簡易檢索 / 詳目顯示

研究生: 杜婷婷
Tu, Ting-Ting
論文名稱: 植物油微波輔助甲酯化方法建立及鑑定方法研究
Rapid microwave-assisted methylation and authentication of plant oil
指導教授: 凌永健
Ling, Yong-Chien
口試委員: 黃賢達
Huang, Shang-Da
吳家誠
Wu, J. C.
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: 2012
畢業學年度: 100
語文別: 中文
論文頁數: 92
中文關鍵詞: 植物油微波輔助甲酯化摻偽
相關次數: 點閱:4下載:0
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 台灣常見的食用油有大豆油、花生油、芝麻油、茶籽油等。不肖業者為降低成本,開始將低價油混入高價油中,嚴重損害了消費者的權益甚至健康。本研究期望能利用植物油中的脂肪酸組成,並輔以指紋圖譜技術建立一植物油鑑定系統,以保障消費者權益、打擊摻偽油品。為使前處理步驟符合環境友好的綠色化學趨勢,將微波輔助加熱技術成功應用於油樣的甲酯化反應中,利用GC-MS定性分析植物油之脂肪酸組成,建立30張樣品標準指紋圖譜以及11張油種標準指紋圖譜,並進行四種油種辨別分析系統的訓練與建立,分別為判別分析、相似度分析、群集分析以及本研究所創新之二維散佈圖分析。系統建立後,將大豆油以10%、25%、40%、50%等比例分別摻入苦茶油與黑芝麻油中作為摻偽樣品,對所建立的四個分析系統進行驗證及摻偽應用。其中以群集分析系統以及二維散佈圖分析系統有較好的辨別能力,並以二維散佈圖分析系統較具有摻偽鑑定能力,可進一步利用此系統推算摻偽比例,經線性迴歸分析後可得苦茶油摻偽樣品及黑芝麻油摻偽樣品之摻偽比例鑑定極限值 (LOA)分別為0.73%、1.94%。本研究成功合併此二種分析系統建立一植物油鑑定系統,並具有分析摻偽比例的潛力。


    There are many kinds of plant oils, such as soybean oil, peanut oil, sesame oil and camellia oil, which are common oils in Taiwan. Unscrupulous businessmen adulterate high-price oils with low-price oil to seek high profit, and which greatly damage the rights, interests and even health of consumers. To protect consumers and defeat the adulteration of commercial oils, this study was going to establish an authenticating system of plant oils. In order to make oil pretreatment fits the rule of green chemistry, microwave–assisted methylation was successfully applied. GC-MS was used to analyze fatty acid in oils qualitatively and establish 30 sample standard fingerprints and 11 species standard fingerprints. Discrimination analysis, similarity analysis, cluster analysis and the innovated 2-D diagram analysis of this study were trained and established by the fingerprints. After setting up these four analysis systems, camellia oil and black sesame oil were adulterated with ratio of 10%、25%、40%、50% of soybean oil as adulterated oil samples that were used to do the validation and application of adulterations of four systems. It shows that both cluster analysis and 2-D diagram analysis have better results, and latter can further get adulterated ratio of samples. Limit of authentication (LOA) of adulterated camellia oil and black sesame oil is 0.73% and 1.94%. In this study, we successfully established an authenticating system of plant oils by combining two analysis systems, and which could be utilized for adulterating ratio evaluated.

    第一章 緒論 1 1-1 前言 1 1-2 研究動機與目的 3 1-3 實驗設計與流程 3 第二章 文獻整理 6 2-1 油脂 6 2-2 植物油 8 2-3 脂肪酸 10 第三章 微波輔助甲酯化條件優化 15 3-1 實驗目的 15 3-2 實驗原理 16 3-2-1 甲酯化反應 16 3-2-2 微波加熱技術 17 3-2-3 氣相層析質譜儀 (GC-MS) 18 3-3 實驗設備與藥品 19 3-3-1 實驗設備 19 3-3-2 實驗藥品 19 3-3-3 藥品配製 19 3-4 實驗方法 20 3-4-1 微波輔助甲酯化條件優化 20 3-4-2 GC-MS分析 21 3-5 結果與討論 21 3-5-1 催化劑濃度優化 21 3-5-2 甲醇/油莫耳比優化 22 3-5-3 微波反應時間優化 23 3-5-4 反應體積縮小化 24 3-6 結論 25 第四章 植物油標準指紋圖譜的建立與辨別 28 4-1 實驗目的 28 4-2 實驗原理 29 4-2-1 指紋圖譜 29 4-2-2 標準指紋圖譜 30 4-2-3 指紋圖譜的數據處理 31 4-3 實驗設備與藥品 33 4-4 樣品來源 33 4-5 實驗方法 34 4-5-1 油樣前處理 34 4-5-2 GC-MS分析 34 4-5-3 指紋圖譜的建立與分析 35 4-6 結果與討論 37 4-6-1 標準指紋圖譜的建立 37 4-6-2 植物油種的鑑別 38 4-6-3 油種關聯性分析 39 4-7 結論 42 第五章 植物油指紋圖譜摻偽鑑定研究 55 5-1 實驗目的 55 5-2 實驗原理 56 5-3 實驗設備與藥品 56 5-4 樣品來源 56 5-5 實驗方法 56 5-5-1 摻偽樣品製備與前處理 56 5-5-2 GC-MS分析 56 5-5-3 指紋圖譜的建立與分析 56 5-6 結果與討論 57 5-6-1 樣品指紋圖譜的建立 57 5-6-2 判別分析系統驗證 57 5-6-3 相似度分析系統驗證 58 5-6-4 群集分析系統驗證 59 5-6-5 二維圖分析系統驗證 60 5-6-6 植物油鑑定系統建立 62 5-7 結論 62 第六章 總論與展望 76 第七章 參考文獻 78 附錄1 植物油樣品總離子層析圖 82 附錄2 植物油摻偽樣品總離子層析圖 90

