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.     

基于指纹图谱和化学计量分析的鳕鱼肝油软胶囊掺假植物油鉴定

目的 建立一种基于脂肪酸气相色谱(gas chromatography, GC) 指纹图谱技术结合化学计量分析的鳕鱼肝油软胶囊中掺假植物油的鉴定方法。方法 采用GC法测定不同来源鳕鱼肝油软胶囊脂肪酸指纹图谱, 经拟合后构建对照指纹图谱, 并进行样品相似度评价。模拟制备鳕鱼肝油软胶囊中掺入不同种类、不同比例植物油的掺假样品, 以其中14个共有脂肪酸峰的相对峰面积作为数据源, 输入SIMCA-P数据分析软件进行主成分分析(principal component analysis, PCA)及掺假模型建立。结果 获得鳕鱼肝油软胶囊GC对照指纹图谱及三维掺假识别模型, 44批样品经相似度评价发现有2批拟似掺假植物油, 将拟似样品色谱数据标准化后导入SIMCA-P软件, 显示2批样品均掺了大豆油, 掺假比例约为15%和35%。结论 脂肪酸GC指纹图谱结合化学计量分析为鳕鱼肝油软胶囊中掺假植物油的鉴定提供一种可靠准确的检测手段, 可快速有效识别鳕鱼肝油掺假行为。     

月见草油气相色谱指纹图谱研究

该实验选取了10批产地不同的月见草,室温自然晾干后,粉碎过50目筛,采用水蒸气蒸馏法提取月见草油,并进行甲酯化处 理后,利用气相色谱法对月见草油指纹图谱进行研究。 将10批月见草油气相图谱积分数据导入药典委指纹图谱评价软件后,建立月 见草油指纹图谱,并进行相似度计算,聚类分析和主成分分析。 结果表明,10批月见草油的相似度为0.914～0.989,所建立的指纹图谱 具有较高的重复性和稳定性,指纹图谱结合化学计量学的方法可用于月见草油的质量控制。     

HS‐SPME/GC‐MS and chemometrics for volatile composition of Chinese traditional aromatic vinegar in the Zhenjiang region

The main purpose of this study was to determine the volatile composition of Zhenjiang aromatic vinegar, one of the four famous China‐style cereal vinegars, by using headspace solid‐phase microextraction (HS‐SPME)/gas chromatography‐mass spectrum (GC‐MS) and chemometrics. For this purpose, the HS‐SPME sampling method for the volatile compounds of Zhenjiang aromatic vinegar was optimized by a second‐order rotatable central composite experimental design (CCD). A HS extraction of the volatile compounds by incubation on a 65 µm thickness polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre during 44.2 min at 69.5°C with 1.9 g NaCl add gave the most effective and accurate extraction. By the optimized method, a total of 58 volatile compounds, including 9 alcohols, 13 acids, 16 esters, 5 aldehydes, 4 ketones and 8 heterocycle compounds, were identified from 13 aromatic vinegar samples manufactured in Zhenjiang region. By principal components analysis (PCA), the thirteen vinegar samples were classified into 3 groups, and 10 volatile compounds were chosen as characteristic compounds of Zhenjiang aromatic vinegars. Copyright © 2012 The Institute of Brewing & Distilling     

Artificial simulated gastrointestinal digestion of four carbohydrates containing beta‐d‐1 → 4 linkages and new GC‐TQ/MS‐MS method for characterising released monosaccharides

Four types of carbohydrates, including Dendrobium officinale polysaccharide, Dendrobium aphyllum polysaccharide and β‐glucans from yeast and barley, were examined, and their structures were found to mainly contain 1,4‐linked‐β‐d ‐Glcp. Artificially simulated gastrointestinal digestion was conducted to characterise the changes of molecular weight, reducing sugars and released free monosaccharides by high‐performance liquid chromatography, kits and the newly developed gas chromatography (GC)‐mass spectrometry (MS)/MS analysis, which indicated that high molecular weight and complex spatial structures contributed to delayed monosaccharide release following exposure to digestive solution. The spatial structures of carbohydrates were changed during gastric digestion, but their primary structures were destroyed during intestinal digestion. Additionally, for the developed 7890A/7000 GC‐TQ/MS‐MS, the new analytical method was successfully used to analyse very low concentrations of monosaccharides in the simulated gastrointestinal digestive system.     

