疏水离子液体/水中相微乳液中导电聚合物的模板生物合成

Template-assisted biosynthesis of conducting polymers is a recently developed new strategy for synthesizing functionalized polymers. As a medium, middle-phase microemulsion based on hydrophobic ionic liquid (HIL) and water has the combined advantages of both HIL and bicontinuous microemulsion. The use of the medium as a template for synthesizing conducting polymer opens up a new way for green synthesis of conducting polymers. In the present proposal, the effects of the component and the structure of HILs on the phase behavior and the microstructure of anionic surfactant stabilized microemulsions will be systematically studied, and the microenvironmental effect of the resulting middle-phase microemulsions (the domain size, interfacial composition and electric charge density) on the activity and the conformation of solubilized oxidoreductases such as laccase will be investigated in detail to formulate middle-phase microemulsions compatible with the enzymes. The kinetics of the enzyme catalyzed oxidative polymerization of arylamine monomers such as aniline in the medium will be thoroughly investigated. In addition to tracking the time-dependent parameters such as the activity of enzyme, the polaron density and the regioselectivity of chain growth, the morphology, the structure and the properties of the resulting polymers will be also characterized to fully understand the template effect of the bicontinuous medium. The intended systematic studies will not only enrich the research content of the enzymatic catalysis in HIL-based microemulsion, but also improve the efficiency of the biosynthesis of a conducting polymer and its performance.

导电聚合物的模板生物合成是近年来发展起来的功能聚合物合成新策略。用疏水离子液体取代油构建集离子液体与中相微乳液优势于一体的离子液体基双连续微乳液并以此为介质和模板生物合成导电聚合物，开辟了导电聚合物绿色合成新途径。本项目拟在系统分析疏水离子液体组成与结构对阴离子表面活性剂稳定的微乳液相行为与微结构的影响规律与机制的基础上，通过介质微环境（微畴大小、界面组成与电荷密度等）对增溶酶活力与构象的影响与机制的全面认识，构建出漆酶等氧化还原酶兼容的中相微乳液；深入研究此介质中苯胺等芳香胺的酶促氧化聚合反应动力学，通过对反应进程中酶活力、极化子密度、链生长区域选择性等参数的动态跟踪和对聚合产物形貌结构与性能的表征分析，探讨双连续微乳液对酶促芳香胺氧化聚合的模板效应。上述研究不但丰富了疏水离子液体基微乳液酶催化研究内涵，也有助于提升生物合成导电聚合物的效率与性能。

导电聚合物的模板生物合成是近年来发展起来的功能聚合物合成新策略。本项目以集离子液体与中相微乳液优势于一体的离子液体基双连续微乳液为介质和模板，在其中尝试开展了导电聚苯胺的绿色生物合成。首先，利用鱼形相图，研究了阴离子表面活性剂/疏水离子液体/水（添加剂）拟三元体系的微乳液相行为，系统考察了微乳液相行为随添加剂、疏水离子液体和阴离子表面活性剂组成与结构的演变规律，构建了数种阴离子表面活性剂稳定的疏水离子液体基双连续微乳液；其次，利用小角X射线散射技术等手段，对相转变温度适中的疏水离子液体基微乳液体系的微结构进行了表征，系统研究了微乳液组成与体系温度对增溶氧化还原酶（漆酶与辣根过氧化物酶）活力与稳定性的影响及其内在机制，筛选出了适宜酶催化转化的阴离子表面活性剂稳定的疏水离子液体基微乳液；然后，利用紫外可见近红外光谱、电子自旋共振谱等技术手段，详细研究了双连续微乳液介质中辣根过氧化物酶催化苯胺氧化聚合反应的过程及其聚合产物的形貌、结果与电学性能，厘清了微乳液组成与微乳液微结构、增溶酶催化性能、酶促氧化聚合反应产物导电性能间的依存关系，最终阐明了微乳液微结构对酶促苯胺氧化聚合反应的模板效应。上述研究不但丰富了疏水离子液体基微乳液酶催化研究内涵，也有助于提升生物合成导电聚合物的性能与效率。