便携式气相色谱-质谱联用技术的应用进展

实时、原位的现场检测技术可以大大提高化学分析工作的速度与效率,特别是在环境损害应急事故、军事化学毒物威胁、刑事侦查鉴定取证等紧急情形中发挥重要作用。近年来,便携式气相色谱-质谱联用(GC-MS)技术的发展使得在受控实验室之外进行准确可靠的确证分析具有了可行性。本文概述了便携式GC-MS技术的发展历程、技术特点与国内应用现状,并总结了该设备在化学战剂识别、爆炸物检测、火灾调查、毒品分析等应急检测领域的应用进展,为国内科研工作者提供借鉴与参考。     

岩香菊精油的气相色谱-气相色谱-质谱联用分析

在植物挥发油等复杂有机混合物的气相色谱-质谱联用(GC-MS)分析中,常遇到分离不良的色谱峰,所取得的质谱不易识别和解析。多维色谱法则是解决复杂有机混合物分离的有力工具。对质谱工作而言,把多维色谱的卓越分离能力与质谱仪的定性鉴定能力结合起来,构成一个气相色谱-气相色谱-质谱联用(GC-GC-MS)系统,就能大大改进常规GC-MS系统的功能,但有关报道很少,尚未得到     

气相色谱-离子阱二级质谱测定食品中丙烯酰胺残留

建立了一种基于气相色谱-离子阱二级质谱(GC-MS/MS)检测食品(薯条,薯片,咖啡,饼干和膨化食品)中丙烯酰胺残留量的方法。样品中丙烯酰胺采用去离子水提取,正己烷脱脂后石墨化碳黑小柱净化,溴水衍生后GC-MS/MS进行分析。方法在10-1 000μg.L-1浓度范围内呈线性关系,相关系数为0.999,检出限为4.02μg.kg-1,在10,100,1 000μg.kg-1三个水平的相对标准偏差为8%-12%,回收率为68.3%-105.2%。结果表明,相对于GC-MS方法,GC-MS/MS分析时间短、无杂质峰干扰、灵敏度高,可以满足食品的丙烯酰胺检测大批量筛选要求。     

气相色谱-四极杆-飞行时间质谱和气相色谱-串联质谱对水果、蔬菜中208种农药残留筛查确证能力的对比

对比研究了气相色谱-串联质谱(GC-MS/MS)与气相色谱-四极杆-飞行时间质谱(GC-QTOF/MS)在水果、蔬菜中208种农药多残留检测中基质效应及方法学效能的差异,提出两种仪器在农药残留检测方面的特点和适用范围,为残留检测分析提供参考。在苹果、柑橘、番茄、黄瓜4种基质,3个添加浓度(5.0、10.0和20.0 μg/kg)下,两种仪器中均有93.0%以上的农药回收率在70%~120%范围内且相对标准偏差(RSD)≤20%(n=5)。检测灵敏度方面,绝大部分农药在两种仪器的检出限均低于5.0 μg/kg,满足各国农药残留限量的要求,且GC-MS/MS灵敏度更高,线性范围更宽,定量能力更加准确。筛查确证方面,GC-QTOF/MS在快速、高通量筛查、准确定性及非目标化合物鉴定等方面表现出了优势。     

