Determination of Aromatic Components of Rosa davurica Pall. by Headspace Solid Phase Microextraction Combined with GC-MS

[Objectives] To determine the aromatic components of Rosa davurica Pall. [Methods] 42 kinds of aromatic components were identified from the flowers of R. davurica by headspace solid phase microextraction( HS-SPME) combined with gas chromatography-mass spectrometry( GC-MS). The main compounds were alcohols( 54. 88%) and aldehydes( 19. 55%). [Results] The top five components with the highest relative content were phenylethyl alcohol( 12. 69%),geraniol( 9. 85%),citronellol( 8. 80%),nerol( 7. 84%) and 2-n-pentylfuran( 7. 45%). [Conclusions] Headspace solid phase microextraction( HS-SPME) combined with gas chromatography-mass spectrometry( GC-MS) can provide basis for further development and utilization of R. davurica.

Integration of GC-MS Based Non-Targeted Metabolic Profiling with Headspace Solid Phase Microextraction Enhances the Understanding of Volatile Differentiation in Tobacco Leaves from North Carolina, India and Brazil

In this report, gas chromatography-mass spectrometry (GC-MS) based non-targeted metabolomics is used to develop appropriate headspace solid phase microextractions (HS-SPME) to enhance the understanding of volatile complexity of flue-cured tobacco leaves. Non-targeted metabolic profiling of GC-MS shows that the extraction condition of HS-SPME at 100?C for 30 min provides a better metabolite profile than other extraction conditions tested. GC-MS and principal component analyses (PCA) show that among five types of fibers tested, 100 μm polydimethylsiloxane (PMDS), 65 μm polydimethylsiloxane/divinylbenzene (PMDS/DVB) and 75 μm carboxen/polydimethylsiloxane (CAR/ PMS) provide a better reproducible metabolite profile. Based on an appropriate PDMS extraction condition optimized, we use GC-MS analysis and PCA to compare metabolite profiles in flue-cured leaves of tobacco plants grown in North Carolina, India and Brazil, respectively. The resulting data of PCA show that the global metabolic profiles in North Carolina samples are separated from those in Brazil and India samples, two groups of which are characterized by a partially overlapped pattern. Several peaks that were differentially accumulated in samples were annotated to known metabolites by deconvolution analysis, such as norsolanadione, solavetivone and rishtin. Norsolanadione is detected only in Brazil samples. Solavetivone is detected in samples of India and Brazil but not in those of North Carolina. Rishtin is detected in samples of North Carolina and India but not in Brazil samples. These data indicate that not only can a non-targeted metabolic profiling approach enhance the understanding of volatile complexity, but also can identify marker volatile metabolites in tobacco leaves produced in different growth regions.

Multiple responses optimization in the development of a headspace gas chromatography method for the determination of residual solvents in pharmaceuticals

An efficient generic static headspace gas chromatography （HSGC） method was developed, optimized and validated for the routine determination of several residual solvents （RS） in drug substance, using a strategy with two sets of calibration. Dimethylsulfoxide （DMSO） was selected as the sample diluent and internal standards were used to minimize signal variations due to the preparative step. A gas chroma- tograph from Agilent Model 6890 equipped with flame ionization detector （FID） and a DB-624 （30 m × 0.53 mm i.d., 3.00 μm film thickness） column was used. The inlet split ratio was 5：1. The influ- encing factors in the chromatographic separation of the analytes were determined through a fractional factorial experimental design. Significant variables： the initial temperature （IT）, the final temperature （FT） of the oven and the carrier gas flow rate （F） were optimized using a central composite design. Response transformation and desirability function were applied to find out the optimal combination of the chromatographic variables to achieve an adequate resolution of the analytes and short analysis time. These conditions were 30 ℃ for IT, 158 ℃ for FT and 1.90 mL/min for F. The method was proven to be accurate, linear in a wide range and very sensitive for the analyzed solvents through a comprehensive validation according to the ICH guidelines.

