基于主-客体包合物的刺激响应超分子多糖凝胶及其在光化学传感器中的应用

①This project aims at designing and synthesizing metal ions-responsive or organic compounds-responsive supramolecular polysaccharide hydrogels using celluloses which grafted with amylose derivatives as host polymers, celluloses which grafted with thioether oligomer, hydroxy-containing fatty acid oligomer or tetrahydrofuran oligomer as guest polymers, and host-guest inclusion complexes as cross-linking structures. By this project, the structure and theory of stimuli-responsive supramolecular hydrogels will be enriched. And the study will provide solid theory basis for applying host-guest molecules based on amylase to optical chemsensor and other host-guest chemistry fields.② The structural characteristics and theory of stimuli-responsive supramolecular hydrogels and the stimuli-responsive supramolecular polysaccharide hydrogels will be applied to developing responsive polymer crystalline colloidal arrays，and polysaccharide-based responsive polymer crystalline colloidal arrays with high sensitivity, high responsive rate, obvious color change to stimulus of special ion metal and organic compounds will be prepared and novel preparation principle and stimuli-responsive theory will be developed.③ Through coupling of stimuli-responsive supramolecular hydrogels with responsive polymer photonic crystal, the recognition signal of amylose inclusion complexes can be transformed into color change, and a kind of optical chemosensors with low-cost, simple preparative, naked-eye detective and easy and feasible applicable properties for monitoring metal ion and organic pollutants in water will be developed.

(1) 设计合成以接枝直链淀粉衍生物的纤维素作为主体高分子、接枝硫醚齐聚物、羟基脂肪酸齐聚物、四氢呋喃齐聚物等的纤维素作为客体高分子、主客体包合物作为交联结构的全新的金属离子和有机物刺激响应超分子多糖凝胶；研究丰富刺激响应超分子凝胶结构和理论，也为直链淀粉主体分子应用于光化学传感器和其他主客体化学领域打下坚实的理论基础。(2) 将刺激响应超分子凝胶的结构特点和理论以及刺激响应超分子多糖凝胶应用于研制响应聚合物胶体晶体阵列，研制出对特定金属离子或有机物的刺激具有高灵敏度、高响应速率、明显颜色变化的多糖基响应聚合物胶体晶体阵列,发展响应聚合物胶体晶体阵列的新的制备原理和刺激响应理论。(3) 通过刺激响应超分子凝胶和响应聚合物光子晶体的耦合，把直链淀粉包合物的识别信号转化为裸眼可视的颜色变化，发展一种价廉、制备简单、裸眼可视、方便实用的光化学传感器，重点用于检测水体中的金属离子以及有机污染物。

刺激响应聚合物胶体晶体阵列在光化学传感器等领域具有广阔的应用前景。.本项目研究由具有资源和结构优势的可再生多糖为原料制备了多糖基刺激响应聚合物胶体晶体阵列。采用thio-ene、thio-yne等点击化学反应，设计合成了一系列含羧基、硫醚键、氨基的多糖衍生物，并通过环氧氯丙烷、二乙烯砜、二环氧丙基聚乙二醇的交联反应制备了上述一系列多糖衍生物凝胶。研究了制得多糖衍生物凝胶的pH、温度、有机物和金属离子刺激响应性能。结果表明根据多糖凝胶结构不同，制得多糖衍生物凝胶具有良好的pH、温度、有机物或金属离子刺激响应性能。将上述刺激响应多糖凝胶成功嵌入聚苯乙烯-丙烯酸共聚物纳米颗粒晶体阵列，研制出了多糖基刺激响应聚合物胶体晶体阵列，并研究了金属离子浓度、pH值等外部刺激的变化对聚合物胶体晶体阵列颜色的影响，结果表明随着金属离子浓度、pH值等变化聚合物胶体晶体阵列具有明显的裸眼可视颜色改变。通过本项目研究发展了一系列温度、pH、有机物、金属离子响应的多糖基刺激响应聚合物。丰富了刺激响应聚合物的结构与理论。通过多糖基刺激响应聚合物和响应聚合物光子晶体的耦合，把多糖基刺激响应聚合物的刺激信号转化为裸眼可视的颜色变化，为发展一种价廉、制备简单、裸眼可视、方便实用的光化学传感器打下来坚实基础。为由具有资源、性能优势的可再生多糖设计合成高附加值的智能聚合物开辟了新途径。