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研究生: 邱若濃
Chiu, Juo-Nung
論文名稱: 以微波輔助萃取技術結合氣相層析質譜儀分析皮革製品中抗生藥劑成份之研究
Microwave-Assisted Extraction Gas Chromatography–Mass Spectrometry Analysis of Biocides in Leather Products
指導教授: 凌永健
Ling, Yong-Chien
口試委員:
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: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 65
中文關鍵詞: 氣相層析質譜儀抗生藥劑皮革製品
外文關鍵詞: GC-MS, biocides, leather products
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  • 自2006年起,全球各地陸續出現消費者因接觸添加抗生藥劑(Biocides)富馬酸二甲酯(Dimethyl Fumarate)之皮革製品,造成接觸性皮膚炎與急性呼吸疾病等危害,引起社會大眾的恐慌。皮革製品為防止發霉、腐敗,在製造過程中常添加抗生藥劑以維持產品的品質,但無論是製造過程中產生的廢水、廢料排放於環境中,或是直接接觸此類產品,皆使我們暴露於抗生藥劑之風險當中,因此市售皮革製品中的抗生藥劑成分與濃度,值得我們探討。
    本研究成功地開發微波輔助萃取技術,萃取皮革製品中富馬酸二甲酯、富馬酸二乙酯、苯並噻唑、對叔丁基苯酚四種抗生藥劑成分,以萃取溶劑甲醇與丙酮混合溶劑(50:50 v/v)、萃取溶劑體積15 mL、微波功率300W、萃取溫度110℃,萃取20分鐘,以中性氧化鋁固相萃取匣淨化的最佳化條件進行萃取,可達到89%以上之回收率,方法偵測極限在0.02~0.06μg/g之間,不僅有良好的回收率且可減少溶劑的用量與萃取的時間。應用於13件市售皮革製品之真實樣品的分析,1件有富馬酸二甲酯的檢出,其濃度為0.5μg/g,超過歐盟所規定之標準0.1 μg/g;13件樣品皆檢出苯並噻唑,濃度在0.04~17.4μg/g之間;8件樣品皆有對叔丁基苯酚的檢出,濃度在0.3~13.0μg/g之間,顯示本研究所開發之微波輔助萃取結合氣相層析質譜儀應用於皮革製品中抗生藥劑成份的分析具有完整確認與可靠檢驗之特點。


    目錄 I 表目錄 III 圖目錄 IV 第一章 緒論 1 1-1前言 1 1-2 研究動機 2 1-3皮革中常見的抗生藥劑 2 1-3-1富馬酸酯類 3 1-3-2苯並噻唑 4 1-3-3對叔丁基苯酚 5 1-3-4皮革萃取方法之回顧 5 1-4微波輔助萃取技術 6 1-4-1微波輔助萃取的原理 7 1-4-2微波輔助萃取裝置介紹 7 1-4-3微波萃取技術之應用 8 1-5氣相層析質譜儀 9 1-6研究目的 10 第二章 實驗方法 16 2-1試藥 16 2-1-1待測物標準品與內標準品 16 2-1-2其他試藥 16 2-1-3標準溶液配製 16 2-2樣品 17 2-3實驗器材與儀器設備 17 2-3-1實驗器材 17 2-3-2儀器設備 17 2-4實驗流程 18 2-4-1微波輔助萃取條件之探討 18 2-4-1.1萃取溶劑種類之探討 19 2-4-1.2萃取溶劑體積之探討 19 2-4-1.3萃取溫度之探討 20 2-4-1.4微波功率之探討 20 2-4-1.5萃取時間之探討 21 2-4-1.6淨化固相萃取匣種類之探討 21 2-4-2 建立GC-MS分析方法 21 2-4-2.1建立檢量線 22 2-4-2.2方法偵測極限 22 2-4-3 微波輔助萃取法回收率測試 23 2-4-4 以GC-MS分析市售真實皮革樣品中抗生藥劑成分 23 2-4-4.1 市售真實樣品的分析 23 2-4-4.2 標準添加法 24 第三章 結果與討論 31 3-1微波輔助萃取參數最佳化 31 3-1-1萃取溶劑種類 31 3-1-2萃取溶劑體積 32 3-1-3萃取溫度 32 3-1-4微波功率 32 3-1-5萃取時間 33 3-1-6淨化固相萃取匣種類 33 3-2儀器檢量線範圍與線性 34 3-3方法偵測極限(MDL) 35 3-4微波輔助萃取之回收率 36 3-5 GC-MS分析市售真實皮革樣品中抗生藥劑成分 37 3-5-1 真實樣品的定量結果 37 3-5-2 標準添加法 38 第四章 結論 60 第五章 參考文獻 61

