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。     

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。     

N,N-二烯丙基-5-甲氧基色胺片剂的GC/MS检验

目的 建立N,N-二烯丙基-5-甲氧基色胺的气相色谱-质谱(GC/MS)定性分析方法。方法 未知片剂样品用甲醇超声溶解,吸取上清液采用气相色谱-质谱(GC/MS)联用仪检测。结果 测得未知组分(tR=10.45min)的质谱特征碎片峰(m/z)信息为110.1(基峰)、270.1、174.1、160.1、145.0、130.1和117.1。查阅资料并对该组分的质谱图谱进行解析,鉴定为N,N-二烯丙基-5-甲氧基色胺,属于色胺类化合物。结论 该方法简单,准确,可用于N,N-二烯丙基-5-甲氧基色胺的鉴定。     

全血中4种新型合成大麻素的快速检测

目的建立准确、快速的方法鉴定血液中4种新型合成大麻素(JWH-203、JWH-122、5F-APINACA和AB-CHMINACA)。方法全血样品经乙腈-甲醇提取后,经气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)进行筛选,采用液相色谱-串联质谱(liquid chromatography-tandem mass spectrometry,LC-MS/MS)进行确认,采用多反应监测模式进行定量分析。结果 GC-MS法于21 min完成分析,LCMS/MS法于5 min完成分析,AB-CHMINACA、JWH-203、5F-APINACA和JWH-122均采用准分子离子峰作为母离子,定量离子对分别为m/z 357.4→312.2、m/z 340.2→125.0、m/z 384.1→135.1、m/z 356.4→169.2。血液中4种合成大麻素在1～250 ng/mL质量浓度范围内线性良好(r0.99),检出限为0.1～0.5 ng/mL,提取回收率为85.4%～95.2%,精密度小于10.0%,基质效应为80.3%～92.8%。结论本研究得到了4种合成大麻素的GC-MS和LC-MS/MS色谱行为和质谱解析信息,初步讨论了色谱行为差异的可能原因,对判断合成大麻素的发展趋势有提示作用。本方法适用于血液中4种合成大麻素的快速检测,在目前新型合成大麻素滥用激增的情况下,可为此类物质的鉴定提供参考。     

高分辨质谱联合核磁共振波谱技术鉴定色胺类新精神活性物质4-OH-MET和4-AcO-DMT

目的利用高分辨质谱和核磁共振波谱技术检测涉毒案件中涉及的未列管的色胺类新精神活性物质。方法将实际案例中缴获的白色和褐色粉末经提取后使用气相色谱-四极杆飞行时间质谱(gas chro-matography-quadrupole time-of-flight mass spectrometry,GC-QTOF-MS)、超高效液相色谱-线性离子阱-四极杆-轨道阱质谱(ultra-high performance liquid chromatography-linear ion trap quadrupole-orbitrap massspectrometry,UPLC-LTQ-Orbitrap MS)和核磁共振氢谱(1H-nuclear magnetic resonance spectroscopy,1H-NMR)等方法进行分析。结果白色粉末经GC-QTOF-MS检测,组分的主要特征碎片离子峰有m/z 218.1410(分子离子峰)、72.080 6(基峰)等;经UPLC-LTQ-Orbitrap MS检测,质子化分子离子为m/z 219.149 4,碰撞诱导解离模式下主要的二级质谱离子有m/z 160.076 3、72.080 8。褐色粉末经GC-QTOF-MS检测,组分的主要特征碎片离子峰有m/z 246.135 7(分子离子峰)、58.065 1(基峰)等;经UPLC-LTQ-Orbitrap MS检测,质子化分子离子为m/z 247.145 0,碰撞诱导解离模式下主要的二级质谱离子有m/z 202.087 1、160.076 3、134.060 5。经NIST 17谱库检索和1H-NMR共同确认白色粉末和褐色粉末分别含有色胺类新精神活性物质N-甲基-N-乙基-4-羟基色胺(4-OH-MET)和N,N-二甲基-4-乙酰氧基色胺(4-Ac O-DMT)。结论 GC-QTOF-MS、UPLC-LTQ-Orbitrap MS和1H-NMR多种方法联合应用可对未知的新精神活性物质进行鉴定。     

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.     

