Separation and quantitation of phenolic compounds in mainstream cigarette smoke by capillary gas chromatography with mass spectrometry in the selected-ion mode

Cigarette smoke condensate is a complex chemical matrix and determination of phenolic compounds in it frequently requires extensive and laborious sample preparation. By utilizing derivatization techniques and capillary column gas chromatography with mass spectrometry in the selected-ion mode, separation and quantitation of selected phenolic compounds found in mainstream cigarette smoke can be accomplished with minimal sample preparation. This method has been used to determine concentrations of phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and hydroquinone in cigarette smoke condensate from a number of commercially available cigarettes and a new cigarette which heats, but does not burn, tobacco. Unlike tobacco-burning cigarettes, levels of the phenolic compounds in the new cigarette smoke are at or below the detection limits for most of the compounds. This result is attributed to the unique design of the new cigarette.     

Determination of trace element concentrations of indian cigarette tobacco by instrumental neutron activation analysis

Lung cancer and smoking are associated. Epidemiological studies show that not only lung cancer but other chest diseases have causative relationship with smoking. Cigarette tobacco and smoke contains many carcinogens. Inorganic and metallic constituents of cigarette tobacco and smoke have not been studied as extensively as the organic compounds. Since some of the metals are highly toxic and also carcinogenic, authors have attempted to measure the levels of some of the trace elements of Indian tobacco by instrumental neutron activation analysis, and compared the results with the tobacco of America, Germany, Iran and New Zealand.     

Magnetic bead-based approach to monitoring of cigarette smoke-induced DNA oxidation damage and screening of natural protective compounds

Cigarette smoking can damage DNA and induce spontaneous mutagenesis or carcinogenesis. Here, we describe a novel strategy for in situ monitoring of cigarette smoke-induced DNA oxidation damage and offer a method for screening natural compounds that protect DNA against tobacco smoke. The present protocol takes advantage of a fast and simple magnetic separation/mixing method and a highly sensitive chemiluminescence (CL) ELISA. The DNA immobilized on the magnetic beads was oxidized by the smoke in the absence or presence of natural compounds, and then oxidative DNA was conveniently held by magnetic force, whereas the complex tobacco smoke matrix and any remaining compounds were completely eliminated by extensive washing, and possible interferences were thus removed and oxidative damage was then sensitively monitored by CL ELISA. A library of 32 natural products was then screened and three were found to protect DNA from oxidative damage and thus may be promising compounds for the development of new drugs. Moreover, the protection effect of these three natural compounds against DNA oxidation damage was successfully classified by directly spiking them in the reference cigarettes. In addition, the potential to screen a mixture in a complex sample matrix, such as crude extracts, was also demonstrated, and hence the proposed technique can screen compounds within a complex matrix and enhance the screening throughput.     

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.     

卷烟主流烟气中相关成分含量的快速检测方法

建立了一种快速测定卷烟主流烟气中相关成分的方法,其中包括一氧化碳、4-(甲基亚硝氨基)-3-吡啶-1-丁酮(NNK)、苯酚、巴豆醛、氨和氰化氢6种相关成分.采用在吸烟机上同时使用溶剂捕集和滤片捕集的方式,溶剂捕集氨、氰化氢和巴豆醛,滤片捕集NNK、氨、氰化氢和苯酚,样品采集后分别在高效液相色谱、离子色谱和液相色谱/质谱...     

Fluorescence Evaluation of Scavenging Efficiency of Antioxidants Against Reactive Oxygen Species (ROS) in Cigarette Smoke

