簡易檢索 / 詳目顯示

研究生: 鄭琦勳
CHENG, CHI-HSUN
論文名稱: 以飛行時間二次離子質譜儀分析食用油組成、斑馬魚內銅重金屬及塑膠製品中之添加劑
Analysis of Copper in Danio Rerio, Plastic Additives, and Adulteration of Edible Oil by TOF-SIMS
指導教授: 凌永健
Ling, Yong-Chien
口試委員: 陳貴通
Tan, Kui-Thong
黃賢達
Huang, Shang-Da
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: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 60
中文關鍵詞: 飛行時間二次離子質譜儀斑馬魚食用油塑膠添加劑
外文關鍵詞: TOF-SIMS, Danio Rerio, Edible Oil, Plastic Additives
相關次數: 點閱:2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
  • 當發生食用油摻偽事件、探討重金屬對生物體的影響、或是日常塑膠用品含環境荷爾蒙的塑膠添加劑時,相較於以往只針對單一目標,如今,該如何針對有害物質進行非目標性的檢測亦備受注目。近年來飛行時間二次質譜儀除了被廣泛用於分析無機材料表面外,因可同時偵測有機分子,故在生化方面亦有相當廣泛的應用。
    因此,本篇研究的第一部分將飛行時間二次離子質譜儀應用於77件動物油品的檢測,並配合階層式群集分析、k平均演算法、與主成分分析進行油種的判別,並成功區分出豬油、奶油、魚油三大類油種。第二部分有別於以往針對生物體受重金屬汙染時,進行總金屬濃度的探討,本研究結合了生物切片與質譜技術,可成功更進一步觀察到銅在斑馬魚體內的分布情形,進而驗證某些毒理機制的論述。最後我們針對28件塑膠製品進行非目標性分析,相較於傳統儀器分析時需考慮到使用溶劑的種類及萃取效率,本實驗不需使用溶劑即可進行非目標性分析,發現其中10件樣品含有對苯二甲酸二異辛酯(DOTP),4件含有鄰苯二甲酸二異壬酯(DINP)、1件含有鄰苯二甲酸二(2-乙基己基)酯(DEHP)。


    When it comes to adulteration of cooking oil, impact of heavy metals on the organism, or the daily plastic products containing additives with endocrine disrupting chemicals, non-target detection of harmful substances also catch our attention. In addition to being widely used to analyze the surface of inorganic materials, the time-of-flight secondary mass spectrometry has a wide range of applications in biochemistry because of simultaneous detection of organic molecules.
    Therefore, the first part of this study will focus on adulteration of 77 animal oils. With hierarchical cluster analysis, K-means algorithm, and principal component analysis for oil species identification, we successfully distinguish eight of five types of oils such as lard, butter and fish oil. Different from the previous measurement on the total metal concentration when the organism is contaminated by heavy metals, our study combines bio-slice and mass spectrometry technology to successfully observe the distribution of copper in zebrafish and may validate certain toxicological mechanisms. In the last part, we conducted non-target analysis on 28 plastic products. Compared with traditional instrument analysis, we have little concern for the type of solvent used and extraction efficiency since our pretreatment is solvent-free and suitable for non-target analysis. It also comes to our concern that, four of twenty-eight plastic products contains DINP, one contain DEHP, which are endocrine disrupting chemicals and ten of twenty-eight products contains DOTP. It may enter human body under long-term use.

