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Convenient Method for Enhancing Hydrophobicity and Dispersibility of Starch Nanocrystals by Crosslinking Modification with Citric Acid

  • Lili Ren ORCID logo EMAIL logo , Yuchen Zhang , Qian Wang , Jiang Zhou , Jin Tong , Donghui Chen and Xingguang Su
Published/Copyright: April 14, 2018

Abstract

This study investigated the chemical, wettability, thermal and structural properties of starch nanocrystals (SNCs) modified through crosslinking modification using citric acid in aqueous medium. The results of Fourier transform infrared spectroscopy analysis suggested that new interactions occurred between starch and citric acid after modification and an increase of the reaction time increased the degree of substitution. X-ray diffraction analysis showed that the crystalline structure of SNCs was maintained after the crosslinking modification by adjusting the pH to 3.5, and destroyed after the modification by pretreatments without adjusting the pH of the citric acid solution. Crosslinking modification decreased the size and aggregation of SNCs and longer reaction time gave rise to the smaller particle size of SNCs modified by the pretreatments of adjusting the pH of the citric acid solution. The crosslinked SNCs had lower polarity and showed stronger hydrophobicity and dispersion stability which allowed them be used as reinforcements in hydrophobic polymer matrices.

Funding statement: This work was supported by the National Natural Science Foundation of China [51405188]; Plan of Science and Technology Development of Jilin Province of China [20180520204JH]; China Postdoctoral Science Foundation [2013M540253], [2015T80307]; and Graduate Innovation Fund of Jilin University; [2017038].

Acknowledgments

The authors are grateful to the National Natural Science Foundation of China (No. 51405188), Plan of Science and Technology Development of Jilin Province of China (20180520204JH), China Postdoctoral Science Foundation (No. 2013M540253 and No. 2015T80307) and Graduate Innovation Fund of Jilin University (No. 2017038).

References

[1] Dufresne A. Crystalline starch based nanoparticles. Curr Opin Colloid Interface Sci. 2014;19:397–408.10.1016/j.cocis.2014.06.001Search in Google Scholar

[2] Le Corre D, Angellier-Coussy H. Preparation and application of starch nanoparticles for nanocomposites: a review. React Funct Polym. 2014;85:97–120.10.1016/j.reactfunctpolym.2014.09.020Search in Google Scholar

[3] Kim HY, Park SS, Lim ST. Preparation, characterization and utilization of starch nanoparticles. Colloids Surf B. 2015;126:607–20.10.1016/j.colsurfb.2014.11.011Search in Google Scholar PubMed

[4] Brenner T, Kiessler B, Radosta S, Arndt T. Processing surface sizing starch using oxidation, enzymatic hydrolysis and ultrasonic treatment methods – preparation and application. Carbohydr Polym. 2016;138:273–9.10.1016/j.carbpol.2015.10.086Search in Google Scholar PubMed

[5] Ghasemian A, Ghaffari M, Ashori A. Strength-enhancing effect of cationic starch on mixed recycled and virgin pulps. Carbohydr Polym. 2012;87:1269–74.10.1016/j.carbpol.2011.09.010Search in Google Scholar

[6] Santander-Ortega MJ, Stauner T, Loretz B, Ortega-Vinuesa JL, Bastos-Gonzalez D, Wenz G, et al. Nanoparticles made from novel starch derivatives for transdermal drug delivery. J Controlled Release. 2010;141:85–92.10.1016/j.jconrel.2009.08.012Search in Google Scholar PubMed

[7] Zhang YH, Ding LL, Gu JY, Tan HY, Zhu LB. Preparation and properties of a starch-based wood adhesive with high bonding strength and water resistance. Carbohydr Polym. 2015;115:32–7.10.1016/j.carbpol.2014.08.063Search in Google Scholar PubMed

[8] Brunnschweiler J, Luethi D, Handschin S, Farah Z, Escher F, Conde-Petit B. Isolation, physicochemical characterization and application of yam (Dioscorea spp.) starch as thickening and gelling agent. Starch/Starke. 2005;57:107–17.10.1002/star.200400327Search in Google Scholar

[9] Garcia NL, Ribbal L, Dufresne A, Aranguren MI, Goyanes S. Physico-mechanical properties of biodegradable starch nanocomposites. Macromol Mater Eng. 2009;294:169–77.10.1002/mame.200800271Search in Google Scholar

