用多维色谱—稳定同位素稀释质谱联用技术测定酒中氨基甲酸乙酯

建立了一个用多维色谱／质谱方法（ＧＣ／ＧＣ／ＭＳ），结合同位素稀释技术（ＩＤＭＳ），测量酒中致癌物质－氨基甲酸乙酯（ＥＣ）的准确方法，主要步骤如下：向精确称取的样品中，加入精确称取为，以＾１３Ｃ，＾１５Ｎ标记的氨基甲酸乙酯（ＬＥＣ）内标溶液，试样经调节，ｐＨ萃取，浓缩等化学前处理步骤后，进行ＧＣ／ＧＣ／ＣＩＭＳ测定。测量以ＧＣ／ＧＣ的中心切割技术排除复杂基体的干扰。以化学电离（ＣＩ）和选择性子检测     

GC／MS检测信息的综合利用

从充分利用气相色谱／质谱（ＧＣ／ＭＳ）提供的信息来鉴定ＧＣ流出组分的目的出发，并以脂肪醇分析为例讨论了ＧＣ保留指数在ＭＳ谱图解析及ＭＳ鉴定结果的合理性检验方面的作用。总结了ＧＣ保留的同系物规律、极性规律、加和规律及异构物规律来指导ＭＳ谱图解析。提出了含氧化合物官能团相对于－ＣＨ２－质量数的保留指数附加贡献值辅助ＭＳ确定化合物的类别。同时采用了ＧＣ／ＭＳ中选择离子检测方法（ＳＩＭ）在分子离子峰受噪音干扰或太弱以至完全未观测到时来进一步佐证其相对分子质量。     

用GC—MS法测定尿中可待因及其代谢物的浓度

建立了用ＧＣ－ＭＳ（ＳＩＭ）内标定量法快速测定人尿中可待因及其代谢物浓度的方法，样品经酸水解、乙醚／异丙醇提取，用ＭＳＴＦＡ－ＭＢＴＦＡ衍生化后进样于ＧＣ－ＭＳＤ，方法灵敏、准确，可用于监测吸毒者尿中可待因，吗啡类药物的浓度。本法已经受ＩＯＣ的１９９２年水平考试的考验。     

用GC－MS法测定尿中可待因及其代谢物的浓度

建立了用ＧＣ－ＭＳ（ＳＩＭ）内标定量法快速测定人尿中可待因及其代谢物浓度的方法。样品经酸水解、乙醚／异丙醇提取，用ＭＳＴＦＡ－ＭＢＴＦＡ衍生化后进样于ＧＣ－ＭＳＤ，方法灵敏、准确，可用于监测吸毒者尿中可待因、吗啡类药物的浓度。本法已经受ＩＯＣ的１９９２年水平考试的考验。     

甲烷直接氧化制甲醇Ⅱ．催化膜反应器（CMR）

采用溶胶－凝胶（Ｓｏｌ－Ｇｅｌ）法制备了微孔结构均匀的“ＳｉＯ＿２／陶瓷”膜和“Ｍｏ－Ｃｏ－·Ｏ／ＳｉＯ＿２／陶瓷”催化功能膜，并用ＸＲＤ、ＳＥＭ和孔径测定等技术进行了表征。在常压、５００～７００℃的条件下，在催化膜反应器（ＣＭＲ）中考察了甲烷氧化制甲醇的反应。在相似的反应条件下（转化率为１．０％），用ＣＭＲ（甲醇选择性１１．２％）可获得较固定床反应器（甲醇选择性４．５％）高得多的甲醇选择性。     

甲烷直接氧化制甲醇：Ⅱ.催化膜反应器（CMR）

采用溶胶－凝胶（Ｓｏｌ－Ｇｅｌ）法制备了微孔结构均匀的“ＳｉＯ２／陶瓷”膜和“Ｍｏ－Ｃｏ－Ｏ／ＳｉＯ２／陶瓷”催化功能膜，并用ＸＲＤ、ＳＥＭ和孔径测定等技术进行了表征。在常压，５００～７００℃的条件下，在催化膜反应器（ＣＭＲ）中考察了甲烷氧化制甲醇的反应。在相似的反应条件下（转化率为１．０％），用ＣＭＲ（甲醇选择性１?．２％）可获得较固定床反应器（甲醇选择性４．５％）高得多的甲醇选择性。     

