Allyldimethylsilyl ethers as derivatives for the characterization of steroids and cannabinoids by combined gas chromatography and mass spectrometry

The effect of 2-, and 4-aminopyridine (4-APYR) on the release mechanism of acetylcholine (ACh) from the nerve terminals of the Auerbach plexus-longitudinal muscle preparation of the guinea-pig ileum, suspended in eserinized Krebs' solution, was investigated. 2- and 4-APYR increased the release of ACh from the nerve terminals at rest and at both low and high frequency stimulation. The enhanced ACh release was found to be due to increased volley output. At lower frequency of stimulation, potentiation of ACh release was much higher than at higher rate of stimulation. 4-APYR was able to increase ACh release in the absence of [Ca2+]o. However, when a Ca-chelating agent, EDTA, was also added to the Ca-free Krebs' solution, 4-APYR was entirely ineffective. The depression of ACh release induced by Mg-excess was completely antagonized by 4-APYR. Tetrodotoxin (TTX) prevented augmentation of ACh release by 4-APYR. It is suggested that 4-APYR lowers the demand of nerve terminals for [Ca2+]o required for the excitation-secretion coupling process. The presence of a low concentration [Ca2+]o, however, is essential for the action of 4-APYR.     

Identification of hydroxyhalobiphenyls as their methyl ethers by gas chromatography mass spectrometry

The mass spectra and gas chromatographic properties of 17 synthetic fluoro-, chloro- and bromomethoxy-biphenyls and 12 dichlorodimethoxybiphenyls have been examined. From this representative series it appears that the position of the methoxy group (ortho, meta and para to the biphenyl bond) in all monomethoxy compounds examined, and the positions of the two methoxy groups in most of the dimethoxy compounds, can be assigned unambiguously by their difference in fragmentation pattern. The value of this method was shown by metabolism experiments in which 4,4'-difluoro- and 4,4'-dibromobiphenyl were fed to rats and 4,4'-dichlorobiphenyl was administered to plants. All hydroxylated metabolites found were identified by gas chromatography mass spectrometry. Relationships between structure and gas chromatographic retention time of these compounds are discussed.     

Quantitation of a urinary tetrasaccharide by gas chromatography and mass spectrometry

A gas chromatographic mass spectrometric method has been developed for the rapid determination of a urinary tetrasaccharide (alpha-D-Glc-(1 leads to 6)-alpha-D-Glc-(1 leads to 4)-alpha-D-Glc-(1 leads to 4)-D-Glc). The urine sample is first fractionated by gel chromatography. An appropriate internal standard is added to the pooled tri-pentasaccharide fraction, which is then reduced, methylated and fractionated by g.c. The identification of the tetrasaccharide derivative is based on the g.c. relative retention time and the mass spectrum of the reduced permethylated tetrasaccharide. The normal excretion rate was in the range of 0.1-2.5 mg per 24 hours. Greatly increased amounts (9.4-89.6 mg 24 h-1) were found in the urine of patients with glycogen storage disease type II and type III and in one patient with unclassified muscular disease. A moderate increase (3.6m6 mg 24 h-1) was observed in one patient with glycogen storage disease type VI, in two patients with Duchenne muscular dystrophy and in two other patients with unclassified muscular disease.     

Determination of tetrahydro-beta-carbolines in rat brain by gas chromatography-negative-ion chemical ionization mass spectrometry without interference from artifactual formation

This paper describes a quantitative method for neuroactive alkaloids, 1-methyl-1,2,3,4-tetrahydro-beta-carboline (MTBC) and 1,2,3,4-tetrahydro-beta-carboline (TBC), in rat brain by gas chromatography-negative-ion chemical ionization mass spectrometry (GC-NICIMS). After addition of tetradeuterated MTBC and TBC (internal standards), the samples were subjected to deproteinization, reaction with fluorescamine, solvent extractions, trifluoroacetylation and GC-NICIMS analysis. In contrast to the other previous methods, the artifactual formation during analysis did not interfere with the determination of MTBC and TBC because their precursor tryptamine was removed as a fluorescamine derivative from the analytical system at the first step of pretreatment. MTBC and TBC were specifically and reliably determined in the range of pg-ng/sample. Application of the proposed method has revealed that the MTBC and TBC contents in rat brain significantly increase after intraperitoneal administration of MTBC and TBC, indicating their ability to easily cross the blood-brain barrier.     

