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請用此 Handle URI 來引用此文件: http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/80390
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dc.contributor.advisor蘇南維(Nan-Wei Su)
dc.contributor.authorChun-Jen Fangen
dc.contributor.author方俊仁zh_TW
dc.date.accessioned2022-11-24T03:05:40Z-
dc.date.available2021-08-10
dc.date.available2022-11-24T03:05:40Z-
dc.date.copyright2021-08-10
dc.date.issued2021
dc.date.submitted2021-07-30
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Caligiani, A.; Acquotti, D.; Palla, G.; Bocchi, V., Identification and quantification of the main organic components of vinegars by high resolution 1H NMR spectroscopy. Anal. Chim. Acta 2007, 585 (1), 110-119. 27. Yu, Y. J.; Lu, Z. M.; Yu, N. H.; Xu, W.; Li, G. Q.; Shi, J. S.; Xu, Z. H., HS-SPME/GC-MS and chemometrics for volatile composition of Chinese traditional aromatic vinegar in the Zhenjiang region. J. Inst. Brew. 2012, 118 (1), 133-141. 28. Nieto, J.; González-Viñas, M. A.; Barba, P.; Martín-Álvarez, P. J.; Aldave, L.; García-Romero, E.; Cabezudo, M. D., Recent progress in wine vinegar R D and some indicators for the future. In Food Flavors, Ingredients and Composition, Charalambous, G., Ed. Elsevier: New York, 1933; pp 469-499. 29. Grégrová, A.; Čížková, H.; Mazáč, J.; Voldřich, M., Authenticity and quality of spirit vinegar: Methods for detection of synthetic acetic acid addition. J. Food Nutr. Res. 2012, 51 (3), 123-131. 30. Erbe, T.; Bruckner, H., Chiral amino acid analysis of vinegars using gas chromatography-selected ion monitoring mass spectrometry. Z. Lebensm.-Unters. Forsch. 1998, 207 (5), 400-409. 31. Bricout, J.; Fontes, J. C.; Merlivat, L., Detection of synthetic vanillin in vanilla extracts by isotopic analysis. J. Assoc. Off. Anal. Chem. 1974, 57 (3), 713-715. 32. Schmidt, H. L., Food quality-control and studies on human-nutrition by mass-spectrometric and nuclear-magnetic-resonance isotope ratio determination. Fresenius' Z. Anal. Chem. 1986, 324 (7), 760-766. 33. Commission Regulation (EC) No 555/2008 of 27 June 2008 laying down detailed rules for implementing Council Regulation (EC) No 479/2008 on the common organisation of the market in wine as regards support programmes, trade with third countries, production potential and on controls in the wine sector. Off. J. Eur. Union 2008, L170, 1-80. 34. AOAC Official Method 998.12. C-4 Plant Sugars in honey. AOAC Official Methods of Analysis. Sugars and Sugar Products; AOAC International: Gaithersburg MD, 1999; Chapter 44, pp 27-30. 35. White, J. W.; Winters, K., Honey protein as internal standard for stable carbon isotope ratio detection of adulteration of honey. J. Assoc. Off. Anal. Chem. 1989, 72 (6), 907-911. 36. Remaud, G.; Guillou, C.; Vallet, C.; Martin, G. J., A Coupled NMR and MS isotopic method for the authentication of natural vinegars. Fresen J Anal Chem 1992, 342 (4-5), 457-461. 37. Hattori, R.; Yamada, K.; Shibata, H.; Hirano, S.; Tajima, O.; Yoshida, N., Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS. J. Agric. Food Chem. 2010, 58 (12), 7115-7118. 38. 钟其顶; 王道兵; 孟镇; 熊正河; 王敏, 有机溶剂稀释与气相色谱-燃烧-同位素质谱(GC-C-IRMS)联用测定食醋中乙酸的δ13C. 质谱学报 2014, 35 (4), 372-377. 39. Ai, G. M.; Sun, T.; Dong, X. Z., Gas chromatography/isotope ratio mass spectrometry: Analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples. Rapid Commun. Mass Spectrom. 2014, 28 (15), 1674-1682. 