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Sol-gel synthesis of biocompatible silica-chitosan hybrids and hydrophobic coatings

Published online by Cambridge University Press:  31 January 2011

S. Smitha
Affiliation:
Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (Formerly Regional Research Laboratory), Council for Scientific and Industrial Research (CSIR), Trivandrum 695019, Kerala, India
P. Shajesh
Affiliation:
Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (Formerly Regional Research Laboratory), Council for Scientific and Industrial Research (CSIR), Trivandrum 695019, Kerala, India
P. Mukundan
Affiliation:
Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (Formerly Regional Research Laboratory), Council for Scientific and Industrial Research (CSIR), Trivandrum 695019, Kerala, India
K.G.K. Warrier*
Affiliation:
Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (Formerly Regional Research Laboratory), Council for Scientific and Industrial Research (CSIR), Trivandrum 695019, Kerala, India
*
a)Address all correspondence to this author. e-mail: warrierkgk@yahoo.com
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Abstract

A new organic–inorganic hybrid synthesized through a sol-gel process starting from alkoxysilane and chitosan is reported. Functionalization of the hybrid was effected through in situ hydrolysis–condensation reaction of methyltrimethoxysilane (MTMS) and vinyltrimethoxysilane (VTMS) in the reaction medium. The process yields highly transparent and hydrophobic silica–chitosan hybrids. The hybrid gel was investigated with respect to chemical modification, thermal degradation, hydrophobicity, and transparency under the ultraviolet-visible region. The extent of hydrophobicity had been tailored by varying the precursor ratio. SiO2–chitosan–MTMS hybrids showed a higher thermal stability than SiO2–chitosan–VTMS (SCV) hybrids with respect to hydrophobicity. Condensation of silsesquioxanes generated from the hydrolysis of MTMS and VTMS over the silica-chitosan particles impart hydrophobicity to the hybrid. The coatings of functionalized SiO2–chitosan precursor sol on glass substrates showed nearly 100% optical transmittance in the visible region. The present hybrid material may find application in optics and other industries.

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Articles
Copyright
Copyright © Materials Research Society 2008