In vivo microdialysis and gas chromatography/mass spectrometry for studies on release of N-acetylaspartlyglutamate and N-acetylaspartate in rat brain hypothalamus

Microdialysis and gas chromatography/mass spectrometry was used for the measurement of extracellular N-acetylaspartate (NAA) and N-acetylaspartylglutamate (NAAG) in rat hypothalamus. The sensitivity of the method for each of these compounds was approximately 5 pmol/30 microliters of dialysate. Baseline NAA concentrations in dialysate were estimated to be approximately 25 pmol/36 microliters, while that for NAAG was at or below the detection limit of 5 pmol/ 36 microliters. In vivo and in vitro calibrations of microdialysis probes showed that the recovery for NAA was approximately 10 percent. For NAAG, the in vitro recovery was 6.3%, and in vivo recovery, 11%. Depolarization stimulation using 100 mM KCl in the microdialysis perfusate was employed to measure extracellular NAA and NAAG concentrations. Extracellular NAA was elevated to approximately 70 pmol/36 microliters dialysate following depolarization. No significant elevation of NAAG was observed. By infusing known amounts of stable isotopically labeled NAAG-d3 via the microdialysis probe and measuring the isotopically labeled catabolic product, NAA-d3, in collected microdialysate, we were able to confirm the existence of one or more hydrolytic enzymes active towards NAAG in the hypothalamus. This finding suggest the possible involvement of active metabolic processes in the relationship between NAAG and NAA releases.     

Determination of acrolein in human urine by headspace gas chromatography and mass spectrometry

The aim of the present study is to examine whether noradrenergic neurons of the locus coeruleus (LC) of the rat contain monoamine oxidase (MAO) activity. Sections were processed initially for MAO enzyme histochemistry using tyramine as a substrate, followed by fluorescence immunohistochemistry for tyrosine hydroxylase (TH). In the LC, virtually all TH-immunoreactive neurons (i.e., noradrenergic neurons) were also positive for MAO. No MAO activity was found in any TH-negative neurons. Neurons in the LC have previously been shown to form dopamine during noradrenaline biosynthesis and to produce serotonin from exogenously administered l-5-hydroxytryptophan. Moreover, dopamine- and serotonin-degrading MAO activity has also been found in LC neurons. Therefore, our results indicate that MAO activity is localized within noradrenergic neurons in the LC and is likely involved in the degradation of dopamine that is endogenously synthesized, and also in the elimination of serotonin that is produced from exogenous precursors.     

褐煤的气相色谱/串联三重四极杆质谱鉴别检测方法

基于传统褐煤鉴别方法操作复杂、定性结果主观影响较大等特点,探索并建立了褐煤的气相色谱/串联三重四极杆质谱鉴别方法(GC-MS/MS)。对煤炭样品采用丙酮溶液提取,提取液用气相色谱/串联三重四极杆质谱仪进行全扫描总离子流色谱和选择离子扫描及多反应监测扫描质谱(色谱和质谱)的采集分析。从总离子流图检测出褐煤的特征峰,结合特征峰的质荷比394.8/187、394.8/95、394.8/161、394.8/159.1对褐煤样品进行多反应监测模式(MRM)分析,使得定性分析更准确可靠。实验方法可广泛应用于煤炭中褐煤与其他种类煤炭区分的定性检测。     

Determination of four anabolic steroid metabolites by gas chromatography/mass spectrometry with negative ion chemical ionization and tandem mass spectrometry

