[目的]制备三乙酸甘油酯滤棒基体标准物质,可解决实验室能力验证无准确对照品的问题,同时也可应用于近红外法测定滤棒中的三乙酸甘油酯建模样品的赋值以及近红外设备的期间核查等.[方法]通过严格控制滤棒生产条件,制备三乙酸甘油酯滤棒基体标准物质,进行均匀性检验、稳定性考察和联合定值.[结果](1)6 个实验室对该标准物质的合作定值结果为 8.50%;(2)在 95%的置信概率下,取扩展因子k=2,则扩展不确定度为 0.24%.[结论]该标准物质符合国家二级标准物质的技术要求,可满足近红外法赋值和实验室能力验证、数据比对的需要.

建立了同时测定人尿液中烟碱及其9种代谢物的高效液相亲水作用色谱-串联质谱分析方法.尿液样品经乙腈和甲醇混合溶剂(体积比3:1)稀释20倍,过0.22μm滤膜后直接进样.采用Atlantis HILIC Silica柱(3.0 mm×100 mm,3.0μm),以10 mmol/L甲酸铵水溶液(用甲酸调至pH 3.0)-乙腈为流动相进行梯度分离,电喷雾正离子电离模式和多反应监测扫描模式下测定,以同位素内标法定量.结果表明,烟碱及其9种代谢物在各自的质量浓度范围内线性关系良好,相关系数(r)均大于0.997,检出限(LOD)和定量下限(LOQ)分别为0.03～0.24 ng/mL和0.10～0.80 ng/mL;在低、中和高3个加标水平下的加标回收率为81.9％～110％,日间和日内相对标准偏差(RSD)为0.50％～6.7％.该方法操作简单、灵敏度高、稳定性好,能够满足大批量人尿液中烟碱及其9种代谢物的检测需求.

Current calibration method of air permeability standards does not take into account the influences imparted by standard’s position in the air circuit and atmospheric pressure variation on measurement results. Therefore, the method was improved by changing the arrangement of air permeability standard in air circuit for measurement from upstream to downstream of the flow-meter and dividing air permeability standards into two types, linear type and non-linear type. The influence of atmospheric pressure on the measurements of non-linear standards was calculated. The repeatability and stability of measuring method before and after improvement were compared, and the improved measuring method was adopted to take part in CORESTA collaborative experiments. The results showed that: 1) After improvement, the standard deviation and variance coefficient of measurements, and the extreme difference of measurement results over five months for non-linear standards reduced by about 50%. 2) The relative extreme difference of volumetric flow mean value of air permeability standards measured by ZTRI (Zhengzhou Tobacco Research Institute of CNTC)laboratory and three foreign laboratories were less than 2%, and the variance coefficients of measurements of each standard were all less than 0.50%.

In order to improve the accuracy of measurement results, the uncertainty in determination of butyl acetate in tipping paper by headspace gas chromatography(HS-GC) was analyzed on the basis of JJF1059.1-2012 Evaluation and Expression of Uncertainty in Measurement, and the uncertainty of individual component affecting measurement was calculated. The results showed that: 1) The factors influencing measurement uncertainty included sample preparation, standard solution preparation, repeatability examination,calibration curve fitting, etc., particularly the calibration curve fitting. 2) When the residue of butyl acetate in tipping paper sample was 0.54 mg/m2, the combined uncertainty and the expanded uncertainty of measurement results were 0.024 and 0.05 mg/m2(P=95%, k=2), respectively. Therefore, the analysis accuracy could be improved by means of abandoning stepwise dilution method during the solution preparation of standard working curve or reducing the concentration range of standard working solution.

Low-tar monitoring cigarette samples were prepared based on YC/T 189-2004 to meet the demand of quality control of low tar cigarettes in tobacco industry. Homogeneity and values were also measured. Results showed that: 1)F test showed no significant differences existed between cartons. 2) mean tar delivery of 16 collaborating laboratory was 7.65 mg/cig, with repeatability standard deviation and reproducibility standard deviation as 0.17 mg/cig and 0.41 mg /cig, respectively.

为解决卷烟感官评价人工试样制备中存在的劳动强度大、效率低、容易产生人为差错等问题,设计了卷烟感官评价自动化试样制备系统.该系统主要由试样生成与打码单元、试样自动封装单元、软件控制与分析系统3部分组成.烟支在试样生成与打码单元中进行料斗选择和烟支喷码,在试样自动封装单元中完成组合封装,通过软件控制与分析系统完成样品编码方案生成、制样过程控制及评价结果的统计分析功能.应用效果表明,卷烟评吸自动制样系统实现了试样制备及结果判定由人工向自动化操作的转变,25个评吸员对20组样品进行三点检验所需制样时间由1260 min减少到198 min,有效提高了制样效率,保证了评吸结果的准确性和可靠性.

In order to study the influences of Health Canada Intense(HCI)regime on the deliveries of tar,nicotine and carbon monoxide(CO) in mainstream smoke of super slim cigarettes,a collaborative study involving 7 rotary smoking machines and 5 linear smoking machines in 9 laboratories was carried out by smoking 4 super slim cigarette brands under ISO and HCI regimes respectively. The results showed that:1)The influences of HCI regime on the deliveries of tar,nicotine and CO were basically the same. 2)Under HCI regime,the deliveries of tar,nicotine and CO increased with the decrease of tar delivery determined under ISO regime and/or with the increase of ventilation rate of cigarette filter. 3) Comparing with ISO regime,the repeatability(r)and reproducibility(R)of tar and nicotine determination results,the repeatability(r)of CO determination results and the relative reproducibility(R/m)of tar determination results under HCI regime were higher,which indicated that the precision of HCI regime for tar,nicotine and CO determination results was lower than that of ISO regime.