    目錄 第一章、動物油指紋圖譜建立與識別 1 1-1 研究動機與目的 1 1-2 油脂概述 4 1-2-1脂肪酸 4 1-2-2 三酸甘油酯 5 1-2-3 二酸甘油酯 5 1-3 儀器原理 5 1-3-1離子源 7 1-3-2質量分析器 7 1-3-3電子槍 8 1-4 多階層多變異統計分析 8 1-4-1 多階層式群集分析 9 1-4-2 k-平均演算法 10 1-4-3 主成分分析 11 1-5 實驗部分 12 1-5-1 樣品資訊 12 1-5-2研究方法探討 12 1-5-3質譜校正 13 1-6 結果與討論 13 1-6-1方法測試 13 1-6-2 訊號選擇 13 1-6-3 離子強度之歸一化 14 1-6-4 以多階層多變數統計分析識別動物油組成 15 1-6-5將該模型應用於食物中的動物油脂 16 1-7 結論與未來展望 17 第二章、偵測斑馬魚體內銅分布 29 2-1研究動機與目的 29 2-2 實驗條件及方法 30 2-2-1斑馬魚 30 2-2-2實驗藥品 31 2-2-3前處理方法探討 31 2-3 實驗結果與討論 33 2-4 結論與展望 34 第三章、非目標性識別塑膠中添加劑與分析 39 3-1 研究動機與目的 39 3-2 實驗方法與樣品資訊 40 3-2-1樣品資訊: 40 3-2-2實驗方法 41 3-3 實驗結果與討論 41 3-3-1 非目標性塑膠添加劑分析 41 3-3-2塑膠中添加劑之縱深分布與轉移情形 43 3-4 結果與展望 44 第四章、總結與展望 53 第五章、參考文獻 54

    1. 食品中脂肪酸之檢驗方法(Method of Test for Fatty Acids in Food),衛生福利部部授食字第1021950978號公告.
    2. Liao, C.-D.; Peng, G.-J.; Ting, Y.; Chang, M.-H.; Tseng, S.-H.; Kao, Y.-M.; Lin, K.-F.; Chiang, Y.-M.; Yeh, M.-K.; Cheng, H.-F., Using phytosterol as a target compound to identify edible animal fats adulterated with cooked oil. Food Control 2017, 79, 10-16.
    3. Casale, M.; Bagnasco, L.; Palermo, R.; Campolongo, G., Class-modeling for the characterization of Italian red wine.
    4. G. Zarkadas, C.; Gagnon, C.; Poysa, V.; Khanizadeh, S.; R. Cober, E.; Chang, V.; Gleddie, S., Protein quality and identification of the storage protein subunits of tofu and null soybean genotypes, using amino acid analysis, one- and two-dimensional gel electrophoresis, and tandem mass spectrometry. 2007, 40, 111-128.
    5. Parisotto, G.; Ferrão, M. F.; Müller, A. L. H.; Müller, E. I.; Santos, M. F. P.; Guimarães, R. C. L.; Dias, J. C. M.; Flores, É. M. M., Total Acid Number Determination in Residues of Crude Oil Distillation Using ATR-FTIR and Variable Selection by Chemometric Methods. Energy & Fuels 2010, 24 (10), 5474-5478.
    6. Zhang, J.; Zhang, X.; Dediu, L.; Victor, C., Review of the current application of fingerprinting allowing detection of food adulteration and fraud in China. Food Control 2011, 22 (8), 1126-1135.
    7. 盧海燕; 王欣; 趙婷婷; 劉寶林, 葵花籽油熱氧化過程的 1H-NMR指紋圖譜與LF-NMR弛豫特性研究。現代食品科技1H-NMR指紋圖譜與LF-NMR弛豫特性研究。現代食品科技. 現代食品科技 2014, 30 (8), 43-50.
    8. Aparicio, R.; Aparicio-Ruı́z, R., Authentication of vegetable oils by chromatographic techniques. Journal of Chromatography A 2000, 881 (1), 93-104.
    9. Ng, T.-T.; So, P.-K.; Zheng, B.; Yao, Z.-P., Rapid screening of mixed edible oils and gutter oils by matrix-assisted laser desorption/ionization mass spectrometry. Analytica Chimica Acta 2015, 884, 70-76.
    10. Hagenhoff, B., High Resolution Surface Analysis by TOF-SIMS. Microchimica Acta 2000, 132 (2), 259-271.
    11. Fisher R, A., THE USE OF MULTIPLE MEASUREMENTS IN TAXONOMIC PROBLEMS. Annals of Eugenics 1936, 7 (2), 179-188.
    12. Mateos-Aparicio, G., Partial Least Squares (PLS) Methods: Origins, Evolution, and Application to Social Sciences. Communications in Statistics - Theory and Methods 2011, 40 (13), 2305-2317.
    13. Pearson, K., LIII. On lines and planes of closest fit to systems of points in space. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science 1901, 2 (11), 559-572.
    14. 宋卓勳, 飛行時間式二次離子質譜術與二次離子質譜術於感熱紙、矽元件、食用油中無機、有機表面與博膜直接分析之研究. 106.
