新型光可调控联萘酚类手性荧光化学传感器的合成及其应用

项目名称： 新型光可调控联萘酚类手性荧光化学传感器的合成及其应用

项目编号： No.21462018

项目类型： 地区科学基金项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 孙晓霞

作者单位： 江西科技师范大学

项目金额： 53万元

中文摘要： 具有独特光学性质的手性化学荧光传感器不但制作成本低，结构简单，检测灵敏度高，而且比较容易实现高通量及实时的检测，广泛应用于手性化合物和金属离子的识别中。但是一个传感器仅仅只能检测一次，无法实现差异化的两次检测。本项目把联萘酚独特的C2轴手性、刚性结构、易修饰和优异的手性识别能力与二噻吩乙烯良好的热稳定性、显著的抗疲劳性、高量子产率及响应时间短等光开关性质结合起来，设计合成系列不同的连接基团（西弗碱、非共轭胺、咪唑盐和三氮唑等）的新型光致变色环状手性联萘酚全氟二噻吩乙烯化合物。利用联萘酚的手性识别能力以及二噻吩乙烯的光致变色作用，研究开环态和闭环态环状手性荧光传感器对手性氨基酸、α-羟基羧酸和金属离子进行检测，研究大环手性荧光传感器结构、构型、溶剂等对客体分子检测结果的影响，考察联萘酚二噻吩乙烯手性荧光化学传感器的对映体选择性和检测灵敏度，并构建分子逻辑门开关。

中文关键词： 荧光传感器；联二萘酚；光控；光致变色；二噻吩乙烯

英文摘要： Chiral fluorescent chemosensors are the molecules or materials that can interact with the chiral targets and convert the enantioselective recognition events into observably optical signal outputs. The chiral fluorescence sensor have drawn substantial interests of researchers owing to their advantageous features including simplicity, low cost, high sensitivity, adaptation to automation and real-time analysis, and diverse signal output modes. BINOL can be used to construct chiral fluorescent sensors to carry out highly enantioselective, sensitive recognition of chiral amino alcohols, α-hydroxycarboxylic acids, and amino acid derivatives due to their particularities, such as special C2 axial chirality and rigid structure and readily selective functionalization. As an attempt to magnify the fluorescence signal and to further elevate the chiral recognition sensitivities of naphthyls toward chiral analytes, diarylethene derivatives are the most promising candidates for fluorophore of fluorescent sensor. Among all photochromic compounds, diarylethenes are one of the most promising candidates for fluorescence applications owing to their excellent thermal-stability, remarkable fatigue-resistance, rapid response and fairly high photocyclization quantum yields. The chiral switch of BINOL-diarylethene derivatives containing nonconjugated amine groups, schiff-base, bisimidazolium group were synthesized by different reaction such as the click reaction. The light harvesting effect of diarylethene can be used to greatly increase the sensitivity of the fluorescent sensors. Sequentially, a double-check chemosensor system was developed with both fluorometric detection in open isomer as the first check and colorimetric measurement in the photostationary state as the second check. This novel idea facilitates the development of double-check chemosensor for future sensors of chiral molecule and ion racognition.The chiral switch of BINOL-diarylethene derivatives should be used to construct a logic circuit and a molecular keypad lock with UV irradiation, host molecule as inputs.

英文关键词： Fluorescent sensor;BINOL;Photoswitching;photochromism;bisthienylethcnes