生物试样中巴比妥类药物固相提取柱上衍生化GC/MS分析

建立生物试样中常见巴比妥类药物的固相提取和柱上衍生化GC／MS分析法。将预制的血或肝分别在pH6．0和pH2.2的条件下过预活化的GDX－403吸附小柱，再用缓冲浪和蒸馏水各4ml顺序洗柱。最后用4ml丙酮／氯仿（1：1）溶剂洗脱样品，离心弃除水相，80℃挥至近干，用50μl乙醇定溶、取净化的样品2～4μl挥至近干，加20μl0．2molTMAH衍生化试剂，直接进样0.5μl，柱上衍生化GC／MS（GC）分析。在试验条件下，当血和肝分别添加2．0μg和5．0μg混合药物，回收率≥80％，相对标准差（RSD）优于±10％，检测限优于5ng（信／噪比≥2）。该法能有效地排除类脂物和组胺的干扰，可用于治疗量级药物分析和婴幼儿中毒案检验。     

SPME-GC\NPD法快速分析尿液中苯丙胺类化合物

建立了ＳＰＭＥ－ＧＣ／ＮＰＤ法同时分析尿液中九种苯丙胺类化合物的方法。取１ｍｌ尿样以４－苯基丁胺为内标,在碱性条件下,将１００μｍＰＤＭＳ纤维头浸入尿液中２０ｍｉｎ,气相色谱进样后热解吸３ｍｉｎ,用ＧＣ／ＮＰＤ进行测定。九种苯丙胺类化合物及内标完全分离,五种苯丙胺类化合物分别在０．０５～１５、０．１～１５、０．２～１５μｇ／ｍｌ浓度范围内线性良好,ｒ为０．９９２８～０．９９９５,变异系数均小于１０％。方法简便、快速、准确,可用于尿液中苯丙胺类违禁药物的检测     

Thin layer chromatography/fluorescence detection of 3,4-methylenedioxy-methamphetamine and related compounds

A rapid and sensitive method for the detection of six methylenedioxylatedphenethylamines, 3,4-methylenedioxymethamphetamine (MDMA); 3,4-methylenedioxyamphetamine; 3,4-methylenedioxyethylamphetamine; N-methyl-1-(3,4-methylenedioxyphenyl)-2-butamine; N-methyl-1-(3,4-methylenedioxyphenyl)-3-butamine; and 3,4-methylenedioxydimethylamphetamine, by thin-layer chromatography with fluorescence detection is proposed. These compounds form fluorophores on the developing plate following spraying with a reagent consisting of sodium hypochlorite, potassium hexacyanoferrate (III), and sodium hydroxide, and heating for 3 min at 100 degrees C. Blue fluorescent spots were observed under ultraviolet light in a wavelength range of 250-400 nm. The detection limits for MDMA and the above related compounds were 50 ng. The proposed method was effectively applied to the detection of MDMA in urine samples.     

Forensic Analysis of Human Autopsy Tissue for the Presence of Polydimethylsiloxane (Silicone) and Volatile Cyclic Siloxanes using Macro FT‐IR,FT‐IR Spectroscopic Imaging and Headspace GC‐MS

This study describes effective and straightforward primary and secondary methods for the detection of silicone in human autopsy tissue. The primary method is polydimethylsiloxane (PDMS) specific and employs either macro‐attenuated total reflection Fourier transform infrared (ATR‐FT‐IR) spectroscopy for samples with a high PDMS concentration (relative to that of the matrix) or micro‐FT‐IR spectroscopic imaging in a reflection/absorption modality for samples with a low PDMS concentration. Although the secondary method is not PDMS specific, it employs headspace gas chromatography with mass spectrometric detection (HS/GC‐MS) for the detection of low molecular weight volatile cyclic siloxanes (VCS), which are characteristic marker compounds for PDMS. Overall, the combined results from the primary and secondary analyses provide reliable evidence for the presence of silicone.     

离子交换柱法萃取血样中4种巴比妥类药物

目的建立血样中4种常见巴比妥类药物的固相萃取方法。方法采用Oasis MAX固相萃取柱对样品进行预处理,以2%氨水淋洗2,%甲酸-甲醇洗脱,GC/NPD定量检验,GC/MS定性检验。结果血样中4种常见巴比妥类药物平均萃取回收率达80%以上,以信噪比10/1计,最小定量限为1～2μg/mL,以信噪比3/1计,检出限为0.5～1μg/mL,在1～50μg/mL范围内,线性相关系数均在0.99以上。结论本文固相萃取方法检出限低,回收率高,选择性强,可应用于血样中4种常见巴比妥类药物的检测。     

