GC/MS/MS和LC/MS/MS在现代农产品分析中的应用

介绍了食品安全的影响及食品中有害物质分析的特点，着重介绍了GC／MS／MS和LC／MS／MS法在食品中的农药残留和兽药残留的分析应用。     

GC/MS仪器与发展及其在环境监测中的应用

综述了近几年ＧＣ－ＭＳ仪器的发展及其在环境监测中的应用。台式、高灵敏度、操作简单、扫描速度快、价格低是未来 ＧＣ－ＭＳ的发展方向。各种不同的电离方式在环境监测中都得到广泛应用。尤其是负化学电离和 ＭＳＭＳ联用技术在农药残留的分析中具有灵敏度高,选择性好的独特优点。对环境水、空气和废气中ＶＯＣｓ、农药类（含除草剂）、ＰＡＨｓ、ＰＣＢｓ、恶臭化合物的分析作了评述。并详细介绍了样品的前处理方法,包括顶空（ＨＳ）、吹扫／捕集（Ｐ／Ｔ）、固相草取（ＳＰＥ）、固相微革取（ＳＰＭＥ）、ＰＴＶ、超临界流体萃取（ＳＦＥ）、ＣＡＮＩＳＴＥＲ采样罐、冷凝聚（ＣＦ）等。另外,对生物食品,二恶咽的分析及样品前处理进行了详细评述。     

气相色谱和质谱联用测定原始细菌Natronobacterium ma gadii中不活泼极性甘油脂的结构

本文报导了气相色谱和质谱联用利用电子电离 (EI)和化学电离 (CI)两种模式测定Natronobacteriummagadii中主要类脂的全甲基化衍生物的方法。实验数据显示 ,Natronobacteriummagadii和一般的原始细菌不一样 ,除含有传统的C2 0-C2 0 类脂甘油醚外 ,还存在一种不太常见的C2 0 -C2 5的类脂甘油醚。EI给出的碎片峰和CI给出的准分子离子峰使我们确证了C2 0 -C2 2 和C2 0 -C2 5结构的存在。质谱电子轰击法和化学电离法已成功地应用于测定原始细菌中主要不活泼类脂的烷基链结构 ,特别是电子轰击法的硬电离 ,获得了众多的烷基碎片峰 ,从而弥补了软电离ESI和APCI未能出现烷基碎片峰的不足。值得注意的是EI质谱显示出烷基是以直链 ,而并非有规律地按叔碳原子排列的支链 ,尽管这种说法尚需进一步确证     

猪肉内瘦肉增长素(MAT)的气相色谱-质谱检测(英文)

对用含瘦肉增长素 (MAT)的饲料喂养猪的猪肉样品进行检查。样品取自添加瘦肉增长素饲料喂养的 6头猪的不同部位 ,经生理盐水浸泡后 ,研磨成乳糜状 ,用乙醚提取。以 MT为内标进行 GC/ MS定量分析。实验结果表明 :41个样品呈阴性 ,只有 6号猪的右耳样品呈阳性 ,经内标定量计算 ,10 g右耳猪肉中含 2 .2 μg MAT。该实验提示可用 GC/ MS定性定量分析 MAT。     

LC/MS/MS法测定血清中的司可异罗叶松甘油二酯、司可异罗叶松酯素、肠内二醇和肠内脂

本实验用 β-葡萄糖醛酸苷酶酶解血清样品，采用电喷雾离子源，负离子MRM扫描,建立了血清中司可异罗叶松甘油二酯（SDG）、司可异罗叶松酯素(Seco)、肠内二醇（EL）、肠内脂(ED)的LC/MS/MS分析方法。本方法线性相关系数 r > 0.999 1，最低检出浓度(LOQ，S/N＝10)分别为SDG 50 ng/mL, Seco 5.0 ng/mL, EL 5.0 ng/mL, ED 5.0 ng/mL。空白血清加标回收率79.0%～105.6%，变异系数（CV，n＝6）<19.4%。该法灵敏可靠，样品处理简单，适用于血清中SDG、Seco、EL、ED的检测。     

质谱新技术在毒品分析中的应用

毒品分析是办理涉毒犯罪案件的重要环节之一,为案件侦破和证据收集提供重要依据。质谱分析法具有灵敏度高、分析速度快、所需样品量少等特点,因其出色的分析性能越来越受到分析人员的重视。本文综述了色谱质谱联用技术和新兴原位直接电离质谱技术在毒品分析领域的应用情况,并展望了质谱新技术在毒品分析领域的发展前景。     

