Preparation of Starch Nanocrystals With Hydrophobic Property by Citric Acid Crosslinking


  • Kanokwan Rittiwut นักศึกษา หลักสูตรวิศวกรรมศาสตรมหาบัณฑิต สาขาวิชาวิศวกรรมเคมี คณะวิศวกรรมศาสตร์ มหาวิทยาลัยขอนแก่น
  • Pasakron Jutakridsada นักศึกษา หลักสูตรวิศวกรรมศาสตรดุษฎีบัณฑิต สาขาวิชาวิศวกรรมเคมี คณะวิศวกรรมศาสตร์ มหาวิทยาลัยขอนแก่น
  • Wimonporn Iamamornphan นักวิทยาศาสตร์ชำนาญการ สาขาวิชาวิศวกรรมเคมี คณะวิศวกรรมศาสตร์ มหาวิทยาลัยขอนแก่น
  • Khanita Kamwilaisak รองศาสตราจารย์ สาขาวิชาวิศวกรรมเคมี คณะวิศวกรรมศาสตร์ มหาวิทยาลัยขอนแก่น


Rice starch, Hydrophobicity property, Crosslinking


This study aims to produce and modify a starch nanocrystal to improve the hydrophobicity property. The rice starch was H2SO4 hydrolysis at 2.2 M with various hydrolysis times (5, 6, and 7 days). Citric acid with different concentrations (30, 40, and 50 %wt) was utilized to modify the surface by crosslinking. The physical and chemical properties of starch, starch nanocrystal, and modified starch nanocrystal were analyzed by X-ray diffraction powder, Fourier transforms infrared spectroscopy particle size analysis, and optical contract angle. The results showed the %crystallinity was increased by 48% when hydrolysis time at six days. The maximum contact angle at 79.0° was obtained at modified starch nanocrystal with 50%wt citric acid, which provided suitable hydrophobic material.  The study can be an alternative way to apply rich flour in the drug and food industries.


Wang X, Huang L, Zhang C, Deng Y, Xie P, Liu L, et al. Research advances in chemical modifications of starch for hydrophobicity and its applications: A review. Carbohydrate Polymers. 2020;240:116292.

Ngernyen Y, Kamwilaisak K. Activated carbon from Thailand's biomass: A review literature. KKU Eng J. 2013;40:267-283.

Saeng-on J, Aht-Ong D. Production of Starch Nanocrystals from Agricultural Materials Using Mild Acid Hydrolysis Method: Optimization and Characterization. Polymers from Renewable Resources. 2017;8(3):91-116.

Kamwilaisak K, Pimsawat N, Khotsakha N, Jutakridsada P. Synthesis and characterization of cellulose nanocrystal from eucalyptus pulp. New Biotechnology. 2018;44:S97.

Angellier H, Choisnard L, Molina-Boisseau S, Ozil P, Dufresne A. Optimization of the Preparation of Aqueous Suspensions of Waxy Maize Starch Nanocrystals Using a Response Surface Methodology. Biomacromolecules. 2004;5(4):1545-1551.

Jayakody L, Hoover R. The effect of lintnerization on cereal starch granules. Food Research International. 2002;35(7):665-680.

Charoenthai N, Wickramanayaka A, Sungthongjeen S, Puttipipatkhachorn S. Use of cassava starch nanocrystals to make a robust rupturable pulsatile release pellet. Journal of Drug Delivery Science and Technology. 2018;47:283-290.

Lin N, Huang J, Chang PR, Anderson DP, Yu J. Preparation, Modification, and Application of Starch Nanocrystals in Nanomaterials: A Review. Journal of Nanomaterials. 2011;2011:573687.

Tan Y, Xu K, Liu C, Li Y, Lu C, Wang P. Fabrication of starch-based nanospheres to stabilize pickering emulsion. Carbohydrate Polymers. 2012;88(4):1358-1363.

Zhou J, Tong J, Su X, Ren L. Hydrophobic starch nanocrystals preparations through crosslinking modification using citric acid. International Journal of Biological Macromolecules. 2016;91:1186-1193.

Nikfarjam N, Taheri Qazvini N, Deng Y. Cross-linked starch nanoparticles stabilized Pickering emulsion polymerization of styrene in w/o/w system. Colloid and Polymer Science. 2013;292:599.

Zhang J, Lei C, Liu G, Bao Y, Balan V, Bao J. In-Situ Vacuum Distillation of Ethanol Helps To Recycle Cellulase and Yeast during SSF of Delignified Corncob Residues. ACS Sustainable Chemistry & Engineering. 2017;5(12):11676-11685.

Pham HN, Nguyen VT, Vuong QV, Bowyer MC, Scarlett CJ. Effect of Extraction Solvents and Drying Methods on the Physicochemical and Antioxidant Properties of Helicteres hirsuta Lour. Leaves. Technologies. 2015;3(4).

Woranuch S, Pangon A, Puagsuntia K, Subjalearndee N, Intasanta V. Rice flour-based nanostructures via a water-based system: transformation from powder to electrospun nanofibers under hydrogen-bonding induced viscosity, crystallinity and improved mechanical property. RSC Adv. 2017;7:19960-19966.