Systematic Toxicological Analysis Revealing a Rare Case of Captan Ingestion

This article presents a case of suicide by intoxication with various pharmaceuticals, particularly anticonvulsants, combined with the fungicide captan. A cause of death could not be ascertained at autopsy. However, systematic toxicological analysis (STA) including a screening via solid‐phase microextraction (SPME) and gas chromatography‐mass spectrometry (GC‐MS) for (semi) volatile organic compounds revealed results suggesting a possible cause of death. The effects of captan on the human organism, its metabolism, and distribution will be discussed. Macroscopically, the cause of death was unascertained. STA revealed clonazepam, citalopram, and its metabolites, lamotrigine, levetiracetam, lacosamide, clonazepam, captan, and its metabolite tetrahydrophthalimide (THPI). For the first time, it was detected in human viscera. A quantification of THPI was performed to obtain distribution in the organs. The significance of a complete STA must be emphasized. The presence of THPI would have been missed without previous detection of captan. Consequently, this fatality would not have been investigated satisfactorily.     

固相萃取-气相色谱法提取全血中的外源性褪黑素

目的建立血样中褪黑素的固相萃取方法。方法采用OasisHLB固相萃取柱提取,GC/NPD定量检验,GC/MS定性检验。结果血样中褪黑素平均萃取回收率达80%以上,最低检出限0.02μg/mL,线性良好,相关系数R2=0.9978。结论该方法操作简便快速,提取回收率高,重现性好,提取物干净,可用于实际案件当中。     

Detection of Brodifacoum and other Rodenticides in Drug Mixtures using Thermal Desorption Direct Analysis in Real Time Mass Spectrometry (TD‐DART‐MS)

In recent months, there has been increased reporting of seized drug and toxicology cases containing rodenticides, the active ingredient in rat poisons. Seeing as rodenticides are not scheduled substances, they are not commonly screened for in seized drug analysis. This work investigates the use of TD‐DART‐MS for the simultaneous detection of rodenticides and drugs. Six rodenticides were evaluated, an optimal method was established, and limits of detection in the tens of nanograms were calculated. Additional studies highlight that detection at less than 1% by weight in mixtures with AB‐FUBINACA, cocaine, heroin, or methamphetamine was possible. This work presents an optimized method for detection of these compounds, allowing for the simultaneous detection of drugs and rodenticides, providing drug chemists with a tool for rapid identification of these compounds for forensic or public health purposes.     

Detection and Classification of Ignitable Liquid Residues in the Presence of Matrix Interferences by Using Direct Analysis in Real Time Mass Spectrometry,

Conventional Gas Chromatography‐Mass Spectrometry (GC‐MS) methods for the analysis of ignitable liquids (ILs) are usually time‐consuming, and the data produced are difficult to interpret. A fast IL screening method using direct analysis in real time mass spectrometry (DART‐MS) is proposed in this study. GC‐MS, QuickStrip DART‐MS, and thermal desorption DART‐MS methods were used to analyze neat ILs and thermal desorption DART‐MS without extraction was used to analyze ILs on five substrates (e.g., carpet, wood, cloth, sand, and paper). Compared to GC‐MS, DART‐MS methods generated different spectral profiles for neat ILs with more peaks in the higher mass range and also provided better detection of less volatile compounds. ILs on substrates were successfully classified (98 ± 1%) using partial least squares discriminant analysis (PLS‐DA) models based on thermal desorption DART‐MS data. This study shows that DART‐MS has great potential for the high‐throughput screening of ILs on substrates.     

固相萃取/气相色谱法检测全血中的扎来普隆

目的建立全血中扎来普隆的固相萃取/气相色谱检测方法。方法采用Oasis HLB固相萃取柱,5%甲醇水淋洗,二氯甲烷洗脱,GC/NPD定量检验,GC/MS定性检验,并对检测条件进行考察。结果扎来普隆与血中杂质分离良好,平均萃取回收率达89%以上,最低检出限20ng/mL,50～2000ng/mL内线性良好,相关系数R2=0.9945,日内RSD为3.1%～4.2%,日间RSD 5.8%～6.7%。结论该方法操作简便快速,提取回收率高,重现性好,提取物杂质少,可用于实际案件的检验。     

Determination of Acetamiprid and IM‐1‐2 in PostMortem Human Blood,Liver, Stomach Contents by HPLC‐DAD

An HPLC‐DAD method was developed to detect and quantify a neonicotinoid insecticide acetamiprid (ATP) and its metabolite IM‐1‐2 in autopsy samples of a fatal intoxication case. The postmortem blood and tissue distribution of ATP and IM‐1‐2 was determined for the first time. The method showed acceptable precisions and recoveries with relative standard deviations of <10% for ATP level and 1.38 % for IM‐1‐2. The detection and quantification limits for ATP were 0.015 μg/mL and 0.030 μg/mL for blood and were 0.035 μg/g and 0.050 μg/g for liver samples, respectively. The mean contents of ATP were 0.79 μg/g in the liver, 47.35 μg/g in the stomach contents and 2.7 μg/mL in the blood. IM‐1‐2 content was 17.0 μg/g in the stomach contents. ATP and IM‐1‐2 were not detected in the urine. The presence of ATP and IM‐1‐2 in the samples was confirmed by GC‐MS. The method can be exploited in future forensic casework.     

