酒花浸膏关键性香气成分分析
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摘要
采用固相微萃取(solid-phase microextraction,SPME)与溶剂辅助蒸发萃取(solvent-assisted evaporative extraction,SAFE)法结合气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)联用技术分析酒花浸膏中的香气成分,同时采用气相色谱-嗅闻仪(gas chromatography-olfactory,GC-O)结合香气提取稀释分析(aroma extraction dilution analysis,AEDA)方法和香气活性值(odor activity value,OAV),最终确定酒花浸膏的关键性香气成分。结果显示,采用2种萃取方法结合GC-MS在酒花浸膏中共鉴定出111种香气成分;经GC-O分析共鉴定出27种香气活性化合物,其中异丁酸乙酯、丁二酸二乙酯、2-甲基丁酸含量最高,结合风味稀释因子和OAV分析共同确认酒花浸膏的关键香气成分为异丁酸乙酯、2-甲基丁酸、异己酸乙酯、辛酸乙酯、癸酸乙酯等化合物。
The volatile compounds of hops extracts were extracted by solid-phase microextraction(SPME) or solventassisted evaporative extraction(SAFE), and analyzed by gas chromatography-mass spectrometry(GC-MS). Then the aromaactive compounds were identified by gas chromatography-olfactory(GC-O) combined with aroma extraction dilution analysis(AEDA), and the key odorants were con?rmed by odor activity values(OAV). Results showed that a total of 111 volatile compounds were identified by the two extraction methods combined with GC-MS. Twenty-seven aroma-active compounds were identi?ed by GC-O/AEDA, with ethyl isobutyrate, diethyl succinate and 2-methyl butyric acid being the most abundant ones. Ethyl isobutyrate, 2-methyl butyric acid, ethyl isocaproate, ethyl octanoate, and ethyl caprate were con?rmed as the key odorants of hops extracts based on ?avor dilution(FD) factors and OAVs.
The volatile compounds of hops extracts were extracted by solid-phase microextraction(SPME) or solventassisted evaporative extraction(SAFE), and analyzed by gas chromatography-mass spectrometry(GC-MS). Then the aromaactive compounds were identified by gas chromatography-olfactory(GC-O) combined with aroma extraction dilution analysis(AEDA), and the key odorants were con?rmed by odor activity values(OAV). Results showed that a total of 111 volatile compounds were identified by the two extraction methods combined with GC-MS. Twenty-seven aroma-active compounds were identi?ed by GC-O/AEDA, with ethyl isobutyrate, diethyl succinate and 2-methyl butyric acid being the most abundant ones. Ethyl isobutyrate, 2-methyl butyric acid, ethyl isocaproate, ethyl octanoate, and ethyl caprate were con?rmed as the key odorants of hops extracts based on ?avor dilution(FD) factors and OAVs.
引文
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[20]ENGEL W,BAHR W,SCHIEBERLE P.Solvent assisted flavour evaporation:a new and versatile technique for the careful and direct isolation of aroma compounds from complex food matrices[J].European Food Research and Technology,1999,209(3/4):237-241.DOI:10.1007/s002170050486.
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[23]NEIENS S D,STEINHAUS M.Odor-Active compounds in the special flavor hops huell melon and polaris[J].Journal of Agricultural and Food Chemistry,2018,66(6):1452-1460.DOI:10.1021/acs.jafc.7b05859.
[24]PRAET T,VAN O F,STEENACKERS B,et al.Changes in the hop-derived volatile profile upon lab scale boiling[J].Food Research International,2015,75:1-10.
[25]KISHIMOTO T,WANIKAWA A,KAGAMI N A,et al.Analysis of hop-derived terpenoids in beer and evaluation of their behavior using the stir bar-sorptive extraction method with GC-MS[J].Journal of Agricultural&Food Chemistry,2005,53(12):4701-4707.DOI:10.1021/jf050072f.
[26]ROBERTS M T,DUFOUR J,LEWIS A C.Application of comprehensive multidimensional gas chromatography combined with time-of-flight mass spectrometry(GC×GC-TOF MS)for high resolution analysis of hop essential oil[J].Journal of Separation Science,2004,27(5/6):473-478.DOI:10.1002/jssc.200301669.
[27]MARTIN S,WOLFGANG W,PETER S.Comparison of the most odour-active volatiles in different hop varieties by application of a comparative aroma extract dilution analysis[J].European Food Research&Technology,2007,226(1/2):45-55.DOI:10.1007/s00217-006-0507-6.