新精神活性物质Dibutylone的鉴定

目的建立基于气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)、高分辨质谱和核磁共振波谱技术联合鉴定未知样品的方法。方法样品用含内标盐酸双苯戊二氨酯(SKF525A)的甲醇溶液溶解后,采用GC-MS和高分辨质谱检测。混合样品经硅胶柱层析分离纯化后,用氘代甲醇溶液溶解进行核磁共振氢谱(~1H nuclear magnetic resonance spectroscopy,~1H NMR)的结构解析。结果 GC-MS检测获得样品中主要组分的质谱特征碎片离子m/z为86.1(基峰)、71.2、121.1、149.0,高分辨质谱实测分子离子峰的精确质量数为236.128 89,经数据分析再结合数据库比对在未知样品中检索出卡西酮类新精神活性物质1-[3,4-(亚甲二氧基)苯基]-2-二甲氨基-1-丁酮(Dibutylone),另外未知样品中还含有少量咖啡因。样品纯化后经~1H NMR鉴定,进一步确证为Dibutylone。此外,样品中主要组分的GC-MS保留时间和特征碎片离子与Dibutylone对照品一致。结论本研究建立的方法可用于混合样品中Dibutylone的鉴定。     

气相色谱-质谱法测定涉案奶粉中辛硫磷的含量

目的 建立基于气相色谱-质谱法（GC-MS）测定奶粉中辛硫磷含量的方法。方法 对待测样品进行乙酸乙酯萃取,利用Florisil固相萃取柱净化,淋洗液供GC-MS分析,设置适当的色谱质谱条件分析检测。结果 该方法在0.10～5.00 mg/L内具有良好的线性关系,辛硫磷在奶粉中的最低检出限为0.05 mg/L,加标回收实验结果表明,辛硫磷在奶粉中的平均回收率为98.2%～101%,相对标准偏差为2.1%～3.1%。案件检材样品在保留时间约8.377 min处出现与辛硫磷标准品相似色谱峰,且质谱定性离子[m/z 109（基峰）、m/z 135、m/z 298]与辛硫磷标准溶液一致,辛硫磷的含量为2.17 mg/kg。结论 该方法操作简单、灵敏度高、可行性强,可用于检测奶粉中的辛硫磷成分,为其他辛硫磷检测提供有益借鉴。     

自主合成标准物质鉴定缴获物中的新精神活性物质ADB-FUBINACA

目的新精神活性物质在世界范围内蔓延迅速,但相关标准物质的短缺制约着其分析方法的研究和案件检验。本文以我国首次出现的N-(1-氨甲酰基-2,2-二甲基丙基)-1-(4-氟苄基)吲唑-3-甲酰胺(ADB-FUBINACA)制毒案件为例,介绍在无法及时获得商业化标准物质的情况下,不得不通过自主合成制备标准物质解决案件检验难题,建立该新精神活性物质检验的方法。方法建立气相色谱-质谱检验方法,分析条件:色谱柱为Aglient DB-5MS石英毛细管柱(30.00m×0.25mm×0.25μm);初始柱温60℃,按15℃/min升至300℃,保持15min;载气为氦,流速1.0mL/min,分流进样,进样量1.0μL,分流比20∶1;进样口温度280℃;电子轰击(EI)离子源,电子能量70eV,离子源温度230℃,四级杆温度150℃,传输线温度280℃,质量扫描范围m/z 40~500amu,全扫描模式(SCAN)采集总离子流图,溶剂延迟3.0min。案件缴获的送检未知样品经甲醇提取,超声、离心后,取上清液以GC-MS分析;将所得主要质谱特征碎片峰(m/z)通过NIST质谱库、SWGDRUG质谱数据库以及相关文献进行检索,初步确定待测目标物。采用有机合成技术制备ADB-FUBINACA标准物质,合成路线为:吲唑-3-甲酸甲酯与4-氟苄溴发生取代反应,生成1-(4-氟苄基)-1H-吲唑-3-甲酸甲酯;取代产物在碱性条件下经水解反应得到有机酸1-(4-氟苄基)-1H-吲唑-3-甲酸;在催化剂作用下,有机酸与L-叔亮酰胺发生酰化反应,制得化合物ADB-FUBINACA。经气相色谱-质谱(GC-MS)、液相色谱-离子阱-飞行时间质谱(LCMS-IT-TOF)、核磁共振(NMR)等分析,合成化合物的结构得以确证;同时采用超高效液相色谱-二极管阵列检测器(HPLC-PDA)进行分析,对其归一化纯度进行测定。将案件未知样品和合成标准物质分别用甲醇提取,超声、离心后,再行上清液GC-MS分析。结果经GC-MS分析,案件未知样品(RT=19.818min)的质谱特征碎片峰(m/z)信息为109.0(基峰)、253.1、338.1、309.1和145.0,经与合成标准物质的保留时间及质谱图检测比对,证实为N-(1-氨甲酰基-2,2-二甲基丙基)-1-(4-氟苄基)吲唑-3-甲酰胺;通过查阅相关资料,对上述质谱特征碎片峰的产生机制进行了推断,并对1H-NMR、13C-NMR和DEPT-135等一维核磁谱图的信号进行了归属分析。结论本文报道的新精神活性物质ADB-FUBINACA其GC-MS分析方法,可用于实际案件检验鉴定;合成化合物的结构表征方法也可用于固体ADB-FUBINACA的定性分析。基于有机合成技术的新精神活性物质制备与案件检验方法,可缓解有关标准物质短缺制约该类案件检验鉴定的现状。     