Analysis of Residual Solvents in Annatto Extracts Using a Static Headspace Gas Chromatography Method

An analytical method for the quantification of residual solvents in annatto extracts, natural food colorants, was established using a static headspace gas chromatography (HSGC) coupled with a flame ionization detector (FID). As a sample diluent in a headspace sampling, dimethylformamide (DMF) was selected owing to its high capacity for dissolving both bixin-based and norbixin-based annatto extracts. The quantification of residual solvents was performed using the external standard method. The linearity of the calibration curves was assured with relative coefficients (R2) that were greater than 0.999. The recoveries of all standard solvents spiked in the annatto extracts were in the range from 95.1% to 107.1% to verify the accuracy and the relative standard deviation (RSD%) values (n = 3) were in the range from 0.57% to 3.31%. The quantification limits (QL) were sufficiently lower than the limits specified by Joint FAO/WHO Expert Committee on Food Additives (JECFA). With the established HSGC method, six residual solvents (methanol, ethanol, 2-propanol, acetone, ethyl acetate, and hexane) in 23 commercial annatto-extract products that consist of seven bixin-based and 16 norbixin-based products were quantified. The levels of residual ethyl acetate and hexane in all products were lower than the specified limits of JECFA. However, three samples of bixin-based products showed higher levels of residual 2-propanol (approximately 313.9 - 427.7 ppm) than the specified limit. Other bixin products also showed higher concentrations of residual methanol (approximately 166.6 - 394.7 ppm) and residual acetone (approximately 75.2 - 179.8 ppm) than the limits of JECFA. In the case of norbixin-based products, nine samples showed higher levels of residual acetone (approximately 42.6 - 139.5 ppm) than the limits of JECFA. This is the first survey of residual solvents in annatto extracts using the validated HSGC method.

Flash Evaporation and Headspace Solid-phase Microextraction for the Analysis of the Essential Oils in Traditional Chinese Medicine,Houttuynia Cordata Thunb

We have investigated the use of flash evaporation, headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) as sample concentration and preparation techniques for the analysis of volatile constituents present in Houttuynia cordata Thunb. The samples were analyzed by gas chromatography (GC) and identified by mass spectrometry (MS). Comparison studies were performed. It was found that the results obtained between Headspace solid-phase microextraction HS-SPME and SD techniques were in good agreement. Seventy-nine compounds in Houttuynia cordata Thunb were identified by MS. In flash evaporation, thirty-nine compounds were identified. Discrimination in the response for many constituents studied was not observed, which can be clearly observed in SD and HS-SPME techniques. As a conclusion, HS-SPME is a powerful tool for determining the volatile constitutes present in the Houttuynia cordata.

Application Progress of Headspace Gas Chromatography in Analytical Chemistry

This paper briefly expounds the basic principle and classification of headspace gas chromatography,summarizes its application in food analysis,environmental analysis and medical analysis,and forecasts the application prospect of headspace gas chromatography in analytical chemistry in the future.

Headspace Solid-Phase Micro-Extraction Gas Chromatography/Mass Spectrometry(HS-SPME-GC/MS)-Based Untargeted Metabolomics Analysis for Comparing the Volatile Components from 12 Panax Herbal Medicines

Quality control of ginseng currently is mainly based on ginsenoside analysis,but rarely focuses on the volatile organic components.In the current work,an untargeted metabolomics approach,by headspace solid-phase micro-extraction gas chromatography/mass spectrometry(HS-SPME-GC/MS),was elaborated and further employed to holistically compare the compositional difference of the volatile components simultaneously from 12 Panax herbal medicines,which included P.ginseng(PG),P.quinquefolius(PQ),P.notoginseng(PN),red ginseng(PGR),P.ginseng leaf(PGL),P.quinquefolius leaf(PQL),P.notoginseng leaf(PNL),P.ginseng flower(PGF),P.quinquefolius flower(PQF),P.notoginseng flower(PNF),P.japonicus(PJ),and P.japonicus var.major(PJvm).Chromatographic separation was performed on an HP-5MS elastic quartz capillary column using helium as the carrier gas,enabling good resolution within 1 h.We were able to characterize totally 259 volatile compounds,including 82 terpenes(T),46 alcohols(Alc),29 ketones(K),25 aldehydes(Ald),21 esters(E),and the others.By analyzing 90 batches of ginseng samples based on the untargeted metabolomics workflows,236 differential ions were unveiled,and accordingly 36 differential volatile components were discovered.It is the first report that simultaneously compares the compositional difference of volatile components among 12 Panax herbal medicines,and useful information is provided for the quality control of ginseng aside from the well-known ginsenosides.