    1. (a) Montealegre, C.; Marina Alrgre, M. L.; Garcia-Ruiz, C., Traceability Markers to the Botanical Origin in Olive Oils. J. Agric. Food Chem. 2010, 58 (1), 28-38;
    (b) Di Bella, G.; Maisano, R.; La Pera, L.; Lo Turco, V.; Salvo, F.; Dugo, G., Statistical characterization of Sicilian olive oils from the Peloritana and Maghrebian zones according to the fatty acid profile. J. Agric. Food Chem. 2007, 55, 6568–6574;
    (c) D’Imperio, M.; Dugo, G.; Alfa, M.; Mannina, L.; Segre, A. L., Statistical analysis on Sicilian olive oils. Food Chemistry 2007, 102, 956–965;
    (d) Brescia, M. A.; Alviti, G.; Liuzzi, V.; Sacco, A., Chemometrics classification of olive cultivars based on compositional data of oils. J. Am. Oil Chem. Soc. 2003, 80, 945-950.

    2. AOAC Official Method 996-06, Fat (Total, Saturated and Monounsaturated) in Foods. In Official Methods of Analysis of AOAC International. 17th edition., 2001; Vol. 2.

    3. (a) Dasgupta, A.; Banerjee, P.; S, M., Use of microwave irradiation for rapid transesterification of lipids and accelerated synthesis of fatty acyl pyrrolidides for analysis by gas chromtography–mass spectrometry: study of fatty acid profiles of olive oil, evening primrose oil, fish oils and phospholipids from mango pulp. Chem Phys Lipids 1992, 62, 281-291;
    (b) Dasgupta, A.; Banerjee, P., Microwave induced rapid preparation of acetyl, trifluoroacetyl and tert-butyl dimethylsilyl derivatives of fatty alcohols and diacylglycerols for gas chromatography-mass spectrometric analysis. Chem Phys Lipids 1993, 65, 217 - 224;
    (c) Dasgupta, A.; Thompson, W.; Malik, S., Use of microwave irradiation for rapid synthesis of perfluorooctanoyl derivatives of fatty alcohols, a newderivative for gas chromatography-mass spectrometric and fast atom bombardment mass spectrometric study. J Chromatogr A 1994, 685, 279–285;
    (d) Dasgupta, A.; Macaulay, R., Microwave-induced rapid synthesis of 4-carbethoxyhexafluorobutyryl derivatives of fatty alcohols – a novel derivative for gas chromatography-chemical ionization mass spectrometric study. J Chromatogr A 1995, 695, 136–141.

    4. (a) Ewald, A.; Peters, F.; Weise, M.; Maurer, H., Studies on the metabolism and toxicological detection of the designer drug 4-methylthioamphetamine (4-MTA) in human urine using gas chromatography–mass spectrometry. . J Chromatogr B 2005, 824, 123–131;
    (b) Theobald, D.; Staack, R.; Puetz, M.; Maurer, H., New designer drug 2,5-dimethoxy-4-ethylthio-β-phenethylamine (2CT-2): studies on its metabolism and toxicological detection in rat urine using gas chromatography/mass spectrometry. J Mass Spectrom 2005, 40, 1157–1172.

    5. Soederholm, S. L.; Damm, M.; Kappe, C. O., Microwave-assisted derivatization procedures for gas chromatography/mass spectrometry analysis. Molecular Diversity 2010, 14 (4), 869-888.

    6. 林秀卿; 林彥斌, 食物學概論. 2007.

    7. Cindy, Do you Saponify. Sagescript Institute & Colorado Aromatics 2010.

    8. 茹絲˙馮˙布朗史萬格, 植物油全書:認識40種植物油的功效. 2009.

    9. (a) 李桂華, 油料油脂檢驗與分析. 北京:化學工業出版社 2006;
    (b) 唐芳, 植物油脂肪酸指紋圖譜的建立及摻假識別方法的研究. 食品科學 2011, 碩士.

    10. Zhang, Y.; Li, Y.; Mei, D.; Hu*, Q., Advances in Lipid Research of Rapeseed. Chin Bull Bot 2007, 24, 435-443.

    11. 台大農藝學系; 種子研究室, 油脂累積. http://seed.agron.ntu.edu.tw/vtseed/formation/for4.htm.

