製備金屬有機骨架材料作為新興吸附劑應用於檢測環境水樣中防腐劑 Parabens殘留之研究

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曾月逸(Yueh-Yi Tseng) 查詢紙本館藏

畢業系所

化學學系

論文名稱

製備金屬有機骨架材料作為新興吸附劑應用於檢測環境水樣中防腐劑 Parabens殘留之研究

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至系統瀏覽論文 (2025-6-30以後開放)

摘要(中)

本研究開發出一套簡單快速且符合綠色化學的萃取方法，用於檢測環境水樣中防腐劑Parabens的殘留。Parabens廣泛應用於個人護理產品中，其乃一種內分泌干擾物質，經使用後產生的民生廢水排放至自然環境，其殘留會對人類健康和生態環境帶來不良影響。
　　本研究使用的是近年十分熱門的吸附材料——金屬有機骨架材料(Metal Organic Frameworks, MOFs)，其具有高比表面積、良好的熱穩定性及多孔結構等特性。而本研究透過無溶劑法成功快速製備MIL-101(Cr)，作為分散式微固相萃取法(Dispersive micro solid phase extraction，簡稱D-µ-SPE)之吸附劑，其表現出良好的吸附效果和穩定性，並利用高效液相層析串聯電灑游離（-）-四極桿飛行時間式質譜儀(UHPLC-ESI（-）-QTOF-MS)進行後續的分析檢測。
　　藉由Multilevel categoric design(MLCD)和Box-Behnkne Design(BBD)中變異數分析(Analysis of variance, 簡稱ANOVA)，針對實驗條件進行優化，減少實驗時間和溶劑使用量，以檢測水樣中的7種Parabens。
　　本方法的偵測極限(LOD)為0.002-0.5 ng/mL，展現優異的靈敏度；在Intra-day和Inter-day的測試中相對標準偏差(RSD)低於8 %，萃取回收率介於61％-120%之間，表現出良好的再現性和穩定性，並於真實環境水樣中檢測到防腐劑MeP和PrP的微量殘留。
　　整體而言，本研究方法使用無溶劑合成的金屬有機骨架材料，並搭配分散式微固相萃取法，實驗過程大幅降低實驗時間和有機溶劑使用量，符合綠色化學之準則，是一種簡易、高效且對環境友善檢測防腐劑Parabens的分析方法。

摘要(英)

Parabens are widely used in personal care products. They have been classified as endocrine disrupting chemicals (EDCs). Wastewater generated by the people′s livelihood is discharged into the natural environment, and the residues will have adverse effects on human health and the ecological environment.
　　In this study, we prepared metal-organic frameworks (Metal Organic Frameworks, MOFs) as adsorbents, which is a group of popular novel adsorbents in recent years. MOFs have the characteristics of high surface area, good thermal stability and porous structure. In this study, MIL-101(Cr) was successfully and quickly prepared by a solvent-free method. As an adsorbent for dispersive micro solid phase extraction (D-µ-SPE), MIL-101(Cr) displayed good adsorption effect and stability. Ultrahigh-performance liquid chromatography and electrospray ionization (-)-quadrupole time-of-flight mass spectrometer (UHPLC-ESI(-)-QTOF-MS) was used for detection and quantitation.
　　By means of Analysis of variance (ANOVA) in Multilevel categoric design (MLCD) and Box-Behnkne Design (BBD), the experimental conditions were optimized and the experimental time and solvent usage were reduced. The developed method was validated after optimization. The method provided low limit of detection (LOD), range from 0.002-0.5 ng/mL, and showed excellent sensitivity. The relative standard deviation (RSD) is less than 8% and the extraction recovery is range from 61% to 120% for both intra- and inter-day analysis, which revealed good reproducibility and stability. The method was applied for the detection of parabens residues in real water samples successfully.

關鍵字(中)

★ 綠色分析化學
★ 防腐劑Parabens
★ 金屬有機骨架材料
★ 分散式微固相萃取法

關鍵字(英)

★ Green Analytical Chemistry
★ Parabens
★ Metal Organic Frameworks
★ Dispersive micro solid phase extraction

論文目次

摘要 i
Abstract iii
謝誌 v
圖目錄 x
表目錄 xii
第一章　前言 1
1-1　研究緣起 1
1-2　研究目標 2
第二章　文獻探討 3
2-1　金屬有機骨架材料 3
2-1-1　介紹 3
2-1-2　無溶劑合成法 (Solvent-Free Synthesis) 4
2-1-3 MIL系列 4
2-1-4 吸附機制 5
2-2分散式微固相萃取法 8
2-2-1前言 8
2-2-2原理 8
2-3防腐劑成份 9
2-3-1對羥基苯甲酸酯(Parabens) 9
2-3-2對環境及人類的影響 9
2-3-3每日暴露量 10
2-3-4相關規範 10
2-3-5相關文獻 11
第三章　實驗步驟與樣品分析 15
3-1實驗藥品與設備 15
3-1-1實驗藥品 15
3-1-2儀器設備 16
3-2實驗步驟 17
3-2-1標準品配製 17
3-2-2超高效液相層析串聯質譜儀參數設定 18
3-2-3質量校正 20
3-2-4金屬有機骨架材料之合成 21
3-2-5分散式微固相萃取法 22
3-2-6樣品來源 23
第四章　結果與討論 25
4-1 UHPLC-QTOF-MS 對待測物之測定 25
4-1-1待測物分析及其層析圖 25
4-1-2待測物之質譜圖 26
4-2金屬有機骨架材料MIL-101(Cr)鑑定與性質探討 27
4-2-1 X射線繞射圖譜 27
4-2-2 場發掃描式電子顯微鏡影像 28
4-2-3 熱重分析圖 29
4-2-4 氮氣等溫吸脫附圖 30
4-2-5 製備MIL-101(Cr)材料之相關文獻整理 31
4-3分散式固相萃取法最佳化條件探討 33
4-3-1單因子最佳化探討 33
4-3-1-1金屬有機骨架材料的選擇 33
4-3-1-2脫附溶劑的種類 34
4-3-1-3吸附過程的機械力 35
4-3-1-4吸附劑的用量 36
4-3-1-5吸附過程的時間 37
4-3-1-6脫附過程的時間 38
4-3-2 Experiment Design 39
4-3-2-1 Multilevel categoric design (MLCD) 39
4-3-2-1-1 Multilevel categoric design(MLCD)分析 41
4-3-2-1-2 Multilevel categoric design(MLCD)殘差分布圖 42
4-3-2-1-3 Multilevel categoric design(MLCD)結果 43
4-3-2-2 Box-Behnkne Design(BBD) 44
4-3-2-2-1 Box-Behnkne Design(BBD)分析 47
4-3-2-2-2 Box-Behnkne Design(BBD)殘差分佈圖 49
4-3-2-2-3 Box-Behnkne Design(BBD)結果 49
4-4檢量線與偵測極限 50
4-5方法準確度與精密度 51
4-6真實樣品檢測 52
4-7Analytical Eco-Scale 56
第五章　結論 59
第六章　參考文獻 61

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2023-5-31

推文