苯二氮卓类新精神活性物质去氯依替唑仑的定性检验方法研究

目的建立苯二氮卓类新精神活性物质去氯依替唑仑的气相色谱-质谱(GC-MS)和超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF MS)定性检验方法。方法未知样品用甲醇和水提取,取上清液,采用GC-MS和UPLC-Q-TOF MS进行分析。结果经GC-MS检测,保留时间为17.73 min的未知组分的质谱碎片主要特征离子峰有m/z 279,308,239,252,225,77,126。经UPLC-Q-TOF MS检测,保留时间为4.781 min的未知组分的准分子离子峰为309.1173,碰撞诱导解离(CID)模式下二级质谱主要离子有m/z 280.0776,255.0952,240.0719,225.0604,206.0748。经缴获毒品分析科学工作组(Scientific Working Group for the Analysis of Seized Drugs,SWGDRUG)分析谱库检索和文献查询获得的信息资料进行比对,鉴定为去氯依替唑仑。结论该方法具有分析简便、快速的特点,可以用于实际案件的检测。     

新型毒品5-甲氧基-α-甲基色胺油状物的GC-MS定性检验

目的通过分析未知检材样本提取后的质谱碎裂峰,建立了5-甲氧基-α-甲基色胺(5-MeO-AMT)的气相色谱-质谱(GC-MS)定性分析方法,并阐述其在EI离子源轰击下的分子裂解机制。方法未知样品油状物用氢氧化钠溶液溶解后加入适量乙酸乙酯,充分振荡后吸取上清液采用气相色谱-质谱(GC-MS)检测。结果测得未知组分(RT=12.754min)的质谱特征碎片峰(m/z)信息为161.1(基峰)、204.2、146.1、130.1、117.1和89.0。经与NIST谱库和DEA报告质谱图比对,确定为5-MeO-AMT;通过查阅文献资料,对上述质谱特征碎片峰的产生机制进行了推断。结论该方法操作简单、结论可靠,可用于5-MeO-AMT的检验。     

合成大麻素类新精神活性物质4F-MDMB-BICA的检测

目的建立基于红外光谱(fourier transform infrared,FT-IR)、气相色谱-质谱联用(gas chromatographymass spectrometry,GC-MS)、高分辩质谱(high resolution mass spectrometer,HRMS)和核磁共振波谱(nuclear magnetic resonance spectroscopy,NMR)多技术联用鉴定可疑未知物的方法。方法样品分别用FT-IR、GC-MS、HRMS(溶剂为甲醇)及NMR(溶剂为氘代甲醇)检测。结果GC-MS测得样品中主要组分的质谱特征离子m/z分别为218(基峰)、362、306、274、246、144、116,HRMS实测的精确质量数[M+H]+为363.20774,经FT-IR、GC-MS和HRMS数据分析,推断未知样品为一种新的合成大麻素类新精神活性物质4F-MDMB-BICA,并用1H NMR对其结构进行确证。结论建立的多技术联合鉴定方法能用于未知样品中4F-MDMB-BICA的鉴定。该方法快速、方便、准确、可靠、实用,能够对今后涉及此类物质的案件检测鉴定提供参考依据。     

