The low temperature catalytic pyrolysis performances of heated tobacco sheets by alkali/alkaline earth metal were investigated by TG-FT-IR and Py-GC-MS. Thermogravimetric analysis showed that the maximum weight loss rate temperature of the heated tobacco sheets significantly reduced from 328 degrees C to 292 degrees C catalyzed by alkali metal Na or K catalysts, and the weight loss between 100 and 300 degrees C increased by 48.83% and 40.05% respectively. While alkaline earth metal Mg or Ca catalysts exerted less influence on the maximum weight loss rate temperature and the weight loss between 100 and 300 degrees C reduced slightly. The online infrared absorption band of pyrolysis gas shifted to lower temperature and the concentration of pyrolysis gas increased over Na catalysts, which matched well with TG results. Moreover, the concentration of carbonyl compounds and compounds containing C-O bonds in pyrolysis gas increased significantly. The content of 2-furanmethanol, butyrolactone and megastigmatrienone in pyrolysis gas increased under the assistance of alkali metal Na or K. Model compounds research confirmed that alkali metal could catalyze low temperature pyrolysis of cellulose in heated tobacco sheets. These results demonstrated that the pyrolysis of heated tobacco sheets could be catalyzed by alkali metal catalysts at low temperature, increasing the concentration of pyrolysis gas and aroma substance. This research provided a new idea for the study of aroma and concentration enhancement of heated cigarettes through catalytic technology.

为了考察样品放置方式对卷烟温湿度调节效果和主要物理指标的影响,研究了散装和盒装剪底两种常用样品放置方式对卷烟质量平衡状态和卷烟单支质量、吸阻、总通风率等指标的影响.结果表明:①不同样品放置方式下,卷烟含水率和达到质量平衡的时间有较大差异,散装卷烟经48 h调节后达到平衡状态,盒装剪底调节的卷烟质量随调节时间增加持续增加.②样品放置方式对卷烟不同物理指标的影响有一定差异,对卷烟硬度的影响最大,会造成产品硬度判定结果的变化;对卷烟单支质量有较大的影响;对卷烟吸阻、总通风率、圆周、长度的影响较小.相同调节时间内散装调节的卷烟的质量、吸阻、总通风率、圆周、长度均大于盒装剪底调节的卷烟,硬度小于盒装剪底调节的卷烟.③烟草及烟草制品调节和测试的大气环境标准中应进一步明确卷烟样品温湿度调节时的放置方式,以避免其差异对测试结果的影响,建议调节卷烟样品时应尽量采用散装方式放置.

为了考察卷烟纸助燃剂对卷烟燃烧特性及主流烟气中CO释放量的影响,探讨了卷烟纸助燃剂的类型、用量、含钾比例与卷烟燃烧主流烟气中CO的释放量、卷烟燃烧特性之间的相关性.结果表明,卷烟纸助燃剂用量与卷烟的阴燃温度、烟碱量、焦油量具有相关性,提高助燃剂用量能提高卷烟燃烧时的阴燃温度、加快烟支的燃烧速度,且烟碱量和焦油量随之减少;保持卷烟纸助燃剂用量不变,助燃剂中的含钾比例与烟气常规成分和卷烟燃烧温度无明显相关性;卷烟纸助燃剂的类型、用量、含钾比例与CO释放量无明显相关性,CO释放量与卷烟燃烧时低温区域面积和高温区域面积的比值R具有强烈的正相关.

为了降低卷烟危害性,全面系统地阐述初烤烟叶中化学成分对卷烟主流烟气有害成分释放量的影响,以2014年浓香型主产区烤烟样品为试验材料,采用因子分析和灰色关联法对初烤烟叶有机酸对主流烟气中有害成分释放量的影响进行研究.结果表明:因子分析共提取出草酸、富马酸、苹果酸、柠檬酸、丙二酸、棕榈酸、油酸、十八酸8种代表性有机酸.灰色关联度分析显示草酸、丙二酸、富马酸、苹果酸、柠檬酸5种非挥发性有机酸对烟气7种有害成分(CO、HCN、NNK、NH3、B[a]P、苯酚和巴豆醛)及焦油释放量和卷烟危害性指数的关联度均较高,尤其是草酸对烟气有害成分的危害性指数有较高的关联度;而棕榈酸、油酸、十八酸等高级脂肪酸对烟气7种有害成分及焦油释放量和卷烟危害性指数的关联度相对较低.总体来说,初烤烟叶中有机酸成分中非挥发性有机酸对卷烟主流烟气有害成分的产生有较大影响,而高级脂肪酸对其影响相对较小.

