開發對質譜和氣相層析分析流程的樣品製備方法

Development of Sample Preparation Methods for Mass Spectrometry and Gas Chromatography-based Analytical Workflows

廖珮涵(Pei-Han Liao)

指導教授 ： 帕偉鄂本 ； 劉學儒

國立交通大學/理學院/分子科學研究所/碩士(2019年)

摘要

在分析流程中，取樣和萃取為基本步驟。在本論文中，我展示表面取樣和水蒸氣-溶劑同時萃取法(simultaneous distillation-extraction) 結合層析系統的方法。在第一項研究(第二章)，發展水凝膠(hydrogels)探針在固體表面上提取化學殘留物。因為水凝膠的高塑造性和含水量特性，而能做為將水溶性分析物從目標表面運送至分析流程的理想載體。我們利用圓盤狀複合水凝膠(blended hydrogels)提取吸附在表面的水溶系物質，以展示膠相微萃取(gel-phase microextraction)方法。在一系列的螢光和質譜法測試中，萃取步驟流程已被優化。以螢光素當作分析物樣品的實驗中，大部分的複合水凝膠相較於單一成分水凝膠，擁有較佳的取樣和萃取效率。將優化過的膠相微萃取法，應用於皮膚、玻璃片和日常使用物品表面化學品(乳酸和雙氯芬酸鈉)殘留分析。在第二項研究中(第三章)，我們展示水蒸氣-溶劑同時萃取法聯結氣相層析質譜儀的線上偵測系統。設計在固定時間，利用蠕動幫浦、控制元件、客製化漏斗狀玻璃瓶和自動取樣系統運送萃取液。此線上偵測系統能夠紀錄不同揮發性有機化合物 (volatile organic compound)的實時萃取數據並顯示其萃取動力學。在比較線上和離線系統的數據中，線上系統可信度較高，能避免離線系統的人為誤差。並利用不同種類的啤酒展示此線上偵測系統的應用性。在實時數據中，能夠顯示樣品中揮發性有機化合物的萃取動力學。總而言之，此線上系統能夠得知不同種類分析物的最佳產率時間，以減少分析物的揮發。

關鍵字

自動化 ； 電噴灑游離三段四極柱串聯質譜儀 ； 氣相層析質譜儀 ； 膠相微萃取 ； 水凝膠 ； 水蒸氣-溶劑同時萃取法

並列摘要

Sampling and extraction are essential steps in analytical workflows. In this thesis, I demonstrate methods for sampling analytes from surfaces and coupling a simultaneous distillation-extraction (SDE) system with a chromatography system. In the first study (Chapter 2), hydrogel probes were developed and used for sampling chemical residues present on solid surfaces. Hydrogels are characterized with high mechanical flexibility and water content. They are an ideal medium for transferring water-soluble analytes from a sampled surface to the next stage of an analytical workflow. We demonstrate gel-phase microextraction (GPME), in which disks of blended hydrogels are utilized to lift traces of water-soluble substances adsorbed on surfaces. The protocol has been optimized in a series of tests involving fluorometric and mass spectrometric measurements. Compared with the pure agarose hydrogel, most of the tested blended hydrogels provide a higher efficiency for sampling/extraction of a model analyte – fluorescein. We exemplify the suitability of this improved GPME approach in sampling chemical residues (lactic acid, and diclofenac sodium) present on skin, glass, and daily-use objects. In the second study (Chapter 3), we demonstrate on-line coupling of SDE apparatus with a gas chromatograph hyphenated with mass spectrometer. For that purpose, we have devised an automated liquid transfer setup comprising peristaltic pump, control unit, customized transfer vial with drain port, and autosampler arm to deliver liquid extract aliquots at defined time points. The on-line SDE-GC-MS system enables recording real-time extraction profiles which reveal extraction kinetics of various VOCs present in the extracted samples. A comparison of on-line and off-line results reveals that the on-line system is more dependable, while the off-line analysis leads to artefacts. To demonstrate the operation of the on-line SDE-GC-MS system, we performed analyses of two types of beer. The real-time datasets revealed extraction kinetics for VOCs present in the samples. The devised extraction-analysis system allows the analysts to make an evidence-based decision on the extraction time for different groups of analytes in order to maximize extraction yield and minimize analyte losses.

並列關鍵字

Automation ； ESI-QQQ-MS ； GC-MS ； Gel-phase microextraction ； Hydrogel ； simultaneous distillation extraction

參考文獻

1. Maitra, J.; Shukla, V. K. Am. J. Polym. Sci, 2014, 4, 25–31.

2. Urbano-Juan, M. M.; Socías-Viciana, M. M.; Ureña-Amate, M. D. React. Funct. Polym. 2019, 141, 82–90.

3. M’barki, N.; Aissaoui, F.; Chehab, H.; Dabbaghi, O.; del Giudice, T.; Boujnah, D.; Mechri, B. Agr. Water Manage. 2019, 216, 70–75.

4. Zhang, X.; Ma, Y.; Ma, L.; Zu, M.; Song, H.; Xiao, B. Carbohydr. Polym. 2019, 223, 115126.

5. Alizadeh, R.; Zarrintaj, P.; Kamrava, S. K.; Bagher, Z.; Farhadi, M.; Heidari, F.; Komeili, A.; Gutiérrez, T. J.; Saeb, M. R. Carbohydr. Polym. 2019, 224, 115161.