GC–MS studies on acylated derivatives of 3-methoxy-4-methyl- and 4-methoxy-3-methyl-phenethylamines: Regioisomers related to 3,4-MDMA

A series of side chain regioisomers of 3-methoxy-4-methyl- and 4-methoxy-4-methyl-phenethylamines have mass spectra essentially equivalent to the controlled drug substance 3,4-methylenedioxymethamphetamine (3,4-MDMA), all have molecular weight of 193 and major fragment ions in their electron ionization mass spectra at m/z 58 and 135/136. The acetyl, propionyl and trifluoroacetyl derivatives of the primary and secondary regioisomeric amines were prepared and evaluated in GC–MS studies. The mass spectra for these derivatives were significantly individualized and the resulting unique fragment ions allowed for specific side chain identification. The trifluoroacetyl derivatives provided more fragment ions for molecular individualization among these regioisomeric substances. These trifluoroacetyl derivatives showed excellent resolution on a non-polar stationary phase such as Rtx-1.     

应用气相色谱电子捕获检测器检测生物体内拟除虫菊酯杀虫剂

本文研究了一种同时测定生物样品中二氯苯醚菊酯、氯氰菊酯、杀火菊酯、溴氰菊酯的方法,并详细介绍了试管提取净化的过程。在安装电子捕获检测器的气相色谱仪上,选择不同极性的色谱柱和优选操作参数,能使上述4种杀虫剂达到基线分离,并在20～25分钟内同时完成分析。添加生物样品肝、胃,脑、血中的回收率达到70～90％;变异系数在±0.03～0.08范围。应用本文建立的方法,对中毒兔(溴氰菊酯和杀灭菊酯)各脏器均检出了原体杀虫剂,并成功地运用于一些法庭中毒案件的鉴定。     

Simultaneous identification/determination system for phentolamine and sildenafil as adulterants in soft drinks advertising roborant nutrition

An easily available, simultaneous identification/determination procedure for phentolamine (PHE) and sildenafil (SIL) in adulterated dietary supplements was established by using a combination of three different analytical methods; thin-layer chromatography (TLC), liquid chromatography–mass spectrometry (LC/MS) and a high-performance liquid chromatography (HPLC)/photo-diode-array. The sample solution for TLC was applied to silica gel 60 F₂₅₄ plates with chloroform/ammonia solution (28)/methanol (70:5:3, lower layer) and chloroform/diethylamine/methanol (15:3:2) as the developing solvent. Spots were located under UV radiation at 254 nm. Mass spectra of PHE and SIL by LC/MS were investigated with electrospray ionization (ESI) interface, under both positive and negative ion mode. The HPLC analysis was performed on a column of Wakosil 5C18 (4.6 mm×150 mm, 5 μm) with water/methanol/acetonitrile/triethylamine (580:250:170:1) adjusted with phosphoric acid to pH 3.0 as the mobile phase, and the effluent was monitored with a photo-diode-array detector. Quantitative HPLC analysis of PHE and SIL were detected at 280 nm. When this procedure was applied to commercial soft drinks, PHE and SIL were identified and determined at a concentration of 17 mg PHE and 44 mg SIL per bottle, respectively. The procedure described here is available for the screening of PHE and SIL in adulterated supplements.     

Drugs in motorists traveling Swedish roads: on-the-road-detection of intoxicated drivers and screening for drugs in these offenders

This paper deals with the police officer's or police doctor's ability to find drivers under the influence of drugs. We have also studied whether the protocol on the driver's previous histories of drug intake is useful for directing the chemist in his analytical approach to revealing intoxicants in the suspects' body fluids. A comprehensive procedure for screening traffic-hazardous drugs in the urine was found necessary and is described. By using this method, we have studied the incidence of drunken drivers with detectable medicinal or illicit agents. The results demonstrate that 91% of those drivers found by the officer or doctor of the police to be on intoxicants other than ethanol, carried some kind of traffic-hazardous drug in their body fluids, and that the doctor was a better judge than the police in identifying these offenders. By using a series of chemical methods for drug screening, we found that every third driver suspected of drunken driving due to ethanol, but not to other intoxicants, held some kind of a traffic-hazardous drug substance in his urine; benzodiazepines and cannabinoids were the most common findings. The data imply that 34% of these suspects revealed their intakes of traffic-dangerous intoxicants. We conclude that the judgements of both the officer and doctor of the police are needed for an efficacious detection of drivers under the influence of drugs. Moreover, the results infer that the chemist has to screen for intoxicants to reveal these in a suspect driver. We also conclude that drugs, particularly the benzodiazepines or cannabinoids, may be commonly encountered in drunken drivers, suspected of being inebriated by ethanol but no other toxicants.     

