MTBSTFA衍生化结合GC-MS分析镇江香醋不挥发羧酸
|
摘要
以镇江香醋为研究对象,利用N-特丁基二甲基硅烷基-N-甲基三氟乙酰胺(N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide,MTBSTFA)衍生化结合气相色谱-质谱法(GC-MS)分离鉴定香醋中不挥发羧酸,共鉴定并定量61种不挥发化合物,包括17种氨基酸、13种芳香酸、11种羟基酸、8种长链脂肪酸、7种二元及多元酸(不含羟基)、1种含硫有机酸、1种酮酸,2种杂环酸和1种不挥发酸酯。新检测到2-糠酸、乙醇酸、3-羟基丙酸、甘油酸、扁桃酸、对羟基苯乙酸、2,6-二羟基苯甲酸、原儿茶酸、阿魏酸、柠檬酸、芥子酸、没食子酸、咖啡酸等24种不挥发有机酸。研究结果表明,香醋中羟基酸(16.01 g/L)含量最高,其次是杂环酸(597. 3 mg/L)和氨基酸(546. 5 mg/L);单个酸含量大于100 mg/L的有乳酸、焦谷氨酸、琥珀酸、精氨酸、草酰乙酸和2-羟基-3-苯丙酸(从高到低依次)。该研究将为我国食醋品质的提升奠定基础。
The non-volatile carboxylic acids in Zhenjiang balsamic vinegar were derivatized by N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide( MTBSTFA) and detected by gas chromatography-mass spectrometry. A total of61 non-volatile compounds were identified,including 17 amino acids,13 aromatic acids,11 hydroxy acids,eight long-chain fatty acids,seven dicarboxylic and polyhydric acids( no hydroxyl groups),one sulfur-containing organic acid,one keto acid,two heterocyclic acids,and one non-volatile ester acid. Among them,the concentrations of hydroxy acids were the highest( 16. 01 g/L),followed by heterocyclic acids( 597. 3 mg/L) and amino acids( 546. 5 mg/L).There were 24 newly identified non-volatile organic acids,including 2-furoic acid,glycolic acid,3-hydroxypropionic acid,glyceric acid,mandelic acid,p-hydroxyphenylacetic acid,2,6-dihydroxybenzoic acid,protocatechuic acid,ferulic acid,citric acid,sinapinic acid,gallic acid,and caffeic acid. In which,lactic acid,pyroglutamic acid,succinic acid,arginine,oxaloacetic,and 2-hydroxy-3-phenylpropionic acid were higher than 100 mg/L. These results lay a foundation to improve the quality of Chinese vinegar.
The non-volatile carboxylic acids in Zhenjiang balsamic vinegar were derivatized by N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide( MTBSTFA) and detected by gas chromatography-mass spectrometry. A total of61 non-volatile compounds were identified,including 17 amino acids,13 aromatic acids,11 hydroxy acids,eight long-chain fatty acids,seven dicarboxylic and polyhydric acids( no hydroxyl groups),one sulfur-containing organic acid,one keto acid,two heterocyclic acids,and one non-volatile ester acid. Among them,the concentrations of hydroxy acids were the highest( 16. 01 g/L),followed by heterocyclic acids( 597. 3 mg/L) and amino acids( 546. 5 mg/L).There were 24 newly identified non-volatile organic acids,including 2-furoic acid,glycolic acid,3-hydroxypropionic acid,glyceric acid,mandelic acid,p-hydroxyphenylacetic acid,2,6-dihydroxybenzoic acid,protocatechuic acid,ferulic acid,citric acid,sinapinic acid,gallic acid,and caffeic acid. In which,lactic acid,pyroglutamic acid,succinic acid,arginine,oxaloacetic,and 2-hydroxy-3-phenylpropionic acid were higher than 100 mg/L. These results lay a foundation to improve the quality of Chinese vinegar.
引文
[1]徐清萍.食醋生产技术问答[M].北京:中国纺织出版社,2011.
[2]余永建.镇江香醋有机酸组成及乳酸合成的生物强化[D].无锡:江南大学,2014.
[3]乔艳霞.食醋陈化过程中有机酸、抗氧化能力及风味物质监测研究[D].杨凌:西北农林科技大学,2014.
[4]李国权,陆震鸣,余永建,等.镇江香醋有机酸风味特征的分析[J].中国调味品,2013,38(11):63-65.
[5]王贵双,唐坤甜,鲁绯,等.离子交换色谱法测定食醋中有机酸[J].中国酿造,2010,29(7):166-168.
[6]HILLMANN H,MATTES J,BROCKHOFF A,et al. Sensomics analysis of taste compounds in balsamic vinegar and discovery of 5-acetoxymethyl-2-furaldehyde as a novel sweet taste modulator[J]. J Agric Food Chem,2012,60(40):9 974-9 990.
[7]BOFFO E F,TAVARES L A,FERREIRA M M C,et al.Classification of Brazilian vinegars according to their l H NMR spectra by pattern recognition analysis[J]. LWTFood Science and Technology,2009,42(9):1 455-1 460.
[8]余宁华,陆震鸣,许伟,等.基于主成分分析的中国发酵食醋有机酸含量差异性分析[J].食品与发酵工业,2010,36(10):144-148.
[9]尹俊玲.传统手工和现代工业化生产镇江香醋风味组分的比较研究[D].镇江:江苏大学,2016.
[10]袁源.镇江香醋挥发性香气物质研究[D].无锡:江南大学,2018.
[11]聂佳慧,李艺,秦雪梅,等.谷物酿造传统食醋化学成分研究进展[J].食品科学,2018,39(19):322-328.
[12]黄志,龙帅,沙云菲,等.硅烷化衍生-气相色谱-质谱联用法测定烟草中的游离氨基酸[J].分析试验室,2017,(11):1 341-1 346.
