高粱酒為台灣國產量前三大酒類，市售高粱酒數不勝數，價格更是高低不一，消費者在購買時往往只能依據酒廠的知名度，而無其他依據。因此，建立完整的高粱酒指紋圖譜，將有助於民眾選購。此外，2011年塑化劑案件顯示出針對特定化合物做偵測無法得到樣品的完整資訊，錯失發現違法添加物的機會。
本研究利用氣相層析質譜儀以全掃描方式鑑定高粱酒中成分，藉由其指紋圖譜區別高粱酒廠家，並利用氣相層析火焰離子化偵測器分析酒中甲醇含量。高粱酒的成分鑑定利用氣相層析質譜儀，並將分析物分成非揮發性及揮發性兩部分，第一部分我們利用分散式液液微萃取以及減壓濃縮方式，將高粱酒非揮發物分成鹼性/中性、酸性和水溶性三種，定性成功的分析物共有74種，利用判別分析以1,3,3-三乙氧基丙烷（propane,1,1,3,triethoxy-）、己酸（hexanoic acid）、異丁醛二乙縮醛（propane,1,1-diethoxy-2-methyl-）、辛酸乙酯（octanoic acid,ethyl ester）、異戊醛二乙縮醛（butane,1,1-diethoxy-3-methyl-）五種分析物區分六家廠家的正確率為100%。第二部分採用吹氣捕捉方式求得高粱酒中揮發性物質，共測得50種化合物，以乙縮醛二乙醇（ethane, 1,1-diethoxy-）、乙醛（acetaldehyde）、異丁醇（1-propanol, 2-methyl-）、丁酸乙酯（butanoic acid, ethyl ester）、3-甲基丁醛（butanal, 3-methyl-）進行判別分析正確率為94.12%。實驗結果發現利用非揮發物鑑定高粱酒品牌的結果較為準確。甲醇以氣相層析火焰離子化偵測器偵測，方法偵測極限為0.34 ppm，全數樣品皆小於1000 ppm，回收率落於80％~120%，符合公告標準。本研究成功地分析高粱酒中成分，並證實特定分析物以區別品牌之可行性。

The production of kaoliang wines in Taiwan is on top three among a wine industry. Varieties of kaoliang wines are available in market with a varying price. Hence, it became difficult to choose among them. This motivated us to develop a method to obtain kaoliang wine’s fingerprint profile. Moreover, in 2011, the Taiwan food scandal demonstrated that detecting specific compounds alone from samples can’t give complete information. We may miss the chance to discover illegal additives.
In this study, we develop gas chromatograph-mass spectrometer method to identify components in 31 kaoliang wines and differentiate 6 brands by their fingerprint profiles. The methanol content of wine was analyzed by gas chromatograph-flame ionization detector. In GC-MS part, the compounds were separated into nonvolatile and volatile. The nonvolatile analytes were divided into three components viz basic/neutral, acid and water soluble by dispersive liquid-liquid microextraction and rotavapor techniques. Qualitative analysis of 74 analytes was successfully carried out. 1,1,3,triethoxypropane, hexanoic acid, 1,1-diethoxy-2-methyl propane, ethyl octanoate, 1,1-diethoxy-3-methylbutane were able to differentiate wine brands and the classification correctness was found to be 100%. We were able to identify 50 volatile components by using purge and trap technique. The classification correctness was found to be 94.12% using 1,1-diethoxyethane, acetaldehyde, 2-methyl-1-propanol, ethyl butanoate, 3-methylbutanal as variables. The results showed nonvolatile components have better ability to differentiate brands. Finally, GC-FID was used to quantify methanol concentration. The method detection limit was 0.34 ppm and recovery was within 80%~120%. This study has successfully analyzed the components in kaoliang wines and confirms the feasibility to distinguish brands of wine by specific analytes.

1. 臧光樓; 司波; 姜雪; 李建, 不同前處理方式下GC-MS法分析白酒中微量成分. 釀酒 2011, 38 (4), 53-56.
2. 洪光住, 中國釀酒科技發展史. 1, Ed. 中國輕工業出版社: 2001.
3. 林志鈞; 張德明; 謝建元; 李秉真, 中式白酒成分、口感及消費者行為之分析. 人文暨社會科學期刊 2006, 2 (2), 25-35.
4. 歐陽港生, 中國傳統白酒香型與酒品. 中華民國酒業發展協進會會員通訊 1998, p 16.
5. Lodolo, E. J.; Kock, J. L.; Axcell, B. C.; Brooks, M., The yeast Saccharomyces cerevisiae- the main character in beer brewing. FEMS yeast research 2008, 8 (7), 1018-36.
6. 李大和, 白酒勾兌技術問答. 1, Ed. 中國輕工業出版社: 1995.
7. 秦含章, 白酒釀造的科學與技術. 1, Ed. 中國輕工業出版社: 1997.
8. 陳順宇, 多變量分析. 華泰書局: 2005.
9. 袁洁; 尹京苑; 高海燕, 指纹圖譜在白酒中的應用研究進展. 食品科學 2008, 29 (11), 680-684.
