SPME萃取头对大菱鲆鱼肉挥发性成分萃取效果分析

采用DVB/CAR/PDMS、PDMS/DVB和CAR/PDMS3种萃取头进行顶空-固相微萃取（HS-SPME）,提取新鲜大菱鲆鱼肉的挥发性成分,结合气质联用仪（GC-MS）进行分析鉴定,确定最佳的萃取头。结果表明,3种萃取头固相微萃取法共检测出81种挥发性成分,主要是醛、酮、醇、烯烃、烷烃和胺类化合物。使用DVB/CAR/PDMS、PDMS/DVB和CAR/PDMS萃取头分别检测出51、37和29种挥发性成分,其中使用DVB/CAR/PDMS萃取头检测出的挥发性物质总峰面积最大且种类最多。因此,DVB/CAR/PDMS萃取头较适合于大菱鲆鱼肉挥发性成分的提取。      

固相微萃取结合气质联用法分析一种奶味香精中的挥发性成分

应用固相微萃取法采用3种不同萃取纤维,结合气相色谱-质谱联用技术,剖析1种国外奶味香精样品中的挥发性成分。结果表明;以Carboxen/聚二甲基硅氧烷(carboxen/polydimethylsiloxane,CAR/PDMS)为萃取纤维的方法鉴定出39种挥发性成分,以聚二甲基硅氧烷/二乙烯基苯(polydimethylsiloxane/divinylbenzene,PDMS/DVB)为萃取纤维的方法鉴定出41种挥发性成分,以二乙烯基苯/Carboxen/聚二甲基硅氧烷(Divinylbenzene/Carboxen/Polydimethylsiloxane,CAR/PDMS/DVB)为萃取纤维的方法鉴定出40种挥发性成分;3种纤维萃取的分析结果相互补充,共鉴定出51种挥发性成分,其中酯类、醛酮类和内酯类化合物的含量最高,分别为26.12%、25.95%和15.16%,是该种奶味香精的主要组成成分。     

Influence of the Type of Extraction Conditions and Fiber Coating on the Meat of Sauced Duck Neck Volatile Compounds Extracted by Solid-Phase Microextraction (SPME)

In this paper, extraction of sauced duck neck meat volatile compounds by solid-phase microextraction (SPME) was optimized. Three extraction temperatures (30, 45, 60 °C), three extraction times (15, 30, 45 min), and three different fiber coatings (divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), and polydimethylsiloxane (PDMS)) were assayed. There were 82 volatile compounds identified and quantified, which belonged to nine families of chemicals including alcohols, acids, esters, ketones, aldehydes, aromatic compounds, heterocycles, monoterpenes, oxygenated monoterpenes, and sesquiterpenes. The major volatile compounds of sauced duck neck came from spices addition, oxidation, Maillard reaction, etc. Almost all the compounds were extracted by the DVB/CAR/PDMS fiber at 45 °C, and the optimal time of extraction in this case was 15 min, during which DVB/CAR/PDMS fiber reached equilibration. Among the fibers tested, DVB/CAR/PDMS fiber favored the extraction of a wide range of compounds with low and high boiling point. On the other hand, PDMS/DVB fiber absorbed more polar and high retention index (RI) aromatic compounds.     

Analysis of volatile composition of siriguela (Spondias purpurea L.) by solid phase microextraction (SPME)

In order to investigate the volatile composition of the siriguela fruit (Spondias purpurea L.), the pulp of the fresh fruit was submitted to solid phase microextracton (SPME) using different fibers, divinylbenzene-carboxen-polydimethylsiloxane (DVB/CAR/PDMS), carbowax-divinylbenzene (CW/DVB), carboxen-polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane (PDMS) fibers. DVB/CAR/PDMS showed to be the more efficient qualitative and semi-quantitatively fiber in trapping these compounds. It was made possible to identify ketones, alcohols, aldehydes, esters and terpenic hydrocarbons in the headspace. The major compounds identified were hexanal, trans-2-hexenal, 3-hexen-1-ol, 2-hexen-1-ol, ethyl acetate and hexyl acetate. To have a clear picture of the retention indices of these compounds a new protocol, in which the standard hydrocarbon mixture is submitted to SPME, was developed and successfully used.     

