超高效液相色谱法快速分离卷烟主流烟气中8种羰基化合物

建立了超高效液相色谱法(UPLC),分离卷烟主流烟气中8种羰基化合物。采用Acquity UPLC BEH 2-EP色谱柱(100×3mm,1.7μm)分离,以纯水-乙腈/异丙醇/四氢呋喃(89.9∶10∶0.1,V/V/V)为流动相,等度洗脱8种羰基化合物在12min内可实现有效分离。采用建立的UPLC法和高效液相色谱法对卷烟主流烟气中8种羰基化合物进行分离,结果表明,相比于传统的高效液相色谱法,UPLC法更为快速、高效。     

溶液捕集-高效液相色谱法测定卷烟主流烟气中主要羰基化合物

卷烟主流烟气中的羰基化合物用含2,4-二硝基苯肼的乙腈-磷酸溶液为吸收液进行捕集,并在此溶液中使羰基化合物衍生化,所得衍生化产物供高效液相色谱分析。采用Merck LichrosphereRP C₁₈色谱柱进行分离,并用不同配比混合的水-乙腈-四氢呋喃-异丙醇（59+30+10+1）、水-乙腈-四氢呋喃-异丙醇（33+65+1+1）和乙腈的混合液作为流动相进行梯度淋洗,用紫外检测器于波长365 nm处测定。方法的检出限（3S/N）在0.04～0.12μg·g^-1之间。方法用于卷烟主流烟气的分析,回收率在75.0%～96.0%之间,测定值的相对标准偏差（n=5）在2.0%～9.3%之间。     

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。     

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.     

高效液相色谱法同时测定化妆品中七种性激素

建立了化妆品中7种性激素(雌二醇、雌三醇、雌酮、睾酮、甲基睾酮、孕酮、己烯雌酚)同时测定的高效液相色谱法。先在试样中加入20 g/L氢氧化钠溶液与油脂进行皂化反应,然后用二氯甲烷-乙酸乙酯(体积比为40∶1)混合液在酸性条件下(pH 3)萃取,选择XTerraTMRP18色谱柱,以水-甲醇-乙腈(体积比为50∶32∶18)混合液为流动相,在波长230 nm处检测。7种性激素分离良好并排除了样品中杂质峰的干扰,低、高浓度平均回收率范围为75.6%~97.8%;相对标准偏差为1.9%~7.2%;检出限为3.7     

液相色谱-串联质谱法测定饲料中三聚氰胺残留

应用液相色谱-串联质谱法测定饲料中三聚氰胺残留。试样用V(乙腈)∶V(H2O)=1∶1溶液,提取,高速离心后,供液相色谱-串联质谱仪定性定量分析。流动相为V(乙腈)∶V(H2O)=80∶20混合溶液。采用电喷雾离子源,定性离子对为127.2/85.2和127.2/68.2;定量离子对为127.2/85.2。在添加了0.5~10.0 mg/kg的三聚氰胺标准品时的回收率为92.6%~103.2%;相对标准偏差(RSD)在0.8%~2.0%;检出限为0.2 mg/kg。     

高效液相色谱法测定卷烟滤嘴对主流烟气中低分子醛酮化合物的截留效率

用高效液相色谱法测定了用过的烟嘴中8种低分子醛酮化合物,据此对烟嘴从主流烟气中截留8种化合物的效率。烟嘴样品用衍生试剂溶液与甲醇(10+90)混合液30 mL萃取10min,分取适量萃取液供高效液相色谱分析。以DIONEX Explosives色谱柱为分离柱,用乙腈和水以不同比例混合的溶液为流动相进行梯度洗脱,在检测波长365nm处进行测定。8种低分子醛酮化合物在一定质量浓度范围内与其峰面积呈线性关系,方法的检出限(3s)在0.07~0.15mg·L-1之间。加标回收率在85.1%~102%之间,测定值的相对标准偏差(n=5)小于6.8%。     

微波辅助提取样品-正相液相色谱法测定面粉中有机锡化合物

面粉样品用乙酸-正己烷（20+80）溶液提取,所得提取液高速离心后于50℃旋转蒸发至2 mL,用流动相定容至8 ml,并用高效液相色谱法测定样品中有机锡化合物含量。选用CN基色谱柱作固定相,用正己烷-乙腈-四氢呋喃（97+1+2）溶液作流动相,二极管阵列检测器测定波长为214 nm。5种有机锡化合物的检出限（3S/N）在0.14～0.31 mg·L^-1之间。以空白面粉样品为基体进行加标回收试验,所得回收率在82%～95%之间。     

