气相色谱-质谱联用法测定卷烟主流烟气中烟草特有亚硝胺

研究了用气相色谱-质谱联用法,用选择离子监测技术测定卷烟主流烟气中烟草特有亚硝胺N'-亚硝基去甲基烟碱(NNN)和4-(N-亚硝基甲氨基)-1-(3-吡啶基)-1-丁酮(NNK).在标准吸烟条件下,将烟气粒相物收集在剑桥滤片上,用柠檬酸-磷酸盐缓冲液和环己烷对粒相物共提取,提取液相继用碱性氧化铝层析柱和固相萃取法进一步纯化.选用选择离子监测技术对亚硝胺定性和定量.在进样量2μL时,方法检出限为9.83μg·L-1(NNN)和16.92 μg·L-1(NNK),线性范围0.1～5.0 mg·L-1,相关系数分别为0.998,0.996,回收率分别为91.0%,94.8%.     

液相色谱-串联质谱法测定卷烟主流烟气中的四种致癌物

N-亚硝基降烟碱（NNN）、4-（亚硝基甲氨基）-1-（3-吡啶基）-1-丁酮（NNK）、N-亚硝基新烟草碱 （NAT）和N-亚硝基假木贼碱（NAB）是4种广泛存在于烟草和烟气中的致癌物,准确测定其含量对评估其对人体健康的影响有着重要的作用。采用液相色谱-电喷雾串联质谱(LC-ESI MS/MS)技术建立了卷烟主流烟气中NNN、NNK、NAT和NAB的测定方法,并将其用于中国烤烟和混合型卷烟主流烟气的分析。卷烟主流烟气通过剑桥滤片捕集,捕集烟气后的滤片在加入100 μL氘代混合内标后用10 mL 100 mmol/L醋酸铵水溶液萃取,萃取液过水相滤膜后直接进行LC-ESI MS/MS检测。选用Agilent Zorbax Eclipse XDB-C18色谱柱,以流动相0.1%(v/v)乙酸水溶液和0.1%（v/v）乙酸甲醇溶液梯度洗脱,质谱检测采用正离子扫描,多反应监测模式。NNN、NNK、NAT和NAB的检出限分别为0.019、0.002、0.008和0.007 μg/L,回收率为84.9%～104.5%,相对标准偏差(n=8)为2.96%～6.65%。该方法的检出限低,特异性好,适用于卷烟主流烟气中NNN、NNK、NAT和NAB释放量的检测。     

离子色谱法测定卷烟主流烟气中的硫化氢

建立了测定卷烟主流烟气中硫化氢含量的离子色谱法.采用玻璃纤维滤片捕集卷烟烟气粒相物,并用0.5%(体积分数)乙二胺-50 mmol/L氢氧化钠-250 mmol/L乙酸钠溶液萃取粒相物,吸收液吸收气相物中的硫化氢,合并粒相萃取液与气相吸收液,经离子色谱柱分离,以1.5 mol/L氢氧化钠-1 mol/L乙酸钠-2%(体积分数)乙二胺(40∶50∶10,体积比)为流动相,安培检测器检测并施加-100 mv的检测电位.运用方法对12种市售卷烟样品进行了测定,结果表明:方法的线性范围为0.1~5.0μg/mL,检出限为1.03μg/mL,定量限为3.41μg/mL,回收率为102.3%~107.2%,相对标准偏差小于5%.方法处理简单、准确度高,可以用于卷烟烟气中硫化氢含量的测定.     

