水样中痕量黑索今的快速质谱法检测

近年来,以RDX为代表的痕量爆炸物检测已经是反恐斗争和国土安全领域的重要课题[1]。本实验将醋酸作为辅助试剂直接添加到待分析水样中,采用电喷雾电离直接进样,在正离子检测模式下,建立了直接快速测定水样中衡量RDX的电喷雾质谱分析方法。在样品流量为10.0μL/m in,喷雾电压为5.0 kV,毛细管温度为200℃条件下获得的RDX的检出限为0.001μg/L,线性范围为0.005~100μg/L。对天然湖水、矿泉水和自来水中添加的衡量RDX的回收率分别在92%~108%之间。单个样品分析(含串联质谱分析)所需时间不超过2 m in。     

激光质谱法分析纸上样品

报道了用激光微探针飞行时间质谱仪进行纸上样品分析的可行性.对纸上涂布的痕量罗丹明B(Rhodamine B)和罗丹明 6G(Rhodamine 6G)进行测试,结果表明纸上分析有极高的灵敏度(优于5×10~(-17)mol)和信噪比,纸纤维干扰峰少;采用液相基体在纸上进行四苯基卟啉(TPP)金属络合物分子量测定也取得良好效果;对纸上样品分析的基体选择进行了研究,表明液相基体明显优于固相基体.激光质谱对纸上有机物作高灵敏度直接测定为某些特殊分析应用如安全检查、刑事侦察和食品卫生检查等提供了新方法.     

质谱快速分析猪肉中痕量沙丁胺醇及克伦特罗

采用内部萃取电喷雾电离质谱( iEESI-MS)技术,在无需样品预处理的前提下,采用标准加入法直接对猪肉组织中沙丁胺醇与克伦特罗进行定性和定量分析。结果表明,本实验对猪肉组织中沙丁胺醇与克伦特罗具有较高的灵敏度,单个样品单一指标的检测时间少于30 s。在0.01~1000μg/kg浓度范围内,信号强度对数(Y)与浓度对数(X)具有较好的线性关系,定量限分别为6.2和9.8 ng/kg。本方法分析速度快、样本耗量少、灵敏度高,适用于猪肉中痕量沙丁胺醇与克伦特罗等“瘦肉精”的快速检测。     

Analysis of Toxaphene (PCC) and Chlordane in Biological Samples by NCI Mass Spectrometry

Abstract

Several recent reports indicate that both toxaphene (polychlorocamphene, PCC) and chlordane are widespread pollutants in our environment. These insecticides, both complex mixtures of chlorinated hydrocarbons, are difficult to separate from each other. Thus the analyses of them in environmental samples are difficult and furthermore complicated by interferences from other chlorinated hydrocarbons such as PCB and DDT compounds. Mass fragmentography using the negative ions formed by chemical ionization proved to be useful to selectively detect the toxaphenes and the chlordanes without interferences from DDT. High concentrations of PCB still influence on the results and have to be removed in the clean-up procedure.     

环境试样分析

本文是《分析试验室》的定期评述中‘环境试样分析’的第６篇评论，它评论了从１９９６年１月至１９９７年１２月期间我国环境试样分析的进展，包括综述、大气分析、水分析、废水和沉积物分析、生物样品分析和有机污染物分析，引用了参考文献６２０篇。     

Analysis of Chemical Neutralization Products of Phosphonothiolates by Gas Chromatography Mass Spectrometry

A series of phosphonothiolates, including the highly toxic O-Ethyl-S-(2-diisopropylamino) ethyl methylphosphonothioate (VX), have been subjected to chemical neutralization reaction with metallic sodium. The phosphonothiolates decompose to their respective phosphonic and phosphonothioic acids and this results in the detoxification of VX. GC/MS technique in both EI and CI mode has been applied for reaction monitoring and final identification of the neutralization products formed in this reaction.     

