老抽酱油储存期间关键气味物质分析及其风味特征的变化

为阐明老抽酱油在不同储存期的关键气味化合物及其风味特征的变化,采用液液萃取与气相色谱-嗅闻-质谱(GC-O-MS)相结合提取并鉴定不同储存期老抽酱油中的挥发性气味化合物,并利用香味提取物稀释分析(AEDA)鉴定关键气味化合物。结果表明:在老抽酱油样品中共检测到56种气味活性物质,其中FD因子>1024的化合物分别为2-甲基吡嗪、2,6-二甲基吡嗪、5-甲基-2(3H)-呋喃酮、2-乙酰基呋喃、2-乙酰基-5-甲基呋喃、1,4-丁内酯、5-甲基-2-呋喃甲醇、2-羟基-3-甲基-2-环戊烯酮、愈创木酚、麦芽酚和4-羟基-2,5-二甲基-3(2H)-呋喃酮 (HDMF),其中,2,6-二甲基吡嗪、5-甲基-2(3H)-呋喃酮、2-羟基-3-甲基-2-环戊烯酮、麦芽酚和HDMF的香气活性值>1,对老抽酱油整体香气起主要贡献作用。感官评价结果表明,老抽酱油随着储存时间的延长,烤香味和烟熏味的气味强度得分升高。该研究分析了老抽酱油的关键气味化合物以及在储存过程中气味特征变化,为老抽酱油相关风味研究提供了理论参考。     

Formation of Volatile Compounds During Bacillus subtilis Fermentation of Soya Beans

The formation of volatile compounds during the Bacillus subtilis fermentation of cooked, roasted soya bean cotyledons was investigated. The materials examined were: dry roasted cotyledons; autoclaved, roasted cotyledons; and autoclaved, roasted cotyledons fermented for 18 h and 36 h at 35°C. Growth of B subtilis led to the formation of many volatile compounds. The volatile compounds formed in the largest amounts during fermentation were 3-hydroxy-2-butanone (acetoin), 2,5-dimethylpyrazine and trimethylpyrazine. Compounds present at concentrations exceeding their odour threshold values included nonanal, decanal, 1-octen-3-ol, butanedione, 3-hydroxy-2-butanone, 3-octanone, 2,5-dimethylpyrazine, 3,6-dimethyl-2-ethylpyrazine, 2-pentylfuran, dimethyl sulfide, benzaldehyde and 2-methoxyphenol. Compounds found in 18 h fermented cotyledons which were absent, or present in much lower concentrations, in roasted or autoclaved cotyledons included several aliphatic ketones, acetic acid, two aliphatic esters, several pyrazines, 2-pentylfuran, dimethyl sulphide, 2-methoxyphenol and trimethyloxazole. The total mass of volatile compounds present after 36 h incubation was less than half that present after 18 h. This was mainly due to the disappearance of 3-hydroxy-2-butanone, 2,5-dimethylpyrazine and 2,6-dimethylpyrazine. The biogenesis of the volatile compounds is discussed. © 1997 SCI.     

Reducing the Influence of the Thermally Induced Reactions on the Determination of Aroma-Active Compounds in Soy Sauce Using SDE and GC-MS/O

A method based on simultaneous distillation extraction (SDE) coupled with gas chromatography–mass spectrometry/olfactometry (GC-MS/O) was developed for the analysis of volatile profiles in soy sauce. Its optimum operating conditions were as follows: 100 mL soy sauce plus 100 mL saturated brine; 2 h extraction using 50 mL dichloromethane. Eighty-eight volatile compounds were identified. Of these, 26 aroma-active compounds were detected by GC-O including 3-(methylthio)propanal, 2-methoxy-4-vinylphenol, 2-methoxyphenol, 2-methylbutanoic acid, 2,3-butanedione, phenylacetaldehyde, 2-ethyl-6-methylpyrazine, 3-methylbutanal, 2-methylbutanal, 3-methyl-1-butanol, and 2-methyl-1-butanol (which occurred at a high odor intensity in both high-salt liquid-state fermentation soy sauce (HLFSS) and low-salt solid-state fermentation soy sauce (LSFSS). SDE analysis of the odorless soy sauce indicated 12 volatiles (mainly Strecker aldehydes and α-dicarbonyl compounds). Thus, the proportions of these compounds (1.94–54.07 %) shown in previous GC-MS results could result from thermal degradation of non-volatile compounds in soy sauce. Especially, the contribution of 3-methylbutanal, 2-methylbutanal, phenylacetaldehyde, 3-(methylthio)propanal, and 2,3-butanedione to the aroma of soy sauce could be overestimated by conventional SDE-GC-O. With a full consideration of such limitations, this study will improve the application of SDE on aroma analysis of complex food matrix.     

