卷烟主流烟气中几种醛酮的光电离质谱研究

为了对卷烟主流烟气中的成分进行定性和定量检测,利用同步辐射光电离-飞行时间质谱装置,对卷烟主流烟气气相成分中的甲醛、乙烯酮、乙醛、丙醛和丙酮进行研究。通过实时获得烟气在不同光子能量下的质谱图,可以获得这些成分的质荷比信息;改变光子能量,对潜在的醛、酮质谱峰扫描光电离效率曲线,与其标准光电离曲线和电离能比对,可以进行准确的定性。     

真空紫外光电离质谱在线检测卷烟主流烟气气溶胶中气体和颗粒物的化学成分

本文采用吸烟机模拟吸烟状态，结合自制的真空紫外光电离质谱仪，在线检测和表征卷烟主流烟气中气体和颗粒物的化学成分，获得各自的特征成分，并开展逐口抽吸特性研究。结果表明，卷烟主流烟气中的气体成分主要为小分子质量的挥发性有机物，而颗粒物的成分复杂，在质谱仪质量分析范围(m/z<400)内均有检出。烟气两相成分的归属结果显示，部分成分主要以气体形式存在于烟气中，而另一些成分仅存在于颗粒物中。此外，研究发现，苯酚、糠醛、二羟基苯、二甲基苯酚、愈创木酚和柠檬烯等成分在气相和颗粒相中均有检出。逐口分析中，气体成分呈现2种变化特征，绝大多数成分的信号强度随抽吸口数增加而增强，而部分不饱和烃则在第2口抽吸中具有较高的相对强度，之后逐渐降低并趋于稳定或略有上升；几乎颗粒相中所有成分都呈现逐口增强的趋势，与气相成分相比，颗粒相成分的增长趋势更平缓。     

气相色谱-串联质谱法测定卷烟主流烟气中7种酚类化合物

建立了气相色谱-串联质谱（GC-MS/MS）法检测卷烟主流烟气中苯酚、邻甲酚、间甲酚、对甲酚、邻苯二酚、间苯二酚、对苯二酚7种酚类化合物。在标准抽吸条件下,用剑桥滤片收集5支卷烟主流烟气粒相物,经异丙醇超声提取后,利用GC-MS/MS的多反应监测模式（MRM）测定,内标法定量。在优化的前处理及仪器条件下,7种酚类化合物呈现良好的线性关系（R²≥0.998 6）,定量限为0.012~0.021 μg/cig,加标回收率为91.1%~107.7%,相对标准偏差（RSD）为2.5%~6.6%。该方法操作简单、分析时间短、准确可靠、灵敏度高,适用于卷烟主流烟气中酚类化合物的检测分析。     

电喷雾萃取电离质谱在线检测卷烟主流烟气

卷烟主流烟气是组成复杂、动态变化的气溶胶。在烟气捕集和处理过程中,具有活性的烟气成分会发生变化,从而使常规的离线分析方法无法准确地反映烟气的化学组成。本研究建立了一种用于卷烟主流烟气在线检测的电喷雾萃取电离质谱（EESI-MS）方法。通过单通道吸烟机对卷烟进行抽吸,卷烟主流烟气无需预处理而被直接引入EESI-MS仪中,得到其质谱图。在优化的工作条件下,通过碰撞诱导解离（CID）实验对烟气中的烟碱进行了定性分析。将该方法用于卷烟逐口抽吸时主流烟气的连续检测,结果显示,主流烟气的总离子（m/z 50~400）信号强度和烟碱离子（m/z 163）信号强度均随卷烟抽吸口数的增加而升高,这反映出卷烟主流烟气随烟支长度的释放规律。此外,对不同品牌卷烟的主流烟气进行EESI-MS在线检测,通过主成分分析（PCA）表明,该方法可以实现主流烟气的快速区分;通过聚类分析表明,该方法可以对主流烟气进行快速聚类和衡量其相似性。     

我国科学家测定出卷烟烟气中50种新的化学成分

12月13日，中国科学院大连化学物理研究所、郑州烟草研究院、长沙卷烟厂联合承担的国家烟草专卖局重点项目“应用全二维气相色谱研究卷烟烟气中化学成分”项目在大连化物所顺利通过了由国家烟草专卖局科教司组织的鉴定。鉴定委员会的专家们一致认为，该课题属于国际前沿性研究，探讨了应用全二维气相色谱技术研究卷烟烟气中化学成分的可行性，研究成果的创新性明显，为国际先进水平，建议将该项目的研究成果推广应用于烟草行业的研发和质量控制。     

