HS-SPME-GC-MS/O联用分析酱油中的香气活性化合物

通过顶空-固相微萃取(HS-SPME)和气相色谱-质谱/嗅闻技术(GC-MS/O)联用,研究酱油的香气组成。GC-MS共分离鉴定出酱油中挥发性化合物109种,其中醇类物质含量最高,占总挥发性化合物的75.82%,其次是醛类、酯类、酸类和呋喃(酮)类等。采用GC-MS/O鉴定出39种为香气活性物质,其中,3-甲基丁醛,2-甲基丁醛,2-甲基丙醛,3-甲硫基丙醛,乙醇,4-羟基-2-乙基-5-甲基-3(2H)-呋喃酮(HEMF),苯乙醛,1-辛烯-3-醇,2-甲基丙酸乙酯,2-甲基丁醇,3-甲基丁醇,二甲基三硫,4-羟基-2,5-二甲基-3(2H)-呋喃酮(HDMF),乙酸和愈创木酚是OAV值大于20且香气强度评分大于2的关键香气活性物质,它们为酱油整体香味贡献麦芽香,烤土豆香味,醇香,焦糖香,花香味,蘑菇香味,果香味,洋葱味,烟熏味等,综合组成了酱油独特的发酵豆制品风味。     

10种市售鸡肉香精的挥发性风味化合物分析

为了研究市售鸡肉香精的香气组成,本文通过顶空-固相微萃取(HS-SPME)与气相色谱-质谱联用(GC-MS)分析10种商业样品,共检出挥发性化合物131种。其中,萜类、醛类和含硫化合物检出种类最多,分别有25、28和29种,另外,检出化合物还包括酯、呋喃(酮)、酮、吡嗪、酚、醇、酸类等。不同香精其香气组成差异较大,以香气组成最复杂的香精为代表,首次通过气相色谱-嗅闻检测技术(GC-O)剖析鸡肉香精的香气组成,共检出香气活性化合物30种。其中代表性香气活性物质及其主要香型分类如下:主体肉香(甲基(2-甲基-3-呋喃基)二硫醚、甲基糠基二硫醚)、特征脂肪香((E,E)-2,4-庚二烯醛、(E,E)-2,4-壬二烯醛)、葱蒜香(二甲基三硫、二烯丙基二硫醚)、辛香(4-甲氧基苯甲醛、4-乙基愈创木酚)、烘烤香(3-甲硫基丙醛)、甜香(2,4-二氢-2,5-二甲基-3(2H)-呋喃酮、4-羟基-2,5-二甲基-3(2H)-呋喃酮)、酸香(乙酸)和奶香(2,3-丁二酮)。     

红枣片热风干制过程中特征香气活性化合物的确定及表征

采用顶空-固相微萃取-气相色谱-嗅闻-质谱联用技术,结合感官分析和偏最小二乘回归（partial least squares regression,PLSR）分析方法,对热风干制过程中不同条件制备的7 个红枣片样品特征香气活性化合物进行了测定及表征。结果表明,红枣片主要挥发性成分为19 种酯类、15 种酮类、15 种酸类、12 种醛类、9 种醇类、6 种烃类和2 种呋喃类化合物。共识别出18 种香气活性化合物气味活度值大于1,包括7 种酮类、4 种醛类、3 种酯类、2 种酸类、1 种醇类和1 种呋喃类物质。感官评价表明,经过热风干制的红枣片中主要特征香气为焦糖香、烤甜香、焦苦味和焦煳味。通过PLSR明确了感官属性与香气化合物之间的相关性：2,3-丁二酮和3-羟基-2-丁酮与烤甜香呈显著正相关;而γ-丁内酯、4-环戊烯-1,3-二酮和2,5-二甲基-4-羟基-3(2H)-呋喃酮对焦糖香有显著贡献;5-甲基呋喃醛和5-甲基-2(5H)-呋喃酮与焦苦味呈正相关;5-羟甲基呋喃醛是焦糊味特性的主要来源;3-羟基-2-甲基-4H-吡喃-4-酮、4H-吡喃-4-酮和2,3-二氢-3,5-二羟基-6-甲基与焦糊味及焦苦味都呈正相关。上述相关性均在感官评价员通过嗅闻仪闻到的具体味道中得到证实。     

