H, I3C, 77Seand '25TeNMR, and X-ray cry~tallography.~~'

'

'

3.26.3 Tellurium ("'Te) - '25Te NMR was used to study some organotellurium compounds using inverse proton detection using multiple-quantum I H- { '25Te) correlation spectroscopy542 and the Te-0 and Te-Te bonds in single crystal Te02.543'H and '25Te NMR were used to characterize the two compounds, transCp2Mo202(p-O)(p-Te) and cis-Cp2M0202(p-O)( P - S ) . '~H~, 13C,and '25Te NMR were used to characterize a new tellurane Te-oxide dimer [ 12-Te-6(C4O2)I2(h6tellane),545 to study novel 6-alkoxy- 12H,14H-[1,2,3]benzoxatellurazino[2,3-b][ 1,2,3]benzoxatellurazines (R = H, Me, OMe, C1, Br; R' = Et, i-Pr),546 and to characterize the new telluranes, [ 10-Te-4(C2X2)I2'2Y- (A4-tellane) (X = S or Se, Y =BF4 or CF3S03).547 Hybrid (Te,O) ligands, 2-(phenyl telluromethyl)tetrahydro-2H-pyran and 2-(2- { 4-methoxyphenyl) telluroethy1)1,3-dioxane, and their palladium(I1) and platinum(I1) complexes were synthesized and characterized by IR, 'H, '25Te and 31P NMR, and UV-visible spectrocopy.^^^ The extremely moisture-sensitive [SnX4(Me2Te)2] and [Sn&(ditelluroether)] [X = C1 or Br; ditelluroether = C6H4(TeMe)2-o, MeTe(CH2)3TeMe or PhTe(CH&TePh] were prepared and characterized by X-ray crystallography and H, '25Te, and 'I9Sn NMR.549 [(q5-C5H5)(C0)2Fe]3Sn-OHand K2[K-(2,2,2crypt)]2SnTe. 1en were prepared and characterized by X-ray crystallography and 'H, I3C, "9Sn, and '25Te NMR.550 The dinuclear Ni tellurato complex [(q5Cp)Ni(PEt3)TeMes] was prepared and characterized by X-ray crystallography and 'H, I3C, 31P, and '25Te NMR.55' Three synthetic routes to the first 1,3distanna-2-chalcogena[3]ferrocenophaneswere described, and their H, I3C, 77Se, I I9Sn and lZ5TeNMR solution spectra were reported.552 Solid-state '25Te NMR studies of inorganic compounds containing Te in oxidation states ranging from -2 to +6 were reported.553

'

'

3.17 Group 17 (19F) - Following chemical shifts and line broadening, I9F and 2H

NMR were used to characterize the interaction between nonionic organic contaminants and dissolved humic material.554

104

Nuclear Magnetic Resonance

Para-substituted 1-aryl-F- 1,3-butadiene derivatives, p-C6H4CF:CFCF:CF2 were prepared and I9F NMR chemical shifts were correlated with (TP Hammett substituent constants.555'H and I9F NMR were used to study several fluorinated diols, such as 1,1,4,4-tetrafluor0-2,3-butanedioland I , 1,2,2,5,5,6,6-0ctafluoro3,4-hexanediol, prepared in the vapor phase556and to study n-hexane, perfluoron-hexane, and 1,l -dihydroperfluorooctyI propionate dissolved in supercritical carbon dioxide using high-pressure, high-resolution N MR.557The reactions of 1(4-fluoropheny1)-1,2-dicarbadodecaborane(12) and 1-(4-fluorophenyl)- 1,7-dicarbadodecaborane(l2) with Bu4NF hydrate in T H F or MeCN were monitored by I9F and IIB NMR."' Variable-temperature 19F MAS NMR involving highpower proton decouping were used to examine the conformational preference and ring-inversion kinetics in the fluorocyclohexane-thiourea inclusion compound.559 The protective Zr. . .F-C interaction in the group 4 metallocene(butadiene)/ B(C6F5)3betaine Ziegler catalyst systems was characterized by X-ray diffraction and I9F NMR.560 The elusive POF4- anion was characterized for the first time by I9F and 31P NMR.56119F and 13C NMR were used to study two isomers of The ligand exchange reactions in complexes of the type U02LF,(H20)3-, (n = 1-3, L = picolinate, oxalate, carbonate, acetate) and U02L2F (L = picolinate, oxalate) were investigated by I9F, 13C, I7O and 'H NMR.563 3.18 Group 18 (3He, 1299131Xe) - 3.18.I Helium ( j H e )

- Photocycloaddition of 1,3-diones to c 6 0 was studied and the adduct structures were characterized by MS (ESI and MALDI), IR, UV, IH, 13C, and 3He NMR.564 Bis- to hexakisadducts of c60 and mono- to tetrakisadducts of C70 containing 3He atoms (endo-hedral He complexes) were prepared and studied by 3He NMR to determine the influence of degree of functionalization and addition pattern on the chemical shift of the 3He atom.565

3.18.2 Xenon ('2yv131Xe)- Laser-polarized 129Xedissolved in a foam from fresh human blood was investigated by 129XeNMR.566 Solid-state 129Xeand X-ray diffraction were used to study Xe enclathrated ptert-butylcalix[4]arene.567 '29Xe NMR was used as a structural probe of solid poly(ethy1ene oxide)/atactic poly(Me methacrylate) (PEO/PMMA) blends of concentrations 10/90 to 75/25.568 The origins of the NMR chemical shift of '29Xe within zeolite Y host framework was studied by evaluating actual spectra and computer simulation data at various temperatures and loading levels.569The role of polarization in the adsorption of Xe in zeolites of type A was considered by direct comparative analysis of the adsorption isotherms, distributions of occupancies, and 129XeN MR chemical shifts of Xe, in cages containing Ca,Na12 2x ions per alpha cage (x=O, 1, 2, 3, 5).570The adsorption of xenon in AgA zeolite has been studied by 129XeNMR to show information on the silver distribution, Xe cluster size and exchange dynamics.571 The A d H Y (4 wt.%) system, prepared by autoreduction of [Au(en)2J3+in inert gas flow at 423 K, was studied by TEM, '29Xe NMR and

3: Applications of Nuclear Shielding

105

diffuse reflectance IR spectroscopy of adsorbed C0.572 '29Xe gas-to-solution NMR chemical shifts for Xe dissolved in pure n-alkanes, n-alkyl alcohols, n-alkyl carboxylic acids, di-n-alkyl ketones, and cycloalkanes and in solutions of lauric acid in n-heptane were reported.573 '29Xe NMR spectra were measured for solutions containing Xe dissolved in a variety of linear 1-haloalkanes, a,odihaloalkanes, and their mixtures.574'29Xe and 13CCP/MAS NMR were used to study coking and deactivation behavior of fouled H-beta, H-mordenite, H-ZSM5, and H-USY zeolites during ethylbenzene disproportionation reaction.575The direct synthesis of arylxenon trifluoromethanesulfonates via electrophilic substitution was described and the products were characterized by 'H, I3C, and '29Xe NMR, mass, and vibrational spectra.576 Multiple-quantum filtered I3'Xe NMR was studied as a surface probe.577

4

References 1

2

3 4 5 6

7

8 9 10

11 12 13 14 15 16 17 18

19 20 21 22

K.-B. Li and B. C. Sanctuary, J. Chem. Inf. Comput. Sci., 1997,37,467. R. J. Abraham, M. A. Warne, and L. Griffiths, J. Chem. Soc., Perkin Trans. 2, 1997, 2151. W. Gronwald, R. F. Boyko, F. D. Sonnichsen, D. S. Wishart, and B. D. Sykes, J. Biomol. NMR, 1997, 10, 165. W. Y. Choy, B. C. Sanctuary, and G. Zhu, J. Chem. Inf. Comput. Sci., 1997,37,1086. K. Huang, M. Andrec, S. Heald, P. Blake, and J. H. Prestegard, J. Biomol. NMR, 1997, 10,45. D. Croft, J. Kemmink, 0. Klaus-Peter, and H. Oschkinat, J. Biomol. NMR, 1997, 10, 207. D. S. Wishart, M. S. Watson, R. F. Boyko, and B. D. Sykes, J. Biomol. NMR, 1997, 10, 329. C.-C. Lin, C.-Y. Fang, D.-Y. Kao, and J.-S. Chen, J. Solution Chem., 1997,26, 8 17. 0. Ivancius, J.-P. Rabine, D. Cabrol-Bass, A. Panaye, and J. P. Doucet, J. Chem. Inf. Comput. Sci., 1997,37, 587. V. Schutz, V. Purtuc, S. Felsinger, and W. Robien, Fresenius' J. Anal. Chem., 1997, 359, 33. M. Bilde and A. E. Hansen, Mol. Phys., 1997,92,237. D. A. Forsyth and A. B. Sebag, J. Am. Chem. Soc., 1997,119,9483. U. Sternberg and W. Prieb, J. Mugn. Reson., 1997, 125,s. R. Koch, B. Wiedel, and C. Wentrup, J. Chem. Soc., Perkin Trans. 2,1997, 1851. A. D. Buckingham and R. M.Olegirio, Mol. Phys., 1997,92,773. F. Mauri, B. G. Pfrommer, and S. G. Louie, Phys. Rev. Lett., 1997,79,2340. M. Pecul, K. Jackowski, K. Wozniak, and J. Sadlej, Solid State Nucl. Magn. Reson., 1997,8. 139. M. Kaupp and 0. L. Malkina, J. Chem. Phys., 1998,108,3648. R. R. Sauers, Tetrahedron, 1998,54, 337. G . Cuevas, E. Juaristi, and A. Vela, THEOCHEM, 1997,418,231. G. A. Olah, T. Shamma, A. Burrichter, G. Rasul, and G. K. S. Prakash, J. Am. Chem. Soc., 1997,119, 12923. A. P. Mazurek, J. Cz. Dobrowolski, and J. Sadlej, J. Mol. Struct., 1997, 436-437, 435.

I06

Nuclear Mugnetic Resonance

23

G. A. Olah, A. Burrichter, G. Rasul, M. Hachoumy, and G. K. S. Prakash, J. Am. Chem. Soc., 1997,119, 12929. M. Barfield and P. Fagerness. J. Am. Chem. Soc., 1997, 119,8699. R. Ludwig, F. Weihold, and T. C. Farrar, J. Phys. Chem. A , 1997, 101,8861. J. W. Wiench, L. Stefaniak, A. Tabaszewska, and G. A. Webb, Electron. J. Theor. Chem., 1997,2, 71. H. Lampert, W. Mikenda, A. Karpfen, and H. Kaehlig, J. Phys. Chem. A , 1997,101, 96 10. G. A. Olah, A. Burricher, G. Rasul, R. Gnann, K. 0.Christe, and G. K. S. Prakash, J. Am. Chem. Soc., 1997,119,8035. C. Fressigne, A. Corruble, J.-Y. Valnot, J. Maddaluno, and C. Giessner-Prettre, J. Organomet. Chem., 1997,549,81. X . Yang, H. Jiao, and P. v. R. Schleyer, Inorg. Chem., 1997,36,4897. J. A. Tossell, J. Non-Cryst. Solids, 1997,215,236. I. Chao, K.-W. Chen, K.-T. Liu, and C.-C. Tsoo, Tetrahedron Lett., 1998,39, 1001. K. Jackowski, M. Jaszunski, and W. Makulski, J. Mugn. Reson., 1997, 127, 139. E. Kraka, C. P. Sosa, J. Grafenstein, and D. Cremer, Chem. Phys. Lett., 1997,279,9. D. B. Chesnut, Chem. Phys., 1997,224, 133. A. Bagno, THEOCHEM, 1997,418,243. R. Musio and 0. Sciacovelli, J. Org. Chem., 1997,62,9031. M. Buehl and F. A. Hamprecht, J. Comput. Chem., 1998,19, 113. J. C. C. Chan and S. C. F. Au-Yeung, J. Phys. Chem. A , 1997,101,3637. J. C. C. Chan, P. J. Wilson, S. C. Au-Yeung, and G. A. Webb, J. Phys. Chem. A , 1997,101,4196. J . C. C. Chan and S. C. F. Au-Yeung, THEOCHEM, 1997,393,93. N. Godbout and E. Oldfield, J. Am. Chem. Soc., 1997,119,8065. H. Nakatsuji, Z.-M. Hu, and T. Nakajima, Chem. Phys. Lett., 1997, 275,429. G. Schreckenbach and T. Ziegler, J. Phys. Chem. A , 1997,101,4121. M. Buehl, S. Patchkovskii, and W. Thiel, Chem. Phys. Lett., 1997,275, 14. A. C. de Dios and C. J. Jameson, J. Chem. Phys., 1997,107,4253. S. S . Wijmenga, M. Kruithof, and C. W. Hilbers, J, Biomol. NMR, 1997, 10,337. L. S. Kivaeva, G. T. Ibragimova, and V. Kutyshenko, Protein Pept. Lett., 1997, 4, 91. M. Yoshikawa, H. Shimada, M. Saka, S. Yoshizumi, J. Yamahara, and H. Matsuda, Chem. Phurm. Bull., 1997,45,464. Y.-M. Chi, F. Hashimoto, W.-M. Yan, T. Nohara, M. Yamashita, and N. Marubayashi, Chem. Phurm. Bull., 1997,45,495. F. Alali, L. Zeng, Y. Zhang, Q. Ye, D. C. Hopp, J. T. Schwedler, and J. L. Mclaughlin, Bioorg. Med. Chem., 1997, 5, 549. M. Juch and P. Ruedi, Helv. Chim. Actu, 1997,80,436. M. S. C. Pedras, Can. J. Chem., 1997,75,314. A. Ichikawa, H. Takahashi, T. Ooi, and T. Kusumi, Biosci., Biotechnol., Biochem., 1997,61, 881. B. Tse, C. M. Blazey, B. Tu, and J. Balkovec, J. Org. Chem., 1997,62, 3236. E. L. M. Da Silva, F. Roblot, and A. Cave, Heterocycles, 1997,45,915. N. Kashiwaba, S. Morooka, M. Kimura, and M. Ono, Nut. Prod. Lett., 1997,9, 177. A. Spinella, E. Zubia, E. Martinez, J. Ortea, and G. Cimino, J. Org. Chem., 1997, 62, 5471. M. Kuramoto, K. Hayashi, Y. Fujitani, T. Tsuji, K. Yamada, Y. Ijuin, and D. Umeura, Tetrahedron Lett., 1997,38, 5683.

24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50

51 52 53 54 55 56 57 58 59

3: Applications of Nuclear Shielding 60

61 62 63 64

65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93

107

G. Shi, K. He, X. Liu, Q. Ye, J. M. MacDougal, and J. L. McLaughlin, Nut. Prod Lett., 1997, 10, 125. R. Duran, E. Zubia, M. J. Ortega, and J. Salva, Tetruhetirun, 1997,53,8675. M. Satoh, N. Takeuchi, and Y. Fujimoto, Chem. Pharm. Bull., 1997,45, 1 1 14. F. Q. Alali, Y. Zhang, L. Rogers, and J. L. McLaughlin, J. Nut. Prod., 1997,60,929. J. G. Ondeyka, G. L. Helms, 0. D. Hensens, M. A. Goetz, D. L. Zink, A. Tsipouras, W. L. Shoop, L. Slayton, A. W. Dombrowski, J. D. Polishook, D. A. Ostlind, N. N. Tsou, R. G. Ball, and S. B. Singh, J. Am. Chem. Soc., 1997,119,8809. L. Xiao, T. Yamazaki, T. Kitazume, T. Yonezawa, Y. Sakamoto, and K. Nogawa, J. Fluorine Chem., 1997,84, 19. V. Amico, M. Piattelli, M. Bizzini, and P. Neri, J. Nut. Prod., 1997,60, 1088. M. Kobaisy, Z. Abramowski, L. Lermer, G. Saxena, R. E. W. Hancock, G. H. N. Towers, D. Doxsee, and R. W. Stokes, J. Nut. Prod., 1997,60, 1210. M. Kobayashi, T. Mahmud, T. Umezome, W. Wang, N. Murakami, and I. Kitagawa, Tetruhedron, 1997,53, 15691. G. Lauktien, F.-J. Volk, and A. W. Frahm, Tetrahedron: Asymmetry, 1997,8, 3457. A. J. Pearson and A. V. Gontcharov, J. Org. Chem., 1998,63, 152. Y. Seo, K. W. Cho, J.-R. Rho, J. Shin, and C. J. Sim, Tetrahedron, 1998, 54, 447. Y. Guo, E. Trivellone, G. Scognamiglio, and G. Cimino, Tetrahedron Lett., 1998,39, 463. X. Shi, A. B. Attygalle, A. Liwo, M.-H. Hao, J. Meinwald, H. R. W. Dharmaratne, W. M. Wanigasekera, and P. Anoja, J. Org. Chem., 1998,63, 1233. V. Hellwig, J. Dasenbrock, S. Schumann, W. Steglich, K. Leonhardt, and T. Anke, Eur. J. Org. Chem., 1998,73. T. Hashimoto, M. Toyota, H. Koyama, A. Kikkawa, M. Yoshida, M. Tanaka, S. Takaoka, and Y. Asakawa, Tetrahedron Lett., 1998,39, 579. A. Fontana, M. L. Ciavatta, and G. Cimino, J. Org. Chem., 1998,63,2845. T. Yabuuchi, T. Ooi, and T. Kusumi, Chirality, 1997,9, 550. M. J. Ferreiro, S. K. Latypov, E. Quinoa, and R. Riguera, Tetrahedron: Asymmetry, 1997,8, 1015. J. M. Seco, S. K. Latypov, E. Quinoa, and R. Riguera, Tetrahedron, 1997, 53,8541. C. M. Garner, C. McWhorter, and A. R. Goerke, Tetrahedron Lett., 1997,38,7717. T. J. Wenzel, R. D. Miles, and S. E. Weinstein, Chirality, 1997,9, 1 . K. Wypchlo, and H. Duddeck, Chirality, 1997,9, 601. A. Meddour, P. Berdague, A. Hedli, J. Courtieu, and P. Lesot, J. Am. Chem. Soc., 1997,119,4502. U. Holzgrabe, H. Mallwitz, S. K. Branch, T. M. Jefferies, and M. Wiese, Chirality, 1997,9,211. T. Kitae, T. Nakayama, and K. Kano, J. Chem. Soc., Perkin Trans. 2, 1998,207. M. Thunhorst and U. Holzgrabe, Magn. Reson. Chem., 1998,36,21 I . K. Kano, S. Negi, R. Takaoka, H. Kamo, T. Kitae, M. Yamaguchi, H. Okubo, and M. Hirama, Chern. Lett., 1997,715. D. Vikic-Topic, P. Novak, V. Smrecki, and Z. Meic, J. Mul. Struct., 1997,410-411,5. P. Novak, Z. Meic, D. Vikic-Topic, and H. Sterk, J. Mol. Struct., 1997,410-411,9. R. M. Jarret, N. Sin, and M. Dintzner, Microchem. J., 1997,56, 19. H. Tsuzuki, T. Goda, S. Mataka, and M. Tashiro, Jpn. J. Deuterium Sci., 1997, 6, 31. P. E. Hansen and S. Bolvig, Mugn. Reson. Chem., 1997,35,520. D. Kh. Zheglova, D. G. Genov, S. Bolvig, and P. E. Hansen, Actu Chem. Scanci., 1997,51, 1016.

108

Nuclear Magnetic Resonance

94

A. R. Katritzky, I. Ghiviriga, D. C. Oniciu, R. A. M. O’Ferrall, and S. M. Walsh, J. Chem. Soc., Perkin Trans. 2, 1997,2605. S . Mazzini, L. Merlini, R. Mondelli, G. Nasini, E. Ragg, and L. Scalioni, J. Chem. Soc., Perkin Trans. 2,1997,2013. T. Dziembowska, Z. Rozwadowski, and P. E. Hansen, J. Mol. Struct., 1997, 436-437, 189. P. E. Hansen, M. Langgard, and S. Bolvig, Pol. J. Chem., 1998,72,269. R. M . Jarret, N. Sin, and M. Dintzner, Microchem. J., 1997,56, 19. M. Ottiger and A. Bax, J. Am. Chem. SOC.,1997,119,8070. T. Pehk, E. Kiirend, E. Lippmaa, U. Ragnarsson, and L. Grehn, J. Chem. Sue., Perkin Trans. 2, 1997,445. P. E. Hansen, S. Bolvig, A. Buvari-Barcza, and A. Lycka, Acta Chem. Scand., 1997, 51,881. T. C. Stringfellow, G. Wu, and R. E. Wasylishen, J. Phyx Chem. B, 1997,101,9651. H. Benedict, H.-H. Limbach, M. Wehlan, W.-P. Fehlhammer, N. S. Golubev, and R. Janoschek, f. Am. Chem. Suc., 1998,120,2939. G. Bianchi, 0.W. Howarth, C. J. Samuel, and G. Vlahov, J. Chem. Soc., Chem. Commun., 1994,627. C . R. Kaiser, R. Rittner, and E. A. Basso, Magn. Resun. Chem., 1997,35,609. R. G. Guy, R. Lau, A. U. Rahman, and F. J. Swinbourne, Spectrochim. Acta, Part A , 1997,53A, 361. V. Koleva, T. Dudev, and I. Wawer, J. Mol. Struct., 1997,412, 153. L. Lamartina, G. Bonfiglio, P. De Maria, and D. Spinelli, G a z . Chim. Ital., 1997, 127, 331. R. Gawinecki, E. Kolehmainen, and R. Kauppinen, J. Chem. Soc., Perkin Trans. 2 , 1998,25. C. Alvarez-Ibarra, M. L. Quiroga-Feijoo, and E. Toledano, J. Chem. Suc., Perkin Trans. 2 , 1998,679. R. G. E. Morales and M. A. Leiva, Spectrosc, Lett., 1997,30, 557. B. Z. Jovanovic, M. Misic-Vukovic, S. Z. Drmanic, and J. J. Canadi, J. Mol. Struct., 1997,410-411, 39. A. M. Orendt, J. Z. Hu, Y.-J. Jiang, J. C. Facelli, W. Wang, R. J. Pugmire, C. Ye, and D. M. Grant, J. Phys. Chem. A , 1997,101,9169. B. Palasek, A. Puszko, Z. Biedrzycka, W. Sicinska, and M. Witanowski, Spectroscopy (Amsterdam), 1997, 13,251. M. De Rosa, D. W. Boykin, and A. L. Baumstark, J. Chem. Soc., Perkin Trans. 2 , 1997, 1547. C. A. van Walree and L. W. Jenneskens, Tetrahedron, 1997,53, 5825. W. Adcock and A. R. Krstic, Magn. Reson. Chem., 1997,35,663. J.-C. Zhuo, Mugn. Reson. Chem., 1997,35,311, M. Michalik, T. Freier, K. Zahn, and K. Peseke, Magn. Reson. Chem., 1997, 35, 859. K. Waisser, J. Kunes, L. Kubicova, M. Budesinsky, and 0. Exner, Magn. Reson. Chem., 1997,35,543. D. G. de Kowalewski, V. J. Kowalewski, E. Botek, R. H. Contreras, and J. C. Facelli, Magn. Reson. Chem., 1997.35, 351. Q. T. H. Le, S. Umetani, M. Suzuki, and M. Matsui, J. Chem. SOC.,Dalton Truns., 1997,643. Y.-F. Yuan, S.-M. Ye, L.-Y. Zhang, B. Wang, Y.-M. Xu, J.-T. Wang, and H.-G. Wang, Inorg. Chim. Acta, 1997,256, 31 3.

95 96 97 98 99 I00 101 102 103 104

105 106 107 I08 109 110 111

I12 113 1 I4

115 1 I6 1 I7

118 119 120 121 122 123

3: Applications of Nuclear Shielding

1 24 125 126 127 128

129 I30 131 132 133 134 135 136 137 138 139 I 40 141 142 143 144

145 146 147 148 149 150

151 152 153 I54

I55

109

V. Bertolasi, P. Gilli, V. Ferretti, and G. Gilli, J. Chem. Soc., Perkin Trans. 2, 1997, 945. B. W. Gung, Z. Zhu, and B. Everingham, J. Org. Chem., 1997,62,3436. A. Simperler and W. Mikenda, Monutsh. Chem., 1997, 128,969. T. Dziembowska, E. Majewski, Z. Rozwadowski, and B. Brzezinski, J. Mol. Struct., 1997,403, 183. F. J. Martinez-Martinez, I. I. Padilla-Martinez, M. A. Brito, E. D. Geniz, R. C. Rojas, J. B. R. Saavedra, H. Hopfl, M. Tlahuextl, and R. Contreras, J. Chem. Soc., Perkin Trans. 2, 1998,401. D. G. Genov, R. A. Kresinski, and J. C. Tebby, J. Org. Chem., 1998,63,2574. T. Ichikawa and K. Sawada, Bull. Chem. Soc. Jpn., 1997,70,829. H. Jiao, P. v. R. Schleyer, B. R. Beno, K. N. Houk, and R. Warmuth, Angew. Chem., Int. Ed, Engl., 1998,36, 2761. S.-N. Ueng, M. Blumenstein, and K. G. Grohmann, J. Org. Chem., 1997,62,2432. G. Yamamoto, Y. Mazaki, R. Kobayashi, H. Higuchi, and J. Ojima, J. Chem. Soc., Perkin Truns. I , 1997, 3 183. C. J. Medforth, C. M. Muzzi, K. M. Shea, K. M. Smityh, R. J. Abraham, S. Jia, and J. A. Shelnutt, J. Chem. Soc., Perkin Trans. 2, 1997,833 and 839. T. D. Lash and S. T. Chaney, Angew. Chem., Int. Ed. Engl., 1997,36,839. T. D. Lash and M. J. Hayes, Angew. Chem., Int. Ed Engl., 1997,36, 840. H. Higuchi, N. Hiraiwa, T. Daimon, S. Kondo, J. Ojima, M. Iyoda, and G. Yamamoto, Bull. Chem. Soc. Jpn., 1998,71,221. R. H. Mitchell, Y.Chen, N. Khalifa, and P. Zhou, J. Am. Chem. Soc., 1998, 120, 1785. Y.-H. Lai and P. Chen, J. Org. Chem., 1997,62,6060. S. Kuroda, M. Oda, S. Kuramoto, A. Fukuta, Y. Mizukami, Y. Nozawa, R. Miyatake, M. Izawa, and I. Shimao, Tetrahedron Lett., 1997,38,8291. P. L. Wash, E. Maverick, J. Chiefari, and D. A. Lightner, J. Am. Chem. Soc'., 1997, 119,3802. A. Michnik and A. Sulkowska, J. Mol. Struct., 1997,410-411, 17. A. Sacco and M. Holz, J. Chem. Soc., Furatiuy Trms., 1997,93, 1101. M. Hoffmann and M. S. Conradi, J. Am. Chem. Soc., 1997,119,38I 1. A. Harada, Y. Kawaguchi, T. Nishiyama, and M. Kamachi, Macromol. Rupid Commun., 1997, 18, 535. W. Herrmann, B. Keller, and G. Wenz, Mucromolecules, 1997,30,4966. J. L. Alderfer and A. V. Eliseev, J. Org. Chem., 1997,62, 8225. R . Castro, L. A. Godinez, C. M. Criss, and A. E. Kaifer, J. Org. Chem., 1997, 62, 4928. Y. Matsui, M. Ono, and S. Tokunaga, Bull. Chem. Soc. Jpn., 1997,70, 535. Y.-Q. Song, B. M. Goodson, R. E. Taylor, D. D. Laws, G. Navon, and A. Pines, Angew. Chem., Int. Ed. Engl., 1991,36, 2368. H. Dodziuk, J. Sitkowski, L. Stefaniak, D. Sybilska, and J. Jurczak, Supramol. Chem., 1996,7, 33. S. Astilean, C. Ionescu, Gh. Cristea, S. I. Farcas, I. Bratu, and R. Vitoc, Biospectroscopy, 1997,3,233. J. R . Moyano, M. J. Arias-Blanco, J. M. Gines, and F. Giordano, Int. J. Pharm., 1997,148,211. J. Nishijo, Y. Ushiroda, H. Ohbori, M. Sugiura, and N. Fujii, Chem. Phurm. Bull., 1997,45, 899. H. Dodziuk, J. Sitkowski, L. Stefaniak, D. Sybilska, J. Jurczak, and K. Chmurski, Pol. J. Chem., 1997, 71, 757.

I10

Nuclear Mugnetic Resonance

156

R. Lu, J. Hao, H. Wang, and L. Tong, J. Inclusion Phenom. Mol. Recognit. Chem., 1997,28, 213. K. Aithal and U. N. Shrinivas, Phurm. Sci., 1996,2,451. F. Caccia, R. Dispenza, G. Fronza, C. Fuganti, L. Malpezzi, and A. Mele, J. Agric. Food Chem., 1998,46, 1500. K. Kano, S. Negi, H. Kamo, T. Kitae, M. Yamaguchi, H. Okubo, and M. Hirama, Chem. Lett., 1998, 151. L. Leclercq, M. Bria, M. Morcellet, and B. Martel, J. Inclusion Phenom. Mul. Recognit. Chem., 1998,30,215. R. Ravichandran and S. Divakar, J. Inclusion Phenom. Mol. Recognit. Chem., 1998, 30, 253. S. Divakar and M. M. Maheswaran, J. Inclusion Phenom. Mol. Recognit. Chem., 1997,27, I 13. U. Holzgrabe, H. Mallwitz, S. K. Branch, T. M. Jefferies, and M. Wiese, Chirality, 1997,9, 21 I . C. J. Easton, S. F. Lincoln, B. L. May, and J. Papageorgious, Aust. J. Chem., 1997, 50,451. S. Anguiano-Igea, F. J. Otero-Espinar, J. L. Vila-Jato, and J. Blanco-Mendez, Eur. J. Pharrn. Sci., 1997,5, 215. P. Montassier, D. Duchene, and M.-C. Poelman, Int. J. Pharm., 1997,153, 199. B. Szafran and J. Pawlaczyk, Pol. J. Chem., 1998,72,480. Y. L. Loukas, J. Pharm. Pharmucol., 1997,49, 944. J. R. Moyano, M. J. Arias-Blanco, J. M. Gines, and F. Giordano, Znf. J. Pharm., 1997,157,239. Y. L. Loukas, V. Vraka, and G. Gregoriadis, J. Pharm. Biomed. Anal., 1997,16,263. A. M. Kaukonen, I. Kilpelainen, and J.-P. Mannermaa, Inl. J. Pharm., 1997, 159, 159. E. Antoniadou-Vyza, G. Buckton, S. G. Michaleas, Y. L. Loukas, and M. Efentakis, Int. J. Phurm., 1997, 158,233. C. A. Ventura, G. Puglisi, M. Zappala, and G. Mazzone, Int. J. Pharm., 1998, 160,

157 158 159 160 161 162 163 I64 165 166 167 168 169 170 171 I72 I73

163.

174 175 176 177 I78 179 180 181

182 I83 184

185

W.-Y. Tseng, Y. H. Chen, I. I. Khairullin, S. Cheng, and L.-P. Hwang, Solidstate Nucl. Mugn. Reson., 1997,8, 219. A. Harada, M. Okada, and M. Kamachi, Bull. Chem. Soc. Jpn., 1998,71, 535. E. Butkus, J. C. Martins, and U. Berg, J. Inclusion Phenom. Mol. Recognit. Chem., 1996,26, 209. M. Weickenmeier and G. Wenz, Macromol. Rupici Cummun., 1997, 18, 1109. S. Ishikawa, S. Neya, and N. Funasaki, J, Phys. Chem. B, 1998,102,2502. 0. A. E. Soliman, K. Kimura, F. Hirayama, K. Uekama, H. M. El-Sabbah, A. E. H. El-Gawad, and F. M. Hashim, Int. J. Pharm., 1997, 149, 73. J. Yan and S. Dong, Lungmuir, 1997,13,3251. A. Harada, H. Adachi. Y. Kawaguchi, and M. Kamachi, Macromolecules, 1997,30, 5181. A. Harada, T. Nishiyama, Y. Kawaguchi, M. Okada, and M. Kamachi, Mucromolecules, 1997,30, 71 15. R. Arnecke, V. Boehmer, R. Cacciapaglia, A. D. Cort, and L. Mandolini, Tefraheciron, 1997,53,490 1. A. R.Fakhari and M. Shamsipur, J. Inclusion Phenom. Mol. Recognit. Chem., 1996, 26,243. Y. Tobe, S. Sasaki, K. Hirose, and K. Naemura, Tetrahedron Lett., 1997,38,4791.

3: Applications of Nuclear Shielding

186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 20 1 202 203 204 205 206 207 208 209 210 21 I 212 213 214 215 216 217 218 219

Ill

X. Fei, Y.-Z. Hui, V. Rudiger, and H.-J. Schneider, J. Phys. Org. Chem., 1997, 10, 305. K. Bartik, M. Luhmer, J.-P. Dutasta, A. Collet, and J. Reisse, J. Am. Chem. Soc., 1998,120,784. B. M. O’Leary, R. M. Grozfeld, and J. Rebek, Jr., J. Am. Chem. Soc., 1997, 119, 11701. J. Ren, C. S. Springer, Jr., and A. D. Sherry, Inorg. Chem., 1997,36, 3493. R. J. Abraham, A. Ghersi, G. Petrillo, and F. Sancassan, J. Chem. Soc., Perkin Truns. 2 , 1997, 1279. M. Sattler and S. W. Fesik, J. Am. Chem. Soc., 1997,119, 7885. N. Gauiter, N. Noiret, C. Nugier-Chauvin, and P. H. Caroline, Tetrukedron: Asymmetry, 1997,8, 501. P. H. Buist, B. Behrouzian, S. Cassel, C. Lorin, P. Rollin, A. Imberty, and S. Perez, Tetrahedron: Asymmetry, 1997,8, 1959. F. J. Troendle, K. S. Venkatasubban, and R. Rothchild, Spectrosc. Lett., 1997, 30, 435. A. Elias, T. G. Roberts, K. S. Venkatasubban, and R. Rothchild, Spectrosc. Lett., 1997,30, 1669. S. E. Weinstein, M. S. Vining, and T. J. Wenzel, Magn. Reson. Chem., 1997,35, 273. T . J. Wenzel, A. C. Bean, and S. Dunham, Mugn. Reson. Chem., 1997,35,395. L. Fauconnot, C. Nugier-Chauvin, N. Noiret, and H. Patin, Tetruheclron Lett., 1997, 38, 7875. G. M. Hanna, J. Pharm. Biomed. Anal., 1997,15, 1805. M.A. Haiza, A. Sanyal, and J. K. Snyder, Chirality, 1997,9, 556. T. K. Green, J. R. Whetstine, and E.-J.-R. Son, Tetruheclron: Asymmetry, 1997, 8, 3175. C. Koy, M. Michalik, C. Dobler, and G. Oehme, J. Prukt. Chem.lChem.-Ztg., 1997, 339,660. J. Lacour, C. Ginglinger, F. Favarger, and S. Torche-Haldimann, Chem. Commun. (Cumbridge), 1997,2285. D. Toronto, F. Sarrazin, J. Pecaut, J.-C. Marchon, M. Shang, and W. R. Scheidt, Inorg. Chem., 1998,37, 526. A. Bilz, T. Stork, and G. Helmchen, Tetrahedron: Asymmetry, 1997,8,3999. R. K. Harris, J. Kowalewski, and S. Cabral de Menezes, Mugn. Reson. Chem., 1998, 36, 145. R. G. Mendez, NATO A S I Ser., Ser. A , 1996,288,57. H. E. Gottlieb, V. Kotlyar, and A. Nudelman, J. Org. Chem., 1997,62,7512. A.-R. Grimmer, A. Kretschmer, and V. B. Cajipe, Mugn. Reson. Chem., 1997, 35, 86. G. Neue and C. Dybowski, Solid State Nucl. Magn. Reson., 1997,7, 333. T. C. Stringfellow and T. C. Farrar, Spectrochim. Acta, Purt A , 1997,53A, 2425. G. H. Penner and J. Hutzal, Mugn. Reson. Chem., 1997,35,222. L. E. Kay and K. H. Gardner, Curr. Opin. Struct. Biol., 1997,7, 722. M. S. F. L. K. Jie and J. Mustafa, Lipids,1997,32, 1019. C. B. Lemaster, Prog. Nucl. Mugn. Reson. Spectrosc., 1997,31, 119. R. G. Barnes, Top. Appl. Phys., 1997,73,93, R . Sacchi, F. Addeo, and L. Paolillo, Mugn. Reson. Chem., 1997,35, S133. J. Wu, J. B. Day, K. Franaszczuk, B. Montez, E. Oldfield, A. Wieckowski, P.-A. Vuissoz, and J.-P. Ansermet, J. Chem. Soc., Faraduy Trans., 1997,93, 1017. L. Ballard and J. Jonas, Annu. Rep. NMR Spectrosc., 1997,33, 1 15.

I12 220 22 I 222 223 224 225 226 227 228 229 230 23 I 232 233 234 235 236 237 238 239 240 24 1 242 243 244 245 246 247 248 249 250 25 1

Nuclear Magnetic Resonunce

0.A. El Seoud, J. Mol. Liq., 1997,72,85. A. Poveda, J. L. Asensio, J. F. Espinosa, M. Martin-Pastor, J. Canada, and J. Jimenez-Barbero, J. Mol. Gruphics Modell., 1997, 15, 9. H. W. Spiess, Annu. Rep. N M R Spectrosc., 1997,34, 1. H. Yasunaga, M. Kobayashi, S. Matsukawa, H. Kurosu, and I. Ando, Annu. Rep. NMR Spectrosc., 1997,34, 39. A. K. Whittaker, Annu. Rep. NMRSpectrosc., 1997,34, 105. A. E. Tonelli, Annu. Rep. NMR Spectrosc., 1997,34, 185. S. D. Samaras, A. Balasubramaniam, and M. E. Johnson, Curr. Meci. Chem., 1997, 4, 151. N. J. Baxter and M. P. Williamson, J. Biomol. N M R , 1997,9, 359. S. M. N. Crawford, A. N. Taha, N. S. True, and C. B. LeMaster, J. Phys. Chem. A , 1997, 101,4699. M. J. Wilson, R. A. Pethrick, D. Pugh, and M. S. Islam, J. Chem. Soc., Furaduy Trans., 1997, 93, 2097. J. J. Fitzgerald, G. Piedra, S. F. Dec, M. Seger, and G . E. Maciel, J. Am. Chem. Soc., 1997, 119, 7832. P. Tekely and P. Palmas, and P. Mutzenhirdt, .I. Mugn. Reson., 1997, 127,238. F. Vianello, M. Scarpa, P. Viglino, and t: . Rigo, Biochem. Biophys. Res. Commun., 1997,237,650. P. Mitrakos and P. M. Macdonald, Biochemistry, 1997,36, 13646. H. Shinar, Y. Seo, and G. Navon, J. M a p . Reson., 1997, 129,98. T. Asakura, M. Minami, R. Shimada, M. Demura, M. Osanai, T. Fujito, M. Imanari, and A. S. Ulrich, Mucromolecults, 1997,30,2429. A. Loaiza, D. Borchardt, and F. Zaera, Spectrochim. Acta, Purt A, 1997, 53A, 248 1. E. Jamin, N. Naulet, and G. J. Martin, Plant, Cell Environ., 1997,20, 589. G. Remaud, A. A. Debon, Y.-I. Martin, G. G. Martin, and G. J. Martin, J. Agric. Food Chem., 1997,45,4042. B.-L. Zhang, S. Buddrus, M. Trierweiler, and G. J. Martin, J. Agric. Food Chem., 1998,46, 1374. A. M. Pupin, M. J. Dennis, I. Parker, S. Kelly, T. Bigwood, and M. C. F. Toledo, J. Agric. Food Chem., 1998,46, 1369. M. Aursand, F. Mabon, and G . J. Martin, Mugn. Reson. Chem., 1997,35, S91. D. F. Shantz and R. F. Lobo, J. Phys. Chem. B, 1998,102,2339. S. Lee, H. Morimoto, and P. G. Williams, J. Lctbelleci Compd. Radiopharm., 1997, 39,461. A. S. Culf, J. T. Gerig, and P. G. Williams, J. Biomol. NMR, 1997, 10,293. X. Su, A. Siddiqui, S. Swaminathan, W. K. Wilson, and G. J. Schroepfer, Jr., J. Labelled Compci, Radiopharm., 1998,41,63. J. F. Remenar, B. L. Lucht, and D. B. Collum. J. Am. Chem. Soc., 1997,119,5567. H. Kawasaki, I. Shimada, Y. Arata, K. Okamura, T. Date, and K. Koga, Tetruheciron, 1997,53, 7 19 I . J. F. Remenar, B. L. Lucht, D. Kruglyak, F. E. Romesberg, J. H. Gilchirst, and D. B. Collum, J. Urg. Chem., 1997,62,5748. D. Sato, H. Kawasaki, and K . Koga, Chem. Pharm. Bull., 1997,45, 1399. G. Hilmersson, P. I. Arvidsson, 0. Davidsson, and M. Haakansson, Orgunometullics, 1997, 16, 3352. C. Guadarrama-Perez, G. Cadenas-Pliego, L. M. R. Martinez-Aguilera, and A. Flores-Parra, Chem. Ber.lRecl., 1997, 130, 813.

3: Applications of Nuclear Shielding

252 253 254 255 256 257 258 259 260 26 1 262 263 264 265 266 267 268 269 270 27 1 272 273 274 275 276 277 278 279 280 28 I 282

I13

F. Becke, F. W. Heinemann, T. Ruffer, P. Wiegeleben, R. Boese, D. Blaser, and D. Steinborn, J. Organomet. Chem., 1997,548,205. J. Kriz, B. Masar, J. Dybal, and D. Doskocilova, Macromolecules, 1997,30, 3302. C. Zune, P. Dubois, R. Jerome, J. Kriz, J. Dybal, L. Lochmann, M. Janata, P. Vlcek, T. M. Werkhoven, and J. Lugtenburg, Macromolecules, 1998,31,2731. C. Zune, P. Dubois, R. Jerome, J. Kriz, J. Dybal, L. Lochmann, M. Janata, P. Vlcek, T. M. Werkhoven, and J. Lugtenburg, Macromolecules, 1998,31,2744. F. Becke, F. W. Heinemann, and D. Steinborn, Organometallics, 1997,16,2736. J. K. Brask, T. Chivers, M. Parvez, and G. Schatte, Angew. Chem., Int. Ed. Engl., 1997,36, 1986. P.-0. Quist, H. Foerster, and D. Johnels, J. Am. Chem. Soc., 1997, 119, 5390. T. Pietrass, F. Taulelle, P. Lavela, J. Oliver-Fourcade, J.-C. Jumas, and S. Steuernagel, J. Phys. Chem. B, 1997, 101,6715. A. R. Lim, K. S. Hong, S. H. Sung, and S.-Y. Jeong, Solid State Commun., 1997, 103, 693. Y. Xia, N. Machida, X. Wu, C. Lakeman, L. van Wuellen, F. Lange, C. Levi, H. Eckert, and S. Anderson, J. Phys. Chem. B, 1997, 101,9180. R. Kemp-Harper, S. P. Brown, C. E. Hughes, P. Styles, and S. Wimperis, Prog. Nucl. Magn. Reson. Spectrosc., 1997,30, 157. L. Cristofolini, K. Kordatos, G. A. Lawless, K. Prassides, K. Tanigaki, and M. P. Waugh, Chem. Commun. (Cambridge), 1997,375. K. R . Kloetstra, M. Van Laren, and H. Van Bekkum, J. Chem. Soc., Furuday Trans., 1997,93, 121 1 , B. Costisella, D. Muller, and H. Baumann, Chem. Ber.lRecl., 1997, 130, 1625. T. Vosegaard, I. P. Byriel, and H. J. Jakobsen, J. Phys. Chem. B, 1997, 101, 8955. M. L. H. Gruwel, 0. Culic, and J. Schrader, Biophys. J., 1997,72,2775. J. T. Davis, S. Tirumala, and A. L. Marlow, J. Am. Chem. Soc., 1997, 119, 527 I . U. C. Meier and C. Detellier, J. Phys. Chem. A , 1998, 102, 1888. P. A. Schornack, S.-K. Song, C. S. Ling, R. Hotchkiss, and J. J. H. Ackerman, Am. J. Physiol., 1997, 272, C1618. P. A. Schornack, S.-K. Song, R. Hotchkiss, and J. J. H. Ackerman, Am. J, Physiol., 1997,272, C1635. K. R. Kloetstra, M. Van Laren, and H. Van Bekkum, J. Chem. SOC.,Farachy Truns., 1997,93, 12 1 1 . S. Kroeker, K. Eichele, R. E. Wasylishen, and J. F. Britten, J. Phys. Chem. B, 1997, 101,3727. 0. B. Lapina, V. V. Terskikh, A. A. Shubin, V. M. Mastikhin, K. M. Eriksen, and R. Fehrmann, J. Phys. Chem. B, 1997,101,9188. M. Hunger, U. Schenk, B. Burger, and J. Weitkamp, Angew. Chem., Int. Ed Engl., 1997,36,2504. P. Norby, F. I. Poshni, A. F. Gualtieri, J. C. Hanson, and C. P. Grey, J. Phys. Chem. B, 1998, 102,839. S . Alzawa, T. Kato, and S. Funahashi, Anal. Sci., 1997, 13, 541. E. Chinea, S. Dominguez, A. Mederos, F. Brito, A. Sanchez, A. Ienco, and A. Vacca, Main Group Met. Chem., 1997,20, 1 1 . F. Cecconi, C. A. Ghilardi, S. Midollini, A. Orlandini, and A. Mederos, Inorg. Chem., 1998,37, 146. M. Niemeyer and P. P. Power, Inorg. Chem., 1997,36,4688. S. E. Dann and M. T. Weller, Solid State Nucl. Magn. Reson., 1997, 10, 89. R. Dupree, A. P. Howes, and S. C. Kohn, Chem. Phys. Lett., 1997,276,399.

114

Nuclear Magnetic Resonance

283

W. J. Evans, M. A. Ansari, J. D. Feldman, R. J. Doedens, and J. W. Ziller, J. Orgunomet. Chem., 1997,545-546, 157. M. Westerhausen, M. Hartmann, and W. Schwarz, Inorg. Chim. Acta, 1998, 269, 91. T. Harazono and T. Watanabe, Bull. Chem. Soc. Jpn., 1997,70,2383. R . Taube, H. Windisch, H. Weissenborn, H. Hemling, and H. Schumann, J. Orgunomet. Chem., 1997,548,229. P. Poremba and F. T. Edelmann, J. Organomet. Chem., 1997,549, 101. P. B. Hitchcock, M. F. Lappert, and S. Tian, J. Orgunomet. Chem., 1997,549, 1. J. M. Keates and G. A. Lawless, Organometallics, 1997, 16, 2842. M. J. Sarsfield, S. W. Ewart, T. L. Tremblay, A. W. Roszak, and M. C. Baird, J. Chem. Soc., Dalton Trans., 1997, 3097. A. Labouriau and W. L. Earl, Chem. Phys. Lett., 1997,270,278. M. Garner, J. Reglinski, W. E. Smith, J. McMurray, I. Abdullah, and R. Wilson, JBIC, J. Biol. Inorg. Chem., 1997,2, 235. K. Elvingson, D. C. Crans, and L. Pettersson, J. Am. Chem. Soc., 1997, 119, 7005. M. Fritzsche, K. Elvingson, D. Rehder, and L. Pettersson, Acta Chem. Scund., 1997, 51,483. P. C. Paul and A. S. Tracey, JBIC, J. Biol. Inorg. Chem., 1997,2,644. M. Buhl, Angew. Chem., Int. Ed. Engl., 1998,37, 142. M. Menetrier, K. S. Han, L. Guerlou-Demourgues, and C. Delmas, Inorg. Chem., 1997,36, 2441. V. Luca, S. Thomson, and R. F. Howe, J. Chem. Soc., Furuciuy Truns., 1997, 93, 2195. P. C. Paul, S. J. Angus-Dunne, R. J. Batchelor, F. W. B. Einstein, and A. S. Tracey, Can. J. Chem., 1997,75,429. V. Conte, F. Di Furia, and S. Moro, J. Mol. Cutal. A: Chem., 1997,120,93. S. J. Angus-Dunne, P. C. Paul, and A. S. Tracey, Cun. J. Chem., 1997,75, 1002. P. D. Hampton, C. E. Daitch, T. M. Alam, and E. A. Pruss, Inorg. Chem., 1997,36, 2879. C. R. Cornman, T. C. Stauffer, and P. D. Boyle, J. Am. Chem. Soc., 1997, 119,5986. B. J. Hamstra, G. J. Colpas, and V. L. Pecoraro, Inorg. Chem., 1998,37,949. Y. Deng, Q. Liu, C. Chen, Y. Wang, Y. Cai, D. Wu, B. Kang, D. Liao, and J. Cui, Polyhedron, 1997, 16,4121. S. Mondal, S. P. Rath, K. K. Rajak, and A. Chakravorty, Inorg. Chem., 1998, 37, 1713. M. Herberhold, G. Frohmader, T. Hofmann, W. Milius, and J. Darkwa, Inorg. Chim. Acta, 1998,267, 19. M.-H. Lee, N. H. Heo, and S. Hayashi, Polyhedron, 1997,17, 55. R. T. Yamaki, E. B. Paniago, S. Carvalho, 0. W. Howarth, and W. Kam, J. Chem. Suc., Dalton Truns., 1997, 4817. A. Karaliota, M. Kamariotaki, and D. Hatzipanayioti, Transition Met. Chern. (London), 1997,22,41 I . J. Malito, Annu. Rep. NMR Spectrosc., 1997,33, 151. M. L. Ramos, M. M. Calderia, and V. M. S. Gil, Carbohyclr. Res., 1997,299,209. M. L. Ramos, M. M. Caldeira, and V. M. S. Gil, Carbohycir. Res., 1997,304,97. M. Hong, Q. Zhang, R. Cao, D. Wu, J. Chen, W. Zhang, H. Liu, and J. Lu, Inorg. Chem., 1997,36,6251 . T . C. Wong, Q. Huang, N. Zhu, and X. Wu, Polyhedron, 1997,16,2987. E. C. Alyea and J. Campo, Polyhedron, 1997,17, 275.

284 285 286 287 288 288 290 29 1 292 293 294 295 296 297 298 299 300 30 1 302 303 304 305 306 307 308 309 3 10

31 1 312 313 314 315 316

3: Applicutions of Nucleur Shielding

317 318 319 320 32 1 322 323 324 325 326 327 328 3 29 3 30

33 1 332 333 3 34 335 336 337

338 339 340 34 1 342 343 344 345 346 347

1 I5

H. Zhu, X. Huang, Y. Deng, D. Wu, C. Chen, and Q. Liu, Inorg. Chim. Actu, 1997, 256,29. M. Hong, D. Wu, R. Cao, X. Lei, H. Liu, and J. Lu, Inorg. Chim. Actu, 1997, 258, 25. A. A. Holder, T. P. Dasgupta, W. McFarlane, N. H. Rees, J. H. Enemark, A. Pacheco, and K. Christensen, Inorg. Chim. Actu, 1997,260,225. E. C. Alyea, G. Ferguson, and S. Kannan, Polyhedron, 1997,16,3533. H. Liu, W. Sun, B. Yue, S. Jin, J. Deng, and G. Xie, Synth. Reuct. Inorg. Met.-Org. Chem., I997,27,55 I . H. Liu, B. Yue, W. Sun, Z. Chen, S. Jin, J. Deng, G. Xie, Q. Shao, and T. Wu, Trunsition Met. Chem. (London), I997,22, 32 1. H. Nakajima, T. Kudo, and N. Mizuno, Chem. Letc., 1997,693. L.-Y. Qu, Q.-J. Shan, J. Gong, R.-Q. Lu, and D.-R. Wang, J. Chem. Soc., Dalton Truns., 1997,4525. C . R. Mayer and R. Thouvenot, J. Chem. Sue., Dalton Truns., 1998,7. J. Baritis, S. Sukal, M. Dankova, E. Kraft, R. Kronzon, M. Blumenstein, and L. C. Francesconi, J. Chem. Soc., Dalton Truns., 1997, 1937. J. Bartis, M. Dankova, M. Blumenstein, and L. C. Francesconi, J. Alloys Compd., 1997,249, 56. D. A. Judd, Q. Chen, C. F. Campana, and C. L. Hill, J. Am. Chem. Soc., 1997, 119, 546 1. K. Ueno, A. Masuko, and H. Ogino, Organometullics, 1997, 16, 5023. K. Nomiya, C. Nozaki, A. Kano, T. Taguchi. and K. Ohsawa, J. Organomet. Chem., 1997,533, 153. M. Herberhold, T. Hofmann, S. Weinberger, and B. Wrackmeyer, 2. Nuturforsch., B: Chem. Sci.,1997,52, 1037. A. M. Hill, W. Levason, M. Webster, and I. Albers, Orgunometullics, 1997, 16, 5641. W. J. Casteel, Jr. D. A. Dixon, N. LeBlond, H. P. A. Mercier, and G. J. Schrobilgen, Inorg. Chem., 1998, 37, 340. A. Abou-Hamdan, A. Roodt, and A. E. Merbach, Inorg. Chem., 1998,37, 1278. X . Xiaoming, T. Matsumura-Inoue, and S. Mizutani, Chem. Lett., 1997,241. A. Gisler, M. Schaade, E. J. M. Meier, A. Linden, and W. von Philipsborn, J. Orgunornet. Chem., 1997,545-546,315. T. Thomson, P. C. Riedi, S. Sankar, and A. E. Berkowitz, J. Appl. Phys., 1997,81, 5549. M. Wojcik, J. P. Jay, P. Panissod, E. Jedryka, J. Dekoster, and G. Langouche, Z. Phys. B: Condens. Matter, 1997, 103, 5. K. Eichele, J. C. C. Chan, R. E. Wasylishen, and J. F. Britten, J. Phys. Chem. A, 1997,101, 5423. A. Medek, V. Frydman, and L. Frydman, J. Phys. Chem. B, 1997,101,8959. M. Fujita, T. Fujihara, M. Kojima, Y. Yoshikawa, and K. Yamasaki, Proc. Jpn. Acud, Ser. B, 1997,73B, 161. P. Granger, T. Richert, K. Elbayed, P. Kempgens, J. Hirschinger, J. Raya, J. Rose, and P. Braunstein, Mol. Phys., 1997,92, 895. Y. Mizuno, A. Yokote, and M. Iida, Bull. Chem. Soc. Jpn., 1997,70,2437. A. Medek, V. Frydman, and L. Frydman, Proc. Natl. Acud. Sci. U S .A., 1997, 94, 14237. P. Kofod, P. Harris, and S. Larsen, Inorg. Chem., 1997,36,2258. Y. Mizuno and M. Iida, J. Phys. Chem. B, 1997,101, 3919. L. Carlton, Mugn. Reson. Chem., 1997,35, 153.

116

Nuclear Magnetic Resonance

348

L. Spiccia, J. M. Aramini, S. J. Crimp, A. Drljaca, E. T. Lawrenz, V. Tedesco, and H. J. Vogel, J. Chem. Soc., Dalton Trans., 1997,4603. L. Carlton, R. Weber, and D. C. Levendis, Inorg. Chem., 1998,37, 1264. C. V. Ursini, Quim. Nova, 1997,20, 72. P. Tsiveriotis, N. Hadjiliadis, and G. Stavropoulos, Inorg. Chim. Acta, 1997,261, '33. Y.-Y. Tong, C. Belrose, A. Wieckowski, and E. Oldfield, J. Am. Chem. Soc., 1997, 119, 11709. P. J. Heard and C. Jones, J. Chem. Soc., Dalton Trans., 1997, 1083. H. B. Brom, J. J. van der Klink, F. C. Fritschij, L. J. de Jongh, R. D. Pergola, and A. Ceriotti, Z. Phys. D: At., Mol. Clusters, 1997,40, 559. F. Pichierri, E. Chiarparin, E. Zangrando, L. Randaccio, D. Holthenrich, and B. Lippert, Inorg. Chim. Acta, 1997,264, 109. P. D. Prenzler, D. C. R. Hockless, and G. A. Heath, Inorg. Chem., 1997,36, 5845. S. Shamsuddin, J. W. van Hal, J. L. Stark, K. H. Whitmire, and A. R. Khokhar, Inorg. Chem., I997,36,5969. F. D. Rochon, S. Boutin, P.-C. Kong, and R. Melanson, Inorg. Chim. Acta, 1997, 264,89. K . R. Koch, T. Grimmbacher, and C. Sacht, Polyhedron, 1997,17,267. N. Pacshke, A. Roendigs, H. Poppenborg, J. E. A. Wolff, and B. Krebs, Inorg. Chim. Acta, 1997,264,239. C. D. W. Frohling and W. S. Sheldrick, J. Chem. Soc., Dalton Trans., 1997,4411. U. Bierbach, T. W. Hambley, and N. Farrell, Inorg. Chem., 1998,37,708. U. Bierbach, J. D. Roberts, and N. Farrell, Inorg. Chem., 1998,37,717. W. Oberhauser, C. Bachmann, T. Stampfl. and P. Brueggeller, Inorg. Chim. Acta, 1997,256,223. G. F. de Sousa, C. A. L. Filgueiras, P. B. Hitchcock, and J. F. Nixon, Inorg. Chim. Acta, 1997, 261, 217. M. J. Arendse, I. R. Green, and K. R. Koch, Spectrochim. Acta, Part A , 1997, 53A, 1537. J. Yoo, J.-H. Kim, Y. S. Sohn, and Y. Do, Inorg. Chim. Acta, 1997,263, 53. J. Connolly, R. J. Forder, and G. Reid, Inorg. Chim. Acta, 1997,264, 137. E. Garcia-Espana, J. Latorre, V. Marcelino, J. A. Ramirez, S. V. Luis, J. F. Miravet, and M. Querol, Inorg. Chim. Acta, 1997,265, 179. U. Bierbach, T. W. Hambley, and N. Farrell, Inorg. Chem., 1998,37,708. J. G. Kraaijkamp, D. M. Grove, G. van Koten, J. M. Ernsting, A. Schmidpeter, K. Goubitz, C. H. Stam, and H. Schenk, Inorg. Chim. Acta, 1997,265,47. B. Wrackmeyer and A. Sebald, J. Orgunomet. Chem., 1997,544, 105. N. Duran, P. Gonzalez-Duarte, A. Lledos, T. Parella, J. Sola, G. Ujaque, W. Clegg, and K. A. Fraser, Inorg. Chim. Acta, 1997,265, 89. A. D. Burrows, D. M. P. Mingos, S. E. Lawrence, A. J. P. White, and D. J. Williams, J. Chem. Soc., Dalton Trans.. 1997, 1295. H. Yamashita, M. Tanaka, and M. Goto, Organometallics, 1997, 16,4696. P. N. W. Baxter, J.-M. Lehn, B. 0. Kneisel, and D. Fenske, Angew. Chem., Int. Ed. Engl., 1997,36, 1978. D. Naumann, W. Wessel, J. Hahn, and W. Tyrra, J. Orgunomet. Chem., 1997,547,79. H. G. Fijolek, P. Gonzalez-Duarte, S. H. Park, S. L. Suib, and M. J. Natan, Inorg. Chem., 1997,36,5299. K. Kanaori, D. Ohta, and A. Y. Nosaka, FEBS Lett., 1997,412,301. D. J. Darensbourg, S. A. Niezgoda, M. W. Holtcamp, J. D. Draper, and J. H. Reibenspies, Inorg. Chem., 1997,36, 2426.

349 3 50 35 1 352 353 354 355 3 56 357

358 359 360 36 1 362 363 3 64 365 3 66

367 368 3 69 3 70 37 1

372 373 374 375 376 377 378 379 380

3: Applications of Nuclear Shielding 38 1 382 383 3 84 385 386 387 388 389 390 39 1 392 393 394 395 396 397 398 399 400 40 1 402 403 404 405 406 407 408

117

J. Ratilainen, K. Airola, E. Kolehmainen, and K. Rissanen, Chem. Ber.lRecl., 1997, 130,1353. P. Gonzalez-Duarte, W. Clegg, I. Casals, J. Sola, and R. Jordi, J. Am. Chem. Soc., 1998,120, 1260. P. R. Meehan, G. Ferguson, R. P. Shakya, and E. C. Alyea, J. Chem. Soc., Dalton Trans., 1997, 3487. D. J. Darensbourg, S. A. Niezgoda, J. H. Reibenspies, J. D. Draper, Znorg. Chem., 1997,36,5686. L. M. Utschig, T. Baynard, C. Strong, and T. V. O’Halloran, Inorg. Chem., 1997,36, 2926. L. Girault, A. Boudou, and E. J. Dufourc, Biochim. Biophys. Acta, 1997, 1325,250. G. Gioia Lobbia, P. Cecchi, R. Gobetto, G. Digilio, R. Spagne, and M. Camalli, J. Orgunornet. Chem., 1997,539,9. F. P. Gabbaie, A. Schier, J. Riede, A. Sladek, and H. W. Goerlitzer, Znorg. Chem., 1997,36,5694. T. S. Lobana, A. Sanchez, J. S. Casas, A. Castineiras, J. Sordo, M. S. GarciaTasende, and E. M. Vazquez-Lopez, J. Chem. Suc., Dalton Trans., 1997,4289. T. S. Lobana, A. Sanchez, J. S. Casas, M. S. Garcia-Tasende, and J. Sordo, Inorg. Chim. Actu, 1998, 267, 169. J. S. Casas, M. S. Garcia-Tasende, A. Sanchez, J. Sordo, and E. M. Vazquez-Lopez, Znorg. Chim. Actu, 1997,256,211. E. C. Alyea, G. Ferguson, R. P. Shakya, and P. R. Meehan, Inorg. Chem., 1997,36, 4749. G . A. Bowmaker, A. V. Churakov, R. K. Harris, and S.-W. Oh, J. Organomet. Chem., 1998,550,89. G. A. Bowmaker, A. V. Churakov, R. K. Harris, J. A. K. Howard, and D. C. Apperley, Znorg. Chem., 1998,37, 1734. P. MacKinnon, X. L. R. Fontaine, J. D. Kennedy, and P. A. Salter, Collect. Czech. Chem. Commun., 1996,61, 1773. J. Holub, B. Stibr, D. Hynk, J. Fusek, I. Cisarova, F. Teixidor, C. Vinas, Z. Plzak, and P. v. R. Schleyer, J. Am. Chem. Soc., 1997,119, 7750. M. P. Groziak, L. Chen, L. Yi, and P. D. Robinson, J. Am. Chem. Soc., 1997, 119, 7817. B. Wrackmeyer, H. E. Maisel, B. Schwarze, W. Milius, and P. Koster, J. Orgunornet. Chem., 1997,541,97. K. S . J. Rao and K. R. K. Easwaran, Mol. Cell. Biochem., 1997, 175,59. J. F. Ma, S. Hiradate, K. Nomoto, T. Twashita, and H. Matsumoto, Plant Physiol., 1997,113, 1033. J. Lewinski, J. Zachara, and I. Justyniak, Organometallics, 1997, 16, 3859. T. Ooi, N. Kagoshima, and K. Maruoka, J. Am. Chem. Soc., 1997,119,5754. J. Turunen, T. T. Pakanen, and B. Loefgren, J. Mul. Catul. A: Chem., 1997,123,35. J. Mueller, R. A. Fischer, H. Sussek, P. Pilgram, R. Wang, H. Pritzkow, and E. Herdtweck, Organometallics, 1998,17, 161. S. Nlate, E. Herdtweck, J. Blumel, and R. A. Fischer, J. Organomet. Chem., 1997, 545-546,543. T. Miyajima, H. Maki, H. Kodama, S. Ishiguro, H. Nariai, and I. Motooka, Phosphorus Res. Bull., 1996,6,281. T. Vosegaard and H. J. Jakobsen, J. Mugn. Reson., 1997, 128, 135. H. Kraus, M. Mueller, R. Prins, and A. P. M. Kentgens, J. Phys. Chem. B, 1998, 102,3862.

I18

Nuclear Mugnetic Resonance

409 410

D. B. Akolekar and R. F. Howe, J. Chem. Soc., Furuciuy Trans., 1997,93,3263. C. A. Fyfe, H. M. zu Altenschildesche, K. C. Wong-Moon, H. Grondey, and J. M. Chezeau, Solid State Nucl. Magn. Reson., 1997,9,97. M. Hartmann, A. M. Prakash, and L. Kevan, J. Chem. Soc., Faraday Trans., 1998, 94, 723. E. P. Talsi, Mucromol. Chem. Phys., 1997, 198, 3845. L.-J. Baker, L. A. Kloo, C. E. F. Rickard, and M. J. Taylor, J. Organomet. Chem., 1997,545-546,249. M. A. Aramendia, V. Borau, C. Jimenez, J. M. Marinas, F. J. Romero, and J. R. Ruiz, J. SolidState Chem., 1997, 131, 78. F. Fredoueil, D. Massiot, D. Pooiary, M. Bujoli-Doeuff, A. Clearfield, and B. Bujoli, Chem. Commun. (Cumbridge), 1998, 175. T. Vosegaard, D. Massiot, N. Gautier, and H. J. Jakobsen, Inorg. Chem., 1997, 36, 2446. T. Takeguchi, K. Kagawa, J.-B. Kim, T. h i , D. Wei, and G. L. Haller, Cutul. Lett., 1997,46, 5 . W. Kolodziejski and J. Klinowski, J. Phys. Chem. B, 1997, 101. 3937. J. W. van Hal, L. W. Alemany, and K. H. Whitmire, Inorg. Chem., 1997, 36, 3152. P. Sipos, S. G. Capewell, P. M. May, G. T. Helter, G. Laurenczy, F. Lukacs, and R. Roulet, J. Solution Chem., 1997, 26,419. A. G. Coutsolelos and D. Daphnomili, Inorg. Chem., 1997,36,4614. R. Han, P. Ghosh, P. J. Desrosiers, S. Trofimenko, and G . Parkin, J. Chem. Soc., Dalton Trans., 1997, 3713. 1. Banyai, J. Glaser, and J. Losonczi, Inorg. Chem., 1997,36, 5900. J. S. Casas, E. E. Castellano, M. C. Rodriguez-Argueelles, A. Sanchez, J. Sordo, and J. Zukerman-Schpector, Inorg. Chim. Acta, 1997,260, 183. H. Borrmann, J. Campbell, D. A. Dixon, H. P. A. Mercier, A. M. Pirani, and G. J. Schrobilgen, Inorg. Chem., I998,37, 1929. K. Akira, T. Taira, H. Hasegawa, and Y. Shinohara, J. Labelled Compcl. Radiophurm., 1997,39,353. G. A. Olah, T. Shamma, A. Burrichter, G. Rasul, and G. K. S. Prakash, J. Am. Chem. Soc., 1997,119,3407. R. Havlin, M. McMahon, R. Srinivasan, H. Le, and E. Oldfield, J. Phys. Chem. A , 1997,101,8908. J. Sandri, T. Soto, J.-L. Gras, and J. Viala, Mugn. Reson. Chem., 1997,35,785. V. Busico, R. Cipullo, G. Monaco, M. Vacatello, and A. L. Segre, Mucromolecules, 1997,30,6251. M. Kvicalova, V. Blechta, K. Kobylczyk, R. Piekos, and J. Schraml, Collect. Czech. Chem. Commun., 1997,62,76 1. M. Kvicalova, J. Cermak, V. Blechta, and J. Schraml, Collect. Czech. Chem. Commun., 1997,62, 816. E. Rikowski and H. C. Marsmann, Polyhedron, 1997, 16, 3357. K. Hatano, K. Morihashi, 0. Kikuchi, and W. Ando, Chem. Lett., 1997,293. N. Tokitoh, K. Wakita, R. Okazaki, S. Nagase, P. v. R. Schleyer, and H. Jiao, J. Am. Chem. Soc., 1997,119,6951. R. West, J. J. Buffy, M. Haaf, T. Mueller, B. Gehrhus, M. F. Lappert, and Y. Apeloig, J. Am. Chem. Soc., 1998, 120, 1639. S. Jarosz, E. Kozlowska, J. Sitkowski, and L. Stefaniak, J. Curbohyrir. Chem., 1997, 16,911.

41 I 412 41 3 414 41 5 416 417 418 419 420 42 1 422 423 424 425 426 427 428 429 4 30 43 I 432 433 434 435 436 437

3: Applications of Nuclear Shielding 438 439 440 44 1 442 443 444

445 446 447 448 449 450 45 I 452 453 454

455 456 457 458 459 460 46 1 462 463 464 465 466

I19

E. Balestrieri, L. Bellugi, A. Boicelli, M. Giomini, A. M. Giuliani, M. Giustini, L. Marciani, and P. J. Sadler, J. Chem. Soc., Dulton Trans., 1997,4099. I. Wharf and M. G. Simard, J. Orgunomet. Chem., 1997,532, 1. A. Lycka, J. Holecek, and D. Micak, Collect. Czech. Chem. Commun., 1997, 62, 1169. S. J. Garden and J. L. Wardell, Muin Group Mel. Chem., 1997,20, 71 1 . R. Balasubramanian, Z. H. Chohan, S. M. S. V. Doidge-Harrison, R. A. Howie, and J. L. Wardell, Polyhedron, 1997, 16,4283. J. Susperregui, M. Bayle, J. M. Leger, G. Deleris, M. Biesemans, R. Willem, M. Kemmer, and M. Gielen, J. Orgunomet. Chem., 1997,545-546,559. C. Pettinari, F. Marchetti, A. Gregori, A. Cingolani, J. Tanski, M. Rossi, and F. Caruso, Inorg. Chim. Actu, 1997,257, 37. B. Wrackmeyer and A. Gloeckle, Muin Group Met. Chem., 1997,20, 181. Y. Z. Voloshin, V. V. Trachevskii, and E. V. Polshin, Pol. J. Chem., 1997,71,428. S . Belwal and R. V. Singh, Appl. Organomet. Chem., 1998,12, 39. B. Wrackmeyer, H. E. Maisel, and W. Millius, Main Group Met. Chem., 1997, 20, 231. B. Wrackmeyer, G. Kehr, H. E. Maisel, and H. Zhou, Mugn. Reson. Chem., 1998, 36,39. M. Biesemans, R. Willem, S. Damoun, P. Geerlings, E. R. T. Tiekink, P. Jaumier, M. Lahcini, and B. Jousseaume, Orgunometullics, 1998,17,90. M. Herberhold, U. Stem, W. Milius, and B. Wrackmeyer, 2. Anorg. Allg. Chem., 1998,624,386. B. Wrackmeyer, S. Kerschl, and H. E. Maisel, Muin Group Met. Chem., 1998,21,89. J. C. Cherryman and R. K. Harris, J. Mugn. Reson., 1997, 128,21. D. R. Armstrong, M. J. Duer, M. G. Davidson, D. Moncrieff, C. A. Russell, C. Stourton, A. Steiner, D. Stalke, and D. S. Wright, Orgunometallics, 1997, 16, 3340. R. Willem, H. Dalil, P. Broekaert, M. Biesemans, L. Ghys, K. Nooter, D. de Vos, F. Ribot, and M. Gielen, Main Group Met. Chem., 1997,20, 535. A. de Mallmann, 0. Lot, N. Perrier, F. Lefebvre, C. Santini, and J. M. Basset, Orgunometullics, 1998,17, 103 I . G. Bergamaschi, A. Bonardi, E. Leporati, P. Mazza, P. Pelagatti, C. Pelizzi, G. Pelizzi, M. C. R. Arguelles, and F. Zani, J. Inorg. Biochem., 1997, 68, 295. R. Altmann, K. Jurkschat, M. Schuermann, D. Dakternieks, and A. Duthie, Organometullics,1997,16, 57 16. R. Selvaraju and K. Panchanatheswaran, Polyhedron, 1997,16,2621. S. M. S. V. Doidge-Harrison, R. A. Howie, J. N. Low, and J. L. Wardell, J. Chem. Crystallogr., 1997, 27, 29 1. K. Gajda-Schrantz, L. Nagy, E. Kuzmann, A. Vertes, J. Holecek, and A. Lycka, J. Chem. Sue., Dulton Trans., 1997, 2201. B. Wrackmeyer, H. E. Maisel, G. Kehr, and H. Noeth, J, Orgunomet. Chem., 1997, 532,201. J. Sharma, Y. Singh, and A. K. Rai, Indian J. Chem., Sect. A: Inorg., Bio-inorg., Phys., Theor. Anal. Chem., 1997,36A, 602. S.-G. Teoh, S.-H. Ang, and J.-P. Declercq, Polyhedron, 1997,16, 3729. F. Huber, R. Schmiedgen, M. Schurmann, R. Barbieri, G. Ruisi, and A. Silvestri, Appl. Organomet. Chem., 1997,11,869. P. R. Deacon, M. F. Mahon, K. C. Molloy, and P. C. Waterfield, J. Chem. SOC., Dulton Truns., 1997, 3705.

120

Nuclear Magnetic Resonance

467 468 469

M. Nath and N. Chaudhary, Synth. React. Inorg. Met.-Org. Chem., 1998,28, 121. M. Veith, S. Mathur, C. Mathur, and V. Huch, Organometallics, 1998,17, 1044. F. Ribot, C. Sanchez, R. Willem, J. C. Martins, and M. Biesemans, Inorg. Chem., 1998,37,91 I . T. Pietrass and F. Taulelle, Magn. Reson. Chem., 1997,35, 363. J. Li, B. Marler, H. Kessler, M. Soulard, and S. Kallus, Inorg. Chem., 1997,36,4697. R. Willem, - A. Bouhdid, A. Meddour, C. Camacho-Camacho, F. Mercier, M. Gielen, M. Biesemans, F. Ribot, C. Sanchez, and E. R. T. Tiekink, Organomet a l k s , 1997,16,4377. A. Meddour, F. Mercier, J. C. Martins, M. Gielen, M. Biesemans, and R. Willem, Inorg. Chem., 1997,36, 5712. J. E. H. Buston, T. D. W. Claridge, R. G. Compton, and M. G. Moloney, Magn. Reson. Chem., 1998,36, 140. D. C. Van Beelen, J. Wolters, and D. De Vos, Main Group Met. Chem., 1998,21, 5 5 . M. Grassi, E. Oldani, and G. Gatti, Ann. Chim. (Rome), 1997,87, 353. D. C. Van Beelen, J. Van Rijn, K. D. Heringa, J. Wolters, and D. De Vos, Main Group Met. Chem., 1997,20, 37. T. D. W. Claridge, E. J. Nettleton, and M. G. Moloney, Magn. Reson. Chem., 1997, 35, 159. L. G. Hubert-Pfalzgraf, S. Daniele, R. Papiernik, M.-C. Daran, B. Septe, J. Vaissermann, and J.-C. Daran, J. Muter. Chem., 1997,7,753. M. Herberhold, V. Trobs, and B. Wrackmeyer, J. Orgunomet. Chem., 1997,541,391. B. Wrackmeyer and J. Weidinger, Z. Naturforsch., B: Chem. Sci., 1997,52, 947. F. Fayon, I. Farnan, C. Bessada, J. Coutures, D. Massiot, and J. P. Coutures, J. Am. Chem. Soc., 1997,119,6837. M. N. Akhtar, A. A. Isab, and A. R. Al-Arfaj, J. Inorg. Biochem., 1997,66, 197. G. Tong, Y. Pan, H. Dong, R. Pryor, G. E. Wilson, and J. Schaefer, Biochemistry, 1997,36,9859. M. Witanowski, Z. Biedrzycka, W. Sicinska, and G. A. Webb, Magn. Reson. Chem., I997,35,262. M. Witanowski, W. Sicinska, Z. Biedrzycka, and G. A. Webb, J. Mol. Struct., 1997, 404,267. M. Witanowski, Z. Biedrzycka, W. Sicinska, and G. A. Webb, J, Chem. Soc., Perkin Truns. 2, 1997,533. H. Mayr, A. R.Ofial, E.-U. Wurthwein, and N. C. Aust, J. Am. Chem. Soc., 1997, 119, 12727. R. Marek, J. Dostal, J. Slavik, and V. Sklenar, Molecules, 1996,1, 166. D. Waldmueller, B. J. Kotsatos, M. A. Nichols, and P. G. Williard, J. Am. Chem. Soc., 1997, 119, 5479. G. Buntkowsky, I. Sack, H. H. Limbach, B. Kling, and J. Fuhrhop, J. Phys. Chem. B, 1997,101, 11265. J. Buschmann, T. Bartolmas, D. Lentz, P. Luger, I . Neubert, and M. Rottger, Angew. Chem., Int. Ed. Engl., 1997,36, 2372. W. Schilf, L. Stefaniak, J. Skolimowski, and G. A. Webb, J. Mol. Struct., 1997,407, 1. R. Ahmad, M. Zia-U1-Haq, H. Duddeck, L. Stefaniak, and J. Sitkowski, Monatsh. Chem., 1997,128,633. P. Cmoch, L. Stefaniak, and G. A. Webb, Magn. Reson. Chem., 1997,35,237. J. Klimkiewicz, L. Stefaniak, E. Grech, and G. A. Webb, J. Mol. Struct., 1997, 412, 47.

470 47 1 472

473 474 475 476 477 478 479 480 48 I 482 483 484 485 486 487 488 489 490 49 1 492 493 494 495 496

3: Applications of Nuclear Shielding 497 498 499 500 50 1

502 503 504 505 506 507 508 509 510

51 1

512 513 514 515 516

517 518 5 19 5 20 52 1 522 523 524 525 526 527 528

121

J. Klimkiewicz, M. Koprowski, L. Stefaniak, E. Grech, and G. A. Webb, J. Mol. Struct., 1997,403, 163. T. D. Ferris, P. T. Lee, and T. C. Farrar, Magn. Reson. Chem., 1997,35, 571. S . H. Bertz, K. Nilsson, 0. Davidsson, and J. P. Snyder, Angew. Chem., Int. Ed. Engl., 1998,37, 314. J. Jazwinski, J. Mol. Struct., 1998,443,27. P. J. B. Edwards, K. W. Jolley, M. H. Smith, S. J. Thomsen, and N. Boden, Langmuir, 1997, 13,2665. P. J. Barrie, E. J. W. Austin, A. Barbieri, and R. J. H. Clark, Inorg. Chim. Acta, 1997,264,81. F. Aguilar-Parrilla, 0. Klein, J. Elguero, and H. H. Limbach, Ber. Bunsen-Ges., 1997,101,889. M. S. Solum, K. L. Altman, R. J. Strohmeier, D. A. Berges, Y. Zhang, J. C. Facelli, R. J. Pugmire, and D. M. Grant, J. Am. Chem. Soc., 1997,119,9804. A. Ramamoorthy, C. H. Wu, and S. J. Opella, J. Am. Chem. SOC.,1997,119,10479. M. Edgar, M. Schubert, H. H. Linbach, and C. C. Goltner, Ber. Bunsen-Ges., 1997, 101, 1769. M. Strohmeier, A. M. Orendt, J. C. Facelli, M. S. Solum, R. J. Pugmire, R. W. Parry, and D. M. Grant, J. Am. Chem. Soc., 1997,119,7114. H.-S. Wu and S.-S. Meng, Ind. Eng. Chem. Res., 1998,37,675. D. Gudat and E. Niecke, Fresenius’ J. Anal. Chem., 1997,357,482. H. Ranaivonjatovo, H. Ramdane, H. Gornitzka, J. Escudie, and J. Satge, Organometallics, 1998, 17, 163 1. W. A. Dollase, M. Feike, H. Foerster, T. Schaller, I. Schnell, A. Sebald, and S. Steuernagel, J. Am. Chem. SOC.,1997,119,3807. T. Ichikawa and K. Sawada, Bull. Chem. SOC.Jpn., 1997,70, 21 1 1. J.-C. Zhuo, Magn. Reson. Chem., 1997,35,432. T. M. Alam, Magn. Reson. Chem., 1998,36, 132. L. Delattre and F. Babonneau, Chem. Muter., 1997,9,2385. L. M. Bull, A. K. Cheetham, T. Anupold, A. Reinhold, A. Samoson, J. Sauer, B. Bussemer, Y. Lee, S. Gann, J. Shore, A. Pines, and R. Dupree, J. Am. Chem. Soc., 1998, 120, 3510. H. Dahn and V. V. Toan, Magn. Reson. Chem., 1998,36,137. E. Toth, L. Burai, E. Brucher, and A. E. Merbach, J. Chem. SOC.,Dalton Trans., 1997,1587. U. Frey, D. M. Grove, and G. van Koten, Inorg. Chim. Acta, 1998,269,322. V. Maemets and I. Koppel, J. Chem. Soc., Faraday Trans., 1997,93, 1539. H. G. Yuan, Y. H. Hua, P. Kois, N. Pronayova, L. Quing, and A. Perjessy, Heterocycl. Commun., 1998,4, 39. D. Hoebbel, M. Nacken, H. Schmidt, V. Huch, and M. Veith, J. Muter. Chem., 1998,8, 171. J. C. Zhuo and K. Schenk, Helv. Chim. Acta, 1997,80,2137. N. Steunou, C. Bonhomme, C. Sanchez, J. Vaissermann, and L. G. HubertPfalzgraf, Inorg. Chem., 1998,37,901. G. Wu, D. Rovnyak, P. C. Huang, and R. G. Griffin, Chem. fhys. Lett., 1997,277, 79. D. M. Smith, C.-W. Park, and J. A. Ibers, Inorg. Chem., 1997,36,3798. T. Murai, K. Kakami, A. Hayashi, T. Komuro, H. Takada, M. Fujii, T. Kanda, and S. Kato, J. Am. Chem. Soc., 1997,119, 8592. N. Choi, K. Asano, S. Watanabe, and W. Ando, Tetrahedron, 1997,53, 12215.

122

Nucleur Magnetic Resonance

5 29 5 30 53 1

D. M. Smith, M. A. Pell, and J. A. Tbers, Inorg. Chem., 1998,37,2340. P. G. Jones, J. Laube, and C. Thoene, Eur. J. Inorg. Chem., 1998,397. P. A. W. Dean, L. Y. Goh, I. D. Gay, and R. D. Sharma, J. Orgunomet. Chem., 1997,533, 1. C. M. Bates and C. P. Morley, J. Orgunomet. Chem., 1997,533, 193 and 197. P. Mathur, A. K. Dash, M. Hossain, C. V. V. Satyanarayana, A. L. Rheingold, L. M. Liable-Sands, and G. P. A. Yap, J. Orgunomet. Chem., 1997,532, 189. P. Mathur, S. Ghosh, A. Sarkar, A. L. Rheingold, and I. A. Guzei, Orgunometullics, 1998, 17, 770. A. Cruz, D. Macias-Mendoza, E. Barragan-Rodriguez, H. Tlahuext, H. Noth, and R. Contreras, Tetrahedron: Asymmetry, I997,8, 3903. P. Mathur, S. Ghose, Md. M. Hossain, C. V. V. Satyanarayana, S. Banerjee, G. R. Kumar, P. B. Hitchcock, and J. F. Nixon, Orgunometullics, 1997, 16,3815. T. E. Burrow, A. J. Lough, R. L. Richards, and R. H. Morris, Inorg. Chim. Actu, 1997,259, 125. P. Bernatowicz, L. Stefaniak, M. Giurg, L. Syper, and G. A. Webb, Pol. J. Chem., 1997,71.441. S . E. Dann, A. R. J. Genge, W. Levason, and G. Reid, J. Chem. SOC.,Dulton Truns., 1997,2207. P. Pazdera, J. Sibor, R. Marek, M. Kuty, and J. Marek, Molecules, 1997,2, 135. P. Mathur, S. Ghose, Md. M. Hossain, C. V. V. Satyanarayana, and M. F. Mahon, J. Organomet. Chem., 1997,543, 189. T. B. Schroeder, C. Job, M. F. Brown, R. S. Glass, N. You, and E. Block, Magn. Reson. Chem., 1997,35,752. T. B. Schroeder, C. Job, M. F. Brown, R. S. Glass, N. You, and E. Block, Mugn. Reson. S. P. Gabuda, S. G. Kozlova, 0. B. Lapina, and V. V. Terskikh, Chem. Phys. Letl., 1998, 282, 245. P. Mathur, S. Ghose, Md. M. Hossain, P. B. Hitchcock, and J. F. Nixon, J. Orgunornet. Chem., 1997,542,265. S. Sato, T. Ueminami, E. Horn, and N. Furukawa, J. Orgunomet. Chem., 1997,543, 77. I. Elyashiv, Z. Goldschmidt, I. Ben-Arie, P. Aped, M. Cojocaru, H. E. Gottlieb, and M. Albeck, Polyhedron, 1997,16,4209. A. B. Bergholdt, E. Horn, 0. Takahashi, S. Sato, K. Kobayashi, N. Furukawa, M. Yokoyama, and K. Yamaguchi, J. Am. Chem. SOC.,1998,120,1230. R. Batheja and A. K. Singh, Polyhedron, 1997, 16,2509 and 4337. A. R. J. Genge, W. Levason, and G. Reid, J. Chem. Soc., Dalton Trans., 1997, 4549. T. F. Fassler and U. Schutz, J. Organomet. Chem., 1997,541,269. J. J. Schneider, J. Kuhnigkh, and C. Kruger, Znorg. Chim. Actu, 1997,266, 109. M. Herberhold, U. Stem, W. Milius, and B. Wrackmeyer, J. Orgunomet. Chem., 1997,533, 109. I. Orion, J. Rocha, S. Jobic, V. Abadie, R. Brec, C. Fernandez, and J.-P. Amoureux, J. Chem. Soc., Dalton Trans., 1997,3741. B. E. Herbert and P. M. Bersch, Nucl. Mugn. Reson. Spectrosc. Environ. Chem., 1997,73. A. B. Shtarev, M. M. Kremlev, andZ. Chvatal, J, Org. Chem., 1997,62,3040. J. Voss, J. Lichnock, and J. Bargon, J. Fluorine Chem., 1997,84, 35. A. Dardin, J. M. DeSimone, and E. T. Samulski, J. Phys. Chem. B, 1998,102, 1775. M. A. Fox, J. A. H. MacBride, and K. Wade, Polyhedron, 1997,16,2499.

