Starch-based Nanomaterials (SpringerBriefs in Food, Health, and Nutrition) 303042541X, 9783030425418

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SPRINGER BRIEFS IN FOOD, HEALTH, AND NUTRITION

Cristian Camilo Villa Zabala

Starch-based Nanomaterials

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SpringerBriefs in Food, Health, and Nutrition

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Cristian Camilo Villa Zabala

Starch-based Nanomaterials

Cristian Camilo Villa Zabala Programa de Química Universidad del Quindío Armenia, QUINDIO, Colombia

ISSN 2197-571X     ISSN 2197-5728 (electronic) SpringerBriefs in Food, Health, and Nutrition ISBN 978-3-030-42541-8    ISBN 978-3-030-42542-5 (eBook) https://doi.org/10.1007/978-3-030-42542-5 © The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Preface

Starch is one of the most important natural and biodegradable polymers on Earth. It is used by many plants as an energy reserve, and due to its biocompatibility and relative easy structural modification, it has been widely used in the cosmetic, food, pharmaceutical, and materials industries. In recent years, there has been a growing interest in starch due to the development of starch-based nanomaterials, which are small particles with diameters ranging from 10 nm up to 500 nm and that can be highly crystalline (nanocrystals) or completely amorphous (nanoparticles). Owing to their versatility, starch-based nanomaterials can be used as carriers of bioactive molecules to improve either medical treatments or nutrient absorption. They can also be used as reinforcements in composite materials, improving their mechanical and barrier properties, and several new potential applications are constantly reported in literature. This book aims to provide a quick guide to the exciting world of starch-­ based nanomaterials including their chemical and physical characteristics, as well as their synthesis methods and most common applications. Armenia, Quindio, Colombia

Cristian Camilo Villa Zabala

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Contents

1 Introduction��������������������������������������������������������������������������������������������������   1 References������������������������������������������������������������������������������������������������������   2 2 An Overview on Starch Structure and Chemical Nature������������������������   3 2.1 Structural Organization of Starch ��������������������������������������������������������   3 2.2 Amylose and Amylopectin ������������������������������������������������������������������   5 2.3 The Starch Granule ������������������������������������������������������������������������������   6 2.4 Functional and Thermal Properties of Starch ��������������������������������������   7 References������������������������������������������������������������������������������������������������������   8 3 Starch Nanoparticles and Nanocrystals����������������������������������������������������  11 3.1 Starch Nanocrystals������������������������������������������������������������������������������  11 3.2 Starch Nanocrystals Synthesis��������������������������������������������������������������  12 3.3 Starch Nanoparticles����������������������������������������������������������������������������  13 3.4 Starch Nanoparticles Synthesis������������������������������������������������������������  13 3.5 Starch Based Quantum Dots����������������������������������������������������������������  14 References������������������������������������������������������������������������������������������������������  16 4 Starch-Based Nanomateriales as Carriers in Drug and Nutrient Delivery����������������������������������������������������������������������������������  19 4.1 Nutrients and Nutraceutical Nanoencapsulation����������������������������������  20 4.2 Pharmaceutics Encapsulation ��������������������������������������������������������������  22 References������������������������������������������������������������������������������������������������������  23 5 Starch-Based Nanomateriales as Fillers in Composite Polymeric Films��������������������������������������������������������������������������������������������  27 5.1 Effect on the Mechanical Properties����������������������������������������������������  27 5.2 Effect on the Barrier Properties������������������������������������������������������������  28 References������������������������������������������������������������������������������������������������������  28

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About the Author

Cristian Camilo Villa  is an assistant professor at the Programa de Quimica in the Universidad del Quindio, Armenia, Quindio, Colombia. He completed his thesis in 2014 at the Universidad Nacional de Río Cuarto in Argentina, with the title “Research of ‘Smart’ Organized Systems to Be Used as Nanoreactors.” His research areas include the development of carbohydrate-based nanovehicles for nutrients and nutraceuticals delivery, specially starch-based materials. Furthermore, he has participated in research focused on the development of active, bioactive, and intelligent biodegradable food packaging.

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Chapter 1

Introduction

The study of materials on the nanoscale, around 1–500  nm, has been one of the greatest scientific revolutions of the last decades, as the properties of these materials drastically changes from their bulk counterpart. Furthermore, their physicochemical, optical and electronic properties heavily depend on their size, morphology and chemical composition, and all those parameters can be easily changed through physical and chemical methods. (Jeevanandam et al. 2018). Is because of this that nanotechnology and nanoscience have emerged in the last decades of the twentieth century and the firsts of the twenty first century, impregnating almost all aspects of science and technology. (Bazak et  al. 2015; Bouwmeester et  al. 2009; De et  al. 2014; Jeevanandam et al. 2018; Labouta and Schneider 2013). Normally, in the bulk scale, materials can be classified as conductors, semiconductors and insulators, however, once those materials are reduced to the nanoscale their properties can change considerably. On the nanoscale materials are dominated by quantum effects that are lost once certain number of atoms or molecules are assembled. For examples, colloidal suspensions of metallic nanoparticles are known to present colors that are quite different from their bulk appearance, and that this colors depend considerably on particle size and morphology. (Amendola et al.2017; Priyadarshini and Pradhan 2017; Shankar et al. 2016; Zeng et al. 2011). This phenomenon, known as surface plasmon resonance, is a result of the interaction between the visible light and the electrons located in the surface of the nanoparticle. As for polymeric nanoparticles, they have become one of the most promising materials for targeted drug delivery, intelligent and active food packaging, and several other fields of science. (Banik et  al. 2016; Karlsson et  al. 2018; Nasir et  al. 2015) Among them, biodegradable polymeric nanoparticles from natural sources are amongst the one with greatest potential due to their biocompatibility and relative easy synthesis. Nanoparticles made from polysaccharides, such as: alginates, ­cellulose, chitosan and others; proteins and lipids can use in diverse food, cosmetic, and medical applications. (Herrera et al. 2015; Swierczewska et al. 2016).

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 C. C. Villa Zabala, Starch-based Nanomaterials, SpringerBriefs in Food, Health, and Nutrition, https://doi.org/10.1007/978-3-030-42542-5_1

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They show excellent biocompatibility since they are broken down by enzymatic degradation into easily metabolized peptides or polysaccharides in the body, and this degradation rate can be tuned for a desired release profile.