10. Fisher, R. A., The use of multiple measurements in taxonomic problems. Annals of eugenics 1936, 7 (2), 179-188.
11. Skoog, D. A.; Holler, F. J.; A.Nieman, T., Principles of Instrumental Analysis. Brooks Cole: 2006.
12. 錢松; 薛惠茹, 白酒風味化學. 1, Ed. 中國輕工業出版社: 1997.
13. 海超, 白酒中微量成分的變化及其利用. 釀酒科技 2010, 5, 72-77.
14. 財政部國庫署菸酒管理網 http://www.nta.gov.tw/dbmode93/index.asp.
15. 金門酒廠 http://www.kkl.gov.tw/intro/intro_4.asp.
16. 蕭冬光, 白酒生產技術. 化學工業出版社: 2005.
17. Ojeda, C. B.; Rojas, F. S., Separation and preconcentration by dispersive liquid–liquid microextraction procedure: recent applications. Chromatographia 2011, 74 (9-10), 651-679.
18. Rezaee, M.; Assadi, Y.; Milani Hosseini, M. R.; Aghaee, E.; Ahmadi, F.; Berijani, S., Determination of organic compounds in water using dispersive liquid-liquid microextraction. J. Chromatogr. A 2006, 1116 (1-2), 1-9.
19. Fan, Y.; Hu, Z.; Chen, M.; Tu, C.; Zhu, Y., Ionic liquid based dispersive liquid–liquid microextraction of aromatic amines in water samples. Chinese Chemical Letters 2008, 19 (8), 985-987.
20. Saleh, A.; Yamini, Y.; Faraji, M.; Rezaee, M.; Ghambarian, M., Ultrasound-assisted emulsification microextraction method based on applying low density organic solvents followed by gas chromatography analysis for the determination of polycyclic aromatic hydrocarbons in water samples. J. Chromatogr. A 2009, 1216 (39), 6673-9.
21. Leong, M. I.; Huang, S. D., Dispersive liquid-liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection. J. Chromatogr. A 2008, 1211 (1-2), 8-12.
22. Chen, H.; Ying, J.; Huang, J.; Liao, L., Dispersive liquid-liquid microextraction followed by high-performance liquid chromatography as an efficient and sensitive technique for simultaneous determination of chloramphenicol and thiamphenicol in honey. Analytica chimica acta 2009, 632 (1), 80-5.
23. 王亞琴. 雲南白酒香味成分的 GC、GC-MS 分離分析研究. 雲南大學, 2006.
24. Park, Y. J.; Kyoung Rae Kim; Kim, J. H., Gas Chromatographic Organic Acid Profiling Analysis of Brandies and Whiskeys for Pattern Recognition Analysis. Journal of agricultural and food chemistry 1999, 47 (6), 2322-2326.
25. Ng, L. K.; Lafontaine, P.; Harnois, J., Gas chromatographic–mass spectrometric analysis of acids and phenols in distilled alcohol beverages Application of anion-exchange disk extraction combined with in-vial elution and silylation. J. Chromatogr. A 2000, 873, 29-38.
26. 任玉蘭; 田密; 李春彥; 羅玉杰; 馬天慧, 白酒中微量組分的氣相色譜分析. 中國釀造 2011, pp 177-179.
27. Fiehn, O.; Kopka, J.; Trethewey, R. N.; Willmitzer, L., Identification of uncommon plant metabolites based on calculation of elemental compositions using gas chromatography and quadrupole mass spectrometry. Anal. Chem. 2000, 72 (15), 3573-3580.
28. Skogerson, K.; Runnebaum, R.; Wohlgemuth, G.; de Ropp, J.; Heymann, H.; Fiehn, O., Comparison of gas chromatography-coupled time-of-flight mass spectrometry and 1H nuclear magnetic resonance spectroscopy metabolite identification in white wines from a sensory study investigating wine body. J. Agric. Food Chem. 2009, 57 (15), 6899-907.
29. Fan, W.; Qian, M. C., Characterization of aroma compounds of chinese “wuliangye” and “jiannanchun” liquors by aroma extract dilution analysis. J. Agric. Food Chem. 2006, 54 (7), 2695-2704.
30. 鄭偉. 白酒非揮發性組份研究. 南京理工大學, 2007.
31. Rahnama Kozani, R.; Assadi, Y.; Shemirani, F.; Milani Hosseini, M. R.; Jamali, M. R., Determination of trihalomethanes in drinking water by dispersive liquid–liquid microextraction then gas chromatography with electron-capture detection. Chromatographia 2007, 66 (1-2), 81-86.
32. Han, Y.; Jia, X.; Liu, X.; Duan, T.; Chen, H., DLLME combined with GC–MS for the determination of methylparaben, ethylparaben, propylparaben and butylparaben in beverage samples. Chromatographia 2010, 72 (3-4), 351-355.
33. Zhang, C.; Ao, Z.; Chui, W.; Shen, C.; Tao, W.; Zhang, S., Characterization of volatile compounds from Daqu-a traditional Chinese liquor fermentation starter. International Journal of Food Science & Technology 2011, 46 (8), 1591-1599.
