Preparation and Sensitivity Behaviors of Chitosan-based Intelligent Hydrogels
SHU Jing1, FENG Xiao-hui1, ZHENG Li-na2, SANG Xi-qin1, WANG Dan-dan3
1. Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang, China;
2. College of Marine Environmental Engineering, Dalian Ocean University, Dalian 116023, Liaoning, China;
3. Petrochina Daqing Oilfield No.9 Oil Production Plant, Daqing 163853, Heilongjiang, China
Abstract:Chitosan-based ternary intelligent hydrogels of pH/temperature-sensibility were prepared on the basis of chitosan/polyvinylpyrrolidone(CS/PVP)hydrogels with polyvinyl alcohol(PVA)introducing,using glutaraldehyde as crosslinking agent and ammonium ceric nitrate as initiator. The results indicated that the introduction of PVA increased the concentration of CS in the hydrogels significantly and made the temperature-sensitive grade increase. Especially, the hydrogels indicated obvious temperature-sensitivity at 35℃. Under the optimal conditions, that is, 6.25%PVA(mass fraction, compared to PVP), 5.1% initiator, 0.4% cross-linking agent, 80℃ and 6h, the maximum swelling ratio of hydrogels was about 1500%. Thermo-sensitive and pH-sensitive experiments showed that the hydrogels were of excellent thermo-sensibility and pH-sensibility. The chitosan-based ternary hydrogels were of four grades temperature-sensitivity and good pH-sensitivity with the abrupt change point at 2.0.
[1] ZHOU Y S, MA G P, SHI S Q, et al. Photopolymerized water-soluble chitosan-based hydrogel as potential use in tissue engineering[J]. International Journal of Biological Macromolecules, 2011, 48(3): 408-413.[2] BHATTARAI N, GUNN J, ZHANG M Q. Chitosan-based hydrogels for controlled, localized drug delivery[J]. Advanced Drug Delivery Reviews, 2010,62(1): 83-99.[3] ZHENG Y A, HUANG D J, WANG A Q. Chitosan-g- poly(acrylic acid) hydrogel with crosslinked polymeric networks for Ni2+ recovery[J]. Analytica Chimica Acta, 2011, 687(2): 193-200.[4] SUBHASH S V, MADHABHAI M P. Hydrogels based on interpenetrating network of chitosan and polyvinyl pyrrolidone for pH-sensitive delivery of repaglinide[J]. Current Drug Discovery Technologies,2011, 8(2): 126-135.[5] VAGHANI S S, PATEL M M. pH-sensitive hydrogels based on semi-interpenetrating network (semi-IPN) of chitosan and polyvinyl pyrrolidone for clarithromycin release[J]. Drug Dev Ind Pharm, 2011, 37(10): 1160-1169.[6] 易国斌, 康正, 杨少华, 等. PVP/CHI交联共混水凝胶的pH敏感性研究[J]. 化学研究与应用, 2006, 18(10): 1175-1178.YI G B, KANG Z, YANG S H, et al. Study on pH sensitivity of PVP/CHI blend hydrogels[J]. Journal of Chemical Research and Application,2006, 18(10): 1175-1178.[7] DERGUNOV S A, MUN G A. γ-irradiated chitosan- polyvinyl pyrrolidone hydrogels as pH-sensitive protein delivery system[J]. Radiation Physics and Chemistry, 2009, 78(1): 65-68.[8] 易国斌, 康正, 崔亦华, 等. 温度敏感性PVP/CHI共混水凝胶的制备与溶胀性能[J]. 化学与生物工程, 2006, 23(5): 24-26YI G B, KANG Z, CUI Y H, et al. Preparation and swelling performance of thermosensitive PVP/CHI blend hydrogel[J]. Chemistry & Bioengineering,2006, 23(5): 24-26.[9] KHURMA J R, ROHINDRA D R, NAND A V. Swelling and thermal characteristics of genipin crosslinked chitosan and poly(vinyl pyrrolidone) hydrogels[J]. Polymer Bulletin, 2005, 54(3): 195-204.[10] LI Y, DU Y M, TANG Y F, et al.A novel pH-sensitive and freeze-thawed carboxymethyl chitosan/poly(vinyl alcohol) blended hydrogel for protein delivery[J]. Polymer International, 2009, 58(10): 1120-1125.[11] 陈欢欢, 昝佳, 林莹, 等. 壳聚糖/聚乙烯醇温敏水凝胶的制备及性质研究[J].清华大学学报, 2006, 46(6): 843-846 CHEN H H, ZAN J, LIN Y, et al. Preparation and physical properties of chitosan-poly (vinyl alcohol) thermosensitive hydrogel[J]. Journal of Tsinghua University(Science and Technology),2006, 46(6): 843-846.[12] 舒静, 李小静, 赵大飙, 等. 温度/ pH 敏感性壳聚糖-聚乙烯吡咯烷酮水凝胶的制备[J].高分子材料科学与工程,2011,27(8):155-158. SHU J, LI X J, ZHAO D B, et al. Preparation of thermo-sensitive/ph-sensitive chitosan/polyvinylpyrrolidone hydrogels[J]. Polymer Materials Science and Engineering, 2011, 27(8):155-158.[13] DAI W S, BARBARI T A. Hydrogel membranes with mesh size asymmetry based on the gradient crosslinking of poly(vinylalcohol)[J]. Journal of Membrane Science, 1999, 156(1):67-69.[14] KHURMA J R, NAND A V. Temperature and pH sensitive hydrogels composed of chitosan and poly(ethylene glycol)[J]. Polymer Bulletin, 2008, 59(6): 805-812.