挥发性硫醇类化合物是对酱香型白酒风味品质具有重要影响的一类“量微香大”风味组分,解析酱香型白酒酿造过程中挥发性硫醇类化合物的含量分布规律,对于酱香型白酒风味品质的科学控制具有重要意义。该研究采用4,4′-联吡啶二硫醚(4,4′-dithiodipyridine,DTDP)衍生化结合固相萃取(solid phase extraction,SPE)前处理,通过超高效液相色谱串联质谱(ultra-performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)技术,建立了酱香型白酒中9种代表性挥发性硫醇类化合物的检测方法,并对酱香型白酒酿造不同轮次(1~7轮次基酒)以及单一轮次不同时间(60 min内)蒸馏出的馏分酒中的挥发性硫醇类化合物的含量变化规律进行了解析。研究结果表明,3组不同轮次酱香型白酒中香气阈值极低的2-甲基-3-呋喃硫醇(含量范围:0.65~17.31 μg/L)、糠硫醇(含量范围:16.96~26.09 μg/L)等重要挥发性硫醇类化合物,随着酿造轮次的升高,其含量整体呈现一定上升的趋势。3层(上层、中层和下层)发酵酒醅蒸馏出来的馏分酒中挥发性硫醇的含量绝大部分呈现出先上升后下降的变化规律,部分硫醇含量变化稳定,蒸馏过程中的热反应促进了挥发性硫醇类化合物的生成。
[1] 崔利. 酱香型白酒“四高两长”酿酒理论的作用、价值、地位之我见[J].酿酒, 2022, 49(5):3-6.
CUI L.My opinion on the role, value and status of the “Four High and Two Long” theory in Maotai-flavor liquor making[J].Liquor Making, 2022, 49(5):3-6.
[2] SHEN T, LIU J, WU Q, et al.Increasing 2-furfurylthiol content in Chinese sesame-flavored Baijiu via inoculating the producer of precursor l-cysteine in Baijiu fermentation[J].Food Research International, 2020, 138:109757.
[3] CHEN S, SHA S, QIAN M, et al.Characterization of volatile sulfur compounds in Moutai liquors by headspace solid-phase microextraction gas chromatography-pulsed flame photometric detection and odor activity value[J].Journal of Food Science, 2017, 82(12):2816-2822.
[4] YAN Y, LU J, NIE Y, et al.Characterization of volatile thiols in Chinese liquor (Baijiu) by ultraperformance liquid chromatography-mass spectrometry and ultraperformance liquid chromatography-quadrupole-time-of-flight mass spectrometry[J].Frontiers in Nutrition, 2022, 9:1022600.
[5] 王露露. 酱香型白酒中呈“盐菜味”异嗅味关键香气化合物解析[D].无锡:江南大学,2020.
WANG L L.Characterization of potent odorants causing a “pickle-like” off-odor in soy sauce-aroma type Baijiu[D].Wuxi:Jiangnan University, 2020.
[6] SHA S, CHEN S, QIAN M, et al.Characterization of the typical potent odorants in Chinese roasted sesame-like flavor type liquor by headspace solid phase microextraction-aroma extract dilution analysis, with special emphasis on sulfur-containing odorants[J].Journal of Agricultural and Food Chemistry, 2017, 65(1):123-131.
[7] SUN J Y, WANG Z, SUN B G.Low quantity but critical contribution to flavor:Review of the current understanding of volatile sulfur-containing compounds in Baijiu[J].Journal of Food Composition and Analysis, 2021, 103:104079.
[8] 乔岩, 李大鹏, 卢红梅, 等.不同贮存条件对酱香型第5轮次酒影响初探[J].食品科技, 2015, 40(6):47-50.
QIAO Y, LI D P, LU H M, et al.The influence of different storage conditions to the fifth batch Moutai flavor liquor[J].Food Science and Technology, 2015, 40(6):47-50.
[9] 王俊, 陈仁远, 赵文武, 等.仁怀大曲酱香轮次基酒质量状况研究[J].中国酿造, 2016, 35(11):103-107.
WANG J, CHEN R Y, ZHAO W W, et al.Research on the quality of basic batch distillates for Renhuai Daqu Moutai-flavor Baijiu (Chinese liquor)[J].China Brewing, 2016, 35(11):103-107.