固相萃取-高效液相色谱法测定乳及乳制品中土霉素、四环素和金霉素残留

建立了固相萃取-高效液相色谱同时测定乳及乳制品中土霉素、四环素和金霉素的方法。样品经pH 4.0的Na2EDTA-mcllvaine缓冲溶液漩涡超声提取后,采用Oasis HLB固相萃取(SPE)小柱净化,洗脱液用N2吹至近干后用流动相溶解并定容,过PTFE滤膜后在Shiseido MG C18色谱柱上,以V(乙腈):V(10 mmol/L草酸)=27∶73的溶液为流动相进行分离,检测波长为360 nm。在最优的色谱条件下,各目标化合物的加标回收率为83.0%~109.2%,相对标准偏差在2.8%~6.1%之间。3种抗生素含量在0.10~20.0 mg/L范围内线性关系良好,相关系数≥0.999,乳及乳制品中土霉素、四环素和金霉素的检出限分别为10,10和20μg/kg。     

LC-ESI/MS分析食品中微量苏丹红Ⅰ~Ⅳ

建立了准确可靠的用LC-ESI/MS分析食品中4种苏丹红色素的方法。样品中的苏丹红用乙腈提取,不需纯化。色谱柱为AgilentC18(15cm×2.1mm,3μm),流动相为乙腈-0.5%乙酸溶液(体积比72∶28)。采用正离子电离方式,每种化合物选择3个碎片离子为定性离子以获得高选择性,选取每个化合物丰度最高的碎片为定量离子以获得高灵敏度。4种苏丹红色素的检出限(LOD)和定量下限(LOQ)均为ng/g水平。标准加入量为0.2μg/g水平时的回收率为86%~98%,且重复性良好。本方法仪器分析时间仅需8min,适合于大量样品的日常快速分析。     

超高效液相色谱β-环糊精流动相添加剂法分析卷烟主流烟气中7种酚类化合物

以β-环糊精(β-CD)作为流动相添加剂,建立了一种超高效液相色谱(UPLC)快速分析卷烟主流烟气中对苯二酚、间苯二酚、邻苯二酚、苯酚、对甲酚、间甲酚、邻甲酚的方法。卷烟主流烟气中7种酚类化合物采用YC/T 255-2008标准方法收集,萃取液经0.22 μm微孔滤膜过滤后直接进行UPLC分析。采用ACQUIT UPLC BEH Shield RP18色谱柱,以含有4 g/L β-CD的流动相进行梯度洗脱,采用优化后的荧光检测条件进行检测,分析时间为10 min。实验结果表明: 与目前国内外普遍应用的HPLC方法相比,该方法实现了间甲酚和对甲酚异构体的有效分离,7种酚类化合物的荧光响应强度显著增加。7种酚类化合物在该方法的线性范围内线性关系良好(r＞0.9999), 3个加标水平上平均回收率为95.5%～103.5%,相对标准偏差(RSD)均小于4%,方法的检出限为4～14 ng/cig。     

卷烟主流烟气中NNK测量不确定度评定

对气相色谱-热能分析联用法测定卷烟主流烟气总粒相物中NNK含量的测量不确定度进行评定,分析了NNK含量检测的影响因素,计算了不确定度分量及合成不确定度,当NNK含量测定结果为27．4ng／支时,扩展不确定度为2．0ng／支。     

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。     

Gas chromatographic-mass spectrometric analysis of acrylamide and acetamide in cigarette mainstream smoke after on-column injection

A method is described for the simultaneous determination of two short-chained amides, acrylamide and acetamide (classified by the International Agency for Research on Cancer as probable and possible human carcinogens, respectively), in total particulate matter using gas chromatography-on-column injection and mass spectrometric detection. Sample preparation is kept to a minimum, and the proposed analytical procedure proves to be fast, sensitive, and precise. Validation studies show good linearity with a regression coefficient of r2=.000 for both compounds. Quantitation limits are 32 ng/mL for acrylamide and 70 ng/mL for acetamide. In the particulate phase of mainstream smoke from the University of Kentucky Reference Cigarette 2R4F, 2.3 microg/cig acrylamide and 4.7 microg/cig acetamide are found; no acetamide and only .0074 microg/cig acrylamide is found in the gas phase. Possible mechanisms of formation in cigarette smoke are discussed.     

