卷烟烟丝和卷烟烟气总粒相物中挥发性和半挥发性成分的分析研究

卷烟中的香味成分是影响卷烟产品风格的重要因素之一,对卷烟中挥发性成分的种类和含量进行分析研究能够更好地了解卷烟产品风格的形成;为卷烟叶组配方和加香加料提供有关理论依据和参考信息[1].固相微萃取(SPME)技术作为一种新颖的样品处理手段,集采样、萃取、浓缩、进样于一体,操作简单、方便、快速,也很快被用于烟草挥发性成分的分析[2].本文对SPME采样条件如纤维头的选择、样品用量、吸附温度、吸附时间等进行了探讨和优化,并对1种品牌卷烟的烟丝及其总粒相物进行了分析比较.     

卷烟烟气中挥发性组分的毛细管气相色谱分析

采用毛细管气相色谱（CGC）和色谱－质谱联用（GC－MS）技术对国内外部分名牌卷烟烟气中的挥发性和半挥发性化学成分进行了定性定量分析,质谱鉴定出107种化合物;对其中重要的32种化合物进行了定量比较,结果发现烤烟型卷烟、混合型卷烟和英式烤烟在烟气的香味组分中存在一些差异和规律,烤烟型烟气组分总含量最高,烤烟烟气中碳氢化合物裂解产物和低级酸类组分含量较高,混合型卷烟烟气中茄酮和异戊酸较高,英式烤烟的烟气组分更接近于混合型卷烟。     

用电子鼻研究不同烘丝过程对卷烟挥发性成分的影响

采用电子鼻对卷烟烟丝挥发性组分进行分析,分别考察了前处理制样与电子鼻顶空平衡时间对结果的影响。确定采用三包卷烟的烟丝作为大样本,混合均匀后称取适量样品直接电子鼻分析,电子鼻顶空平衡温度为55℃。应用电子鼻在该参数下对不同烘丝方式和温度参数处理的卷烟烟丝挥发性成分进行气味指纹图谱和PCA分析,同连续流动法测定的常规化学成分结果作了比较,结果表明电子鼻能够反映规常规化学成分检测手段不能区分的不同烘丝过程带来的挥发性组分改变。     

中药党参挥发性成分分析

采用“乙醚冷浸－索氏提取－水蒸汽蒸馏”方法对党参中挥发性成分进行提取,用ＧＣ分离,加标定性和ＧＣ－ＭＳ联用鉴定其组分。分离出２６８种化合物,鉴定出６４种。     

固相微萃取-气相色谱-质谱法分析香樟籽挥发性成分

采用固相微萃取-气相色谱-质谱法分离和鉴定香樟籽的挥发性成分,用归一化法测定其相对含量。共分离出76种组分,鉴定出47种化合物,其含量占总挥发性成分的97.4%。主要挥发成分为樟脑(57.89%)、柠檬烯(12.68%)、α-蒎烯(4.42%)、莰烯(2.69%)、香橙烯(2.34%)、伞花烃(2.26%)及β-蒎烯(2.12%)。     

顶空-固相微萃取-气相色谱-质谱法测定烟气中挥发性和半挥发性成分

提出了顶空-固相微萃取-气相色谱-质谱法测定烟气中挥发性和半挥发性成分。结合信息量最大的原则,确定了固相微萃取时萃取纤维头为碳分子筛/聚二甲基硅烷萃取纤维头,萃取温度为70℃,萃取时间为60min。在气相色谱分离中用Agilent DB-1色谱柱为固定相,在质谱分析中采用全扫描模式。结果表明:共鉴定出107种成分,含量最大的成分是烟碱(18.07%),其次是新植二烯(11.46%),主要的3类挥发性和半挥发性成分依次为苯系物、酮类以及杂环类。     

生姜挥发性成分的分析

本文采用水蒸气蒸馏法提取了生姜挥发性成分，并用GC／MS方法对提取的挥发性成分进行了鉴定。共鉴定了30种化学成分，并进行了讨论。     

顶空固相微萃取-气相色谱-质谱法用于白术中挥发性成分的分析

采用顶空固相微萃取-气相色谱-质谱法(HS-SPME-GC-MS)分离鉴定了白术中的挥发性成分,并与采用传统的水蒸气蒸馏法(SD)提取的挥发性成分进行了比较。实验中筛选了固相微萃取纤维头,优化了SPME的操作条件。样品在70 ℃下平衡30 min后,用65 μm聚二甲基硅氧烷-二乙烯基苯(PDMS-DVB)纤维头对白术样品顶空吸附30 min,于250 ℃下解吸4 min, 然后采用GC-MS对解吸物进行分离鉴定;采用HS-SPME-GC-MS鉴定出41种组分,占总峰面积的90.81%;采用SD-GC-MS鉴定出31个组分,占总峰面积的88.19%,且采用SD所提取的组分基本上都被固相微萃取所提取。结果表明, HS-SPME可取代耗时的SD用于白术中挥发性物质的提取。     