    15. Gui, M. M.; Lee, K. T.; Bhatia, S., Feasibility of edible oil vs. non-edible oil vs. waste edible oil as biodiesel feedstock. Energy 2008, 33 (11), 1646-1653.
    16. Vickerman, J. C.; Briggs, D., ToF-SIMS: Surface analysis by mass spectrometry. IM: 2001.
    17. Sodhi, R. N., Time-of-flight secondary ion mass spectrometry (TOF-SIMS):—versatility in chemical and imaging surface analysis. Analyst 2004, 129 (6), 483-487.
    18. Mas, S.; Perez, R.; Martinez-Pinna, R.; Egido, J.; Vivanco, F., Cluster TOF-SIMS imaging: A new light for in situ metabolomics? ROTEOMICS 2008, 8 (18), 3735-3745.
    19. Plog, C.; Gerhard, W., Secondary ion production by latent energy of neutrally emitted particles. Surface Science 1985, 152 (1), 127-134.
    20. Passarelli, M. K.; Winograd, N., Lipid imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Biochimica et Biophysica Acta (BBA) - Molecular and Cell Biology of Lipids 2011, 1811 (11), 976-990.
    21. Ninomiya, S.; Ichiki, K.; Yamada, H.; Nakata, Y.; Seki, T.; Aoki, T.; Matsuo, J., Molecular depth profiling of multilayer structures of organic semiconductor materials by secondary ion mass spectrometry with large argon cluster ion beams. Rapid Communications in Mass Spectrometry: An International Journal Devoted to the Rapid Dissemination of Up‐to‐the‐Minute Research in Mass Spectrometry 2009, 23 (20), 3264-3268.
    22. Hierarchical Cluster Analysis. In Wiley StatsRef: Statistics Reference Online.
    23. Jain, A. K., Data clustering: 50 years beyond K-means. Pattern recognition letters 2010, 31 (8), 651-666.
    24. Sprague, J. B., Measurement of pollutant toxicity to fish I. Bioassay methods for acute toxicity. Water Research 1969, 3 (11), 793-821.
    25. S., S. N.; Stephanie, P.; B., K. T., Zebrafish—As an integrative model for twenty-first century toxicity testing. Birth Defects Research Part C: Embryo Today: Reviews 2011, 93 (3), 256-267.
    26. Rougier, F.; Menudier, A.; Bosgiraud, C.; Nicolas, J. A., Copper and Zinc Exposure of Zebrafish,Brachydanio rerio(Hamilton–Buchaman): Effects in Experimental Listeria Infection. Ecotoxicology and Environmental Safety 1996, 34 (2), 134-140.
    27. Weissleder, R.; Tung, C.-H.; Mahmood, U.; Bogdanov Jr, A., In vivo imaging of tumors with protease-activated near-infrared fluorescent probes. Nature Biotechnology 1999, 17, 375.
    28. Gao, X.; Cui, Y.; Levenson, R. M.; Chung, L. W. K.; Nie, S., In vivo cancer targeting and imaging with semiconductor quantum dots. Nature Biotechnology 2004, 22, 969.
    29. Kobayashi, H.; Ogawa, M.; Alford, R.; Choyke, P. L.; Urano, Y., New Strategies for Fluorescent Probe Design in Medical Diagnostic Imaging. Chemical Reviews 2010, 110 (5), 2620-2640.
    30. Griffitt, R. J.; Weil, R.; Hyndman, K. A.; Denslow, N. D.; Powers, K.; Taylor, D.; Barber, D. S., Exposure to Copper Nanoparticles Causes Gill Injury and Acute Lethality in Zebrafish (Danio rerio). Environmental Science & Technology 2007, 41 (23), 8178-8186.
    31. Fisher, G. L.; Bruinen, A. L.; Ogrinc Potočnik, N.; Hammond, J. S.; Bryan, S. R.; Larson, P. E.; Heeren, R. M. A., A New Method and Mass Spectrometer Design for TOF-SIMS Parallel Imaging MS/MS. Analytical Chemistry 2016, 88 (12), 6433-6440.
    32. Böhme, S.; Baccaro, M.; Schmidt, M.; Potthoff, A.; Stärk, H.-J.; Reemtsma, T.; Kühnel, D., Metal uptake and distribution in the zebrafish (Danio rerio) embryo: differences between nanoparticles and metal ions. Environmental Science: Nano 2017, 4 (5), 1005-1015.