[10] Lin N, Huang J, Chang PR, Feng L, Yu J. Effect of polysaccharide nanocrystals on structure, properties, and drug release kinetics of alginate-based microspheres. Colloids Surf B. 2011;85:270–9.10.1016/j.colsurfb.2011.02.039Search in Google Scholar PubMed

[11] Kristo E, Biliaderis CG. Physical properties of starch nanocrystal-reinforced pullulan films. Carbohydr Polym. 2007;68:146–58.10.1016/j.carbpol.2006.07.021Search in Google Scholar

[12] Angellier H, Molina-Boisseau S, Dufresne A. Mechanical properties of waxy maize starch nanocrystal reinforced natural rubber. Macromolecules. 2005;38:9161–70.10.1021/ma0512399Search in Google Scholar

[13] Angellier H, Molina-Boisseau S, Dufresne A. Waxy maize starch nanocrystals as filler in natural rubber. Macromol Symp. 2006;233:132–6.10.1002/masy.200690009Search in Google Scholar

[14] Zheng H, Ai FJ, Chang PR, Huang J, Dufresne A. Structure and properties of starch nanocrystal-reinforced soy protein plastics. Polym Compos. 2009;30:474–80.10.1002/pc.20612Search in Google Scholar

[15] Chen Y, Cao XD, Chang PR, Huneault MA. Comparative study on the films of poly (vinyl alcohol)/pea starch nanocrystals and poly(vinyl alcohol)/native pea starch. Carbohydr Polym. 2008;73:8–17.10.1016/j.carbpol.2007.10.015Search in Google Scholar

[16] Wang YX, Tian HF, Zhang LN. Role of starch nanocrystals and cellulose whiskers in synergistic reinforcement of waterborne polyurethane. Carbohydr Polym. 2010;80:665–71.10.1016/j.carbpol.2009.10.043Search in Google Scholar

[17] Habibi Y, Dufresne A. Highly filled bionanocomposites from functionalized polysaccharide nanocrystals. Biomacromolecules. 2008;9:1974–80.10.1021/bm8001717Search in Google Scholar PubMed

[18] Duan B, Sun PD, Wang XL, Yang C. Preparation and properties of starch nanocrystals/carboxymethyl chitosan nanocomposite films. Starch-Starke. 2011;63:528–35.10.1002/star.201000136Search in Google Scholar

[19] Li C, Sun PD, Yang C. Emulsion stabilized by starch nanocrystals. Starch/Starke. 2012;64:497–502.10.1002/star.201100178Search in Google Scholar

[20] Alila S, Aloulou F, Thielemans W, Boufi S. Sorption potential of modified nanocrystals for the removal of aromatic organic pollutant from aqueous solution. Ind Crop Prod. 2011;33:350–7.10.1016/j.indcrop.2010.11.010Search in Google Scholar

[21] Angellier H, Molina-Boisseau S, Belgacem MN, Dufresne A. Surface chemical modification of waxy maize starch nanocrystals. Langmuir. 2005;21:2425–33.10.1021/la047530jSearch in Google Scholar PubMed

[22] Namazi H, Dadkhah A. Convenient method for preparation of hydrophobically modified starch nanocrystals with using fatty acids. Carbohydr Polym. 2010;79:731–7.10.1016/j.carbpol.2009.09.033Search in Google Scholar

[23] Chang PR, Ai FJ, Chen Y, Dufresne A, Huang J. Effects of starch nanocrystal-graft-polycaprolactone on mechanical properties of waterborne polyurethane-based nanocomposites. J Appl Polym Sci. 2009;111:619–27.10.1002/app.29060Search in Google Scholar

[24] Labet M, Thielemans W, Dufresne A. Polymer grafting onto starch nanocrystals. Biomacromolecules. 2007;8:2916–27.10.1021/bm700468fSearch in Google Scholar PubMed

[25] Namazi H, Dadkhah A. Surface modification of starch nanocrystals through ring-opening polymerization of ε-caprolactone and investigation of their microstructures. J Appl Polym Sci. 2008;110:2405–12.10.1002/app.28821Search in Google Scholar

[26] Song SW, Wang C, Pan ZL, Wang XF. Preparation and characterization of amphiphilic starch nanocrystals. J Appl Polym Sci. 2008;107:418–22.10.1002/app.27076Search in Google Scholar

[27] Thielemans W, Belgacem MN, Dufresne A. Starch nanocrystals with large chain surface modifications. Langmuir. 2006;22:4804–10.10.1021/la053394mSearch in Google Scholar PubMed

