Development of automated on-line analytical system of drugs and environmental pollutants using an in-tube solid-phase microextraction technique

采用管内固相微萃取（SPME）技术，在不使用有机溶剂的情况下，以毛细管柱为萃取装置，对药物和环境污染物进行自动萃取和浓缩，建立了一种实用的药物和环境污染物自动在线分析方法。经过三年的研究，结果如下：采用Supel-Q PLOT毛细管柱，管内SPME/HPLC浓缩18-125倍邻苯二甲酸酯等内分泌干扰物。在1 ~ 500 ng/mL范围内，校准曲线呈线性，检出限为0.1 ~ 4 ng/mL。从若干食品样品中检测到DBP、OP、DEHP，发现这些化合物是从容器塑料中迁移而来的。在输液溶液和一些液体药物中也检测到DBP，并且很容易从粘合剂中洗脱到水和酒精中，并且很容易通过塑料。这些结果表明，DBP的来源是用于粘贴纸质标签的粘合剂，DBP通过塑料污染输液。建立了植物雌激素大豆黄素和染料木素的管内高效液相色谱法。该方法灵敏度高，可在ng/mL水平检测异黄酮。该方法成功地应用于大豆食品的无干扰峰分析。食品样品中大豆黄素和染料木素的加标回收率均在97%以上，在大豆及其加工食品中检出，而在其他豆类中未检出。建立了一种简便、快速、灵敏的测定雌酮、17 β-雌二醇、雌三醇、乙炔雌二醇和己烯雌酚5种雌激素的方法。该方法在5 ~ 200 pg/mL范围内线性良好。5种雌激素的检出限为0.5 ~ 3.7 pg/mL，管内SPME法的灵敏度比直接注射法高30 ~ 150倍。该方法成功地应用于环境水样的分析，无需任何预处理和干扰峰。建立了嘧啶类、三嗪类除草剂和磺胺类抗菌剂的管内SPME/LC/MS分析方法，并应用于环境水样的分析。研制了一种对雌激素具有高度选择性和浓度效应的分子识别毛细管。该方法可方便地与LC/MS、CE和CE/MS相结合。本研究开发的在线管内SPME/HPLC和LC/MS方法从样品前处理到数据分析完全自动化，具有简单、快速、溶剂消除、灵敏度高、成本低等特点。因此，它有望在食品、环境和临床分析中成为一种实用的方法。此外，通过开发包覆或填充新材料的新型毛细管，可以提高萃取效率和选择性。少

Practical automated on-line analytical method for the determination of drugs and environmental pollutants was developed by in-tube solid-phase microextraction (SPME), in which these compounds were automatically extracted and concentrated using a capillary column as extraction device without organic solvent. Results of research for three years are as follows.1.Endocrine disruptors such as phthalate esters were concentrated 18-125 times by in-tube SPME/HPLC using a Supel-Q PLOT capillary column. Calibration curves were linear in 1-500 ng/mL, and the detection limit was 0.1-4 ng/mL. DBP, OP, DEHP were detected from several food samples, and it was found that these compounds were migrated from container plastic. DBP was also detected in infusion solutions and some liquid medicines, and shown to be readily eluted from the adhesive into water and alcohol, and to easily pass through the plastic. These results indicated that the source of the DBP was the adhesive used to affix the paper labels … More , and DBP contaminated the infusion solutions by passing through the plastic.2.In-tube SPME/HPLC method of phytoestrogens daidzein and genistein, was developed. This method is highly sensitive and can detect these isoflavones at ng/mL level. This method was successfully applied to the analysis of soybean foods without interference peaks. The recoveries of daidzein and genistein spiked into food samples were above 97%, and these compounds were detected in soybeans and their processed foods, but not detected in other beans.3.A simple, rapid and sensitive method for the determination of five estrogens, estrone, 17 β-estradiol, estriol, ethynyl estradiol, and diethylstilbestrol, was developed using a fully automated method consisting of in-tube solid-phase SPME coupled with LC/MS/MS. Using this method, good linearity of the calibration curve was obtained in the range from 5 to 200 pg/mL. Detection limits of the five estrogens ranged from 0.5 to 3.7 pg/mL, and the in-tube SPME method showed 30〜150-fold higher sensitivity than the direct injection method. This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks.4.In-tube SPME/LC/MS methods of diazine and triazine herbicides and sulfonamide antibactericides were developed and applied to the analysis of environmental water samples.5.A molecule recognition capillary having a highly selectivity and concentration effect for estrogens was developed.6.The in tube SPME technique could be easily combined to LC/MS, CE and CE/MS.On-line in tube SPME/HPLC and LC/MS methods developed in this study can completely automate from pre-treatment of sample to data analysis, and it is simple, rapid, solvent elimination, high sensitive and lower cost. Therefore, it is expected as a practical method in food, environmental and clinical analysis. In addition, it is possible to improve the extraction efficiency and selectivity by the development of new capillaries coated or packed with new materials. Less