硝西泮、氯硝西泮甲基衍生物的气相色谱-质谱分析

对硝西泮和氯硝西泮的衍生化条件、色谱及质谱行为进行了研究,确立了猪肉中硝西泮、氯硝西泮残留的GC-MS检测方法.应用5因素4水平的正交试验,最终确定衍生化条件为反应温度60℃、反应时间30 min、丙酮用量0.5 mL、衍生化试剂20μL、催化剂无水碳酸钾20mg,在此条件下可生成较完全的甲基衍生物.衍生物具有较好的气相色谱和电子轰击质谱行为.硝西泮衍生物的分子离子峰为m/z 295,基峰离子为m/z 267,主要碎片离子分别为m/z 206、220、248、294;氯硝西泮衍生物的分子离子峰为m/z 329,基峰离子为m/z 328,主要碎片离子分别为m/z205、220、248、266、294、331,并对这些离子的产生进行了解析.这些离子均具有较强的相对丰度,可作为其微量检测的多离子选择定性和确证,而基峰离子可用于单离子选择定量.用乙腈提取药物,C18固相萃取柱净化,GC-MS分析.本方法采用外标法定量,两种药物的标准曲线线性回归系数均在0.99以上,线性范围20～500 μg/L,回收率80%左右,相对标准偏差6.9%～14.9%,检出限16.7 μg/kg.     

超高效合相色谱及气相色谱-质谱联用测定茶叶中联苯菊酯

建立了UPC2检测茶叶中联苯菊酯的方法。样品经石油醚提取,Waters Sep-Pak襆 Carbon NH2固相萃取柱萃取,采用 UPC2对茶叶中的联苯菊酯进行检测。流动相以CO2为主体,乙腈为助溶剂进行梯度洗脱。选用ACQUITY UPC2TM BEH色谱柱(100 mm伊3.0 mm,1.7μm),流速1.5 mL/min,检测波长220 nm。方法确定的实验条件下,信噪比(S/N)=3确定的检出限为20μg/L;联苯菊酯线性范围为0.32~10.30 mg/L;加标回收率为88.7%~98.2%;相对标准偏差为1.4%~2.8%。与GC-MS方法进行比较,结果表明,UPC2检测茶叶中联苯菊酯比GC-MS更加高效快速,方便简单,成本低廉,能够满足茶叶中联苯菊酯的检测要求。并对能力验证的茶叶样品中联苯菊酯的检测进行了UPC2与GC-MS的比较,结果满意。     

气相色谱-质谱联用法测定大蒜中的嘧霉胺、噻螨酮残留量

建立了大蒜中嘧霉胺、噻螨酮残留量的气相色谱-质谱联用(GC-MS)检测方法.大蒜样品经过微波处理,乙酸乙酯提取,硅胶柱净化,采用EI源、选择离子监测方式(SIM),并通过基质添加标准消除了基质效应.结果证明,方法定量下限噻螨酮为0.01 mg/kg,嘧霉胺为0.001 mg/kg,加标回收率范围73.5%～97.8%,相对标准偏差在2.3%～12.5%之间,该方法可实现快速、灵敏、准确的检测分析.     

聚γ-谷氨酸对气相色谱-质谱检测地衣芽孢杆菌胞内代谢物的影响

通过添加外源聚γ-谷氨酸(γ-PGA),利用气相色谱-质谱法(GC-MS)评估了γ-PGA对地衣芽孢杆菌胞内代谢物检测的影响。结果表明:终浓度为10g/L的γ-PGA会使除谷氨酸外的氨基酸、有机酸和糖类标准品的检测峰面积明显降低;另外,终浓度为10g/L的γ-PGA对分析地衣芽孢杆菌胞内代谢物中的谷氨酸、葡萄糖和6-磷酸葡萄糖(G6P)的影响较为显著。因此,在利用GC-MS定量分析地衣芽孢杆菌的胞内代谢物前,应将γ-PGA和细胞分离。     

顶空气相色谱-质谱联用技术的应用进展

顶空分析作为一种无有机溶剂萃取的样品处理技术,通常与气相色谱-质谱（GC-MS）技术结合用来分析复杂基质中的挥发性有机物。顶空气相色谱-质谱（HS-GC-MS）技术具有快速、高效、环保、灵敏度高等特点,在常规分析中发挥着重要作用。该文简要概述了静态顶空、动态顶空、顶空固相微萃取分析以及GC-MS联用技术,并介绍了整个顶空分析系统的影响因素和优化过程。根据基质类型的分类,综述了HS-GC-MS在食品和饮料、环境、生物等样品中的应用实例。HS-GC-MS的研究非常活跃,不断出现新应用,在分析挥发性有机物方面具有广阔前景。     