Application of the fast sensory method ‘Rate‐All‐That‐Apply’ in chocolate Quality Control compared with DHS‐GC‐MS

This paper studied the fast sensory Rate‐All‐That‐Apply (RATA) method as a contributor to existing quality control (QC) in chocolate production by comparing it with the outcome of dynamic headspace sampling combined with gas chromatography–mass spectrometry (DHS‐GC‐MS). Seven different chocolates were evaluated by a semi‐trained panel using RATA. RATA showed potential as a sensory evaluation tool which could be part of QC programmes in chocolate production as RATA was efficient to perform and captured important sensory deviations, herein addition of excess lecithin and prolonged roasting. However, product deviations caused by long conching were only detected by DHS‐GC‐MS. A more extreme conching process must occur before it can be perceived by humans. RATA and DHS‐GC‐MS should be used as complementary methods in detecting future important issues in chocolate production. DHS‐GC‐MS detects product deviation from chemical perspectives while sensory evaluation gives information on quality parameters from a perceivable perspective influencing consumer satisfaction.     

羊肉特征风味指纹图谱的构建

采用SPME-GC-MS结合GC-O技术对不同产区的15个羊肉样品中挥发性成分进行分析鉴定,以系统聚类分析法优选了14个羊肉样品,共筛选出34种检测频率大于50%的共有成分作为羊肉特征风味化合物构建羊肉特征风味指纹图谱。为了考察测定方法的准确性,通过精密度实验、重复性实验和样品的稳定性实验对所建立的指纹分析方法进行了验证,同时进行了相似度分析,14个羊肉样品的相似度均大于0.80,结果表明不同批次的羊肉样品较为一致,该方法符合指纹图谱建立的要求,可以应用于羊肉指纹图谱的构建。依据所建立的指纹图谱信息,采用PCA分析法对其它不同肉类样品和掺假样品进行对照研究,显示羊肉样品和其它肉类样品和掺假样品均存在明显差异,表明该风味指纹图谱可用于羊肉样品质量的鉴定和监控。     

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     

Characterization of volatile compounds from Daqu‐a traditional Chinese liquor fermentation starter

Daqu is a fermentation starter and substrate complex that is used to initiate the solid fermentations for the production of Chinese liquor. The aroma of Daqu is one of the most important factors that influence the flavour of Chinese liquor. To further study the aroma of Daqu, volatile compounds in ten Daqu samples were extracted by headspace solid‐phase microextraction (HS‐SPME) and analysed by gas chromatography–mass spectrum (GC‐MS). The samples were pre‐equilibrated at 50 °C for 10 min and extracted with stirring at the same temperature for 30 min prior to injection into a GC‐MS. A total of 75 volatile compounds were characterised by GC‐MS, including twelve alcohols, eleven esters, eight acids, nine aromatic compounds, four phenols, two furans, fourteen nitrogen‐containing compounds and fifteen aldehydes and ketones. By a principal component analysis (PCA), the ten Daqu samples could be classified into three groups according to their origins and, in particular, the production technologies.     

Rice vinegars of different origins: discriminative characteristics based on solid‐phase microextraction and gas chromatography with mass spectrometry,an electronic nose,electronic tongue and sensory evaluation

