Determination of sorbic acid in urine by gas chromatography-mass spectrometry.

The average daily uptake of the common food preservative sorbic acid is estimated to range from 0.01 to 1.1 mg kg-1. Sorbic acid mainly is metabolised to carbon dioxide. Minor amounts are converted to trans,trans-muconic acid (ttMA) as well as excreted unchanged into the urine. Since urinary ttMA is a biomarker for the occupational and environmental exposure to benzene, there is an additional need for monitoring the uptake of sorbic acid, particularly at low, environmental benzene exposure levels. For this purpose, a simple, robust and rapid method for the determination of sorbic acid in urine at trace levels was developed. After addition of 10 ml of water and 5 ml of 8 M hydrochloric acid to 10 ml of the thawed urine, the sample was water steam distilled using an automated distillation device. A total of 100 ml of the distillate were solid-phase extracted. After washing, the sorbic acid was eluted with 4 ml methanol. The eluate was reduced under a stream of nitrogen to a volume of 300 microliters. After addition of 500 microliters boron trifluoride in methanol and incubation for 1 h at 60 degrees C, the resulting sorbic acid methyl ester was extracted three times with 1 ml heptane. To the combined heptane layers, sorbic acid ethyl ester was added as an internal standard. After reducing to a volume of 100 microliters in a stream of nitrogen, the final analysis was performed by GC-MS using the fragment ions m/z 126 for the analyte and m/z 140 for the internal standard. The limit of detection was 0.7 ng ml-1 urine and the R.S.D. of 69 duplicate determinations was 7.5%. In a controlled, experimental study and in a field study, we were able to show that urinary sorbic acid is a marker for the dietary uptake of sorbic acid and that sorbic acid is converted to ttMA. On average, 0.1% of the dietary sorbic acid is excreted unchanged into the urine. Excretion is complete within 24 h. We found that, on average, 0.23% of the oral dose of sorbic acid is excreted as urinary ttMA. There was a significant correlation between urinary excretions of sorbic acid and ttMA (r = 0.74, n = 69). We conclude that urinary sorbic acid can be used to correct the urinary ttMA level in order to determine the portion related to benzene exposure. This appears to be necessary particularly at low, environmental benzene levels.     

Determination of atenolol in human urine by gas chromatography-mass spectrometry method

A sensitive and efficient method was developed for the determination of atenolol in human urine by gas chromatography-mass spectrometry (GC-MS). Atenolol and metoprolol (internal standard, IS) were extracted from human urine with a mixture of chloroform and butanol at basic pH with liquid-liquid extraction. The extracts were derivatized with N-Methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and analyzed by GC-MS using a capillary column. The standard curve was linear (r = 0.99) over the concentration range of 50-750 ng/mL. Intra- and inter-day precision, expressed as the relative standard deviation were less than 5.0%, and accuracy (relative error) was better than 7.0%. The analytical recovery of atenolol from human urine has averaged 91%. The limit of quantification was 50 ng/mL. Also, the method was successfully applied to a patient with hypertension who had been given an oral tablet of 50 mg atenolol.     

Determination of pyrethroid metabolites in human urine by capillary gas chromatography-mass spectrometry

Summary An analytical method for the simultaneous determination of the pyrethroid metabolites cis and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid, cis 3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid, 3-phenoxybenzoic acid and 4-fluoro-3-phenoxybenzoic acid in human urine samples is described. The urine is subjected to acid-induced hydrolysis followed by exhaustive solvent extraction, covering both conjugated and free acids, followed by a common derivatisation step yielding the corresponding methyl esters. Quantitation was by diastereomeric, capillary gas chromatography-mass spectrometry. It appears that 4-fluoro-3-phenoxybenzoic acid is a characteristic urinary marker for cyfluthrin exposure. The limits of determination are 0.5–1.0 g L^–1 urine depending on the metabolites concerned. The applicability of the method was tested on urine samples from pest control operators exposed occupationally to cypermethrin and cyfluthrin.     

Determination of debrisoquine and metabolites in human urine by gas chromatography-mass spectrometry.

A gas chromatographic-mass spectrometric analysis has been developed for the determination of debrisoquine and its metabolites in the urine of healthy individuals (controls) and patients with chronic renal failure. The sensitive and specific assay comprises selected-ion monitoring of the drug and the metabolites 4-hydroxydebrisoquine and 8-hydroxydebrisoquine using guanoxan as the internal standard. The limit of detection is ca. 0.2 microgram/ml. The clinical study shows that the healthy individuals and patients with chronic renal failure can be divided in two groups of extensive metabolizers and poor metabolizers, respectively. The extensive metabolizers excreted large amounts of 4-hydroxydebrisoquine and minor amounts of 8-hydroxydebrisoquine. The poor metabolizers excreted small amounts of 4-hydroxy metabolite, and no 8-hydroxydebrisoquine was detected in the urine.     