A gas chromatography/mass spectrometry method is described which uses negative ion chemical ionization and tandem mass spectrometry for the determination of anabolic steroid metabolites. Four anabolic steroid metabolites to be derivatized by Pentafluoropropionic anhydride (PFPA) were determined using gas chromatography/mass spectrometry (GC/MS) with negative chemical ionization (NCI) and NCI/MS/MS. The repeatability and reproducibility of this procedure were in the range of 5.3-9.7% and 6.1-10.2%, respectively. This method of derivatization with PFPA for NCI and NCI/MS/MS was useful to determine four metabolites of nandrolone, dromostanolone, methenolone and boldenone. The derivatized metabolites of boldenone could be detected to 2 ppb and the other three steroids could be detected to 25 ppb in urine at a signal-to-noise ratio of S/N = 3.     

气相色谱-质谱法测定汽油中醇类、醚类和酯类添加剂

目前市场上一些加油站中存在着在汽油中非法添加一些醇类、醚类、酯类氧化物添加剂的现象,对车辆的机动性、安全性和环保性存在潜在危害。实验建立了气相色谱-质谱法测定汽油中19种醇类、醚类和酯类添加剂含量的分析方法。通过试验优化了色谱分析的主要条件,确定了最佳分流比为1∶100,溶剂为正十一烷,稀释倍数10～100倍,同时研究了溶剂的切换时间。利用选择离子法(SIM)确定定量离子和参考离子,可以有效消除汽油中复杂成分对目标组分的影响。以各目标组分的峰面积对其相应的质量浓度作图,发现甲醇、乙醇质量浓度在5.0～100.0 mg/L、其他化合物质量浓度在1.0～20.0 mg/L范围内线性良好,校准曲线的线性相关系数在0.998 6~0.999 9之间。各组分的检出限为0.5~1.0 mg/L。对添加了标准溶液的实际样品进行精密度和正确度考察,19种组分测定结果的相对标准偏差(RSD,n=8)为2.1%～6.2%,回收率为85%～108%。对市售92#、95#、98#常见标号汽油样品进行测定,结果发现部分汽油中含有甲醇、甲基叔丁基醚(MTBE)、乙酸仲丁酯等氧化物添加剂,质量浓度在20~1 200 mg/L之间。     

煤中天然有机物的高效液相色谱-质谱/质谱分析

运用红外光谱法测定褐煤氧化前后的结构变化,在1580cm-1及1400cm-1处的两个特征峰表明氧化煤中含有大量的羧酸类物质。以此为基础,采用温和的碱氧化方法对煤进行氧化处理,选择了合适的分离条件,建立了氧化煤中天然有机物质预分离样品的高效液相色谱方法,并通过电喷雾串联质谱(ESI(-)-MS/MS)法对其中一组质量数相差58的物质进行了细致的分析。选择m/z268为特征吸收峰,并依据煤的大分子结构,对分析得到的物质进行细致的结构推测,认为该物质应为含有两个乙酸基侧链的炔基喹啉,其化学式为C15H11NO     

气相色谱质谱法测定食品塑料保鲜袋中塑化剂

目的 对市售食品塑料保鲜袋中塑化剂的检测.方法 用正已烷萃取塑料食品保鲜袋中的邻苯二甲酸酯类,应用气相色谱-质谱联用测定17种邻苯二甲酸酯类.结果 市售十二种食品PE保鲜袋中,均检出DEHP邻苯二甲酸二(2-乙基)己酯.结论 应加强对食品塑料保鲜袋中邻苯二甲酸酯类的限值制订和市场监管.     

Determination of bitertanol residues in strawberries by liquid chromatography with fluorescence detection and confirmation by gas chromatography/mass spectrometry

Heart rate (HR) and blood oxygen saturation (SaO2) were monitored before and during clinically indicated MR examinations of newborns to (a) identify any temporal relationship between MR scanning and vital sign fluctuations and (b) assess the reliability of SaO2 monitoring of dynamic changes. Fluctuations in HR (but not in SaO2) that are temporally linked to the MR image acquisition occur in most neonates during routine clinical MR examinations.     