欧姆加热对豆浆风味物质的影响

为研究欧姆加热对豆浆挥发性物质的影响,采用顶空固相微萃取结合气相色谱-质谱联用技术,对豆浆的风味物质进行分析,利用内标法对各风味物质成分定量分析。通过对比50/30?μm二乙基苯/碳分子筛/聚二甲基硅氧烷（divinylbenzene/carboxen/polydimethylsiloxane,DVB/CAR/PDMS）、100?μm PDMS、65?μm PDMS/DVB 3 种萃取头对豆浆风味物质的萃取效果,筛选出最佳的萃取头,并在最适条件下分析豆浆的风味物质成分,为排除热效应对实验结果的影响,2?种热处理历程尽可能保持一致。结果表明：65?μm PDMS/DVB纤维萃取头较100?μm PDMS和50/30?μm DVB/CAR/PDMS纤维萃取头更适宜豆浆风味物质的测定;从豆浆样品中共检测到35?种挥发性物质,其中醛类物质16?种,醇类物质5?种,酮类物质3?种,酯类物质1?种,杂环烃类物质10?种,主要包括己醛、（E）-2-庚烯醛、1-辛烯-3-醇等,这些物质共同组成豆浆的特征香气;不同加热处理对豆浆风味物质种类的影响不大,但是对特征香气含量有显著影响（P＜0.05）;欧姆加热处理组样品中己醛、1-辛烯-3-醇、（E）-2-辛烯醛的含量分别比传统加热处理组约低45.55%、58.60%、25.56%,且在欧姆加热处理样品组中未检测到（E）-2-己烯醛和正己醇,而这些物质是豆腥味的主要组成成分。因此,利用欧姆加热方式加热豆浆可以显著降低豆浆的豆腥味。本研究可以为欧姆加热技术在豆浆加工业中的应用提供理论依据。     

Identification of volatile components in Chinese Sinkiang fermented camel milk using SAFE,SDE, and HS-SPME-GC/MS

The volatile components of Chinese Sinkiang fermented camel milk were isolated by solvent assisted flavour evaporation (SAFE), simultaneous distillation extraction (SDE, dichloromethane and diethyl ether as solvent, respectively) and headspace solid-phase microextraction (HS-SPME, CAR/PDMS, PDMS/DVB and DVB/CAR/PDMS fibre extraction, respectively) and analysed by GC/MS. A total of 133 volatile components were identified under 6 different conditions, including 30 esters, 20 acids, 18 saturated alcohols, 15 unsaturated aliphatic alcohols, 8 saturated ketones, 9 saturated aldehydes, 8 unsaturated aliphatic aldehydes, 6 furans, 5 sulphur-containing compounds, 5 ethers, 5 lactones, 3 other compounds, and 1 unsaturated aliphatic ketone. Three pretreatment methods were compared, assisted by principal component analysis (PCA). The results indicated that the volatile components obtained using different methods varied greatly both in categories and in content, and therefore, a multi-pretreatment method should be adopted together with GC/MS. A total of 71 aroma-active compounds were detected by gas chromatography-olfactometry (GC–O), among which 66 aroma-active compounds were found by SDE (60, dichloromethane as solvent; 24, diethyl ether as solvent), 26 by SAFE.     

