高效液相色谱法测定工人尿中三硝基甲苯及五种代谢物(二)——分析方法的建立及应用

本文建立了高效液相色谱(HPLC)测定工人尿中TNT及五种代谢物的方法。TNT、4-A、2-A、2,6-DA和2,4-DA的平均回收率66.6～95.0％,变异系数在2.1～10.6％之间,最小检测限为3.0～8.1μg/L尿。本方法已用于35个接触TNT工人尿样的分析。     

高效液相色谱法测定工人尿中三硝基甲苯及五种代谢物(二)分析方法的建立及应用

本文建立了高效液相色谱(HPLC)测定工人尿中TNT及五种代谢物的方法.TNT、4-A、2-A、2,6-DA和2,4-DA的平均回收率66.6～95.0%,变异系数在2.1～10.6%之间,最小检测限为3.0～8.1μg/L尿.本方法已用于35个接触TNT工人尿样的分析.     

接触TNT工人尿中代谢物及致诱变活性

关于TNT对接触工人的遗传毒性尚未阐明,本文作者在1985年的研究中,发现接触TNT工人尿样的致诱变活性增加;TNT工人中胃癌发生率高。本文研究旨在分析接触TNT工人尿样中的TNT及其代谢物4—DNAT(2,6二硝基-4-氨基甲苯)和2-DNAT(4,6二硝基-2-氨基甲苯)的水平,进一步评价不同接触水平的TNT工人尿样的致诱变活性,查明这些参数间的     

气相色谱法测定尿中4—氨基—2,6—二硝基甲苯的研究

本文建立了气相色谱法(GC)测定尿中4-氨基-2,6-二硝基甲苯(4-A或DNAT)的方法,尿样加HCl于100℃加热1h,使4-A水解,在pH7～8用甲苯萃取尿样中4-A,然后进行GC分析。采用1.5％OV-17/Shimalite W(AW—DMCS)201D(80—100目)玻璃柱,电子捕获检测器(Ni~(63)源)2 6-二硝基甲苯为内标。本方法的检测限为7.2×10~(-12)g,尿样的最低检测浓度为4μg/L,批内精密度2.2～1.3％,批间精密度4.1～3.4％。回收率为85～100％,本方法已用于78名职业接触TNT工人的尿样分析。     

三硝基甲苯的代谢物—2-氨基-4,6-二硝基甲苯和2,4-二氨基-6-硝基甲苯的合成

本文报告了2,4,6-三硝基甲苯(TNT)的代谢物,2-氨基-4,6-二硝基甲苯2和2,4-二氨基-6-硝基甲苯3的合成。以邻甲基苯甲酸为原料,经硝化(HNO_3-H_2SO_4)和Schmidt反应(NaN_3-H_2SO_4)得到2,用NaHS还原TNT的方法合成化合物3。     

血中三硝基甲苯及代谢物的测定和应用

三硝基甲苯(TNT)为氧化应激毒物~[1,2]。其毒作用范围很广。因此,测定职业接触TNT工人血中TNT及代谢产物,对中毒机理研究及生物监测都具有重要意义。本文根据巳经建立的液相色谱分离、萃取和血样水解条件~[3],对现场接触和不接触TNT工人血中TNT及两种代谢产物4—氨基—2,6-二硝基甲苯(4A)和2—氨基—4,-二硝基甲苯(2A)分别进行了测定,并获得了满意的测定效果。     

TNT作业工人尿中TNT及其代谢物DNAT的排出规律

本文为进一步研究职业性接触三硝基甲苯(TNT)的生物监测指标提供依据,对某炸药厂部分TNT生产工人尿中TNT原形及其代射物DNAT(2,6—二硝基—4—氨基甲苯)的排出规律进行现场观察。 一、对象和方法 选TNT接触工龄5年以上,年龄20～40岁男性工人5名,作为长期接触TNT组;另选该厂男性行政人员3名,年龄20～40岁,以往无直接接触史,作为短期接触TNT组。两组观察对象均无慢性TNT中毒史。     

高效液相色谱法测定工人尿中三硝基甲苯及五种代谢物(一)——色谱分离及水解、提取条件的选择

本文用高效液相色谱法在5μm反相C~(13)离子对柱、甲醇/水系统下,分离了TNT及五种代谢物。确定了尿样的水解采用两种方式:在40℃下加6N HCl(0.1ml/ml尿)水解10分钟,中和后提取4-HA;在100℃下加浓HCl(0.1ml/ml尿)水解60分钟,中和后提取其它TNT代谢物。提取剂用苯,提取比为1:1,溶液pH=7,振荡时间5分钟。在上述水解条件下可使各代谢物水解量达到最大。     

血浆中三硝基甲苯及代谢产物的反相高效液相色谱分析方法

应用高效液相色谱(HPLC)测定三硝基甲笨及其代谢物2,6-二硝基-4-氨基甲苯的方法已有介绍,但多局限于标准品测定的研究。目前尚未见有血样品的分析和测试的报道。本文对此进行了研究。实验方法1.仪器:美国Waters 高效液相色谱仪;510型泵,M490紫外检测器,840型色谱数据处理机,U6K 型进样阀。2.试剂:2,4,6-三硝基甲苯(TNT),军工     