References Amendola, V., Pilot, R., Frasconi, M., Maragò, O. M., & Iatì, M. A. (2017). Surface plasmon resonance in gold nanoparticles: A review. Journal of Physics: Condensed Matter, 29(20), 203002. https://doi.org/10.1088/1361-648x/aa60f3. Banik, B. L., Fattahi, P., & Brown, J. L. (2016). Polymeric nanoparticles: The future of nanomedicine. WIREs Nanomedicine and Nanobiotechnology, 8(2), 271–299. https://doi.org/10.1002/ wnan.1364. Bazak, R., Houri, M., El Achy, S., Kamel, S., & Refaat, T. (2015). Cancer active targeting by nanoparticles: A comprehensive review of literature. Journal of Cancer Research and Clinical Oncology, 141(5), 769–784. https://doi.org/10.1007/s00432-014-1767-3. Bouwmeester, H., Dekkers, S., Noordam, M. Y., Hagens, W. I., Bulder, A. S., de Heer, C., et al. (2009). Review of health safety aspects of nanotechnologies in food production. Regulatory Toxicology and Pharmacology, 53(1), 52–62. https://doi.org/10.1016/j.yrtph.2008.10.008. De, A., Bose, R., Kumar, A., & Mozumdar, S. (2014). A brief overview of nanotechnology. In A. De, R. Bose, A. Kumar, & S. Mozumdar (Eds.), Targeted delivery of pesticides using biodegradable polymeric nanoparticles (pp. 35–36). New Delhi: Springer India. Herrera Estrada, L. P., & Champion, J. A. (2015). Protein nanoparticles for therapeutic protein delivery. Biomaterials Science, 3(6), 787–799. https://doi.org/10.1039/C5BM00052A. Jeevanandam, J., Barhoum, A., Chan, Y. S., Dufresne, A., & Danquah, M. K. (2018). Review on nanoparticles and nanostructured materials: History, sources, toxicity and regulations. Beilstein Journal of Nanotechnology, 9, 1050–1074. https://doi.org/10.3762/bjnano.9.98. Karlsson, J., Vaughan, H.  J., & Green, J.  J. (2018). Biodegradable polymeric nanoparticles for therapeutic Cancer treatments. Annual Review of Chemical and Biomolecular Engineering, 9(1), 105–127. https://doi.org/10.1146/annurev-chembioeng-060817-084055. Labouta, H. I., & Schneider, M. (2013). Interaction of inorganic nanoparticles with the skin barrier: Current status and critical review. Nanomedicine: Nanotechnology, Biology and Medicine, 9(1), 39–54. https://doi.org/10.1016/j.nano.2012.04.004. Nasir, A., Kausar, A., & Younus, A. (2015). A review on preparation, properties and applications of polymeric nanoparticle-based materials. Polymer-Plastics Technology and Engineering, 54(4), 325–341. https://doi.org/10.1080/03602559.2014.958780. Priyadarshini, E., & Pradhan, N. (2017). Gold nanoparticles as efficient sensors in colorimetric detection of toxic metal ions: A review. Sensors and Actuators B: Chemical, 238, 888–902. https://doi.org/10.1016/j.snb.2016.06.081. Shankar, P. D., Shobana, S., Karuppusamy, I., Pugazhendhi, A., Ramkumar, V. S., Arvindnarayan, S., & Kumar, G. (2016). A review on the biosynthesis of metallic nanoparticles (gold and silver) using bio-components of microalgae: Formation mechanism and applications. Enzyme and Microbial Technology, 95, 28–44. https://doi.org/10.1016/j.enzmictec.2016.10.015. Swierczewska, M., Han, H.  S., Kim, K., Park, J.  H., & Lee, S. (2016). Polysaccharide-based nanoparticles for theranostic nanomedicine. Advanced Drug Delivery Reviews, 99, 70–84. https://doi.org/10.1016/j.addr.2015.11.015. Zeng, S., Yong, K.-T., Roy, I., Dinh, X.-Q., Yu, X., & Luan, F. (2011). A review on functionalized gold nanoparticles for biosensing applications. Plasmonics, 6(3), 491. https://doi.org/10.1007/ s11468-011-9228-1.

Chapter 2

An Overview on Starch Structure and Chemical Nature

Starch is considered the second most common biomass on earth, as it is produced by green plants as an energy reserve. It is found as granules of different morphologies (depending of the botanical source) in plant tissues, mainly seed, roots, tubers, leaves and fruits. (Odeku 2013; Pérez and Bertoft 2010; Zia ud et al. 2017). On a cellular level, starch is synthesized in two types of plastids, chloroplasts and amyloplasts, through three main pathways: The Calvin cycle, sucrose synthesis and storage starch biosynthesis. (Hsieh et al. 2019; Tappiban et al. 2019). Chemically, starch can be defined as a polysaccharide composed of α-D-glucopyranosyl units that can be linked in either α-D-(1–4) and/or α-D-(1–6) linkages. These molecular linkages form to types of molecules: the linear amylose formed by approximately 1000 glucose units linked in α-D-(1–4) manner and the branched amylopectin, formed by approximately 4000 glucose units, branched through α-D-(1–6) linkages, as shown in Fig. 2.1. The union of both amylose and amylopectin forms a semi-crystalline structure arranged as small granules with diameters between 1–100 μm. Most of the native starches have amylose percentages that range between 70 and 80% and amylopectin ranging from 20 to 30%. Furthermore, some types of starch can have a very high amylose content, such as starch extracted from amylomaize with a 70% of amylose and some can have very low amylose content such as waxy maize starch with a 1% amylose content.

2.1  Structural Organization of Starch One of the most accepted models of the starch granules is that of concentric growth rings originating from the hilium of the granules, with alternating amorphous and semi-crystalline regions of 120–400 thickness. (Blazek and Gilbert 2011; Donald et al. 2001; Vanier et al. 2017). Each growth ring is composed of blocklets of around 20–50 nm and each blocklet consist of semicrystalline lamellae, of approximately © The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 C. C. Villa Zabala, Starch-based Nanomaterials, SpringerBriefs in Food, Health, and Nutrition, https://doi.org/10.1007/978-3-030-42542-5_2

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Fig. 2.1  Schematic representation of the structure of amylose and amylopectin