SYNTHESES， CHARACTERIZATION AND CATALYSIS OF （dppe）Rh（μ－CO）_2M（CO）_3（M＝CR，Mo，W） CARBONYL COMPOUNDS

ＳＹＮＴＨＥＳＥＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ ＡＮＤ ＣＡＴＡＬＹＳＩＳ ＯＦ （ｄｐｐｅ）Ｒｈ（μ－ＣＯ）_２Ｍ（ＣＯ）_３（Ｍ＝ＣＲ，Ｍｏ，ｗ）ＣＡＲＢＯＮＹＬ ＣＯＭＰＯＵＮＤＳ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ；ＪａｉｅＹｕＷＡＮＧ；ＸｉｕＺ...     

QUANTUM CHEMICAL STUDY ON THE MECHANISM OF PRODUCING OXYGENATES IN FISCHER－TROPSCH SYNTHESIS ON M／SiO＿2 （M＝Ni， Ru， Rh， Pd） CATALYSTS

ＱＵＡＮＴＵＭ　ＣＨＥＭＩＣＡＬ　ＳＴＵＤＹ　ＯＮ　ＴＨＥ　ＭＥＣＨＡＮＩＳＭ　ＯＦ　ＰＲＯＤＵＣＩＮＧ　ＯＸＹＧＥＮＡＴＥＳ　ＩＮ　ＦＩＳＣＨＥＲ－ＴＲＯＰＳＣＨ　ＳＹＮＴＨＥＳＩＳ　ＯＮ　Ｍ／ＳｉＯ＿２　（Ｍ＝Ｎｉ，　Ｒｕ，　Ｒｈ，　Ｐｄ）　ＣＡ...     

气相色谱/质谱/质谱法分析石油基引燃物

应用Ｖａｒｉａｎ ３８００ ＧＣ／Ｓａｔｕｒｎ ２０００ ＭＳ 气相色谱／质谱联用分析仪（简称ＧＣ／ＭＳ／ＭＳ）对以汽油、煤渍和紫油为引燃物，燃烧聚丙稀化纤地毯和土壤时的模拟现场物品进行了引燃物的检出。发现采用ＧＣ／ＭＳ／ＭＳ方法比用ＧＣ／ＭＳ方法可以较彻底地排队由于柱注失、地毯燃物分解产物、土壤背景产物和地毯增塑剂等引起的干扰，而且可以提高检测灵敏度。详细考察了以不同质荷比的离子作母离子时对ＧＣ     

SYNTHESIS,CRYSTAL STRUCTURE AND MAGNETISM OF THE COMPLEX:GdFe(CN)_64H_2O

ＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ　ＡＮＤ　ＭＡＧＮＥＴＩＳＭ　ＯＦ　ＴＨＥ　ＣＯＭＰＬＥＸ：ＧｄＦｅ（ＣＮ）_６４Ｈ_２ＯＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＡＮＤＭＡＧＮＥＴＩＳＭＯＦＴＨＥＣＯＭＰＬＥＸ：ＧｄＦ...     

Determination of estrogens and progestogens by mass spectrometric techniques (GC/MS, LC/MS and LC/MS/MS)

Steroid sex hormones and related synthetic compounds have been shown to provoke alarming estrogenic effects in aquatic organisms, such as feminization, at very low concentrations (ng/L or pg/L). In this work, different chromatographic techniques, namely, gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS), are discussed for the analysis of estrogens, both free and conjugated, and progestogens, and the sensitivities achieved with the various techniques are inter-compared. GC/MS analyses are usually carried out after derivatization of the analytes with bis(trimethylsilyl)trifluoroacetamide (BSTFA). For LC/MS and LC/MS/MS analyses, different instruments, ionization techniques (electrospray (ESI) and atmospheric pressure chemical ionization (APCI)), ionization modes (negative ion (NI) and positive ion (PI)) and monitoring modes (selected ion monitoring (SIM) and selected reaction monitoring (SRM)) are generally employed. Based on sensitivity and selectivity, LC/ESI-MS/MS is generally the method of choice for determination of estrogens in the NI mode and of progestogens in the PI mode (instrumental detection limits (IDLs) 0.1-10 ng/mL). IDLs achieved by LC/ESI-MS in the SIM mode and by LC/ESI-MS/MS in the SRM mode were, in general, comparable, although the selectivity of the latter is significantly higher and essential to avoid false positive determinations in the analysis of real samples. Conclusions and future perspectives are outlined.     