[28] Xu Y, Ding WQ, Liu J, Li Y, Kennedy JF, Gu Q, et al. Preparation and characterization of organic-soluble acetylated starch nanocrystals. Carbohydr Polym. 2010;80:1078–84.10.1016/j.carbpol.2010.01.027Search in Google Scholar

[29] Yu JH, Ai FJ, Dufresne A, Gao SJ, Huang J, Chang PR. Structure and mechanical properties of poly(lactic acid) filled with (starch nanocrystal)-graft-poly(ε-caprolactone). Macromol Mater Eng. 2008;293:763–70.10.1002/mame.200800134Search in Google Scholar

[30] Ren LL, Jiang M, Wang LY, Zhou J, Tong J. A method for improving dispersion of starch nanocrystals in water through crosslinking modification with sodium hexametaphosphate. Carbohydr Polym. 2012;87:1874–6.10.1016/j.carbpol.2011.08.070Search in Google Scholar

[31] Ren LL, Wang Q, Yan XX, Tong J, Zhou J, Su XG. Dual modification of starch nanocrystals via crosslinking and esterification for enhancing their hydrophobicity. Food Res Int. 2016;87:180–8.10.1016/j.foodres.2016.07.007Search in Google Scholar PubMed

[32] Yang JL, Huang YJ, Gao CM, Liu MZ, Zhang XJ. Fabrication and evaluation of the novel reduction-sensitive starch nanoparticles for control drug release. Colloids Surf B. 2014;115:368–76.10.1016/j.colsurfb.2013.12.007Search in Google Scholar PubMed

[33] Zhou J, Tong J, Su XG, Ren LL. Hydrophobic starch nanocrystals preparations through crosslinking modification using citric acid. Int J Biol Macromol. 2016;91:1186–93.10.1016/j.ijbiomac.2016.06.082Search in Google Scholar PubMed

[34] Valodkar M, Thakore S. Isocyanate crosslinked reactive starch nanoparticles for thermo-responsive conducting applications. Carbohydr Res. 2010;345:2354–60.10.1016/j.carres.2010.08.008Search in Google Scholar PubMed

[35] Ren LL, Fu YJ, Chang YJ, Jiang M, Tong J, Zhou J. Performance improvement of starch films reinforced with starch nanocrystals (SNCs) modified by cross-linking. Starch/Starke. 2017;69:1600025.10.1002/star.201600025Search in Google Scholar

[36] Ren LL, Dong Z, Jiang M, Tong J, Zhou J. Hydrophobization of starch nanocrystals through esterification in green media. Ind Crop Prod. 2014;59:115–8.10.1016/j.indcrop.2014.05.014Search in Google Scholar

[37] Shin SI, Lee CJ, Kim DI, Lee HA, Cheong JJ, Chung KM, et al. Formation, characterization, and glucose response in mice to rice starch with low digestibility produced by citric acid treatment. J Cereal Sci. 2007;45:24–33.10.1016/j.jcs.2006.05.001Search in Google Scholar

[38] Shin SI, Lee CJ, Kim MJ, Choi SJ, Choi HJ, Kim Y, et al. Structural characteristics of low-glycemic response rice starch produced by citric acid treatment. Carbohydr Polym. 2009;78:588–95.10.1016/j.carbpol.2009.05.017Search in Google Scholar

[39] Yu JG, Wang N, Ma XF. The effects of citric acid on the properties of thermoplastic starch plasticized by glycerol. Starch/Starke. 2005;57:494–504.10.1002/star.200500423Search in Google Scholar

[40] Ma XF, Jian RJ, Chang PR, Yu JG. Fabrication and characterization of citric acid-modified starch nanoparticles/plasticized-starch composites. Biomacromolecules. 2008;9:3314–20.10.1021/bm800987cSearch in Google Scholar PubMed

[41] Tian HF, Xu GZ. Processing and characterization of glycerol-plasticized soy protein plastics reinforced with citric acid-modified starch nanoparticles. J Polym Environ. 2011;19:582–8.10.1007/s10924-011-0304-6Search in Google Scholar

[42] Ma XF, Chang PR, Yu JG, Stumborg M. Properties of biodegradable citric acid-modified granular starch/thermoplastic pea starch composites. Carbohydr Polym. 2009;75:1–8.10.1016/j.carbpol.2008.05.020Search in Google Scholar