532 533 534 535 536 537 538 539 540 54 I 542 543

544 545 546 547 548 549 550 551 5 52 553

5 54 555 556 557 5 58

3: Applications of Nuclear Shielding 559 560 561 562 563 564 565 566 567 568 569 570 57 1 572 573 574 575 576 577

123

A. Nordon, R. K. Harris, L. Yeo, and K. D. M. Harris, Chem. Commun. (Cambridge), 1997,961. J. Karl, G. Erker, and R. Froehlich, J. Am. Chem. SOC.,1997,119, I 1 165. K. 0. Christe, D. A. Dixon, G. J. Schrobilgen, and W. W. Wilson, J. Am. Chem. Soc., 1997, 119, 3918. 0. V. Boltalina, J. M. Street, and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1998, 649. Z. Szabo, W. Aas, and I. Grenthe, Inorg. Chem., 1997,36, 5369. A. W. Jensen, A. Khong, M. Saunders, S. R. Wilson, and D. I. Schuster, J. Am. Chem. Soc., 1997, 119,7303. M. Ruttimann, R. F. Haldimann, L. Isaacs, F. Diederich, A. Khong, H. JimenezVazquez, R. J. Cross, and M. Saunders, Chem.-Eur. J., 1997,3, 1071. C. H. Tseng, S. Peled, L. Nascimben, E. Oteiza, R. L. Walsworth, and F. A. Jolesz, J. Magn. Reson., 1997, 126,79. E. B. Brouwer, G. D. Enright, and J. A. Ripmeester, Chem. Commun. (Cambridge), 1997,939. S. Schantz and W. S. Veeman, J. Polym. Sci.,Part B: Polym. Phys., 1997,35, 2681. T. G. Neville, M. E. Hagerman, and R. W. Zoellner, Chemtracts, 1997,10, 366. C . J. Jameson, H.-M. Lim, and A. K. Jameson, Solid State Nucl. Magn. Reson., 1997,9, 277. I. L. Moudrakovski, C. I. Ratcliffe, and J. A. Ripmeester, J. Am. Chem. SOC.,1998, 120,3123. D. Guillemot, V. Yu. Borovkov, V. B. Kazansky, M. Polisset-Thfoin, and J. Fraissard, J. Chem. SOC.,Farachy Trans., 1997,93,3587. M . Luhmer and K. Bartik, J. Phys. Chem. A, 1997,101,5278. Y. H. Lim, A. R. Calhoun, and A. D. King, Jr., Appl. Magn. Reson., 1997,12,555. A. R. Pradhan, J. F. Wu, S. J. Jong, W. H. Chen, T. C. Tsai, and S. B. Liu, Appl. Cutal., A, 1997, 159, 187. D. Naumann, W. Tyrra, R. Gnann, D. Pfolk, T. Gilles, and K. F. Tebbe, 2. Anorg. Allg. Chem., 1997,623, 182 1 . T. Meersmann, S. A. Thomas, and G. Bodenhausen, Phys. Rev. Lett., 1998, 80, 1398.

4 Theoretical Aspects of Spin-Spin Couplings BY H. F U m

1

Introduction

The theory for the calculation of the indirect nuclear spin-spin coupling constants is well known since the Ramsey's work,' and one can in principle apply any standard perturbation scheme to their computation. More than forty years later from the Ramsey's publication, the application of ab initio methods to the calculation of the indirect nuclear spin-spin coupling constants is becoming increasingly popular. Nevertheless, although the calculation of nuclear shielding constants now may be considered routine, this is far from true for the calculation of the indirect nuclear spin-spin coupling constants. This is almost certainly due to the difficulty of calculating the Fermi-contact contribution exactly. The aim of this review is to provide readers with information about important developments in theoretical aspects of spin-spin couplings in the last year.

2

Multiconfigurational Self-Consistent Field Calculations

During the last year three papers2 - 4 have been published about calculations of nuclear spin-spin couplings with the use of multiconfigurational self-consistent field (MCSCF) linear response theory. First we briefly describe the MCSCF linear response theory along the paper by Olsen and Jsrgensen.' After that we introduce the MCSCF calculation results.

2.1 MCSCF Linear Response Theory - Consider a molecular system with a time-independent Hamiltonian Ho. When a general field W(t) is applied to the molecular system, the system will interact with the field. The interaction operator may be denoted V'. We assume that W(t) approaches to zero at t = --co adiabatically, i.e., very slowly. The interaction operator V' can be expressed as V'(t)=

1:

doV"exp[(-io

+ t-)t],

(4.1)

where E is a positive infinitesimal ensuring that V'(-oo) is zero. We assume that at t = -m the molecular system is in an exact eigenstate 10) of Ho: Hop) = EOlO)

Nuclear Magnetic Resonance, Volume 28 0The Royal Society of Chemistry, 1999 124

(44

4: Theoreticul Aspects of Spin-Spin Couplings

125

and that {En} and {In)} denote the residual sets of exact eigenvalues and eigenstates, respectively, of the noninteracting system:

When a time-dependent perturbation V‘ is introduced to the system, the ground state wave function 10) turns into a time-dependent state function 10). The time developed state 10) can be given by the exponential unitary transformation of 10) as

10) = e x p [ i ~ ( t ) ] l ~ ) .

(4.4)

The operator P(t) is

w

= C(Pnln)(Ol

+ ~;Io)(nl)+ (Po + mlo)(Ol

n>O

= f‘ P ( t )

+ 2P,R10)(01,

(4.5)

where P,,are the time-dependent expansion coefficients, i.e., the time-dependent scalar quantities. P: is the real part of PO.The unitary transformation of 10) in eq. (4.4)may be written as

where

10) = e x p [ i N ~ ( t ) l l ~ ) .

(4.7)

We note that the time-dependent phase factor, exp(i2P:) in eq. (4.6) does not influence the time development of the average value of an operator A. That is, the average value of A is given by ( A ) = (OlAlO) = (OlAlO).

(4.8)

The coefficients P, can be expanded in the Perturbation V‘: p, = P p

+ P p + . .. ,

(4.9)

where Pio’ vanishes since 10) is identical with 10) without V‘. The time-dependent coefficients Pi1’,P ( 2 ) n , . . are determined by the time-dependent Schrodinger equation for the system. It is shown that the first-order expansion coefficients P i 1 ) are given by a

(4.10)

where

The average value of A is expanded as

Nuclear Magnetic Resonance

I26

( A ) = (OlAlO)

+ Jrn doexp[(-iw+

E ) ~ ] ( ( A ; v +~ .) -) -~,

(4.12)

--oo

where

Equation (4.13) is the linear response function for the exact state. We assume here that the unperturbed molecular system 10) can be described by an MCSCF wave function: (4.14) g

where {I&)} is a set of configuration state functions (CSFs). Each CSF is a linear combination of Slater determinants. When a time-dependent perturbation V' is introduced, the spin orbitals (+,) and the configuration expansion coefficients {Cgo} vary in time, and (0) turns into a time-dependent state 10). The time evolution of (0) can be conveniently described in terms of an exponential unitary transformation of 10) like eq. (4.4). The unitary transformation operator includes the Hermitian operator K ( t ) , generating the unitary transformation of the orbitals, and the Hermitian operator S( t ) , generating the unitary transformation of the configuration expansion coefficients. The operator K ( t ) + S ( t ) can now be written as K ( t ) + S(t) = (O)(O),

(4.15)

where

and

(4.17)

Here X is a nonsingular matrix. The operators (q+,R+, q, R ) are defined as

q: = a,+a,, qy = as+ar, r > s

(4.18)

and R,S

=

In)(Ol, R, = IO)(nl, TI > 0.

(4.19)

We collected the operators in the row vector (U), and the amplitudes in the column vector (a).The parameters Q of eq. (4.17) which determine the response of the MCSCF wave function to the perturbation V' can be expanded in orders of the perturbation.

127

4: Theoretical Aspects of Spin-Spin Couplings

The matrix X in eqs. (4.16) and (4.17) is obtained by solving the generalized eigenvalue problem E M XJ. -- AJ.s

x.

(4.20)

I21 J *

The matrix E121 is (4.21) where (4.22) and (4.23) The matrix S121is (4.24) where

and

a=

[

(01lqi, qjllo) (01[Ri, qjl 10)

1

(01[ q i y Rjl 10) (01[Ri,Rjl 10)

(4.26)

It is shown that the matrix X diagonalizes the matrices E[*] and S12] simultaneously. The excitation energies ttoj are eigenvalues of El2]: (X+E[21X),= ttojs,,

o j

> 0.

(4.27)

The matrix X can be normalized such that the condition of

is fulfilled. We will collect all eigenvectors with aj = 1 in the columns of X with positive index, and the eigenvectors with cj = -1 in the columns with negative index. Then, the MCSCF linear response function may be given by

Nucleur Magnetic Rrsonunce

I28

In the exact limit an MCSCF wave function becomes a full CI (configuration interaction) wave function and the MCSCF orbital excitation operators are all redundant operators. The MCSCF response functions then become identical with the exact response functions. That is, eq. (4.29) becomes eq. (4.13).

2.2 MCSCF Calculation of Indirect Nuclear Spin-Spin Couplings - Helgaker et aL2 reported the results of MCSCF calculation of the nuclear spin-spin coupling constants for fluoroethylene (C2H3F) molecule. The calculation was carried out using the 'Dalton' program system6 at the experimental g e ~ m e t r y . ~ The t , u ( t , u E x, y , z ) element of the indirect nuclear spin-spin coupling tensor between magnetic nuclei N and M , J ( N , M ) , , , consists of the four different contributions' :

where JDSois the diamagnetic spin-orbit (DSO) and Jpso the paramagnetic spinorbit (PSO) contributions, respectively. J FC is the Fermi-contact (FC) and JSD the spin-di ole (SD) contributions, respectively. The DSO contribution J ( N , M)F8is an expectation value of the operator H DSO

N M , , , = h-'

2

r i i r 2 k [FNk

2 2

(zP0/4n) ( e h /me)TNTM

TMk 61,

-

rNk,urMk.r](4.31)

k

using the unperturbed electron density, and it can therefore be straightforwardly evaluated following the numerical integration method by Matsuoka and Aoyama.' In eq. (4.31) we have introduced the symbols e and m, for the elementary charge and the electronic rest mass, respectively. po is the vacuum permeability, and Y N is the magnetogyric ratio of nucleus N . FNk is tJe position vector of electron k with respect to nucleus N . That is, FNk = f i - RN with the nuclear position &. The remaining three contributions to the spin-spin coupling tensor component J ( N , M ) , , can be calculated using the linear response functions at zero frequency: J(N,

w;, = h-'((H;,,; H ; , , ) ) d ,

(4.32)

where the perturbation operators H a are either PSO, FC, or SD interaction. The perturbing operators in eq. (4.32) are given as

and

4: Theoretical Aspects of Spin-Spin Couplings

129

where p~gis the Bohr magneton, i:e., p~g= eA/2me. The electronic spin vector of and the orbital angular momentum of electron k with electron k is denoted by respect to nucleus N is given by

a,

where F k is the momentum vector of electron k. g, is the electronic g factor for free electrons, i.e., g, = 2,0023. The isotropic coupling constant J is the one third of the trace of the tensor j ( N , M). That is, J = T r ( j ( N ,M ) ) / 3 . The restricted Hartree-Fock (HF) approximation gave (because of its instabilities with respect to triplet excitations) unreliable results for the spin-spin coupling constants in C2H3F. For example, for the J ( C , F) coupling in C2H3F, the 631G* H F value was in total -32000 Hz, with both the FC and the SD contributions not being physical. Fortunately, this problem was solved with the use of a small MCSCF wave function; even with fairly modest MCSCF active spaces, Helgaker et ~ 1obtained . ~ reasonable values for all the constants and all their four contributions. Helgaker et al. treated each contribution separately, calculating the dominant FC contributions with the most accurate wave function and the remaining (smaller but more expensive) contributions with less flexible wave functions. Their approach seems attractive since the basis set and correlation requirements for the various contributions to the nuclear spin-spin coupling are different. All basis sets used were constructed from the unpolarized quadruple-zeta [6s4p/ 3s] contraction of the (1 ls7p/7s) primitive set of Ahlrichs and his coworker^.^^'^ The smallest [6s4p2d/3s2p]basis used by them contains 1 11 contracted Gaussianbasis contains 189 type orbitals (CGTOs), and the largest [12~5p2dlj78~2pld] CGTOs. The largest configuration space consists of 776 920 Slater determinants. The results are shown in Table 4.1. To investigate the convergence of the results further, they carried out a series of calculations using wave functions designed to explore separately the importance of higher excitations and of a more flexible representation of the inner valence regions. As a result they determined the FC correction to be added. The FC correction is listed as AFC in Table 4.1. The total couplings including this correction are given as the 'final' results which may be compared with experiment." l6 Most of the calculated indirect spin-spin coupli!gs agree fairly well with the experimental data or estimates. Astrand et d 3calculated solvent effects on the nuclear magnetic shieldings and the spin-spin couplings of hydrogen selenide (H2Se). The calculations reported by them were not only the first ab initio calculations of the nuclear spin-spin couplings in H2Se, but the work was the first attempt, both theoretically and experimentally, at investigating the solvent dependence of the spin-spin couplings in this molecule. Broadly speaking, the response of a molecule to a dielectric medium is twofold: the electronic charge distribution is polarized and the geometry is altered. In the solvent model that they used in their calculation, the solute molecule is contained in a spherical cavity, embedded in a dielectric medium. The charge distribution of the solute molecule induces polarization moments in the dielectric medium. The

I30

Nuclear Magnetic Resonance

Table 4.1 The individual contributions to the total spin-spin coupling constants and the experimental data for fluoroethylene (in Hz). The contributions are calculated using different wavefunctions. The estimated correction to the FC term is A F C , and the total coupling including this correction is given as tfinal'. (Taken from reJ:[ 2 ] ) Coupling

J ( C , F)

2J(c? F) 2J(F, Hgenz) 3J(F,Hrrrrns) 3J(F, Hcis) J(C,C ) ' J ( C , Hgenz) 2J(C, 2J(C, HCi.') 2J(C, Hgenl) ' J ( C , Hfr"ns) J ( C , Hci') 3J(H8"' HfrCgnJ) 3J(Hgen',H"".) 2J(HtrOnS, HCt.7)

'

'

3

DSO 0.5 - 0.4 - 1.9

-2.5 -0.6 0.2 0.9 -0.4 -0;5 -0.7 0.5 0.6 - 1. 1 - 3.4 - 3.9

PSO -4.8 - 20.2

4.3 - 2.3 - 3.5 - 8.8 - 0.2 - 1.2 - 1.2 - 0.4 0.8 0.7 0.8 2.7 3.8

SD

FC

-0.4 -241.0 11.0 -33.1 -3.3 84.3 0.6 41.6 -0.7 14.1 4.8 97.8 0.1 197.8 0.0 3.8 0.0 -12.2 0.1 11.8 -0.1 159.7 -0.1 162.0 - 0.2 7.0 0.4 14.9 0.1 -6.9

Total

AFc

- 2.0 23.5 -2.9 0.3 83.4 37.4 5.2 9.3 3.8 94.0 - 1.1 198.5 3.9 2.2 2.6 -- 13.9 2 .o 10.8 2.9 160.9 3.3 163.1 3.3 6.5 - 1.1 14.6 -0.7 - 6.8 I .2

- 245.6 --

Final

Experiment"

- 247.6 ( - 236.2)

-20.6 (20.5) 83.7 84.56 51.60 42.5 13.1 19.46 93.0 (90) 202.3 200.2 4.8 (7.6) - 12.0 ( - 13.4) 13.7 14.3 164.2 162.2 166.4 159.2 5.5 4.70 13.9 12.68 -5.6 -3.06

'' Exyerimental values are taken from refs. [ I 1]-[16]. The values in parentheses are estimates polarization moments induced in the medium are described by the polarization vector:

(4.37) where p + l o f is the total polarization vector; Finis the inertial polarization vector related to the static dielectric constant ( c S t ) ; and Fop is the optical polarization vector which is related to the optical dielectric constant (cop). In the time scale relevant for NMR experiments, we may only use the static dielectric constant Esf to describe the induced polarization of the surrounding medium. This leads to the following energy expression for the solvated system in the presence of the external magnetic field17

(4.38) where E,, is the energy in the vacuum and Esol is the dielectric polarization energy given by

(4.39) The factor gl( eft) is

(4.40)

131

4: Theoreticul Aspecls of Spin-Spin Couplings

where a is the cavity radius and (T/,n(p)) are the charge moments for the solute molecule's charge distribution p. The cavity radius a was kept fixed at 4.9 bohrs, corresponding to the distance from the center of mass of the molecule to. theohydrogen nucleus plus the van der Waals radius of the hydrogen atom (1.1 A). Astrand et al. employed the atomic natural orbital (ANO) basis sets proposed by Pierloot et a1.," which have given excellent results for molecular magnetic properties." 2 1 For the geometry optimizations they used the 7331RAS:;;: orbital space together with the contracted A N 0 [6s5p4d/3s2p] basis set. For all contributions to the spin-spin coupling constants other than the FC term they used the 733'RAS:iit orbital space together with the primitive A N 0 (17s15p9d/7s3p) basis. For the FC contribution they used the 7331RAS;:; orbital space and the primitive ANO+fs (an f function and a tight s function to selenium and one diffuse s function and two core s functions to hydrogen added) basis set. The MCSCF wave functions are denoted by i n a c t i v e R A(RAS1 S ~ ~ ~space ~ not used), where the superscripts and subscripts give the numbers of orbitals in each space. Figure 4.1 shows the changes of 'J(Se, H) as a function of the static dielectric constant E , ~ . The dominating solvent shift arises from the changes in the FC term. The changes in the DSO term are negligible and not included in Figure 4.1. The changes in the SD term are also small, whereas the PSO teem gives a significant contribution to the solvent shift of the order of a few Hz. Astrand et al. showed further that the geometry effects due to the dielectric medium are small, that is, the solvent effect on 'J(Se, H) arises mainly from the polarization of the charge distribution in the solute molecule. 'J(Se, H) has been measured in the liquid phase to 63.4 f 0.5 Hz22 and for SeHD in 30% CH2C12 at -56°C to 65.4 0.2 H z . The ~ ~ calculation yielded a gas-phase value of 106.3 Hz and a solvent shift of 15 Hz but in the wrong direction relative to experiment. However, relativistic effects which were not included in the present calculation are likely to reduce 'J(Se, H),24 possibly improving the agreement with experiment. 2J(H, H) has been measured for SeHD in 30% CH2C12 at - 56 "C to - 13.5 Ifr 0.3 H z . They ~ ~ obtained a gas-phase value of - 16.5 Hz and the computed solvent effect is 1.1 Hz, in reasonable agreement with experiment. In particular, the solvent effect for 2J(H, H) in H2Se improves the agreement with experiment. Kaski et aL4 calculated the nuclear spin-spin coupling tensors in ethane, ethene, and ethyne. The indirect nuclear spin-spin coupling tensor j is the response of the molecular electronic system to the magnetic fields coming from magnetic nuclei in the system. When measured in isotropic solutions, molecular tumbling motion averages the j tensor to the scalar number, i.e., spin-spin coupling constant J . Thus, information on the individual tensor elements Jlu(t, u E x, y , z ) is not available through NMR experiments performed in isotropic environments. On the contrary, when molecules are introduced in an anisotropic environment, the determination of the anisotropy of the tensor, A J = J,, - 1/2(Jx.x .Iyy), the difference Jx-x- J,,, and certain combinations of off-diagonal tensor elements becomes feasible, depending on the symmetry of the solute molecule. N MR spectroscopy of molecules partially oriented in liquid-crystalline (LC)

-

+

132

Nuclear Magnetic Resonance

h

N

E

-

M

.-

P

8 c 2-

.C

.-!i r A a

Dielectric constant

Figure 4.1 Selenium-proton spin-spin coupling changes as a function of the dielectric constant. The optimized gas-phase geometries are used. The DSO term is negligible for all dielectric constants. 'J(Se, H)"*(c = 1 ) = 17.8 Hz, 'J(Se, H)SD(t = 1 ) = -0.7 Hz, 'J(Se, H)FC(t= I ) = 89.2 Hz, and 'J(Se, H)(c = 1 ) = 106.3 Hz. (Taken from Fig. 3 in ref: [ 3 ] )

solutions (LC NMR) appears to be the most applicable experimental means to derive information on the spin-spin coupling tensor and the nuclear shielding tensor. Unlike solid-state NMR where small effects are masked by broad lines, the LC NMR method allows even the determination of small anisotropies reliably, provided that the effects of molecular vibrations25 and medium-induced deformation26 28 on the experimental anisotropic couplings Dexpas well as the solvent effects on the spin-spin coupling are properly taken into account. Kaski et a f . used the [7s6p2d/4s2p]contraction of the ( 1 ls7p2d/6s2p) primitive GTO set. The MCSCF results for ethane is given in Table 4.2. The experimentally determined anisotropy A J ( C , C) in ethane was 56 Hz which is considerably larger than the calculated value of 32.1 Hz. However, it must be noted that the treatment of the internal rotation of ethane performed in the analysis of the experimental couplings introduces uncertainties mainly through its use of geometrical relaxation parameters, and the present level of agreement may be considered rather satisfactory. The FC contribution is found to overwhelmingly dominate all the coupling constants, while the SD/FC term emerges as the most important contribution in the anisotropies. For couplings other than CC, the

133

4: Theoreticul Aspects of Spin-Spin Couplings

Table 4.2 Results of the MCSCF calculations for the spin-spin coupling tensors (in H z ) in ethane". (Takenfrom r e ? [ 4 ] ) Property

Totul

DSO

PSO

38.8 32.1 119.8 6.0 -14.1 -8.3 -5.3 - 1.8 3.5 1.6 14.7 3.2 7.2 2.2

0.1 3.3 0.5 -6.3 -2.9 -7.5 -0.3 2.3 -0.9 4.0 -3.1 1.o - 1.6 3.0

0.2 - 2.3 1.2 4.8 3.0 5.2 0.4

SD 1 .o

1.5 - 0.2 0.1 0.4 - 0.4 0.1 0.1 0.1 0.1 0.0 -0.1

- 1.3

0.8 - 2.9 3 .O - 0.5 1.6 -2.1

0.1 0.0

FC

SDIFC

37.5 29.6 118.4 7.4 - 14.7 - 5.6 - 5.4 - 2.9

3.5 0.4 14.7 2.8 7.2

I .2

+

The anisotropy is defined as AJ = JZr- 1/2(J,,, Jyy) Between hydrogens belonging to dierent methyl groups and at guuclze-position to each other ' As in footnote b but for hydrogens at lruns-position to each other Rotational average of the 3J(H, H) tensor: "(H, H)(uv)= (23J(H, H)(a) + 3 J ( H , H) (b))/3 and similarly for A3J(H, H)(uv)

'

latter fact arises from the cancellation of the PSO and DSO contributions. The SD contributions are small and can generally be neglected. Kaski et al. investigated the correlation between the CC spin-spin couplings and the hybridization of CC bond. It was shown that the SD/FC contribution decreases drastically from sp3 to sp' whereas the PSO contribution shows a strong trend in the opposite direction. N o clear trends were found for the FC contribution.

3

Nuclear Motion Effects

Accurate theoretical determination of indirect nuclear spin-spin coupling constants has been a challenge to theoreticians ever since the first work by Ramsey.' Theory has come a long way since then29 33 and an accuracy in the electronic calculations has been reached that makes it necessary to take into account the effect of nuclear motion on the coupling constants. While it has become quite common to include estimates of nuclear motion effects in the ab initio calculation of some molecular magnetic properties such as shieldings and magnetizabili t i e ~ 36 , ~there ~ have been very few ab initio investigations of rovibrational effects on the indirect nuclear spin-spin coupling constants.37 39 Kirpekar et d4'reported the first-order effect of nuclear motion on the

134

Nuclear Magnetic Resonance

indirect nuclear spin-spin coupling constants of CH4, SiH4, GeH4, and SnH4. For small displacements from equilibrium geometry it is possible to expand the coupling constant J (or any other electronic molecular property) as a power series of the dimensionless reduced normal coordinate qs (defined later) as

where f is the freedom of vibrational motions, i.e., 3N - 6 with the number of atoms N. For the investigation of the first-order effect of nuclear motion the expansion is truncated at the first order. For tetrahedral XH4 molecules there are nine normal coordinates with four distinct vibrational modes: one totally symmetric, v I , one doubly degenerate of e symmetry, v2, and two triply degenerates of t 2 symmetry, v3 and v4. Hence, there are four harmonic wave numbers as (s = 1,2,3, and 4). Since the average value of any non-totally symmetric coordinate vanishes, only the totally symmetric reduced normal coordinate q l contributes to the first-order vibational effect on the spin-spin couplings in a tetrahedral XH4 molecule. That is, the average value of J is given by (4.42)

( J ) = Je + J ; ' ) ( q l ) ,

where J : ' ) is the first derivative of the coupling surface with respect to q1 at equilibrium. The derivation of the pure vibrational contributions to (qs) and (4,') has been described in detail by Kern and M a t ~ h a . ~We ' expand the potential energy surface as

C asq: + ( h c / 6 )C 4stuqsqrqu +

= (hc/2)

*

- . *

(4.43)

stu

S

To obtain the expectation values of qs, the first-order rovibrational wave function is needed. The total Hamiltonian must be totally symmetric,42 and therefore the potential energy surface V should contain only even powers of any antisymmetric reduced normal coordinate qn. The expression for the expectation value of a symmetric reduced normal coordinate qs is written as

+ (qs)cent,

( q s ) = (qs)anh

(4.44)

where the first term is caused by anharmonic vibrations and is given by (qJanh = -(2os)-'

~4s,,(+ b 1/2)g,

(4.45)

l

and the second term originates from centrifugal distortion. v, and g, in eq. (4.45) are the quantum number and the degeneracy, respectively, of the tth vibration. The expressions for the ensumble average of ( q s ) , at thermal equilibrium at temperature T, have been presented by Toyama et al.42as

4: Theoretical Aspects of Spin-Spin Couplings

135

(4.46) and (4.47) I&' is the moment of inertia at the equilibrium geometry along the principal axis a and a:& is the derivative of I, with respect to the normal coordinate Qsat equilibrium. The moments of inertia I$: and the coefficients a:& are for a tetrahedral XH4 molecule given by 12; = (8/3)m~R:,

(4.48)

and for s = 1

where mH is the mass of hydrogen atom and R, is the equilibrium distance between the central atom X and each of the hydrogen atoms. Thus we can write fors= 1 ( a ~ " ' / I ~=)3/ (mil2R e ) .

(4.50)

n

The reduced normal coordinate q9 is defined from the normal coordinate Qs by qs = (4a2c~,/h)1f2Qs.

(4.51)

The totally symmetric normal coordinate Ql is given by

QI = (mi2/2)(AR1 = 2ARmi2.

+ AR2 + AR3 + A&) (4.52)

Here ARi(i = 1, 2, 3, and 4) label the displacement of the X - Hi bond length from the equilibrium length Re, and all ARi are constrained to the same value AR such that the Td symmetry is preserved. Therefore, q1 is proportional to A R. Using q5lss parameters Kirpekar et af.calculated (QI). The results for nuclear motion effects on coupling constants in XH4 (X2 = C, Si, Ge, and Sn) are shown in Table 4.3. The experimental values of the nuclear spin-spin coupling constants are as follows: lJ(l3C, H) = 120.87 f0.05 H z , ~ ~ 1J(29Si,H) = 201.28 k 0.42 H z , ~ 'J(73Ge, H) = 97.6 f 0.3 H z , ~ ' and IJ("'Sn, H) = -1933.3 f O . 1 Hz:~ 2 J ( H , H) = -12.1 Hz for CH4,47 2.62 a 0.08 Hz for SiH4,487.69 Hz for GeH4,49and 15.3 Hz for SnH4." Although the vibrational corrections J i ' ) ( q l ) are much smaller compared with the experimental ' J o r 2J values themselves, it is clear that vibrational corrections are relatively more important for the 2J(H, H) than for the 'J(X, H). Gelabert et af.51indicated the significance of varying population of the vibrational excited states for the 'J(H, D) in the Ru - H2 complex. A good

-

10.99 0.01 1.0813 0.2467 0.2563

CAS

11.46 -25.56 - 16.50 - 16.20 0.36 3.67 2.86 2.99 1.1006 1.4750 1.4744 1.5014 0.2701 0.1962 0.1992 0.2133 0.2063 0.2094 0.2240 0.2804

MP2

5.64 1.5279 0.1879 0.1973

- 11.00

SCF

GeH4

-6.54 4.04 1.5046 0.1943 0.2033

MP2

SCF MP2

CAS

-6.31 -210.77 - 119.14 - 110.88 4.29 6.74 4.79 4.49 1.5528 1.7274 1.7058 1.7556 0.2109 0.1690 0.1762 0.1944 0.2210 0.1765 0.1826 0.2016

CAS

Sn H4

A for GeH4, and 1.6909 A for SnH4

" The experimental value? of Re, derived from vibration and rotation spectral data, are as follows: Re = 1.0835 A for CH4, 1.4707 A for SiH4, 1.5143

J") (X, H) HZ 18.84 J \ * )(H, H).Hz -1.45 R,(calc.)"lA 1.0814 (41)OK 0.2369 0.2463 (q 1) 300 K

SCF

CAS

SCF

MP2

SiH4

CH4

Table 4.3 Coupling surface derivatives, equilibrium distances, and vibrationally averaged reduced normal coordinates for XH4 ( X = C, % Si, Ge, and Sn). (Takenfrom reJ [ 4 0 ] )

4: Theoretical Aspects of Spin-Spin Couplings

137

linear correlation between 'J(H, D ) coupling constants and H - H distances was found experimentally by Maltby et al.52 for a series of dihydrogen complexes whose structures have been determined by means of neutron diffraction, X-ray diffraction, or solid-state NMR techniques: ~ H - H=

1.42- 0.0167' J ( H , D),

(4.53)

where it has been implicity assumed that the distance between hydrogen isotopes is not affected by the nature of the isotopic substitution. In this equation 'J(H, D) comes in hertz, and ~ H - Hin angstroms. However, there is a remarkably poor agreement between the experimental values of the H-CH distance and the corresponding theoretical results for the complex [Ru(H - H)(C2H5)(dppm)]+. The theoretical results showed that the most stable structure is a dihydrogen ( d H - H = 0.888 A),5' whereas the struSture experimentally detected is clearly an elongated dihydrogen (& - H = 1.10 A).53 Gelabert et d 5 'calculated the electronic energy of the model cationic complex [Ru(H - H)(C2Hs)(H2 - PCH2PH2)I' against variation of the H - H distance and the Ru-H2 distance. They found that the electronic energy surface has a considerable asymmetry around the energy minimum point. They computed the two-dimensional vibrational wave functions and :valuated the thermal average of the H - H distance, (dt1-H).They obtained 1.02 A for (dH-t{) at 0 K,owhich is in much better agreement with neutron diftraction data ( d H - H = 1.10 A) than the energy minimum distance (dH- = 0.888 A). Table 4.4 presents the thermal average values for the H - H distance and the 'J(H, D) coupling constant estimated from eq. (4.53)as a function of temperature. As can be seen in Table 4.4,there are noticeable differences between mean H - H and H - D distances. As expected, mean thermal H - D distances are shorter than the corresponding mean thermal H - H ones. The theoretical 'J(H, D ) values shown in Table 4.4 are evaluated through use of the empirical relation of eq. (4.53)and the theoretically estimated ( ~ H - H ) .

4

Isotope Effects

Nuclear motion effects can also be investigated from analysis of isotope effects on the indirect nuclear spin-spin coupling constants and the nuclear magnetic shielding constants. Wigglesworth et a/.54 calculated the isotope effects on the nuclear spin-spin coupling constants of methane at various temperatures. The effect of isotopic substitution on nuclear spin-spin coupling has been far less studied (in terms of both experimental measurement and theoretical calculation) than has the effect of isotopic substitution upon nuclear magnetic shielding. Experimental difficulties stem partly from the fact that coupling constants are much less affected by isotropic substitution than are chemical shifts. There is the further difficulty in experiment arising from the need to allow for the change in magnetogyric ratios. When J(C, D) is multiplied by the magnetogyric ratio, YH/YD = 6.5144,the experimental error in the J(C, D) value is also multiplied.

Nuclear Mugnetic Resonunce

138

Table 4.4 Mean thermal hydrogen-hydrogen distances and I J(H, D) coupling constants as a function of temperature. (Takenfrom ref 1.511)

213 233 253 273 295

1.030 1.033 1.035 1.038 1.042

1.003 1.006 1.009 1.013 1.017

22.3 22.0 21.6 21.5 21.1

23.4 23.2 23.1 22.9 22.6

('Data for complex [Ru(H - D)(C,Me,)(dpprn)]+ from ref. [53]

This magnifies the experimental error in comparing (r,/r~)J(c, D) with J(C, H). On the theoretical side, problems stem from the need to use highly correlated wave functions and large basis sets to obtain good values of coupling constants and the further need to calculate separately the four contributing terms, namely, FC, SD, PSO, and DSO terms. To obtain isotope effects, one requires the full spin-spin coupling surface (the variation in coupling with a full set of internal displacement coordinates) which therefore requires all four contributions to be calculated for each of a whole grid of points on the coupling surface so that the Taylor coefficients of this surface can be determined. Displacements of the methane molecule from its equilibrium geometry can be described in terms of nine symmetry coordinates Si(i = 1,2, . . . ,9). The symmetry coordinates are written in terms of ten internal valence coordinates S, ( i = 1,2, . . . , I O y 5 which consists of the four C - H bond stretches rl, r2, r3, and r4 and the six interbond angle changes ~ 1 2 ~, 1 3 0, 1 4 , Q23, a 2 4 , and 0 3 4 . The ten internal valence coordinates are not of course independent because the freedom of internal motions in methane is nine. The full symmetry coordinate carbonproton coupling surface to second order in the Siis given by eq. (1 1 ) of ref. [55]. The ' J ( C , H) coupling in CH4 includes 16 independent parameters. The relations between the symmetry coordinate coefficients (SCCs) and the internal valence coordinate coefficients (VCCs) are given in Table 3 of ref. [%I. The transformation between the internal valence coordinates Riand the dimensionless reduced . 'J(C, ~ ~ H) normal coordinates qr is presented in the paper by Hoy et ~ 1 The coupling in CH4 can therefore be written with the reduced normal coordinates. Using the reduced normal coordinate Wigglesworth et al. 54 showed that owing to the Td symmetry the thermal average expression for the 'J(C, H) coupling in CH4 and the ' J ( C ,D) coupling in CD4 contains only 7 coefficients. The full symmetry coordinate proton-proton coupling surface to second order in the Siis given by eq. (12) of ref. [55]. The 2J(H, H) coupling in CH4 includes 22 independent parameters. Using the transformation by Hoy et al. the 2J(H, H) coupling in CH4 can also be written with the reduced normal coordinates. The thermal average of the 2J(H, H) in CH4 or the 2J(D, D) in CD4 can then

139

4: Theoreticul Aspects of Spin-Spin Couplings

'

Table 4.5 Direct comparison of calculated deuterium isotope effects on J(C, D) and 'J*(C, D) with those measured experimentally (re$ [SS]). No experimental result for I3CH2D2 is available. A'J(C, H) values are relative to 'J(C, D) in 13CH3; A'J*(C, D) values are relative to 'J*(C, D) in I3CH3D. (Takenfrom ref: [ 5 4 ] ) A'J*(C, D)IHz

A'J(C, H)IHz "CH3D

I3CHD3

13CHD3

13CD4

TIK Observed" Culculuteci Observed" Calculated ObservedhCulcululed ObservedhCalculated 200 230 260 300 325 350 370

-0.358 -0.357 -0.354 -0.356 -0.361 -0.355 -0.355

-0.401 -0.400 -0.399 -0.397 -0.396 -0.394 -0.393

-1.044 -1.045 -1.039 - 1.046 -1.043 -1.031 -1.032

- 1.184 -1.183 - 1.182 -1.179 -1.176 - 1.173 -1.170

-0.749

-0.997

-1.107

-1.408

-0.727

-0.983

-1.099

-1.390

-0.691

-0.961

-1.075

-1.360

'' Experimental error in A'J(C, H) is *0.010 Hz Experimental error in A'J*(C, H) is f.0.06 Hz

be formulated. Furthermore Wigglesworth et al. 54 presented expressions for the thermal averages of *J(H, D) in CH3D, CH2D2, and CHD3. Wigglesworth et al. reported the calculated results for the temperature dependence of 'J(C, H) in I3CH4 and of the isotope effects. For I3CH4, 'J(C, H) was calculated to increase by 0.088 Hz on raising the temperature from 180 to 380 K. The deuterium isotope effects on 'J(C, H) and 'J*(C, D) (= ( y ~ / y ~ ) ' J (D)) c, with respect to I3CH4 were all negative and predicted to decrease with increasing temperature in this range. The basic physical reason for this latter change, of course, is that for the heavier isotopomers the low-frequency bending and stretching modes are more easily excited with increase in temperature and so their coupling constants will increase more rapidly than the 'J(C, H) in 13CH4. This is because the 'J(C, H) in I3CH4 has the positive derivative of the coupling surface with respect to the bond stretch. In Table 4.5 the isotope effects calculated by Wigglesworth et al. are compared with the experimentally measured values.47The calculated results are seen to be about 10% higher numerically than the observed ones. There is, nevertheless, very good overall agreement between them. Table 4.6 gives the results of temperature dependence calculations for 2J(H, D) in the methane isotopomers over the temperature range 180-380 K. The calculated results in Table 4.6 bear out the room-temperature experimental observations of Bernheim and L a ~ e r y , in ~ *which no temperature dependence in any isotopomer could be detected. The calculations in Table 4.6 explain why. An improvement of more than two orders of magnitude in precision would be required to detect the predicted isotope change of 2J(H, D).

1 40

Nucleur Magnetic Resonunce

Table 4.6 Temperature dependence of 2J(H, D) in methane isotopomers. Results under the heading CH3D are calculated values of *J(H, D) for the relevant temperature. Values of A2J(H, D) are differences of 2J(H, D) from the corresponding value for CH3D at the same temperature. (Takenfrom ref (541) TIK

CHlD J(H, D)/Hz

CH2D2 AJ(H, D)/Hz

CHD3 AJ(H, D)/Hz

180 220 260 300 340 380

-2.3235 -2.3235 - 2.3236 - 2.3238 - 2.341 - 2.3245

- 0.0002 - 0.0002

0.0005 0.0004 0.0004 0.0002 - 0.000 1 - 0.0005

5

0.0000 0.0002 - 0.0002 - 0.0003 -

Relativistic Effects

Substituent effects on chemical shifts have been of interest since the early days of N M R spectroscopy. Many years ago Schneider, Bernstein, and P ~ p l reported e ~ ~ that the proton chemical shift of hydrogen halides, HX, shows the abnormal high-field resonance when X = Br or I. The number of different explanations were proposed for explanation of the observed abnormal shifts. Most NMR textbooks explain heavy atom effects in terms of large diamagnetic shielding due to the many electrons around the heavy atom.60 65 Other arguments include electronegativity effects of the heavy atom induced by the paramagnetic However, as early as 1969 Nakagawa et al.68369suggested, in the context of 'H chemical shifts of disubstituted benzenes, that the unusual halogen substituent effects observed are due to electronic spin polarization in the molecule induced by the relativistic spin-orbit coupling. Since the pioneering work of Nakagawa et al. there have been a large number of papers treating relativistic effects on the chemical shifts69 76 and the indirect nuclear spin-spin coupling constants.77 79 Kirpekar et al.24 reported the calculated results for the spin-orbit coupling effect on the indirect nuclear spin-spin coupling constants of XH4 (X = C, Si, Ge, and Sn). They used the quadratic response function at the ab initio SCF level of approximation. The quadratic response function ( ( A ;VoI, V"*)),, ,02 provides information on the process where one photon of frequency 01 and one of frequency 02 are absorbed and one of frequency 01 + 0 2 is emitted. The quadratic response function can be used for calculations of the third-order perturbation energies such as the hyperpolarizability. The expression for the quadratic response function at zero frequencies is given by

141

4: Theoreticul Aspects of Spin-Spin Couplings

where hok and hn are excitation energies. Having a singlet ground state and using the fact that the quadratic response function in the static limit is symmetric in the perturbing operators, Kirpekar et ai.24proved that there are only four non-zero spin-orbit correction terms to the nuclear spin-spin coupling constants as a result of the Wigner-Eckart theorem. They performed calculation for the following two major spin-orbit correction terms: ( ( HPSO ( N 1; HFC( M ) H S O ) 0,o 7

(4.55)

and (4.56)

Here, Hso is the spin-orbit operator. The spin-orbit operator including both of the one-electron and the two-electron parts is

(4.58) --+

is defined in eq. (4.36). L' is the velocity of light and Z N is the atomic number of atom N . The first term in eq. (4.55) can be viewed as the interaction of electron j's spin magnetic moment with its angular moment due to the motion of the electron j relative to the charged nucleus. For this one-electron part we use the symbol HSoc').The last two terms constitute a two-electron part, Hso(2), composed of the spin-own-orbit interaction and the spin-other-orbit interaction (the last term). The effect of the two-electron operator can be construed as a shielding by the other electrons k of the actual field from the nucleus felt by electron j , which reduces the one-electron part.*' The difficult two-electron effect may be mimicked by the introduction of an effective nuclear charge, z"", such that eq. (4.55) is replaced by the following effective one-electron operator INj

(4.59)

If we assume that Zgr is equal to one, we will obtain for an XH4 molecule

I 42

Nuclear Magnetic Resonance

(4.60) Here, in H;"') the contributions from the hydrogen nuclei are excluded, whereas in HSo(')they are retained. Kirpekar et al.24investigated the effectiveness of the effective nuclear charge approximation. Kirpekar et al. obtained the following results for the spin-orbit correction to the nuclear spin-spin coupling constant, Jso: ' J ( 13C, H)" = -0.058 Hz, H)" = 0.059 Hz., 'J(73Ge, H)" = 0.071 Hz, and 'J("'Sn, H)" = 21.173 Hz. The spin-orbit correction is only important for SnH4, yet it is merely 1% of the total coupling constant even in this case. The effective nuclear charges obtained from ' J ( X , H)'O calculation are as follows: ZEfl = 3.63, ZeK = 9.53, Z&! = 20.46, and 2:: = 43.31. The Slater effective nuclear charges, 2% sir(Slater), for the outermost p electron are 3.25 for C, 4.14 for Si, and 5.65 for Ge and Sn. We can see that the Slater effective nuclear charge is much too small for all atoms but carbon. Kaupp et af.8' investigated the relation between the spin-orbit-induced shift and the Fermi-con tact spin-spin coupling constant. The spin polarization induced in a molecule by heavy-atom spin-orbit coupling is known to interact with the nuclear spins of the system mainly by a Fermi-contact mechanism and to produce the spin-orbit shift. In the Fermi-contact spin-spin coupling the spin polarization is induced by the Fermi-contact interaction between electron spins and one of the coupled nuclear spins, and it interacts with the other nuclear spin through the Fermi-contact mechanism. It seems reasonable to assume that the rules governing the propagation of these induced spin polarizations through the molecule are thus closely related to each other. We can assume that the spin-orbit shift will be simulated by the well-established mechanism for indirect Fermi-contact nuclear spin-spin coupling. Kaupp et al. tested this assumption by density functional theory (DFT) calculations of spin-orbit shifts and of Fermi-contact spin-spin coupling constants in some simple iodo-substituted compounds. Kaupp et al. found a proportional relationship between spin-orbit shifts and reduced Fermicontact coupling constants KFc. Typically, a negative reduced coupling constant corresponds to a shielding spin-orbit shift, and a positive coupling to a deshielding spin-orbit contribution. For example, the magnitude of the spinorbit-induced, shift observed on direct neighbor nucleus B of the heavy atom A increases with increasing s-orbital contribution from the atom B to the B - A ) bond. For the P-hydrogen atoms in iodoethane, a modified Karplus-type relationship was found to hold between the spin-orbit shift and the dihedral angle formed by the intervening bonds.

6

New Operators for the Fermi-Contact Interaction

The Fermi-contact interaction, which makes an important contribution to indirect nuclear spin-spin coupling constants, is sensitive to the electronic behavior at the positions of the coupled nuclei. Unfortunately, the electronic

4: Theoretical Aspects of Spin-Spin Couplings

143

behavior at the nuclei is not described well by most commonly used approximate molecule wave functions. If we could replace the delta function operator of the Fermi-contact interaction by a well behaved global operator, the accuracy of indirect nuclear spin-spin coupling constant calculations would be improved. First-order properties such as isotopic hyperfine coupling constants are proportional to diagonal matrix elements of the delta function.82 For such expectation values, Hiller, Sucher, and Feinberg (HSF)83have shown that the delta function operator can be replaced by a certain global operator. Second-order properties (such as indirect nuclear spin-spin coupling constants) formally involve a sumover-states expression requiring off-diagonal matrix elements. G e e r t ~ e nhas ~~ previously considered replacement of the delta function operators with the corresponding HSF operators for the calculation of FC contributions to nuclear spin-spin coupling constants. The results obtained for 'J(H, D) in the HD molecule were promising. It is known that the HSF operator shows improper long-range behavior with approximate wave functions. Rassolov and Chipman have recently derived 85 a whole class of new global operators that can replace the delta function properly. In contrast to the HSF operator, these have correct long-range behavior even with approximate wave functions. Calculations on several simple atoms and small moleculess6 gave very encouraging results for the first-order properties corresponding to charge and spin density at the nucleus. Chipman and Rass0lovs7tested their new operators for calculation of second-order properties such as indirect Fermi-contact nuclear spin-spin coupling constants. We first explain their new operator. For simplicity of notation we assume a one-electron system throughout the derivations, then generalize the result to a many-electron system at the end. In the fixed-nuclei approximation the electronic Hamiltonian operator has the general form (in atomic units) (4.61) with L2 the operator for the squared orbital angular momentum and U the total one-electron Coulomb potential energy. Next we introduce the generating operator (4.62) where the weight function F(r) is some as yet unspecified radial function restricted only in that it should be real and not vanish at the origin or grow rapidly at infinite r. The anti-Hermitian component 2 of the generating operator @ is given by T(r) = ( ii/

-

+ + ) / 2 = F(r)(d/dr + l/r)

+~ ' ( r ) / 2 .

(4.63)

Here the prime notation denotes differentiation with respect to r. We used as the definition of k t the identity

144

Nucleur Magnetic Resonance

The commutator of an anti-Hermitian operator (such as 2)with a Hermitian operator (such as fi) produces a Hermitian operator. Assuming that F(r) does not vanish at the origin, we obtain the commutator

[ H , k]= 27rF(O)(S(J)

-

(4.65)

J(F)},

where

Therefore, we get the results for a many-electron system r

1

where H is the many-electron Hamiltonian operator for the system including electron-nuclear attraction and electron-electron repulsion interactions. The potential energy I/ is extended to include the Coulomb interactions with the other electrons. Selecting an origin located at the position of nucleus k,we introduce the weight function FA and the following notations:

zA

(4.68) (4.69) and

The weight function FA is the radial function around the point eigenfunctions are used, we obtain the relation

XA.

If exact

in which both of the delta function operators have been replaced with the global operators in the sum-over-states term. Chipman and Rassolov proposed two specific choices of the new global

4: Theoreticul Aspects of Spin-Spin Couplings

145

operators which are associated with the following two weight functions. One of them is the Heaviside step function Fe and the other one is the Gaussian function F G .That is, (4.72) and (4.73) In principle, the two range parameters r o ~and roB associated with the new operators at the two centers A and B, respectively, need not have the sam2 value. Usually r o + ~ r o is ~ chosen to be sufficiently less than the distance IR'B - R A such ~ that the nonoverlap criterion is satisfied. Provided that the nonoverlap condition is fulfilled, the diagonal matrix element terms over the wave function 10) in eq. ~ t - 0 ~the cumbersome (4.69) can be safely omitted. Furthermore, with small r o and two-electron contributions can also be neglected. Chipman and R a s s ~ l o vtested ~ ~ the two functions, Fe and F G , for the calculation of the Fermi-contact contribution to the indirect nuclear spin-spin coupling constant 'J(H, D) in the HD molecule. They showed that both of the two new global operators lead to improved results for the use of poor basis sets.

7

Dependence on Conformation and Bond Character

Relations between N M R parameters (chemical shifts and spin-spin coupling constants) and molecular structure (bond structure and conformation) are of primary importance for determination of the structure of chemical compounds both in solution and in solid state. Since experimental relations rely mostly on empirical data without detailed understanding of their physical origin, there is a need for more fundamental studies based on theoretical analysis. Moreover, in principle, theoretical calculations might provide NMR parameters vs. structure relations where experimental data are limited. In this section we introduce the papers describing about dependence of indirect nuclear spin-spin coupling constants on molecular conformation and bond character. 7.1 Conformation Dependence of Spin-Spin Couplings - The sensitivity of vicinal proton-proton coupling constants 3J(H, H) to variations of diheral angle 4 was first rationalized in terms of a valence bond (VB) theory by K a r p h d 8 in 1959. The Karplus type equation, 'J(H, H) = A cos2 4 + B cos 4 + C, has been a major tool in the structure determination for 40 years. Since the first report by Karplus, many theoretical studies of 3J(H, H) have been made.89 However, most theoretical calculations of 3J(H, H) have been based on semiempirical methods and included only the FC contribution. Conversely, ab initio calculations including the four contributions to 3J(H, H) are very scarce." 92

146

Nuclear Magnetic Resonance

Fukui et reported results of ab initio SCF and MP3 (3rd-order MsllerPlesset perturbation) calculations for the dihedral angle dependence of the 3J(H, H) in methanol and methylamine. The angle dependence of the 3J(H, H) in methylamine is represented as 'J(H, H)

=

+

CO CI cos 4

+ C2 cos24 + C3 cos 34 + S1 sin 4 + S2 sin24.

(4.74)

Because of molecular symmetry, the 3b(H, H) in methanol has no S,(i= 1,2) terms. The four contributions to the 3J(H, H) were computed. The results showed that the FC contribution is largest and the SD term is smallest. It was shown that the PSO and DSO contributions are comparable in magnitude and have opposite signs. The second-order correlation effect was very large whereas the third-order one was very small (but not negligible). The calculated curves for 3J(H, H) vs. 4 well reproduced the experimental dihedral angle dependences in both the molecules. Hricovini et calculated spin-spin coupling constants in a monosaccharide, methyl-P-D-xylopyranosideby using DFT based approaches. They investigated effect of torsion angle on the coupling constants. They found torsion angle dependences in 'J(C, H ) between anomeric proton and anomeric carbon and 3J(C, H) between anomeric proton and methyl carbon. Excellent agreement was obtained between the computed and experimental data. Stahl et ~ 1 . ~calculated ' 3J(C,C) for a 1,3-dimethylated model compound by a DFT method using ab initio optimized geometries. They found that Boltzmann averaging of the calculated coupling constants for individual conformers results in good agreement with the experimental data. The comparison to calculated values provided a more quantitative interpretation of the experimental coupling constants. Kolehmainen et a1.96 performed the complete analysis of the 'H NMR spectrum of 0-pinene, (1 s)-(-)-6,6-dimethyl-2-methylenebicyc10[3.1.llheptane, which is of the ABCDEFGHIJX3Y3 type, and corrected earlier results of coupling constants.97 99 In order to analyze the observed complex spectrum the vicinal coupling constants, 3J(H, H), were compared with the theoretical values calculated by using the Altona and co-workers' for the structure derived by molecular modelling.

7.2 Spin-Spin Couplings and Bond Character - Borrmann et d ' 0 2 investigated the 2J(203Tl,205Tl), 'J(203,20'Tl, 77Se), and '.I(~*~TI,I2'Te) spin-spin coupling constants in the seleno- and tellurothallate anions TI2Ch:- (Ch = Se and/or Te) and the 77Se-enriched T12Sei- anion. The relative magnitudes of the spin-spin coupling constants may be understood in terms of the calculated s-characters of the corresponding bonding interactions. In general, spin-spin couplings between nuclei of heavy atoms connected by single rather than multiple bonds are dominated by the FC r n e c h a n i ~ m . ' The ~ ~ magnitudes of the relativistically corrected reduced coupling constants, K(TI, Ch)Rc, were consistent with essentially pure p-bonded rings whereas the magnitudes of K(TI, TI)Rc suggested significant s electron density along the TI. . . TI axes. These were confirmed by

4: Theoretical Aspects of Spin-Spin Couplings

147

DFT calculations. It was shown that the TI . . . TI interaction predominantly arises from overlap of the valence s-orbitals on the TI atoms. Maerker et al. Io4 presented computational results on DFT calculations for hydrogen fluoride species (HF), (with 1 5 n 5 6) and compared them to results from other approaches and experiments. The D F T values calculated for 'J(H, F) coupling constants showed significant discrepancy with experimental ones. The computed IJ(H, F) in HF monomer, 380 Hz, varied non-monotonically in the oligomers (to 395 Hz in the S, hexamer), with a minimum 'J(H, F) of 373 Hz in the C3jzsymmetric trimer. The measured 'J(H, F) in gaseous HF, 529 f 23 Hz,Io5 is much greater than their computational value. This discrepancy may be attributed to underestimation of the FC term in the DFT Similarly, the experimental IJ(H, F) in the bihalide anion FHF- is 120.5 f 0.1 Hz in aprotic solvents'07 whereas the computed 'J(H, F) in FHF- was only 20 Hz. The development of more accurate functionals, which are especially designed for calculations of magnetic response properties, might resolve the current d i s c r e p a n ~ i e s . ~ ~ . ' ~ ~ Zhan and WanIo8 proposed a new generalized semiempirical expression for calculating indirect nuclear spin-spin coupling constants between directly bonded atoms. In the previous paper Zhan and HuIo9 related IJ(A, B) with the ( s % ) ~and (s%),, the s-characters of hybrid orbitals of atoms A and B, respectively, and QA and QB,the net charges of atoms A and B, respectively. The new expression for 'J(A,B) presented by Zhan and WanIo8is

'

+ I J ( A , q S D+ ' J ( A , B ) m o + ' J ( A , B ) D S o = kn, Won WOE 4-ken QAWOA4-kQsQs WOE+ k~ WOA+ k~ WOE + ~ E A Q A+ ~ E E Q B+ CAE,

' J ( A , B )= J ( A , f q F C

(4.75)

which involves in total eight independent parameters to be determined by fitting some reliable experimental data. Here, WOA3 ( s % ) ~ and WOB= (s%),. For illustration, they employed the new expression to elucidate ' J ( C , F) coupling constants and obtained good agreement with the corresponding experimental data. 8

References

1 2

N. F. Ramsey, Phys. Rev., 1953,91,303. T. Helgaker, M. Taszunski, and K. Ruud, Mol. Phys., 1997,91,881. P . - 0 . Astrand, K. V. Mikkelsen, P. Jargensen, K. Ruud, and T. Helgaker, J. Chem. Phys., 1998,108,2528. J. Kaski, P. Lantto, J. Vaara, and J. Jokisaari, J. Am. Chem. Soc., 1998, 120,3993. J. Olsen and P. Jargensen, J. Chem. Phys, 1985,82,3235. T. Helgaker, H. J. Aa. Jensen, P. Jargensen, H. Koch, J. Olsen, H. Agren, T. Anderson, K. L. Bak, V. Bakken, 0. Christiansen, P. Dahle, E. K. Dalskov, T. Enevoldsen, A. Halkier, H. Heiberg, D . Jonsson, S. Kirpekar, R. Kobayashi, A. S. de Meras, K. V. Mikkelsen, P. Norman, M. J. Packer, K . Ruud, T. Saue, P. R. Taylor, and 0. Vahtras, DALTON, an ab initio electronic structure calculation program.

3 4 5

6

I48 7

8 9 10

11 12 13 14 15 16 17 18

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

Nuclear Mugnetic Resonance

M. D. Harmony, V. W. Laurie, R. L. Kuczkowski, R. H. Scwendeman, D. A. Ramsey, F. J. Lovas, W. J. Lafferty, and A. G. Maki, J. Chem. Phys. Ref. Dutu, 1997,8,619. D. Matsuoka and T. Aoyama, J. Chem. Phys., 1980,73,5718. A. Schafer, H. Horn, and R . Ahlrichs, J. Chem. Phys., 1992,97,2571. A. Schafer, C. Huber, and R. Ahlrichs, J. Chem. Phys., 1994,100,5829. V. S. Watts and J. H. Goldstein, J. Chem. Phys., 1965, 42, 228. K. Kamienska-Trela, Z. Biedrzycka, and A. Dabrowski, Mugn. Reson. Chem., 1991, 29, 1216. K. Kamienska-Trela and Z. Biedrzycka, Bull. Pol. Acud. Sci. Chem., 1988,36,285. J. L. Marshall, in ‘Carbon-Carbon and Carbon-Proton NMR Couplings’, Verlag Chemie International, Deerfield Beach, 1983, p. 42. V. Wray, Ann. Rep. N M R Spectrosc., 1983, 14, 1. N. J. Koole, M. J. A. de Bie, and P. E. Hansen, Org. Mugn. Reson., 1984,22, 146. K. V. Mikkelsen, P. Jerrgensen, K. Ruud, and T. Helgaker, J. Chem. Phys., 1997, 106, 1170. K. Pierloot, B. Dumez. P.-0. Widmark, and B. 0. Roos, Theor. Chim. Actu, 1995, 90,87. P.-0. Astrand and K. V. Mikkelsen, J. Chem. Phys., 1996, 104,648. P.-0. Astrand, K. V. Mikkelsen, K. Ruud, and T. Helgaker, J, Phys. Chem., 1996, 100, 19771. K. Ruud, P.-0. Astrand, T. Helgaker, and K. V. Mikkelsen, J. Mol. Struct. (Theochem), 1996,388,23 1. T. Birchall, R. J. Gillespie, and S. L. Vekris, Cun. J. Chem., 1965,43, 1672. G. Pfisterer and H. Dreeskamp, Ber. Bunsenges., 1969,73,654. S. Kirpekar, H. J. Aa. Jensen, and J. Oddershede, Theor. Chim. Acta, 1997,95,35. S. Sykora, J. Vogt, H. Bosiger, and P. Diehl, J. Mugn. Reson., 1979,36, 53. J. Lounila and P. Diehl, J. Mugn. Reson., 1984,56, 254. J. Lounila and P. Diehl, Mol. Phys., 1984,52, 827. J. Lounila, Mol. Phys., 1986, 58, 897. J. A. Pople, W. G. Schneider, and H. J. Bernstein, in ‘High Resolution Nuclear Magnetic Resonance’, McGraw-Hill, New York, 1959. J. A. Pople and D. P. Santry, Mol. Phys., 1964,8, I. J. A. Pople, J. W. McIver, and N. S. Ostlund, J. Chem. Phys., 1968,49,2965. J. Kowalewski, Prog. N M R Spectrosc., 1977, 11, I . J. Kowalewski, Ann. Rep. NMR Spectrosc., 1982, 12, 81. W. T. Raynes, P. W. Fowler, P. Lazzeretti, R. Zanasi, and M. Grayson, Mol. Phys., 1988,64, 143. S. P. A. Sauer, Chem. Phys. Lett., 1996,260, 271. S. P. A. Sauer and I. Paidarova, Chem. Phys., 1995,201,405. J. Oddershede, J. Geertsen, and G. E. Scuseria, J. Chem. Phys., 1988,92, 3056. J. Geertsen, J. Oddershede, and G . E. Scuseria, J. Chem. Phys., 1982,87, 2138. A. Barszcewicz, T. Helgaker, M. Jaszunski, P. Jerrgensen, and K. Ruud, J. Mugn. Reson. A, 1995, 144,212. S. Kirpekar, T. Enevoldsen, J. Oddershede, and W. T. Raynes, Mol. Phys., 1997,91, 897. C. W. Kern and R. L. Matcha, J. Chetn. Phys., 1968,49,2081. M. Toyama, T. Oka, and Y. Morino, J. Mol. Spectrosc., 1964,13, 193. W. T. Raynes, J. Geertsen, and J. Oddershede, Chem. Phys. Lett., 1992,197,576. P. W. Fowler, Mol. Phys., 1981,43, 591.

4: Theoretical Aspects of Spin-Spin Couplings

45 46 47 48 49 50

51 52 53 54

55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74

75 76 77 78 79

149

A. L. Wilkins, P. J. Watkinson, and K. M. MacKay, J. Chem. Soc., Dalton Truns., 1987,2365. H. Dreeskamp, Z. NuturJ:, 1964,19, 139. B. Bennett, W. T. Raynes, and C. W. Anderson, Spectrochim. Acta A , 1989,45,821. R. A. Nicholls and W. T. Raynes, unpublished work, 1995. Cited in ref. [40]. E. A. V. Ebsworth, S. G. Frankiss, and A. G. Robiette, J. Mol. Spectrosc., 1964, 12, 299. W. Briigel, in ‘Handbook of NMR Spectral Parameters’, Heyden, London, 1979, VOl. 13. R. Gelabert, M. Moreno, J. M. Lluch, and A. Lledos, J. Am. Chem. Soc., 1997, 119, 9840. P. A. Maltby, M. Schlaf, M. Steinbeck, A. J. Lough, R. H. Morris, W. T. Klooster, T. F. Koetzle, and R. C. Srivastava, J. Am. Chem. Soc., 1996,118, 5396. W. T. Kooster, T. F. Koetzle, G. Jia, T. P. Fong, R. H. Morris, and A. Albinati, J. Am. Chem. SOC.,1994,116,7677. R. D. Wigglesworth, W. T. Raynes, S. P. A. Sauer, and J. Oddershede, Mol. Phys., 1997,92, 77. J. Geertsen, J. Oddershede, W. T. Raynes, and T. L. Marvin, Mol. Phys., 1994, 82, 29. W. T. Raynes, P. Lazzeretti, and R. Zanasi, Mol. Phys., 1987,61, 1415. A. R. Hoy, I. M. Mills, and G. Strey, Mol. Phys., 1972,24, 1265. R. A. Bernheim and B. J. Lavery, J. Chem. Phys., 1965,42, 1464. W. G. Schneider, H. J. Bernstein, and J. A. Pople, J. Chem. Phys., 1958,28, 601. C. J. Jameson and J. Mason, in ‘Multinuclear NMR’, ed. J. Mason, Plenum Press, New York, 1987, p. 5 1. L. M. Jackman and S. Sternhill, in ‘Applications of Nuclear Magnetic Resonance in Organic Chemistry’, 2nd ed., Oxford University Press, New York, 1969. J. B. Stothers, in ‘Carbon-13 NMR Spectroscopy’, Academic Press, New York, 1972. E. Breitmaier and W. Voelter, in ‘13CNMR Spectroscopy’ 3rd ed., VCH, Weinheim, 1987. J. Mason, A h . Inorg. Chem., 1976,18, 197. J. Mason, A h . Inrog. Chem., 1979,22, 199. R. G. Kidd, Ann. Rep. N M R Spectrosc,, 1980,10A, 2. R. G. Kidd, Ann. Rep. N M R Spectrosc., 1991,23,85. N. Nakagawa, S. Sinada, and S. Obinata, in ‘The 6th NMR Symposium’, Kyoto, 1967, p. 8. Y. Nomura, Y. Takeuchi, and N. Nakagawa, Tetrahedron Lett., 1969,8,639. I. Morishima, K. Endo, and T. Yonezawa, J. Chem. Phys., 1973,59, 3356. P. Pyykko, Chem. Phys., 1983,74, 1. N. C. Pyper, Chem. Phys. Lett., 1983,96,204. N. C. Pyper, Chem. Phys. Lett., 1983,96,211. V. G. Malkin, 0. L. Malkina, L. A. Eriksson, and D. R. Salahub, in ‘Theoretical and Computational Chemistry’, ed. J. M. Seminario and P. Politzer, Elsevier, Amsterdom, 1995, Vol. 2, p. 273. H. Nakatsuji, H. Takashima, and M. Hada, Chem. Phys. Lett., 1995,233,95. H. Fukui and T. Baba, J. Chem. Phys., 1998,108,3854. P. Pyykko and L. Wiesenfeld, Mol. Phys., I98 1,43,557. L. L. Lohr Jr. and P. Pyykko, Chem. Phys. Lett., 1979.62,333. P. Pyykko, J. Orgunometul Chem., 1982,232,21.

I50

Nuclear Magnetic Resonance

80

W. G. Richards, H. P. Trivedi, and D. L. Copper, in ‘Spin-Orbit Coupling in Molecules’, Clarendon Press, Oxford, 198 1. M. Kaupp, 0. L. Malkina, V. G. Malkin, and P. Pyykko, Chem. Eur. J., 1998, 4, 118. P. W. Atkins, in ‘Molecular Quantum Mechanics’, Oxford University Press, Oxford, 1983. J. Hiller, J. Sucher, and G. Feinberg, Phys. Rev. A , 1978, 18,2399. J. Geertsen, Chem. Phys. Lett., 1985,116,89. V. A. Rassolov and D. M. Chipman, J. Chem. Phys., 1996,105, 1470. V. A. Rassolov and D. M. Chipman, J. Chem. Phys., 1996,105, 1479. D. M. Chipman and V. A. Rassolov, J. Chem. Phys., 1997,107,5488. M. Karplus, J. Chem. Phys., 1959,30, 11. M. J. Minch, Cuncep. Magn. Reson., 1994,6,41. J. San-Fabian, J. Guilleme, E. Diez, P. Lazzeretti, M. Malagoli, and R. Zanasi, Chem. Phys. Lett., 1993,206, 253. J. San-Fabian, J. Guilleme, E. Diez, P. Lazzeretti, M. Malagoli, R. Zanasi, A. L. Esteban, and F. Mora, Mu/. Phys., 1994,82,913. H. Fukui, H. Inomata, T. Baba, K. Miura, and H. Matsuda, J. Chem. Phys., 1995, 103,6597. H. Fukui, T. Baba, H. Inomata, K. Miura, and H. Matsuda, Mol. Phys., 1997, 92, 161. M. Hricovini, 0. L. Malkina, F. Bizik, L. Turi Nagy, and V. G. Malkin, J. Phys. Chem. A , 1997,101,9756. M. Stahl, U. Schopfer, G. Frenking, and R. W. Hoffmann, J. Org. Chem., 1997,62, 3 702. E. Kolehmainen, K. Laihia, R. Laatikainen, J. Vepsalainen, M. Niemitz, and R. Suontamo, Magn. Reson. Chem., 1997,35,463. W. B. Smith, Mugn. Resun. Chem., 1994,32, 316. K. Laihia, E. Kolehmainen, P. Malkavaara, J. Karvola, P. Manttari, and R. Kauppinen, Magn. Reson. Chem., 1992,30,754. A. Y. Badjah-Hadj-Ahmed, B. Y. Meklati, H. Watson, and Q. T. Pham, Magn. Resun. Chem., 1992,30, 807. C. Altona, R. Francke, R. de Haan, J. H. Ippel, G. J. Daalmans, A. J. A. Westra Hoekzema, and J. van Wijk, Magn. Reson, Chem., 1994,32,670. C. A.G. Haasnoot, F. A. A. M. de Leeuw, and C. Altona, Tetrahedron, 1980, 36, 278 3. H. Borrmann, J. Campbell, D. A. Dixon, H. P. A. Mercier, A. M. Pirani, and G. J. Schrobilgen, Inorg. Chem., 1998,37, 1929. C. J. Jameson, in ‘Multinuclear NMR’, ed. J. Mason, Plenum Press, New York, 1987, p. 89. C. Maerker, P. v. R. Schleyer, K. R. Liedl, T.-K. Ha, M. Quack, and M. A. Suhm, J. Cuniput. Chem., 1997,18, 1695. J. S. Muenter and W. Klemperer, J, Chem. Phys., 1970,52,6033. 0. L. Malkina, D. R. Salahub, and V. G. Malkin, J. Chem. Phys., 1996,105,8793. J. S . Martin and F. Y. Fujiwara, J. Am. Chem. Soc., 1974,95, 7632. C.-G. Zhan and J. Wan, Chem. Phys. Lett., 1997,279, 35. C.-G. Zhan and Z. -M. Hu, Magn. Reson. Chem., 1994,32,465.

81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99

I 00 101

102 103 1 04

105 106 107 108 109

5 Applications of Spin-Spin Couplings BY KRYSTYNA KAMIENSKA-TRELA AND JACEK WOJClK

1

Introduction

The material in this chapter has been arranged as was done previously,' i.e. according to (i) the increasing atomic number of the nuclei involved, and (ii) the number of the bonds separating them. It covers the period from 1 June 1997 to 31 May 1998. We follow recently published I UPAC2 recommendations with one notable exception, namely the nucleus with a smaller mass is given first. This is in accord with the notation used by us in our previous reviews. For the sake of simplicity the following symbols are used throughout the paper: H for 'H, D 2H, T - 3H, Li - 7Li, B - "B, C - 13C, N - 15N,0 - 170,F - I9F, Si - 29Si,P 31P,Mn - "Mn, Cu - %u, Se - 77Se,Y - 89Y, Tc - 99Tc, Rh - lo3Rh, Ag IWAg, C D - '13CD, Sn - l19Sn, Te - '25Te, I - '271, W - '83W, 0 s 1870s, Pt - 19'Pt, Hg I99 Hg, T1- *05Tl,Pb - 207Pb.All the other isotopes are described explicitly. An excellent book on NMR spectroscopy of the non-metallic elements has been written recently by Berger, Braun and K a l i n ~ w s k i . ~ An extensive review on high resolution 6*7LiNMR of organolithium compounds has been written by Giir~ther.~ Investigations on intramolecular hydrogen bonds by nitrogen magnetic resonance methods including an analysis of the JHN couplings have been reviewed by Schilf and Stefaniak.' A review on the chemical shift and spin-spin coupling NMR data of mesoionic thiatriazoles, oxatriazoles and tetrazoles has been published by JaiwinskL6 A review on NMR data concerning nitroazoles including some amount of J coupling data has been published by Larina and lo pyre^.^ 'JCX couplings ( X z 2 H , 35Cl, 79Br, 1271) obtained on the basis of relaxation data for trimethylethynylsilane derivatives have been collected by Gryff-Keller' in his short review on the influence of a quadrupole nucleus on the shape of the signal of an adjacent spin 1/2 nucleus in high resolution NMR spectra of liquid samples. Applications of polarization transfer and indirect detection NMR spectroscopic methods based on 31Pin organic and organometallic chemistry have been reviewed by Lopez-Ortiz and Carbajo.' The review contains a large number of Jpx coupling data. 31Pchemical shifts and Jpp coupling data for a large number of variously substituted cyclotriphosphazenes have been collected by Wu and Meng" and analysed in terms of substituent effects. A review which covers the entire scientific literature of xenon NMR has been Nuclear Magnetic Resonance, Volume 28 0The Royal Society of Chemistry, 1999 151

152

Nuclear Magnetic Resonance

published by Ratcliffe. It contains an extensive updated tabulation of chemical shifts and J couplings. The problems of the NMR spectroscopy of molecules in the gas phase including the temperature dependence of couplings have been reviewed by LeMaster. I 2 A review on physical methods in carbohydrate research, which also included a section devoted to NMR investigations, has been published by Widmalm.I3 NMR studies on paramagnetic hemoproteins have been reviewed by YamamotoI4 with special emphasis on characterization of both structural and dynamic properties of the haem active site. Kleinpeter in his reviewI5 has pointed out that direct, geminal and vicinal proton-proton and proton-heteronuclei couplings are commonly used parameters for studying the conformation and configuration of satiirated six-membered oxygen containing heterocyclic rings.

2

Methods

New pulse sequences are being continuously designed in order to achieve precise coupling values and their signs. In particular, efforts have been made to characterize the structure of molecules of biological origin. The importance of good quality 3J homo- and heteronuclear couplings as restraints in obtaining NMR structures of proteins and protein complexes beyond 20.000 D (more than 250 residues) has been underlined in a short analysis given by Clore and Gronenborn. A novel experiment for the determination of homonuclear couplings called SIAM, Simultaneous acquisition of In-phase and Anti-phase Multiplets, has been proposed by Prasch et al. l7 The authors using BPTI showed that DQFSIAM sequence yields 2D spectra with a smaller overlap and more enhanced sensitivity than regular DQF-COSY. Uhrin et al.'* have proposed a modified version of the X ( q ) half-filtered TOCSY experiment for measuring long-range proton-heteronuclei couplings in compounds with natural abundance. The experiment applied for a trisaccharide and a heptapeptide yielded spectra with increased sensitivity and resolution. The same group also proposed sensitivity-enhanced 2D HSQC-TOCSY for long range n J H X coupling measurements. l 9 The psge-2D HMBC method for measuring long-range proton-heteronuclei couplings for compounds with natural abundance has been proposed by Sheng ~ ~ for raffinose. and van Halbeek2' and used by them to measure 2 y 3 J couplings Poveda et aL2' have shown that the difficulties in the characterization of the solution conformation of the compounds possessing C2 symmetry may be solved by the measurement of long range heteronuclear couplings with selective, DANTE-Z based, I3C NMR editing experiments. The authors applied this method to measure interglycosidic 3 J ~ 1 ~couplings 1j in the trehalose system. A new approach for measurements of homo and heteronuclear long-range couplings has been developed by Meissner and S a r r e n ~ e n It . ~ is ~ based on the exploitation of large JIs couplings for efficient conversion of homonuclear multiple-quantum coherence to longitudinal or observable I-spin magnetization

153

5: Applications of Spin-Spin Couplings

with no overall perturbation of the S spin. They have introduced it as new pulse sequence elements: spin-state-selective excitation (S3E) and spin-state-selective coherence transfer (S3CT). Two subspectra obtained by the use of these two new elements show a relative peak displacement which is suitable for easy extraction of homo- and/or heteronuclear couplings. The same group of authors applied (S3E) E.COSY-type experiments to uniformly 15N labelled N-terminal domain of RAP( 17-97) protein for extraction of small 3 J ~ u couplings23 ~ p and for measurements of 2 ' 3 J ~ a and ~ 3 J ~ cpo u~ p ~ i n g s ;(S3E) ~ ~ H(N)CA,CO experiment to 13C/15Ndoubly labelled NCAM(2 13-308) protein for simultaneous measurement Of 3 J H N H a and 3 J ~ couplings2s a ~ and (S3CT) E.COSY-type experiment to I5N labelled a 3 ( ~ 1 collagen ) for determination of 3 J ~ ~ H 2a . ,3 ~ H a Nand 3 ~ H p Ncouplings.26 The achieved precision of coupling estimation was about 0.2 Hz and very small, close to zero, values could be measured. A modified HNHB sequence has been used by Vuister and c o - ~ o r k e r sto~ ~ obtain the magnitude of 3JHNcouplings in "N labelled proteins. For PYP protein they measured 146 couplings of that type providing very precise cp,$ dihedral constrains. Using H(N)CA,CO-E.COSY experiments Riiterjans and coworkers28 have measured 246 3JHc and 3Jcc couplings for uniformly 13C/'5N labelled oxidized flavodoxin and recalibrated the angular dependencies for these couplings. Bax and co-workers have devised an [PAP [15N,1HI-HSQC experiment29 for the measurement of 'JHN and *JHNC, that produces the sum and the difference of complementary in-phase and anti-phase J-coupled spectra. As a result, the spectra contain only the downfield and upfield components of a doublet making an analysis possible even in the case when the measured proton-carbon coupling is smaller then the carbon linewidth. The U-l3C/I5N ubiquitin served as a model compound. Using the same protein this group have also developed a new quantitative J correlation experiment, 3D HNCG, for accurate measurements of 3 J ~couplings y ~ in uniformly I3C/I5Nenriched proteins.30 New pulse schemes for the exclusive measurement of 3 J ~and ~ 3yJ ~ y Ncouplings for C, containing residues in uniformly I3C/l5N labelled proteins have been developed in Kay's l a b ~ r a t o r y .The ~ ' underestimations of the measured couplings were found to lie in the range of 6Y0-9% for staphylococcal nuclease and the method of correcting the error was proposed. A new variant of the basic 2D-INADEQUATE technique which allows one to avoid rapid pulsing artifacts often observed in the conventional phase-cycled carbon-13 2D INADEQUATE spectra has been designed by Bourdonneau and An~ian.~~ An experiment which allows one to determine Jcc couplings at natural abundance of C- 13 (GRECCO, gradient-enhanced C-C coupling measurement) has been designed by Facke and B e r g e ~ - ;the ~ ~ method is based on a suitable signal selection (ge-SELTOCSY). Sich et have proposed a method of obtaining 3 J ~ couplings p from a set of spin-echo difference constant time HSQC spectra. Using the method for I3C/l5N labelled 19-nucleotide RNA hairpin they measured 70 couplings providing restraints for backbone angles p and E.

+

Nuclear Magnetic Resonance

I54

The incorporation of (5’R)- and (5’S)-deuterium-labellednucleotides in a DNA decamer has enabled Kojima et to assign unambiguously pro-R and pro-S protons at almost all 5’ positions. Thus, 15 3 J Hcouplings ~ between H4’ and H5‘/ H5” protons were measured, which was crucial in determination of the backbone torsion angles. Stereospecific deuteration at position H2” in two sugar moieties of 12 bp DNA has been done by Yang et ~ 1 and. demonstrated ~ ~ as a means of measuring very small but conformation indicative 3JHTH3, couplings (cu. 1-2 Hz) in P.E.COSY spectra of DNA. A simplified method for quantitative measurements of 3 J ~ has ~ been ~ a developed by Wang at ul. 37 They proposed the following relationship for TOCSY spectra: 3 J ~ ~ ~ , = 0 . 5 ( A v 1 / 2-) MW/5000 + 1.8 and for NOESY spectra: 3JHNHa=0.6(Av1/2) - MW/5000 - 0.9. The method tested on I 1 different polypeptides with 650 separate coupling measurements yielded couplings with the rmsd error of less than 0.9 Hz. However, one should remember that the molecular dependence of the coupling value may cause a problem. Zhang et d 3 *have proposed a novel procedure that uses intraresidue H-H distances as references for converting NOE intensities into distance restraints. In this procedure HN-Ha distances are calibrated against 3 J ~couplings ~ ~ aand the possible ambiguities are solved with the help of 3JHac couplings. A transformation algorithm applied to time domain data which yields multiplicity as a function of possible J values has been published by Bourg and N ~ z i l l a r dBy . ~ ~the use of this algorithm JHH couplings in m-bromonitrobenzene have been determined. A new method of analysing high-resolution NMR spectra based on the pattern recognition of the multiplet structure of NMR spectra has been suggested by Golotvin and C h e r t k ~ v . ~To ’ show its usefulness, they used this method to calculate the values and relative signs of the inter-ring JHH and JHC couplings in 1,2,3-trichloronaphtalene. The problems connected with correct analysis of ABX spectra have been extensively discussed by Edgar et ~ f . , ~who ’ used 2,2’-difluorobiphenyl as an example. Andrec and P r e ~ t e g a r dhave ~ ~ applied the Metropolis Monte Carlo sampling algorithm in the Bayesian parameter estimation formalism to accurately estimate couplings and their errors from antiphase doublets.

3

One-Bond Couplings to Hydrogen

New examples of cationic molecular hydrogen complexes of manganese have been recently reported by Albertin et The ‘JHD couplings of 32 Hz found by them for [Mn(q2-HD)(CO){P(OEt)3}4]BPh4 and [Mn(q2-HD)(CO){PPh(OEt)2}4]BPh4are typical values of the dihydrogen complexes. ~ of Protonation studies have been performed by Oldham Jr. et ~ 1on .a series new hydrotris(pyrazoly1)borate (Tp) dihydrogenlhydride of rhodium and iridium complexes of the form TpM(PR3)H2, M = R h , Ir. A weak temperature dependence has been observed for ‘JHD couplings. Additionally, lJHT couplings

5: Applications of Spin-Spin Couplings

155

ranging from 51.7 to 65.7 Hz have been reported for partially tritiated complexes. The existence of a linear correlation between the experimental 'JHB coupling values and the calculated complexation energies of the H3BL compounds (L = OH-, Ph2-, SH-, CI-, NH3 and Ph3) has been suggested by Anane et al.4S ' J H B couplings have been measured by Ezhova et al.46for 1-Li and l-Na(THF)*2,4-(SiMe3)2-2,4-C2B4H5;rather small I JHccoupling values have been observed in the spectra of these two compounds. The NMR parameters including JHB couplings have been used by Cendrowski-Guillaume and Spencer47in the studies on the interactions between SmI2(tetrahydrofuran)x and nido-pentaborane(9) compounds. The calculation and analysis of isotope effects on the nuclear spin-spin couplings of methane at various temperatures have been performed by Wigglesworth et aL4*The authors declare that their results are the most accurate ab initio results for the spin-spin coupling in any polyatomic molecule performed so far. The ab initio calulations performed by Kirpekar et al.49 have shown that rovibrational corrections are as important as the non-contact terms and must be included in accurate determinations of indirect nuclear spin-spin couplings of the molecules. The compounds studied were XH4, where X = C, Si, Ge and Sn. Afonin et al. have continued their studies on the stereochemical dependence of one-bond I J H C couplings in vinyl substituted heteroaromatic systems. The compounds studied were vinylpyridines. Calculations of N M R chemical shifts and J couplings including those across one H-C bond using the density functional theory approach have been performed by Hricovini et a/. 5 1 for the monosaccharide methyl-P-D-xylopyranoside. The 'JHC couplings have been measured by PongraEiC et a1.52for several acyclic analogues of purine nucleosides with dimethylaminoethyl and dimethylaminoethoxyalkyl side chains. A linear correlation between the changes induced by substituents on JHc couplings in polysubstituted furans and the inductive effects of substituents attached to the furan ring has been reported by AlvarezIbarra et ~ 1 . ~ ~ A large set of the NMR data has been obtained and analysed by Claramunt et al.54 for twenty-three 1-substituted pyrazoles in order to answer the questions how substituent effects are transmitted through the nitrogen atom and how aromaticity of the pyrazole ring is affected by N-substituents. The data include, among others, 3 J and ~ ~ 3 J coupling ~ ~ values. Recently, the mesoionic compounds have become a subject of live interest. A spectral characteristic of sixteen pyrazolo[ I ,2-a]pyrazole derivatives, which included a set of 3JH~ couplings, has been published by Claramunt et al? The IJHcSp2 couplings in these compounds cover the range of 154-205 Hz. J-coupled heteronuclear multiple quantum coherence method, JHMQC, has been applied by Marzilli and ~ o - w o r k e r sin~ order ~ to measure 'JHC couplings in the imidazole ring in the compounds of the general formula Me3BzmCo(DH)2CH3, where Me3Bzm = 1,5,6-trirnethylbenzimidazole and DH = the monoanion of dimethylglyoxime. The authors come to the conclusion that, for the assessment of electronic properties of the metal centre, the ' J H C couplings

'

'

'

I56

Nuclear Mugnetic Resonunce

appear to be a more reliable parameter than the traditionally used I3C chemical shifts. It is also worth noting that the standard coupled 1D I3C NMR spectra gave similar ' J values, but the JHMQC method gave a better resolution and much higher signal-to-noise ratios. A set of I 4 J couplings ~ ~ has been measured by Chimichi et al.57 for all four fully aromatic thiazolopyridine isomers and the values of lJHC compared with those in unsubstituted pyridine and oxazolopyridines. ' J H C couplings have been applied by Anderson et d 8 in their studies on stereoelectronic anomeric and homoanomeric effects on the axial and equatorial C-H bonds in 1,3-diazacycIohexanes and 1,5-diazabicyclo[3.2.lloctanes. I J HC couplings have been measured for seven salicylaldoximes and linear dependence on CT+parameter has been observed for 'JH3c3 and 'JHTc7 couplings.59 Conformational effects o n I3C NMR parameters in alkyl formates have been studied by de Kowalewski et This also included an analysis of 3 J H ~ couplings. I J HC couplings have been used to characterize two heterofullerene molecules, hydroazofullerene and cyanohydrofullerene.6' The effect of (po1y)amine and polyether ligands on the solution structure of [6Li]-~-(phenylthio)benzyllithium in tetrahydrofuran has been studied by Schade and B o ~ h e . This ~ ~ ,included ~~ measurements of I JHC couplings whose values varied considerably depending on the nature of the ligand involved. In particular, correlations between the chemical shifts of the para phenyl carbon C-5, the para phenyl proton H-5, the benzylic carbon C-1, and the proton-carbon coupling 'JH 1 ~ in1 [6Li]-a-(phenylthio)benzyllithium have been found to be useful probes in determining the charge distribution within the carbanionic fragment of the compound studied. A significant increase of this coupling can be interpreted in terms of rehybridization of the carbon from sp3 to sp2. A significant influence of the lithium substituent on the one-bond lJHC couplings in substituted (aminomethyl)lithium compounds, such as LiCH2N RR'exTHF: NRR' = NMez (x = 0), NNR' = NPhMe (x = 2), NRR' = NPh2 (x = 1 . . . 1 3 ) etc. has been found but not discussed by Becke et al.h4 The one-bond coupling, l J H C = 176 Hz, found in the coordinated benzene in the (q6-benzene)Fe(H)2(SiMeC12)2complex is substantially larger than that in benzene itself (157 Hz) and slightly smaller than the coupling in (q6-benzene)Fe(H)2(SiC13)2 ( 182 H z ) . ~ ~ A very small 'JHC coupling, of 178 Hz only, has been found by Haack et ~ 1 . for the ethyne ligand involved in the dabnNi(C2H2) complex, where dabn is the tertiary diamine N,N"dimethyl-3,7-diazabicyclo[3.3. llnonane. This is the smallest coupling of this type reported so far for a mononuclear nickel(0)-ethyne complex. The lJHC coupling of 142 Hz has been found in the analogous ethene complex, dabnNi(C2H4). A linear relationship has been found between 15N chemical shifts and one-bond 'J H N couplings measured by Hansen et al. 67 for a large series of "N enriched Schiff bases. Deuterium isotope effects on the I5N chemical shifts in these compounds plotted against the l J H N couplings have revealed a characteristic S-shape.

