全二维气相色谱/飞行时间质谱分析传统工艺与机械化工艺老白干原酒的挥发性成分
|
摘要
应用顶空固相微萃取法(HS-SPME)结合全二维气相色谱-飞行时间质谱联机对7种传统工艺老白干原酒与3种机械化工艺老白干原酒中的挥发性成分进行分析。从10种原酒中共检测到322种化合物,其中223种经保留指数定性,95种化合物经标准品比对准确定性。从7种传统工艺原酒中共检出305种共有成分,从3种机械化工艺原酒中共检出294种共有成分,两类工艺原酒中有286种共有成分,其中酯类107种,醇类44种,醛类28种,酮类28种,酸类2种,含氮类5种,含硫类6种,呋喃类13种,缩醛类16种,酚类1种,醚类6种,酸酐类3种,烃类27种。这说明老白干香型原酒中的挥发性成分的种类相对稳定。3种机械化工艺原酒中均缺失丙醛和2,3-戊二酮。使用Fisher比率法(F值)对传统工艺与机械化工艺老白干原酒中共有挥发性成分的相对浓度进行了比较,其中F值大于5的化合物有43个。
An effective and reliable method based on comprehensive two-dimensional gas chromatography/time of flight mass spectrometry was established for qualitative analyses of volatile compounds of 7 kinds of base Baijiu of Laobaigan manufactured by traditional technology and 3 kinds of base Baijiu of Laobaigan manufactured by mechanized technology respectively. A total of 322 compounds were tentatively identified by NIST search from ten kinds of Laobaigan base Baijiu. Furthermore, comparison with the retention time of volatile standards was used as a reliable qualitative method to identify volatiles with aid of their retention indices(RIs). Among them, 223 volatiles were identified after the comparison with the RIs and 95 compounds were confirmed by their RIs and mass spectra of the authentic standards.According to statistical comparison, a total of 305 compounds were detected in 7 kinds of the traditional technology base Baijiu and 294 compounds were detected in 3 kinds of the mechanized technology base Baijiu. 286 Volatiles were detected in all samples, including 107 esters, 44 alcohols, 28 aldehydes, 28 ketones, 2 acids, 5 nitrogen-containing compounds, 6 sulfur compounds, 13 furans, 16 acetals, 1 phenols, 6 ethers, 3 anhydrides, and 27 hydrocarbons. This indicated the kinds of volatiles were relatively stable between the Baijiu manufactured by traditional technology and mechanized technology respectively. Only propanal and 2,3-pentanedione couldn't be found in all mechanized technology base Baijiu. The differences of the volatiles in 10 kinds of base Baijiu were compared by Fisher Ratio and 43 compounds shown Fisher Ratio bigger than 5.
An effective and reliable method based on comprehensive two-dimensional gas chromatography/time of flight mass spectrometry was established for qualitative analyses of volatile compounds of 7 kinds of base Baijiu of Laobaigan manufactured by traditional technology and 3 kinds of base Baijiu of Laobaigan manufactured by mechanized technology respectively. A total of 322 compounds were tentatively identified by NIST search from ten kinds of Laobaigan base Baijiu. Furthermore, comparison with the retention time of volatile standards was used as a reliable qualitative method to identify volatiles with aid of their retention indices(RIs). Among them, 223 volatiles were identified after the comparison with the RIs and 95 compounds were confirmed by their RIs and mass spectra of the authentic standards.According to statistical comparison, a total of 305 compounds were detected in 7 kinds of the traditional technology base Baijiu and 294 compounds were detected in 3 kinds of the mechanized technology base Baijiu. 286 Volatiles were detected in all samples, including 107 esters, 44 alcohols, 28 aldehydes, 28 ketones, 2 acids, 5 nitrogen-containing compounds, 6 sulfur compounds, 13 furans, 16 acetals, 1 phenols, 6 ethers, 3 anhydrides, and 27 hydrocarbons. This indicated the kinds of volatiles were relatively stable between the Baijiu manufactured by traditional technology and mechanized technology respectively. Only propanal and 2,3-pentanedione couldn't be found in all mechanized technology base Baijiu. The differences of the volatiles in 10 kinds of base Baijiu were compared by Fisher Ratio and 43 compounds shown Fisher Ratio bigger than 5.
引文
[1]余乾伟.传统白酒酿造技术[M].北京:中国轻工业出版社, 2014:8-10.
[2]孙宝国,吴继红,黄明泉,等.白酒风味化学研究进展[J].中国食品学报, 2015, 15(9):1-8.
[3]宋书玉. 2015年中国酒业协会白酒分会、市场专业委员会、名酒收藏委员会、科教设计装备委员会工作报告[J].酿酒科技, 2016, 264(6):17-28.
[4]吕浩.衡水老白干酒的历史、文化解析[J].酿酒,2008, 35(5):110-112.
[5]丁云连,范文来,徐岩,等.老白干香型白酒香气成分分析[J].酿酒, 2008, 35(4):109-113.