为验证ISO 2965-2009中透气度流量盘测量结果修正公式的准确性,在可调节大气压实验舱中,分别选择22℃,24℃两个温度点,及86,93,99,101,106 kPa 5个大气压力点的不同环境条件对18个流量盘进行了流量值测量实验.结果表明:①线性流量盘的测量结果不需修正,可直接用作流量值;②非线性流量盘测量结果修正到标准条件后,将修正结果作为非线性流量盘的流量值.并通过线性流量盘和非线性流量盘在结果修正后和未修正两种情况下对卷烟纸透气度测量结果的影响实验,验证了以上实验结论的正确性.

The certified reference material(CRM) of acetone solution in triacetin was prepared by taking high purity acetone and triacetin reagent as raw materials and strict control of preparation and packaging process.The homogeneity and stability of the CRM were verified with GC-FID method.The results showed that the CRM concentration tested by seven collaborative laboratories was 0.95 mg/mL with an expanded uncertainty(α= 0.05,k=2) of 0.03 mg/mL.The prepared CRM satisfied the technical requirements of national secondary reference material and could be used in the determination of residual volatile organic compounds in cigarette paper.

Development of four smoking regimes including ISO,FTC,Massachusetts and Canadian Intense were introduced.The controversy on ISO/FTC smoking regimes,as well as WHO’s perspective and research carried out by ISO/TC 126 on smoking regimes for cigarettes were also discussed.

Ethyl acetate solution certified reference material was prepared under strict control of preparation and packaging processes with high purity Ethyl acetate reagent as raw material. Homogeneity and stability were measured using GC-FID method. Concentration value of the reference material was 1.02 mg/mL, with an expanded uncertainty of 0.03 mg/mL based on cooperation analysis of 7 laboratories. Results indicated that the certified reference material met all technical requirements of national secondary reference material.

High purity Cyclehexanone reagent was used as a raw material of CRM,the Cyclehexanone solution certified reference material was developed under strictly controlled process of preparation and packaging.Homogeneity and stability tests were measured by GC-FID method.Set by cooperation analysis of 7 laboratories,the concentration value of the reference material was 0.98mg/mL,with an expanded uncertainty of 0.02 mg/mL.The results of homogeneity and stability tests showed that the certified reference material met the technical requirements of the national secondary reference material.The "Cyclohexanone Solution Standard Substance in Glyceryl Triacetate" developed in this project belongs to innovative standard substance varieties.At present,there is no certified standard substance either in China or around the world.Therefore,the "Cyclohexanone Solution Standard Substance in Glyceryl Triacetate" acquired in the project study will provide standard substance and substance standards for the dissemination of quantity value within China,and provide substance standard for the analysis of volatile organic compound in cigarette paper of tobacco industry;therefore,the project research has included extensive application value to the related field.

In order to ensure the accuracy and traceability of the test results of chlorine content in tobacco by continuous flow method,the sodium chloride of primary reference material was used as the raw material of solution reference material(SRM).The SRM was prepared via weighing,dissolving,repacking and heat sealing and went through homogeneity and stability test.The mass concentration of the SRM was 0.1001 mg/mL valued by gravimetric method.The main factors influencing the uncertainty of the SRM,including mass,purity,volume,homogeneity and stability,were also analyzed,its uncertainty was of 0.0005 mg/mL.

在参考大量国内外文献的基础上,从自由基反应角度探讨多环芳烃的形成机理及反应途径,试图为从源头上减少多环芳烃的形成提供理论依据。

The supporting effect of standardization on the tobacco leaf production and the development of brands are summa- rized.Method and steps for achieving the object of the standardization construction in major tobacco leaf production zones is in- troduced.

The volatile and semi-volatile acidic components in tobacco were analyzed qualitatively by(comprehensive) two-dimensional gas chromatography/time-of-flight mass spectrometry(GC×GC/TOFMS) and GC/TOFMS.The results showed that only 24 organic acids and 4 phenols were identified by GC/TOFMS;however,a total of 107 acidic components,including 82 organic acids and 25 phenols,were characterized by GC×GC/TOFMS via automated data processing combined with chromatogram aided qualitative analysis and manual rectification.

FT-NIR was evaluated as a method to simultaneously analyze 17 chemical components in tobacco leaf. Spectra of 700 typical samples were collected to develop the calibration models, among which the raw spectra were pretreated with first derivative and partial least square. About 50 randomly selected validation samples were used to test the accuracy of each calibration model. The values of root mean square error of prediction (RMSEP) for total volatile acids, total volatile bases, total petroleum ether extracts, petroleum ether extracts neutral, polyphenol, starch, cellulose, sulfate, pH, ash, water soluble ash bases, total sugar, reductive sugar, total nitrogen, alkaloids, chlorine, and potassium were 0.020, 0.009, 0.402, 0.393, 0.578, 0.583, 0.932, 0.139, 0.117, 0.634, 0.235, 1.720, 1.407, 0.104, 0.173, 0.037, 0.300 respectively. The satisfactory results indicated that FT-NIR could be an alternative to the traditional wet chemical method to simultaneously analyze the above 17 chemical components in tobacco leaf. The utilization of FT-NIR as a quality control method will reduce costs and enhance efficiency for the tobacco industry.

The near infrared (NIR) spectra of 730 representative tobacco samples were measured with Fourier transform near infrared spectroscopy. The calibration models between spectral data and the contents of total volatile base (TVB) or total volatile acid (TVA) of tobacco samples were established by partial least square regression and verified with a set of 50 tobacco samples. The root mean square errors of prediction (RMSEP) for TVB and TVA were 0.020 and 0.009, respectively; the relative standard deviations of TVB and TVA were 1.120% and 0.919% respectively for the 50 validation samples.