光控二芳烯荧光探针的合成、结构与性质关系及应用研究

Diaryethenes have broad applications in the fields of photoelectric materials and fluorescence probe due to their superior photoisomerization with different chemical and physical properties.On the basis of the excellent photoisomerizational nature of diarylethene, a serial novel diarylethenes be modificated by functional groups on both sides. A novel diarylethene with the properties of molecular/ion recognition and strong fluorescence switches will be designed and synthesized. In this research proposal, a serial novel type of diarylethenes bearing functional groups, which can respond to special molecular/ion via molecular self-assembly, will be used as fluorescent probe to analyze and detect specific molecular/ion in complex system. In this work, different chemical synthesis methods will used to connect molecular/ions recognition functional groups on one side of diarylethene and strong fluorescence emission groups on the other side. These diarylethene can be controlled fluorescence switches through intramolecular charge transfer(ICT) by UV/vis light. After the identification of photoisomerizational diarylethene compounds respond to specific target molecular/ion, their fluorescence emission will change and the changed fluorescence can be controlled by UV/vis light that can be used to complex environment for the research of analysis and fluorescence probe.This work will expand the application of diarylethenes and provide a new approach for studding on multi-functional diarylethene compounds. We will explore the mechanism of response of diarylethenes with different molecular/ions and photo-control of fluorescent switch in this work. It is great significant to reveal the self-assembled diarylethene with the properties of photo-controllable strong fluorescent switch.This work will expand the application of diarylethenes in the field of fluorescence probe and provide a new approach for studding on multi-functional diarylethene compounds.

二芳烯分子具有优异的光致异构特性，在光电材料和荧光探针领域具有广阔的应用前景。本课题利用二芳烯两侧可功能化修饰的特性，设计合成具有分子/离子识别功能及强荧光开关特性的二芳烯分子。旨在开发具有光控荧光开关及具有自组装特性的二芳烯化合物，发展成为具有分子/离子识别能力的荧光探针。通过在二芳烯结构单元上进行修饰，采用化学合成方法在二芳烯的一侧引入强荧光发光基团，在分子的另一侧构建具有对特定分子/离子具有专一性识别能力的结构单元，再利用光控二芳烯异构实现分子内电荷转移，以实现荧光可控，并将其用作荧光探针。该类化合物最大的优势是可通过光控改变二芳烯的荧光信号，克服周围复杂环境荧光干扰。本项目在实验的基础上探索二芳烯与特定分子/离子及光控荧光的作用机制，对揭示光控强荧光自组装二芳烯化合物的作用机理具有重要意义，为可视化复杂体系中荧光探针的发展奠定基础，也为二芳烯的多功能化研究提供新的思路。

有机光致变色材料是一类具有特殊光响应特性的新型功能材料，在可擦写信息存储、分子开关、防伪、传感等领域具有巨大的应用潜力。而全氟环戊烯为桥头的光致变色二芳烯具有抗疲劳性好、易于修饰等特点，是一类可设计为光控荧光开关的新材料。本项目在以下三个方面做了创新而又系统的研究工作：.1. 设计系列新型的含不同芳杂环及供/吸电子取代基二芳烯分子。利用元素分析、核磁、质谱、单晶解析等技术确定了化合物的结构；采用紫外可见光谱仪和荧光光谱仪研究了化合物的光致变色及光控荧光开关特性。研究结果表明：芳香能低的基团有利于提高二芳烯的抗疲劳性和热稳定性，而取代基的供电子基团有利于提高其摩尔吸收系数；不同溶剂对二芳烯的晶体结构、晶胞堆积方式等有影响。.2. 筛选以低芳香能基团为骨架的二芳烯化合物，并在其一侧链接含氮杂吲哚、三联吡啶、含氨基喹啉、6-芳基[1,2-c]喹唑啉、硫脲、8-氨基喹啉-2-氨甲基吡啶等功能基团。通过核磁、质谱等技术手段对其分子结构进行确认，并研究了分子所连基团结构与性质的影响。研究发现具有功能基团的二芳烯能与金属离子作用，Zn2+、Al3+、Hg2+都表现出荧光显著增强效应，而Cu2+和Cr3+则表现为荧光猝灭现象。二芳烯与Zn2+、Al3+、Hg2+等作用后，其荧光显著增加，可通过紫外/白光照射来实现分子的开闭环，从而达到光控强荧光开关效果。.3. 利用可与金属离子作用，表现为荧光增强的二芳烯，应用于对特定金属离子的荧光检测，其检测限可低至10-8mol/L；以光、金属离子或质子为输入信号，以荧光的强弱为输出信号，构建逻辑门开关；以二芳烯分子作为探针，通过荧光信号跟踪，实现二芳烯对细胞中Zn2+、Al3+的荧光成像标记。.在项目执行期间在Sensors and Actuators B、Dyes Pigm.、New J. Chem.等杂志上共发表标注该项目基金号的SCI论文29篇，申请专利5项，获江西省自然科学奖二等奖1项。通过本项目的实施将进一步拓展二芳烯分子的应用范围，为分析检测及荧光探针研究提供新的工具，也为二芳烯的多功能化研究提供新的思路。