Eight kinds of commercial rice vinegars from Korea, China and Japan were selected to evaluate their flavour‐related discriminative characteristics based on solid‐phase microextraction and gas chromatography with mass spectrometry (SPME/GC–MS), an electronic nose (e‐nose), electronic tongue (e‐tongue) and subjective sensory evaluation. Principal component analysis patterns based on SPME/GC–MS provided a clear categorical discrimination among the vinegars of three origins. The distribution patterns of the samples were similar between SPME/GC–MS and e‐nose analyses and Korean vinegars were clearly discriminated. A high correlation coefficient was determined between SPME/GC–MS and e‐nose on acetaldehyde (0.948) and diacetyl (0.970). e‐Tongue‐based principal component analysis patterns were subdivided into three regions according to the origin, and Chinese vinegars were clearly discriminated. Sensory panelists recorded origin‐specific scores on flavours for all the samples. In conclusion, SPME/GC–MS, e‐nose and e‐tongue analyses may be useful for discrimination of flavour profiles of rice vinegars of different producer origin. Copyright © 2017 The Institute of Brewing & Distilling     

Analysis and characterization of aroma‐active compounds of Schizandra chinensis (omija) leaves

Volatile components from leaves of Schizandra chinensis (omija), a native plant of Korea, were extracted by simultaneous distillation–extraction (SDE) and analyzed by gas chromatography–mass spectrometry (GC‐MS) using two types of capillary column with different polarities (DB‐5MS and DB‐Wax). The GC‐MS analysis of volatile compounds obtained by SDE revealed that germacrene D is the most abundant compound (22.6%) in omija leaves, followed by β‐elemene (17.4%), (E)‐2‐hexenal (8.7%), and (E)‐β‐ocimene (7.2%). Aroma‐active compounds were determined by gas chromatography–olfactometry (GC‐O) using the aroma‐extract‐dilution analysis method. (E,Z)‐2,6‐Nonadienal (cucumber) was the most intense aroma‐active compound due to its higher flavor‐dilution factor (243–729) than any other compound. (Z)‐3‐Hexenal (green/apple), (E)‐2‐hexenal (green/fruity), and (E)‐β‐ocimene (wither green/grass) were also identified as important aroma‐active compounds by GC‐O. In addition, the volatile compounds were extracted by solid‐phase microextraction (SPME), and the quantitative analysis of the SPME samples gave slightly different results, depending on the type of SPME fiber, compared with those from SDE, However, the aroma‐active compounds identified in SPME were similar to those in SDE. Copyright © 2004 Society of Chemical Industry     

GC‐MS‐Based Metabolite Profiling of Cosmos caudatus Leaves Possessing Alpha‐Glucosidase Inhibitory Activity

Cosmos caudatus, which is known as “Ulam Raja,” is an herbal plant used in Malaysia to enhance vitality. This study focused on the evaluation of the α‐glucosidase inhibitory activity of different ethanolic extracts of C. caudatus. Six series of samples extracted with water, 20%, 40%, 60%, 80%, and 100% ethanol (EtOH) were employed. Gas chromatography‐mass spectrometry (GC‐MS) and orthogonal partial least‐squares (OPLS) analysis was used to correlate bioactivity of different extracts to different metabolite profiles of C. caudatus. The obtained OPLS scores indicated a distinct and remarkable separation into 6 clusters, which were indicative of the 6 different ethanol concentrations. GC‐MS can be integrated with multivariate data analysis to identify compounds that inhibit α‐glucosidase activity. In addition, catechin, α‐linolenic acid, α‐D‐glucopyranoside, and vitamin E compounds were identified and indicate the potential α‐glucosidase inhibitory activity of this herb.     

Analysis of flavour compounds in beer with extruded sorghum as an adjunct using headspace solid‐phase micro‐extraction and gas chromatography–mass spectrometry

Sorghum is a widely used adjunct that is used in the production of beer and increasingly affects beer flavour as the amount added increases. The aim of this work was to establish a simple, solvent‐free technique, without derivatization, to analyse flavours and typical volatile compounds present in extruded and unextruded sorghum beer, and to compare the flavour differences of the two types of beer. Headspace solid‐phase micro‐extraction gas chromatography–mass spectrometry was used to determine the flavours in the two beers and eight typical volatile compounds were quantified using GC. Forty‐five flavour compounds were identified and quantified in extruded white sorghum beer, while 31 flavour compounds were identified in unextruded white sorghum beer. Extruded or unextruded white sorghum can be used to produce ale beer, but the primary flavour content in the extruded white sorghum beer was higher than in the unextruded white sorghum beer. Copyright © 2016 The Institute of Brewing & Distilling     