Determination of inositol isomers and arabitol in human urine by gas chromatography-mass spectrometry

Summary A capillary gas chromatography method for the analysis of inositol isomers and arabitol (extendable to threitol and adonitol) is described and applied to urine after derivatization. The single ion monitoring technique allows a notable improvement in sensitivity and selectivity.     

Determination of clenbuterol in urine as its cyclic boronate derivative by gas chromatography-mass spectrometry

A rapid and reliable gas chromatographic-mass spectrometric method for the determination of clenbuterol in urine is described. Penbutolol was used as internal standard. Four derivatization procedures have been tested, of which 1-butaneboronic acid gave the best results. The method includes extraction of the alkalinized urine (3 ml) with tert.-butyl methyl ether-n-butanol (9:1), derivatization with 1-butaneboronic acid (15 min at room temperature), and analysis in the selected-ion monitoring mode of the derivatives of clenbuterol at m/z 243, 327 and 342 and of penbutolol at m/z 342 and 357. The detection limit is 0.5 ng/ml and the recovery better than 90%.     

Determination of cocaine and cocaethylene in urine by solid-phase microextraction and gas chromatography-mass spectrometry

In order to evaluate recent cocaine exposure or its coingestion with ethanol, a simple and sensitive solid-phase microextraction (SPME) procedure for determination of cocaine and cocaethylene in urine was developed and validated. A polydimethylsiloxane fibre (100 microm) was submersed in the urine sample for 20 min under magnetic stirring after alkalinization with solid buffer (NaHCO(3):K(2)CO(3), 2:1). Gas chromatography-mass spectrometry (GC-MS) was used to identify and quantify the analytes in selected ion monitoring mode (SIM). The limits of quantification were 5.0 ng/mL for both analytes. Good inter- and intra-assay precision was also observed (coefficient of variation <9%).     

Measurement of imidazoleacetic acid in urine by gas chromatography-mass spectrometry

Imidazoleacetic acid (IAA), a histamine and histidine metabolite, was quantified in human urine by gas chromatography-mass spectrometry (GC-MS). The acid was separated by ion-exchange chromatography, derivatized as the n-butyl ester with boron trifluoride-butanol and the derivative extracted with chloroform. GC-MS analysis was carried out by selected-ion monitoring of ions m/z 81 and m/z 83 corresponding, respectively, to IAA and [15N,15N']IAA used as internal standard. The mean IAA content in urine was about 8.02 nmol/mg of creatinine. The specificity of measurement was rigorously established by GC retention time, peak shape, ion abundance ratios, and recovery experiments. The method is capable of quantifying IAA in 0.05 ml of urine and in amounts as low as 0.20 nmol.     

GC-MS直接测定芥酸酰胺

通常衍生后的酰胺才能用气相色谱测定.在实验几种酰胺衍生化方法时发现衍生反应不彻底剩余的芥酸酰胺也能出峰.进一步实验表明:芥酸酰胺在295 ℃气化后可直接测定,该法以邻苯二甲酸二丁酯为内标,质量浓度在115.4～923.2 mg/L 范围内线性关系良好,样品回收率94.85%～98.04%,芥酸酰胺的检出限5.77 mg/L.     

Determination of amino acid enantiomers in human urine and blood serum by gas chromatography-mass spectrometry

Amino acid (AA) enantiomers were determined as N(O)-pentafluoropropionyl-(2)-propyl esters by chiral gas chromatography-mass spectrometry (GC-MS) in 24 h samples of the urine of three healthy volunteers and in their blood sera. In urine the largest amounts were determined for D-Ser (64-199 micromol/day) and D-Ala (24-138 micromol/day). In blood sera, D-Ala (2.3-4.2 micromol/L) and D-Ser (1.0-2.9 micromol/L) were most abundant. Varying amounts of the D-enantiomers of Thr, Pro, Asx, Glx, Phe, Tyr, Orn and Lys were also found, albeit not in all urines and sera. Further, enantiomers were quantified in urine samples of two volunteers fasting for 115 h. Quantities of renally excreted D-AAs decreased in fasting, although amounts of D-Ser (69 and 77 micromol/L urine) as well as other D-AAs were still detectable. Time-dependent analyses of urine showed that D-AAs are continuously excreted. Copyright -Copyright 2001 John Wiley & Sons, Ltd.     

