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標題: Novel Pseudo-Solvent Based Cloud-Point Microextraction for the Rapid Determination of Parabens in Aqueous Samples by HPLC-UV
以新型有機酸雲點微萃取法結合 HPLC-UV快速分析水樣中 Parabens 含量
作者: 李心儀
Hsin-Yi Li
關鍵字: Pseudo-solvent;Cloud point microextraction;Shampoo;Parabens;HPLC-UV;有機酸雲點微萃取;洗髮乳;Parabens;高校液相層析儀-紫外光偵: 測器
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A green analytical method for the determination of parabens in shampoo by pseudo-solvent based cloud point microextraction (PS-CPME) was investigated. In this study, fatty acid was investigated as pseudo-solvent due to it is soluble in basic medium and insoluble (as extractant) in acid medium. After a dilution of shampoo sample with water, parabens in 5 mL aqueous sample solution were measured under the selected conditions. A home-made glass extraction barrel inbuilt with a scaled capillary tube was utilized as a PS-CPME device to collect the separated extractant. 40μL of heptanoic acid (as pseudo-solvent) and 30μL of NH4OH were added into a 8 mL extraction barrel filled with 5 mL sample solution, after shakily mixing for 10 sec, 750 mg of NaCl and 600μL of H2SO4 was added and also shake for 10 sec to form the insoluble heptanoic acid. The cloudy solution was centrifuged at 3200 rpm for 1min, and the separated extractant was push into scaled capillary tube and collected 10μL for HPLC analysis. Under these conditions, the linear dynamic range for the detection was 0.04-8μg/mL for methyl paraben, 0.02-4 μg/mL for ethyl paraben, and 0.01-2 μg/mL for propyl paraben and butyl paraben, with relative standard derivation (RSD) below 6.8%. Detection limits were achieved at the level of 0.0005-0.008 μg/mL. Quantitative limits were achieved at the level of 0.002-0.03 μg/mL. Recoveries were ranged in between 92.2% to 104.1% and its RSD less than 8.8%. The proposed PS-CPME method was proven to be a simple, rapid, low-cost and eco-friendly sample preparation process to extract parabens in shampoo samples for chromatographic analysis.

本研究利用有機酸所具有之溶劑與界面活性劑轉換特性開發為雲點 萃取之前處理技術,結合高效能液相層析儀 (HPLC-UV),檢測洗髮精中 四種對羥基苯甲酸酯 ( Methyl Paraben, Ethyl Paraben, Propyl Paraben 與 Butyl Paraben )。研究中以脂肪酸類化合物作為偽溶劑,當脂肪酸溶解於 鹼性溶液中呈現離子態,具有界面活性劑性質,而當溶液 pH 值下降至 pKa 以下時,脂肪酸呈現分子態,此時則具有有機溶劑性質。萃取過程於 水樣中加入少量的氨水使水溶液成鹼性,再加入有機酸進行皂化反應, 形成界面活性劑,利用為雲點萃取。之後加入適量的硫酸,使當為界面 活性劑之有機酸皂被中和轉成為分子態,產生分散雲團現象。離心後, 取出上層 10μL 脂肪酸注入 HPLC-UV 中進行偵測。為了求得此方法的 最佳萃取條件,分別對脂肪酸,脂肪酸的體積,氨水的體積,硫酸的體 積,鹽類添加量等進行探討。研究結果顯示,在 5 mL 水樣中加入 30μL 的氨水與 40μL 的庚酸,混合均勻進行萃取後,加入 15% 的 NaCl,並 加入 600μL 的硫酸即可獲得最佳的萃取效果。在最佳條件下分析四種對 羥基苯甲酸酯,其線性範圍介於 0.01 ~ 8 μg/mL,線性相關係數高於 0.9980,偵測極限小於 0.008 μg/mL,定量極限小於 0.003 μg/mL,RSD 低於 6.3%。將本方法應用在真實樣品中回收率為 92.2% ~ 104.1%。本開 發方法之分析過程僅使用數微升的脂肪酸及常見的酸與鹼,所使用之材 料不會造成環境負擔,為一操作簡單、方便、快速與高效率,且兼具環 保的綠色化學分析方法。
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