基于壳聚糖的QuEChERS-气相色谱-串联质谱法测定人参中30种农药残留

建立了一种以壳聚糖为净化材料的QuEChERS-气相色谱-串联质谱检测人参中30种农药残留的检测方法。探究了吸附剂及其用量对样品提取和净化效果的影响,确定壳聚糖为吸附剂净化。采用选择离子监测(SRM)模式,基质匹配标准曲线外标法定量。30种农药在各自的浓度范围内,线性关系良好(r> 0.996);检出限范围为1.5~3.0μg/kg,定量限范围为5.0~10.0μg/kg。3个添加水平(10,20,100μg/kg)的回收率在84.1%~113.7%之间,相对标准偏差均小于15%。该方法适用于检测人参中农药残留。     

A reliable analytical approach based on gas chromatography coupled to triple quadrupole and time‐of‐flight mass analyzers for the determination and confirmation of polycyclic aromatic hydrocarbons in complex matrices from aquaculture activities

The potential of gas chromatography coupled to tandem mass spectrometry (GC/MS/MS) with a triple quadrupole analyzer (QqQ) has been investigated for the quantification and reliable identification of sixteen polycyclic aromatic hydrocarbons (PAHs) from the EPA priority list in animal and vegetable samples from aquaculture activities, whose fat content ranged from 5 to 100%. Matrices analyzed included fish fillet, fish feed, fish oil and linseed oil. Combining optimized saponification and solid‐phase extraction led to high efficiency in the elimination of interfering compounds, mainly fat, from the extracts. The developed procedure minimized the presence of these interfering compounds in the extracts and provided satisfactory recoveries of PAHs. The excellent sensitivity and selectivity of GC/(QqQ)MS/MS in selected reaction monitoring (SRM) allowed to reach limits of detection at pg/g levels. Two SRM transitions were acquired for each analyte to ensure reliable identification of compounds detected in samples. Confirmation of positive findings was performed by GC coupled to high‐resolution time‐of‐flight mass spectrometry (GC/TOFMS). The accurate mass information provided by GC/TOFMS in full acquisition mode together with its high mass resolution makes it a powerful analytical tool for the unequivocal confirmation of PAHs in the matrices tested. The method developed was applied to the analysis of real‐world samples of each matrix studied with the result of detecting and confirming the majority of analytes at the µg/kg level by both QqQ and TOF mass spectrometers. Copyright © 2009 John Wiley & Sons, Ltd.     

Two new standard reference materials for the determination of drugs of abuse in human hair

Two new standard reference materials (SRM) for drugs of abuse in human hair have been developed. SRM 2379 consists of hair spiked with cocaine, benzoylecgonine, cocaethylene, phencyclidine, amphetamine, and methamphetamine. SRM 2380 consists of hair spiked with codeine, morphine, monoacetylmorphine, and tetrahydrocannabinol (THC). The SRMs were prepared by soaking the hair in a solution of the target analytes in water-dimethylsulfoxide. The concentration of each analyte was determined using two methods, one based upon gas chromatography/mass spectrometry (GC/MS) and one based upon liquid chromatography/mass spectrometry (LC/MS). Both methods used 0.1 M HCl for extraction of all the analytes from the hair, except for THC, which was extracted with 1 M NaOH. For isolation of the analytes from the extracts, the GC/MS-based methods used different clean-up procedures from those used for the LC/MS-based methods. The results from the two methods were in good agreement with mean differences for the analytes ranging from 4% to 16%. These materials will enable laboratories performing analyses of hair for drugs of abuse to test the accuracy of their methods.     