固相微萃取-气相色谱-质谱技术分析槐花的挥发性成分

用顶空固相微萃取操作,结合气相色谱-质谱联用技术对槐花挥发性成分进行了鉴定,并用面积归一化法测定其相对含量.共鉴定出化合物31种,包括酮、醇、酸、甾醇、酚、醛、酯、烷烃、烯烃及杂环等10类化合物,其中酮类化合物占总色谱馏出峰面积的21.15%;醇类化合物占13.78%;酸类占9.15%.其主要化合物有:1,9,12三氧-4,6-二氨基环十四烷-5-硫酮(20.58%),棕榈酸(9.05%),9,12,15-十八三烯醇(7.05%),(Z,Z)-9,12-十八碳二烯酸(6.85%),β-谷甾醇(6.11%).该技术可以简便快捷准确地进行槐花挥发性成分的分析鉴定.     

固相微萃取/气相色谱-质谱法对乌梅浸膏挥发性成分的分析研究

对乌梅浸膏挥发性物质的固相微萃取条件进行了研究。运用正交实验设计,比较了不同萃取头、平衡温度及采样时间对分析结果的影响,通过气相色谱-质谱(GC-MS)的分析监控,结合信息量最大原则,确定了固相微萃取的最佳条件:萃取纤维头为聚二甲基硅氧烷,平衡温度为70℃,采样时间45 min。通过GC-MS进行定性定量分析,共鉴定出38种成分,主要挥发性成分依次为糠醛(24.88%)、2-甲基-3-羟基苯甲醛(13.57%)和5-甲基糠醛(10.16%)。     

Puff-by-puff resolved characterisation of cigarette mainstream smoke by single photon ionisation (SPI)-time-of-flight mass spectrometry (TOFMS): comparison of the 2R4F research cigarette and pure Burley, Virginia, Oriental and Maryland tobacco cigarettes

Soft single photon ionisation (SPI)-time-of-flight mass spectrometry (TOFMS) is applied for the characterisation and comparison of puff-by-puff resolved and total yields of cigarette mainstream smoke from single tobacco type cigarettes (Virginia, Oriental, Burley, and Maryland) and the 2R4F University of Kentucky research cigarette. Puff-by-puff characteristics of various smoke components within one cigarette type as well as between different cigarette types can differ tremendously. This is demonstrated by means of a few selected compounds. Puff yields vary between 15 and 106 μm for acetaldehyde, 6 and 57 μm for NO, and between 1 and 8 μm for butadiene. Thereby, cigarettes containing 100% Oriental and Burley tobacco exhibit a very unique behaviour for the first and last puff. Different cultivation and processing methods as well as burning characteristics are most likely responsible for this. Since the 2R4F cigarette contains all four tobacco types it combines features of all of them. However, for some smoke constituents, smoking of the 2R4F reference cigarette results in exceptionally high yields which might not be attributable to the four pure tobacco types, but to other factors. In addition, comparison of the different cigarettes was also carried out by normalising the yields to puff resolved particulate matter. This procedure minimises effects caused by unequal smoke formation and represents another approach in evaluating the data.     

Application of comprehensive two-dimensional gas chromatography mass spectrometry and different types of data analysis for the investigation of cigarette particulate matter

In tobacco research, the comparison of different tobacco blends as well as the puff-dependent behaviour of cigarettes is a matter of particular interest. For the investigation of smoke characteristics, GC x GC offers different ways for data analysis, namely, compound target analysis, automated peak-based compound classification and comprehensive pixel-based data analysis. This study will show the application as well as the pros and cons of these types of data analysis for very complex matrices like cigarette particulate matter. In addition, new aspects about the recently discovered puff-dependent behaviour of compounds in cigarette smoke will be presented. Automated peak-based compound classification including mass spectrometric pattern recognition is used for the classification of tobacco particulate matter samples and the puff-dependent investigation of different compound classes. This compound group specific analysis is further reinforced by applying an even more comprehensive pixel-based analysis. This kind of analysis is used to generate fingerprints of different types of cigarettes. The combination of fast feature reduction methods like analysis of variance (ANOVA) and t-test with multivariate feature transformation methods like partial least squares discriminate analysis (PLSDA) for feature selection provides a powerful tool for a detailed inspection of different types of cigarettes.     

