Copper Tannic Acid Coordination Nanosheet: A Potent Nanozyme for Scavenging ROS from Cigarette Smoke

The global tobacco epidemic is still a devastating threat to public health. Toxic reactive oxygen species (ROS) in the cigarette smoke cannot be efficiently eliminated by currently available cigarette filters. The resultant oxidative stress causes severe lung injury and further diseases. To tackle this challenge, herein, a novel copper tannic acid coordination (CuTA) nanozyme is reported as a highly active and thermostable ROS scavenger. The CuTA nanozyme exhibits intrinsic superoxide dismutase‐like activity, catalase‐like activity, and hydroxyl radical elimination capacity. These synergistic antioxidant abilities make the CuTA nanozyme a promising candidate for the improvement of commercial cigarette filters. Mouse model results show that commercial cigarettes loaded with CuTA nanozyme efficiently scavenge ROS in the cigarette smoke, reduce oxidative stress–induced lung inflammation, and minimize the resultant acute lung injury. The developed CuTA nanozyme offers an efficient ROS scavenger with multiple antioxidant ability and opens up new opportunities for the modification of cigarette filters to reduce the toxic effects of cigarette smoke.     

The detection of nitro pesticides in mainstream and sidestream cigarette smoke using electron monochromator-mass spectrometry

Over the past decade, electron monochromator-mass spectrometry (EM-MS) has been shown to be a selective and sensitive technique for the analysis of a wide variety of electrophilic compounds in complex matrixes. Here, for the first time, three different dinitroaniline pesticides, flumetralin, pendimethalin, and trifluralin, have been shown to be present in both mainstream and sidestream tobacco smoke using an EM-MS system. A number of cigarettes were tested that included three pure-tobacco-type cigarettes, an experimental reference cigarette, and 11 commercial cigarettes. Due to the complexity of the smoke particulate matter, the pesticides were identified only after each sample was subjected to a multistep cleanup process that included phenyl solid-phase extraction; an acid wash; aminopropyl solid-phase extraction; and finally, normal phase LC fractionation. All cigarette types tested showed the presence of the three pesticides in the tobacco smoke, with flumetralin ranging from trace levels up to 37 (+/- 9) ng/cig, pendimethalin ranging from trace levels up to 10.4 (+/- 0.6) ng/cig, and trifluralin ranging from trace levels up to 47 (+/- 17) ng/cig. Acute toxicity information is presented for the three pesticides.     

烟支内烟丝分布对卷烟烟气的影响

通过对不同规格平准器卷烟机卷制的烟支进行试验对比分析,研究了相同条件下烟支内烟丝分布对卷烟烟气指标以及逐口分析的影响。结果表明,使用6槽和3槽平准器卷烟机卷制的烟支,他们的烟支重量和吸阻均较稳定,但6槽与3槽平准器卷烟机卷制的烟支相比,其烟气中的焦油、烟碱和一氧化碳量更低,卷烟逐口间烟气的焦油、烟碱含量变化更小。     

Development of a quantitative method for the analysis of tobacco-specific nitrosamines in mainstream cigarette smoke using isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry

An improved method has been developed for the determination of the four major tobacco-specific nitrosamines (TSNA) in mainstream cigarette smoke. The new method offers decreased sample preparation and analysis time as compared to traditional methodologies. This method uses isotope dilution liquid chromatography coupled to a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than traditional methods. It also shows no evidence of artifactual formation of TSNA. Sample concentrations were determined for four TSNA in mainstream smoke using two isotopically labeled TSNA analogues as internal standards. Mainstream smoke was collected on an industry standard 44-mm Cambridge filter pad, extracted with an aqueous buffer solution, and analyzed without further sample cleanup. This method has been validated through intra- and interlaboratory studies and has shown excellent recoveries, sensitivity, and repeatability. The limits of detection of each TSNA varied from 0.01 to 0.1 ng/mL, and the linear calibration range of the instrument in sample matrix spanned 0.5-200 ng/ mL, which allowed for the determination of the TSNA levels in cigarettes with a wide range of deliveries. Data are also reported from two commercially available industry reference cigarettes and show excellent agreement and reproducibility over a six-month time period (n > 50).     