'

~

157

5: Applications of Spin-Spin Couplings

Two coupling values, ' J H N of 21.8 and 40.4 Hz, have been found by Klimkiewicz et al.68 for the protonated form of 4-nitro- 1,8-bis(dimethylarnino)naphtalene; the smaller value has been ascribed to the N1 atom and the larger to the N8 one. This result shows that the [NHN]+ structure in the studied compound is, as expected, unsymmetrical. The further compounds studied by this group of authors69 were three proton sponges 1,2-bis(dirnethylaminomethyl)benzene, bis(diethylaminomethy1)benzene and bis(diethylaminomethy1)benzene and their salts. The presence of a [NHN]+ structure in the perchlorate salts of these compounds has been deduced on the basis of the ' J H N coupling values measured at low temperatures. A study performed by Olah and co-workers7*on protonation of guanidine in superacid conditions included measurement of ' J H N and JCN couplings. A considerable difference has been observed between J H measured ~ for the -NH3+ and -NH2 groups, 79.5 and 99.7 Hz respectively. for a series of The I 3JHN couplings have been reported by Licht et nitrotriazoles in their studies on tautomerism of these compounds. Recent studies on proton-transfer equilibrating phenol-N-base systems including an analysis of the ' J H N couplings have been reviewed by S ~ b c z y k Low-temperature .~~ NMR studies on the salicylic acid complexes with 'N-enriched 2,4,6-collidine which included measurements of ' J H N couplings have been performed by Golubev et

'

a1.73

A full set of J HH, JHc and JHN couplings has been remeasured by the use of the modern NMR techniques for propiolamide, formamide and acetamide. This also included ' J H N couplings for cis and trans forms of all three corn pound^.^^ The "NMR study of coordinated amine, aminocarbyne and carboxamido The l J H N groups in triosmium clusters has been performed by Chen et couplings measured for the complexes Os~(CO)lo(p2-CONHi-Pr)(p2C=NHR) and Os3(CO)g(NH2i-Pr)(p2-CONHi-Pr)(p2C=NHR) (R = Pr, CH2Ph) fall in characteristic regions for each of the coordinated amine, aminocarbyne and carboxamido ligands. Two papers have been devoted to the NMR experimental and theoretical studies of hydrogen bonded clusters (HF),. A critical analysis of electronic density functionals for structural, energetic, dynamic, and magnetic properties of This also hydrogen fluoride species has been performed by Maerker et included the calculations of the lJHF coupling in H-F monomer and its oligomers. Liquid state 'H and 19F NMR experiments in the temperature range between 110 and 150 K have been performed by Shenderovich et al.77 on mixtures of tetrabutylammonium fluoride with H F dissolved in a 1:2 mixture of CDF3 and CDFZCI, which allowed them to measure for the first time both one-bond couplings, ' J H and ~ IJHPt and a two-bond coupling, 2JFF. The DFT calculation only qualitatively corroborated the presence of * J F ~couplings, rather a poor agreement between the DFT calculated J values and experimental ones having been observed. J H s i couplings have been determined for a large series of halogenated trisilanes X,Si3Hg-,, where X = Cl, Br, I and n = 2--7, and for some tetrasilanes H2XSiSiX2SiX2SiX2H.78

158

Nuclear Magnetic Resonance

An analysis of the NMR spectra of the ruthenium trihydride adduct with the (C~H which reveals exchange Ag cation, [ { R u ( ~ - C S M ~ S ) H ~ [ P11)3]}2Ag]BF4-Et20, H,H couplings included determination of the H-'"'Io9Ag couplings whose values were between 70 to 85 H z . ~ ~ The NMR characteristics have been reported by Concolino et a1.80 for W 2 ( p H)2C14(p-dppm)2 complex (dppm = bis(dipheny1phosphino)methane); it included 'JHWof 108 Hz and 'Jpw of 126 Hz. The NMR characteristic of several novel neutral diplatinum complexes [Ptz(pX ) ( P - H ) ( C ~ H ~ ) ~(X=C L ~ ] = CPh, C6F5, C1; L = PPh3, PEt3) also included lJHR couplings whose magnitudes are in the range previously found in other hydridediplatinum derivatives (515-642 Hz).*' lJDc couplings of perdeuterated 3,5-dimethylpyrazole and 3,Sdiphenylpyruole have been measured and their values compared with those of the unlabelled compounds by Jimeno et a1.82

4

One-Bond Couplings Not Involving Hydrogen

6Li-'3C couplings have been applied by Sekiguchi et al.83in elucidation of the solution structure of the tetraanion tetralithium with 8 centre/l2 electron xsystem obtained by reduction of octasilyltrimethylenecyclopentene with lithium metal in THF. The reports on the couplings between 6Li and "N nuclei in organolithium clusters stabilized through coordination with donor ligands such as e.g. N,N,N"'-tetramethylenediamine (TMEDA) are very scarce. Recently, Hiils et aZ.84have reported the observation of such couplings in the 2:2 aggregate (Figure 5.1) which was obtained in the reaction between 1,3-bis(dirnethylaminomethyl)2,4,6-trimethylbenzene and n-butyllithium; JLiANA = 3.6 Hz and JLiBNB= 4.2 Hz have been measured. A scalar coupling of this type has been detected so far nearly exclusively for lithium amides.*'

L

Figure 5.1

lJBpcouplings of ca. 139 Hz have been reported for ditymidine boranomonophosphate.86 Also 2JHBp and lJHB couplings have been measured for this compound, their values being 22.0 and ca. 105 Hz, respectively.

159

5: Applications of Spin-Spin Couplings

Jokisaar?' and his group have continued their studies on determination of spin-spin couplings in small molecules by the use of liquid-crystal NMR. The results of the experimental and theoretical ab initio study of the 'JCC coupling tensors in ethane, ethene and ethyne have been published recently by this group of authors. An ab initio calculation of the NMR shielding and spin-spin couplings of fluoroethene has been performed by Helgaker et This also included 'JCC coupling whose theoretical value of 94.0 Hz is very close to that estimated on the basis of the experimental data and the additivity rule, 93.0 H z . SCPT ~ ~ INDO calculations of I Jcc couplings have been performed by Krivdin and his coworkers for a series of sterically strained bicyclopentanes and bicyclohe~anes,~~ for tricyclopentane~'~ and for small heterocycle^.^^ Recently, Warmuth has made a great effort to measure 'JCC couplings for obenzyne, an interesting but very unstable molecule.93In an elegantly performed experiment the totally I3C-enriched o-benzyne has been trapped in a molecular container and its 13CNMR spectrum (AA'MM'XX system) measured at -98 "C. An analysis of this spectrum yielded the following coupling values: ' J c l C l j = 177.9, 1 1 IJCIc2= JcI,czr = 75.7 Hz, 1Jc2c3 = 1Jc2.c3' = 50.9, Jc3c3, = 71.0 Hz, which has been interpreted by the author in terms of o-benzyne having a cumulenic character and being dominated by the mesomeric structure b (see Figure 5.2).

Figure 5.2 The stereospecific influence of the Nf-O- group on 'JCC couplings in nonaromatic amine oxides has been studied by Potmischil et al.94 IJCc couplings have been measured for a series of (E)-2-alken-4-yn-1-oh, (9-2alken-4-yn- 1-yl acetates and (9-2-alken-LC-yn- 1 for several mono-, di- and t r i n i t r ~ a l k a n e s ,and ~ ~ for I3C-enriched indole and t r y p t ~ p h a n e ;(the ~ ~ latter paper was overlooked in our earlier reports). Serianni and his c o - ~ o r k e r shave ~ ~ continued their studies on the application of n J and ~ ~n J H ~couplings in conformational studies of carbohydrates; 37 couplings have been measured for methyl P-D-ribofuranoside and methyl 2deoxy-P-D-erythro-pentofuranosideby the use of I3C-enriched samples. The influence of the conformation on the coupling values has been carefully analysed. Kiistermann et al.99 for the first time used 'JCc couplings in measurements carried out in vivo. Since the occurrence of a l3C-I3C segment in compounds at natural abundance has the probability of 0.012% only, the lJCc couplings are usually not observed. When a I3C-l3C segment is artificially introduced into the molecule it leads to characteristic doublets of IJCc coupling that can be readily distinguished in the carbon spectrum. This property of labelled C2 segments

I 60

Nucleur Magnetic Resonance

allowed the authors to measure [5,6-'3C2]ascorbic acid formation in a rat liver using in vivo NMR technique after infusion of doubly labelled [ 1,2-13C2]glucose. 2D INADEQUATE spectra have been applied to assign the I3C spectra of sarsasapogenin, steroidal sapogenin, loo trans and cis myrtanol, lo' several parasubstituted benzaldoximesIo2 and to reinvestigate the structure of galbanic acid. A solvent dependence of one-bond coupling between the carbon nucleus of the cyano group and the nitrogen nucleus has been reported by Stringfellow and Farrarlo4 for isocyanomethane. Any possible solvent or temperature dependencies for the other spin-spin coupling parameters were within experimental uncertainty . Ultrahigh resolution I5N NMR spectra have been recorded by Wrackmeyer and Kuph105for a series of nitrogen containing compounds with a purpose to determine the precise 'JCN values and their signs; the couplings vary from - 50.40 Hz in MeNCS up to +4.10 in t-BuNSO. IJCN couplings have been a great help in fullerene carbon resonance assignments and location of the sp3 carbon atoms of (C59N)2*106 102 out of 103 IJCN couplings have been measured for [U-'3C/15N] RNase T1 by Pfeiffer et al. Io7 Ten of them revealed raised values corresponding to the water molecule binding to the neighbouring carbonyl group, and five showed decreased values which corresponds to the amide NH involvement in hydrogen bonding with water. The results allowed the authors to demonstrate that part of the water molecules observed in crystals is also bonded in the solution and to support the existence of a chain of water molecules in the interior of the protein which serves as a space filler. The literature data on the calculation of the coupling constants in formaldehyde have been reviewed by Bruna et al.'O8 It is of interest to note that in the case of the 'JCo coupling the PSO contribution is greater than the Fermi contact term, 26.7 and 21.2 Hz, respectively; this is rather a non-typical situation as far as the couplings across one bond are concerned. A correlation between the IJCF couplings and the degree of interaction between C F units and the alkali and alkali earth ions has been observed for the fluorophane cryptands by Plenio et al. Io9 The largest decrease (from 262 to 232 Hz) has been found for the lithium complex of 1,10-diaza-25,26-difluoro-4,7dioxatetracycl0[8.7.7~~.'~. 1 '9.23]hexaeicosa-12,14,16(25),19,21,23(26)-hexene. The 'JCF couplings have been measured for a large series of cyclopentadienyl-, indenyl-, and fluorenylbis(pentafluoropheny1)boranes and their titanium and zirconium complexes. lo The spectroscopic data including Jcsi couplings have been reported by Wrackmeyer et al. ' I for a series of newly synthesized 1,2-dihydro-l,2,5-disilaborepines; the typical coupling values have been found for both Csp3 and Csp2 carbons involved. The 'JcSi couplings of 50-70 Hz found in the spectra of organometallic derivatives such as NaC(SiMe3)(SiMe2Ph)2TMEDA (TMEDA = tetramethylethylenediamine), KC(SiMe3)(SiMe2Ph)2, RbC(SiMe2Ph)3 and CsC(SiMezPh), have been invoked by Eaborn and co-workers1I2as evidence that these compounds

'

161

5: Applications of Spin-Spin Couplings

in solutions, as in the solid state, contain carbanionic species with a significant delocalization of the negative charge over the almost planar CSi3 skeletons. A series of tetraamide esters of methylene- and (dichloromethy1ene)bi.sphosphonates of the general structure (Zl)(Z2)P(O)CX2P(O)(Z3)(24) where Z1 = OAlk, 2 2 , Z 3 , 2 4 = OAlk or NAlk2 and X = H or C1, has been characterized by the use of 'Jcp couplings, which were found to be sensitive to the number of amino groups attached to the phosphorus atom. A significant decrease in the coupling value has been observed in the order, P(O)(OAlk)2, 'Jcp = 150 Hz, P(0)(OAlk)(NAlk2), Jcp = 123 Hz, and P(O)(NAlk&, I Jcp = 105 Hz. l 3 The example of a phosphorylide-mediated vinyl polymerization has been reported by " ~ presence of the intermediate compound of the ylide type Baskaran et ~ 1 . The containing C=P bond has been proved by the presence of the large 'Jcp coupling of 134.5 Hz typical of the ylide bond. C-35Cl and C-37Cl couplings have been measured by Torocheschnikov and Sergeyev' I 5 for some chloroorganic compounds. The determination of the spin-spin couplings between spin-1/2 nuclei I and quadrupolar nuclei S with spin >1 can be accomplished either via a lineshape analysis of the solution spectra or by solving high-resolution solid-state spectra. Both approaches have been recently applied by von Philipsborn and his group'16 in order to determine 'JCMn and 'JpMn couplings in some organomanganese complexes of the type Mn(CO)5-n(R)Ln,where L = PPh3 or PAlk3. An excellent agreement between the solution and the solid state data has been observed. The influence of substituents on these couplings has been also studied by the same group of and a large dependence has been observed for the axial (CO) ligands. An analysis of the very complex higher-order 13C NMR spectra recorded for the square-planar silver (111) anions, [Ag(CF3)4]- and [Ag(CF2H)4]-, allowed Eujen and Hoge"' to determine all the possible couplings for these two anions including their signs; this included lJCAg couplings of - 120.0 and -88.5 Hz, respectively and cis and trans 4 J couplings ~ ~ for both anions, the trans couplings being considerably larger than the cis ones. 4 J ~ couplings ~ n have been measured by Wharf and Sirnard"' for variously substituted Ar4Sn and Ar3SnX compounds where X = C1, Br, I and the magnitude of the couplings across one bond interpreted in terms of ortho, meta and para subst i tuen t effects. A new classification of solvents has been developed by Grishin et a1.,I2O who applied a cluster analysis for this purpose. The 'JCSn coupling and the Sn chemical shift of tetramethyltin and I/& ( E denotes the dielectric constant of the solvent) were included in the solvent description. 'JCSn couplings reported by Wrackmeyer et a1.'21 for a series of the [p2-,q2alkyne-hexacarbonyldicobalt]organotin complexes cover the range from - 19.0 up to (-)565.5 Hz, but no explanation of this fact has been given by the authors. 'JCSn couplings have been determined by Pettinari et a1.'22 for several dialkyltin( IV) complexes of the Alk2SnQ2type, where (Q)- is 1-phenyl-3-methyl4-trichloroacetyl-pyrazolon-5-atoor 1-phenyl-3-methyl-4-metoxy-pyrazolon-5-

'

'

'

I62

Nuclear Magnetic Resonance

ato ligand. The couplings have been used by the authors in order to estimate the C-Sn-C angles. Yasuda et al. 123 have continued their studies on the reactivity and selectivity of tin compounds of the general formula, R1C(0)CHR2SnBu3,which can exist in the form of four- and five-coordinated enolates. The equilibrium between these forms strongly depends on the nature of the ligands (Bu4NBr or HMPA) involved and on the tin compoundligand ratio which is reflected in considerable changes observed in the Sn chemical shifts and 'JCSn couplings. The density functional theory (DFT) calculations have been carried out by Kaupp et ~ 1 . onl ~some ~ simple iodo compounds as iodoethane, iodoethylene, iodoacetylene and iodobenzene providing, among others, 2JCrcoupling values; the absolute 'JcI value calculated for iodoacetylene agrees well with the experimental value reported by Gryff-Keller' for trimethylsilyliodoacetylene. According to the authors, a simple analogy exists between spin-orbit-induced heavyatom effects on NMR chemical shifts and on the spin-spin coupling. A reasonably good correlation has been observed by Abou-Hamdan et al. 125 between the absolute (IJCwl coupling values measured for the equatorial cyano ligands of [WO(X)(CN)4]"- complexes (X = 02-,CN-, OH-, CN-, F-, py etc.) and the CN-W bond lengths obtained from the X-ray crystallographic data. Only one example of a 1Jc,p30scoupling has been reported in the literature so far; a coupling of 56.6 Hz has been found by Michelman et ~ 1 . for l ~(p~ ~yrnene)Os(CH(C02Me)~)(NH-t-B~). Two other examples have been reported ; ~ ~ of ~ 48.9 and 51.5 Hz have been measured by recently by Gisler et ~ 1 .couplings them for CpOs(C0)zMe and Cp*Os(C0)2Me, respectively. A paper has been devoted by Wrackmeyer12' to the determination of all possible couplings and their signs in (ethene)bis(triphenylphosphane)platinum(O) complex. In particular, lJCpt of a positive sign and equal to 196.0 Hz has been found by the author. High resolution solid state 13C MAS NMR measurements performed by Ding et al. 129 for potassium tetracyanoplatinate (11) trihydrate (K2Pt(CN)4.3H20) revealed that anisotropy for the Jcpl coupling in this compound is equal to zero; I JCPtiso = 5 17 Hz. The factors governing the 'JCpb coupling values in aromatic lead (IV) compounds of the type (C6H&PbR, R=alkyl, alkenyl and alkynyl, have been thoroughly discussed by van Beelen et al.13' The values of the 1JC.7p20ro,npb couplings increase monotonically in the order R = alkyl, alkenyl and alkynyl, ca. 350 Hz, 490 Hz, 670 Hz, respectively. However, the trends observed in I JCsp3Pb= 363-404 Hz, I J ~ ~ =~126-468 2 ~ bHz and JcspPb = 3 1 - 121 Hz are less regular. One-bond 14N-Sn and 14N-Pb couplings have been obtained by Wrackmeyer and Weidinger131 for bis[9-(9-borabicyclo[3.3.l]nonyl)-trimethylsilylamino] derivatives of tin(I1) and lead(I1) respectively; 'J(I4N-Sn) = 234 Hz and IJ(14NPb) = 355 Hz. The coupling found in the 9,(9,borabicyclo[3.3.l]nonyl)trimethylsilylaminotrimethyltin(1V) is substantially smaller, 'J(14N-Sn) = 14 Hz only. lJNsi and 'JCsi couplings have been measured for a series of trisilyl amines by Wrackmeyer et al. and considerably smaller values have been found for

'

163

5: Applications of Spin-Spin Couplings

[Me2(Br)SiI3N than for the other compounds studied, such as [Me3Si)3N or [Me2(HC=C)Si)3N. This result has been invoked by the authors as proof that SiBrSi bridging exists in the [Me2(Br)SiI3Ncompound. The lJNsi couplings of ca. 1.5 Hz have been reported by Wrackmeyer et al. 133 for two N-trimethylsilylaminotitanium trichlorides. I JNsicouplings of the range for a series of cyclic silylamines 8.6-16.5 Hz have been found by Mitzel et such as e.g. 1-isopropyl- 1-aza-2,5-disilacyclopentane, 1-isopropyl- 1-aza-2,6the disilacyclohexane and 1,5-diisopropyI- 1,5-diaza-2,4,6,8-tetrasilacyclooctane, compounds in which no aryl and/or stabilizing alkyl substituents attached to the silicon atoms are present. 'JNp couplings have been determined for 1 1 cyclic and non-cyclic phosphoramidates by Modro et af.135 and their magnitude interpreted in terms of the hybridization of the nitrogen atom involved. The coupling values were rather large, ranging in most cases from 23.9 Hz up to 65 Hz. However, in the case of I-ox0-2,8diphenyl-2,5,8-triaza-l-phosphabicyclo[3.3.O]octane (Figure 5.3) 'JNp = 5.7 Hz has been found for the bridgehead nitrogen atom. This is the smallest ' J N p value for the nitrogen-containing phosphoryl compounds reported so far.

Figure 5.3

Newly developed inverse detection techniques offer one a unique possibility to measure 15N NMR spectra at natural isotope abundance, with rather diluted samples and, what is important, using short measuring times (ca. 1 hr). The J N R h couplings across one bond have been measured by Hopp R e n t ~ c hby ' ~ the ~ use of gradient-selected (1 H,lSN)HSQC experiments for a large series of XRh(III)(Hdmg)2L rhodoximes (Hmdg = dimethylglyoximate, L = PPh3 or pyridine, X =halide, alkyl or haloalkyl). ' J N R h = 18-21 Hz have been found when the equatorial oxime nitrogen atoms were involved, and ' J N R h of cud 6-9 Hz (X= alkyl) for the axial pyridine nitrogen. An increase of the latter couplings up to 16- 18 Hz has been observed in the halide complexes. The ' J N R h couplings have been measured by Della Pergola et for two iron-rhodium mixed-metal nitrido-carbonyl clusters, [Fe5RhN(C0)15]2- and [Fe4Rh*N(CO)i5]-, ' J N R h of 8 and 9 Hz, respectively, the value slightly larger than that observed for [Rh6N(CO)I~]-(6 Hz). An especially interesting set of coupling data has been obtained by Wrackmeyer and coworker^,'^^ who measured 'JNSn couplings for triorganostannyl (R$n)-substituted pyrroles and indoles and for N-trimethylstannylcarbazole. The coupling values varied from k14.8 Hz up to 143.1 Hz, the largest absolute values being observed for R = t-butyl. This dramatic increase of the absolute J value has been interpreted by the authors in terms of steric interactions occurring upon the introduction of the bulky tertiary butyl group.

164

Nuclear Magnetic Resonance

'JNptcouplings have been collected by Nagao et al. 139 for platinum complexes with various dipeptides including those with diglycine. Platinum(I1) complexes of para-substituted 4-phenylthiosemicarbazides, RPhNHCSNHNH2 (R = H, CH3, Br, F, NOz) studied by Arendse et a1." exist in solution as mixtures of cis and trans isomers with the trans isomer prevailing. The lJNpt coupling of 238 Hz observed for the I5N enriched [Pt(p-BrPhNHCS'5NH15NH2)2]C12complex which dominates in the DMSO solution provided unequivocal evidence for its trans structure. The 'JNpt couplings were a useful source of information on the structure of platinum ammine complexes including the platinum oxidation state in a study performed by Barrie et aE.14' The spectral characteristic for tri(tert-buty1)plumbyl-amine and its N-phenyl and N-dimetylsilyl derivatives has been published by Herberhold et aI.I4* This included 'JNpb coupling whose values for these compounds were +343.2 Hz, 450.2 Hz and 372 Hz, respectively. for hexacoordinate The 'JFSi couplings have been reported by Kane et silicon(1V) porphyrin complexes, (Por)SiF*, where Por = the dianions of octaethylporphyrin, tetra-p-tolylporphyrin, tetraphenylporphyrin and tetrakisb(trifluoromethy1)-pheny1)porphyrin. Despite the fact that the electron-donating abilities of the porphyrin rings in these complexes vary, practically constant coupling values have been observed, 'JFsi = 205 k 2 Hz. Two substantially different J F T ~coupling values have been observed by Casteel et ~ 1 . in' N(CH3)4+T~02F4~ (see Figure 5.4), the coupling between the Tc nucleus and the cis fluorine atom being considerably larger than that between Tc and the trans arranged fluorine; in other words, 27r1J~,,.0,,~c T I - ' and 2 7 1 ' J ~ ~ , , ~ ~ z T I- I . As a result, the F,,,,, and F,,, nuclei which are in two different chemical environments exhibit a large difference in their degree of quadrupolar collapse. The Tc03F3(CH3CN is the only other compound where a similar phenomenon has been observed.

Figure 5.4 The structure and solution chemistry of a fluorotris(dimethy1tin)disalicylaldoximate complex containing one seven-coordinate and two five-coordinated tin atoms with a fluoride anion bridging the five-coordinate tin atoms (see Figure 5.5) have been studied by Meddour et a1.'45 In the spectra of this compound two large 'JFSn couplings of ca. 1300 Hz to five-coordinated tin atoms are observed. The coupling to the Sn(2) tin atom disappears when, in solution, the nucleophilic substitution with weak nucleophiles like water and methanol takes place. This

165

5: Applications of Spin-Spin Couplings

result provides evidence that the entering nucleophile is bound to this tin atom. The presence of the JFsn(3)coupling in the spectrum of the intermediate indicates that the fluorine is still linked to the Sn(3) atom.

Figure 5.5 lJS,s, couplings ranging from 129.3 Hz to 161.3 Hz have been found for substituted aminosilanes, Me(EtzN)2SiSMe(EtzN)R (R = C1, vinyl, P-allyl), and olefinic chlorodisilanes, Me(R)C1Si-SiMeC12 (R = Et2N, P-allyl, vinyl). 14' The influence of different side chains on the 29Si chemical shifts and the 'Jsisi couplings in methyl-, phenyl-substituted tri- and tetra-silanes has been studied by Notheis et a1.147 The possibilities of estimating the 'JSip couplings in the 29Si CP/MAS NMR spectra of phosphorus-bearing organosilicon compounds have been discussed by Sebald and her co-workers; the main conclusion of this work is that the J values obtained for the solid-state are very close to those derived for solution.'48 A full set of coupling data which included 'JsiP and 'Jmn couplings and their signs has been determined for two 2,5-dihydro- 1-phosphonia-2-stanna-3-boratolesby ' ~ ~ couplings are positive and the authors draw our Wrackmeyer et ~ 1 . Both attention to the fact that the negative sign has been attributed (most probably erroneously) to 'JSip in a recent t e ~ t b o o k . ~ Two ' J s , ~couplings have been observed by Kollegger et al. I5O in the 29SiNMR spectrum of decamet hy 1-1,4-diphospha-2,3,5,6,7-pentasilabicycl0[2.2.1]heptane, P*(SiMe2)5. 'Jsip of 51 Hz has been measured for the Si-atom which is bonded to two P-atoms and lJSip of 51.7 Hz for the Si-atoms which are within the sixmembered ring. The large 'Jsiw couplings have been observed by Ueno et al. 1519152for donorstabilized bis(sily1ene)tungsten complexes: CpW(CO)2(SiMe3)(=SiMe2.base) (see Figure 5.6), 'Jsiw = 121 Hz (base = HMPA) and lJsiw = 132 Hz (base = THF)IS2 and for CpW(CO),{(SiMe2). .Do.. .(SiMez)>, 'Jsiw = 91.5 Hz (Do = NEt2) and 99.3 Hz (Do=OMe).15' These results have been invoked by the authors as the evidence of the partially double character of the Si-W bond. Considerably smaller 'Jsiw couplings, of 41.8-64.1 Hz only, have been reported for structurally similar silyltungsten complexes in the literature. 153,154 'JSipb, 'JSnpb and 'Jpbpt, couplings and their signs have been determined by

I66

Nuclear Magnetic Resonance

&ma

= HMPA or THF

Figure 5.6

Herberhold et al. for tri(tert-buty1)plumbyl-silanes, tri(tert-buf r1)plumbyl-sta Inanes and hexaorganodiplumbanes, respectively. The Jpbpb couplings are negdtive; their absolute values are very large and vary between 6386 and 9200 Hz. An analysis of A2A'MX performed by Heckmann et for a phosphorus-tin cage molecule, P4[Sn(C6H5)2]3 with an extremely shielded 3'P nucleus gave a full set of couplings for this compound including lJPp and I JPSn couplings. New examples of lJpcu couplings obtained from 31PCP MAS spectra have been reported by Asaro et al.'57 The compounds studied were [CUS~CPh(PPhd21, [{CuS2C-pT}4(PPh3)2], [{CuS2C-Ph}4(PPh3)21, [CuS2C-Ph(dPPm)lz and [Cu02C-Ph(dppm)12, where T = tolyl and dppm = bis(diphenyphosphin0)methane. The coupling values are between 1160 and ca. 1500 Hz, which reflects a covalent character of the copper-dithiocarboxylatebonding. Two different 'Jpy couplings have been observed in the spectrum of dimeric yttrium tris[bis(trimethylsilyl)phosphanide]: the 'Jpy couplings for the triply coordinated terminal phosphorus atoms are 122.4 Hz and for the p-coordinated phosphorus atom of 56.7 Hz only;15*(see Figure 5.7).

'

Figure 5.7

A JPRh coupling of 188 Hz has been found in the 31P NMR spectrum of the mixed ruthenium-rhodium carbonyl cluster complex, [Ru3Rh(CO)I2(PPh3)]-, providing evidence that a direct P-Rh bond exists in this compound.'59 The JPPt couplings are a very useful parameter characterizing platinum complexes. Their magnitude strongly depends on the state of oxidation of the PtP bond, the couplings in the Pt(IV) compounds being considerably smaller than

'

5: Applicutions of Spin-Spin Couplings

167

those in Pt(1I) species, which is in accord with the reduction in the s-orbital character in the Pt-P bond upon oxidation of the square planar Pt(I1) bond to octahedral Pt(1V). This relationship has been recently observed by Connolly et ~ l . , ' who ~ ' studied a series of Pt(I1) and Pt(IV) complexes involving tetradentate diphosphadithia ligands; thus, for example, in complexes [Pt(L)](PF& and [PtC12(L)](PF6)2where L = Ph2P(CH2)2S(CH2)2S(CH2)2PPh2the observed coupling values were 3 130 and 1410 Hz, respectively. A careful analysis of the 'Jppt couplings has been performed by Rademacher and his co-workersI6' for three chird platinum (11) complexes with phosphorus derivatives of the amino acid L-proline. The compounds studied were Pt(P-P)C12, where P-P were (S)-l-diphenylphosphino-2-(diphenylphosphinomethyl)pyrrolidine, (S, 27)-1 , l '-bis(diphenylphosphino)-2,2'-bipyrrolidine and (5')-I -diphenylphosphino-2-(diphenyIphosphinoxymethyl)pyrrolidine; the authors came to the conclusion that the coupling values are dominated by the Fermi contact term and vary mainly with the electron density in the platinum 6s valence orbital. A correlation between 'Jppt coupling values and Hammett substituent constants has been studied by Cobley and Pringle'62 for phosphites and phosphines coordinated to platinum (11) and platinum (0); two opposite trends have been observed. The more electron-withdrawing the substituent the larger the Jppt has been found for Pt(0) and vice versa for Pt(II), the more electron-withdrawing the substituent the smaller the 'Jpp, coupling value. A dependence of the 'Jppt values upon the size and the 0-donor ability of the ligands has been observed by Romeo et a1.'63 in complexes obtained upon substitution of the chlorine atom by various phosphines in the cyclometalated complex [Pt(N-N-C)CI] where N-N-CH=6-( 1-methylbenzyl)2,2'bipyridine. The 'Jppt couplings have been measured by McCaffrey et al. for the products of the reactions of five-membered ring complexes [Pt(SCHRC02)(PPh3)2 (R = H or Me) and [Pt(SC6H4C02)(PPh3)2] with a range of metal cations; the changes observed in their values have been discussed in terms of coordination to various metal halide moieties. One of the smallest 'Jppl couplings observed so far for a phosphorus trans to a The coupling carbon atom, 'Jppt = 861 Hz, has been reported by Bennett et was measured for the cis-[Pt (C,H4(PPh2)-2}(q1-CgH9)(PPh3)]complex obtained during studies on orthometallation of the Pt(PPh3)z complex of benzyne C6H4. The 'Jppt couplings have been measured by Wrackmeyer and Sebald'66 for complexes obtained as the products of the reaction between I -alkynylplatinum complexes and trialkylboranes, and by Tanase et al. '67 for linear complexes, [Pt2M(pdpmp)2(XyINC)2](PF& and for A-frarne ones [Pt2M(pdpmp)2(RNC),] (PF6)2, where M = Pt or Pd and R = Xyl o r Mes. The solid state 'JMnSn couplings and nuclear quadrupole couplings have been measured by Christendat et al. 168 for a series of para-substituted triaryltin(pentacarbony1)manganese complexes, (para-XC6H4)3SnMn(CO)S; the couplings range from ca. 130 to 250 Hz and ca. -8 to 21 MHz, respectively and reveal inverse linear correlation, which has been attributed by the authors to the dominance of the Fermi contact contribution to the 'JMnSn couplings. I J(Se-203'205T1), J(Te-203/205T1) and 2J(203'205T1-203/205T1) couplings have been

'

Nuclear Magnetic Resonance

I68

determined by Borrmann et a1.'69 in the seleno- and tellurothallate anions, T12Chz2-,and furthermore re-calculated into the relativistically corrected reduced couplings, K(Se-TI)RC, K(Te-T1)RC and K(TI-TL)RC. It has been concluded by the authors that the magnitudes of K(Se-Tl)RC, K(Te-TI)RC are consistent with pure p-bonded rings, whereas the magnitudes of K(TI-TL)RC indicate significant s electron density along the TI.. .TI axes. It is of interest to note that the 'JTeTl couplings with their values of ca. 16000 Hz belong to the largest couplings observed. A 'JRhTe coupling of 65.9 Hz has been observed by Badyal et ~ 1 . ' ~ in ' the spectrum of the coordination complex of 2-telluraindane with rhodium, [(Cp*Rh)(C8HsTe)][03SCF3]2. This result has been invoked by the authors as evidence that the metal is directly bonded to the tellurium in the ligand and not to the aryl ring. A coupling 'JAgSn of 2951 Hz has been observed by Hitchcock et uf.17' in the spectrum of [(Ag(SCN){Sn(CHR2)2})(THF)2](Ag-Sn', Ag'-Sn), and a coupling of 4632 Hz in the spectrum of (l/n)[(Ag(CN){Sn(CHR,)2})n]. These are the first examples of 'J( '09'107Ag-Sn)couplings reported in the literature. The 'JTept couplings of 658-704 Hz found for [PtL2](C104)2 and [Pt(PPh&L2](C104)2 complexes, where L = 2-(phenyIteIluromethyI)tetrahydro2H-pyran or 2-2 {4-methoxyphenyltelluoroethyl})1,3-dioxane, have been invoked by Batheja et af.172 as evidence that the compounds have the trans structure. The first example of a one-bond coupling between Sn atoms of different valence has been reported by Cardin et af.,'73who observed it in the 'I9Sn{'H) NMR spectrum of the divalent-tetravalent compound, [Sn(2-{(Me3Si)2C}C5H4N){Sn(SiMe3)3}];'J('17Sn-Sn) of ca. 6400 and 'Jsnsnof ca. 6700 Hz have been found. 'J( 17Sn-Sn) couplings have been measured and thoroughly discussed by Shibata et al. 174 for a new series of oligostannanes, X-n-Bu2Sn-[n-Bu2Sn],-tBu2Sn-[n-Bu2Sn1,-Sn-n-Bu2CH2CH20Et. Dramatic perturbations, which were not always clear, have been observed in the 'J(' 17Sn-Sn) couplings across the SnSn bonds with t-butyl groups attached, relative to the per-n-butyl derivatives. A new series of four binuclear platinum-thallium cyano compounds containing a direct and unsupported by ligands metal-metal bond of the general formula [(NC)~P~-TI(CN)~_I]'"-''(n = 1-4) has been prepared by Maliarik et al. 17' The 'JplTl coupling of 71060 Hz found for the compound [(NC)SPt-TI] is the largest reported coupling between two different nuclei.

'

5

Two-Bond Couplings to Hydrogen

A new method which allows one to determine the sign and the magnitude of the geminal scalar couplings between two enantiotopic protons in a methylene group It involves measurements of the spectra in a has been designed by Merlet et polypeptide liquid crystalline system such as poly-P-(benzyl-L-glutamate)where a magnetic equivalence of prochiral nuclei is removed. The method has been applied to measure the couplings in the spectra of several linear alcohols, which

169

5: Applicutions of Spin-Spin Couplings

gave the 2 J H H values very close to those obtained from an analysis of the proton spectra of selectively deuteriated compounds. An influence of the oxygen lone pair and the ring strain on the geminal protonproton coupling magnitude has been recently reported by Camps et af.,1777178 and extensively studied by Upadhyaya et af.'79 It has been reported by these authors that the geminal couplings of the ring methylene protons of the five-membered ring ketals are of the order of 8 Hz, while those of the exocyclic hydroxymethyl methylene protons are always larger, approaching 12 Hz (see Figure 5.8). A dependence of geminal 2JHH and 2JHp couplings on the specific intramolecular C-H-X interaction has been studied by Afonin et uf.I8Oby the use of ab initio calculations. *JrnCI. 12

1

CI'

Figure 5.8

~ ~ has been determined for a series of new esters A set of 4 J couplings and for crown derived from 2-methyl-2-azabicyclo[2.2.2]octan-5-syn(ant~)-ol~~~' ether derived from resorcinol, dibenzo-26-crown-8, with two 0-C-C-0 units possessing unusual trans geometries. Enaminones are a very interesting group of compounds, which, due to the low energy barriers around the C=C double bond and the relatively high one around the C-C and the C-N single bonds, can exist in the form of various configurational and conformational isomers. Recently, Gomez-Sinchez and his L'Uworkers'83 have published the results of their studies on the NMR spectra of several 3-aminoacroleins measured in various solvents. This included a set of 2.3 J HC and 3 + 4 J couplings. ~~ In polar solvents the compounds exist, as expected, in the E-E-E form. Two short reviews (in Japanese) have been written by Murata et al. 184,185 on the methodology devised for configurational assignments of acyclic structures in natural products or synthetic compounds. The method which allows the elucidation of the relative configuration of the compounds under study is based on the combination of 2 ' 3 J and ~ ~ 3JHH couplings without referring to NOE experiments. The authors emphasized that conventional methods based on NOE effects often suffer from the ambiguity in assigning the configurations of compounds with acyclic structures and conformational alternation. The compounds studied were maitoxin, okadaic acid, fumonisin B2 and filipin 111. A large 2 J D o ~coupling of 8 f 1 Hz has been found by Klug et af.'86 for the dihydrated sodium salt of hydrogen bis(4-nitrophenoxide) which corresponds to

I 70

Nu cleur Mugnet ic Resonance

2 J H ~=C52 Hz. The measurements have been performed for the solid state phase using Terao's approach.Ig7This result combined with the results of REDOR l3C NMR experiments with D dephasing for the single I3C-l resonance allowed the authors to come to the conclusion that the bridging hydrogen (or deuterium) in this compound oscillates rapidly between the two basic oxygen sites. The stereospecifity of the 2JHNcouplings has been used by MarekIg8 to establish the configuration on a C=N double bond in substituted 2,2-dimethylpenta-3,4-dienal hydrazones. Ab initio calculations for 1-methyltetrazole which included 2JHNcouplings have been performed by Jaszunski and R i z z ~ ' ~A ~ . remarkably good agreement between calculated experimental values, and reported recently by Svieshnikov and Nelson, I9O with experimental data being observed in most cases. ~ ' a large 2JHo and 3 J ~ couplings o have been measured by Borisov et ~ 1 . ' for series of the compounds with an intramolecular hydrogen bond. A reasonably good correlation has been observed between the sum (Jc(~)oH+ J,-(~)oH) and 80~1 (Figure 5.9).

X=C.NorO

Figure 5.9 A two-bond coupling, 2 J H ~ i17.6 = Hz, found in 7c-arene Fe(IV) complexes, (q6arene)Fe(H)2(SiRC12)2 (arene = toluene, benzene; R = H, Me), indicates that interaction between Si and H is rather negligible in these corn pound^.^^ The couplings between 30 and 70 Hz are typical of three centered SiMH fragments in which bonding interaction takes place. 2JHsi couplings have been found to be useful in structural assignments of trimethylsilyl and butyldimethylsilyl derivatives of purines and pyrimidines. 192 2JHp couplings of ca. 30 Hz observed by Castillo et in the spectra of several dihydrido diolefin complexes stabilized by the Os(P-i-Pr3)2 unit indicate that both hydrido ligands are cis arranged to the phosphine ligands. The OsH2(q4-tetrafluorobenzobarrelene)(P-i-Pr3)~, compounds studied were 0 s H2( 4-2,5-nor bornadiene)( P- i- Pr 3)2 and OsH2( q 4-1,3-cyclohexadiene)(P-iPr3)2. The coupling value decreased significantly upon protonation of the compounds. Monohydride complexes of W(IV) containing bulky selenolate ligands, [WH(SeR),(L)(PMe,Ph)]) R = C6H3-i-Pr2-2,6 or C6H2Me3-2,4,6, L = PMe2Ph, pyridine and N-methylimidazole, have been studied by Burrow et A large 2JHp coupling of 99 Hz has been found for the [WH(SeCbH3-i-Prz2,6)3(PMe2Ph)z] complex as a result of the small H-W-P angle of 53". 2JHp couplings have been also measured and analysed for a series of new iridium(II1)

5: Applications of Spin-Spin Couplings

171

pyrazolate complexes, such as [II-~(~-H)(~-Pz)~H~(L)(P-~-P~)~], where L = C2H4, CO, HPz.19' 2JHpand 2JHSncouplings, which are extremely sensitive to the geometry of a given complex, are very often used in the studies of these compounds; thus, two geometrical isomers of the complex IrH[SiMe(CH2CH2CH2PPh2)2](CO)(SnC13) could be easily distinguished by the use of the 2JHSncoupling, 2JHSntrans = 1072 Hz and 'JHSncjs= 172 H z . ' ~ ~ Two- and three-bond H-'17" 19Sn couplings have been measured by Steenwinkel et al. 197 for two hypercoordinated aryltrialkylstannanes, [Me3Sn{C6H3(CH2NMe2)2-2,6}] and [(Me3Sn)2-1,4-(Cb(CH2NMe2)4-2,3,5,6}]; 2J(H-117/'19Sn) of ca. 50 and 3J(H-117/'19Sn) of 25 Hz have been found. A variety of spin-spin couplings including those between H and Sn nuclei in the SnRhH fragment has been used by Carlton et al. 19* in order to assess information on the electronic structure of triphenyltin hydride complexes of rhodium. A threefold increase in the 'JHRhSn coupling value (from 29 Hz up to 99 Hz) has been observed on going from [Rh(NCBPh3)(H)(SnPh3)(PPh3)2] to [Rh(NCBPh3)(H)(SnPh3)(PPh3)(Py)]complex, i.e. on exchanging one phosphine group for the more nucleophilic pyridine. A decrease from 109/104 to 87/83 Hz has been observed by Wardell and cow o r k e r ~ for ' ~ ~2J(H-' 17'119Sn)couplings in estertin compounds, (Me02C-CH2CH2)2SnX2in the order X2 = (NCS)2, CI2, Br2, CIBr, 12. A similar trend has been found for 1J(C-117'"9Sn)couplings. The first paper describing inverse proton detection of Te in organotellurium compounds employing multiple-quantum H-{ 125Te}correlation spectroscopy has been published by Schroeder et aL200The values of 'JHTe couplings measured and applied vary from 20.9 to 102.5 Hz.

6

Two-Bond Couplings Not Involving Hydrogen

Scalar and dipolar coupling studies have been performed by Berger and his coworkers2" on three organocuprates: Me2CuLi, Me3CuLi2 and MezCu(CN)Liz. The authors emphasize that an examination of the coupling pattern allows one to determine the number of methyl groups bound to the copper centre. In particular, a large 2Jcc coupling of 21 Hz provides direct proof that two methyl groups present in dimethylcuprate Me2CuLi are covalently bound to the copper . 2JcN couplings, which are highly stereospecific, have been applied by LyCka et aL2O2 in their studies on the structure of the 2:1 aluminium(II1) complexes of some azo dyes. 2J~- and 3 J ~ couplings F have been applied by Laali et al.203in their studies on the structure of a-CF3-substituted (1-pyrenyl)dimethyl-, (1-pyrenyl)phenylmethyl-, (4-pyrenyl)dimethyl-, and (9phenanthrenyl)dimethylcarbenium ions. Small 2 ' 3 J ~ couplings p in cyclic phosphoric amides (Figure 5.10) studied by Modro et a1.204are of particular interest since the two-path coupling mechanism should be taken into account in this case. Considering their own data and those taken from the literature, the authors came to the conclusion that the spin-spin

172

Nuclear Magnetic Resonance

interaction between the 31Pnucleus and the ring carbons is transmitted mainly via the two-bond mechanism, whereas the three-bond path can be almost neglected. The full NMR characteristics including 2Jcp and 3Jcp couplings have been published by Herberhold et aL205for a series of mono- to trinuclear ferrocenolato derivatives such as Ph3,P(OFc),, where Fc denotes ferrocenol.

Figure 5.10 A 2Jcw coupling of 35 Hz has been reported by Thomas et a1.206 for LW { NC(O)Me)X(CO) complexes, where X = CI, I and L = hydrotris(3,5-dimethylpyrazol- 1-yl)borate. Two products have been obtained by oxidation of [0sF,(CO)l2- with Cl2: mer[OsF3C12(CO)]- and [OsF5(CO)]-, whose spectra revealed ' J F ~couplings of 9.5 Hz and 94.9 Hz, re~pectively.~'~ 2Jsip and 2JpSn couplings have been found to be of particular use in the conformational analysis of PhP(R)CH2EMe3, PhP(CH2EMe3)2, (E = Si, Sn; R = H, Ph), Ph2PCH(SiMe3)(SnMe3), the stannylene-bridged raclmeso(Ph2PCHSiMe3)2(SnMe2) and the a-silylated silylphosphine PhP(SiMe3)CH2SiMe3 performed by Kowall and Heinicke.208 The magnitude of *JpAPs in CD2P207has been determined by Dusold et al.209 by the use of a 31Psolid NMR experiment. The coupling found is rather small, of 23 2 4 Hz only, and was assumed to be negligible in the study performed by Kubo and McDowellY2"when spectral line shape simulations of 31PMAS NMR spectra of analogous compounds were performed. 2Jpp couplings have been determined by Crochet et a1.211 for a large series of new ruthenium complexes. The coupling values vary from 26.5 Hz in [Ru(C=C=CP~~)(C,H~)(PP~~){(I~ '(P)-P~~PCH~C(O)~-BU)][PF~] UP to 43.8 HZ in [RuCI(CgH7)(PPh3){q I ( P ) - P ~ ~ P C H ~ C ( O ) ~ - B U ) ] . Iterative fitting procedure combined with efficient numerical simulation which allows accurate measurements of the magnitudes and relative orientations of chemical shielding, two-bond J coupling and dipolar coupling tensors for isolated homonuclear P--P spin pairs by the use of standard 31PMAS NMR experiments has been described by Dusold et aL2I2 A strong dependence of the 2JpSe couplings on the P-M-Se angles or the P-MSe-C dihedral angle has been observed by Burrow et al. Ig4 in [WH(SeR)3(L)(PMe2Ph)], R = C6H3-i-Pr22,6 or C6H2Me3-2,4,6, L= PMe,Ph, pyridine and Nmethylimidazole, complexes. The results of the interesting off-magic-angle-spinning I 19Sn NMR studies on anisotropy of the two-bond Sn-O-1'7Sn coupling in the linear fragment of solid (benzyl3Sn)20 have been reported by Marichal and Sebald.213The measurements

5: Applications of Spin-Spin Couplings

173

have been carried out using not a single crystal as it is usually done but the polycrystalline powder of the compound. The anisotropy of 2J(Sn-’ 17Sn) coupling was determined as 842 k 350 Hz and found to be of a similar magnitude as 12J(Sn”7SnJ= 950 Hz.

7

Three-Bond Hydrogen-Hydrogen Couplings

The growing attention is being paid to the unfolded and/or denaturated stage of the proteins and peptides. In this stage specific nonlocal interactions between residues are non-existent. However, individual residues might preserve their local conformational preferences and therefore proton-proton couplings appear to be an indispensable structural parameter for studying the protein structure. Thus, the mean backbone 3 J couplings ~ ~ have been measured for oxidized and reduced forms of denaturated hen lysozyme by Dobson and co-workers214and compared with the so called ‘random coil’ ones estimated from a data set originated from 85 high resolution protein structures. The variation of couplings along the sequence allowed the authors to conclude that in the denaturated state each residue samples ~ ~ of a 130-residue the conformational space independently. The 3 J couplings fragment of Staphylococcus aureus fibronectin-binding protein have been measured by Smith and his co-workers215and compared with the ‘random coil’ values. The comparison showed that the local structure of the protein approximates very closely to a statistical random coil structure; in spite of this, the protein reminds functionally active. Fong et ~ 1 . have ~ ’ measured ~ urea-denaturated states of Igl8’, immunoglobulin superfamily domain. From the values of 3 J they ~ concluded ~ that the presence of non-random local structures may be suggested in the denaturated form of the protein. Dobson and co-workers217 have studied the influence of the concentration of GuHCl on the conformational behaviour of the peptide in a series of 20 peptides of the sequence Ac-GGXGG-NH2 ,where X was each of the proteogenic amino acids. They found that the backbone 3 J couplings ~ ~ are not dependent on the concentration of GuHCl and concluded that there are no specific interactions between the denaturating agent and the peptide -denaturation is caused rather by unspecific changes in the solvation properties of water. An interesting study with the use of 3 J couplings ~ ~ has been undertaken by Laity et aL218 with RNase A and its analogue lacking the C40-C95 disulfide bond. Comparing 56 backbone proton-proton couplings of both proteins the authors selected 12 couplings with the difference larger than f1.5 Hz and interpreted them in terms of differences in backbone conformation and/or conformational flexibility of the two proteins. The conformation of inactivating ball domain of Skaker voltage gated K+ channel has been analysed with the help of proton-proton vicinal couplings by Schott et al.219No well-defined spatial structure could be found for that peptide on the basis of spectroscopical parameters and the authors described the conformation as ‘a dynamic equilibrium of locally non-random structures’. For seven P-hairpin peptides which populate P-hairpin 4:4, type I turn and/or Phairpin 3:5 I+Gl P-bulge turn the 3 J couplings ~ ~ have been found to be

I 74

Nuclear Magnetic Resonunce

averaged.220The values of 3 J couplings ~ ~ measured for a series of peptides with the sequence RGITVXGKTYGR (where X=D,G,A,S,N) were slightly larger that those expected for a random This finding allowed the authors to propose the existence of a fast equilibrium between p-hairpin and a random coil for all these peptides. The averaged experimental values of couplings have been included explicitly in an ensemble-averaging (EA) protocol in a conformational analysis of small cyclic peptides, which accounted for their con format ional variability .222 3 J H couplings ~ have been included as input data in a neural-network-based prediction of a secondary structure from NMR data.223Significant changes in the ~ ~ (+I Hz) have been observed for C-terminal residues in backbone 3 J couplings [A2032 I] PKI(5-24), a peptide derived from the inhibitor of CAMP-dependent protein kinase, upon phosphorylation of S21.224 The helical structure of ypeptides has been characterized by the use of proton-proton vicinal couplings by Hintermann et ul.225 The values of measured backbone 3 J couplings ~ ~ served as important supportive data in concluding on the secondary structure of such peptides as a prototypic a-helical peptide, LYQELQKLTQTLK;226of a micelle-bound hybrid natriuretic peptide analogue, pBNPl 227 Lqh-8/6, a toxin-like peptide from a scorpion venom;228peptides and pseudopeptides incorporating an endo-(2S,3R)norborn-5-ene residue as a turn inducer;229a fragment of C4 region of gp120 of HIV (residues 397-440);230 ETB selective agonist, ET-I -[Cy~(Acm)'~'~,Ala~,L e ~ ~ , A i b " ]more ; ~ ~ ' examples are listed in Table 5.1. The 3D structures of the following peptides and proteins have been established with the help of 3 J couplings: ~ ~ N21(4-23), R18(170-186) and Y21(200-219) antigenic peptides from riboflavin carrier protein,324 a-conotoxin MI,325 the FADD (Mort 1) death-effector domain,326and drosomycin, the first inducible antifungal protein from insects.327 Other peptides and proteins whose 3D structures have been elucidated are included in Table 5.1. Vicinal proton-proton couplings have been very useful in determining thermodynamic parameters of the conformational equilibrium of nucleosides and nucleo~ ~ Luyten et ul. 328 have evaluated the N+S tides. Thus, using 3 J couplings equilibrium in a set of C- and N-nucleosides and proved that the strength of the intrinsic anomeric effect is pH-dependent. has described a thermodynamic cycle for DNA and RNA components and finally extracted the constant contribution of 1.75 [kJ/mol] per one sugar moiety as a driving force for the N+S conformational shift. Polak et al.330 have analysed thermodynamic parameters of conformational equilibrium in a series of p- and a-u-glycero-pent-2'-enopyranosyl nucleosides showing that the equilibrium is driven by the fine tuning of anomeric effect, gauche effect, n-system interactions and steric effects of the components; the same group using the model compound with the furanose ring replaced by a cyclopentane evaluated anomeric effect in purine n u c l e ~ s i d e s . The ~ ~ ' H 1' to H2' crosspeaks intensities as observed in I3C-edited 3D TOCSY experiments have been used as qualitative parameters in conformational analyses of a classical RNA p s e ~ d o k n o tSeveral . ~ ~ ~ other examples of RNA and DNA molecules for which 3 J couplings ~ ~ have been used as a quantitative parameter are given in Table 5.2.

J

derivatives of D, DF, and DDV lissoclinamide 7, cyclopeptide alkaloid

Peptides andproteins for which the solution structure has been calculated with 'JHH

LKGKKYSP, I F N - a 2 interferon (residues 130-137) novel nonpolar host peptides containing a,a-disubstituted glycines phosphorus containing peptides Ala-rich helical peptide labeled with nitroxide M PAK pilin peptide (residues 128-144) C-terminal end of human complement serine protease C 1s (residues 656-673) W 7 0 , RRWCYRKDKPYRKCR, HIV-cell fusion inhibitor L-m- and D- a-peptides which generate antibodies that cross-react with the gp120 cGH[C136,C153], GH loop of the capsid protein VP1 of FMDV (residues 134-155) INP24, peptide with three repeats of the consensus sequence of Pseudomonas syringae caerin 1.1, an antimicrobial peptide from the Australian green frog Litoria splendida [C/Nl CMPcc, C-terminal domain of chicken CMP (residues 451-493 [Nlel 181 bacteriorhodopsin fragment from Halobacterium salinarium (residues 87- 136) [CW Glgs protein from E. coli Hpr, histidine-containing phosphocarrier protein from Enterococcus fuecalis NTHP12, hemolymph protein from the mealworm beetle Tenebrio rnolitor binase, guanylospecificribonuclease from Bacillus intermedius [C/Nl myotrophin [C/Nl Der p 2, Group 2 house dust-mite allergen from D. pteronyssinus [ C W Sak, staphylokinase from Staphylococcus aureus [D/C/NI NusB protein of E. coli [C/Nl apoLp-111, apolipophorin 111 from the insect Manduca sexta [D/C/NI e-gp41, ectodomain of gp41 of the SIV, trimeric

Peptides and proteins for which the secondary structure has been determined with 3

Name

~

~

1-3 3

5-7 3

73 67 84 49 ca. 105 99 ca. 100 >122 28x3

52

66 89 108 109 118 128 136 139 166 123x3

50

6 6-7 9 16 15 11 12 10-14 12 20 9 29 >57

b)

8 9-12 3 16 17 18 18 20 22 24 25 43

a)

Table 5.1 Peptides andproteins for which 'JHHcouplings have been applied as a structural parameter

256

255

254

253

250 25 I 252

249

248

247

246

245

243 244

242

24 1

239 240

238

237

236

235

234

233

232

Reference

5

5 6 6 6 6,8,10,12,14,1 7 8 9 9 10 10 I1 12 13 13 16 17 19 20 22 23 24 24 26 27 29 33 33 34 5

>10 >10 14 0,1S 14 12 13 43 5 16 23 10 25 22 20 >I6 >16 27 18

285

284

283

282

28 1

280

279

278

277

276

215

274

273

272

27 1

270

269

268

261

266

265

264

263

262

26 1

260

222

259

258

257

4

4

Ac-CPXaa-C-NHMe, disulfide-linked tetrapeptides cyclo(RGD-FXaa), where Xaa = lipophilic or-amino acid LAV6 peptide, refolding nucleation site of the CD4-binding domain of HIVl gp120 cyclo(GPFGPXaa), Xaa=Nle cESA, cyclic peptidic analog of FK506 homologs of gramicidin S axinastatins 2, 3 and 4 Boc-LLK(Por)-Aib-Aib-LLK(Nap)-OtBu, Por=protoporphyrin IX, Nap=naphthalene desmopressin, l-desamino-[D-Arg8]vasopressin [Xaa’, cyclo(Glu4,Lys8)]0T, Xaa= Mpa, dPen, bicyclic antagonists of oxytocin [G6]- and [G9]-antamanide analogs, sodium complexed cyclo(2,9)-Ac-QCRSVEGSCG-OH, from the C-terminal of hGH dodecapeptidomimetic containing p-turn mimetic BTD with RGD sequence cyclic peptide derived from ICAM-1, intercellular adhesion molecule-1 or-conotoxin GI, three disulfide bond isomers compstatin, a potent complement inhibitor or-conotoxin MI1 conontokin G, conotoxin with y-carboxyglutamic acid, from Conus geographus actagardine. ]antibiotic Ib-AMP1 , Impatiens balsamina antimicrobial protein porcine motilin gp41(512-534)peptide of HTV-1 conotoxin q-PIIIE from Conus purpurascens human salivary histatin 5 McbA( 1-26) propeptide of antibiotic microcin MccB17 K-conotoxin PVIIA from the venom of Conus purpurascens leiuropeptide 11, toxin-like peptide from the venom of Leiurus quinquestriatus hebraeus huwentoxin-I from the venom of the spider Selenocosrniahuwena secretoneurin, a neuropeptide from secretogranin I1 N-terminal silkworm eclosion hormone (residues 1-34) 2 10 29 n-2 15 6 18 19

Reference

b)

a)

Name

SZ

66 6f ZP 61 I I1+901 fII

SI€ E If

Zf 09 OP 60I< 99 06 ‘03 82

1 If

E x €2

*If ZIE

SOf

E Of

812 f8 €9 Pf 65 LS
30 kDa) species. The prediction is that for "N-' H correlation-based spectroscopies the maximurn TROSY effect will be obtained at magnetic field strengths around 1 GHz, and we can anticipate that this observation will fuel the drive towards bigger magnets. Yang et al. have developed an experiment for the measurement of the crosscorrelation relaxation rate between the 'Ha-13Ca dipolar and the 13C' CSA relaxation mechanisms.252The experiment relies on the cross-correlation relaxation of zero- and double-quantum coherence and is related to the pulse-sequence concept described by Brutscher et al. (see below).253In analogy with the approach taken in the very recent pioneering study of dipole/dipole cross correlation by Reif et al.,254the cross-correlation relaxation rates are transformed into \I, dihedral angles. The authors measure cross-correlation relaxation rates for the proteins ubiquitin and CheY and demonstrate a very convincing correlation with \I, dihedral angles derived from the crystal structures. The authors stress that the experiment has a higher intrinsic sensitivity than the experiment by Reif et al. In their search for new parameters for the characterization of the dynamics of the backbone peptide plane, Brutscher et al. have developed a general procedure for the measurement of dipolar/CSA cross-correlation rates by combined doubleand zero-quantum spectroscopy.253 The procedure is demonstrated by the measurement of dipolar/CSA cross-correlation rates involving the amide proton and amide nitrogen (I5N) and the carbonyl carbon (I3C) of the preceding residue in [15N,13C]double-labelled ubiquitin. The experiment enables the determination of two aggregate cross-correlation rates rlocal and rremote which hold complementary information about the dynamics of the peptide plane.

9.4 Rotational Diffusion Anisotropy - In the past few years, there has been a substantial interest in the effects of rotational diffusion anisotropy on the analysis of relaxation data and research groups have succeeded in determining the principal components of the rotational diffusion tensor for a number of proteins and protein domains. There is a general concern about the effects of disregarding rotational diffusion anisotropy in the analysis of "N and 13C relaxation data. Luginbuhl et al. have investigated the effects of rotational diffusion anisotropy on the 15N relaxation rates of the N-terminal DNA binding domain of the 434 repressor at two magnetic field strengths255and estimates an anisotropy, Dparallel/ Dorthogonal, of 1.2 which is in good agreement with hydrodynamic bead-model calculations based on the NMR solution structure. The study shows, in accord with other recent studies, that if the rotational diffusion anisotropy is disregarded in a subsequent model-free analysis of the relaxation data, the effects of the anisotropy may erroneously be identified either as local dynamics on the nanosecond time scale or as conformational-exchange contributions to the transverse relaxation rates. An interesting and important application of rotational diffusion anisotropy

9: N M R of Naturul Macromolecules

347

measurements is in the investigation of the relative orientation of linked protein modules for which inter-domain distance restraints are sparse or are not available. Copie et al. have determined the solution structure of the linked ninth and tenth fibronectin type I11 modules of the mouse fibronectin cell attachment domain and have estimated the rotational diffusion anisotropy of the protein fragment from 15N relaxation data.256They find anisotropies in the range from 1.7 to 2.1 which is significantly less than the value of 2.7 predicted by hydrodynamic bead-model calculation based on the crystal structure in which the two domains form an elongated unbent structure. In contrast, the measured rotational diffusion anisotropy is in good agreement with hydrodynamic calculations based on NMR solution structures in which the two domains are bent more than 20 relative to the crystal structure. O

Aspects of Model-Free Analysis - Jin et al. have investigated the sensitivity of the model-free method towards experimental uncertainties and have developed a graphical procedure for estimating the uncertainties in the model-free param e t e r ~ . ~It~ ’is shown that the information content in I5N relaxation spectra is rapidly degraded with increasing experimental uncertainties and that derived model-free parameters often are highly correlated. In certain cases it is even possible to find a discontinuous solution space in which case conventionally calculated model-free parameters may completely depend on the nature of the experimental uncertainties. The method is, however, not straightforward to generalize to model functions with three or more dynamic parameters, such as the extended model-free spectral-density function or a model including an exchange term. Philippopoulos et al. have investigated the accuracy and the precision of order parameters derived from NMR I5N relaxation measurements and moleculardynamics (MD) simulations.258 In the study, the reproducibility of the data is assessed by a comparison of three independent NMR data sets and data from two MD simulations. It is shown that the differences in order parameters observed for pairs of NMR data sets are in agreement with the uncertainties estimated from the individual data sets. Also, it is shown that the distributions of differences between NMR data sets and MD calculations are comparable to the distributions between pairs of NMR data sets, and that MD calculations accordingly can be used to predict fast internal dynamics (riO. 1) of order parameters between the NMR data sets and the MD simulations are discussed in relation to a lack of consensus between the experimental data sets, rare motional events in the MD trajectories and a disruption of a structural element in one of the MD simulations. Two studies are concerned with the estimation of the overall rotational correlation time. The correct estimation of the overall correlation time is crucial for a model-free analysis. Korzhnev et al. point out that if the majority of I5N sites are affected by fluctuations on the nanosecond time scale, the common procedure of determining the correlation time from an average R2/RI ratio completely fails. It is shown that it is still possible to estimate the overall

9.5

348

Nuclear Magnetic Resonance

correlation time under these circumstances if R2/RI ratios are measured at multiple magnetic field strengths.259 The studies by Akke et af.260also have implications for the estimation of the overall correlation time (see below).

9.6 I5N, I3C and *H Relaxation Applications - Several research teams have investigated the changes in dynamics of proteins caused by ligand binding. In their search for a correlation between the binding affinities of SH2 domains for specific phosphotyrosine peptides and changes in the dynamics at the SH2domain ligand-binding interface upon phosphotyrosine-peptide binding, Kay et al. have measured the methyl group dynamics261 of the uncomplexed and phosphotyrosine-bound states of the N-terminal SH2 domain of Syp tyrosine phosphatase by recently developed deuterium-relaxation.244 The data are compared with the results from the recent study of the C-terminal SH2 domain from phospholipase Cy- 1,24' and together with extensive binding studies of the two SH2 domains and numerous truncated forms of the phosphotyrosine peptides a correlation between binding energy and restriction of the motions on the pico- to nanosecond time scale at the binding interface is demonstrated. Marcel Ottiger et al. have studied the backbone "N dynamics of the human cyclophilin A in the unligated form and in complex with cyclosporin A.30 A comparison of the relaxation data shows that polypeptide loops close in space to the ligand-binding site are becoming dynamically restricted upon ligand binding, Alexandrescu et af. have measured 15N relaxation rates of a free S peptide and of the S peptide in complex with S protein and have interpreted changes in order parameters induced by binding within the framework of changes in 'H-15N bond-motion entropy .262 Folmer et al. have investigated the backbone dynamics of the 18 kDa singlestranded DNA-binding protein encoded by the filamentous Pseudomonas bacteriophage Pf3 by means of I5N relaxation techniques both in the absence of and in the presence of DNA.Is3 Especially the protruding beta hairpin formed by residue 12-24 becomes significantly restricted upon binding to DNA. Foster et al. have measured I5N relaxation rates of the three N-terminal zinc fingers of transcription factor IIIA bound to DNA and show that the two linker regions have increased local mobility as evidenced from low R2 relaxation rates and low *H-I5N NOE values. Van Heijenoort et al. have determined 15N relaxation parameters for the DN A-binding domain of fructose repressor and have analyzed the data within the framework of the reduced spectral density mapping approach.263 Complex internal dynamics on the nanosecond time scale is identified with the linear correlation approach.264 Three studies are concerned with the changes in dynamics caused by the mutation of one or more residues in a protein. Yamasaki et al. have investigated the "N backbone dynamics of native ribonuclease H 1 and a penta mutant with a 20.2 higher melting temperature and observed increased order parameters and conformational exchange contributions in the vicinity of the mutations.26s Mossing has investigated a monomer variant of the lambda Cro repressor by means of I5N relaxation methods and has identified substantial conformational exchange contributions for residues in four major secondary structure ele-

349

9: N M R of Natural Macromolecules

ments.266Malmendal et al. have investigated the 15N properties of an engineered variant of calbindin Dgk in which the N-terminal pseudo EF-hand loop was changed so as to correspond to the C-terminal consensus EF-hand loop sequence and the data was compared with data for the native-like P43G mutant.267The dynamics of the protein core is virtual invariant to the mutations but both the engineered N-terminal EF hand and the native C-terminal E F hand show drastically increased order parameters compared with the native-like form. The changes in loop dynamics are explained by changes in key hydrogen-bonding interactions. An interesting study of the partially unfolded A state of ubiquitin by Brutscher et af. shows that the C-terminal half of the protein has undergone a structural transition from beta sheet to a helix-rich structure.268 5Nrelaxation parameters and chemical-shift values show that both the N-terminal and the C-terminal half of the A state of ubiquitin have substantial internal flexibility and exist as an equilibrium mixture of multiple flexible states. Riek et al. have measured 15N relaxation parameters for the murine prion protein mPrP(23-23 1) and show that the N-terminal segment 23- 120 is flexible and disordered in solution." Daughdrill et af. have investigated the transcription factor 028 inhibitor FlgM which is a 97-residue polypeptide.269When unbound, FlgM is nearly unstructured, but a carbon chemical shifts and order parameters indicates the existence of transient helical structure in the C-terminal half of the protein sequence. Akke et al. have used their recently developed off-resonance rotating-frame constant-relaxation-time "N relaxation experiment270in the characterization of conformational exchange processes taking place on the microsecond time scale in the third fibronectin type 111 domain of tenascin-C260 and have identified conformational exchange processes throughout the protein backbone. Surprisingly, conformational exchange phenomena are also observed for several residues with R2 values close to the mean R2 value. The authors note that such pervasive conformational exchange processes may interfere with the common procedure for estimation of the overall correlation time from R2/R I ratios. Undetected exchange contributions may translate into an artificially increased overall correlation time and in artificially increased order parameters in a subsequent modelfree treatment. Zinn-Justin et al. have employed an off-resonance 5Nrelaxation experiment in the characterization of conformational exchange on the microsecond time scale in toxin a and have identified 11 residues (out of 66) which are affected by exchange processes.271 Ssrensen et af. reported the 15N derived analysis of the backbone dynamics of the human a 3 chain type VI C-terminal kunitz domain.272 A number of residues in the vicinity of the Cys14-Cys38 disulfide bond show conformational exchange contributions to the "N R2 relaxation rate and are suggestive of disulfide isomerization in analogy with what is observed for the homologous disulfide bridge in BPTI. Moy et al. have assigned and determined the secondary structure of the inhibitor-free catalytic fragment of human fibroblast collagenase by triple-resonance techniques and have determined the 15N backbone dynamics.273 The data indicate a slow conformational exchange process affecting residues in the active site region. Upon binding of inhibitor, the exchange phenomena disappears.

'

3 50

Nuclear Magnetic Resonance

A number of research teams report overall correlation times which are either unusually short or long when compared to the size of the investigated proteins. of the oxidized Zhang et ul. have performed a backbone 15N relaxation state of flavodoxin from Anacystis niduluns. It is shown that this 19 kDa protein has an unusual lack of internal dynamics and a very short overall rotational correlation time of 7.4 to 7.8 ns (at 303 K). It is suggested that there is a correlation between the lack of internal dynamics and the short correlation time. The very limited internal mobility is in contrast to the crystallographic B factors derived for the X-ray structure. Hrovat et al. have performed 15N relaxation measurements on both reduced and oxidized Desulfovibrio vulgaris flavodoxin (a 16.3 kDa protein) and observes a general loss of internal dynamics upon o ~ i d i z a t i o n This . ~ ~ ~group also measured astonishingly short correlation times of 4.5 ns for both the oxidized and the reduced form in agreement with the observations by Zhang et al.274 Fairbrother et al. have studied the receptor-binding domain of vascular endothelial growth factor (VEGF) which is a 23 kDa homodimeric protein. Based on I5N relaxation measurements performed at 45 "C, they estimate an unusually high overall correlation time of 15 ns.276 Akke et al. have studied the base dynamics of a 14-nucleotide RNA hairpin with a UUCG tetraloop by means of I5N relaxation measurements.277It is shown that the overall tumbling of the molecule can be described by a symmetrical rotational diffusion tensor with an axial ratio Dparallel/Dorthogona1of 1.34k0.12. A model-free treatment indicates that guanine G9 positioned in the tetraloop is the most rigid nucleotide with an order parameter of 0.807, and that the terminal guanine G1 has the highest flexibility with an order parameter of 0.74. It is noted that because I5N CSA values are not known in detail for nucleotides, order parameters of different nucleotide types should be compared with caution. Carr et al. have compared the 15N backbone dynamics of two homologous and structurally similar fibronectin type I11 domains from fibronectin and tenascin-C, respectively, and have identified significant differences in dynamics in the (ArgGly-Asp) tri-peptide motif which is involved in the interaction with i n t e g r i n ~ . ~ ~ ~ The tripeptide motif has substantial dynamics in the tenth type-I11 domain in fibronectin and is rigid in the third type-I11 domain in tenascin-C. This difference is discussed in relation to binding specificity and the induced-fit binding mechanism. Hansson et al. have determined the solution structure and investigated I5N backbone dynamics of the SH3 domain from Bruton's tyrosine kinase.62 There is evidence of increased mobility of the RT loop and in particular the n-Src loop. Grzesiek et al. have characterized the backbone dynamics of HIV-1 Nef by means of 15N R l , R2 and NOE relaxation experiments.16 NOE and R2 values show that secondary-structure elements are inflexible and that the two major loops are highly mobile. Almeida and Opella have measured 15N relaxation data for f d coat protein bound to m i ~ e l l e sThe . ~ ~protein ~ which consists of an amphipathic and a hydrophobic a-helix is shown to have increased flexibility in the connecting linker. Also, the amphipathic helix is displaying dynamics on the nanosecond time scale. The dynamic properties of the 61-residue toxin alpha from Naja nigricollis have been investigated by Guenneugues et al. by means of

9: N M R of Natural Macromolecules

35 1

'

I5N relaxation, H ROESY and 'H/2H exchange techniques.280Order parameters follow closely the secondary structure and reveal increased dynamics in the four loop regions. Walters et al. have characterized the backbone dynamics of the transcriptional activator PUT3(31- 100) dimer by means of I5N relaxation methods.48 The study shows that the dimerization domain and the zinc clusters have very different overall dynamic properties consistent with the loose connection of the domains by a flexible linker. Landry et al. have investigated the temperature dependence of the dynamics of two flexible loops in HsplO. From the temperature dependence of the 15N relaxation parameters it is concluded that the tip of the loops are dominated by dynamics on a faster time scale than the hinge regions of the loops, and that the transverse "N relaxation rates is affected by conformational exchange contributions.28' Thijssen-van Zuylen et al. have continued their studies of the a subunit of the glyco protein human chorionic g ~ n a d o t r o p i n .By ~ ~ means of 13C R2 and RIP relaxation measurement and identification of protein-glycan NOESY cross peaks, it is shown that the three innermost glycan units attached to Am78 have significantly restricted mobility. These results are discussed in relation to the observed stabilizing effect of the glycan at this position on the protein. Feher et al. have assigned and carried out 15N relaxation measurements of the Bacillus subtilis response regulator S ~ O O FRothemund .~~ et al. have assigned a 12.4 kDa hemolymph protein from the mealworm beetle Tenebrio molitor consisting of six a-helices, and have measured "N backbone relaxation rates which nicely correlates with the secondary structure.282 Berglund et al. have measured "N relaxation rates of the glucocorticoid receptor DNA-binding domain.283The backbone dynamics of murine leukemia inhibitory factor (LIF) has been studied by Purvis and M a b b ~ t t LIF . ~ ~ is~ a 180-residue four-helix bundle protein with an up-up-down-down topology and 15N relaxation parameters show less variation with secondary structure than the related cytokine G-CSF. Connelly and McIntosh have made extensive investigations of the dynamic properties of the neutral buried His 149 in Bacillus circulans ~ y l a n a s e . ~ ' ~ 15N relaxation techniques were used to calculate an order parameter of 0.83 for the NE2Hbond vector which indicates restricted mobility. By means of I5N R l , R2 and 'H-15N steady-state NOE relaxation measurement, Liu et al. have characterized the backbone dynamics in the reactive site of two reactive-site cleaved serine proteinase protein inhibitors and have compared the results with the dynamics for the native forms.285 The increases in fast dynamics upon reactive-site cleavage are discussed in relation to the structural scaffold around the reactive site. Lee et al. have characterized the backbone dynamics of cardiotoxin 11, a 6.8 kDa protein from Taiwan cobra, by natural-abundance 3C-relaxat ion methods. 286

'

Related Topics - Hoogstraten and Pardi have investigated the advantages of spin-diffusion suppressed NOESY experiments (BD-NOESY and CBDNOESY) in the estimation of inter-proton distances in RNA and it is shown that it is possible to obtain more accurate distances with these experiments when compared to the traditional NOESY Also, the use of longer mixing

9.7

3 52

Nuclear Magnetic Resonunce

times, which are possible with spin-diffusion suppressed experiments, are shown to provide better sensitivity and a wider range of distances which can be measured with confidence. In two s t ~ d i e s ,Bertini ~ ~ ~ and , ~ ~co-workers ~ exploit the use of paramagnetic 'H longitudinal relaxation contributions for the estimation of intra-molecular distances in protein with paramagnetic centres. In the first study, the method is critically investigated and applied in the solution-structure determination of Clostridium pasteurianum ferrodoxin, and it is shown that 69 new restraints significantly improve the resolution of the solution In the second study, paramagnetic longitudinal relaxation restraints are used in the structure determination of the N-terminal domain of calmodulin complexed with two Ce3+ ions.289Coxon et al. have investigated the oxidized form of putidaredoxin and have used electron-nucleus dipolar relaxation contributions to the longitudinal 15N relaxation rates to estimate distances to the paramagnetic centre and finds distances in agreement with the NMR solution structure.290

10

Miscellaneous Topics

Bockmann et al. reported on the determination of Fast proton exchange rates of biomolecules by NMR using water selective diffusion experiment^.^^' Fefeu et ul. studied amide proton exchange in "N-enriched cryptogein using pH dependent off-resonance ROESY-HSQC experiments.292Cai et al. described methodology for efficient isotope labelling of proteins expressed in bacteria in a f e r m e n t ~ rGardner . ~ ~ ~ et al. reported methods for the production and incorporation of I5N,l3C,*H ('H6 1 methyl) isoleucine into proteins for multidimensional NMR studies.294 Bagby and co-workers described the 'button test' - a small scale method using microdialysis cells for assessing protein solubility at concentrations suitable for NMR.295 Wright and co-workers wrote about the utility of PCR-based gene synthesis for protein NMR spectroscopy.296 Gibbs et al. described intriguing observations of unusual p-sheet periodicity in small cyclic pep tide^.^^^ Pressure denaturation of proteins and an evaluation of compressibility effects was reported by Prehoda et al.298NMR characterization of the phosphocysteine form of the IIBGIc domain and its binding interface with the HAG'' subunit was described by Gemmecker et al.299Arginine side chain assignments in uniformly "N-labelled proteins using the novel 2D HE(NE)HGHH experiment were reported by Pellecchia et al.300Prompers et al. described a suite of two-dimensional NMR experiments for the assignment of aromatic side chains in '3C-labelled proteins.30' Whitehead and co-workers described a 15Nfiltered 2D H TOCSY experiment for assignment of aromatic ring resonances and selective identification of tyrosine ring resonances in proteins.302 In the field of chemical shift analysis, chemical shift homology in proteins was analyzed by Potts and C h a ~ i n . ~Wishart '~ described mechanisms for automated H and I3C chemical shift prediction using the Bi~MagResBank.~'~ Gronwald et al. have written ORB, a homology-based program for the prediction of protein NMR chemical shifts,305 and GSC, a graphical program for NMR chemical shift

'

9: N M R of Natural Macromolecules

353

comparison.306 Finally Wijmenga et a / . have analyzed 'H chemical shifts in DNA and assessed the reliability of 'H chemical shift calculations for use in structure refinement.307 11 1

2 3 4 5 6 7 8 9 10 11 12 13

14 15

16 17

18 19 20

21 22

23 24

References G. Wagner, Nature Struct. Biol., 1997,4, 841 -844. A. T. Brunger, Nature Struct. Biol., 1997,4, 862-865. K. Y. Chang and G. Varani, Nature Struct. Biol., 1997,4, 854-858. M. Kainosho, Nature Struct. Biol., 1997,4, 858-861. G. M. Clore, A. M. Gronenborn, Nuture Struct. Biol., 1997,4,849-853. L. E. Kay, Nature Struct. Biol., 1998,5, 5 13-5 17. J. L. Markley, A. Bax, Y. Arata, C. W. Hilbers, R. Kaptein, B. D. Sykes, P. E. Wright and K. Wuthrich, Pure Appl. Chem., 1998,70, 1 17- 142. G. M. Clore and A. M. Gronenborn, Proc. Nut1 Acad. Sci. USA, 1998, 95, 5891 -5898. G. M. Clore and A. M. Gronenborn, Trends Biotech., 1998 16,22-34. K. H. Gardner and L. E. Kay, Ann. Rev. of Biophys. Biomol. Struct., 1998, 27, 3 57 -406. L. E. Kay and K. H. Gardner, Curr. Opin. Struct. Biol., 1997,7,722-731. I. Radhakrishnan, G. C. PerezAlvarado, D. Parker, H. J. Dyson, M. R. Montminy and P. E. Wright, Cell, 1997,91, 741 -752. M. Eberstadt, B. H. Huang, Z. H. Chen, R. P. Meadows, S. C. Ng, L. X. Zeng, M. J. Lenardo and S. W. Fesik, Nature, 1998,392,941 -945. J. B. Ames, R. Ishima, T. Tanaka, J. 1. Gordon, L. Stryer and M. Ikura, Nature, 1997,389, 1 98 -202. F. Y . Yuh, S. J. Archer, P. J. Domaille, B. 0. Smith, D. Owen, D. H. Brotherton, A. R. C. Raine, X. Xu, L. Brizuela, S. L. Brenner and E. D. Laue, Nature, 1997, 389,999- 1003. S. Grzesiek, A. Bax, J. S. Hu, J. Kaufman, I. Palmer, S. J. Stahl, N. Tjandra and P. T. Wingfield, Protein Science, 1997,6, 1248- 1263. M. Eberstadt, B. H. Huang, E. T. Olejniczak and S. W. Fesik, Nature Struct. Biol., 1997,4,983-985. M. L. Cai, R. L. Zheng, M. Caffrey, R. Craigie, G. M. Clore and A. M. Gronenborn, Nature Struct. Biol., 1997,4,567-577. M. L. Cai, R. L. Zheng, M. Caffrey, R. Craigie, G. M. Clore and A. M. Gronenborn, Nuture Slruct Biol., 1997,4839-840. A. Eijkelenboom, F. M. I. vandenEnt, A. Vos, J. F. Doreleijers, K. Hard, T. D. Tullius, R. H. A. Plasterk, R. Kaptein and R. Boelens, Current Biology, 1997, 7, 739- 746. R. Glockshuber, S. Hornemann, R. Riek, G. Wider, M. Billeter and K. Wiithrich, Trends Biochem. Sci., 1997,22,241-242. D. G. Donne, J. H. Viles, D. Groth, I. Mehlhorn, T. L. James, F. E. Cohen, S. B. Prusiner, P. E. Wright and H. J. Dyson, Proc. Natl Acad Sci. USA, 1997, 94, 13452- 13457. S. Hornemann, C. Korth, B. Oesch, R. Riek, G. Wider, K. Wiithrich and R. Glockshuber, FEBS Lett., 1997,413,277-281. R. Riek, S. Hornemann, G. Wider, R. Glockshuber and K. Wiithrich, FEBS Lett., 1997,413,282-288.

