基于金属配位和主客体相互作用分级自组装构筑超分子凝胶

发布时间：2018-02-21 02:53

本文关键词： 超分子聚合物超分子凝胶分级自组装多重刺激响应自修复　出处：《高分子学报》2017年01期 　论文类型：期刊论文

【摘要】：将金属配位和主客体相互作用引入到同1个超分子体系中,设计合成了2个超分子单体1和2.通过这2个超分子单体分级自组装形成的交联网状超分子聚合物构建了一种多重刺激响应性和良好自修复性能的超分子凝胶.同时,进一步将具有聚集诱导发光性能的四苯乙烯引入到这种超分子体系中,以赋予超分子体系新颖的发光性能.单体分子1是由中间为双苯并24-冠-8的冠醚连接2个四苯基乙烯荧光生色团,两端为2个三联吡啶分子构成的1个主体分子.单体分子1两端的三联吡啶基团可以与过渡金属Zn(OTf)2进行金属配位形成线型超分子聚合物3;而中间的冠醚基团与双二级铵盐客体分子2通过主客体相互作用进一步形成交联超分子聚合物4.当该交联超分子聚合物的浓度达到30 mmol/L时,可形成荧光超分子聚合物凝胶.通过核磁共振(1H-NMR和DOSY)与黏度等测试方法,证明了线形和交联超分子聚合物的形成,并进一步通过流变的测试证明了超分子聚合物凝胶的形成及其良好的自修复性能.除此之外,由于引入的主客体相互作用以及金属配位固有的刺激响应性,该荧光超分子聚合物凝胶表现出对温度、p H值、K+离子和竞争配体的刺激响应性能.
[Abstract]:The metal coordination and host-guest interactions are introduced into the same supramolecular system. Two supramolecular monomers, 1 and 2, were designed and synthesized. A supermolecular gel with multiple stimuli response and good self-repair properties was constructed by using these two supramolecular monomers to form cross-linked network supramolecular polymers. Furthermore, tetrastyrene with aggregation induced luminescence was introduced into this supramolecular system. In order to endow the supramolecular system with novel luminescent properties, monomeric molecule 1 is connected with two tetraphenyl ethylene fluorescent chromophore groups by crown ethers with dibenzo-24-crown-8 intermediate. The tripyridine group at the two ends of monomeric molecule 1 can coordinate with transition metal Zn(OTf)2 to form linear supramolecular polymer 3, while the middle crown ether group can form a linear supramolecular polymer, while the intermediate crown ether group can coordinate with the transition metal Zn(OTf)2 to form a linear supramolecular polymer 3. The second order ammonium salt guest molecule 2 further forms the crosslinked supramolecular polymer 4 through the host and guest interaction. When the concentration of the crosslinked supramolecular polymer reaches 30 mmol/L, Fluorescence supramolecular polymer gels can be formed. The formation of linear and cross-linked supramolecular polymers has been proved by means of 1H-NMR and DOSYN NMR and viscosity measurements. Furthermore, the formation of supramolecular polymer gels and their good self-repair properties were proved by rheological tests. In addition, due to the host and guest interactions introduced and the intrinsic stimulus response of metal coordination, The fluorescent supramolecular polymer gels exhibit the stimulative response to temperature H value K ions and competitive ligands.
【作者单位】：杭州师范大学材料与化学化工学院;
【基金】：国家自然科学基金(基金号21574034,2174034) 浙江省自然科学基金(基金号LY16B040006) 浙江省大学生新苗计划(项目号2016R423042)资助项目
【分类号】：O648.17;O641.3

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