尿中2,6—二硝基—4—氨基甲苯(即TNT的代谢物)的测定(重氮—偶合比色法)

原理 TNT接触者尿中的主要代谢物为2,6-二硝基-4-氨基甲苯(简称DNAT),经酸水解游离后,可用乙醚萃取之;乙醚液经蒸干后,     

Ames试验检测三硝基甲苯及其还原代谢产物的诱变性

应用Ａｍｅｓ试验检测系统观察了三硝基甲苯及其还原代谢产物４－羟氨基－２，６－二硝基甲苯（４－ＨＡ），４－氨基－２，６－二硝基甲苯（４－Ａ），２－氨基－４，６－二硝基甲苯（２－Ａ）和２，４－二氨基－６－硝基甲苯（２，４－ＤＡ）的诱变活性，实验结果显示，三硝基甲苯及其代谢产物具有明显的致突变作用，４－Ａ的直接诱变活性最强，而且移码型诱变性更为显著，在微粒体酶系统的参与下，ＴＮＴ的诱变活性增强，其代谢产     

三硝基甲苯及其代谢产物与脱氧核糖核酸的结合作用

运用吸收光谱移动法观察了三硝基甲苯（ＴＮＴ）及其代谢产物与脱氧核糖核酸（ＤＮＡ）的结合作用。结果表明：在ＴＮＴ及其代谢产物浓度一定的条件下，改变ＤＮＡ浓度，结果随着ＤＮＡ浓度的降低，ＴＮＴ及其代谢产物的最大吸收峰λｍａｘ出现短移，且吸收强度也随之增大。当ＤＮＡ浓度固定时，改变ＴＮＴ及其代谢产物浓度时，发现ＴＮＴ（１００μｍｏｌ／Ｌ）、４－Ａ（５０，２５μｍｏｌ／Ｌ）使ＤＮＡλｍａｘ２２８ｎｍ峰消失。提示：ＴＮＴ及其代谢产物与ＤＮＡ有不同程度的结合作用。     

Trinitrotoluene: assessment of occupational absorption during manufacture of explosives.

Trinitrotoluene (TNT) absorption was assessed in groups of workers at two explosives factories by measuring the urinary concentrations of dinitroaminotoluene (DNAT) metabolites. DNAT was detected in most of the urine samples analysed and for postshift samples the mean (SD) concentration was 9.7 (7.9) mg/l (range 0.1-44 mg/l (n = 219)). Individual workers showed substantial day to day variations in DNAT concentrations in postshift urine samples, but on a group basis the concentrations remained fairly constant throughout the working week. Preshift urine samples taken at the beginning of a working week showed low concentrations of DNAT which initially suggested that the elimination of TNT metabolites is fairly rapid. A survey carried out of preshift and postshift urine samples collected from a group of workers for a full working week showed wide variations in the rate of clearance of TNT metabolites from the body and in some cases higher concentrations of metabolites were seen in the samples taken the morning after exposure. When urine samples were collected from the same group of workers after 17 days away from the workplace DNAT was still detectable in samples from eight of the nine subjects, indicating that a proportion of TNT or its metabolites is slowly excreted. When five subjects were monitored more intensively during two workshifts TNT was shown to be absorbed rapidly during the exposure period. In most cases the highest concentrations were seen in the postshift urine samples but significant proportions were still present in samples taken the morning after exposure. Atmospheric levels of TNT were found to be too low to account for the observed excretion of DNAT and dermal uptake rather than inhalation appears to be the major route of absorption.     

Trinitrotoluene: assessment of occupational absorption during manufacture of explosives

Trinitrotoluene (TNT) absorption was assessed in groups of workers at two explosives factories by measuring the urinary concentrations of dinitroaminotoluene (DNAT) metabolites. DNAT was detected in most of the urine samples analysed and for postshift samples the mean (SD) concentration was 9.7 (7.9) mg/l (range 0.1-44 mg/l (n = 219)). Individual workers showed substantial day to day variations in DNAT concentrations in postshift urine samples, but on a group basis the concentrations remained fairly constant throughout the working week. Preshift urine samples taken at the beginning of a working week showed low concentrations of DNAT which initially suggested that the elimination of TNT metabolites is fairly rapid. A survey carried out of preshift and postshift urine samples collected from a group of workers for a full working week showed wide variations in the rate of clearance of TNT metabolites from the body and in some cases higher concentrations of metabolites were seen in the samples taken the morning after exposure. When urine samples were collected from the same group of workers after 17 days away from the workplace DNAT was still detectable in samples from eight of the nine subjects, indicating that a proportion of TNT or its metabolites is slowly excreted. When five subjects were monitored more intensively during two workshifts TNT was shown to be absorbed rapidly during the exposure period. In most cases the highest concentrations were seen in the postshift urine samples but significant proportions were still present in samples taken the morning after exposure. Atmospheric levels of TNT were found to be too low to account for the observed excretion of DNAT and dermal uptake rather than inhalation appears to be the major route of absorption.     

