固相微萃取气质联用技术对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研究

采用固相微萃取－气相色谱－质谱（SPME－GC－MS）法对成品卷烟烟丝和卷烟烟气总粒相物中挥发性和半挥发性成分进行了分析鉴定，并对鉴定出的70种成分和96种成分进行了比较。     

毛细管气相色谱和气相色谱/质谱法分析五灵脂挥发性成分

利用同时蒸馏萃取法（SDE）提取五灵中的挥发性组分。SE－54柱和PEG－20M柱上用气相色谱－质谱法分别检出122个和96个峰。其中有51种峰质谱检索结果相同,它们占总峰面积的56.3％。进一步用程序升温保留指数确认了其中33种化合物,占总峰面积的35.7%。含量较高的组分有：十二酸（7.00%),α－雪松醇（4.41％）,四甲基吡嗪（4.10%）,寸上酸（3.37％）,1－（3－甲苯基）乙酮（2.53%),苯甲醛（2.42％）,2－甲氧基苯酚（2.11%)。从化合物的种类来看,主要为醇类（10种）,酮类（8种）,醛类（8种）,醛类（6种）、烯类（5种）、酸类（4种）,酚类（4种）。     

超临界流体色谱与气相色谱-质谱联用测定卷烟主流烟气中醛酮类化合物的研究

建立了一种卷烟主流烟气中醛酮类香气化合物的超临界流体色谱/气相色谱-质谱测定方法。将捕集卷烟主流烟气粒相物的剑桥滤片用超临界流体萃取醛酮类香气成分后,通过配备高效分离柱的超临界流体色谱(SFC)先对香气成分进行划段,分离后的各段馏分再用GC-MS分析。结果表明:经SFC分离后的各段化合物之间基本不重叠,解决了GC-MS峰容量有限的问题,且分离出的醛酮类香气成分数量远多于直接进样分析法;样品直接进样后经GC-MS分析仅鉴定出29种醛酮类化合物,其中醛类7种、酮类22种;而经SFC分段后再用GC-MS分析,可鉴定出57种醛酮类化合物,包括13种醛类和44种酮类。3种不同焦油量卷烟主流烟气中醛酮类化合物种类和含量存在较大差异,每种卷烟主流烟气中分别含有不同特有醛酮类化合物。该研究为卷烟主流烟气中醛酮类香气成分的测定提供了新方法。     

液相色谱-串联质谱法测定卷烟主流烟气中的四种致癌物

N-亚硝基降烟碱（NNN）、4-（亚硝基甲氨基）-1-（3-吡啶基）-1-丁酮（NNK）、N-亚硝基新烟草碱 （NAT）和N-亚硝基假木贼碱（NAB）是4种广泛存在于烟草和烟气中的致癌物,准确测定其含量对评估其对人体健康的影响有着重要的作用。采用液相色谱-电喷雾串联质谱(LC-ESI MS/MS)技术建立了卷烟主流烟气中NNN、NNK、NAT和NAB的测定方法,并将其用于中国烤烟和混合型卷烟主流烟气的分析。卷烟主流烟气通过剑桥滤片捕集,捕集烟气后的滤片在加入100 μL氘代混合内标后用10 mL 100 mmol/L醋酸铵水溶液萃取,萃取液过水相滤膜后直接进行LC-ESI MS/MS检测。选用Agilent Zorbax Eclipse XDB-C18色谱柱,以流动相0.1%(v/v)乙酸水溶液和0.1%（v/v）乙酸甲醇溶液梯度洗脱,质谱检测采用正离子扫描,多反应监测模式。NNN、NNK、NAT和NAB的检出限分别为0.019、0.002、0.008和0.007 μg/L,回收率为84.9%～104.5%,相对标准偏差(n=8)为2.96%～6.65%。该方法的检出限低,特异性好,适用于卷烟主流烟气中NNN、NNK、NAT和NAB释放量的检测。     

佛手挥发油的化学成分

用色谱－质谱－计算机联用法对佛手挥发油的化学成分和相对含量进行了系统分析,得到６７种组分,鉴定出３１个组分,主要组分是柠檬烯（４８．４％）、１－甲基－２－（１－甲乙基）－苯（３０．８％）。     

银杏叶挥发油化学成分的研究

本文采用气相色谱以及气相色谱-质谱（GC－MS）联用技术对银杏挥发油的化学成分进行了研究，初步鉴定出其中的17种化合物。研究表明，挥发油中棕润酸和2，6-二特丁基-4-甲基苯酚的含量较高。     