    1. Williams, J. D. L.; Coulson, I. H.; Susitaival, P.; Winhoven, S. M.,
    An outbreak of furniture dermatitis in the UK. British Journal of
    Dermatology 2008, 159 (1), 233-234.

    2. Rantanen, T., The cause of the Chinese sofa/chair dermatitis
    epidemic is likely to be contact allergy to dimethylfumarate, a
    novel potent contact sensitizer. British Journal of Dermatology
    2008, 159 (1), 218-221.

    3. Anastas, P. T., Green Chemistry and the Role of Analytical
    Methodology Development. Critical Reviews in Analytical
    Chemistry 1999, 29 (3), 167 - 175.

    4. EPA, U., US Environmental Protection Agency, Office of
    Pollution Prevention and Toxics . Green Chemistry Program Fact
    Sheet., #EPA 742-F-02-003.

    5. Keith, L. H.; Gron, L. U.; Young, J. L., Green Analytical
    Methodologies. Chemical Reviews 2007, 107 (6), 2695-2708.

    6. Official Journal of the European Union, L74 (17 March 2009) 32.

    7. 中國黑心沙發 引發皮膚潰爛.
    http://www.libertytimes.com.tw/2010/new/jan/21/today-life13.htm.

    8. EU, Directive 98/8/EC of the European Parliament and of the
    Council of 16 February 1998 concerning the placing of biocidal
    products on the market.

    9. Rajendran, S.; Hajira Parveen, K. M., Insect infestation in stored
    animal products. Journal of Stored Products Research 2005, 41
    (1), 1-30.

    10. Gershon, H.; Shanks, L., Antifungal properties of
    2-bromo-3-fluorosuccinic acid esters and related compounds.
    Journal of Medicinal Chemistry 1977, 20 (4), 606-609.

    11. Lammintausta, K.; Zimerson, E.; Winhoven, S.; Susitaival, P.;
    Hasan, T.; Gruvberger, B.; Williams, J.; Beck, M.; Bruze, M.,
    Sensitization to dimethyl fumarate with multiple concurrent
    patch test reactions. Contact Dermatitis 2010, 62 (2), 88-96.

    12. Gimenez-Arnau, A.; Silvestre, J. F.; Mercader, P.; De la Cuadra,
    J.; Ballester, I.; Gallardo, F.; Pujol, R. M.; Zimerson, E.; Bruze,
    M., Shoe contact dermatitis from dimethyl fumarate: clinical
    manifestations, patch test results, chemical analysis, and source
    of exposure. Contact Dermatitis 2009, 61 (5), 249-260.

    13. Xin-xia, M. H.-w. Z. D.-y. H., HPLC和GC-MS檢測皮革中富馬
    酸二甲酯效果對比. Leather Science And Engineering 2009, 19 (3).

    14. 曹華娟, 馮家力, 潘振球, 王春蛾, 李劍, 魯兵, 食品中富馬酸二
    甲酯殘留量的GC-MS法測定. 實用預防醫學 2005, 12 (01).

    15. Xi-dan, K. Z.-m. L. J.-y. W., Rapid Determination of Dimethyl
    Fumarate in Food Poisoning by Gas Chromatographic-Mass
    Spectrometry. 2007.

    16. Lamas, J. P.; Sanchez-Prado, L.; Regueiro, J.; Llompart, M.;
    Garcia-Jares, C., Determination of dimethyl fumarate and other
    potential allergens in desiccant and antimould sachets.
    Anal.Bioanal. Chem. 2009, 394 (8), 2231-2239.

    17. Narizzano, R.; Risso, F.; Venturelli, G.; Devia, C.; Carlini, E.;
    Maggiolo, S., Gas-chromatography-mass spectrometry analysis of
    dimethyl fumarate in consumer products. Journal of
    Chromatography A 2009, 1216 (39), 6762-6766.