顶空-固相微萃取和同时蒸馏萃取法提取肉桂的挥发性成分

挥发性成分的提取方法对分析武夷肉桂香气成分具有重要影响。本文比较顶空固相微萃取法(HS-SPME)和同时蒸馏萃取法(SDE)提取武夷肉桂的挥发性成分的的差异,采用气相色谱-质谱联用技术(GC-MS)表征其挥发性成分。首先优化HS-SPME的萃取条件,其最优萃取条件为:50/30μm DVB/CAR/PDMS萃取纤维,萃取温度50℃,萃取时间50 min,NaCl添加量30%。在此条件下共检出84种挥发性成分;再通过SDE法提取到40种挥发性成分,两种方法共同检出的成分有26种,对酯类的萃取效率相当。HS-SPME在提取杂环类化合物、中、低沸点脂肪族醇类、烯烃类、酮类的效率高于SDE;而SDE更有利于萃取沸点较高的醇类、酸类和酚类等成分。结论:分析武夷肉桂的香气成分应结合HS-SPME和SDE两种方法。     

同时蒸馏萃取与顶空固相微萃取法分析豆豉挥发性成分

采用同时蒸馏萃取法(SDE)和顶空固相微萃取法(HS-SPME)提取豆豉样品中挥发性成分,经气相色谱-质谱联用仪分析后共检测到96种挥发性化合物,其中烃类最多有40种,其次是酯类13种和醛类11种,另外醇类、酸类、酮类、酚类和杂环类分别有9、7、6、7、3种。SDE法和HS-SPME法分别鉴定出60种和43种风味组分,比较两种提取挥发性成分的方法可知,SDE法具有较高的萃取量,适合对高沸点、低挥发性的物质的分离;HS-SPME具有快速简便、不使用溶剂和样品检测非破坏性等优点,适合易挥发性化合物的检出。只有将两种方法结合起来,才能得到对产品的挥发性物质的综合评价。     

SPME或SDE结合GC-MS分析贾永信十香酱牛肉的挥发性风味成分

采用固相微萃取(SPME)法或同时蒸馏萃取(SDE)法提取贾永信十香酱牛肉的挥发性风味成分,用气相色谱-质谱联用技术对其进行分析。结果显示:共鉴定出78种挥发性风味成分,包括烃类7种、醛类15种、醇类23种、酮类12种、脂肪酸类2种、酯类3种、醚类2种、杂环化合物14种。两种方法不同之处在于,SPME法提取到较多的醇类(38.92%)和杂环化合物(21.40%),SDE法提取到较多的醇类(42.63%)和醛类(42.61%)。两种方法均检测到的化合物有21种:3-甲基丁醛、己醛、苯甲醛、1-辛烯-3-醇、糠醇、2,3-戊二酮、3-羟基-2-丁酮、茴香脑、2,5-二甲基吡嗪等。     

顶空-固相微萃取法并气相色谱-质谱法测定八角茴香挥发性成分

采用顶空-固相微萃取法(HS-SPME)分离富集八角茴香中挥发性成分,再利用气相色谱-质谱法(GC-MS)分析八角茴香中的挥发性成分,然后与传统的同时蒸馏萃取(SDE)并GC-MS法测定结果进行对比.结果表明,以萃取量作为考察指标时,最佳萃取条件为:称取1.0 g样品,选用100μm PA萃取头,温度50℃,萃取40 min,250℃下解吸10 s,GC-MS分析得到102种成分,定性确认其中69种成分,占总峰面积的85.46%.此时测出的八角茴香中主要挥发性成分为反式茴香脑(58.75%)、1-[3-甲基-2-丁烯基]-4丙烯基苯(12.68%)、茴香脑(7.50%)、3,7-二甲基-1,6-辛二烯-3-醇(2.22%)等.SDE法提取出93种成分,定性确认其中61种,占总峰面积的92.62%.此时测出的八角茴香主要挥发性成分与HS-SPME法测得的相同,其中58种为2种方法所共有.HS-SPME法可以代替SDE法对八角茴香中挥发性成分进行分离富集.     