An UPLC‐MS3 Method for Rapid Separation and Determination of Four Tobacco‐specific Nitrosamines in Mainstream Cigarette Smoke

An ultra‐high‐pressure liquid chromatography/MS³ (UPLC‐MS³) method has been developed and validated for the quantitative determination of four major TSNAs in mainstream cigarette smoke using MS³ scan mode on a hybrid triple quadrupole‐linear ion trap mass spectrometer. The new method combining the UPLC with MS³ scan mode offers decreased sample analysis time and good selectivity. After mainstream cigarette smoke was collected on a Cambridge filter pad, the particulate matter was extracted with ammonium acetate solution and analyzed by UPLC‐MS³ using isotopically labeled analogues as internal standards. Four TSNAs were completely separated on an Agilent XDB‐C₁₈ UPLC column using isocratic elution during a 6 min LC run time. Excellent linearity was obtained over the concentration range of 1.0‐150.0 ng/mL for all TSNAs with values for correlation coefficient (r) between 0.9985‐0.9994. Limits of detection (LOD) of each TSNA varied from 0.023 to 0.067 ng/mL, and lower limits of quantification (LLOQ) varied from 0.077 to 0.223 ng/mL, respctively. The recovery of each TSNA was from 89.2 to 106.8%. The method achieved excellent reproducibility with RSD 2.1‐6.8% for intra‐assay and 3.4‐9.1% for inter‐assay. This method can be used as an effective approach to significantly improve the detection capability for TSNAs in complex matrices.     

Analysis of pyridines in mainstream cigarette smoke

A new technique has been developed for the quantitative analysis of pyridines in mainstream cigarette smoke using a GC-MS technique. For analysis, 10 cigarettes are smoked using conditions based on US Federal Trade Commission recommendations. The smoke is collected in a water trap and analyzed using a GC-MS technique. A standard or a fast GC separation can be applied for the analysis. The standard separation was followed by MS detection using selected ion monitoring (SIM) acquisition on a quadrupole instrument. The fast GC was followed by MS detection with total ion acquisition on a time-of-flight instrument. The levels of pyridine depend on the type of cigarette: for a full flavor cigarette pyridine is as high as 18.0 microg/cigarette (cig.). and for an ultra light cigarette is about 3.0 microg/cig. Substituted pyridines vary between 5.0 microg/cig. to 0.1 microg/cig. for a full flavor cigarette, and between 0.2 microg/cig. and a few ng/cig. for an ultra light cigarette. The reproducibility of the technique is very good, with less than 7-8% RSD in both separation procedures for most of the analyzed compounds.     

固相萃取-气相色谱/质谱联用法测定卷烟主流烟气中的香兰素和乙基香兰素

采用固相萃取-气相色谱/质谱联用技术,建立了一种同时测定卷烟主流烟气中香兰素和乙基香兰素的方法。方法优化了萃取条件,考察了萃取溶剂、萃取时间对检测结果的影响。通过硅藻土固相萃取柱净化并浓缩后,选取DB-HeavyWAX毛细管柱进行目标物分离,以香兰素-d3作为内标,对香兰素和乙基香兰素进行定量分析。结果表明,香兰素和乙基香兰素在浓度0.2~20.0 mg/L范围内具有良好的线性关系,其检出限分别为9.1 ng/支和6.5 ng/支,回收率均在96.3%~107.7%之间。     

Rapid and sensitive method for simultaneous determination of six carcinogenic aromatic amines in mainstream cigarette smoke by liquid chromatography/electrospray ionization tandem mass spectrometry

Aromatic amines are one of the sources of carcinogenicity in cigarette and tobacco smoke. Accurate quantification of these chemicals is needed to assess public health risk. A new validated rapid, sensitive and analyte specific liquid chromatography/electrospray ionization tandem mass spectrometric (LC/MS/MS) method has been developed for the simultaneous determination of six aromatic amines in mainstream cigarette smoke using research reference cigarette 2R4F. Three popular Indian brand cigarettes were also analyzed using the same procedure. The limit of detection of this method ranged from 0.04 to 0.59 ng/cig using an injection volume of 7 μl. The identification of each amine was established by chromatographic retention times, analyte specific fragmentation pattern and relative peak area ratios of two product/precursor ion pairs. The method showed excellent reproducibility and was also rapid, selective and robust for aromatic amine determination from cigarette smoke.     

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。