    33. Turbett, G. R.; Sellner, L. N., The Use of Optimal Cutting Temperature Compound Can Inhibit Amplification by Polymerase Chain Reaction. Diagnostic Molecular Pathology 1997, 6 (5), 298-303.
    34. Kimura, N.; Mizokami, A.; Oonuma, T.; Sasano, H.; Nagura, H., Immunocytochemical localization of androgen receptor with polyclonal antibody in paraffin-embedded human tissues. Journal of Histochemistry & Cytochemistry 1993, 41 (5), 671-678.
    35. Sato, Y.; Mukai, K.; Watanabe, S.; Goto, M.; Shimosato, Y., The AMeX method. A simplified technique of tissue processing and paraffin embedding with improved preservation of antigens for immunostaining. The American journal of pathology 1986, 125 (3), 431.
    36. Peters, S. R., A practical guide to frozen section technique, 2010.
    37. Carter, C. L.; Jones, J. W.; Farese, A. M.; MacVittie, T. J.; Kane, M. A., Lipidomic dysregulation within the lung parenchyma following whole-thorax lung irradiation: Markers of injury, inflammation and fibrosis detected by MALDI-MSI. Scientific Reports 2017, 7 (1), 10343.
    38. Iman, Z.; Alireza, P.; Hossein, A.; Sayyed Hossein, K., Acute Toxicity and the Effects of Copper Sulphate (CuSO4.5H2O) on the Behavior of the Black Fish (Capoeta Fusca). Iranian Journal of Toxicology 2013, 6 (19), 771-778.
    39. Plasticizers. In Kirk‐Othmer Encyclopedia of Chemical Technology.
    40. Halden, R. U., Plastics and Health Risks. Annual Review of Public Health 2010, 31 (1), 179-194.
    41. Jen, J.-F.; Liu, T.-C., Determination of phthalate esters from food-contacted materials by on-line microdialysis and liquid chromatography. Journal of Chromatography A 2006, 1130 (1), 28-33.
    42. Schabron, J. F.; Fenska, L. E., Determination of BHT, Irganox 1076, and Irganox 1010 antioxidant additives in polyethylene by high performance liquid chromatography. Analytical Chemistry 1980, 52 (9), 1411-1415.
    43. Cherif Lahimer, M.; Ayed, N.; Horriche, J.; Belgaied, S., Characterization of plastic packaging additives: Food contact, stability and toxicity. Arabian Journal of Chemistry 2017, 10, S1938-S1954.
    44. 食品中鄰苯二甲酸酯類塑化劑檢驗方法(Method of Test for Phtahlate Plasticizers in Foods).TFDAA0008.02.
    45. Timko, M. T.; Yu, Z.; Kroll, J.; Jayne, J. T.; Worsnop, D. R.; Miake-Lye, R. C.; Onasch, T. B.; Liscinsky, D.; Kirchstetter, T. W.; Destaillats, H.; Holder, A. L.; Smith, J. D.; Wilson, K. R., Sampling Artifacts from Conductive Silicone Tubing. Aerosol Science and Technology 2009, 43 (9), 855-865.
    46. J. Carrott, M.; Davidson, G., Identification and analysis of polymer additives using packed-column supercritical fluid chromatography with APCI mass spectrometric detection. Analyst 1998, 123 (9), 1827-1833.
    47. Lapshin, R. V.; Alekhin, A. P.; Kirilenko, A. G.; Odintsov, S. L.; Krotkov, V. A., Vacuum ultraviolet smoothing of nanometer-scale asperities of Poly(methyl methacrylate) surface. Journal of Surface Investigation. X-ray, Synchrotron and Neutron Techniques 2010, 4 (1), 1-11.
    48. Gleadall, A.; Pan, J.; Kruft, M.-A.; Kellomäki, M., Degradation mechanisms of bioresorbable polyesters. Part 1. Effects of random scission, end scission and autocatalysis. Acta Biomaterialia 2014, 10 (5), 2223-2232.
    49. Gioia, P. J. L. a. A. J. D., Rapid Analysis of 25 Common Polymer Additives, 2008

    QR CODE