    12. 韓燕; 宋歡, 膳食脂肪生理功能及脂肪酸膳食的研究進展. 中國食物與營養 2007, 5, 54-56.

    13. 蔡妙顏; 李冰, 膳食中的脂肪酸平衡. 糧油食品科技 2008, 4, 9-11.

    14. Stefanoudaki, E.; Kotsifaki, F.; Koutsaftakis, A., Classification of virgin olive oils of the two major cretan cultivars based on their fatty acids composition. J. Am. Oil Chem. Soc. 1999, 76, 623-626.

    15. (a) 張越華; 曾和平, 脂肪酸在生命過程中的作用研究進展. 中國油脂 2006, 12, 11-13;
    (b) 張美麗; 吳繼紅, 食品功能成分的製備及其應用. 中國輕工業出版社 2007.

    16. U.S. Soybean Export Council, http://www.asaimtaiwan.org/p4-1-1.php?flag=about-15.

    17. Zu, Y.; Zhang, S.; Fu, Y.; Liu, W.; Liu, Z.; Luo, M.; Efferth, T., Rapid microwave-assisted transesterification for the preparation of fatty acid methyl esters from the oil of yellow horn (Xanthoceras sorbifolia Bunge.). European Food Research and Technology 2009, 229 (1), 43-49.

    18. Kappe, C.; Dallinger, D., Controlled microwave heating in modern organic synthesis: highlights from the 2004–2008 literature. Mol Divers 2009, 13, 71–193.

    19. (a) Maurer, H.; Pfleger, K.; Weber, A., Mass spectral and GC data of drugs, poisons, pesticides, pollutants and their metabolites. . 3rd edn. Wiley-VCH, Weinheim 2007;
    (b) Maurer, H., Hyphenated mass spectrometric techniques: indispensable tools in clinical and forensic toxicology and in doping control. J Mass Spectrom 2006, 41, 1399–1413.

    20. David, F.; Sandra, P.; Vickers, A. K., Column selection for the analysis of fatty acid methyl esters. Agilent Technologies 2006.

    21. 謝志誠, 生質柴油之技術與文獻探討. 分享與跨越門檻與障礙 2007.

    22. (a) Kappe, C., Microwave dielectric heating in synthetic organic chemistry. Chem Soc Rev 2008, 37, 1127-1139;
    (b) Gabriel, C.; Gabriel, S.; Grant, E., Dielectric parameters relevant to microwave dielectric heating. Chem Soc Rev 1998, 27, 213–224.

    23. 何佩俞; 凌永健, 以代謝物指紋圖譜區別紅茶產源. 國立清華大學碩士論文 2010.

    24. (a) 鄭百乘; 凌永健, 台灣地區周界環境中戴奧辛指紋圖譜和分佈之探討. 國立清華大學博士論文 2002;
    (b) 袁玉潔; 凌永健, 氣相層析同位素比質譜儀及頂空氣相層析質譜儀鑑定酒類摻假之研究 國立清華大學碩士論文 2009;
    (c) 陳思偉; 凌永健, 新竹科學工業園區高科技產業廢水分析與對承受水體之影響研究. 國立清華大學博士論文 2004.

    25. Idea 皮紋科學中心 http://www.idea-print.com.tw/evaluation13.php.

    26. 朱潘煒, 紹興加飯黃酒風味物質指紋圖譜的建立. 浙江大學碩士論文 2009.

    27. 袁潔; 尹京苑, 指紋圖譜在白酒中的應用研究發展. 食品科學 2008, 29 (11), 680-683

    28. 李靈霞; 師伯省, 指紋圖譜技術的應用概況. 健康大視野 2006, 8, 42.

    29. 趙青, 中藥色譜指紋圖譜輔助分析系統. 瀋陽藥科大學碩士論文 2006.

    30. 梁逸臣; 杜一平, 分析化學計量法. 重慶大學出版社 2004.

    31. 張玉榮; 張秀華, 主成分分析法綜合評價大米的食味品質. 河南工業大學學報 2008, 29 (5), 208.

    32. 范璐, 利用脂肪酸特徵分析區分五種植物油脂. 河南工業大學學報: 自然科學版 2007, 5, 26-27.

    33. Zhang, Q.; Liu, C.; Sun, Z.; Hu, X.; Shen, Q.; Wu, J., Authentication of edible vegetable oils adulterated with used frying oil by Fourier Transform Infrared Spectroscopy. Food Chemistry 2012, 132, 1607-1613.

    34. Vlachos, N.; Skopelitis, Y.; Psaroudaki, M.; Konstantinidou, V.; Chatzilazarou, A.; Tegou, E., Applications of Fourier transform-infrared spectroscopy to edible oils. Analytica Chimica Acta 2006, 573-574, 459-465.

    無法下載圖示 全文公開日期 本全文未授權公開 (校內網路)
    全文公開日期 本全文未授權公開 (校外網路)

    QR CODE