40. Thomas, F.; Jamin, E., 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: International collaborative study report. Anal. Chim. Acta 2009, 649 (1), 98-105. 41. Perini, M.; Paolini, M.; Simoni, M.; Bontempo, L.; Vrhovsek, U.; Sacco, M.; Thomas, F.; Jamin, E.; Hermann, A.; Camin, F., Stable isotope ratio analysis for verifying the authenticity of balsamic and wine vinegar. J. Agric. Food Chem. 2014, 62 (32), 8197-8203. 42. Camin, F.; Simoni, M.; Hermann, A.; Thomas, F.; Perini, M., Validation of the 2H-SNIF NMR and IRMS methods for vinegar and vinegar analysis: An international collaborative study. Molecules 2020, 25 (12), 2932-2942. 43. de la Torre, X.; Curcio, D.; Colamonici, C.; Molaioni, F.; Cilia, M.; Botre, F., Development and validation of a GC-C-IRMS method for the confirmation analysis of pseudo-endogenous glucocorticoids in doping control. Drug Tes.t Anal. 2015, 7 (11-12), 1071-1078. 44. Perini, M.; Carbone, G.; Camin, F., Stable isotope ratio analysis for authentication of red yeast rice. Talanta 2017, 174, 228-233. 45. Chen, G. L.; Zheng, F. J.; Lin, B.; Lao, S. B.; He, J.; Huang, Z.; Zeng, Y.; Sun, J.; Verma, K. K., Phenolic and Volatile Compounds in the Production of Sugarcane Vinegar. ACS Omega 2020, 5 (47), 30587-30595. 46. Xiao, Z. B.; Dai, S. P.; Niu, Y. W.; Yu, H. Y.; Zhu, J. C.; Tian, H. X.; Gu, Y. B., Discrimination of chinese vinegars based on headspace solid-phase microextraction-gas chromatography mass spectrometry of volatile compounds and multivariate analysis. J. Food Sci. 2011, 76 (8), C1125-C1135. 47. Xiao, Z. J.; Lu, J. R., Generation of acetoin and Its derivatives in foods. J .Agric. Food Chem. 2014, 62 (28), 6487-6497. 48. Xiao, Z. J.; Zhao, L.; Tian, L.; Wang, L. H.; Zhao, J. Y., GC-FID determination of tetramethylpyrazine and acetoin in vinegars and quantifying the dependence of tetramethylpyrazine on acetoin and ammonium. Food Chem. 2018, 239, 726-732. 49. Wu, L. P.; Kummel, S.; Richnow, H. H., Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment. Anal .Bioanal. Chem. 2017, 409 (10), 2581-2590. 50. Folin, O.; Wu, H., A system of blood analysis. J. Biol. Chem. 1919, 38 (1), 81-110. 51. Rumsey, L. A., The precipitation of proteins from cereal extracts by sodium tungstate. Ind. Eng. Chem. 1923, 15, 270-272. 52. Hanzlik, P. J., Precipitation of serum-albumin and glutin by alkaloidal reagents. J. Biol. Chem. 1915, 20 (1), 13-24. 53. Berkman, S.; Henry, R. J.; Golub, O. J.; Segalove, M., Tungstic acid precipitation of blood proteins. J. Biol. Chem. 1954, 206 (2), 937-943. 54. De Ley, J., On the formation of acetoin by Acetobacter. J. Gen. Microbiol. 1959, 21 (2), 352-365. 55. Sakurai, K.; Arai, H.; Ishii, M.; Igarashi, Y., Transcriptome response to different carbon sources in Acetobacter aceti. Microbiology 2011, 157, 899-910. 56. Adler, P.; Frey, L. J.; Berger, A.; Bolten, C. J.; Hansen, C. E.; Wittmann, C., The key to acetate: Metabolic fluxes of acetic acid bacteria under cocoa pulp fermentation-simulating conditions. Appl. Environ. Microb. 2014, 80 (15), 4702-4716. 57. Yanagida, F.; Koizumi, Y.; Nakazato, A.; Araki, M.; Yoshino, H.; Wakamatu, K., Studies on acetic acid bacteria and their utilization (part 14): Formation of acetoin in synthetic medium with added various carbon sources. J. Soc. Brew. 1976, 71 (7), 574-579. 58. Romano, P.; Suzzi, G., Origin and production of acetoin during wine yeast fermentation. Appl .Environ. Microb. 1996, 62 (2), 309-315.