34. 胡鳳綬, 酒類中之香氣成分. 台灣菸酒公司酒類試驗所製酒科技專論彙編 1988, pp 139-173.
35. 李大和, 新型白酒生產與勾調技術問答. 1, Ed. 中國輕工業出版社: 2001.
36. 周圍; 周小平; 趙國宏; 劉紅衛; 高黎紅; 陳立仁; 劉向東; 唐煜, 名優白酒質量指紋專家鑑別系統. Chinese Journal of Analytical Chemistry 2004, 32 (6), 735-740.
37. 郝恩; 白慧芝, 白酒中雜醇油的毛細管柱氣相色譜法測定. 上海預防醫學 2004, 16 (7), 345-346.
38. Perestrelo, R.; Barros, A. n. S.; Câmara, J. S.; Rocha, S. l. M., In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction. J. Agric. Food Chem. 2011, 59 (7), 3186–3204.
39. Zhu, S.; Lu, X.; Ji, K.; Guo, K.; Li, Y.; Wu, C.; Xu, G., Characterization of flavor compounds in Chinese liquor Moutai by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry. Analytica chimica acta 2007, 597 (2), 340-8.
40. Fan, W.; Qian, M. C., Headspace solid phase microextraction and gas chromatography−olfactometry dilution analysis of young and aged chinese “yanghe daqu” liquors. J. Agric. Food Chem. 2005, 53, 7931-7938.
41. Delfini, C.; Gaia, P.; Mariscalco, G.; Contiero, M.; Pagliara, A., Production of benzaldehyde, benzyl alcohol and benzoic acid by yeasts and Botrytis cinerea isolated from grape musts and wines. Vitis 1991, 30, 253–263.
42. 尋思穎; 董睿; 彭黔榮; 馮永渝; 楊敏; 孫棣; 耿平蘭, 醬香型白酒中揮發性酚類物質的測定-高效液相色譜法. 食品科學 2012.
43. Mo, X.; Fan, W.; Xu, Y., Changes in volatile compounds of chinese rice wine wheat qu during fermentation and storage. Journal of the institute of brewing 2009, 115 (4), 300-307.
44. 許漢英; 趙曉君, 分光光度法測定白酒中的糠醛. Chinese Journal Of Applied Chemistry 1997, 3 (14), 84-86.
45. Muller, R.; Rappert, S., Pyrazines: occurrence, formation and biodegradation. Appl. Microbiol. Biotechnol. 2010, 85 (5), 1315-20.
46. 吳建峰, 中國白酒中健康功能性成分四甲基吡嗪的研究. 釀酒科技 2007, 1, 117-120.
47. Swinnerton, J. W.; Linnenbom, V. J., Determination of the C1 to C4 hydrocarbons in sea water by gas chromatography. J. Chromatogr. Sci. 1967, 5 (11), 570-573
48. Lee, M. R.; Lee, J. S.; Hsiang, W. S.; Chen, C. M., Purge-and-trap gas chromatography–mass spectrometry in the analysis of volatile organochlorine compounds in water. J. Chromatogr. A 1997, 775, 267–274.
49. 袁玉潔. 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, 2009.
50. 胡國棟; 陸久瑞; 蔡心堯, 採用動態頂空進樣技術分析白酒的微量揮發性組分. 釀酒 1992, 19 (1), 67-71.
51. Nykänen, L.; Suomalainen, H., Aroma of beer, wine and distilled alcoholic beverages. Kluwer: 1983.
52. Escudero, A.; Cacho, J.; Ferreira, V., Isolation and identification of odorants generated in wine during its oxidation a gas chromatography–olfactometric study. Eur. Food Res. Technol. 2000, 211, 105-110.
53. Revilla, I.; Luisa, M.; González-SanJosé, Methanol release during fermentation of red grapes treated with pectolytic enzymes. Food Chemistry 1998, 63 (3), 307–312.
54. 酒類衛生標準. 行政院衛生署: 2008.
55. 環境檢驗方法偵測極限測定指引. 環境檢驗所, 2006.
56. Nonato, E. A.; Carazza, F.; Silva, F. C.; Carvalho, C. R.; Cardeal, Z. d. L., A headspace solid-phase microextraction method for the determination of some secondary compounds of brazilian sugar cane spirits by gas chromatography. J. Agric. Food Chem. 2001, 49, 3533-3539.
57. Benn, S. M.; Peppard, T. L., Characterization of tequila flavor by instrumental and sensory analysis. J. Agric. Food Chem. 1996, 44, 557-566.
58. Coldea, T. E. R.; Socaciu, C.; Maria Pârv, D. V., Gas-chromatographic analysis of major volatile compounds found in traditional fruit brandies from Transylvania, Romania. Not. Bot. Hort. Agrobot. 2011, 39 (2), 109-116.
59. Aylott, R. I.; MacKenzie, W. M., Analytical strategies to confirm the generic authenticity of scotch whisky. Journal of the institute of brewing 2010, 116 (3), 215-229.