Cigarette smoke can cause cellular oxidative stress that contributes to various adverse health effects associated with smoke exposure, partially due to reactive oxygen species (ROS) present in cigarette smoke. Reduction of abundant ROS in the cigarette mainstream smoke (MSS) is of importance for human health. In this work, a simple, rapid, and reliable fluorescence evaluation of scavenging efficiency of antioxidants as potential filter additives against ROS in cigarette smoke is reported. This method was based on the combination of model glass reactor and a fluorescence assay of ROS in cigarette smoke using dihydrorhodamine 6 G (DHR-6 G). The antioxidant was added into a glass reactor attached to cigarette filter, which simplified the preparation of combined filter containing additives. The ROS scavenging efficiency of antioxidants was then determined using spectrofluorimetry by the change in fluorescence intensity of whole smoke-bubbled solutions before and after addition of antioxidants into the glass reactor. The proposed method was successfully applied to the determination of ROS scavenging efficiency of several potential additives, such as tert-butylhydroquinone (TBHQ), vitamin C, β-carotene, grape seed extract, and Ginkgo biloba extract. Moreover, the relationship between MSS ROS scavenging efficiency and antioxidant activities (DPPH radicals scavenging efficiency and Fe²⁺ reducing power) of these compounds was also investigated.     

Rapid and sensitive method for simultaneous determination of six carcinogenic aromatic amines in mainstream cigarette smoke by liquid chromatography/electrospray ionization tandem mass spectrometry

Aromatic amines are one of the sources of carcinogenicity in cigarette and tobacco smoke. Accurate quantification of these chemicals is needed to assess public health risk. A new validated rapid, sensitive and analyte specific liquid chromatography/electrospray ionization tandem mass spectrometric (LC/MS/MS) method has been developed for the simultaneous determination of six aromatic amines in mainstream cigarette smoke using research reference cigarette 2R4F. Three popular Indian brand cigarettes were also analyzed using the same procedure. The limit of detection of this method ranged from 0.04 to 0.59 ng/cig using an injection volume of 7 μl. The identification of each amine was established by chromatographic retention times, analyte specific fragmentation pattern and relative peak area ratios of two product/precursor ion pairs. The method showed excellent reproducibility and was also rapid, selective and robust for aromatic amine determination from cigarette smoke.     

A rapid and selective method for simultaneous determination of six toxic phenolic compounds in mainstream cigarette smoke using single-drop microextraction followed by liquid chromatography–tandem mass spectrometry

Cigarette smoke contains several toxic phenolic compounds, measurements of which are essential from a public health standpoint. This article describes a simple and selective analytical method for quantitative determination of six toxic phenolic compounds (phenol, catechol, resorcinol, hydroquinone, o-cresol, and p-cresol) from mainstream cigarette smoke using single-drop microextraction in combination with liquid chromatography–tandem mass spectrometry. Single-drop microextraction was applied prior to analysis by liquid chromatography–tandem mass spectrometry for the extraction and preconcentration of target phenolic compounds from raw cigarette smoke extract. The effects of the extraction solvent, sampling time, solution pH, salt addition, sample agitation rate, and temperature on the extraction efficiency were examined and optimized. The identification of each analyte was established by chromatographic retention times, analyte-specific fragmentation patterns, and relative peak area ratios of two product/precursor ion pairs. Analytical parameters such as the detection limit, relative recovery, reproducibility, linearity, and enrichment factor were evaluated under the optimized experimental conditions. 1-Decanol was selected as the extraction solvent and the limits of detection were found to be in the range of 0.05-0.3 ng mL^-1 using an extraction time of 12 min. Gradient chromatographic conditions were optimized for the separation of the six phenolic compounds in a run time of 10 min including reequilibration of the column. The present method for determination of phenolic compounds from mainstream cigarette smoke is simple and specific and shows good reproducibility, with relative standard deviations less than 10 % for all targeted phenolics.

Magnetic solid‐phase extraction of tobacco‐specific N‐nitrosamines using magnetic graphene composite as sorbent

Tobacco‐specific N‐nitrosamines are carcinogenic components in mainstream cigarette smoke. To explore tobacco‐specific N‐nitrosamine release levels in cigarettes, a magnetic solid‐phase extraction procedure using magnetic graphene composite as sorbent for fast enrichment of tobacco‐specific N‐nitrosamine was developed. Under optimal conditions, a tobacco‐specific N‐nitrosamine determination method was successfully proposed by combining magnetic solid‐phase extraction procedure and high‐performance liquid chromatography coupled with tandem mass spectrometry. The method's limit of detection for tobacco‐specific N‐nitrosamines in mainstream cigarette smoke ranged from 0.018 to 0.057 ng/cigarette. Good linearities were obtained with correlation coefficients above 0.9992. The accuracies of tobacco‐specific N‐nitrosamines in a spiked mainstream cigarette smoke sample were from 89.3 to 109.4%, with a relative standard deviation of less than 11.2%. The proposed method has the merits of rapidity and high sensitivity. Finally, the method was successfully applied to tobacco‐specific N‐nitrosamine analysis in real samples.     