354 25 26 27 28 29 30 31 32

33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49

Nuclear Magnetic Resonance

M. Billeter, R. Riek, G. Wider, S. Hornemann, R. Glockshuber and K. Wiithrich, Proc. Natl Acad Sci. USA, 1997,94,7281-7285. S . Schumacher, R. T. Clubb, M. L. Cai, K. Mizuuchi, G. M. Clore and A. M. Gronenborn, EMBO J., 1997,16,7532-7541. L. P. Yu, A. M. Petros, A. Schnuchel, P. Zhong, J. M. Severin, K. Walter, T. F. Holzman and S. W. Fesik, Nature Struct. Biol., 1997,4,483-489. L. P. Yu, A. M. Petros, A. Schnuchel, P. Zhong, J. M. Sevetin, K. Walter, T. F. Holzman and S. W. Fesik, Nature Struct. Biol., 1997,4, 592-592. Y. Chen, D. A. Case, J. Reizer, M. H. Saier and P. E. Wright, Proteins-Struct. Funct. Genet., 1998,31,258-270. M. Ottiger, 0.Zerbe, P. Guntert and K. Wuthrich, J. Mol. Biol., 1997,272, 64-81. W. Gronwald, M. C. Loewen, B. Lix, A. J. Daugulis, F. D. Sonnichsen, P. L. Davies and B. D. Sykes, Biochemistry, 1998,37,4712-4721. M. P. Crump, J. H. Gong, P. Loetscher, K. Rajarathnam, A. Amara, F. ArenzanaSeisdedos, J. L. Virelizier, M. Baggiolini, B. D. Sykes and I. ClarkLewis, EMBO J., 1997,16,6996-7007. J. Pascual, M.-Pfuhl, D. Walther, M. Saraste and M. Nilges, J. Mol. Biol., 1997, 273, 740-751. P. Fucini, C. Renner, C. Herberhold, A. A. Noegel and T. A. Holak, Nuture Struct. Biol., 1997,4, 223-230. H. Kovacs, D. Comfort, M. Lord, I. D. Campbell and M. D. Yudkin, Proc. Nut1 Acad. Sci. USA, 1998,95,567-5071. M. Sunnerhagen, M. Nilges, G. Otting and J. Carey, Nature Struct. Biol., 1997, 4, 8 19 -826. G. Musco, A. Kharrat, G. Stier, F. Fraternali, T. J. Gibson, M. Nilges and A. Pastore, Nature Struct. Biol., 1997,4, 712-716. G. Musco, A. Kharrat, G. Stier, F. Fraternali, T. J. Gibson, M. Nilges and A. Pastore, Nature Struct. Biol., 1997,4, 840-840. H. Sticht, A. R. Pickford, J. R. Potts and I. D. Campbell, J. Mol. Biol., 1998, 276, 177- 187. T. D. Mulhern, G. L. Shaw, C. J. Morton, A. J. Day and I. D. Campbell, Strucfure, 1997,5, 1313-1323. A. P. Wiles, G. Shaw, J. Bright, A. Perczel, I. D. Campbell and P. N. Barlow, J. Mol, Biol., 1997,272,253-265. E. Brun, F. Moriaud, P. Gans, M. J. Blackledge, F. Barras and D. Marion, Biochemistry, 1997,36, 16074- 16086. B. Bersch, J. F. Hernandez, D. Marion and G. J. Arlaud, Biochemistry, 1998, 37, 1204- 1214. S. Tassin, W. F. Broekaert, D. Marion, D. P. Acland, M. Ptak, F. Vovelle and P. Sodano, Biochemistry, 1998,37, 3623- 3637. X. Yao, D. Wei, C. Soden, M. F. Summers and D. Beckett, Biochemistry, 1997,36, 15089- 15 100. H. J. Schirra, C. Renner, M. Czisch, M. HuberWunderlich, T. A. Holak and R Glockshuber, Biochemistry, 1998,37,6263- 6276. J. L. Feltham, V. Dotsch, S. Raza, D. Manor, R. A. Cerione, M. J. Sutcliffe, G. Wagner and R. E. Oswald, Biochemistry, 1997,36, 8755-8766. K. J. Walters, K. T. Dayie, R. J. Reece, M. Ptashne and G. Wagner, Nuture Struct. Biol., 1997,4, 744-750. E. Liepinsh, M. Kitamura, T. Murakami, T. Nakaya and G. Otting, Nature Struct. Biol., 1997,4, 975-979.

9: N M R of Nuturul Mucromolecules

50

51 52 53 54 55 56 57

58 59 60 61

62 63

64 65 66 67 68 69 70 71 72 73 74

355

E. Liepinsh, M. Anderson, J. M. Ruysschaert and G. Otting, Nature Struct. Biol., 1997,4793-795. E. Liepinsh, L. L. Ilag, G. Otting and C. F. Ibanez, EMBO J., 1997,16,4999-5005. G. Siegal, B. Davis, S. M. Kristensen, A. Sankar, J. Linacre, R. C. Stein, G. Panayotou, M. D. Waterfield and P. C. Driscoll, J. Mol. Biol., 1998,276,461-478. X . M. Yuan, A. K. Downing, V. Knott and P. A. Handford, EMBO J., 1997, 16, 6659 -6666. M. Sette, P. vanTilborg, R. Spurio, R. Kaptein, M. Paci, C. 0. Gualerzi and R Boelens, EMBO J., 1997,16, 1436-1443. J. M. McDonnell, D. Fushman, S. M. Cahill, W. J. Zhou, A. Wolven, C. B. Wilson, T. D. Nelle, M. D. Resh, J. Wills and D. Cowburn, J. Mol. Biol., 199,279,921 -928. J. Zheng, R. H. Chen, S. CorblanGarcia, S. M. Cahill, D. BarSagi and D. Cowburn, J. Biol. Chem., 1997,272, 30340-30344. D. Fushman, T. NajmabadiHaske, S. Cahill, J. Zheng, H. LeVine and D. Cowburn, J. Biol, Chem., 1998, 273,2835-2843. J. E. Caldwell, F. Abildgaard, Z. Dzakula, D. Ming, G. Hellekant and J. L. Markley, Nature Struct. Biol., 1998,5,427-431. J. F. Wang, D. M. Truckses, F. Abildgaard, Z. Dzakula, Z. Zolnai and J. L. Markley, J. Biomol. N M R , 1997,10, 143-164. C. Y. Chien, R. Tejero, Y. P. Huang, D. E. Zimmerman, C. B. Rios, R. M. Krug and G. T. Montelione, Nature Struct. Biol., 1997,4,891-895. M. Tashiro, R. Tejero, D. E. Zimmerman, B. Celda, B. Nilsson and G. T. Montelione, J. Mol. Biol., 1997,272, 573-590. H. Hansson, P. T. Mattsson, P. Allard, P. Haapaniemi, M. Vihinen, C. I. E. Smith and T. Hard, Biochemistry, 1998,37,2912-2924. V. A. Feher, J. W. Zapf, J. A. Hoch, J. M. Whiteley, L. P. McIntosh, M. Rance, N. J. Skelton, F. W. Dahlquist and J. Cavanah, Biochemistry, 1997, 36, 1 00 1 5 - 10025. L. Banci, 1. Bertini, M. A. DelaRosa, D. Koulougliotis, J. A. Navarro and 0. Walter, Biochemistry, 1998,37,4831-4843. F. Arnesano, L. Banci, I. Bertini and I. C. Felli, Biochemistry, 1998,37, 173- 184. M. Caffrey, M. L. Cai, J. Kaufman, S. J. Stahl, P. T. Wingfield, A. M. Gronenborn and G. M. Clore, J. Mol. Biol., 1997,271, 819-826. X. Shan, K. H. Gardner, D. R. Muhandiram, L. E. Kay and C. H. Arrowsmith, J. Biomol. N M R , 1998,11, 307-318. H. Matsuo, H. J. Li, A. M. McGuire, C. M. Fletcher, A. C. Gringras, N. Sonenberg and G. Wagner, Nature Struct. Biol.,1997,4,7 17-724. R. T. McKay, B. P. Tripet, R. S. Hodges and B. D. Sykes, J. Biol. Chem., 1997,272, 28494- 28500. J. A. M. Hubbard, D. P. Raleigh, J. R. Bonnerjea and C. M. Dobson, Protein Science, 1997,6, 1945- 1952. F. Hayashi, R. Ishima, D. J. Liu, K. I. Tong, S. Kim, D. Reinberg, S. Bagby and M. Ikura, Biochemistry, 1998,37,7941-7951. M. Osawa, M. B. Swindells, J. Tanikawa, T. Tanaka, T. Mase, T. Furuya and M. Ikura, J. Mol. Biol., 1998,276, 165-176. J. M. Johnson, E. M. Meiering, J. E. Wright, J. Pardo, A. Rosowsky and G. Wagner, Biochemistry, 1997,36,4399-441 I . H. C. Siebert, R. Kaptein, J. J. Beintema, U. M. Soedjanaatmadja, C. S. Wright, A. Rice, R. G. Kleineidam, S. Kruse, R. Schauer, P. J. W. Pouwels, J. P.Kamerling, H. J. Gabius and J. F. G. Vliegenthart, Glycoconjugate Journal, 1997,14,531-534.

3 56

75

76

77 78 79 80 81 82 83 84

85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 I00 101

102 103 1 04

Nuclear Mugnetic Resonance

H. C. Siebert, C. W. vonderlieth, R. Kaptein, J. J. Beintema, K. Dijkstra, N. vanNuland, U. M. S. Soedjanaatmadja, A. Rice, J. F. G. Vliegenthart, C. S. Wright and H. J. Gabius, Proteins-Struct. Funct. Genet., I997,28,268-284. H. C. Siebert, R. Adar, R. Arango, M. Burchert, H. Kaltner, G. Kayser, E. Tajkhorshid, C. W. VonderLieth, R. Kaptein, N. Sharon, J. F. G. Vliegenthart and H. J. Gabius, Eur. J. Biochem., 1997,249,27-38. J. L. Weaver and J. H. Prestegard, Biochemistry, 1998,37, 116- 128. S. K. Sia, M. X. Li, L. Spyracopoulos, S. M. Gagne, W. Liu, J. A. Putkey and B. D. Sykes, J. Biol. Chem., 1997,272, 18216-18221. L. Spyracopoulos, M. X. Li, S. K. Sia, S. M. Gagne, M. Chandra, R. J. Solaro and B. D. Sykes, Biochemistry, 1997,36, 12138-12146. M. X. Li, S. M. Gagne, L. Spyracopoulos, C. Kloks, G. Audette, M. Chandra, R. J. Solaro, L. B. Smillie and B. D. Sykes, Biochemistry, 1997,36, 12519-12525. B. Rosinke, C. Renner, E. M. Mayr, R. Jaenicke and T. A. Holak, J. Mol. Biol., 1997,271,645-655. M. Sastry, R. R. Ketchem, 0. Crescenzi, C. Weber, M. J. Lubienski, H. Hidaka and W. J. Chazin,.Structure, 1998,6,223-231. C. Thijssen-van Zuylen, T. deBeer, B. R. Leeflang, R. Boelens, R. Kaptein, J. P. Kamerling and J. F. G. Vliegenthart, Biochemistry, 1998,37, 1933-1940. H. C. Siebert, S. Andre, G. Reuter, R. Kaptein, J. F. G. Vliegenthart and H. J. Gabius, Glycoconjugute Journal, 1997,14,945-949. 0. C. Uhlenbeck, A. Pardi and J. Feigon, Cell, 1997,90,833-840. A. Ramos, C. C. Gubser, G. Varani, Curr. Opin.Struct. Biol., 1997,7, 317-323. F. H. T. Allain and G. Varani, J. Mol. B i d , 1997,267, 338-351. C. G. Hoogstraten, A. Pardi, J. Biomol. NMR, 1998,11, 85-95. T. J. Tolbert, J. R. Williamson, J. Amer. Chem. SOC.,1997,119, 12100-12108. K. T. Dayie, T. J. Tolbert and J. R. Williamson, J. Magn. Reson., 1998, 130, 97- 101. V. Sklenar, T. Dieckmann, S. E. Butcher and J. Feigon, J. Mugn. Reson., 1998, 130, 119-124. J. P. Marino, J. L. Diener, P. B. Moore and C. Griesinger, J. Amer. Chem. SOC., 1997,119,7361 -7366. B. Reif, V. Wittmann, H. Schwalbe, C. Griesinger, K. Worner, K. JahnHofmann, J. W. Engels and W. Bermel, Helveticu Chimica Actu, 1997, 80, 1952- 1971. M. H. Kolk, M. vanderGraaf, S. S. Wijmenga, C. W. A. Pleij, H. A. Heus and C. W. Hilbers, Science, 1998,280,434-438. M. H. Kolk, H. A. Heus and C. W. Hilbers, EMBO J., 1997,16,3685-3692. H. A. Heus, S. S. Wijmenga, H. Hoppe and C. W. Hilbers, J. Mol. Biol., 1997, 271, I47 - 158. A. Ramos and G. Varani, Nucl. Acids Res., 1997,25,2083-2090. S. E. Butcher, T. Dieckmann and J. Feigon, EMBO J., 1997,16,7490-7499. S. E. Butcher, T. Dieckmann and J. Feigon, J. Mof. Biol., 1997,268,348-358. E. V. Puglisi, R. Green, H. F. Noller and J. D. Puglisi, Nature Struct. Biol., 1997, 4, 775 - 778. J. P. Simorre, P. Legault, N. Baidya, 0. C. Uhlenbeck, L. Maloney, F. Wincott, N. Usman, L. Beigelman and A. Pardi, Biochemistry, 1998,37,4034-4044. K. J. Addess, J. P. Basilion, R. D. Klausner, T. A. Rouault and A. Pardi, J. Muf. Biol., 1997,274,72-83. D. Fourmy, S. Yoshizawa and J. D. Puglisi, J. Mol. Biol., 1998,277, 333-345. D. Fourmy, M. I. Recht and J. D. Puglisi, J. Mol. Biol., 1998,277, 347-362.

9: NMR of Natural Macromolecules

105 106 107 108 I09 110 111

112 1 I3 114 I15 116 1 I7

I I8 1 I9

I20 I21 122 123 124 125 I26 127 128 129 130 131 132 133

357

J. M. Louis, R. G. Martin, G. M. Clore and A. M. Gronenborn, J. Bid. Chem., 1998,273,2374-2378. J. E. Masse, P. Bortmann, T. Dieckmann and J. Feigon, Nucl. Acids Res., 1998, 26, 2618-2624. G. Mer and W. J. Chazin, J. Amer. Chem. Soc., 1998,120,607-608. D. J. Patel, 8 . Mao, Z. T. Gu, B. E. Hingerty, A. Gorin, A. K. Basu and S. Broyde, Chem. Res. Toxicol., 1998, 11,391-407. M. Leijon and J. L. Leroy, Biochimie, 1997,79, 775-779. A. Kettani, S. Bouaziz, W. Wang, R. A. Jones and D. J. Patel, Nature Struct. Biol., 1997,4,382-389. M. Tarkoy, A. K. Phipps, P. Schultze and J. Feigon, Biochemistry, 1998, 37, 5810-581 9. A. K . Phipps, M. Tarkoy, P. Schultze and J. Feigon, Biochemistry, 1998, 37, 5820 - 5830. C. H. Gotfredsen, P. Schultze and J. Feigon, J. Amer. Chem. Soc., 1998, 120, 428 1 -4289. S. Nonin, A. T. Phan and J. L. Leroy, Structure, 1997,5, 1231 -1246. X . G. Han, J. L. Leroy and M. Gueron, J. Mol. Biol., 1998,278,949-965. B. B. Feng, A. Gorin, B. E. Hingerty, N. E. Geacintov, S. Broyde and D. J. Patel, Biochemistry, 1997,36, 13769- 13779. B. B. Feng, A. Gorin, A. Kolbanovskiy, B. E. Hingerty, N. E. Geacintov, S. Broyde and D. J. Patel, Biochemistry, 1997, 36, 13780-13790. B. Mao, A. Gorin, Z. T. Gu, B. E. Hingerty, S. Broyde and D. J. Patel, Biochemistry, 1997,36, 14479- 14490. B. Mao, Z. T. Gu, A. Gorin, B. E. Hingerty, S. Broyde and D. J. Patel, Biochemistry, 1997,36, 14491-14501. B. Mao, B. E. Hingerty, S. Broyde and D. J. Patel, Biochemistry, 1998,37,81-94. B. Mao, B. E. Hingerty, S. Broyde and D. J. Patel, Biochemistry, 1998, 37, 95- 106. P. S. Eis, J. A. Smith, J. M. Rydzewski, D. A. Case, D. L. Boger and W. J. Chazin, J. Mol. Biol., 1997,272,237-252. S. M. Miick, R. S. Fee, D. P. Millar and W. J. Chazin, Proc. Nut1 Acad. Sci. USA, 1997, 94,9080-9084. M. Bachelin, G. Hessler, G. Kurz, J. G. Hacia, P. B. Dervan and H. Kessler, Nuture Struct. Biol., 1998,5, 27 1 -276. C. Kojima, E. Kawashima, K. Toyama, K. Ohshima, Y. Ishido, M. Kainosho and Y. Kyogoku, J. Biomol. N M R , 1998, 11, 103-109. A. Ono, T. Shiina, A. Ono and M. Kainosho, Tetrahedron Letters, 1998, 39, 2793-2796. Y. Oogo, A. Ono, A. Ono and M. Kainosho, Tetrahedron Letters, 1998, 39, 2873 -2876. D. J. Patel, A. K. Suri, F. Jiang, L. C. Jiang, P. Fan, R. A. Kumar and S. Nonin, J. Mol. Biol., 1997,272,645-664. D. J. Patel, Curr. Opin. Chem. Biol., 1997,1,32-46. C . H. Lin and D. J. Patel, Chem. h Biol., 1997,4,817-832. S. Nonin, F. Jiang and D. J. Patel, J. Mol. Biol., 1997,268, 359-374. T. Dieckmann, S. E. Butcher, M. Sassanfar and J. W. Szostak and J. Feigon, J. Mol. Biol., 1997, 273,467-478. G. R. Zimmermann, R. D. Jenison, C. L. Wick, J. P. Simorre and A. Pardi, Nature Struct. Biol., 1997,4, 644-649.

358

Nuclear Magnetic Resonance

134

G. R. Zimmermann, T. P. Shields, R. D. Jenison, C. L. Wick and A. Pardi, Biochemistry, 1998,37, 9 186-91 92. G. Varani, Accounts of Chemical Research, 1997,30, 189- 195. G. Varani and K. Nagai, Ann. Rev. of Biophys. Biomol. Struct., 1998,27,407-445. F. Aboulela and G. Varani, Theochem-J. Mol. Struct., 1998,423,29-39. F. H. T. Allain, P. W. A. Howe, D. Neuhaus and G. Varani, EMBO J., 1997, 16, 5764-5774. P. W. A. Howe, F. H. T. Allain, G. Varani and D. Neuhaus, J. Biomol. NMR, 1998, 11,59-84. R. N. DeGuzman, Z. R. Wu, C. C. Stalling, L. Pappalardo, P. N. Borer and M. F. Summers, Science, 1998,279, 384-388. P. Legault, J. Li, J. Mogridge, L. E. Kay and J. Greenblatt, Cell, 1998,93, 289-299. Z. P. Cai, A. Gorin, R. Frederick, X. M. Ye, W. D. Hu, A. Majumdar, A. Kettani and D. J. Patel, Nature Struct. Biol., 1998,5,203-212. A. S . Brodsky and J. R. Williamson, J. Mol. Biol., 1997,267,624-639. A. S . Brodsky, H. A. Erlacher and J. R. Williamson, Nucl. Acids Rex, 1998, 26, 1 99 1 - 1995. M. R. Starich, M. Wikstrom, S. Schumacher, H. N. Arst, A. M. Gronenborn and G. M. Clore, J. Mol. B i d . , 1998,277,621-634. M. R. Starich, M. Wikstrom, H. N. Arnst, G. M. Clore and A. M. Gronenborn, J. Mol. B i d , 1998,277, 605-620. J. R. Huth, C. A. Bewley, M. S. Nissen, J. N. S. Evans, R. Reeves, A. M. Gronenborn and G. M. Clore, Nature Struct. Biol.,1997,4,657-665. M. H. Milton, A. M. Gronenborn and G. M. Clore, Science, 1997,276, 1957-1957. M. H. Werner, G. M. Clore, C. L. Fisher, R. J. Fisher, L. Trinh, J. Shiloach and A. M. Gronenborn, J. Biomol. N M R , 1997,10,317-328. D. S . Wuttke, M. P. Foster, D. A. Case, J. M. Gottesfeld and P. E. Wright, J. Mol. Biol., 1997, 273, 183-206. M. P. Foster, D. S. Wuttke, I. Radhakrishnan, D. A. Case, J. M. Gottesfeld and P. E. Wright, Nature Struct. Biol., 1997,4, 605--608. P. Zhou, L. J. Sun, V. Dotsch, G. Wagner and G. L. Verdine, Cell, 1998,92,687-696. R. H. A. Folmer, M. Nilges, C. H. M. Papavoine, B. J. M. Harmsen, R. N. H. Konings and C. W. Hilbers, Biochemistry, 1997,36,9120-9135. S. Klimasauskas, T. Szyperski, S. Serva and K. Wiithrich, EMBO J., 1998, 17, 3 17-324. J. R. Tolman, J. M. Flanagan, M. A. Kennedy and J. H. Prestegard, Nature Struct. Biol., 1997,4, 292-297. N. Tjandra, S. Grzesiek and A. Bax, J. Amer. Chem. Soc., 1996, 118,6264-6272. N. Tjandra, J. G. Omichinski, A. M. Gronenborn, G. M. CIore and A. Bax, Nature Struct. Biol., 1997,4, 732-738. M. Ottiger, N. Tjandra and A. Bax, J. Amer. Chem. Soc., 1997,119,9825-9830. G. M. Clore, A. M. Gronenborn and N. Tjandra, J. Magn. Reson., 1998,131,159- 162. N. Tjandra and A. Bax, Science, 1997,278, 1 1 1 1 -- 1 1 14. N. Tjandra and A. Bax, Science, 1997,10,289-292. A. Bax and N. Tjandra, J. Biomol. NMR, 1997, 10,289-378. M. Ottiger, F. Delaglio and A. Bax, J. Magn. Reson., 1998, 131, 373-378. J. A. Losonczi and J. H. Prestegard, Biochemistry, 1998,37, 706-716. M. Ottiger and A. Bax, J. Amer. Chem. SOC.,1997,119,8070-8075. B. Xia, S. J. Wilkens, W. M. Westler and J. L. Markley, J. Amer. Chem. SOC.,1998, 120,4893-4894.

135 136 137 138 139 140

141 I42 143 144 145 146 I47 148 149 150

151

152 153 154 155

156 157 158 159 160 161 I62 163 164 165 166

9: N M R of Natural Macromolecules

167 168 169 170 171 172 173 174

175 176 177 178

179

180

181 182 183 184 185 186 187 188 I89

1 90

191 192 193 194

359

J. Boyd, T. K. Mal, N. Soffe and I. D. Campbell, J. Magn. Reson., 1997,124,61-71. J. S. Hu and A. Bax, J. Biomol. NMR, 1997,9,323-328. R. Konrat, D. R. Muhandiram, N. A. Farrow and L. E. Kay, J. Biomol. NMR, 1997,9,409-422. F. Lohr, M. Blumel, J. M. Schmidt and H. Ruterjans, J. Biomol. NMR, 1997, 10, 107-1 18. F. Lohr and H. Riiterjans, J. Magn. Reson., 1998, 132, 130- 137. K. Theis, A. J. Dingley, A. Hoffmann, J. G. Omichinski and S. Grzesiek, J. Biomol. N M R , 1997, 10,403-408. J. D. Baleja, V. Thanabal and G. Wagner, J. Biomol. NMR, 1997,10,397-401. T. Szyperski, A. Ono, C. Fernandez, H. Iwai, S. Tate, K. Wuthrich and M. Kainosho, J. Amer. Chem. Soc., 1997,119,9901 -9902. T. Szyperski, C. Fernandez, A. Ono, M. Kainosho and K. Wuthrich, J. Amer. Chem. Soc., 1998,120,821-822. P. J. Hajduk, R. P. Meadows and S. W. Fesik, Science, 1997,278,497. H. Kessler, Ang. Chem-Intl Ed. Engl., 1997,36, 829-831. P. J. Hajduk, G. Sheppard, D. G. Nettesheim, E. T. Olejniczak, S. B. Shuker, R. P. Meadows, D. H. Steinman, G. M. Carrera, P. A. Marcotte, J. Severin, K. Walter, H. Smith, E. Gubbins, R. Simmer, T. F. Holzman, D. W. Morgan, S. K. Davidsen, J. B. Summers and S. W. Fesik, J. Amer. Chem. Soc., 1997, 119,5818-5827. E. T. Olejniczak, P. J. Hajduk, P. A. Marcotte, D. G. Nettesheim, R. P. Meadows, R. Edalji, T. F. Holzman and S. W. Fesik, J. Amer. Chem. Soc., 1997, 119, 5828-5832. P. J. Hajduk, J. Dinges, G. F. Miknis, M. Merlock, T. Middleton, D. J. Kempf, D. A. Egan, K. A. Walter, T. S. Robins, S. B. Shuker, T. F. Holzman and S. W. Fesik, J. Med Chem., 1997,40, 31443150. P. J. Hajduk, E. T. Olejniczak and S. W. Fesik, J. Amer. Chem. Soc., 1997, 119, 12257- 12261. C. Mumenthaler, P. Guntert, W. Braun and K. Wuthrich, J. Biomol. NMR, 1997, 10,351 -362. M. Nilges and S. 1. Odonoghue, Prog. Nucl. Magn. Reson. Spect., 1998, 32, 107- 139. P. Guntert, C. Mumenthaler and K. Wuthrich, J. Mol. Biol., 1997,273,293-298. E. G. Stein, L. M. Rice and A. T. Brunger, J. Mugn. Reson., 1997,124, 154-164. A. T. Brunger, P. D. Adams and L. M. Rice, Structure, 1997,5,325-336. R. Abseher, L. Horstink, C. W. Hilbers and M. Nilges, Proteins-Strucf. Funct. Genet., 1998,31, 370-382. M. Leutner, R. M. Gschwind, J. Liermann, C. Schwarz, G. Gemmecker and H. Kessler, J. Biomol. NMR, 1998, 11, 31 -43. D. E. Zimmerman, C. A. Kulikowski, Y. P. Huang, W. Q. Feng, M. Tashiro, S. Shimotakahara, C. Y. Chien, R. Powers and G. T. Montelione, J. Mol. Bid., 1997,269,592-610. K. Huang, M. Andrec, S. Heald, P. Blake and J. H. Prestegard, J. Biomol. NMR, 1997,10,45-52. L. M. Zhu, H. J. Dyson and P. E. Wright, J. Biomol. NMR, 1998,11, 17-29. C . M. Dobson and P. J. Hore, Nature Struct. Biol., 1998,5504-507. J. A. Jones, D. K. Wilkins, L. J. Smith and C. M. Dobson, J. Biomol. NMR, 1997, 10,199-203. P. J. Hore, S. L. Winder, C. H. Roberts and C. M. Dobson, J. Amer. Chem. Soc., 1997,I19,5049-5050.

360 195 196 I97 198 199 200 20 1 202 203 204 205 206 207 208 209 210 21 1 212 213 214 215 216 217 218 219 220 22 I 222 223 224

Nuclear Mugnetic Resonance

E. W. Chung, E. J. Nettleton, C. J. Morgan, M. Gross, A. Miranker, S. E. Radford, C. M. Dobson and C. V. Robinson, Protein Science, 1997,6, 1316- 1324. J. 1. Guijarro, C. J. Morton, K. W. Plaxco, I. D. Campbell and C. M. Dobson, J. Mol. B i d , 1998,276, 657-667. J. Balbach, V. Forge, W. S. Lau, J. A. Jones, N. A. J. VanNuland and C. M. Dobson, Pruc. Nutl Acucl. Sci. USA, 1997,94, 7182-7185. S. E. NiebaAxmann, M. Ottiger, K. Wuthrich and A. Pluckthun, J. Mol. Biol., 1997, 271,803-818. Y. W. Bai, A. Karimi, H. J. Dyson and P. E. Wright, Protein Science, 1997, 6, 1449- 1457. C. Freund, P. Gehrig, T. A. Holak and A. Pluckthun, FEBS Lett., 1997,407,42-46. J. H. Laity, C. C. Lester, S. Shimotakahara, D. E. Zimmerman, G. T. Montelione and H. A. Scheraga, Biochemistry, 1997,36, 12683- 12699. J. Yao, H. J. Dyson and P. E. Wright, FEBS Lett., 1997,419,285-289. B. A. Schulman, P. S. Kim, C. M. Dobson and C. Redfield, Nuture Struct. Biol., 1997,4,630-634. D. Eliezer, P. A. Jennings, H. J. Dyson and P. E. Wright, FEBS Lett., 1997, 417, 92-96. D. Eliezer, J. Yao, H. J. Dyson and P. E. Wright, Nuture Struct. Biol., 1998, 5, 148- 155. J. I. Guijarro, M. Sunde, J. A. Jones, 1. D. Campbell and C. M. Dobson, Proc. Nutl Acacl. Sci. U S A , 1998,95,4224-4228. S. Bagby, S. Go, S. Inouye, M. Ikura and A. Chakrabartty, J. Mol. Biol., 1998, 276, 669 -68 I . K. W. Plaxco, C. J. Morton, S. B. Grimshaw, J. A. Jones, M. Pitkeathly, I. D. Campbell and C. M. Dobson, J. Biomol. N M R , 1997, 10,221-230. C. J. Penkett, C. Redfield, I. Dodd, J. Hubbard, D. L. McBay, D. E. Mossakowska, R. A. G. Smith, C. M. Dobson and L. J. Smith, J. Mol. Biol., 1997,274, 152- 159. H. Schwalbe, K. M. Fiebig, M. Buck, J. A. Jones, S. B. Grimshaw, A. Spencer, S. J. Glaser, L. J. Smith and C. M. Dobson, Biochemistry, 1997,36,8977-8991. G. Otting, Prug. Nucl. Magn. Reson. Spect., 1997,31,259-285. G. Otting, Prug. Nucl. Magn. Reson. Spect., 1998,32, 191-191. G. Otting, E. Liepinsh, B. Halle and U. Frey, Nature Struct. B i d , 1997,4, 396-404. E. Liepinsh and G. Otting, Nature Biotech., 1997, 15,264-268. H. Ponstingl and G. Otting, J. Biomol. N M R , 1997,9,441-444. A. Mesgarzadeh, S. Pfeiffer, J. Engelke, D. Lassen and H. Ruterjans, Eur. J. Biochem., 1998,251,781-786. S. Pfeiffer, N. Spitzner, F. Lohr and H. Ruterjans, J. Biomol. N M R , 1998, 11, 1-15. I. Bertini, C. Dalvit, J. G. Huber, C. Luchinat and M. Piccioli, FEBS Lett., 1997, 415,45548. G. P. Connelly and L. P. McIntosh, Biochemistry, 1998,37, 18 10- 18 18. A. G. Sobol, G. Wider, H. Iwai and K. Wuthrich, J. Mugn. Reson., 1998, 130, 262-271. A. M. Torres, S. M. Grieve, B. E. Chapman and P. W. Kuchel, Biophys. Chem., 1997,67, 187 - 198. A. M. Torres, S. M. Grieve and P. W. Kuchel, Biophys. Chem., 1998,70,231-239. D. S . Garrett, Y. J. Seok, A. Peterkofsky, G. M. Clore and A. M. Gronenborn, Protein Science, 1998,7, 789-793. A. U. Singer and J. D. FormanKay, Protein Science, 1997,6, 1910- 1919.

9: N M R of Nuturul Macromolecules

225 226 227 228 229 230 23 1 232 233 234 235 236 237 238 239 240 24 1 242 243 244 245 246 247 248 249 250 25 1 252 253 254 255

36 1

P. T. Chivers, K. E. Prehoda, B. F. Volkman, B. M. Kim, J. L. Markley and R. T. Raines, Biochemistry, 1997,36, 14985 - 14991, M. D. Joshi, A. Hedberg and L. P. McIntosh, Protein Science, 1997,6,2667-2670. F. Lohr and H. Ruterjans, J. Biomol. NMR, 1997,9,371-388. T. Diercks, M. Schwaiger and H. Kessley, J. Mugn. Reson., 1997, 130,335-340. 0 .W. Zhang, J. D. FormanKay, D. Shortle and L. E. Kay, J. Biomol. NMR, 1997, 9,181-200. 0.W. Zhang, L. E. Kay, D. Shortle and J. D. FormanKay, J. Mol. Biol., 1997,272, 9-20. C. Zwahlen, K. H. Gardner, S. P. Sarma, D. A. Horita, R. A. Byrd and L. E. Kay, J. Amer. Chem. Soc., 1998,120,7617-7625. C. Zwahlen, S. J. F. Vincent, K. H. Gardner and L. E. Kay, J. Amer. Chem. Soc., 1998,120,4825-4831. M. Sattler and S. W. Fesik, J. Amer. Chem. Suc., 1997,119,7885-7886. K. J. Walters, H. Matsuo and G. Wagner, J. Amer. Chem. SOC., 1997, 119, 5958-5959. A. G. Palmer, Curr. Opin. Struct. Bid., 1997, 7 , 732-737. K. T. Dayie and G. Wagner, J. Amer. Chem. SOC.,1997,119,7797-7806. J. Engelke and H. Riiterjans, J. Biomol. NMR, 1997,9,63-78. P. Allard and T. Hard, J. Magn. Reson., 1997,126,48-57. M. W. F. Fischer, L. Zeng, Y. X. Pang, W. D. Hut A. Majumdar and E. R. P. Zuiderweg, J. Amer. Chem. SOC.,1997, 119, 12629- 12642. V. A. Daragan, K. H. Mayo, J. Magn. Reson. Series B, 1995,107,274-278. D. W. Yang, Y. K. Mok, J. D. FormanKay, N. A. Farrow and L. E. Kay, J. Mol. Biol., 1997,272, 790-804. T. Bremi, R. Bruschweiler and R. R. Ernst, Amer. Chem. Soc., 1997, 119, 4272-4284. D. W. Yang, A. Mittermaier, Y. K. Mok and L. E. Kay, J. Mul. Biol., 1998, 276, 939-954. D. R. Muhandiram, T. Yamazaki, B. D. Sykes and L. E. Kay, J. Amer. Chem. Soc., 1995,117, 11536-11544. L. E. Kay, D. R. Muhandiram, N. A. Farrow, Y. Aubin and J. D. Formankay, Biochemistry, 1996,35, 361 -368. V. A. Daragan and K. H. Mayo, J. Magn. Reson., 1998,130,329-334. D. R. Muhandiram, P. E. Johnson, D. W. Yang, 0. W. Zhang, L. P. McIntosh and L. E. Kay, J. Biomol. NMR, 1997,10,283-288. N. Tjandra and A. Bax, J. Amer. Chem. SOC.,1997,119,9576-9577. N. Tjandra and A. Bax, J. Amer. Chem. Suc., 1997,119,8076-8082. M . Tessari, H. Vis, R. Boelens, R. Kaptein and G. W. Vuister, J. Amer. Chem. Soc., 1997,119,8985-8990. K. Pervushin, R. Riek, G. Wider and K.Wuthrich, Proc. Natl Acud. Sci. USA, 1997, 94, 12366-12371. D. W. Yang, R. Konrat and L. E. Kay, J. Amer. Chem. SOC., 1997, 119, 11938- 11940. B. Brutscher, N. R. Skrynnikov, T. Bremi, R. Bruschweiler and R. R. Ernst, J. Magn. Reson., 1998,130,346-351. B. Reif, M. Hennig and C. Griesinger, Science, 1997,276, 1230-1233. P. Luginbuhl, K. V. Pervushin, H. Iwai and K. Wuthrich, Biochemistry, 1997, 36, 7305-7312.

362

Nuclear Mugnetic Resonunce

256

V. Copie, Y. Tomita, S. K. Akiyama, S. Aota, K. M. Yamada, R. M. Venable, R. W. Pastor, S. Krueger and D. A. Torchia, J. Mol. Biol., 1998,277,663-682. D. Q . Jin, F. Figueirido, G . T. Montelione and R. M. Levy, J. Amer. Chem. Soc., 1997,119,6923-6924. M. Philippopoulos, A. M. Mandel, A. G. Palmer and C. Lim, Proteins-Struct. Funct. Genet., 1997,28,481-493. D. M. Korzhnev. V. Y. Orekhov and A. S. Arseniev, J. Mugn. Reson., 1997, 127, 184- 191. M. Akke, J. Liu, J. Cavanagh, H. P. Erickson and A. G . Palmer, Nuture Struct. Biol., 1998,5, 55-59. L. E. Kay, D. R. Muhandiram, G . Wolf, S. E. Shoelson and J. FormanKay, Nuture Struct. Biol., 1998,5, 156- 163. A. T. Alexandrescu, K. RathgebSzabo, K. Rumpel, W. Jahnke, T. Schulthess and R. A. Kammerer, Protein Science, 1998,7, 389-402. C. van Heijenoort, F. Penin and E. Guittet, Biochemistry. 1998,37, 5060-5073. J. F. Lefevre, K. T. Dayie, J. W. Peng and G. Wagner, Biochemistry, 1996, 35, 2674-2686. K. Yamasaki, A. AkasakoFurukawa and S. Kanaya, J. Mol. Biol., 1998, 277, 707 - 722. M. C. Mossing, Protein Science, 1998,7, 983-993. A. Malmendal, G. Carlstrom, C. Hambraeus, T. Drakenberg, S. Forsen and M. Akke, Biochemistry, 1998,37,2586-2595. B. Brutscher, R. Bruschweiler and R. R. Ernst, Biochemistry, 1997, 36, 13043- 13053. G. W. Daughdrill, L. J. Hanely and F. W. Dahlquist, Biochemistry, 1998, 37, 1076- 1082. M. Akke and A. G. Palmer, Amer. Chem. Soc., 1996,118.91 1-912. S. ZinnJustin, P. Berthault, M. Guenneugues and H. Desvaux, J. Biomol. NMR, 1997,10,363-372. M. D. Smensen, S. Bjorn, K. Norris, 0. Olsen, L. Petersen, T. L. James and J. J. Led, Biochemistry, 1997,36, 10439- 10450. F. J. Moy, M. R. Pisano, P. K. Chanda, C. Urbano, L. M. Killar, M. L. Sung and R. Powers, J. Biomol. NMR, 1997, 10,9-19. P. L. Zhang, K. T. Dayie and G. Wagner, J. Mol. Biol., 1997,272,443-455. A. Hrovat, M. Blumel, F. Lohr, S. G. Mayhew and H. Ruterjans, J. Biomol. N M R , 1997,10, 53--62. W. J. Fairbrother, M. A. Champe, H. W. Christinger, B. A. Keyt and M. A. Starovasnik, Protein Science, I997,6,2250-2260. M. Akke, R. Fiala, F. Jiang, D. Patel and A. G . Palmer, RNA-Publ. RNA Soc., 1997,3,702--709. P. A. Carr, H. P. Erickson and A. G. Palmer, Structure, 1997,5949-959. F. C. L. Almeida and S. J. Opella, J. Mol. Biol., 1997, 270,481 -495. M. Guenneugues, P. Drevet, S. Pinkasfeld, B. Gilquin, A. Menez and S. ZinnJustin, Biochemistry, 1997,36, 16097-16108. S. J. Landry, N. K. Steede and K. Maskos, Biochemistry, 1997,36, 10975-10986. S. Rothemund, Y. C. Liou, P. L. Davies and F. D. Sonnichsen, Biochemistry, 1997, 36, 1 3791 - 1 3801. H. Berglund, M. WolfWatz, T. Lundback, S. vandenBerg and T. Hard, Biochemistry, 1997,36, 1 1 188- 1 1 197. D. H. Purvis and B. C. Mabbutt, Biochemistry, 1997,36, 10146-10154.

257 258 259 260 26 1 262 263 264 265 266 267 268 269 270 27 1 272 273

2 74 275 276 277 278 279 280 28 1 282 283 284

9: N M R of Nuturul Mucromolecules

285 286 287 288 289 290 29 1 292 293 294 295 296 297 298 299 300 30 1 302 303 304 305 306 307

363

J. H. Liu, W. X. Gong, 0. Prakash, L. Wen, I. S. Lee, J. K. Huang and R. Krishnamoorthi, Protein Science, 1998,7, 132.- 141. C. S. Lee, T. K. S. Kumar, L. Y. Lian, J. W. Cheng and C. Yu, Biochemistry, 1998, 37,155-164. I. Bertini, A. Donaire, C. Luchinat and A. Rosato, Proteins-Strucf. Funct. Genet., 1997,29,348-358. D. Bentrop, I. Bertini, M. A. Cremonini, S. Forsen, C. Luchinat and A. Malmendal, Biochemistry, 1997,36, 11605-1 1618. D. Bentrop, I. Bertini, C. Luchinat, W. Nitschke and U. Muhlenhoff, Biochemistry, 1997,36, 13629- 13637. B. Coxon, N. Sari, M. J. Holden and V. L. Vilker, Mugn. Reson. Chem., 1997, 35, 743-751. A. Bockmann and E. Guittet, FEBS Lett., 1997,418, 127--130. S. Fefeu, N. Birlirakis and E. Guittet, Eur. Biophys. J. Biophys. Lett., 1998, 27, 167-171. M. L. Cai, Y. Huang, K. Sakaguchi, G. M. Clore, A. M. Gronenborn and R. Craigie, J. Biomol. N M R , 1998, 11,97-102. K. H. Gardner and L. E. Kay, J. Amer. Chem. Soc., 1997,119,7599-7600. S . Bagby, K. I. Tong, D. J. Liu, J. R. Alattia, M. Ikura, J. Biomol. N M R , 1997, 10, 279-282. D. R. Casimiro, P. E. Wright and H. J. Dyson, Structure, 1997,5, 1407-1412. A. C . Gibbs, L. H. Kondejewski, W. Gronwald, A. M. Nip, R. S. Hodges, B. D. Sykes and D. S. Wishart, Nature Struct. Biol., 1998,5,284-288. K. E. Prehoda, E. S. Mooberry and J. L. Markley, Biochemistry, 1998, 37, 5785-5790. G. Gemmecker, M. Eberstadt, A. Buhr, R. Lanz, S. G. Grdadolnik, H. Kessler and B. Erni, Biochemistry, 1997,36, 7408-7417. M. Pellecchia, G. Wider, H. Iwai and K. Wuthrich, J. Biomol. N M R , 1997, 10, 193- 197. J. J. Prompers, A. Groenewegen, C. W. Hilbers and H. A. M. Pepermans, J. Mugn. Reson., 1998, 130,68-75. B. Whitehead, M. Tessari, P. Dux, R. Boelens, R. Kaptein and G. W. Vuister, J. Biomol. N M R , 1997,9, 313-316. B. C . M. Potts and W. J. Chain, J. Biomol. N M R , 1998, 11,45-57. D. S. Wishart, M. S. Watson, R. F. Boyko and B. D. Sykes, J. Biomol. NMR, 1997, 10,329-336. W. Gronwald, R. F. Boyko, F. D. Sonnichsen, D. S. Wishart and B. D. Sykes, J. Biomol. N M R , 1997,10, 165-179. W. Gronwald, R . F. Boyko and B. D. Sykes, Comp. Appl, Biosci., 1997, 13, 557558. S. S. Wijmenga, M. Kruithof and C. W. Hilbers, J. Biomol. NMR, 1997, 10, 337350.

10 Synthetic Macromolecules BY H. KUROSU AND T. YAMANOBE

1

Introduction

For synthetic macromolecules, physical properties and functions are very important to the material. In most cases physical properties and functions are determined by structure of the synthetic macromolecules. NMR is used to characterize synthetic macromolecules for a variety of purposes. In this chapter we report about synthetic macromolecules analyzed by NM R spectroscopy. Spiess’ reviews developments in multidimensional NMR in the solid state. This review describes the unique information obtainable from solid state NMR with specific examples of structural studies of chain conformation, advanced aspects of chain dynamics, phase separation and interfacial effects. Further, the new development of high resolution multiple quantum NMR of abundant nuclei in the solid state is emphasized. Mori and Koenig2 described recent advances in the application of high resolution solid state NMR to the characterization of network structures and vulcanization chemistry of elastomers. Tonelli3 produced a review about the connections between the NMR spectra and microstructures of polymers from the point of view of the microstructurally sensitive local conformations of polymer chains based on y-gauche effect. Spange et al. reviewed their own work;4 they applied cationic polymerization to grafting and coating of silica particles. The produced polymers were characterized by ‘H MAS NMR and 13C CPMAS NMR. Other reviews have been published about bacterially synthesized cop~lyesters~, the morphology of polymer latex6, acid-soaps7, the microstructure of ring-opened methathesis polymers*, various techniques for structural characterization of polymers using NMR’, stereoregularity and imaging of elastomers’ I .

2

Liquid crystals

The conformational distribution of the main chain liquid crystal polymer, poly(3((methyltrimethy1ene)oxy)trimethylene p,p’-bibenzoate) was investigated by analysis of NMR vicinal coupling constants and dipole moment12. Two liquid crystalline polyethers which were polycondensed 1-(4-hydroxy-4’-bipheny1)-2-(4hydroxypheny1)propane with 1,12-diibromododecane or 1,l Sdibromopentadecane were characterized to study the molecular motion and conformation of Nuclear Magnetic Resonance, Volume 28

0The Royal Society of Chemistry, 1999 364

10: Synthetic Macromolecules

365

space and mesogenic group by solid state NMRi3. Phase separated poly(4,4’phthaloimidobenzoyldodecamethyleneoxycarbonyl) was studied by solid state NMR. The difference of conformational ordering in the flexible spacers between two crystalline forms was observed in NMR spectra“. For crystalline, liquid crystalline and noncrystalline phases of thermotropic liquid crystalline polyurethane which was polymerized from 3,3’-dimethyl-4,4’-biphenyl diisocyanate, 1,lO-decanediol and 1-hexanol, chain conformation of spacer group was investigated15. Orientation and dynamics of polyacetylene substituted by liquid crystalline side chains were investigated by anisotropic chemical shift tensor16. Pulse N MR studies were carried out for liquid crystalline polyesters with fumaroyl-bisoxybenzoate connected by (CH& (CH& and CH2(CH2CH20)2 to investigate chemical exchange and dynamicsI7. The structure and dynamics of ionic polymers which are based on 4,4’-bipyridyl and ditosylate of trans- 1,4-cycIo-hexane dimethanol and 1,8-octanediol in polar solvent were studied by DEPT, ‘H-IH COSY and NOESY 1 8 . The nematic-to-isotropic phase transition was observed by deuterium N MR for a liquid crystalline polyamide composed of p-phenylenediamine and 2,5-thiophenedicarboxylicacid”. The flow behavior of a liotropic liquid crystalline polymer is investigated by deuterium NMR. The director orientation was determined from deuterium splitting2’. The influence of surface anchoring strength and nonspherical cavity shape on the nematic structures was investigated by deuterium NMR2’. The influence of a magnetic field on curing of a polymer based on the diglycidyl ester of terephthaloyl-bis(4-hydroxybenzoic acid) in the liquid crystalline state was investigated22. The local motions of a liquid crystalline sequence-ordered polymer prepared from isophthalic acid and 4-hydroxyphenyl-4-hydroxybenzoatewas investigated by solid state NMR23. Solid state NMR is used to study liquid crystal-polymer interactions in polymerdispersed liquid crystals24.

3

Primary Structure

NMR spectroscopy is one of the most powerful tools which can characterize the primary structure of polymers, such as tacticity, regioregularity, end group, irregular structure, sequence distribution and so on. Table 10.1 summarizes the papers in which NMR is used to characterize primary structure of polymers. Table 10.1 N M R studies of primary structure of polymers Polymer

Nucleus Contents

Ref.

(1 -6)-2,5-anhidro-3,4-di-O-methyl-~-gluciH

end group

25

tols amylose, amylopectin H,C copo1yester:o-phthalic anhydride, oleic acid, H,C trimethylolpropane

branch esterification degree, end group

26

27

Nuclear Magnetic Resonance

366 ~

Polymer

Ref. 28

H,C H,C H

methodology, sequence analysis cyclic structure substitution aggregation structure

H,C C H,C

reactivity, composition sequence distribution fullerene-polymer linkage

32 33 34

C,N H,C H

cross link cross link degree of hydrogenation composition

35 36 37 38

polymerization mechanism cyclic oligomer degradation structure tactici ty sequence distribution cross link polymerization mechanism irregular structure sequence distribution composition

39 40 41 42 43 44 45 46 47 48

regiotactici ty

49

H,C

sequence distribution

50

C,Si H

irregular structure composition, tactici ty, sequence distribution composition, sequence distribution