Analysis of volatile organic compounds emitted from aircraft carpets:comparison using headspace and dynamic chamber tests

Volatile organic compounds(VOCs) emitted from three types of carpets used in aircrafts were compared by using headspace and dynamic chamber tests. The headspace samples contained many compounds that were not detected in the dynamic chamber test; in addition, the dominant VOCs found by these two methods were different. The findings indicate that for highly sorptive materials such as carpets, headspace analysis may give inaccurate indication of actual VOC emissions, and it is necessary to conduct dynamic chamber tests over a certain period of time in order to identify the true emission characteristics. From the dynamic chamber tests, 2-ethyl-1-hexanol was the main VOC emitted from all three carpets. The study also examined the emission characteristics of aircraft carpets. In all experiments, total VOC(TVOC) concentration peaked within a few hours after the start of the experiment and was followed by rapid decay. The emission parameters of TVOC emitted by all three carpets were calculated and the simulated data matched the measured data well.

Theoretical and numerical investigations on the headspace of cartridge cases considering axial deformation and movement

The cartridge case headspace is the axial clearance between the cartridge and bolt of an automatic weapon,and influences the reliability and security of the weapon.Accordingly,theoretical and numerical studies were conducted to analyze the dynamic response of cartridge cases during internal impact considering the initial radial clearances between the cartridge case and chamber.A theoretical model was proposed to predict the cartridge case headspace considering both the deformation and movement of the cartridge case and confirmed by the results of nonlinear finite element simulations.The differences between the results of the conventional static model and the dynamic model were then comprehensively evaluated.The effects of the angle between the cartridge and chamber,the cartridge case material,and the intermal impact pressure on the predicted headspace value were also analyzed.The dynamic response of the cartridge case predicted by the dynamic model was more accurate than that predicted by the conventional static model.The internal impact pressure,pressure change rate,and cartridge material were all found to affect the predicted headspace.

Effect of Replacement of Headspace Gas on N_2O and CO_2Emissions in Anaerobic Incubation of Soil

To study effect of C2H2 and change of headspace gas on N2O emission, denitrification, as well as CO2emission, slumes of an agricultural soil were anaerobically incubated for 7 da3’s at 25 ℃. Both N2O reduction and CO2 emissions were inhibited by the addition of 100 mL L-1 of C2H2. However, the inhibition to CO2 emission was alleviated by the replacement of headspace gas, and the N2O emission was enhanced by the replacement. Acetylene disappeared evidently from the soil slumes during the incubation. Consequently results obtained from the traditional C2H2 blocking technique for determination of denitrification rate, especially in a long-time incubation, should be explained with care because of its side effect existing in the incubation environments without change of headspace gas. To reduce the possible side effect on the processes other than denitrification, it is suggested that headspace gas should be replaced several times during a long-time incubation.