Toxic metals distribution in different components of Pakistani and imported cigarettes by electrothermal atomic absorption spectrometer

It was extensively investigated that a significant flux of toxic metals, along with other toxins, reaches the lungs through smoking. In present study toxic metals (TMs) (Al, Cd, Ni and Pb) were determined in different components of Pakistani local branded and imported cigarettes, including filler tobacco (FT), filter (before and after normal smoking by a single volunteer) and ash by electrothermal atomic absorption spectrometer (ETAAS). Microwave-assisted digestion method was employed. The validity and accuracy of methodology were checked by using certified sample of Virginia tobacco leaves (ICHTJ-cta-VTL-2). The percentages (%) of TMs in different components of cigarette were calculated with respect to their total contents in FT of all branded cigarettes before smoking, while smoke concentration has been calculated by subtracting the filter and ash contents from the filler tobacco content of each branded cigarette. The highest percentage (%) of Al was observed in ash of all cigarettes, with range 97.3-99.0%, while in the case of Cd, a reverse behaviour was observed, as a range of 15.0-31.3% of total contents were left in the ash of all branded cigarettes understudy.     

A new look at radicals in cigarette smoke

Radicals in cigarette smoke have been proposed to contribute to the harm caused by cigarette smoking. For the first time, using HPLC and high-resolution mass spectrometry analysis of stable radical adducts, we have identified specific radical species in cigarette smoke: 7 acyl and 11 alkylaminocarbonyl radicals. Their combined abundance measured in fresh whole smoke from a single 2R4F cigarette is approximately 225 nmol (1.4 x 10(17) radicals). The fiberglass Cambridge filter pad conventionally employed to separate the gas phase from mainstream smoke was found to reduce the apparent yield of these radicals, introducing artifacts of measurement. The long-accepted steady-state mechanism for the formation of carbon-centered radicals in cigarette smoke involving NO2 chemistry cannot account for these newly identified radicals, and it does not in general appear to be a major source of carbon-centered radicals in fresh mainstream cigarette smoke. Consequently, we suggest that the precise nature of radicals in cigarette smoke warrants reexamination.     

Development of nitroxide radicals–containing polymer for scavenging reactive oxygen species from cigarette smoke

We developed a nitroxide radicals–containing polymer (NRP), which is composed of poly(4-methylstyrene) possessing nitroxide radicals as a side chain via amine linkage, to scavenge reactive oxygen species (ROS) from cigarette smoke. In this study, the NRP was coated onto cigarette filters and its ROS-scavenging activity from streaming cigarette smoke was evaluated. The intensity of electron spin resonance signals of the NRP in the filter decreased after exposure to cigarette smoke, indicating consumption of nitroxide radicals. To evaluate the ROS-scavenging activity of the NRP-coated filter, the amount of peroxy radicals in an extract of cigarette smoke was measured using UV–visible spectrophotometry and 1,1-diphenyl-2-picrylhydrazyl (DPPH). The absorbance of DPPH at 517 nm decreased with exposure to cigarette smoke. When NRP-coated filters were used, the decrease in the absorbance of DPPH was prevented. In contrast, both poly[4-(cyclohexylamino)methylstyrene]- and poly(acrylic acid)-coated filters, which have no nitroxide radical, did not show any effect, indicating that the nitroxide radicals in the NRP scavenge the ROS in cigarette smoke. As a result, the extract of cigarette smoke passed through the NRP-coated filter has a lower cellular toxicity than smoke passed through poly[4-(cyclohexylamino)methylstyrene]- and poly(acrylic acid)-coated filters. Accordingly, NRP is a promising material for ROS scavenging from cigarette smoke.     

Real-time fourier transform-infrared analysis of carbon monoxide and nitric oxide in sidestream cigarette smoke

Fourier transform infrared (FT-IR) spectroscopy was compared directly to independent standard analytical techniques for the routine measurement of carbon monoxide (CO) and nitric oxide (NO) yields from cigarette sidestream smoke. The FT-IR instrument was configured in-line with a nondispersive infrared (NDIR) analyzer for CO analysis and a chemiluminescence (CL) analyzer for NO analysis to monitor the sidestream smoke from a single port of a linear smoking machine. A cold trap was inserted prior to the FT-IR to minimize the levels of vapor phase interferents, such as water. Univariate and multivariate regression analysis were evaluated for the prediction of cigarette yield from time-resolved spectral data at 1, 2, 4 and 8 cm-1 spectral resolution. Regressions were developed using three different spectral ranges including unique rotation-vibration lines, the R-branch, and the entire absorption band. As per standard methods, yields were calculated from the concentration traces generated during the smoke runs for five different cigarettes spanning the expected range of mainstream total particulate matter deliveries. The FT-IR traces for the smoke runs revealed improved temporal resolution yielding analytical information from smoke generated in between puffs. The performance between the validation methods and the FT-IR calibrations was statistically compared. In general, for the determination of CO, the FT-IR calibrations underestimated the yield measured by NDIR by less than 10%. For the NO measurement, the univariate FT-IR calibrations overestimated the NO yield measured by the CL analyzer, whereas the partial least squares (PLS) calibrations showed good agreement. PLS calibrations were developed for both analytes providing no significant difference when compared to the respective standard analytical techniques. Results for sidestream CO and NO yields for Kentucky reference cigarette 1R4F utilizing 8 cm-1 calibrations compared favorably to values reported elsewhere in the literature. Hence, calibration of the FT-IR system at 8 cm-1 spectral resolution clearly revealed the potential of this method, providing enhanced temporal resolution, simultaneous determination of several smoke components, and reduced complexity of the experimental setup in contrast to the standard techniques.     