合成大麻素类新精神活性物质4F-MDMB-BUTINACA和MDMB-4en-PINACA的检测

目的建立联合傅里叶变换红外光谱(Fourier transform infrared spectrum,FTIR)、气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)、高分辨质谱和核磁共振波谱(nuclear magnetic reso-nance spectroscopy,NMR)多种技术鉴定可疑未知物的方法。方法对实际案件中缴获的可疑检材(灰白色粉末和黄色晶体)分别采用FTIR、GC-MS(溶剂为甲醇)、高分辨质谱(溶剂为甲醇)及NMR(溶剂为氘代甲醇)方法进行检测。结果 GC-MS测得样品中主要组分的质谱特征离子m/z分别为219(基峰)、363、307、304、275、145、131和213(基峰)、357、301、298、269、185、171、145、131,高分辨质谱实测的精确质量数[M+H]+分别为364.203 61和358.212 34。经查阅资料和数据库检索比对再结合红外分析和质谱数据分析,可判断未知样品为合成大麻素类新精神活性物质2-[1-(4-氟丁基)-1H-吲唑-3-甲酰氨基]-3,3-二甲基丁酸甲酯(4F-MDMB-BUTINACA)和3,3-二甲基-2-[1-(4-戊烯-1-基)-1H-吲唑-3-甲酰氨基]丁酸甲酯(MDMB-4en-PINACA),并采用1H-NMR对其结构进行了确证。结论建立的多技术联合鉴定方法能用于未知样品中4F-MDMB-BUTINACA和MDMB-4en-PINACA的鉴定。该方法快速、方便、准确、可靠、实用,能够对今后涉及此类物质的案件鉴定提供参考依据。     

新型合成大麻素ADB-BUTINACA的波谱分析及结构确证

本文旨在对新型氨基烷基吲哚类合成大麻素ADB-BUTINACA进行结构确认。对缴获的电子烟油经柱层析法提取纯化后，用气相色谱-质谱(GC-MS)、高效液相色谱-四极杆串联飞行时间质谱(UPLC-QTOF)、核磁共振(¹H-NMR、¹³C-NMR)、红外光谱(IR)进行分析，确定化合物结构式。通过UPLC-QTOF获得未知化合物的精确质量数为330.212 7，结合¹H-NMR确定质子数为26及其归属，¹³C-NMR确定碳的类型，GC-MS及UPLC-QTOF二级质谱裂解碎片离子为m/z 286.2、201.1(基峰)、145.0、257.1推断其结构可能断裂路径，IR的吸收特征确定其含有苯环、酰胺、伯胺、仲胺、叔胺、甲基及偕二甲基等官能团，确认该化合物分子式为C₁₈H₂₆N₄O₂，化学名称为N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-butyl-1H-indazole-3...     

5F-UR-144的热不稳定性研究

目的利用气相色谱-质谱法(GC-MS)、液相色谱-四级杆-飞行时间质谱(LC-Q-TOF/MS)和核磁共振光谱法(NMR)研究合成大麻素5F-UR-144遇热分解的具体变化情况。方法对照品用无水乙醇定容稀释后,经GC-MS和LC-Q-TOF/MS检测得到对应的色谱图和质谱图;对照品分别于常温和280℃密封加热后用无水乙醇定容稀释,经LC-Q-TOF/MS和NMR检测得到对应的质谱图、¹H和¹³C核磁共振波谱;对照品分别于常温逐步提升至300℃密封加热后用无水乙醇定容稀释,经LC-Q-TOF/MS检测得到对应的色谱图。结果5F-UR-144在高温下会开环产生新的物质;5F-UR-144从130℃开始分解,随着温度升高分解程度提升,240℃时分解率达到98%;随着温度继续升高,超过260℃,分解产物会碳化。结论基于5F-UR-144的热不稳定性,在检测时应考虑若通过烫食方式吸食5F-UR-144,其进入人体的成分会发生变化;气相色谱或气相色谱-质谱法不适合定量检测5F-UR-144。     

3,4-亚甲二氧基甲卡西酮的鉴定

目的 建立基于傅里叶变换红外光谱(FTIR)、气相色谱-质谱(GC-MS)结合高分辨质谱技术联合鉴定未知样品的方法.方法 未知样品采用红外专用取样器直接检测;甲醇溶解后采用GC-MS和组合型高分辨质谱检测,以MDMA为内标物.结果 未知样品获得的红外光谱特征吸收峰为1679(C=O键),1603,1502,1453,1423,1259,1121,1090,1035,930,887,838,768,742和717cm-1,质谱特征碎片峰(m/z)为58.1,91.0,120.9,149.0和207.0,测得的精确质量数[M+H]+为208.0966.经信息分析未知样品鉴定为3,4-亚甲二氧基甲卡西酮,该物质属于新型化学合成卡西酮类精神活性物质,已经列入部分欧盟国家的管制药物目录.结论 本方法可用于3,4-亚甲二氧基甲卡西酮的鉴定.     