9 nm of length, containing amylopectine and amylose chains. (Le Corre et al. 2010). In brief, the multilevel can be described as follow: the last level is that of the starch granule, preceded by the alternating semicrystalline and amorphous growth rings. The next level down is formed by the blocklets, with the smallest ones proposed to be located in the amorphous rings and the largest ones in the semicrystalline growth rings. (Baldwin et al. 1998; Pérez and Bertoft 2010; Ptaszek et al. 2009; Wang et al. 2015). Down from the blocklets level are left-handed helices, with an approximated width of 18 nm, and beneath them are the crystalline and amorphous lamellae with a periodicity of 9 nm. Finally, the smallest unit of the starch structure are the individual glucosyl units. Figure  2.2 shows the structural organization of the starch granule according to the multilevel model. One of the most common techniques used in the characterization of the starch structure is X-ray diffraction (XRD), as according to their XRD diffraction pattern starches can be classified into three crystalline types called A, B, and C. (Le Corre et al. 2010; Magallanes-Cruz et al. 2017) The main reason behind the different XDR patterns of starch is the packing configuration of the double helices and their interaction with water molecules. In A-type structures, double helices are closely packed with water molecules between each helical structure, as shown in Fig. 2.3. On the other hand, B-type structures have a more open organization, with a central cavity formed by six double helices in which water molecules are located. Finally, the C-type starch is considered a mixture of both A and B-types, as their XDR diffraction pattern can be resolved as a combination of the other two types. (Bogracheva et al. 1998; Imberty et al. 1987; Imberty and Perez 1988) Starch from cereals tend to have the A-type pattern, while starches from tubbers and other amylose rich

2.2  Amylose and Amylopectin

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Fig. 2.2  The different levels of starch structure. Reproduced with permission from (T. T. B. Tran et al. 2011) Fig. 2.3 Crystalline Packaging of the double helices in A and B-type starches

starches have a B-type pattern. On the other hand, legumes, roots, some fruits and plantain starches present a C-type pattern. (Copeland et al. 2009). Figure 2.4 shows typical XDR patterns for A, B and C-type starches. Most native starch granules are known to present a Maltese cross when observed under polarized light, indicating a radial orientation of the principle axis of the crystallites. (Pérez and Bertoft 2010).

2.2  Amylose and Amylopectin Amylose is a long, linear α-glucan, with a molecular weight of approximately 1x105  – 1x106 and a degree of polymerization of 300–5000, with around 9–20 branch points that are equivalent to 3–11 chains per molecule and the side chains range in length from 4 to over 100. (Ratnayake et  al. 2002; Tester et  al. 2004) Amylose crystallizes rapidly in solution in the form of left-handed double helices that are packed in parallel fashion forming either A or B-type allomorphs, in a

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Intensity (A.U)

Corn Starch Potato Starch Banana Starch

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2q Fig. 2.4  XRD patterns of corn starch (A-type); potato starch (B-type) and banana starch (C-type)

phenomenon known as retrogradation. (Ratnayake et al. 2002). Amylopectin, on the other hand, is a more complex structure, with molecular weights in the range of 1x107 – 1x109 and a polymerization degree of 9000–16,000, with an average chain length of 20–25. It’s been reported, that amylopectin molecules contain several types of chains, classified as either A, B or C chains. The A chains are unbranched and linked to B chains; the B chains carry one or more A and/or B chains and the C chains, which contains the reducing end of the molecule. The distribution of the different types of chains depend on the botanical source of the starch. (Ratnayake et al. 2002). As mentioned before, the ration of amylose and amylopectin content in the different starches depends on their botanical origin, as Table 2.1 shows the amylose content of different types of starch.

2.3  The Starch Granule The size and morphology of starch granules are dependent of their botanical source, as their shape can vary from spherical, oval, polygonal, lenticular, and kidney shapes and their size can range for 40%) than common starch granules (~ 25%). SNc are mostly composed of platelet-like structures with a nanosize diameter and as a result of their high crystallinity they can withstand high temperatures, as those encounter in both food and materials processing. (Kumari et al. 2020)

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 C. C. Villa Zabala, Starch-based Nanomaterials, SpringerBriefs in Food, Health, and Nutrition, https://doi.org/10.1007/978-3-030-42542-5_3

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3.2  Starch Nanocrystals Synthesis SNc are commonly are obtained by using either HCl or H2SO4 as hydrolyzing agents during long periods of time (usually beyond 5 days) and followed by a neutralization with NaOH. (Villa et al. 2019). Acid hydrolysis of starch can be described in two steps. First a fast initial hydrolysis in which the outer layers of amorphous material are removed, and the is followed by a slow hydrolysis corresponding to the erosion of the crystalline regions. (Jayakody and Hoover 2002; Kim et  al. 2015; Kumari et  al. 2020). It’s been reported that several parameters such as botanical source, degree of crystallinity, time, temperature and acid type can have a great impact on the yield, size and morphology of the SNc. For example, increasing temperatures can increase hydrolysis rates, however, high temperatures can cause gelatinization and decomposition of the starch granule. (H.-Y. Kim et al. 2015). Of the two main acids used in SNc synthesis, H2SO4 allows faster hydrolysis rates and higher yields, while HCl hydrolysis is more time consuming. Normally, nanosized particles can be obtained after 5–7 days of H2SO4 hydrolysis, while this can take up to 15 days using HCl.(H.-Y. Kim et al. 2015; Kumari et al. 2020; Putaux et al. 2003). Furthermore, during H2SO4 hydrolysis sulfate groups are incorporated on the surface of the SNc, increasing their dispersability and stability in aqueous solution, when compared to SNc obtained by HCl hydrolysis. (Angellier et  al. 2006). Figure 3.1 shows a schematic representation of the surface modification of SNc obtained by using different hydrolyzing agents. As mentioned before, starch structure also plays an important role in SNc acid hydrolysis, Low amylose and waxy starches are more susceptible to acid hydrolysis with higher SNc yields. Furthermore, reports by D.  LeCorre et  al. (2011) and D. S. LeCorre et al. (2012a) showed that maize starches with higher amylose content produce large sized SNc, as amylose disrupts the hydrolysis process of the amorphous regions, making it slower and harder. One of the main concerns of acid hydrolysis SNc synthesis are the high amount of hydrolyzing agent and the long periods of time needed for a complete process have led to the development of new method SNc synthesis methods. (Villa et al. 2019) In recent years, several authors have reported the use of enzymatic hydrolysis followed by acid hydrolysis as an alternative in SNc synthesis. Most of the e­ xamples

Fig. 3.1  Schematic representation of SNc obtained by using (a) H2SO4 and (b) HCl as hydrolyzing agents. Adapted with permission of Le Corre and Angellier-Coussy (2014)