51 52

endgroup configuration composition

54 55 56

copolymer cyclic poly(propy1ene oxide) cyclodext rin-poly(vinylamine) dendritic-linear block copo1ymer:isophthalate ester-functionalized dendrimer, styrene dextran 1 -naphthylacetate EPDM, sequenced EPDM fullerene-poly(propion ylet hyleneimine-coethyleneimine) fullerol-containing polymer furfuryl alcohol resin hydrogenated styrene-butadiene elastomer imide-dimethylsiloxane block copo1ymer:bis(aminopropy) oligomer, 4,4'-oxydianiline, pyromellitic dianhydride di ethyl ester chloride melamine reskacetone, formaldehyde nylon I 1 nylon-66 oligostyrene pectin, chemical modified pectin phenol-formaldehyde resol resin PMR resin poly((3-hexylthiopheneylene)ethynylenes) poly((L)-lactide-co-ethyleneoxide) poly((R,S)-P-butyro1actone)-block-poly(pivalolactone) poly((R,S)-0-butyro1actone)-block-poly(Ecaprolactone) poly((R)-3-hydroxybutyric acid-co-(S,S)lactide) poly( (S)-(+)-2-methylbutyl)pentylsiloxane poly( 1, I , 1-trifluoropropylmethyIsiloxaneco-dimet hylsiloxane) poly( 1,3-butadiene-co-(E)-1,3-pentadiene), 1,3-pentapoly( 1,3-butadiene-co-4-methyldiene), poly(4-methyl- 1,3-pentadiene-co(2)-1,3-pentadiene) poly( I ,3-dioxepane) poly( 1,3-pentadiene) poly( I ,3-pentadiene-co-l,3-~ycIopentadiene)

~~~

Nucleus Contents

H H H H C H H,C H

H,C H,C H

29 30 31

53

10: Synthetic Macromolecules

poly( I ,4,4a,5,8,8a-hexahydro-l,4,5,8-exo, endo-dimethanonapht halene) poly( 1-hexene) C poly( 1-PP-(4'-acetylphenyl) vinyl-3- 1,1,3,3- H,C,Si tet rame thy Idisiloxane) poly(2,4,8,1O-tetraoxaspiro(5,5)undecane-3- C one), poly(2,4,8,10-tetraoxasppiro(5,5)-undecane-3-one-co-trimethylene carbonate) poly(2,5-bis(3-sulfonatopropoxy)- I ,4-phe- H nylene-alt-1,Cphenylene)sodium salt, poly(2,5-bis(3-sulfonatopropoxy)- 174-phenylene-alt-4,4'-biphenylene)sodium salt poly(2-((2-methyl-1 -(triethylsiloxy)-1-prope- C ny1)oxy)ethyl methacrylate) poly(2-hydroxy-5-N-methacrylamidoben- C zoic acid) H poly(2-hydroxyethyl methacrylate-graft-ccaprolactone), poly(c-capro1actone)-blockpoly(trimethy1ene carbonate) poly(3,3-dimethylcyclopropene),poly(3C ethyl-3-methylcyclopropene), poly(3-npentyl-3-methylcyclopropene) pol y( 3-amino-~tyrosine) C.N poly(3-hexylthiophene) poly(3-h ydroxy butyrate-co-4-hydroxyvalerate) pol y( 3-hydroxybutyrate-co-hydroxyvalerate) poly(3-hydroxybutyric acid-co-3-hydroxy- C propionic acid) poly(3-octylthiophene-co-thiophene) H poly(4,6-di-n-butoxy-1,3,phenylene) H,C poly(4-(dimethyleamino)benzyl methacryH late-co-methyl methacrylate) poly(4-allyanisole) H poly(4-hydroxybutyl terephthalate-co-4-h~- H droxy buty 1 naph t hala te) poly(4-nitrophenyl acrylate), poly(4-nitro- H phenyl acrylate-co-glycidylmethacrylate) poly(4-vin ylpyridine-co-N-dodecy lacrylaC mide) poly(4-vinylpyridine-co-p-met hoxyst yrene), H poly(4-viny lpyridine-co-p-met hylstyrene), poly(4-vinylpyridine-co-a-me thy 1styrene), poly(4-vinylpyridine-co-p-tert-butylstyrene), poly(4-vinylpyridine-co-styrene) poly(acry1amide) poly(alky1ene p,p'-bibenzoate-co-adipate)

367 configuration, tacticity

57

sequence structure hyperbranch, polymerization mechanism tacticity, composition

58 59 60

end group

61

branch

62

tacticity

63

graft structure, block structure, end group

64

tac ticit y

65

linkage regioregularity, end group composition, end group

66 67 68

compostion, sequence distribution sequence distribution

69

regioregularity regioregularity composition reactivity

71 72 73

polymerization mechanism sequence distribution

74 75

composition

76

tacticity

77

composition

78

reaction mechanism sequence distribution

79 80

70

3 68

Nuclear Mugnetic Resonance

Polymer

Nucleus

Contents

poly(allylmethacry1ate) poly(amide-imide):flexible aromatic diamine,isomeric tricarboxylic acid anhydride,monoesters of trimellitic anhydride poly(ary1 ether oxazole) poly(bisma1eimide) poly(buty1 vinyl ether) poly(buty1ene succinate)-block-poly(butylene terephthalate) poly(buty1ene terephthalate-co-ethylene-covinyl-acetic acid) poly(capro1actone) poly(carb0xybetain) poly(ch1oroprene)-graft-poly(ethy1 methacrylate), poly(ch1oroprene)-graftpol y( methyl methacry late) poly(ch1oroprene-co-a-cyanoet hy lacrylate)

H H,C

structure sequence distribution, composition

81 82

€I,C,F H,C H H

polymerization mechanism polymerization mechanism end group sequence distribution

83 84 85 86

H

sequence distribution

87

H,C H,C H

star macromolecule, branch characterization end group, graft polymer

88 89 90

H,C

91

poly(cis-1,4-butadiene)

H C H,C

composition, sequence distribution aging, cross link substitution main chain conjugation

C C

tact icity tacticity sequence distribution

95 96 97

sequence distribution, end group end group composition reaction mechanism end group

98

poly(cyc1odextrin-co-epichloroh ydrin)

poly(di-ethyl dipropargyl malonate), poly(triethyl dipropargyl phosphoneacetate) poly(di-ethyl(Z,Z)-2,4-hexadienedioate) poly(di-methyl fumara te) poly(diallyldimethy1ammoniumchloridecopacry lamide) poly(diethy1eneglycol carbonate)

H, C

poly(diphenylsi1oxane-co-dimethylsiloxane) H poly(ethy1ene terephthalate) H C pol y(ester-anhydride) poly(ester-urethane):lactic acid, 1,4-butane- C dio1,diisocyanate poly(ethene-co-styrene-co1 -octene) C H poly(ether ketone ketone) poly(ether sulfone) H poly(ethy1cr-benzoyloxymethylacrylate-co- H,C methyl methacrylate) H poly(ethy1ene glycol) macromonomer H,C poly(ethy1ene oxide) H poly(ethy1ene oxide), poly(ethy1ene glyco1)Et ether methacrylate

sequence distribution irregularity end group sequence distribution, stereoregularity end group sequence distribution composition

Ref.

92 93 94

99 100 101 102

103 I04 105 106 107 108 109

10: Synthetic Macromolecules

poly(ethy1ene terephthalate), poly(ethy1ene 2,6-naphthalate) poly(ethy1ene-co- I -hexene) poly(ethy1ene-co-methyl acrylate) poly(ethy1ene-co-norbornene) poly(eth ylene-co-norbornene) poly(ethy1ene-co-norbornene) poly(ethy1ene-co-propylene) poly(eth ylene-co-propylene) poly(ethy lene-co-propylene) poly(ethy1ene-co-propylene), poly(ethy1eneco- I -octene) poly(ethylmethylsiloxane), poly(n-propylmethylsilloxane), poly(n-butylmethylsiloxane), poly(n-pen tylmethylsiloxane), poly(n- hexylmet hylsiloxane) poly(exo-5-methyl-hept-2-ene), poly(endo-

369 transesterification

110

sequence distribution end group, branch sequence distribution sequence distribution composition end group block structure tacticity, crystal structure polymerization mechanism

114 1 I5 1 I6 117 118 1 I9

tacticity

120

tacticity

121

poly(imid-amide):4,4-methylenedi(phenyl

molecular weight

122

isocyanate),trimellitic anhydride, benzoic acid poly(isatoic anhydride-co-N-(2-hydroxyethy1)ethylenimine) poly(isobuty1ene)

composition

123

end group, reaction mechanism reaction mechanism sequence distribution

124

125 126

tacticity tactici ty stereoregularity s tereochemical configuration graft structure

127 128 129 130 131

end group polymerization mechanism end group tacticity, catalyst multiarmed structure end group, polymerization mechanism tacticity end group

132 133 134 135 136 137

Ill

112 113

5-methyl-hept-2-ene),5,5-dimethyl-hept-2ene)

poly(L,L-lactide) poly(L-lactide-co-2,2-[2-pentene1,5-dily]trimethylene carbonate) poly(lactic acid) poly(1actic acid) poly(1actide) poly(ma1eic acid) poly(ma1eic acid-graft-polyethylene, poly(maleic acid)-graft-polypropylene poly(methy1 methacrylate) poly(methy1 methacrylate) poly(methy1 methacrylate) poly(met hyl methacry late) pol y(met hy 1 me thacrylate) poly(methy1 methacrylate) poly(methy1 methacrylate) poly(methy1 methacrylate), poly(acry1onitrile-co-ethyl vinyl ether), polystryrene, pol yacrylonitrile

138 139

3 70 ~

Nucleur Magnetic Resonance ~~

Polymer

Nucleus Contents

poly(methy1 methacrylate), polystyrene, polyisoprene, poly(viny1pyridine) €1 poly(methy1 methacrylate)-block-poly(dimethylaminoethylmethacry late)-blockpoly(tetrahydropyrany1methacrylate) poly(methy1 methacrylate)-block-poly(viny1 H acetate) poly(methy1 methacrylate-co-4-acetylphenyl H,C acrylate), poly(buty1 methacrylate-co-4acetylphenylacr y late) PO 1y( met hyl me thacry la te-co-but yl acrylate) C poly(methylmethacry1ate) C H pol y( met hylmet hacry late) poly(methylmethacry1ate-co-poly(ethy1ene H glyco1)monomethacrylate) poly(methylphenylsilylenetrimethylene) €I poly(methyltriethoxysilane), poly(methy1Si triethoxysilane-co-tetraethoxysilane) poly(methylvinylsiloxane-co-dimethylsiSi loxane) poly(methy1cr-trifluoroacetoxyacrylate), C poly(methy1cr-trifluoroacetoxyacrylate-co-crmethylstyrene) poly(N,N-diallyl-2-(methoxy-carbonyl)ally- C lamine) poly(n-butyl acrylate) C poly(N-o-tolyl nadimide) H,C poly(norbornene) H,C poly(oxy- 1,3-phenylenecarbonyl- ,4-pheny- H,C lene) poly(p-methylstyrene)-block-pollsoprene- H,C block-poly(p-methylstyrene) C pol y( p-phen ylene(3-(alk yl t hio)-2,5-thieny 1ene)-p-phenylene) pol y(p-phenylene) P pol y(p-pheny lene) C poly(p-phenyleneterephthalamide) H,C poly(p-xylylene carbonate-co-p-xylylene H,C oxide) poly(perfluoro(oxylmethy1ene-ran-oxyethy- C,F 1ene)macromer poly(pheny1glydicyl ethers)

Ref.

end group

i40

block structure

141

block copolymer

142

composition

143

sequence distribution tacticit y stereoregularity monomer reactivity, sequence distribution tacticity sequence distribution

144 145 146 147

sequence distribution

150

reactivity

151

sequence regularity

152

branch configuration tacticity reactivity

153 154 155 156

degree of substitution

157

regiostructure

158

polymerization mechanism backbone linkage grafting mechanism end group

159

composition

163

tactici ty

164

148 149

160

161 162

10: Synthetic Macromolecules

371

poly(phenylacety1ene-co-norbornene), H 'poly(phenylacety1ene-co-benzonorbornadiene), 'poly(pheny1-acetylene-co-ethylidene-bicycloheptene) poly(pheny1acetyleneco-trimethylsilyl-norbornadiene), poly(phenylacetylene-co-dimethanooctahydronaphthalene), poly(phenylacety1ene-codelta-cyclene) 'poly(phenylacety1ene-co-norbornadiene) pol y( phenylnorbornene-co-ethylene) poly( phenylsilsesquioxane) H,Si poly( propene-co- I -hexene) C poly(propy1ene imine) H poly(propy1ene imine) dendrimer poly(propy1ene oxide) C poly(propy1ene oxide), poly(cyc1ohexene oxide) Poly(propylene), poly(styrene) fr poly( yropylene-co-butene) c poly( silane-co-ferrocenylsilane) H,Si poly(styrene-block-methacrylate)-blockpolystyrene pol y (styrene-co-acrylonitrile) H poly(s tyrene-co-acrylonitri1e)-graft-polybu- C tadiene poly(st yrene-co-aminoethylmethacrylate), H poly(styrene-co-vinyl benzyl amine) poly( st yrene-co-ethylene) C pol y(styrene-co-ethy lene-co-butene-1 ) poly(styrene-co-maleic anhydride) poly(styrene-co-maleic anhydride)

C C C

poly(styrene-co-tetrahydrofufurylmethacrylate) poly(succinic acid-co-ethylene oxide) poly( tetramethylene)-block-poly(2,6naph thalenedicarboxy late) poly(trimethy1enecarbonate) pol y (uret hane rot axane) poly(viny1acetate) poly(viny1 butyral) poly(viny1chloride)

H

poly(viny1chloride), poly(~-caprolactone), poly(ethy1ene adipate), poly(ethy1ene oxide). poly(ethy1ene glycol)

H H H H C

H,C C

c

composition

165

composition irregular structure tacticity end group regularity tacticity tacticity

166 167

168 169 170 171 172

end group, molecular weigh1 tac tici ty sequence distribution block structure

173 174 175 176

sequencz distribution grafting point

177 178

polymerization mechanism

179

tacticity, sequence distribution sequence distribution sequence distribution configuration, sequence distribution composition

180

end group composition, sequence distribution end group branch irregular structure conformation substit ut ion, sequence distribution tacticity

181 182 183

184 185

186 187

188 189 190 191 192

3 72

Polymer

Nuclear Magnetic Resonance

Contents

Ref.

poly(viny1 formal-co-vinyl acetate-co-vinyl C alcohol) poly(vinylfroma1-co-vinyl acetate-co-vinyl H,C alcohol) poly(viny1idene chloride-co-ethyl acrylate) H,C poly(ct-benzoyloxymethylacrylate-co-methyl H,C methacrylate)

composition

193

composition

194

tacticity sequence distribution

195 196

poly(ct-chlorostyrene), poly(a-chlorosH,C tyrene-co-styrene), poly(a-chlorostyrene-comethyl methacrylate) C poly( p-(4-acetoxyphenyl)propionicacid) poly(y-butyrolactone-co-L-lactide), poly(y- H,C butyrolactone-co-glycolide),poly(y-butyrolactone-co-glicolide), poly(y-butyrolactoneco-a-propiolactone), poly(P-butyrolactoneco-p-valerolactone), poly(y-butyrolactoneco-s-caprolactone)

configuration

197

sequence composition, sequence distribution

198 199

H,C C H,C

regioregularity polymerization mechanism sequence distribution

200 20 1 202

C H,C

tactici ty pyrolysis polymerization mechanism

203 204 205

C

reaction control

206

sequence distribution

207

molecular weight main chain structure end group, irregular structure structure

208 209 210

degradation, y-radio1ysis sequence distribution

212 21 3

poly(ecapro1actone) poly(s-caprolactone) poly(&-caprolactone-co-vinylphosphonic acid), poly(&-caprolactone-co-dirnethyl vinylphosphonate) poly[(2R,3S)-benzyl p-3-methylmalate] poly[(di-i-butylsilylene)methylene] poly[(ortho- 1,3-dioxolan-2-yl)phenylethyl fumarate] poly[(R)-3-hydroxybutyric acid], poly(&-caprolactone), poly(&-capro1actone)-co-glycolide)

Nucleus

poly[(S)-4-[N(2-emthacryloyloxyethyl)-N- H (2-rnethyIbutyl)]amino-4-cyanoazobenzene],’poly[(S)-4-[N(2-emthacryloyloxyethy1)N-(2-rnethylbutyl)]amino-4-cyanoazobenzene-co-butyl methacrylate] H pol yacrylonitrile polyaniline C polyaspartate polybenzoquinone, polyquinone, polyhydroquinone polycarbonate, polyester polycarbonate: 1,I’dihydroxyethyl-2,2’-biimidazole

H,C

21 1

10: Synthetic Mucromolecules

polycarbonate:4,4'-dihydroxychalcone, methylhydroquinone, 4,4'-dihydroxybiphenyl polydimethylsiloxane, polyceram Si polydimethy lsiloxane-block-polycarbonate H,C,Si polyester,copolyester:trimethylsilylester of acetylated P-(4-hydroxyphenyl)propionic acid,6-hydroxy-2-naphthoicacid, 4-hydroxycinnamic acid, 4-hydroxybiphenyl-4-carboxylic acid, acetylated 4-hydroxybenzoic acid, vanillic acid polyester: I ,4-butylene terephthalamide C H polyester: 1,4-butylene terephthalamide polyester:4,4'-dicarboxy-1,lO-diphenoxyde- H,C cane and halogenated bisphenol A po1yester:dodecanedial H H.C po1yester:o-phthalic anhydride, oleic acid, neopentyl glycol po1yester:o-phthalic anhydride, oleic acid, trimethylopropane po1yester:o-phthalic anhydride, trimethlol- H.C propane polyethene polyethylene polyethylene polyethylene polyethylene polyethylene polyethylene polyethylene, polypropylene H polyethylene/octanoated starch polyethylene-graft-poly(di-ethylfumarate) po1yimide:ethynyl-terminatedaminies,4,4- H (hexafluoroisopropy1idene)diphthalic an hydride,pyromellitic dianhydride pol yimide:hexafluoroisopropy lidene-2,2'H,F bis(phtha1ic acid anhydride),p-aminostyreneamine po1yimide:nadic anhydride, hexafluoroisopropylidene-2,2-bis(phthalicanhydride), mphenylenediamine, p-phenylenediamine polyimide:ct,u-diazidoalkane, 1,I '-(methylene-di-4,l -phenylene)bismaleimide,N,N'1,Cphenylene dimaleimide,isopropylidene1,4-phenylenedimethacry late polyketon:phenylallen, (4-methoxyphenyH l)allene, carbon monoxide

373 sequence distribution

214

porosity composition sequence distribution

215 216 217

sequence distribution composition com posi t ion

218 219 220

end group sequence distribution

22 I 222

composition

223

composition, end group

224

polymerization mechanism branch branch branch polymerization mechanism branch catalitic mechanism end group, tacticity degree of substitution,blend graft structure polymerization mechanism

225 226 227 228 229 230 23 1 232 233 234 235

structure

236

configuration

237

composition, sequence distribution

238

sequence distribution, end group

239

Nuclear Magnetic Resonance

374

Polymer

Nucleus Contents

polylactide H polylactide polymethacrylate H polymethylsiloxane, polyvinylsiloxane H,C,Si polypentadiene-graft-pol yst y rene H polypheno1,tannins polypropylene C polypropylene C polypropylene H polypropylene C polypropylene C polypropylene H,C polypropylene H polypropylene C polypropylene polypropylene polypropylene macromonomer, poly(ehty- C lene-co-polypropylene) polyrotaxane H polysaccharide C polysiloxane-graft-poly(N-acet y iiminoeth y- H lene), polysiloxane-block-poly(N-acetyliminoethy lene) pol ysilsesquioxane H,Si polystyrene H polystyrene H polystyrene polystyrene C polystyrene, poly(buty1 acrylate), polycarbonate polystyrene, poly(methy1 methacrylate) F polystyrene-block-poly(ethy1eneglycol)H block-polyst yrene polystyrene-block-polybutadiene-blockpolystyrene polystyrene-graft-poly(2-hydroxyethylH methacrylate), polystyrene-graft-poly(acrylic acid) polyurethane:benzyl2-amino-2-deoxy-cr-~glucopyranoside hydrochloride, carbon dioxide, triphenylphosphine

Ref.

end group stereochemistry tacticity ladder polymer graft polymer primary structure tacticity tacticity tacticity tacticity tacticity tacticity tacticity, end group tacticity tacticity end group composition

240 241 242 243 244 245 246 247 248 249 250 25 1 252 253 254 255 256

stereosequence composition block, graft structure

257 258 259

ladder-like polymer tacticity end group tacticity tacticity end group

260 26 1 262 263 264 265

end group end group

266 267

configuration

268

end group

269

regioselectivity

270

10: Synthetic Macromolecules

375 structure

27 I

mechanism of cross linking catalitic mechanism

272 273 274

C Si H H

composition, sequence distribution cross link mechanism end group end configuration

275 276 277 278

H

end group

279

po1yurethane:difunctional linear glycidyl C azide polymer, isophorone diisocyanate po1yurethane:diisocyanate and sucrose C polyurethane:poly(tetrahydrofuran-co-ethylene oxide),N- 100 pooy(ch1oroprene-co-a-cyanoethylacrylate) H, c rubber silane terminated polyethylene star-shapedpoly(tetrahydr0furan) unsaturated polyester:styrene,maleicanhydride,phthalicanhydride,diols wallyl-a-halopolystyrene

4

Characterizationof the Synthetic Macromoleculesin the Solid State

4.1 Solid state '3CN M R Studies for Synthetic Macromolecules - Solid state NMR is a powerful tool for characterizing the structure of macromolecules. High resolution solid state I3C NMR is widely used to obtain information about structure and mobility of macromolecules. The chain conformation and crystal packing of syndiotactic poly(4-methyl- 1-pentene) were studied using solid state 13CNMR CP/MAS spectroscopy2*'. Four crystalline forms of i-P4MP have been studied through solid state 13C NMR CPIMAS spectroscopy. The assignment of the resonance was made by dipolar dephasing experiments281.One-dimensional and rhombohedra1 two-dimensional polymers of C60 obtained under high pressure have been studied by I3C MAS NMR. The I3C NMR line shape simulation of the obtained spectra are compatible with the suggested polymeric structures where the C60 molecules are connected by [2+2] cycloadditions282.The phase structures of ethylene-dimethylaminoethyl methacrylate(EDAM) copolymer samples were investigated by solid-state high-resolution I3C NMR spectrocopy^^^. Several variable temperature solid state 13C NMR methods have been carried out on copolymers of ethylene and 1-octene, 1-hexene, 1-butene and vinyl acetate to determine comonomer type and content in p ~ l y o l e f i n s ~Solid ~ ~ . state I3C NMR was used to determine the effect of spinneret diameters and postspinning draw ratio on the secondary structure of alanine residues in the silk protein285. 13C CP/MAS NMR spectra of powder pectins were recorded and interpreted. NMR spectral results were applied for the calculation of galacturonic acid content degrees of methylation and acetylation286. The thermal transition behaviour and phase structure of chitin/poly(glycidyl methacrylate) composites were characterized by DSC, dynamic mechanical analysis and solid state I3C NMR spectro~copy~~'. The structural characteristics of the polymer and network obtained by polymerization of 1,1,l -trimethylolpropane triacrylate were studied by solid state I3CNMR spectroscopy288.A wood adhesive-type phenol-formaldehyde(PF) resol resin synthesized with a typical formaldehyde to phenol mol ratio

376

Nuclear Magnetic Resonance

of 2.10 was thoroughly cured and studied by solid state CP/MAS 13C NMR spectroscopy289. The size and shape of a single fifth generation benzyl ether dendrimer and the nature of packing of dendrimers in the solid state have been determined by a combination of stable isotope labeling, rotational-echo doubleresonance NMR and molecular modeling290.Malleic acid adsorbed on alumina can copolymerize with 1-alkanes to form monolayers of polymer coating that are tightly anchored on the alumina surface. The structure of the copolymer formed on the alumina surface was characterized by means of solid state 13C NMR and proton NMR of the extractable polymer fraction291.The structure of the 7cmolecular complex was assigned on the basis of the solid state I3C NMR spectrum292.Solid state 13CNMR is used to identify the conformation of alanine residues in minor ampullate gland silk from Nephila clavipes and in a genetically engineered protein based on the consensus sequence of MaSp2, a protein present in low concentrations in major ampullate gland293.The structure of the ladder polymer composed of two polydiacetylenes linked by methylene chains was confirmed by the solid state I3C CP/MAS technique294. Slow-magic-anglespinning DECODER NMR based on the anisotropy of chemical shift tensors is used to determine molecular level orientation in three samples of poly(4oxybenzonate-co-1 ,4-phenylene isophthalate) of comparable composition but different process histories295.The vulcanization chemical and network formation of carbon black filled natural rubber vulcanized with sulfur and TBBS were studied using solid state 3C NMR and equilibrium swelling m e a s ~ r e r n e n t s ~ ~ ~ . The phase structure of uniaxially drawn poly(ethy1ene terephthalate)(PET) has been studied by CP/MAS I3C NMR spectroscopy and X-ray diffraction. CP/ MAS I3C NMR spectra show that the chemical shift values of the carbonyl and ethyleneglycol carbons of the non-annealed PET shift to high field as the draw ratio increases, but that thk chemical shift values of the crystalline peak for the heat-set PET shift to high field as the draw ratio decreases297.

4.2 Solid State Multi-Nuclear NMR Studies for Synthetic Macromolecules "N-labeled polyaniline powders have been examined by 13C, I5N and 19F solid state NMR as a function of HF doping298.Sodium polyaspartate was synthesized by the hydrolysis of poly(succinimide) prepared by the thermal polycondensation of L-aspartic acid at 260°C for 6 h. and the microstructures of the polymer were analyzed in detail using 'H and I3C NMR spectroscopy299.29Siand 13CCP/MAS NMR spectroscopy were used to investigate the influence of substance specific parameters such as silane concentration type of silane, pH, and moisture content of the filler on the silicdorganosilane reaction mechanics300.29Si spin lock CP NMR measurements were performed to characterize the solid structure of different polysilanes in the solid state3". Structure of acrylic silanes after heat treatment have been studied by 13Cand 29Si solid state NMR302.Solid state 29Si NMR analyses of the solid structure and dynamics have been performed for poly(di-n-butylsilane) with the order-disorder transition at 76 "C. 29Si chemical shift anisotropy spectra are measured with an ultraslow magic angle spinning at a rate less than 1OOHZ"~. Hybrid materials incorporating polyethylene glycol(PEG) with tetraethoxysilane(TE0S) via a sol-gel process were studied for a wide range

10: Synthetic Macromolecules

377

of components of PEG by DSC and high resolution solid state 13C and 29Si NMR spectroscopy304.The covalent bonding of the dendrimer to silica surface was studied by elemental analysis, 29Si NMR, 29Si CP/MAS and 13C CP/MAS methods3". Solid state I9F NMR investigation of poly(viny1idene fluoride) have been carried out by high-power proton decoupling and high speed MAS306. The y-radiolysis of Kalrez poly(tetrafluoroethy1ene-co-perfluoromethyl vinyl ether)(TFE/PMVE) perfluoroelastomer was investigated using solid state I9Fand 13C NMR spectroscopy307.Triple-channel solid state NMR investigations of two different poly(viny1idene fluoride)(PVDF) materials have been carried out by H to 3C and 19F to I3C cross polarization experiments3o8.N,N-diaryl-substituted polyformamidine, polyacylamidines and polybebzamidine were investigated by "N CP/MAS spectroscopy309.A solid azobenzene dye has been studied by a combination of single crystal X-ray diffraction and "N CP/MAS NMR310. 13C and 15N MAS NMR have been used to study the conversion of methanol and ammonia over H-SAPO-34 and H-RHO using sealed glass ampoules as microreactors under static batch conditions3' '. 13C rotational echo double resonance (REDOR) NMR with 13C dephasing, has been obtained for fully cross-linked epoxy resin3l2. A study of a fire-retarded ethylenevinyl acetate copolymer has been studied by 13C, 25Mgand I'B solid state NMR313. 4.3 Dynamics of the Synthetic Macromolecules in the Solid State - An extensive study of both 'H and I3C Tl(spin-lattice) and TI, (spin-lattice in the rotating frame) relaxation times as well as TCH(proton-carbon cross-polarization times) was undertaken in order to investigate the morphological and dynamics of an ethylene/propylene/ethylene-norbornene terpolymer and two ethylene/propylene random copolymers obtained using different catalytic systems314. The dipolar rotational spin echo 13C NMR spectra at 15.1 MHz were obtained for a series of copolymers of polycarbonate made from monodispersed oligomers of bisphenol A polycarbonate, alternating(via connecting carbonate linkages) with single units of 3,3',5,5'-tetramethylbisphenolA315. Solid state 13C NMR relaxation experiments were carried out on an ethylene-1-hexene copolymer with molecular weight lo5, having 7.8 Bu branches/1000 C atoms. The partitioning of side branches between the crystalline and noncrystalline regions are studied by direct measurement of the dipolar dephase rate of the side chain3I6. 13Chigh-pressure CP/MAS NMR is applied to examine the interaction between a C 0 2 gas and polystyrene under C02 gas pressures of 0-7 MPa317, 13C CP/MAS NMR techniques were used to investigate dynamics of new combined type liquid crystal polymers, [poly[oxy- 1,4-phenyleneoxy-2-{ 6-(4-(4-butylphenylao)phenoxy)decyloxy} terephthalo yl] and Lpoly[oxy-1,4-phenyleneoxy-2-{ 10-(4-(4- butylpheny1azo)phenox18. Dipolar rotational spin-echo 3C NMR spectra at y)decyloxy}] terephtyal~yl]~ 15.1 MHz have been obtained for 12 homopolymers, copolymers, and blends of polycarbonate, poly(ether sulfone), di-Me polycarbonate and tetra-Me polycarbonate319. A study was made of the macrodefect-free(MDF) composite based on aluminate cement and a poly(viny1 alcohol)-poly(viny1acetate)(PVAc) copolymer by 13C cross-polarization magic-angle spinning NMR320. The conformational dynamics both in the solution state and in the structurally modified polycarbo-

378

Nuclear Magnetic Resonance

nate of Bisphenol-A with a cyclohexyl moiety in place of the isopropylidine group has been examined using NMR321.The molecular motion of the long alkyl chains (n-CI4H,,,) of the precursor monomers and the polymers for PDAs of a butadiyne, an octatetrayne, a dodecahexayne and a p-dibutadiynylbenzene has been studied by using solid state high resolution I3C NMR322.The anti-plasticization of epoxy networks based on diglycidylether of bisphenol A and hexamethylene diamine was investigated by both dynamic mechanical analysis and high resolution solid state I3C NMR spectroscopy323.The dynamics of the a relaxation in polystyrene is investigated by applying specific multidimensional solid state NMR echo techniques to evaluate multitime correlation functions324.The longitudinal relaxation time constants(T1) of the protons in a series of dendrimers that alternatively had paramagnetic([Fe4S4(SR)4I2-, R = denron) and diamagnetic (tetraphenylethane) cores were compared325.Solid state NMR have been used to probe cation dynamics on the timescales relevant to spatial diffusional motion of Li+, Na+, Rb+, and Cs+ in these n a n o c o m p ~ s i t e s Chain ~ ~ ~ . modes of entangled polymer melts can directly be probed in a frequency range lo2 Hz < n < lo8 Hz with the aid of field-cycling proton or deuteron relaxometery. The frequency dispersion of proton spin-lattice relaxation universally shows crossovers between the power laws T,Nv0.5'0.05 (region I), TINv0.25'0.05 (region 11), T~~v0.4.5+0.05 (region 111) from high to low frequencies327. Multidimensional NMR experiments on polymers are reported that yield insight into the nature of the non-exponential relaxation above the glass transition328. Chain dynamics in thermoreversible polybutadiene networks were studied in comparison to linear polybutadiene using field-cycling NMR r e l a ~ o m e t r y Molecular ~~~. motions in low-molar-mass(46200g/mol) poly(diethylsi1ozane) are studied by 2H NMR330. The order and molecular dynamics of'wholly aromatic thermotropic copolyesters prepared from hydrooxybenzonic acid, hydroquinone and phenoxyterephthalic acid were studied by X-ray analysis and deuteron NMR spectroscopy of specimens containing either deuterated hydroquinone or deuterated phenoxy sidechain units331. 'H, 13C and 23Na solid state NMR measurements have been used to characterize the morphology and dynamics of several NaSCN-PEO mixt u r e ~ ~The ~ ~ chain . flexibility of halogenated poly( thiony lpho sphazenes) (PTPs) { (NSOX)(NPCI&} n(X=F,CI) was investigated by measuring the 31P spinlattice relaxation times of PTP melts333. Polystyrene-polydimethylsiloxane diblock copolymer with lamellar morphology was investigated by deuterium NMR spectroscopy334.The mobility of each silicone atom of the siloxane at 4position of polystyrene could be evaluated by measuring the spin-lattice relaxation using solid state 29Si NMR335. The effect of 'H spin diffusion on the relaxation process in poly(g-methyl-L-glutamate)/poly(vinylpyrrolidone)blends has been studied by CP/MAS I3C NMR spectroscopy336. Deuterium solid state quadrupole echo NMR techniques were used to probe the dynamics of bulk and silica adsorbed methyl-labeled poly(Me a ~ r y l a t e ) - d ~Using ~ ~ ~ deuteron . NMR, the dynamics of supercooled polystyrene-d3 was investigated near the calorimetric glass transition338. The dynamics of polymer chains grafted on solid substrates is investigated using deuterium NMR339. Fully-aromatic, thermotropic, liquid crystal random copolyesters of 4-hydroxybenzonic acid and 6-hydroxy-2-

10: Synthetic Macromolecules

379

naphthoic acid were studied at elevated temperatures with 1H NMR340. The main chain dynamics of amorphous poly(Et methacrylate) and poly(Me methacrylate) below and above their glass transition temperatures Tg are analyzed by two-dimensional solid state exchange deuteron NMR spectroscopy341. In an attempt to directly study the dynamics of the Naf ions of poly(propy1ene oxide), (I=3/2) NMR spin-lattice relaxation times, T I , and spin-spin relaxation times, T2, at a resonance frequency of 77.OMHz have been measured over the temperature range from 150 to 390 K342. 4.4 Gels and Crosslinked Macromolecules - Recent fundamental research on hydro-polymer gel systems by means of NMR techniques such as pulse NMR, pulsed field-gradient spin-echo NMR, solid state high resolution NMR and NMR imaging methods have been reviewed343.New chemical hydrogels, potentially suitable for biomedical applications, have been synthesized and characterized by I3C CP/MAS NMR s p e c t r o s ~ o p y ~The ~ . structural and dynamical analyses of crosslinked poly(y-Me L-glutamate) gel were carried out by means of high resolution solid state 13C NMR spectroscopy345.The 13C CP/MAS NMR spectra of isotactic, syndiotactic and atactic poly(viny1 alcohol) gels were measured in order to clarify the structure of the immobile component of PVA gel346.Solid state N MR measurements of slightly syndiotactic poly(viny1 alcohol) films have been used to explore the effect of H 2 0 and 2 H 2 0 absorptions, in these hydro gel^^^^. The mobility and activation energy for motion of water molecules in unfrozen poly(viny1 alcohol) hydrogels were investigated by using pulsed NMR measurements348.Dynamics and structure of swollen methylenebisacrylamide-crosslinked N,N-dimethylacrylamide (DMAA)-acrylic acid(AA) copolymer, poly(N,N-dimethylacrylamide)(PDMAA) and poly(acry1ic acid)(PAA) gels have been studied as a function of the degree of swelling under a state of equilibrium with deuterated water (D20) as a solvent and polyethylene glycol(PEG) as a probe polymer by NMR methods349.IH and 13CNMR techniques were used to study the microscopic structure of NMNVP copolymer hydrogels350.The technique of magnetization-transfer NMR(MT-NMR) was used to probe the effects of concentration, degree of hydrolysis and storage temperature on the formation of a network in aqueous solutions and gels of atactic poly(viny1 alcohol)351.13C rotational echo double-resonance(RED0R) NMR with I5N or 2H dephasing, combined with 15N REDOR NMR with 13C dephasing, has been obtained for a fully cross-linked epoxy resin prepared from a nominally uniform mixture of two parts of diglycidyl ether of Bisphenol A, one part of hexamethylenediamine and 19% antiplaticizer made from a carbonyl-I3C-1abeled aromatic a ~ e t a r n i d eThe ~ ~ ~chemical . substitution of amine nitrogens in cured, 15N -labeled epoxy resins has been determined by a combination of REDOR 13C and dipolar rotational spin echo I5N NMR353. In an effort to support the recycling of rubbery polymers and composites, 'H NMR relaxation and pulsed gradient spin echo diffusion measurements have been performed on virgin and unfilled vulcanized styrene-butadiene rubber(SBR) and networks after various extents of devulcanization using an ultrasound technique354.The effect of moistures on the curing of wood-based phenol-formaldehyde resin composites was studied using

380

Nuclear Magnetic Resonance

13CCP/MAS NMR techniques355.Crosslinking of alkyd resins was studied using Et linoleate and Me ricinate as model compounds. Quantitative I3C NMR data indicate that ether- and peroxy-crosslinks were formed in roughly equal amounts356. CD, Raman and NMR spectroscopies were used to characterize ordering processes which occur in gelatin and their relationship to absorbency357. The chemical crosslinking by glutaraldehyde(1) between amino groups, which had a wide range of application, was investigated using UV, light scattering, 13C NMR and electrospray ionization mass spectrometry, paying attention to the possible solvent effect on the chemical and the quantitativeness of the analyses358. The structure of polyphosphoramide esters containing a photo-sensitive bisbenzylidene group in the main chain was confirmed by IR and 'H,I3C and 31P NM R359.The reaction between 3-(3,5-dimethyl-2-hydroxybenzyl)-6,8-dimethyl3,4-dihydro-(2H)- 1,3-benzoxazine and either 2,4-xylenol or 2,6-xylenol was benzoxazine by 13C NMR techniques360.The combination of solid state MAS NMR of 29Si and I3C and FT-IR spectroscopy provided a quantitative description of the crosslinked poly[(methylsiloxane)-co-(oxymethylene)]copolymer microstruct ~ r e ~Solid ~ ' . state 13C NMR was used to study the competitive vulcanization of blends of natural rubber and high cis p ~ l y b u t a d i e n e ~The ~ ~ .reaction of the reaction between 2,6-xylenol and hexamethylenetetramine, and the thermal decomposition of their first-formed products bis- and trans(4-hydroxy-3,5dimethylbenzy1)amines were studied by 13C and 15N NMR spectroscopy363. NMR studies of the reaction of malonate- and acetoacetate-blocked polyisocyanates with OH-functional compounds show difference in the reaction mechanisms of the two blocking agents which might be important concerning the durability of such crosslinked clear oat^^^. The network formation of silica-filled, TBBS accelerated sulfur vulcanization of cis- 1,4-polyisoprene was studied by solid state I3cNMR spectroscopy365.

5

Studies for Polymer Blend and Diffusion of the Synthetic Macromolecules

The miscibility of cellulose acetate and poly(ethy1ene succinate) has been investigated using a variety of thermal techniques and by solid state I3C NMR spectrocopy^^^. Blends of one part of carbonyl- 13C, ring-13C, or methyl- 13C-labeled bisphenol A polycarbonate with nine parts of poly(p-fluorostyrene) or poly(ofluorostyrene) have been examined by I3C-I9F REDOR NMR367. Transverse magnetic relaxation properties of protons attached to PEO chains were investigated in compatible blends of hydrogenated PEO and deuterated PMMA by varying the PEO column fraction and temperature368. A study was made of the macrodefect-free composite based on aluminate cement and a poly(viny1 alcohol)-poly(viny1acetate) copolymer by I3C CP/MAS NMR369.The dispersion of brominated flame retardants in polymers is monitored with 81Br NQR using a pulse NQR spectrometer370.Xenon has been used as a structural probe of solid poly(ethy1ene oxide)/acetic poly(Me methacrylate) blends of concentrations 10/90 to 75/25371.The polystyrene/poly(vinyl Me ether)(PS/PVME) blend is studied by I D and 2D 129XeNMR. The signal of '29Xe dissolved in miscible PS/PVME

10: Synthetic Macromolecules

38 1

blends exhibits a single peak, and the chemical shift shows nonlinear dependence on the PVME content372.Carbon black-filled EPDM were investigated by means of '28Xe NMR spectroscopy373.Time and q resolved light scattering and NMR spin-lattice relaxation time have been performed on PSlPVME blends during the early stage of the spinodal d e c o m p o ~ i t i o n The ~ ~ ~size . of domains in a series of compatibilized polystyrene-(ethylene-propylenerubber(EPR)) blends were measured by solid state NMR spin diffusion measurements375.The compatibilizing effect of graft copolymer, ethylene-1-hexene copolymer-y-polystyrene(LL-DPEy-PS), on immiscible blends of LLDPE with styrene-butadiene-styrenetriblock copolymer(SBS) has been investigated by means of I3C CP/MAS NMR and DSC techniques376.In the polycarbonate-poly(viny1 pyrrolidone) blends, the response of 1H spin-lattice relaxation time in the rotating frame(TIp) was the determinant to obtain information on the transition when the quantity of PVP is close to 40% by wt. and a better organization of amorphous phase was detected377.The effect of 1H spin diffusion on the relaxation process in poly(y-methyl-L-glutamate)/poly (vinylpyrrolidone)(PMLG/PVP) blends was studied by 13C CP/MAS NMR spectroscopy378.A 19F pulsed-field gradient(PFG)-NMR diffusion study shows that the diffusion coefficients of anionic species in the electrolyte system PPG4000-LiC F3S03 decrease mono tonically with increasing salt concentrations over a wide range of components379. The diffusion coefficients of CHC13 and trifluoroacetic acid(TFA) in poly(y-Me L-glutamate) gel with TFA, CHC13 and its mixture were measured by pulsed-gradient spin-echo H NMR spectroscopy as a function of the TFA content in the gel380.'H T2 and self-diffusion coefficient (D) NMR measurements of water in three hydrogels based on poly(2-hydroxyethyl methacrylate) have been performed in order to investigate the state of water and its interaction with the polymer network38'. The self-diffusion behaviour of a triblock copolymer(poly(ethy1ene oxide)-poly(propy1ene oxide)poly(ethy1ene oxide)) in an aqueous solution of 20%(m/m) was investigated during a temperature-induced phase transition from liquid to gel state using pulsed field-gradient NMR and static light scattering382. Self-diffusion coefficients for binary systems containing water and an oligomer of ethylene glycol were measured at 25 O in the whole concentration range by a pulsed gradient spinecho NMR technique383. Solid state molecular chain diffusion in linear highdensity polyethylene(HDPE) is established as the dominant mechanism for the crystalline 13C longitudinal relaxation at 60 0C384.Multivariate curve resolution(MCR) was successfully applied to the analysis of diffusion-ordered spectroscopy experiments on polymer mixtures and GPC-NMR experiments on industrial copolymer samples385,The pulsed gradient spin-echo NMR method was used to study the diffusivity D of 2 highly polydisperse OH-terminated dimethylsiloxane blends in the melts and sorbed into networks made by linking the same material with Si(OEt)4386.The self-diffusion in a polystyrene-&polyisoprene diblock copolymer with a strongly asymmetric composition was investigated with dependence on temperature by pulsed field gradient (PFG) NMR387. The global dynamics of polyisoprene(P1) in the controlled porous glass Bioran were studied by pulsed field gradient NMR and shows that all polymer chains are localized within the pores;no free PI

382

Nuclear Magnetic Resonance

Characterization of the Synthetic Macromoleculesin the Solution State

6

A series of three dimensional(3D) NMR pulse sequences, utilizing PFG techniques, were developed or adapted from biological experiments for applications in the characterization of the structures of polymers and other heteroatom-containing organic materials; in much the same way that the data from multiple 3D NMR experiments have been used in biological structure determination389.The formation of the poly(viny1 borate)(PVBO) and PVBO-Na was confirmed by IR and 'H NMR spectra3go.The surface interactions of sodium perfluorooctanoate(SPF0) and cetylt-rimethylammonium bromide(CTAB) mixed micellar solutions were studied by using ESR, NMR and surface tension measurements at the aidwater interface39'. Proton and 13CNMR as well as energy minimization and molecular dynamics calculations were all used to study chemical structures and single chain contributions of non-oxidized, completely oxidized and completely reduced polymerization products of p - b e n z ~ q u i n o n e ~13C ~ ~NMR . spectra(75.5 MHz) of Me methacrylate-lauryl methacrylate copolymer prepared by group transfer polymerization were analyzed for sequence distribution and relative stereochemical configuration of monomer units along the macromolecular chains393. Interactions of living oligomers of tert-Bu methacrylate(tBuMA) with a Li counterion and of the model living dimer di-tert-Bu 2-lithio-2,4,4-trimethylglutarate with LiCl were studied in tetrahydrofuran-d8 solution by 7Li, 6Li, 'H and 13C, 1D and 2D, NMR spectroscopy394. Use of binary fluorinated alcoholchloroalkane solvents is demonstrated for solution 'H, 13C and "N NMR analysis of nylons395.The 27Al, "N, I3C and 1H NMR spectra of 2:l aluminum(II1) complexes derived from 5-chloro-2-hydroxyanilineazo coupling products with acetoacetanilide, 3-methyl- 1 -phenylpyrazol-5-one and 2-naphthol were measured and analyzed396. The protonation behaviour of poly(propy1ene imine) dendrimers and some related oligo amines was measured using natural abundance 15N NMR397.The aggregation in aqueous solution of a hydrophobically modified polyelectrolyte was investigated by 19FNMR398. Natural abundance NMR methods were employed to analyze static and dynamic properties of poly(p-benzamide), the parent compound of the aramide family of polymers, dissolved in sulfuric acid399.The anisotropy of the local dynamics of poly(ethy1ene oxide) in toluene solution has been characterized using molecular dynamics simulations and NMR-coupled spin relaxation experimentsm. 'H NMR solvent relaxation has been used to probe the effect of SDS on the adsorption of poly(ethy1ene oxide) at the silica-water interfacea'

References

7 1 2 3 4

H. W. Spiess, Annu. Rep. N M R Spectrosc., 1997,34, 1-37 M . Mori and J. L. Koenig, Annu. Rep. N M R Spectrosc., 1997.34,231-299 A. E. Tonelli, Annu. Rep. N M R Sepctrosc., 1997.34, 185-229 S . Spange, U. Eismann, S. Hoechne, E. Langhammer, Macromol. Symp. 1998, 126, 223 -236

10: Synthetic Macromolecules

5 6 7 8 9 10

I1 12 13 14 15

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

383

Y. Inoue, J. Mol. Struct., 1998,441, 119-127 K . Landfester, H. W. Spiess, NATO ASIser., ser. E, 1997,335,203-216 M. L. Lynch, Collid Interface Sci., 1997,2,495-500 J. G. Hamilton, Polymer, 1997,39, 1669- 1689 V. McBriety, Solidstate Nucl. Magn. Reson., 1997,9,21-27 K . Matsuzaki, T. Uryu and T. Asakura, NMR Sepctroscopy and Stereoregularity of Polymers, Japan Sci. SOC.Press, 1996 P. Blumler, B. Blumich, Rubber Chem. Technol. 1997,70,468-5 18 N. J. Heaton, P. Bello, A. Bello, E. Riande, Macromolecules, 1997,30,7536-7545 J. Cheng, S. Z. D. Cheng, P. Chu, V. Percec, Macromolecules, 1997,30,4688-4694 W. Chen, M. Pyda, A. Habenschuss, J. D. Londono, B. Wunderlich, Polym. Adv. Technol., 1997,8,747-760 H . Ishida, H. Kaji, F. Horii, Macromolecules, 1997,30, 5799-5803 K . Masuda, K. Akagi, H. Shirakawa, T. Nishizawa, J. Mol. Struct., 1998, 441, 173- 181 E. R. Gasilova, V. V. Zuev, S. Y. Frenkel, Polymer, 1998,39, 1939-1944 P. K. Bhowmik, A. H. Molla, H. Han, M. E. Gangoda, R. N. Bose, Macromolecules, 1998,31,621-630 S. Stompel, E. T. Samulski, J. Preston, B. S. Hsiaoll, K. C. Gardner, H. Shih, High Perform. Polym, 1997,9,229-249 H . Siebert, D. A. Grabowski, C. Schmidt, Rheol. Acta, 1997,36,618-627 M. Ambrozic, P. Formoso, A. Golemme, S. Zumer, Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top., 1997,56, 1825- 1832 L. L. Gureva, V. P. Tarasov, K. V. Erofeev, B. A. Rozenberg, Appl. Magn. Reson., 1997,12,581-588 B. W. Jo, J. I. Jin, F. Laupretre, Macromol. Symp. 1997, 118,275-288 P. Mirau, M. Srinvasarao, Appl. Spectrosc., 1997,51, 1639-1643 T. Satoh, T. Miura, T. Hatakeyama, K. Yokota, T. Kakuchi, Macromol. Rapid Commun., 1997,18, 1041 - 1048 H. Falk, M. Stanek, Monatsh. Chem., 1997,128,777-784 M. M. C. Lopez-Gonzalez, M. J. Callejo Cudero, J. M. Barrales-Rienda, J. Polym. Sci., Part A: Polym. Chem., 1997,35,3409-3429 H . N. Cheng, Int. J. Polym. Anal. Charact. 1997,471 -85 G. E. Yu, P. Sinnathamby, T. Sun, F. Heatley, C. Price, C. Booth, Macromol. Rapid Commun., 1997,18, 1085-1093 G. Crini, G . Torri, M. Guerrini, B. Martel, Y. Lekchiri, M. Marcellet, Eur. Polym. J., 1997,33, 1143-1151 M. R. Leduc, W. Hayes, J. M. J. Frechet, J. Polymer. Sci., Part A: Polym. Chem., 1998,36, I - 10 M. Sanchez-Chaves, J. L. Rodriguez, F. Arranz, Macromol. Chem. Phys., 1997,198, 3465-3475 S. D. Brgnac, H. W. Young, Gummi Asern Kunstst., 1998,51,51-58 Y.-P. Sun, B. Liu, G. E. Lawson, Photochem. Photobiol., 1997,66,301-308 L. Dai, A. W. H. Mau, X. Zhang, J. Muter. Chem. 1998,8,325-330 X. Zhang, D. H. Solomon, J. Polym. Sci., Part B: Polym. Phys., 1997, 35, 2233-2243 M. De Sarkar, P. De Prajna, A. K. Bhowmick, J. Appl. Polym. Sci., 1997, 66, 1151 - 1 I62 W. Volksen, J. L. Hedrick, T. P. Russell, S. Swanson, J. Appl. Polym. Sci., 1997,66, 199-208

384

Nuclear Magnetic Resonance

39 40 41 42 43

Z. Wirpsza, M. Kucharski, J. Lubczak, J. Appl. Sci., 1998,67, 1039-1049 P. Peng, P. Hodge, Polymer, 1998,39,981-990 M. R. Krejsa, K. Udipi, J. C. Middleton, Mucromolecules, 1997,30,4695-4703 H. Pasche, W. Hiller, H. R. Wolf, Polymer, 1998,39, 1515-1523 T. G. Neiss, H. N. Cheng, P. J. H. Daas, H. A. Schols, Polym. Prepr, 1998, 39, 688-689 T. Holopainene, L. Alvila, J. Rainio, T. T. Pakkanen, J. Appl. Polym. Sci., 1997, 66, 1183-1193 D. Gonzales, J. Francillette, M. F. Greinier-Loustalot, J. Muter. Sci., 1997, 32, 3129-3 134 J. Li, Y. Pang, Macromolecules, 1997,30, 7487-7493 X. Chen, S. P. McCarthy, R. A. Gross, Macromolecules, 1997,30,4295-4301 M. Scandola, M. L. focarete, M. Gazzano, A. Matuszowicz, W. Sikorska, G. Adamus, P. Kurocok, M. Kowalczuk, Z. Jedlinski, Macromoleculesl997, 30, 7743- 7748 P. Kurcok, P. Dubois, W. Sikorska, Z. Jelinski, R. Jerome, Macromolecules, 1997, 30,5591 -5595 H. Abe, Y. Doi, Y. Hori, T. Hagiwara, Polymer, 1998,39,59-67 D. Michalke, M. Moller, T. Pieper, J. Poly. Sci.,Purt A: Polym. Chem., 1998, 36, 169- 177 J. Liu, S. G. Park, S. W. KO, Polymer, 1998,39, 1051-1057 G. Ricci, L. Porri, Macromol. Chem. Phys., 1997, 198, 3647-3655 Y. Liu, H. B. Wang, C. Y. Pan, Macromol. Chem. Phys., 1997, 198,2613-2622 C . Vautrin-U1, F. Pla, Macromol. Symp., 1997,119, 197-205 Y. X. Peng, H. S. Dai, L. F. Cun, J. L. Liu, J. Appl. Polym. Sci., 1997, 65, 1883- 1887 M. R. Buchneiser, N. Atzl, G. K. Bonn, J. Am. Chem. Soc., 1997,119,9166-9174 S . Nemes, J. Borbely, J. Macromol. Sci.,Pure Appl. Chem., 1997, AM, 2355-2370 T. M. Londergan, W. P. Weber, Polym. Bull, 1998,40, 15-20 X. Chen, S. P. McCarthy, R. A. Gross, J. Appl. Polym. Sci.,1998,67,547-557 S. Kim, J. Jackiw, E. Robinson, K. S. Schanze, J. R. Reynolds, J. Baur, M. F. Rubner, D. Boils, Macromolecules, 1998,31,964-974 K. Sakamoto, T. Amiya, M. Kira, Chem. Lett., 1977, 1245-1246 C. Elvira, J. S. Roman, Polymer, 1977,38,4743-4750 Y. Liu, M. Schulze, A.-C. Albertsson, J. Macromol. Sci., Pure Appl. Chem., 1998, A35,207-232 S. Rush, A. Reinmuth, W. Risse, Macromolecules, 30, 7375-7385 J. R. Wright, J. Kiel, E. Holwitt, J. aT. aSmith, K. Roberts, J. Studer, C. Mclemore, K. Campbell, B. Russo, K. Wood, Polym. Prepr., 1998,39,365-366

44

45 46 47 48

49 50 51

52 53 54 55 56 57 58 59 60 61 62 63 64 65 66

67 68 69 70 71 72 73

A. Iraqui, G. W. Barker, J. Muter. Chem., 1998,8,25-29 C. W. Lee, R. Urakawa, Y. Kimura, Eur. Polym. J., 1998,34, 117-122 C. Eldsaester, A. C. Albertsson, S. Karlsson, Acta Polym., 1977,48,478-483 A. Cao, M. Ichikawa, T. Ikejima, N. Yoshie, Y. Inoue, Macromol. Chem., Macromol. Chem. Phys., 1977,198, 3539-3557 A. Bolognesi, F. Bertini, R. Consonni, R. Mendichi, A. Giacometti Scheeroni, A. Provasoli, Acta Polym., 1977,48, 507-512 T. Okada, N. Fujiwara, T. Ogata, 0. Haba, M. Ueda, J. Polym. Sci., Purt A: Polym. Chem., 1977,35,2259-2266 B. Vazquez, C. Elvira, J. San Roman, B. Levenfeld, Polymer, 1977,38,4365-4372

10: Synthetic Macromolecules

74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100

101

102 103 104

385

J. Y. Chang, P. J. Park, M. J. Han, Bull. Korean Chem. SOC.,1977,18, 1288-1291 C.-S. Wang, C.-H. Lin, J. Polym. Res., 1977,4, 139-145 S. Thamizharasi, P. Gnanasundaram, B. S. R. Reddy, J. Appl. Polym. Sci., 1977,65, 1285-1291 L. Lalloz, C. Damas, A. Brembilla, P. Lochon, Eur. Polym. J., 1977,33, 1099-1 103 T. Kanbara, M. G. Mikhael, A. B. Padias, H. K. Hall Jr., J. Polym. Sci., Part A: Polym. Chem., 1977,35,2878-2793 P. Bera, S. K. Saha, Polymer, 1998,39,1461- 1469 D.-K. Lee, H.-B. Tsai, J. Appl. Polym. Sci., 1977,65,893-900 H. Zhang, E. Ruckenstein, J. Polym. Sci., Part A: Polym. Chem., 1977, 35, 290 1 - 2906 G. Malio, R. Palumbo, A. Schioppa, D. Tesauro, Polymer, 1977,38,5849-5856 G. Maier, J. M. Schneider, Macromolecules, 1998,31, 1798- 1807 M.-F. Grenier-Loustalot, L. Da Cunha, Eur. Polym. J. 1998,34,95- 102 M.'G. Oliveira, A. C. F. Ana, G. T. Brandao, Macromol. Chem. Phys., 1977, 198, 1933-1942 S. S. Park, S. H. Chae, S. S. Im, J. Polym. Sci., Part A: Polym. Chem., 1998, 36, 147- 156 I. Pesneau, M. F. Llauro, M. Gregoire, A. Michael, J, Appl. Polym. Sci., 1977, 65, 2457 -2469 M. Trollsas, J. L. Hedrick, D. Mecerreyes, Ph. Dubois, R. Jerome, H. Ihre, A. Huh, Mucromolecules,1997,30,8508-8511 D. J. Liaw, C.-C. Huang, W.-F. Lee, J. Borbely, E.-T. Kang, J. Polym. Sci., Part A: Polym. Chem., 1977,35,3527-3536 N . Radhakrishnan, Periyadaruppan, K. S. V. Srinivasan, J. Adhes., 1977, 61, 27-36 Y. Mashiko, M. Yoshida, M. Koga, Polymer, 1977,38,4757-4763 P. Denner, B. Walter, T. Willing, Macromol. Symp., 1977, 119, 339-352 E. Renard, G. Barnathan, A. Deratani, B. Sebille, Macromol. Symp., 1977, 122, 229-234 Y.-S. Gal, W.-C. Lee, H.-J. Lee, S.-H. Jang, S.-K. Choi, J. Mucromol. Sci., Pure Appl. Chem., 1977, A M ,225 1 -2267 A. Matsumoto, K. Yokoi, S. Aoki, K. Tashiro, T. Kamae, M. Kobayashi, Macromolecules, 1998,31, 2129-2136 A. Matsumoto, K. Shimizu, T. Otsu, J. Macromol. Sci., Pure Appl. Chem., 1977, AM, 941 -953 F. Brand, H. Dauzenberg, W. Jaeger, M. Hahn, Angew. Mukromol. Chem., 1977, 248,41-71 H. R. Kricheldorf, M. Lossin, A. Mahler, Macromol. Chem. Phys., 1977, 198, 3559-3570 M.-H. Yang, C. Chou, C.-H. Lin, J. Chin. Chem. SOC.,1998,45, 199-207 M. Jayakannan, S. Ramakrishnan, J. Polym. Sci., Part A: Polym. Chem., 1998, 36, 309- 3 I 7 H. R. Kricheldorf', Z. Gomourachvili, J. Macromol. Sci., Pure Appl. Chem., 1998, A35,359-373 K. Hiltunen, Acta Polytech. Scand., Chem. Technol. Ser., 1977,251, 1-2,5-56 F. G. Sernetz, R. Mulhaupt, J. Polym. Sci., Part A: Polym. Chem., 1977, 35, 2549-2560 M. G. Zolotukhin, D. R. Rueda, M. Bruiz, M. E. Cagiao, C. F. J. Balta, A. Bulai, N. G. Gileva, L. Van der Elst, Polymer, 1977,38,3441-3453

386 105 106

I07 108 109 110

111 112 113

114 I15 116

I17 118 119 120 121 122 I23 124 I25 I26 127 128 129 130 131 132 133 134 135

Nuclear Magnetic Resonance

K. J. Eichhorn, D. Voigt, H. Komber, D. Pospiech, Macromol. Symp., 1977, 119, 325-338 R. Cuervo-Rodriguez, M. C. Fernandez-Monreal, M. Fernandez-Garcia, E. L. Madruga, J. Polym. Sci., Part A: Polym. Chem., 1977,35,3483-3493 Y. Nagasaki, R. Ogawa, S. Yamamoto, M. Kato, K. Kataoka, Macromolecules, 1977,30,6489-6493 H. M. Janssen, E. Peeters, M. F. van Zundert, M. H. P. Genderen, E. W. Meijer, Macromolecules, 1977,30,81 1 3 -8 1 28 J. S. Gnanaraj, R. N. Karekar, S. Skaria, C. R. Rajan, S. Ponrathnam, Polymer, 1977,38,3709-3712 S. C. Lee, K. H. Yoon, I. H. Park, H. C. Kim, T. W. Son, Polymer, 1977, 38, 4831 -4835 Y. S. KO,T. K. Han, H. Sadatoshi, S. I. Woo, J, Polym. Sci., Part A: Polym. Chem., 1998,36,291-300 S . Mecking, L. K. Johnson, L. Wang, M. Brookhart, J. Am. Chem. SOC.,1998, 120, 888-899 T. Rische, A:J. Waddon, L. C. Dichinson, W. J. MacKnight, Macromolecules, 1998, 31, 1871-1874 Q. Wang, C. Song, J. Xu, L. Feng, Chin. J. Polym. Sci., 1977, 15,248-253 Q. Wang, J. H. Wenig, Z. Fan, Q. Zhi, L. X . Feng, Macromol. Rapid Commun., 1977,18, 1101-1 107 A. C. Kolbert, J. G. Didier, J. Polym. Sci., Part B;Polym. Phys., 1977, 35, 1955- 1961 J. Xu, L. Feng, S. Yang, Y. Wu, Y. Yang, X. Kong, Polymer, 1977,38,4381-4385 Y. Feng, X. Jin, J. N. Hay, J. Appl. Polym. Sci., 1998,68,381-386 P. Starck, C. Lehtinen, B. Lofgren, Angew. Makromol. Chem., 1977,249, I 15- 135 Q. Shen, L. V. Interrante, Macromolecules, 1997,30,5485-5489 A. G . Carvill, R. M. E. Greene, J. G. Hamilton, K. J. Ivin, A. M. Kenwright, J. J. Rooney, Macromol. Chem. Phys., 1998,199,687-693 Q. T. Pham, J. Dubois, P. Michaud, Macromol. Chem. Phys., 1977,198,2017-2026 S . A. Pooley, G. S. Canessa, B. L. Rivas, E. Espejo, Polym. Bull,, 1977, 39, 407-414 R. F. Storey, C. L. Curry, L. B. Brister, Macromolecules, 1998,31, 1058-1063 A. Kowalski, A. Duda, S. Penczek, Macromolecules, 1998,31,2114-2122 X . Chen, S. P. McCarthyl, R. A. Gross, Macromolecules, 1998,31,662-668 J. Coudane, C. Usariz-Peyret, G. Schwach, M. Vert, J. Polym. Sci., Part A: Polym. Chem., 1977,35, 1651-1658 G. Kister, G. Cassanas, M. Vert, Polymer, 1998,39,267-273 K. A. M. Thakur, R. T. Kean, E. S. Hall, A. Mattew, E. J. Munson, Anal. Chem., 1977,69,4303-4309 J. de Groot, J. G. Hollander, J. de Bleijser, Macromolecules, 1977,30,6884--6887 W. Heinen, M. Van Duin, C. H. Rosenmoeller, C. B. Wenzel, H. J. M. De Groot, J. Lugtenburg, Macromol. Symp., 1998, 129, 119- 125 G. Maineau, Ph. Dubois, R. Jerom, T. Senninger, Ph. Teyssie, Macromolecules, 1998,31,545-547 M. Akakura, H. Yamamoto, S. G. Bott, A. R. Barron, Polyhedron, 1977, 16, 4389-4392 K. Hatada, T. Kitayama, K. Ute, Y.Terawaki, T. Yanagida, Macromolecules, 1977, 30,6754-6759 J. Sun, Chem. Res. Chin. Univ., 1977,13, 344-349

10: Synthetic Macromolecules

136 137 138 139

140 141 142 I43 144

145 146 147 148 I49 150 151

152 153 154 155

I56 I57 158 I59 160 161 162 163 164 165 I66

387

J. Ueda, M. Matsuyama, M. Kamigaito, M. Sawamoto, Macromolecules, 1998, 31, 557-562 D. Baskaran, A. H. E. Mueller, H. Kolshorn, A. P. Zagala, T. E. Hogen-Esch, Mucromolecules, 1977,30,6695-6697 Y. Grohens, M. Brogly, C. Labbe, J. Schultz, R. E. Prudhomme, Macromol. Symp., 1977,119, 165-171 W. K. Busfield, I. D. Jenkins, T. Nakamura, M. J. Monteiro, E. Rizzardo, S. Sayama, S., H. Thang, P. Van Le, C, 1. Zayas-Holdsworth, Polym. Adv. Technol., 1998,9,94-100 J. J. Cernohous, C. W. Macosko, T. R. Hoye, Macromolecules, 1977,30,5213-5219 C. S . Patrickios, A. B. Lowe, S. P. Armes, N. C. Billingham, J. Polym. Sci., Part A: Polym. Chem., 1998,36,617-63 1 X. Huang, Z. Lu, J. Huang, Polymer, 1998,39, 1369- 1374 S. Thamizharasi, P. Gnanasundaram, B. S. R. Reddy, Eur. Polym. J., 1977, 33, 14g7-1494 Y. Zou, D. Lin, X. Liao, R. Pan, Bopuxue Zushi, 1977,14,379-386 M. Brogly, Y. Grohens, C. Labbe, J. Schultz, Int. J. Adhes. Adhes., 1977, 17, 257-261 T. Nonobe, S. Tsuge, H. Ohtani, T. Kitayama, K. Hatada, Mucromolecules, 1977, 30,4891 -4896 B. Smith, J. Klier, J. Appl. Polym. Sci., 1998,68, 1019-1025 Y. Kawakami, K. Takeyama, K. Komuro, 0. Ooi, Macromolecules, 1998, 31, 55 1-553 C. A. Fyfe, P. P. Aroca, J. Phys. Chem. B, 1977,101,9504-9509 L. Herczynska, J. Chojnowski, L. Lacombe, L. Lestel, S. Polowinski, S. Boileau, J. Polym. Sci., Part A: Polym. Chem., 1998,36, 137-145 H. Tanaka, T. Takeichi, T. Hongo, J. Polym. Sci., Part A: Polym. Chem., 1977, 35, 3537- 354 1 T. Kodaira, Q. Q. Liu, M. Urushisaki, Macromol. Chem. Phys., 1977, 198, 3089-3 I04 N. M. Ahmad, F. Heatley, P. A. Lovell, Macromolecules, 1998,31,2822-2827 R. Madan, R. C. Anand, I. K. Varma, J. Polym. Sci., Part A: Polym. Chem., 1977, 35,29 17- 2924 J. G. Hamilton, Polymer, 1998,39, 1669-1689 M. F. Teasley, D. Q. Wu, R. L. Harlow, Macromolecules, 1998,31,2064-2074 H.-C. Hou, R. C.-C. Tsiang, C-C. Henry, J. Polym. Sci., Part A: Polym. Chem., 1977,35,2969-2980 M.Ueda, T. Hayakawa, 0. Haba, H. Kawaguchi, J. Inoue, Macromolecules, 1977, 30,7069- 7074 F. E. Goodson, T. I. Wallow, Macromolecules, 1998,31,2047-2056 A. Manna, K. Bandyopadhyay, K. Vijayamohanan, P. R.Rajamohanan, S. Sainkar, B. D. Kulkarni, Langmuir, 1998,14,84-90 R. Tirasirichai, A. C. Watterson, Polym. Muter. Sci. Eng., 1977,77, 178-179 I. Yamaguchi, H. Tanaka, K. Osakada, T. Yamamoto, Macromolecules, 1998, 31, 30-35 S. Turri, A. Sanguineti, M. Levi, Macromol. Chem. Phys., 1977,198, 3215-3228 J. C. Ronda, A. Serra, V. Cadiz, Macromol. Chem. Phys., 1977,198,2935-2948 Y. Misumi, T. Maekawa, T. Masuda, T. Higashimura, Polymer, 1998, 39, 1663-1667 C. H. Bergstrom, P. G. Strarck, J. V. Starck, J. Appl. Polym. Sci., 1998,68,385-393

388

Nuclear Magnetic Resonance

167 168 169 170

E.-C. Lee, Y . Kimura, Polym. J., 1998,30,234-242 Z. Fan, M. C. Sacchi, P. Locatelli, Chin. J. Polym. Sci., 1977,15217-225 M. W. P. L. Baars, E. W. Meijer, Polym. Muter. Sci. Eng., 1977,77, 149-150 P. R. Ashton, S. E. Boyd, C. L. Christopher, S.A. Nepogodiev, A. Sergey, E. W. Meijer, H. W. I. Peerlings, J. F. Stoddart, Chem. Eur., 1977,3,974-984 R. Goriot, R. Petiaud, M. F. Llauro, T. Hamaide, Macromol. Symp., 1977, 119, 173-188 W. Kuran, T. Listos, M. Abramczyk, A. Dawidek, J. Macromol. Sci., Pure Appl. Chem., 1998, A35,427 -437 M. Schoech, U. Gopp, S. Steurich, B. Sandner, Polym. Bull., 1977,39,721-727 J. Xu, L. Feng, S. Yang, Y. Yang, X. Kong, Macromolecules, 1977,30,7655-7660 R. Rulkens, R. Resendes, A. Verma, I. Manners, K. Murti, E. Fossum, P. Miller. K. Matyjaszewski, Macromolecules, 1977,30, 8615-8171 A. Neubauer, S. Poser, M. Arnold, J. Macromol. Sci., Pure Appl. Chem., 1977, AM, 171 5- 1725 D. S. Bag, S. Maiti, J. Polym. Sci., Part B: Polym. Phys., 1977,35,2049-2056 M. 0kaniwa;Y. Ohta, J. Polym. Sci., Part A; Polym. Chem., 1977,35,2607-2617 F. Ganachaud, F. Sauzedde, A. Elaissari, C. Pichot, J. Appl. Polym. Sci., 1977, 65, 2315-2330 K.-J. Chu, J.-W. Ha, Muter. Lett., 1998,33, 301-304 N. K. Singha, T. P. Mahandas, J. Macromol. Sci., Pure Appl. Chem., 1977, AM, 2269-2278 T. H. H. Nguyen, K. Fujimori, D. J. Tucker, Top Chi Hoa HOC,1977,35,89-92 N. T. H. Ha, K. Fujimori, I. E. Craven, Macromol. Chem. Phys., 1977, 198, 3507-351 6 A. Kampes, B. Tieke, Colloid Polym. Sci., 1977,275, 1 136- 1 143 Y. Maeda, A. Nakayama, N. Kawasaki, K. Hayashi, S. Aiba, N. Yamamoto, Polymer, 1977,38,4719-4725 R.-S. Tsai, Y.-D. Lee, J. Appl. Polym. Sci., 1977,66, 141 1 - 1418 K. S. Bisht, Y. Y. Svirkin, L. A. Henderson, R. A. Gross, D. L. Kaplan, G. Swift, Macromolecules, 1977,30,7735-7742 C. Gong, H . W. Gibson, J. Am. Chem. Soc., 1977,119,8585-8591 D. Britton, F. Heatley, P. A. Lovell, Macromolecules, 1998,31,2828-2837 P. A. Berger, J. R. Garbow, A. M. DasGupta, E. E. Remsen, Macromolecules, 1977, 30,5178-5180 D. Lpez, H. Reinecke, M. Hidalgo, C. Jijangos, Polym. fnt., 1977,44, 1 - 10 N. Guarrotxena, G. Martinez, J. Millan, Eur. Polym. J., 1977,33, 1473-1479 P. Ortiz Del Toro, A. Suzarte, C. I. Sergio, C. Zaldivar, Polymer, 1998, 39, 1759- 1763 P. 0. Del Toro, A. Suzarte, 1. S. Colas, C. Zaldivar, A. Rosado, Polymer, 1998, 39, 1759- 1763 A. S. Brar, M.Malhotra, J. Appl. Polym. Sci., 1998,67,417-426 R. Cuervo-Rodriguez, M. C. Fernandez-Monreal, M. Fernandez-Garcia, E. L. Madruga, J. Polym. Sci.. Part A : Polym. Chem., 1977,35,3488-3493 I. Chung, H. J. Harwood, J. Macromol. Sci., Pure Appl. Chem., 1998, A35, 51 1-530 H. R. Kricheldorf, T. Stukenbrock, Polymer, 1977,38,3373-3383 A. Nakayama, N. Kawasaki, Y. Maeda, S. Aiba, I. Arvanitoyannis, N. Yamamoto, Polymer, 1998,39, 1212- 1222 K. S. Bisht, F. Deng, R. A. Gross, D. L. Kaplan, G. Swift, J. Am. Chem. SOC.,1998, 120,1363-1367

171 172 173 174 175 I76

177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200

10: Synthetic Macromolecules

20 1 202 203 204 205 206 207 208 209 210 21 1 212 21 3 214 215 216 217 218 219 220 22 1 222 223 224 225 226 227 228 229 230 23 1 232 233

389

D. H. Donabedian, S. P. McCarthy, Macromolecules, 1998,31, 1032- 1039 S. Jin, K. E. Gonsalves, Mucromolecules, 1998,31, 1010-1015 S. Cammas, V. Langlois, P. Guerin, C. R. Acad Sci., Ser. Ilb: Mec., Phys., Chim., Astron., 1977,325, 165- 172 C.-H. Yuan, M. Fujino, K. Ebata, K. Furukawa, Macromolecules, 1977, 30, 76 18-7620 T. Sato, S. Shimooka, M. Seno, J. Polym. Sci., Part A: Polym. Chem., 1998, 36, 563- 572 G. ciardelli, K. Kojima, A. Lendlein, P. Neuenschwander, U. W. Suter, Macromol. Chem. Phys., 1977,198,2667-2688 F. Ciardelli, M. S. Ghiloni, R. Solaro, Gazz. Chim. Ital., 1977,127, 143-149 K. Matyjaszewski, S. M. Jo, H.-J. Paik, S. G. Gaynor, Macromolecules, 1977, 30, 6398-6400 X.-R. Zeng,T.-M. KO, Polymer, 1998,39, 1187-1195 K. Matsubara, T. Nakato, M. Tomida, Macromolecules, 1998,31, 1466-1472 T. M. Madkour, Polym. J., 1977,29,670-377 A. Babanalbandi, D. J. T. Hill, A. K. Whittaker, Polym. A h . Technol., 1998, 9, 62 -74 H. L. Collier, I. Y. Cho, Korean Polymer J., 1977,5, 179-184 H. R. Kricheldorf, S. J. Sun, B. Sapich, J. Stump, Macromol. Chem. Phys., 1977, 198,2197-2210 T. Suratwala, K. Davidson, Z. Gardlund, D. R. Uhlmann, Proc. SPIE-Int. SOC.Opt. Eng., 1977,3136,36-47 C.-C. M. Ma, J.-T. Gu, L.-H. Shauh, J.-C. Yang, W.-C. Fang, J. Appl. Polym. Sci., 1977,66, 57-66 H. R. Kricheldorf, T. Stukenbrock, Macromol. Chem. Phys., 1977,198,3753-3767 P. J. M. Serrano, E. Thuss, R. J. Gaymans, Polymer, 1977,38,3893-3902 P. J. M. Serrano, B. A. Van De Werff, R. J. Gaymans, Polymer, 1998,39,83-92 E.-J. Choi, D. J. T. Hill, K. Y. Kim, J. H. ODonnell, P. J. Pomery, Polym. Adv. Technol., 1998,9,52-61 I. Yamaguchi, T. Kimishima, K. Osakada, T. Yamamoto, J. Polym. Sci., Part A: Polym. Chem., 1977,35,2821-2825 M. M. C. Lopez-Gonzalez, M. J. C. Cudero, J. M. Barrales-Rienda, Polymer, 1977, 38,6219-6233 M. M. C. Lopez-Gonzalez, C. Callejo, J. M. Barrales, J. Polym. Sci., Part A: Polym. Chem., 1977,35, 3409-3429 C . M. J. Callejo, M. M. C. Lopez-Gonzalez, J. M. Barrales-Rienda, Polym. Znt., 1977,44,61-77 S. Y. Desjardins, K. J. Cavell, J. L. Hoare, B. W. Skelton, A. N. Sobolev, A. H. White, W. Keim, J. Organomet. Chem., 1977,544, 163-174 K. B. Wagener, D. Valenti, S. F. Hahn, Macromolecules, 1977,30,6688-6690 E. W. Hansen, R. Blom, 0. M. Bade, Polymer, 1977,38,4295-4304 R. W. Barnhart, G. C. Bazan, T. Mourey, J. Am. Chem. SOC.,1998,120,1082-1083 P. A. Deck, C. L. Beswick, T. J. Marks, J. Am. Chem. Soc., 1998,120, 1772- 1784 K. B. Wagner, D. J. Valenti, S. F. Hahn, Polym. Prepr., 1977,38,394-395 M. Buehl, F. A. Hamprecht, J. Comp. Chem., 1998,19, 113- 122 S. W. Ewart, M. J. Sarsfield, D. Jeremic, T. L. Tremblay, E. F. Williams, M. C. Baird, Organometallics, 1998, 17, 1502- 1510 J. Aburto, S. Thiebaud, I. Alric, E. Borredon, D. Bikiaris, J. Prinos, C. Panayiotou, Carbohydr. Polym., 1977,34, 10 1 - 1 12

390

Nuclear Magnetic Resonance

234

E. Passaglia, M. Marrucci, G. Ruggeri, M. Aglietto, Gazz. Chim. Ital., 1977, 127, 91 -95 N. T. Karangu, M. E. Rezac, H. W. Beckham, Chem. Mater., 1998,10,567-573 M.-F. Grenier-Loustalot, L. Billon, Polymer, 1998,39, 1815- 1831 M. F. Grenier-Loustalot, L. Billon, A. Louartani, V. Bounor-Legare, P. Mison, M. Senneron, B. Sillion, Polym. Int., 1977,44,435-447 H. A. Nguyen, B. J. Herve, E. Marechal, Macromol. Symp., 1977,122,257-262 K. Osakada, J.-C. Choi, T. Yamamoto, J. Am. Chem. Soc., 1977,119, 12390-12391 G. Schwach, J. Coudane, R. Engel, M. Vert, J. Polym. Sci., Part A: Polym. Chem., 1977,35,3431-3440 M. H. Chisholm, S. S. Iyer, M. E. Matison, D. G. McCollum, M. Pagel, Chem. Commun., 1977,1999-2000 S . Zheng, D. Y. Sogah, Tetrahedron, 1977,53,15469-15485 X . Cao, L. Wang, B. Li, R. Zhang, Polym. Adv. Technol., 1977,8,657-661 Y. X. Peng, H. S. Dai, J. Macromol. Sci., Pure Appl. Chem., 1977, AM, 1285- 1297 P. Laouenan, V. Michon, C. Herve de Penhoat, I. Mila, A. Scalbert, Analusis, 1977, 25, M29-M32 A. M. Aladyshev, V. I. Tsvetkova, P. M. Nedorezova, V. A. Optov, T. A. Ladygina, D. V. Savinov, M. V. Borzov, D. PO. Krut’Ko, D. A. Lemenovskii, Polimery, 1977, 42,595-598 I. Kim, R. F. Jordan, Polym. Bull., 1977,39,325-331 V. Busico, R. Cipullo, G. Talarico, A. L. Segre, J. C. Chadwick, Macromolecules, 1977,30,4786-4790 M . D. Bruce, G. W. Coates, E. Hauptman, R. M. Waymouth, J. W. Ziller, J. Am. Chem. Soc., I977,119,11174- I I 182 V. Busico, R. Cipullo, Guglielmo, M. Vacatello, A. L. Segre, Mucromolecules, 1977, 30,625 1-6263 A. M. P. Ros, 0. Sudmeijer, Int. J. Polym. Anal. Charuct., 1977,4, 39-56 T. Siono, K. K. Kang, H. Hagihara, T. Tkeda, Macromolecules, 1977,30, 5997-6000 H. Hagihara, T. Shiono, T. Tkeda, Macromolecules, 1977,30,4783-4785 1. Kim, J. Macromol. Sci., Pure Appl. Chem., 1998, A35, 293-304 M. R. Thompson, C. Tzoganakis, G. L. Rempel, Polymer, 1998,39,327-334 T. Shiono, Y. Moriki, T. Ikeda, K. Soga, Macromol. Chem. Phys., 1977, 198, 3229- 3237 C. Gong, H. W. Gibson, Macromol. Chem. Phys., 1977,198,2321 -2332 R. C. M. De Paula, F. Heatley, P.M. Budd, Polym. Int., 1998,45,27-35 C. I. Simonescu, M. Rusa, G. David, M. Pinteala, V. Harabagiu, B . C. Simonescu, Angew. Mukromol. Chem., 1977,253, 139- 149 L. Zhang, D. Dai, R. Zhang, Polym. Adv. Technol., 1977,8,662-665 C. A. Terraza, F. M. Rabagliati, Polym. Bull, 1977,39,29-35 K. Matyjaszewski, Y. Nakagawa, S. G. Scott, Macromol. Rapid Commun., 1977, 18, 1057- 1066 R. Po, N. Cardi, L. Abis, Polymer, 1998,39,959-964 J.-W. Ha, K.-J. Chu, Mater. Lett., 1977,33, 149-152 M. W. F. Nielen, S. Malucha, Rapid Commun. Muss Spectrom, 1977, 11, 1194- 1204 J. C. Bevington, S. W. Breuer, T. N. Huckerby, B. J. Hunt, R. Jones, Eur. Polym. J., 1977,33, 1225- 1229 K. Jankova, X. Chen, J. Kops, W. Batsberg, Macromolecules, 1998,31,538-541 R. C.-C. Tsiang, Polym. Prep., 1977,38,205-206 G. Carrot, J. Hilborn, D. M. Knauss, Polymer, 1977,38,6401-6407

235 236 237 238 239 240 24 1 242 243 244 245 246

247 248 249 250 251 252 253 254 255 256 257 258 259 260 26 1 262 263 264 265 266 267 268 269

10: Synthetic Macromolecules

270 27 I 272 273 274 275

276 277 278 279 280 28 1 282 283 284 285 286 287 288 289 290 29 1 292 293 294 295 296 297 298 299 300 301

39 1

J. Kodokawa, T. Horiguchi, E. Sunaga, M. Karasu, H. Tagaya, K. Chiba, Actu Polym. 1977,48,310-313 S. Desilets, S. Villenuve, M. Valcartier, J, Polym. Sci., Part A: Polym. Chem., 1977, 35,299 1 -2998 D. Jhurry, A. Deffieux, Eur. Polym. J., 1977,33,1577-1582 S.-G. Luo, H.-M. Tan, J.-G. Zhang, Y.-J. Wu, F.-K. Pei, X.-H. Meng, J. Appl. Polym. Sci., 1977,65, 1217-1225 Y. Mashiko, M. Yoshida, M. Koga, Polymer, 1977,38,4757-4763 R. N. Datta, A. H. M. Schotman, A. J. M. Weber, F. G. H. van Wijk, P. J. C. van Haeren, J. W. T. Hofstraat, A. G. Talma, A. G. V. D. BovenkampBouwman, Rubber Chem. Technol., 1977,70, 129- 145 J. Duchet, J.-P. Chapel, R. Spitz, J.-F. Gerard, J. Appl. Polym. Sci., 1977, 65, 248 1 -2492 Y. Liu, C. Pan, J. Polym. Sci., Part A: Polym. Chem., 1977,35,3403-3408 J. C. Milano, A. Louakfaoui, J. L. Vernet, Eur. Polym. J. 1997,33,571-576 Y. Nakagawa, K. Matyjaszewski, Polym. J. 1998,30, 138-141 C. De Rosa, A. Grassi and D. Capitani, Macromolecules, 1998,31, 3163-3169 C. De Rosa, D. Capitani, S. Cosco, Macromolecules, 1997,30,8322-8331 F. Rachdi, C. Goze, L. Hajji, M. Nunez-Regueiro, L. Marques, J. L. Hodeauc and M. Mehring, J. Phys. Chem. Solids, 1977,58, 1645- 1647 H. J. Luo, Q. Chen, G. Yang and D. Xu, Polymer, 1998,39,943-947 M. Guo, S. Z. D. Chen and R. P. Quirk, Polym. Prepr. (Am. Chem. Soc.., Div. Polym. Chem.), 1998,39,207-208 0. Liivak, A. Blye, N. Shah and L. W. Jelinski, Mucromolecules, 1998, 31, 2947-295 1 A. Sinitsya, J. Copikova and H. Pavlikova, J. Curbohydr. Chem., 1998,17,279-292 Y. Miyashita, Y. Yamada, N. Kimura, H. Suzuki, M. Iwata and Y. Nishio, Polymer, 1977,38,6181-6187 J. E. Dietz, B. A. Cowans, R. A. Scott and N. A. Peppas, ACS Symp. Ser., 1977, 673,28-34 G. M. Kim, Y. Wu and L. W. Amos, J. Polym. Sci., Part A: Polym. Chem., 1997.35, 3275-3285 C. Klug, T. Kowalewski, J. Schaefer, T. Straw, K. Tasaki and K. Wooley, Polym. Mutter. Sci. Eng., 1997,77,99- 100 Y. Mao and B. M. Fung, Chem. Muter., 1998,10,509-517 B. S. Joshi, T. Rho, P. L. Rinaldi, W. Liu, T. A. Wagler, N. G. Newton, D. Lee and S. W. Pelletier, J. Chem. Crystullogr., 1997,27, 553-559 0 . Liivak, A. Flores, R. Lewis and L. W. Jelinski, Mutromolecwles, 1997, 30, 7 127- 7 I 30 H. Matsuzawa, S. Okada, H. Matsuda and H. Nakanishi, Chem. Lett., 1997, 11, 1105-1 106 M. Y . Liao and G. C. Rutledge, Mucromolecules, 1997,30,7546-7553 M. Mori and J. L. Koenig, Rubber Chem. Technol., 1997,70,671-680 Y. Miwa, Y. Takahashhi, Y. Kitano and H. Ishida, J. Mol. Struct., 1998, 441, 295-301 M. P. Espe, B. R. Mattes and J. Schaefer, Mucromolecules, 1997,30,6307-6312 K. Matsubara, T. Nakato and M. Tomida, Macromolecules, 1998,31, 1466- 1472 A. Hunsche, U. Mueller, M. Knaack and T. Goebel, Kuutsh. Gummi Kunstst., 1997, 50,881 -889 T. Takayama, J. Mol. Struct., 1998,441. 101- 117

392

Nuclear Magnetic Resonunce

302

H. Jo and F. D. Blum, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1998, 39,359 - 360 H. Kaji and F. Horii, ICR Annu. Rep., 1997,3, 28-29 W. Chen, H. Feng, D. He and C. Ye, J. Appl. Polym. Sci., 1998,67,139- 147 R. S. Majerle, C. M. Bambenek and J. A. Rice, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1997,38,690 P. Holstein, R. K. Harris and B. J. Say, Solid State Nucl. Mugn. Reson., 1997, 8, 201 -206 J. S. Forsythe, D. J. T. Hill, A. L. Logothetis, T. Seguchi and A. K. Whittaker, Mucromolecules, 1997,30, 8101 -8108 P. Holstein, U. Scheler and R. K. Harris, Mugn. Reson. Chem., 1997,35,647-649 H. Komber, C. Klinger and F. Boehme, Macromolecules, 1997,30,8066-8068 G. McGeorge, R. K. Harris, A. S. Batsanov, A. V. Churakov, A. M. Chippendale, J. F. Bullock and Z. Gan, J. Phys. Chem. A , 1998,102,3505-3513 A. Thursfield, M. W. Anderson, J. Dwyer, G. Hutchings and D. Lee, J. Chem. Soc., Furucluy Truns., 1998,94, I 1 19- I I22 M. E. Merritt, J. M. Goetz, D. Whitney, C. Duane, P. P. Chang, L. Heux, J. L. Halary and J. Schaefer, Macromolecules, 1998,31, 1214- 1220 N. Pecoul, S. Bourbigot and B. Revel, Macromol. Symp., 1997,119,309-315 M. Geppi, F. Ciardelli, C. A. Verachini, C. Forte, G. Cecchin and P. Ferrai, Polymer, 1997, 1997,38,5713-5723 C. A. Klug, J. Xu, C. Xiao, A. F. Yee and J. Schaefer, Mucromolecules, 1997, 30, 6302-6306 M. Guo, Q. Fu and S. Z. D. Cheng, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1997,38,341--342 T. Miyoshi, K. Takegoshi and T. Terao, Macromolecules, 1997,30,6582-6585 G. Cho, 0.H. Han and J. Jin, Bull. Koreun Chem. SOC.,1998,19, 178-183 J. Wu, A. F. Yee and J. Schaefer, Mucromolecules, 1998,31,3016-3020 A. Comotti, R . Simonutti and P. Sozzani, J. Muter. Sci., 1997,32,4237-4245 J. Zhao, A. A. Jones, P. T. Inglefield and J. T. Bendler, Polymer, 1998, 39, 1339- 1 344 K. Hayamizu, W. S. Price, H. Matsuda, S. Okada and H. Nakanishi, J. Mol. Struct., 1998,441,205-21 I L. Heux, F. Laupretre, J. L. Halary and L. Monnerie, Polymer, 1998,39, 1269-1278 S . C. Kuebler, A. Heuer and H. W. Spiess, Phys. Rev. E: Slut. Phys., Plusmas, Fluids, Relat. Interdiscip. Top., 1997,56, 741 -749 C. B. Gorman, M. W. Hager, B. Parkhurat, L. Brandon and J. C. Smith, Macromolecules, 1998,31, 815-822 S. Wong and D. B. Zax, Electrochim. Actu, 1997,42,3513-3518 R. Kimmich, R.-0. Seitter and K. Gille, J. Chem. Phys., 108, 2173-2177(1998). A. D. English, P. T. Inglefield, A. A. Jones and Y. Zhu, Polymer, 1998,39, 309-313 A. Heuer, S. C. Kuebler, U. Tracht and H. W. spiess, Appl. Mugn. Reson., 1997, 12, 183-191 R. Kimmich, K. Fille, N. Fatkullin, R. Seitter, S. Hafner and M. Muller, J. Chem. Phys., 1997, 107,5973-5978 V. M. Litvinov, V. Macho and H. W. Spiess, Actu. Polym., 1997,48,471-477 S. F. Von, A. Martin, W. Gronski, J. Blackwell, S. N. Chvalun and H. R. Kricheldorf, Actu. Polym., 1997,48, 527-535 A. Bartolotta, C. Forte, M. Geppi, D. Minniti and G . Visalli, Solid Stute Nucl. Mugn. Reson., 1997,8,231 - 239

303 304 305 306 307 308 309 310 31 1 312

313 3 14

315 316 317 318 3 19 320 32 I

322 323 324 325 326 327 328 329 3 30 33 I 332

10: Synthetic Mucromolecules

333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365

393

R. Jager, G. J. Vancso, D. Gates, Y. Ni and 1. Manners, Macromolecules, 1997, 30, 6869-6872 S. Valic, B. Deloche and Y. Gallot, Macromolecules, 1997,30, 5976-5978 N. Kishimoto, K. Takeshita, T. Watanabe and Y . Kawakami, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1998,39,60 1 -602 A. Asano and T. Kurotu, J. Mol. Struct., 1998,441, 129- 135 W. Y. Lin and F. D. Blum, Mucromolecules, 1997,30, 5331 -5338 A. Doess, G. Hinze, G. Diezemann, Rboehmer and H. Sillescu, Acta Poly., 1998,49, 56-58 M. Zeghal, B. Deloche, P.-A. Albouy and P. Auroy, Phys. Rev. E: Stat. Phys., Plusmus, Fluids, Relut. Interdiscip. Top., 1997,56,5603-5614 M. Gentzler and J. A. Reimer, Macromolecules, 1997,30,8365-8374 S. C. Kuebler, D. J. Schaefer, C. Boeffel, U. Pawelzik and H. W. Spiess, Mcrcromolecules, 1997,30, 6597-6609 S. H. Chung, K. R. Jeffrey and J. R. Stevens, J. Chem. Phys., 1998,108,3360-3372 H. Yasunaga, M. Kobayashi, S. Matsukawa H. Kurosu and I. Ando, Annu. Rep. N M R Spectrosc., 1997,34, 39- 104 A. A. De Angelis, D. Capitani and V. Crescenzi, Macromolecules, 1998, 31, 1595.- 1601 S. Matsukawa, M. Kobayashi and I. Ando, J. Mol. Struct., 1998,442,235-241 M. Kobayashi, I. Ando, T. Ishii and S. Amiya, J. Mol. Struct., 1998,440, 155-164 T. J. Bastow, R. M. Hodge and A. J. Hill, J. Membr. Sci., 1997,131,207-215 M. Nagura, N. Takahi, H. Katakami, Y. Gotoh, Y. Ojkoshi, T. Koyano and N. Minoura, Polym. Gels Networks, 1998,5,455-468 S . Matsukawa and I. Ando, Mucromolecules, 1997,30, 8310-8313 I. Calderara, R. Gougeon, L. Delmotte, V. Lemee and D. J. Lougnot, J. Polym. Sci., Purr A: Polym. Chem., 1997,35,3619-3625 L. E. Stephans and N. Foster, Macromolecules, 1998,31, 1644- 1651 M. E. Merritt, J. M. Coetz, D. Whitney, C. P. Chang, L. Heux, J. L. Halary and J. Schaefer, Macromolecules, 1998,31, 1214-1220 M. E. Merritt, L. Heux, L. Jean and J. Schaefer, Macromolecules, 1997, 30, 6760-6763 S. T. Johnston, J. Massey, E. Meerwall, S. H. Kim, V. Y. Levin and A. I. Isayev, Rubber Chem. Technol., 1997,70, 183- 193 R. G. Schmidt, A. A. Ballerini, F. A. Kamke and C. E. Frazier, Proc. Annu. Meet. Acihes. Soc., 1996, 19,464-465 W. J. Muizebelt, J. J. Donkerbroek, M. W. F. Nielen, J. B. Hussem, M. E. F. Biemond, R. P. Klaasen and K. H. Zabel, J. Coat. Technol., 1998,70, 83-93 K. L. Kiick-Fischer and D. A. Tirrell, J. Appl. Polym. Sci., 1998,68,281-292 J. Kawahara, K. Ishikawa, T. Uchimaru and H. Takaya, Polym. Mod$, [Pup. Symp.], 1997, 119--131 S. C. Murugavel, C. S. Swaminathan and P. Kannan, Polymer, 1997,38,5179-5183 X. Xiaoqing and D. H. Solomon, Polymer, 1998,39,405-412 M. Rodriguez-Baeza, M. Zapata, I. Yoshida and P. Valeria, Macromol. Rupid Commun., 1997,18,747-754 B. Klei and J. L. Koenig, Rubber Chem. Technol.. 1997,70,231 -242 X. Zhang, A. Potter and D. H. Solomon, Polymer, 1998,39, 1957-1966 U. Rochrath, K. Brockkotter, T. Frey, U. Poth and G. Wigger, Prog. Org. Coat., 1997,32, 173-182 M. C. Hill and J. L. Koenig, Polym. BuN(Berlin), 1998,40, 275-282

394

Nuclear Mugnetic Resonunce

366

C. M. Buchanan, B. G . Pearcy, A. W. White and M. D. Wood, J. Environ. Polym. Degrucl., 5, 209 -223 G. Tong and J. Schaefer, Mucromolecules, 1997, 30,7522-7528 A. Guillerrno, C. Lartigue and A. J. P. Cohen, Mucromolecules, 1998,31,769 775 A, Cornotti, R. Sirnonutti and P. Sozzani, J. Muter. Sci., 1997,32,4237-4245 A. A. Mrse, Y. Lee, P. L. Bryant, F. R. Fronczek, L. G . Butler and L. S. Simeral, Chem. Muter., 1998, 10, 1291-1300 S. Schants and W. S. Veeman, J. Polym. Sci., Purt B: Polym. Phys., 1997, 35, 268 I -2688 T. Miyoshi, K. Takegoshi and T. Terao, Polymer, 1997,38,5475-5480 K. Sperling, W. S. Veeman and V. M. Litvinov, Kuutsch. Gummi Kunstsl, 1997, 50, 804- 806 N. Parizel, F. Kempkes, C. Cirman, C. Picot and G. Weill, Polymer, 1998, 39, 29 1 -298 K. S. Jack, A. Natansohn, J. Wang, B. D. Favis and P. Cigana, Chem. Muter,, 1998, 10, 1301 - 1308 H. Feng, C. Ye, J. Tian, Z. Feng and B. Huang, Pdymrr, 1998,39, 1787-1792 E. P. Da Silva and M. I. B. Tavares, J. Appl. Polym. Sci., 1998,67,449-453 A . Asano and T. Kurotu, J. Mul. Struct., 1998,441, 129-135 A . Ferry, G. Oraedd and P. Jacobsson, Mucromolecules, 1997,30,7329-7331 C. Zhao, S. Matsukawa, H. Kurosu and I . Ando, Mucromolecules, 1998, 31, 3139 3141 R. Barbieri, M. Quaglia, M. Delfini and E. Brosio, Polymer, 1998,39, 1059-1066 H. Scheller, G. Fleischer and J. Karger, Colloid Polym. Sci., 1997,275, 730-735 L. Ambrosone, G. D’Errico, R. Sartorio and L. Costantino, J. Chem. Soc., Furucluy Trans., 1997,93,3961-3966 M. B. Robertson, I. M. Ward, P. G. Klein and K. J. Packer, Mucromolecules, 1997, 30,6893 -6898 L. C. M. Van Gorkorn and T. M. Hancewicz, J. Mugn. Reson., 1998, 130, 125-130 E. D. Meerwall, T. Pryor and V. Galiatsatos, Mucromolecules, 1998,31, 669-674 G. Fleischer, J. Karger and B. Stuhn, Colloid Polym. Sci., 1997, 275,807-8 I3 L. Petychakis, G. Floudas and G. Fleischer, Euruphys. Lett., 1997,40, 685-690 T. Saito and P. L. Rinaldi, J. Mugn. Resun., 1998, 130, 135- 139 P. Chetri, N. Sarrna and N. N. Dass, J. Polym. Muter., 1997, 14, 165-169 J. Hao, R. Lu and H. Wang, J. Dispersion Sci. Technol., 1997, 18,379-388 T. M. Madkour, Polym. J. (Tokyo), 1997,29,670-677 B. Scannigrahi and B. Garnaik, Polym. J. (Tokyo), 1998,30,340-344 C. Zune, P. Dubois, R. Jerome, J. Kriz, J. Dybal, L. Lochmann, M. Janata, P. Vleek, T. M. Werkhoven and J. Lugtenburg, Mucromolecules, 1998, 31, 2744 -2755 S. J. Steadrnan and L. J. Mathias, Polymer, 1997,38, 5297-5300 A. Lycka, P. Paul and L. Skrabal, Mugn. Reson. Chem., 1998,36,279-284 M. H. P. van Genderen, C. Elissen-Roman, M. W. Baars, E. W. Meijer and M. Borkovec, J. Am. Chem. Soc., 1997,119,6512-6521 I. Iliopoulos and R. Audebert, Polymer, 1998,39,751-753 M. Zhou, V. Frydrnan and L. Frydman, Mucrumolecules, 1997,30,5416-5428 M. M. Fuson, K. H. Hanser and M. D. Ediger, Macromolecules, 1997, 30, 57 14-5720 S. J. Mears, T. Coagrove, L. Thompson and I. Howell, Lungmuir, 1997, 14, 997-1001( 1997)

367 368 369 370 37 1 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 39 I 392 393 394

395 396 397 398 399 400 40 1

11 Conformational Analysis BY HEIDE KOGELBERG

1

Introduction

The format of this review has been kept similar to those of previous years.

2

Methods

Pulsed field gradient versions of sensitivity-enhanced 2D HSQC-TOCSY I and

X(ol)half-filtered TOCSY experiments were presented for long-range heteronuclear coupling constant measurements. A 3D heteronuclear pulse sequence was presented for homonuclear I3Cp13C coupling constant measurements between aliphatic carbons in perdeuterated protein^.^ A new pulse scheme, HN(CO)C, for simultaneous measurements of 3JC'Cp and 3JC'Cy couplings was described and a Karplus relation ~ b t a i n e d Pulse .~ schemes for the measurements of 3 J ~ and ~ y 3 J ~ coupling ~ y constants were presented and correlated with xl .5 Three novel pulse sequences of H(N)CA,CO-E.COSY type were presented for the calibration of 4 from J(C',- 1,HUi),J(Cti- ,,CBi)and J(C',_ l,C'J.6 A 'H-'5N-{13CyJ differ. 7 experiments with ence experiment was presented for measurements of 3 J N ~ y 3D improved sensitivity for Jccp8 and 3JNN9correlations have been reported. The spin-state-selective excitation pulse sequence element was presented combined p J N H ~ ,with " COSY for JH,H,lI with NOESY for the measurements of 3 J N ~ and with E-COSY for 3 J ~ and ~ pJNHa,12and 3JHN,Huand 3JC7,Hu,13and also for heteronuclear long-range coupling constants.14 Quantitative measurements of coupling constants from pure-phase homo- and hetero-nuclear J spectra with tilted cross peaks," selectively excited NMR spectra," and E.COSY-type cross peaks from HECADE (HMQC- and HSQC-based) 2D NMR spectral7 were presented. Stripe-COSY and superstripe-COSY experiments combined with selective deuteration were presented for measurements of 3 ~ H , Hcoupling constants in DNA.l8 A high-resolution triple resonance method was presented for direct measurements of $ in proteins, based on cross-correlated relaxation between 'Ha-l3CU and 13C'CSA relaxation mechanism^.'^ A suite of triple-resonance NOESY -type pulse schemes with improved spectral resolution was presented.20 Flip-back ROESY and NOESY sequences, incorporating intentional radiation damping prior to mixing, were reported.21New pulse

Nuclear Magnetic Resonance, Volume 28 1999

0The Royal Society of Chemistry,

395

Nuclear Magnetic Resonance

396

schemes for recordings of intermolecular NOES in a molecular complex, which made use of frequency swept carbon inversion pulses, were presented.22 An efficient and straightforward approach to identify intermolecular proteinprotein NOE's in homodimeric proteins was presented.23 Long-range order information was obtained from the dependence of heteronuclear relaxation times on rotational diffusion a n i ~ o t r o p y An . ~ ~ increase in molecular alignment was achieved in an aqueous liquid crystalline medium, allowing for accurate measurements of D D The dependence of amide 15N chemical shifts on magnetic field strength was reported for a protein-DNA complex, allowing for additional constraints in the structure determination protocol.27 Transverse relaxation-optimised spectroscopy (TROESY), for attenuation of T2 relaxation by interference between D D coupling and CSA, was proposed as an avenue to N MR structures of very large biological macromolecules.28 A new method was presented for obtaining relaxation rates of 'H longitudinal modes, which largely eliminated effects from cross r e l a ~ a t i o n2H . ~ ~auto-correlation and I3C cross-correlation experiments were presented to study protein sidechain dyna~nics.~'Relaxation rates of transverse and longitudinal deuterium magnetisation of Asn and Gln side chains in uniformly "N-labelled proteins were proposed as novel parameters to investigate side-chain dynamics in protein-DNA c ~ m p l e x e s . The ~ ' dependence of the apparent overall correlation time (derived from the T1/T2 ratios) on the spectrometer frequency was presented for interpreting molecular motions on the ns time scale, if the major part of the molecule is involved in these motions.32 Comparison of I5N transverse self-relaxation rates from off-resonance sequences with those from CPMG sequences identified slow motional processes in "N-labelled proteins.33 New approaches were presented for the interpretation of relaxation Models of backbone ps dynamics were derived from quantification of auto- and cross-correlation relaxation mechanisms that involved different nuclei of the peptide plane.36

3

Small Organic Molecules

Studies of named drugs and natural products not named in the text are summarised in Table 11.1. A review addressed the use of 'H and 13C NMR in conformational studies of flavan-3-ols, proanthocyanidins and their derivatives. 37 NMR and MM calculations identified the conformations of some ethereal and ~ 3 , l O. isomers of cinchona alkaloids.38 A conformational analysis was presented for the cyclic peptides, segetalin D and E,39 and segetalin G and H.40 Potent inhibitors of stromelysin were identified by a structure-activity (SAR) approach, which involved the identification, optimisation and linking of compounds that bind to proximal sites on the protein.41Conformational studies were presented for two prolyl-endopeptidase inhibit01-s~~ and for glutamic acid analogues, inhibitors of vitamin K-dependent c a r b ~ x y l a s eThe . ~ ~ conformational analysis of a wl selective (zolpidem) and a non-selective (saripidem) ligand of w modulatory sites of GABAA receptors suggested that the single set of conformations observed with zolpidem could account for its selective properties.4 Conformational

I I: Conformutionul Analysis

397

analysis of the P-blockers, metoprolol, atenolol, timolol and the corresponding oxazolidine derivatives, indicated that oxazolidine formation resulted in the general preservation of the solution c ~ n f o r m a t i o n .The ~ ~ preferred overall c ~ n f o r m a t i o nand ~ ~ the conformational distribution around the V/W junction47 of highly toxic maitotoxin was assessed through studying small model compounds. The conformational analysis of the rigid opioid antagonist, cyco[Tyr(Me)z-Tic-], and a model for antagonism was presented.48 A dynamical model was presented for two potent bicyclic antagonists of o ~ y t o c i n The .~~ EFGH ring skeleton of brevetoxin A revealed unusual conformational properties for the 9-membered ring.50 Two conformers were identified for the twelvemembered o-bridged cyclic ethers, obtusallene I, 10-bromoobtusalle I, obtusallene I1 and obtusallene Ill." A conformational study on a diastereoisomeric pair of tricyclic nonclassical cannabinoids was presented.52 Conformational properties and of the imof 11-benzoyl-9,9a, 10,ll -tetrahydr0-4H-indol0[4,3-ab]carbazole~~ munomodulator l i n ~ m i d ewere ~ ~ studied. The conformational behaviour of a peptidic analogue of FK506 macrolide was p r e ~ e n t e d .A~ ~conformational ~~ analysis of a series of lanthionine and disulfide analogues of ~ a n d o s t a t i nwas presented. A detailed structural analysis was carried out for three conformational constrained parathyroid hormone related protein mono- and bicyclic lactam containing analogues in order to characterise the putative bioactive conformat i ~ n MM . ~ ~calculations and NMR studied the conformation of a (+)-catechinacetaldehyde condensation product.58 The solution conformations were reported for short-chain phosphatidylinositol molecules, both in monomer and micelle states. 59

3.1 Small Peptides and Peptide Analogues - A dipeptide mimic, constrained to a type VI p-turn, formed a singly exceptional stable intramolecular hydrogenbonded c ~ n f o r m a t i o nwhen ; ~ ~ coupled to L-Phe at the carboxyl group and to AcGly at the amino group a doubly hydrogen-bonded conformation was f ~ r m e d . ~ ' An extended P-strand mimic and its application to the creation of an artificial 0-sheet was presented.98The design of a fully flexible 011-hairpin peptidomimetic, based on 2,4-dimethylpentane units, was described.99 (R)-2-amino-3-oxohexahydroindolizino[8,7-b]indole-5-carboxylate was shown to suitably mimic the type 11' p-turn conformation of gramicidin S.Ioo A 3D structure of a hemoprotein mimetic was presented for the first time."' The solution structures of Fc~R1achain mimics, a P-hairpin peptide and its retroenantiomer, were presented. lo* Conformational studies were presented for an R G D containing novel dodecapeptidomimetic that showed potent binding to the a& receptor. lo3 A combinatory library of chemical models for parallel P-sheets was presented and the propensities of different amino acids to form parallel P-sheet were studied. Conformational interconversions of P-turn structures were reported for a model tripeptide.Io5 An L-shape conformation, believed to be crucial for eliciting sweet taste, was accessible to various potent dipeptide analogues. 106,107 The Schellman motif was identified in solution in a synthetic heptapeptide helix. lo8 The 5-amino-2-methoxybenzoic hydrazide template formed a hydrogenbonded antiparallel p-sheet."' The helix-helix motif of a synthetic 15-residue

398

Nucleur Magnetic Resonance

Table 11.1 Conformational studies of named drugs and natural products Compound

Comment

Ref:

Acetamiprid Actagardine

Active conformation of novel insecticide Rigid compact globular shape with two putative binding pockets Bradykinin Bl and B2, B2 and Bl specific receptor antagonists Similar conformation in solution and solid states 3D structure of HIV- 1 protease inhibitors

60

Wide spread sesquiterpene, three conformations in solution Conformational equilibrium in CHC13 Charged local anesthetic, conformational features in solution Calcium channel antagonist, aryl-dihydropyridine rotational barriers and rotameric preferences Solution and crystal structures for three diterpens

65

Conformations of sesquiterpene lactones by NMR and molecular modelling Principal ‘4E-envelope’conformer 3D structures of two serine protease inhibitors Preference of yt rotamer around C(5’) C(4‘) bond, of N conformation of ribose ring, and of syn conformation around C-N glycosyl bond Conformational eects on activity of u I -and u2-adrenergicreceptors

70

NMR and MD study, implications for bioactive conformation Conformational study by NM R and molecular modelling Conformational behaviour of rigid photosynthesis models by high-temperature MD simulations and VT IH NMR Metabolically stable, receptor 5-selective, backbone-cyclic somatostatin analogue Dimer, two conformations in solution Antimalarial agent, two conformational forms in solution Bulbs of ornithogalum saundersiae, conformational features Two contiguous a-helices Conformational behaviour of two novel triterpenoid saponins HIV-inhibitory nucleosides, rare sugar ring conformation

75

Free and to phosphoglycerate kinases bound conformations Anxiolytic agent, high proportion of folded conformations Bound conformation of gastric H+/K+-ATPaseinhibitor Two conformers each for stereoisomeric DNA adducts Backbone conformations, important factor in estrogen-like activity ‘Helix bundle’ structure was proposed for peptaibol channels Y2 receptor agonist, helical fragment Leu30-Tyr36 Structural dierences compared with parent hormone and correlation with anities for VI and V2 subtype receptors Dierences between X-ray and solution structure

86

B-9430,89436, 89858 Bradicardisant N-tert-Butoxycarbonylphenylalanyl enol family (-)-P-Caryophyllene (+)-Corydalic acid methyl ester Di bucaine Di hydropyridine Grandiflorenic acid, kaurenoic acid and monogynoic acid Helanolides Kainic acid LDTI and RB 6-Methyl-5-azacytidine

2- and 6-Methyl-substituted

(3,4-dihydroxyphenyl)-3piperidinols Muroctasin Paclitaxel analogues Porphyrin-quinone systems PTR 3046 Procyanidin B-2 Quinine Saundersioside A and B and cholestane glycoside Secretoneurin Snatzkein A and B 3’-Spironucleosides and analogues Suramin Tandospirone TMPIP Tetrol Thiosegetalins A and B Trichosporin-B-Vla Tyrosine 13-36 Vasopressin trisulfide (-)-Woodinine

61

62

63

64

66 67

611 69

71 72 73

74

76.77 78

79

80 81

82

83 84

R5

87 88

89 90,YI

92

93 94

95

399

1I : Conformutionul Analysis

peptide formed an antiparallel arrangement in CDC13, whereas a parallel arrangement was favoured in DMSO. lo Two 2-oxopiperazine-containingtetra-' peptide analogues adopted an inverse y-turn conformation in CDC13.' I Conformational analysis of Dnp-pNA derivatives of tetrapeptides containing a,adicyclopropylglycine revealed an extensive stacking interaction of the chromoformed phores. l 2 A peptide analogue, Boc(Leu-Leu-Ala)2-(Leu-Leu-Lac)3-OEt, a 310 helix in hexane and CDC13.' l 3 The cyclic tetrapeptide, cyclo(P-Ala-Pro)2 had a y-turn conformation, whereas cyclo(y-Aba-Pro)2 and cyclo(6-Ava-Pro)2 adapted different conformations depending on solvent polarity.' l4 The Thr residue was found to be conformational restricted to a fully extended C5 structure in the model peptides, Boc-Ile-Thr-NH2 and Boc-Leu-Thr-NH2. l 5 The conformations of a bicyclic lactam-based Leu-Pro building block and of the surConformational studies were rounding peptide fragment were assigned. reported for cyclic dipeptides' l 8 and the sodium chloride salts of N-t-Bocphenylalanyl-proline and the dihydrate of N-t-Boc-tyrosyl-proline. I l 9 RPhe-containing peptides, Boc-Gly-VAPhe-Val-0Me and Boc-Phe-APhe-Phe-OMe, favoured the formation of a type I1 p-turn conformation in CDC13 and DMS0.I2' Conformational features of cyclo(-y-Abu-l-Pr0-)2 were investigated in CDC13, CD2C12, CD30H, DMSO and D20.12' A restrained molecular modelling study was presented for a functionalized Aib-based octapeptide. 122 A novel irregular helix, containing 10- and 12-membered H-bonded rings, was identified for a phexapeptide.123 A distribution of conformations was found for the dichromophore-appended a-helical peptides, Boc-Ala-Aib-Ala-X-Ala-Aib-Ala-Ala-AibAla-Y-Ala-Aib-Ala-OEt [X=3-(1-pyrenyl)-1-alanine (pyrAla), Y =4(dimethylamino)-1-phenylalanine(dmaPhe) and X=dmaPhe, Y =pyrAla]. 124 Conformational states for cyclo(H-Lys-Asp-OH) and cyclo(H-Glu-Lys-OH) were determined by the atom-atom potentials with flexible geometry method, NMR and CD.I2' p-Loop, y-loop and helical peptide conformations were shown to exist in cyclopeptides, which contained a steroidal pseudo-amino acid. 126 Endo-(2S,3R)-norborn-5-ene induced the formation of p-turn, parallel P-sheet or antiparallel (3-sheet formation in peptides and pseudopeptides in apolar solvents. 27 A bicyclic diacid template was exceptionally effective in inducing helical behaviour in an appended peptide. 28 2-Amino-2-carboxyadamantane was shown to induce a high population of y-turn conformation in peptide mimics.129 The cycloaliphatic C">*-disubstituted glycine 1-aminocyclononane-1-carboxylic acid (Acgc) residue was identified in model peptides as a p-turn and helix former.13' The AzXaa residue was found to be a strong p-turn inducing motif in various Ala, Asp and Asn aza-derivatives. 3 1 3-Aminopyrazole derivatives stabilised the P-sheet conformation in N/C-protected dipeptides. 32

'

'

1791

'

3.2 Nucleotide Analogues, - Through-space 7 J and ~ 6~ J coupling ~ ~ constants were used to study the sugar ring conformation in 2',3'-dideoxy-4'-fluoroalkylnucle~sides.'~~ Conformational analysis of the complete series of 2' and 3' monofluorinated dideoxyuridines showed that the furanose ring pucker is governed by the highly electronegative fluorine atom. 134Depurinated adducts of the extremely potent carcinogens, dibenzo(a, l)pyrene, syn-DB[a,l]PDE-N7Gua,

400

Nuclear Mugnetic Resonance

syn-DB[a, I]PDE-N7Ade, and syn-DB[a, l]-PDE-N3Ade, adopted two conformations. 135 The boran group in dithymidine boranomonophosphate diastereoisomers showed a minimal influence on the sugar c ~ n f o r m a t i o n . 'The ~~ conformational behaviour of acyclic purine nucleoside analogue^,'^' two 5heteroaromati~-2'-deoxyuridines anc. their 5-bromine-heteroaromatic analogues"8 and N-(deoxyguanosin-8-yI)-n-aminopyrene adducts (dG-C8-n-AP, n= 1 ,2,4)'39 were reported. The populations of deoxypentofuranose ring conformers for (R)- and (S)-l-(2-deoxy-3,5-0-ethylidene-4-C-hydroxymethyl-~-l-threopentofuranosy1)uracil were obtained from vicinal coupling constants in combination with semiempirical PM3 calculations. I4O A preferential C3'-endo sugar conformation was detected in novel 3'-submide linked dinucleotide analogues. 14' The conformations of epimeric thymidine-3'-yl benzoin phosphates were estimated from 31P-13Cand 31P-'H coupling constants.'42 A new conformation with both A- and B-form DNA elements was observed for the peptide nucleic 143 Preferred solution acid-DNA hybrid H-GCTATGTC-NH2.d(GACATAGC). conformations of 2'-C-alkylribonucleotide were discussed. 144 A conformational analysis of various 2',3'-O-alkylidene (01 arylmethylene) adenosines was reported. 145 Conformational features of two RNA U-turn mimetics were studied.'46 Conformational features of 3-hydroxy-4-(hydroxymethyl)-l-cyclohexanyl purines and pyrimidines were correlated with antiviral activity. '47

3.3 Heterocycles - Conformational studies on polyazolylbenzenes and polyazolylpyridines, propellene-like aromatic compounds, were reviewed.'41 A review addressed the conformational behaviour of sulfur-containing six-membered cycles and macrocycles. '49 A conformational analysis of some 2-aryl- 1,3-dihydroxy-4,4,5,5-tetramethylimidazolidines was performed using both experimental data and results from quantum mechanical semiempirical calculation^.'^^ Semiempirical AM 1 calculations and ' H NMR carried out a conformational study on 1,4-di (pyrazol-1-yl)2,3,5,6-tetra kis (3 ,5-dimethylpyrazol- 1-yl) benzene (pz) 2-(dmpz) 4bz. I I Conformations of N-(pyridiny1)carboxamides' 52 '54 and pyrazolines, precursors to gemdimethylcy~lopropane'~~ were investigated. Electrostatic effects were found to favour the anti atropisomer of charged and dipolar derivatives of 1,8-di(2'-pyridy1)naphthalene. 156Two pairs (image and mirror image) of ground state conformations were obtained for 2-amino-3-aroyl-4,6,diarylpyryliumsalts.'57 Oligotridentate ligands, based on pyridine and pyrimidine, adopted a helical conformation in solution and solid states. An unusual antiperiplanar conformation was identified for 4-biaryl-substituted dihydropyridines. 159Semiempirical calculations and 'H NMR obtained the most favoured conformations of novel 2 2-amino -5 -aryl- 1,4,5,6,7,8-hexahydro -4,7 -dioxopyrido [2,3-d]-pyrimidir~es.'~~ [(2-pyrimidinyIthio)acetyl]hydrazoneswere found to exist as a mixture of El and Z' conformers in DMS0.I6' The effect of the electrostatic interactions on conformations of a series of zwitterionic w-pyridinium alkanoates, pyridine betaines, was examined.'62 'H NMR studied the conformational features of some 3-chlor0-2,6-diarylpiperidin-4-ones.'~~ A conformational study of some t(4)acetoxy-r(2),~(6)-diphenyl-N-acetylpiperidines provided evidence for the contri-

I1: Conformational Analysis

401

bution of boat forms with a substituent in the flagpole position.164V T NMR studied the conformations of aza- and 1,6-diazacyclodeca-3,8-diynesin solut i ~ n . NMR ’ ~ ~ and X-ray indicated that 1,3,4-0xadiazines adopted rigid cis- or trans-fused ring conformations, depending on the parent ring size and the 3Nsubstituent.166 H NMR, X-ray and modelling, investigated the conformational preferences of a series of tetrazolo [ 1,5-d] [ 1,4] benzoheterazepines. 167 Three N-ethoxycarbonyl derivatives of r-2,~-7-diphenylhexahydro1,4-diazepin-5-ones were found to prefer flattened boat conformations with fast equilibrium between N-CO rotamers. 168 The conformational behaviour of some 2-(2’-hydroxyphenyl)-4-aryl-3 H- 1,5-ben~odiazepines’~~ and of 2,3-dihydro-2,2-dimethyl1,4benzoxazepines and their 1 , 5 - i ~ o m e r s was ’ ~ ~ studied by VT NMR. Two interconverting pseudo-boat conformers were detected for 7-aryl-4,5-dihydro-2-0~03H,8H-furo[3,4-b][ 1,4]diazepines.17’ The conformational behaviour of a series of 22 2-methyl-2-alkyl(Ph, aryl)-4-N-methyl- 1,2,3,4-tetrahydro-SH- 1,3,4-benzotriazepin-5-ones and their open-chain hydrazone tautomers, 172 and hexahydroisoquino[3,2-b][3] benzazepines(is0- B- h~moberbines)”~was presented. The structures of h y d a n t ~ i n sand ’ ~ ~2 - t h i o h y d a n t o i n ~in ’ ~ solution ~ and solid states were discussed. Ring conformations for 5-amino-5-deoxypentonolactamswere investigated.’76 The predominant conformations for stereoisomeric 6-methylsubstituted pyrimido[6,1 -a]isoquinolines were presented. 177 Conformations of the potentially biological active 5-hydrazono-5,6,7,8-tetrahydro-2H-l-benzopyran-2ones and 5,6,7,8-tetrahydroquinoline-2,5(1 H)-diones, 178 four N-nitroso-2-phenyl~rans-decahydroquinolin-4-0nes~~~ and a fluorescent rotor, 6-(2,2-dicyanovinyl)1-(2-hydroxyethyl)- 1,2,3,4-tetrahydroquinoline, I8O were investigated. The conforand mational equilibrium of 1 -,3-, and 4-methyl- 1,2,3,4-tetrahydroisoquinoIines diastereomeric pairs of 1,3- and 1,4-dimethyl homologous were obtained from H3/H4(trans) coupling constants and MM calculations. I 8 l A pronounced conformational preference of the 3’-a-cumyl substituent in 2-(2’-methoxy-3’-a-cumylpheny1)-benzotriazole was suggested. 182 A conformational analysis on 6-amino acid-substituted indoloquinolizidones was presented. 183 The conformations of the antiaromatic [28]tetraoxaporphyrinoids(4.2.4.2) and aromatic [26]tetraoxaporphyrin(4.2.4.2)dications were analysed and a new type of molecular dynamics was described. An unusual twist-boat conformation was identified in cis-cyclohexane-bridged porphyrin quinones. NMR, X-ray and MD simulations investigated the conformational distribution of the potentially neurotoxic metabolite of haloperidol, HPP+.186I4N/I5N NMR determined the solution structures of nine pyrophthalone-type substances. 187 Conformational analysis of a 10-membered diamide disulfide ring was undertaken. Conformations of the cyclic polysulfids, 6,lO-disubstituted [ 1,2,3]trithiolo[h]benzopentathiepin monoxides, 189and 2-bis(~-chloroethyl)amino-4,5;7,8dibenzo- and dinaphtho- 1,3,2-dioxaphosphocine 2-0xides”~ were investigated. NMR studies of the preferred conformations of cate~hin-(4a-8)-epicatechin’~’ and some lac tone^'^^ were presented. NMR and Monte Carlo simulations explored the conformational space accessible to macrocyclic pol yethers. 193 NMR combined with computational approaches studied the conformations of 1 1 cisand 13 trans-3,4-dihydro-2-a1koxy -4-( a1ky 1- or aryl-subs ti tu ted)-2H, 5 H-pyrano

402

Nucleur Magnetic Resonance

[3,2-c] [ llbenzopyran-5-one derivative^.'^^ A series of trans-4,5-disubstituted-ybutyrolactones were found to assume two different envelope conformations. 195

3.4 Aromatic Compounds - Con formational aspects of the 4-nitrosophenolate anion and related compounds were studied by liquid and solid-state NMR in com bination with ab initio calculations. 196 Conformational studies were performed on enantiomers of the atropisomers of hindered naphthylcarbinol~'~~ and on unsymmetrical N-t-butyl-N-substituted 2-phenylacetamides. 19' NMR and semiempirical AM 1 calculations assessed the effect of different para-substituents on the conformational state of a series of azobenzene and N-benzylideneaniline derivative^.'^^ 'H- and I3C NMR studies and MO calculations investigated the conformational features of benzamidoximes.200 Solution conformations and rotational barriers of decaethylbipheny1201and of a-monoalkyl- and a,a-dialkylo-methoxy-benzyl alcohols202 were presented. Conformational studies for a number of 1,2-diacylben~enes'~~ and for four dibenzo-polycyclic hydrocarbons204 were presented. A NM R study on N-(aminoalkyl)-9-phenanthrenecarboxamides identified E and Z isomers for tertiary amides and extended and folded conformers for aminoalkyl Conformational properties of benzylamino derivatives of 1,4-diphenyl-2-butene-1,4-dione were described.206Solution structure and dynamic behaviour was investigated for dimethylsulfonium fluoren-9~ l i d e . ~A" conformational preference of the folded form of model compounds of Wilcox was observed, resulting from edge-to-face aromatic-aromatic ring interactiom208 The conformations of two trifluoromethyl-triaryl-ethane diastereomer pairs209 and cycloteraveratrilene derivatives2" were determined. AM 1 calculations and NMR studied conformational features of phenyl and (1 -pyrenyl)triarylmethylcarbenium ions under stable ion conditions.21 3.5 Hosts, Guests and Host Guest Interactions - Conformational properties of [p-( 1-methyl-~yclohexyl)][caIix[4]arene]were determined by dynamic N M R and MM2P MM calculations.212Conformations and dynamics were investigated for p-~ulfonatocalix[4]arene.~ l 3 Dynamical properties of the calix[4]arene-based (hemi)carcerands and amide or sulfoxide complexes were presented.214 NMR studies showed that a 2,4-diethoxycalix[4]arene-1,3-diquinone underwent an unusally slow conformational change (h range) in the presence of Na2+ ion.215 The conformational behaviour of the oxyanions of calix[4]arene were found to depend on the countercation.216Conformational studies on calix(aza)~rowns,~'~ 4-tert-butyldihomooxacalix[4]arenederivatives,2 polyaza~alix[5]arenes,~'~ chiral upper and lower rim (R)-binaphthyl-bridged c a l i ~ [ 4 ] a r e n e sextended ,~~~ calix[4]arenes and a doubly bridged bi~-calix[4]arene,~~' and inherently chiral monoalkyl were reported. A VT-NMR ethers of p-tert-butyldihomoo~acalix[4]arene~~~ study on the conformational behaviour of tetraalkylated dihomooxacalix[4]arenes was presented.223 Mono-0-substituted p-tert-butylcalix[6]arenes were restricted in cone conformations by the interplay of steric hindrance and hydrogen bonding.224NMR and MD simulations investigated the influence of CH2C12 and CHC13 on the conformational distributions of a tetramethoxycali~[4]arene.~~~ Two conformations were detected for cis-cyclohexyl-1O - c r 0 w n - 3 . ~Conforma~~

11: Conformutionul Anulysis

403

tional analysis of benzo-10-crown-3-ether was performed in solution and solid states.227Conformational studies by NMR and MM calculations of thia crown ether derivatives were presented.228The solution structure and complexational behaviour of bis-benzo crown ethers was in~estigated.~~’ Conformational studies of a proton ionisable ester crown of 3,5-disubstituted 1 H-pyrdzole complexed with lipophilic phenylethylarnine~~~’ and of dibenzo- 16-crown-5 lariat ethers23’ were presented. Conformations and rotameric distributions of ( )-trans-2,3-bis(2-naphthyl)-l5-crown-5 and IS-crown-6 were investigated by MM2 and dynamic NMR.232 Conformational studies of tetrahydroxy[3.1.3.l]metacyclophanes,233*234 0-benzylated calixarene analogous of trihydroxy[3.3.3]metacyclop h a n e ~ , ~and ~ ~ isomers of 9-methyI-2,l l-dithia[3.3]( 4 4 ) triphenylenometacyclophane and 2,23-dithia[3.3]( 1,4)triphenylen0phane~’~were presented. regioConformational studies on novel macrocyclic [3.1.1]meta~yclophanes,~~~ and conformational isomers derived from 0-benzylation of tetrahydroxy[3.1.3. I]m e t a c y c l o p h a n e ~ ,and ~ ~ ~tri heter0[9](9,10)anthracenophanes~~~ were presented. Cystinophanes, a novel family of aromatic-bridged cystine cyclic peptides, adopted a P-turn-like structure in solution.240An exo and endo conformational equilibrium was detected for ph~sphahemispherand.~~’

3.6 Acyclic Compounds - A combined X-ray, CD, NMR and ab initio approach addressed factors that affected the conformations of (R,R)-tartaric acid esters, amides and nitrile derivatives.242 A peference for eclipsed conformations was The molecular structure and conformation found for ne~pentyldialkylamines.~~~ of methyl acrylate was determined in a nematic liquid Populations and free-energy differences for the E and Z conformations of S-methyl, cyclopropyl, isopropyl and cyclopentyl thioformate were determined.245The conformational analysis of aminomethylene- and (1-aminoethylidene)pr~panedinitriles~~~ and of 1,3-dioxane was reported.247 NMR and M D simulations carried out the conformational analysis of four glutamic acid analogues.248 3.7 Mono-, Bi and Tri-Cyclic Compounds - VT ‘H NMR and quantum mechanics calculations studied the conformations of (S)-4-(cyclohexoxy~arbonyl)-2-azetidinone.~~~ MM calculations and NMR identified a preferred The confordiaxial conformation for trans- 1,2-bis(trimethylsilyI)cy~lohexane.~~~ mations of cis and trans isomers of 3- and 4-aminocyclohexylalkanoicacids were ~ t u d i e d . ~ Cyclohexane ” ring conformations were reported for several inositol derivatives.252Conformational studies of bicyclo[5.3.1.I-undecene-8, 1 1-dione by NMR, CD and MM3 calculations were presented.253 MM calculations, X-ray and ‘H NMR results showed that N,N’-dinitrosation of 2,4,6,8-tetrdaryl-3,7diazabicyclo[3.3. Ilnonanes changed the conformation from a chair-boat to a twin-chain with two aryl groups occupying axial positions and remaining two equatorial positions.254 Preferred flattened chair-chair conformations were reported for a series of 3-azabicyclo[3.3. llnonane derivatives2553256 and for carba257 Conformational differences mates of the (endo,endo,anti)-azabicyclononanol. were observed between 3-tert-butyldimethylsiloxy- and 9-methyl-8-oxa-9azabicyclo[3.2.2]non-6-en-3-ol,intermediates for bridgehead hydroxylated

Nucleur Mugnetic Resonance

404

tropane alkaloid derivative^.^^' A conformational study of new amides derived syn (anti) amines was presented.259 from 2-methyl-2-azabicyclo[2.2.2]-octan-5 Hexaspiro[2.0.4.0.2.0.4.0.2.0.4.0.]tetracosane was found to exist as mixtures of rapidly interconverting twist-boat conformations and a fixed chair conformation.260 The conformations and barrier to conformational interchange for .he triazapropellane, 3,7,1O-trimethyl-3,7,lO-triazatricyclo[3.3.3 .O 1,5]undecane, have been studied by dynamic NMR, MM2 and PM3 calculations.26' The conformational analysis of 5,9-propanobenzo[7]annulenederivatives by MM calculations and ' H NMR data was described.262

4

Nucleic Acids

Developments in NMR methods for structure determination of nucleic acids were NMR methods for the structure determination of unlabelled RNA and DNA were presented.265A new method was presented for determining DNA sugar conformations from the joint use of 2D and 3D NMR data.266 Methods and results for obtaining site-specificdynamics in DNA were reviewed.267 The application of the Uppsala 'NMR-widow' concept for the conformational analysis of biologically functional DNA and RN A molecules was reviewed.26g Technical progress in NMR studies of nucleic acids and their complexes and novel principles of their structure and recognition were highlighted.269 NMR structures of RNA and its c o m p l e ~ e s ~and ~ ~those * ~ ~of' unusual DNA's were reviewed.272 Models for the A-site region of 16s rRNA complexes with paromomycin were reviewed.273The use of synthetic polynucleotides and analogues for conformational studies of DNA and DNNdistamycin complexes were reviewed.274Solution conformations of both free and peptide-bound TAR RNA were reviewed.275 A review presented NMR studies of nucleotide-metal ion complexes.276 Structural work on eukaryotic transcription factor-DNA complexes was reviewed.277The complete matrix analysis of off-resonance ROESY spectra was shown to offer an advantage for the refinement of distance constraints and investigations of internal molecular dynamics.278Three-dimensional structures of nucleic acids and nucleic acid-ligand complexes were tabulated.279

4.1 Dynamics - NMR relaxation parameters determined the dynamics of the DNA oligomer d(GCGTACGC)* and the 4'-(hydroxymethyl)-4,5',8-trimethylpsoralen-DNA furanoside monoadduct.280Intramolecular dynamics of guanine and uracil bases in a 14-nt RNA hairpin including the extraordinarily stable UUCG tetraloop were studied by I5N relaxation experiments and interpreted with the anisotropic model-free formalism.28'

5

Proteins and Peptides

NMR methods to analyse protein structure2827283 and dynamics were reviewed.284 Motional models to interpret 13C and 15N relaxation measurements were

405

1 I : Conformutionul Anulysis

reviewed.285 Aspects on NMR structure determinations of large proteins and protein complexes were addressed.286 288 3D structure determination^,^^^ 292 dynamics and ligdnd interactions of proteins were reviewed.293Structural determinations of paramagnetic proteins were reviewed.2947295The relationship between protein stability and structure was reviewed.296Developments of experimental and calculated procedures, which accurately determine cross-relaxation rates, were reviewed.297Homo- and hetero-nuclear relaxation studies and their interpretations were summarised for proteins and pep tide^.^^^ Methods to measure and to interpret relaxation data were reviewed299 301 and d i s c ~ s s e d . ~ ' ~ Structural studies on neuropeptide Y and its analogue,303class I cytochrome q304pore-lining segments of neurotransmitter-gated channels,305and endothelins and analogues306 were reviewed. 3D structures of a-conotoxin MVIIA307 and venom toxins308 were reviewed. 3D structure/function studies on CXC chemokines309 and cystatin A3I' were reviewed. Recent developments to understand structure-function relationships of high-potential iron proteins were r e ~ i e w e d . ~ Structural properties of peroxidases, with particular emphasis to their implications in the catalytic process, were reviewed.312The sequence dependent nature of conformational features of the collagen triple-helix were addressed in a review.313 The structural determination of the EGF-like domain 4 of thrombomodulin, a thrombin cofactor protein, was reviewed.314 N MR and crystal structures of components of tissue-type plasminogen activator were reviewed.315 Solution structures of ribonuclease A and its complexes with mono- and din ~ c l e o t i d e sand ~ ~ ~those of FKBPs both free and d r u g - c ~ m p l e x e dwere ~~~ reviewed. The structural basis of antibody-antigen recognition was reviewed.3187319 Conformational studies of substrate and coenzyme A bound to chloramphenicol acetyltransferase and of protein G complexes with Fab and Fc were reviewed.320 Structural studies on protein-DNA complexes were reviewed.32' The structural basis of recognition of phage-displayed peptides by targets322 and peptide recognition by SH2, SH3 and PTB domains323 was reviewed. A new concept was presented that would allow the direct determination of protein structures from NOE data without prior assignment.3249325 A neural network which determined amino acid class and secondary structure from 'H,"N N MR data was presented.326 Multidimensional hypersurface correlations of backbone chemical shifts were presented for protein and $ dihedral determinat i o n ~ An . ~ ~ ensemble-averaging ~ protocol was described for determining the interconverting conformations in NMR structures of c y ~ l o p e p t i d e sThe . ~ ~ most ~ relevant NMR information to define the solution structure of flexible peptides was discussed and demonstrated for an argine-vasopressin-like insect factor.329 A new procedure (COMBINE) which combined merits of the FISINOE method with the DIANA program was presented for protein structure calculat i o n ~ . ~The ~ ' development and validation of the program GENFOLD, a genetic algorithm that calculates protein structures from NMR restraints, was pre~ented.~~ Three-dimensional structures of proteins and protein-ligand complexes were tabulated.279

+

406

Nuclear Mugnetic Resonance

Dynamics - Dynamic studies of methyl groups detected a correlation between binding energy and restriction of motion at interfacial binding sites of phosphopeptide complexes of phospholipase Cy 1 and Syp phosphatase SH2 domains.332Experiments with the 434-repressor demonstrated that the assumption of isotropic rotational reorientation might result in artefacts of model-free interpretations of spin relaxation data even for proteins with small deviations from spherical shape.333 NMR relaxation mechanisms for backbone carbonyl carbons in 13C,15N-labelledSso7d were found to predominantly involve CSA and IH-13C’ D D interactions, for which physical and geometrical parameters are uncertain, thus complicating their use as sequence-specific probes for protein backbone dynamics.334 In contrast, it was demonstrated that at high magnetic fields, useful relations between relaxation rates and spectral density functions could be derived from carbonyl carbon probes, because the CSA autocorrelation dominates carbonyl relaxation.335 Backbone dynamics were presented for HIV- 1 Nef under non-aggregating conditions (pH8, 0.6mM).336 Backbone and side-chain dynamics were investigated in a partially folded P-sheet peptide (P20) from platelet factor4 and some type of ‘folded’ or ‘collapsed’ structure could be detected.337A dynamic investigation on cardiotoxin analogue I1 revealed that the functionally important residues located at the tips of the three loops are For glutaredoxin-1 from E. coli backbone dynamics found increased motions on both ns-to-ps and ps-toms time scales in the reduced form relative to the oxidised form.340A rigid body movement of the second helix and twisting motions of the P-sheet were obtained for C40/82A barsterA from ”N relaxation results and amide proton exchange experiments.341 The long C D loop in murine leukemia inhibitory factor was found to be relatively rigid, in contrast to observations for related c y t o k i n e ~ . ~ ~ ~ Reduced flavodoxin showed significantly more flexibility, in particular in the 2 loop regions enclosing FMN, if compared to the oxidised which showed almost no internal mobility but fast overall tumbling.344 Backbone dynamics for the three-finger toxin, toxin a, were found in the ps-to-h regime and were correlated with toxicity and antigenic properties.345 Internal motions of the trp repressor in solution were correlated with function.346 Dynamic features of the DNA binding domain of fructose repressor were obtained from analysis of linear correlations between ”N-’H bonds spectral densities.347The flexibility of nucleoside diphosphate kinase was investigated by I H NMR filtering.348A dynamical N M R study on the ribosomal protein L9 identified those regions that contain the likely RNA-binding residues in each of the two domains as the most flexible parts.”’ 15N backbone dynamics of the 2 putative RNA binding domains of human U l A protein were found to be considerably different.350 The flexible linker between the two domains of the a subunit of RNA polymerase would allow for different locations or orientations in various kinds of initiation c ~ m p l e x e s . Collective ~~’ motions among helices, sheets, and wings on a time scale of ns-to-ms were identified for the winged helix protein, Genesis.352 A slow conformational exchange for residues comprising the active site and a high mobility for residues in the vicinity of the active site were described for the inhibitor-free catalytic fragment of human fibroblast collagena~e.’~~ The T1p-RI

5.1

11: Conformational Analysis

407

CRT experiment revealed pervasive conformational fluctuations on the ps time scales in a fibronectin type I11 domain.354 Residual DD couplings provided insights into slow collective motion for the paramagnetic protein cyanometmyogl~bin.~ The ~ ? backbone dynamics in cytochrome b5 were studied using "NNMR relaxation measurements and analysed with the model-free approach and with reduced spectral density mapping approaches.356 Motional dynamics of residues in a P-hairpin peptide were obtained from 13C relaxation measurem e n t ~ Internal . ~ ~ ~ dynamics of intact and reactive-site hydrolysed trypsin inhibitor, (CMT1)-11, of the squash family were determined and compared with those of counterparts of CMTI-V of the potato I family.358 Protein Engineering - Co-operative effects on the stabilisation of a de novo designed three-stranded antiparallel P-sheet were dissected.359Model studies were presented that identified optimal residues for antiparallel sheet formation in Ppeptide f ~ l d a m e r s . ~A~de ' novo designed peptide folded as a compact B-sheet sandwich tetramer.361De novo designed HLH dimer proteins with an interhelical salt bridge and shape-complementary hydrophobic interfaces were presented.3627363 A synthetic peptide, composed of alternating bulky hydrophilic and hydrophobic amino acids, formed P-helical fibrils.364Relative populations of 310helix and a-helix were obtained for Ala-rich pep tide^.^^^ The solution structure of a 38-residue de nova designed peptide identified a ata motif.366Conformational studies on RGITVLlGKTYGR (LI =N,D,A,G,S) peptides, indicated that the design of a specific hairpin structure must involve a sequence at the turn region favouring the desired turn type, and a sequence at the strands that avoids alternative interstrand side-chain pairings.367The influence of cross-strand sidechain interactions in P-hairpin formation was in~estigated.~~' De novo protein design, implementing buried core, solvent exposed surface, and boundary between core and surface methodologies, generated a peptide, pda8d, with the desired PPol motif fold.369 A de novo designed peptide, aZD, adopted an unexpected novel bisecting U topology.370An unconstrained 16-residue peptide was shown to closely mimic the DNA binding face of the met repressor dimer.37' A 42 amino acid polypeptide, designed to fold into a hairpin HLH motif, formed a four-helix bundle upon d i m e r i ~ a t i o n . ~ ~ ~ 5.2

5.3 Folding - NMR probing of molten globule states was reviewed.373Conformational studies of chaperonin bound proteins were reviewed.374 Residue contacts in a a-lactalbumin folding intermediate were probed by NOES, which were generated in the partially folded state but observed in the native state.375Results for cytochrome c showed the fundamental co-operative substructural design of the protein.376 An ensemble of structures for the denatured state of staphylococcal nuclease showed that the global topology was strikingly similar to that of the native state;377-378 secondary structural elements of the denatured state, however, were not observed in isolated peptide fragm e n t ~ NMR . ~ ~ ~structural analysis was presented for an analogue of an intermediate formed in the rate-determining step during oxidative folding of RNase A.380The A-states (pH=2.0) of equine lysozyme were less ordered than the native

408

Nuclear Magnetic Resonance

protein but did not contain significant regions of random coil stru~ture.~"The structure and dynamics of two partially folded states of apomyoglobin have been characterised at equilibrium.382 The partially folded A state of ubiquitin was characterised to contain a combination of native and non-native secondary structural elements with high internal mobility.383 A well-defined hydrophobic cluster was identified in partially folded P-lactoglobin at pH 2.384Structural and dynamical properties were reported for denatured reduced and oxidised lysozyme in 8M urea.385 A core region of a-lactalbumin remained collapsed even under extremely denaturing conditions.386 3D structures of disulfide lacking analogues of the neurotoxin, leiurotoxin 1, revealed a differential involvement of the disulfide bridges on folding.387 The analysis of conformational properties of isolated myoglobin peptides supported the hypothesis that spontaneous structure formation in local regions of the polypeptide may play an important role in the initiation of protein folding.388 Observations on an engineered N-terminal domain of yeast phosphoglycerate kinase suggested that the C-terminal peptide and interdomain helix are sufficient for maintaining a native-like fold.389Bis(cysteiny1)peptideswere folded by a zinc ion into structures that were superimposable on those of the natural prot e i n ~ . A~ conformational ~ ~ * ~ ~ ~ study on an isolated peptide fragment (19-41) of protein G indicated that the non-native hydrophobic staple did form in water and stabilised the helix, while the Schellman motif did not contribute to this stabilisat i ~ n The . ~ conformational ~ ~ analysis of a 23-residue peptide fragment, corresponding to the structurally conserved H-Schellman motif-H domain of cellular retionic acid binding protein (CRABP l), showed that local interactions in the Schellman motif dictated the interhelical arrangement.393 Local segmental motions and co-operative unfolding were detected in the partially folded [ 14-38]~,,, BPTI variant.394 Ligand Binding - Conformational studies on protein-ligand complexes are summerised in Table 11.2. A model building study was presented that incorporated information from NMR chemical shift changes upon ligand binding.395The use of organic solvents to identify specific ligand-binding sites on protein surfaces was illustrated.396 A I3C NMR paramagnetic study was used to probe biotins interaction sites with a ~ i d i n . ~ ~ ~ TRNOE's studied the structure of adenine nucleotide bound at the active site of yeast h e x o k i n a ~ ethe , ~ ~conformation ~ of bound glutathione in the active site of human glutathione transferase PI - 1,399and the interactions of the receptor binding domains of pseudornonas aeruginosa pili strains PAK, PAO, KB7 and P1 with a cross-reactive antibody and with a receptor a n a l o g ~ e . ~ "Structural changes in the protein were observed when NADP+ bound to the flavoenzyme, UDP-N-acetylenolpyruvyl-glucosamine reductase ( M u ~ B ) . ~Changes " in conformation and dynamics were identified for the free and GMP-bound forms of yeast guanylate kina~e.~'* Binding modes of GDP and GTP analogues to human c-HaRas protein were inve~tigated.~'~ NMR studies on the interaction of bradykinin with an antibody mimic of the bradykinin receptor were reported.404 Insights into interactions of the Leu-Pro binding pocket of the Src SH3 domain

5.4

1 I : Conformational Analysis

409

Table 11.2 Studies of protein-ligand complexes ~~

Prolein