[28]VAN O F,PRAET T,AERTS G,et al.Characterization of novel single-variety oxygenated sesquiterpenoid hop oil fractions via headspace solid-phase microextraction and gas chromatographymass spectrometry/olfactometry[J].Journal of Agricultural&Food Chemistry,2013,61(44):10555.DOI:10.1021/jf402496.
[29]SHARPE F R,LAWS D R J.The essential oil of hops:a review[J].Journal of the Institute of Brewing,2013,87(2):96-107.
[30]HALEY J,PEPPARD T L.Differences in utilization of the essential oil of hops during the production of dry-hopped and late-hopped beers[J].Journal of the Institute of Brewing,1983,89(2):87-91.DOI:10.1002/j.2050-0416.1983.tb04153.x.
[31]LERMUSIEAU G,BULENS M,COLLIN S.Use of GC-olfactometry to identify the hop aromatic compounds in beer[J].Journal of Agricultural&Food Chemistry,2001,49(8):3867-3874.DOI:10.1021/jf0101509.
[32]NANCE M R,SETZER W N.Volatile components of aroma hops(Humulus lupulus L.)commonly used in beer brewing[J].Journal of Brewing&Distilling,2011,2:16-22.
[33]EISENREICH W,SAGNER S,ZENK M H,et al.Monoterpenoid essential oils are not of mevalanoid origin[J].Tetrahedron Letters,1997,38(22):3889-3892.DOI:10.1016/S0040-4039(97)00761-2.
[34]TAKOI K,KOIE K,ITOGA Y,et al.Biotransformation of hop-derived monoterpene alcohols by lager yeast and their contribution to the flavor of hopped beer[J].Journal of Agricultural and Food Chemistry,2010,58(8):5050-5058.DOI:10.1021/jf1000524.
[35]刘玉梅.啤酒花的分析评价及六氢蛇麻酮类的合成与应用[D].无锡:江南大学,2007.
[36]何敏,陆健,张志军.里那醇在啤酒酒花风味建模中的作用[J].啤酒科技,2011(5):71-73.
[37]范有成.香料及其应用[M].北京:化学工业出版社,1990:16-20.
[38]FENAROLI G,PROF D R,BELLANCA N,et al.Fenaroli’s handbook of flavor ingredients[M].2nd ed.Ohio,USA:CRI Press,1975.
[39]孙宝国,陈海涛.食用调香术[M].3版.北京:化学工业出版社,2017:122-130.
[40]刘强,冒德寿,汤峨,译.化合物香味阈值汇编[M].2版.北京:科学出版社,2015.
[41]CZERNY M,CHRISTLBAUER M,CHRISTLBAUER M,et al.Re-investigation on odour thresholds of key food aroma compounds and development of an aroma language based on odour qualities of defined aqueous odorant solutions[J].European Food Research&Technology,2008,228(2):265-273.DOI:10.1007/s00217-008-0931-x.
[42]刘霞.干加酒花工艺、干加酒花品种及品种组合对啤酒特征的影响[J].啤酒科技,2017(5):22-31.
[43]全巧玲,江伟,王德良,等.单萜醇类在啤酒发酵过程中的变化及对酒花香气的贡献[J].食品与发酵工业,2013,39(5):170-175.DOI:10.13995/j.cnki.11-1802/ts.2013.05.043.
[44]李祖光,李建亮,曹慧,等.紫藤鲜花在不同开花期的头香成分[J].浙江林学院学报,2009,26(3):308-313.
[45]SCHIEBERLE P.New developments in methods for analysis of volatile flavor compounds and their precursors[J].Characterization of Food,1995,65(7):403-431.DOI:10.1016/B978-044481499-9/50018-4.
[2]董延虎.酒花浸膏提取及应用研究[J].农业科技与信息,2017(18):43-44.DOI:10.15979/j.cnki.cn62-1057/s.2017.18.021.
[3]刘新平,杜金华,张开利.酒花浸出物制品及其应用[J].酿酒,1998(4):20-23.
[4]雷静,黄文书,舒翔,等.响应面法优化微波提取啤酒花浸膏工艺的研究[J].食品科技,2010,35(9):258-260.DOI:10.13684/j.cnki.spkj.2010.09.014.
[5]邵悦,李雷,崇立明,等.两种啤酒花浸膏对雄性小鼠生殖毒性的研究[J].生殖与避孕,2014,34(5):354-359.DOI:10.7669/j.issn.0253-357X.2014.05.0354.