建立了顶空气相色谱/质谱(HS-GC/MS)法测定卷烟烟丝吸附的甲苯.考察了色谱柱升温程序、项空平衡温度、顶空平衡时间、传输线温度及样品环温度、样品加入量、基质校正剂加入量对分析结果的影响,确定的最优分析条件为:顶空平衡温度140℃,顶空平衡时间45 min,样品环温度190℃,传输线温度210℃,样品加入量为1.0g,不添加基质校正剂.结果表明,方法相对标准偏差(RSD)为2.76％,检出限为0.013 μg/g,定量限为0.043 μg/g.该方法简便、快速、重现性好,可用于卷烟烟丝吸附的甲苯的测定.

In order to investigate the adsorption characteristics of tobacco materials (cut leaf strip, cut reconstituted tobacco and cut stem) in a cigarette for volatile organic compounds (VOCs), a headspace-gas chromatography-mass spectrometry (HS-GC/MS) method was developed to determine 10 VOCs (benzene, toluene, ethylbenzene, styrene, acetone, butanone, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate) adsorbed by these tobacco materials. The amounts of VOCs adsorbed by different tobacco materials at different VOC concentrations during different adsorption time were determined, and the variations of amount of VOCs adsorbed by the tested samples along with their storage duration in a workshop were analyzed. The results showed that: 1) The optimized headspace equilibrium condition was 90 ℃ for 40 min. 2) The VOCs were quantified by an external standard method with the good linearity (R2>0.99) of calibration curves. The recoveries were 85.6%-102.1% with the relative standard deviations ranged from 2.4% to 6.4%. The limits of detection and quantification for the 10 VOCs were 0.01-0.04 and 0.03-0.13 μg/g, respectively. 3) The amount of VOCs adsorbed by cut reconstituted tobacco was the highest, while that by cut leaf strip was the lowest. Basically, the adsorption amount increased gradually with the increase of adsorption time and VOC concentrations in the environment. 4) Trace amount of several VOCs were detectable in the tobacco samples from newly built workshop, however the adsorbed VOCs were desorbed gradually with the prolongation of storage in clean air.

以尼龙酸和L-薄荷醇为原料合成了清凉剂尼龙酸薄荷酯,采用单因素实验优化了合成工艺,并对产物的主要成分进行了分析和结构表征;利用热重-微商热重(TG-DTG)和在线裂解气相色谱/质谱联用(Py-GC/MS)法分别对尼龙酸薄荷酯的热失重和热裂解行为进行了考察.得到最佳合成条件为:当尼龙酸酐的投料量为0.1mol时,催化剂4-二甲氨基吡啶(DMAP)的用量为尼龙酸酐质量的0.4％、反应温度为70℃、反应时间为9.0h、薄荷醇和尼龙酸酐的摩尔比为1.2∶1、环己烷用量50 mL,在该条件下产品收率达到89.3％.尼龙酸薄荷酯在301.5℃时失重速率最快为-19.17％/min,341.6 ℃时总失重率为99.72％;在300～450℃下尼龙酸薄荷酯的主要裂解产物为L-薄荷醇,随着裂解温度的提高,薄荷醇的释放量降低.

为研究口含烟食用过程中重金属向唾液转移的情况,利用人工模拟唾液作为提取液,在超声条件下对口含烟样品进行提取,并利用微波消解–电感耦合等离子体质谱（ICP–MS）测定重金属含量,建立了口含烟中6种重金属（Cd、Pb、Cr、Ni、As和Se）向唾液转移的模拟测定方法。对人工唾液提取液体积、提取时间进行了优化;绘制了口含烟6种重金属元素标准曲线,在考察浓度范围内各组分线性关系良好,相关系数均在0.999 7以上,检出限和定量限低于0.1 ng/m L,测定口含烟样品中重金属加标回收率为93.8% 1 01.8%。运用所建立的方法分别测定7个口含烟样品在人工唾液提取液中的6种重金属Cr、Ni、Cd、Se、As、Pb的转移率分别为2.52% 1 6.62%、7.97% 2 2.51%、8.44% 3 1.40%、10.71% 3 8.70%、18.94% 4 0.84%、10.71% 4 3.60%。