~~~~

Comments

~

ReJ:

409 Probing DNA bound orientations 410 Interactions with chloramphenicol 41 1 Interactions with active site-directed inhibitor 412 Model of ascorbate binding site 413 Binding of myristoylated Ala-rich c kinase substrate peptides, disruption of central helical linker 414 Chloroperoxidase Nuclear paramagnetic relaxation study on cyclopentanedione interactions 415 Models for substrate binding Cytochrome P450 2C9 FlgM C-terminal half became structured upon 02’binding 416,417 418 3D structure of an extracellular domain G-CSF and ligand interactions 419 Gl yceraldeh yde-3-phosphate NMR structure of bound band 3 peptide inhibitor dehydrogenase 420 G protein Bound conformation of mastoparan-X 421 Ten-residue peptide derived from SOS, dynamical Grb2 N-terminal averaging HTV- 1 protease Distinct protonation state of catalytic aspartyl side-chain 422 carboxyl groups in complex with KNI-272 inhibitor 423 HPg K2 Model conformations of the 6-aminohexanoic acid binding site 424 Lactate dehydrogenase NAD+ bound conformation 425 Phospholipase C Bound conformation of lipophilic inhibitor SH3 NL2, NL2R, protein receptor interactions with ligands 426 of opposite chirality 421 Staphylococcal nuclease Ternary complex with Ca2+and (H 124L) thymidine-3’,5’-bis-phosphate 428 Stromelysin Bioactive conformation of potent inhibitor, model of complex 429 Trp-repressor TRNOE’s for corepressor-pro tein/operator complex

ADR 1 zinc-finger protein Albumin Arylmalonate decarboxylase Ascorbate peroxidase Calmodulin

with a non-peptide ligand were obtained from multidimensional NMR.405 During NADPH oxidase assembly, the C-terminus of gp9lphoXbinds to p47phox in an extended conformation between gp9lphoXresidues 555 and 564, with immobilisation of all the amino acid side chains in the 558 to 564 region except for His561.406 Correlated bond rotations were observed in the interactions of Arg residues with ligand carboxylate groups in Lactobacillus casei dihydrofolate reductase/methotrexate complexes.407 The conformations of isepamicin and butirosin A in the active site of aminoglycoside 6’-N-acetyltransferase-Iiwere determined.408

6

Carbohydrates

Current modelling protocols for the conformational analysis of oligosaccharides were reviewed.430Conformational and dynamic studies of oligosaccharides and glyco-c~njugates,~~’ glycoprotein g l y c a n ~and ~ ~carbohydrates ~ in the free and

410

Nuclear Mugnetic Resonance

receptor bound state433were reviewed. Conformational studies on carbohydrateprotein interactions434were reviewed. NMR experiments for the detection of NOES and scalar coupling constants between equivalent protons in trehalose-containing molecules were presented.435 3D heteronuclear NMR techniques were presented for assignments and conformational analysis of uniformly I3C-enriched oligosaccharides that used exchangeable protons.436 A new search algorithm, the so-called CICADA procedure, has been validated by the successful simulation of experimentally obtained NMR data for sucrose.437 The GMMX global searching program was used for the prediction of 3 ~ H , Hring coupling constants.438 A continuous conformational space searching method that explores pyranose ring flexibilities was presented.439 The conformational behaviour of new sugar isourea ethers was investigated.u0 The ring conformations of the 0-specific polysaccharide of Shigellu so~lne,@~ anti t hrom bo t ic t h i o g l y c ~ s i d e s ,1~-glycosyl-2-acetyl ~~ h ydrazines of hexoses and 2-acetamido-2-deoxyhexoses,43 and 0-(3-~tannylpropyloxy)carbohydrate derivativesu were investigated. A correlation between 3C-'H and 13C-13C coupling constants and conformation was described for methyl P-u-ribofuranoside and methyl 2-deoxy-p-uerythro-pentof~ranoside.~~ A best fit between calculated and experimental coupling constants using Karplus equations established the conformations for methyl 5-deoxy-cr and ~ - u - x y l o f ~ r a n o s i d eConformational s.~~~ similarities were reported for synthetic oligosaccharides that bound monoclonal antibodies against Chlamydia lipop~lysaccharides.~~ The conformation of ring A of the aglycon of the sugar moieties and the preferred orientations around the glycosidic linkages of the doxorubicin disaccharide, 4-demethoxy-7-0-[2,6-dideoxy-4-0(2,3,6-trideoxy-3-arnino-c~ - L-lyxo-hexopyranosy1)-a -L-lyxo-hexopyranosyl]adriamicinone, were obtained using the NAMDIS program (NMR analysis of molecular flexibility in solution).448 A conformational study of asialo-GM 1 gangliosides was p r e ~ e n t e d . ~ ' Substantial conformational changes occurred upon protonation of the ring NMR and MM calculations oxygen of 2-deo~y-P-u-glycero-tetrafuranose.~~~ studied the solution conformation of methyl ~t-lactoside.~~' Solution conformations and dynamics for a Lewis' related tetrasaccharide, GalNAc(crl-3)Gal(~l-4) [Fuc(crl-3)]Glc(POMe), were presented.4527453The solution conformation of Lewis"-derived selectin ligands were shown to be unaffected by anionic substituents at the 3'- and 6'-po~itions.'~~ The solution conformations of heparin-derived h e x a s a ~ c h a r i d e s , the ~ ~ ~trisaccharide, P-D-Glcp-(1-2)-P-~-Glcp-(1-3)-a-~-GlcpOMe,456 and a heptasaccharide hapten of Shigellu JEexneri variant Y polysaccharide457 were investigated. The conformational flexibility of a-D-Manp(1-2)-P-~-Glcp-OMewas studied by MMC and LD simulations and validated by comparison with experimental long-range heteronuclear coupling constants.458 Conformational features of four anomeric methyl glycosides of the trisaccharide ~ - G l c p -1(-3)-[~-Glcp-(1-4)]-a-~-Glcpwere investigated by N MR and Metropolis Monte Carlo simulations with the HSEA force field.459Two L-fucose containing disaccharides, a-L-Fuc( I,~)-P-D-GICNAC-OM~ and c~-L-Fuc-(1,6)-P-~-GlcNAcOMe, have been studied conformationally by a combined NMR, grid search/

1 I : Conformational Anulysis

41 1

MM3 and Metropolis Monte Carlo/GEGOP approach.460 NMR and unrestrained MD simulations studied conformational and dynamic features of p-DGlcA-( 1 , 4 ) - ~ - R h a . ~ Experimental ~l data for a variety of oligosaccharides indicated similar timescales for internal and overall motion.462 Motional properties were studied by NMR and molecular modelling for GlcNAc(P1 ,3)Gal(P)OMe.463 The 3D structure and dynamics of the glyco-conjugate, estrone-3-glucuronide, have been probed both in free state and when bound by an antibody Fv fragment.464 The bioactive conformations of sialyl Lewis' and a potent sialyl Lewis' mimic were compared.465A model structure for the complex of C-lactose and E. coli P-galactosidase was presented.466Thiocellobiose was bound in a single conformation by P - g l u c ~ s i d a s e .The ~ ~ ~solution structure of the granular starch binding domain of Aspergillus niger glucoamylase bound to P-cyclodextrin was presen ted.468 Limited internal mobilities were observed for E. Coli polysaccharide K5 when compared with iduronic acid containing glyc~saminoglycans?~~ Conformational and dynamical features have been deduced for extracellular deacetylated polysaccharides from B r ~ d y r h i z o b i u r n . ~ ~A~ complete .~~' heteronuclear relaxation study on the cyclic glucan of R. sofanacearum revealed slow dynamics, with The protein was found to restrict exchange rates of the order of several p.472 mobilities of the inner three core residues and the Man(a1-6) branch of the glycan at Am78 of the wsubunit of hCG.473

7

Membrane Environments

Aspects on structural studies of membrane proteins were presented.474 A new membrane mimetic (isotropic solutions of phospholipid bicelles) was presented for high-resolution structural studies of m a ~ t o p a r a n ~and ~ ' myristoylated N-terminal fragments of ADP-ribosylation factor 1 .476 NMR and C D studies of the interaction of the neurotoxic P-amyloid fragment (1 2-28) with cellular membrane model systems revealed that SDS micelles altered the pH-dependent conformational transitions of the peptide whereas the weak interaction with DPC micelles caused little changes.477 A benzodiazepine-like decapeptide adopted an amphipathic 3 10-helicoid structure in SDS m i c e l l e ~A .~~~ conformational motif typical for neurokini- 1 selective ligands was adopted by the tachykinin, substance P, in a lipid environment.479 A cytoplasmic peptide of neurotrophin receptor p75NTR induced apoptosis and adopted a helical conformation oriented parallel to the surface of DPC m i c e l l e ~A. ~bovine ~ ~ asl-casein decapeptide adopted an amphipathic helicoid structure with distinct hydrophobic and hydrophilic faces in a H*O/SDS micelle medium.481The conformation and topological orientations of a dimer of vancomycin in a membrane-like environment has been determined.482Angiotensin I1 adopted a well-defined structure in phospholipid environments.483 'H NMR and C D studied the structures of the C-terminal secretion signal of the Serratia marcescens haeme acquisition protein484and synthetic peptides from human apolipoprotein A-1485and C-1486in various membrane-mimetic environments. Conformational changes induced in

412

Nuclear Magnetic Resonance

the structure of human and chicken parathyroid hormone (1-34) peptides in the presence of T F E and SDS were investigated and correlated with biological activities.487 Membrane conformations and their relations to cytotoxicity of asimicin and its analogues were i n ~ e s t i g a t e d . ~The ~ ' structure of the second potential membrane anchor region in the thromboxane A2 synthase N-terminal domain was investigated in TFE and DPC m i ~ e l l e s . ~ ~ ~ Conformational preferences of Leu-enkephalin were studied in reverse mi~ e l l e s . ~The ~ ' solution structure of the porcine gastrointestinal peptide hormone motilin was found to be rigid in the presence of SDS m i ~ e l l e s . ~Hydrophobic ~' forces were found to be responsible for the folding of a highly potent natriuretic peptide analogue at a membrane mimetic surface.492 Structural features of the final intermediate in the biosynthesis of the lantibiotic nisin were investigated in aqueous solution and when complexed to micelles of DPPC.493The ionophoric antibiotic monensin adopted a wide range of conformations in SDS r n i c e l l e ~ . ~ ~ ~ Magainin adopted a a-helix in DPC, SDS micelles and in TFE/H20.4953D structures of the type IIa bacteriocin from lactic acid bacteria, leucocin A, were compared in TFE and DPC m i ~ e l l e s A . ~ conformational ~~ study in SDS and DPC micelles was presented for a peptide mimetic of the third-cytoplasmic loop of G - ~ r o t e i n . ~Solution ~' state NMR of an active K-opiodid agonist, a cyclic dynorphin A analogue, indicated a cis-trans isomerism about the Arg9-Pro" w bond in aqueous solution and when bound to DPC.498Conformational features of endothelin receptor subtype B specific agonist, IRL 1620, and its analogues were investigated in the presence of phospholipid vesicles.499 Motional properties of the terminal sugar of Gb3 were measurably influenced by the fluidity of the host matrix, without conformational or orientational variation^.^'' Motions in the amphipathic a-helix on the ns timescale and additional flexibility of several residues in the loop connecting the helices were determined for fd coat protein in membrane environment^.^" Motions of the indol rings for seven gramicidin A analogues were found to systematically decrease from the aqueous interface to the interior of the SDS m i ~ e l l e . ~ ' ~

8

Inorganic and Organometallic Compounds

2D N M R methods were presented that elucidated structure and dynamical features of chiral organometallic phosphine c ~ m p l e x e s . ~ ' ~

8.1 Transition Metal Complexes - The solution structures of a series of [4Fe-4S] ferredoxin model arenethiolate complexes were based o n 'H NMR TI data and MD simulation^.^^ Organotransition metal modified D-galacto and L-arabino complexes adopted extended planar zigzag conformation^.^'^ A conformational study on organotransition metal modified monosaccharides was presented.'06 The sugar conformation was investigated in TI' mononucleotides.507~508 Solution conformations of bis(ethy1ene) complexes of W(0) and Mo(O), containing the CH3C(CH2PMe2)3 ligands, were studied.509 A chiral, tripodal tris(phosphine) ligand adopted a left-handed helical conformation when coordinated to a

I I : Conformutionul Analysis

413

rhodium( I ) metal R M ( DH)( DBPh2) N-Melm and RM(DBPh2)2 N-Melm, M =Co, Rh, assumed different interconverting conformations in s~lution.~' Configurational and conformational isomeric processes of the complex, [(dppe)Pt {p-SCH(CH2CH2)2NMe}2PtIMe3],were studied by NMR and ab initio calculation^.^'^ Conformational studies on binary and ternary complexes of Pt(I1) with dipeptide esters and with nucleosides were presented.513 Preferred chelate ring conformations were determined for [PtX2(Me2DAP)] (X=I or C1, Me2DAP=2,4-bis(methylamino)pentane) by NMR and MM/MD calculation^.^'^ Rapidly interconverting conformers were identified for [(PEt3)2(Ar)Pt(p-H)PtH(PEt3)2][BPh4] (Ar=Ph, 2,4-M&&3, 2,4,6-Me3C6H2).5'5 The conformational behaviour in solution was investigated for the tetranuclear open cluster anions, [Re4H(p-H)2(CO)I,]- and [Re4(p-H)(CO)lg]- .5'6 The BIP ligand in Fac[ReX(C0)3(BIP)] (X=Cl, Br or I) existed in three conformational forms in solution.517' H NMR studied the conformational equilibrium of DOTA complexes of lanthanide metal ions in aqueous s o l ~ t i o n .Two ~ ' ~ dominant conformers were identified for the do Y(II1) pentenyl chelate complex, Cp*2Y[q ',q2CH2CH2C(CH3)2CH=CH2], from quantitative analysis of NOESY time courses with the conformer population analysis method.519

'

8.2 Main Group Metal Complexes - Solution structures of zinc(I1)-pyropheophytin-anthraquinone dyads, model compounds for photoinduced electron transfer, were presented.520 Ph-C6F5 x-stacking interactions were found in B(C6F5)3 adducts of PhC(0)X (X= OEt, NPr'2) in solid and solution states.521 Conformational features of dialkyldithiophosphinate stibocanes X(CH2CH2S)2SbS2PR2,522 some substituted ~ i l a t r a n e s , [CpCr(CO)2]2Se ~~~ and [CpCr(C0)2]2Se2,524and new 4-pho~phaphosphorinanes~~~ were presented. VT H N MR detected a conformational diastereoisomerism in tris(2-alky1imino)t r i p h e n y l p h ~ s p h i n e sA .~~ multinuclear ~ NMR study indicated preferred conformations for the silyl-, stannyl- and the mixed silylstannyl derivatives, PhP(R)CH2EMe3 (R=H,Ph;E=Si,Sn), PhP(CH2EMe3)2 (E=Si,Sn), PhzPCH(SiMe3)(SnMe3), (Ph2PCHSiMe3)2(SnMe2) and PhP(SiMe3)CH2SiMe3.527NMR, X-ray, ab initio MO and MM calculations investigated conformations of the eightmembered 12H-dibenzo[d,g][1,3,2]dioxasilocin ring system.528 31P NMR and X-ray revealed a planar structure of the PCPCP skeleton with E,E-conformation for bis(ylidy1)-phosphenium halides.529 A single preferred conformation was indicated for the secondary phosphine, But-MesPH (Mes-2,4,6-trimethyl~henyl).'~' The conformational analysis of three unconstrained eight-membered heterocycles, 1,5-dithiacyclooctane, 1-phenyl- 1-phospha-5-thiacyclooctane,and trans- 1,5-diphenyl- 1,5-diphosphacyclooctane 1,5-dioxide, was carried out .531 'H NMR analysis identified an antiperiplanar conformation with respect to the P-CH2 bond in the chloromethylchlorophosphines, R(Cl)PCH2Cl (R=cyclohexyl, Ph2N, Et,N, The conformational analysis of 2-0-aryl-2-oxo-4,6and Ga(II1) complexes dimethyl- and -4-methyl- 1,3,2h5-dioxaphosphorinanes533 of F e ( ~ p y was ~ ) ~presented. ~ ~ Conformational preferences were obtained for bis(q-heter0arene)titanium complexes.535NMR and X-ray determined the ligand

'

Nuclear Magnetic Resonance

414

conformation of a lithium complex, hexacoordinated with 1,3,5-tris[oxymethylene(N,Ndicyclohexyl)carboxyamido]cyclohexane.536 Two chiral N,N’disubstituted-3-aminopyrrolidine lithium amides adopted different conformations in solution, which became similar upon addition of B u ~ L ~For . ’ ~cryptand~ (2,2) rapidly interconverting conformations were identified.538

References

9 1

2 3 4 5 6 7 8 9 10 11 12 13

14 15 16 17 18 19 20 21 22

23 24 25 26 27 28

K. E. Kover, V. J. Hruby, D. Uhrin, J. Magn. Reson., 1997,129, 125-129. D. Uhrin, G. Batta, V. J. Hruby, P. N. Barlow, K. E. Kover, J. Magn. Reson., 1998, 130, 155-161. M. Hennig, D. Ott, P. Schulte, R. Loewe, J. Krebs, T. Vorherr, W. Bermel, H. Schwalbe, C. Griesinger, J. Am. Chem. Soc., 1997,119, 5055-5056. J.-S. Hu, A. Bax, J. Am. Chem. Soc., 1997,119,6360-6368. R. Konrat, D. R. Muhandiram, N. A. Farrow, L. E. Kay, J. Biomol. NMR, 1997,9, 409-422. F. Lohr, M. Blumel, J. M. Schmidt, H. Ruterjans, J. Biomol. NMR, 1997, 10, 107-118. J.-S. Hu, A. Bax, J. Biomol. NMR, 1997,9, 323-328. S. Grzesiek, A. Bax, J, Biomol. N M R , 1997,9,207-211. K. Theis, A. J. Dingley, A. Hoffmann, J. G. Omichinski, S. Grzesiek, J. Biomol. NMR, 1997,10,403-408. A. Meissner, J. 0. Duus, 0. W. Sorensen, J. Biomol. N M R , 1997,10, 89-94. A. Meissner, J. 0. Duus, 0. W. Sorensen, J. Magn. Reson., 1997,128,92-97. M. D. Sorensen, A. Meissner, 0. W. Sorensen, J. Biomol. N M R , 1997, 10, 181-186. A. Meissner, T. Schulte-Herbrueggen, 0. W. Sorensen, J. Am. Chem. Soc., 1998, 120,3803-3804. A. Meissner, 0. W. Sorensen, Chem. Phys. Lett., 1997,276,97- 102. W. Kozminski, S. Bienz, S. Bratovanov, D. Nanz, J. Magn. Reson., 1997, 125, 193-196. X. Miao, X. Zhang, L. Li, C. Ye, Bopuxue Zazhi, 1997,14,69-75. W. Kozminski, D. Nanz, J. Magn. Reson., 1997,124, 383-392. J. Yang, L. Silks, R. Wu, N. Isern, C. Unkefer, M. A. Kennedy, J. Magn. Reson., 1997,129,212-218. D. Yang, R. Konrat, L. E. Kay, J. Am. Chem. Soc., 1997,119, 11938-1 1940. 0. Zhang, J. D. Forman-Kay, D. Shortle, L. E. Kay, J. Biomol. NMR, 1997, 9, 18 1-200. D. B. Fulton, F. Ni, J. Magn. Reson., 1997, 129,93-97. C . Zwahlen, P. Legault, S. J. F. Vincent, J. Greenblatt, R. Konrat, L. E. Kay, J. Am. Chem. Soc., 1997,119,671 1-6721. K. J. Walters, H. Matsuo, G. Wagner, J. Am. Chem. SOC.,1997, 119, 5958-5959. N. Tjandra, D. S. Garrett, A. M. Gronenborn, A. Bax and G. M. Clore, Nature Struct. Biol., 1997,4443-449. A. Bax, N. Tjandra, J. Biomol. NMR, 1997,10,289-292. N. Tjandra, A, Bax, Science, 1997,278, 11 1 1 - 1 1 14. M. Ottiger, N. Tjandra, A. Bax, J. Am. Chem. SOC.,1997, 119,9825-9830. K . Pervushin, R. Riek, G. Wider, K. Wuthrich, Proc. Natl. Acad. Sci. USA, 1997, 94, 12366-12371.

11: Conformational Analysis

29 30 31 32 33 34 35 36

37 38 39 40 41 42 43 44

45 46 47 48 49 50

51 52 53 54

55 56

41 5

T. J. Norwood, J. M a p . Reson., 1997,125,265-279. D. Yang, A. Mittermaier, Y.-K. Mok, L. E. Kay, J. Mol. Biol., 1998, 276, 939-954. K. Pervushin, G. Wider, K. Wuethrich, J. Am. Chem. Soc., 1997,119,3842-3843. D. M. Korzhnev, V. Y. Orekhov, A. S. Arseniev, J. Magn. Reson., 1997, 127, 1 84- 1 9 1 . S. Zinn-Justin, P. Berthault, M. Guenneugues, H. Desvaux, J. Biomol. NMR, 1997, 10,363-372. V. A. Daragan, K. H. Mayo, J. Magn. Reson., 1998,130,329-334. T. Bremi, R. Brueschweiler, R. R. Ernst, J. Am. Chem. Soc., 1997,119,4272-4284. M. W. F. Fischer, L. Zeng, Y. Pang, W.Hu, A. Majumdar, E. R. P. Zuiderweg, J. Am. Chem. Soc., 1997,119, 12629-12642. A. D. Vdovin, Z. A. Kuliev, N. D. Abdullaev, Chem. Nat. Compd, 1997,33, 1 1 -24. J. Thiel, P. Fiedorow, J. Mol. Struct., 1997,405, 219-230. H. Morita, Y. S. Yun, K. Takeya, H. Ttokawa, Chem. Pharm. Bull., 1997, 45, 883--887. H. Morita, Y. S. Yun, K. Takeya, H. Itokawa, Bioorg. Med Chem., 1997, 5, 2063 -2067. S. B. Shuker, P. J. Hadjuk, R. P. Meadows, S. W. Fesik, Science, 1996, 274, 1531-1534. M. Feher, K. Kanai, B. Podanyi, I. Hermecz, Quant. Struct.-Act. Relat., 1997, 16, 136- 141. V Larue, J. Gharbi-Benarous, F. Acher, V. Arulmozhi, C. Tisne, N. Todeschi, R. Azerad, J.-P. Girault, Int. J. Biol. Macrumul., 1997,20, 131 -159. A. Olivier, M. Sevrin, F. Durant, P. George, Bioorg. Med. Chem. Lett., 1997, 7, 2277-2282. G. P. Moloney, D. J. Craik, M. N. Iskander, T. L. Nero, J. Chem. Soc., Perkin Trans. 2 , 1998, 199-206. M. Sasaki, M. Murata, Yuki Gosei Kagaku Kyokaishi, 1997,55,535-546. L. R. Cook, H. Oinuma, M. A. Semones, Y. Kishi, J. Am. Chem. Suc., 1997, 119, 7928-7937. 0. Crescenzi, F. Fraternali, D. Picone, T. Tancredi, G. Balboni, R. Guerrini, L. H. Lazarus, S. Salvadori, P. A. Temussi, Eur. J. Biochem., 1997,247,66-73. M. D. Shenderovich, K. E. Koever, S. Wilke, N. Collins, V. J. Hruby, J. Am. Chem. Soc., 1997,119,5833-5846. K. C. Nicolaou, Z. Yang, M. Ouellette, G.-Q. Shi, P. Gaertner, J. L. Gunzner, C. Agrios, R. Huber, R. Chadha, D. H. Huang, J. Am. Chem. Soc., 1997, 119, 8105- 8106. G. Guella, G. Chiasera, I. Mancini, A. Oztunc, F. Pietra, Chem. Eur. J., 1997, 3, 1223- 123 I . X.-Q. Xie, S. Pavlopoulos, C. M. di Meglio, A. Makriyannis, J. Med. Chem., 1998, 41, 167-174. T. Mavromoustakos, I. K. Stamos, C. Kamoutsis, E. Theodoropoulou, M. Zervou, E. Humpfer, J. Pharm. Biomed. Anal., 1998,16,723-732. T. Mavromoustakos, M. Zervou, D. Panagiotopoulos, E. Theodoropoulou, J. Matsoukas, D. Karussis, J. Pharm. Biomed Anal., 1998,16,741-751. L. D. D’Andrea, M. Mazzeo, C. hernia, F. Rossi, M. Saviano, P. Gallo, L. Paolillo, C. Pedone, Biopolymers, 1997,42,349-361. G. Melacini, Q. Zhu, G. Osapay, M. Goodman, J. Med. Chem., 1997, 40, 2252-2258.

416 57 58

59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79

80 81 82

83 84 85

86 87

Nuclear Magnetic Resonance

D. F. Mierke, S. Maretto, E. Schievano, D. DeLuca, A. Bisello, S. Mammi, M. Rosenblatt, E. Peggion, M. Chorev, Biochemistry, 1997,36, 10372- 10383. C. Saucier, C. Guerra, I. Pianet, M. Laguerre, Y. Glories, Phytochemistry, 1997, 46, 229-234. C. Zhou, V. Garigapati, M. F. Roberts, Biochemistry, 1997,36, 15925- 159? 1. A. Nakayama, M. Sukekawa, Y. Eguchi, Pestic. Sci., 1997,51, 157 -164. N. Zimmermann, G. Jung, Eur. J. Biochem., 1997,246, 809-819. J. Sejbal, Y. Wang, J. R. Cann, J. M. Stewart, L. Gera, G. Kotovych, Biopolymers, 1997,42,521-535. D. Duval, P. Hennig, J. P. Bouchet, J. Vian, J. L. Peglion, J. P. Volland, N. Platzer, J. Guilhem, Magn. Reson. Chem., 1997,354 175-183. Y. Boulanger, A. Larocque, A. Khiat, F. Deschamps, G. Sauve, Tetrahedron, 1997, 53,423 1 -4238. M. Hubner, B. Rissom, L. Fitjer, Helv. Chim. Actu, 1997,80, 1972-1982. M. Kamigauchi, Y. Noda, K. Iwasa, M. Sugiura, Z. Nishijo, Y. In, T. Ishida, J. Chem. Soc., Perkin Truns. 2, 1997,631 -636. E. Gaggelli, N. Gagelli, A. Maccotta, G. Valensin, Spectrochim. Acta, Purt A , 1997, 53A, 1663- 1660. R. B. Palmer, N. H. Andersen, Trends Org. Chem., 1995,5, 171- 187. R. G. Enriquez, J. Barajas, B. Ortiz, A. J. Lough, W. F. Reynolds, M. Yu, I. Leon, D. Gnecco, Can. J. Chem., 1997,75, 342-347. T. J. Schmidt, Rev. Latinoum. Quim., 1997,25,7 I -76. N. Todeschi, J. Gharbi-Benarous, J.-P. Girault, Bioorg. Mecl. Chem., 1997, 5, 1943-1957. T. A. Holak, R. A. Engh, NATOASISer., Ser. A, 1996,288,9-27. N. B. Hanna, J. Zajicek, A. Piskala, Nucleosides Nucleotides, 1997, 16, 129- 144. B. Macchia, M. Macchia, A. Martinelli, E. Martinotti, E. Orlandini, F. Romagnoli, R. Scatizzi, Eur. J. Med. Chem., 1997,32, 231-240. P. Pristovsek, J. Kidric, Biopolymers, 1997,42, 659-671. I. Ojima, S. D. Kuduk, S. Chakravarty, M. Ourevitch, J.-P. Begue, J. Am. Chem. Soc., 1997,119, 5519-5527. G. Moyna, H. J. Williams, A. I. Scott, I. Ringel, R. Gorodetsky, C. S. Swindell, J. Med. Chem., 1997,40,3305-3311. M. Frank, K. Peraus, H. A. Staab, J. Mol. Model (Electronic Publication], 1996, 2, 383-385. C. Gilon, M. Huenges, B. Mathae, G. Gellerman, V. Hornik, M. Afargan, 0. Amitay, 0. Ziv, E. Feller, A. Gamliel, D. Shohat, M. Wanger, 0. Arad, H. Kessler, J. Med. Chem., 1998,41,919-929. M. L. Khan, E. Haslam, M. P. Williamson, Magn. Reson. Chem., 1997,35,854-858. T. H. A. Silva, A. B. Oliveira, W. B. De Almeida, Strucf. Chem., 1997,8,95-107. M. Kuroda, Y. Mimaki, Y. Sashida, T. Hirano, K. Oka, Y. Dobashi, H.-y. Li, N. Harada, Tetrahedron, 1997,53, 1 1549- 1 1562. H. Oulyadi, D. Davoust and H. Vaudry, Eur. J. Biochem., 1997,246,665-673. M. H. A. Elgamal, H. S. M. Soliman, D. T. Elmunajed, G. Toth, A. Simon, H. Duddeck, Magn. Reson. Chem., 1997,35,637-642. R. Alvarez, M.-L. Jimeno, F.J. Tomas-Gil, M.-J. Perez-Perez, M.-J. Camarasa, Nucleosides Nucleotides, 1997, 16, 1399- 1402. T. Polenova, T. Iwashita, A. G. Palmer, 111, Biochemisrry, 1997,36, 14210-14225. J.-E. Igarashi, T. Nishimura, M. Sunagawa, Bioorg. Med Chem. Lett., 1997, 7 , 1659- 1664.

I I : Conformational Analysis 88 89 90 91 92 93 94 95 96 97 98 99 1 00

101

102 103 104 105

106 107 108 109

110 111

112 I I3 1 I4

417

D. A. Middleton, R. Robins, X. Feng, M. H. Levitt, I. D. Spiers, C. H. Schwalbe, D. G. Reid, A. Watts, FEBS Lett., 1997,410,269-274. R. Jankowiak, F. Ariese, D. Zamzow, A. Luch, H. Kroth, A. Seidel, G. J. Small, Chem. Res. Toxicol., 1997, 10,677-686. H. Morita, Y. S. Yun, K. Takeya, H. Itokawa, 0. Shirota, Bioorg. Med Chem., 1997,5,631-636. H. Morita, Y. S. Yun, K. Takeya, H. Itokawa, Heterocycles, 1998,47,391-396. Y. Nagaoka, A. Iida, S. Hatanaka, K. Tomioka, K. Asami, T. Fujita, Pept. Chem., 1996,34th, 189- 192. M. Labelle, S. St-Pierre, R. Savard and Y. Boulanger, Eur. J. Biochem., 1997, 246, 780--785. M. Moutiez, G. Lippens, C. Sergheraert, A. Tartar, Bioorg. Med. Chem. k t t . , 1997, 7,719-724. S . Mahboobi, S. Dove, P. J. Bednarski, S. Kuhr, T. Burgemeister, D. Schollmeyer, J. Nat. Prod., 1997,60,587-591. K. Kim, J. P. Germanas, J. Org. Chem., 1997,62,2847-2852. K . Kim, J. P. Germanas, J. Org. Chem., 1997,62,2853-2860. J. S. Nowick, M. Pairish, I. Q. Lee, D. L. Holmes, J. W. Ziller, J. Am. Chem. SOC., 1997,119, 5413-5424. U. Schopfer, M. Stahl, T. Brandl, R. W. Hoffmann, Angew. Chem., Int. Ed. Engl., 1997,36, 1745-1747. D. Andreu, S. Ruiz, C. Carreno, J. Alsina, F. Albericio, M. A. Jimenez, N. de la Figuera, R. Herranz, M. T.Garcia-Lopez, R. Gonzalez-Muniz, J. Am. Chem. SOC., 1997,119, 10579- 10586. G. D’Auria, 0. Maglio, F. Nastri, A. Lombardi, M. Mazzeo, G. Morelli, L. Paolillo, C. Pedone, V. Pavone, Chem. Eur. J., 1997,3,350-362. J. M. McDonnell, D. Fushman, S. M. Cahill, B. J. Sutton, D. Cowburn, J. Am. Chem. Soc., 1997,119,5321-5328. T.-A. Tran, R.-H. Mattern, Q. Zhu, M. Goodman, Bioorg. Med. Chem. Lett., 1997, 7,997- 1002. J. S. Nowick, S. Insaf, J. Am, Chem. SOC.,1997,119, 10903-10908. S. Raghothama, M. Chaddha, S. Banumathi, K. Ravikumar, D. Velmurugan, P. Balaram, Biopolymers, 1998,45, 19 1 -202. M. Goodman, Q. Zhu, D. R. Kent, Y. Amino, R. Iacovino, E. Benedetti, A. Santini, J. Pept. Sci., 1997, 3, 231-241. R.-H. Mattern, Y. Amino, E. Benedetti, M. Goodman, J. Pept. Res., 1997, 50, 286 -- 299. S. Datta, N. Shamala, A. Banerjee, A. Pramanik, S. Bhattacharjya, P. Balaram, J. Am. Chem. SOC.,1997,119,9246-9251. E. M. Smith, D. L. Holmes, A. J. Shaka, J. S. Nowick, J. Org. Chem., 1997, 62, 7906-7907. A. Banerjee, S. Raghothama, P. Balaram, J. Chem. Soc., Perkin Trans. 2, 1997, 2087 - 2094. A. Pohlmann, D. Guillaume, J.-C. Quirion, H.-P. Husson, J. Pept. Res., 1998, 51, 116-120. T. Yamada, A. Sano, R.Yanagihara, T. Miyazawa, Pept. Chem., 1996,34,357-360. T. Ohyama, A. Hiroki, K. Kobayashi, R. Katakai, Pept. Chem., 1996, 34, 365 -368. M. Tamaki, M. Yabu, S. Komiya, E. Watanabe, S. Akabori, I. Muramatsu, Pept. Chem.. 1996,34,393- 396.

418

Nucleur Magnetic Resonance

1 I5

Ashish, R. Kishore, Tetruhedron Lett., 1997,38, 2767-2770. J. Kao, W. Li, K. D. Moeller, Mugn. Reson. Chem., 1997,35,267-272. R. C . Noe, A. Weigand, S. Pirker, Monatsh. Chem., 1996,127, 108 1 - 1097. C. R. Noe, A. Weigand, S. Pirker, P. Liepert, Monutsh. Chem., 1997,128,301 -316. P. J. Milne, D. W. Oliver, P. H. van Rooyen, H. M. Roos, J. Chem. Crystallogr., 1997,27, 167-175. P. Sharma, T. P. Singh, Curr. Top. Biophys., 1996,20, 158-166. M. Tamaki, S. Komiya, M. Yabu, E. Watanabe, S. Akabori, I. Muramatsu, J. Chem. Soc., Perkin Truns. I , 1997,3497-3500. B. Pispisa, A. Palleschi, M. E. Amato, A. L. Segre, M. Venanzi, Mucromolecules, I997,30,4905-49 10. D. Seebach, K. Gademann, J. V. Schreiber, J. L. Matthews, T. Hintermann, B. Jaun, L. Oberer, U. Hommel, H. Widmer, Helv. Chim. Actu, 1997,80,2033-2038. A. Knorr, E. Galoppini, M. A. Fox, J, Phys. Org. Chem., 1997,10,484-498. P. V. Kostetsky, S. F. Arkhipova, I. V. Artem’ev, I. L. Rodinov, L. N. Rodinova, V. T. Ivanov, Bioorg. Khim., 1997,23,531-538. D. Albert, M:Feigel, Helv. Chim. Acta, 1997, 80,2168-2181. I. G. Jones, W. Jones, M. North, J. Org. Chem., 1998,63, 1505- 151 3. R. E. Austin, R. A. Maplestone, A. M. Sefler, K. Liu, W. N. Hruzewicz, C. W. Liu, Ho S. Cho, D. E. Wemmer, P. A. Bartlett, J. Am. Chem. Soc., 1997,119,6461 -6472. Y. Kuroda, H. Ueda, H. Nozawa, H. Ogoshi, Tetruhedron Lett., 1997, 38, 790 1 - 7904. M. Gatos, F. Formaggio, M. Crisma, G. Valle, C. Toniolo, G. M. Bonora, M. Saviano, R. Iacovino, V. Menchise, S. Galdiero, C. Pedone, E. Benedetti, J. Pept. Sci., 1997,3, 367-382. F. Andre, A. Vicherat, G. Boussard, A. Aubry, M. Marraud, J. Pept. Res., 1997, 50, 372-381. C. N. Kirsten, T. H. Schrader, J. Am. Chem. Soc., 1997,119, 12061-12068. A. Mele, G. Salani, F. Viani, P. Bravo, Mugn. Reson. Chem., 1997,35, 168-174. J. J. Jr. Barchi, L.-S. Jeong, M. A. Siddiqui, V. E. Marquez, J. Biochem. Biophys. Methods, 1997,34, I 1-29. R. Jankowiak, F. Ariese, M. Suh, G. J. Small, Polycyclic Aromut. Compd., 1996, 10, 291 -298. H. Li, F. Huang, B. R. Shaw, Bioorg. Med. Chem., 1997,5,787-795. S. Raic, M. Mintas, A. Danilovski, M. Vinkovic, M. Pongracic, J. Plavec, D. VikicTopic, J. Mol. Struct., 1997, 410-411, 31-33. I. Creuven, F. Lebon, R. Busson, P. Herdewijn, F. Durant, Nucleosides Nucleotides, 1997,16,339-346. L. Zhou, P. B. Cho, Chem. Res. Toxicol., 1998, 11, 35-43. H. Hrebabecky, M. Budesinsky, M. Masojidkova, Z. Havlas, A. Holy, Collect. Czech. Chem. Commun., 1997,62,957-970. J. Micklefield, K. J. Fettes, Tetrahedron Lett., 1997,38, 5387-5390. Y.-P. Feng, X. Chen, N.-J. Zhang, Y.-F. Zhao, Phosphorus, Sulfur Silicon Relut. Elem., 1996,118,219-225. M. Eriksson, Nucleosides Nucleotides, 1997, 16,617-621. R. E. Harry-O’kuru, E. A. Kryjak, M. S. Wolfe, Nucleosides Nucleotides, 1997, 16, 1457- 1460. H. Wakuda, M. Ide, Y. Maeda, J. Kimura, Nippon Kuguku Kuishi, 1998,40-44. K. Seio, T. Wada, K. Sakamoto, S. Yokoyama, M. Sekine, J. Org. Chem., 1998,63, I429 - 1443.

116 I17 1 I8 1 I9 120 121 122 I23 124 125 126 127 I28 129 130

131 132 133 134 135 136 137 I38 139 140 141 1 42

143 144

145 146

1I : Conformational Analysis

147

I48 1 49

150 151

152 I53 154 155 156 157 I58 I59 160 161 162 163 164 165 166 167 I68 169 170 171 172 173 174 175 I76

177

419

Y. Maurinsh, J. Schraml, H. de Winter, N. Blaton, 0. Peeters, E. Lescrinier, J. Rozenski, A. van Aerschot, E. de Clercq, R. Busson, P. Herdewijn, J. Org. Chem., 1997,62,2861-2871. R. M. Claramunt, J. Elguero, C. Escolastico, C. Fernandez-Castano, C. FocesFoces, A. L. Llamas-Saiz, D. S. Maria, Targets Heterocycl. Syst., 1997, 1, 1-56. V. V. Samoshin, E. I. Troyansky, Phosphorus, Surfur Silicon Relat. Elem., 1997, 120 & 121, 181 -196. A. F. de C. Alcantara, D. Pilo-Veloso, H. 0. Stumpf, W. B. de Almeida, Tetrahedron, I997,53, 1691 1 - 16922. C. Foces-Foces, A. L. Llamas-Saiz, C. Fernandez-Castano, R. M. Claramunt, C. Escolastico, J. L. Lavandera, M. D. Santa Maria, M. L. Jimeno, J. Elguero, J. Chem. Soc., Perkin Trans. 2,1997, 2173-2177. N. C. Singha, D. N. Sathyanarayana, J. Mol. Struct., 1997,403, 123-135. N. C. Singha, J. Anand, D. N. Sathyanarayana, Spectrochim. Acta, Part A, 1997, 53A, 1459- 1462. N. C. Singha, J.Anand, D. N. Sathyanarayana, J. Mol. Struct., 1998,443, 1-8. M.-T. Martin, R. Gharbi, A. Khemiss, Z. Mighri, Mugn. Reson. Chem., 1997, 35, 251 -256. J. A. Zoltewicz, N. M. Maier, W. M. F. Walter, J. Org. Chem., 1997,62, 2763-2766. M. Heydenreich, A. Koch, E. Kleinpeter, T. Zimmermann, Fresenius’ J. Anal. Chem., 1997,357, 517-521. G. S. Hanan, U. S. Schubert, D. Volkmer, E. Riviere, J.-M. Lehn, N. Kyritsakas, J. Fischer, Cun. J. Chem., 1997,75, 169-182. A. Straub, A. Goehrt, L. Born, Bioorg. Med. Chem. Lett., 1997,7,2519-2522. R. Rodriguez, M. Suarez, E. Ochoa, B. Pita, R. Espinosa, N. Martin, M. Quinteiro, C. Seoane, J. L. Soto, J. Heterocycl. Chem., 1997,34,957-961. M. M. Burbuliene, P. Vainilavicius, Chemiju, 1997, 55-57. M. Szafran, Z. Dega-Szafran, A. Katrusiak, G. Buczak, T. Glowiak, J. Sitkowski, L. Stefaniak, J. Org. Chem., 1998,63, 2898-2908. P. M. Krishna, M. M. I. Fazal, Indian J. Chem., Sect. B:Org. Chem. Incl. Med. Chem., 1997,36B, 50-53. K. Pandiarajan, A. Manimekalai, N. Kalaiselvi, Mugn. Reson. Chem., 1997, 35, 372 - 378. J. Ritter, R. Gleiter, H. Irngartinger, T. Oeser, J. Am. Chem. SOC., 1997, 119, 10599- 10607. A. Rosling, F. Fulop, R. Sillanpaa, J. Mattinen, Heterocycles, 1997,45,927-942. R. B. English, P. T. Kaye, M. J. Mphahlele, S. Afr. J. Chem., 1997,50, 55-58. R. Jeyaraman, S. Ponnuswamy, J. Org. Chem., 1997,62,7984-7990. R. Ahmad, M. Zia-UI-Haq, H. Duddeck, L. Stefaniak, J. Sitkowski, Monatsh. Chem., 1997,128,633-640. G. Toth, J. Halasz, A. Levai, B. Rezessy, Monatsh. Chem., 1997, 128,625-632. H. Zimmer, J. L. Nauss, A. Amer, J. Heterocycl. Chem., 1998,35,25-28. K. Pihlaja, M. F. Simeonov, F. Fueloep, J. Org. Chem., 1997,62, 5080-5088. D. P. Zlotos, W. Meise, Heterocycles, 1997,452137-2157. E. Kleinpeter, Strucf. Chem., 1997,8, 161 -- 173. E. Osz, L. Szilagyi, J. Marton, J. Mol. Struct., 1998,442,267-274, K. Kefurt, J. Havlicek, M. Hamernikova, A. Kerfurtova, H. Votavova, Collect. Czech. Chem. Commun., 1997,62, 19 19- 1930. F. Fulop, J. Tari, G. Bernath, P. Sohar, A. Dancso, G. Argay, A. Kalman, Liebigs Ann.lRecl., 1997, 1165-1171.

420

Nuclear Magnetic Resonance

178

S. G. Grdadolnik, P. Trebse, M. Kocevar, T. Solmajer, J. Chem. In$ Comput. Sci., 1997,37,489-494. D. Natarajan, N. Bhavani, A. Manimekalai, Magn. Reson. Chem., 1997, 35, 597 -600. Y. Yamamoto, T. Okajima, Y. Fukazawa, T. Fujii, Y. Hata, S. Sawada, J. Chem. Soc., Perkin Trans. 2, 1998, 561 -564. E. M. Olefirowicz, E. L. Eliel, J. Org. Chem., 1997,62,9154-9158. A. D. Debellis, R. K. Rodebaugh, J. Suhadolnik, C. Hendricks-Guy, J. Phys. Org. Chem., 1997,10, 107-1 12. S. Peng, M. Guo, X.Mao, E. Winterfeldt, Bopuxue Zazhi, 1997, 14,431 -436. G. Maerkl, J. Stiegler, P. Kreitmeier, T. Burgemeister, F. Kastner, S. Dove, Helv. Chim. Acta, 1997,80, 14-42. H. Dieks, M. 0. Senge, B. Kirste, H. Kurreck, J. Org. Chem., 1997,62, 8666-8680. F. Ooms, J. Wouters, F. Durant, N., Jr., Castagnoli, C. van’t Land, G. Dockendolf, T. Glass, C. J. van der Schyf, J. Chem. Soc., Perkin Trans. 2, 1997,2627-2632. E. T. K. Haupt, M. Eggers, Spectrosc. Lett., 1998,31, 521 -528. R. B. Maharajh, J. P. Snyder, J. F. Britten, R. A. Bell, Can. J. Chem., 1997, 75, 140- 161. T. Kimura, M. Hanzawa, E. Horn, Y. Kawai, S. Ogawa, R. Sato, Tetrahedron Lett., 1997,38, 1607-1610. N. V. Timosheva, I. V. Anonimova, R. P. Arshinova, P. P. Chernov, A. P. Timosheva, Russ. J. Gen. Chem., 1997,67, 1212-1217. T. Hatano, R. W. Hemingway, J. Chem. SOC.,Perkin Truns. 2, 1997, 1035-1043. R. J. Abraham, A, Ghersi, G. Petrillo, F. Sancassan, J. Chem. Soc., Perkin Truns. 2, 1997,1279- 1286. A. Philippon, M. Laguerre, M. Petraud, I. Pianet, Magn. Reson. Chem., 1997, 35, 69 1 -696. R. Annunziata, L. Raimondi, G. M. Nano, G. Palmisano, S. Tagliapietra, Magn. Reson. Chem., 1997,35,721-729. F. A. Kang, C. L. Yin, Chin. Chem. Lett., 1997,8,885-888. K. Albert, G. Hafelinger, M.P. Gunter, T.M. Krygowski, T. Kuhn, M. Pursch, S. Strohschein, Z. Naturforsch., B: Chem. Sci., 1997,52, 263-280. D. Casarini, L. Lunazzi, A. Mazzanti, J. Org. Chem., 1997,62,3315-3323. S . D. Petrovic, N. D. Stojanovic, D. G. Antonovic, D. Z. Mijin, A. D. Nikolic, J. Mol. Struct., 1997,410-411, 35-38. V. Koleva, T. Dudev, I. Wawer, J. Mol. Struct., 1997,412, 153-159. R. M. Srivastava, I. M. Brinn, J. 0. Machuca-Herrera, H. B. Faria, G. B. Carpenter, D. Andrade, C. G. Venkatesh, L. P. de Morais, J. Mol. Struct., 1997,406, 159- 167. V. Marks, H. E. Gottlieb, S. E. Biali, J. Am. Chem. Soc., 1997,119,9672-9679. H. Suezawa, H. H. Wada, H. Watanabe, T. Yuzuri, K. Sakakibarba, M. Hirota, J. Phys. Org. Chem., 1997,10,925-934. D. Casarini, L. Lunazzi, A. Mazzanti, J. Org. Chem., 1997,62,7592-7596. C. Hada, J.-C. Roussel, P. Beccat, R. Boulet, M. D. Banciu, Rev. Roum. Chim., 1997,42,777-785. F. D. Lewis, E. L. Burch, C. L. Stern, J. Phys. Org. Chem., 1997, 10,525-530. S . T. Abu-Orabi, S. R. Salman, J. M. Gillam, J. C. Lindon, Spectrochim. Actu, Part A, 1997,53A, I521 - 1525. V. K. Aggarwal, S. Schade, B. Taylor, J. Chem. Soc., Perkin Trans. I , 1997, 28 I 1-281 3. T. Ren, Y.Jin, K. S. Kim, D. H. Kim, J . Biomol. Struct. Dyn., 1997,15,401-405.

179 180 181 182

I83 184 185 186 I87 188 I89 190 191 192 193 194 195 196 197 198 199 200 20 1 202 203 204 205 206 207 208

I I : Conformational Analysis

209 210 21 1 212 213 214 21 5 216 217 218 219 220 22 I 222 223 224 225 226 227 228 229 230 23 I 232 233 234 235 236 237

42 1

R. Kapiller-Dezsofi, G. Nemeth, G. Lax, G. Simig, P. Sohar, J. Mol. Struct., 1998, 441,89-92. M. M. Garcia, P. A. Ortega, F. L. Ochoa, G. E. Perez, S. H. Ortega, M. I. C. Uribe, M. Salmon, R. Cruz-Almanza, Tetrahedron, 1997,53, 17633- 17642. P. E. Hansen, J. Spanget-Larsen, K. K. Laali, J. Org. Chem., 1998,63, 1827-1835. E. S. Maksimov, M. G. Levkovich, N. D. Abdullaev, A. M. Yuldashev, S. U. Ubaidullaeva, Zh. Org. Khim., I996,32, 1344- 1347. J. H. Antony, A. Doelle, T. Fliege, A. Geiger, J. Phys. Chem. A, 1997, 101, 45 17-4522. A. M. A. van Wageningen, P. Timmerman, J. P. M. van Duynhoven, W. Verboom, F. C. J. M. van Veggel, D. N. Reinhoudt, Chem. Eur. J., 1997,3,639-654. M. Gomez-Kaifer, P. A. Reddy, C. D. Gutsche, L. Echegoyen, J. Am. Chem. Soc., 1997,119,5222--5229. K. C. Nam, D. S. Kim, J. M. Kim, Bull. Korean Chem. Soc., 1997, 18,636-640. I. Bitter, A. Grun, G. Toth, B. Balazs, L. Toke, Tetrahedron, 1997,53,9799-9812. P. M. Marcos, J. R. Ascenso, R. Lamartine, J. L. C. Pereira, Supramol. Chem., 1996, 6,303-306. H. Graubaum, G. Lutze, B. Costisella, J. Prakt. Chem.lChem.-Ztg., 1997, 339, 266-271. E. Pinkhassik, I. Stibor, A. Casnati, R. Ungaro, J. Org. Chem., 1997,62,8654-8659. M. Jorgensen, M. Larsen, P. Sommer-Larsen, W. B. Petersen, H. Eggert, J. Chem. Soc., Perkin Trans. I , 1997,2851-2855. P. M. Marcos, J. R. Ascenso, R. Lamartine, J. L. C. Pereira, J. Org. Chem., 1998, 63,69-74. P. M. Marcos, J. R. Ascenso, R. Lamartine, J. L. C. Pereira, Tetrahedron, 1997, 53, 11791 - 1 1802. J. 0. Magrans, A. M. Rincon, F. Cuevas, J. Lopez-Prados, P. M. Nieto, M. Pons, P. Prados, J. deMendoza, J. Org. Chem., 1998,63, 1079-1085. W. P. vanHoorn, W. J. Briels, J. P. M. vanDuynhoven, F. C. J. M. vanVeggel, D. N. Reinhoudt, J. Org. Chem., 1998,63, 1299-1308. G. W. Buchanan, M. Gerzain, K. Bourque, Magn. Reson. Chem., 1997,35,283-289. G. W. Buchanan, M. Gerzain, C. Bensimon, R. Ellen, V. M. Reynolds, J. Mol. Struct., 1997,404, 307-317. R. Meusinger, J. Heinicke, K. Mohle, M. Muhlstadt, Monatsh. Chem., 1996, 127, 1 145- 1 152. E. Kleinpeter, I. Starke, D. Stroehl, H.-J. Holdt, J. Mol. Struct., 1997,404,273-290. L. Campayo, J. M. Bueno, P. Navarro, C. Ochoa, J. Jimenez-Barbero, G. Pepe, A. Samat, J. Org. Chem., 1997,62,2684-2693. R. A. Bartsch, J. S. Kim, U. Olsher, D. M. Purkiss, Supramol. Chem., 1996, 6, 327-331. A. Merz, L. Gromann, A. Karl, L. Parkanyi, 0. Schneider, Eur. J. Org. Chem., 1998, 403-408. T. Yamato, Y. Saruwatari, M. Yasumatsu, J. Chem. Soc., Perkin Trans. 1 , 1997, 1725- 1730. T. Yamato, Y. Saruwatari, M. Yasumatsu, J. Chem. Soc., Perkin Trans. I , 1997, 1731 -1737. T. Yamato, M. Haraguchi, J.4. Nishikawa, S. Ide, J, Chem. SOC.,Perkin Trans. I , 1998,609-614. Y.-H. Lai, Y.-L. Yong, S.-Y. Wong, J. Org. Chem., 1997,62,4500-4503. T. Yamato, L. K. Doamekpor, H. Tsuzuki, Liebigs Ann.lRecl., 1997, 1537- 1544.

422

Nuclear Magnetic Resonance

238

T. Yamato, Y. Saruwatari, M. Yasumatsu, I. Seiji, Eur. J. Org. Chem., 1998, 309-3 16. B. Blackwell, S. Ngola, H. Peterson, S. Rosenfeld, C. W. Tingle, J. P. Jasinski, Y. Li, J. E. Whittum, J. Org. Chem., 1998,63, 181-184. D. Ranganathan, V. Haridas, 1. L. Karle, J. Am. Chem. Soc., 1998,120,2695-2702. P. Delangle, J.-P. Dutasta, J.-P. Declercq, B. Tinant, Chem. Eur. J., 1998, 4, 100-106. J. Gawronski, K. Gawronska, P. Skowronek, U. Rychlewska, B. Warzajtis, J. Rychlewski, M. Hoffmann, A. Szarecka, Tetrahedron, 1997,53,6113-6144. J. E. Anderson, D. Casarini, A. 1. Ijeh, L. Lunazzi, J. Am. Chem. Soc., 1997, 119, 8050- 8057. H. Takeuchi, R. Watanabe, J.4. Enmi, T. Egawa, S. Konaka, Struct. Chem., 1998,9, 33-38. D. M. Pawar, A. A. Khalil, D. R. Hooks, K. Collins, T. Elliott, J. Stafford, L. Smith, E. A. Noe, J. Am. Chem. Soc., 1998,120,2108-2112. V. Milata, A. Gatial, L. Zalibera, S. Biskupic, D. Scheller, Chem. Papers, 1997, 51, 367-371. C. Dietrich, T. Beuerle, B. Withopf, P. Schreier, P. Brunerie, C. Bicchi, W. Schwab, J. Agric. Food Chem., 1997,45, 3178-3182. [148561v] V. Larue, J. Gharbi-Benarous, F. Acher, R. Azerad, J.-P. Girault, J. Pept. Res., 1997,49,28-45. S. Leon, A. Martinez de Ilarduya, C. Aleman, M. Garcia-Alvarez, S. MunozGuerra, J. Phys. Chem. A , 1997,101,4208-4214. R. Nunez, R. J. Unwalla, F. K. Cartledge, S. G. Cho, B. H. Riches, M. P. Glenn, N. L. Hungerford, L. K. Lambert, D. J. Brecknell, W. Kitching, J. Chem. Soc., Perkin Trans. 2, 1997, 1365-1368. A. Palaima, Z. Staniulyte, A. Juodvirsis, Chemija, 1997, 74-82. V. Salazar-Pereda, F. J. Martinez-Martinez, R. Contreras, A. Flores-Parra, J. Carbohydr. Chem., 1997,16, 1479-1507. U. Berg, E. Butkus, T. Frejd, S. Bromander, Tetrahedron, 1997,53,5339-5348. M. Gdaniec, M. Pham, T. Polonski, J. Org. Chem., 1997,62,5619-5622. I. Iriepa, B. Gil-Alberdi, E. Galvez, J. Bellanato, P. Carmona, J. Mol. Struct., 1997, 408409,487-492. M. S. Arias-Perez, A. Alejo, A. Maroto, Tetrahedron, 1997,53, 13099- 131 10. I. Iriepa, B. Gil-Alberdi, E. Galvez, J. Bellanato, P. Carmona, J. Mol. Struct., 1997, 406,233-240. R. Glaser, G. J. Tarrant, J. B. Bremner, Magn. Reson. Chem., 1997,35, 389-394. M. S. Toledano, M. J. Fernandez, R. Huertas, E. Galvez, J. Server, F. H. Cano, J. Bellanato, P. Carmona, J. Mol. Struct., 1997,406,223-232. K. Wulf, U. Klages, B. Rissom, L. Fitjer, Tetrahedron, 1997,53,6011-6018. U. Berg, N. Bladh, Acta Chem. Scand, 1997,51,778-784. P. Camps, D. Gorbig, V. Munoz-Torrero, F. Perez, Collect. Czech. Chem. Commun., 1997,62,1585-1598. C. W. Hilbers, S. S. Wijmenga, H. Hoppe, H. A. Heus, NATO ASI Ser., Ser. A, 1996,288, 193-207. D. E. Wemmer, NMR Spectrosc. Its Appl. Biomed Res., 1996,281 -312. P. N. Borer, L. Pappalardo, D. J. Kerwood, I. Pelczer, Adv. Biophys. Chem., 1997,6, 173-2 16. M. Chaoui, 0. Mauffret, A. Lefebvre, E. Lescot, G. Tevanian, S. Fermandjian, J. Biomol. NMR, 1997,10, 187-192.