匀浆提取-超高效液相色谱-串联质谱法测定烟草中亚硝胺含量

提出了超高效液相色谱-串联质谱法测定烟草中N-亚硝基降烟碱(NNN)、N-亚硝基新烟草碱(NAT)、N-亚硝基假木贼碱(NAB)和4-甲基亚硝基吡啶基丁酮(NNK)等4种亚硝胺含量的方法。烟草样品经0.1mol.L-1乙酸铵溶液匀浆提取,离心分离取上清液过Waters AcquityUPLC BEH C18色谱柱(2.1mm×100mm,1.7μm)分离,以乙腈和0.01mol.L-1乙酸铵溶液按不同体积混合作流动相梯度洗脱。串联质谱测定中采用电喷雾离子源正离子模式和多反应监测模式检测,同位素内标法定量。NNK、NNN、NAB和NAT的检出限(3s)分别为0.06,0.17,0.15,0.053μg.L-1。方法的加标回收率在92.1%～104%之间;日内和日间相对标准偏差(n=7)分别为2.7%～3.3%和3.5%～4.2%。     

气相色谱-三重四极杆质谱联用法检测市售腊肠中9种挥发性亚硝胺

采用QuEChERS方法对市售腊肠中的N-亚硝基二甲胺(NDMA)、N-亚硝基二乙胺(NDEA)、N-亚硝基甲乙胺(NMEA)、N-亚硝基二丙胺(NDPA)、N-亚硝基吡咯烷(NPYR)、N-亚硝基哌啶烷(NPIP)、N-亚硝基二丁胺(NDBA)、N-亚硝基吗啉(NMOR)、N-亚硝基二苯胺(NDPhA)9种对人体有致癌活性的挥发性亚硝胺进行分离净化,气相色谱-三重四极杆质谱联用法(GC-MS/MS)检测。最佳实验条件下,9种挥发性亚硝胺的线性范围为0.25~200μg/L,检出限为0.01~0.10μg/kg,加标回收率为90.7%~116.0%,相对标准偏差(RSD)为1.8%~14.0%。市售腊肠样品中NDMA,NMOR,NPYR,NDPA,NPIP,NDBA,NDPhA均有不同程度的检出,总挥发性亚硝胺的含量为1.85~13.44μg/kg。该方法灵敏度高、操作简单,适合批量样品的快速检测。     

水蒸气蒸馏-活性炭柱固相萃取/GC-MS/MS法测定火腿中8种N-亚硝胺

建立了水蒸气蒸馏提取,活性炭柱固相萃取,气相色谱-串联质谱(GCM S/M S)检测火腿中8种N-亚硝胺的新方法。样品经水蒸气蒸馏提取,馏出液经Sep-Pak AC-2活性炭柱固相萃取进行净化与富集,二氯甲烷洗脱,以多重反应监测(MRM)方式进行GC-MS/MS检测。在考察的浓度范围内(1~400 ng/m L)方法线性良好,R20.9995,除N-二甲基亚硝胺(NDM A)和N-亚硝基甲乙胺(NMEA)检出限≤0.1 ng/g外,其它分析物的检出限为≤0.04 ng/g;在0.3,3和10μg/kg 3个水平的添加回收率为78.7%~118.2%,除N-亚硝基吗啉(NM OR)回收率略低,为45.2%~58.2%,相对标准偏差为2.5%~21%。应用该方法对市售的4种火腿进行检测,结果表明NDMA和N-亚硝基吡咯烷(NPYR)是主要的挥发性N-亚硝胺,含量分别为0.30 ng/g和0.56~0.99 ng/g,N-二乙基亚硝胺(NDEA)、NMOR和N-二丁基亚硝胺(NDBA)均有检出,但含量低于定量限,NM EA、N-二丙基亚硝胺(NDPA)和N-亚硝基哌啶(NPIP)未检出。     

一种加拿大深度抽吸条件下烟草特有亚硝胺的检测方法

本发明是在加拿大深度抽吸条件下,采用超高效液相色谱–串联质谱联用法测定烟草特有亚硝胺(TSNAs),属于一种烟草特有亚硝胺检测方法。本方法是在加拿大深度抽吸条件下抽吸卷烟后,往捕集卷烟烟气总粒相物的滤片中加入含内标物的乙酸铵水溶液,超声提取后,取1~2 m L萃取液,过0.22μm有机滤膜,用UPLC–MS/MS仪分析TSNAs,根据组分峰和同位素内标物峰的面积比定量。本发明的检测方法可用于加拿大深度抽吸条件下检测烤烟型和混合型卷烟主流烟气中的TSNAs,具有前处理简单、定量准确、仪器分析速度快、检出限低、样品处理通量高等优点。     