To selectively reduce delivery of hydrogen cyanide in mainstream cigarette smoke,amine functionalized SBA-15/ polyethersulfone composite materials was prepared.Pore structure,surface morphology and thermal stability of the prepared composite materials were characterized by nitrogen adsorption,SEM and thermal gravimetric analysis.The composite material was added to cigarette filter to test its harm reduction effect.Results showed that:1) Material obtained by modifying SBA-15 with APTS still retained its orderly mesoporous structure.2) Amine functionalized SBA-15/polyethersulfone was a spongy porous composite material with excellent thermal stability under 200 oC.3) When amine functionalized SBA-15/polyethersulfone was added to a dual-filter at a rate of 20 mg/cig,the HCN in mainstream cigarette smoke was reduced by 29.6 ％,and the hazard index (H) of cigarette decreased by 0.2.The amine functionalized material SBA-15/polyethersulfone proved to possess good adsorption ability to HCN in cigarette smoke.

对果胶酶高产菌株黑曲霉(Aspergillus niger)SW06进行液体发酵工艺条件优化.首先采用单因素试验设计果胶酶发酵的最适温度和pH值,并筛选了最适的碳源、氮源和无机盐.在此基础上,采用中心组合设计进行回归分析及响应面分析,确定培养基的最佳组合.结果表明,果胶酶发酵的最适温度为28℃,最适pH值为5,最适碳源、氮源分别为果糖、蛋白胨.回归分析得到的优化发酵条件为:100 mL培养基中含果糖4.89 g、蛋白胨0.50 g、果胶0.60 g.在最优条件下发酵,果胶酶活最高可达4 175.65 U/mL.

为降低再造烟叶中果胶合量,采用正交实验法考察了微紫青霉（Penicillium janthinellum sw 09）产果胶酶的加酶量、料液比、处理时间和温度4个因素对烟梗原料中果胶降解效果的影响。采用傅立叶变换红外光谱仪测定果胶的结构官能团,并采用在线裂解气相色谱/质谱法（PY/GC-MS）研究了烟梗酶解前后在氦气中600℃下的热裂解行为,并对其热裂解产物进行分析。结果表明,烟梗果胶降解最佳反应条件为:酶活力14 000 U/m L、料液比1∶5、反应温度50℃、处理时间2 h,果胶降解率达到最大41.35%。由红外光谱、热裂解对比可知,烟梗果胶酶解前后其结构官能团并未发生明显改变,但其中裂解产物成分的组成、含量均发生了明显的变化,烷烃、烯烃类物质显著减少,醇类、酚类等香气成分增加。感官评价实验表明,经酶解后的卷烟吸食品质提高。

采用亚临界萃取技术处理卷烟烟丝,考察处理后烟丝加工性能、化学成分、挥发性有机物、农药残留、烟气常规指标及感官质量的变化情况.结果表明:亚临界萃取处理后的烟丝耐加工性略微变差,但不影响其可用性;萃取过程无溶剂残留;在对照样中检出的三种农残,二甲醚处理的样品中均未检出,丁烷处理样三种农残的去除率分别为50.0％、43.8％和70.0％;二甲醚和丁烷处理样制成卷烟后主流烟气中焦油的释放量分别降低了12.7％和8.5％,水分、CO和烟气烟碱量也有不同程度降低;感官评吸显示柔细程度、余味、刺激性均好于对照;二甲醚处理样卷烟烟气中除NNK和巴豆醛的释放量基本不变外,苯酚、HCN、氨、CO及苯并[a]芘的释放量分别下降了19.7％、18.8％、33.3％、 19.5％和25.2％,卷烟危害指数由13.5降至10.9.说明亚临界萃取技术适用于卷烟的减害降焦.

Transfer of heavy metal to the cigarette smoke was briefly reviewed focus on the affecting factors of the transfer. The mechanisms and the dynamical formulation of heavy metal in cigarette smoke were summarized, which was expected to provide reference for heavy metal control. The prospect of further study in cigarette smoke was further discussed.