基于HS-GC-IMS和HS-SPME-GC-MS的蛋白酶对豆粕挥发性风味的影响分析

为研究不同蛋白酶酶解对豆粕挥发性风味成分的影响,选用4种蛋白酶(碱性蛋白酶、中性蛋白酶、木瓜蛋白酶、风味蛋白酶)对豆粕进行酶解,采用顶空-气相色谱-离子迁移谱(Headspace-gas chromatography-ion mobility spectroscopy,HS-GC-IMS)和顶空固相微萃取-气相色谱-质谱(Headspace solid phase microextraction-gas chromatography-mass spectrometry,HS-SPME-GC-MS)联用技术分析不同豆粕酶解物(Soybean meal hydrolysates,SMH)的挥发性风味成分,并结合主成分分析(Principal component analysis,PCA)、热图聚类和正交偏最小二乘判别法(Orthogonal partial least squares-discriminant analysis,OPLS-DA)对不同SMH进行分析。结果表明:碱性蛋白酶、中性蛋白酶、木瓜蛋白酶和风味蛋白酶酶解豆粕的挥发性风味成分存在较大差异。HS-GC-IMS鉴定出84种挥发性成分,筛选得到33种差异风味物质,发现酶解后酮类物质显著降低而醛类、醇类和酯类物质含量明显增加。PCA结果表明不同SMH之间的风味存在显著差异。最终通过OPLS-DA筛选出贡献较大的挥发性化合物,同时构建出可靠的用以鉴别SMH的模型。HS-SPME-GC-MS检测出103种差异风味物质,可用于区分不同SMH,被检出的挥发性组分中醛类、醇类和酮类等化合物为SMH风味的形成做出主要贡献,明晰了部分风味化合物形成的原因。PCA和聚类热图结果表明不同蛋白酶酶解对豆粕的挥发性风味物质的种类和含量有显著影响,其中,风味蛋白酶和木瓜蛋白酶对豆粕的风味改善最为显著。

不同产地沃柑挥发性成分的差异分析

该研究旨在分析4个主产地(四川、重庆、云南和广西)的沃柑果皮中挥发性成分的差异性,并为沃柑的产地溯源和深加工提供数据支撑。利用顶空固相微萃取-气相色谱-质谱联用技术测定了沃柑果皮挥发性成分,共鉴定出50种挥发性成分,其中萜烯类18种、醇类11种、醛类10种、酯类8种、酮类1种、其他类2种。柠檬烯是主要的挥发性物质,月桂烯、α-蒎烯、芳樟醇、正辛醇、正辛醛、香茅醇、己醛、反式-2-己烯醛、桧烯、香芹酮和α-松油醇等次之。基于挥发性成分半定量结果,建立四川和重庆,云南和广西沃柑的正交偏最小二乘法判别分析模型,进而筛选出潜在生物标志物。结果表明,柠檬烯、芳樟醇和香茅醇可作为区分重庆和四川的潜在生物标志物,醋酸辛酯和α-松油醇可作为区分广西和云南的潜在生物标志物。

顶空气相色谱法测定棉毛纺织品中氯化溶剂残留量

采用顶空自动进样器进样,利用DB-1色谱柱分离、电子捕获检测器检测,通过基质匹配校正法建立标准曲线,外标法定量,建立了一种基于静态顶空-气相色谱法(HS-GC)测定棉、毛纺织品中二氯甲烷等9种氯化溶剂残留量的方法,探讨了顶空进样的平衡温度、平衡时间对测试结果的影响,以及该方法的准确度、精密度和检出限。结果表明:顶空进样平衡温度为60℃、平衡时间为15 min较为合适;基质空白样中添加浓度为1.0 mg/kg的9种氯化溶剂标准混合溶液进行测试,9种氯化溶剂的检出限为0.002~0.190 mg/kg;在0.5~20.0 mg/kg的加标水平下进行测试,9种氯化溶剂的加标回收率为77.7%~114.1%,相对标准偏差为1.02%~8.76%;该方法准确性好,灵敏度高,适用于棉、毛纺织品中氯化溶剂的定性定量分析。

肉桂茶纯露挥发性成分分析

分析肉桂茶纯露和茶叶之间挥发性成分差异,为肉桂茶纯露的开发利用提供科学依据。采用顶空-气质联用法检测肉桂茶茶叶和水蒸气蒸馏提取的肉桂茶纯露中挥发性成分。结果表明:从肉桂茶纯露和茶叶中分别鉴定出55种、12种挥发性成分,含醇类、醛类、萜烯类、酯类、生物碱类、酮类等10类成分,其中肉桂茶纯露以醇类成分的数量最多,达10种,醛类成分的相对含量最高,达38.92%,相对含量较高的挥发性成分有2-甲酰组胺、2,4a,5,6,7,8,9,9a-八氢-3,5,5-三甲基-9-亚甲基-1H-苯并环庚烯、S-甲基-半胱氨酸、异丁醛、2-甲基丁醛、异戊醛、正己醛,相对含量分别为17.91%、15.20%、14.51%、14.37%、11.93%、7.91%、3.41%。肉桂茶纯露能很好的还原茶叶的香气,且香气成分数量和种类更多,香气层次更丰富,具有花香、果香等多种香韵。

