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研究生: 陳億展
Chen, Yi-Zhan
論文名稱: 磁性強陰離子交換吸附劑的製備及其檢測辣椒油中四種蘇丹紅染料
Preparation of Magnetic Strong Anion Exchange Adsorbent and Its Determinations of Four Sudan Dyes in Chili Oil
指導教授: 凌永健
Ling, Yong-Chien
口試委員: 黃賢達
Huang, Shang-Da
杜敬民
Duh, Jing-Min
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 65
中文關鍵詞: 磁性固相萃取陰離子交換蘇丹染料辣椒油
外文關鍵詞: magnetic solid phase extraction, anion exchange, Sudan dyes, chili oil
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  • 顏色是食品的重要外觀表象之一,是其在市場銷售中成功與否的重要因素。由於消費者看重色澤,因而著色劑被廣泛應用於食品和飲料著色,用以刺激食慾。由於合成染料有著更好的穩定性和色澤,成本低廉,顏色範圍廣,因而常被食品工業用於替代天然色素。
    近年來,出於對公眾健康潛在性健康危害的考慮,合成染料的使用受到了嚴格的監管。偶氮染料型的蘇丹紅類染料(Sudan dyes)具有著色性好及價格便宜等特性,常被不肖業者用於辣椒製品著色,雖然蘇丹紅早於1975年已被國際癌症研究機構(IARC)歸類為第三類致癌物。FDA和歐盟都將其列為非法的食品添加物。歐盟曾設定其檢出限為0.5-1 mg/kg,而任何含量高於此的食品必須從市場上召回。在此,我們首次製備磁性強陰離子吸附劑,開發了樣品的前處理方法,再用超高效液相層析儀(UPLC)快速分離測定四種蘇丹紅。
    本研究採用化學共沉澱法合成磁性奈米粒子,作為內核,再以四乙氧基矽烷(TEOS)和三甲氧基矽基丙基-氮,氮,氮位-三甲基氯化銨(TMSPTMA)縮聚包覆其外層,製備磁性強陰離子交換吸附劑(Magnetic Strong Anion Exchange Adsorbents,MSAEA)。通過Z-potential、FTIR等進行表徵分析,證實TMSPEMA成功包覆在磁性奈米粒子表面。
    蘇丹紅類染料具有酚羥基,在一定的pH條件下會被解離,生成陰離子態,被上述MSAEA吸附,因此干擾較少。然後通過磁分離,使用適當流洗溶劑,被脫附下來,調態回原來的自由態,得以後續再用UPLC分析,在添加回收方面,五個樣品的添加回收率在76.4-86.8%之間,同日間相对标准偏差和異日間相对标准偏差在3.1-7.6%和5.2-10.3%之間。結果顯示這個新方法可以成功的應用於辣椒油中的蘇丹紅染料檢測。本研究製備的磁性強陰離子交換吸附劑,相較於國家標準中使用的氧化鋁吸附劑,具有高選擇性,且有易合成、低溶劑等特點,符合綠色化學之理念。


    Color is an essential part of the characteristics of food and can affect the products’ success in the food market. Since the visual aspect of a product can be an important factor in a consumer’s decision, artificial color additives are widely used to enhance the appearance of food and beverages to stimulate appetite. Considering the advantages from synthetic dyes including better stability, brightness, lower cost and availability of a range of colors are frequently chosen over natural dyes by food industries.
    However, in recent years, consumption of synthetic colorants are subject to stringent regulation because of concerns about the potential health risks in public health. As a family compounds in the class of azo dyes, mostly Sudan dyes have been used for coloring chili products by illegal manufacturer due to their strong color giving nature and low cost. Even, Sudan dyes are categorized as Class 3 carcinogens by the International Agency for Research on Cancer (IARC) and, therefore, are illegal as food additives according to both the FDA and the EU. The EU has set detection limits at 0.5-1 mg/kg, and any food material containing more than the limit should be withdrawn from the market. Here, we synthesized a kind of magnetic strong anion exchange adsorbents for the first time, developed sample pretreatment, used UPLC to rapid separate four Sudan Dyes.
    In this work, firstly magnetic nanoparticles were synthesized using chemical coprecipitation method and followed by coating with polymers of Tetraethoxysilane (TEOS) and N-trimethoxysilylpropyl-N,N,N- trimethylammonium chloride (TMSPTMA) through polymerization process to obtain magnetic strong anion exchange adsorbent (MSAEA). Further the synthesized material was characterized using Z-potential, FT-IR, SEM and SQUID. Sudan dyes contain hydroxyl groups which can be ionized under certain pH range and formed anions, which can be attracted by MSAEA and make it less interference. Consequently, they can be separated by external magnet and eluted using proper solvent and become free state to be detected by UPLC. The result showed that the method had good linearity (r= 0.990–0.997), and the limits of detection (LODs) of four Sudan dyes were from 15 ng/mL. Recoveries obtained by analyzing the five spiked chili oil samples were in the range of 76.4-86.8% and the intra-day and inter-day relative standard deviations (RSDs) were between 3.1-7.6% and 5.2-10.3%, respectively. The results indicated that the novel method could be applied successfully for the determination of Sudan dyes in chili oil samples. MSAEA prepared by this method has high selectivity, easy synthesis, and low solvent consumption, compared to aluminum oxide adsorbent used in national standard method. In addition, our material is consistent with the requirements of green chemistry.

    第一章 緒論 1 1.1 研究背景 1 1.2 蘇丹紅染料簡介 2 1.3 蘇丹紅檢測方法 5 1.3.1 固相萃取法 7 1.3.2 分子印跡固相萃取法 7 1.3.3 磁固相萃取法 8 1.3.4 離子液體液液微萃取法 11 1.3.5 其他方法 12 1.4 磁性固相萃取的應用 14 1.5 研究動機與目標 17 第二章 工作原理 18 2.1 磁性材料 18 2.2 磁性強陰離子交換吸附劑合成原理 19 2.3 吸附劑吸附原理 23 第三章 實驗方法 25 3.1 試劑 25 3.2 實驗設備與儀器 26 3.3 磁性強陰離子交換吸附劑的合成 27 3.4 磁性強陰離子交換吸附劑的表征 28 3.4.1 傅立葉轉換紅外光譜儀 29 3.4.2 場發射電子掃描顯微鏡 29 3.4.3 Zeta 電位及激光粒度分析儀 30 3.4.4 超導量子干涉磁量儀 30 3.5 標準溶液配製 30 3.6 樣品製備 31 3.7 藥品配製 31 3.8 磁性固相萃取流程 32 3.9 超高效液相層析儀(UPLC)及層析條件 33 第四章 結果與討論 34 4.1 磁性奈米粒子溶液濃度的測定 34 4.2 磁性強陰離子交換劑的特性分析 36 4.3 萃取條件的優化 41 4.3.1 關於提取溶劑的選擇 41 4.3.2 吸附劑MSAEA的用量 43 4.3.3 萃取時間 44 4.3.4 洗脫溶劑體積 46 4.3.5 洗脫時間 47 4.3.6 洗脫溶劑組成對回收率的影響 48 4.4 檢量線和檢出限 49 4.5 精密度 52 4.5 實際樣品分析 54 4.6 方法對比 56 第五章 結論與展望 58 第六章 參考文獻 60

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