A method of gas chromatography mass spectrometry was established,which could accurately analysze the amount of benzene,toluene and ethyl benzene in the pyrolysis products of cigarette lap adhesive samples.The parameters of pyrolysis temperature,moisture,dryness temperature and dryness time were op-timized.The results showed that the linear possessed good in the range of 2 ~500 μg/mL,the linear correla-tion coefficients were above 0.990 0,the limits of detection were from 0.378 ng/mL to 0.996 ng/mL,the limits of quantification were from 1.26 ng/mL to 3.32 ng/mL.The method was suitable for determining the benzenes in cigarette lap adhesive samples.The determined concentration range of benzene was 138.7 ~188.4 mg/g,toluene was 44.0 ~75.2 mg/g and ethyl benzene was 3.0 ~19.1 mg/g in the pyrolysis products of cigarette lap adhesive samples.

[目的]建立离子色谱法测定再造烟叶中的钠、氨、钾、镁、钙的含量.[方法]采用0.05 mol/L盐酸溶液作为提取溶液,在超声波辅助条件下提取30 min,离子色谱法准确快速地同时检测出再造烟叶中的钠、氨、钾、镁、钙5种阳离子的含量.[结果]该方法对于钠、氨、钾、镁、钙5种阳离子的捡出限和定量限分别为0.01和0.05 μg/ml,0.06和0.019 μg/ml,0.03和0.012μg/ml,0.04和0.013 μg/ml,0.15和0.048 μg/ml,5种阳离子3个浓度梯度的加标回收率范围均在91.7％～109.9％.用建立的方法对市场上常用的几种再造烟叶进行了测定显示,低含量的氨离子和钠离子含量的偏差分别为51.17％和51.96％,而高含量的镁、钾和钙离子含量偏差均在20％以内.[结论]该研究建立的方法具有操作简便、准确度高、重复性好、适用性强等优点,适用于大批量样品分析.

In order to develop a new natural cigarette flavor,the fruits of Hippophae rhamnoides L.(Seabuckthorn) were extracted with Soxhlet extraction,heating reflux extraction and water extraction-alcohol precipitation in turn.Petroleum ether extract,crude flavone and crude polysaccharide were obtained respectively.The petroleum ether extract was analyzed with GC/MS and applied in cigarette as a flavor.The results showed that: 1) 49 components in petroleum ether extract were identified,main compounds included esters,carboxylic acids,ketones,alkanes,alcohols and aldehydes.2) The extracts reduced the dryness and irritation,while improved sensory pleasurableness of cigarette smoke.3) Compared with the control,the tobacco specific N-nitrosamines(TSNAs) in mainstream cigarette smoke reduced by about 20%,the free radicals in gas phase and solid phase decreased by about 31% and 26%,respectively.

A method of reversed-phase high performance liquid chromatography(RP-HPLC) with VWD was developed for the determination of 3 isomers of chlorogenic acid(neochlorogenic acid,chlorogenic acid,cryptochlorogenic acid)in tobacco flavorings.Using this method,the contents of 3 chlorogenic acid isomers in 9 tobacco flavoring samples were quantitatively determined respectively.It is showed that: ①3 chlorogenic acid isomers in tobacco flavorings were extracted with methanol by oscillation of 5 min;②Separation within 20 min by RP-HPLC was achieved by gradient elution on a Symmetry C18 column with acetonitrile and water(0.1% formic acid) as mobile phase at detection wavelength 325 nm;③The R.S.D of 6 repeat tests were in the range of 1.8%-4.7% with the recoveries range 101.3%-104.5%for neochlorogenic acid,99.9%-102.7% for chlorogenic acid,100.0%-104.4% for cryptochlorogenic acid;④High content of chlorogenic acid isomers were presented in coffee tincture and Yunyan tobacco concrete;The content of chlorogenic acid isomers was different according to the source of coffee tincture.Chlorogenic acid was detected in part of the samples.

[Objective] The aim was to establish a pyrolysis method for cigarette water-based adhesive.[Method] The pyrolysis temperature,GC capillary column and programmed temperature were optimized.The qualitative analysis of pyrolysis material and normalization quantitative analysis of peak area were carried out on 50 cigarette water-based adhesive samples.[Result] Pyrolysing cigarette water-based adhesives at the temperature of 800 ℃ and separating by DB-FFAP column(60 m×320.0 μm×0.5 μm) was the best.Eighteen kinds of pyrolysis products were determined,the pyrolysis material content produced by different water-based adhesive was differences,which indicates that the quality of different water-based adhesive varies significantly and they have effects on cigarette sensory quality and harmfulness.[Conclusion] Using high-quality water-based adhesive could improve cigarette sensory quality and decrease harmfulness of cigarette.