| 摘要: | 中文摘要
本研究目的在於分散式液液微萃取技術的開發以及利用微波輔助一鍋化合成螢光探針。本論文可分為三個主題，第一個主題為利用實驗設計法快速優化分散式液液微萃取技術，第二部分使用自動化動態單滴技術提升分散式液液微萃取技術，第三個主題為合成新型螢光分子作為探針使用。
第一部分，我們使用田口法和響應曲面法優化分散液液微萃取技術 (DLLME) 的連續性和不連續性參數。並使用DLLME結合負化學游離法氣相層析質譜，檢測農產品中六種擬除蟲菊酯農藥：芬普寧、芬化利、護賽寧、λ-賽洛寧、賽滅寧與第滅寧。
通過田口方法和響應曲面法優化所得的最佳條件顯示:在pH 4環境下，氯仿70 μL (萃取劑)，丙酮300 μL (分散劑)和5%氯化鈉 (鹽類添加濃度)，超聲波輔助3分鐘，離心3分鐘。
在最佳提取條件下，該方法的線性範圍為20-50000 pg / mL，相關係數為0.991-0.996，方法檢出限為5-35 pg / mL，inter-day與intra-day的相對標準偏差值介於3.2-8.5%。該方法成功應用於測定飲料，水果，蔬菜，藥材等目標分析物的13個實際樣品，標準添加法的最高濃度方法為1500 pg / mL，回收率介於74％-130％。
第二部分驗證一種概念性的突破，涉及自動化動態混合單滴液液微萃取技術 (ADMD-DLLME)。為了有效檢驗環境水樣中有機磷酸酯的濃度，開發了一種ADMD-DLLME方法並與結合氣相層析質譜儀。藉由注射幫浦，可以簡單而穩定地產生液滴，當樣品和提取溶劑接觸時相互混合，立即完成提取。ADMD-DLLME克服了傳統DLLME中需要手動操作的局限性，並避免了使用昂貴的設備來自動化DLLME。此外，使用一次性樣品注射注射器可防止樣品殘留物污染。響應面方法用於優化影響ADMD-DLLME的參數，並使用變異數分析進行統計分析。在最佳條件下，該方法具有良好的線性範圍 (1-800 µg / L)，偵測極限 (0.1-0.4 µg / L) 和再現性 (RSD = 1.3％-10.7％)。該方法已成功應用於真實水庫水，海水和河水。
第三部分開發了一種快速，便宜和方便的方法用於微波輔助合成吲哚-3-丙酸 - 雙酚A二縮水甘油醚 (IPA-SR3) 熒光探針。 該熒光探針根據濃度而有光誘導電子轉移和聚集誘導發射的雙重發光特性。 聚集的IPA-SR3具有波長依賴性光致發光行為對Cu 2+離子具有高度選擇性 (Ksv = 1.5×104 M-1) 以及低檢測限 (2.9 μM)。因此，它可用於檢測水樣中的低濃度Cu 2+離子。
;Abstract
The purpose of this study is to develop a dispersive liquid-liquid microextraction (DLLME) technology and to develop fluorescent probes using microwave-assisted one-pot synthesis. This thesis consists of three themes, the first of which involves the rapid optimization of the DLLME technology using the experimental design method. The second theme concerns the improvement of the DLLME technology using the automatic dynamic mixing droplet technology. Finally, the third theme involves the synthesis of a new type of probe using fluorescent molecules.
In the first part, we adopted the Taguchi method and response surface methodology to optimize parametric continuity and discontinuity of the DLLME technology. The DLLME technology was integrated with the gas chromatography involving negative ion chemical ionization mass spectrometry to test six pyrethroid pesticides in agricultural products, namely Fenpropathrin, Fenvalerate, Flucythrinate, λ-Cyhalothrin, Cypermethrin, and Deltamethrin.
By using the Taguchi method and the response surface methodology, the following optimal conditions were achieved: hloroform 70 μL (extraction solvent), acetone 300 μL (dispersant), and 5% sodium chloride (salt addition concentration) were mixed in a pH 4 environment. Ultrasound was utilized in the extraction for 3 minutes, and the mixture was centrifuged for 3 minutes.
Under the optimum extraction condition, the linear range of this method was 20–50000 pg/mL, the correlation coefficient was 0.991–0.996, the detection limit was 5–35 pg/mL, and the relative standard deviation values of the inter- and intra-day analysis was 3.2%–8.5%.
This method was applied to analyze 13 real samples of the target analytes, including beverages, fruits, vegetables, and herbs. In the standard addition method, the highest concentration used was 500 pg/mL, and the relevant extraction recovery was 74%–130%.
In the second part concerned the verification of a conceptual breakthrough, which involved automatic dynamic mixing droplet DLLME (ADMD-DLLME). To effectively test the organophosphate ester concentration in the environmental water samples, the ADMD-DLLME method was developed and integrated with the gas chromatography-mass spectrometry. Droplets were stably generated with ease using syringe pumps. When the sample and the extraction solvent contacted each other and temporarily mixed, the extraction was conducted immediately. The ADMD-DLLME overcame the conventional limitation of the DLLME method that required manual handling, and no expensive equipment was involved in the automation of the DLLME method. In addition, the use of disposable sample injection syringes prevented contaminations caused by sample residue. The response surface methodology was adopted to optimize parameters affecting the ADMD-DLLME. Analysis of variance was conducted for statistical analysis. Under the optimized condition, the ADMD-DLLME method exhibited favorable linearity (1–800 µg/L), detection limit (0.1–0.4 µg/L), and reproducibility (RSD = 1.3%–10.7%). The method had been applied to samples from reservoir water, sea water, and river water.
In the last part, a rapid, inexpensive, and convenient method was developed and applied in the microwave assisted synthesis of indole-3-propionic acid–bisphenol A diglycidyl ether (IPA–SR3) fluorescent probes. The fluorescent probe exhibited the dual illumination characteristics of photo-induced electron transfer and aggregation-induced emission based on concentrations. The aggregated IPA–SR3 displayed a wavelength-dependent photoluminescence behavior; it was highly selective to Cu 2+ (Ksv = 1.5×104 M-1) and had a low limit of detection (2.9 μM). Therefore, it was applicable to detecting low-concentration Cu 2+ in water samples. |