热分析-傅里叶红外光谱-气相色谱-质谱联用技术分析果胶的热分解产物

将热分析-傅里叶红外光谱-气相色谱-质谱组成同步联用检测系统,对果胶在N2气和N2/O2氛围中,243、270和335 ℃ 3个温度点的热解产物经傅里叶红外光谱和GC-MS进行同步分析,在2种氛围下共检测鉴别了26种热分解产物。     

Mass spectrometry/gas chromatography-mass spectrometry approach for rapid screening/quantitative determination of perchloroethylene in air

A new mass spectrometry/gas chromatography-mass spectrometry (MS/GC-MS) approach has been developed for the screening and quantitative determination of perchloroethylene (PERC) in workplace and outdoor air samples, which could be extended to the screening and analysis of other analytes and samples. This approach may be rapidly modified in order to be used directly as an MS detector for screening purposes or alternatively as a common GC-MS, for confirmation. The screening alternative by MS is approximately 20 times faster than the quantitative-confirmatory determination by GC-MS. Detection limits of both alternatives are sufficiently low to screen and determine PERC in the above-mentioned matrixes. The advantage of this approach over others previously described is that, in the present case, the sample passes through the chromatographic column only when the confirmatory GC-MS is used. For the MS screening method, the chromatographic column is bypassed by using an appropriate selection valve. In this way, the column lifetime is extended and screening time is considerably shortened.     

Identification of certain chemical agents in complex organic solutions by gas chromatography/tandem mass spectrometry

Analytical methods that are used for the detection and identification of chemicals related to the Chemical Weapons Convention in complex organic solutions were developed. A matrix modified by the addition of complex diesel oil background compounds and interferences was used for the development of a gas chromatography-mass spectrometry or gas chromatography-tandem mass spectrometry (GC-MS or GC-MS/MS) method for unambiguous identification of the scheduled chemicals. Co-elution of diethyl N,N-dimethylphosphoramidate and ethyl N,N-dimethylphosphoramidocyanidate, which are not separated by GC, was identified by GC-MS. Although GC-MS can identify the compounds, GC-MS/MS identification has greater accuracy and sensitivity in the case of complex matrixes. Four scheduled chemicals were accurately and selectively identified against numerous interfering substances by GC-MS/MS. The fragmentation chemistry of these compounds using MS/MS analysis was investigated.     

Quantification of Transformation Products of Unsymmetrical Dimethylhydrazine in Water Using SPME and GC-MS

Quantification of trace concentrations of transformation products of rocket fuel unsymmetrical dimethylhydrazine (UDMH) in water requires complex analytical instrumentation and tedious sample preparation. The goal of this research was to develop a simple and automated method for sensitive quantification of UDMH transformation products in water using headspace (HS) solid-phase microextraction (SPME) in combination with GC-MS and GC-MS/MS. HS SPME is based on extraction of analytes from a gas phase above samples by a micro polymer coating followed by a thermal desorption of analytes in a GC inlet. Extraction by 85 µm Carboxen/polydimethylsiloxane fiber at 50 °C during 60 min provides the best combination of sensitivity and precision. Tandem mass spectrometric detection with positive chemical ionization improves method accuracy and selectivity. Detection limits of twelve analytes by GC-MS/MS with chemical ionization are about 10 ng L^?1. GC-MS provides similar detection limits for five studied analytes; however, the list of analytes detected by this method can be further expanded. Accuracies determined by GC-MS were in the range of 75–125% for six analytes. Compared to other available methods based on non-SPME sample preparation approaches (e.g., liquid–liquid and solid-phase extraction), the developed method is simpler, automated and provides lower detection limits. It covers more UDMH transformation products than available SPME-based methods. The list of analytes could be further expanded if new standards become available. The developed method is recommended for assessing water quality in the territories affected by space activities and other related studies.     

