活性氧介导的PPCPs超敏发光新体系及HPLC联用研究

The residues and pollution of pharmaceutical and personal care products (PPCPs) have been increasingly the focus of international attention. Hence, accurate monitoring of PPCPs is urgently required by public health agencies in both food stuffs and environmental samples. With significant advantages, chemiluminescence (CL) has attracted the attention of many users and scientists. Although it would be important to expand the analytical application of classical CL reactions, it is a great challenge for chemists to develop novel CL system with high sensitivity and strong response to numerous compounds based on the detailed researches on the CL mechanisms. In our previous researches, tetracyclines (TCs) showed ultrasensitive chemiluminescence (CL) based on the novel CL system of methoxylated Cypridina luciferin analogues (MCLA) and Ce(IV). An ultrasensitive CL method for the detection of tetracyclines based on MCLA-Ce(IV) was proposed. Moreover, it was found that PPCPs could react with many different oxidants accompanying weak CL and reactive oxygen species (ROS) were intermediate products as a result. In this proposal, ROS generating from the reaction between PPCPs and oxidants were measured by using electronic spin resonance spectroscopy. By the aid of ROS probes, LC-MS/MS and NMR, the information about the final stable products of the proposed CL reaction could be resolved. In addition, a satisfactory compatibility level between the chemical environment required for efficient chromatographic separation (mainly the composition of the mobile phase) and that required for efficient and sensitive CL emission would be studied in detail. On the basis of above experiment results, the CL mechanisms between PPCPs and oxidants will be clarified and a platform for ultrasensitive determination of PPCPs using HPLC-CL method should be developed. The research conclusions will propose not only new idea for the research of CL mechanism but also green and friendly project for the advanced oxidative degradation of PPCPs in the wastewater.

药物与个人护理用品(PPCPs)的残留和污染问题引发全球关注，因此，研究和建立PPCPs的分析方法具有非常重要的意义。化学发光因独特的优点倍受青睐，但目前PPCPs的化学发光方法灵敏度低、新体系少且缺乏系统研究。我们的前期研究发现：PPCPs与多种氧化剂反应会产生活性氧介导的化学发光；Ce(IV)-MCLA体系可实现四环素族的化学发光超灵敏检测。在此基础上，本项目拟采用电子自旋共振技术研究PPCPs与氧化剂化学发光反应中的活性氧中间体的种类，并结合LC-MS/MS和NMR技术解析稳态产物结构，辅以优选的化学发光探针，阐明PPCPs的化学发光反应机理；系统研究液相色谱分离条件与化学发光体系的匹配性，构建超灵敏PPCPs类污染物HPLC-CL检测平台，为发展化学发光方法提供新思路和理论依据。相关研究结果还将为污水中PPCPs的绿色、环境友好型高级氧化处理提供新方案。

药物与个人护理用品(PPCPs)的残留和污染问题引发全球关注，因此，研究和建立PPCPs的分析方法具有非常重要的意义。化学发光因独特的优点倍受青睐，但目前PPCPs的化学发光方法灵敏度低、新体系少且缺乏系统研究。我们的前期研究发现：PPCPs与多种氧化剂反应会产生活性氧介导的化学发光；Ce(IV)-MCLA体系可实现四环素族的化学发光超灵敏检测。在此基础上，本项目开展了以下五个方面的工作：（1）基于MCLA-Ce(IV)化学发光体系，采用分子印迹固相萃取法提取牛奶中的FQs，提出了一种超灵敏的化学发光法检测牛奶中氟喹诺酮（FQs）总残留量。通过CL光谱和UV光谱研究MCLA-Ce(IV)-FQs体系的机制，其结果表明，Ce(IV)与FQs反应产生的单线态氧导致了CL增强。（2）成功开发出13分钟内同时测定牛奶中8种四环素类抗生素残留的超灵敏HPLC-UV方法。创新性地选择甲烷磺酸作为流动相改性剂，不但为被分离物质与硅胶基质间作用导致的峰拖尾和基线漂移问题提供了新的理论依据，还提出了相关解决方案，并与质谱已有良好的兼容性。（3）基于H2O2-NaIO4-g-CNQDs化学发光体系，建立了一种HPLC-CL同时检测蔬菜中的三氯生（TCS）、双酚A（BPA）、双酚F（BPF）和双酚S（BPS）。（4）建立了金霉素、多西环素、4-差向金霉素、土霉素、美他环素和四环素同时选择性分析的高效液相色谱-柱后化学发光联用新方法。以乙腈和3.5 mM甲烷磺酸为溶剂，通过简单有效的等度液相色谱实现了6种四环素类残留的高效分离。（5）基于H2O2-NaIO4-g-CNQDs化学发光体系，通过优化碳氮量子点的合成模式与化学发光体系的反应条件，建立了一种化学发光法检测化妆品中对羟基苯甲酸甲酯残留量的新方法。相关研究结果还将为污水中PPCPs的绿色、环境友好型高级氧化处理提供了新的理论依据。