Evaluation of hydrazine reduction by cellulose acetate filters using infrared tunable diode laser spectroscopy

Cellulose acetate (CA) filters have been investigated to determine their hydrazine (N2H4) breakthrough characteristics using a system based on tunable diode laser absorption spectroscopy (TDIAS). The breakthrough mass loading sorption curves for hydrazine were dependent on both the flow rate and the concentration. In experiments using a 4.5 ppmv hydrazine standard, the amounts of hydrazine retained by the CA filter were 4.25 microg at a flow rate of 2.82 L/min and 65 microg at a flow rate of 0.28 L/min. These loadings are much greater than the 31.5 ng/cigarette of hydrazine reported in smoke for unfiltered cigarettes. Further, CA filters exposed to four and eight puffs of smoke actually made the filter more efficient in retaining hydrazine compared to CA filters that had not been exposed to smoke. Therefore, if hydrazine is present in smoke at the levels reported in unfiltered cigarettes, all of the hydrazine would be trapped by the CA filter, and would be unable to break through during smoking. A unique feature of this analytical method is that the instrument does not require calibration after molecular parameters have been determined, in this case from previously acquired quantitative hydrazine FT-IR reference spectra.     

吸烟机机型对主流烟气释放量的影响

为了比较直线型和转盘型两种吸烟机对主流烟气释放量的影响,分别使用SM400直线型吸烟机和RM200A转盘型吸烟机在同一实验条件下对监控卷烟进行抽吸,并对卷烟主流烟气释放量(焦油、烟气烟碱量、烟气一氧化碳及烟气水分)进行差异性分析。结果表明:用两种机型测得总粒相物、烟碱基本一致,但RM200A测得一氧化碳、烟气水分均高于SM400测得结果,焦油则低于SM400。     

Simultaneous determination of five tobacco-specific nitrosamines in mainstream cigarette smoke by isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry

Tobacco-specific nitrosamines (TSNAs) have been previously implicated as a source of carcinogenicity in tobacco and cigarette smoke. Accurate quantification of these chemicals is needed to help assess public health risk. We have developed and validated a specific and sensitive method to simultaneously measure five TSNAs in the particulate phase of mainstream tobacco smoke. Cigarette smoke particulate, produced using standardized machine smoking protocols, was collected on a Cambridge filter pad. The particulate matter was extracted using methylene chloride, back extracted into aqueous solution, further purified by solid-phase extraction, and analyzed by liquid chromatography/electrospray ionization tandem mass spectrometry using isotopically labeled analogues as internal standards. Limits of detection for this method ranged from 0.05 to 1.23 ng/mL using an injection volume of 20 microL. A linear calibration range spanning 2.5-2500 ng/mL was adequate to measure TSNA levels in cigarette smoke. The method achieved excellent reproducibility and accuracy. The identity of each TSNA was established by chromatographic retention time, analyte-specific fragmentation patterns, and relative peak area ratios of two product/precursor ion pairs. This new method provides higher sensitivity, specificity, and throughput than earlier methods for TSNA determination.     