Recent advances in mass spectrometry analysis of phenolic endocrine disruptors and related compounds

This article reviews recent literature on current methodologies based on chromatography coupled to mass spectrometry to analyze phenolic compounds with endocrine‐disrupting capabilities. For this review we chose alkylphenol ethoxylates, bisphenol A, bisphenol F, and their degradation products and halogenated derivatives, which are considered important environmental contaminants. Additionally, some related compounds such as bisphenol diglycidylethers were included. Growing attention has been paid to the mass spectrometric characterization of these compounds and the instrumentation and strategies used for their quantification and confirmation. The current use of gas chromatography–mass spectrometry (GC–MS) and liquid chromatography–mass spectrometry (LC–MS) methodologies with different mass spectrometers and ionization and monitoring modes is discussed. Practical aspects with regards to the use of these analytical techniques, such as derivatizing reagents in GC–MS, ion suppression in LC–MS, and the most problematic aspects of quantification, are included in the discussion. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:776–805, 2010     

Residue analysis of 500 high priority pesticides: Better by GC–MS or LC–MS/MS?

This overview evaluates the capabilities of mass spectrometry (MS) in combination with gas chromatography (GC) and liquid chromatography (LC) for the determination of a multitude of pesticides. The selection of pesticides for this assessment is based on the status of production, the existence of regulations on maximum residue levels in food, and the frequency of residue detection. GC-MS with electron impact (EI) ionization and the combination of LC with tandem mass spectrometers (LC-MS/MS) using electrospray ionization (ESI) are identified as techniques most often applied in multi-residue methods for pesticides at present. Therefore, applicability and sensitivity obtained with GC-EI-MS and LC-ESI-MS/MS is individually compared for each of the selected pesticides. Only for one substance class only, the organochlorine pesticides, GC-MS achieves better performance. For all other classes of pesticides, the assessment shows a wider scope and better sensitivity if detection is based on LC-MS.     

Multiclass mycotoxin analysis in food, environmental and biological matrices with chromatography/mass spectrometry

Mold metabolites that can elicit deleterious effects on other organisms are classified as mycotoxins. Human exposure to mycotoxins occurs mostly through the intake of contaminated agricultural products or residues due to carry over or metabolite products in foods of animal origin such as milk and eggs, but can also occur by dermal contact and inhalation. Mycotoxins contained in moldy foods, but also in damp interiors, can cause diseases in humans and animals. Nephropathy, various types of cancer, alimentary toxic aleukia, hepatic diseases, various hemorrhagic syndromes, and immune and neurological disorders are the most common diseases that can be related to mycotoxicosis. The absence or presence of mold infestation and its propagation are seldom correlated with mycotoxin presence. Mycotoxins must be determined directly, and suitable analytical methods are necessary. Hundreds of mycotoxins have been recognized, but only for a few of them, and in a restricted number of utilities, a maximum acceptable level has been regulated by law. However, mycotoxins seldom develop alone; more often various types and/or classes form in the same substrate. The co-occurrence might render the individual mycotoxin tolerance dose irrelevant, and therefore the mere presence of multiple mycotoxins should be considered a risk factor. The advantage of chromatography/mass spectrometry (MS) is that many compounds can be determined and confirmed in one analysis. This review illustrates the state-of-the-art of mycotoxin MS-based analytical methods for multiclass, multianalyte determination in all the matrices in which they appear. A chapter is devoted to the history of the long-standing coexistence and interaction among humans, domestic animals and mycotoxicosis, and the history of the discovery of mycotoxins. Quality assurance, although this topic relates to analytical chemistry in general, has been also examined for mycotoxin analysis as a preliminary to the systematic literature excursus. Sample handling is a crucial step to devise a multiclass analytical method; so when possible, it has been treated separately for a better comparison before tackling the instrumental part of the whole analytical method. This structure has resulted sometimes in unavoidable redundancies, because it was also important to underline the interconnection. Most reviews do not deal with all the possible mycotoxin sources, including the environmental ones. The focus of this review is the analytical methods based on MS for multimycotoxin class determination. Because the final purpose to devise multimycotoxin analysis should be the assessment of the danger to health of exposition to multitoxicants of natural origin (and possibly also the interaction with anthropogenic contaminants), therefore also the analytical methods for environmental relevant mycotoxins have been thoroughly reviewed. Finally, because the best way to shed light on actual risk assessment could be the individuation of exposure biomarkers, the review covers also the scarce literature on biological fluids.     