[6]DU L, HE T, LI W, et al. Analysis of volatile compounds in Chinese Laobaigan liquor using headspace solid-phase microextraction coupled with GC-MS[J]. Analytical Methods, 2015, 7(5):1906-1913.
[7]王敏,张煜行,李泽霞,等.顶空固相微萃取-气质联用法分析衡水老白干酒风味物质[J].酿酒科技,2015, 255(9):111-114.
[8]WU J, ZHENG Y, SUN B, et al. The occurrence of propyl lactate in Chinese Baijius(Chinese liquors)detected by direct injection coupled with gas chromatography-mass spectrometry[J]. Molecules,2015, 20(10):19002-19013.
[9]朱会霞,张煜行,程宗志,等.衡水老白干酒发酵主要风味物质变化规律研究[J].酿酒科技, 2015(2):36-39.
[10]王敏,张煜行,李泽霞,等.老白干酒风味物质HS-SPME-GCMS指纹图谱的建立[J].酿酒科技,2015, 256(10):32-34.
[11]LIU Z, PHILLIPS J B. Comprehensive two-dimensional gas chromatography using an on-column thermal modulator interface[J]. Journal of Chromatographic Science, 1991, 29(6):227-231.
[12]MARRIOTT P, SHELLIE R. Principles and applications of comprehensive two-dimensional gas chromatography[J]. Trac Trends in Analytical Chemistry,2002, 21(9/10):573-583.
[13]WELKE J E, ZANUS M, LAZZAROTTO M, et al.Main differences between volatiles of sparkling and base wines accessed through comprehensive two dimensional gas chromatography with time-of-flight mass spectrometric detection and chemometric tools[J]. Food Chemistry, 2014, 164C(20):427-437.
[14]ZHU S, LU X, JI K, et al. Characterization of flavor compounds in Chinese liquor Moutai by comprehensive two-dimensional gas chromatography/time-offlight mass spectrometry[J]. Analytica Chimica Acta,2007, 597(2):340-348.
[15]ROCHAT S, LAUMER J Y, CHAINTREAU A.Analysis of sulfur compounds from the in-oven roast beef aroma by comprehensive two-dimensional gas chromatography[J]. Journal of Chromatography A,2007, 1147(1):85-94.
[16]DUAN Y, ZHENG F, CHEN H, et al. Analysis of volatiles in Dezhou Braised Chicken by comprehensive two-dimensional gas chromatography/high resolution-time of flight mass spectrometry[J]. Lebensmittel-Wissenschaft und-Technologie, 2015, 60(2):1235-1242.
[17]FENG Y, YI B, SHEN C, et al. Chemical Analysis of the Chinese liquor Luzhoulaojiao by comprehensive two-dimensional gas chromatography/time-offlight mass spectrometry[J]. Scientific Reports, 2015,9553(5):1-6.
[18]周庆伍,李安军,汤有宏,等.基于全二维气相色谱-飞行时间质谱对古井贡酒风味成分的剖析研究[J].酿酒, 2016, 43(2):75-81.
[19]季克良,郭坤亮,朱书奎,等.全二维气相色谱/飞行时间质谱用于白酒微量成分的分析[J].酿酒科技,2007, 2007(3):100-102.
[20]WELDEGERGIS B T, VILLIERS A D, MCNEISH C, et al. Characterisation of volatile components of Pinotage wines using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry(GC×GC-TOFMS)[J]. Food Chemistry2011, 129(1):188-199.
[21]CARLIN S, VRHOVSEK U, FRANCESCHI P, et al. Regional features of northern Italian sparkling wines, identified using solid-phase micro extraction and comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry[J]. Food Chemistry, 2016, 208(2016):68-80.
[22]ZHENG Y, SUN B G, ZHAO M, et al. Characterization of the key odorants in Chinese Zhima aroma-type Baijiu by gas chromatography-olfactometry,quantitative measurements, aroma recombination,and omission studies[J]. Journal of Agricultural&Food Chemistry, 2016, 64(26):5367-5374.
[23]MüHLEN C V, ZINI C A, CARAM魨O E B, et al.Comparative study of Eucalyptus dunnii, volatile oil composition using retention indices and comprehensive two-dimensional gas chromatography coupled to time-of-flight and quadrupole mass spectrometry[J].Journal of Chromatography A, 2008, 1200(1):34-42.
[24]何坚,孙宝国.香料化学与工艺学[M].北京:化学工业出版社, 2004.
[25]张媛媛,孙金沅,张国锋,等.扳倒井芝麻香型白酒中含硫风味成分的分析[J].中国食品学报, 2012,12(12):173-179.
[2]孙宝国,吴继红,黄明泉,等.白酒风味化学研究进展[J].中国食品学报, 2015, 15(9):1-8.
[3]宋书玉. 2015年中国酒业协会白酒分会、市场专业委员会、名酒收藏委员会、科教设计装备委员会工作报告[J].酿酒科技, 2016, 264(6):17-28.