不同萃取纤维对荔枝冰酒香气分析

采用顶空固相微萃取与气相色谱-质谱联用相结合对荔枝冰酒中的香气成分进行初步分析,通过对不同固相微萃取纤维萃取香气成分的数量、种类以及各类化合物累积峰面积标准化值的比较,评价3 种固相微萃取纤维萃取荔枝冰酒香气成分的效果。结果发现,不同萃取纤维对荔枝冰酒香气成分的萃取效果差别较大,85 μm PA纤维萃取出化合物62 种,75 μm CAR/PDMS萃取出56 种,50/30 μm DVB/CAR/PDMS萃取出52 种。荔枝冰酒中主要香气成分是酯类、醇类、酸类、羰基类和少量的萜烯类,相对含量较高的物质是辛酸乙酯（38.96%）、癸酸乙酯（25.14%）、己酸乙酯（9.31%）、异戊醇（7.89%）、异丁烯酸甲酯（1.52%）、月桂酸乙酯（1.49%）、3-呋喃甲醛（1.26%）、癸酸（1.25%）、苯甲醇（1.21%）、β-大马士酮（1.21%）和苯乙醇（0.30%）。累积峰面积标准化值表明,85 μm PA萃取酸类物质的灵敏度高,但对其他化合物灵敏度都较低;75 μm CAR/PDMS萃取酯类和醇类物质的灵敏度高;50/30 μm DVB/CAR/PDMS萃取醛、酮等羰基类物质的灵敏度高。综合考虑得出结论,75 μm CAR/PDMS纤维最适合对荔枝冰酒香气成分的萃取富集。     

HS-SPME-GC-MS分析新疆胡麻油挥发性成分的技术优化

采用顶空固相微萃取-气相色谱-质谱(headspace solid phase microextraction-gas chromatography-mass spectrometry,HS-SPME-GC-MS)联用技术对新疆胡麻油挥发性成分测定分析进行优化,以期获得HS-SPME-GCMS分析胡麻油挥发性香气的最佳条件。结果表明,采用DVB/CAR/PDMS萃取头,在磁力搅拌条件下,胡麻油SPME最佳萃取条件为萃取温度50℃、萃取时间40 min、解吸时间4 min,在该条件下采用HS-SPME-GC-MS鉴定出的胡麻油挥发性物质达到46种,主要包括醛类、酮类、醇类、酸类、酯类、烷烃类、杂环类及其他类物质,其中醛类、杂环类和醇类总相对含量较高,分别为30.14%、12.73%和9.25%,分离鉴定效果较好。     

不同萃取头固相微萃取分析小米清酒挥发性成分的研究

采用PA、PDMS、PDMS/DVB、CAR/PDMS和DVB/CAR/PDMS 5种萃取头,并通过固相微萃取（SPME）与气质联用（GC-MS）对小米清酒中挥发性成分进行提取、鉴定,运用聚类热图分析不同SPME萃取头提取小米清酒挥发性成分差异。结果表明：5种萃取头SPME检测到小米清酒挥发性成分含有醇、酯、醛、碳氢化合物、含苯衍生物和其他化合物,使用不同萃取头进行固相微萃取能得到较为相似的主挥发性成分：1-戊醇、苯乙醇、正己酸乙酯、丁二酸二乙酯、辛酸乙酯、十六烷,DVB/CAR/PDMS萃取头检测效果最好。聚类热图显示,不同萃取头SPME提取到的挥发性成分效果差异较大,按萃取效果可分为PA萃取头、PDMS萃取头和复合萃取头（PDMS/DVB、CAR/PDMS和DVB/CAR/PDMS）三类,使用不同种萃取头SPME可较为全面地了解小米清酒挥发性成分构成。     

Influence of the type of fiber coating and extraction time on foal dry-cured loin volatile compounds extracted by solid-phase microextraction (SPME)