Analysis of acetamiprid in vegetables using gas chromatography-tandem mass spectrometry.

A new analytical method has been validated for determining the insecticide acetamiprid in vegetables using gas chromatography (OC) and different mass spectrometric detection techniques, such as full-scan mass spectrometry (MS), and tandem mass spectrometry (MS/MS). For this purpose, a previous extraction of the vegetable sample was carried out with ethyl acetate. In GC-MS/MS, the lowest detectable concentration was 0.001 mg kg(-1), the average recovery rates at various fortification levels (0.015 and 0.030 mg kg(-1)) ranged between 82.4 and 85.7% and the relative standard deviations were lower than 12.2% in all cases.     

气相色谱-质谱法测定乳制品中光引发剂异丙基硫杂蒽酮的残留量

建立了采用气相色谱（GC）-质谱(MS)检测由包装材料迁移到乳制品中的光引发剂异丙基硫杂蒽酮残留量的方法。使用氘代蒽为内标,样品经Carrez试剂除蛋白质后用丙酮-正己烷(体积比为1∶1)提取,上层提取液用氟罗里硅土固相萃取小柱净化。采用单四极杆质谱进行样品筛选和定量,选取的监测离子为m/z 184,m/z 224,m/z 239,m/z 254(异丙基硫杂蒽酮)和m/z 80,m/z 94,m/z 188,m/z 160(氘代蒽)。疑似样品采用离子阱串联质谱法进行确证,选取的母离子和子离子分别为m/z 254,m/z 239(异丙基硫杂蒽酮)和m/z 188,m/z 160(氘代蒽)。本方法的测定低限(LOQ)分别为7.0 μg/L(GC-MS)和5.0 μg/L(GC-MS/MS),回收率为74.9%~89.6%。采用该方法对11种不同类型的乳制品进行了检测,发现了两例阳性样品。     

气相色谱-三重四极杆串联质谱法检测环境空气中的多环芳烃

建立了气相色谱-三重四极杆串联质谱检测环境空气中多环芳烃的方法,并利用同位素稀释法对多环芳烃进行了测定。将该方法应用于华南地区某大型石化企业周边环境空气中多环芳烃的检测,并与气相色谱-质谱方法进行了对比。结果表明,该方法的仪器检出限（0.01~0.15 μg/L）和定量限（0.03~1.5 μg/L）均优于气相色谱-质谱法（0.1~0.8 μg/L和0.3~3.5 μg/L）,并有更好的灵敏度与选择性。当利用气相色谱-质谱作为检测手段时,回收率指示物氘代菲和进样内标六甲基苯均受到了杂质的严重干扰,影响了定量结果的准确性,而三重四极杆串联质谱很好地解决了这些问题。实际样品分析时,标准曲线中16种多环芳烃相对响应因子的相对标准偏差为2.60%~15.6%,氘代化合物的回收率为55.2%~82.3%,空白加标样品的回收率为98.9%~111%,平行样品的相对标准偏差为6.50%~18.4%,采样空白含量范围为未检出~44.3 pg/m³,实验室空白含量范围为未检出~36.5 pg/m³。上述研究表明,分析环境空气中的多环芳烃时,气相色谱-三重四极杆串联质谱方法值得推广。     

气相色谱-串联质谱法快速测定调味品中3种糠醛类物质

建立了同时测定调味品中糠醛、5-甲基糠醛和5-羟甲基糠醛的气相色谱-串联质谱法(GC-MS/MS)。对样品的前处理方法及GC-MS/MS分析条件进行优化,样品经乙酸乙酯萃取,GC-MS/MS多反应监测模式(MRM)进行测定。3种糠醛类物质在0.001～20 mg/L范围内均呈良好的线性关系,相关系数为0.999 0～0.999 5;检出限(S/N=3)均为0.005 mg/kg,加标回收率为86%～95%。该法简便、快速、溶剂用量少,可消除调味品中复杂基质的干扰,结果准确可靠、灵敏度高,适用于调味品中3种糠醛类物质的同时测定。     