3.4  Starch Nanoparticles Synthesis

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found in literature use amylases (α and β) as the hydrolyzing agent. (Kumari et al. 2020). α-amylase us a type of endo-amylase that hydrolyses internal α-1,4 bonds, while β-amylase is an exo-amylase that causes cleavage of alternated α-1,4 bonds from non-reducing ends. (Qiu et al. 2019). There are few reports on the use of only enzymes in SNc synthesis, as it seems that enzymatic hydrolysis needs to be accompanied by further acid treatment. Reports show that use of α-amylose as the solely hydrolyzing agent for waxy maize and rice starch results in starch particles or 11 μm and 3.6 μm, respectably. (Foresti et al. 2014; Kim et al. 2008). Moreover, D. LeCorre, Vahanian, Dufresne, and Bras (2012b) used combined approach in the synthesis of waxy maize starch SNC by using consecutive steps of α-amylase and H2SO4 acid hydrolysis, reducing hydrolysis time by three days. A similar behavior was reported for waxy potato starch combining both enzymatic and acid hydrolysis. (Hao et al. 2018). Other physical methods have been used in combination with acid hydrolysis, such a as ball milling and ultrasonication. (Boufi et al. 2018; Dai et al. 2018).

3.3  Starch Nanoparticles Starch nanoparticles (SNp) are commonly confuse with SNc, however they both have very different structures and synthesis approaches. (Le Corre et  al. 2010). SNps are mostly obtained from anti-solvent (nanoprecipitaion) and other physical methods. They have a completely amorphous structure and tend to have bigger particle size than SNc and present a higher water solubility. However, as with SNc, their morphology, particle size and characteristics depend heavily on the starch botanical origin and synthesis method.

3.4  Starch Nanoparticles Synthesis One of the most common method in SNp synthesis is the nanoprecipitation of starch. It involves either hot or cold (addition of NaOH) gelatinization followed by a slow addition of an anti-solvent, mostly ethanol or acetone. (Acevedo-Guevara et al. 2018; H.-Y. Kim et al. 2015; Ma et al. 2008; Qin et al. 2016). This method is based in the nucleation and growth theory, as the anti-solvent is added dropwise to gelatinized starch, causing a supersaturation that is followed by nuclei and particle growth. (Qiu et al. 2019). These steps can be explained as follow: once the anti-­ solvent is added to the gelatinized starch paste, supersaturation begins to increase and changes in the interfacial tension allow the formation of the SNp. (Tan et al. 2009) After the critical overlapping concentration in reached nucleation stars and particles are formed. Furthermore, as nuclei are formed and growth supersaturation decreases quickly allowing a controlled process of growing nuclei. (Kumari et al. 2020). Figure 3.2 shows a schematic representation of the nanoprecipitation process.

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Fig. 3.2 (A) Schematic representation of the nanoprecipitation SNp synthesis and (B) of the change of superasaturation degree as a function of time. Reproduced with permission of Qiu et al. (2019)

Nanoprecipitation is a simple method for SNp synthesis, and characteristics of the nanoparticles can be controlled by the addition of surfactants (Chin et al. 2011) anb by changing the anti-solvent or the amylopectin/amylose ratios of the starch. (Chin et al. 2011; Sadeghi et al. 2017). Other methods that have been used in SNp synthesis include reactive extraction in which starch granules are subjected to high temperatures and undergo structural changes such as melting, fragmentation an incomplete gelatinization (due to limited water prencese). As the starch granules soften and melt they are subjected to high-­ pressure homogenization and get torn into nano-sized particles. (Liu et  al. 2009). Gamma irradiation has also been used as a technique to reduce the starch granule size. In this technique a homogenous starch paste is irradiated with gamma rays inducing hydrolysis by breaking the amorphous region. (Kumari et al. 2020; Lin et al. 2011).

3.5  Starch Based Quantum Dots In the last decades the development of quantum dots (QDs) has been one of the most important areas in nanotechnology research. (Duan et al. 2015; Li et al. 2015) QDs are semiconductor nanocrystals with sizes ranging from 1 to 10 nm and that have

3.5  Starch Based Quantum Dots

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size-selective optical properties due to their quantum confinement effect generating great interest in optoelectronics, biosensing, bioimaging and medicine.(Al-Douri et  al. 2018). However, most of the reported QDs are made from toxic materials, limiting their application in some areas. Due to this carbon based quantum dots have emerged as an alternative to traditional QDs. (Al-Douri et al. 2018). As interest in

Fig. 3.3  Schematic representation of the starch based QDs synthesis. Reproduced with permission from Al-Douri et al. (2018)

Fig. 3.4  Starch based QDs of different light emitting properties (a) normal (b) blue, (c) green and (d) yellow. Reproduced with permission from (Al-Douri et al. (2018))

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3  Starch Nanoparticles and Nanocrystals

carbon based QDs has increased, so has the search of new materials for their precursors and recent reports have shown that starch can be used as a material in QDs synthesis. Carbon based QDs have been made from starch of different botanical sources, including potato, yam, rice and maize and cassava. (Al-Douri et al. 2018; M. Liu et al. 2016; Qiang et al. 2019; Yan et al. 2015). In general, starch based QDs are synthetized through decomposition of the starch structure into graphene, either through strong acid hydrolysis assisted with microwave irradiation or ultrasound or hydrothermal methods. Al-Douri et al. (2018) synthetized starch based QDs from different botanical sources using either H2SO4 or H3PO4 as hydrolyzing agent and different micro way irradiation times. Results showed that light emission properties of the QDs can be tuned by changing the hydrolyzing agent and irradiation time, as for example blue light emitting QDs were obtained by using H2SO4 and 4 minutes’ irradiation and increasing irradiation time to 8 minutes the emitted green light. Figure 3.3 shows a schematic representation of the starch based QDs synthesis and while Fig.  3.4 shows their light emitting properties.