卷烟内在质量的气相色谱－数学聚类法研究

采用吸附丝色谱方法采集和分析了红塔山牌卷烟的挥发性成分,对 10个真品进行 R型聚类分析和 R型因子分析,从 26个组分提取出对卷烟质量起主导作用的 7个特征变量（组分）,并对其丰度进行了讨论,进而建立了红塔山卷烟的质量数学模型,用 2个真品和 2 个假冒品对模型进行了检验,结果令人满意。     

卷烟内在质量的气相色谱—数学聚类法研究

采用吸附丝色谱方法采集和分析了红塔山牌卷烟的挥发性成分,对10个真品进行R型聚类分析和R型因子分析,从26个组分提取出对卷烟质量起主导作用的7个特征变量（组分）,并对其丰度进行了讨论,进而建立了红塔山卷烟的质量数学模型,用2个真品和2个假冒品对模型进行了检验,结果令人满意。     

滤嘴对卷烟主流烟气中挥发性羰基化合物截留效率的测定

本文采用HPLC和GC分别对国内市场占有率较高的18种牌号卷烟主流烟气及其滤嘴中挥发性羰基化合物的含量进行了测定,并对滤嘴截留挥发性羰基化合物效率和机制进行了探讨。结果表明:卷烟主流烟气中挥发性羰基化合物含量高低的顺序是乙醛、丙酮、甲醛、丙稀醛、巴豆醛、丁酮和丁醛;滤嘴中挥发性羰基化合物含量高低的顺序是甲醛、丁酮、巴豆醛、丁醛、丙稀醛、丙酮和乙醛;滤嘴对羰基化合物截留效率高低的顺序是巴豆醛、丁酮、甲醛、丁醛、丙烯醛、丙酮和乙醛。二醋酸纤维丝束对挥发性羰基化合物的截留效率较聚丙烯丝束好。     

全二维气相色谱/飞行时间质谱用于卷烟主流烟气中酚类化合物的表征

建立了卷烟主流烟气粒相物中酚类化合物组成研究的全二维气相色谱／飞行时间质谱方法，并用所建立的方法对一种市售混合型卷烟主流烟气粒相物中的酚类馏分组成进行了表征．采用TOFMS谱图库检索辅以二维“结构谱图”的定性手段，初步鉴定出了其中250个酚类化合物．这些酚类化合物包括66个烷基苯酚、47个烯基苯酚、57个萘酚、17个苯基苯酚、32个甲氧基苯酚、9个酚酮和15个酚醛化合物．同时对不同类型的酚类化合物在二维气相色谱上的分布模式进行了讨论．     

不同材料滤嘴对卷烟主流烟气中挥发性羰基化合物截滤性能的研究

吸烟是引起肺癌及相关疾病的主要原因[1]。挥发性羰基化合物(如甲醛、乙醛、丙醛、丙酮、丙烯醛、巴豆醛、丁酮和丁醛)是卷烟主流烟气中含量较高的一类有害成分,含量从几十到几百微克不等[2-3]。这些挥发性羰基化合物特别是甲醛、丙烯醛及巴豆醛具有纤毛毒性,与氰化氢和氨一起,     

Investigation,by single photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS), of the effect of different cigarette-lighting devices on the chemical composition of the first cigarette puff

Soft single-photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff. Lighting devices examined were a Borgwaldt electric lighter, a propane/butane gas lighter, a match, a candle, and the burning zone of another cigarette. To eliminate the effects of the different masses of tobacco burnt by use of the different lighting methods a normalisation procedure was performed which enabled investigation of changes in the chemical patterns of the resulting smoke. When another cigarette was used as the lighting device, elevated levels of ammonia and other nitrogen-containing substances were observed. These are high in the sidestream smoke of the cigarette used for lighting and would be drawn into the mainstream smoke of the cigarette being lit. In contrast, smoke from the cigarette lit by the electric lighter contained slightly higher normalised amounts of isoprene. Lighting the cigarette by use of a candle resulted in larger amounts of substances, e.g. benzene, which most probably originated from thermal decomposition of wax. The composition of the first puff of smoke obtained by use of the three lighting methods with open flames (gas lighter, match, and candle) was usually similar whereas the composition of the smoke produced by use of the electric lighter and the cigarette as the lighter were more unique. The chemical patterns generated by the different lighting devices could, however, be separated by principal-component analyses. Two additional test series were also studied. In the first the cigarette was lit with an electric lighter, then extinguished, the ash was cut off, and the cigarette was re-lit. In the second the cigarette was heated in an oven to 80 °C for 5 min before being lit. These treatments did not result in changes in the chemical composition compared with cigarettes lit in the ordinary way. Figure Time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff     

New insights into the formation of volatile compounds in mainstream cigarette smoke