同位素稀释-火花源质谱法分析人参样品中微量元素

本文采用同位素稀释-火花源质谱法定量分析了吉林野山参,园参及高丽参中30多种微量元素的含量。测定下限2μg/g,相对标准偏差在5～28％以内。     

Sequence Analysis of Polypeptide by Mass Spectrometry

The method described in this work provides a sensitive and fast technique for investigating the primary structure of peptides with molecular weight up to 3340 amu. Usually, the metastable ion kinetic energy spectra (MIKES) and collisional activated decomposition (CAD) spectra provide complementary information for the FAB mass spectra, the MIKES and CAD spectra generally contain high-mass sequence ions.     

高效液相色谱–电感耦合等离子体质谱法分析水中硒的形态

采用高效液相色谱法(HPLC)分离水中硒两种常见形态Se(Ⅳ),Se(Ⅵ),通过电感耦合等离子体质谱系统进行检测鉴定,由此建立了水中硒形态的分析方法。以0.15 mmol/L EDTA(钾)–0.1 mmol/L四丁基氢氧化铵–0.15 mmol/L乙酸铵–5%甲醇为流动相,调节流动相p H值至6~7,两种不同形态的硒可在4 min内得到有效分离。测定Se(Ⅳ),Se(Ⅵ),的线性范围为2~100μg/L,线性相关系数(r2)不低于0.999,Se(Ⅳ)和Se(Ⅵ)的检出限分别为0.01,0.05μg/L。分别以水源水、管网水等为基体进行加标回收试验,Se(Ⅳ)和Se(Ⅵ),的回收率分别为102.3%~106.2%,104.7%~108.3%,测定结果的相对标准偏差分别为6.4%~9.6%,4.4%~7.3%(n=5)。该方法灵敏度高,具有良好的精密度和准确度,可用于环境水体中元素硒形态分析。     

高效液相色谱-串联质谱法测定环境水样中多种杀菌剂残留量

建立了环境水样中多种杀菌剂残留量的高效液相串联质谱(LC-MS/MS)分析方法。通过氟吗啉和烯酰吗啉的光照实验,研究了其顺反异构体的转化规律,确定了它们的色谱行为。优化了固相萃取(SPE)过程参数,选择HLB为固相萃取柱,4 mL甲醇水(12:88,V/V)为淋洗液,3 mL甲醇为洗脱液。分析了环境水样中多种杀菌剂的基质效应影响,采用基质匹配曲线消除了基质效应。采用液相色谱分离,正离子多反应监测模式进行质谱分析。多种杀菌剂的方法定量限为0.003～0.03μg/L(环酰菌胺0.3μg/L)。在各自分析物的线性范围内,回收率为70.2%～108.9%,相对标准偏差均小于16.7%。本方法具有快速、准确、灵敏度高、选择性好等特点。在辽宁地区环境水样检测中,蒲河水检出嘧菌酯0.051μg/L、精甲霜灵0.217μg/L和烯酰吗啉0.05μg/L,浑河水检测出烯酰吗啉0.004μg/L。     

电感耦合等离子体-质谱联用及其在环境和生物样品中铂族金属分析的应用进展

本文简述了电感耦合等离子体-质谱联用(LCP-MS)技术和仪器的发展,分析了环境和生物样品中铂族金属分析的主要困难,综述了90年代以来国内外ICP-MS技术在环境和生物样品中铂族金属分析的最新进展,引用文献47篇.     

电感耦合等离子体质谱方法在生物样品分析中的应用

介绍了电感耦合等离子体质谱方法在生物样品分析中应用研究的新进展。针对ICP－MS的特点阐述了样品处理、进样方式、干扰校正的主要方法和应注意的问题。     

在线气体分析的电晕放电大气压电离质谱

研制了适合在线气体分析的电晕放电大气压电离源(corona discharge atmospheric pressure ionization source)及其与商品质谱仪(LTQ-MS)的接口,对其试剂离子的产生机理进行了研究,以H2O. (H2O)为试剂离子,对乙醇气体进行检测,并分析了该离子的产生机制。实验结果表明:在潮湿氮气中电晕放电产生的主要试剂离子是m/z36、37和55;而在含丙酮的潮湿氮气中则产生m/z59和76等离子。利用静态顶空-电晕放电大气压电离质谱对不同浓度的乙醇水溶液进行分析,结果表明:以m/z64为检测对象,乙醇气体浓度的最低检出限可达2.4×10-7g/L;而以m/z47为检测对象,检出限为5.9×10-6g/L。同时还利用动态顶空-电晕放电大气压电离质谱对栀子花香气成分进行了检测,为生物挥发性物质的在线检测提供了一种新方法。     