References Acevedo-Guevara, L., Nieto-Suaza, L., Sanchez, L.  T., Pinzon, M.  I., & Villa, C.  C. (2018). Development of native and modified banana starch nanoparticles as vehicles for curcumin. International Journal of Biological Macromolecules, 111, 498–504. https://doi.org/10.1016/j. ijbiomac.2018.01.063. Al-Douri, Y., Badi, N., & Voon, C.  H. (2018). Synthesis of carbon-based quantum dots from starch extracts: Optical investigations. Luminescence, 33(2), 260–266. https://doi.org/10.1002/ bio.3408. Angellier, H., Molina-Boisseau, S., Dole, P., & Dufresne, A. (2006). Thermoplastic starch−waxy maize starch nanocrystals nanocomposites. Biomacromolecules, 7(2), 531–539. https://doi. org/10.1021/bm050797s. Boufi, S., Bel Haaj, S., Magnin, A., Pignon, F., Impéror-Clerc, M., & Mortha, G. (2018). Ultrasonic assisted production of starch nanoparticles: Structural characterization and mechanism of disintegration. Ultrasonics Sonochemistry, 41, 327–336. https://doi.org/10.1016/j. ultsonch.2017.09.033. Chin, S.  F., Pang, S.  C., & Tay, S.  H. (2011). Size controlled synthesis of starch nanoparticles by a simple nanoprecipitation method. Carbohydrate Polymers, 86(4), 1817–1819. https://doi. org/10.1016/j.carbpol.2011.07.012. Dai, L., Li, C., Zhang, J., & Cheng, F. (2018). Preparation and characterization of starch nanocrystals combining ball milling with acid hydrolysis. Carbohydrate Polymers, 180, 122–127. https://doi.org/10.1016/j.carbpol.2017.10.015. Duan, J., Zhang, H., Tang, Q., He, B., & Yu, L. (2015). Recent advances in critical materials for quantum dot-sensitized solar cells: A review. Journal of Materials Chemistry A, 3(34), 17497–17510. https://doi.org/10.1039/C5TA03280F. Foresti, M. L., Williams, M. d. P., Martínez-García, R., & Vázquez, A. (2014). Analysis of a preferential action of α-amylase from B. licheniformis towards amorphous regions of waxy maize starch. Carbohydrate Polymers, 102, 80–87. https://doi.org/10.1016/j.carbpol.2013.11.013. Hao, Y., Chen, Y., Li, Q., & Gao, Q. (2018). Preparation of starch nanocrystals through enzymatic pretreatment from waxy potato starch. Carbohydrate Polymers, 184, 171–177. https://doi. org/10.1016/j.carbpol.2017.12.042.

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Jayakody, L., & Hoover, R. (2002). The effect of lintnerization on cereal starch granules. Food Research International, 35(7), 665–680. https://doi.org/10.1016/S0963-9969(01)00204-6. Kim, H.-Y., Park, S. S., & Lim, S.-T. (2015). Preparation, characterization and utilization of starch nanoparticles. Colloids and Surfaces B: Biointerfaces, 126, 607–620. https://doi.org/10.1016/j. colsurfb.2014.11.011. Kim, J.-Y., Park, D.-J., & Lim, S.-T. (2008). Fragmentation of waxy rice starch granules by enzymatic hydrolysis. Cereal Chemistry, 85(2), 182–187. https://doi.org/10.1094/CCHEM-85-2-0182. Kumari, S., Yadav, B.  S., & Yadav, R.  B. (2020). Synthesis and modification approaches for starch nanoparticles for their emerging food industrial applications: A review. Food Research International, 128, 108765. https://doi.org/10.1016/j.foodres.2019.108765. Le Corre, D., & Angellier-Coussy, H. (2014). Preparation and application of starch nanoparticles for nanocomposites: A review. Reactive and Functional Polymers, 85, 97–120. https://doi. org/10.1016/j.reactfunctpolym.2014.09.020. Le Corre, D., Bras, J., & Dufresne, A. (2010). Starch nanoparticles: A review. Biomacromolecules, 11(5), 1139–1153. https://doi.org/10.1021/bm901428y. LeCorre, D., Bras, J., & Dufresne, A. (2011). Influence of botanic origin and amylose content on the morphology of starch nanocrystals. Journal of Nanoparticle Research, 13(12), 7193–7208. https://doi.org/10.1007/s11051-011-0634-2. LeCorre, D., Vahanian, E., Dufresne, A., & Bras, J. (2012b). Enzymatic pretreatment for preparing starch nanocrystals. Biomacromolecules, 13(1), 132–137. https://doi.org/10.1021/bm201333k. LeCorre, D. S., Bras, J., & Dufresne, A. (2012a). Influence of the botanic origin of starch nanocrystals on the morphological and mechanical properties of natural rubber nanocomposites. Macromolecular Materials and Engineering, 297(10), 969–978. https://doi.org/10.1002/ mame.201100317. Li, X., Rui, M., Song, J., Shen, Z., & Zeng, H. (2015). Carbon and Graphene quantum dots for optoelectronic and energy devices: A review. Advanced Functional Materials, 25(31), 4929–4947. https://doi.org/10.1002/adfm.201501250. Lin, N., Yu, J., Chang, P. R., Li, J., & Huang, J. (2011). Poly(butylene succinate)-based biocomposites filled with polysaccharide nanocrystals: Structure and properties. Polymer Composites, 32(3), 472–482. https://doi.org/10.1002/pc.21066. Liu, D., Wu, Q., Chen, H., & Chang, P. R. (2009). Transitional properties of starch colloid with particle size reduction from micro- to nanometer. Journal of Colloid and Interface Science, 339(1), 117–124. https://doi.org/10.1016/j.jcis.2009.07.035. Liu, M., Huang, H., Wang, K., Xu, D., Wan, Q., Tian, J., et al. (2016). Fabrication and biological imaging application of AIE-active luminescent starch based nanoprobes. Carbohydrate Polymers, 142, 38–44. https://doi.org/10.1016/j.carbpol.2016.01.030. Ma, X., Jian, R., Chang, P.  R., & Yu, J. (2008). Fabrication and characterization of citric acid-­ modified starch nanoparticles/plasticized-starch composites. Biomacromolecules, 9(11), 3314–3320. https://doi.org/10.1021/bm800987c. Putaux, J.-L., Molina-Boisseau, S., Momaur, T., & Dufresne, A. (2003). Platelet Nanocrystals resulting from the disruption of waxy maize starch granules by acid hydrolysis. Biomacromolecules, 4(5), 1198–1202. https://doi.org/10.1021/bm0340422. Qiang, R., Yang, S., Hou, K., & Wang, J. (2019). Synthesis of carbon quantum dots with green luminescence from potato starch. New Journal of Chemistry, 43(27), 10826–10833. https://doi. org/10.1039/C9NJ02291K. Qin, Y., Liu, C., Jiang, S., Xiong, L., & Sun, Q. (2016). Characterization of starch nanoparticles prepared by nanoprecipitation: Influence of amylose content and starch type. Industrial Crops and Products, 87(Supplement C), 182–190. https://doi.org/10.1016/j.indcrop.2016.04.038. Qiu, C., Hu, Y., Jin, Z., McClements, D. J., Qin, Y., Xu, X., & Wang, J. (2019). A review of green techniques for the synthesis of size-controlled starch-based nanoparticles and their applications as nanodelivery systems. Trends in Food Science & Technology, 92, 138–151. https://doi. org/10.1016/j.tifs.2019.08.007.