A sampling system has been set up to monitor a group of volatile smoke analytes (nitric oxide, acetaldehyde, acetone, benzene, toluene, 1,3 butadiene, isoprene and carbon dioxide) from mainstream cigarette smoke on a puff-resolved basis. The system was able to record gas evolution profiles during puffing and interpuff periods without interruption (e.g. taking clearing puffs). Gas phase smoke analytes were sampled as close to the mouth end of the cigarette filter as possible in order to minimise any dead volume effect. The results revealed that, for some volatile species, a significant fraction (e.g. up to 30% for benzene) in the cigarette mainstream smoke had been generated during the preceding smoulder period. These species were trapped or absorbed within the cigarette rod and then subsequently eluted during the puff. The identification of the two sources of the mainstream smoke, a smouldering source and a puffing source, has not been reported before. The observation contributes to the fundamental knowledge of the cigarette smoke formation and may have implications on wider smoke chemistry and associated effects.     

卷烟主流烟气中挥发性羰基化合物分析研究进展

挥发性羰基化合物是卷烟烟气中主要有害成分之一,在抽吸卷烟的过程中会不同程度地刺激人体的感觉器官和呼吸系统,长期吸入会对人体造成严重的危害。文章介绍了卷烟主流烟气中挥发性羰基化合物的形成机制和前提物,综述了羰基化合物的捕集方法、衍生化和检测手段。     

烟气中有机酸的分析

 应用甲酯衍生化试剂对卷烟烟气粒相物中有机酸进行甲酯衍生化 ,经固相微萃取 (SPME)后通过气 质联用仪分离鉴定。分析了 4个品牌的卷烟烟气 ,共鉴定了 60多种挥发及半挥发性有机酸。对丁酸、己酸、糠酸、辛酸、壬酸、苯甲酸、苯乙酸、十四酸、十六酸进行了定量分析。该方法用于烟气中有机酸的定性、定量分析 ,灵敏度较高 ,快速简便。     

Chemical Studies on Tobacco Smoke. LXI. Volatile Pyridines: Quantitative Analysis in Mainstream and Sidestream Smoke of Cigarettes and Cigars

Abstract

A quantitative analytical method has been developed for volatile pyridines in tobacco smoke using pyridine- ¹⁴C as an internal standard. Mainstream and sidestream smoke are trapped in 0.05 N sulfuric acid anti partitioned with chloroform. The acidic portion is then concentrated, adjusted to pH 3 and extracted with chloroform. Methanol and a trace of 2N sulfuric acid are added to this chloroform portion and the mixture is carefully concentrated.

A trace of sodium hydroxide is added and the final concentrate is analyzed by gas chromatography. Twenty-one volatile pyridines have been identified. The mainstream stroke of a popular. 85-mm U.S. cigarette without filter tip contained the following major pyridines: 33.4 μg pyridine, 12.3 μg α-picoline, 24.2 μg. β+γ-picoline, 7.6 μg 3-ethylpgridine, 5.9 μg: 4-ethylpyridine, and 23.3 μg 3,4-lutidine + 3-vinylpyridine. The sidestream smoke of this cigarette contained up to 28 times higher concentrations of pyridines.

Volatile pyridines were also determined in the mainstream smoke of other non-filter cigarettes, filter cigarettes, little cigars and, a non-tobacco cigarette. Of special interest were the much greater quantities of volatile pyridines in the mainstream and sidestream of cigars in comparison to those of cigarettes. The ratio of pyridines in sidestream to those in mainstream was 5 to 50 in large cigars. Selective filtration was observed with both cellulose acetate and charcoal filter tips. The analytical method resulted in reproducible values for pyridine, with an average recovery rate of more than 90%. In addition to pyridines, two pyrazines were also isolated from the smoke. Processed tobacco contained minute amounts of some volatile pyridines.     

Improved real-time puff-by-puff GC-MS system for whole smoke analysis

An automated puff-by-puff mainstream smoke (MSS) system is developed to monitor real-time whole smoke in mainstream cigarette smoke using gas chromatography (GC)-mass spectrometry (MS). The whole-smoke analysis is based on automated sample collection and injection into the GC-MS system. The important feature of this system is the real-time rapid analysis that is simple, sensitive, precise, flexible, and exhibits low carryover of volatile and semivolatile smoke constituents. The system is equipped with an automated sampling and switching valve and a smoking machine. The key improvements of the system, as compared with current and alternative methodologies, include minimizing variations caused by operator sampling techniques, the real-time analysis of MSS, the detection of flavorants in MSS from a single puff of cigarette smoke, the ability to analyze numerous smoke constituents from either whole smoke or the gas phase of a single puff, the ability to monitor a few selected smoke constituents in whole smoke using multiple puffs, and its good feasibility compared with solvent extraction and impinger trapping procedures for volatile organic compounds in MSS. System configuration and sampling methodologies are described. Sensitivity, flexibility, precision, feasibility, carryover, and applications of the system are discussed.     

