不同年份黄酒基酒HS-SPME-GCMS指纹图谱的建立

为鉴别不同年份的黄酒基酒以及使基酒生产标准化,建立1～10年陈基酒的GC-MS指纹图谱。采用顶空固相微萃取-气相色谱联用质谱法分析黄酒的挥发性和半挥发性成分,利用平均值法构建不同年份基酒的标准指纹图谱。通过与标准图谱的相似度比较,不同生产批次的黄酒基酒具有较好的相似性,其相似度值都大于0.9900,表明该方法可用于黄酒基酒的鉴别和质量评价。     

The Influence of Yeast Strains on the Volatile Flavour Compounds of Chinese Rice Wine

In order to assess the influence of yeast strains on volatile flavour profiles of Chinese rice wine, small‐scale Chinese rice wine brewing was carried out with eight yeast strains from three different typical Chinese rice wine brewing regions. The volatile flavour compounds were extracted by headspace solid phase microextraction (HS‐SPME) and analyzed by gas chromatography‐mass spectrometry (GC‐MS). The volatile flavour profiles of the different Chinese rice wines showed statistically significant differences depending on the yeast strains used. Yeast strains from the Shaoxing region showed a higher capacity to produce the esters 2‐phenylethanol and 3‐methylthiopropanol, while yeast strains from the Shanghai region stood out for their production of branched‐chain higher alcohols. Chinese rice wine fermented with a yeast strain from the Jiangsu region had the highest levels of organic acids. Using principal component analysis of the Chinese rice wine volatile flavour compounds, the eight yeast strains could be classified into three groups according to their origins. This is the first report about the volatile flavour characteristics of Chinese rice wine yeast. The data obtained in this work shows that the yeast strains contributed significantly to the flavour differences of the Chinese rice wines from the different regions.     

Analysis of Volatile Compounds in Shochu Koji,Sake Koji,and Steamed Rice by Gas Chromatography‐Mass Spectrometry

The volatile compounds in three types of koji (yellow, white, and black) and steamed rice were investigated using gas chromatography‐mass spectrometry. The objective of this study was to characterize each koji type based on its profile of volatile compounds. From the steamed rice and rice koji samples examined, a total of 29 volatile compounds were identified. Butanal, hexanal, dimethyl trisulfide and cyclohexyl isothiocyanate were detected only in steamed rice. The volatile profile of yellow koji (sake koji) was distinct from those of white and black kojis (shochu koji). On the basis of relative peak areas, alcohols and aldehydes were identified as being more abundant in yellow koji. White and black kojis had similar volatile profiles, and had a greater abundance of furans than yellow koji. We assume that the different suites of volatile compounds identified in shochu and sake kojis impart the respective characteristic flavours to shochu and sake.     

顶空固相微萃取(HS-SPME)和气相色谱-质谱(GC-MS)联用分析黄酒中挥发性和半挥发性微量成分

利用顶空固相微萃取(HS-SPME)对黄酒中的挥发性和半挥发性成分进行萃取.采用气相色谱-质谱(GC-MS)技术对其进行分析,在黄酒中共检测到63种化合物,其中有32种化合物是首次检测到.酯类和芳香族化合物分别是黄酒中种类最多和含量最多的两类化合物.结果表明,该方法适合分析黄酒中挥发性和半挥发性微量成分,比传统预处理方法更简单、效果更好.     

Quantification of Volatile Compounds in Chinese Ciders by Stir Bar Sorptive Extraction (SBSE) and Gas Chromatography‐Mass Spectrometry (GC‐MS)

A new method for the quantification of volatile compounds in ciders was developed using stir bar sorptive extraction (SBSE) followed by gas chromatography (GC)‐mass spectrometry (MS). The optimized conditions consisted of 10 mL cider sample with NaCl addition to a final concentration of 30% (w/v) extracted by SBSE at 55°C during 60 min, stirring at 1100 rpm. Under the conditions described above, the method linearity was satisfactory, with correlation coefficients (R²) higher than 0.99 in all cases. The detection limits of this method ranged from 0.01 to 6.37 μg/L, and quantification limits ranged from 0.03 to 21.25 μg/L. The recoveries of analyzed compounds varied between 70.92 and 111.38%. The relative standard deviations (RSD) were all below 10%. A total of 54 volatile compounds in six samples from Chinese cider were quantified, mainly esters, alcohols, terpenoids, aromatics, and acids.     