顶空-气相色谱法与顶空-气质联用法测定饮用水中苯系物的方法建立及比较

目的:建立顶空-气相色谱法及顶空-气质联用法测定饮用水中常用7种苯系物(苯、甲苯、乙苯、间二甲苯、对二甲苯、邻二甲苯和苯乙烯),探讨两种测定方法的一致性。方法:优化了顶空、色谱、质谱等测定条件,对两种方法的检出限、精密度、准确度进行比较。结果:两种方法的回收率均在90.4%~100.2%,相对标准偏差均在1.1%~4.3%,顶空-气相色谱法的最低检出浓度分别为0.03~0.08μg·L^(-1),顶空-气质联用法的最低检出浓度分别为0.002~0.005μg·L^(-1),测定结果无显著性差异。结论:两种方法操作简单、快速,准确度和灵敏度高,均适用于饮用水中苯系物的日常检测。顶空-气质联用法的灵敏性更高,适用于痕量、基质复杂样品的测定;顶空-气相色谱法适用于高浓度样品的测定。

燃料油中硫化氢在线检测系统研制与验证

针对当前燃料油中硫化氢检测技术中存在的样品处理过程复杂、仪器损耗大、烃类干扰严重以及测试周期长等问题,提出了一种顶空气相色谱-荧光检测联用技术。利用顶空气相色谱-荧光检测联用技术实现了燃料油硫化氢的实时在线检测。测得的硫化氢浓度的相对标准偏差为3.21%,且其结果重现性较好。实际样品测试结果表明,顶空气相色谱-荧光检测联用技术与船用燃料油国家标准GB 17411—2015规定使用的英国石油学会标准IP 570/15方法测试结果相近,无显著差异,可以满足日常测试需求。同时,该检测方法针对不同理化性质的燃料油均表现出较高的适用性,有望应用于现场快速检测燃料油质量。

不同萃取方法下绿萼梅花蕾挥发性成分的差异研究

2023年3月13日,从浙江省长兴县东方梅园有限公司梅花基地采集绿萼梅花蕾,采用顶空-固相微萃取、水蒸气蒸馏、超临界二氧化碳3种萃取方法,结合气相色谱-质谱联用仪(GC-MS)分析绿萼梅Prunus mume f.viridicalyx花蕾中的挥发性成分,以明确其花蕾中挥发性成分组成、含量及不同萃取方式对挥发性成分萃取效果的影响。结果表明,三种萃取方法获得的绿萼梅花提取物中共鉴定出醛、醇、酮、烯等9类57种化合物,主要挥发性成分是苯甲醛、壬醛、金合欢醇、苯甲酸、α-香树脂醇、D-柠檬烯,其中苯甲醛含量最高。绿萼梅花顶空-固相微萃取物中共鉴定出21种化合物,以醛、醇和酯类化合物为主;水蒸气蒸馏物中共鉴定出30种化合物,以酯、烯、酮等水难溶化合物为主;而超临界二氧化碳提取物中共鉴定出30种化合物,以长链烷、酯类化合物为主。三种提取方法中超临界二氧化碳萃取物中蜡质含量较高,顶空-固相微萃取和水蒸气蒸馏法结合更适合作为植物芳香类挥发物的检测手段。