Simple and Fast Sample Preparation Followed by Gas Chromatography‐Tandem Mass Spectrometry (GC‐MS/MS) for the Analysis of 2‐ and 4‐Methylimidazole in Cola and Dark Beer

We have developed a simple and fast sample preparation technique in combination with a gas chromatography‐tandem mass spectrometry (GC‐MS/MS) for the quantification of 2‐methylimidazole (2‐MeI) and 4‐methylimidazole (4‐MeI) in colas and dark beers. Conventional sample preparation technique for GC‐MS requires laborious and time‐consuming steps consisting of sample concentration, pH adjustment, ion pair extraction, centrifugation, back‐extraction, centrifugation, derivatization, and extraction. Our sample preparation technique consists of only 2 steps (in situ derivation and extraction) which requires less than 3 min. This method provided high linearity, low limit of detection and limit of quantification, high recovery, and high intra‐ and interday repeatability. It was found that internal standard method with diluted stable isotope (4‐MeI‐d₆) and 2‐ethylimidazole (2‐EI) could not correctly compensate the matrix effects. Thus, standard addition technique was used for the quantification of 2‐ and 4‐MeI. The established method was successfully applied to colas and dark beers for the determination of 2‐MeI and 4‐MeI. The 4‐MeI contents in colas and dark beers ranged from 8 to 319 μg/L and from trace to 417 μg/L, respectively. Small quantity (0 to 8 μg/L) of 2‐MeI was found only in dark beers. The contents of 4‐MeI (22 μg/L) in colas obtained from fast food restaurants were significantly lower than those (177 μg/L) in canned or bottled colas.     

Headspace solid‐phase micro extraction coupled to comprehensive two‐dimensional with time‐of‐flight mass spectrometry applied to the evaluation of Nebbiolo‐based wine volatile aroma during ageing

This study presents the application of a headspace solid‐phase microextraction (HS‐SPME) method on the analysis of Nebbiolo‐based wine volatiles by comprehensive two‐dimensional gas chromatography (GC×GC) and time‐of‐flight mass spectrometry (TOF‐MS). The aroma patterns were established for different samples of Nebbiolo‐based wines, aged in oak wood barrels for 18 months at constant temperature. The methodology allowed for the simultaneous analysis of over 130 different volatile compounds detected in the headspace. The odour activity values (OAVs) were assessed to identify potentially important odorants of Nebbiolo‐based wine during ageing. The highest OAVs were obtained for several compounds such as ethyl octanoate, ethyl hexanoate, isoamyl acetate, β‐damascenone, ethyl cinnamate, ethyl 3‐methylbutanate and acetaldehyde. Ethyl butanoate, octanoic acid, ethyl dihydrocinnamate and γ‐nonalactone were also at concentrations higher than their corresponding threshold. Also vanillin, (E)‐whisky lactone, (Z)‐whisky lactone, guaiacol and 4‐ethyl guaiacol seem to be important odorants after oak wood ageing period.     

Determination of flavour compounds in beer using stir‐bar sorptive extraction and solid‐phase microextraction

The analysis of volatile compounds in beer is important for quality control in the brewing industry. In this study, stir‐bar sorptive extraction (SBSE) and solid‐phase microextraction (SPME), two solvent‐less enrichment techniques, were applied in combination with gas chromatography flame ionization detection (GC/FID) for the determination of four flavour compounds (isoamyl acetate, ethyl hexanoate, benzaldehyde, myrcene) in beer. Limits of detection, linearity and repeatability of both methods were determined using standard ethanol solutions, while accuracy was determined by conducting recovery tests on commercial beer samples. Both methods were characterized by high linearity (r > 0.996) and repeatability (RSD = 1.76–10.66%). When both methods were compared, higher recoveries were obtained by SBSE, with limits of detection 1.8–2.8 times lower compared with SPME. In the analysis of commercial beer samples using both methods, SBSE analysis resulted in higher recoveries, therefore demonstrating promise for the analysis of beer volatiles. Copyright © 2015 The Institute of Brewing & Distilling     