Multivariate Classification of Cherry Wines Based on Headspace Solid Phase Microextraction and Gas Chromatography-Mass Spectrometry of Volatile Compounds

Headspace solid phase microextraction and gas chromatography-mass spectrometry was applied for cherry wine volatile analysis. Multivariate statistical analyses were used to track the influence of cultivar, fermentation method, wine type, vintage, and origin on the aroma of cherry wine. The major compounds in cherry wines are isoamylol, ethyl acetate, benzyl alcohol, benzaldehyde, and diethyl succinate. The principal component analysis results showed that classifying cherry wines by gas chromatography-mass spectrometry was highly related to fermentation methods and wine types. The agglomerative hierarchical clustering result indicated fermentation method has a greater effect on classification of cherry wines than other factors.     

HS-SPME-GC-O-MS分析红枣发酵酒中的挥发性成分

采用顶空固相微萃取、气相色谱-嗅闻-质谱(gas chromatography-olfactometry-mass spectrometry,GC-O-MS)联用,对红枣发酵酒中易挥发性成分进行萃取条件及GC-MS分离检测条件的系统研究,并采用气味活度值结合香气强度值评价了主要成分对总体香味的贡献。选定的顶空固相微萃取最优参数为:50/30μm DVB/CAR/PDMS固相微萃取头、样品用量8.0 m L/20.0 m L样品瓶、加盐量0.40 g/m L、萃取温度55℃、萃取时间40 min、平衡时间20 min、解吸时间5 min。选用Rtx-Wax色谱柱,经GC-O-MS联用对红枣发酵酒挥发性成分进行分析,共检出108种组分,结构推断86种,占挥发性成分总峰面积的97.09%。其中,乙酸-3-甲基丁酯、3-甲基丁醇、己酸乙酯、2-己烯酸乙酯、庚酸乙酯、乙酸、辛醇、癸酸乙酯、苯甲酸乙酯、戊酸、乙酸-2-苯乙酯、己酸、苯甲醇、苯丙酸乙酯、苯乙醇、辛酸、n-癸酸为红枣发酵酒的主体香气成分。其结果为红枣发酵酒的质控及香味评价提供一定理论依据。     

Characterization of Aroma Compounds in Chinese Bayberry (Myrica rubra Sieb. et Zucc.) by Gas Chromatography Mass Spectrometry (GC‐MS) and Olfactometry (GC‐O)

Abstract: The aroma‐active compounds in Chinese bayberry were identified using gas chromatography‐olfactometry (GC‐O) and GC‐mass spectrometry techniques. The volatile compounds were extracted using Liquid–liquid extraction, solvent‐assisted flavor evaporation and headspace solid‐phase microextraction (HS‐SPME), respectively. On the basis of odor intensity, the most important aroma compounds in Chinese bayberry samples were caryophyllene, menthol, 4‐terpineol, linalool oxide, linalool, benzyl alcohol, α‐methylbenzyl alcohol, β‐phenylethanol, 3‐methylbutanoic acid and acetic acid, and so on. Moreover, HS‐SPME technique was employed to investigate the aroma compounds among immature and mature waxberry fruits. The results showed that terpenes (for example, β‐caryophyllene) was predominant and its concentration represented over 89.9% of the overall compounds, and alcohols, aldehydes, ketones, esters, acids, and others were typically present in lesser amounts. Finally, principal component analysis revealed that there was also significant difference between immature and mature waxberry fruits     

HS-SPME-GC-MS分析石榴酒中易挥发性成分

采用顶空固相微萃取和气相色谱-质谱联用法分析石榴酒中易挥发成分,并对其分析条件进行优化,为石 榴酒香气特征研究提供适宜方法。选用50/30 μm DVB/CAR/PDMS固相微萃取头、FFAP色谱柱,对影响萃取效果 明显的因素进行单因素和正交试验,确定适宜分析条件为样品用量8.0 mL/20.0 mL样品瓶、加盐量0.30 g/mL、萃取 时间50 min、萃取温度45 ℃、平衡时间30 min、解吸时间4 min,对石榴酒易挥发物的化学组成进行分离及结构鉴 定,共检出76 种化合物,确定结构67 种,占总易挥发成分总量的99.39%。     