固相微萃取/气相色谱-质谱联用法测定橡胶密封材料中N-亚硝胺

建立了固相微萃取/气相色谱-质谱联用法(SPME/GC-MS)测定橡胶密封材料中N-亚硝基-N-甲基苯胺(NMPh A)、N-亚硝基-N-乙基苯胺(NEPh A)和N-亚硝基二苯基胺(NDPhe A)3种N-亚硝胺化合物含量的方法。样品参考国标GB/T 24153-2009进行预处理后,采用固相微萃取进行提取,对影响固相微萃取效率的纤维涂覆种类、萃取时间、搅拌速度和萃取温度等条件进行优化。在优化条件下,方法的线性范围为5~500μg/L,相关系数(r)均大于0.99,检出限为0.5μg/kg,回收率为77%~92%,相对标准偏差(RSD,n=6)为3.8%~7.7%。     

磁固相萃取技术应用于主流烟气中烟草特有N-亚硝胺的测定

合成了甲基丙烯酸改性的Fe3O4磁性纳米颗粒(Fe3O4@Si O2@MAA),建立了磁固相萃取技术与高效液相色谱-串联质谱联用检测主流烟气中烟草特有N-亚硝胺(TSNAs)的方法。该方法通过加入磁性纳米颗粒对萃取液中TSNAs进行富集,洗脱液在HPLC-MS/MS多反应监测模式下进行检测,可满足低焦油和新型烟草制品等低含量TSNAs的检测要求。结果表明:Fe3O4@Si O2@MAA纳米颗粒粒径均一,分散性好,具有超顺磁性,其表面的羧基可吸附溶液中的TSNAs,实现分离富集;该前处理方法操作快速简便,适用于大批量样品分析;4种烟草特有N-亚硝胺的定量下限为0.10~0.48μg/L,加标回收率为88.3%~112.8%,该方法满足复杂烟气背景下痕量TSNAs的检测要求。     

欧盟EN12868方法与固相微萃取-气质联用法检测乳胶气球中亚硝胺模拟迁移量

利用欧盟EN12868方法对市售乳胶气球中的8种挥发性亚硝胺及其前体物的模拟迁移量进行了检测,包括N-亚硝基二甲胺(NDMA),N-亚硝基二乙胺(NDEA),N-亚硝基二丙胺(NDPA),N-亚硝基异丙胺(NDiPA),N-亚硝基二丁胺(NDBA),N-亚硝基哌啶(NPIP),N-亚硝基吡咯烷(NPYR),N-亚硝基吗啉(NMOR)。其中NDMA,NDEA和NDBA 3种亚硝胺及其前体物被检出,且均超标。建立了顶空-固相微萃取-气相色谱-质谱法(HS-SPMEGC-MS)快速测定乳胶气球中亚硝胺模拟迁移量的分析方法。样品置于人工唾液40℃浸提1h来模拟气球的使用情况,考察了不同的萃取条件对分离检测的影响,综合评价了4种检测系统的性能。8种亚硝胺的方法检出限为0.26~5.38μg/kg。利用所建方法检测9种市售乳胶气球中亚硝胺的模拟迁移总量为31.37~337.72μg/kg。     