固相萃取-气相色谱-质谱法测定卷烟主流烟气中4种芳香胺化合物

采用氘代-1-氨基萘作为内标,利用剑桥滤片捕集肯塔基参比卷烟（1R5F、2R4F）烟气,经盐酸超声,二氯甲烷、正己烷萃取,盐酸三甲胺和五氟丙酸酐衍生化,固相萃取仪萃取洗脱纯化后,使用气相色谱-质谱（GC/MS）建立卷烟主流烟气中4种芳香胺化合物的测定方法。4种芳香胺化合物的变异系数均小于5%,回收率在89.8%~106.0%之间,检测限在每支卷烟0.03~0.07 ng之间。该方法具有良好的重复性、准确性,适用于卷烟烟气总粒相物中芳香胺的定量分析。     

固相微萃取和气相色谱-质谱法测定北京酱牛肉中的挥发性成分

采用顶空固相微萃取和气相色谱-质谱法（Head Space Solid Phase Microextraction Gas Chromatgraphy-Mass Spectrometry,HSSPME—GC—MS）对北京传统酱牛肉中的挥发性香气物质进行了测定,总共检测出68种风味化合物,其中包括醛类49.12%、酮类0.84%、醇类4.85%、烃类13.29%、酯类2.61%、酚醚类11.33%和含硫含氮及杂环化合物6.55%,另外还有11.41%的其它类物质,其中醛、酮和含硫含氮及杂环化合物中含有北京传统酱牛肉的主要香味成分。     

气相色谱-串联四极杆质谱法测定主流烟气中的苯并[a]芘

为了给低焦油卷烟产品中的有害物质检测提供方法参考,本工作建立了卷烟主流烟气中苯并[a]芘的气相色谱-三重串联四极杆质谱联用测定方法。使用标准抽吸条件采集20支卷烟烟气粒相物,用含内标的环己烷超声萃取,经固相萃取净化后,以正离子多反应监测方式进样分析,内标法定量。方法经优化后,苯并[a]芘在0.4～20 μg/cig范围内具有良好线性,r²为0.999 92,定量限为0.073 μg/L,重复性变异系数最大为3.71%,加标回收率为95.7％～103.9％。该方法操作简便、流程短、溶剂用量少,尤其适合低焦油卷烟产品的苯并[a]芘检测。     

超声雾化萃取大气压光电离质谱法快速分析烟草化学成分

随着烟草工业的发展,对烟草样品进行快速、准确和高灵敏度地分析检测已经成为烟草化学发展的必然趋势和产品研发的现实需求.本工作利用超声雾化萃取大气压光电离质谱(EAPPI-MS)技术,无需样品预处理和色谱分离,对1R5F、3R4F、都宝、七星和王冠5种卷烟烟丝中的化学成分进行直接、快速分析,鉴别出醇、酮、酸、酯、醛、酚、生...     

吹扫捕集-气相色谱/质谱法测定不同饼干中挥发性成分

本研究将吹扫捕集进样技术与气相色谱/质谱法相结合应用于5种市售饼干样品中挥发性组分的分析,分离并鉴定39种挥发性化合物。所鉴定出的物质中,要包括醇类、醛类、酮类、烷烃类、酯类及杂环类等化合物。在5种饼干样品定性分析化合物中,TIC图峰面积比均较大的化合物主要为2-甲基丁醛、异戊醛、苯甲醛、己醛等芳香醛类物质。     

Fluorescent human lung macrophages analyzed by spectral confocal laser scanning microscopy and multispectral cytometry