Characterization of Volatile Flavor Compounds in Chinese Rice Wine Fermented from Enzymatic Extruded Rice

Enzymatic extrusion, instead of traditional steam cooking, to treat rice is an efficient and alternative pretreatment for Chinese rice wine fermentation. In order to determine the formation of volatiles in enzymatic extrusion‐processed rice wine (EE), and to confirm its characteristic flavor compounds, headspace solid‐phase micro‐extraction followed by GC–MS was used. A total of 66 volatile compounds were identified in EE. During fermentation, most volatiles generated from enzymatic extruded rice had the similar trends with those from steam‐cooked rice, but the differences in the concentration of volatiles indicated a changed balance of flavors release caused by enzymatic extrusion. Besides, the concentrations and sorts of volatiles in EEs fermented from different rice particle sizes, were not dramatically different. By principal component analysis, EE could be distinctly separated from other traditional Chinese rice wines according to its characteristic volatiles, namely, 2‐heptanol, 1‐octen‐3‐ol, ethyl 4‐hydroxybenzoate, methylpentyl 2‐propenoate, γ‐hexalactone, and 4‐vinylguaiacol.     

顶空固相微萃取-气相色谱质谱联用技术比较赤霞珠干化葡萄和干化葡萄酒香气成分

采用顶空固相微萃取-气相色谱质谱联用技术,对赤霞珠干化葡萄和干化葡萄酒香气成分进行分析比较。检测出干化赤霞珠葡萄的香气成分34种,包括12种醇类、8种酯类、5种有机酸、5种醛类和4种其他类物质;干化葡萄酒得到香气成分45种,包括16种醇类、22种酯类、5种有机酸、2种酮类。     

Profile of Volatile Compounds in 11 Brandies by Headspace Solid-Phase Microextraction Followed by Gas Chromatography-Mass Spectrometry

ABSTRACT:  A headspace solid-phase microextraction (HS-SPME) method coupled with gas chromatography-mass spectrometry (GC-MS) was applied for the qualitative or semiquantitative characterization of brandy volatiles. SPME variables (SPME fiber, extraction temperature and time, and ethanol concentration) were optimized. A total of 144 compounds were from the brandies' volatiles, tentatively identified or identified by comparing mass spectra and retention indices of the standards or from literature. Of these, 57 are common to 11 brandies. They were mainly represented by esters and alcohols, such as 2-methyl propanol, 3-methyl butanol, 1-hexanol, ethyl octanoate, and ethyl decanoate, which were quantitatively determined. Chromatographic peaks were integrated using selective ion method (SIM) and the semiquantitative data analyzed using principal component analysis (PCA) and cluster analysis (CA) to study relationships between volatile composition and brandy. Eleven brandies were differentiated into 3 groups: 1 for Hennessy VSOP and XO samples, 1 for Changyu PEGASE VSOP and XO-1, 2, 3 samples, and the other for Changyu PEGASE brandy and VO, Taro brandy, Baiyang River brandy, and Wealth XO samples. The classification of groups is consistent with the brandy samples by variety and grade.     

Rapid Analysis of Flavor Volatiles in Apple Wine Using Headspace Solid‐Phase Microextraction

Flavor volatiles are important components of alcoholic beverages. In this study, headspace solid‐phase microextraction and gas chromatography—mass spectrometry (HS‐SPME‐GC‐MS) were investigated for the determination of flavor‐contributing volatiles for apple wine. HS‐SPME parameters were defined, including fiber coatings, extraction time, and extraction temperature. Good linearity, recoveries, and repeatability of the SPME method using carboxen‐polydimethylsiloxane (carboxen‐PDMS) fiber were obtained with r² values, recoveries, and relative standard deviations ranging from 0.9112 to 0.9960, 80.23% to 110.21%, and 1.5% to 6.4% respectively using standard solution. No significant effects of ethanol concentration on headspace concentrations of analytes were observed when ethanol concentration changed from 0% to 12% (v/v), indicating that the HS‐SPME‐GC‐MS method can be used for the determination of flavor volatiles in apple wine with an alcohol content below 12% (v/v) as well as in apple juice, and the method enables the monitoring of volatiles in mash during fermentation.     