利用高分辨液质联用仪检测新型合成大麻素

目的介绍一种鉴别非法合成大麻素(AMB-FUBINACA)结构的方法。方法巧用GC-MS质谱谱库检索提示信息,利用高分辨液质联用仪的一级质谱碎片推导的分子式与GC-MS的质谱谱库检索物质的分子式进行比较,推测目标物的结构式。目标物的结构式符合液质联用仪(LC-MS/MS)的二级质谱碎片(误差4×10-7)和GC-MS的质谱碎片归属,并结合文献报道进行综合研判。结果对一例网络售卖合成大麻素的案件进行了检验,准确判定缴获样品“小树枝”中含有的合成大麻素为AMB-FUBINACA。结论该方法可为解析一些未知物的结构提供新途径。     

液相色谱-三重四级杆/线性离子阱串联质谱法测定血液中1-(4-甲氧基苯基)哌嗪

目的建立血液中1-(4-甲氧基苯基)哌嗪的液相色谱-三重四级杆/线性离子阱串联质谱(LC-QTrap-MS/MS)的快速检测方法。方法血液经乙腈沉淀蛋白后,振荡、离心、经微孔滤膜过滤后供仪器分析;选用Phenomenex Kinetx®5.0μm Biphenyl 100Å(100mm×2.1mm)分离,柱温40℃;以0.1%甲酸水溶液-乙腈为流动相,流速0.5mL/min,梯度洗脱5.5min;以多反应监测(MRM)-信息依赖性采集(IDA)-增强子离子扫描(EPI)-谱库检索的模式进行分析,外标-标准曲线法进行定量分析。结果血液中1-(4-甲氧基苯基)哌嗪的浓度在2~200ng/mL范围内呈现良好的线性关系,相关系数达到0.9984,回收率在87%以上,日内精密度在5%以下,日间精密度在10%以下,方法的检出限是0.8ng/mL,定量限是2ng/mL。结论该方法采用LC-QTrap-MS/MS和MRM-IDA-EPI模式,既保持与MRM相同的定量灵敏度,也能提供更为丰富的二级质谱碎片,使定性结果更加准确。方法简单快捷,专属性好,回收率高,重现性好,能够用于血液中1-(4-甲氧基苯基)哌嗪同时定性和定量分析。     

可疑电子烟油中5种吲哚或吲唑酰胺类合成大麻素的GC-MS定性和定量分析

目的 建立可疑电子烟油样品中合成大麻素及其主要基质、添加物的GC-MS定性定量分析方法。方法 电子烟油样品用甲醇稀释后进行GC-MS分析,以特征碎片离子和保留时间对电子烟油中的合成大麻素及其主要基质、添加物进行定性分析,在选择离子监测模式下对合成大麻素进行定量分析。结果GC-MS定量方法中各化合物的线性范围为0.025～1 mg/mL,基质加标回收率为94%～103%,日内精密度相对标准偏差小于2.5%,日间精密度相对标准偏差小于4.0%。在25份电子烟油样品中检出了5种吲哚或吲唑酰胺类合成大麻素类物质。电子烟油的基质主要为丙二醇、丙三醇,部分样品中还检出了N,2,3-三甲基-2-异丙基丁酰胺、三乙酸甘油酯和尼古丁等添加物。25份电子烟油样品中合成大麻素的含量范围为0.05%～2.74%。结论 所建立的电子烟油样品中合成大麻素、基质、添加物的GC-MS方法选择性好、分离度高、检出限低,可用于多组分同时定性和定量分析;所探讨的吲哚或吲唑酰胺类化合物的电子轰击离子源碎片离子碎裂机制有助于鉴定该类物质或其他具有类似结构的化合物。     

