手性聚合物基化学传感器的设计、合成及对映选择性识别性能

项目名称： 手性聚合物基化学传感器的设计、合成及对映选择性识别性能

项目编号： No.21474089

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 无机化学

项目作者： 江黎明

作者单位： 浙江大学

项目金额： 80万元

中文摘要： 用于对映异构体识别的化学传感器因其在生物、化学、制药等诸多学科研究中占有重要地位而受到广泛关注。本项目借鉴立体动态探针概念，根据手光分子开关原理探索新型的荧光-圆二色双检测通道聚合物基手性传感器。为此，设计反应型和配位型两类手性功能单体，通过活性/可控自由基聚合方法合成结构明确的线形、嵌段及梳状结构聚合物。利用模型化合物结合量子化学计算探讨主-客体分子手性识别机理，研究立构中心位置、侧基类型、溶剂性质等因素对聚合物主链高层次结构的影响规律，系统考察聚合物溶液对手性a-氨基酸、a-羟基酸和氨基醇的对映选择性光学响应行为。采用旋涂、层层自组装和共价键合等方法制备以石英片为基材的手性聚合物薄膜，研究薄膜传感器的手性识别性能与聚合物结构、成膜方式以及表面聚集形态的内在联系，阐释固-液界面上的分子相互作用。本项研究有助于深入了解手性识别机理，将为设计、开发高选择性手性传感器提供新的途径。

中文关键词： 手性聚合物；分子识别；化学传感器；对映选择性；合成

英文摘要： Investigations on both chiral recognition of organic molecules and enantioselective chemosensors have received intensive attention due to its importance in many disciplines such as chemistry, biology, and pharmacy. This project is proposed for designing and development of a new kind of chiral polymer-based sensors with FL-CD double detection channel for the discrimination of enantiomers. We will design two types of chiral monomers, i.e., reactive and coordinate, on the basis of the chiroptical switch mechanism and stereodynamic probe concept, and then synthesize the corresponding chiral polymers with linear, block or comb architectures via living/controlled radical polymerization techniques. The studies on the host-guest interaction will be conducted by quantum chemistry calculation for model compounds for exploring the chiral recognition mechanism. The effect of various factors including configuration center, lateral group, and solvent nature on the secondary structure of the polymers will be examined in detail. We will evaluate the sensing performance of the polymers towards chiral compounds such as alpha-amino acid, alpha-hydroxyl acid, and amino alcohol for selecting desired enantioselective chemosensors. Another task in the project is exploring the polymeric films as a chiral probe for enantioselective discrimination of the above-mentioned organic molecules. The polymer films are formed on the piezoid by using spin coating, layer-by-layer or covlent grafting method. In addition, we are to examine the relationship between the surface property of polymeric films and its chiral selectivity for gaining some additional insight into the molecular interaction on the solid-liquid surface. It is anticipated that this research would provide not only a suitable platform for understanding of the chiral molecular recognition but also a new avenue in the developing of chiral chemosensors with high enantioselectivity.

英文关键词： chiral polymer;molecular recognition;chemosensor;enantioselectivity;synthesis