Numerous highly fluorescent macrophages (MPhi), designated "smoker cells," exist in the lungs of smokers and subjects who have quit smoking within 5 years. The brightly fluorescent MPhi, however, are not present in the lungs of never smokers. Some investigators have speculated that the intense fluorescence of the MPhi is due to smoke-induced changes in the autofluorescence of naturally occurring (i.e., endogenous) compounds (e.g., NADP). In contrast, other researchers have theorized that the fluorescence is due to the uptake of tobacco smoke particulates (i.e., "tar"). Studies reported herein were undertaken to test the hypothesis that the origin of the MPhi fluorescence could be profiled with the novel technologies afforded by spectral confocal laser scanning microscopy (sCLSM) and multispectral cytometry (MSC). To this end, spectral emissions were obtained by sCLSM of optical sections of live MPhi isolated from fresh surgically excised human lung tissue and in air-dried lung tissue imprints. Confirmation of spectral profiles of these single cell observations was obtained in population studies with the use of high-throughput MSC in which multispectral analyses were performed with three different lasers. Proof of concept experiments demonstrated that relatively nonfluorescent MPhi from the lungs of nonsmokers became fluorescent upon short-term ex vivo exposure to tobacco smoke tar. Summarily, the studies reported herein document that the fluorescence of human lung MPhi is due to tobacco tar.     

三重四极杆气质联用法测定卷烟主流烟气中NNK

为了测定卷烟主流烟气中4-(甲基亚硝胺基)-1-(3-吡啶基)-1-丁酮（NNK）的含量,建立了三重四极杆气质联用仪（GC-MS/MS）测定方法。按照标准条件抽吸卷烟,捕集在剑桥滤片上的卷烟烟气粒相物用二氯甲烷萃取并以氘代NNK为内标,经固相萃取净化后,用三重四极杆气质联用仪测定卷烟烟气中NNK的含量。方法的相对标准偏差为2.3%～2.7%（n=6）、回收率为98.9%～116.8%、定量下限为0.087 ng/cig,完全可以满足日常检测的要求。本方法采用商品化固相萃取柱,避免了样品浓缩、转移等操作步骤,节省试剂并且提高了工作效率。应用本方法对2R4F和其他不同类型的卷烟样品烟气中NNK进行了检测,检测数据与国家标准方法GB/T 23228 2008（GC-TEA）一致性好,验证了本方法的准确性。     

Quantification of increased MUC5AC expression in airway mucus of smoker using an automated image-based approach

Microscopic analysis of mucus quantity and composition is crucial in research and diagnostics on muco-obstructive diseases. Currently used image-based methods are unable to extract concrete numeric values of mucosal proteins, especially on the expression of the key mucosal proteins MUC5AC and MUC5B. Since their levels increase under pathologic conditions such as extensive exposure to cigarette smoke, it is imperative to quantify them to improve treatment strategies of pulmonary diseases. This study presents a simple, image-based, and high-processing computational method that allows determining the ratio of MUC5AC and MUC5B within the overall airway mucus while providing information on their spatial distribution. The presented pipeline was optimized for automated downstream analysis using a combination of bright field and immunofluorescence imaging suitable for tracheal and bronchial tissue samples, and air–liquid interface (ALI) cell cultures. To validate our approach, we compared tracheal tissue and ALI cell cultures of isolated primary normal human bronchial epithelial cells derived from smokers and nonsmokers. Our data indicated 18-fold higher levels of MUC5AC in submucosal glands of smokers covering about 8% of mucosal areas compared to <1% in nonsmoking individuals, confirming results of previous studies. We further identified a subpopulation of nonsmokers with slightly elevated glandular MUC5AC levels suggesting moderate exposure to second-hand smoke or fine particulate air pollution. Overall, this study demonstrates a novel, user-friendly and freely available tool for digital pathology and the analysis of therapeutic interventions tested in ALI cell cultures.     

MRT letter: Auto‐fluorescence by human alveolar macrophages after in vitro exposure to air pollution particles