Rapid determination of parabens in personal care products by stable isotope GC‐MS/MS with dynamic selected reaction monitoring

In this study, a rapid and sensitive analytical method for the determination of methyl‐, ethyl‐, propyl‐, and butyl esters of para‐hydroxy benzoic acid (parabens) in personal care products was developed and fully validated. Test portions were extracted with methanol followed by vortexing, sonication, centrifugation, and filtration without derivatization. The four parabens were quantified by GC‐MS/MS in the electron ionization mode. Four corresponding isotopically labeled parabens were selected as internal standards, which were added at the beginning of the sample preparation and used to correct for recovery and matrix effects. Sensitivity, extraction efficiency, and recovery of the respective analytes were evaluated. The coefficients of determination (r²) were all greater than 0.995 for the four parabens investigated. The recoveries ranged from 97 to 107% at three spiked levels and a one‐time (single) extraction efficiency greater than 97% was obtained. This method has been applied to screen 26 personal care products. This is the first time that a unique GC‐MS/MS method with dynamic selected reaction monitoring and confirmation of analytes has been used to determine these parabens in cosmetic personal care products.     

Determination of nitrated polycyclic aromatic hydrocarbons in diesel particulate-related standard reference materials by using gas chromatography/mass spectrometry with negative ion chemical ionization

Gas chromatography/mass spectrometry (GC/MS) with negative ion chemical ionization (NICI) detection was utilized for quantitative determination of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in diesel particulate-related standard reference materials (SRMs). Prior to GC/MS analysis, isolation of the nitro-PAHs from the complex diesel particulate extract was accomplished using solid phase extraction (SPE) and normal-phase liquid chromatographic (LC) fractionation using an amino/cyano stationary phase. Concentrations of eight to ten mononitro-PAHs and three dinitropyrenes were determined in three diesel particulate-related SRMs: SRM 1650a Diesel Particulate Matter, SRM 1975 Diesel Particulate Extract, and SRM 2975 Diesel Particulate Matter (Industrial Forklift). The results from GC/MS NICI using two different columns (5% phenyl methylpolysiloxane and 50% phenyl methylpolysiloxane) were compared to each other and to results from two other laboratories for selected nitro-PAHs. 1-Nitropyrene was the most abundant nitro-PAHs in each of the diesel particulate SRMs (19.8+/-1.1 micro g g(-1) particle in SRM 1650a and 33.1+/-0.6 micro g g(-1) particle in SRM 2975). Three dinitropyrene isomers were measured in SRM 1975 at 0.5-1.4 micro g g(-1) extract and in SRM 2975 at 1-3 micro g g(-1) particle.     

Determination of the enantiomer fraction of PBB 149 by gas chromatography/electron capture negative ionization tandem mass spectrometry in the selected reaction monitoring mode

Enantioselective determination of the atropisomers of 2,2',3,4',5',6-hexabromobiphenyl (PBB 149) in a purified sample from a bird egg was attempted in this work. By application of the classic method for PBB determination, i.e. gas chromatography coupled to electron capture negative ionization mass spectrometry (GC/ECNI-MS) using the bromide ions, the enantiomers interfered with another brominated compound. Subsequent measurements clarified that this interference did not occur in the mass chromatogram of the molecular ion of PBB 149. Therefore, a GC/ECNI tandem mass spectrometry (MS/MS) method was developed, based on the fragmentation of [M]-. A suitable precursor-product ion transition was found for m/z 627.5 --> 80 +/- 1.5, representing the most abundant ion trace of the molecular ion and the bromide ions. Optimization of the ion source temperature, the methane gas pressure, and the collision voltages resulted in a robust method that could solve the problem. Subsequent injections of a technical PBB product (Firemaster BP-6) resulted in the anticipated racemic proportion (enantiomer fraction (EF) = 0.50 +/- 0.02 (n = 8)). By contrast, the EF in the purified extract of a bird egg was found to be 0.42 +/- 0.02 (n = 10), indicative of a significant enantioenrichment of the second eluting atropisomer. Additional measurements were performed on a non-chiral column. These measurements allowed for the detection of 16 hexabromobiphenyls (hexa-BBs) in Firemaster BP-6. These comparisons verified that PBB 149 enantiomers did not interfere with an isomer that could falsify the enantiomer fraction in the sample. The novel method using GC/ECNI-MS/MS in the selected reaction monitoring (SRM) mode was eight times more sensitive than application of conventional GC/ECNI-MS selected ion monitoring (SIM) analysis of the molecular ion.     