不同酱醅层挥发性物质组成的差异

在高盐稀态酱油生产工艺中,采用大型发酵罐替代传统发酵池是酱油工业现代化的重要趋势,然而发酵池酿造酱油比发酵罐酿造酱油酱香更为浓郁,推测这与不同酱醅接触光照、空气的表面积差异有关。因此,本研究对比了不同酱醅层的香气物质组成和浓度。结果发现,发酵池酱油部分优势的关键香气活性物质,如2-甲基丙醇,3-甲基丁醇,2-甲基丁醇,苯乙醇,苯乙醛,3-甲基丁酸,2-甲基丁酸,4-乙基苯酚,4-乙基愈创木酚和愈创木酚在表层酱醅含量高于下层酱醅,而发酵罐酱油的优势香气物质1-辛烯-3-醇和3-甲硫基丙醛在下层酱醅含量高于表层酱醅,这些物质差异的一致性表明酱醅表面积会影响酱油香气物质形成,而表层酱醅美拉德反应程度更强烈、下层酱醅酵母菌和乳酸菌更加活跃是引起表层酱醅和下层酱醅香气物质差异的重要原因。     

Volatile profiles of thua nao, a Thai fermented soy product

Thua nao, a Thai traditional fermented soybean has a unique odour due to the presence of several volatile components. In this investigation, the cooked non-fermented soybeans and soybean (thua nao) fermented by pure Bacillus subtilis TN51 (TNB51) and naturally fermented soybean (TNMX) were analysed for odour components by GC–MS, using the PDMS-SPME head space technique. The quantities of total volatiles in both TNB51 and TNMX were analogous, but the major volatile classes present in TNB51 and TNMX were pyrazines and ketones, respectively. The predominant volatiles in pure Bacillus-fermented thua nao included 2,5-dimethylpyrazine, 2-methylbutanoic acid, 2,3,5-trimethylpyrazine, 2-methylpropanoic acid and acetic acid, whereas the major volatiles in the naturally fermented soybean included 2,5-dimethylpyrazine, benzaldehyde, 5-methyl-3-hexanone, 2-butanone and 3-methyl-2-pentanone. In total, 85 volatile compounds were detected.     

气相色谱-嗅闻/质谱联用分析酵母菌发酵酱油中香气物质

酱油香气物质的形成与酵母菌的代谢息息相关,本文旨在研究酵母菌对发酵酱油中香气物质形成与含量的影响。采用固相微萃取(SPME)结合气相色谱-嗅闻-质谱(GC-O/MS)联用技术分别对不加酵母菌、加AY酵母菌以及加入T酵母菌发酵制得酱油中的香气物质进行检测分析。结果显示:加入酵母菌的酱油中形成的各类香气物质更加丰富,其中AY型鲁氏酵母菌能够产生更多种类的酯类(11种)及醇类(12种)物质;T型鲁氏酵母菌有助于醛类(7种)物质的形成。且AY型鲁氏酵母菌在酱油酿造过程中产生的酯类(155.19 μg/L)、呋喃酮类(68.53 μg/L)、醛类(86.46 μg/L)等物质的含量更高,T型鲁氏酵母菌的产醇类(1260.64 μg/L)物质能力则更加优越。通过对酱油样品中OAV的计算,发现,AY酵母菌酿造酱油中的4-羟基-2-甲基-5-乙基-3(2H)-呋喃酮(HEMF),2/3-甲基丁醛、及苯乙醛的OAV高于其他样品的OAV值,T型鲁氏酵母菌的1-辛烯-3-醇及3-甲硫基丙醛的OAV值高于其他样品的OAV值。将OAV值与PCA结合分析,可以看出,AY型鲁氏酵母菌发酵酱油的香气优势明显,并且T型鲁氏酵母菌发酵酱油以熟土豆气味为主,并伴有蘑菇香气;AY型鲁氏酵母菌发酵酱油以甜香香气为主,并伴有麦芽香气。综上,AY型鲁氏酵母菌的整体产香优于T型鲁氏酵母菌的产香效果。     