[43] Wing RE. Starch citrate: preparation and ion exchange properties. Starch/Starke. 1996;48:275–9.10.1002/star.19960480709Search in Google Scholar

[44] Xie XJ, Liu Q. Development and physicochemical characterization of new resistant citrate starch from different corn starches. Starch/Starke. 2004;56:364–70.10.1002/star.200300261Search in Google Scholar

[45] Yang CQ, Xu L, Li S, Jiang Y. Nonformaldehyde durable press finishing of cotton fabrics by combining citric acid with polymers of maleic acid. Text Res J. 1998;68:457–64.10.1177/004051759806800611Search in Google Scholar

[46] Shi R, Zhang ZZ, Liu QY, Han YM, Zhang LQ, Chen DF, et al. Characterization of citric acid/glycerol co-plasticized thermoplastic starch prepared by melt blending. Carbohydr Polym. 2007;69:748–55.10.1016/j.carbpol.2007.02.010Search in Google Scholar

[47] Delval F, Crini G, Bertini S, Morin-Crini N, Badot PM, Vebrel J, et al. Characterization of crosslinked starch materials with spectroscopic techniques. J Appl Polym Sci. 2004;93:2650–63.10.1002/app.20851Search in Google Scholar

[48] Yuan HY, Nishiyama Y, Wada M, Kuga S. Surface acylation of cellulose whiskers by drying aqueous emulsion. Biomacrolecules. 2006;7:696–700.10.1021/bm050828jSearch in Google Scholar

[49] Shi R, Bi JL, Zhang ZZ, Zhu AC, Chen DF, Zhou XH, et al. The effect of citric acid on the structural properties and cytotoxicity of polyvinyl alcohol/starch films when molding at high temperature. Carbohydr Polym. 2008;74:763–70.10.1016/j.carbpol.2008.04.045Search in Google Scholar

[50] Katopo H, Song Y, Jane JL. Effect and mechanism of ultrahigh hydrostatic pressure on the structure and properties of starches. Carbohydr Polym. 2002;47:233–44.10.1016/S0144-8617(01)00168-0Search in Google Scholar

[51] Matveev YI, Van Soest JJG, Nieman C, Wasserman LA, Protserov VA, Ezernitskaja M, et al. The relationship between thermodynamic and structural properties of low and high amylose maize starches. Carbohydr Polym. 2001;44:151–60.10.1016/S0144-8617(00)00211-3Search in Google Scholar

[52] Soest JJG, Hulleman SHD, De Wit D, Vliegenthart JFG. Crystallinity in starch bioplastics. Ind Crops Prod. 1996;5:11–22.10.1016/0926-6690(95)00048-8Search in Google Scholar

[53] Xie XJ, Liu Q, Cui SW. Studies on the granular structure of resistant starch (type 4) from normal, high amylase and waxy corn starch citrates. Food Res Int. 2004;39:332–41.10.1016/j.foodres.2005.08.004Search in Google Scholar

[54] Angellier H, Molina-Boisseau S, Dufresne A. Starch nanocrystal fillers in an acrylic polymer matrix. Macromol Symp. 2005;221:95–104.10.1002/masy.200550310Search in Google Scholar

[55] Wei BX, Zhang B, Sun BH, Jin ZY, Xu XM. Aqueous re-dispersibility of starch nanocrystals powder improved by sodium hypochlorite oxidation. Food Hydrocolloid. 2016;52:29–37.10.1016/j.foodhyd.2015.06.006Search in Google Scholar

[56] Müller R, Jacobs C. Buparvaquone mucoadhesive nanosuspension: preparation, optimisation and long-term stability. Int J Pharm. 2002;237:151–61.10.1016/S0378-5173(02)00040-6Search in Google Scholar PubMed

[57] Varma CAK, Panpalia SG, Kumar KJ. Physicochemical and release kinetics of natural and retrograded starch of Indian palmyrah shoots. Int J Biol Macromol. 2014;66:33–9.10.1016/j.ijbiomac.2014.02.018Search in Google Scholar PubMed

[58] Castano J, Bouza R, Rodríguez-Llamazares S, Carrasco C, Vinicius RVB. Processing and characterization of starch-based materials from pehuen seeds (Araucaria araucana (Mol) K. Koch). Carbohydr Polym. 2012;88:299–307.10.1016/j.carbpol.2011.12.008Search in Google Scholar

Received: 2017-7-25
Revised: 2018-3-23
Accepted: 2018-4-1
Published Online: 2018-4-14

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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