Simultaneous selective detection of organophosphate and phthalate esters using gas chromatography with positive ion chemical ionization tandem mass spectrometry and its application to indoor air and dust

A selective and sensitive method for the simultaneous determination of 14 organophosphate and six phthalate esters using gas chromatography (GC) and mass spectrometry (MS) is presented. Both of these compound classes are frequently found in the indoor environment due to their use as bulk additives in numerous polymers, consumer products and building materials. GC/MS utilizing positive ion chemical ionisation (PICI) in selected reaction monitoring (SRM) mode with isobutane as the reagent gas was found to be the best of the tested methods; it proved superior to electron ionisation (EI) in selected ion monitoring (SIM) mode and to PICI using methane as the reagent gas. The method was applied to indoor air samples collected by active air sampling using solid‐phase extraction (SPE) cartridges. Organophosphates and phthalates were simultaneously determined with method detection limits (MDLs) in the range of 0.1–47 ng m^?3. For most compounds the MDLs were ≤0.2 ng m^?3, but due to the presence of some of these ubiquitous indoor air pollutants in the blanks, significantly higher MDLs were observed for a few compounds. Finally, the method was also applied in the screening of a much more complex sample matrix, indoor dust. Copyright © 2010 John Wiley & Sons, Ltd.     

Rapid simultaneous determination of 14 sulfonamides in wastewater by liquid chromatography tandem mass spectrometry

This paper describes a rapid method for the determination of 14 kinds of sulfonamides (SAs) in wastewater using SPE, and LC-MS/MS with positive ESI (ESI(+)) and selected reaction monitoring (SRM) mode. The SPE was performed on an Oasis hydrophilic-lipophilic-balanced (HLB) cartridge. Chromatographic separation on a C18 column was achieved using a binary eluent containing methanol and water with 0.2% formic acid. Typical recoveries of the analytes ranged from 22.3 to 87.0% at a fortification level of 100 ng/L. The LODs in wastewater except sulfathiazole (3 ng/L) could be detected and quantified at levels as low as 1 ng/L. Finally, the method was applied to water from the municipal outlet and the aquaculture wastewater effluent. Sulfamethazine (SM(2)), sulfamethoxypyridazine (SMP), and sulfamethoxazole (SMZ) were most frequently found in wastewater in a concentration range between 1.2 and 31.7 ng/L.     

Analysis of polybrominated diphenyl ethers (PBDEs) by liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS): application to house dust

Eight polybrominated diphenyl ether (PBDE) congeners of primary interest to the US EPA were separated using reverse-phase liquid chromatography on an octadecylsilane column. BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209 were baseline-resolved under isocratic conditions in 92:8 methanol/water (v/v). Negative-ion atmospheric pressure photoionization (NI-APPI) with a toluene dopant produced precursor ions corresponding to [M–Br+O]^– for the eight congeners studied. Each congener was quantified by tandem mass spectrometry through a unique multiple reaction monitoring (MRM) transition. On-column limits of detection were between 2.4 and 27.8 pg for the eight congeners studied, with an intra-day method precision of 9%. The LC/NI-APPI/MS/MS method was validated for the analysis of the eight PBDE congeners in NIST SRM 2585 (Organics in House Dust). Pressurized liquid extraction (PLE) with subsequent LC/NI-APPI/MS/MS analysis afforded quantitative recovery for all eight PBDE congeners with recoveries ranging from 92.7 to 113%. The liquid-phase separation of the LC/NI-APPI/MS/MS method is not prone to the thermal degradation issues that plague splitless GC based analyses of highly brominated PBDEs such as BDE-209.