dc.identifier.urihttp://tdr.lib.ntu.edu.tw/jspui/handle/123456789/80390-
dc.description.abstract醋在傳統飲食文化中扮演重要的角色,常用作調味或防腐之用。近年來,更逐漸被視可促進健康之食品。傳統食醋之釀造過程包含酒精發酵及醋酸發酵兩階段,發酵過程需耗費許多時間,然而伴隨食醋市場規模日益增加,可能發生釀造食醋混摻醋酸以縮短釀造時間及降低生產成本之情形。 為鑑別釀造米醋之真實性,本研究自釀造米醋中所萃取得到之揮發性成分中篩選出乙醯乙醇作為內生性參考物,並成功建立以GC-IRMS同步分析釀造米醋中醋酸及乙醯乙醇穩定碳同位素比值之檢驗方法,另以釀造米醋經鎢酸鈉及硫酸溶液處理所得米醋蛋白質作為另一內生性參考物,並建立以EA-IRMS測定其穩定碳同位素比值之檢驗方法,前述檢驗方法皆完成方法確效,具有良好之精密度及準確度。 本研究測定16件釀造米醋樣品中醋酸、乙醯乙醇及蛋白質之穩定碳同位素比值(δ13Cacetic acid、δ13Cacetoin及δ13Cprotein)及10件冰醋酸樣品之δ13Cacetic acid,並分別計算釀造米醋樣品δ13Cacetic acid與δ13Cacetoin之差值(Δδ13Cacetoin)及δ13Cacetic acid與δ13Cprotein之差值(Δδ13Cprotein),並以δ13Cacetic acid、Δδ13Cacetoin及Δδ13Cprotein作為鑑別釀造米醋真實性之純度指標,計算其95%信賴區間,建立釀造米醋中穩定碳同位素比值特徵模型,其中δ13Cacetic acid為-26.97至-25.38‰;Δδ13Cacetoin為0.61至2.27‰;Δδ13Cprotein為0.27至2.10‰。 另依據前述釀造米醋樣品及冰醋酸樣品之分析結果,分別建立δ13Cacetic acid、Δδ13Cacetoin及Δδ13Cprotein之釀造米醋混摻模式曲線,並以釀造米醋摻加不同比例之冰醋酸作為模擬摻偽食醋樣品進行驗證,其中δ13Cacetic acid、Δδ13Cacetoin及Δδ13Cprotein皆隨混摻比例增加而下降,惟δ13Cacetoin及δ13Cprotein則不受到影響,結果顯示與所建立之混摻模式曲線相符。由本研究所建立之釀造米醋混摻模式曲線及各純度指標之95%信賴區間下界,推估本研究所建立之方法可鑑別出摻加約10%以上冰醋酸之摻偽食醋。 本研究之結果亦發現δ13Cacetoin及δ13Cprotein可反應出釀造原料之碳源,而不會受到額外添加酒精或醋酸之影響。乙醯乙醇及米醋蛋白質可作為鑑別釀造米醋真實性之良好內生性參考物。zh_TW
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dc.description.tableofcontents口試委員會審定書 i 縮寫表 ii 中文摘要 iii Abstract v 第一章、研究動機 1 第二章、文獻整理 2 第一節、 食醋之定義與標示規定 2 第二節、 食醋之釀造 4 壹、 奧爾良法 4 貳、 發酵槽法 4 參、 浸沒發酵法 5 第三節、 醋酸之合成 6 壹、 甲醇羰基化反應 6 一、 孟山都法 6 二、 Cativa催化法 6 貳、 乙醛氧化反應 6 參、 乙烯氧化反應 6 第四節、 食醋摻偽之檢驗 7 壹、 揮發性成分 7 貳、 胺基酸 8 參、 無機元素 8 第五節、 穩定同位素比值分析技術 10 壹、 穩定同位素比值 10 貳、 同位素分餾效應 10 參、 食品摻偽檢驗之應用 11 肆、 食醋摻偽檢驗之應用 12 第三章、材料與方法 14 第一節、 實驗架構 14 壹、 釀造米醋之化合物別穩定碳同位素比值分析 15 貳、 釀造米醋蛋白質之整體性穩定碳同位素比值分析 16 參、 釀造米醋真實性之鑑別 17 第二節、 實驗材料 18 壹、 樣品來源 18 貳、 試藥、試液及溶劑 18 參、 標準溶液之配製 18 肆、 試劑之調製 19 伍、 合成醋樣品之製備 19 陸、 國際參考物質 20 柒、 