米曲霉发酵高盐稀态酱油过程中典型挥发性风味物质的形成

米曲霉是发酵酱油的主要菌种,为了更加具体了解米曲霉发酵酱油过程中典型挥发性风味物质的形成,该研究利用气相色谱-质谱联用（GC-MS）仪对沪酿3.042米曲霉单菌种发酵高盐稀态酱油在不同发酵阶段的酱醪进行挥发性风味物质检测,并与12种市售高盐稀态酱油的挥发性风味物质进行对比验证。结果表明,酱醪发酵0～6个月的过程中,醇酚类、酸类物质、酯类物质、含氮化合物含量逐渐增加,挥发性风味物质之间组成比例更加协调,典型的挥发性风味物质包括乙醇、乙酸、3-甲基丁酸、苯乙酸乙酯、十六酸乙酯、2,5-二甲基吡嗪、2,3,5-三甲基吡嗪、苯甲醛、苯乙醛,与市售酱油中典型的挥发性风味物质相同,这些物质保证了酱油风味的相似性。     

不同淀粉质原料对高盐稀态酱油香气品质的影响

为了研究不同淀粉质原料(面粉、麸皮)对高盐稀态酱油香气品质的影响,本文利用定量描述分析(QDA)对面粉类酱油(FSS)、麸皮类酱油(WSS)的感官特征进行分析,通过顶空-固相微萃取(HS-SPME)和液液萃取(LLE)结合气相色谱-质谱联用(GC-MS)定量对比分析了两种酱油挥发性化合物组成。FSS中酸香、土豆香、麦芽香显著性高于WSS,焦糖香、烟熏香显著性低于WSS(p0.05)。GC-MS共分离鉴定出94种挥发性化合物,其中以酸类、酮类、醛类占主要比例,HS-SPME法能萃取出较多的醛类、含硫化合物,LLE法对呋喃(酮)类、酸类化合物萃取效果较好。通过对酱油中17种关键香气活性物质定量分析以及香气活性值(OAV)的计算,有9种化合物OAV值大于20。其中3-甲基丁醛OAV值最高,HDMF、愈创木酚均有较高的OAV值,且在WSS中高于FSS,与感官分析中的焦糖香、烟熏香结果一致;FSS中2-甲基丁醛、3-甲硫基丙醛的OAV值高于WSS,与麦芽香、土豆香感官分析结果相符。     

SPME-DSE联用分析不同固形物浓度发酵对酱油香气物质的影响

通过固相微萃取(SPME)、直接溶剂萃取(DSE)以及气相色谱-质谱(GC-MS)结合的方法,研究不同固形物浓度(S1.1,S1.5,S2.0,S2.5)发酵对酱油香气物质的影响。SPME和DSE共检测出114种挥发性香气成分,其中含量较多的物质是醇(12种),酸(6种),醛(12种)、酮(14种)、酯(15种)。GC-MS分析得出,四种固形物浓度测得的香气物质种类相同,但含量却有较大差异。随着固形物浓度的增加,酸和醛类化合物的含量呈现增长趋势,其中酸类物质在S1.1中的含量分别是S1.5的2.5倍,S2.0的2.2倍,S2.5的1.99倍。另外除2,3-丁二醇,愈创木酚在高固形物浓度中呈现较低含量外,其他如苯乙醇、2-3甲基-丁醛、乙酸、4-羟基-2,5-二甲基-3(2H)-呋喃酮(HDMF)和4-羟基-2-乙基-5-甲基-3(2H)-呋喃酮(HEMF)等重要香气物质均随固形物浓度的增加而提高,进一步表明提高固形物浓度有利于酱油香气的平衡。     