论信息防伪在卷烟防伪中的“立体化”应用

目的：——对于烟草行业，防伪的意义不仅在于减少公司经济利益的损失，还在于烟草品牌的保护。方法——利用高科技的信息防伪技术，打击质量或包装十分低劣的假冒卷烟的销售，会使消费者远离这些品牌。在全球范围内，打击假冒和走私卷烟是世界烟草行业共同面临的一个十分重大的问题。对于假冒和走私卷烟的数量，谁也无法给出一个确切的统计数字。据有关专家介绍，早在2000年，仅在中国境内就有1000亿支以上的假冒走私卷烟流入市场，这个数字相当于西班牙等中等产烟国一年合法的卷烟生产量。当年我国共收缴假冒卷烟57万件（合285亿支）。结果--假冒走私卷烟的质量和其假冒的品牌卷烟的包装的质量是无法相比的，但是，随着经济的繁荣，市场的诱惑，假冒走私卷烟也在花价钱追踪正宗厂家包装防伪技术。结论--毫不夸张地说，烟草的品牌保护是烟草公司的生命线。     

滤棒重量、压降稳定性对卷烟重量、吸阻稳定性的影响

烟支吸阻及重量稳定性是影响卷烟质量的重要指标。为解决卷烟吸阻及重量稳定性方面存在的问题,本文从理论方面分析了滤棒段压降、重量与烟支段吸阻、重量对整支卷烟吸阻及重量稳定性的影响,并结合实例进行了分析。结果表明,滤棒段的压降波动对整支卷烟的吸阻影响很大,而滤棒和材料重量的波动对整支卷烟重量的影响很小。     

基于田口分析的烟包偏好评价方法

目的通过包装设计实现科学禁烟控烟需要掌握香烟包装设计与吸烟者对香烟偏好程度之间的联系,提出一种基于田口分析的烟包评价方法。方法对烟包的关键要素进行分割,确定主要控制参数,对烟包主要控制参数进行实验评价,建立偏好程度与参数间的田口模型。结果针对市场上主流香烟包装的形态、色彩、图案进行综合分析,确定吸烟者偏好的包装方案。结论在烟包要素分割明确的前提下,田口方法能够有效地评价吸烟者对各类烟包的反应,相关研究可以为香烟销售调控、禁烟控烟执行提供有效的技术手段与分析方法。     

GC-AED Studies of Nicotine Fate in a Burning Cigarette

An atomic emission detector (AED) for a gas chromatograph (GC) can be used to selectively detect compounds labeled with stable isotopes, such as D, (13)C, and (15)N. This capability can be used to determine precursor-fate relationships within complex matrixes, using stable isotopes rather than radiolabeled isotopes. Employing stable isotopes removes the safety consideration associated with radiolabeling studies. Two previous reports have employed GC-AED in fate studies for (13)C-labeled precursors. The goal of this study was to evaluate the utility of GC-AED for precursor-fate determinations in tobacco science. In this work, GC-AED was used to determine the fate of nicotine-d(4) in a burning cigarette. GC-MSD was then employed to identify the compounds that the AED indicated contained D. Spectral confirmation of the presence of D was performed on each chromatographic peak of interest with both AED and MSD to ensure that the identification of the products was correct. Nicotine and nicotine-d(4) standards were used to evaluate the effect of coelution of unlabeled compounds with the labeled compounds on the AED response for D. It was shown that the AED response for D at λ = 308 nm decreases with increased concentration of unlabeled compound. Detection at λ = 656 nm, however, is unaffected by the presence of the unlabeled compound. Compound-independent calibration is also possible at this wavelength. GC-AED studies with nicotine-d(4) core injected into cigarettes demonstrated that most of the nicotine (79%) is distilled, unchanged, into the mainstream (MS) and sidestream (SS) smoke. The degradation products that do occur include 3-substituted pyridines and nicotine-oxidation products. These are found only in the SS smoke.     

Determination of nicotine and other minor alkaloids in international cigarettes by solid-phase microextraction and gas chromatography/mass spectrometry

Nicotine, nornicotine, anabasine, and anatabine are the most abundant alkaloids in tobacco. Along with the addictiveness of nicotine, other properties, including their occurrence in tobacco at relatively high concentrations, and as the primary precursors for the highly carcinogenic tobacco-specific nitrosoamines, make these chemicals important from a public health standpoint Therefore, developing a fast and accurate quantitative method to screen large numbers of cigarette samples for these alkaloids was important. This report describes the first use of headspace analysis using solid-phase microextraction combined with gas chromatography/mass spectrometry for the unambiguous detection of tobacco alkaloids. Detection and confirmation of each analyte isestablished by both chromatographic retention times and the ratio of reconstructed ion chromatogram peak areas from characteristic quantitation ion and confirmation ion. Twenty-eight cigarette brands from 14 countries were analyzed. Surprisingly, the minor alkaloids' response factors varied considerably among different styles of cigarettes. Accurate quantification was achieved using a three-point standard addition protocol. The standard addition approach was essential to obtain accurate measurements by minimizing matrix effects that would otherwise have contributed to quantitation bias. Significant differences in the alkaloid profiles were measured in the different cigarette brands. These results strongly suggest that such differences reflect variations associated with blend compositions, tobacco quality, and manufacturing practices.     

