光诱导极性原位可调固定相的制备及其芯片多维液相色谱分离应用

Stationary phase is one of the core elements of a chromatographic system, hence developing an innovative stationary phase and explore the chromatographic behavior are of great significance for promoting technological advancement. The present study intends to fabricate an in situ photosensitive polarity-controllable stationary phase based on the characteristics of azobenzene compounds including high switching rate, cis-trans reversible isomerization and changeable polarity. The polarity of photosensitive stationary phase is adjusted by optimizing photoinduced parameters to control the conversion rate of cis-trans isomerization of azobenzene compounds. The photosensitive stationary phase is integrated with chip-based liquid chromatography to develop a novel multidimensional liquid chromatography consisted of singular separation column, which is a new strategy to solve some technical problems such as the impracticality for integration, complexity of combination and unachievable requirement of high-precision switching valve. The research contents are as follows: 1) Preparation of a photosensitive stationary phase and evaluate its photosensitive behavior; 2) Fabrication of a chip-based photosensitive chromatographic column and the assessment on retention mechanism; 3) Study on the development and separation application of single-column chip-based multidimensional liquid chromatography. The achievements will contribute to the miniaturization, integration, and intellectualization of multidimensional chromatography and the realization of a high-throughput detection technique for complex biological samples.

固定相是色谱系统的核心部分，开发新型固定相并研究其色谱行为对解决复杂样品的分离分析，推动色谱技术的发展具有重要意义。本研究基于偶氮苯类化合物光响应快、顺反式构型可逆互变且极性不同等性质，拟制备光敏型极性原位可调固定相，通过优化光诱导参数，控制偶氮苯类化合物顺反式构型转换率，实现固定相极性的原位实时调控，并将其与芯片液相色谱集成，开发一种新颖的单分离柱多维液相色谱分离方法，为解决芯片多维液相色谱集成难、色谱柱组合复杂、切换阀精度要求高等技术难题提供新的研究策略。研究内容：1）光敏固定相的制备及光敏行为研究；2）芯片光敏色谱柱的制备及保留机理研究；3）单分离柱芯片多维液相色谱分离方法的建立及应用研究。本项目研究成果将为多维色谱技术向智能化、微型化和集成化发展以及复杂生物样品的高通量快速分离检测提供研究基础。

固定相是色谱分离的核心。本项目利用偶氮苯类化合物光诱导顺反式构型可逆互变且极性不同等性质，先后采用设计合成的硅烷化偶氮苯分子作为气相色谱液膜固定相和薄层色谱光敏修饰剂开展了光敏型气相色谱和液相色谱的制备及其光诱导下色谱保留行为的研究工作。研究结果表明，基于偶氮苯衍生物分子可逆反顺异构化的性质，可实现气相色谱和液相色谱固定相光诱导极性原位可调，更进一步地，气相色谱光敏固定相可通过调节紫外光和可见光诱导时间控制顺/反式偶氮苯比例，实现固定相可逆、连续和动态调控。与其它刺激响应色谱相比，光敏色谱具有操作简便、时间和空间控制自由度高等优点，而且通过极性“转换阀”来简化色谱柱使用，非常有利于发展“微-智能”色谱。此外，在本项目的支持下，亦开展了一些样品前处理领域的工作， 如微纳尺度物质分离技术开发、碳纳米纤维限域快速高效萃取海水中苯系物、往复运动式磁固相萃取联用质谱在线检测水中痕量四环素药物等。相关研究成果已在Analytical Chemistry、Analytical Chimica Acta、Talanta、Dalton Transactions等期刊共计SCI论文9篇，项目成员共计在全国性学术会议上作口头报告2次，受到广泛关注。