    18. Kloepfer, A.; Jekel, M.; Reemtsma, T., Occurrence, sources, and fate
    of benzothiazoles in municipal wastewater treatment plants. Environ.
    Sci. Technol. 2005, 39 (10), 3792-3798.

    19. Orlita, A., Microbial biodeterioration of leather and its control: a
    review. International Biodeterioration & Biodegradation 2004, 53
    (3), 157-163.

    20. Nawrocki, S. T.; Drake, K. D.; Watson, C. F.; Foster, G. D.; Maier, K.
    J., Comparative aquatic toxicity evaluation of
    2-(thiocyanomethylthio)benzothiazole and selected degradation
    products using Ceriodaphnia dubia. Arch. Environ. Contam. Toxicol.
    2005, 48 (3), 344-350.

    21. Kloepfer, A.; Jekel, M.; Reemtsma, T., Determination of
    benzothiazoles from complex aqueous samples by liquid
    chromatography-mass spectrometry following solid-phase
    extraction.Journal of Chromatography A 2004, 1058 (1-2), 81-88.

    22. van Leerdam, J. A.; Hogenboom, A. C.; van der Kooi, M. M. E.; de
    Voogt, P., Determination of polar 1H-benzotriazoles and
    benzothiazoles in water by solid-phase extraction and liquid
    chromatography LTQ FT Orbitrap mass spectrometry. International
    Journal of Mass Spectrometry 2009, 282 (3), 99-107.

    23. Jover, E.; Matamoros, V.; Bayona, J. M., Characterization of
    benzothiazoles, benzotriazoles and benzosulfonamides in aqueous
    matrixes by solid-phase extraction followed by comprehensive
    two-dimensional gas chromatography coupled to time-of-flight mass
    spectrometry. Journal of Chromatography A 2009, 1216 (18),
    4013-4019.

    24. Bellavia, V.; Natangelo, M.; Fanelli, R.; Rotilio, D., Analysis of
    benzothiazole in Italian wines using headspace solid-phase
    microextraction and gas chromatography-mass spectrometry. J.
    Agric. Food Chem. 2000, 48 (4), 1239-1242.

    25. Helaleh, M. I. H.; Takabayashi, Y.; Fujii, S.; Korenaga, T., Gas
    chromatographic-mass spectrometric method for separation and
    detection of endocrine disruptors from environmental water samples.
    Analytica Chimica Acta 2001, 428 (2), 227-234.

    26. Saito, I.; Onuki, A.; Seto, H., Indoor air pollution by alkylphenols in
    Tokyo. Indoor Air 2004, 14 (5), 325-332.

    27. Haavisto, T. E.; Adamsson, N. A.; Myllymaki, S. A.; Toppari, J.;
    Paranko, J., Effects of 4-tert-octylphenol, 4-tert-butylphenol, and
    diethylstilbestrol on prenatal testosterone surge in the rat. Reprod.
    Toxicol. 2003, 17 (5), 593-605.

    28. Rani, Z.; Hussain, I.; Haroon, T. S., Common allergens in shoe
    dermatitis: our experience in Lahore, Pakistan. International Journal
    of Dermatology 2003, 42 (8), 605-607.

    29. Zimerson, E.; Bruze, M., Sensitizing capacity of some trimers in
    p-tert-butylphenol-formaldehyde resin. Contact Dermatitis 2002, 47
    (1), 40-46.

    30. Badoil, L.; Benanou, D., Characterization of volatile and semivolatile
    compounds in waste landfill leachates using stir bar sorptive
    extraction-GC/MS. Anal. Bioanal. Chem. 2009, 393 (3), 1043-1054.

    31. Rudel, R. A.; Camann, D. E.; Spengler, J. D.; Korn, L. R.; Brody, J.
    G., Phthalates, alkylphenols, pesticides, polybrominated diphenyl
    ethers, and other endocrine-disrupting compounds in indoor air and
    dust. Environ. Sci. Technol. 2003, 37 (20), 4543-4553.

    32. Font, J.; Marsal, A., Determination of organochlorine pesticides in
    skins and leather by gas chromatography. Journal of
    Chromatography A 1998, 811 (1-2), 256-260.