[6]陈金娥,王晓文,张海容.HPLC测定啤酒花中α-酸的研究进展[J].食品研究与开发,2011,32(9):141-145.DOI:10.3969/j.issn.1005-6521.2011.09.043.
[7]卫生部,药典委员会.药典:一部[M].北京:人民卫生出版社,1977:541-542.
[8]栗德林.中国药物大辞典:上册[M].北京:中国医药科技出版社,1999:868.
[9]BLAND J S,MINICH D,LERMAN R,et al.Isohumulones from hops(Humulus lupulus)and their potential role in medical nutrition therapy[J].Pharmanutrition,2015,3(2):46-52.DOI:10.1016/j.phanu.2015.03.001.
[10]PRAET T,OPSTAELE F V,JASKULA-GOIRIS B,et al.Biotransformat ions of hop-derived aroma compounds by Saccharomyces cerevisiae upon fermentation[J].Elsevier,2012,36(4):125-132.DOI:10.1016/j.cervis.2011.12.005.
[11]NIONELLI L,PONTONIIO E,GOBBETTI M,et al.Use of hop extract as antifungal ingredient for bread making and selection of autochthonous resistant starters for sourdough fermentation[J].International Journal of Food Microbiology,2018,266:173-182.DOI:10.1016/j.ijfoodmicro.2017.12.002.
[12]ABERL A,COELHAN M J.Determination of volatile compounds in different hop varieties by headspace-trap GC/MS-in comparison with conventional hop essential oil analysis[J].Journal of Agricultural&Food Chemistry,2012,60(11):2785-2792.DOI:10.1021/jf205002p.
[13]王露,江伟,刘玉梅,等.GC-O-MS法对酒花中香气活性成分的分析[J].分析试验室,2015,34(6):640-644.DOI:10.13595/j.cnki.issn1000-0720.2015.0139.
[14]RICHTERT M,EYRES G T,SILCOCK P,et al.Comparison of four extraction methods for analysis of volatile hop-derived aroma compounds in beer[J].Journal of Separation Science,2017,40(22):4289-4476.DOI:10.1002/jssc.201700676.
[15]陶鑫凉,闫鹏,郝俊光,等.气相色谱-质谱法分析啤酒中酒花香气成分[J].分析试验室,2012,31(6):24-29.DOI:10.13595/j.cnki.issn1000-0720.2012.0161.
[16]王辉.酒花品种、新鲜度、配方和工艺对啤酒风味的影响[D].无锡:江南大学,2012:46-48.
[17]INUI T,TSUCHIYA F,ISHIMARU M,et al.Different beers with different hops.Relevant compounds for their aroma characteristics[J].Journal of Agricultural&Food Chemistry,2013,61(20):4758.DOI:10.1021/jf3053737.
[18]舒翔.啤酒花浸膏提取、抗氧化及香气成分研究[D].乌鲁木齐:新疆农业大学,2009:47-50.
[19]张璟琳,李娟,黄明泉,等.3种桂花浸膏的挥发性物质分析[J].食品安全质量检测学报,2016,7(4):1554-1560.
[20]ENGEL W,BAHR W,SCHIEBERLE P.Solvent assisted flavour evaporation:a new and versatile technique for the careful and direct isolation of aroma compounds from complex food matrices[J].European Food Research and Technology,1999,209(3/4):237-241.DOI:10.1007/s002170050486.
[21]YANG Z Y,BALDERMANN S,WATANABE N.Recent studies of the volatile compounds in tea[J].Food Research International,2013,53(2):585-599.DOI:10.1016/j.foodres.2013.02.011.
[22]刘廷竹,黄明泉,邹青青,等.GC-O与GC-MS结合分析竹荪牛肉香精中的挥发性成分[J].食品科学,2016,37(2):92-98.DOI:10.7506/spkx1002-6630-201602016.
[23]NEIENS S D,STEINHAUS M.Odor-Active compounds in the special flavor hops huell melon and polaris[J].Journal of Agricultural and Food Chemistry,2018,66(6):1452-1460.DOI:10.1021/acs.jafc.7b05859.
[24]PRAET T,VAN O F,STEENACKERS B,et al.Changes in the hop-derived volatile profile upon lab scale boiling[J].Food Research International,2015,75:1-10.
[25]KISHIMOTO T,WANIKAWA A,KAGAMI N A,et al.Analysis of hop-derived terpenoids in beer and evaluation of their behavior using the stir bar-sorptive extraction method with GC-MS[J].Journal of Agricultural&Food Chemistry,2005,53(12):4701-4707.DOI:10.1021/jf050072f.