卷烟主流烟气中碳中心自由基的自旋标记荧光表征

以自旋标记荧光探针4-((9-acridinecarbonyl)amino)-2,2,6,6-tetramethylpiperidin-1-oxyl(TEMPO-9-AC)研究了卷烟主流烟气中的碳中心自由基。以吸烟机抽吸卷烟,以弱荧光的TEMPO-9-AC作为捕集剂捕集卷烟主流烟气中的碳中心自由基,生成稳定的强荧光的碳中心自由基捕集加合物,以高效液相色谱-三重四极杆串联质谱联用仪(HPLC-MS/MS)对其结构进行了确认,并建立了高效液相色谱-荧光检测(HPLC-FLD)的定量方法。结果表明,方法的检出限为0.318 nmol/cig,相对标准偏差(RSD)为3.5%～9.7%;利用TEMPO-9-AC捕集体系鉴别出了10种碳中心自由基;对5种代表性卷烟烟气中的碳中心自由基进行了定量计算,获得了它们在主流烟气中碳中心自由基的含量数据,并发现碳中心自由基总量与焦油释放量之间具有高度的相关性。本法检出限低,重复性好,适用于卷烟主流烟气中碳中心自由基的结构验证及释放量的检测分析。     

Separation and quantitation of monovalent anionic and cationic species in mainstream cigarette smoke aerosols by high-performance ion chromatography

A simple method has been developed to separate and quantitate monovalent ionic species in mainstream cigarette smoke aerosols based on ion chromatography (IC) with conductivity detection. The method entails collecting the smoke aerosol particulate phase by electrostatic precipitation, dissolving the smoke condensate in methanol (MeOH), and separating the ionic species on either a cation- or anion-exchange column. The method has been applied to the analysis of smoke aerosols from two cigarettes, 1R4F Kentucky Reference cigarettes and a new cigarette that heats but does not burn tobacco. The predominant cations in smoke aerosols from 1R4F Kentucky Reference and the new cigarettes are sodium (Na+), ammonium (NH4+), and potassium (K+) ions; the predominant anions are acetate (AcO-) and formate (HCOO-). Trace amounts of chloride (Cl-), nitrite (NO2-), and nitrate (NO3-) ions are also present.     

Two new alkaloids from cigarette smoke condensate

Chemical constituents of MeOH extracts of cigarette smoke were studied. Two new alkaloids, named cigatin A (1), 2-(Pyridine-3-yloxy)-benzene-1',4'-diol and B (2), 2-(4-Methyl-pyridin-3-yloxy)-benzene-1',4'-diol, were isolated from a mainstream condensate of cigarette together with seven known alkaloids. Their structures were determined on the basis of spectral data and chemical methods.     

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...     

Measurement of nitrogen dioxide in cigarette smoke using quantum cascade tunable infrared laser differential absorption spectroscopy (TILDAS)

Although nitrogen dioxide (NO(2)) has been previously reported to be present in cigarette smoke, the concentration estimates were derived from kinetic calculations or from measurements of aged smoke, where NO(2) was formed some time after the puff was taken. The objective of this work was to use tunable infrared laser differential absorption spectroscopy (TILDAS) equipped with a quantum cascade (QC) laser to determine if NO(2) could be detected and quantified in a fresh puff of cigarette smoke. A temporal resolution of approximately 0.16s allowed measurements to be taken directly as the NO(2) was formed during the puff. Sidestream cigarette smoke was sampled to determine if NO(2) could be detected using TILDAS. Experiments were conducted using 2R4F Kentucky Reference cigarettes with and without a Cambridge filter pad. NO(2) was detected only in the lighting puff of whole mainstream smoke (without a Cambridge filter pad), with no NO(2) detected in the subsequent puffs. The measurement precision was approximately 1.0 ppbVHz(-1/2), which allows a detection limit of approximately 0.2 ng in a 35 ml puff volume. More NO(2) was generated in the lighting puff using a match or blue flame lighter (29+/-21 ng) than when using an electric lighter (9+/-3 ng). In the presence of a Cambridge filter pad, NO(2) was observed in the gas phase mainstream smoke for every puff (total of 200+/-30 ng/cigarette) and is most likely due to smoke chemistry taking place on the Cambridge filter pad during the smoke collection process. Nitrogen dioxide was observed continuously in the sidestream smoke starting with the lighting puff.     