239 240 24 1 242 243 244 245 246 247 248 249 250

25 I 252 253 254 255 256 257 258 259 260 26 1 262 263 264 265 266

I I : Conformutionul Analysis 267 268 269 270 27 1 272 273 2 74 275 276 277 278 2 79 280 28 1 282 283 284 285 286 287 288 289 290 29 I 292 293 294 295 296 297 298 299 300 30 I 302 303 304 305 306

423

B. H. Robinson, C. Mailer, G. Drobny, Annu. Rev. Biophys. Biomol. Struct., 1997, 26,629-668. A. Foldesi, S.-I. Yamakage, F. P. R. Nilson, T. V. Maltseva, C. Glemarec, J. Chattopadhyaya, Nucleosides Nucleotides, 1997, 16, 5 17-522. K.-Y. Chang, G. Varani, Nut. Struct. Biol., 1997,4, 854-858. A. Ramos, C. C. Gubser, G. Varani, Curr. Opin. Struct. Biol., 1997,7,317-323. E . V. Puglisi, J. D. Puglisi, Cold Spring Monogr. Ser., 1998,35, 117- 146. E. Westhof, D. J. Patel, Curr. Opin. Struct. Biol., 1997,7, 305-309. P.B . Moore, Curr. Opin. Struct. Biol., 1997,7, 343-347. B. Catalanotti, A. Galeone, L. Mayol, A. Pepe, V. Lanzotti, Guzz. Chim. Itul., 1997, 127,231 -246. F. Aboul-ela, G. Varani, THEOCHEM, 1998,423,29-39. E. Sletten, NATO ASISer., Ser 2 , 1997,26,493-509. G. Patikoglou, S. K. Burley, Annu. Rev. Biophys. Biomol. Struct., 1997,26, 289-325. K. Kuwata, H. Liu, T. Schleich, T. L. James, J. Magn. Reson., 1997, 128,70-81. Macromolecular Structures, 1998, Ed. W. A. Hendrickson, K. Wuthrich, Curr. Biol., Ltd. H. P. Spielmann, Biochemistry, I998,37, 5426-5438. M. Akke, R. Fiala, F. Jiang, D. Patel, A. G. Palmer, 111, RNA, 1997,3,702-709. S. Tsuda, S. M. Gagne, B.D . Sykes, K. Hikichi, Shin Tunpukushitsu Oyo Koguku, I996,75-79. K. Wuethrich, Roentgen Centen., 1997,242-257. L. E. Kay, Biochem. Cell Biol., 1997,75, 1 - 15. V. A. Daragan, K. H. Mayo, Prog. Nucl. Mugn. Reson. Spectrosc., 1997,31,63-105. G. M . Clore, A. M. Gronenborn, Nut. Struct. Biol., 1997,4, 849-853. L. E. Kay, K. H. Gardner, Curr. Opin. Struct. Biol., 1997,7,722-731. G. M. Clore, A. M. Gronenborn, Trends Biotechnol., 1998,16,22-34. A. L. Macedo, E. Brian, J. Goodfellow, Quimicu, 1996,63, 10-17. H. Yamamoto, Osaku Kogyo Gijutsu Kenkyusho Kiho, 1995,46, 106- I 1 1. I. M. Russu, Adv. Mol. Cell Biol., 1997,22A, 133-175. P. L. Weber, N M R Spectrosc. Its Appl, Biomed. Res., 1996, 187-239. A. J. Petrescu, G. Turcu, Stud Cercet. Biochim., 1996,39, 123-140. I . Bertini, C. Luchinat, A. Rosato, Prog. Biophys. Mol. Biol, 1996,66,43-80. M. J. Osborne, D. Crowe, S. L. Davy, C. Macdonald, G. R. Moore, Methods Mol, B i d , 1997,60, 233-269. A. D. Robertson, K. P. Murphy, Chem. Rev., 1997,97, 1251-1267. C. G. Hoogstraten, J. L. Markley, NATO ASI Ser., Ser. A, 1996,288,73- 1 11. R. Bruschweiler, Chimiu, 1997,51, 140-144. E. Suzuki, Tunpukushitsu Kakusun Koso, 1997,42,989-995. A. G. Palmer, 111, Curr. Opin. Struct. Biol., 1997,7,732-737. L. K . Nicholson, L. E. Kay, D. A. Torchia, N M R Spectrosc. Its Appl. Biomed. Res., 1996,241-279. K. T. Dayie, G. Wagner, J.-F. Lefevre, NATO AS1 Ser., Ser. A, 1996,288, 139- 162. S. D. Samarasinghe, A. Balasubramaniam, M. E. Johnson, Curr. Med. Chem., 1997, 4, 151-158. G. J. Pielak, D. S. Auld, S. F. Betz, S. E. Hilgen-Willis, L. L. Garcia, Cytochrome C, 1996,203-284. S. J. Opella, J. Gesell, A. P. Valente, F. M. Marassi, M.Oblatt-Montal, W. Sun, A. Ferrer-Montiel, M. Montal, Chemtructs, 1997, 10, 153-174. J. T. Pelton, Endothelins Biol. Mecl., 1997, 287-305.

424

Nuclear Magnetic Resonance

307

L. K. Maclachlan, D. A. Middleton, A. J. Edwards, D. G . Reid, Methods Mol. Biol., 1997,60,337-362. S.-H. Chiou, S.-H. Wu, J. Chin. Chem. Soc., 1997,44, 337-348. H. Haruyama, H. Hanazawa, Tunpakushitsu Kukusun Koso, 1997,42,982-988. S. Tate, M. Kainosho, T. Samejima, Tunpakushitsu Kukusun Koso, 1997, 42, 2454-2464. J. A. Cowan, S. M. Lui, A h . Znorg. Chem., 1998,45, 313-350. L. Banci, J. Biotechnol., 1997,53,253-263. B. Brodsky, J. A. M. Ramshaw, Mutrix Biol., 1997,15,545-554. E. J. Sadler, Thromb. Huemostusis, 1997,78, 392-395. W. Bode, M. Renatus, Curr. Opin. Struct. Biol., 1997, 7, 865-872. C. Gonzales, J. Santoro, M. Rico, Ribonucleases, 1997, 343-381. J. Liang, J. Clardy, Guicieb. Mol. Chaperones Protein-Folding Cutal., 1997, 397- 399. I. Shimada, Immunol. Front., 1997,7, 213-218. K. Kato, I. Shimada, Kobunshi, 1997,46,328-332. G. C. K. Roberts, NATO ASI Ser., Ser. A , 1996,288, 37-47. M. Giel-Pietraszuk, M. Z. Barciszewska, J. Barciszewski, Postepy Bid. Komorki, 1997,24, 1 - 19. B. A. Katz, Annu. Rev. Biophys. Biomol. Struct., 1997, 26,27-45. J. Kuriyan, D. Cowburn, Annu. Rev. Biophys. Biomol. Struct., 1997,26,259-288. R. A. Atkinson, V. Saudek, NATO ASI Ser., Ser. A, 1996,288,49-55. R. A. Atkinson, V. Saudek, J. Chem. Soc., Furaduy Trans., 1997,93,3319-3323. K. Huang, M. Andrec, S. Heald, P. Blake, J. H. Prestegard, J. Biomol. NMR, 1997, 10,45-52. R. D. Beger, P. H. Bolton, J. Biomol. N M R , 1997,10, 129-142. P. Cuniasse, I. Raynal, A. Yiotakis, V. Dive, J. Am. Chem. Soc., 1997, 119, 5239- 5248. B. Busetta, P. Picard, J. Peptide Sci., 1997,3, 133-140. L. Kirnarsky, 0. Shats, S . Sherman, THEOCHEM, 1997,419, 213-220. M. J. Bayley, G. Jones, P. Willett, M. P. Williamson, Protein Sci.,1998,7,491-499. L. E. Kay, D. R. Muhandiram, G. Wolf, S. E. Shoelson, J. D. Forman-Kay, Nut. Struct. Biol., 1998, 5, 156- 163. P. Luginbuehl, K. V. Pervushin, H. Iwai, K. Wuthrich, Biochemistry, 1997, 36, 7305-7312. P. Allard, T. Haerd, J. Mugn. Reson., 1997, 126,48-57. K. T. Dayie, G . Wagner, J. Am. Chem. Soc., 1997,119,7797-7806. S . Grzesiek, A. Bax, J . 4 . Hu, J. Kaufman, I. Palmer, S. J. Stahl, N. Tjandra, P. T. Wingfield, Protein Sci., 1997,6, 1248- 1263. V. A. Daragan, E. E. Ilyina, C. G. Fields, G. B. Fields, K. H. Mayo, Protein Sci., 1997,6,355-363. C.-S. Lee, C. Yu, Huuxue, 1997,55,91-99. C.-S. Lee, T. K. S. Kumar, L.-Y. Lian, J.-W. Cheng, C . Yu, Biochemistry, 1998, 37, 155- 164. J. J. Kelley, 111, T. M. Caputo, F. Steven, T. M. Laue, J. H. Bushweller, Biochemistry, 1997,36, 5029 - 5044. K.-B. Wong, A. R. Fersht, S. M. V. Freund, J. Mol. Biol., 1997, 268,494-51 I . D. H. Purvis, B. C. Mabbutt, Biochemistry, 1997,36, 10146-10154. A Hrovat, M.Blumel, F. Lohr, S. G. Mayhew, H. Ruterjans, J. Biomol. NMR, 1997, 10,53-62. P. Zhang, K. T. Dayie, G . Wagner, J. Mol. Biol., 1997,272,443-455.

308 309 310 31 1 312 313 314 315 316 317 318 319 320 32 1 322 323 324 325 326 327 328 329 330 33 1 332 333 334 335 336 337 338 339 340 34 1 342 343 344

I I : Conformutionul Anulysis 345 346 347 348 349 350 35 1 352 353 354 355 356 357 358 359 360 36 1 362 363 364 365 366 367 368 369 370 37 1 372 373 374 375 376 377 378 379

425

M. Guenneugues, P. Drevet, S. Pinkasfeld, B. Gilquin, A. Menez, S. Zinn-Justin, Biochemistry, 1997,36, 16097-16108. 0.Jardetzky, Z. Zheng, NATO AS1 Ser., Ser. A , 1996,288,209-222. C. vanHeijenoort, F. Penin, E. Guittet, Biochemistry, 1998,37, 5060-5073. Y . Xu, A. Lecroisey, M. Veron, M. Delepierre, J. Janin, Proteins: Struct., Funct., Genet., 1997,28, 150- 152. J. Lillemoen, C. S. Cameron, D. W. Hoffman, J. Mol. Biol., 1997,268,482-493. J. Lu, K. B. Hall, Biochemistry, 1997,36, 10393-10405. Y. H. Jeon, T. Yamazaki, T. Otomo, A. Ishihama, Y. Kyogoku, J. Mol. Biol., 1997, 267,953-962. C. Jin, I. Marsden, X. Chen, X. Liao, Biochemistry, 1998,37,6179-6187. F. J. Moy, M. R. Pisano, P. K. Chanda, C. Urbano, L. M. Killar, M.-L. Sung, R. Powers, J. Biomol. NMR, 1997, 10,9-19. M. Akke, J. Liu, J. Cavanagh, H. P. Erickson, A. G. Palmer, 111, Nat. Struct. B i d , 1998,5,55-59. J. R. Tolman, J. M. Flanagan, M. A. Kennedy, J. H. Prestegard, Nut. Struct. Biol., 1997,4,292-297. G. P. Kelly, F. W. Muskett, D. Whitford, Eur. J. Biochem., 1997,245, 349-354. M. Ramirez-Alvarado, V. A. Daragan, L. Serrano, K. H. Mayo, Protein Sci., 1998, 7,720-729. J. Liu, Y. Gong, 0. Prakash, L. Wen, 1. Lee, J.-K. Huang, R. Krishnamoorthi, Protein Sci., 1998,7, 1 32- 141. G. J. Sharman, M. S. Searle, Chem. Commun., 1997,1955-1956. S. Krauthaeuser, L. A. Christianson, D. R. Powell, S. H. Gellman, J. Am. Chem. Soc., 1997,119, 11719-1 1720. E. Ilyina, V. Roongta, K. H. Mayo, Biochemistry, 1997,36,5245-5250. L. Brive, G. T. Dolphin, L. Baltzer, J. Am. Chem. Soc., 1997, 119,8598-8607. G. T. Dolphin, L. Baltzer, Fold. & Des., 1997,2, 319-330. N. D. Lazo, D. T. Downing, Biochem. Biophys. Res. Cummun., 1997, 235, 675-679. G. L. Millhauser, C. J. Stenland, P. Hanson, K. A. Bolin, F. J. M. van de Ven, J. Mol. Biol., 1997,267,963-974. Y . Fezoui, P. J. Connolly, J. J. Osterhout, Protein Sci., 1997,6, 1869- 1877. M. Ramirez-Alvarado, F. J. Blanco, H. Niemann, L. Serrano, J. Mul. Biul., 1997, 273,898-912. E. deAlba, M.Rico, M. A. Jimenez, Protein Sci., 1997,6,2548-2560. B. I. Dahiyat, C. A. Sarisky, S. L. Mayo, J. Mol. Biul., 1997,273, 789-796. R. B. Hill, W. F. DeGrado, J. Am. Chem. Soc., 1998,120, 1138-1 145. A. J. Maynard, G. J. Sharman, M. S. Searle, J. Am. Chem. Soc., 1998, 120, 1996- 2007. K. S. Broo, L. Brive, P. Ahlberg, L. Baltzer, J. Am. Chem. Soc., 1997, 119, 11362-11372. J. N. Onuchic, Proc. Natl. Acud. Sci. U.S.A., 1997,94, 7129-7131. S. E. Nieba-Axmann, A. Pluckthun, Bioforum Int., 1997,20,22-24. J. Balbach, V. Forge, W. S. Lau, J. A. Jones, N. A. J. vanNuland, C. M. Dobson, Proc. Natl. Acad. Sci. U.S.A., 1997,94, 7182-7185. Y. Bai, S. W. Englander, NATO AS1 Ser., Ser. A, 1996,288, 1 -7. J. R. Gillespie, D. Shortle, J. Mol. Biol., 1997, 268, 170-184. J. R. Gillespie, D. Shortle, J. Mol. Biul., 1997, 268, 158-169. Y. Wang, D. Shortle, Fold & Des., 1997,2,93-100.

426

Nuclear Magnetic Resonunce

380

S. Shimotakahara, C. B. Rios, J. H. Laity, D. E. Zimmerman, H. A. Scheraga, G. T. Montelione, Biochemistry, 1997,36, 69 15-6929. L. A. Morozova-Roche, C. C. Arico-Muendel, D. T. Haynie, V. I. Emelyanenko, H. van Dael, C. M. Dobson, J. Mol. B i d , 1997,268,903-921. D. Eliezer, J. Yao, H. J. Dyson, P. E. Wright, Nuf. Sfruct. B i d , 1998,5, 148-155. B. Brutscher, R. Brueschweiler, R. R. Ernst, Biochemistry, 1997,36, 13043- 13053. L. Ragona, F. Pusterla, L. Zetta, H. L. Monaco, H. Molinari, Fold. & Des., 1997, 2, 281 -290. H. Schwalbe, K. M. Fiebig, M. Buck, J. A. Jones, S. B. Grimshaw, A. Spencer, S. J. Glaser, L. J. Smith, C. M. Dobson, Biochemistry, 1997,36, 8977-899 1. B. A. Schulman, P. S. Kim, C. M. Dobson, C. Redfield, Nut. Struct. B i d . , 1997, 4, 630-634. V. Calabro, J. M. Sabatier, E. Blanc, C. Lecomte, J. vanRietschoten, H. Darbon, J. Pept. Res., 1997,50, 39-47. M. T. Reymond, G. Merutka, H. J. Dyson, P. E. Wright, Protein Sci., 1997, 6, 706- 716. M. A. Sherman, Y. Chen, M. T. Mas, Protein Sci., 1997,6,882-891. A. Meissner, W. Haehnel, H. Vahrenkamp, Chem. Eur. J., 1997,3,261-267. J. L. Neira, L. S. Itzhaki, A. G. Ladurner, B. Davis, G. de Prat Gay, A. R. Fersht, J. Mol. Biol., 1997,268, 185-197. F. J. Blanco, A. R. Ortiz, L. Serrano, Fold. & Des., 1997, 2, 123-133. M. Sukumar, L. M. Gierasch, Fold. & Des., 1997,2, 21 1-222. E. Barbar, V. J. Li Cata, G. Barany, C. Woodward, Biophys. Chem., 1997, 64, 45-57. A. Heger, J. Higo, H. Nakamura, Proc. Jpn. Acucl, Ser. B, 1997,73B, 109- I 13. E. Liepinsh, G. Otting, Nut. Biotechnol., 1997, 15,264-268. M. Scarselli, A. Vasco, A. Bonci, M. Rustici, N. Niccolai, Spectrosc. Lett., 1997, 30, 1201 1209. H. Maity, G. K. Jarori, Eur. J. Biochem., 1997,250, 539-548. M. Nicotra, M. Paci, M. Sette, A. J. Oakley, M. W. Parker, M. LoBello, A. M. Caccuri, G. Federici, G. Ricci, Biochemistry, 1998,37, 3020-3027. A. P. Campbell, W. Y. Wong, M. Jr Housten, F. Schweizer, P. J. Cachia, R. T. Irvin, 0. Hindsgaul, R. S. Hodges, B. D. Sykes, J. Mol. B i d , 1997,267,382-402. K. L. Constantine, L. Mueller, V. Goldfarb, M. Wittekind, W. J. Metzler, J. Yanchunas, Jr., J. G. Robertson, M. F. Malley, M. S. Friedrichs, B. T., 11, Farmer, J. Mol. Biol., 1997,267, 1223- 1246. Y. Zhang, Y. Li, Y. Wu, H. Yan, J. Bid. Chem., 1997,272, 19343-19350. Y. Ito, K. Yamasaki, J. Iwahara, T. Terada, A. Kamiya, M. Shirouzu, Y. Muto, G. Kawai, S. Yokoyama, E. D. Laue, M. Waelchli, T. Shibata, S. Nishimura, T. Miyazawa, Biochemistry, 1997,36,9109-9 1 19. H. Ottleben, M. Haasemann, R. Ramachandran, M. Gorlach, W. Muller-Esterl, L. R. Brown, Eur. J. Biochem., 1997,244,471 -478. J. P. Morken, T. M. Kapoor, S. Feng, F. Shirai, S. L. Schreiber, J. Am. Chem. Soc., 1998,120,30-36. E. R. Adams, E. A. Dratz, D. Gizachew, F. R. DeLeo, L. Yu, B. D. Volpp, M. Vlases, A. J. Jesaitis and M. T. Quinn, Biochem. J., 1997,325,249-257. P. M. Nieto, B. Birdsall, W. D. Morgan, T. A. Frenkiel, A. R. Gargaro, J. Feeney, FEBS Lett., 1997,405, 16-20. E. L. DiGiammarino, K.-a. Draker, G. D. Wright, E. H. Serpersu, Biochemistry, 1998,37,3638-3644.

38 1 382 383 384 385 386 387 388 389 390 39 1 392 393 394 395 396 397 398 399 400 40 1

402 403

404 405 406 407 408

1 I : Conformational Analysis

409 410 41 1 412

41 3 414 415 416 417 418 419 420 42 1 422 42 3 424 425 426 427 428 429 430 43 1 432 433 434 435 436 437 438

427

M. Schmiedeskamp, R. E. Klevit, Biochemistry, 1997,36, 14003- 1401 I . I. Shchipanova, V. Panov, S. Egorova, N. Shimanovsky, P. Sergeev, L. Sibeldina, Antibiot. Khimioter., 1995,40, 8- 10. T. Kawasaki, K. Saito, H. Ohta, Chem. Lett., 1997,351-352. A. P. Hill, S. Modi, M. J. Sutcliffe, D. D. Turner, D. J. Gilfoyle, A. T. Smith, B. M. Tam, E. Lloyd, Eur. J. Biochem., 1997,248,347-354. T. Porumb, A. Crivici, P. J. Blackshear, M. Ikura, Eur. Biophys. J., 1997, 25, 239- 247. X. Wang, H. M. Goff, Biochim. Bioph;v. Actu, 1997,1339, 88-96. S . Poli-Scaife, R. Attias, P. M. Dansette, D. Mansuy, Biochemistry, 1997, 36, 12672-12682. G. W. Daughdrill, L. J. Hanely, F. W. Dahlquist, Biochemistry, 1998, 37, 1076- 1083. G. W. Daughdrill, M. S. Chadsey, J. E. Karlinsey, K. T. Hughes, F. W. Dahlquist, Nut. Struct. Biol., 1997,4, 285-291. K. Yamasaki, S. Naito, H. Anaguchi, T. Ohkubo, Y. Ota, Nut. Struct. Biol., 1997,4, 498-503. E. Z. Eisenmesser, C.B. Post, Biochemistry, 1998,37, 867-877. H. Kusunoki, K. Wakamatsu, K. Sato, T. Miyazawa, T. Kohno, Biochemistry, 1998, 37,4782-4790. M. Wittkind, C. Mapelli, V. Lee, V. Goldfarb, M. S. Friedrichs, C. A. Meyers, L. Mueller, J. Mol. Biol., 1997, 267, 933-952. T. Yamazaki, Y. Kiso, Y.-X. Wang, D. I. Freedberg, D. A. Torchia, P. Wingfield, S. J. Stahl, J. D. Kaufman, Pept. Chem., 1996,34th, 337-340. D. N. Marti, C-K. Hu, S. S. A. An, P. von Haller, J. Schaller, M. Llinas, Biochemistry, 1997,36, 1 1591 - 1 1604. S. J. F. Vincent, C. Zwahlen, C. B. Post, J. W. Burgner, G. Bodenhausen, Proc. Nutl. Acud. Sci. U.S.A., 1997,94,4383-4388. M. F. Roberts, Y. Wu, C. Zhou, D. Geng, C. Tan, Adv. Enzyme Regul., 1996, 36, 57-71. S. Feng, S. L. Schreiber, J. Am. Chem. SOC.,1997,119, 10873-10874. J. Wang, D. M. Truckses, F. Abildgaard, Z. Dzakula, Z. Zolnai, J. L. Markley, J. Biomol. NMR, 1997,10, 143-164. N. C. Gonnella, Y.-C. Li, X. Zhang, C. G. Paris, Bioorg. Med Chem., 1997, 5, 2193-2201. H. N. B. Moseley, W. Lee, C. H. Arrowsmith, N. R. Krishna, Biochemistry, 1997, 36,5293-5299. C.-W. von der Lieth, T. Kozar, W. E. Hull, THEOCHEM, 1997,395-396,225-244. L. E. Lerner, NMR Spectrosc. Its Appl. Biomed. Res., 1996, 313-344. T. J. Rutherford, Glycopept. Relat. Compd., 1997, 661 -706. A. Imberty, Curr. Opin. Struct. Biol., 1997,7, 617-623. H.-C. Siebert, C.-W. von der Lieth, M. Gilleron, G. Reuter, J. Wittmann, J. F. G. Vliegenthart, H.-J. Gabius, Glycosciences, 1997, 291 -310. A. Poveda, C. Vicent, S. Penades, J. Jimenez-Barbero, Carbohydr. Rex, 1997, 301, 5 - 10. R. Harris, T. J. Rutherford, M. J. Milton, S. W. Homans, J. Biomol. N M R , 1997, 9, 47 - 54. F. Casset, A. Imberty, C. H. duPenhoat, J. Koca, S. Perez, THEOCHEM, 1997, 395-3%,211-224. F. L. Tobiason, G. Vergoten, J. Mazurier, THEOCHEM, 1997,395-396, 173-185.

428

Nuclear Magnetic Resonance

439

S. Ernst, G. Venkataraman, V. Sasisekharan, R. Langer, C. L. Cooney, R. Sasisekharan, J. Am. Chem. Soc., 1998,120,2099-2107. G. Toth, I. Pinter, J. Kovacs, R. Haessner, Mugn. Reson. Chem., 1997,35,203-208. A. Medgyes, E. Farkas, A. Liptak, V. Pozsgay, Tetrahedron, 1997,53,4159-4178. E. Boza, S. Boros, J. Kuszmann, Curbohyclr. Rex, 1997,29!9,59-67. B. Bendiak, Curbohydr. Res., 1997,304,85-90. S . J. Garden, J. L. Wardell, Main Group Met. Chem., 1997,20,711--721. T. J. Church, I. Carmichael, A. S. Serianni, J, Am. Chem. Soc., 1997, 119, 8946-8964. J. Moravcova, J. Capkova, J. Stanek, I. Raich, J. Carbohydr. Chem., 1997, 16, 1061-1073. L. Brade, K. Zych, A. Rozalski, P. Kosma, K. Bock, H. Brade, Glycobiology, 1997, 7,819-827. E. Monteagudo, A. Madami, F. Animati, P. Lombardi, F. Arcamone, Curbohydr. Rex, 1997,300, 1 1 - 16. H. J. Park, G.-J. Jhon, S. J. Han, K. Y. Kang, Biopolymers, 1997,42, 19-35. J. Kennedy, J. Wu, K. Drew, I. Carmichael, A. S. Serianni, J. Am. Chem. Soc,, 1997, 119,8933-8945. J. L. Asensio, M. Martin-Pastor, J. Jimenez-Barbero, THEOCHEM, 1997,395-396, 245 -270. A. Poveda, J. L. Asensio, M. Martin-Pastor, J. Jimenez-Barbero, Curbohyclr. Res., 1997,300,3- 10. A. Poveda, J. L. Asensio, M. Martin-Pastor, J. Jimenez-Barbero, J. Biomol. N M R , 1997,10,29-43. J. W. Kurutz, L. L. Kiessling, Glycobiology, 1997,7, 337-347. D. Mikhailov, R. J. Linhardt, K. H. Mayo, Biochem. J., 1997,328, 51-61. C. Landersjoe, R. Stenutz, G. Widmalm, J. Am. Chem. Soc., 1997, 119, 8695- 8698. U. C. Kreis, V. Varma, B. M. Pinto, THEOCHEM, 1997,395-396,389-409. C. Hoog, G. Widmalm, Glycoconjugute J., 1998,15, 183- 186. P. Soderman, P.-E. Jansson, G. Widmalm, J. Chem. Soc., Perkin Trans. 2 , 1998, 639-648. T. Weimar, T. Peters, S. Perez, A. Imberty, THEOCHEM, 1997,395-396,297-311. L. You, Q. Liu, Y. Shi, C.-X. Wang, M. Lahaye, V. Tran, Chem. Phys., 1997, 224, 8 1 -94. L. Catoire, I. Braccini, N. Bouchemal-Chibani, L. Jullien, C. H. duPenhoat, S. Perez, Glycoconjugate J., 1997, 14,935-943. G. Shim, S. Lee, Y. Kim, Bull. Koreun Chem. Soc., 1997,18,415-424. D. G. Low, M. A. Probert, G. Embleton, K. Seshadri, R. A. Field, S. W. Homans, J. Windust, P. J. Davis, Glycobiology, 1997,7, 373- 38 1. W. Jahnke, C. Hartmuth, M. J. J. Blommers, J. L. Magnani, B. Ernst, Angew. Chem., Int. Ed, Engl., I997,36,2603 - 2607. J. F. Espinosa, E. Montero, A. Vian, J. L. Garcia, H. Dietrich, R. R. Schmidt, M. Martin-Lomas, A. Imberty, F. J. Canada, J. Jimenez-Barbero, J. Am. Chem. Soc., 1998, 120, 1309-1318. E. Montero, M. Vallmitjana, J. A. Perez-Pons, E. Querol, J. Jimenez-Barbero, F. J. Canada, FEBS Lett., 1998,421,243-248. K. Sorimachi, M.-F. Le Gal-Coeffet, G. Williamson, D. B. Archer, M. P. Williamson, Structure, 1997,5,647-66 I . M. Hricovini, M. Guerrini, G. Torri, B. Casu, Curbohydr. Rex, 1997,300,69-76.

440 44 I 442 443 444 445

446 447 448 449 450 45 I 452 453 454 455 456 457 458 459 460 46 1 462 463 464 465 466

467 468 469

11: Conformutional Analysis

470 47 1 472 473 474 475 476 477 478 479 480 48 1

482 483 484 48 5 486 487 488 489 490 49 1 492 493 494 495 496 497 498 499

500 50 1 502

429

A. Poveda, M. Santamaria, M. Bernabe, A. Rivera, J. Corzo, J. Jimenez-Barbero, Curbohycir. Res., 1997,304,219-228. A. Poveda, M. Santamaria, M. Bernabe, A. Prieto, M. Bruix, J. Corzo, J. JimenezBarbero, Carbohydr. Res., 1997,304,209-217. G. Lippens, J.-M. Wieruszeski, D. Horvath, P. Talaga, J.-P. Bohin, J. Am. Chem. SUC.,1998,120, 170-177. C. W. E. M. Thijssen-vanZuylen, T. deBeer, B. R. Leeflang, R. Boelens, R. Kaptein, J. P. Kamerling, J. F. G. Vliegenthart, Biochemistry, 1998,37, 1933-1940. S. J. Opella, Nut. Struct. Biol., 1997,4, 845-848. R. R. Vold, R. S. Prosser, A. J. Deese, J. Biomol. NMR, 1997,9, 329-335. J. A. Losonczi, J. H. Prestegard, Biochemistry, I998,37, 706- 7 16. T. G. Fletcher, D. A. Keire, Protein Sci., 1997, 6, 666-675. M. Lecouvey, C. Frochot, L. Miclo, P. Orlewski, M. Marraud, J.-L. Gaillard, M. T. Cung, R. Vanderesse, Lett. Pept. Sci., 1997,4, 359-364. S . M. Cowsik, C. Lucke, H. Ruterjans, J. Biomol. Struct. Dyn., 1997,15,27-36. M. R. Hileman, B. S. Chapman, S. Rabizadeh, V. V. Krishnan, D. Bredesen, N. Assa-Munt, L. A. Plesniak, FEBS Lett., 1997,415, 145- 154. M. Lecouvey, C. Frochot, L. Miclo, P. Orlewski, A. Driou, G. Linden, J.-L. Gaillard, M. Marraud, M. T. Cung, R. Vanderesse, Eur. J. Biochem., 1997, 248, 872-878. S. G. Grdadolnik, D. F. Mierke, Biopolymers, 1997,42,627-632. K. A. Carpenter, B. C. Wilkes, P. W. Schiller, Eur. J. Biochem., 1998,251,448-453. N. Wolff, P. Delepelaire, J. M. Ghigo, M. Delepierre, Eur. J. Biochem., 1997, 243, 400-407. G. Wang, J. T. Sparrow, R. J. Cushley, Biochemistry, 1997,36, 13657- 13666. A. Rozek, G. W. Buchko, P. Kanda, R. J. Cushley, Protein Sci., 1997,6, 1858- 1868. K. Kanaori, M. Takai, A. Y. Nosaka, Eur. J. Biochem., 1997,249,878-885. H. Shimada, J. B. Grutzner, J. F. Kozlowski, J. L. McLaughlin, Biochemistry, 1998, 37,854-866. K.-H. Ruan, D. Li, J. Ji, Y.-Z. Lin, X . Gao, Biochemistry, 1998,37, 822-830. S. Rudolph-Bohner, D. Quarzago, M. Czisch, U. Ragnarsson, L. Moroder, Biopolymers, 1997,41, 591 -606. J. Jarvet, J. Zdunek, P. Damberg, A. Graeslund, Biochemistry, 1997,36,8153-8163. K. A. Carpenter, B. C. Wilkes, A. DeLean, A. Fournier, P. W. Schiller, Biopolymers, 1997,42,37-48. H. W. van den Hooven, H. S. Rollema, R. J. Siezen, C. W. Hilbers, 0. P. Kuipers, Biochemistry, 1997,36, 14137- 14145. E. Mercurio, M. Pellegrini, D. F. Mierke, Biopolymers, 1997, 42, 759-769. J. Gesell, M. Zasloff, S. J. Opella, J. Biomol. NMR, 1997, 9, 127- 135. N. L. F. Gallagher, M. Sailer, W. P. Niemczura, T. T. Nakashima, M. E. Stiles, J. C. Vederas, Biochemistry, 1997,36, 15062- 15072. M. Pellegrini, M. Royo, M. Chorev, D. F. Mierke, Biopolymers, 1996,40,653-666. M. R. Tessmer, J.-P. Meyer, V. J. Hruby, D. A. Kallick, J. Med Chem., 1997, 40, 2 I48 -2 155. R. Katahira, I. Umemura, M. Takai, K. Oda, T. Okada, A. Y. Nosaka, J. Pept. Res., 1998, 51, 155-164. D. H. Jones, C. A. Lingwood, K. R. Barber, C. W. M. Grant, Biochemistry, 1997, 36,8539-8547. F. C. L. Almeida, S. J. Opella, J. Mol. Biol., 1997, 270,481 -495. J. F. Hinton, A. M. Washburn-McCain, J. Magn. Reson., 1997,125,259-264.

430 503 504 505 506 507 508 509 510 511

512 513 5 I4 515

516

517

518 519

5 20 52 1 522 523

5 24 525

5 26 527 528

5 29

Nuclear Magnetic Resonance

P. S. Pregosin, G. Trabesinger, J. Chem. Soc., Dalton Trans., 1998,727-734. T. Ueno, M. Tnohara, N. Ueyama. A. Nakamura, Bull. Chem. SOC.,Jpn., 1997, 70, 1077- 1083. K. H. Dotz, R.Ehlenz, W. Straub, J. C. Weber, K. Airola, M. Nieger, J. Organomet. Chem., 1997,548,91-98. R. Ehlenz, M. Nieger, K. Airola, K. H. Dotz, J. Curbohydr. Chem., 1997, 16, 1305- 1318. S. Nafissi, H. Aghabozorgh, S.A.S. Sadjadi, J. Inorg. Biochem., 1997,66,253-258. D. Boghai, S. Nafisi, Iran. J. Chem. Chem. Eng., 1996, 15,98-107. A. Pastor, A. Galindo, J. Chem. Soc., Dalton Trans., 1997,3749-3754. Y. Yao, C. J. A. Daley, R. Mc Donald, S. H. Bergens, Orgunometallics, 1997, 16, 1 890 - 1896. F. Asaro, R. Dreos, S. Geremia, G. Nardin, G. Pellizer, L. Randaccio, G. Tauzher, S. Vuano, J. Orgunomet. Chem., 1997,548,211-221. N. Duran, P. Gonzalez-Duarte, A. Lledos, T. Parella, J. Sola, G. Ujaque, W. Clegg, K. A. Fraser, Inorg. Chim. Acra, 1997, 265,89-102. E. Katsarou, A. Troganis, N. Hadjiliadis, Inorg. Chim. Acta, 1997, 256,21-28. L. Cerasino, K. M. Williams, F. P. Intini, R. Cini, L. G. Marzilli, G. Natile, Inorg. Chem., 1997,36,6070-6079. A. Albinati, G. Bracher, D. Carmona, J. H. P. Jans, W. T. Klooster, T. F. Koetzle, A. Macchioni, J. S. Ricci, R. Thouvenot, L. M. Venanzi, Inorg. Chim. Acta, 1997, 265,255-265. M. Bergamo, T. Beringhelli, G. D’Alfonso, P. Mercandelli, M. Moret, A. Sironi, Orgunometullics, 1997, 16,4129-41 37. K. G. Orrell, A. G. Osborne, V. Sik, M. Webba da Silva, M. B. Hursthouse, D. E. Hibbs, K. M. Abdul Malik, N. G. Vassilev, J. Organomet. Chem., 1997, 538, 171 - 183. S. Aime, M. Botta, M. Fasano, M. P. M. Marques, C. F. G. C. Geraldes, D. Pubanz, A. E. Merbach, Inorg. Chem., 1997,36,2059-2068. C. P. Casey, S. L. Hallenbeck, J. M. Wright, C. R. Landis, J. Am. Chem. Soc., 1997, 119,9680--9690. J. Helaja, A. Y. Tauber, I. Kilpelainen, P. H. Hynninen, Magn. Reson. Chem., 1997, 35,619-628. D. J. Parks, W. E. Piers, M. Parvez, R. Atencio, M. J. Zaworotko, Orgunometallics, 1998,17, 1369--1377. M.-A. Munoz-Hernandez, R. Cea-Olivares, R.-A. Toscano, S. Hernandez-Ortega, Z. Anorg. Allg. Chem., 1997,623,642-648. X.-D. Zhang, S.-Z. Mao, L.-F. Shen, Z.-R. Lu, R.-X. Zhuo, Huuxue Xuebao, 1997, 55,290-295. P. A. W. Dean, L. Y. Goh, I. D. Gay, R. D. Sharma, J. Orgunomet. Chem., 1997, 533, 1-5. M. L. J. Hackney, D. M. Schubert, P. F. Brandt, R. C. Haltiwanger, A. D. Norman, Inorg. Chem., 1997,36,1867- 1872. M. R. Whitnall, K. K. Hii, M. Thornton-Pett, T. P. Kee, J. Orgunornet. Chem., 1997,529,35-50. B. Kowall, J. Heinicke, Main Group Met. Chem., 1997, 20, 379-386. L. P. Burke, A. D. DeBellis, H. Fuhrer, H. Meier, S. D. Pastor, G. Rihs, G. Rist, R. K. Rodebaugh, S. P. Shum, J. Am. Chem. Soc., 1997,119,8313-8323. A. Schmidpeter, G. Jochem, C. Klinger, C. Robl, H. Noth, J. Organomet. Chem., 1997,529,87- 102.

11: Conformational Analysis

43 I

530 53 I 532

W. McFarlane, C. T. Regius, Polyhedron, 1997,16, 1855- 1861. C. P. Nash, S. D. Toto, W. K. Musker, Tetruhedron, 1997,53,7461-7468. J. Fischer, P. Machnitzki, 0. Stelzer, 2. Naturforsch., B: Chem. Sci., 1997, 52,

533

E. L. Eliel, B. Gordillo, P. S. White, D. L. Harris, Heferoaf. Chem., 1997, 8,

534

J. Ohkanda, J. Kamitani, T. Tokumitsu, Y. Hi&, T. Konakahara, A. Katoh, J. Org. Chem., 1997,62, 3618-3624. P. L. Arnold, F. G. N. Cloke, K. Khan, P. Scott, J. Orgunomet. Chem., 1997, 528,

883-894. 509-516.

535

77-81. 5 36 537 538

M. Bochenska, V. C. Kravtsov, V. E. Zavodnik, J. Inclusion Phenom. Mol. Recognit. Chem., 1997,28, 125-140. A. Corruble, J.-Y. Valnot, J. Maddaluno, Y. Prigent, D. Davoust, P. Duhamel, J. Am. Chem. SOC.,1997,119, 10042-10048. Y. Li, F. Tian, Z. Xu, G . Xu, Beijing Duxue Xuebao, Ziran Kexueban, 1996, 32, 441 -447.

I2 Nuclear Magnetic Resonance Spectroscopy of Living Systems BY M. J. W. PRIOR

1

Reviews and New Methodology

1.1 General Applications - A review which catalogues the T1 and T2 data obtained from animals and man to date has been produced with 234 references'. The application of 'H, I9F, 3'P and I3C NMR to the study of in vivo drug metabolism has been reviewed with seven references*. A review of wave separation of 3 1 PNMR spectra has been produced with w references3. The history of the development of biological NMR has been reviewed4. 1.2 Spectral Editing, Localisation and Instrumentation A review of NMR methodologies covering NOE, INEPT, DEPT, INADEQUATE and 2 dimensional J-resolved spectroscopy, COSY, NOESY, 13C and 31Ptechniques and their application to biochemistry and medicine has been produced with 3 1 references5. A method for normalisation of metabolite images in 'H NMR spectroscopic imaging, using point-resolved spectroscopy (PRESS) has been developed. Nonuniformaties of the excitation profile of the volume of interest and chemical shift artefacts were corrected for by the use of measurements in phantoms. The technique was then used to examine 14 stroke patients and metabolite maps of choline-containing compounds (Cho), the H resonance from creatine and phosphocreatine (Cr) and N-acetylaspartate (NAA) were constructed. In uncorrected data only a reduction of NAA was detected whereas, in corrected data there was a reduction in all three metabolites studied6. A homonuclear J-resolved version of the double-echo PRESS sequence has been developed and used to obtain enhanced citrate signals compared to the conventional double-echo PRESS sequence7. An improved detection of citrate has also been developed using PRESS in which the pulse sequence timing has been optimised. After the application of PRESS the outer lines of the citrate multiplet often appear with dispersion lineshapes which interfere with quantitation. It was calculated, and demonstrated in vivo, that this problem could be eliminated by using values of T I = 11 MS and t2 = 60 MS8. A method has been developed for the improved detection of 2.6 ppm aspartate multiplet of N-acetyl aspartate. This aspartate multiplet is the AB part of an ABX system and gives rise to a significant field-strength dependence in the echo-time-dependent modula~

Nuclear Magnetic Resonance, Volume 28 0The Royal Society of Chemistry, 1999 432

12: Nucleur Magnetic Resonunce Spectroscopy of Living Systems

433

tions of the response to typical spatial localisation sequences. The echo-time dependence of this response has been analysed for STEAM and PRESS localisation sequences and for a spin-echo sequence and has been confirmed experimentally'. The visibility of lactate by double quantum 'H NMR (150 MS echo time) has been investigated in excised rat skeletal muscle and compared to results from extracts of the same tissue. After 1 to 2 hours and 10 to 12 hours of ischaemia, lactate was 32% and 21% visible, respectively. At these time the T2 of lactate was 140 and 184 MS, respectively. A significant improvement in the detection of lactate was achieved with an echo time of 79 MS in the double quantum 'H NMR sequence". In an investigation of the lineshape of lactate, a weakly J-coupled resonance, the expected lineshape resulting from the use of the PRESS technique has been calculated and the results have been compared to experimental data. A similar comparison was also made for the case of PRESS-localised spectroscopic imaging where the lineshape varies from voxel to voxel in the entire field of view. The implications of these results for the assessment of lactate in vivo have been discussed' I . An improved method for the detection of paramagnetically shifted resonances from deoxymyoglobin, for the determination of oxygen tension in striated muscle, has been developed. The sequence, based on an inversion recovery method, suppresses water and fat signals, can be implemented with surface coils and is suitable for fast repetition ratesI2. A comparison between a recently developed adiabatic coherent polarisation transfer enhancement technique and I3C spectra obtained with conventional nuclear Overhauser effect enhancement has been performed using an infusion of [2-I3C]acetate in the intact canine heart. The results demonstrate that both methods can be performed with surface coils and that coherent polarisation transfer provides better enhancement for [2-I3C]acetate but not for short T2 compounds13. A water suppression factor of 35000 has been obtained in a 'H NMR localisation method which utilised a combination of the STEAM and DRYSTEAM sequence~'~.

1.3 Intracellular Ions, Metabolites and pH - A review of NMR methods for the determination of intracellular pH (pHJ in protists, plants and animals has been produced with 140 reference^'^. The role of intracellular Ca2+ and its measurement (using 45Ca exchange, fluorescence probes and I9F NMR methods) in sepsis has been reviewed with 56 referencesI6. A review on many aspects of magnesium, including analysis by NMR, has been produced with 164 reference^'^. The experimental observations of phosphocreatine, creatine and P-guanidinopropionic acid metabolism and transport investigated with NMR in heart and skeletal muscle have been reviewed with 89 references". A review of the potential role of chemical shift imaging in cancer pathology has been produced with 29 references 19. A comparison has been made of several different methods for the calculation of intracellular Mg2+ (Mg2'i) concentrations from 31P NMR measurements of Mg2+,bound to ATP (Mg-ATP). Spectra were obtained from pig brain during and following hypoxic ischaemia with MgS04 infusion. The analysis revealed

434

Nuclear Magnetic Resonance

that the calculated value of Mg2+ivaried widely between algorithms and that the calculated pHi was the most important factor2'. The apparent dissociation constant of Mg2+-ATP (Kapp) has been measured in conditions pertinent to 31P NMR measurements of intracellular Mg2+.The values of Kappat 37 " were 106.6, 87.4 and 78.1 pM at pH values of 6.7, 7.2 and 7.7, respectively. Values of Kappat 25 " and at different ionic strengths were also measured. The reported values of Kapp are larger than those that have been most commonly used in the literature (87.4 pM compared to 38 pM at pH 7.2 and 37 ") in previous calculations of the concentration of Mg2+;from 31PNMR data. It was found that the application of this higher value of Kappto 31PNMR data in the literature increased the values of the concentration of Mg2'i by approximately 1.5 fold and makes some previous 31PNMR estimates of the concentration of Mg2+ in agreement with measurements made by Mg2+ microelectrodes2'. A re-evaluation of some previous measurements of the concentration of Mg2+in erythrocytes from 3 1 PNMR data has been performed. The affinities between cellular metabolites and haemoglobin were taken into account in the re-evaluation of previous NMR measurements of Mg2+i and it was found that this reassessment produced results that agreed with measurements made by conventional methods. It was also found that there was an affect on the chemical shift of the a- and p-resonance of ATP caused by the association of ATP or MgATP with haemoglobin which may lead to further errors of 5- 10% in the estimation of free Mg2+i22. 133CsNMR has been used as an analogue to measure the Na+-K+ ATPase activity in endothelial cells without the use of a chemical shift reagent to distinguish between intracellular and extracellular Cs. The rate of the Na+-K+ ATPase pump was measured to be 12?3 nmol '33Csmin-' mg protein-' under control conditions. When intracellular ATP was depleted to 5% the activity of the Na+-K+ ATPase pump fell to 33Yi3. The use of 133CsNMR to assess ion transport in perfused rat heart has also been i n ~ e s t i g a t e dThe ~ ~ . T1 and T2 values for intracellular 133Cs were determined to be 2.1 s and 0.065 s, respectively. The rate constant for the Na+-K+ ATPase pump influx was measured to be 0.25 min-I. A new method for the estimation of the amount of relative anaplerosis which occurs in '3C-labelling experiments has been investigated. Relative anaplerosis, described as the ratio of anaplerotic flux compared to the flux catalysed by citrate synthase, recalculated from data in the literature was found to be double previous estimates25.

2

Cells

2.1 Bacteria - A review with 71 references has been produced on the applications of multi-nuclear NMR to the study of bacterial physiology26 and the materials and methods for the study of Helicobacter pylori using NMR have been described27. The application of I3C NMR to the screening of urease inhibitors (especially from Cinnamomum cassia) on the growth of Helicobacter pylori in the control of digestive tract ulcers has been reviewed with three references28. A

12: Nucleur Magnetic Resonance Spectroscopy of Living Systems

435

review of techniques for non-invasive monitoring of the physiological state of microbial cultures, including the use of 31PNMR, has been produced29. The sugar-induced inhibition of malolatic fermentation in cell suspensions of Leuconostoc oenos (Oenococcus oeni) has been investigated with NMR in vivo and in vitro, and with manometric technique^^^. 31P NMR has been used in an investigation of the energetic and metabolic differences brought about by the genetic modification of the glucose uptake and phosphorylation system in Escherichia coli. The engineered strain of E. coli (PPA361), which uses the galactose-proton symport system for glucose uptake, had a fivefold reduction in anaerobic growth rate and 60% reduced growth rate in aerobic conditions. Furthermore, PPA316 had lower levels of sugar phosphates, NTP, NAD(H) and phosphoenolpyruvate, and higher levels of ADP compared to the parent strain3'. The carbon metabolism of three strains of Fibrobacter succinogenes and one strain of Fibrobacter intestinalis have been studied with I3C NMR and 13C-filtered spin-echo difference 'H NMR. In resting cells a reversal of glycolysis at the triose phosphate level was observed and glycogen futile cycling was demonstrated by following the simultaneous metabolism of [ '3C]glycogen and exogenous unlabelled glucose. The labelling pattern from the metabolism of unlabelled glycogen and [l-'3C]glucose was compared and differences were found in the labelling of succinate and acetate. It was found that succinate labelling reflected glycogen futile cycling whilst, acetate labelling reflected other mechanisms. In all strains 12 to 16%0of glucose in the metabolic pathway came from glycogen32. Blood - The action of vanadate on intact human erythrocytes has been investigated with spin-echo 'H NMR and "V NMR. Vanadate was found to be transported across the cell membrane as vanadate(V), reduced by glutathione and depleted by exchange reactions33. The influence of pulsed electric fields on the concentration of intracellular Na' (Na+,) in the human erythrocyte has been measured using 23Na NMR in the presence of a shift reagent. The concentration of Na+, was found to increase exponentially with increasing intensity of the pulsed electric field at the highest field value tested. However, Na+, decreased at lower pulsed electric field values. This decrease could be inhibited with oubain in a dose dependent manner suggesting that the Na+-K'-ATPase was activated by low intensity pulsed electric fields34. The techniques of 13C, 'H and 31P NMR have been used in a study of [Fe('3CN)6]2- reduction in high-haemocrit suspensions of human erythrocytes. It was found that the l3C NMR signal from [Fe(I3CN)6l2- was narrow whereas, the 13C NMR signal from [Fe(I3CN)6l3- was very broad. When cells were incubated with ['3C]glucose it was possible to simultaneously measure the rate of ferricyanide reduction, glucose utilisation, and lactate and bicarbonate p r o d ~ c t i o n ~''F~ . NMR with the intracellular N,N,'N'-tetraacetic calcium indicator 1,2-bis(2-amin0-5-fluorophenoxy)ethane-N, acid (SFBAPTA) and 31PNMR have been used to measure intracellular Ca2+ (Ca2+i) and intracellular Mg2+ (Mg2'i) levels, respectively, in erythrocytes from hypertensive subjects. Erythrocytes from hypertensive patients had higher Ca2+i levels and lower Mg2+ilevels compared to normotensive subjects. Furthermore, when cells from hypertensive subjects were incubated with insulin the increase in 2.2

436

Nuclear Magnetic Resonance

Ca2+, was less, and there was no increment in Mg2+i, compared to cells from normotensive subjects36. Erythrocytes from patients with myelodysplastic syndrome have been examined with 31PNMR and compared to erythrocytes from normal volunteers to explore the possible differences and responses to treatment37.

2.3 Mammalian - The application of NMR to the study of apoptosis has been reviewed with 28 reference^^^. 'H NMR has been used in a method for the assessment of apoptotic cell death in doxorubicin-treated Jurkat T-cell acute lymphoblastic leukaemia cell cultures. The ratio of the methylene resonance at 1.3 ppm to the methyl resonance at 0.9 ppm was found to be directly proportional to the percentage of apoptotic l y m p h ~ b l a s t s The ~ ~ . effects of the potential antineoplastic agent tetraphenylphosphonium chloride (TPP) on the transformed human breast cell line HBL-100 has been investigated with ' H NMR. Treatment with TPP caused an increase in mobile lipid, measured as the ratio of the methylene peak to the methyl peak (internal reference) or to p-aminobenzoic acid (external reference) and caused a slowing of the passage through S phase. Time-dependent changes in, mobile lipids were caused by 2 pM TPP and removal of the drug did not reduce the lipid signals. Two-dimensional H-' H COSY spectra of cells demonstrated concentration-dependent increases in lipid acyl chains. Furthermore, increases in choline and glycerophosphocholine were also observed4'. The relationship between H N M R-detected mobile lipids and cellular activation, cell cycle and phosphatidylcholine-specific phospholipase C activity has been investigated in stimulated lymphocytes4'. The production of lactate by HSP-1, HSR-8 and HET-SR fibroblasts has been investigated with 'H NMR in monolayer cultures and cells immobilised on collagen lattices42. A method for the immobilisation of primary brain cells for use in NMR studies has been developed and 31PNMR was used to confirm the metabolic status of the cells43. The transport of Li in perfused human neuroblastoma cells has been investigated with NMR44. The toxic effects of the macrolide immunosuppressant sirolimus on primary astrocytes has been studied with multinuclear NMR in viable cells and perchloric acid extracts of cells. The addition of 5.5 pmol d m P 3 sirolimus induced cellular swelling to 110% and affected osmolite and amino acid levels; myo-inositol decreased by 58%, taurine by 44% and glutamine by 13'Yo. Furthermore, sirolimus altered glucose metabolism, partially inhibited the TCA cycle and increased the concentration of PDE, indicating a disruption in phospholipid metabolism. These changes were accompanied by a decrease in phosphocreatine (PCr) by 250/0 within 60 min of treatment and a decrease in nucleoside triphosphates (NTP) by 15Y0within 90 min of treatment. The effects of sirolimus were similar to those of cyclosporine and tacrolimus both of which are known to be n e ~ r o t o x i c The ~ ~ . effects of 3,3',5'-triiodothyronine(rT3) and 3,3',5-triiodothyronine (T3) have been compared in 3T3 cells using 'H and 31P NMR. Treatment of cells incubated at pH 7.4 with 5 nM T3 caused an increase in the ATP/ADP ratio from 6.9 to 8.4whereas, rT3 caused a decrease, to 6.1, in the ATP/ADP ratio. Incubation of the cells at pH 6.7 caused a decrease in ATP/ADP

'

'

12; Nuclear Magnetic Resonunce Spectroscopy of Living Systems

437

to 6.6 and 5.2 at I and 2 hours, respectively. Treatment with rT3 at this pH augmented the fall in ATP/ADP but, treatment with T3 enabled cells to maintain the ratio of ATP/ADP above the control level. Administration of T3 to rT3treated cells reversed the effects of rT3 on the ATP/ADP ratio46. The role of protein kinase C in the Pb2+-induced rise in Ca2'i has been investigated with I9F NMR and the intracellular Ca-indicator SFBAPTA in the osteoblast cell line ROS 17/2.8. Treatment of the cells with 1 pM and 5 pM Pb2' caused a rise in Ca2fi from 125 nM to 170 nM and 230 nM, respectively, while treatment with 10 pM of an activator of protein kinase C (phorbol 12-myristate 13-acetate) produced a rise in Ca2+i to 210 nM. Pre-treatment of cells with calphostin C, a potent inhibitor of protein kinase C activation, prevented any rise in Ca2+iin response to Pb2+47. 2.4 Plant - Inverse correlated 2D IH-l3C NMR of naturally abundant signals has been used to follow the metabolism of vanillin in plant cell suspension cultures of Nicotiana plumbaginifolia48. 31PNMR has been used to measure the pH, of cultured rice cells in response to exposure to N-acetylchitooligosaccharides, which are fragments of a main backbone polymer of fungal cell walls. Exposure induced efflux of Kf and influx of Hf with a corresponding decrease in pH,. Deacetylated chitosan oligomers had no effect49.The effects of acidification of the culture medium and the regulation of pHi has been investigated with 3'P NMR in cells in cultures of Catharanthus roseus 50.

2.5 Reproductive - The creatine kinase (CK) reaction and phosphorous metabolites of inactive and active sea-urchin spermatozoa has been investigated with 31PNMR". In inactive sperm no CK-mediated exchange flux was detected, pHi was 6.6 and the concentration of free intracellular ADP was 9 pM. In activated, mobile sperm pHi rose to 7.6 and free intracellular ADP rose to 114 pM. Furthermore, there was a CK-mediated exchange flux detected in mobile sperm with a forward pseudo-first-order rate constant of 0.31 S - I at lo", corresponding to a steady-state CK flux of 3.1 pmol s- I .

2.6 Tumour - A review of applications of NMR in cancer cell metabolism has been produced52. A difference between the response of normal and leukaemic bovine cells to incubation without glucose has been observed with 31PNMR. Leukaemic cells had a more rapid fall in pH, and a more rapid fall in the ratio of ATP/ADP compared to normal cells53. The effects of extracellular glutamine on the primary and secondary metabolism of murine hybridoma cells have been studied in a hollow-fibre bioreactor using I3C NMR to follow the metabolism of [I-13C]glucose.A brief reduction in extracellular glutamine from 4 to 0 mM, which caused a change in residual glutamine from 0.67 to 0 mM, produced large changes in metabolites associated with energy production, stimulated antibody synthesis and altered nitrogen metabolism. When a more prolonged change in glutamine was imposed, from 2.4 to 1.2 mM which changed residual glutamine from 0.30 to 0.08 mM, smaller changes in metabolites associated

438

Nuclear Mugnetic Resonunce

with energy production were observed and energy production did not appear to be limited54. 31PNMR has been used in the study of the effects of tumour necrosis factor-rx (TNFct) on perfused human breast cancer cells. The cytotoxic affects of TNFa on breast cells in culture were not seen in perfused cells where TNFa also had no effect on the 31Pspectra55.The effects of reduced cell proliferation, without acute cytotoxicity, caused by dexamethasone treatment has been studied in perfused RIF-1 fibrosarcoma cells using 31PNMR. The ratio of PCr/NTP was increased by 30% in treated cells but there was no effect on pH, or the phosphocholine (PCho) to NTP ratio. The ratio of phosphomonoesters (PME) to NTP was effected by cell density and not treatment with d e ~ a m e t h a s o n eThe ~ ~ . techniques of 31Pand I3C NMR have been used in a study of the effects of Lonidamine (LND) on intact perfused drug-sensitive (WT), and 33-fold resistant to Adriamycin (Adr), MCF-7 cells embedded in alginate micro capsules. Treatment with LND caused a greater decrease in the pHi and NTP levels in the WT cells compared to the Adr cells and, 13C NMR detected a greater increase in intracellular lactate in WT cells. The results indicated that the mechanism of LND action is the inhibition of lactate transport and subsequent intracellular acidosis which may be exploited in combination with alkaloid chemotherapy where alkaloid uptake is improved by intracellular acidosis57. 2.7 Yeast and Fungi - 31PNMR has been used to study the effects of vanadium on the yeast Hansenula polymorpha which is able to grow on vanadate concentrations that are toxic to other organisms. The results showed a change in the intracellular polyphosphate level accompanied ultrastrutural modifications5*. The transport of aluminium across the yeast cell membrane has been studied with 27Al NMR and a dysprosium chemical shift reagent. The results showed that an equilibrium between intracellular and extracellular 27Aloccurs within 4 hours of exposure, that citrate did not favour the entry of 27Alinto yeast at pH 5 and that EDTA caused 27Alto be removed from the cells59. The fate of exogenously supplied glycine betaine has been investigated in saltstressed strains of Sinorhizobium meliloti which differ in their ability to metabolise glycine betaine. 13C NMR demonstrated the accumulation of the exogenously supplied osmolite glycine betaine in wild type cells until the accumulation of glutamate and N-acetylglutaminylglutamine amide in the second half of the exponential growth phase at which time glycine betaine is much reduced. Glycine betaine disappeared in stationary phase when the cells accumulated the disaccharide trehalose. In the mutant strain of S. meliloti, which does not metabolise glycine betaine, the accumulation of this metabolite was dominant at all stages of growth 60. The role of plasma membrane H'-ATPase in the regulation of cytoplasmic pH in Saccharomyces cerevisiae has been investigated with 31P NMR. The results indicated that the H+-ATPaseand the vacuole play a role in pHi homeostasis6'. In a study of the changes in the level of CAMP during the growth cycle in Saccharomyces cerevisiae 31PNMR has been used to determine intracellular pH62. The effects of '291Rgamma irradiation on Saccharomyces cerevisiae has been measured with 31P

439

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

NMR. During irradiation (8 G y k ) there was a rapid decrease in ATP and polyphosphate which was followed by a slow recovery of p ~ l y p h o s p h a t e ~ ~ .

3

Plants and Algae

A review of NMR methods for the study of the metabolic response of plant tissues to anoxia has been produced with 47 referencesa.

Several methods for the detection of sucrose in developing pea (Pisum sativum L.) seeds have been compared. It was found that heteronuclear correlation via 13C-'H coupling (HMCQ) and homonuclear correlation via H-'H coupling (DQF) were not as effective as an enhanced version of chemical shift selective imaging (CHESS) for water suppression and sucrose detection6'. A family of fast chemical shift imaging techniques which take advantage of the cylindrical symmetry found in some plants have been described. The experimental time of these techniques is reduced compared to conventional chemical shift imaging and correlation peak imaging. Radial 'H NMR images of metabolites in Ancistrocladus heyneanus have been produced with these techniques66. The distribution and fluctuation of sugars in germinating barley seeds has been investigated. Maltose, sucrose, fructose and oils were detected by I3C NMR. The maltose content was observed to increase during the first six days of germination whilst the oil content decreased and the level of fructose and sucrose remained constant. Sugars were located, using 'H NMR localised spectroscopy, in the vascular bundle of the seeds as well as the solubilised end0~pex-m~~. The metabolism of maize (Zea mays) root tips labelled [l-'3C]glucose has been followed with HMQC 13C--lH NMR and the metabolism of l5NH3+ has been followed with "N-'H HMQC NMR in the same system68. The effects of external pH on the vacuolar pH (pH,) in maize (Zea mays L. cv. FRB 73) seedlings has been followed using fluorescence microscopy, utilising a pH sensitive fluorescent dye, and compared to results from 31P spectroscopy. Fluorescence microscopy showed that 10 mM NH4Cl caused a fast change in the pH, of root hair cells with the magnitude being proportional to the external pH. However, 31PNMR detected Pi in an acidic compartment in the presence of 10 mM NH4CI even at an external pH of 9.0 indicating that a small but significant proportion of vacuoles in the root tissue did not alter their pH in response to external ammonium69. The regulation of pH in acid-stressed leaves of pea plants grown in the presence of nitrate or ammonium salts has been investigated using 31PNMR. Acidification of leaves by the addition of C 0 2 to the air caused a fall in pH, by 0.1 unit and a decrease in cytoplasmic pH (pH,) by 0.5 units which then slowly increased but did not completely recover. Under anaerobic conditions pH, decreased by 1.0 and pH, increased by 0.4, though, these changes were reversed when C02 was removed. The addition of mannose caused an accumulation of mannose phosphate, an increase in Pi and prevented the aerobic-recovery from anaerobic acidosis. The results suggest a role for ATP-dependent pumping of protons into the vacuole to restore pH,. No differences in pH regulation were observed for plants grown on nitrate or ammonium salts7'. 31PNMR has been

'

440

Nuclear Magnetic Resonance

used to investigate maize seeds (Zea Mays) during germination for 10 days. A single broad resonance was detected and assigned to the Mg2+,Ca2' and K' salts of phytin in a subcellular compartment of the embryo scutellar cells. The chemical shift of the peak indicated that the acidification of this compartment reached a minimum of pH 4 around three days after germination7'. Salt stressinduced changes of pHi and 31Pmetabolites have been monitored in intact root tips of barley (Hordeum vulgare cv. Akashinriki) seedlings72. The nitrogen metabolism and pH regulation of Sphagnum flexuosum have been explored using 15N and 31PNMR. The exposure of S. flexuosum to I5NH4' led to the formation of y-'5N-glutamine followed by the formation of a-amino glutamate/glutamine. No assimilation was observed in the presence of the glutamine synthetase inhibitor Met sulfoximine suggesting that the glutamine synthetase/ glutamate synthase pathway is the main route of NH4+ assimilation. Cytoplasmic pH was not affected by exposure to NH4' but, vacuolar pH fell slightly73. The mechanism of water transport in plant tissues has been investigated with ' H NMR using model membranes, sediment of Chlorella sp. and plant material74. ' H NMR has been used to investigate rates and pathways for water diffusion and bulk flow through leaf tissue from Acer platanoides. Data from leaf disks floating on either s u ~ r o s e / ~ H 2or0 polyethylene glycoV'H20 solutions show that water diffusion and bulk flow follow different pathways through leaf tissue. The rate of diffusion was too high to be consistent with transport through apoplastic channels and suggests that water molecules move directly through contiguous compartment^^^. The relaxation rates TI and T2 have been measured in seeds using 'H NMR. The temperature dependence of T1 helped to distinguish the thermodynamic properties of water in dry and germinating seeds. Pea, maize and wheat seeds had two components of T2 and lettuce, tomato and radish seeds had a single component of T2. The two components of T2 were attributed to water (short T2) and lipids (long T2) in oil bodies76. Phosphate uptake and polyphosphate metabolism in mycorrhizal and nonmycorrhizal roots of pine (Pinus sylvestris) and in the fungus Suillus bovinus has been studied by 3'P NMR. Mycorrhizal roots and pure fungus transformed accumulated Pi into mobile polyphosphate with a medium chain length. Maximal phosphate uptake occurred at an external pH of 5.5 in mycorrhizal and nonmycorrhizal roots and pure fungus. A lag in the uptake of phosphate occurred when the external pH was 8.5 but this was abolished at pH 7.577.The toxic effects of linear alkylbenzenesulphonate and quaternary alkylammonium chloride have been assessed in Dunaliella sp. using 'H NMR. The detectable level of intracellular glycerol was shown to reflect toxicity and was used to measure the effects of different levels of surfactant treatment. No leakage of glycerol into the extracellular media was detected7'.

4

Tissue Studies

Brain and Spinal Cord - A review of multinuclear NMR studies of perfused rat brain slices has been produced with many reference^^^.

4.1

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

441

The kinetics of labelling of [4-' 3C]glutamate from [I - '3C]glucose has been observed with 'H-I3C-edited NMR in superfused brain slices. Data from label incorporation into, and from, [4-13C]glutamate suggested that there were two compartments with large differences in their rates of labelling and pool sizes. Stimulation of oxygen consumption, by either 40 mM KCl or 5 pM carbonyl cyanide m-fluorophenyl hydrazone increased the rate of labelling of [4-' 3C]glutamate and data for the appearance or disappearance of the label could only be fitted into a monoexponential equation8'. The oxidative metabolism of [1,6-"C]glucose has been studied in the rat brain during single forepaw stimulation. Spatially localised H, 13C-edited NMR was used to detect the rate of [4-'3C]glutamate turnover which was then used to calculate the flux through the TCA cycle (VTCA). During stimulation VTCA increased from 0.47 to 1.44 mmol g - ' min-' in the sensorimotor region8'. 2H NMR has been used to study the distribution of *H atoms in brain lactate after injections of 2H20 in rats. The ratio of [3-2H]lactate/[2-2H]lactatewas very sensitive to the oxygen content of inspired airs2. The effects of feline immunodeficiency virus on the cat brain has been investigated with ' H NMR to measure glutamate levels whilst neuronal losses where measured with histological methods. The results provide evidence of raised levels of glutamate in conjunction with neuronal loss, supporting the hypothesis of glutamate-mediated neurotoxicity as a major mechanism in the neuropathagenesis of feline immunodeficiency virus infectionp3. 31PNMR has been used to determine PCr and ATP levels, and the rate of the creatine kinase (CK) reaction in the brains of 7 and 21 day old rats before and during pentylenetetrazole-induced seizures. In older rats the CK rate constant was three times higher than in the younger rats and increased by 60% during seizures in older rats. Small decreases in PCr were observed in all rats during seizures and a small decrease in ATP was seen in 7-day-old, but not 21-day-old, rats84. The progress of neuronal cell death and gliosis resulting from unilateral hippocampal injections of kainate have been followed using localised MRS, T2weighted imaging and diffusion weighted imaging (DWI). The results from localised MRS were compared with histological examinations in this model of temporal lobe epilepsy85. Hippocampal H-metabolite changes in kainic acid induced rat temporal lobe epilepsy have also been followed with localised 'H NMR. Increases in the NAA and N-acetyl aspartyl glutamate to Cr ratio were observed in the ictal phase. An increase in the lactate to Cr ratio was observed for up to 24 hourss6. 31PNMR has been used in a study of brain PCr and ATP levels in mice which have been fed on creatine or the creatine analogue b-guanidinopropionic acid. During hypoxia and seizures, survival was higher, and brain phosphagen and ATP losses were less in P-guanidinopropionic-fed mices7. The effects of exposure to aromatic white spirit on metabolites levels of the rat hippocampus has been investigated with localised 'H NMR. Rats were exposed to 0, 400 ppm or 800 ppm of aromatic white spirits 6 hours per day, 7 days per week for 3 weeks. ' H NMR measurements of NAA, Cr and choline containing compounds (Cho) in the hippocampus and surrounding tissue revealed no significant differences between the groupss8.

'

'

442

Nuclear Magnetic Resonance

The reliability of the detection of NAA by magnetic resonance spectroscopic imaging (MRSI) as a measurement of neuronal loss has been investigated in a comparison with histological analysis of cell viability and tissue shrinkage following administration of quinolinic acid. There were discrepancies between the NMR data and histological analysis that may be accounted for by the susceptibility of NMR data to partial volume effects and tissue shrinkage but, sparing of axons by quinolinic acid may also have ~ o n t r i b u t e d ‘H ~ ~ .MRSI has also been used to investigate the measurement of NAA as a marker of neuronal loss following severe global ischaemia induced by bilateral carotid occlusion and hypertension in the rat brain. NAA was decreased by 29-74% in vulnerable regions including the cortex, striatum, hippocampus and the thalamus. No changes were observed in the brain stem or cerebellum. Regions with decreased NAA also had evidence of neuronal necrosis and had increased lactate and alanine concentrationsg0. 31Pand ‘H CSI have been used in an investigation of the effects of the middle cerebral artery occlusion model of brain ischaemia on pH, and lactate accumulation. Lactate accumulation in the infarcted region gradually and consistently increased during a 15 hour observation period. However, severe acidosis was observed between 2 and 4.7 hours after middle cerebral artery occlusion and decreased after this period showing a dissociation between lactate accumulation and pH:’. The effects of ischaemia and hypoxia on the metabolites of the newborn piglet brain have been investigated with ‘H and 3’P NMR. Temporary occlusion of the carotid artery caused a rise from 0.14 to 4.34 in the lactate/Cr ratio. At two hours post-resuscitation the lactate/Cr ratio had fallen to 0.75 and then rose to 2.43 by 48 hours post-resuscitation. The increase in lactate was concomitant with a fall in the PCr/Pi ratio and the maximum level of lactate during delayed energy failure correlated strongly with the minimum NTP/ exchangeable phosphate pool ratio92. 31PNMR has been used in an investigation of the effects of bilateral focal compression ischaemia on energy metabolism and intracellular pH in the rat brain93. An experimental rat model of kaolin-induced hydrocephalus has been investigated using ‘H and 31P NMR. Hydrocephalic animals had a reduced PCr/Pi ratio and detectable lactate indicating a compromised energy metabolism possibly caused by cerebral ischaemiag4. Localised ‘ H NMR has been used to measure the accumulation of lactate in the rabbit brain during and following hypoxia. Regional blood flow (rBF) was measured with laser Doppler flowmetry. The results suggested that the increase in lactate during hypoxia is due to deficiency of oxygen delivery and that this increase in lactate prolongs the period of enhanced rBF during recovery from hypoxia9’. The effects of hypoxia on the mouse brain have been investigated with 31PNMR. The mice were subjected to 5% oxygen until the ratio of Pi/PCr was about one when re-oxygenation took place. It was found that if the ratio of Pi/ PCr was larger than one before re-oxygenation, and pH increased immediately during re-oxygenation, then the mice recovered from the effects of h y p ~ x i a ~ ~ . The technique of H-”N heteronuclear multiple quantum coherence (HMQC) transfer has been used to observe [5-”N]glutamine amide protons in the hyperammonaemic rat during [ ’N]ammonium acetate infusion and subsequent

’

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

443

recovery. When the concentration of brain ammonia increased from 1.7 to 3.5 pmol g- the linewidth of [5-"N]glutamine amide protons increased from 36 to 58 Hz. The linewidth increase of [5-"N]glutamine amide protons indicated an ~ ~ . rate of the cerebral TCA increase in pH from 7.1 to 7.4-7.5 in a ~ t r o c y t e sThe cycle and the rate of glutamine synthesis have been measured in the rat under normal and hyperammonaemic conditions using 13C NMR. The time courses of glutamate and glutamine C-4 labelling, following a [ 1-13C]glucoseinfusion, were analysed with a mathematical model to yield the TCA cycle rate and the rate of flux from glutamate to glutamine. In hyperammonaemia, the TCA cycle rate was not unaffected but, the rate of glutamine synthesis was significantly increased reflecting ammonia deto~ification~~. The concentration of the anorectic drug dexfenfluramine and its active metabolite have been detected in the brain of the rhesus monkey. The results agreed with those obtained by gas chromatography analysis when an adjustment was made for the drug distribution in non-brain tissue indicating that dexfenfluramine and its active metabolite are fully detectable in viva*. 4.2 Eye - The distribution of Na+ in the vitreous body of the eye has been studied with 23Na NMR. Intensity measurements indicate that 1000/0of the Na+ is detectable and relaxation studies suggest that there are two states of Na+ with different mobilities that are in slow exchange"'.

4.3 Heart - Reviews of the application of 31PNMR methods for the study of heart metabolism'" and myocardial work and metabolic stressIo2 have been produced with many references. 31P NMR and the information it can provide from isolated and perfused hearts has been reviewed with 33 referencesIo3. A review that focuses on the theory of 3'P NMR saturation transfer techniques and the information that it can provide from the intact myocardium has been produced with 68 referenceslM. An isolated, perfused fish heart preparation has been studied with 31PNMR. Hearts from the rainbow trout (Oncorhynchus mykiss, Wilbaum) and the European eel (Anguilla anguilla, L.) were studied and showed low Pi, high levels of PCr, ATP and a high adenylate charge all of which were stable over a 120 min periodlo5. Mechanisms of pHi recovery from NH4C1-induced acidosis have been investigated in the isolated perfused turtle (Chrysemys picta bellii) heart using 31P NMR.It was found that recovery of pHi occurred 2-3 faster at 30"compared to 20". Although ATP was unaffected, PCr and mechanical performance of the heart changed in parallel to PHi. Results from experiments with the Na+-H+ antiport inhibitor 5-(N-ethyl-N-isopropyl)-amiloride(EIPA) and the anion exchange inhibitor 4,4'-diisothiocyanostilbene-2,2'-disulphonic acid (DIDS) in the presence or absence of HC03- indicated that recovery from acidosis is dominated by a DIDS-sensitive Na' and HC03--dependent mechanism. The EIPAsensitive Na+-H+ antiport played a less important rolelo6. The preservation of phosphagen kinase activity during transient hypoxia has been studied in smooth muscle from porcine ileum, the myocardium of Limulus polyphemus and the myocardium of Argopecten irradians using 31P NMR. The phosphagen pool

444

Nuclear Magnetic Resonunce

recovered concomitant with ATP during reoxygenation in all tissues revealing competent kinase functionio7. In a study of the effects of changes in thyroid state on the pHi and Na+i homeostasis in rat ventricular myocytes and rat heart 3'P NMR has been used to measure pHi in Langendorff-perfused hypothyroid and hyperthyroid rat hearts. Differences in the functional activity, pHi and Na+i homeostasis detected in ventricular myocytes could be partially accounted for by increased expression of the Na'/Ca2+ exchanger and the Na+/Hf antiporter in the hyperthyroid rat heartIo8. 3'P NMR has been used in a study of the resistance to hypoxic insult of hypertrophied hearts from swim-trained and sedentary rats. During hypoxia, the trained hearts exhibited improved systolic and diastolic function and also showed more rapid and complete recovery of function during post-ischaemic reoxygenation. The relative preservation of function in hearts from trained rats could not be accounted for by overall high energy phosphate metabolite levels but, saturation transfer demonstrated an increase in the forward rate of creatine kinase in beating trained hearts"'. Cardiac mechanics and metabolic performance have been studied in isolated perfused hearts from rats subjected to swimtraining with or without acclimatisation to heat. Cardiac performance was greater in swim-trained heat-acclimatised rats during ischaemia and recovery. Furthermore, hearts from swim-trained heat-acclimatised rats retained 30% of ATP levels and had a delayed decline in pH, during total ischaemia. During reperfusion these hearts also had improved ATP and PCr recovery']'. Cardiac energy status has been studied with 3'P NMR in perfused hearts from rats subjected to thermal injury. The ionic balance and functional status were determined by conventional means. The data suggested that the decreased functional response of hearts following bum trauma alters intracellular cardiomycete Ca2+ and Na+ homeostasis, and that these ionic derangements are not related to altered pH, or deficits in high energy phosphates' I . 31PNMR has been used in an investigation of the role of Pi in the regulation cardiac adenosine The dependence of the forward flux of creatine kinase (CK) on its substrates and products has been investigated by "P NMR in the isovolumetric, acetate-perfused rat heart which has been depleted of PCr and adenylate by perfusion with 2-deoxy-~-glucosein the presence of insulin. When the PCr content was reduced twofold the rate of CK flux remained the same because the apparent rate constant for the CK reaction was doubled. At the lowest PCr and ATP concentration the CK flux was reduced to 50% but, it remained higher than the rate of ATP synthesis1I3.The kinetics of phosphorous metabolism in the under-perfused rabbit heart has been investigated with 3'P NMR. When coronary perfusion was reduced by 950/0the level of PCr fell to 25% and then rose to 42% whilst the level of ATP fell steadily to 65%. The kinetics of PCr and ATP were found to fit a model where ATP synthesis matches ATP hydrolysis with a reduction in cytosolic AMP caused by its conversion to adenosine and subsequent efflux from the cell. It was suggested that the removal of AMP may be beneficial during ischaemia by improving the free energy of ATP hydrolysis and delaying or preventing Ca-overload' 14. 3'P NMR has been used in a study of cardiac recovery following ischaemia in

'

12: Nucleur Mugnetic Resonunce Spectroscopy of Living Systems

445

rat hearts perfused with erythrocyte suspensions. When hearts were subjected to different periods of ischaemia a strong correlation between the fraction of ATP measured after reperfusion and the fractional recovery of external work output was revealed1I5.3 1 PN M R has been used in an investigation of the influence of ischaemic blood flow, heart rate and systolic blood pressure on the recovery of PCr during prolonged hypoperfusion in the heart of open-chest dogs. Coronary blood flow and systolic wall thickening did not alter significantly during four hours of hypoperfusion. In the epicardium PCr and ATP fell to 80% and 93%, respectively, during the first 30 rnin of hypoperfusion, and then PCr recovered to 8770 and ATP fell to 83% by the end of 240 rnin of hyperperfusion. Over the same time periods in the endocardium, PCr fell to 53% and recovered to 85% whilst ATP fell to 77% and decreased further to 68% by the end of hypoperfusion. The level of ADP was significantly increased at 30 rnin but had recovered to baseline values by 240 rnin of hypoperfusion. The magnitude of the initial fall in PCr, and its subsequent recovery could not be accounted for by changes in blood flow but, the rate of the recovery of PCr was significantly correlated with the level of blood flow116. The effects of no-flow ischaemia followed by low-flow ischaemia has been compared to the effects of low-flow ischaemia in the isolated rat heart using 31PN M R . The period of no-flow ischaemia prevented the onset of contracture and was associated with higher PCr and ATP levels and an increased pHi during the period of low-flow ischaemia117. In a study of the effects of intermittent ischaemia on the heart, 31PN M R has been used to measure pHi and phosphorous metabolites. After a period of intermittent ischaemia, hearts developed pressure comparable to continuous perfused hearts, the concentration of ATP fell after the first period of ischaemia but, remained stable at the end of subsequent reperfusions. Intermittent ischaemia also decreased cardiac glycogen, increased lactate efflux from the heart, decreased the phosphorylation potential and induced cellular shrinkage. Administration of the adenosine receptor blocker 8-Ph theophylline during intermittent ischaemia depressed the developed pressure, attenuated the decrease in phosphorylation potential, abolished cellular shrinkage, reduced lactate efflux and blunted the decrease in ADP"*. In an investigation of the mechanism of improvement of cardiac tolerance to ischaemia by coenzyme Q pre-treatment 3'P N M R has been used to determine ATP and PCr levels. Treated hearts showed higher myocardial coenzyme Q levels, improved developed pressure at the end of reperfusion and preserved preischaemic myocardial aerobic efficiency during reperfusion. Treated hearts also showed higher ATP and PCr levels before ischaemia and after reperfusion showing a protection of creatine kinase from oxidative inactivation during reperfusion' ''.The effects of acetylsalicylic acid (ASA) on the contractility and metabolism of the ischaemic reperfused heart has used 31P N M R to measure phosphorus metabolism. Langendorff perfused rabbit hearts were subjected to 15 rnin of low-flow ischaemia, or 15 or 30 rnin of zero-flow ischaemia followed by 65 rnin of reperfusion. When ASA was infused for the entire period of the experiment there was a significant reduction in the decline of ATP and pHi, and the rise in Pi and fall in PCr was also reduced. ASA had some protective effect when administered during reperfusion only'*'. 3 1 PN M R has been used in a study

446

Nuclear Magnetic Resonance

of the influence of L-carnitine, acetyl-L-carnitine and propionyl-L-carnitine on the energy metabolism of the Langendorff rat heart subjected to 20 min of ischaemia. In control hearts ischaemia resulted in a decrease in PCr and a rise in Pi followed by an eventual decrease in ATP. A partial recovery of PCr and ATP was observed following reperfusion. In the presence of L-carnitine there was an improved recovery of the PCr/Pi ratio. Acetyl-L-carnitine gave a further enhancement of the early recovery of PCr/Pi but there was a faster decrease of this ratio in the late perfusion period. The inclusion of propionyl-L-carnitine resulted in a stabilisation of the PCr/Pi ratio during the reperfusion period. Measurements of pHi indicated that L-carnitine and its derivatives offer protection against acidosis'21. Onedimensional 'H CSI has been used to assess the transmural triglyceride content of the canine heart during ischaemia and reperfusion. An infusion of Liposan during reperfusion increased the triacylglycerol content in the subepicardium area-at-risk but did not cause an increase in the area-at-risk'22. The effects of MnC12 and the contrast agent manganese dipyridoxyl diphosphate (MnDPDP) on the isolated perfused rat heart have been studied with 31P NMR to investigate the cardiovascular effects that are reported to arise from the partial release of Mn2+ from MnDPDP. Cardiac function was monitored from the heart rate, left ventricular pressure and coronary flow and the influx of Mn2+ into the heart was monitored by the line broadening effects in the 31P spectra. Compared with MnDPDP, MnCI2 induced more pronounced line broadening as well as coronary vasodilatation. Treatment with Ca*'-channel blockers or EDTA inhibited MnCI2 influx and reduced the effects of MnDPDP'23. The effects of cromakalin (an ATP-sensitive potassium channel opener) and glibenclamide (an ATP-sensitive potassium channel blocker) on the myocardial function, pH, and high energy phosphates of rat hearts subjected to 25 min ischaemia and 45 min of reperfusion have been investigated with 31P NMR. Treatment with cromakalin attenuated the loss of ATP, delayed the time to ischaemic contracture and improved recovery of function compared to controls. Glibenclamide pre-treatment caused a more rapid depletion of ATP, attenuated end-ischaemia acidosis and decreased the time to ischaemic contracture. However, treatment with glibenclamide also improved functional recovery on r e p e r f ~ s i o n ' ~The ~ . role of the Na'-channel in the ischaemic accumulation of Na+i has been investigated with 31PNMR. Isolated rat hearts, paced at 5 Hz, were perfused with 200 pM lidocaine 5 min prior to ischaemia. Lidocaine did not affect the decline of PCr during ischaemia but significantly attenuated the initial decrease of pHi, attenuated the initial decline of ATP and delayed the time to contracture. At the end of ischaemia, pH, and ATP were not significantly different compared to control values but, developed diastolic pressure and enddiastolic pressure, PCr and ATP levels recovered better in lidocaine treated hearts'25. 31PNMR has been used to investigate the affects of verapamil pretreatment against ischaemia-reperfusion injury in the isolated rat myocardium. Pre-treatment with verapamil resulted in the preservation of PCr (20% remaining detectable), a higher recovery of PCr upon reflow, a slower decrease of ATP (53% remaining at the end ischaemia compared to 34% in controls), an attenuation of

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

447

acidosis during ischaemia and prevented the development of very acidic areas of the myocardium during reperfusion' 26. In a study of the effects of 5-(N,N-dimethyl)amiloride (DMA) in isolated perfused rabbit hearts subjected to ischaemia and reperfusion 31PNMR has been used to measure pHi, ATP and PCr. Treatment with DMA resulted in a decreased pHi at the end of ischaemia and caused no effect on the decline or resynthesis of high energy phosphates. However, treatment with DMA reduced the elevation of left ventricular end-diastolic pressure during and after ischaemia and improved the post ischaemic recovery of developed pressure'27. 31PNMR has been used in an investigation of the effects of DMA, with or without bicarbonate, on the recovery of the rat heart following ischaemia and reperfusion. Hearts were subjected to 28 rnin of global ischaemia and DMA was administered before ischaemia, during reperfusion or both. DMA had no effect on pHi during ischaemia. The recovery of pHi during reperfusion was slower in the absence of bicarbonate. All regimes of DMA treatment improved cardiac function following reperfusion and slowed the recovery of pHi during reperfusion12*. The effects of inhibition of the Na+-H+ exchanger, by treatment with ethylisopropylamiloride (EIPA), prior to and during ischaemia in the perfused rat heart has been investigated with 31PNMR. Hearts that were exposed to EIPA for 40 rnin or 10 min before ischaemia had a marked reduction in ischaemic injury. Prior exposure to EIPA for 40 rnin resulted in a higher pHi during ischaemia, a slower recovery of pHi upon reperfusion and a rapid depletion of ATP during i ~ c h a e m i a ' The ~ ~ . effects of EIPA have been investigated in the new-born rabbit myocardium using NMR to determine pHi, Na+i, Ca2+i, and high energy phosphates. Hearts were subjected to 40 rnin of global ischaemia followed by 40 rnin of reperfusion with or without EIPA. Treatment with EIPA resulted in a higher pHi, diminished increases in Na+i and Ca2+,, and preserved ATP during ischaemia. Furthermore, EIPA pre-treatment preserved ATP, decreased Pi and improved LVDP during reperf~sion'~'. The role of carbonic anhydrase in cardiac pH regulation has been studied by 3' P NMR in the Langendorff-perfused ferret heart. Treatment with carbonic anhydrase inhibitors caused a significant decrease in the rate of change of pHi, and the recovery of contractile function, following a period of ischaemia suggesting a role for carbonic anhydrase in the recovery of pHi during reperfusion' 3'. The effects of the pH of cardioplegic solutions on post-ischaemic cardiac function in neonatal hypothermic circulatory arrest and reperfusion has been investigated with 31PNMR in the pig heart. Recoveries of peak elastance, stroke work and diastolic stiffness were superior in the group perfused with a basic (pH 7.8) cardioplegic solution compared to hearts perfused with acidic (PH 6.8) cardioplegic solution or the group not perfused with a cardioplegic solution. indexes of ischaemic ATP use and PCr depletion were not different between the groups. However, acidic cardioplegia resulted in a lower end-ischaemia pHi compared to basic cardioplegia; basic cardioplegia also resulted in a reduced rate of re-alkalinisation during reperf~sion'~'.3'P NMR has been used to assess the

448

Nucleur Magnetic Resonunce

energy metabolism of cold-preserved hearts during reperfusion in an assessment of the alteration in mitochondria1 respiration during cold storage'33. The role of the level of ADP-bound Mg2' (MgADP) in the development of diastolic dysfunction in the intact beating rat heart has been investigated with 31P NMR. The concentration of MgADP was manipulated by the application of a low dose of iodoacetamide to selectively inhibit the creatine kinase reaction. There was a three-fold increase in left ventricular end diastolic pressure (LVEDP) and a 38% increase in the time constant of pressure decay in the heart. The increase in LVEDP was closely related to the increase in the concentration of free MgADP'34. The possibility that isoproterenol-induced myocardial injury is mediated through the depletion of the concentration of Mg2+, has been investigated with 31PNMR. Isolated rabbit hearts were perfused at constant flow and subjected to 10 pM isoproterenol for 30 minutes. During isoproterenol infusion ATP, PCr and pH, fell and Pi increased. After isoproterenol treatment PCr recovered but, ATP, pH, and Pi recovered only partially and there was a rise in end-diastolic pressure and perfusion pressure. However, there was only a small, insignificant, rise in Mg2+i which recovered 45 minutes after the isoproterenol infusion'35. The role of Pi in the down-regulation of myocardial contractile force has been investigated with 31PNMR. Forty cycles of hypoperfusion were used to achieve a time resolution of 0.512 s in 31Pspectra for the comparison of dynamic changes in Pi and contractile force. During the first ten seconds of hypoperfusion Pi increased at a rate faster than the decrease in LVDP; Pi and LVDP then changed at the same rate during the remainder of the hypoperfusion. There was no change in pHi and ADP levels did not change in advance of changes in LVDP. The results indicated that Pi plays an important role in the down-regulation of myocardial contractile force at the onset of i ~ c h a e m i a ' The ~ ~ . effects of nitric oxide (NO) on cardiac contractile function and energy generation measured by 31P NMR has been studied in isolated perfused guinea pig hearts. At low concentrations NO increased coronary flow whereas, at high concentrations coronary flow remained elevated and left ventricular developed pressure (LVDP) was reduced. Changes in LVDP and coronary flow occurred within 2 to 5 s after the start o r cessation of NO infusions. Contractile dysfunction was correlated to an increased release of adenosine, a 78% decrease in PCr, a 25% decrease in ATP and a decrease in the free energy of the hydrolysis of ATP. Furthermore, there was a significant decrease in oxygen consumption and a tenfold increase in lactate formation in parallel to these changes137. The effects of glutamate and aspartate on the metabolic pathways feeding the citric acid cycle of the isolated rat heart during cardioplegic arrest has been studied by 13CNMR. Glutamate and aspartate had a minor effect when added to potassium cardioplegic solutions containing physiological metabolite^'^^. The metabolism of [3-13C]pyruvateand [3-'3C]lactate in the left ventricle of the canine myocardium, under basal and elevated work loads, has been investigated with I3C NMR. Highly variable 13C-enrichments of glutamate, alanine, aspartate and citrate were observed under low, intermediate and high rate pressure products. At low work loads [3-13C]pyruvateand [3-I3C]lactate were oxidised and incorporated

12: Nucleur Magnetic Resonance Spectroscopy of Living Systems

449

into glutamate, though, this did not happen in all cases. However, an infusion of dichloroacetic acid usually enhanced the level of [4-'3C]glutamate139. In a study of the role of myocardial glycogen in cardiac protection during ischaemia 31P NMR has been used to measure pH, phosphorylated glycolytic intermediates and high energy phosphates. The increase in myocardial glycogen caused by fasting protected hearts from the affects of ischaemia in contrast to the effects of increased myocardial glycogen produced by insulin treatment prior to i~chaemia'~'. The effects of adenosine on glucose transport in the perfused rat heart has been studied using 19F NM R and the glucose analogues 2-fluoro-2-deoxy-~-glucose and 3-fluoro-3-deoxy-~-glucose.One-dimensional magnetisation transfer and two-dimensional exchange spectroscopy were used to demonstrate inhibition of transport by adenosine in all cases in~estigated'~'. The rate of 2-deoxy-glucose uptake in stunned myocardium has been measured using 31PNMR to determine the time-course of the 2-deoxy-glucose phosphate peak. The results indicated that there was an augmented glucose uptake in stunned myocardium which is maintained by the glucose transporter and the rate of transport was almost equal to that which can be caused by insulin'42. An assessment of the use of multiple-quantum-filtered 23Na NMR, without the use of chemical shift reagents, for monitoring Na+i content in the isolated perfused rat heart has been carried out. Measurements of changes in Na+i in triple-quantum-filtered (TQF) and single-quantum spectra during no-flow ischaemia indicated that both methods observe the same Na+i population. The effects of ischaemia on T2 relaxation resulted in a 6% over estimation of Na+i in T Q F spectra. It was concluded that Na+i could be reliably measured in TQF spectra when the contribution from extracellular Na+ (Na+,) does not vary. However, when perfusion pressure was completely reduced double-quantumfiltered 23Na NMR, compared to the T Q F method, provided a better estimate of Na+,143.In an investigation of Na+i levels in perfused rat hearts during St. Thomas cardioplegic arrest T Q F 23Na NMR has been used without the need for chemical shift reagents to distinguish intracellular and extracellular signals. The contribution of Na+, to the TQF 23Na signal was determined in wash-out experiments and then used to determine changes in Na+i during ischaemia and reperfusion. The estimated Na+i level was 222% of control values after cardioplegic arrest and reperfusion compared to an Na+, level of 340% of control values in stop-flow ischaemia14. An assessment of the value of 31PNMR in the detection of cardiac allogenic rejection has been performed. The ratio of PCr/ATP did not indicate the extent of rejection and the signal to noise ratio of the PCr peak was only an indicator in the late, severe stage of Changes in the relationship between myocardial high energy phosphates and oxygen consumption that occur with development from new born to mature have been investigated with 31PNMR. Increases in myocardial oxygen consumption (MV&) were induced with adrenaline infusions in new-born (0-32 hour-old) and mature (30-32 day-old) sheep. Western blot analyses, for the adenine nucleotide translocator (ANT) and the psubunit of FI-ATPase, and Northern blot analyses, to assess steady state RNA

450

Nucleur Magnetic Resonance

transcripts, were performed. Kinetic analyses of 3 1 P data revealed that the relationship between ADP and MVo2 in the new-born myocardium conformed to a Michaelis-Menten model but, data from mature myocardium did not conform to first- or second-order kinetic control through the ANT. The results indicated that the respiratory control pattern in the new-born myocardium is via kinetic regulation through ANT and that maturational decreases in control through ANT are paralleled by increases in ANT content. Furthermore, the regulation of these changes in ANT may be related to increases in steady-state transcript levels of its gene'46. 31PNMR has been used in an investigation of the effects of volume loading on Langendorff guinea pig hearts. Increased wall tension caused a rise in the concentration of Ca2+i, Na+i and H+, elevated the ratio of left ventricular developed pressurehransient Ca2', and caused a reduction in ATP and PCr with an increase of Pi. Furthermore, experiments with 31PNMR saturation transfer showed that the creatine phosphokinase reaction was shifted in the direction of increased ATP ~ y n t h e s i s ' ~ ~ . Kidney - The use of 'H NMR for the evaluation of kidneys after cold ischaemia and transplantation has been assessed in an isolated perfused pig kidney model. Perfusate flow, glomerilar filtration rate, fractional reabsorption of Na+, and glucose excretion were worse in kidneys subjected to normothermic ischaemia, 24 hr cold storage and reperfusion compared to kidneys subjected to cold ischaemia and reperfusion or perfusion only. A higher amino acid secretion, and elevated levels of trimethylamine-N-oxide and lactate, were detected by H NMR in kidneys subjected to normothermic ischaemia, 24 hr cold storage and r e p e r f ~ s i o n ' ~The ~ . beneficial effects of trimetazidine on renal injury in the isolated perfused pig kidney exposed to prolonged ischaemia has been investigated with biochemical methods and 'H NMR'49. 3'P NMR has been used to measure the PME/Pi ratio in an assessment of pig kidneys following various periods of warm and cold ischaemia. It was shown that NMR was able to assess the extent of warm ischaemia that a kidney was subjected to but, this assessment was confused if kidneys were exposed to periods of cold i~chaemia'~'.