[26]ROBERTS M T,DUFOUR J,LEWIS A C.Application of comprehensive multidimensional gas chromatography combined with time-of-flight mass spectrometry(GC×GC-TOF MS)for high resolution analysis of hop essential oil[J].Journal of Separation Science,2004,27(5/6):473-478.DOI:10.1002/jssc.200301669.
[27]MARTIN S,WOLFGANG W,PETER S.Comparison of the most odour-active volatiles in different hop varieties by application of a comparative aroma extract dilution analysis[J].European Food Research&Technology,2007,226(1/2):45-55.DOI:10.1007/s00217-006-0507-6.
[28]VAN O F,PRAET T,AERTS G,et al.Characterization of novel single-variety oxygenated sesquiterpenoid hop oil fractions via headspace solid-phase microextraction and gas chromatographymass spectrometry/olfactometry[J].Journal of Agricultural&Food Chemistry,2013,61(44):10555.DOI:10.1021/jf402496.
[29]SHARPE F R,LAWS D R J.The essential oil of hops:a review[J].Journal of the Institute of Brewing,2013,87(2):96-107.
[30]HALEY J,PEPPARD T L.Differences in utilization of the essential oil of hops during the production of dry-hopped and late-hopped beers[J].Journal of the Institute of Brewing,1983,89(2):87-91.DOI:10.1002/j.2050-0416.1983.tb04153.x.
[31]LERMUSIEAU G,BULENS M,COLLIN S.Use of GC-olfactometry to identify the hop aromatic compounds in beer[J].Journal of Agricultural&Food Chemistry,2001,49(8):3867-3874.DOI:10.1021/jf0101509.
[32]NANCE M R,SETZER W N.Volatile components of aroma hops(Humulus lupulus L.)commonly used in beer brewing[J].Journal of Brewing&Distilling,2011,2:16-22.
[33]EISENREICH W,SAGNER S,ZENK M H,et al.Monoterpenoid essential oils are not of mevalanoid origin[J].Tetrahedron Letters,1997,38(22):3889-3892.DOI:10.1016/S0040-4039(97)00761-2.
[34]TAKOI K,KOIE K,ITOGA Y,et al.Biotransformation of hop-derived monoterpene alcohols by lager yeast and their contribution to the flavor of hopped beer[J].Journal of Agricultural and Food Chemistry,2010,58(8):5050-5058.DOI:10.1021/jf1000524.
[35]刘玉梅.啤酒花的分析评价及六氢蛇麻酮类的合成与应用[D].无锡:江南大学,2007.
[36]何敏,陆健,张志军.里那醇在啤酒酒花风味建模中的作用[J].啤酒科技,2011(5):71-73.
[37]范有成.香料及其应用[M].北京:化学工业出版社,1990:16-20.
[38]FENAROLI G,PROF D R,BELLANCA N,et al.Fenaroli’s handbook of flavor ingredients[M].2nd ed.Ohio,USA:CRI Press,1975.
[39]孙宝国,陈海涛.食用调香术[M].3版.北京:化学工业出版社,2017:122-130.
[40]刘强,冒德寿,汤峨,译.化合物香味阈值汇编[M].2版.北京:科学出版社,2015.
[41]CZERNY M,CHRISTLBAUER M,CHRISTLBAUER M,et al.Re-investigation on odour thresholds of key food aroma compounds and development of an aroma language based on odour qualities of defined aqueous odorant solutions[J].European Food Research&Technology,2008,228(2):265-273.DOI:10.1007/s00217-008-0931-x.
[42]刘霞.干加酒花工艺、干加酒花品种及品种组合对啤酒特征的影响[J].啤酒科技,2017(5):22-31.
[43]全巧玲,江伟,王德良,等.单萜醇类在啤酒发酵过程中的变化及对酒花香气的贡献[J].食品与发酵工业,2013,39(5):170-175.DOI:10.13995/j.cnki.11-1802/ts.2013.05.043.
[44]李祖光,李建亮,曹慧,等.紫藤鲜花在不同开花期的头香成分[J].浙江林学院学报,2009,26(3):308-313.
[45]SCHIEBERLE P.New developments in methods for analysis of volatile flavor compounds and their precursors[J].Characterization of Food,1995,65(7):403-431.DOI:10.1016/B978-044481499-9/50018-4.