镀陶烟用内衬纸防潮保润保香性研究

目的 研究对比陶制直镀内衬纸与常规直镀内衬纸的防潮保润保香性能。方法 对镀陶和常规直镀内衬纸进行SEM,BET和透湿率及透氧率检测,并将2种内衬纸卷制的成品卷烟放置于高温高湿、干燥、常温常湿等条件下平衡85 d,随后对拆包不同时长的卷烟进行烟支含水率检测,同时采用静态顶空气相色谱-质谱联用仪测定卷烟滤棒及烟丝中香精的主要成分含量。结果 与常规直镀内衬纸相比,镀陶直镀内衬纸的表面致密性和比表面积明显较优,且其氧气透过率略小,水蒸气透过率较小。在高温高湿和干燥条件下,镀陶样品的烟支含水率与初始设计值较为接近;在常温常湿条件下,2种内衬纸包装的烟支含水率虽在拆包前30 h无明显区别,但在35 h后,常规直镀内衬纸包装的烟支含水率显著下降,不满足设计要求。结论 镀陶直镀内衬纸的防潮效果较好、保香效果较好、保润效果略好。镀陶烟用内衬纸的工艺还有待进一步调整,以进一步提高其防潮保香保香效果。     

女士香烟包装设计探究

针对女性烟民呈现逐年上升趋势的现状,以及通过分析女性香烟包装的现状,透析女性吸烟群体心理特点,进而对女性香烟名称、外包装设计、烟盒形态进行新的定位,并围绕吸烟有害健康、倡导健康生活主题,通过运用设计的包装语言,对女性香烟包装进行设计创新,起到鼓励女性烟民吸低害香烟、弱化香烟心理依赖,以此体现女性香烟包装设计的未来之路。     

一种面向卷烟混合生产线的优化调度模型研究

目的 基于多品种、小批量的生产制造模式,在规定的8 h工作之内,快速有效地生产出多品种、多批量的卷烟,并对所需物料进行准确调度,达到经济效益最大化的目的。方法 针对某烟草生产企业订单需要生产6种型号的品牌香烟,通过分析卷烟生产线的工艺流程,提出一种解决卷烟厂车间资源优化调度的CSS模型,该模型可以根据产品之间的销售需求情况来匹配生产线资源配置,按需求比采用粒子群优化算法计算出单次投料后混合生产香烟所需的最小时间与最大收益。结果 将所得方案进行综合对比后,计算得出在规定工期内,生产香烟获取利益的最优分配方案,在迭代在10次以内时已完成了优化过程,最大获利为3.65万元。结论 该优化模型通过改变相关工艺参数能够实现对不同混合生产线的资源调度优化,并对其他制造行业提供借鉴价值。     

Single photon ionization time-of-flight mass spectrometry with a pulsed electron beam pumped excimer VUV lamp for on-line gas analysis: setup and first results on cigarette smoke and human breath

Single-photon ionization (SPI) using vacuum ultraviolet (VUV) light produced by an electron beam pumped rare gas excimer source has been coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). The novel device enables real-time on-line monitoring of organic trace substances in complex gaseous matrixes down to the ppb range. The pulsed VUV radiation of the light source is employed for SPI in the ion source of the TOFMS. Ion extraction is also carried out in a pulsed mode with a short time delay with respect to ionization. The experimental setup of the interface VUV light source/time-of-flight mass spectrometer is described, and the novel SPI-TOFMS system is characterized by means of standard calibration gases. Limits of detection down to 50 ppb for aliphatic and aromatic hydrocarbons were achieved. First on-line applications comprised real-time measurements of aromatic and aliphatic trace compounds in mainstream cigarette smoke, which represents a highly dynamic fluctuating gaseous matrix. Time resolution was sufficient to monitor the smoking process on a puff-by-puff resolved basis. Furthermore, human breath analysis has been carried out to detect differences in the breath of a smoker and a nonsmoker, respectively. Several well-known biomarkers for smoke could be identified in the smoker's breath. The possibility for even shorter measurement times while maintaining the achieved sensitivity makes this new device a promising tool for on-line analysis of organic trace compounds in process gases or biological systems.