Extraction of dry-cured loin volatile compounds by solid-phase microextraction (SPME) was optimized. Two different fiber coatings: carboxen/polydimethylsiloxane (CAR/PDMS) and divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), and three extraction times (15, 30 and 45 min) were assayed. Between the fibers tested, CAR/PDMS coated fibers extracted between two and three times more total amount of volatile compounds than the DVD/CAR/PDMS coating (1314 × 10⁶ vs. 526 × 10⁶ area units). Fifty five compounds were extracted by the CAR/PDMS fiber, while only 48 of these were found with the DVB/CAR/PDMS fiber. On the other hand, 6 additional volatile compounds were extracted by the CAR/PDMS coating, all of them being of low molecular weight. Three of the major compounds extracted, hexanoic acid, methyl ester; butanoic acid, 3-methyl-, methyl ester and hexanal, were found in high proportion in both fiber coatings. The effect of exposure time was more marked for the DVD/CAR/PDMS fiber than for the CAR/PDMS coating. Fifteen minutes of extraction provided a volatile compounds profile with lower area counts for most compounds and significantly different to that obtained with 30 and 45 min of extraction. The extraction yields of dry-cured loin volatile compounds varied according to the fiber coating used and the time of exposure. Therefore, extraction conditions should be selected depending on the objective of the study. Finally, it can be concluded that both porous fibers tested, CAR/PDMS and DVB/CAR/PDMS, provide a similar volatile compounds profile for dry-cured foal loin.     

Profile of Volatile Compounds in 12 Chinese Soy Sauces Produced by a High‐Salt‐Diluted State Fermentation

There have been limited studies on the flavour compounds in Chinese soy sauces. In order to obtain wider information about the chemical composition of the volatile fractions in 12 brands of Chinese soy sauces produced by high‐salt‐diluted state fermentation (HSDSF) and to compare them, a headspace solid microextraction method coupled to gas chromatography‐mass spectrometry (HS‐SPME‐GC‐MS) method was proposed and developed. A 50/30μm Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) fibre was used for extraction of volatiles. The adsorption time and temperature of the SPME fibre were optimized separately for various aroma compounds in the soy sauce (50°C and 40 min for alcohols and esters; 40°C and 50 min for ketones, aldehydes and pyrazines; 60°C and 50 min for acids, phenols and furans). From the study, a total of 80 compounds were identified in the 12 samples, of which 34 volatiles were in common. Alcohols and acids were the main volatiles present in the soy sauces. Dominant volatile alcohols were ethanol, 2/3‐methyl butanol and β‐phenylethyl alcohol; and important acids were acetic acid, butanoic acid, and 3‐methylbutanoic acid. Miscellaneous, esters, furans and phenols also made large contributions to the total volatiles of the soy sauces. According to the scatter point plot obtained from principal component analysis, the 12 soy sauces could be classified into four groups.     

基于SPME-GC-MS和PCA的不同萃取头对新疆烤羊肉香气成分萃取效果比较

以烤羊肉中关键挥发性物质的萃取效果为目的进行萃取头类别筛选。采用固相微萃取、气相色谱-质谱联用检测技术,对新疆石河子地区烤羊肉样品的挥发性风味物质的种类和组成进行提取和分析。以灵敏性及主成分分析（principal component analysis,PCA）法得到的载荷矩阵中投影大于0.80的关键共有物质作为筛选最优萃取头的依据,研究不同纤维涂层萃取头（75?μm?CAR/PDMS、65?μm?DVB/PDMS、85?μm?PA、100?μm?PDMS、50/30?μm?DVB/CAR/PDMS）与所萃取的挥发性物质之间的相关性。结果表明：经灵敏度检验、PCA后确认75?μm?CAR/PDMS为萃取烤羊肉样品中关键挥发性物质的最优萃取头,萃取得到样品中的关键香气成分为1-辛烯-3-醇、庚醛、正戊醛、十二醛、己醛、苯甲醛、1-十四炔、萘、4-甲基壬酸、反-2-癸烯醛、6-甲基庚醛、对异丙基苯甲醛、癸醛、壬醛、2-甲基-3-甲硫基呋喃、辛醛、联二苯。     