Determination of alprazolam and alpha-hydroxyalprazolam in human plasma by gas chromatography/negative-ion chemical ionization mass spectrometry

A sensitive and specific method was developed for the determination of alprazolam and its major metabolite alpha-hydroxyalprazolam in plasma. After the addition of deuterium-labeled internal standards, plasma samples were buffered to pH 9 with 1 ml of saturated sodium borate buffer, extracted with toluene-methylene chloride (7:3) and evaporated to dryness. The residues were treated with N,O-bis(trimethylsilyl)trifluoroacetamide containing 1% of trimethylchlorosilane and analyzed on a Finnigan-MAT mass spectrometer operated in the negative-ion chemical ionization mode with methane as the reagent gas. Chromatographic separation was achieved on a Restek-200 capillary column using hydrogen as the carrier gas. The assay was linear from 0.25 to 50 ng ml-1 for both compounds. The intra-assay precision for alprazolam was 16.1% at 0.5 ng ml-1 and 4.6% at 50 ng ml-1 and that for alpha-hydroxyalprazolam was 15.8% at 0.5 ng ml-1 and 4.2% at 50 ng ml-1. The method was used to determine alprazolam and alpha-hydroxyalprazolam in human plasma samples collected after a single 2 mg oral does of alprazolam. A peak concentration of 32.9 ng ml-1 of alprazolam was detected at 1 h following the dose.     

Quantitative determination of pentaerythrityl tetranitrate and its metabolites in human plasma by gas chromatography/mass spectrometry

Levels of anticeramide antibodies and S-100 antigen in leprosy patients with and without reaction are compared in this study. The increase in levels of IgM anti ceramide antibody in the tuberculoid group of patients with reaction, when compared to those without reaction, is significant (P < 0.05). Similarly, significant increase (P < 0.01) was observed in the borderline group with reaction. No significant change in anti ceramide antibody level was observed in the lepromatous group of patients with and without reaction. Mean levels of S-100 were slightly lower in all three groups of patients with reaction, but the differences were not statistically significant.     

Determination of halogenated hydrocarbons by helium microwave plasma torch time-of-flight mass spectrometry coupled to gas chromatography

A helium microwave plasma torch (MPT) was coupled to time-of-flight mass spectrometry (TOFMS) for the detection of halogenated hydrocarbons separated by capillary gas chromatography (GC). The GC-MPT-TOFMS system offered excellent stability over the course of the experiments and avoided mass spectral peak distortions caused by spectral skew. In the initial studies, empirical formulas based on the halogen-to-carbon ratio were predicted utilizing a flow cell apparatus. The MPT proved to be very robust and could handle large amounts of organic vapor. Results from this study indicate that, for both aromatic and aliphatic halogenated hydrocarbons, the ratios of carbon to chlorine signals correlate well (r = 0.994) with the ones expected from their chemical composition. This study was later extended to include chromatographic separation. For a series of homologous aliphatic halogenated hydrocarbons, a correlation coefficient of 0.999 was obtained for both peak heights and peak areas obtained from a single chromatogram. A novel Nichrome wire-heated transfer line was developed to ensure that the capillary column was heated efficiently from the GC oven to the MPT and then through the length of the MPT up to the microwave plasma itself. No appreciable peak broadening and no detectable memory effects were associated with the heated transfer line. The GC-MPT-TOFMS system offered equal sensitivity for I, Br, and Cl. Absolute detection limits for the halogenated hydrocarbons ranged from 160 to 330 fg, constituting an improvement by a factor of 5-35 over earlier results obtained with MIPs supported in a TM010 cavity and combined with quadrupole-based mass spectrometry. In addition, the effect of molecular gases on the MPT performance was investigated. Up to about 1% (v/v) of either oxygen or hydrogen in the central channel helium flow attenuated the signal levels for both carbon and chlorine, with the larger loss seen in the chlorine signal.     

