基于ICT的萘酚基D-π-A型比色/荧光探针构筑及其对次氯酸盐的可视化检测性能研究

It is of great significance for homeland security to realize the rapid and trace identification of hypochlorite in liquid and particulate states, considering hypochlorite is one of the common raw materials for improvised explosives. However, most probes reported so far for specific detection of hypochlorite in organisms or drinking water are suffering from limited sensitivity, low molar absorptivity, long response time and complicated multi-step synthesis. In our previous work, the D-π-A structure within the chromophore molecule was found to be favorable for hypochlorite in terms of lowering the detection limit and speeding the response. Therefore, a serial of colorimetric-fluorescent probes with D-π-A structure are proposed here, in which the naphthol electron donating group and the cyano-containing electron accepting group is linked by an unsaturated double bond featuring the active site during detection. The designed probes are supposed to have increased molar absorption coefficient and fluorescence intensity for improving the detection sensitivity of hypochlorite. For the purpose of rapid and trace detection, the colorimetric-fluorescent sensing fiber membrane with high porosity will be prepared to achieve enlarged specific surface area. Finally, the detection of hypochlorite solid particles will be enabled by the introduction of the hydrogel substrate. Furthermore, the response mechanism of probes towards hypochlorite will be determined, while the effects of the electron-withdrawing strength of electron acceptors and the structure of fiber membranes on the the hypochlorite detection performance will be explored. This research will open up a new way to prepare colorimetric-fluorescent sensing materials for the highly sensitive, fast, trace, and visual detection of hypochlorite.

次氯酸盐是非制式爆炸物原料之一，实现对其液体及固体颗粒的快速、痕量识别对维护国家公共安全至关重要。目前，针对生物体或饮用水中次氯酸盐的检测研究较多，但存在检测限差，摩尔吸光系数低，响应慢且需多步合成等缺点。我们前期工作发现具有D-π-A结构的生色团对于次氯酸盐的检测具有检测限低、响应快的优点。因此，本研究拟通过以萘酚为电子给体，含氰基吸电子基为电子受体，C=C双键为活性位点的D-π-A型比色-荧光探针结构的设计，增加摩尔吸光系数及荧光强度，提高次氯酸盐检测灵敏度；通过制备孔隙率高的比色-荧光传感纤维膜，提高材料比表面积，达到快速、痕量检测的目的；通过水凝胶基底的引入，实现对次氯酸盐固体颗粒的检测。深入探讨探针对次氯酸盐的响应机理；进一步阐明电子受体的吸电子强弱及传感纤维膜结构对次氯酸盐检测性能的影响机制。此研究将为制备高灵敏、快速、痕量、可视化检测次氯酸盐的比色-荧光传感材料开辟新途径。

次氯酸盐、高锰酸钾等是重要的非制式爆炸物原料，实现对其液体及固体颗粒的快速、痕量识别对维护国家公共安全至关重要。本项目从探针分子设计、传感材料制备、传感元件构建入手，主要开展了三个方面的研究内容：1）提出了比色/荧光探针分子设计策略，揭示不同探针分子结构对检测性能的影响，实现对次氯酸盐等非制式爆炸物的检测；2）提出了比色/荧光纤维膜等传感材料构建策略，揭示传感材料结构对可视化检测性能的影响机制，实现对目标物的高灵敏检测；3）提出了比色人工嗅觉系统构建策略，突破了传感基底稳定性差的难题，为非制式爆炸物探测仪研制提供了核心技术。.取得了四个方面的重要结果和关键数据：1）通过调控识别位点位置和数量，获得了萘酚基比色-荧光探针，对次氯酸盐的响应时间＜3s，检测限最低至9.086nM；水杨酸基比色探针对次氯酸盐的响应时间＜10s，检测限为25.36nM；构建了香豆素基探针实现了对非制式爆炸物高锰酸钾的荧光点亮检测，检测时间＜3s，检测限为0.95nM；2）提出了降维限域概念，构建了聚乙烯醇（PVA）凝胶纸，与滤纸检测效果相比，其对固体颗粒的信号强度平均增强了5.6倍，对液体的信号强度平均增强了3.3倍，检测时间从42s缩短到1.7s；3）首次构建比色人工嗅觉系统，实现了对空气中次氯酸盐等悬浮非制式爆炸物颗粒的定性检测，响应时间小于1s，检测限达到pg级；4）提出了YES/NO比色逻辑门的判别模式，实现了对黑火药、硝酸脲和硝铵等非制式爆炸物混合物的精准判别。.项目发表SCI论文4篇，授权中国发明专利6项，申请中国发明专利3项；协助培养硕/博士研究生3名，1人获中国科学院院长优秀奖，1人获中国科学院朱李月华优秀博士生和中国科学院优秀毕业生。项目负责人晋升副研究员，2020年获自治区科技进步一等奖（9/12）和中国仪器仪表学会科技进步二等奖（5/15），2022年入选天山英才-青年拔尖人才。.本项目为制备高灵敏、快速、痕量、可视化检测次氯酸盐、高锰酸钾等非制式爆炸物的比色-荧光传感材料开辟了新途径。