[4]吕浩.衡水老白干酒的历史、文化解析[J].酿酒,2008, 35(5):110-112.
[5]丁云连,范文来,徐岩,等.老白干香型白酒香气成分分析[J].酿酒, 2008, 35(4):109-113.
[6]DU L, HE T, LI W, et al. Analysis of volatile compounds in Chinese Laobaigan liquor using headspace solid-phase microextraction coupled with GC-MS[J]. Analytical Methods, 2015, 7(5):1906-1913.
[7]王敏,张煜行,李泽霞,等.顶空固相微萃取-气质联用法分析衡水老白干酒风味物质[J].酿酒科技,2015, 255(9):111-114.
[8]WU J, ZHENG Y, SUN B, et al. The occurrence of propyl lactate in Chinese Baijius(Chinese liquors)detected by direct injection coupled with gas chromatography-mass spectrometry[J]. Molecules,2015, 20(10):19002-19013.
[9]朱会霞,张煜行,程宗志,等.衡水老白干酒发酵主要风味物质变化规律研究[J].酿酒科技, 2015(2):36-39.
[10]王敏,张煜行,李泽霞,等.老白干酒风味物质HS-SPME-GCMS指纹图谱的建立[J].酿酒科技,2015, 256(10):32-34.
[11]LIU Z, PHILLIPS J B. Comprehensive two-dimensional gas chromatography using an on-column thermal modulator interface[J]. Journal of Chromatographic Science, 1991, 29(6):227-231.
[12]MARRIOTT P, SHELLIE R. Principles and applications of comprehensive two-dimensional gas chromatography[J]. Trac Trends in Analytical Chemistry,2002, 21(9/10):573-583.
[13]WELKE J E, ZANUS M, LAZZAROTTO M, et al.Main differences between volatiles of sparkling and base wines accessed through comprehensive two dimensional gas chromatography with time-of-flight mass spectrometric detection and chemometric tools[J]. Food Chemistry, 2014, 164C(20):427-437.
[14]ZHU S, LU X, JI K, et al. Characterization of flavor compounds in Chinese liquor Moutai by comprehensive two-dimensional gas chromatography/time-offlight mass spectrometry[J]. Analytica Chimica Acta,2007, 597(2):340-348.
[15]ROCHAT S, LAUMER J Y, CHAINTREAU A.Analysis of sulfur compounds from the in-oven roast beef aroma by comprehensive two-dimensional gas chromatography[J]. Journal of Chromatography A,2007, 1147(1):85-94.
[16]DUAN Y, ZHENG F, CHEN H, et al. Analysis of volatiles in Dezhou Braised Chicken by comprehensive two-dimensional gas chromatography/high resolution-time of flight mass spectrometry[J]. Lebensmittel-Wissenschaft und-Technologie, 2015, 60(2):1235-1242.
[17]FENG Y, YI B, SHEN C, et al. Chemical Analysis of the Chinese liquor Luzhoulaojiao by comprehensive two-dimensional gas chromatography/time-offlight mass spectrometry[J]. Scientific Reports, 2015,9553(5):1-6.
[18]周庆伍,李安军,汤有宏,等.基于全二维气相色谱-飞行时间质谱对古井贡酒风味成分的剖析研究[J].酿酒, 2016, 43(2):75-81.
[19]季克良,郭坤亮,朱书奎,等.全二维气相色谱/飞行时间质谱用于白酒微量成分的分析[J].酿酒科技,2007, 2007(3):100-102.
[20]WELDEGERGIS B T, VILLIERS A D, MCNEISH C, et al. Characterisation of volatile components of Pinotage wines using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry(GC×GC-TOFMS)[J]. Food Chemistry2011, 129(1):188-199.
[21]CARLIN S, VRHOVSEK U, FRANCESCHI P, et al. Regional features of northern Italian sparkling wines, identified using solid-phase micro extraction and comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry[J]. Food Chemistry, 2016, 208(2016):68-80.
[22]ZHENG Y, SUN B G, ZHAO M, et al. Characterization of the key odorants in Chinese Zhima aroma-type Baijiu by gas chromatography-olfactometry,quantitative measurements, aroma recombination,and omission studies[J]. Journal of Agricultural&Food Chemistry, 2016, 64(26):5367-5374.
[23]MüHLEN C V, ZINI C A, CARAM魨O E B, et al.Comparative study of Eucalyptus dunnii, volatile oil composition using retention indices and comprehensive two-dimensional gas chromatography coupled to time-of-flight and quadrupole mass spectrometry[J].Journal of Chromatography A, 2008, 1200(1):34-42.
[24]何坚,孙宝国.香料化学与工艺学[M].北京:化学工业出版社, 2004.
[25]张媛媛,孙金沅,张国锋,等.扳倒井芝麻香型白酒中含硫风味成分的分析[J].中国食品学报, 2012,12(12):173-179.