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References

REFERENCES

1Mennig, M., Fries, K., Lindenstruth, M.Schmidt, H.: Development of fast switching photochromic coatings on transparent plastics and glass. Thin Solid Films 351, 230 1999CrossRefGoogle Scholar
2Awazu, K.Onuki, H.: Photo-induced synthesis of amorphous SiO2 film from tetramethoxy-silane on polymethylmethacrylate at room temperature. J. Non-Cryst. Solids 215, 176 1997CrossRefGoogle Scholar
3Matejec, V., Rose, K., Hayer, M., Pospisllova, M.Chomat, M.: Development of organically modified polysiloxanes for coating optical fibers and their sensitivity to gases and solvents. Sens. Actuators, B 39, 438 1997CrossRefGoogle Scholar
4Mimura, S., Naito, H., Kanemitsu, Y., Matsukawa, K.Inoue, H.: Optical properties of organic–inorganic hybrid thin films containing polysilane segments prepared from polysilane–methacrylate copolymers. J. Organomet. Chem. 611, 40 2000CrossRefGoogle Scholar
5Chou, T.P., Chandrasekaran, C., Limmer, S.J., Seraji, S., Wu, Y., Forbess, M.J., Nguyen, C.Cao, G.Z.: Organic–inorganic hybrid coatings for corrosion protection. J. Non-Cryst. Solids 290, 153 2001CrossRefGoogle Scholar
6Yano, S., Iwata, K.Kurita, K.: Physical properties and structure of organic-inorganic hybrid materials produced by sol-gel process. Mater. Sci. Eng., C 6, 75 1998CrossRefGoogle Scholar
7Chen, W.C.Lee, S.J.: Synthesis and characterization of poly(methyl methacrylate)-silica hybrid optical thin films. Polym. J. 32, 67 2001CrossRefGoogle Scholar
8Chan, C.K.Chu, I.M.: Phase behavior and molecular chain environment of organic–inorganic hybrid materials based on poly(n-butyl methacrylate-co-(3- (methacryloxypropyl)) trimethoxysilane). Polym. 42, 6823 2001CrossRefGoogle Scholar
9Jethmalani, J.M.Ford, W.T.: Diffraction of visible light by ordered monodisperse silica-poly(methyl acrylate) composite films. Chem. Mater. 8, 2138 1996CrossRefGoogle Scholar
10Wang, C., Yen, W., George, R.F., Wei, L.Tiejin, L.: Poly(ethylene oxide)–silica hybrid materials for lithium battery application. Mater. Lett. 39, 206 1999CrossRefGoogle Scholar
11Kim, K.M.: Organic-inorganic nanocomposites of polystyrene with polyhedral oligomeric silsesquioxane. Polym. 30, 380 2006Google Scholar
12Coradin, T., Bah, S.Livage, J.: Gelatine/silicate interactions: From nanoparticles to composite gels. Colloids Surf., B 35, 53 2004CrossRefGoogle ScholarPubMed
13Watzke, H.J.Dieschbourg, C.: Novel silica-biopolymer nanocomposites: The silica sol-gel process in biopolymer organogels. Adv. Colloid Interface Sci. 50, 1 1994CrossRefGoogle Scholar
14Schuleit, M.Luisi, P.L.: Enzyme immobilization in silica-hardened organogels. Biotechnol. Bioeng. 72, 249 20013.0.CO;2-B>CrossRefGoogle ScholarPubMed
15Liu, D.M.Chen, I.W.: Encapsulation of protein molecules in transparent porous silica matrices via an aqueous colloidal sol-gel process. Acta Mater. 47, 4535 1999CrossRefGoogle Scholar
16Yuan, G.L., Yin, M.Y., Jiang, T.T., Huang, M.Y.Jiang, Y.Y.: Catalytic behaviors of silica-supported chitin–platinum complex for asymmetric hydrogenation of α-phenylethanol. J. Mol. Catal. A: Chem. 159, 45 2000CrossRefGoogle Scholar
17Brasack, I., Bottcher, H.Hempel, U.: Biocompatibility of modified silica-protein composite layers. J. Sol-Gel Sci. Technol. 19, 479 2000CrossRefGoogle Scholar
18Smitha, S., Mukundan, P., Pillai, P. KrishnaWarrier, K.G.K.: Silica–gelatin bio-hybrid and transparent nano-coatings through sol-gel technique. Mater. Chem. Phys. 103, 318 2007CrossRefGoogle Scholar
19Karine, M., Francoise, Q., Daniel, B., Michel, B.Jean-Marie, D.: Porous chitosan-silica hybrid microspheres as a potential catalyst. Chem. Mater. 16, 3367 2004Google Scholar
20Schephend, R., Reader, S.Falshaw, A.: Chitosan functional properties. Glycoconjugate J. 14, 535 1997Google Scholar
21Huang, A., Liu, Y., Chen, L.Hua, J.: Synthesis and property of nanosized palladium catalysts protected by chitosan/silica. J. Appl. Polym. Sci. 85, 989 2002CrossRefGoogle Scholar