液相色谱-串联质谱法检测血液中的美西律

目的建立测定血液中美西律(mexiletine)的液相色谱-串联质谱联用法(LC-MS/MS)。方法采用简便的乙腈蛋白沉淀法对血液进行预处理,应用Allure PFP Propyl液相柱分离,用电喷雾正离子模式离子化,多反应监测模式对美西律进行分析。结果美西律与内标纳洛酮分离良好,在0.02～10.00μg/mL内线性关系良好,相关系数为0.9999,回归方程为y=0.0283x-0.0151,日内与日间精密度的RSD均小于15%,最低检测限为0.01μg/mL。结论建立的LC-MS/MS方法简单、灵敏、可靠,可同时适用于美西律临床药物监测和法医毒物分析的需要。     

Development of a harmonised method for the profiling of amphetamines V: Determination of the variability of the optimised method

This paper is the fifth in a series of six in relation to the development of a harmonised method for the profiling of amphetamine [L. Aalberg, K. Andersson, C. Bertler, H. Borén, M.D. Cole, J. Dahlén, Y. Finnon, H. Huizer, K. Jalava, E. Kaa, E. Lock, A. Lopes, A. Poortman-van der Meer, E. Sippola, Development of a harmonised method for the profiling of amphetamines I. Synthesis of standards and compilation of analytical data, Forensic Sci. Int. 149 (2005) 219-229; L. Aalberg, K. Andersson, C. Bertler, M.D. Cole, Y. Finnon, H. Huizer, K. Jalava, E. Kaa, E. Lock, A. Lopes, A. Poortman-van der Meer, E. Sippola, J. Dahlén, Development of a harmonised method for the profiling of amphetamines II. Stability of impurities in organic solvents, Forensic Sci. Int. 149 (2005) 231-241]. The third paper [K. Andersson, K. Jalava, E. Lock, L. Aalberg, Y. Finnon, H. Huizer, E. Kaa, A. Lopes, A. Poortman-van der Meer, M.D. Cole, J. Dahlén, E. Sippola, Development of a harmonised method for the profiling of amphetamines III. Development of the gas chromatographic method, Forensic Sci. Int., in press] dealt with the optimisation of the gas chromatographic and detection methods whereas the fourth paper [K. Andersson, K. Jalava, E. Lock, Y. Finnon, S. Stevenson, L. Aalberg, H. Huizer, E. Kaa, A. Lopes, A. Poortman-van der Meer, M.D. Cole, J. Dahlén, E. Sippola, Development of a harmonised method for the profiling of amphetamines IV. Optimisation of sample preparation, Forensic Sci. Int., in press] concerned the optimisation of the extraction method prior to GC analysis. This paper is a study of the optimised method in order to determine its stability. Investigations of within and between day variations were carried out in four laboratories. Moreover, variations between laboratories were also determined. Both flame ionisation detector (FID) and MS detection were used. One laboratory studied nitrogen-phosphorous detector (NPD) detection as well. For this task, 12 batches of amphetamine were prepared. Six of them were synthesised via the Leuckart route, three via the nitrostyrene route and three via the reductive amination route [A.M.A. Verweij, Impurities in illicit drug preparations: amphetamine and methamphetamine, Forensic Sci. Rev. 1 (1989) 2-11]. Taking into account all studied target compounds and the average results from four laboratories, the within day variation was around 6% for FID and 5% for MS, the between days variation was around 10% for FID and 8% for MS. For NPD detection, within day variation was 5% and between days variation 9% (only one laboratory). Finally, the inter-laboratory variation was about 12% for FID (four laboratories) and 10% for MS (three laboratories).     

Hair as a specimen to document tetramethylene disulfotetramine exposure

Tetramethylene disulfotetramine (tetramine) is a rodenticide that has been banned for many years in China. Since 2005, inhabitants of a village in the Henan Province have been suffering from grand mal seizures. To investigate the possibility of tetramine as the cause, we developed a method to determine tetramine in human hair. Sample preparation involved external decontamination, frozen pulverization, and ultrasonication in 2 mL ethyl acetate in the presence of cocaine-d3 as an internal standard. The method exhibited good linearity; calibration curve was linear over a range of 0.1-20 ng/mg hair. The limit of detection for the assay was 0.05 ng/mg hair. Except for one subject (No. 4), all head and pubic hair samples were positive for tetramine. The concentrations of tetramine in pubic hair were significantly higher than those in the same subjects' head hair samples. Because of a long retention in body, segmental head hair analysis cannot provide an accurate exposure history of tetramine in the body.     

GC/MS衍生化测定精浆中游离支链氨基酸和果糖

目的 建立人精浆中支链氨基酸和果糖的气相质谱衍生化分析方法.方法 精液样本液化离心后,按精子活率的临床标准分为正常组和非正常组,经TMS微波衍生化,GC/MS分析两组支链氨基酸、果糖衍生物含量差异.结果 正常组与非正常组的缬氨酸,亮氨酸,异亮氨酸在相对含量上均有一定差异.正常组3种氨基酸相对含量高于非正常组.果糖分析观察到同样的特征,正常组相对含量高于非正常组.结论 精子活率低的精浆样本仍可检出支链氨基酸和果糖,其差异有助于无精子、少精子精斑的法医学鉴别.     

GC/MS法联合分析生物检材中的尼美舒利、二氧丙嗪

目的建立生物检材中尼美舒利、二氧丙嗪的GC/MS检验方法。方法采用浸取法提取,GC/MS定性检验,内标法选择离子检测（SIM）模式定量检验。结果最低回收率为69%,尼美舒利的线性相关系数为0.998,克咳敏的线性相关系数为0.9973。结论该方法操作简便快速,提取率高,可用于实际案件中尼美舒利、二氧丙嗪的检验。