Carboxymethylchitosan-based hydrogels crosslinked with polydimethylsiloxane


  • Nantharak Rodkate Faculty of Science, Naresuan University
  • Nunthiya Deepuppha Faculty of Science, Naresuan University
  • Boonjira Rutnakornpituk Faculty of Science, Naresuan University
  • Metha Rutnakornpituk Faculty of Science, Naresuan University


Carboxymethylchitosan, Polydimethylsiloxane, Hydrogel, Crosslinking


Synthesis and properties of hydrophilic carboxymethylchitosan (CMC) hydrogels containing hydrophobic polydimethylsiloxane (PDMS) were herein presented. Fourier transform infrared spectroscopy indicated that PDMS can covalently bound to CMC chains with the use of hexamethylene-1,6-di-(aminocarboxysulfonate) (HDA), a water soluble crosslinker. Also, according to scanning electron microscopy, PDMS microphases with the size of 0.2-0.5 µm in diameter were thoroughly dispersed in CMC matrix. Addition of PDMS improved properties of the CMC hydrogels including increasing water vapor permeability and water swellability, improving tensile properties and increasing surface hydrophobicity. PDMS with different amounts (1-20 wt%) and molecular weights (2,000 and 8,000 g·mol-1) were added into CMC hydrogels in order to investigate the effect of its concentrations and chain lengths on these properties. It was found that increasing the concentrations and molecular weights of PDMS seemed to further improve these properties, indicating the feasibility in tuning these properties of CMC hydrogels for specific applications.


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J. Cai, Q. Dang, C. Liu, B. Fan, J. Yan, Y. Xu, and J. Li, “Preparation and characterization of Nbenzoyl-O-acetyl-chitosan,” International Journal of Biological Macromolecules, 2015, vol. 77, pp. 52-58, 2015.

M. Khemkhao, B. Nuntakumjorn, S. Techkarnjanaruk, and C. Phalakornkule, Bioresour Technol, “Effect of chitosan on UASB treating POME during a transition from mesophilic to thermophilic conditions,” Bioresource Technology, vol. 102, pp. 4674- 4681, 2011.

J. Cai, Q. Dang, C. Liu, T. Wang, B. Fan, J. Yan, and Y. Xu, “Preparation, characterization and antibacterial activity of O-acetyl-chitosan-N-2- hydroxypropyl trimethyl ammonium chloride,” International Journal of Biological Macromolecules, vol. 80, pp. 8-15, 2015.

P. K. Dutta, S. Tripathi, G.K. Mehrotra, and J. Dutta, “Perspectives for chitosan based antimicrobial films in food applications,” Food Chemistry, vol. 114, pp. 1173-1182, 2009.

T. G. Liu, B. Li, W. Huang, B. Lv, J. Chen, J.X. Zhang, and L.P. Zhu, “Effects and kinetics of a novel temperature cycling treatment on the N-deacetylation of chitin in alkaline solution,” Carbohydrate Polymers, vol. 77, pp. 110-117, 2009.

R. Mahjub, T. Heidari Shayesteh, M. Radmehr, S. Y. Vafaei, M. Amini, R. Dinarvand, and F. A. Dorkoosh, “Preparation and optimization of N-trimethyl-Ocarboxymethyl chitosan nanoparticles for delivery of low-molecular-weight heparin,” Pharmaceutical Development and Technology, vol. 21, pp.14-25, 2016.

T. D. A. Senra, D. M. Santos, J. Desbrières, and S. P. Campana-Filho, “Extensive Nmethylation of chitosan: evaluating the effects of the reaction conditions by using response surface methodology,” Polymer International, vol. 64, pp. 1617-1626, 2015.

K. Wang, J. Zhuang, Y. Liu, M. Xu, J. Zhuang, Z. Chen, Y. Wei, and Y. Zhang, “PEGylated chitosan nanoparticles with embedded bismuth sulfide for dual-wavelength fluorescent imaging and photothermal therapy,” Carbohydrate Polymers, vol. 184, pp. 445-452, 2018.

T. Ouchi, H. Nishizawa, and Y. Ohya, “Aggregation phenomenon of PEG-grafted chitosan in aqueous solution,” Polymer, vol. 39, pp. 5171-5175, 1998.