利用QuEChERS-UPLC-MS/MS法测定甘蓝、草莓中7种农药残留的实验条件优化探索

为了给农药残留检测工作提供新的技术和方法,建立了一种通过QuEChERS方法和超高效液相色谱-串联质谱法快速测定不同基质中多种农药残留的方法。样品用乙腈提取,经QuEChERS方法C18净化,以T3色谱柱(100 mm×2.1 mm×1.8 μm)通过超高效液相色谱分离,电喷雾离子源正离子多反应监测(MRM)模式进行测定。通过流动相、吸附剂种类和吸附剂用量的选择,以及加标回收率实验,建立和优化了QuEChERS-UPLC-MS/MS测定农药多残留的方法。结果表明：除咪鲜胺外,其他农药在1~200 μg/L范围内各待测物线性良好,高、中、低浓度回收率在93.4%~99.1%之间,变异系数小于4%,方法的检出限为0.1~1.0 μg/kg。基质效应对定量结果影响可忽略不计。QuEChERS-UPLC-MS/MS方法简便、快速、准确、灵敏、节省有机溶剂,可满足甘蓝、草莓中多种农药残留同时检测的实际需要。     

LC/MS用于匹多莫德有关物质结构鉴定

采用液相色谱-质谱（LC/MS）技术鉴定匹多莫德的有关物质,选取Sepax GP-C8色谱柱(250 mm×4.6 mm×5 μm),以甲醇-三氟乙酸溶液为流动相,梯度洗脱,对匹多莫德有关物质进行分离;采用电喷雾正离子化-高分辨飞行时间质谱法（ESI-TOF MS）测定各有关物质离子的准确质量和元素组成,三重四极杆串联质谱（ESI-MS/MS）测定子离子特征。结果表明：在所建立的条件下,匹多莫德及其有关物质的分离良好,检测并鉴定出11个主要有关物质。该技术能有效地分离鉴定匹多莫德中的有关物质,其鉴定结果可为质量控制和工艺优化提供参考。     

（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体的GC/MS研究

为了研究钯催化的2,4-二甲氧基苯甲酸与烯丙基丙二酸二乙酯的脱羧Heck反应的产物结构,建立了（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯同分异构体的分离与鉴定的气相色谱-离子阱质谱方法。首先通过脱羧Heck反应制得（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体混合物,然后利用GC/MS联用技术对混合物进行分析,得到各组分的EI和CI全扫描模式质谱信息。通过对照各组分的分子离子峰确定互为异构体的组分,再对异构体组分采用MS/MS模式获取各自的裂解碎片。通过分析异构体的不同的裂解碎片,讨论质谱裂解方式,从而确定异构体的结构。该方法省时、经济、高效,可为此类化合物的分析与鉴别提供参考。     

HPLC-MS/MS联用技术定量测定人血浆中奥洛他定浓度

建立HPLC-MS/MS方法定量测定人血浆中奥洛他定浓度。血浆样品在酸性条件下，经Tomtec全自动固相萃取仪处理后，以v（甲醇）:v(0.05%甲酸）＝50∶50溶液为流动相，经Alltima C₁₈色谱柱初步分离，利用串联质谱在正离子电离模式下，以多反应离子监测（MRM）方式定量测定奥洛他定及其内标。结果表明：奥洛他定的最低定量浓度为0.1 ng/mL，线性范围为0.1～100 ng/mL，精密度和准确度均在±15%以内。此方法专属、灵敏、准确，可以用于测定人血浆中奥洛他定浓度。     

Analytical strategies for identifying drug metabolites

With the dramatic increase in the number of new chemical entities (NCEs) arising from combinatorial chemistry and modern high-throughput bioassays, novel bioanalytical techniques are required for the rapid determination of the metabolic stability and metabolites of these NCEs. Knowledge of the metabolic site(s) of the NCEs in early drug discovery is essential for selecting compounds with favorable pharmacokinetic credentials and aiding medicinal chemists in modifying metabolic "soft spots". In development, elucidation of biotransformation pathways of a drug candidate by identifying its circulatory and excretory metabolites is vitally important to understand its physiological effects. Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have played an invaluable role in the structural characterization and quantification of drug metabolites. Indeed, liquid chromatography (LC) coupled with atmospheric pressure ionization (API) MS has now become the most powerful tool for the rapid detection, structure elucidation, and quantification of drug-derived material within various biological fluids. Often, however, MS alone is insufficient to identify the exact position of oxidation, to differentiate isomers, or to provide the precise structure of unusual and/or unstable metabolites. In addition, an excess of endogenous material in biological samples often suppress the ionization of drug-related material complicating metabolite identification by MS. In these cases, multiple analytical and wet chemistry techniques, such as LC-NMR, enzymatic hydrolysis, chemical derivatization, and hydrogen/deuterium-exchange (H/D-exchange) combined with MS are used to characterize the novel and isomeric metabolites of drug candidates. This review describes sample preparation and introduction strategies to minimize ion suppression by biological matrices for metabolite identification studies, the application of various LC-tandem MS (LC-MS/MS) techniques for the rapid quantification and identification of drug metabolites, and future trends in this field.     