    33. Meyer, A.; Kleibohmer, W., Determination of pentachlorophenol in
    leather using supercritical fluid extraction with in situ derivatization.
    Journal of Chromatography A 1995, 718 (1), 131-139.

    34. Favaro, G.; De Leo, D.; Pastore, P.; Magno, F.; Allardin, A. B.,
    Quantitative determination of chlorophenols in leather by
    pressurized liquid extraction and liquid chromatography with
    diode-array detection. Journal of Chromatography A 2008, 1177 (1),
    36-42.

    35. Ganeshjeevan, R.; Chandrasekar, R.; Kadigachalam, P.;
    Radhakrishnan, G., Rapid, one-pot derivatization and distillation of
    chlorophenols from solid samples with their on-line enrichment.
    Journal of Chromatography A 2007, 1140 (1-2), 168-173.

    36. Liu Ying-feng, Z M.h., Li Dan, Zhai Cui-ping, Li Quan-zhong,
    Zheng Jian-guo, Yue Da-lei, Xiao Da-hui, Determination of
    Dimethyl Fumarate in Leather and Leather Products by C/MS-SIM.
    質譜學報 2009, 30.

    37. Camel, V., Microwave-assisted solvent extraction of environmental
    samples. TrAC Trends in Analytical Chemistry 2000, 19 (4),
    229-248.

    38. 陳崇宇,李茂榮, 微波萃取技術之應用. 科儀新知 2003, 25 (2),
    72-82.

    39. Sanchez-Prado, L.; Garcia-Jares, C.; Llompart, M.,
    Microwave-assisted extraction: Application to the determination of
    emerging pollutants in solid samples. Journal of Chromatography A
    2010, 1217 (16), 2390-2414.

    40. Ganzler, K.; Salgo, A.; Valko, K., Microwave extraction : A novel
    sample preparation method for chromatography. Journal of
    Chromatography A 1986, 371, 299-306.

    41. Li, K.; Landriault, M.; Fingas, M.; Llompart, M., Pressurised solvent
    extraction of environmental organic compounds in soils using a
    supercritical fluid extractor. Analusis 1998, 26 (9), 365-369.

    42. Tomaniova, M.; Hajslova, J.; Pavelka, J.; Kocourek, V.; Holadova,
    K.; Klimova, I., Microwave-assisted solvent extraction -- a new
    method for isolation of polynuclear aromatic hydrocarbons from
    plants. Journal of Chromatography A 1998, 827 (1), 21-29.

    43. Chee, K. K.; Wong, M. K.; Lee, H. K., Microwave-assisted solvent
    elution technique for the extraction of organic pollutants in water.
    Analytica Chimica Acta 1996, 330 (2-3), 217-227.

    44. Hummert, K.; Vetter, W.; Luckas, B., Fast and effective sample
    preparation for determination of organochlorine compounds in fatty
    tissue of marine mammals using microwave extraction.
    Chromatographia 1996, 42 (5-6), 300-304.

    45. Eskilsson, C. S.; Davidsson, R.; Mathiasson, L., Harmful azo
    colorants in leather - Determination based on their cleavage and
    extraction of corresponding carcinogenic aromatic amines using
    modern extraction techniques. Journal of Chromatography A 2002,
    955 (2), 215-227.

    46. Ahlstrom, L. H.; Raab, J.; Mathiasson, L., Application of standard
    addition methodology for the determination of banned azo dyes in
    different leather types. Analytica Chimica Acta 2005, 552 (1-2),
    76-80.

    47. Font, N.; Hernandez, F.; Hogendoorn, E. A.; Baumann, R. A.; van
    Zoonen, P., Microwave-assisted solvent extraction and
    reversed-phase liquid chromatography-UV detection for screening
    soils for sulfonylurea herbicides. Journal of Chromatography A
    1998, 798 (1-2), 179-186.

    48. 中華民國環境保護署環境檢驗所, 環境檢驗方法偵測極限測定指
    引. 2005.

    49. 中華民國環境保護署環境檢驗所,NIEA M165.00C. 2002.

    50. 中華民國環境保護署環境檢驗所, NIEA D901.01B. 2009.

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