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Sadeghi, R., Daniella, Z., Uzun, S., & Kokini, J. (2017). Effects of starch composition and type of non-solvent on the formation of starch nanoparticles and improvement of curcumin stability in aqueous media. Journal of Cereal Science, 76, 122–130. https://doi.org/10.1016/j. jcs.2017.05.020. Tan, Y., Xu, K., Li, L., Liu, C., Song, C., & Wang, P. (2009). Fabrication of size-controlled starch-­ based nanospheres by nanoprecipitation. ACS Applied Materials & Interfaces, 1(4), 956–959. https://doi.org/10.1021/am900054f. Villa, C. C., Sanchez, L. T., & Rodriguez-Marin, N. D. (2019). Starch nanoparticles and Nanocrystals as bioactive molecule carriers. 91–98. doi:https://doi.org/10.1007/978-3-030-19416-1_6. Yan, Z., Shu, J., Yu, Y., Zhang, Z., Liu, Z., & Chen, J. (2015). Preparation of carbon quantum dots based on starch and their spectral properties. Luminescence, 30(4), 388–392. https://doi. org/10.1002/bio.2744.

Chapter 4

Starch-Based Nanomateriales as Carriers in Drug and Nutrient Delivery

Nanoencapsulation is an expanding field among nanoscience, as it has a lot of potential applications, especially in the pharmaceutical and food industries. It involves the introduction of small particles in nano sized capsules of a wall material. (Ezhilarasi et al. 2013) There is a variety of bioactive molecules that have generated great interest in both pharmaceutical and food industries due to their antimicrobial, antioxidant, anti-inflammatory or anticancer activities, among others. Nevertheless, their application has been limited due to several factors, such as sensibility to O2, CO2 and light; low-water solubility and low bioavailability. (Akhavan et al. 2018; Pathakoti et  al. 2017; Rostamabadi et  al. 2019). Hence, nanoencapsulation has probe to be a powerful technique in the protection and controlled release of several bioactive molecules, proteins, enzymes and peptides. Several biopolymers such as proteins, lipids and carbohydrates, have been use as nanocapsules for bioactive molecules. (Akhavan et al. 2018). Among carbohydrates, hydrocolloids such as alginate, chitosan, cellulose, xanthan gum and pectin have shown great potential for nanoencapsulation. (Burapapadh et al. 2016; Divya and Jisha 2018; Paques et al. 2014; Xu et al. 2015) More recently, starch based nanomaterials have joined this group, as they offer several advantages. Starcm materials are known for their biocompability and are consider safe for use in the pharmaceutical, cosmetical and food industries. Their characteristics can be easily tuned by controlling the synthesis process or the botanical source. Finally, they can be relative cheap to produce. (Ades et al. 2012; Hasanvand et al. 2015; Li et al. 2018).

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 C. C. Villa Zabala, Starch-based Nanomaterials, SpringerBriefs in Food, Health, and Nutrition, https://doi.org/10.1007/978-3-030-42542-5_4

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4.1  Nutrients and Nutraceutical Nanoencapsulation Most of the times the selected nanovehicles for bioactive molecules encapsulation are SNp, as their amorphous structure and relative high water solubility that can be used in order to increase bioavailability of the bioactive molecules. One of the most common methods for encapsulation of the bioactive molecules is the anti-solvent synthesis, as bioactive molecules are dissolved in the organic solvent and added in a controlled manner to the previously gelatinized starch. The molecules are then entrapped in highly hydrophobic interior of the starch nanovehicles and, furthermore, by reducing starch polarity through chemical modifications like acetylation or cross-linking with other molecules, the entrapment capacity can be considerably increased.(Acevedo-Guevara et al. 2018; Santoyo-Aleman et al. 2019). Among nutraceutical molecules, polyphenols such as curcumin and quercetin have generated great interest due to several health related benefices. Curcumin, is present in the rhizomes of turmeric and have been used as a food colorant for several centuries. It has been reported that curcumin has anti-cancer, antioxidant, anti-­ inflammatory, antimicrobial and antiviral activity, however, use of curcumin is limited by its low water solubility, fast degradation in acid and basic media, and low bioavailability. (Anand et al. 2007; Maghsoudi et al. 2017); (Mai et al. 2017; Menon and Sudheer 2007; Mirzaei et  al. 2017; Nelson et  al. 2017; Oliveira et  al. 2015; Stanić 2017). Chin et al. (2014) using sago starch SNp for encapsulation of curcumin. They reported a loading capacity reaching 78% and particle sizes around 50–80 nm. In order to increase entrapment efficiency Pang et al. (2014) used maleate ester modified sago starch SNp reaching a loading capacity of 85%. They explained that the increasing hydrogen bond interactions between curcumin and ester molecules incorporated into the nanoparticles structure lead to more curcumin molecules incorporated into the nanovehicles. However, chemical modification lead to larger particles sizes, around 120  nm. This was also observed by Acevedo-­ Guevara et al. (2018), using native and acetylated banana starch SNp with higher encapsulation capacity and particle size in the modified SNp than in their native counterpart due to the intramolecular forces between the acetyl groups and curcumin molecules. Finally, Sadeghi et al. (2017) used corn starch with different amylose/amylopectin ratios for curcumin encapsulation, reporting that SNp size increases at higher amylose content, and that SNps can protect curcumin from photodegradation, as more than 83% of the encapsulated polyphenol remained after 10 days of storage as shown in Fig. 4.1. Likewise, Farrag et al. (2018) used SNp from different botanical sources (potato, pea and corn) to encapsulate quercetin, a polyphenol found in many leaves, fruits and vegetables such as onions, apples and tea. (Bose et al. 2013; Jeszka-Skowron et al. 2015). They observed that starch’s amylopectin content has a significant effect on quercetin encapsulation and release kinetics, as the potato starch SNp can encapsulate more quercetin molecules due to their higher amylopectin content with respect of corn starch SNp. It was also reported that SNP encapsulation preserves quercetin antioxidant activity, however, their antioxidant activity its related to the

4.1  Nutrients and Nutraceutical Nanoencapsulation

Curcumin in PBS (control)

Curcumin in PBS and 0.15 mg/ml starch NPs

21

Curcumin in PBS and 1.0 mg/ml starch NPs

Fig. 4.1  Curcumin encapsulated in corn starch SNp after 10 days of storage. Reproduced with permission of Sadeghi et al. (2017)

