以新開發雙重震盪輔助基質固相分散萃取法檢測蔬菜樣品中防曬乳成分之殘留

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邱意騰(I-Teng Chiu) 查詢紙本館藏

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化學學系

論文名稱

以新開發雙重震盪輔助基質固相分散萃取法檢測蔬菜樣品中防曬乳成分之殘留

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摘要(中)

本研究開發了一套快速方便、直接萃取且符合綠色分析化學的樣品前處理方法來檢測市售蔬菜樣品中五種防曬乳成分－二苯基甲酮 (benzophenones, 簡稱 BPs) 的殘留。由於在護膚保養品、汽車部件、食品外包裝塗料當中都有使用 BPs，然而近期研究指出，BPs 在生物系統中不僅含有潛在的危害性，且藉由生物積累的方式，易對環境生物及人類造成負面影響。
而本研究新開發了雙重震盪輔助基質固相分散萃取法（double-vortex-assisted matrix solid-phase dipersion, 簡稱 DVA-MSPD），省去了使用研缽研磨及固相萃取過程中管柱沖提的過程，接著再利用超高效液相層析串聯電灑游離 (+) −四極桿飛行時間質譜儀 (UHPLC−ESI(+)−QTOF−MS) 進行後續檢測。並利用 Multilevel Categoric Design 選擇實驗過程中非數值因子的種類，以及使用 Box−Behnken Design （BBD）中的變異數分析（Analysis of Variance, ANOVA）優化各項數值因子以找出實驗的最佳條件。本實驗方法最佳條件為：取0.2 g 蔬菜粉末與0.2 g C18吸附劑，震盪1分鐘使其均勻分散，省去了傳統研缽的使用。加入7 mL 萃取劑甲醇並震盪3分鐘進行萃取，代替了以往 SPE 管柱沖提的部分。以5500 rpm 離心15分鐘，取出上層液，吹氮濃縮到乾，再以200 μL 甲醇回溶，然後以3 μL 進樣到UHPLC-ESI-QTOF-MS 進行檢測。
使用 DVA-MSPD 方法，成功測量5種 BPs，定量極限（LOQ）介於1-9.5 ng/g， Inter−day 和 Inter−day 的相對標準偏差（RSD）介於2 %−14 % 之間，而萃取回收率則介在67 %−120 % 之間，表示本方法呈現良好的準確性及穩定度。而在市售的蔬菜樣品中都有檢測到不同濃度的 BPs 殘留。

摘要(英)

In this study, A novel double-vortex-assisted matrix solid-phase（DVA-MSPD）technique, without the use of motor/pestle and SPE-column elution procedure, was developed to determine the presence of five benzophenone-type （BPs） UV-filters in marketed vegetables. This procedure is a straightforward, simple and efficient method. The target analyte were rapidly extracted from the vegetable and then detected by an ultrahigh-performance liquid chromatography and electrospray ionization(+)-quadrupole time-of-flight mass spectrometry （UHPLC-ESI(+)-QTOF- MS）. The DVA-MSPD extraction factors were screened by means of a multilevel categorical design and a Box-Behnken Design plus with response surface methodology was used to overcome the challenges related to different experimental conditions.
The optimal conditions of DVA-MSPD were: powdered vegetable sample 0.2 g was dispersed with 0.2 g C18 adsorbent by vortex- homogenized for 1 min (without using mortar/pestle), and 8 mL of methanol （as an extractant） was added, and the content was thoroughly vortex-extracted for 5 min（SPE-column-free）. Then for 15 min, the phase was separated by centrifugation at 5500 rpm. The supernatant was evaporated to dryness, and re-dissolved in a 200 μL of methanol. The extract 3 μL was then directly injected into UHPLC-QTOF-MS for detection.
The developed method was validated, and provided low limits of quantification （LOQs） ranging from 1 to 9.5 ng/g ; high precisions for both repeatability and reproducibility ranging from 2 to 14 %; and high accuracy (mean extraction recovery) ranging from 67 to 120 % at two spiked concentration levels. The developed method was then successfully applied for the analysis of BPs in marketed vegetables.

關鍵字(中)

★ 雙重震盪輔助基質固相分散萃取法
★ 二苯基甲酮
★ 防曬乳成分
★ 超高效液相層析儀串聯電灑游離-四極桿飛行時間質譜儀
★ 實驗設計
★ 綠色化學分析方法

關鍵字(英)

論文目次

摘要 i
Abstract iii
謝誌 v
第一章前言 1
1-1研究源起 1
1-2研究目標 2
第二章文獻回顧 5
2-1基質固相分散萃取法 5
2-1-1 前言 5
2-1-2 原理 6
2-1-3 流程 7
2-1-4影響因素 8
2-2 Core-shell column 11
2-3防曬乳成分 12
2-3-1 二苯基甲酮(Benzophenone, 簡稱 BPs) 13
2-3-2二苯基甲酮用途 15
2-3-3環境分布 15
2-3-4對人體及環境的影響 16
2-3-5毒性研究 18
2-4 相關檢測文獻 21
第三章實驗步驟與樣品分析 25
3-1實驗藥品與設備 25
3-1-1實驗藥品 25
3-1-2 儀器設備 26
3-2 實驗步驟 27
3-2-1標準品配製 27
3-2-2超高效液相層析串聯質譜儀參數設定 28
3-2-3 質荷比校正 30
3-2-4空白蔬菜樣品的製備 31
3-2-5震盪輔助基質固相分散萃取法實驗步驟 (最佳化後的步驟) 32
3-3蔬菜的採集及真實樣品的製備 33
第四章結果與討論 35
4-1 UHPLC−QTOF−MS 對待測物的測定 35
4-1-1 待測物分析及其層析圖 35
4-1-2待測物及其質譜圖 36
4-2雙重震盪輔助基質固相分散萃取法條件探討 37
4-2-1單因子最佳化條件 37
4-2-2 Experiment Design 43
4-3 檢量線與偵測極限 60
4-4方法準確度與精密度 61
4-5真實樣品的檢測 62
4-6前處理方法比較 67
4-7 Analytical Eco-Scale 70
第五章結論 73
第六章參考文獻 75

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指導教授

丁望賢

審核日期

2022-7-27

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