SDE和HS-SPME结合GC-MS分析霍山黄大茶香气成分的比较

分别采用同时蒸馏萃取法(simultaneous distillation and extraction,SDE)和顶空固相微萃取法(headspacesolid phase microextraction,HS-SPME)提取霍山黄大茶中的香气成分,通过气相色谱-质谱定性定量分析,对2种方法所得的香气成分进行比较。结果表明,2种方法提取的香气成分和相对含量有很大差异,SDE法检测出的挥发性成分有74种,HS-SPME法检测到的挥发性成分有76种,2种方法共同检出的组分有44种。糠醛、5-甲基呋喃醛、3-乙基-2,5-二甲基吡嗪、水杨酸甲酯等是构成霍山黄大茶香气的重要物质,2种方法测出的相对含量都在2%以上。2种方法特有香气化合物分别有30、32种,苯乙烯、苯乙醛、顺式芳樟醇氧化物(呋喃)、亚麻酸等仅在SDE法中检出,HS-SPME法中特有苯甲醛、十四烷、香叶基丙酮等香气组分。     

顶空固相微萃取和同时蒸馏萃取用于兔肉挥发性风味成分分析的比较研究

采用顶空固相微萃取法(head space-solid phase micro-extraction,HS-SPME)和同时蒸馏萃取法(simultaneous distillation extraction,SDE)提取兔肉中的挥发性风味物质,经气相色谱-质谱联用仪分析,共检测出风味化合物47种,其中烃类最多,有17种,其次是醛类14种和醇类6种,另外有酯类5种,醚类2种,酸类1种,酮类1种,杂环类1种。HS-SPME法和SDE法分别鉴定出23种和26种挥发性组分,比较两种提取方法可知,SDE法能萃取到更多的挥发性化合物,适合对高沸点,低挥发性物质的分离;HS-SPME法快速简便、更接近真实挥发风味,适合易挥发性化合物的检出。     

乙醚萃取法分析郫县豆瓣酱重要香气成分

为明确郫县豆瓣酱的重要香气成分,应用不同提取方法萃取豆瓣酱香气物质,分析出乙醚为最优。将乙醚萃取液分成酸-水溶性和中-碱性2 个组分,使用气相色谱-闻香法和气相色谱-质谱法,在郫县豆瓣酱中鉴定出46 种香气物质,其中醇类5 种、挥发性有机酸类13 种、醛酮类7 种、酚类11 种、芳香族类5 种、杂环类3 种以及吡嗪类2 种。首次在郫县豆瓣酱中鉴定出3,4-二甲基-2,5-呋喃二酮、巴豆酸、2,6-二甲氧基苯酚、3-甲基-1,2-环戊二酮、γ-丁内酯和3,4-二甲基苯甲醛6 个香气物质。研究发现香气强度较大的物质有乙酸、3-甲基丁酸、3-甲基戊酸、2-苯乙醇、2,5-二甲基-4-羟基-3(2H)-呋喃酮、苯酚、1-辛烯-3-酮、3-甲硫基丙醛和丁子香酚,这些化合物是郫县豆瓣酱重要的香气物质。     

Potent aroma-active compounds of cooked Korean non-aromatic rice

To characterize the aroma of cooked Korean non-aromatic rice, volatiles were extracted by simultaneous steam distillation and solvent extraction (SDE) and dynamic headspace sampling (DHS). The potent aroma-active compounds were then evaluated using gas chromatography-olfactometry. A total of 16 aroma-active compounds with log3 flavor dilution >1 were detected by SDE. On the other hand, 10 aroma-active compounds were detected by DHS. 2-Methyl-3-furanthiol (2-MF) and 2-acetyl-1-pyrroline were considered the most potent aroma-active compounds in cooked Korean non-aromatic rice. Especially, 2-MF was identified for the first time as a potential aroma-active compound of cooked Korean non-aromatic rice.     