氣體 20 捌、 器具及材料 20 第三節、 儀器設備 23 第四節、 實驗方法 24 壹、 釀造米醋之化合物別穩定碳同位素比值分析 24 一、 內生性參考物篩選 24 二、 萃取條件優化 24 三、 釀造米醋中醋酸及乙醯乙醇含量測定 25 四、 GC-MS分析條件 26 五、 穩定碳同位素比值分析 27 六、 GC-IRMS分析條件 29 貳、 釀造米醋蛋白質之整體性穩定碳同位素比值分析 31 一、 分析方法建立 31 二、 分析方法確效 32 三、 EA-IRMS分析條件 33 參、 釀造米醋真實性之鑑別 33 一、 釀造米醋真實性鑑別指標之穩定碳同位素比值特徵模型 33 二、 釀造米醋混摻模式曲線之建立 34 三、 釀造米醋混摻模式曲線之驗證 35 第四章、結果與討論 36 第一節、 釀造米醋之化合物別穩定碳同位素比值分析 36 壹、 內生性參考物篩選 36 貳、 萃取條件優化 42 參、 釀造米醋中醋酸及乙醯乙醇含量測定 46 肆、 穩定碳同位素比值分析 46 一、 工作參考物質之標定 46 二、 標準化曲線之製作 46 三、 查核樣品之重複分析 47 四、 樣品分析之品質管制 47 五、 分析方法確效 54 第二節、 釀造米醋蛋白質之整體性穩定碳同位素比值分析 58 壹、 米醋蛋白質之萃取 58 貳、 穩定碳同位素比值分析 58 一、 標準化曲線之製作 58 二、 查核樣品之重複分析 58 三、 樣品分析之品質管制 58 四、 分析方法確效 59 第三節、 釀造米醋真實性之鑑別 66 壹、 釀造米醋真實性鑑別指標之穩定碳同位素比值特徵模型 66 一、 樣品之穩定碳同位素比值分析結果 66 二、 鑑別指標之穩定碳同位素比值特徵模型 68 貳、 釀造米醋混摻模式曲線之建立及驗證 71 第五章、結論 78 第六章、參考文獻 79
dc.language.isozh-TW
dc.subject乙醯乙醇zh_TW
dc.subject摻偽zh_TW
dc.subject穩定碳同位素zh_TW
dc.subject蛋白質zh_TW
dc.subject醋zh_TW
dc.subject醋酸zh_TW
dc.subjectvinegaren
dc.subjectstable carbon isotopeen
dc.subjectacetic aciden
dc.subjectacetoinen
dc.subjectproteinen
dc.subjectadulterationen
dc.title穩定同位素比值分析技術應用於鑑別釀造米醋真實性之研究zh_TW
dc.titleStudies on Stable Isotope Ratio Technique to Determine the Authenticity of Brewed Rice Vinegaren
dc.date.schoolyear109-2
dc.description.degree博士
dc.contributor.author-orcid0000-0001-6172-1651
dc.contributor.oralexamcommittee李敏雄(Hsin-Tsai Liu),古國隆(Chih-Yang Tseng),鍾玉明,邱淑媛
dc.subject.keyword醋酸,乙醯乙醇,蛋白質,醋,摻偽,穩定碳同位素,zh_TW
dc.subject.keywordacetic acid,acetoin,protein,vinegar,adulteration,stable carbon isotope,en
dc.relation.page85
dc.identifier.doi10.6342/NTU202100802
dc.rights.note同意授權(限校園內公開)
dc.date.accepted2021-08-01
dc.contributor.author-college生物資源暨農學院zh_TW
dc.contributor.author-dept農業化學研究所zh_TW
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