Proton-induced X-ray emission analysis of Jordanian cigarettes

Proton-induced X-ray emission spectroscopy was applied to determine the concentration of 11 elements in cigarette tobacco of four brands commercially made in Jordan, and one foreign brand. The results are expressed in absolute amount per cigarette. Cigarette wrapping paper and cigarette smoke were also analyzed. The significance of some of the elements found in the samples are discussed. Work carried out at the Department of Nuclear Physics, Lund Institute of Technology, Solvegatan 14, S-223 62, Lund, Sweden.     

烟草中β-胡萝卜素的热裂解产物的研究

为了研究烟草中β-胡萝卜素的高温裂解产物对卷烟抽吸品质的影响,利用热裂解气相色谱/质谱联用仪在不同裂解氛围(空气、氮气中含10%O2及N2)和不同温度(300,600和900 ℃)下对β-胡萝卜素进行裂解,裂解产物用固相微萃取装置进行吸附,然后将吸附到的裂解产物用气相色谱/质谱联用仪(GC/MS)进行分析。结果表明,β-胡萝卜素在不同裂解条件下主要的裂解产物是甲苯、对二甲苯、1,2,3,4-四氢-1,1,6-三甲基萘和2,7-二甲基萘等化合物,另外还生成异佛尔酮、β-环柠檬醛、β-紫罗兰酮、二氢猕猴桃内酯等香味化合物,这些物质随裂解温度和裂解氛围的不同其含量有所差异。     

沸石在去除卷烟烟气中亚硝胺的应用

吸烟污染;沸石;添加剂;沸石在去除卷烟烟气中亚硝胺的应用     

Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine

An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette.     

快速分离柱高效液相色谱法测定卷烟主流烟气中的主要羰基化合物

选择2,4-二硝基苯肼(DNPH)为羰基化合物的衍生化试剂,建立了快速分离柱高效液相色谱测定卷烟主流烟气中8种羰基化合物的方法。采用经2,4-二硝基苯肼酸性溶液处理过的剑桥滤片捕集烟气,再用含2%（体积分数）吡啶的乙腈溶液进行萃取,以ZORBAX Stable Bound色谱柱(50 mm×4.6 mm,1.8 μm)进行快速分离,最后由二极管阵列检测器于365 nm下进行检测。该方法的回收率为89.1%～99.2%,相对标准偏差（RSD)在6.0%以下。该方法分析时间短,流动相消耗少,且操作简便、重复性好、回收率高。     

Simultaneous determination of nicotine and 3-vinylpyridine in single cigarette tobacco smoke and in indoor air using direct extraction to solid phase

The aim of the present study was to develop a new analytical method of chromatographic determination of two important markers of ETS exposure: nicotine and 3-vinylpyridine (3-ethenylpyridine, 3-EP) in mainstream (MS) and sidestream (SS) smoke of one single cigarette and in indoor air using direct solid phase extraction combined with gas chromatography. The method can be utilised for both nicotine and 3-EP determination in SS and MS of one single cigarette as well as it allows for a precise determination of compound distribution in indoor air. The application of the same analytical method for both kinds of samples allows anticipating indoor air distribution of both analysed compounds in a very precise way. The precision of the method (calculated as a relative standard deviation) was 9.78% for nicotine and 2.67% for 3-EP; whereas the accuracy (evaluated by a recovery study conducted at three different levels) was 70.1 and 87.3%, respectively. The limit of detection was 0.06 µg per cigarette for both nicotine and 3-EP. The method was evaluated by determining the compounds of interest in two commercially available brands of cigarettes as well as in the reference cigarettes 3R4F and also in indoor air polluted with tobacco smoke. Determined levels of compounds of interest in MS varied from 586 to 772 (nicotine) µg per cigarette and from 3.5 to 10.7 (3-EP) µg per cigarette. In SS smoke the level varied from 14,370 to 22,590 (nicotine) µg per cigarette and from 185 to 550 (3-EP) µg per cigarette, whereas levels in indoor air polluted with tobacco smoke varied from 50.1 to 157.3 (nicotine) µg m^?3and from 7.7 to 20.8 (3-EP) µg m^?3.     