Comparison of Four Extraction Methods,SPME, DHS,SAFE, Versus SDE,for the Analysis of Flavor Compounds in Natto

Natto is a kind of traditional fermentation food. Organic soybean of china northeast was selected as the material to produce natto according to the condition optimized before. Four extraction methods (SAFE (solvent-assisted flavor evaporation), SDE (simultaneous distillation and extraction), SPME (solid phase microextraction), and DHS (dynamic headspace sampling)) were applied to extract the volatile compounds of natto. Aroma compounds were separated and analyzed with gas chromatography-olfactometry-mass spectrometry (GC-MS/O) of DB-5 and DB-Wax capillary columns. Seventy-seven compounds were identified by four extraction methods. Among them, 42, 23, 31, and 36 compounds were identified by SPME, DHS, SDE, and SAFE, respectively. SAFE and SDE had a better extraction effect on ester, ether, and aromatic compounds, while SPME and DHS could extract ketone, acid, and pyrazine compounds effectively. SPME was fit for the extraction of natto aroma compounds. These compounds included 14 ketones, 9 alcohols, 4 aldehydes, 6 acids, 4 sulfur compounds, 5 esters, 8 pyrazines, 19 aromatics, and 8 others. Fourteen compounds were identified as key aroma compounds in natto, including 2,3-butanedione, 5-methyl-2-hexanone, 3-hydroxy-2-butanone, 2-nonanone, furaldehyde, acetic acid, 2-ethyl butyric acid, ethyl acetate, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 3,5-dimethyl-2-ethylpyrazine, 2,3,5,6-tetramethylpyrazine, 2,3,5-methyl-6-ethylpyrazine, and benzaldehyde. Pyrazine was the important aroma compound with the high FD (flavor dilution) value in natto.     

同时蒸馏萃取和固相微萃取对双孢蘑菇风味物质的提取分析

采用同时蒸馏萃取法和固相微萃取法对双孢蘑菇的挥发性风味物质进行提取,并通过气相色谱-质谱联用分析及鉴定。采用同时蒸馏萃取法鉴定出36种化合物,采用固相微萃取法鉴定出34种风味化合物,2种方法分析出蘑菇的特征风味物质为1-辛烯-3-醇、1-辛烯-3-酮、2-辛烯-1-醇、2,6-二甲基吡嗪、2-戊基呋喃、甲基吡嗪、1-辛醇等,均以1-辛烯-3-醇含量最高。2种提取方式相互补充相互验证。     

不同方法提取的海南黑、白胡椒香气物质GC-MS比较分析

分别采用固相微萃取法(SPME)、水蒸气蒸馏法(DDE)和同时蒸馏萃取法(SDE)对海南黑、白胡椒的香气成分进行提取,然后经气相色谱-质谱联用法结合计算机检索对其香气成分进行分析和鉴定。研究结果表明,从海南黑、白胡椒中共鉴定出香气物质96种。其中,对白胡椒,采用SPME法的提取物中鉴定出了59种化合物,占整个峰面积的90.20%;采用DDE法的提取物中共鉴定出了52种化合物,占整个峰面积的90.25%;采用SDE法的提取物中共鉴定出了26种化合物,占整个峰面积的84.64%。对黑胡椒,采用SPME法的提取物中鉴定出了36种化合物,占整个峰面积的93.07%;采用DDE法的提取物中共鉴定出了37种化合物,占整个峰面积的81.98%;采用SDE法的提取物中共鉴定出了34种化合物,占整个峰面积的78.17%。海南黑、白胡椒的主体香气物质主要有α-蒎烯、3-蒈烯、α-水芹烯、β-月桂烯、D-柠檬烯、石竹烯等烯烃类物质。同时,三种提取方法中,采用SPME法可更加全面地鉴定出胡椒的香气物质,而采用SDE法则可更好地对胡椒的主体香气物质进行浓缩。将这三种方法相结合可以更加全面地检测出海南黑、白胡椒的香气物质。     