SNP loading capacity. The more loading percentage of quercetin, the more released quercetin into the media which lead to higher radical scavenging activity. Furthermore, they observed that starch nanoparticles can release molecules through a Fickian diffusion mechanism as revealed by the use of several mathematical models. This has also been reported by as they used native and citric acid modified banana starch to encapsulate β-carotene, a precursor to vitamin A. Like previous reports, SNp modification increased encapsulation efficiency by reducing starch polarity, but also that release into different food simulant media is controlled by a Fickian type diffusion. Besides vitamin A, vitamin D has also been encapsulated in starch based nanosystems, due high lipophilic nature and easy degradation by light and oxygen. (Ballard et al. 2007; Mahmoodani et al. 2017; Walia et al. 2017). Hasanvand et al. (2015) reported that high amylose maize SNp can be use as carriers of vitamin D, reaching encapsulation values up to 78%. They used several techniques like differential scanning calorimetry and Fourier transform infrared spectroscopy and observed that hydrogen bond formations are the main force for vitamin D encapsulation. Likewise, Hasanvand et al. (2018) studied the effect of amylose content in the encapsulation of vitamin SNp. They used high and low amylose corn and potato SNp, respectably and observed that loading capacity increased in low amylose SNp with respect of their high amylose counterpart. Furthermore, structural studies showed that this behavior is not directly related to amylose content, but to particle size as low amylose SNp have a larger particle size and can accommodate more vitamin D molecules. Antioxidant molecules have also been targeted for encapsulation in starch based nanomaterials. de Oliveira et al. (2017) reported that native and acetylated cassava starch SNp can be used as nanocarriers of gallic acid and butylated hidroxytoluene (BHT). They observed that starch acetylation allows higher loading capacities for

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both antioxidant molecules through formation of hydrogen bonds between the starch nanovehicles and the bioactive molecules. Ahmad et al. (2019) used horse chestnut, water chestnut, and lotus stem starch SNp as vehicles for catechin encapsulation. Likewise, Shabana et al. (2018) use potato SNc obtained through ultrasound assisted acid hydrolysis to encapsulated ascorbic and oxalic acid, observing that ultrasound treatment not only allows smaller particle sizes, but also can increase antioxidant loading capacity. Starch nanoparticles have been of special interest as vehicles for controlled release of bioactive molecules in specific conditions of the gastro-intestinal track. SNp have shown the capability of shielding different bioactive molecules from the low pH and enzymatic conditions of the stomach and promote release in the small intestine. (Qiu et  al. 2019; Rostamabadi et  al. 2019; Villa et  al. 2019). Acevedo-­ Guevara et al. (2018) studied the release of curcumin from native and acetylated banana SNp in simulated gastric and intestinal conditions. They observed that curcumin degradation in the harsh environment of the stomach is reduced by nanoencapsulation, while most of the molecule release occurred in intestinal conditions. This was also observed by Santoyo-Aleman et al. (2019) using native a citric acid modified banana starch SNps for β-carotene release and encapsulation. They observed that the resistant nature of banana starch increases stability of the molecule in the stomach while allowing a controlled release in the intestine. Similarly, Ahmad et  al. (2019) studied the behavior of catechin from horse chestnut, water chestnut and lotus stem SNP in simulated gastric conditions. They observed that starch based nanoencapsulation is an efficient tool in the preservation of catechin bioactive properties, such as lipase, cholesterol esterase and glucosidase inhibition in gastric conditions, decreasing its degradation due to the stomach low pH values.

4.2  Pharmaceutics Encapsulation Although most of the literature have focused on the use of starch based nanovehicles for encapsulation of nutrients and nutraceutical molecules, there are some example of studies focused on pharmaceutics encapsulation. Ab’lah Norul et  al. (2018) reported that corn SNc obtained by acid treatment can encapsulate 5-­fluoracil, a synthetic molecule of great interest in the treatment of several gastric related cancers. (Jordan 2016) Once formed, corn SNc have shown to be specially resistant to acid environment, increasing their stability in gastric conditions and allowing release on both intestinal and colonic conditions. Qi et al. (2017) studied the encapsulation and release of indomethacin, an anti-inflammatory drug, in native and octenyl succinic anhydride (OSA) modified maize starch SNp synthetized through a microemulsion method. They reported that OSA modified SNp allowed higher encapsulation efficiency and increased initial release rate and total release of the encapsulated drug. Likewise, Xiao et  al. (2012) reported that esterification can increase drug loading capacity into SNp and drug release.

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Santoyo-Aleman, D., Sanchez, L.  T., & Villa, C.  C. (2019). Citric-acid modified banana starch nanoparticles as a novel vehicle for β-carotene delivery. Journal of the Science of Food and Agriculture, 0(0). https://doi.org/10.1002/jsfa.9918. Shabana, S., Prasansha, R., Kalinina, I., Potoroko, I., Bagale, U., & Shirish, S. H. (2018). Ultrasound assisted acid hydrolyzed structure modification and loading of antioxidants on potato starch nanoparticles. Ultrasonics Sonochemistry. https://doi.org/10.1016/j.ultsonch.2018.07.023. Stanić, Z. (2017). Curcumin, a compound from natural sources, a true scientific challenge – A review. Plant Foods for Human Nutrition, 72(1), 1–12. https://doi.org/10.1007/s11130-016-0590-1. Villa, C.  C., Sanchez, L.  T., & Rodriguez-Marin, N.  D. (2019). Starch nanoparticles and Nanocrystals as bioactive molecule carriers. In T. J. Gutierrez (Ed.), Polymers for agri-food applications (pp. 91–98). Cham: Springer. https://doi.org/10.1007/978-3-030-19416-1_6. Walia, N., Dasgupta, N., Ranjan, S., Chen, L., & Ramalingam, C. (2017). Fish oil based vitamin D nanoencapsulation by ultrasonication and bioaccessibility analysis in simulated gastro-intestinal tract. Ultrasonics Sonochemistry, 39, 623–635. https://doi.org/10.1016/j.ultsonch.2017.05.021. Xiao, S., Liu, X., Tong, C., Zhao, L., Liu, X., Zhou, A., & Cao, Y. (2012). Dialdehyde starch nanoparticles as antitumor drug delivery system: An in  vitro, in  vivo, and immunohistological evaluation. Chinese Science Bulletin, 57(24), 3226–3232. https://doi.org/10.1007/ s11434-012-5342-5. Xu, W., Jin, W., Li, Z., Liang, H., Wang, Y., Shah, B. R., et al. (2015). Synthesis and characterization of nanoparticles based on negatively charged xanthan gum and lysozyme. Food Research International, 71, 83–90. https://doi.org/10.1016/j.foodres.2015.02.007.