Influence of filter ventilation on the chemical composition of cigarette mainstream smoke

Total yields of cigarette smoke constituents are greatly influenced by smoking behaviour, the tobacco blend as well as a variety of cigarette design parameters. Thereby, filter ventilation, i.e. diluting the smoke by providing a zone of microscopic holes around the circumference of the filter is one method to reduce the yield of ‘tar’ and other smoke compounds. However, little is known how these design variations influence the combustion conditions, and therefore, the overall chemical pattern of the smoke. In this paper single photon ionization-time-of-flight mass spectrometry (SPI-TOFMS) is used to characterize and compare cigarettes on a puff-by-puff basis, which differ only in filter ventilation magnitude. The research cigarettes investigated were made from Virginia tobacco and featured filter ventilations of 0% (no ventilation), 35%, and 70%. The cigarettes were smoked under two different puffing regimes, one using the puffing parameters of the conventional International Organization for Standardization (ISO) smoking regime and a more intense smoking condition. Results show that every variation entails a change of the chemical pattern, whereby, in general, cigarettes with 0% filter ventilation as well as the intense smoking regime lead to a more complete combustion compared to the ISO smoking conditions and the high ventilated cigarettes. Changes in the overall patterns can also be observed during the smoking for individual puffs. Some substances dominate the first puff, some species are more pronounced in the middle puffs, whereas others are preferably formed in the last puffs. This demonstrates the high complexity of the occurring processes. Results might help to understand the formation and decomposition reactions taking place when a cigarette is smoked and offer scope for targeted reduction strategies for specific toxicants or groups of toxicants in the smoke.     

Analytical study of cigarette smoke enriched in benzo[a]pyrene for use in model animal studies

Cigarette smoke has been significantly enriched in benzo[a]pyrene (BAP) by injecting 200 μl of a cyclohexane solution, containing a total of 40 μg of BAP, into a cigarette. After injection, the cigarette is conditioned and smoked according to standard protocol. When the cigarette smoke condensate is analyzed by fluorescence spectroscopy, liquid scintillation counting, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry, it is found that the level of BAP has increased by 1000 times with respect to levels reported for unenriched cigarette smoke. No chemical transformation of the BAP has been detected, and the BAP-enriched fraction does not appear to be perturbed to a detectable degree. Approximately 28% of the BAP is measured in the mainstream smoke, 46–48% in the sidestream smoke from the burning end of the cigarette, and 7% in the butt and ash. Correcting for analytical losses, about 10% appears to escape in the gaseous state. This material may prove suitable for model animal studies.     

Determination of formaldehyde and acetaldehyde in mainstream cigarette smoke by high-performance liquid chromatography

A method is described for the determination of formaldehyde and acetaldehyde in mainstream cigarette smoke. This involved the collection and reaction of the aldehydes with 2,4-dinitrophenylhydrazine in aqueous acetonitrile. The high-performance liquid chromatographic separation and measurement of the various components directly in this reaction solution eliminated the need for a clean-up stage. Cigarette yields of greater than 5 micrograms of formaldehyde and 50 micrograms of acetaldehyde could be determined to estimated relative standard deviations of 0.07 and 0.05, respectively.     

Generation,sampling and chromatographic analysis of particulate matter in dilute sidestream tobacco smoke

The sampling and gas chromatographic separation of the particulate matter of sidestream tobacco smoke for high-molecular-weight compounds are described. Four n-alkanes (C₂₇, C₂₉, C₃₁ and C₃₃) were identified and their relationship to the particulate levels was established. The sidestream yields of these compounds for several cigarette types, including regular, low- and ultra-low-tar filtered and high-tar unfiltered varieties are reported. Concentrations in diluted smoke at particulate levels similar to ambient tobacco smoke were also determined. Methods for generating test atmospheres of sidestream smoke at low-level, uniform concentrations are described.     

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.