[10] HOFMANN T, SCHIEBERLE P, GROSCH W.Model studies on the oxidative stability of odor-active thiols occurring in food flavors[J].Journal of Agricultural and Food Chemistry, 1996, 44(1):251-255.
[11] PIANO F, FRACASSETTI D, BUICA A, et al.Development of a novel liquid/liquid extraction and ultra-performance liquid chromatography tandem mass spectrometry method for the assessment of thiols in South African Sauvignon Blanc wines[J].Australian Journal of Grape and Wine Research, 2015, 21(1):40-48.
[12] MATEO-VIVARACHO L, CACHO J, FERREIRA V.Selective preconcentration of volatile mercaptans in small SPE cartridges:Quantitative determination of trace odor-active polyfunctional mercaptans in wine[J].Journal of Separation Science, 2009, 32(21):3845-3853.
[13] CAPONE D L, RISTIC R, PARDON K H, et al.Simple quantitative determination of potent thiols at ultratrace levels in wine by derivatization and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis[J].Analytical Chemistry, 2015, 87(2):1226-1231.
[14] MATEO-VIVARACHO L, CACHO J, FERREIRA V.Improved solid-phase extraction procedure for the isolation and in-sorbent pentafluorobenzyl alkylation of polyfunctional mercaptans[J].Journal of Chromatography A, 2008, 1 185(1):9-18.
[15] LEIS D, VISKIĆ M, JEROMEL A, et al.Analysis of varietal thiols in Sauvignon Blanc wines-Optimization of a solid-phase extraction gas chromatography tandem mass spectrometry method[J].Food Analytical Methods, 2022, 15(6):1591-1605.
[16] HERBST-JOHNSTONE M, PIANO F, DUHAMEL N, et al.Ethyl propiolate derivatisation for the analysis of varietal thiols in wine[J].Journal of Chromatography A, 2013, 1312:104-110.
[17] WU Z Y, QIN D, DUAN J W, et al.Characterization of benzenemethanethiol in sesame-flavour Baijiu by high-performance liquid chromatography-mass spectrometry and sensory science[J].Food Chemistry, 2021, 364:130345.
[18] MAFATA M, STANDER M, THOMACHOT B, et al.Measuring thiols in single cultivar South African red wines using 4,4-dithiodipyridine (DTDP) derivatization and ultraperformance convergence chromatography-tandem mass spectrometry[J].Foods, 2018, 7(9):138.
[19] RIENER C K, KADA G, GRUBER H J.Quick measurement of protein sulfhydryls with Ellman′s reagent and with 4,4′-dithiodipyridine[J].Analytical and Bioanalytical Chemistry, 2002, 373(4-5):266-276.
[20] 杨萍, 胡萍, 樊敏, 等.酱香型酒曲及窖内酒醅挥发性成分的分析[J].中国酿造, 2018, 37(11):166-171.
YANG P, HU P, FAN M, et al.Analysis of the volatile components from Jiuqu and fermented grains in the pits of the sauce-flavor Baijiu[J].China Brewing, 2018, 37(11):166-171.
[21] 张春林, 杨亮, 李喆, 等.酱香型白酒酒醅堆积微生物多样性及其与风味物质的关系[J].食品科技, 2022, 47(4):111-118.
ZHANG C L, YANG L, LI Z, et al.Microbial community and its relationship with volatile compounds in Moutai-flavor Baijiu stacking fermentation process[J].Food Science and Technology, 2022, 47(4):111-118.
[22] LANDAUD S, HELINCK S, BONNARME P.Formation of volatile sulfur compounds and metabolism of methionine and other sulfur compounds in fermented food[J].Applied Microbiology and Biotechnology, 2008, 77(6):1191-1205.
[23] ZHA M S, YIN S, SUN B G, et al.STR3 and CYS3 contribute to 2-furfurylthiol biosynthesis in Chinese sesame-flavored Baijiu yeast[J].Journal of Agricultural and Food Chemistry, 2017, 65(27):5503-5511.
[24] MOTTRAM D S, NOBREGA I C C.Formation of sulfur aroma compounds in reaction mixtures containing cysteine and three different forms of ribose[J].Journal of Agricultural and Food Chemistry, 2002, 50(14):4080-4086.