A. Shirdast, A. Sharif, and M. Abdollahi, “Effect of the incorporation of sulfonated chitosan/sulfonated graphene oxide on the proton conductivity of chitosan membranes,” Journal of Power Sources, vol. 306, pp. 541- 551, 2016.

K. R. Holme and A. S. Perlin, “Chitosan Nsulfate. A water-soluble polyelectrolyte,” Carbohydrate Research, vol. 302, pp. 7-12, 1997.

M. Wu, Z. Long, H. Xiao, and C. Dong, “Preparation of N, N, N-trimethyl chitosan via a novel approach using dimethyl carbonate,” Carbohydrate Polymers, vol. 169, pp. 83-91, 2017.

Z. Jia, D. shen and W. Xu, “Synthesis and antibacterial activities of quaternary ammonium salt of chitosan,” Carbohydrate Research, vol. 333, pp. 1-6, 2001.

Z. Zhang, F. Jin, Z. Wu, J. Jin, F. Li, Y. Wang, Z. Wang, S. Tang, C. Wu, and Y. Wang, “O-acylation of chitosan nanofibers by short-chain and long-chain fatty acids,” Carbohydrate Polymers, vol. 177, pp. 203- 209, 2017.

Y. Machida, T. Nagai, M. Abe, and T. Sannan, “Use of chitosan and hydroxypropylchitosan in drug formulations to effect sustained release,” Drug Design and Delivery, vol. 1, pp. 119-130, 1986.

A. Fiamingo and S. P. Campana-Filho, “Structure, morphology and properties of genipin-crosslinked carboxymethylchitosan porous membranes,” Carbohydrate Polymers, vol. 143, pp. 155-163, 2016.

X. G. Chen and H.-J. Park, “Chemical characteristics of O-carboxymethyl chitosans related to the preparation conditions,” Carbohydrate Polymers, vol. 53, pp. 355-359, 2003.

D. Lv, M. Zhang, J. Cui, J. Lu, and W. Li, “Grafting of edible colorants onto Ocarboxymethyl chitosan: preparation, characterization and anti-reduction property evaluation,” New Journal of Chemistry, vol. 40, pp. 3363-3369, 2016.

R. Jankaew, N. Rodkate, S. Lamlertthon, B. Rutnakornpituk, U. Wichai, G. Ross, and M. Rutnakornpituk, ““Smart” carboxymethyl chitosan hydrogels crosslinked with poly(Nisopropylacrylamide) and poly(acrylic acid) for controlled drug release,” Polymer Testing, vol. 42, pp. 26-36, 2015.

N. Rodkate and M. Rutnakornpituk, “Multiresponsive magnetic microsphere of poly(Nisopropylacrylamide)/ carboxymethylchitosan hydrogel for drug controlled release,” Carbohydrate Polymers, vol. 151, pp. 251-259, 2016.

L. Fan, Y. Du, B. Zhang, J. Yang, J. Zhou, and J. F. Kennedy, “Preparation and properties of alginate/carboxymethyl chitosan blend fibers,” Carbohydrate Polymers, vol. 65, pp. 447-452, 2006.

S. Yu, F. Mi, S. Shyu, C. Tsai, C. Peng, and J. Lai, “Miscibility, mechanical characteristic and platelet adhesion of 6-Ocarboxymethylchitosan/polyurethane semiIPN membranes,” Journal of Membrane Science, vol. 276, pp. 68-80, 2006.

Y. Chen, Y. Zhang, F. Wang, W. Meng, X. Yang, P. Li, J. Jiang, H. Tan, and Y. Zheng, “Preparation of porous carboxymethyl chitosan grafted poly (acrylic acid) superabsorbent by solvent precipitation and its application as a hemostatic wound dressing,” Materials Science & Engineering. C, Materials for Biological Applications, vol. 63, pp. 18-29, 2016.

Q.B. Wei, F. Fu, Y.-Q. Zhang, and L. Tang, “Synthesis and characterization of pHresponsive carboxymethyl chitosan-gpolyacrylic acid hydrogels,” Journal of Polymer Research, vol. 22, pp. 1-8, 2015.

Y. Chen, W. Liu, G. Zeng and Y. Liu, “Microporous PDMAEMA-based stimuliresponsive hydrogel and its application in drug release,” Journal of Applied Polymer Science, vol. 134, p. 45326, 2017.