气相色谱-质谱联用研究聚乙烯在氩气中的裂变行为

模拟电弧炉的燃烧环境,利用气相色谱-质谱联用法研究了聚乙烯在氩气气氛中不同温度、不同氩气流量下的裂变行为。结果表明:聚乙烯在氩气气氛中,在温度低于700℃时主要裂变形成链烃;在温度达到900℃时开始形成多环芳烃,温度越高,所形成的多环芳烃的种类越多,烷基化程度越高,相对浓度越大。氩气流量的变化明显影响了聚乙烯的裂变产物,实验结果验证了烯烃、二烯烃(炔烃)是多环芳烃前体化合物的假设,高温下多环芳烃生成数量和相对浓度比低温下高的主要原因是高温下聚乙烯的裂解程度增大,使得更多量烯烃、二烯烃(炔烃)形成。因此,控     

Recognition of chitin and proteins in invertebrate cuticles using analytical pyrolysis/gas chromatography and pyrolysis/gas chromatography/mass spectrometry

Flash pyrolysis/gas chromatography (py/GC) and py/GC/mass spectrometry (MS) have been utilized to characterize the cuticles of invertebrates chemically. Pyrolysis products have been identified and assigned to specific cuticular components. Acetylpyridones, acetamidofuran, 3-acetamido-5-methylfuran and 3-acetamido-(2 and 4)-pyrones are proposed as characteristic pyrolysis markers for chitin. Pyrolysis products displaying ions of m/z 70, 154, 168, 194 are thought to derive from diketopiperazine structures and provide potential markers for proteins and peptides in which proline, alanine, valine, arginine and glycine are the dominant amino acids. These products, constituting specific pyrolysis markers for invertebrate cuticles, may reflect the amino acid composition of their constituent structural proteins. The source of the various pyrolysis products of proteins has been verified by pyrolysis of reference proteins, peptides and amino acid mixtures. The presence of additional pyrolysis products related directly to histidine and catechol moieties is consistent with the chemical structure and composition proposed for arthropod cuticles based on recent work utilizing solid state 13C and 15N nuclear magnetic resonance. This study constitutes the first comprehensive chemical characterization of the pyrolysis products of invertebrate cuticles and provides the basis for future investigations requiring qualitative screening for cross-linked chitin and proteins in modern and fossil cuticles and in materials, e.g. geopolymers, that may be derived from them.     

Determination of linear alkylbenzenesulfonates and their degradation products in water samples by gas chromatography with ion-trap mass spectrometry

One hundred and five patients with traumatic brain injury (TBI) were assessed for depressive symptomatology at 6 months postinjury and 66 of those patients were examined again at 12 months postinjury. At 6 months, 42% of the patients with TBI and 20% of the Other Injury Control Group (OIC) were identified as depressed. Individuals with poor outcome (as measured by Glasgow Outcome Score [GOS]) had a higher frequency of depressive symptomatology than those with good GOS outcome. At 12 months, 36% of the patients with TBI and 28% of the OIC group were identified as depressed. At 12 months, there was no difference in terms of frequency of depressive symptomatology among patients with TBI with poor, moderate, or good outcome.     

Determination of 17 beta-estradiol and its metabolites in sewage effluent by solid-phase extraction and gas chromatography/mass spectrometry

The paper describes a simple and quantitative method for monitoring non-conjugated 17 beta-estradiol (E2) and its metabolites estrone (E1) and estriol (E3) as environmental contaminants in municipal sewage effluents. Estrogens were preconcentrated and cleaned up by solid-phase extraction using a reversed-phase C18 cartridge. They were derivatized with pentafluoropropionic acid anhydride, and the products were analyzed by gas chromatography/mass spectrometry. Recoveries from spiked distilled water and sewage were better than 87% at fortification levels of 100 and 20 ng/L. For a 1 L sewage sample and a concentration factor of 5000, detection limits were 5 ng/L for E1 and E2 and 10 ng/L for E3. In a brief survey of Canadian wastewater, these estrogens were detected in many raw sewage and effluent samples at concentrations ranging from 6 to 109 ng/L for E1, from < 5 to 15 ng/L for E2, and from < 10 to 250 ng/L for E3.