Functional effects of Japanese style fermented soy sauce (shoyu) and its components

The functional effects of Japanese style fermented soy sauce (shoyu) have been studied. Soy sauce promotes digestion, because the consumption of a cup of clear soup containing soy sauce enhances gastric juice secretion in humans. Soy sauce possesses antimicrobial activity against bacteria such as Staphylococcus aureus, Shigella flexneri, Vibrio cholera, Salmonella enteritidis, nonpathogenic Escherichia coli and pathogenic E. coli O157:H7. Soy sauce also contains an antihypertensive component. An angiotensin I-converting enzyme inhibitor having antihypertensive effects was found in soy sauce. The active compound was identified as nicotianamine, which comes from soybeans. Soy sauce exhibits anticarcinogenic effects. Giving diets containing soy sauce to mice inhibit benzo[a]pyrene (BP)-induced forestomach neoplasia. The anticarcinogenic compounds in soy sauce were identified. The flavor components of Japanese style fermented soy sauce, such as 4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2H)-furanone (HEMF), which is a characteristic flavor component of Japanese style fermented soy sauce and 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF) and 4-hydroxy-5-methyl-3(2H)-furanone (HMF) exhibit antioxidant activities and anticarcinogenic effects on BP-induced mice forestomach neoplasia when fed following carcinogen exposure. The feeding of a diet containing 10% soy sauce to male C3H mice for 13 months also reduces the frequency and multiplicity of spontaneous liver tumors. HDMF and HEMF also exhibit anticataract effects in the spontaneous cataract rat (ICR/f rat). Fermented soy sauce contains three tartaric isoflavone derivatives called shoyuflavones. These shoyuflavones were shown to have inhibitory activities against histidine decarboxylase, which produces histamine, a mediator of inflammation, allergy and gastric acid secretion. Soy sauce also exhibits antiplatelet activity. beta-Carbolines were isolated from soy sauce as the active compounds. Soybeans and wheat, which are the main raw materials of soy sauce, are allergenic foods. However, recent studies by enzyme-linked immunosorbent assay showed the absence of soybean and wheat allergens in soy sauce.     

细菌型豆豉香气成分的研究

用干馏法提取细菌型豆豉香气成分，气相色谱法分离，质谱法鉴定结构并与计算机系统储存的己知物质的质谱进行比较，其鉴定出27个挥发性化合物，主要挥发性成分有：十四烷、4－甲基－2，6－二叔丁基－4－羟基－2，5－环－己烯－1－酮、2，6－二叔丁基对苯醌、月桂醇、十五烷、4－甲基－2，6－二叔丁基苯酚、十六烷、1－（2－辛基环丙基）辛酮、丙烯酸月桂醇酯、十七烷、肉豆蔻酸、十八烷、2，6－二叔丁基－4－硝基苯酚、鳖酸、棕榈酸、油酸、硬脂酸等，其中关键香味化合物是：月桂醛、12－羟基－7α－桉叶－4－烯－6－酮、月桂醇、4－甲基－2，6－二叔丁基－4－羟基－2，5－环己二烯－1－酮，2，6－二叔丁基对－1－苯醌、4－甲基－2，6－二叔丁基苯酚、2－丁基－5－异丁基噻吩、1－（2－辛基环丙基）－1－辛酮、丙烯酸月桂醇酯、十五醛、六氢金合欢基丙酮，2，6－二叔丁基－4－硝基苯酚，5－十二烷基－2（3H）－呋喃酮13个化学物。     

Improvement of Fish-sauce Odor by Treatment with Bacteria Isolated from the Fish-sauce Mush (Moromi) Made from Frigate Mackerel