A feasibility study on oxidation state of arsenic in cut tobacco,mainstream cigarette smoke and cigarette ash by X-ray absorption spectroscopy

This work describes the application of synchrotron-based X-ray Absorption Near-Edge Structure spectroscopy to study the oxidation state of arsenic in cigarette mainstream smoke, cut tobacco and cigarette ash. The level of arsenic in the total particulate matter of the smoke is approximately 1 ppm for the standard research reference cigarette 2R4F and its replacement 3R4F. Smoke particulate samples collected by a conventional glass-fiber membrane (commercially known as Cambridge filter pad) and a jet-impaction method were analyzed and compared. In addition smoke particulate samples were aged either at ambient temperature or at 195 K. X-ray Absorption Near-Edge Structure spectroscopy results revealed that the cut tobacco powder and cigarette ash contained almost exclusively As^V. The smoke particulate samples however contained a mixture of As^III and As^V. The As^V in the smoke particulate was reduced to As^III upon aging. Stabilizing the smoke particulate matter at 195 K by solid CO₂ slowed down this aging reaction and revealed a higher percentage of As^V. This behavior is consistent with the redox properties of the arsenic species and the smoke particulate matrix.     

Analysis of aromatic amines in cigarette smoke

A method for the analysis of o-toluidine, o-anisidine, 2-naphthylamine, and 4-aminobiphenyl in cigarette mainstream smoke has been developed, which combines the sensitivity of their pentafluoropropionyl (PFP) derivatives in negative ion chemical ionization (NICI) mode with the selectivity of the gas chromatography/tandem mass spectrometry (GC/MS/MS) technique. The use of four deuterated analogues as internal standards along with the application of the standard addition method results in accurate and precise results; the interday precision for the aromatic amines was 3-10% and the accuracy ranged from 97-100%. This method was applied to two American-blend University of Kentucky reference cigarettes, eight American-blend market cigarettes, a bright (flue-cured) tobacco cigarette, and an electrically heated cigarette smoking system (EHCSS). For the American-blend cigarettes there was a linear correlation between aromatic amine yields and mainstream smoke 'tar' ('tar' = total particulate matter - (nicotine + water)), whereas the bright tobacco cigarette and the EHCSS demonstrated significantly lower aromatic amine yields on an equal 'tar' basis. The results support the hypothesis that the nitrogen content of the tobacco, and above all the cigarette combustion temperature, are determining factors for the yields of aromatic amines in smoke.     

The Distribution of Total Particulate Matter (TPM) And Nicotine Between Mainstream and Sidestream Smoke in Bidis and Cigarettes

ABSTRACT

The mainstream (MS) and sidestream (SS) smoke of three types of popular Indian cigarettes, a brand of low tar Indian cigarettes, a brand of US cigarettes and two brands of popular Indian bidis were analysed for carcinogenic total particulate matter (TPM) and nicotine levels employing standard smoking conditions and/or modified smoking standards.

The analysis clearly demonstrated relatively higher levels of TPM and nicotine in MS of three types of popular Indian cigarettes when compared with a brand of low tar Indian cigarettes or a brand of US cigarettes or reported values for MS of western cigarettes. This was also reflected in MS/SS ratios of TPM and nicotine as TPM and nicotine levels in SS of Indian and US cigarettes were similar, when tested employing standard smoking conditions.

Comparative analysis of Indian bidis/cigarettes and a brand of US cigarettes employing modified smoking standard (i.e. 2 puffs/min instead of 1 puff/min) revealed significantly lower values of TPM and nicotine in SS of Indian bidis when compared with corresponding values in Indian/US cigarettes. This shows that contribution of TPM and nicotine in SS from a single bidi to environmental tobacco smoke (ETS) is very much less than that of a single cigarette, and contribution of SS from Indian and US cigarettes to ETS appear to be similar. Reduced levels of TPM and nicotine in SS of bidis, probably due to lack of added burning agents, result into relatively higher deliveries of TPM and nicotine in MS as reflected by higher MS/SS values.     