N. Rodkate, B. Rutnakornpituk, U. Wichai, G. Ross, and M. Rutnakornpituk, “Smart carboxymethylchitosan hydrogels that have thermo- and pH-responsive properties,” Journal of Applied Polymer Science, vol. 132, p. 41505, 2015.

Y. Chen, C. Peng, Y. Lu, W. Liu and W. Xu, “Responsiveness and release characteristic of semi-IPN hydrogels consisting of nano-Sized clay crosslinked poly(dimethylaminoethyl methacrylate) and linear carboxymethyl chitosan,” Journal of Nanoscience and Nanotechnology, vol. 15, pp.164-171, 2015.

M. G. Antoniraj, C. S. Kumar, and R. Kandasamy, “Synthesis and characterization of poly(N-isopropylacrylamide)-g-carboxymethyl chitosan copolymer-based doxorubicinloaded polymeric nanoparticles for thermoresponsive drug release,” Colloid and Polymer Science, vol. 294, pp. 527-535, 2015.

B. L. Guo and Q. Y. Gao, “Preparation and properties of a pH/temperature-responsive carboxymethyl chitosan/poly(N-isopropyl acrylamide)semi-IPN hydrogel for oral delivery of drugs,” Carbohydrate Research, vol. 342, pp. 2416-2422, 2007.

F. Yoshii, L. Zhao, R. A. Wach, N. Nagasawa, H. Mitomo, and T. Kume, “Hydrogels of polysaccharide derivatives crosslinked with irradiation at paste-like condition,” Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, vol. 208, pp. 320-324, 2003.

Y. F. Liu, K. L. Huang, D. M. Peng, P. Ding, and G.Y. Li, “Preparation and characterization of glutaraldehyde cross-linked O-carboxymethyl chitosan microspheres for controlled delivery of pazufloxacin mesilate,” International Journal of Biological Macromolecules, vol. 41, pp. 87-93, 2007.

A. Kadnaim, W. Janvikul, U. Wichai, and M. Rutnakornpituk, “Synthesis and properties of carboxymethylchitosan hydrogels modified with poly(ester-urethane),” Carbohydrate Polymers, vol. 74, pp. 257- 267, 2008.

M. Rutnakornpituk, P. Ngamdee, and P. Phinyocheep, “Synthesis, characterization and properties of chitosan modified with poly(ethylene glycol)-polydimethylsiloxane amphiphilic block copolymers,” Polymer, vol. 46, pp. 9742-9752, 2005.

M. Rutnakornpituk and P. Ngamdee, “Surface and mechanical properties of microporous membranes of poly(ethylene glycol)-polydimethylsiloxane copolymer/ chitosan,” Polymer, vol. 47, pp. 7909-7917, 2006.

W. C. Huang, K. H. Liu, T. C. Liu, D. M. Liu, and S.Y. Chen, “Synergistic hierarchicalsilicone-modified polysaccharide hybrid as a soft scaffold to control cell adhesion and proliferation,” Acta Biomaterialia, vol. 10, pp. 3546-3556, 2014.

M. Bračič, T. Mohan, T. Griesser, K. StanaKleinschek, S. Strnad, and L. Fras-Zemljič, “One-Step noncovalent surface functionalization of PDMS with chitosan-based bioparticles and their protein-repellent properties,” Advanced Materials Interfaces, vol. 4, pp. 1700416, 2017.

W. C. Huang, S. Y. Chen, and D. M. Liu, “An amphiphilic silicone-modified polysaccharide molecular hybrid with in situ forming of hierarchical superporous architecture upon swelling,” Soft Matter, vol. 8, pp. 10868, 2012.

N. Rodkate, U. Wichai, B. Boontha, and M. Rutnakornpituk “Semi-interpenetrating polymer network hydrogels between polydimethyl siloxane/polyethylene glycol and chitosan”, Carbohydrate Polymer, vol. 81, pp. 617-625, 2010.




How to Cite

N. . Rodkate, N. . Deepuppha, B. . Rutnakornpituk, and M. Rutnakornpituk, “Carboxymethylchitosan-based hydrogels crosslinked with polydimethylsiloxane”, J Met Mater Miner, vol. 28, no. 1, Jun. 2018.



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