基于氟代醇诱导的阴阳离子表面活性剂凝聚层同时萃取多种不同极性有机污染物的样品预处理方法及HPLC联用研究

Organic pollutants (OPs) in water have been one of the focus researches in environment sanitation fields. Analysis and detection of the type and concentration of OPs in water occupy primary bases for contamination assessment and treatment research. Because of some problems such as extremely low concentration, complex matrix, large varieties, different polarity of OPs in water, high-efficiency and high-throughput sample preparation techniques play a key role in analysis and detection of OPs. Catanionic Surfactant Coacervate (CASC) extraction method is especially appropriate for the extraction and preconcentration of various OPs with different polarity because CASC contains both hydrophilic and hydrophobic region and also can be charged. Unfortunately, it has been reported that only in strict conditions can CASC be formed and the formed CASC is very viscous and its surfactants would interfere with the separation and detection in chromatography, which severely restricts theoretical development and practical applications of CASC. This project will establish CASC extraction systems by creatively utilizing fluoroalcohols to induce the formation of coacervate. This fluoroalcohol-induced CASC system has quite large two-phase regions in the phase diagrams. On the other hand, on-line and off-line coupling techniques of CASC extraction and HPLC, which are simple,fast,low-cost and able to effectively eliminate surfactant interference, will be developed. Then, the HPLC-MS analytical methods of representative OPs will be established using fluoroalcohol-induced CASC extraction and its on-line and off-line coupling techniques with HPLC. After methodological assessment, the methods would be used to analyze OPs in actual water samples, which can further demonstrate their reliability.

水体有机污染物（OPs）是环境卫生领域研究的重点之一，分析检测以明确水体中OPs的种类和浓度，是污染评估和治理研究的首要依据。因水体中OPs浓度极低、基体复杂、种类多、极性差异大，高效高通量的样品预处理技术是分析检测的关键。阴阳离子表面活性剂凝聚层（CASC）因同时具有疏水亲水区域及可带电性，特别适合于高效高通量地萃取富集多种不同极性的OPs。但"凝聚层形成条件十分严苛"、"凝聚层粘稠干扰色谱进样、表面活性剂干扰色谱分离和检测"这两个瓶颈问题严重制约了CASC萃取方法的广泛应用。本项目开创性地利用氟代醇诱导，构建"凝聚层的形成几乎不受条件限制"的CASC萃取体系,建立简单、快捷、低成本、能有效去除表面活性剂干扰的CASC萃取/HPLC离线和在线联用技术。在此基础上，结合质谱检测建立代表性OPs的分析方法并进行方法学评价；通过应用于实际水体中OPs的分析检测，进一步验证方法的可靠性。

有机物污染问题是环境卫生、食品卫生等领域重点关注的研究课题。分析检测以明确有机污染物（OPs）的种类和浓度，是污染评估和治理研究的首要依据。因环境、食品等样品基质复杂, OPs 浓度极低、种类多、极性差异大，高效高通量的样品预处理技术是分析检测的关键。表面活性剂（特别是阴阳离子表面活性剂）凝聚层(surfactant coacervate, SCA)萃取体系，因凝聚层兼具疏水亲水区域及可带电性，特别适合于高效高通量地萃取富集不同极性的OPs。但“凝聚层形成条件十分严苛”问题严重制约了SCA萃取方法的广泛应用。. 本项目开创性地利用氟代醇（主要是性质优越的六氟异丙醇，HFIP）介导，构建了“凝聚层的形成几乎不受体系条件限制”的SCA萃取体系，包括HFIP-含盐型阴阳离子SCA萃取体系、HFIP-无盐型阴阳离子SCA萃取体系和HFIP-非离子SCA萃取体系。将这些萃取体系与HPLC分析方法联用，建立了从强极性到非极性的不同性质代表性 OPs（包括磺胺类和氟喹诺酮类抗生素、邻苯二甲酸酯类塑化剂、多环芳烃类内分泌干扰素、对羟基苯甲酸酯类防腐剂、蛋白质等）的分析检测方法并进行方法学评价；通过应用于实际样品中OPs的分析检测，进一步验证方法的可靠性。. 结果表明：10%(v/v) 以下含量的HFIP即能够高效介导各种表面活性剂水溶液发生凝聚和相分离，形成液-液两相体系（下相：凝聚层，上相：水相），在相图中呈现非常宽的液-液两相区域。与有盐型体系相比，HFIP -无盐型阴阳离子SCA体系的液-液两相区域更宽、凝聚层相的体积更小，因而更适合应用于萃取富集。很少量HFIP（≤3 %，v/v）就能将Triton X-100（浊点64～67 oC）和Brij-35（浊点＞100 oC）非离子表面活性剂的浊点温度降到室温以下，且体系在室温或以下都能快速分相，大大简化了萃取操作。HFIP分子与表面活性剂分子间高强度的氢键、静电或/和疏水等相互作用是HFIP介导表面活性剂水体系形成凝聚层、产生相分离的主要分子机理。HFIP介导的三种SCA萃取体系对不同极性（强极性-非极性）的目标物均显示较好的萃取富集效果；HFIP-SDS/DTAB凝聚层萃取体系能高效萃取溶菌酶（萃取率约90%），且酶活性保持约65%。