液态SERS定量分析器原位检测分子光控配位反应的研究

It is of great scientific significance to develop new chemical methods for measuring the molecular reaction mechanism on microscale. Current tracking of many molecular reactions is still limited by destructive methods. Recently, the emerging of liquid-state surface enhanced Raman spectroscopy (SERS) provides new ideas for real-time tracking reaction process and molecular activity changes, understanding molecular coordination mechanism, and designing new strategies for reaction control. By taking the advantages of SERS fingerprint feature, high sensitivity, and multiple detection, this project aims for developing in situ, real-time liquid-state SERS analyzer, which performs both as a SERS sensing platform and a liquid-phase space for new molecular coordination reaction. In a “one-pot” coordination reaction, the photo-isomerization of azobenzene groups is used as a reaction control stimuli. Molecular analysis with high spatial and temporal resolutions will be performed on SERS fingerprint spectra of the reactant, product and possible intermediate molecular structures. Eventually, we will establish the preparation of path for liquid-state SERS analyzer and the example of liquid-state SERS technique for in situ real-time tracking of reaction process. The expected results will provides a general method and system for the real-time detection of chemical reaction process. This platform offers vast possibilities for on-site sensing of various analytes and paves a new way for the quantitative and high-throughput SERS analyzer just as convenient as the Microplate Reader. It will improve the generality of liquid-state SERS and expand the application fields of SERS technology.

发展微尺度上分子反应机制的新型化学测量方法具有重大科学意义。当前许多分子反应机制的原位实时跟踪仍受限于破坏性的非原位方法。近来，液态表面增强拉曼光谱（SERS）技术的出现，为实时跟踪分子反应机制提供了新思路。本项目拟设计发展原位、实时的液态SERS定量分析器，构筑双相体系中三维液/液界面上自愈合、可动态调谐的纳米阵列，提出利用连续有机溶剂相做内标校正目标分子SERS信号的方案。设计“一锅法”分子光控配位反应，利用偶氮基团光照异构化作为控制反应的刺激因素，高时空分辨率的解析反应物、产物及可能的中间态结构的SERS指纹谱。最终实现SERS检测和分子反应控制的同步，建立液态SERS定量分析器的通用路径、使用范例，为分子反应机制的原位、实时、定量分析提供标准化体系，有望推动SERS技术发展成类似于酶标仪或光度计一样简便却更灵敏的多通道定量化液态测量技术，拓展SERS技术的应用领域。

发展分子反应机制的新型化学测量方法具有重大科学意义，但目前仍然缺乏有效的原位化学测量手段。本项目设计了全新的反应控制策略，提供了新型的通用化SERS光谱测量方法；建立了自愈合、动态可调谐三维液/液界面等离子体阵列平台；阐明了有机相作为内标校正液态SERS测量信号的机制；建立了液态SERS定量分析器实现对分子反应过程及分子结构变化的高灵敏、高稳定、定量化捕获分析，阐明了等离子体光化学反应机理；提出了多种发射类型的金纳米团簇结构的的制备方法，揭示了光致发光增强机制，实现了重金属离子的检测及活细胞、斑马鱼的生物成像。在分子结构测量和分子反应体系的原位、实时、定量、准确分析方面取得系列研究成果，显著拓展SERS技术的应用领域。