Separation and structural characterization of the synthetic cannabinoids JWH-412 and 1-[(5-fluoropentyl)-1H-indol-3yl]-(4-methylnaphthalen-1-yl)methanone using GC-MS, NMR analysis and a flash chromatography system

The 'herbal highs' market continues to boom. The added synthetic cannabinoids are often exchanged for another one with a high frequency to stay at least one step ahead of legal restrictions. While most of these substances were synthesized for pharmaceutical purposes and have been described in the scientific literature before, others originate from clandestine laboratories supplying this lucrative market. In this paper, the identification and structure elucidation of two synthetic cannabinoids is reported. The first compound, 1-[(5-fluoropentyl)-1H-indol-3yl]-(4-methylnaphthalen-1-yl)methanone, was found along with AM-2201 in a 'herbal mixture' obtained via the Internet. For isolation of the substance from the mixture, a newly developed flash chromatography method was used providing an inexpensive and fast way to gain pure reference substances from 'Spice' products for the timely development or enhancement of analytical methods in the forensic field. The second substance, 4-fluoronaphthalen-1-yl-(1-pentylindol-3-yl)methanone (JWH-412) was seized by German authorities as microcrystalline powder, making it very likely that it will be found in 'herbal mixtures' soon.     

The affect of tissue depth variation on craniofacial reconstructions

The consumption of synthetic drugs, generally known as designer drugs, has increased drastically in all parts of the world. Typical constituents of designer synthetic drugs are chemical substances derived from amphetamine but significant differences in effects caused and duration may result. In May, 2005, the civil state police of Sao Paulo seized thirty-one gelatinous capsules containing a very small quantity of a white powder inside (approximately 1.5 mg per capsule). This paper describes the analytical assays that were used to identify the seized material. Preliminary assays using colorimetric tests and high performance thin-layer chromatography indicated that the capsules content could be an amphetamine derivative. In the capillary zone electrophoresis assay, it was possible to observe that the analyzed material had basic characteristics. Mass spectrometry analysis revealed that the compound had the same molecular mass as 2,5-dimethoxy-4-bromoamphetamine (DOB) and its identity was confirmed through collision-induced dissociation (CID) experiments. Finally, the comparison of infrared sample spectrum with a spectra library provided further evidence of the DOB presence in the seized material. Although a reference standard material was not available, the information gathered from the different assays allowed the conclusion that the substance was, in fact, DOB, a substance with a powerful hallucinogenic action of proscribed use in the country and which was seized and identified for the first time in Brazil.     

Bank security dye packs: synthesis, isolation, and characterization of chlorinated products of bleached 1-(methylamino)anthraquinone

Banknote evidence is often submitted after a suspect has attempted to disguise or remove red dye stain that has been released because of an anti-theft device that activates after banknotes have been unlawfully removed from bank premises. Three chlorinated compounds have been synthesized as forensic chemical standards to indicate bank security dye bleaching as a suspect's intentional method for masking a robbery involving dye pack release on banknotes. A novel, facile synthetic method to provide three chlorinated derivatives of 1-(methylamino)anthraquinone (MAAQ) is presented. The synthetic route involved Ultra Clorox bleach as the chlorine source, iron chloride as the catalyst, and MAAQ as the starting material and resulted in a three-component product mixture. Two mono-chlorinated isomers (2-chloro-1-(methylamino)anthraquinone and 4-chloro-1-(methylamino)anthraquinone) and one di-chlorinated compound (2,4-dichloro-1-(methylamino)anthraquinone) of the MAAQ parent molecule were detected by gas chromatography mass spectrometry (GC-MS), and subsequently isolated by liquid chromatography (LC) with postcolumn fraction collection. Although GC-MS is sensitive enough to detect all of the chlorinated products, it is not definitive enough to identify the structural isomers. Liquid-state nuclear magnetic resonance (NMR) spectroscopy was utilized to elucidate structurally the ortho- and para-mono-chlorinated isomers once enough material was properly isolated. A reaction mechanism involving iron is proposed to explain the presence of chlorinated MAAQ species on stolen banknotes after attempted bleaching.     