ABSTRACT: A bacterium, which was isolated from fish-sauce mush (moromi) of frigate mackerel and identified as Staphylococcus xylosus , could change notes of an odor in fish sauce made in Thailand. Volatile compounds of the fish sauce after incubation at 32 °C for 24 d with the cultured bacterium were analyzed by gas chromatogra-phy. Although the contents of 2-ethylpyridine and dimethyl trisulfide were reduced during the incubation, 4 volatile compounds, including 2-methylpronal, 2-methylbutanal, 2-pentanone, and 3-(methylthio)propanal, showed no significant quantity changes. On the other hand, although 3-methyl-1-butanol and 2,6-dimethylpyrazine were markedly increased, 3-methylbutanoic acid was slightly increased. As a result of sensory evaluation, fishy, sweaty, fecal, and rancid notes of the fish sauce treated with the bacterium were all weaker than those of the nontreated fish sauce. No changes were found with respect to burnt, cheesy, meaty, and ammoniacal notes between fish sauce treated with the bacterium and that without treatment. Taken together, the odor of fish sauce was much improved by treatment with the isolated bacterium.     

高盐稀态酿造酱油中香气活性成分在灭菌前后的变化

为了确定高盐稀态酿造酱油中香气活性成分在灭菌前后的变化情况,采用液液萃取结合溶剂辅助风味成分蒸发法提取灭菌前后酱油样品中的挥发性成分,采用气相色谱-嗅觉检测器联用仪对提取物进行分析,从中检测到24?种香气活性物质,经过与标准品的香气特征、质谱、保留指数进行比对,对其结构进行确定。以2-辛醇为内标,采用内标标准曲线的方法对其进行定量;根据定量结果和香气阈值,计算香气活性值。结果表明,导致灭菌前后香气差别的主要原因为3-甲硫基丙醛、麦芽酚、5-乙基-4-羟基-2-甲基-3(2H)-呋喃酮、4-羟基-2,5-二甲基-3(2H)呋喃酮、己醛、香兰素、愈创木酚和4-乙基愈创木酚质量浓度的变化,此结果与香气评价的结果一致。     

Identification of 2-ethyl-4-methyl-3-thiazoline and 2-isopropyl-4-methyl-3-thiazoline for the first time in nature by the comprehensive analysis of sesame seed oil

Toasted sesame seed oil was comprehensively analyzed. It was extracted using the SAFE (Solvent-Assisted Flavor Evaporation) technique. The extract was analyzed by GC and GC-MS on 2 phases and a total of 87 components were identified, confirmed, and are presented in this paper. The major components were methylpyrazine; 2,5-dimethylpyrazine; 2,6-dimethylpyrazine; 2-ethyl-3,6-dimethylpyrazine; furfuryl alcohol; and guaiacol. In addition, as part of this analysis, 2-ethyl-4-methyl-3-thiazoline and 2-isopropyl-4-methyl-3-thiazoline were confirmed as being present in a natural product for the first time. Their identification, confirmation, and sensory evaluation have been documented here.     

Olfactometric characterization of aroma active compounds in fermented fish paste in comparison with fish sauce,fermented soy paste and sauce products

Aroma active compounds in commercial fermented fish meat paste product (fish miso), fermented soy paste (soy miso), fish sauce and soy sauces were characterized by using a dynamic headspace method for volatile isolation and GC olfactometry for odor perception. A total of 123 volatile compounds consisting mainly of aldehydes, alcohols, esters, ketones, furans, sulfur and nitrogen-containing compounds, aromatics and acids were consistently identified. A major 16 odor-active compounds were distinguished to contribute as key aroma compounds for the miso and sauce products. Olfactometric and sensory findings clearly differentiated miso products with caramelic, fruity aroma notes, whereas fish sauce products were characterized by ammoniacal, fishy, nutty and cheesy odor note. Soy sauce products, however, were dominated by nutty and cheese aroma. Use of koji for fish miso production was found effective to enhance sweet aroma to the product with a reduction of nutty, meaty and rancid nuance. Principal component analysis employed for statistical interpretations clearly elucidated the relationship among different types of fermented products.     