酒花浸膏关键性香气成分分析

采用固相微萃取（solid-phase microextraction,SPME）与溶剂辅助蒸发萃取（solvent-assisted evaporative extraction,SAFE）法结合气相色谱-质谱（gas chromatography-mass spectrometry,GC-MS）联用技术分析酒花浸膏中的香气成分,同时采用气相色谱-嗅闻仪（gas chromatography-olfactory,GC-O）结合香气提取稀释分析（aroma extraction dilution analysis,AEDA）方法和香气活性值（odor activity value,OAV）,最终确定酒花浸膏的关键性香气成分。结果显示,采用2 种萃取方法结合GC-MS在酒花浸膏中共鉴定出111 种香气成分;经GC-O分析共鉴定出27 种香气活性化合物,其中异丁酸乙酯、丁二酸二乙酯、2-甲基丁酸含量最高,结合风味稀释因子和OAV分析共同确认酒花浸膏的关键香气成分为异丁酸乙酯、2-甲基丁酸、异己酸乙酯、辛酸乙酯、癸酸乙酯等化合物。     

同时蒸馏与固相微萃取法对酱油香气成分提取的比较研究

采用同时蒸馏萃取（SDE）和固相微萃取（SPME）对酱油中挥发性香气成分进行提取,结合气-质联用（GC-MS）仪进行检测,并采用峰面积归一化法分析各成分的相对含量。结果显示,SDE法检测出73种挥发性物质,SPME法检测出61种挥发性物质,两种方法共检测出114种物质。SDE法有利于萃取出酱油中重要的挥发性风味物质碳氢类及呋喃类（18.16%）,SPME法未检出碳氢类且对呋喃类（2.55%）的吸附相对较少,但萃取出的其他类化合物（18.98%）相对较多,而SDE法检测出的其他化合物（5.38%）较少。     

固相微萃取法分析凤凰单枞乌龙茶香气组分

本文以凤凰单枞乌龙茶（Camellia sinensis）为材料，采用固相微萃取（solid Phase Microextraction，SPME）对其呈香组分进行研究。结果表明采用SPME萃取凤凰单枞乌龙茶香气组分，从桂花香型乌龙茶干茶样中检测出41种香气组分，而SDE法则检测到55种香气组分，两种方法都检测出高比例的芳樟醇、橙花叔醇、茉莉酸甲酯和吲哚。SPME法萃取了乌龙茶自身散发出的香气组分，避免了茶叶中易挥发或热不稳定的香气组分被破坏，减少了香气组分的测定误差和不稳定性。     

Comparison of isolation methods for the determination of buckwheat volatile compounds

Five different isolation techniques were combined with gas chromatographic–mass spectrometric determination of aroma compounds from buckwheat: dynamic headspace (DHS) with cryotrapping or sorbent trapping, solid-phase microextraction (SPME), headspace sorptive extraction (HSSE), solvent extraction (SE) and simultaneous distillation–extraction (SDE). Optimisation of each technique is presented, as well as comparison of the chemical profiles obtained by them. Solvent extraction with methanol resulted in the isolation of rather polar and less volatile compounds and was deemed least suitable for the odour-active compounds. Only SPME with DVB/CAR/PDMS fibre was suitable for the isolation of highly volatile compounds in a wider polarity range. DHS extracted the smallest number of compounds, but with the comparable chemical profile as obtained by SDE, which was chosen as the most suitable technique to obtain the aroma compounds of cooked buckwheat. The applied isolation techniques are complementary in their ability to extract a representative aroma profile of buckwheat.     

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.