GC–MS analysis of eight aminoindanes using three derivatization reagents

Aminoindanes are a class of novel psychoactive substances (NPSs) that have become more prevalent over the past decade. GC–MS is often utilized for identifying seized drugs and is well regarded for its ability to separate mixtures. However, certain aminoindanes have similar mass spectral data and require specific gas chromatographic stationary phases for separation. Derivatization is an alternative method that can be applied to GC–MS to enhance chromatographic results, providing more selective analysis in seized-drug identification. This study investigates derivatization techniques to provide options for forensic science laboratories in accurately identifying aminoindanes. Three derivatization reagents, N-methyl-bis(trifluoroacetamide) (MBTFA), heptafluorobutyric anhydride (HFBA), and ethyl chloroformate (ECF) were evaluated for the analysis of eight aminoindanes by GC–MS using two common gas chromatographic stationary phases, Rxi®-5Sil MS and Rxi®-1Sil MS. All three derivatization methods successfully isolated eight aminoindanes, including the isomers 4,5-methylenedioxy-2-aminoindane (4,5-MDAI), and 5,6-methylenedioxy-2-aminoindane (5,6-MDAI) that could not be differentiated prior to derivatization. Reduced peak tailing and increased abundance were observed after derivatization for all the compounds, and mass spectra of the derivatives contained individualizing fragment ions that allowed for further characterization of the aminoindanes. This excluded 4,5-MDAI and 5,6-MDAI as they shared the same characteristic ions and were only distinguishable by their retention times. All three derivatization techniques used in this study allow for successful characterization of the aminoindanes and give forensic science laboratories flexibility in their analysis approach when they encounter these compounds.     

NIST Mass Spectrometry Data Center standard reference libraries and software tools: Application to seized drug analysis

The standard reference libraries and associated custom software provided by the National Institute of Standards and Technology's Mass Spectrometry Data Center (NIST MSDC) are described with a focus on assisting the seized drug analyst with the identification of fentanyl-related substances (FRS). These tools are particularly useful when encountering novel substances when no certified sample is available. The MSDC provides three standard reference mass spectral libraries, as well as six software packages for mass spectral analysis, reference library searching, data interpretation, and measurement uncertainty estimation. Each of these libraries and software packages are described with references to the original publications provided. Examples of fentanyl identification by gas chromatography–mass spectrometry (GC–MS) and by direct analysis in real-time (DART) mass spectrometry are given. A link to online tutorials is provided.     

A survey of reported synthesis of methaqualone and some positional and structural isomers.

Methaqualone (2-methyl-3-o-tolyl-4(3H)-quinazolinone) is the illicit synthetic drug of choice amongst South African drug users. Historically police and forensic investigation has proven that all methaqualone seized by the South African Police Service originates from illicit manufacturing sites both inside, and outside South Africa's borders. From a drug enforcement, and forensic point of view it is, thus, of utmost importance that the various synthetic routes available to the illicit "chemist" are fully documented and understood. This is a prerequisite for effective illicit laboratory investigation, as well as chemical and precursor monitoring. This paper gives a brief introduction to the current status with regard to methaqualone use and production in South Africa, as well as an extensive review of the synthesis of methaqualone and selected isomers reported since 1946. A table summarizing synthetic routes reported in 32 reference sources is provided.     