Optimization and validation of a gas chromatographic method for analysis of (RS,SR)-diastereoisomeric impurity in formoterol fumarate

The levels of 2-amino-9H-pyrido[2,3-b]indole (AalphaC or 2-amino-alpha-carboline), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAalphaC or 2-amino-3-methyl-alpha-carboline), 9H-pyrido[3,4-b]indole (norharman), and 1-methyl-pyrido[3,4-b]indole (harman) have been determined in the mainstream smoke condensate from three reference cigarettes, namely Kentucky reference 1R5F, Kentucky reference 2R4F, and CORESTA CM4. The amino-alpha-carbolines, and norharman and harman (beta-carbolines) can be classified as heterocyclic aromatic amines (HAAs) and are listed as biologically active agents in the mainstream smoke of cigarettes. For the analysis, the mainstream smoke condensate from cigarettes was collected on a filter pad, the analytes were isolated using solid-phase extraction (SPE), and quantified without derivatization on a GC-MS. Total amounts of carbolines found in the condensate increased from ultralight 1R5F to full-flavor CM4 cigarettes. The level of harman was about 250 ng/cigarette for the 1R5F cigarette and about 1025 ng/cigarette for the CM4 cigarette. Norharman was typically three times more abundant than harman. The AalphaC was found at about 10 times lower level compared to harman, and MeAalphaC was about 50 times lower than harman. The use of reference cigarettes can provide a common measure for laboratories to assess carboline amounts among cigarette brands.     

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。     

固相萃取-超高效液相色谱法测定卷烟主流烟气中丙烯酰胺

建立了一种固相萃取-超高效液相色谱法(SPE-UPLC)快速检测主流烟气中丙烯酰胺的方法。使用剑桥滤片和吸收瓶捕集主流烟气后,蒸馏水做萃取溶剂,采用C18固相萃取小柱对样品液进行纯化,用UPLC检测,外标法定量。UPLC方法采用ACQUITY UPLCTMBEH C181.7μm 2.1×50 mm色谱柱,柱温30℃,流动相为V(乙腈)∶V(水)=6∶94,流速为0.15 mL/min,紫外检测器(TUV)检测波长为202 nm,分析时间为6 min。烤烟型香烟主流烟气中丙烯酰胺的含量为4.75μg/cig。方法的线性范围为0.1~10 mg/mL,线性相关系数为0.9999;平均回收率为98.7%;检出限为10 ng/mL(S/N=3);相对标准偏差为2.3%。该方法适合主流烟气中丙烯酰胺的快速检测。     

在线液相-气相二维色谱高灵敏测定卷烟主流烟气中的4-（N-甲基亚硝胺基）-1-（3-吡啶基）-1-丁酮

建立了在线液相-气相二维色谱测定卷烟主流烟气中4-(N-甲基亚硝胺基)-1-(3-吡啶基)-1-丁酮(NNK)的方法。 NNK 的分析在在线凝胶气质联用仪上进行,采用自行装填的微型碱性氧化铝柱,并把仪器上的凝胶柱换成氧化铝柱,用于 NNK 的分析。捕集有主流烟气总粒相物的剑桥滤片用二氯甲烷提取,以 D4-NNK 为内标,提取液经微型氧化铝柱分离,含 NNK 的部位切割进入气相色谱,排干溶剂后启动气相色谱升温经毛细管柱进行分离,用质谱检测。本方法将烟气国标方法 NNK 测定中的氧化铝柱色谱净化和气相色谱-质谱分析在线连接起来,可不经样品前处理净化直接进样分析;每次进样可达40μL,是常规气相色谱-质谱分析最大进样量(2.0μL)的20倍,显著提高了分析灵敏度。方法线性范围达1.2~120 ng/ mL,相关系数为r=0.9998,回收率为93.9%~96.0%;检出限和定量限分别为0.25 ng/ mL 和0.9 ng/ mL,样品分析结果与中国烟草总公司企业标准方法进行对比,结果相符合。