气相色谱-质谱法检测饮用水新生含氮消毒副产物氯代乙酰胺

建立了气相色谱-质谱(GC-MS)法检测饮用水中新生致突变含氮消毒副产物(N-DBPs)二乙酰胺(DCAcAm)和三乙酰胺(TCAcAm)的分析方法.考察了GC/MS和GC/ECD两种检测仪器及不同样品前处理技术对氯代乙酰胺(CAcAms)的检测效果.对比发现,酸催化水解+GC/ECD的分析方法容易受其它消毒副产物(DBPs)的影响,直接液液萃取(LLE)+GC/MS更适合CAcAms的分析;乙酸乙酯(ETAC)的萃取效果优于DBPs分析常用萃取剂甲基叔丁基醚(MTBE).在选定条件下,DAcAm和TAcAm在10～1000 μg/L的范围内线性关系良好,r＞0.9995; 方法回收率在82.0%～111.9%之间;RSD小于10%;检出限(MDL)和测定限(RQL)均低于1 μg/L.     

One step derivatization with British Anti-Lewsite in combination with gas chromatography coupled to triple-quadrupole tandem mass spectrometry for the fast and selective analysis of inorganic arsenic in rice

We developed a new fast and selective analytical method for the determination of inorganic arsenic (iAs) in rice by a gas chromatography – tandem mass spectrometry (GC-MS/MS) in combination with one step derivatization of inorganic arsenic (iAs) with British Anti-Lewsite (BAL). Two step derivatization of iAs with BAL has been previously performed for the GC-MS analysis. In this paper, the quantitative one step derivatization condition was successfully established. The GC-MS/MS was carried out with a short nonpolar capillary column (0.25 mm × 10 m) under the conditions of fast oven temperature ramp rate (4 °C/s) and high linear velocity (108.8 cm/s) of the carrier gas. The established GC-MS/MS method showed an excellent linearity (r² > 0.999) in a tested range (0.2–100.0 μg L⁻¹), ultra-low limit of detection (LOD, 0.08 pg), and high precision and accuracy. The GC-MS/MS technique showed far greater selectivity (22.5 fold higher signal to noise ratio in rice sample) on iAs than GC-MS method. The gas chromatographic running time was only 2.5 min with the iAs retention time of 1.98 min. The established method was successfully applied to quantify the iAs contents in polished rice. The mean iAs content in the Korean polished rice (n = 27) was 66.1 μg kg⁻¹ with the range of 37.5–125.0 μg kg⁻¹. This represents the first report on the GC-tandem mass spectrometry in combination with the one step derivatization with BAL for the iAs speciation in rice. This GC-MS/MS method would be a simple, useful and reliable measure for the iAs analysis in rice in the laboratories in which the expensive and element specific HPLC-ICP-MS is not available.     

气相色谱-串联质谱法测定皮革和纺织品中的富马酸二甲酯

建立了气相色谱-串联质谱(GC-MS/MS)准确、快速测定皮革和纺织品中富马酸二甲酯(DMF)的分析方法。样品经乙酸乙酯提取、浓缩及固相萃取柱净化处理,通过VF-5ms色谱柱分离、串联质谱对DMF进行定性和定量分析。实验结果表明: 优化样品预处理条件、固相萃取条件、质谱分析条件后,该方法可进一步消除杂质干扰,结果准确可靠,灵敏度、精密度、线性关系良好,回收率较高。3种浓度水平的加标回收率(n=6)保持在84%～93%之间,相对标准偏差小于7.2%;DMF在8种皮革和纺织品中的检出限 (S/N=3)为0.012～0.039 mg/kg, 0.05～100 mg/L质量浓度范围内线性相关系数为0.9990,适用于皮革和纺织品中DMF的日常检测。