基于HS-SPME-GC-MS和PCA的不同萃取头对鸡肉香精香气成分萃取效果比较

为提高鸡肉香精香气成分分析的可靠性,比较不同纤维涂层萃取头萃取鸡肉香精香气成分的效果,采用顶空固相微萃取(headspace solid-phase micro-extraction,HS-SPME)结合气相色谱质谱联用仪(gas chromatography-mass spectrometry,GC-MS)检测技术对热反应鸡肉香精中的挥发性风味物质种类和组成进行提取分析,通过灵敏性及主成分分析(principal component analysis,PCA)法比较香气成分数量及含量建立香气品质评价模型,研究不同纤维涂层萃取头(75μm CAR/PDMS、65μm DVB/PDMS、85μm PA、50/30μm DVB/CAR/PDMS)与所萃取挥发性物质间的相关性。结果表明,75μm CAR/PDMS萃取头为萃取鸡肉香精样品挥发性物质的最优萃取头,萃取得到样品中共含有146种挥发性物质,包括醇类24种(16.44%)、醛类16种(10.96%)、吡嗪类12种(8.22%)、呋喃(酮)类13种(8.91%),含硫化合物10种(6.85%)等多种香气物质,检测到2-甲基-3-呋喃硫醇、2-甲基-3-戊烷硫醇、(E,E)-2,4-癸二烯醛、(E,E)-2,4-庚二烯醛及反式-2-壬烯醛等关键肉香味化合物。     

Analysis of volatile compounds in traditional smoke-cured bacon(CSCB) with different fiber coatings using SPME

The volatile compounds of Chinese traditional smoke-cured bacon (CSCB) were studied using SPMS-GC/MS. There were 48 volatile compounds identified and quantified, which belonged to several classes of chemical: 1 alkane, 16 aldehydes, 5 ketones, 9 alcohols, 4 thioethers and thiols, 3 furans and 10 phenols compounds. All the volatile compounds except for alkane was responsible for CSCB characteristic flavor. The major volatile compounds of CSCB came from smoking, oxidation and Maillard reaction, etc. Many volatile compounds were not reported in previous paper isolated by steam distillation method or nitrogen purge-and-steam distillation method on CSCB. It should be because of different method of isolating volatile substances from CSCB. Among the fibers tested, CAR/PDMS (carboxen/polydimethylsiloxane) fiber coating showed the highest area counts for most volatile compounds. CAR/PDMS coating extracted better those compounds whose linear retention indices (LRI) was lower than 926 (on average) and DVB/CAR/PDMS (divinylbenzene/carboxen/polydimethylsiloxane) those with higher LRI.     

跷碛火腿发酵过程中挥发性风味成分的变化

为探索宝兴县硗碛火腿的风味形成机制,以火腿发酵第1、45、90、135、180、225 天的股二头肌为研究对象,采用以75μm CAR/PDMS 为萃取纤维头的固相微萃取法结合气质联用仪对硗碛火腿发酵过程中挥发性风味成分的变化进行分析。结果表明：硗碛火腿的挥发性风味成分总计71 种,包括醛、醇、酸、烃、酮、酯、酚类及其他化合物类;相对含量最高的风味成分为醛类;在火腿的整个发酵过程中,酸类、醛类、烃类、类、酚类和其他化合物类的相对含量总体呈上升趋势,醇类、酮类的相对含量逐渐下降。醛、醇、酸、烃、酮、酯、酚类等化合物的共同作用形成了硗碛火腿独特的风味特征。     

发酵牛肉肠挥发性成分固相微萃取条件优化分析

利用固相微萃取法和气相色谱-质谱法分析发酵牛肉肠中的挥发性风味物质。通过单因素和正交试验对其萃取条件进行优化,所得最佳萃取条件为DVB/CAR/PDMS萃取头、萃取时间60 min、萃取温度65 ℃、样品萃取量3 g、解吸时间2 min。在此条件下,检测到发酵牛肉肠中的挥发性成分共88 种,分别为17 种醛类、23 种醇类、9 种酮类、7 种酸类、16 种烃类、10 种杂环类、3 种酯类和3 种其他种类的物质。     