Han F, Gao C, Liu M. Fabrication and characterization of size-controlled starch-based nanoparticles as hydrophobic drug carriers. Journal of nanoscience and nanotechnology. 2013;13(10):6996-7007.

Lopez-Rubio A, Flanagan BM, Gilbert EP, Gidley MJ. A novel approach for calculating starch crystallinity and its correlation with double helix content: a combined XRD and NMR study. Biopolymers. 2008;89(9):761-768.

Li C, Hu Y. Effects of acid hydrolysis on the evolution of starch fine molecular structures and gelatinization properties. Food Chemistry. 2021;353:129449.

Zuo Y, Gu J, Tan H, Qiao Z, Xie Y, Zhang Y. The characterization of granule structural changes in acid-thinning starches by new methods and its effect on other properties. Journal of Adhesion Science and Technology. 2014;28.

Navaf M, Sunooj KV, Aaliya B, Sudheesh C, Akhila PP, Sabu S, et al. Talipot palm (Corypha umbraculifera L.) a nonconventional source of starch: Effect of citric acid on structural, rheological, thermal properties and in vitro digestibility. International Journal of Biological Macromolecules. 2021;182:554-563.

Miskeen S, An YS, Kim J-Y. Application of starch nanoparticles as host materials for encapsulation of curcumin: Effect of citric acid modification. International Journal of Biological Macromolecules. 2021;183:1-11.

Wang Y, Zhang G. The preparation of modified nano-starch and its application in food industry. Food Research International. 2021;140:110009.

Wani AA, Singh P, Shah M, Schweiggert-Weisz U, Gul K, Wani I. Rice Starch Diversity: Effects on Structural, Morphological, Thermal, and Physicochemical Properties-A Review. Comprehensive Reviews in Food Science & Food Safety. 2012;11:417-436.

Pérez S, Bertoft E. The molecular structures of starch components and their contribution to the architecture of starch granules: A comprehensive review. Starch - Stärke. 2010;62(8):389-420.

Ali A, Xie F, Yu L, Liu H, Meng L, Khalid S, et al. Preparation and characterization of starch-based composite films reinfoced by polysaccharide-based crystals. Composites Part B: Engineering. 2018;133:122-128.

Visakh P, Mathew A, Oksman K, Thomas S. Starch-based bionanocomposites: processing and properties. Polysaccharide Building Blocks: A Sustainable Approach to the Development of Renewable Biomaterials. 2012:287-306.

Taherimehr M, Bagheri R, Taherimehr M. In-vitro evaluation of thermoplastic starch/ beta-tricalcium phosphate nano-biocomposite in bone tissue engineering. Ceramics International. 2021;47(11):15458-15463.

Odeniyi MA, Omoteso OA, Adepoju AO, Jaiyeoba KT. Starch nanoparticles in drug delivery: A review. Polim W Med. 2018;48:41-45.

Chung H-J, Liu Q, Lee L, Wei D. Relationship between the structure, physicochemical properties and in vitro digestibility of rice starches with different amylose contents. Food Hydrocolloids. 2011;25(5):968-975.

Aijun H, Li Y, Zheng J. Dual-frequency ultrasonic effect on the structure and properties of starch with different size. LWT. 2019;106.

Saari H, Rayner M, Wahlgren M. Effects of starch granules differing in size and morphology from different botanical sources and their mixtures on the characteristics of Pickering emulsions. Food Hydrocolloids. 2019;89:844-855.

Tinus T, Damour M, van Riel V, Sopade PA. Particle size-starch–protein digestibility relationships in cowpea (Vigna unguiculata). Journal of Food Engineering. 2012;113(2):254-264.

Kuchaiyaphum P, Yamauchi T, Watanesk R, Watanesk S. Hydrophobicity Enhancement of the Polyvinyl Alcohol/Rice Starch/Silk Fibroin Films by Glycerol. Applied Mechanics and Materials. 2013;446-447:360-365.

Tai NL, Adhikari R, Shanks R, Adhikari B. Starch-polyurethane films synthesized using polyethylene glycol-isocyanate (PEG-iso): Effects of molecular weight, crystallinity, and composition of PEG-iso on physiochemical characteristics and hydrophobicity of the films. Food Packaging and Shelf Life. 2017;14:116-127.

Lam S, Velikov KP, Velev OD. Pickering stabilization of foams and emulsions with particles of biological origin. Current Opinion in Colloid & Interface Science. 2014;19(5):490-500.

Chang R, Xiong L, Li M, Chen H, Xiao J, Wang S, et al. Preparation of octenyl succinic anhydride-modified debranched starch vesicles for loading of hydrophilic functional ingredients. Food hydrocolloids. 2019;94:546-552.

Sufi-Maragheh P, Nikfarjam N, Deng Y, Taheri-Qazvini N. Pickering emulsion stabilized by amphiphilic pH-sensitive starch nanoparticles as therapeutic containers. Colloids and Surfaces B: Biointerfaces. 2019;181:244-251.