超高效液相色谱-串联质谱法快速分析环境水样中的碘海醇和碘帕醇残留量

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)法测定环境水样中碘代造影剂碘帕醇和碘海醇.样品加入等体积乙腈稀释后离心后,采用PHNOMON Kinetex F5柱(100 mm×3 mm,2.6 μm)进行分离,以0.1％甲酸水溶液-乙腈为流动相,梯度洗脱,在电喷雾离子源、正离子模式下,采用多反应检测模式检测,...     

Determination of Halide Traces in Environmental Samples by Mass Spectrometric Isotope Dilution Analysis

Abstract

Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ± 18% for [²H₁₀]diazinon to 15 ± 13% for 4,4′-[²H₈]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11-to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.     

质谱的无机痕量分析进展

概述了电感耦合等离子体质谱(ICP-MS)、激光电离质谱(LIMS)和共振电离质谱(RIMS)、火花源质谱(SSMS)、辉光放电质谱(GDMS)、二次离子质谱(SIMS)、热电离同位素稀释质谱法(ID-TIMS)等无机质谱分析方法的基本原理、方法特点和应用进展,概括了ICE-MS和IDMS方法的优缺点;采用溶液进样的ICP-MS和TIMS稀释法,给出的测量结果不确定度要高于固体进样的质谱法。     

Determination of Rosiglitazone by Direct Analysis in Real-Time Mass Spectrometry

The determination of rosiglitazone in dietary supplements by direct analysis in real-time mass spectrometry normally provides low repeatability. The [M+H]⁺ signal sharply decreased in the presence of strong-base and weak-acid ionic compounds because rosiglitazone decomposition occurred due to the hydrolysis of strong-base and weak-acid anions. The repeatability was improved and the influence of ionic compounds was minimized by the use of pioglitazone as an internal standard. Orbitrap mass spectrometry was used to provide high resolution in which isotopic interferences from M?+?1 of pioglitazone upon M of rosiglitazone were eliminated. This approach was used to determine rosiglitazone in tablet and dietary supplements in 1?min per sample.     

组织样品的直接质谱分析及其应用

质谱技术具有灵敏度高、分析速度快、能提供分子结构信息等特点,在生命科学研究领域扮演着重要角色,常用于组织样品分析。传统地,组织样品分析一般需经过研磨、萃取、分离等繁杂的预处理过程,导致耗时低效,无法满足大量样品高通量分析的实际需求,且不可避免地使组织样品中的一些活性成分损失。近年来,随着新型常压质谱技术的发展,使得组织样品可在无需样品预处理的条件下进行实时、非破坏、在线直接质谱分析,大大提高了分析效率。该文着重介绍了新型直接质谱技术在组织样品分析中的应用,并简要展望了该技术在生命科学、临床医学、食品科学、活体分析等领域的发展趋势。     

生物材料中克伦特罗的气相色谱-质谱法测定

建立了生物材料中克伦特罗 (clenbuterol)的气相色谱 -质谱测定方法 ;大白鼠喂食克伦特罗获得阳性生物材料 ,生物材料中克伦特罗经0.01mol/L盐酸溶液提取 ,乙醚脱脂净化 ,乙酸乙酯提取后蒸发至干 ,用乙醇溶解后加样到氧化铝柱上 ,用0.01mol/L盐酸溶液洗脱 ,蒸发至干后 ,用BSTFA(双三甲基硅烷基三氟乙酰胺 ) +1 % (φ)TMCS(三甲基氯硅烷 )衍生 ,采用GC -MS进行测定 ,外标法定量 ;试验表明 ,生物材料中添加0.056×10 -6～0.54×10 -6(w)含量水平的克伦特罗 ,方法回收率在89 %～107 % ,相对标准偏差为7.3 %～16 % ,线性相关系数r为0.998,克伦特罗的检出限为2.0×10-9(w)。