卷烟主流烟气粒相物中中性化学成分的全二维气相色谱飞行时间质谱(GC×GC-TOF MS)谱图特征识别

建立了全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)分析卷烟主流烟气中中性化学成分的方法。以较长的弱极性柱HP-5MS(50 m×0.2 mm i.d.×0.33μm)作为第一维柱,较短的薄液膜中等极性柱DB-17MS(1.7 m×0.1 mm i.d.×0.1μm)作为第二维柱,对优质烟叶单料卷烟烟气的中性成分进行定性分析,经过人工纠错等分析初步鉴定出匹配度大于700的1 464种成分,重点讨论了中性香味羰基化合物全二维点阵的谱图特征,为烟气和复杂体系的深入研究提供了方法学基础。     

Tobacco smoke particulate matter chemistry by NMR

The submicron liquid droplets constituting the particulate matter of mainstream tobacco smoke (PMMTS) are viscous and of a composition that is complex and poorly understood. PMMTS is often approximately 80% w/w 'tar' where 'tar'=total PMMTS- (nicotine+water). Many of the chemical agents in MTS responsible for smoking-related cancers are found at least partially in the PMMTS portion of MTS. The properties of PMMTS vary with brand and with puffing patterns. The chemical forms and total levels of nicotine, the identities/levels of other compositionally dominant compounds, and the identities/levels of carcinogens are of interest. Most studies of the composition of PMMTS have involved extraction then chromatography. Such methods allow the determination of low-level constituents, but alter the samples such that direct information regarding chemical conditions within the PMMTS cannot be obtained. Here, we utilize nuclear magnetic resonance spectroscopy (NMR) to examine native PMMTS in conventional cigarettes, including measurements of the brand-dependent fraction of PMMTS nicotine that is in the free-base form (increasing this fraction in inhaled tobacco smoke affects the rates of the processes governing nicotine deposition in the respiratory tract, and so has implications for smoking behavior and addiction). We also demonstrate the use of NMR for characterizing the composition of PMMTS (including the levels of selected cigarette additives) when the cosolvent DMSO-d6 is added to improve spectral resolution. The native and solvent-assisted results open the door to a range of future studies.     

Isotope dilution gas chromatography-mass spectrometry in the determination of benzene, toluene, styrene and acrylonitrile in mainstream cigarette smoke

A cryogenic trapping method with isotope dilution gas chromatography-mass spectrometry analysis has been developed for the determination of benzene, toluene, styrene and acrylonitrile in mainstream vapor phase cigarette smoke. The method is simple, direct, and quantitative. Vapor phase samples are collected cryogenically in a series of four traps following removal of the particulate phase with a Cambridge filter pad. For all four analytes, 75-85% of the total amounts recovered were found in the initial trap and less than 1% in the final trap. Assessment of instrumental precision by multiple injections of a sample gave relative standard deviations of less than 2%. Linear calibration for all analytes over the analysis range gave an r2 value greater than 0.99 with average relative standard deviations at the mean ranging from 1.4 to 8.2%. The cigarettes analyzed include a reference cigarette (Kentucky 1R4F), a commercial ultra-low "tar" mentholated cigarette, and two cigarettes that heat but do not burn tobacco. The values determined for the four analytes in the 1R4F samples are comparable to reported values of similar cigarettes. The cigarettes which heat rather than burn tobacco yield less of all four analytes compared to the other cigarettes in the study.     

Determination of the elemental distribution in cigarette components and smoke by instrumental neutron activation analysis

Cigarette smoking is a major source of particles released in indoor environments. A comprehensive study of the elemental distribution in cigarettes and cigarette smoke has been completed. Specifically, concentrations of thirty elements have been determined for the components of 15 types of cigarettes. Components include tobacco, ash, butts, filters, and cigarette paper. In addition, particulate matter from mainstream smoke (MS) and sidestream smoke (SS) were analyzed. The technique of elemental determination used in the study is instrumental neutron activation analysis. The results show that certain heavy metals, such as As, Cd, K, Sb and Zn, are released into the MS and SS. These metals may then be part of the health risk of exposure to smoke. Other elements are retained, for the most part, in cigarette ash and butts. The elemental distribution among the cigarette components and smoke changes for different smoking conditions.