Rapid determination of ethyl carbamate in Chinese rice wine using headspace solid‐phase microextraction and gas chromatography–mass spectrometry

Ethyl carbamate (EC) is a naturally occurring toxic contaminant that may imply a risk to human health and is usually found in alcoholic beverages such as Chinese rice wine. An automated procedure for the rapid determination of EC in Chinese rice wine was developed by headspace solid‐phase microextraction (HS‐SPME) coupled to gas chromatography–mass spectrometry (GC‐MS). Using propyl carbamate as internal standard, the optimized HS‐SPME sampling with a polyacrylic fibre was 45 min at 70°C after applying 38.8% NaCl to saturate the sample. This method showed good linearity over a range of 25–600 µg L^?1 (R² = 0.997). The recovery, relative standard deviation and limit of detection were 90.21–97.35%, lower than 2.89% and 1.19 µg L^?1, respectively. Additionally, the ethanol concentration had no effect on the analysis of EC. The total analysis time of 57 min per sample in continuous determination was twice as fast as the widely used solid‐phase extraction–GC‐MS method. This solvent‐free HS‐SPME‐GC‐MS procedure is suitable for the rapid, automated, and therefore convenient, determination of EC in Chinese rice wine. Copyright © 2012 The Institute of Brewing & Distilling     

中国黄酒中挥发性和不挥发性物质的研究现状与展望

简要回顾了中国黄酒风味成分分析的历史与现状.从微量成分的种类上看,中国黄酒中目前已经检测到的微量成分达100种以上,包括醇类、醛类、酸类、酯类、酚类、含氮化合物,以及其它化合物.近年来,顶空取样、液液萃取、色谱分离技术、固相微萃取等技术已经开始应用于黄酒的风味成分研究.随着先进技术的应用,必将对中国黄酒风味物质以及特征香味成分的研究起到决定性的作用.     

刺玫果挥发性成分的顶空固相微萃取-气质联用分析

采用顶空固相微萃取方法对刺玫果的干、鲜果挥发性成分进行萃取,运用气相色谱-质谱法分析其挥发性成分,用面积归一法确定各组分的相对含量。从刺玫果干果中分离得到61种挥发性成分,其中乙醇含量最高(28.00%),其次为4-萜烯醇(8.17%);从刺玫果鲜果中分离得到23种挥发性成分,1-己醇含量最高(37.08%),其次为乙苯(15.20%)。     

固相微萃取-气相色谱-质谱法分析中高温大曲发酵、贮存过程中挥发性风味成分的变化

采用顶空固相微萃取-气相色谱-质谱联用(HS-SPME-GC-MS)技术,分析大曲在发酵和贮存过程中香气成分变化规律。结果表明,多数挥发性化合物含量从发酵的第1天开始增加,到第5天达到最大值,随后下降,20 d后趋于稳定;含氮类化合物从发酵的第5天快速增加,第9天达到最大值,发酵20天后含量趋于稳定。     

Differentiation of Turkish Rakies through Headspace Solid‐Phase Microextraction and Gas Chromatography‐Mass Spectrometry Analysis

Composition of flavour compounds from several commercial raki samples was determined through headspace solid‐phase microextraction (HS‐SPME) and gas chromatography coupled to mass spectrometry (GC‐MS). The extraction of volatile compounds was performed using a 75 μm CAR/PDMS fibre. Forty three volatile compounds were identified. The major compounds were trans‐anethole (86.47–94.19%), valencene (1.15–6.77%), estragole (2.66–5.46%), and cis‐anethole (0.72–2.33%). Principal component analysis (PCA) enabled the differentiation of the raki samples thanks to compounds arising mainly from aniseed.     

4种果酒中的挥发性成分分析比较

应用顶空固相微萃取法(HS-SPME)和气质联用(GC-MS)快速测定果酒中的挥发性微量成分.在4种果酒中共检测出113种挥发性成分,鉴定出80种,在苹果酒(CW)中49种,荔枝酒(LW)、木瓜酒(PW)和桑椹酒(MW)中分别检测出40种、49种、51种化合物.检测结果显示,有20种化合物是4种果酒中共有的成分;在CW中9种成分是特有的,4、5和9种成分分别只在LW、PW和MW中检测出;酯类和醇类化合物是果酒主要组分,4种果酒的主要成分差异较大.