Chapter 5

Starch-Based Nanomateriales as Fillers in Composite Polymeric Films

One of the most common applications of starch based nanosystems is as fillers in composite polymeric films, as they have shown the capability to improve mechanical, barrier and electrical properties of the films. (Le Corre and Angellier-Coussy 2014). Starch based nanosystems, specially SNc, have been of use in order to improve properties of biodegradables films made from biodegradables polymers, however some examples can be found of their use in non-biodegradables composite polymers.

5.1  Effect on the Mechanical Properties Several author have use SNc and SNp, in order to reinforce mechanical and barrier properties of starch based films. Starch films tend to be odorless, tasteless, colorless, nontoxic, as well as semipermeable to moisture, gases (carbon dioxide and oxygen), and flavor components. (Nieto-Suaza et al. 2019; Pinzon et al. 2018; Pinzon et al. 2019; Restrepo et al. 2018). Nevertheless, starch based films have shown high water solubility and poor water vapor barrier due to their hydrophilicity. Li et al. (2015) used waxy maize SNc in order to improve mechanical and barrier properties of films made from pea starch. They observed that inclusion of SNc up to 5%, improved mechanical barriers (Tensile strength and elastic modulus) on the reinforced films. It’s been reported that due to their small size, SNc form strong hydrogen bonds with the polymeric matrix. The strong interaction between the nanoparticles and the polymeric matrix allows the transfer of stress from the matrix to the nanoparticles that carries the load and enhances the film’s strength. Furthermore, water vapor barrier values decreased due to the tortuous path created by the SNc on the polymeric

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2020 C. C. Villa Zabala, Starch-based Nanomaterials, SpringerBriefs in Food, Health, and Nutrition, https://doi.org/10.1007/978-3-030-42542-5_5

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film, stopping water vapor transmission though the film. Similar behavior was observed by Silva et al. (2019) and Oliveira et al. (2018) using SNc from mango kernel as reinforcers of corn and mango kernel starch films.

5.2  Effect on the Barrier Properties Barrier properties of polymeric films refer to their capability to stop or decrease water vapor, oxygen or other gases permeation through the polymeric matrix. In general, several authors have reports that incorporation of SNc and SNp significantly reduces water vapor and oxygen permeability through the film. (Angellier et al. 2006; Angellier et al. 2005; Chen et al. 2008; Kristo and Biliaderis 2007; Li et al. 2015) This effect has been attributed to the formation of a tortuous path that reduces diffusivity of the gases across the polymeric matrix.

References Angellier, H., Molina-Boisseau, S., & Dufresne, A. (2005). Mechanical properties of waxy maize starch nanocrystal reinforced natural rubber. Macromolecules, 38(22), 9161–9170. https://doi. org/10.1021/ma0512399. Angellier, H., Molina-Boisseau, S., Dole, P., & Dufresne, A. (2006). Thermoplastic starch−waxy maize starch nanocrystals nanocomposites. Biomacromolecules, 7(2), 531–539. https://doi. org/10.1021/bm050797s. Chen, Y., Cao, X., Chang, P.  R., & Huneault, M.  A. (2008). Comparative study on the films of poly(vinyl alcohol)/pea starch nanocrystals and poly(vinyl alcohol)/native pea starch. Carbohydrate Polymers, 73(1), 8–17. https://doi.org/10.1016/j.carbpol.2007.10.015. Kristo, E., & Biliaderis, C. G. (2007). Physical properties of starch nanocrystal-reinforced pullulan films. Carbohydrate Polymers, 68(1), 146–158. https://doi.org/10.1016/j.carbpol.2006.07.021. Le Corre, D., & Angellier-Coussy, H. (2014). Preparation and application of starch nanoparticles for nanocomposites: A review. Reactive and Functional Polymers, 85, 97–120. https://doi. org/10.1016/j.reactfunctpolym.2014.09.020. Li, X., Qiu, C., Ji, N., Sun, C., Xiong, L., & Sun, Q. (2015). Mechanical, barrier and morphological properties of starch nanocrystals-reinforced pea starch films. Carbohydrate Polymers, 121, 155–162. https://doi.org/10.1016/j.carbpol.2014.12.040. Nieto-Suaza, L., Acevedo-Guevara, L., Sánchez, L.  T., Pinzón, M.  I., & Villa, C.  C. (2019). Characterization of Aloe vera-banana starch composite films reinforced with curcumin-loaded starch nanoparticles. Food Structure, 100131. https://doi.org/10.1016/j.foostr.2019.100131. Oliveira, A.  V., da Silva, A.  P. M., Barros, M.  O., de sá, M., Souza Filho, M., Rosa, M.  F., & Azeredo, H. M. C. (2018). Nanocomposite films from mango kernel or corn starch with starch nanocrystals. Starch – Stärke, 70(11–12), 1800028. https://doi.org/10.1002/star.201800028. Pinzon, M. I., Garcia, O. R., & Villa, C. C. (2018). The influence of Aloe vera gel incorporation on the physicochemical and mechanical properties of banana starch-chitosan edible films. Journal of the Science of Food and Agriculture, 98(11), 4042–4049. https://doi.org/10.1002/jsfa.8915. Pinzon, M.  I., Sanchez, L.  T., Garcia, O.  R., Gutierrez, R., Luna, J.  C., & Villa, C.  C. (2019). Increasing shelf life of strawberries (Fragaria ssp) by using a banana starch-chitosan-Aloe vera gel composite edible coating. International Journal of Food Science & Technology. https://doi. org/10.1111/ijfs.14254.

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Restrepo, A. E., Rojas, J. D., García, O. R., Sánchez, L. T., Pinzón, M. I., & Villa, C. C. (2018). Mechanical, barrier, and color properties of banana starch edible films incorporated with nanoemulsions of lemongrass (Cymbopogon citratus) and rosemary (Rosmarinus officinalis) essential oils. Food Science and Technology International, 24(8), 705–712. https://doi. org/10.1177/1082013218792133. Silva, A. P. M., Oliveira, A. V., Pontes, S. M. A., Pereira, A. L. S., Men de sá Souza Filhoc, M., Rosa, M.  F., & Azeredo, H.  M. C. (2019). Mango kernel starch films as affected by starch nanocrystals and cellulose nanocrystals. Carbohydrate Polymers, 211, 209–216. https://doi. org/10.1016/j.carbpol.2019.02.013.