一种高强度准聚轮烷水凝胶的制备及性能研究  

Preparation and Properties Investigation on a Kind of Pseudopolyrotaxane Hydrogel with High Intensity

作　　者：李晓珍[1] 田思超 孙鹏飞[1] 范曲立[1] 黄维[1,2] 

机构地区：[1]南京邮电大学有机电子与信息显示国家重点实验室培育基地信息材料与纳米技术研究院江苏先进生物与化学制造协同创新中心,南京210023 [2]南京工业大学江苏省柔性电子重点实验室先进材料研究院江苏先进生物与化学制造协同创新中心,南京211816

出　　处：《高分子学报》2017年第6期952-958,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21104033);江苏高校优势学科建设工程资助项目(项目号YX03001);江苏省自然科学基金青年基金(基金号BK20150843);南京邮电大学引进人才科研启动基金(基金号NY215017);南京邮电大学基金(基金号NY215080)资助项目

摘　　要：通过点击化学在聚乙二醇单甲醚(MPEG)端基分别修饰了葡萄糖(Glc)、甘露糖(Man)和半乳糖(Gal),制备了一系列端基为糖的聚乙二醇单甲醚(MPEG-Glc、MPEG-Man和MPEG-Gal),此类端基为糖的MPEG和α-环糊精(α-CD)混合后能够形成稳定的准聚轮烷(PPR)水凝胶,而端基没有修饰糖的MPEG和α-CD只能形成黏度较大的溶液而无法形成稳定存在的凝胶.通过流变仪测试可知水凝胶的弹性模量高达1.0×105 Pa,远大于文献中通过黏土等增强的PPR水凝胶的强度,我们认为该MPEG端基的糖之间能够形成新的"糖交联"点从而有效提高了凝胶的强度.通过向水凝胶中加入和MPEG端基的糖具有相互作用的苯硼酸半酯聚合物(PNIPAM-co-PBOB)或刀豆蛋白(Con A),发现在凝胶中加入PNIPAM-co-PBOB或Con A后可明显降低PPR水凝胶的强度.通过扫描电镜(SEM)和X射线衍射(XRD)对水凝胶的形貌以及微观结构进行表征分析,发现此凝胶的微观结构和文献中报道的PPR水凝胶基本一致,进一步证明了上述结论.As an important member of supramolecular hydrogel, pseudopolyrotaxane（PPR） hydrogel has attracted tremendous attention in recent years due to its good biocompatibility. Compared with conventional approaches reported, a new method was developed for PPR hydrogel preparation in this study, which can increase the strength of the hydrogel more efficiently. First, monoaccharide group-functionalized methoxypolyethylene glycols（MPEG）（MPEG-Glc, MPEG-Man and MPEG-Gal） were synthesized by click chemistry. After that, a series of PPR hydrogels（Glc-PPR, Man-PPR and Gal-PPR） with high stability and strength were successfully prepared via the ＂host-guest＂ interactions between α-CD and monoaccharide group-functionalized MPEG（MPEG-Glc, MPEG-Man and MPEG-Gal, respectively）. However, similar hydrogel cannot be obtained using α-CD and MPEG without monoaccharide modification. The properties of Glc-PPR, Man-PPR and Gal-PPR were characterized by rheometer test, X-ray diffraction（XRD） and scan electron microscopy（SEM）. Surprisingly, rheometer test results indicated that the elasticity modulus of Glc-PPR, Man-PPR and Gal-PPR could be up to 1.0 × 105 Pa, which was much higher than that of the clay-enhanced hydrogel in the previous reports. As for this phenomenon, we propose that new sugar cross-linking agents from ＂carbohydrate-carbohydate interaction＂ have constructed among monoaccharide terminals of MPEG, so that the strength of Glc-PPR, Man-PPR and Gal-PPR could be improved efficiently. Furthermore, in order to demonstrate the mechanism of the strength enhancement of PPR hydrogel, phenylboronic acid cyclic monoester（PNIPAM-co-PBOB） and concanavalin A（Con A） were added into Glc-PPR, Man-PPR and Gal-PPR, respectively to eliminate the sugar cross-linking agents, which led to a significant decrease in the strength of Glc-PPR, Man-PPR and Gal-PPR. SEM and XRD results showed that the microstructures of Glc-PPR, Man-PPR and Gal-PPR were basically identical with PPR hydrogel reported in the refere

关 键 词：Α-环糊精 包结络合 PPR水凝胶 糖-糖相互作用 

分 类 号：TQ427.26[化学工程]