Characterization of Important Odorants in Steamed Male Chinese Mitten Crab (Eriocheir sinensis) using Gas Chromatography‐Mass Spectrometry‐Olfactometry

Chinese mitten crab (Eriocheir sinensis) from Yangcheng Lake in Jiangsu Province is a popular species due to its unique pleasant aroma and intensive umami taste. In this study, odorants in steamed male E. sinensis were investigated using the headspace‐monolithic material sorptive extraction technique coupled with gas chromatography‐mass spectrometry‐olfactometry (GC‐MS‐O). A total of 74 volatile compounds were found, and the results of the GC‐MS‐O analysis, combined with odor activity values, showed that trimethylamine (fishy, ammonia‐like odor), (Z)‐4‐heptenal (mushroom‐like odor), and benzaldehyde (paint‐like odor) were the important odorants (IOs) in all 4 of the edible parts of steamed male E. sinensis. Furthermore, heptanal (mushroom‐like odor) was common to the abdomen, claw, and leg meat but was not found as the IO in the gonad. The abdomen meat also contained 3‐methylbutanal (vegetable‐like, grassy odor), while 2 additional IOs were found in claw meat (2‐methylbutanal, which has a mushroom odor and 3‐ethyl‐2,5‐dimethylpyrazine, which has a chocolate‐like, musty odor). Another IO (2‐nonanone, chocolate‐like odor) was also found in leg meat, while (E)‐2‐nonenal (green, fruity odor) was the IO found exclusively in the gonad.     

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.     

Analysis of volatile compounds in L. edodes blanched by hot water and microwave

The comprehensive flavour characterisation and volatile compounds of raw L. edodes, hot water blanching (HB) sample and microwave blanching (MB) sample were comparatively analysed by electronic nose technology and headspace solid‐phase micro‐extraction combined with gas chromatography‐mass spectrometry (HS‐SPME‐GC‐MS). Results indicated that volatile components in L. edodes markedly changed after HB and MB. Volatile compounds of raw L. edodes consisted mainly ketones, sulphide and alcohols, and 3‐octanone, as well as 1‐octen‐3‐one, were the major compounds. The content of ketones and sulphides in blanched samples markedly decreased, while the relative content of aldehydes, hydrocarbons and esters increased, which became the major volatile compounds of treatment samples. In addition, the percentage contents of esters, alcohols and sulphides in MB samples were significantly (P < 0.05) higher than that in HB samples, especially 1‐octen‐3‐ol, which contributes more to mushroom flavour. Therefore, MB is a better pretreatment method of L. edodes processing and cooking according to the results of experiment.     

Characterization of Volatile and Semi‐Volatile Compounds in Chinese Rice Wines by Headspace Solid Phase Microextraction Followed by Gas Chromatography‐Mass Spectrometry

The volatile and semi‐volatile compounds of Chinese rice wines were extracted by headspace solid phase microextraction (HS‐SPME) and analyzed by gas chromatography‐mass spectrum (GC‐MS). The original Chinese rice wine samples were diluted with deionized water to a final concentration of 6% (v/v) ethanol and then extracted by HS‐SPME. The samples were pre‐equilibrated at 50°C for 15 min and extracted with stirring at the same temperature for 45 min prior to injection into a GC‐MS. A total of 97 volatile and semi‐volatile compounds were identified from ten Chinese typical rice wine samples, including 13 alcohols, 8 acids, 28 esters, 4 aldehydes and ketones, 17 aromatic compounds, 3 lactones, 6 phenols, 3 sulphides, 9 furans and 6 nitrogen‐containing compounds, of which, 39 compounds were firstly reported in Chinese rice wine. By stepwise linear discrimination analysis, the ten Chinese rice wine samples could be classified into three groups according to the production area, and in particular, the production technologies.