22Yin, M., Yuan, G., Wu, Y., Hyang, M.Jiang, Y.: Asymmetric hydrogenation of ketones catalyzed by a silica-supported chitosan–palladium complex. J. Mol. Catal. A: Chem. 147, 93 1999CrossRefGoogle Scholar
23Li-Ming, T., Mei-Yu, H.Ying-Yan, J.: Selective hydrogenation of phenol to cyclohexanone catalyzed by a silica-supported chitosan-palladium complex. Macromol. Rapid Commun. 15, 527 1994Google Scholar
24Liu, Y., Su, Y.Lai, J.: In situ cross linking of chitosan and formation of chitosan–silica hybrid membranes with using γ- glycidoxypropyltrimethoxysilane as a cross linking agent. Polym. 45, 6831 2004CrossRefGoogle Scholar
25Corrado, M.Riccardo, A.: Natural and artificial chitosan– inorganic composites. J. Inorg. Biochem. 92, 89 2002Google Scholar
26Shi, Q., Tian, Y., Dong, X.Sun, Y.: Chitosan-coated silica beads as immobilized metal affinity support for protein adsorption. Biochem. Eng. J. 16, 317 2003CrossRefGoogle Scholar
27Takahiro, S.Yasuyuki, M.: Characteristics of silica-chitosan complex membrane and their relationships to the characteristics of growth and adhesiveness of L-929 cells cultured on the biomembrane. J. Ferment. Bioeng. 84, 128 1997Google Scholar
28Tan, X., Tian, Y., Cai, P.Zou, X.: Glucose biosensor based on glucose oxidase immobilized in sol–gel chitosan/silica hybrid composite film on Prussian blue modified glass carbon electrode. Anal. Bioanal. Chem. 381, 500 2005CrossRefGoogle ScholarPubMed
29Ji, J., Chen, G., Huang, M.Jiang, Y.: Catalytic hydrogenation behaviours of palladium complexes of chitosan-polyacrylic acid and chitosan-polymethacrylic acid. React. Polym. 23, 95 1994Google Scholar
30Zhang, J.Xia, C.: Natural biopolymer-supported bimetallic catalyst system for the carbonylation to esters of Naproxen. J. Mol. Catal. A: Chem. 206, 59 2003CrossRefGoogle Scholar
31Miao, Y.Tan, S.N.: Amperometric hydrogen peroxide biosensor with silica sol-gel/chitosan film as immobilization matrix. Anal. Chim. Acta 437, 87 2001CrossRefGoogle Scholar
32Fuentes, S., Retuert, P., Ubilla, A., Fernandez, J.Gonzalez, G.: Relationship between composition and structure in chitosan-based hybrid films. Biomacromolecules 1, 239 2000CrossRefGoogle ScholarPubMed
33Chen, Q., Miyaji, F., Kokubo, T.Nakamura, T.: Apatite formation on PDMS-modified CaO–SiO2–TiO2 hybrids prepared by sol–gel process. Biomaterials 20, 1127 1999CrossRefGoogle ScholarPubMed
34Smitha, S., Shajesh, P., Mukundan, P.Warrier, K.G.K.: Antiwetting silica–gelatin nanohybrid and transparent nano coatings synthesised through an aqueous sol–gel process. J. Sol-Gel Sci. Technol. 42, 157 2007CrossRefGoogle Scholar
35Smitha, S., Shajesh, P., Mukundan, P., Nair, T.D.R.Warrier, K.G.K.: Synthesis of biocompatible hydrophobic silica–gelatin nano-hybrid by sol-gel process. Colloids Surf., B 55, 38 2007CrossRefGoogle ScholarPubMed
36Ren, L., Tsuru, K., Hayakawa, S.Osaka, A.: Synthesis and characterization of gelatin-siloxane hybrids derived through sol-gel procedure. J. Sol-Gel Sci. Technol. 21, 115 2001CrossRefGoogle Scholar
37Thierry, A., Béatrice, L.Michel, M.: Rheological study of fumed silica suspensions in chitosan solutions. Langmuir 15, 2380 1999Google Scholar
38Yadienka, M., Jaime, R., Yazdani-Pedram, M.Helmut, C.: Hybrid ternary organic–inorganic films based on interpolymer complexes and silica. Polym. 45, 3257 2004Google Scholar
39Xuecai, T., Minjian, L., Peixiang, C., Lijun, L.Xiaoyong, Z.: An amperometric cholesterol biosensor based on multiwalled carbon nanotubes and organically modified sol-gel/chitosan hybrid composite film. Anal. Biochem. 337, 111 2005Google Scholar
40Gellermann, C., Storch, W.Wolter, H.: Synthesis and characterization of the organic surface modifications of monodisperse colloidal silica. J. Sol-Gel Sci. Technol. 8, 173 1997CrossRefGoogle Scholar
41Ding, P., Huang, K., Li, G.Liu, Y.: Preparation and properties of modified chitosan as potential matrix materials for drug sustained-release beads. Int. J. Biol. Macromol. 41, 125 2007CrossRefGoogle ScholarPubMed