本研究開發了使用多孔中空纖維液相微萃取技術 (Hollow fiber liquid phase microextraction，簡稱HF-LPME)結合纖維電噴灑質譜法 (fiber-spray/mass spectrometry)的檢測技術。由3D列印製作一個纖維容槽，用於連接中空纖維和電噴灑針。平口纖維前端於電噴灑時亦可形成泰勒錐，其中產生的離子可透過質譜儀進行檢測。本研究設計和測試的微萃取槽由離心管（用於樣品溶液儲存）和一枚多孔中空纖維（用於樣品萃取）所構成。當萃取槽的纖維被放置於質譜入口和電噴灑針間時，從樣品溶液中被萃取出來分析物，因蒸發而隨溶劑從纖維表面逸出。當蒸發出來的分析物與電噴灑輔助溶劑的帶電粒子接觸時，分析物將被游離而能透過質譜儀進行檢測。使用此裝置，以濫用藥物3,4-亞甲二氧基甲基苯丙胺 (MDMA)為分析物時，透過中空纖維液相微萃取可將偵測極限提高約360倍，此方法對MDMA的偵測極限為2 ng/mL。此方法除可應用於濫用藥物的檢測外，亦可應用於農藥殘留的檢驗，本研究使用非侵入性方法採樣，以沾水的毛筆在青椒表面來回塗抹10次，收集殘留於青椒表面的嘉磷塞 (glyphosate)，再將採樣後的毛筆放入已完成萃取準備的微萃取槽中，讓筆毛上的嘉磷塞脫附並溶解於微萃取槽的0.1 M氫氧化鈉溶液中進行萃取，最終以纖維電噴灑質譜法進行檢測。使用此方法，嘉磷塞的偵測極限為1 ng/cm2，與青椒樣品均質化再添加嘉磷塞後所測得的偵測極限相同。在樣品均質化的黃豆基質中檢測嘉磷塞，透過線上微萃取技術則可將偵測極限提升1000倍。

關鍵字：纖維/電噴灑質譜法，中空纖維液相微萃取，嘉磷塞

A novel fiber-spray/mass spectrometry method using a piece of a porous hollow fiber is described. An adapter, fabricated by a 3D-printer, was designed to connect the fiber and a standard ESI (electro-spray ionization) needle, in which a Taylor cone was formed and the resulting ions were detected by a mass spectrometer. Since a porous hollow fiber is usually used for microextraction, the so-called hollow fiber liquid-phase microextraction (HF-LPME) method, a new methodology that involves coupling HF-LPME and fiber-spray, was developed for the first time. We reported herein on the design and testing of a microextraction kit. The kit consists of a centrifuge tube (reservoir for the sample solution) and a piece of a porous hollow fiber (for sample extraction). The kit was placed between the mass inlet and the ESI needle. Using the kit, analytes can be extracted from a very dilute solution and then evaporate and escape from the fiber surface. When they make contact with the ESI plume, which arises from the ESI needle tip, the molecules are ionized and then detected by a mass spectrometer. Using the setup, it was possible to improve the limit of detection after microextraction by ∼360-fold when MDMA (3,4-methylenedioxymethamphetamine) was analyzed, and the limit of detection of 2 ng/mL was achieved. We also reported on a novel on-line microextraction technique, in which a watercolor pen was used for sample collection and a section of porous-polypropylene hollow fiber was used for sample concentration by means of liquid-liquid microextraction. In order to achieve this, a kit was well designed and tested. The kit consists of a watercolor pen, a section of porous-polypropylene hollow fiber and a centrifuge tube. It can be placed between the mass inlet and the ESI needle. Using this configuration, glyphosate, collected from a green pepper surface, can be extracted from a very dilute solution and then evaporates and escapes from the fiber surface. When glyphosate molecules make contact with the ESI plume, which arises from the ESI needle tip, they were ionized and then detected by a mass spectrometer. Using the setup, it was possible to improve the limit of detection for glyphosate after microextraction by ~1000-fold, resulting in a limit of detection of 1 ng/cm2.

key words: fiber spray/mass spectrometry, hollow fiber liquid phase microextraction, glyphosate

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