4.4

Liver - 31PNMR has been used to examine the isolated rat liver perfused with normothermic, acidic (pH 6.5), bicarbonate-free perfusate. In the presence of 50 nM valinomycn or 10 pM N,N'-dicyclohexylcarbodiimide,normothermic perfusion resulted in the appearance of a second Pi peak which was assigned to mitochondria1 phosphate. The level of this peak increased linearly with cellular ATP depletion"'. The effects of the loop diuretics furosemide and bumetanide on ischaemic liver injury has been investigated with 23Na NMR to measure Na+i concentrations. The data suggested that a mechanism for the accumulation of Na+i during ischaemia might be the activity of the Na'-K+-2Cl- co-transporter which can be blocked by treatment with furosemide or b ~ m e t a n i d e ' ~The ~. impact of the presence of spin-traps on the outcome of warm ischaemia and reperfusion has been investigated with 31PNMR. Isolated livers, subjected to 1 hour of warm ischaemia and reperfusion, were exposed to 5,5,-dimethyI-l -pyrro-

4.5

12: Nucleur Mugnetic Resonance Spectroscopy of Living Systems

45 1

line-N-oxide (DMPO) or 5-(diethoxiphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO). After reperfusion pH, had recovered to its initial value in both treatment regimes and ATP had recovered to control values in DEPMPO-treated livers but, ATP recovered to only 37% of control values in DMPO-treated livers. This difference was attributed to the production of deleterious catabolites by DMPO. There was no apparent affect of free-radical scavenging by DMPO or DEPMP0153. The relationship between the phosphoenergetic state and gluconeogenesis in the liver following ischaemic damage has been investigated with 13C and 31P NMR in vivo. ATP levels were depleted to 20% by 10 rnin of ischaemia and this level was maintained through a 30 rnin period of ischaemia. The level of ATP was partially restored during reperfusion but less so after 30 rnin ischaemia compared to that after 10 min ischaemia. After 60 rnin reperfusion with [3-13C]alanine the ATP level had a negative correlation with level of [3-13C]alanine and a positive correlation with 13C-measurements of glucose and glycogen'54. The effects of alanine infusions with or without glucagon on hepatic metabolic function has been followed with 31PNMR. Changes in PME, Pi and P-NTP resonances were at their highest 40 rnin post-infusion and were associated with g l ~ c o n e o g e n e s i s ~ ~ ~ . 31PNMR has been used in a study of the hepatotoxicity of halothane in the rat. 'H NMR imaging revealed an area of oedema proximal to the hepatic portal vein and 31PNMR of the liver revealed a decrease in ATP/Pi and an increase in PME/PDE as anaesthesia progressed. These changes were accompanied by a decrease in the pHi and an increase in the free Mg2+ic ~ n c e n t r a t i o n l ~ ~ . Muscle - The difference in concentration of phosphorous metabolites in muscles with different fibre composition has been studied with localised 31P NMR in the soleus and gastrocnemius muscles of the rat. The gastrocnemius muscle had a higher concentration of PCr and ATP, a lower concentration of Pi and a higher pHi compared to the soleus muscle157. The quantitative bioenergetics of phosphorous metabolite distribution in skeletal muscle has been investigated using 31P NMR and creatine analogue^'^'. The ATP cost of isometric contractions has been measured in the arterially perfused cat biceps and soleus muscles under normocapnia and hypercapnia conditions. Hypocapnia reduced extracellular pH (pH,) from 7.4 to 6.7 and pHi from 7.1 to 6.5 (soleus) or 6.6 (biceps) but had no effect on the PCr/ATP ratio at rest. Acidosis was shown to have no effect on the ATP cost of muscle c ~ n t r a c t i o n ' ~ ~ . The effects of increased free fatty acids (FFA) on intramuscular glucose metabolism in the awake rat have been studied with 31Pand 13CNMR following the infusion of glycerol or Liposyn. An increase in glucose-6-phosphate was detected by "P NMR under both infusion conditions. The incorporation of [l-13C]glucoseinto [l-'3C]glycogen in the rat hind limb was used as a measure of glycogen synthesis whereas, the production of [3-' 3C]lactate and [3-13C]alanine was used as a measure of glycolytic flux. The relative flux of pyruvate compared to FFA and ketone entering the tricarboxylic acid (TCA) cycle was assessed by [4-13C]glutamate/[3-13C]lactate steady state isotopic enrichment measurements. The results suggested that the increased levels of plasma FFA inhibited insulin-

4.6

452

Nuclear Magnetic Resonance

stimulated muscle glucose metabolism through inhibition of glycolysis'60, 3 1P NMR has been used to investigate the pH, and high energy phosphates of white muscle in the fish tilapia (Oreochromis mossambicus) during exposure to environmental acidosis, hypoxia or both. Whilst acidification had no effect on pHi or high energy phosphates, and hypoxia caused moderate changes, the exposure to both conditions resulted in 50% mortality, retarded recovery of pHi and a larger decrease in PCrI6'. The effects of the electrical stimulation regime on the energy metabolism in the tail muscle of Palaemon serratus has been investigated with 3'P NMR. Changes in AMP, IMP, phosphomonoesters, adenylate energy charge and the ATP/ADP ratio were measured during electrical stimulation at 1, 2 or 4 Hz or, during the escape response16*. The energy metabolism of the abdominal muscles of the crayfish (Procambarus clarkii) has been investigated following electrical stimulation of the antennae. 31PNMR detected a fall in phosphoarginine to 60% of control values and a rise in Pi to 260%of control values following the first stimulatiqn. After repetitive tail flips, ATP and pHi decreased. Repeated measurements indicated a change in response with h a b i t ~ a t i o n ' ~ ~ . 'H NMR, in combination with ultrasound examination, has been used to measure intra-muscular fat contents of pig muscle and the results were compared to biopsy samples. Intra-muscular fat content was measured in pigs grown from 20 to 100 kg but, measurements made with ultrasound and 'H NMR were not sufficiently reliablelU.

4.7 Tumour - The effects of pentobarbitone on the core body temperature, tumour temperature and tumour pH have been measured in anaesthetised and restrained mice bearing the RIF-1 tumour. There was a maximum temperature difference between anaesthetised and restrained mice at about 2 hours after the onset of anaesthesia. Furthermore, in anaesthetised mice intracellular pH fell by 0.32 units whilst extracellular pH (measured by fibre-optic probe) fell 0.28 units'65. 31PNMR has been used in an evaluation of the combination of N-(phosphonacety1)-Laspartate, 6-methylmercaptopurine riboside (MMPR) and 6-aminonicotinamide with adriamycin or radiation therapy'66. The effects of hydralazine and hyperthermia on the metabolism of Ehrlich carcinoma have been investigated with 31P NMR'67. I9F NMR has been used to examine the effects of 5benzylacyclouridine (BAU), a uridine phosphorylase inhibitor, on the metabolism of 5-fluorouracil (5FU) in mouse colon 38 tumours. The results indicated that there was increased activation of 5FU to fluoronucleotides and fluorouridine, and a decrease in the catabolic products a-fluoro-P-ureidopropionic acid and afluoro-P-alanine. Furthermore, treatment with BAU did not appear to affect metabolism in normal tissue and augmented the antineoplastic effects of 5FU treatment'68. The effects of single dose irradiation on the 31Pmetabolites of RIF1 tumours have been investigated. Changes in the pH,, ATP and Pi were observed post-treatment and there was a correlation (r = - 0.56) between the reduction in ATP at 48 hours after irradiation and the extent of tumour ~ h r i n k a g e ' ~ ~ . The lipid composition of GL6 gliomas in rats, compared to contralateral hemispheres, have been investigated with 'H, I3C, 31Pand 14N NMR. The results

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

453

indicate that sterol metabolism and the sphingolipidglycerolipids ratio are significantly modified in the presence of the t u m ~ u r ' ~ The ~ . detection of "B in a mouse melanoma by NMR in vivo has been described171and the measurement of pharmacokinetics of boron-containing compounds in the rat has been performed'72. The feasibility of the use of 2-fluoro-2-deoxy-~-glucose(FDG) in combination with 19F NMR to detect tumours in vivo has been investigated. In heart and tumour tissue 19F NMR signals remained two days after administration of FDG due to its conversion to 2-fluoro-2-deoxy-~-mannose; this signal was detected by I9F NMR and I9F chemical shift imaging (CSI) in ~ivo''~. The techniques of 3 1 Pand 23Na NMR in vivo have been used to assess pancreatic cancer diagnosis and its treatment in perfused MIA PaCa-2 human pancreatic cells, implanted pancreatic tumours and tumours induced by the direct application of 7,12-dimethyl benzathracene. The 31Pspectra of tumours were similar to intact organs except for the levels of PME which were dependent on the tumour proliferation rate and environmental conditions. There were no differences between the concentration of Na in solid tumours or normal pancreas. Some differences were found between tumours and pancreas in H spectra of perchloric acid extracts'74. A study of the use of 31PNMR for the detection of the phosphonium analogue of choline and its metabolites has been performed in C3H/He mice bearing a mammary carcinoma and fed a choline-free diet supplemented with the analogue. The metabolites of this analogue, including the phosphonium analogues of phosphatidylcholine, phosphocholine, glycerophosphocholine and betaine, were detected after 2-3 weeks of feeding. The clearance of the metabolites were measured after the mice were fed a choline-containing diet; significant decreases in the analogues of betaine and phosphatidylcholine were seen by day four and an increase in authentic phosphocholine occurred over the same period175.

4.8 Vascular - The effects of acetate and octanoate on the metabolism of glycogen in the contracting pig carotid artery has been studied with 13C NMR. Arteries were allowed to synthesise [l-13C]glycogenbefore exposure to 5 mM [2-13C]glucosein combination with 2 mM sodium acetate or 0.5 mM octanoic acid during a 3 hour contraction. The inclusion of sodium acetate or octanoic acid increased glycogen utilisation by 74% and 71%, re~pectively'~~. The effects of glycogen content on glycogenolysis in pig artery segments have been studied with I3C NMR. After a period of labelling to produce different amounts of [l-'3C]glycosy1 units of glycogen artery segments were isometrically contracted in the presence of [2-'3C]glucose. Tissue glycogen content decreased exponentially during a 4.5 h period of isometric contraction. Glycogen utilisation and lactate production from glycogen varied linearly with pre-contraction glycogen concentration. Neither glucose utilisation nor lactate production from glucose varied with the pre-contraction glycogen concentration. It was concluded that glycolysis and glycogenolysis behave independently in vascular smooth muscle'77. 4.9 Whole Animal - The effects of the exposure to copper on the energy metabolism of the common carp (Cyprinus carpio) have been studied by 31P

Nuclear Magnetic Resonance

454

NMR during hypoxia and subsequent recovery. Chronic exposure to copper resulted in an incomplete recovery of PCr, Pi and pHi following hypoxia. After exposure to copper for one week there was a greater recovery of PCr and Pi following hypoxia. However, pHi was decreased following exposure to copper for one week even before exposure to h y p ~ x i a 'The ~ ~ .effects of exposure to hypoxia, sodium azide or pentachlorophenol on the activity of arginine kinase has been studied in red abalone (Haliotis rufescens) with 31PNMR saturation transfer. All treatments caused an increase in the pseudo-first order rate constant for ATP formation and the increases were inversely correlated to the decline in ATP'79. 3'P and 'H MR have been used to study the response of Arenicola marina to limited oxygen supplies. The 'H signal from oxygenated myoglobin (Mb02) at - 2.6 ppm was detected and used to estimate tissue oxygenation whilst 31P signals from phosphotaurocyamide were used to measure the metabolic response. It was found that the level of phosphotaurocyamide remained constant until the Mb02 saturation fell below 33Y0'~'. The effects of dietary sugar on pyruvate cycling during gluconeogenesis in Manduca sexta L. has been investigated using 13C NMR to follow the fate of [2-I3C]pyruvate. The extent of pyruvate recycling was approximately three-fold lower and the level of gluconeogenesis was higher in insects maintained on a diet lacking sucrose 18'. I9F NMR has been used to measure the effects of vasodilators on the signals of a perfhorocarbon (FC-43) in vivo. Treatment with nitro-glycerine, a venodilator which acts on venous smooth muscle, increased the signals from FC-43 whereas, the arteriola dilator hydralazine, which acts upon arteriol smooth muscle, decreased the signal intensity from FC-43182.

5

Clinical Studies

5.1 Reviews - A review of the development and applications of in vivo clinical NMR has been produced with many reference^.'^^ The development of methods for improved characterisation of bone marrow has been reviewed'84. A review of in vivo methods for the study of the regulation of muscle glycogenolysis and glycolysis during intense exercise has been produced with 56 references' 85. The recent advances in the understanding of carbohydrate metabolism which have been made possible by the application of NMR have been reviewed with 73 references'86. A review on the regulation of non-oxidative glucose metabolism in skeletal muscle has been produced with 21 reference^'^^. The basic principles of human in vivo NMR, practical information about its use in metabolic investigations and the metabolic parameters which may be accessed has been reviewed with 25 referencesI8*. A review of the measurement of in vivo high energy phosphate metabolism in the human heart has been produced with many references 89.

'

5.2 Brain - Patients with a minimal or mild manifestation of acquired immunodeficiency syndrome dementia complex (ADC) have been examined with H NMR.

'

12: Nuclear Mugnetic Resonance Spectroscopy of Living Systems

455

The CholCr ratio detected in the frontal lobe was found to be significantly higher in ADC patients compared to age-matched control subjects'90. 'H NMR has also been used to investigate metabolite changes in ADC in a separate study. Patients with HIV infection, but no indications of ADC, had a significant increase in the ratio of myo-inositol/Cr in white matter of the frontal lobe. This increased ratio was not observed in HIV-infected patients with ADC but, there was a reduced ratio of NAA/Cr in gray matter of the cortex'". Localised 'H has been used in a study of motor neurone disease to obtain absolute quantities of the metabolites NAA, Cho and Cr from a 20 mm3 volume of the motor cortex and cerebellum. The study examined patients with amyotrophic lateral sclerosis (ALS), patients with suspected ALS and normal volunteers. It was found that patients with upper and lower motor neurone signs had a small, significant decrease of NAA in the motor cortexi9*.Multiple sclerosis has been investigated with ' H NMR to detect metabolite levels, positron emission tomography to assess glucose metabolism and magnetic resonance imaging to detect brain lesions. A decrease in the NAA concentration in apparently normal and lesioned white matter was observed in all patients compared to controls whereas, glucose metabolism was increased in lesions'93. 'H NMR has been used to examine arachnoid brain cysts in two patients with epilepsy. Increased levels of the excitatory amino acids glutamate and aspartate were detected in the cystic fluid whilst there was only a moderate increase of glutamate in the epileptogenic brain tissue adjacent to the cyst. In non-epileptic tissue no increment of excitatory amino acids was observedi94. In a study of four women with a unique combination of central nervous system white matter disease and primary ovarian failure 'H CSI has been used to examine brain metabolites. There was a reduced amount of Cho in the affected white matter of all patients and a reduction in NAA in the unaffected frontal white matter of two patientsig5.An analysis of the metabolites of the gray matter (temporal lobe) and the white matter (frontal region) has been able to distinguish between normal ageing and Alzheimer's disease patients. A significant decrease in the 'H NMR-detected level of NAA in the white and gray matter and an increase in myo-inositol in the gray matter was observed in Alzheimer's patients. White matter myo-inositol was significantly associated with severity and duration of dementia and no association with age was detected'96. 31PNMR has been used to examine the left and right perietal cortex of 18 patients with Alzheimer's disease. In stage 2 patients (Cummings' criteria), 80% of which had right hemispheric syndrome, there was a significant decrease in PME and PDE in the right perietal cortex, and no change in the left perietal cortex, compared with stage 1 patients. The reduction in PME correlated with the severity of cognitive d y s f ~ n c t i o n ' ~ ~ . The metabolites of the putamen in untreated and levadopa-treated Parkinson's disease patients have been investigated with ' H NMR. There was a reduction in the ratio of NAA/Cho in the putamen contralateral to the most affected side in untreated patients but not in levadopa-treated patients or age-matched controls. There were no changes in the ratios of NAA/Cr or Cho/Cri9*. 'HNMR has been used to examine the ratio of NAA/Cr, NAA/Cho and Cho/ Cr, and used to identify the presence of raised levels of lactate, in children with central nervous system disease. Patients with an identifiable lactate peak were

456

Nuclear Magnetic Resonance

more likely to have suffered cardiac arrest, were more often hyperglycaemic, had a lower Glasgow Coma Scale score and a worse prognosis compared to patients without a lactate peak. Furthermore, patients with an identifiable lactate peak were more likely to have abnormal metabolite ratios compared to controls or patients without a lactate peak'99. ' H NMR has been used to measure the metabolites in the brains of patients with severe stenosis or obstruction of the unilateral internal carotid artery. The levels of NAA and Cr were reduced in the ischaemic side of the brain, though, the level of Cho remained similar in both sides2''. The detection of y and p resonances of glutamate and glutamine in patients with raised blood ammonia and normal volunteers has been investigated with ' H NMR at 0.5 T compared to 1.5 T. The detection of NAA at 0.5 T compared to 1.5 T was disproportionally small whereas, the detection of glutamate and glutamine at 0.5 T compared to 1.5 T was improved by the better magnetic field homogeneity and the reduced effects of J-coupling of glutamate and glutamine resonances2". In a study of medication-free outpatients with major depression ' H NMR has been used to measure the metabolites of the basal ganglia. Depressed subjects had a lower ratio of Cho/Cr compared to control subjects and this difference was more pronounced in those subjects which subsequently responded to fluoxetine treatment202.The brain metabolites of 19 patients with social phobia have been investigated with ' H NMR. Compared with controls, social phobics had higher Cho/Cr, mI/Cr and mI/NAA and lower NAA/Cho in cortical grey matter. Higher mI/Cr and mI/NAA was also observed in subcortical gray matter. The inclusion of age and sex in statistical modelling strengthened differences compared to controls but eliminated any differences observed with symptom severity. No changes were observed with clonazepam treatment203. 'H NMR has been used to determine the levels of y-aminobutyric acid (GABA) in the brains of patients with intractable epilepsy following a single oral dose of vigabatrin. Brain levels of GABA increased from 0.95 to 1.34 mmol/kg within 2 hours of treatment and increased further to 1.44 mmol/kg on the following day. Levels of GABA declined to 1.16 and 1.03 mmol/kg by days 5 and 8, re~pectively~'~. 3 ' P NMR has been used to study the effects of anorexia nervosa on the phosphorous metabolites of the brain. Before treatment patients had raised PDE levels compared to normal volunteers. Lower levels of PDE were also associated with malnutrition which was reflected in endocrinological abnormalities. The differences in the 31Pdata from anorexia nervosa patients may reflect abnormalities in membrane phospholipid metabolism205. The ratio of GABA to Cr in the occipital lobe of normal volunteers has been performed with spatially localised, double-quantum filtered ' H NMRZo6.The temporal evolution of the relationship between perfusion and oxidative metabolism in human primary visual cortex during prolonged visual stimulation has been investigated. Various 'H NMR techniques were used to measure cerebral energy metabolism, oxygen utilisation and flow parameters207. 31PNMR saturation transfer has been used to examine the effects of visual stimulation on the turnover of PCr in the visual cortex. Creatine kinase kinetics were evaluated by measuring the apparent unidirectional rate constant (K,) in the forward direction

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

457

(from PCr to ATP). There was a 34% increase in Kt in the visual cortex during stimulation without significant changes in the steady-state concentration of high energy phosphate compounds208. 5.3 Liver - Proton-decoupled, nuclear Overhauser effect enhanced, phospholipid saturated 31Pspectra localised to specific regions of the normal liver have been produced by using 3D CSI. Quantitative 31Pspectra were obtained which contained two major peaks in the PME region, three peaks in the PDE region and a diphosphodiester peak209.The effects of ethanol and fructose on the liver metabolism has been investigated with 3'P NMR one-dimensional CSI. There were some differences between the 31P spectra of liver following ethanol and following fructose administrations. Following a fructose load there were no significant differences in the 31Pspectra of the liver with or without co-administration of ethanol2". 5.4 Muscle - The effects of single nightly injections of growth hormonereleasing hormone (GHRH) in healthy elderly men has been studied with 31P NMR. The administration of GHRH appeared to increase muscle strength and altered the relationship between muscle strength and muscle bioenergetics in a manner consistent with a reduced need for anaerobic metabolism during exercise2'I . The kinetics of PCr in human muscle during exercise have been studied with 31P NMR. Experiments with or without preceding exercise showed that there were no effects on the rate of adjustment of oxidative mechanisms and the results confirmed previous findings2I2. One-dimensional image-guided, localised 31P NMR has been used to study the kinetics of PCr in the medial gastrocnemius muscle of healthy volunteers. After 9 s of maximal rate exercise PCr was decreased to 61.4 f 2.4 YO,pH, was 7.4 & 0.03, PCr recovered with a rate constant (KPCr)of 1.87 f 0.15 min and a V,,, of 67.2 f 6.0 mM min-'. After 30 s of maximal exercise PCr was decreased to 92.0 f 1.2 YO,pHi was 6.45 f 0.07. The intracellular acidosis was found to separate the direct relationship between Kwr and Vm,, but, did not affect the initial PCr resynthesis rate2I3. 3'P NMR has been used in a quantitative investigation of mitochondria1 function in human skeletal muscle. High time resolution measurements were made of PCr, ATP and Pi in human forearm flexor muscle during involuntary twitch contraction at eight different frequencies. Mitochondria1 and glycolytic ATP synthesis fluxes, and the cytosolic free energy of ATP hydrolysis were calculated at incremental steadystates of energy balance2I4.The effects of high levels of sympathetic tone, evoked by lower body negative pressure (LBNP), on pH and PCr in muscle during graded exercise has been investigated with "P NMR. Exposure to LBNP caused lower levels of pH and PCr recovery after exercise though, mean arterial pressure was not affected during exercise. However, mean blood velocity was reduced at rest, during exercise and during recovery, and venous haemoglobin saturation was lower during exercise in subjects exposed to LBNP2I5. The measurement of muscle glucose by 13CNMR in vivo has been tested in five normal volunteers during euglycaemic [ 1-13C]glucoseinfusion. The concentration

458

Nuclear Magnetic Resonance

of glucose detected with 13C NMR was calibrated with an external reference and compared to the plasma glucose concentration. The consistent higher glucose concentrations detected with 13C NMR were interpreted to indicate the contamination of [I -13C]glucosesignals with [ 1-'3C]glucose-6-phosphate signals and that this indicates that [ 1-I3C]glucose is 100% NMR visible216. The energy metabolism of the calf muscle in a patient with adenylosuccinate lyase deficiency and severe psychomotor retardation has been investigated with 31PNMR. Spectra showed that there was a reduced PCr/Pi ratio and a reduced amount of ATP in resting muscle compared to control values. After a period of exercise there was a reduced rate of recovery of PCr and lower ATP compared to control subjects217.3'P NMR has been used in an investigation of the effects of propionyl L-carnitine (PLC) administration on the bioenergetic defect caused by carnitine loss during dialysis in renal failure patients. Examination during rest, exercise and recovery revealed that there was no effect of PLC on the aerobic and anaerobic metabolism of the muscle and that the concentration of haemoglobin was the rate limiting factor. In those patients with haemoglobin concentrations ~ , muscle metabolism was improved2I8. above 10 g 10 ~ m - skeletal 5.5 Tumour - 3'P NMR has been performed on 24 patients with liver metastases and 20 normal volunteers. The PME/P-ATP ratio and the ratio of PDE/P-ATP of patients was increased and significantly different from that of controls. Analysis of the NMR data showed that the results could be summarised with a single numeric quantity of total entropy219. The simultaneous acquisition of 'H-decoupled 3 1 Pand 19F3D CSI spectra of the liver has been performed in a patient receiving 5-fluorouracil chemotherapy220. The effects of radiation therapy on ' H NMR-detected peak of lactate plus lipid from eight patients with a primary or metastatic brain tumour has been investigated. The ratio of the lactate plus lipid peak area to ' H NMR-detected total water peak area was found to be substantially reduced in radiosensitive cases221.The in vivo and in vitro 'H NMR spectra of glioblastomas have been reported along with spectra of contralateral brain tissue. The results suggest that cholesterol esters may be markers for glioblastomas222.

5.6 Adipose Tissue - I3C NMR has been used to investigate changes in the composition of adipose tissue in neonates and their mothers. Neonates had more saturated fat and less unsaturated fat compared to their mothers. An increase in the proportion of unsaturated fat, particularly polyunsaturated fat, was observed from birth to 6 weeks of age in full-term infants. Pre-term infants had relatively fewer unsaturated fatty acids compared to full-term infants223.

5.7 Skin - The effects of suberythema UVA radiation on the phosphorous metabolites of the skin in four healthy volunteers has been investigated with 31P NMR. An increase in PME and PDE was observed with a decrease in PCr and ATP. The results appeared to be similar to the effects observed from dexamethazone treatment224.

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

459

References

6 1

2 3 4 5 6 7 8 9 10 11

12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

Akber, S. F. Physiol. Chem. Phys. Med N M R 1996,28(4), 205-238. Si, Y. Yuoxue Xuebao 1997,32(3), 236-240. Kusakabe, M. and Tanaka, K. Seirigaku Gijutsu Kenkyukai Hokoku 1996, 18, 47-50. Cohn, M. Biol. NMR Spectrosc. [Symp.] 1994 (Pub. 1997), 16-19. Akgun, H. FABAD Farm. Bilimler Derg., 1996,21(4), 163- 174. Wild, J. M. and Marshall, I. Magn. Reson. Imaging 1997, 15(9), 1057-1066. Mulkern, R. V.; Bowers, J. L.; Peled, S.; Kraft, R. A. and Williamson, D. S. Magn. Reson. Med., I996,36(5), 775-780. Van Der Graaf, M.; Jager, G. J. and Heerschap, A. Magn. Reson. Muter. Phys., Biol., Med. 1997,5(1), 65-69. Wilman, A. H. and Allen, P. S. J. Magn. Reson., Ser. B 1996, 113(3), 203-213. Jouvensal, L.; Carlier, P. G. and Bloch, G. Magn. Reson. Med 1997,38(5), 706-71 1. Marshall, I. and Wild, J. M. Magn. Reson. Men. 1997,38(3), 415-419. Noyszewski, E. A.; Chen, E-L.; Reddy, R.; Wang, Z. and Leigh, J. S. Magn. Reson. Med. 1997,38(5), 788-792. Wei, H.; Merkle, H.; Xu, Y.; Ellerman, J.; Sipprell, K. and Urgurbil, K. Magn. Reson. Med. 1997,37(3), 327-330. Hu, H.; Li, L.; Mao, X. and Ye, C. Prog. Nut. Sci. 1997,7(1), 41-45. Petroff, A. C. Eur. J. Lab. Med. 1996,4(2), 143-156. Bhattacharyya, J. and Sayeed, M. M. Indian J. Physiol. Pharmacol. 1997, 41(4), 344- 352. Shils, M. E. Clin. Nutr. Health Dis. 1997, 2(Handbook of Nutritionally Essential Mineral Elements), 117- 152. Clark, J. F.; Odoom, J.; Tracey, I.; Dunn, J.; Boehm, E. A.; Paternotro, G. and Radda, G. K. Creatine Creatine Phosphate 1996,33-50. Mountford, C. C.; Doran, S.; Lean, C. L. and Russell, P. Biophys. Chem. 1997, 68(1-3), 127- 135. Corbett, R. J. T. and Laptook, A. R. NeuroReport 1996,8(1), 287-291. Zhang, W.; Truttman, A. C.; Luthi, D. and Meguigan, J. A. S.; Anal. Biochem. 1997, 251(2), 246-250. Mulquiney, P. J. and Kuchel, P. W. N M R Biomed 1997, 10(3), 129-137. Gruwel, M. L. H.; Culic, 0.and Schrader, J. Biophys. J. 1997,72(6), 2775-2782. Schornack, P. A.; Song, S-K.; Ling, C. S.; Hotchkiss, R. and Ackerman, J. J. H. Am. J. Physiol. 1997,272(5, Pt. I), C1618-Cl634. Cohen, D. M. and Bergman, R. N. Am. J. Physiol. 1997,273(6 Pt. l), E1228-E1242. Santos, H.; Fareleira, P.; Ramos, A.; Pereira, H. and Miranda, M. Rev. Port. Quim. 1995,2,3-11. Chalk, P. A.; Roberts, A. D.; Davidson, A. A.; Kelly, D. J. and White, P. J. Helicobacter Pylori Protoc. 1997, 69-80. Kajiwara, M. Bio Znd 197, 14(9), 5-10. Lestan, D. and Perdih, A. Acta Chim. Slov. 1997,44(1), 1 - 15. Miranda, M.; Ramos, A.; Veiga-Da-Cunha, M.; Loureiro-Dias, M. C. and Santos, H. J. Bacteriol. 1997, 179(17), 5347-5354. Chen, R.; Yap, W. M. G. J.; Postma, P. W.;Bailey, J. E. Biotechnol. Bioeng. 1997, 56(5), 583-590. Matheron, C.; Delort, A-M.; Gaudet, G.; Forano, E. and Liptaj, T. Appl. Environ. Microbiol. 1998,64(1), 74-81.

460

Nuclear Magnetic Resonance

33

Garner, M.; Reglinski, J.; Smith, W. E.; McMurray, J.; Abdullah, I. and Wilson, R. JBIC, J. Biol. Inorg. Chem. 1997,2(2), 235-241. Zhang, J.; Sun, T.; Chen, Y.; Zhou, S.; Chen, Y. and Pang, S. Sci. Chinu, Ser. C: Life Sci. 1997,40(5), 488-495. Himmelreich, U. and Kuchel, P. W. Eur. J. Biochem. 1997,246(3), 638-645. Bardicef, M. and Resnick, L. M. J. Clin. Barbagallo, M.; Gupta, R. K.; Bardicef, 0.; Endocrinol. Metab. 1997,82(6), 1761 - 1765. Chen, L.; Xia, M.; Lu, F.; Wang, Y.; Lin, Y. and Huang, Z. Fenxi Ceshi Xuebao 1997, 16(2), 73-76. Bhakoo, K. K. and Bell, J. D. Cell. Mol. Biol. (Paris) 1997,43(5), 621-629. Blackenberg, F. G.; Katsikis, P. D.; Storrs, R. W.; Beaulieu, C.; Spielman, D.; Chen, J. Y.;Naumovski, L. and Tait, J. F. Blood 1997,89(10), 3778-3786. Roman, S. K.; Jeitner, T. M.; Hancock, R.;Cooper, W. A.; Rideout, D. C. and Delikatny, D. J. Int. J. Cancer 1997,73(4), 570-579. Veale, M. F.; Roberts, N. J.; King, G. F. and King, N. J. C. Biochem. Biophys. Res. Cummun. 1997,239(3), 868-874. Yurkevich, D. I.; Kutyshenko, V. P.; Selezneva, I. I. and Rochev, Y. A. Biofizika 1996,41(6), 1284-1288. Alves, P. M.; Carrondo, M. J. T. and Santos, H. Anim. Cell Technol.: Vaccines Genet. Men, [Proc. Meet. ESACT], 14th 1996 (Pub. 1997), 91-98. Castro, M. M. C. A.; Nikolalopoulos, J.; Zachariah, C.; Freitas, D. M. and Stubbs, E. B., JR. Met. Ions Biol. Med., Proc. Int. Symp., 4th 1996, 192- 194 Serkova, N.; Christians, U.; Floegel, U.; Pfeuffer, J. and Leibfritz, D. Chem. Res. Toxicol. 1997,10(12), 1359-1363. Okamoto, R. and Leibfritz, D. Res. Exp. Med. 1997,197(4), 211-217. Schanne, F. A. X.; Long, G. J. and Rosen, J. F. Biochim. Biophys. Acta 1997, 1360(3), 247 -254. Schroeder, C.; Sommer, J.; Humrfer, E. and Stoeckigt, J. Tetrahedron 1997, 53(3), 927-934. Kuchitsu, K.; Yazaki, Y.; Sakano, K. and Shibuya, N. Plant Cell Physiol. 1997, 38(9), I01 2- 10 I 8. Sakano, K.; Kiyota, S. and Yazaki, Y. Plant Cell Physiol. 1997,38(9), 1053-1059. Van Dorsten, F. A.; Wyss, M.; Wallimann, T. and Nicolay, K. Biochem. J. 1997, 325(2), 41 1-416. Kaplan, 0. and Cohen, J. S. Biol. NMR Spectrosc., [Symp.] 1994 (Pub. 1997), 317-339. Zinchenco, L. V.; Kucherenko, Y. V.; Bzhezovskii, V. M.; Beious, A. M. Dopov. Nuts. Akad. Nauk Ukr. 1996, (2), 129- 132. Mancuso, A.; Sharfstein, S. T.; Fernandez, E. J.; Clark, D. S. and Blanch, H. W. Biotechnol. Bioeng. 1998, S7(2), 172.- 186. Kaplan, 0.;Ruiz-Cabello, J. and Cohen, J. S. FEBS Lett. 1997,406(1,2), 175- 178. Abraha, A.; Shim, H.; Wehrle, J. P. and Glickson, J. D. NMR Biomed. 1996, 9(4), 173- 178. Vivi, A.; Tassini, M.; Ben-Horin, H.; Navon, G. and Kaplan, 0. Breast Cuncer Res. Treat. 1997,43(1), 15-25. Mannazzu, I.; Guerra, E.; Strabbioli, R.; Masia, A.; Maestrale, G. B.; Zorroddu, M. A. and Fatichenti, F. FEMS Microbiol. Lett. 1997, 147(1), 23-28. Rao, K. S. J. and Easwaran, K. R. K. Mol. Cell. Biochem. 1997,175(1&2),59-63. Talibart, R.; Jebbar, M.; Gouffi, K.; Pichereau, V.; Gouesbet, G.; Blanco, C.; Bernard, T. and Pocerd, J-A. Appl. Environ. Microbiol. 1997,63(12), 4657-4663.

34

35 36 37 38 39

40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58

59 60

461

12: Nuclear Mugneric Resonunce Spectroscopy of Living Systems 61

Carmelo, V.; Santos, H. and Sa-Correia, I. Biochim. Biophys. Acta 1997,1325(1),

63-70. 62 63 64 65

Ma, P.; Goncalves, T.; Maretzek, A.; Dias, M. C. and Loureiro, T. J. M. Microbiology (Reading, U. K . ) 1997,143(11), 3451 -3459. Magnes, J. E. and McFarland, E. W. Biochem. Biophys. Res. 1997,233(1), 238-243. Ratcliffe, R. G. Ann. But. (London) 1997,9(Suppl. A), 39-48. Tse, T.Y.; Spanswick, R. M. and Jelinski, L. W. frotoplusma, 1996 194(1-2),

54-62. 67 68

Meininger, M.; Akob, P. M.; Von Kienlin, M.; Koppler, D.; Bringmann, G. and Hasse, A. J. Mugn. Reson. 1997,125(2), 325--331. Ishida, N.; Koizumi, M. and Kano, H. Plunt, Cell Environ. 1996,19(12), 1415-1422. Shachar-Hill, Y.; Pfeffer, P. E. and Germann, M. W. And. Biochem. 1996,243(1),

69

Brauer, D.; Uknalis, J.; Triana, R. and Tu, S-I. Plunt fhysiol. Biochem. (Puris)

70

Bligny, R.; Gout, E.; Kaiser, W.; Heber, U.; Walker, D. and Douce, R. Biochim. Biophyfx A d a 1997,1320(2), 142-152. Barba, I.; Gasparovic, C.; Cabanas, M. E.; Alonso, J.; Murillo, I.; San Segundo, B. and Arus, C. Cell. Mol. Bid. 1997,43(5), 609-620. Katsuhara, M.; Yazaki, Y.; Sukano, K. and Kawasaki, T. Plant Cell Physiol. 1997,

66

110-1 18.

1997,35(1), 31-39. 71 72

38(2), 155- 160. 73 74 75 76 77 78

Gerendas, J.; Heeschen, V.; Kahl, S.; Ratcliffe, R. G. and Rudolph, H. Isot. Environ. Health Stud. 1997,33(1-2), 21 -29. Shvaleva, A. L. Biofiiku 1997,42(4), 933-940. McCain, D. C. Plunt Sci. (Shannon, Irel. ), 1997,125( I), 1 I3 I 17. Pouliquen, D.; Gross, D.; Lehmann, V.; Ducournau, S.; Demilly, D. and Lechappe, J. C. R. Acaci. Sci., Ser. III 1997,320(2), 131-138. Gerlitz, T. G. M. and Gerlitz, A. Micorrhiza 1997,7(2), 101- 106. Utsunomiya, A.; Watanuki, T.; Matsushita, K. and Tomita, I. Chemosphere 1997, ~

35(6), 12I5- 1226. 79 80

Litt, L.; Espanol, M. T.; Xu, Y.; Cohen, Y.;Chang, L-H.; Weinstein, P. R.; Chan, P. H. and James, T. L. Bid. NMR Spectrosc., (Symp. / 1994 (Pub. I997),340-357. Lukkarinen, J.; Oja, J. M. E.; Turunen, M. and Kauppinen, R. A. Neurochem. Int.

1997,31(1), 95-104. 81 82

Hyder, F.; Rothman, D. L.; Mason, G. F.; Rangarajan, A.; Behar, K. L. and Shulman, R. G. J. Cereb. BloodFlorv Metab. 1997,17(10), 1040-1047. Vianello, F.; Scarpa, M.; Viglino, P. and Rigo, A. Biochem. Biuphys. Rex Commun.

1997,237(3), 650-652. 83 84 85 86 87 88

Power, C.; Peeling, J.; Kong, P-A. and Langelier, T. Neuroscience (Oxford) 1997, 77(4), 1 175- I 185. Holtzman, D.; Mefers, R.; Khait, I. and Jensen, F. Epilepsy Res. 1997,27(1), 7-1I . Tokumitsu, T.; Mancuso, A.; Weinstein, P. R.; Weiner, M. W.; Naruse, S. and Maudsley, A. A. Bruin Res. 1997,744(1), 57-67. Najm, I. M.; Wang, Y.; Hong, S. C.; Luders, H. 0.; Ng, T. C.and Comair, Y. G. Epilepsiu 1997,38(1), 87-94. Holtzman, D.; Meyers, R.; OGorman, E.; Khait, I.; Walliman, T.; Allred, E. and Jensen, F. Am. J. Physiol. 1997,272(5, Pt.I), C1567-Cl577. Steensgaard, A., Oestergaard, G.; Jensen, C.V.; Lam, H. R.;Topp, S.; Lagedfoged, 0.; Arlien-Schoeborg, P. and Henriksen, 0. Neurotoxicology 1996, 17(3-4),

785-792.

462 89 90 91 92 93 94 95 96 97 98 99 100 101 I02 103 104 105 106 I07 108

109 110 111

112 113 114

1 I5

Nuclear Magnetic Resonance

Strauss, I.; Williamson, J. M.; Bertram, E. H.; Lothman, E. W. and Fernandez, E. J. Magn. Reson. Med. 1997,37(1), 24-33. Higuchi, T.; Graham, S. H.; Fernandez, E. J.; Rooney, W. D.; Gaspary, H. L.; Weiner, M. W. and Maudsley, A. A. Magn. Reson. Men. 1997,37(6), 851-857. Morikawa, S.; Inubushi, T.; Takahashi, K.; Ishii, H. and Shigemori, S. Magn. Reson. Imaging 1996, 14(10), 1197- 1204. Penrice, J.; Lorek, A.; Cady, E. B.; Amess, P. N.; Wylezinska, M.; Cooper, C. E.; Dsouza, P.; Brown, G. C.; Kirkbride, V.; et a1 Pediatr. Res. 1997,41(6), 795-802. Semenova, N. A.; Konradov, A. A. and Romanova, G. A. BioJzika, 1996, 41(5), 1 106- 1 1 1 1 Braun, K. P. J.; Dijkhuizen, R. M.; de Graaf, R. A.; Nicolay, K.; Vandertop, W. P.; Gooskens, R. H. J. M. and Tulleken, K. A. F. Brain Res. 1997,757(2), 295-298. Yanai, S.; Nisimaru, N.; Soeda, T. and Yamada, K. Neurosci. Res. (Shannon, Irel.) 1997,27(1), 75-84. Yan, X.; Yan, L.; Xu, J. and Wu, B. Bopuxue Zazhi 1997,14(2), 147-152. Kanamori, K. and Ross, B. D. J. Neurochem. 1997,68(3), 1209-1220. Sibson, N. R.; Dhankhar, A.; Mason, G. F.; Behar, K. L.; Rothman, D. L. and Shulman, R. G. Proc. Natl. Acad. Sci. U.S.A. 1997,94(6), 2699-2704. Christensen, J. D.; Babb, S. M.; Cohen, B. M. and Renshaw, P. F. Magn. Reson. hied 1998,39(I), 149- 154. Boicelli, C. A. and Giuliani, A. M. Magn. Reson. Muter. Phys., Biol., Med 1996,4(3/ 4), 241 - 245. Kasparova, S.; Dobrota, D. and Horecky, J. Biologicu (Bratislava) 1996, 51(6), 707-7 16. Dobrota, D.; Kasparova, S. and Horecky, J. Biologicu (Bratislava) 1996, 51(6), 7 17 - 722. Cheng, Z. and Du, Z. Bopuxue Zazhi 1997,14(1), 89-98. Joubert, F.and Hoerter, J. A. Cell. Mol. Biol. 1997,43(5), 763-772. Thebault, M. T.; Raffin, J. P.; Kaletha, K. and Pichon, R. Mol. Mar. Biol. Biotechnol. 1996,5(4), 352-356. Shi, H.; Hamm, P. H.; Mayers, R. S.; Lawler, R. G. and Jackson, D. C. Am. J. Physiol. 1997,272(1, Pt. 2), R6-RI5. Dykens, J. A.; Wiseman, R. W. and Hardin, C. D. J. Comp. Physiol. 1996, 166(6), 359- 368. Wolska, B. M.; Averyhart-Fullard, V.; Omachi, A.; Stojanovic, M. 0.; Kallen, R. G. and Solaro, R. J. J. Mol. Cell. Cardiol. 1997, 29(10), 2653-2663. Spencer, R. G. S.; Buttrick, R. G. M.; Ingwall, J. S. Am. J. Physiol. 1997, 272(1, Pt. 2), H409-H417. Levy, E.; Hasin, Y.; Navon, G. and Horowitz, M. Am. J. Physiol. 1997, 272(5, Pt. 2), H2085-H2094. Xia, Z-F.; Horton, J. W.; Zhao, P.; Lin, C.; Sherry, A. D. and Malloy, C. R. J. Surg. Res. 1997,69(1), 212-219. Gorman, M. W.; He, M-X.; All, C. S. and Sparks, H. V. Am. J. Physiol. 1997,272(2, Pt. 2), H913-H920. Stepanov, V.; Mateo, P.; Gillet, B.; Beloeil, J. C.; Lechene, P. and Hoerter, J. A. Am. J. Physiol. 1997,273(4 Pt. I), CI397-Cl408. Kroll, K.; Kinzie, D. J. and Gustafson, L. A. Am. J. Physiol. 1997, 272(6, Pt. 2), H2563-H2576. Houston, R. J. F.; Heerschap, A.; Skotnicki, S. H.; Verheugt, F. W. A. and Oeseburg, B. J. Mol. Cell. Cardiol. 1997,29(6), 1763-1766.

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

463

I16 Zhang, J.; Ishibashi, Y.; Eijgelshove, M. H. J.; Duncker, D. J.; Merkle, H.; Bache, R. J.; Ugurbil, K. and From, A. H. L Am. J. Physiol. 1997, 273(3, Pt. 2), H1452-Hl463. 117 van Binsbergen, X. A.; van Emous, J. G.; Ferrari, R.; van Echteld, C. J. A. and Ruigrok, T. J. C. J. Mol. Cell. Curdiol., 1996,28(12), 2373-2381. 118 Askenasy, N. and Navon, G. J. Mol. Cell. Curdiol. 1997,29(6), 1715- 1730. 119 Crestanello, J. A.; Kamelgard, J.; Lingle, D. M.; Mortensen, S. A.; Rhode, M. and Whitman, G. J. R. J. Thoruc. Curdiovusc. Surg. 1996,111(2), 443-450. 120 Kawabata, H.; Sugiyama, K. and Katori, R. Jpn. Circ. J. 1996,60(12), 961 -971. 121 Grunder, W. and Loster, H. Curnitine Pathobiochem. Busies Clin. Appl., Proc. Leipzig Curnitine Symp. 1996,237-260. 122 Balschi, J. A.; Hai, J. 0.; Wolkowicz, P. E.; Straeter-Knowlen, I.; Evanochko, W. T.; Caulfield, J. B.; Bradley, E.; Ku, D. D. and Pohost, G. M. J. Mol. Cell. Curdiol. 1997,29(2), 47 1-480. 123 Elst, L. V.; Colet, J-M. and Muller, R. N. Invest. Rudiol. 1997,32(10), 581-588. I24 Docherty, J. C.; Gunter, H. E.; Kuzio, B.; Shoemaker, L.; Yang, L. and Deslauriers, R. J. Mol. Cell Curdiol. 1997,29(6), 1665-1673. 125 Van Emous, J. G.; Nederhoff, M. G. J.; Ruigrok, T. J. C. and Van Echteld, C. J. A. J. Mol. Cell. Curdiol. 1997,29(1), 85-96. 126 Cheng, Z.; Du, Z.; Feng, R.; Li, G. and Dong, H. Bopuxue Zuzhi 1997, 14(4), 291 -298. 127 Koike, A.; Akita, T.; Hotta, Y.; Takeya, K.; Kodama, I.; Murase, M.; Abe, T. and Toyama, J. J. Thoruc. Curdiovusc. Surg. 1996,112(3), 765-775. 128 Docherty, J. C.; Yang, L.; Pierce, G. N. and Deslauriers, R. Mol. Cell. Biochem. 1997,176(1&2), 257-264. 129 Schaefer, S. and Ramasamy, R. Curdiovusc. Rex 1997,34(2), 329-336. 130 Liu, H.; Cala, P. M. and Anderson, S. E. J. Mol. Cell. Curdiol. 1997, 29(8), 2077- 2086. 131 Vandenberg, J. I.; Carter, N. D.; Bethell, H. W. L.; Norgradi, A.; Ridderstrale, Y.; Metcalfe, J. C. and Grace, A. A. Am. J. Physiol. 1996, 271(6, Pt. l), C1838-Cl846. 132 Portman, M. A.; Panos, A. L.; Xiao, Y.; Anderson, D.L; Alferis, G. M.; Ning, X-H. and Lupinetti, F. M. J. Thoruc. Curdiovusc. Res. 1997,114(4), 601-608. 133 Kay, L.; Daneshrad, Z.; Saks, V. A. and Rossi, A. Curdiovasc. Res. 1997, 34(3), 547-556. 134 Tian, R.; Christe, M. E.; Spindler, M.; Hopkins, J. C. A.; Halow, J. M.; Camacho, S. A. and Ingwall, J. S. J. Clin. Invest. 1997,9(4), 745-751. 135 Mottet, I.; Goudemant, J-F.; Francau, M.; Demeure, R. and Sturbois, X. Can. J. Physiol. Phurmucol. 1 997,75(8), 1015- 1021. 136 He, M-X.; Wang, S. and Downey, H. F. Am. J. Physiol. 1997, 272(3, Pt. 2), HI 333 -Hl341. 137 Kelm, M.; Schafer, S.; Dahmann, R.; Doh, B.; Perings, S.; Decking, U. K. M.; Schrader, J. and Strauer, B. E. Curdiovusc. Res. 1997,36(2), 185-194. 138 Reed, M. K.; Barak, C.; Malloy, C. R.; Maniscalco, S. P. and Jessen, M. E. J. Thoruc. Curdiovasc. Surg. 1996,112(6), 1651- 1660. 139 Rath, D. P.; Zhu, H.; Tong, X.; Jiang, Z.; Hamlin, R. L. and Robitaille, P-M. L. Mugn. Reson. Med. 1997,38(6), 896-906. I40 Schafer, S. and Ramasamy, R. Curdiovusc. Res. 1997,35(1), 90-98. 141 Gabel, S. A.; OConnell, T. M.; Murphy, E. and London, R. E, Am. J. Physiol. 1997, 272(5, Pt. l), C1415-CI419. .

464

Nucleur Mugnetic Resonunce

142 Hashimoto, K.; Nisimura, T.; Ishikawa, M.; Koga, K.; Mori, T.; Matsuda, S.; Hori, M. and Kusuoka, H. Am. J. Pliysiol. 1997,272(3, Pt. 2), HI 122-HI 130. 143 Tauskela, J. S.; Dizon, J. M.; Whang, J. and Katz, J. J. Mugn. Reson. 1997, 127(1), 1 15- 1 27. 144 Schepkin, V. D.; Choy, I. 0. and Budinger, T. F. J. Appl. Physiol. 1996, 81(6), 2696 -2702. 145 van Dobbenberg, J. 0.; Kasbergen, C.; Slootweg, P. J.; Ruigrok, T. J. C. and van Echteld, C. J. A. Mol. Cell. Biochem., 1996, 163/164, 247-252. 146 Portman, M. A.; Xiao, Y.; Song, Y. and Ning, X-€1. Am. J, Physiol. 1997, 273(4, Pt. 2), €11977 -H1983. 147 Nakagawa, J. Aichi Iku Duiguku Igakki Zusshi 1997,25(1), 11 1-123. 148 Hauet, T.; Mothes, D.; Goujon, J. M.; Caritez, J. C.; Le Moyec, L.; Carretier, M. and Eugene, M. J. Surg. Res. 1997,68(2), 1 16- 125. 149 Hauet, T.; Mothes, D.; Goujon, J-M.; Caritez, J. C.; Carretier, M.; Le Moyec, L.; Eugene, M. and Tillement, J-P. Transplantution 1997,64(7), 1082-1086. 150 Cadrobbi, R.; Rigotti, P.; Baldan, N.; Toffano, M.; Corazza, A.; Scarpa, M.; Rigo, A. and Ancona, E. Trunsplunt Proc. 1997,29(8), 3415-3416. 151 Vidal, G.; Gallis, J.L., Dufour, S. and i'anioni, P. Arch. Biochem. Biophys. 1997, 337(2), 317-325. 152 Fiegen, R. J.; Rauen, U.; Hartmann, M.; Decking, I!. K. M. and De Groot, H. Heputology (Philudelphiu) 1997, 25(6), 1425- 1431. 153 Delmas-Beauvieux, M. C.; Pietri, S.; Culcasi, M.; Leducq, N.; Valeins, H.; Liebgott, T.; Diolez, P.; Canioni, P. and Gallis, J. L. Mugn. Reson. Muter. Phys., Biol., Med 1997,5(1), 45--52. 154 Morikawa, S.; Inubushi, T.; Takahashi, K.; Shigemori, S. and Ishii, H. N M R Biomed 1997, 10(1), 18-24, 155 Changani, K. K.; Barnard, M. L.; Bell, J. D.; Thomas, E. L.; Williams, S. C. R.; Bloom, S. R. and Iles, R. A. Biuchim. Biophys. Actu 1997, 1335(3),290-304. 156 Noseworthy, M. D.; Janzen, E. G.; Towner, R. A. and Yamashiro, S. J. Biochem. Biophys. Methods 1997,34(2), 107- 122. 157 Madhu, B.; Lagerwall, and Soussi, B. N M R Biomed. 1997,9(8), 327-332. 158 Wiseman, R. W. and Kushmerick, M. J. Mol. Cell. Biochem. 1997, 174(1&2), 23-28. 159 Harkema, S. J.; Adams, G. R. and Meyer, R. A. Am. J. Physiul. 1997, 272(2, Pt. I), C485-C490. 160 Jucker, B. M.; Rennings, A. J . M.; Cline, G. W. and Shulman, G. I. J. Bid. Chem. 1997,272(16), 10464-10473 161 Van Ginneken, V.; Van Den Thillart, G.; Addink, A. and Erkelens, C. Am. J. Physiol., 1996,271(6, Pt. 2), R1746-R1752. 162 Thebault, M.T.; Raffin, J. P. and Pichn, R. Comp. Biochem. Physiol., A: Physiol. 1997,116A(4), 337-340. 163 Chiba, A. and Chichibu, S. Actu Med Kinki Univ. 1997,22(1), 41 -48. 164 Ville, H.; Rombouts, G.; Van Hecke, P.; Perremans, S.; Maes, G.; Spincemaille, G. and Geers, R. J. Anim. Sci. 1997,75(11), 2942-2949. 165 Jayasundar, R.; Hall, L. D. and Bleehen, N. M. Mugn. Reson. Imuging 1997, 15(7), 847 855. 166 Koutcher, J. A.; Alfieri, A. A.; Tsai, J. C.; Matei, C.; Stolfi, R. L.; Ballon, D. and Martin, D. S. Cancer Invest. 1997, 15(2), 11 1 120. 167 Semenova, N. A.; Kozin, S. V.; Kozina, L. V.; Zaitsev, A. V. and Rosantseva, T. V. Dukl. Akud Nuuk 1996,351(3), 410-412. -

-

12: Nuclear Magnetic Resonance Spectroscopy of Living Systems

465

I68 Holland, S. K.; Bergman, A. M.; Zhao, Y., Adams, E. R. and Pizzorno, G. Magn. Reson. Med. 1997,38(6), 907-916. 169 Sijens, P. E.; Baldwin, N. J. and Ng, T. C. Invest. Rudiol. 1997,32(1), 39-43. 170 Debouzy, J-C.; Fauvelle, F.; Fouilhe, N.; Sam-Lai, E.; Nemoz, C.; Girault, L. and Mazet, L. Ann. Pharm. Fr. 1997,55(1), 35-41. 171 Bendel, P.; Zilberstein, J.; Salomon, Y. and Kabalka, G. W. Cancer Neutron Capture Ther., [Proc. Int. Symp. Neutron Capture Ther. Cancer], 6th 1994, (Pub. 1996), 233-238. 172 Hendee, S. P.; Bradshaw, K. M.; Hadley, J. R.; Tang, P-P. Z. and Schweizer, M. P. 173 Kanazawa, Y.; Umayahara, K.; Shimmura, T. and Yamashita, D. N M R Biomed 1997,10(1), 35-41. 174 Kaplan, 0.;Kushnir, T.; Askenazy, N.; Knubovets, T. and Navon, G. Cancer Res. 1997,57(8), 1452- 1459. 175 Street J. C.; Szwergold, B. S.; Matei, C.; Kappler, F.; Mahmood, U.; Brown, T. R. and Koutcher, J. A. Magn. Reson. Med. 1997,38(5), 769-775. 176 Gann, V. K . and Hardin, C. D. Physiol. Chem. Phys. Med. 1997,29(1), 23-32. I77 Hardin, C. D. and Roberts, T. M. Biochemistry 1997,36(23), 6954-6959. I78 De Boeck, G.; Borger, R.; Van Der Linden, A. and Blust, R. Environ. Toxicol. Chem. 1997, 16(4), 676-684. I79 Shofer, S. L.; Willis, J. A. and Tjeerdema, R. S. Comp. Biochem. Physiul., C: Pharmacol., Toxicol. Endocrinol. 1997, 117C(3), 283-289. 180 Kreutzer, U. and Jue, T. Eur. J. Biochem. 1997,243(1/2), 233-239. 181 Thompson, S. N. and Borchardt, D. Insect Biochem. Mol. Bio., 1996, 26(10), 1047 - 1054. 182 Sogabe, T.; Imaizumi, T., Mori, T.; Tominaga, M.; Koga, K. and Yabuuchi, Y. Mugn. Reson. Imaging 1997, 15(3), 341 -345. I83 Cox, I . J. Prog. Biophys. Mol. Biol. 1996,65(1/2), 45-81. 184 Schick, F. Prog. Nucl. Mugn. Reson. Spectrosc. 1996,29(3/4), 169-227. I85 Bangsbo, J. Biochem. Exercise I X [Int. Biochem. Exercise Con$], 9th 1994 (Pub. 1996), 261 -275. 186 Taylor, R. and Shulman, G. I. Clin. Res. Diabetes Obes. 1997, 1, 287-303. I87 Kawano, N. Saishin Nuikagaku Tuikei 1996,8, 16-20. 188 Bloch, G. and Velho, G. Diabetes Metub. 1997,23(4), 343-350. 189 Conway, M. A.; Ouwerkerk, R.; Rajagopalan, B. and Radda, G. K. Creutine Creatine Phosphate 1996, 127- 1 59. 190 English, C. D.; Kaufman, M. J.; Worth, J. L.; Babb, S. M.; Drebing, C. E.; Navia, B. A. and Renshaw, P. F. Biol. Psychiatry 1997,41(4), 500-502. 191 Lopez-Villegas, D.; Lenkinski, R. E. and Frank, I. Proc. Nutl. Acad Sci. U.S.A. 1997,94(18), 9854-9859. 192 Gredal, 0.; Rosenbaum, S.; Topp, S.; Karlsborg, M.; Strange, P. and Werdelin, L. Neurology 1997,48(4), 878-881. 193 Schiepers, C.; Van Hecke, P.; Vandenberghe, R.; Van Oostende, S.; Dupont, P.; Demaerel, P.; Bormans, G. and Carton, H. Mult. Scler. 1997,3(1), 8-17. 194 Hajek, M.; Do, K. Q.; Duc, C.; Boesiger, P. and Wieser, H. G. Epilepsy Res. 1997, 28(3), 245-254. 195 Schiffmann, R.; Tedeschi, G.; Kinkel, R. P.; Trapp, B. D.; Frank, J. A.; Kaneski, C. R.; Brady, R. 0.;Barton, N. W.; Nelson, L. and Yanovski, J. A. Ann. Neurol. 1997, 41(5), 654-661. 196 Parnetti, L.; Tarducci. R.; Presciutti, 0.;Lowenthal, D. T.; Pippi, M.; Palumbo, B.; Gobbi, G.; Pelliccioli, G. P. Senin, U. Mech. Aging Dev. 1997,97(1), 9-14.

466

Nuclear Magnetic Resonance

197 Murata, S.; Toyoda, K.; Hiraishi, K.; Narabayashi, I. and Naritomi, H. Bull. Osaka Med. Coll. 1996,42(1), 5- 10. 198 Ellis, C. M.; Lemmens, G.; Williams, S. C. R.; Simmons, A.; Dawson, J.; Leigh, P. N. and Chaudhuri, K. R. Neurology 1997,49(2), 438-444. 199 Ashwal, S.; Holshouser, B. A.; Tomasi, L. G.; Shu, S.; Perkin, R. M.; Nystrom, G. A. and Hinshaw, D. B., Jr. Ann. Neurol. 1997,41(4), 470-481. 200 Harada, M.; Miyoshi, H.; Ootsuka, H.; Taoka, Y.; Tanouchi, M. and Nishitani, H. Nippon Iguku Hshasen Gakkai Zasshi 1997,57(8), 487-492. 20 1 Prost, R. W.; Mark, L.; Mewissen, M. and Li, S-J. Magn. Reson. Med 1997, 37(4), 61 5-61 8. 202 Renshaw, P. F.; Lafer, B.; Babb, S. M.; Fava, M.; Stoll, A. L.; Christensen, J. D.; Moore, C. M.; Yurgelun-Todd, D. A.; Bonello, C. M.; Pillay, S. S.; Rothschild, A. J.; Nierenberg, A. A.; Rosenbaum, J. F. and Cohen, B. M. Biol. Psychiatry 1997, 41(8), 837-843. 203 Tupler, L. A.; Davidson, J. R. T.; Smith, R. D.; Lazeyras, F.; Charles, H. C. and Krishnan, K. R. R. Biol. Psychiatry 1997,42(6), 419-424. 204 Petroff, 0. A. C.; Rothman, D. L.; Behar, K. L.; Collins, T. L. and Mattson, R. H. Neurology, 1996,47(6), 1567- 1571. 205 Kato, T.; Shioiri, T.; Murashita, J. and Inubushi, T. Prog. Neuro-Psychopharmacol. Biol. Psychiatry 1997, 21(4), 719-724. 206 Keltner, J. R.; Wald, L. L.; Frederick, B. de B. and Renshaw, P. F. Magn. Reson. Med. 1997,37(3), 366-371. 207 Frahm, J.; Krueger, G.; Merboldt, K . D. and Kleinschmidt, A. Adv. Exp. Med Biol. l997,413(0ptical Imaging of Brain Function and Metabolism 2), 195-203. 208 Chen, W.; Zhu, X-H.; Adriany, G. and Ugurbil, K. Magn. Reson. Med. 1997,38(4), 551 -557. 209 Li, C. W.; Negendank, W. G.; Murphy-Boesch, J.; Padavic-Shaller, K. and Brown, T. R. N M R Biomed 1996,9(4), 141-155. 210 Boesch, C.; Elsing, C.; Wegmuller, H.; Felblinger, J.; Vock, P. and Reichen, J. Magn. Reson. Imaging 1997,15(9), 1067- 1077. 21 1 Vittone, J.; Blackman, M. R.; Busby-Whitehead, J.; Tsiao, C.; Stewart, K. J.; Tobin, J.; Stevens, T.; Belatoni, M. F.; Rogers, M. A.; Baumann, G.; Roth, J.; Harman, S,M. and Spencer, R. G . S. Metab., Clin. Exp. 1997,46(1), 89-96. 212 Binzoni, T.; Hiltbrand, E.; Yano, T. and Cerretelli, P. Acta Physiol. Scand. 1997, 159(3), 209-215. 213 Walter, G.; Vandenbourne, K.; McCully, K. K . and Leigh, J. S. Am. J. Physiol. 1997,272(2, Pt. I), C525-C534. 214 Jeneson, J. A. L.; Wiseman, R. W. and Kushmerick, M. J. Mol. Cell. Biochem. 1997, 174(1&2), 17-22. 215 Shoemaker, J. K.; Pandey, P.; Herr, M. D.; Silber, D. H.; Yang, Q. X.; Smith, M. B.; Gray, K. and Sinoway, L. I. J. Appl. Physiol. 1997,82(6), 1932-1938. 216 Roussel, R.; Carlier, P. G.; Wary, C.; Velho, G. and Bloch, G. Magn. Reson. Med. 1997, 37(6), 821-824. 217 Salerno, C.; Iotti, S.; Lodi. R.; Crifo, C. and Barbiroli, B. Biochim. Biophys. Acta 1997,1360(3), 27 1 - 276. 218 Thompson, C. H.; Irish, A. B.; Kemp, G. J.; Taylor, D. J. and Radda, G. K. Clin. Nephrol. 1997,47(6), 372-378. 219 Brinkmann, G.; Melchert, U. H.; Lalk, G.; Emde, L.; Link, J.; Muhle, C.; Steffens, J. C. and Heller, M. Invest. Radiol. 1997,32(2), 100- 104.

12: Nuclear Mugnetic Resonance Spectroscopy of Living Systems

467

220 Gonen, 0.; Murphy-Boesch, J.; Li, C-W.; Padavic-Shaller, K.; Negendank, W. G. and Brown, T. R. Mugn. Reson. Med. 1997,37(2), 164-169. 221 Tomoi, M.; Kimura, H.; Yoshida, M.; Itoh, S.; Kawamura, Y.; Hayashi, N.; Yamamoto, K.; Kubota, T. and Ishi, Y. Invest. Radiol. 1997,32(5), 288-296. 222 Tugnoli, V.; Tosi, M. R.; Bertoluzza, A.; Barbarella, G. and Ricci, R. Spectrosc. Biol. Mol.: Mod. Trends, [Eur. ConJ], 7th 1997,439-440. 223 Thomas, E. L.; Hanrahan, J. D.; Ala-Korpela, M.; Jenkinson, G.; Azzopardi, D.; Iles, R.A and Bell, J. D. Lipids 1997,32(6), 645-651. 224 Zemtov, A. Photodermatol., Photoimmunol. Photomecl. 1997, 13(1/2), 24-26.

13 Nuclear Magnetic Resonance Imaging BY TOKU KO WATANASE

1

Introduction

This report covers literature published on NMR imaging (NMRI), NMR microimaging or microscopy, and magnetic resonance imaging by a whole body machine (MRI) over the period June 1997 to May 1998. Further literature on the subject can be traced back from the relevant earlier volumes.' The topic was limited to mainly the non-clinical research field, such as physicochemical, biological, physiological, geological, environmental, and industrial applications, and has been arranged as previously. During the period under review, applications of NMRI to solid materials and solid-like polymers have successfully expanded, which yields unique information about different aspects of structure and dynamics of disordered systems and their relation with their material properties. Many reviews not only on the solid polymer systems, but also on fluid in the polymer have appeared as shown below. Advances of characterization of porous media and flow visualization using NMRI are also worthy of special mention this year. It is also shown that NMRI promises to have a broad impact in a range of studies involving the flow of multiphase systems.

2

General Aspects and Reviews

Many reviews concerning NMR imaging have been written during this period, and are listed in the references. For convenience, some authoritative reviews in the subject area are quoted in this section and more specialized reviews will be discussed in the corresponding section. Radiofrequency (rf) field gradient experiments in NMR spectroscopy and imaging are discussed with 140 references by Cane, which covers the modes of action of pulsed gradients, probing of selfdiffusion and flow by rf field gradients, imaging and spectroscopic application.* Contrast in solid state NMRI is the central feature that makes NMRI of interest for application of solid materials. The principles of contrast in solid state NMRI are introduced with 52 reference^.^ The application to polymer systems, such as plastics (1 12 reference^),^ elastomers (1 53 reference^),^ and hydro-polymer gel systems (68 references),6 was described. A review, with 81 references, is given on the use of in situ methods to study the synthesis of materials from sol-gel Nuclear Magnetic Resonance, Volume 28 0The Royal Society of Chemistry, 1999 468

13: Nuclear Mugnetic Resonance Imuging

469

precursors, with particular emphasis on the formation of crystalline phases from solid gel precursors and the crystallization of zeolitic materials from solution under hydrothermal condition^.^ The ability of NMR imaging and spectroscopy to noninvasively probe fluids with porous media provides new opportunities for characterizing of fluids and flow in porous media and of pore structures and surface properties. A review with 18 1 references was described at both the microscopic and macroscopic scale.8 Pulp flow visualization of suspensions of cellulose pulp fibers in water was reviewed with numerous references, where the velocity profiles, turbulent velocity fluctuations, influence of the flow rates on the flow type, the associated flowmicrostructure interaction and rheological parameters are discussed.' A review (39 references) of the principles of NMR imaging techniques to visualize and unravel complex, heterogeneous transport processes in porous systems was presented with discussing applications and limitations, based on results obtained in model and artificial soil systems." The basics of diffusion measurement in biological systems were described with 70 references, in which free diffusion, restricted diffusion, diffusion anisotropy, population weighting and the difference between diffusion-weighted imaging and apparent diffusion coefficient maps are included. I Rf microcoil solenoids and their applications in EPR and NMR are reviewed with 183 references which covers EPR imaging and NMR imaging, high resolution NMR spectroscopy and magic angle spinning NMR spectroscopy.I2 A review on the use of the toroids in high-pressure NMR and NMRI was presented with 71 references.I3

3

Instruments

For clinical use a prototype positron emission tomography (PET) scanner compatible with clinical MRI and NMR spectroscopy was developed. Simultaneously acquired PET and MR phantom images as well as simultaneous PET images and NMR spectra showed no significant artifacts o r distortions, demonstrating the power of obtaining temporally correlated PET and NMR information in biological systems.14A new NMR structure which is composed of ferrite magnets and has an open-H-shape was proposed.I5 Magnetic shielding by cylinders made of Fe-Ni magnetic alloy" and Nb-Ti billets for superconductor product ion were presented. Radiofrequency microcoi1s,l2 spherical gradient coil for ultrafast imaging," and a half-volume coil for efficient proton decoupling in humans at 4 Tesla" were developed. Significant amplitude and phase distortion of the Rf magnetic field by conducting dielectric samples especially in high field were theoretically analyzed and experimentally demonstrated.20The effect of RF-coil geometry on the coherences was also modeled, using homogeneous resonators such as the birdcages design being preferred.20 Double-tuned four-ring birdcage resonators (a highly sensitive 31P channel and an additional 'H channel for 'H-NMRI, shimming, 'H decoupling and NOE) were designed for in vivo 3'P-NMR

'

Nucleur Magnetic Resonance

470

spectroscopy at 1.75 Tesh21 The coil design offers the advantage of circular polarization on both channels.

4

Pulse Sequences

A group of generic radiofrequency based ultrafast imaging techniques using DANTE (delays alternating with nutations for tailored excitation) pulse sequence is reviewed with 25 references and a new frequency-modulated DANTE (FMDANTE) fast imaging sequence is discussed together with several application areas developed recently (extended three-dimensional gradient echo imaging, chemical shift imaging, and susceptability compensation imaging etc.).22 Fast spiral MRI with trapezoidal gradient was developed.23The radio-frequency pulse scheme for Tl,ffimaging using a magic-echo phase-encording procedure for the recording of spatial distributions in solids and quasi-solids was introduced and a method for Tl,f,-weighted imaging using a gradient spin-echo valid for weak dipolar solids was also discussed.24 In order to image the second moment of proton NMR dipolar, two methods, e.g., a quasi-multidimensional FT approach and the fast version of the former approach, were proposed.25 Pulsed-gradient spin-echo (PGSE) NMR methods for the measurement of flow and diffusion in porous media was presented, in which the fluid dynamics was proved over welldefined temporal and spatial domains.26 Various NMR techniques based on PGSE encording are described on the context of studying theories of dispersion, with references to Eulerian and Lagrangian coordinate frames.26 The observation of a 'H double quantum filtered (DQF) NMR signal of water in the tissue was reported. The origin of the DQ signal was found to be a result of residual dipolar interaction between water proton and macromolecular protons.27 '70-decoupled proton NMR spectroscopy and imaging were implemented at 2 Tesla in a tissue model. Excellent agreement between a simple theoretical model based on Meiboom's model and experiments was obtained.28 A method for indirect detection of HZi7O via a combination of 'H spin-echo sequence and 170decoupling was applied to image H2I7O distribution in a phantom and in liver mice.29A 31PNMR signal was obtained through polarization transfer between I7O and 31P in l70-labeled phosphoric acid by using a double resonance NMR detector and a designed pulse train.30

5

Data Processing

A technique based on the singular value decomposition (SVD) method was developed to analyze time series consisting of an exponential function and a noisy b a c k g r o ~ n d . ~A' novel application of the generalized rank annihilation method (GRAM) for a single spectral mixture data set with exponentially decaying contribution profiles, which is called DECRA (direct exponential curve resolution algorithm), was described.32 Examples were given of pulsed gradient spin echo NMR data. A robust technique for quantification of NMRI data was

13: Nuclear Magnetic Resonance Imaging

47 1

i n t r ~ d u c e dThe . ~ ~ method is based on modeling the relaxation behavior with a continuous distribution of relaxation rates.

6

Solid State NMR Imaging

Polymer analysis and characterization via the solid state N M R spectroscopy and NMRI has taken a growing interest in these years. Many reviews on the application of the solid state NMRI to solid or quasi-solid materials and newly developed pulse sequences or devices to obtain a fine contrast and a high spatial resolution appeared.3.24.25*34 -36 A review with 10 references described the contribution to chemical microstructure, morphology, interactions, dynamics and reactions of polymers.34 Preparation of thermodynamically non-equilibrium magnetization for high contrast3, the second moment imaging,25 and Tlem imaging24 were reviewed. The ID proton TleK image using the Ostroff-Waugh pulse sequence in combination with a frequency-encoding imaging procedure was presented for a phantom of poly(ethy1eneoxide) and poly(methylmethacry1ate). The distribution of mechanical stress in an acrylate film and the spin density image for a mixture of two elastomers with different crosslink density was investigated by TieK imaging method.24 Two-dimensional, or double quantum solid state NMR and imaging in high magnetic field was reviewed with 20 reference^.^^ Specific examples which include heterogeneities due to stereochemically or packing irregularities and spatial heterogeneities due to phase separation or nonlinear deformation were presented. A refined solid-state imaging technique of the MARF (magic angle in the rotating frame) was described and preliminary initial phases were also ~ u m m a r i z e d .The ~ ~ easier experimental set-up and increased sensitivity of the method were demonstrated with polyethylene, adamantane, and vulcollan samples. Applying a novel method of proton NMR imaging which probes magnetization transfer by spin diffusion, a spatial distribution of microscopic domain sizes in the lamellar morphology was investigated for low density polyethylenes, which were aged until partial discharge and electrical treeing occurred.37 Length scales in heterogeneous polymers from solid state NMR was discussed. NMRI techniques allow on the macroscopic scale to spatially resolve differences in order and mobility in the necking region or in the shearbands of deformed polymers, which were applied to amorphous polymers, elastomers, and core-shell system.38Stray-field imaging of quadrupolar nuclei of half integer spin in solids was presented.39 The first proton NMR images of elastomeric materials at the highest spatial resolution (8.5 x 8.5 pm) at 14.1 T(600 MHz) was reported.40 The images of solid rocket propellant materials, consisting of a polybutadiene binder material filled with 82% solid particles revealed the distribution of individual filler particles in the polymer matrix as well as a thin polymer film of about 10-30 pm which was found to surround some of the larger filler particles. A laser confocal microscopy and NMR imaging of flexible polyurethane foam under different mechanical compression were ~ o m p a r e d . NMR ~' multiple echoes were observed in solid para-hydrogen (H2) and the experimental results were compared with the

472

Nucleur Mugnetic Resonunce

theory of the formation of NMR multiple echoes for isotropic impurities (HD) in H2 which had been developed for the case of weak quantum tunneling of the imp~rities.~~

7

Other Nuclei

Some applications of laser-polarized 3He and '29Xe have reported. Medical NMR sensing was reviewed with 19 references from the view point of Laser-polarized xenon could be a unique probe of living tissue, because xenon is highly sensitive to the local environment. For the realization of clinical and medical science applications, however, it is very important to deliver the polarized gas efficiently because of its short spin-lattice relaxation times and relatively low concentrations of xenon attainable in the body. A polarized xenon injection technique for in vivo NMR/MRI was newly designed. The peak local concentration of polarized xenon delivered to tissues by injection may exceed that delivered by respiration by severalfold.4 Spin-lattice relaxation times and self diffusion coefficients of hyperpolarized '29Xe in gas phase were measured.45 This paper involved optimum use of the perishable hyperpolarized magnetization of '29Xe. 3He was applied to low-field magnetic resonance in human lung.46 7Li NMRI was used for in vivo monitoring the degree of damage produced by photodynamic therapy after i.v. administration of zinc phtharocyanine disulfonate ( Z ~ P C S ~Phamacokinetics ).~~ of boronated compound (BSH and liposomeencapsulatedamine borane) in rat model was monitored by 'B NMRI.48 Three dimensional 19F NMRI of rat lung was presented by using inert fluorinated gases such as hexafluoroethane, mixed with 20% oxygen to form the inhaled gas.49 It was demonstrated that inert fluorinated gas imaging may be less expensive than polarized noble gas imaging and is appropriate for imaging steady-state rather than transient concentrations. 19F N MR signal of 2-deoxy-2-fluoro-u-glucose was used for tumor diagnosis in mice.50 NDP-bound hexose analog,50 bis(hexafluoropropyl)benzene" and p e r f l ~ o r o c a r b o nwas ~ ~ proposed as a new target for biological imaging using 19F NMR. 'H and I9F MRI of solid heptafluorodimethyloctanedionate rare earth complex was obtained by using large magnetic field gradients and Hahn echo^.^^ The effect of 5-fluor0 uracil (5FU) on the "P NMR profile of a mouse mammary carcinoma, implanted on the foot of CH3/He mice, was studied both in vivo and in perchloric acid extraction^.'^

'

8

Diffusion, Flow, and Velocity Image

8.1 Pulse Sequence and Model Experimental The DANTE-based, or more generally radiofrequency based, ultrafast imaging techniques, particularly FM DANTE was used in motion and flow imaging for tagging purposes.22 Distribution of displacement of fluids in porous medium can be acquired by NMRI. By combination of the displacement imaging with the line scan technique, onedimensionally resolved measurement with a high temporal resolution (