摘要: | 我們沿襲以往的研究開創精神,發展快速、方便、合乎環保又可靠的微檢測技術,提出此三年型研究計畫。計畫主要有三部分:(i)製備及選擇適當的深共熔溶劑(簡稱DESs)作為微萃取的綠色化學溶劑; (ii)應用於檢測液態樣品中新興污染物(如微囊藻毒素、Parabens、高產量化學品)殘留; (iii)應用於檢測固態樣品如生物檢體、蔬果類樣品中上述污染物的殘留。深共熔溶劑是一種新興的綠色化學溶劑,通常利用有機鹵化鹽(如氯化膽鹼)作為氫鍵接受者和可提供氫鍵的化合物(如尿素或醇類)作為氫鍵提供者相混合,經快速攪拌相互熔解下形成溶劑,不需純化。本研究將製備不同性質的DESs,取代傳統有機溶劑(尤其是含鹵溶劑),藉由多樣性的DESs對不同待測物的選擇性,將新興污染物由不同環境基質或食物中萃取出來,並搭配多變量實驗設計統計法,評估以DESs為基礎的微萃取方法(如VA-LLME、改良式MSPD萃取法、改良式QuEChERS)的萃取效能,及其萃取方法最佳化的條件。在定性和定量上,由於目前大多使用HPLC-UV/Vis技術,缺乏檢測選擇性及靈敏度,因此本計畫將首次探討DESs的使用,對以電灑法為介面之HPLC-MS影響,並找尋其檢測最佳條件。此研究計畫於綠色分析化學及檢測新興污染物研究議題上,具有對技術之突破性與研發上的主導性。 ;In this three-year proposal, we will focus on (i) preparation of deep eutectic solvents (DESs) as green extracting solvents for microextraction; (ii) application of DESs for the extracting solvents of various emerging contaminants in aquatic and urine samples; (iii) application of DESs to extract various emerging contaminants in indoor dust, biota and vegetable/fruits samples. Deep eutectic solvents, a group of novel “green” solvents, formed by mixing of various quaternary ammonium salts (i.e., choline chloride) and different hydrogen-bond donors (HBD, such as urea, amines or alcohols). They are easily synthesized at room temperature, and no need purification afterward. Therefore, DESs have become attractive alternative solvents for various scientific research, and substituted conventional volatile organic solvents, especially for hazardous chlorinated solvents. In this proposal, we will focus on preparing various properties DESs (i.e., hydrophilicity or lipophilicity) to extract different emerging contaminants from various environmental matrices, biota and food samples. To minimize the number of experiments, costs, and reagents required, optimization of the parameters affecting microextraction sample pretreatment procedures will be done via multivariate experimental designs. The state-of-the-art UHPLC-HRMS will be developed and evaluated for the identification and quantitation of the target analytes at trace-level. Followings four major Tasks are going to be investigated and studied: Task 1. Deep eutectic solvents preparation, characterization and selection to extract various emerging contaminants (i.e., Microcystins, parabens preservatives, high production volume chemicals (HPVs): Benzotriazoles and Benzothiazoles, as the model compounds) in various sample matrices;Task 2. For liquid samples, evaluating DES-based vortex-assisted liquid-liquid microextraction (VA-LLME), ultrasound-assisted liquid-liquid microextraction (UA-LLME). For solid samples, such as indoor dust, biota samples, and vegetables/fruits samples, evaluating modified matrix solid-phase dispersion (MSPD) and modified QuEChERS procedures; Task 3. Optimizing the main parameters affecting microextraction procedures by various multivariate experimental designs (i.e., response surface design coupled with Box-Behnken Design, Plackett-Burman design or central composite design);Task 4. Evaluating the influence of DES in final extract, and for the first time, to evaluate the feasibility of the UHPLC-ESI-HRMS for the identification and quantitation of the target analytes at trace-level.The tasks studied in this proposal will significantly contribute to wide spectrum of DES-based applications in sample pretreatment and microextraction techniques, and also developed the state-of-the-art hyphenated mass spectrometric to determine various emerging contaminants in various environmental and biota samples at trace-level. Eventually, we hope many advantages of DES-based microextraction procedures could fulfill the “green analytical chemistry” guidelines, and could greatly aid future routine analysis and monitoring programs on the occurrence of selected emerging contaminants. Moreover, the results of this research should be highly in response to our environmental protection trends, promote food safety and public health concern, as well as conservation and pollution control policies in Taiwan. |