GC-MS法测定煎炸食品中反式脂肪酸含量

本文建立了气相色谱-质谱法测定煎炸食品中反式脂肪酸含量的分析方法,油脂提取、皂化及甲酯化后,经DB-225ms毛细管柱分离,采用质谱全扫描方式外标法定量。结果表明：该方法快速、准确、分离良好,在10—100μg／mL浓度范围内线性良好,各反式脂肪酸组分检出限为0．03g／100g,含量测定的相对偏差均小于1O％,加标回收率在85．3％-91．8％之间,可作为检测煎炸食品中TFA含量的推广方法。     

气相色谱-质谱法测定茶叶中4种有机氯农药

The determination method of 4 organochlorine pesticides in tea by GC/MS was established. The extraction effectiveness of analytes with different extraction methods(shaking extraction and ultrasonic extraction) and different shaking time(40, 60 and 80 min) was compared. The results showed that shaking extraction 40 min was superior to other shaking time and ultrasonic extraction. This method is suitable to determine pyrethroid pesticides in tea.     

Application of mass spectrometry in the analysis of polybrominated diphenyl ethers

This review summarized the applications of mass spectrometric techniques for the analysis of the important flame retardants polybrominated diphenyl ethers (PBDEs) to understand the environmental sources, fate and toxicity of PBDEs that were briefly discussed to give a general idea for the need of analytical methodologies. Specific performance of various mass spectrometers hyphenated with, for example, gas chromatograph, liquid chromatograph, and inductively coupled plasma (GC/MS, LC/MS, and ICP/MS, respectively) for the analysis of PBDEs was compared with an objective to present the information on the evolution of MS techniques for determining PBDEs in environmental and human samples. GC/electron capture negative ionization quadrupole MS (GC/NCI qMS), GC/high resolution MS (GC/HRMS) and GC ion trap MS (GC/ITMS) are most commonly used MS techniques for the determination of PBDEs. New analytical technologies such as fast tandem GC/MS and LC/MS become available to improve analyses of higher PBDEs. The development and application of the tandem MS techniques have helped to understand environmental fate and transformations of PBDEs of which abiotic and biotic degradation of decaBDE is thought to be one major source of Br_1‐9BDEs present in the environment in addition to direct loading from commercial mixtures. MS‐based proteomics will offer an insight into the molecular mechanisms of toxicity and potential developmental and neurotoxicity of PBDEs. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:737–775, 2010     

在线凝胶色谱-串联三重四极杆质谱法测定大豆油中42种农药残留

建立了在线凝胶色谱-串联三重四极杆质谱（GPC-GC-MS/MS）法测定大豆油中的42种农药残留。采用在线凝胶色谱进行在线净化,除去大豆油中大部分油脂,有效缩短样品前处理时间;结合多反应监测（MRM）采集方式,可减少基质干扰,提高方法的选择性。结果表明：在1~50 μg/L浓度范围内,大部分农药的线性相关系数均在0.999以上;方法检出限为0.02~2.59 μg/kg,方法定量限为0.08~8.62 μg/kg;在10、50、300 μg/kg加标浓度下,农药的加标回收率在70.4%~119%之间。以α-666等11种农药为例,比较了GPC-GC-MS/MS法、GPC-GC/MS法、GC-MS/MS法的实验结果,发现采用GPC-GC-MS/MS法的MRM数据采集模式测定大豆油中农药残留具有良好的抗基质干扰能力,可获得最低的方法检出限及最高的回收率。该方法操作简单、灵敏度高、稳定性好,可用于大豆油中农药残留的测定,也适用于复杂基质中痕量农药残留的定性和定量分析。     

裂解气质联用技术用于微量物证中的聚乙烯分析

Pyrolysis and GC/MS methods were applied to the determination of Polythene in forensic micromaterial evidence in criminal analysis. Pyrolysis’ temperature was 700 ℃, and characteristic peak and corresponding mass fragment peak were used to qualitative analysis.