固相萃取-气相色谱-质谱法分析尿液中邻苯二甲酸单酯和双酯

建立了固相萃取-气相色谱-质谱测定尿液中邻苯二甲酸单酯和双酯的分析方法。尿液经 β-葡萄糖苷酸酶酶解后进行固相萃取净化,用乙腈、乙酸乙酯和乙醚-正己烷(1: 19, v/v)分别洗脱,合并洗脱液,氮气吹干后,用N,O-双三甲基硅基三氟乙酰胺(BSTFA)对邻苯二甲酸单酯进行硅烷化处理,使用气相色谱-质谱法检测。邻苯二甲酸单酯和双酯的线性范围为5~1000 μ g/L,检出限为0.3~1.1 μ g/L,回收率为77.9%~97.7%,相对标准偏差为3.7%~10.9%。应用该方法对50份尿液进行检测,检出邻苯二甲酸二(2-乙基己基)酯(DEHP)等7种邻苯二甲酸单酯和双酯类物质,平均质量浓度为6.0~142.7 μ g/L。该方法准确、可靠、灵敏度高,适用于尿液中邻苯二甲酸单酯和双酯的同时测定。     

气相色谱-质谱法测定化妆品中的三氯叔丁醇

建立了测定化妆品中三氯叔丁醇的气相色谱-质谱分析方法.膏霜、水剂、散粉、香波、唇膏等不同类型的化妆品样品加入50％甲醇-无水乙醇或无水乙醇超声提取后,样品提取液高速离心处理,取上清液经无水硫酸钠脱水,进行气相色谱-质谱定性及定量分析.选用DB-1701(30 m×0.25 mm×0.25μm)石英毛细管柱,程序升温,流...     

气相色谱-质谱法测定水中痕量的四乙基铅

建立了气相色谱-质谱(GC-MS)测定水中痕量四乙基铅的分析方法。用正己烷萃取水样中的四乙基铅,萃取液浓缩后加入同位素内标萘-d8,采用GC-MS选择离子方式(SIM)进行检测,在200 mL水样中四乙基铅的检出限可达0.04 μg/L;添加回收率为92.2%～103%,准确度好;平行5次测定的相对标准差为4.4%～13.3%。结果表明: 方法简便、快速、准确、实用,可用于水中痕量四乙基铅的测定。     

气相色谱-质谱法检测涂料中的六溴环十二烷

建立了防火涂料中阻燃剂六溴环十二烷(HBCD)的气相色谱-质谱(GC-MS)分析方法。样品用二氯甲烷进行萃取,萃取液经有机滤膜过滤后,用气相色谱-质谱联用仪进行测定。在选择离子检测模式下以m/z 157、239、319、401为定性离子,m/z 239为定量离子进行结构确证和定量检测。在优化的实验条件下,六溴环十二烷标准溶液在5~100 mg/L的质量浓度范围内线性关系良好,相关系数大于0.999。对市售的空白丙烯酸树脂涂料样品及环氧树脂涂料样品进行加标回收试验,结果表明本方法的平均回收率为92.9%~116.3%, RSD不超过8%。方法的检出限(S/N=3)为30 μg/g,定量限(S/N=10)为100 μg/g。本方法简便、快速、准确性好、精密度高,能够满足检测工作的实际要求。     

蜂蜜中氯霉素残留的气质分析方法研究

氯霉素(chloramphenicol)又名左旋霉素,是一类广谱抗生素,作为药物常用于家禽疾病治疗和预防.氯霉素对人的造血系统、消化系统具有严重的毒性反应,有可能引发人的再生障碍性贫血.因此欧盟等国家规定蜂蜜及其它动物源食品中氯霉素的最高残留量不得超过0.1μg/kg.本文对蜂蜜样品的提取、净化和富集方法进行了较为系统地研究,建立了固相萃取-气相色谱-质谱联机分析蜂蜜中的氯霉素残留量的方法.对氯霉素在固相萃取柱上的保留行为进行了研究,优化固相萃取条件,发现在选定的条件下,不同浓度的氯霉素在硅胶柱和C18柱上的回收率均在90%以上,蜂蜜加标的回收率在80%～95%,相对标准偏差在7.2%～18.2%,最低检出限为0.1μg/kg.对氯霉素的三甲基硅烷化衍生物采用选择离子的模式进行检测(376,378,466、468、470),衍生物的峰面积与样品浓度在0.55～220 ng/mL范围内呈良好的线性关系,线性回归系数为0.9998.     

Determination of free salsolinol concentrations in human urine using gas chromatography-mass spectrometry.

The urine concentrations of free salsolinol were determined in six healthy volunteers, using a gas chromatographic-mass spectrometric method with electron-capture negative-ion chemical ionization after derivatization with pentafluoropropionyl anhydride. The sensitivity of this method allows the quantification of salsolinol concentrations of 0.55 pmol/ml. The synthesis of [2H4]salsolinol from dopamine and [2H4]acetaldehyde via a Pictet-Spengler condensation is described; [2H4]salsolinol was used as the internal standard for salsolinol quantification. The urine concentrations of free salsolinol ranged from ca. 1 to 6 pmol/ml.