Trapping volatile nitrosamines with copper incorporated zeolites

Modification of zeolite with copper oxide significantly promotes the selectively adsorption of volatile nitrosamines, beneficial for the removal of nitrosamines in cigarette smoke.     

Reduction of aldehydes and hydrogen cyanide yields in mainstream cigarette smoke using an amine functionalised ion exchange resin

Background

Cigarette smoking is a well recognized cause of diseases such as lung cancer, chronic obstructive pulmonary disease and cardiovascular disease. Of the more than 5000 identified species in cigarette smoke, at least 150 have toxicological activity. For example, formaldehyde and acetaldehyde have been assigned as Group 1 and Group 2B carcinogens by IARC, and hydrogen cyanide has been identified as a respiratory and cardiovascular toxicant. Active carbon has been shown to be an effective material for the physical adsorption of many of the smoke volatile species. However, physical adsorption of acetaldehyde, formaldehyde and also hydrogen cyanide from smoke is less effective using carbon. Alternative methods for the removal of these species from cigarette smoke are therefore of interest. A macroporous, polystyrene based ion-exchange resin (Diaion^®CR20) with surface amine group functionality has been investigated for its ability to react with aldehydes and HCN in an aerosol stream, and thus selectively reduce the yields of these compounds (in particular formaldehyde) in mainstream cigarette smoke.

Results

Resin surface chemistry was characterized using vapour sorption, XPS, TOF-SIMS and ¹⁵N NMR. Diaion^®CR20 was found to have structural characteristics indicating weak physisorption properties, but sufficient surface functionalities to selectively remove aldehydes and HCN from cigarette smoke. Using 60 mg of Diaion^®CR20 in a cigarette cavity filter gave reductions in smoke formaldehyde greater than 50% (estimated to be equivalent to >80% of the formaldehyde present in the smoke vapour phase) independent of a range of flow rates. Substantial removal of HCN (>80%) and acetaldehyde (>60%) was also observed. The performance of Diaion^®CR20 was found to be consistent over a test period of 6 months. The overall adsorption for the majority of smoke compounds measured appeared to follow a pseudo-first order approximation to second order kinetics.

Conclusions

This study has shown that Diaion^®CR20 is a highly selective and efficient adsorbent for formaldehyde, acetaldehyde and HCN in cigarette smoke. The reductions for these compounds were greater than those achieved using an active carbon. The results also demonstrate that chemisorption can be an effective mechanism for the removal of certain vapour phase toxicants from cigarette smoke.

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Measurement of acrolein and 1,3-butadiene in a single puff of cigarette smoke using lead-salt tunable diode laser infrared spectroscopy

Acrolein and 1,3-butadiene in cigarette smoke generally are measured using two separate analytical methods, a carbonyl derivative HPLC method for acrolein and a volatile organic compound (VOC) GC/MS method for 1,3-butadiene. However, a single analytical method having improved sensitivity and real-time per puff measurement will offer more specific information for evaluating experimental carbon filtered cigarettes designed to reduce the smoke deliveries of these constituents. This paper describes an infrared technique using two lead-salt tunable diode lasers (TDLs) operating with liquid nitrogen cooling with emissions at 958.8 cm(-1) and 891.0 cm(-1) respectively for the simultaneous measurement of acrolein and 1,3-butadiene, respectively, in each puff of mainstream cigarette smoke in real time. The dual TDL system uses a 3.1l volume, 100 m astigmatic multiple pass absorption gas cell. Quantitation is based on a spectral fit that uses previously determined infrared molecular line parameters generated in our laboratory, including line positions, line strengths and nitrogen-broadened half-widths for these species. Since acrolein and ethylene absorption lines overlap and 1,3-butadiene, ethylene and propylene absorption lines overlap, the per puff deliveries of ethylene and propylene were determined since their overlapping absorption lines must be taken into account by the spectral fit. The acrolein and 1,3-butadiene total cigarette deliveries for the 1R5F Kentucky Reference cigarette were in agreement with the HPLC and GC/MS methods, respectively. The limit of detection (LOD) for 1,3-butadiene and acrolein was 4 ng/puff and 24 ng/puff, respectively, which is more than adequate to determine at which puff they break through the carbon filter. The retention and breakthrough behavior for the two primary smoke constituents depend on the cigarette design and characteristics of the carbon filter being evaluated.