Macrophages from smokers demonstrate an increased auto‐fluorescence. Similarly, auto‐fluorescence follows in vitro exposure of macrophages to cigarette smoke condensate (i.e., the particulate fraction of cigarette smoke). The composition of particles in cigarette smoke can be comparable to air pollution particles. We tested the postulate that macrophages exposed to air pollution particles could demonstrate auto‐fluorescence. Healthy nonsmoking and healthy smoking volunteers (both 18–40 years of age) underwent fiberoptic bronchoscopy with bronchoalveolar lavage and alveolar macrophages isolated. Macrophages were incubated at 37°C in 5% CO₂ with either PBS or 100 μg/mL particle for both 1 and 24 h. Particles included a residual oil fly ash, Mt. St. Helens volcanic ash, and ambient air particles collected from St. Louis, Missouri and Salt Lake City, Utah. At the end of incubation, 50 μL of the cell suspension was cytocentrifuged and examined at modes for viewing fluorescein isothiocyanate (FITC) and rhodamine fluorescence. Both emission source air pollution particles demonstrated FITC and rhodamine auto‐fluorescence at 1 and 24 h, but the signal following incubation of the macrophages with oil fly ash appeared greater. Similarly, the ambient particles were associated with auto‐fluorescence by the alveolar macrophages and this appeared to be dose‐dependent. We conclude that exposure of macrophages to air pollution particles can be associated with auto‐fluorescence in the FITC and rhodamine modes. Microsc. Res. Tech., 2010. © 2009 Wiley‐Liss, Inc.     

国内外造纸法烟草薄片的烟气主要有害物释放量研究及其烟气危害性评估

本文通过常规烟气化学与七种主要烟气有害物的分析,比较了一些有代表性的国内和国外加工进口造纸法烟草薄片产品的烟气特性与差异,并对这些样品的烟气危害性进行了评估。研究结果表明(:1)国内外造纸法烟草薄片的烟气均具有低焦油、抽吸口数、烟碱和低苯酚、HCN、苯并[a]芘、氨等有害物质释放量的特性;(2)国内外产品的烟气苯酚释放量基本低于烟丝一个数量级,但NNK的释放量较高;(3)国产造纸法烟草薄片虽具有更低总粒相物、焦油、烟气烟碱、水分的常规烟气特性,但因CO/焦油比值较高,又是其不足之处;(4)国产造纸法烟草薄片的苯酚、氨、及NNK释放量相对较低,而进口产品则表现为苯并[a]芘与CO释放量低;(5)烟气危害性指数计算与评估的结果表明,国产与进口造纸法烟草薄片的危害性大致相当,但均远低于烟丝,由此也证实造纸法烟草薄片是一种比卷烟烟丝"更加安全"的烟草配方原料。     

烟气苦味成分的感官导向鉴定和液相色谱-高分辨质谱分析

烟气中苦味化合物多为难挥发成分,种类多、含量低。本研究采用感官导向鉴定法与液相色谱-高分辨质谱法（LC-HRMS）相结合分析烟气苦味成分,利用凝胶色谱分离主流烟气粒相物水溶性成分,并对各流分进行感官评价以确定苦味流分,合并后得到苦味特征组分。采用Q-Exactive型LC-HRMS仪器分析苦味特征组分,通过保留时间和二级质谱定性,对化合物标准品水溶液进行味觉评价,确定苦味化合物。在苦味特征组分中共鉴定出16种化合物,其中有苦味特征的是新烟草碱、降烟碱、麦斯明、可替宁、2-丁基咪唑、2-异丙基咪唑、烟酰胺、N-甲基烟酰胺、N-乙基烟酰胺和3-乙基-4-甲基-3-二氢吡咯-2-酮。该方法可为鉴定烟气中关键的苦味成分,实现卷烟产品的定向设计,提高卷烟的感官舒适性提供参考。     

烟气暴露对大鼠代谢轮廓谱的影响

运用基于液相色谱-质谱联用技术的代谢组学方法研究了不同卷烟烟气暴露对大鼠内源小分子代谢物组的影响。分别建立了大鼠血清和尿液的代谢轮廓谱,分析了烟气暴露7天、14天和30天时对照组大鼠、普通卷烟暴露组大鼠及含有天然本草添加剂的某品牌卷烟暴露组大鼠的血浆和尿液样本,采用偏最小二乘判别分析（PLS-DA）对数据进行模式识别。结果表明,普通卷烟和天然本草添加卷烟均会影响大鼠整体代谢状态,干扰大鼠磷脂、能量代谢,并对其造成氧化损伤,但天然本草添加卷烟对大鼠的损伤程度低于普通卷烟。在烟气暴露30天时,一些重要标志物在各组相对含量的变化进一步证实了天然本草添加卷烟可降低烟气对大鼠整体代谢的影响,减轻烟气造成的损伤。因此,在烟草中加入天然本草添加剂可在一定程度上减少烟气对机体的伤害,改善体内因烟气干扰而紊乱的磷脂和能量代谢。