顶空箭形固相微萃取–气相色谱质谱法分析烃源岩和稠油中的金刚烷类化合物

采用顶空箭型固相微萃取–气相色谱质谱联用技术(HS-SPME Arrow-GC/MS)直接检测分析烃源岩粉末样品和稠油中的单金刚烷类和双金刚烷类化合物,考察并优化了影响萃取效率的萃取纤维头类型、萃取温度、萃取时间和解析时间等关键因素。对于小于80目的烃源岩样品,推荐最优HS-SPME Arrow实验条件为:使用250μm PDMS箭形固相微萃取头, 120℃下萃取20 min, 260℃下解析8 min。对于稠油,当使用250μm PDMS萃取纤维头、萃取温度为120~150℃、萃取时间为15~20 min、解析时间为3~8 min时,稠油中的单金刚烷类和双金刚烷类化合物都能取得较理想的质谱响应。该方法实现了对烃源岩粉末和稠油中金刚烷类化合物的直接分析,灵敏度高,检出限低(0.004~0.977 ng/g),重现性好,测量峰面积和比值参数的相对标准偏差分别小于20%和5%,避免了复杂的前处理过程,是一种快捷可靠的分析方法。

不同油炸工艺对牦牛肉品质及风味物质的影响

为探究油炸对牦牛肉风味物质及品质的影响,对不同油炸温度和时间下的牦牛肉进行感官评分、水分含量、色差值、质构指标的测定;采用顶空固相微萃取-气相色谱-质谱联用技术(headspace solid phase microextraction combined with gas chromatography-mass spectrometry,HS-SPME-GC-MS)分析油炸前后牦牛肉风味物质的种类和含量变化。结果表明:E_2组(160℃、80 s)牦牛肉感官评分、色差值、质构品质指标均最优。HS-SPME-GC-MS共鉴定出41种挥发性风味物质,包括醛类20种、醇类5种、酯类2种、酮类1种、呋喃类1种、烃类7种、有机酸类1种、其它类4种化合物;A组(参照组)检测出27种化合物,E_2组检测出38种化合物,两组牦牛肉中挥发性成分种类及相对含量有较大差异。根据香气特征雷达图得出,E_2组的香气种类更丰富。利用相对气味活度值对牦牛肉关键风味成分分析得出,A组关键挥发性风味物质有10种,E_2组关键挥发性风味物质有17种,其中反式-2-癸烯醛、壬醛、1-辛烯-3-醇相对气味活度值最大,分别为47.35、35.14、17.63,赋予油炸牦牛肉烤肉味、果香味、蘑菇香味。通过韦恩图得出,A组特有的挥发性风味物质有3种,E_2组特有的挥发性风味物质有14种,A组特有关键香气成分2种,E_2组特有关键香气成分9种。综合风味指标、质构指标和感官评价指标得出,油炸工艺对牦牛肉的风味及品质有明显提升。

基于多元统计学分析^(60)Co-γ射线辐照对川芎挥发性成分的影响

川芎挥发性成分是其主要活性成分之一,也是评价川芎药用品质的重要指标。为探究^(60)Co-γ射线辐照对川芎挥发性成分的影响,本研究以不同吸收剂量处理川芎样品,采用电子鼻结合顶空固相微萃取-气相色谱-质谱技术(HS-SPME-GC-MS),通过主成分分析、线性判别分析、正交偏最小二乘法和聚类分析的多元统计学方法分析数据,以期了解川芎辐照前后挥发性成分的变化。电子鼻与GC-MS结果都表明:川芎气味主要由烷烃类、醇类、醛类、酮类贡献,10 kGy剂量以下的辐照处理对川芎挥发性气味成分影响不大;川芎经0 kGy(对照组)、3 kGy、7 kGy、10 kGy剂量辐照处理后,共鉴定出60种化合物,其中烃类23种,醇类12种,脂类10种,醛酮类4种,其他类11种;筛选到21种辐照前后的差异特征性指标物,它们在川芎挥发性成分中只占约12.92%,不是川芎的主要挥发性成分。经10 kGy剂量以下的辐照处理后,川芎中没有新生成的物质被鉴定出来。研究结果提示经10 kGy以下剂量处理川芎不会影响其主要挥发性成分。