不同干制方式对新疆哈密大枣香气成分的影响

通过不同干制方式对新疆哈密大枣进行处理,采用顶空固相微萃取联合气相色谱-质谱联用分析鉴定40℃干制、45℃干制、晒干、阴干和鲜枣的香气成分及相对含量,探索不同干制方式对红枣香气成分的影响。结果表明:50/30 μm DVB/CAR/PDMS纤维头对红枣香气成分的灵敏度最佳,检出的香气成分种类和相对含量也最多,明显优于其他纤维头。5种红枣样品中共分离出66种香气成分,主要香气物质种类为醛类、酯类、酸类和酮类。采用主成分分析法对香气物质种类评价结果可知:45℃干制处理的红枣香气品质最佳,其次是40℃干制和晒干处理的红枣,阴干处理的样品香气品质最差。     

桑葚风味构成特点研究

应用固相微萃取-气质联用技术(solid-phase microextraction-gas chromatography-mass spectrometry,SPME/GCMS)对桑葚的挥发性风味物质分析。结果发现:萃取头为50/30μm DVB/CAR/PDMS,饱和时间30 min,萃取60 min效果最好;在此条件下共鉴定出28种挥发性化合物,包括醛类8种,芳香族化合物6种,酯类6种,醇类4种和酸类4种。同时,对已鉴定出的风味化合物进行定量分析,并结合挥发性物质的气味活度值确定桑葚的香气活性物质,结果包括醛类6种,酯类4种,有机酸类3种,芳香族2种和醇类2种被确定为桑葚的气味活性物质,而异辛醇、糠醛、苯甲醛和己酸的气味活度值(odor activity value,OAV)小于1,对桑葚风味贡献度较小。     

HS-SPME-GC-MS analysis of volatile aromatic compounds in alcohol related beverages made with mulberry fruits

Wine aroma is one of the most important parameters responsible for its quality, and hence for consumer acceptance. In order to obtain an appropriate technique to study volatile aroma compounds in mulberry wines, headspace-solid phase microextraction (HS-SPME) comb 40°C for 30 min with a 50/30 μm divinylbenzenecarboxen-polydimethylsiloxane (DVB-CAR-PDMS) fiber. Approximately 80 volatile compounds have been quantified in the mulberry wine, pertaining at several chemical groups, mainly higher alcohols, fatty acids, esters, and some volatile phenols whose concentration range from few to 138.36 mg/L. This work describes a novel methodology for the analysis of mulberry wines by HS-SPME coupled to GC-MS. HS-SPME using a 50/30 μm DVB-CAR-PDMS fiber is provided the higher extraction efficiency (p<0.05) for the volatiles including the most esters, higher alcohols, and fatty acids than by the other fibers.     

Detection of Tribolium castaneum (Herbst) volatile defensive secretions by solid phase microextraction–capillary gas chromatography (SPME-CGC)

The solid phase microextraction (SPME) technique was used for the collection of the volatile defensive secretions released by Tribolium castaneum (Herbst), the red flour beetle. The detection of the major components methyl-1,4-benzoquinone (MBQ) and ethyl-1,4-benzoquinone (EBQ), together with 1-pentadecene (C15:1), was performed by capillary gas chromatography (CGC). SPME samples were identified by CGC coupled to mass spectrometry (MS). Volatile organic compounds (VOC) released from insects were compared employing different SPME fibers. The relative amounts of the major volatiles collected varied with the fiber coating. Quinones accounted for 75% of the volatiles trapped by the carboxen/polydimethylsiloxane (CAR/PDMS) fiber, whereas they only represented 45% of the volatiles trapped with the PDMS fiber. The PDMS/divinylbenzene (DVB) coating exhibited intermediate affinity. In a 15-min extraction period, the highest amounts of VOC extracted from disturbed insects with CAR/PDMS were 349±107 ng/beetle of MBQ, 780±290 ng/beetle of EBQ, and 144±69 ng/beetle of C15:1. The total VOC amounts extracted by SPME were estimated by adding the disturb-released VOC to heat-released VOC of the same insects, resulting in 742±93 ng/beetle of MBQ, 1672±244 ng/beetle of EBQ, and 946±237 ng/beetle of C15:1. SPME-CGC is a simple method to detect and estimate T. castaneum volatiles. This method has the potential to detect insect infestation in stored products.