三硝基甲苯及其代谢产物对兔肝匀浆谷胱甘肽水平的影响

三硝基甲苯（ＴＮＴ）及其代谢产物与兔肝匀浆于３７℃孵育１ｈ。随着ＴＮＴ、４－ＡＨ浓度的增大，肝匀浆中ＧＳＨ的含量呈明显的下降趋势，而２－Ａ、４－Ａ及２，４－ＤＡ之肝匀浆中ＧＳＨ的水平与对照相比无显著性差异。５６０μｍｏｌ／ＬＴＮＴ及５６０μｍｏｌ／Ｌ４－ＡＨ与肝匀浆孵育不同时间，肝匀浆中ＧＳＨ含量随着时间的延长而降低，结果表明：在ＴＮＴ及其代谢产物中，除ＴＮＴ外，４－ＡＨ对动物肝也表现出毒性作用。     

Excretion of p-chloroaniline metabolites into urine. Excretion of 2,4-dichloroaniline and p-chloroformanilide]

Previously, we identified by gas chromatography/mass spectrometry (GC/MS) urinary metabolites of p-chloroaniline (p-CA) in a patient with acute p-CA poisoning. Among these metabolites there is a possibility that 2,4-dichloroaniline (2,4-DCA) and p-chloroformanilide (p-CFA) are produced through some unknown metabolic pathways in human. In order to clarify whether 2,4-DCA and p-CFA were produced within the human body or not, an attempt was made to detect these metabolites in the patient's urine samples prepared by various pretreatments, using both GC/MS and high performance liquid chromatograph. In addition, the detection of these metabolites in non-exposed person's urine samples spiked with p-CA and 2-amino-5-chlorophenol was attempted by GC/MS using same the procedures in order to examine whether p-CA and 2-amino-5-chlorophenol excreted as metabolites were further changed to 2,4-DCA or p-CFA in the urine or not. 2,4-DCA was found abundantly in the ethereal extracts from the patient's urine samples hydrolyzed with hydrochloric, sulfuric and nitric acids, but only small amounts from intact urine samples by GC/MS. No 2,4-DCA was detected in the urine samples to which were added p-CA and 2-amino-5-chlorophenol. p-CFA was found in the ethereal samples which were extracted at acidic conditions from the patient's urine samples by GC/MS at the injection port temperature of 250 degrees C of the gas chromatograph, but the p-CFA peak disappeared at the injection port temperature of 150 degrees C.(ABSTRACT TRUNCATED AT 250 WORDS)     

Identification and quantitative analysis of urinary metabolites of dichloropropanols in rats.

Urinary metabolites of dichloropropanols in rats were analyzed by gas chromatography-mass spectrometry (GC/MS). Solutions of dichloropropanols consisting of 1, 3-dichloro-2-propanol (DC2P) and 2, 3-dichloro-1-propanol (DC1P) were diluted in a saline at the concentration of 100 mg/ml, and 0.1 ml of the solutions were subcutaneously injected into male Wistar rats weighing about 160g. The urine samples were collected over a period of 24 hours after the injections. DC2P and DC1P in the urine were extracted with ethylacetate and analyzed by a GC/MS. The derivatization procedure with 4-bromophenylboric acid after acetonitril extraction was applied for the analyses of diols in the urine. By the GC/MS analysis, 3-chloro-1, 2-propanediol (3CPD), 2-chloro-1, 3-propanediol (2CPD) and 1, 2-propanediol (PPD) were identified as the hydroxylated metabolites of dichlorpropanols. Based on the analytical results, the metabolic pathways of dichlorpropanols forming 3CPD and 2CPD, and then hydroxylating to PPD were elucidated.     

Occupational exposure to aromatic hydrocarbons at a coke plant: Part I. Identification of hydrocarbons in air and their metabolites in urine by a gas chromatography-mass spectrometry method

A method for the qualitative analysis of aromatic hydrocarbons in air and their various urinary metabolites is presented. The air was sampled in charcoal tubes and extracted with carbon disulfide. The hydrocarbons were identified as being aliphatic hydrocarbons (C(9)-C(19)), aromatic hydrocarbons and heterocyclic compounds. The urinary metabolites after enzymatic hydrolysis were analyzed by solid-phase extraction with a styrene-divinylbenzene resin, silylation with N,O-bis(trimethylsilyl)acetamide and GC/MS for separation and detection. Satisfactory separation of all compounds investigated was achieved without interference due to matrix peaks. The following compounds were identified in the urine of workers: dimethylphenol isomers, 4-ethyl-1,3-benzenediol, 2-ethoxybenzoic acid and methoxyphenols. Trimethylsilyl derivatives of aromatic hydroxyacids and hydroxymethoxyacids were found in the urine of occupationally exposed workers by means of a silylation procedure.