LSD and 9,10-dihydro-LSD Analyses in Street Drug Blotter Samples via Easy Ambient Sonic-Spray Ionization MassSpectrometry (EASI-MS)

Normally, the identification of the LSD drug is performed by forensic laboratories, using the Ehrlich spot test. However, this is a nonspecific analysis. Additionally, the Brazilian Federal Police has identified the presence of a new compound in seized blotters: 9,10-dihydro-LSD, an uncontrolled substance. In this work, easy ambient sonic-spray ionization mass spectrometry in the positive ion mode, EASI(+)-MS, was used to characterize LSD and 9,10-dihydro-LSD compositions directly from the surface of blotters. The presence of LSD in the seized blotter samples were also confirmed via high-performance liquid chromatography with ultraviolet detector. In a set of 41 blotters analyzed by EASI(+)-MS, 28 showed positive results for LSD, seven for 9,10-dihydro-LSD, and another six samples showed negative results for both LSD and 9,10-dihydro-LSD. The combination of thin layer chromatography with EASI-MS also demonstrated to be a relatively simple and powerful screening tool for forensic analysis of street drugs.     

4F‐MDMB‐BINACA: A New Synthetic Cannabinoid Widely Implicated in Forensic Casework

This is the first report regarding the characterization of the new synthetic cannabinoid 4F‐MDMB‐BINACA. 4F‐MDMB‐BINACA was first analytically confirmed in seized drug material using gas chromatography–mass spectrometry (GC‐MS), liquid chromatography–quadrupole time‐of‐flight mass spectrometry (LC‐QTOF), and nuclear magnetic resonance (NMR) spectroscopy. Subsequent to this characterization, 4F‐MDMB‐BINACA was detected in biological specimens collected as part of forensically relevant casework, including medicolegal death investigations and drug impaired driving investigations, from a variety of regions in the United States. Further analysis of biological specimens resulted in the identification of the metabolites 4F‐MDMB‐BINACA 3,3‐dimethylbutanoic acid and 4‐OH‐MDMB‐BINACA. 4F‐MDMB‐BINACA is appearing with increasing frequency as a contributory factor in deaths, creating morbidity and mortality risks for drug users. Laboratories must be aware of its presence and impact, incorporating 4F‐MDMB‐BINACA into workflows for detection and confirmation.     

Impurities,adulterants and cutting agents in cocaine as potential candidates for retrospective mining of GC-MS data

Cocaine is one of the most widely used illicit drugs worldwide. Cocaine powders seized by the Police may contain numerous other substances besides the drug itself. These can be impurities originating from the coca plant or the production process, or be purposely added to the drug formulation as adulterants and cutting agents. In forensic laboratories, identification of cocaine is routinely done through GC-MS analysis, but other components are often ignored even if the method allows for their detection. Yet, they can provide valuable insight into the history of a seizure and its potential connection to other samples. To explore this idea, an extensive review of common impurities and adulterants encountered in cocaine is presented. Based on their incidence, concentration in the end product and compatibility with GC-MS methods, their overall usefulness as candidates for the statistical investigation of existing forensic data is evaluated. The impurities cis- and trans-cinnamoylcocaine, tropacocaine, norcocaine and N-benzoylnormethylecgonine as well as the adulterants lidocaine, procaine, tetracaine, benzocaine, caffeine, acetylsalicylic acid, phenacetin, ibuprofen, levamisole, hydroxyzine and diltiazem are promising candidates to provide additional forensic intelligence. Future research on optimized routine GC-MS methods, signal reproducibility, comparison, statistics and databases is suggested to facilitate this concept. Ultimately, such an approach may significantly advance the amount of information that is extracted from routine casework data, elucidate developments in the cocaine markets in the past and facilitate Police work in the future. Preliminary assessment of existing data from the forensic laboratory of the Amsterdam Police has been included to show that the detection of the identified target impurities is feasible, and that small adjustments to the analysis method could significantly increase the detectability of these analytes in prospective drug screenings. Forensic intelligence based on retrospective data mining of cocaine containing casework samples may thus be realized with minimal additional laboratory efforts by using already available instrumentation, samples and data.