面粉对发酵酱油品质的影响研究

在工业化生产条件下,以面粉和小麦粉混合发酵酱油(FWSS)和纯小麦粉发酵酱油(WSS)为研究对象,通过测定其理化指标、氨基酸组成以及挥发性化合物组成,结合感官评价结果分析两类酱油风味品质差异的形成原因。结果显示：除总酸外,其他理化指标均无显著性差异;FWSS酱油中大部分氨基酸含量均高于WSS酱油,差异较大的为谷氨酸含量(FWSS=21.11%,WSS=20.35%)。挥发性化合物测定结果显示FWSS酱油挥发性化合物相对含量较高,其中酱油中常见的香气活性物质4-羟基-5-乙基-2-甲基-3(2H)-呋喃酮(HEMF,焦糖香),4-乙基愈创木酚(4-EG,烟熏香)含量差异较为明显,与感官评价结果中FWSS酱油其烟熏香味、焦糖香味更加丰富的结果一致。表明在工业生产中,加入40%的面粉替代小麦粉发酵酱油(FWSS),可明显降低酱油中总酸含量(FWSS的总酸含量为1.15 g/100 g,WSS的总酸含量为1.24 g/100 g),提高酱油的香气饱满度和滋味特征。本研究可为高盐稀态酱油的风味品质提升提供理论指导。     

基于气相色谱-质谱技术与多元统计方法分析大河乌猪火腿自然发酵过程中风味特征

为揭示大河乌猪火腿自然发酵过程中特征风味物质的变化,采用固相微萃取-气相色谱-质谱技术并结合多元统计分析方法对大河乌猪火腿挥发性风味物质进行分析.结果表明:发酵过程中共鉴定出135种挥发性风味物质,其中醛类21种、醇类26种、烃类30种、酮类14种、酯类8种、酸类11种、芳香族化合物7种、其他18种;基于变量重要性投影...     

Identification of aroma compounds in Parmigiano-Reggiano cheese by gas chromatography/olfactometry

The volatile compounds in Parmigiano-Reggiano cheese were isolated by solvent extraction/high vacuum distillation, followed by separation into acidic, basic, water-soluble, and neutral fractions. The neutral fraction was further fractionated by a normal-phase liquid chromatography. Aroma compounds were identified using gas chromatography/Osme-mass spectrometry and confirmed with retention index of standards. Butanoic, hexanoic, octanoic, and decanoic acids are the major free fatty acids contributing to cheesy, lipolyzed aroma. Ethyl butanoate, ethyl hexanoate, ethyl octanoate, ethyl propanoate, ethyl pentanoate, ethyl heptanoate, and ethyl decanoate are the major esters contributing to fruity aroma. 2-Methylbutanal, 3-methylbutanal, 2,4-hexadienal, 2-butenal, pentanal, hexanal, heptanal, diacetyl, phenylacetaldehyde, dimethyltrisulfide, and methional were identified to be odor-active. It was found that 2,3-dimethylpyrazine, 2,6-dimethyl-pyrazine, 2,5-dimethyl-3-ethylpyrazine, trimethyl-pyrazine, 5-ethyl-2-methylpyridine, 2,3-dimethyl-5-ethylpyrazine, 2,3,5-trimethyl-6-ethyl-pyrazine, furfural, and 2-furanmethanol contribute to the nutty, roasted aroma in this cheese.     

顶空固相微萃取气质联用分析泡椒凤爪的香气成分

采用顶空固相微萃取结合气质联用分析了泡椒凤爪的挥发性香气成分,共检出21种香气成分,其中酚类6种、酸类5种、酯类4种、醛类3种、其他3种。检测到的含量较高的化合物有对丙烯基苯甲醚、乙基麦芽酚、4-乙基-愈创木酚、苯甲醛、4-乙基苯酚,水杨酸甲酯,乙酸,己醛,苯甲酸乙酯。