Rapid analysis of 3,4-methylenedioxymethamphetamine: a comparison of nonaqueous capillary electrophoresis/fluorescence detection with GC/MS

Because of the increasing use of 3,4-methylenedioxymethamphetamine (3,4-MDMA), a rapid and sensitive analytical technique is required for its detection and determination. Using nonaqueous capillary electrophoresis/fluorescence spectroscopy (NACE/FS) detection, it is possible to determine this drug at the level 0.5 ppm without any pre-treatment in less than 5 min. After liquid-liquid extraction, the sample can be condensed and a detection limit of 3,4-MDMA in urine of 50 ppb (S/N = 3) can be achieved. The precision of the method was evaluated by measuring the repeatability and intermediate precision of migration time and the corrected peak height by comparison with a 3,4-MDMA-D5 internal standard. With the conventional GC/MS method, it is necessary to derivatize the 3,4-MDMA before injection and the GC migration time also is in excess of 20 min. Therefore, NACE/FS represents a good complementary method to GC/MS for use in forensic analysis.     

Rapid Identification of Synthetic Cannabinoids in Herbal Incenses with DART‐MS and NMR

The usage of herbal incenses containing synthetic cannabinoids has caused an increase in medical incidents and triggered legislations to ban these products throughout the world. Law enforcement agencies are experiencing sample backlogs due to the variety of the products and the addition of new and still‐legal compounds. In our study, proton nuclear magnetic resonance (NMR) spectroscopy was employed to promptly screen the synthetic cannabinoids after their rapid, direct detection on the herbs and in the powders by direct analysis in real time mass spectrometry (DART‐MS). A simple sample preparation protocol was employed on 50 mg of herbal sample matrices for quick NMR detection. Ten synthetic cannabinoids were discovered in fifteen herbal incenses. The combined DART‐MS and NMR methods can be used to quickly screen synthetic cannabinoids in powder and herbal samples, serving as a complementary approach to conventional GC‐MS or LC‐MS methods.     

Comparative Analysis of the Chemical Profiles of 3,4-Methylenedioxymethamphetamine Based on Comprehensive Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry (GC × GC-TOFMS)*

Abstract: The chemical profiling of illicit drugs is an important analytical tool to support the work of investigating and law enforcement authorities. In our work, comprehensive two‐dimensional gas chromatography–time‐of‐flight mass spectrometry (GC × GC‐TOFMS) combined with nontargeted, pixel‐based data analysis was adapted for the chemical profiling of 3,4‐methylenedioxymethamphetamine (MDMA). The validity and benefit of this approach was evaluated by analyzing a well‐investigated set of MDMA samples. Samples were prepared according to a harmonized extraction protocol to ensure the comparability of the chemical signatures. The nontargeted approach comprises preprocessing followed by analysis of variances as a fast filter algorithm for selection of a variable subset followed by partial least squares discriminant analysis for reduction to promising marker compounds for discrimination of the samples according to their chemical profile. Forty‐seven potential marker compounds were determined, covering most of the target impurities known from the harmonized one‐dimensional profiling as well as other compounds not previously elucidated.     

分子印迹固相萃取法在血中苯丙胺类毒品分析中的应用

目的建立分子印迹固相萃取（MISPE）、GC/MS分析方法,用于血液中苯丙胺类毒品检测。方法 10mmol/L醋酸铵缓冲液（pH8.0）4倍稀释空白添加血液,1mL甲醇,1mL10mmol/L醋酸铵缓冲液（pH8.0）活化苯丙胺类分子印迹固相萃取柱;2×1mL去离子水、1mL60%的乙腈去离子水、1mL1%醋酸乙腈洗涤杂质;2×1mL1%甲酸/甲醇洗脱,洗脱液挥干定容,经GC/NPD、GC/MS分析检测。结果各种苯丙胺类毒品回收率均在90%以上,在20～5 000ng/mL浓度范围内线性关系良好,r2为0.995 7～0.998 9,LOQ在16～30ng/mL之间,LOD在8～15ng/mL之间。结论本方法回收率高,净化效果显著,稳定性好,杂质干扰少,可用于血液中低浓度苯丙胺类毒品的分析检测。     