[13]杨会.白酒中不挥发呈味有机酸和多羟基化合物研究[D].无锡:江南大学,2017.
[14]江流.芝麻香型酒醅中游离态不挥发物质的研究[D].无锡:江南大学,2017.
[15]CLAUDE S,OLIVIER D,APPENZELLER B M R,et al. Comparison of MTBSTFA and BSTFA in derivatization reactions of polar compounds prior to GC/MS analysis[J]. Talanta,2009,77(4):1 473-1 482.
[16]ESTEFANíA J M,JORGE R,TRINIDAD P P,et al.Gas chromatography-mass spectrometry method for the determination of free amino acids as their dimethyl-tert-butylsilyl(TBDMS)derivatives in animal source food[J].Journal of Agricultural and Food Chemistry,2012,60(10):2 456-2 463.
[17]范文来,徐岩.酒类风味化学[M].北京:中国轻工业出版社,2014.
[18]王琳,陈双,徐岩.固相萃取-超高效液相色谱法测定黄酒中的有机酸[J].食品与发酵工业,2016,42(10):142-148.
[19]GB/T 18623—2011,地理标志产品镇江香醋[S].北京:中国标准出版社,2011.
[20]朱其瀚.镇江香醋发酵过程中微生物分离及其产酸特性[D].无锡:江南大学,2008.
[21]张宝善.食醋酿造学[M].北京:科学出版社,2014.
[22]MANDAL S M,CHAKRABORTY D,DEY S. Phenolic acids act as signaling molecules in plant-microbe symbioses[J]. Plant signaling&behavior,2010,5(4):359-368.
[23]HILLMANN H,HOFMANN T. Quantitation of key tastants and re-engineering the taste of parmesan cheese[J]. J Agric Food Chem,2016,64(8):1794-805.
[24]王镜岩,朱圣庚,徐长法.生物化学[M].北京:高等教育出版社,2002.
[2]余永建.镇江香醋有机酸组成及乳酸合成的生物强化[D].无锡:江南大学,2014.
[3]乔艳霞.食醋陈化过程中有机酸、抗氧化能力及风味物质监测研究[D].杨凌:西北农林科技大学,2014.
[4]李国权,陆震鸣,余永建,等.镇江香醋有机酸风味特征的分析[J].中国调味品,2013,38(11):63-65.
[5]王贵双,唐坤甜,鲁绯,等.离子交换色谱法测定食醋中有机酸[J].中国酿造,2010,29(7):166-168.
[6]HILLMANN H,MATTES J,BROCKHOFF A,et al. Sensomics analysis of taste compounds in balsamic vinegar and discovery of 5-acetoxymethyl-2-furaldehyde as a novel sweet taste modulator[J]. J Agric Food Chem,2012,60(40):9 974-9 990.
[7]BOFFO E F,TAVARES L A,FERREIRA M M C,et al.Classification of Brazilian vinegars according to their l H NMR spectra by pattern recognition analysis[J]. LWTFood Science and Technology,2009,42(9):1 455-1 460.
[8]余宁华,陆震鸣,许伟,等.基于主成分分析的中国发酵食醋有机酸含量差异性分析[J].食品与发酵工业,2010,36(10):144-148.
[9]尹俊玲.传统手工和现代工业化生产镇江香醋风味组分的比较研究[D].镇江:江苏大学,2016.
[10]袁源.镇江香醋挥发性香气物质研究[D].无锡:江南大学,2018.
[11]聂佳慧,李艺,秦雪梅,等.谷物酿造传统食醋化学成分研究进展[J].食品科学,2018,39(19):322-328.
[12]黄志,龙帅,沙云菲,等.硅烷化衍生-气相色谱-质谱联用法测定烟草中的游离氨基酸[J].分析试验室,2017,(11):1 341-1 346.
[13]杨会.白酒中不挥发呈味有机酸和多羟基化合物研究[D].无锡:江南大学,2017.
[14]江流.芝麻香型酒醅中游离态不挥发物质的研究[D].无锡:江南大学,2017.
[15]CLAUDE S,OLIVIER D,APPENZELLER B M R,et al. Comparison of MTBSTFA and BSTFA in derivatization reactions of polar compounds prior to GC/MS analysis[J]. Talanta,2009,77(4):1 473-1 482.
[16]ESTEFANíA J M,JORGE R,TRINIDAD P P,et al.Gas chromatography-mass spectrometry method for the determination of free amino acids as their dimethyl-tert-butylsilyl(TBDMS)derivatives in animal source food[J].Journal of Agricultural and Food Chemistry,2012,60(10):2 456-2 463.
[17]范文来,徐岩.酒类风味化学[M].北京:中国轻工业出版社,2014.
[18]王琳,陈双,徐岩.固相萃取-超高效液相色谱法测定黄酒中的有机酸[J].食品与发酵工业,2016,42(10):142-148.
[19]GB/T 18623—2011,地理标志产品镇江香醋[S].北京:中国标准出版社,2011.
[20]朱其瀚.镇江香醋发酵过程中微生物分离及其产酸特性[D].无锡:江南大学,2008.
[21]张宝善.食醋酿造学[M].北京:科学出版社,2014.
[22]MANDAL S M,CHAKRABORTY D,DEY S. Phenolic acids act as signaling molecules in plant-microbe symbioses[J]. Plant signaling&behavior,2010,5(4):359-368.
[23]HILLMANN H,HOFMANN T. Quantitation of key tastants and re-engineering the taste of parmesan cheese[J]. J Agric Food Chem,2016,64(8):1794-805.
[24]王镜岩,朱圣庚,徐长法.生物化学[M].北京:高等教育出版社,2002.