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用作反应性和热敏性共聚物的硫醇/丙烯酸酯改性聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物。

Thiol/acrylate-modified PEO-PPO-PEO triblocks used as reactive and thermosensitive copolymers.

作者信息

Niu Guoguang, Zhang Hongbin, Song Li, Cui Xiaopeng, Cao Hui, Zheng Yudong, Zhu Siquan, Yang Zhou, Yang Huai

机构信息

School of Materials Science and Engineering, University of Science and Technology Beijing, China.

出版信息

Biomacromolecules. 2008 Oct;9(10):2621-8. doi: 10.1021/bm800573e. Epub 2008 Aug 19.

Abstract

The reactive thermal-sensitive hydrogels, which combined the reversible thermosensitive and mild reactive property, were designed based on thiol-ene reaction in physiological conditions between thiol and acrylate capped thermosensitive Poloxamer 188. The modified P188A, P188SH, and their reactivity were characterized by (1)H NMR, FT-IR, GPC, DSC, Ellman method, and Rheometer. It was found that the thiol-ene reaction was pH and thermal-sensitive. There was 77.7% SH involved into the reaction at 37.0 degrees C and pH 7.4 within the first 30 min. The most of molecules reacted as CC/SH mol ratio was 1.5. The exothermic thiol-ene reaction was mild, with about DeltaH = -91.18 J/g changes. The multiblocks or network structure limited the dissolution of hydrogel, correspondingly the gel's duration and the release time of methylene blue were prolonged to 124 h. The experimental results indicated the reactive thermal-sensitive hydrogel's potential applications in drug delivery, tissue engineering, and cell encapsulation.

摘要

基于生理条件下硫醇与丙烯酸酯封端的热敏性泊洛沙姆188之间的硫醇-烯反应,设计了兼具可逆热敏性和温和反应性的反应性热敏水凝胶。通过核磁共振氢谱(¹H NMR)、傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)、差示扫描量热法(DSC)、埃尔曼法和流变仪对改性后的P188A、P188SH及其反应活性进行了表征。结果发现硫醇-烯反应对pH值和温度敏感。在37.0℃、pH 7.4条件下,前30分钟内有77.7%的硫醇参与反应。当CC/SH摩尔比为1.5时,大多数分子发生反应。硫醇-烯放热反应较为温和,焓变约为ΔH = -91.18 J/g。多嵌段或网络结构限制了水凝胶的溶解,相应地,凝胶持续时间和亚甲基蓝的释放时间延长至124小时。实验结果表明反应性热敏水凝胶在药物递送、组织工程和细胞封装方面具有潜在应用价值。

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