SPE-GC／MS检测生物样品中利多卡因、罗哌卡因、布比卡因

目的建立生物样品中利多卡因、罗哌卡因、布比卡因的固相萃取提取方法和气质检测方法。方法采用Oasis HLB固相萃取柱,以GC／MS定性定量。结果生物样品中利多卡因、罗哌卡因、布比卡因平均萃取回收率达74％以上,检测限0．01μg／mL,线性关系良好,相关系数R2=0．9900以上。结论方法操作简便快速,萃取回收率高,重现性好,可用于实际案件。     

GC/MS法测定人体血液和肾、肝组织中的丙泊酚

目的 采用气相色谱/质谱法检测人体血液和肾、肝组织中的丙泊酚.方法 心血和肾、肝组织中的丙泊酚经环己烷提取,采用气相色谱/质谱法,丙泊酚选择m/z 163、178,内标百里香酚选择m/z 150、135进行测定;并考察方法专属性、线性范围、定量线与检出限、回收率与精密度.结果 丙泊酚的保留时间为8.17min,与内标百里香酚分离良好;其在心血和肾、肝组织中的检测浓度线性关系良好,r值均大于0.992,最低检测质量浓度分别为0.05 μg/mL、0.10μg/g及0.05 μg/g,方法回收率90％ ～ 110％,日内、日间RSD均小于7％.结论 本文方法简便、灵敏、快速,其准确度、精密度和回收率均可满足生物检材中丙泊酚浓度的测定,可在相关研究及实践中选用.     

GC法检测血液和尿液中甲基苯丙胺和咖啡因

目的建立同时测定血、尿中甲基苯丙胺和咖啡因含量的方法。方法应用GC／NPD技术,以4-苯基丁胺为内标,直接碱化,用氯仿提取,三氟乙酸酐衍生化,8CB熔融石英毛细管柱（30m×0．25mm×0．25μm）分析。结果生物样品中甲基苯丙胺与咖啡因在0．012—7．5μg/mL浓度范围内线性关系良好,检测限（S／N=3）依次为1．2ng／mL,0．6ng／mL（血）;1．6ng／mL,0．8ng／mL（尿）。苯丙胺在0．017—10．0μg／mL浓度范围内线性关系良好,检测限为1．6mg／mL（血）,3．2ng／mL（尿）。所有样本回收率均大于85％。结论本方法准确、灵敏,适用于血、尿中甲基苯丙胺及其代谢物苯丙胺的三氟乙酸酐衍生化物和咖啡因的同时检测,为判定滥用毒品种类、追查毒品来源以及研究生物体内甲基苯丙胺和咖啡因的交互影响提供了检测手段。     

GC/MS、GC/NPD法检测毛发中的氯胺酮

目的采用液-液萃取、衍生化和GC/MS、GC/NPD方法,进行毛发中氯胺酮定性定量分析。方法选择4-苯基丁胺为内标,毛发样本用NaOH、HCl及芳基硫酸酯酶/β-葡萄糖醛酸酶等3种方式进行水解,再进行衍生化后,采用GC/MS和GC/NPD方法定性定量分析。对不同水解和衍生化条件以及提取溶剂进行比较优化,并考察方法精密度、稳定性和检出限。结果方法的提取回收率大于95%,精密度和样品稳定性良好,日内和日间标准偏差小于6%;采用GC/NPD和GC/MS直接分析毛发中的氯胺酮,检出限为0.2ng/mg和2.0ng/mg,线性范围为10.0～250.0ng/mg,相关系数均大于0.99;采用酰化衍生化后分析,GC/NPD和GC/MS检出限分别提高至0.1ng/mg和0.2ng/mg。结论该方法回收率高、检测限低,可以用于毛发中氯胺酮的定性定量分析检验。     

The analysis of quaternary ammonium compounds in human urine by direct inlet electron impact ionization mass spectrometry.

An accurate and rapid screening test for nine quaternary ammonium compounds (suxamethonium chloride, pancuronium bromide, ambenonium chloride, benzethonium chloride, distigmine bromide, methylbenactyzium bromide, neostigmine bromide, propantheline bromide and pyridostigmine bromide) by direct inlet electron impact ionization mass spectrometry (DI/EI-MS) was investigated. Each compound was extracted from urine as an ion pair with KI3 into dichloromethane. The reliability of the identification of these compounds was verified by the mass chromatographic analysis of their characteristic fragment ions. The analysis of these drugs by DI/EI-MS could be performed within 5 min. The detection limits were between 20-150 ng/ml for the nine compounds. This method appears to be efficient, rapid and suitable as a screening procedure for the quaternary ammonium compounds found in urine.