三种酸类易制毒化学品的衍生化气相色谱—质谱鉴定

基于五氟苄基溴（PFBBr）微波衍生化的气相色谱—质谱（GC-MS）鉴定N-乙酰邻氨基苯甲酸、邻氨基苯甲酸和苯乙酸三种酸类易制毒化学品,以苯甲酸为内标物。N-乙酰邻氨基苯甲酸衍生化产物特征碎片峰为119、181、317、359;邻氨基苯甲酸衍生化产物特征碎片峰为119、181、317;苯乙酸衍生化产物特征碎片峰为91、181、316。检测结果与直接测试比较,色谱峰型明显改善,检测灵敏度提高,检测限（S/N=3∶1）3~12ng。该方法可以用于N-乙酰邻氨基苯甲酸、邻氨基苯甲酸和苯乙酸的鉴定。     

The general toxicology unknown. II. A case report: doxylamine and pyrilamine intoxication

A general toxicology unknown case is presented to demonstrate our systematic approach. A 20-year-old male was found dead with multiple suicide notes. Overdose was suspected but substances were not known. Blood alcohol was negative. Urine was analyzed by enzyme-multiplied immunoassay technique and was negative for all drugs assayed. Urine was then extracted with ethyl acetate:hexane (1:1) at pH 10 and back-extracted into 1.0N sulfuric acid. The acidic layer was adjusted to pH 10, and re-extracted with ethyl acetate:hexane (1:1). The residue was analyzed by gas chromatography (GC) on a 3% OV-101 column. It was found to be negative for all commonly screened substances. However, several unknown peaks were observed. Electron impact mass spectra of these unknown peaks were obtained and searched for in our computer library of more than 25000 mass spectra. These unknown peaks were identified as doxylamine and pyrilamine by gas chromatography/mass spectrometry. The base peak and molecular ion for pyrilamine were at m/z 121 and 285, respectively. The base peak for doxylamine was at m/z 58. No molecular ion was observed for doxylamine. Both doxylamine and pyrilamine are antihistamines, but are promoted and used in the management of insomnia. Quantitation was performed on a GC using dexbrompheniramine as an internal standard. Blood concentrations for doxylamine and pyrilamine were 0.7 and 7.0 mg/L, respectively. Concentrations in other tissues were determined. Death was caused by combined doxylamine and pyrilamine intoxication; the manner of death was suicide.     

Characterization of the explosive triacetone triperoxide and detection by ion mobility spectrometry

The improvised explosive triacetone triperoxide (TATP) was synthesized and characterized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, Raman and infrared (IR) spectroscopy. Triacetone triperoxide was subsequently analyzed by ion mobility spectrometry (IMS) in positive ion mode, and detected as a cluster of three peaks with a drift time of the most intense peak at 13.06 ms. Triacetone triperoxide was then analyzed after dissolution in toluene, where a dramatic increase in peak intensity was observed, at a flight time of 12.56 ms (K0=2.71 cm2V(-1)s(-1)). Triacetone triperoxide was subsequently analyzed by coupling the ion mobility spectrometer to a triple quadrupole mass spectrometer, where a single peak at m/z of 223 atomic mass units identified the species present in the ion mobility spectra as being triacetone triperoxide.     

GC‐MS and IR Studies on the Six Ring Regioisomeric Dimethoxyphenylpiperazines (DOMePPs)

A number of N‐substituted piperazines have been described as drugs of abuse in recent years. This new drug category includes several series of aromatic ring substituted phenylpiperazines. The wide variety of available precursors makes regioisomerism a significant issue in these totally synthetic compounds. In this study, a complete series of regioisomeric dimethoxyphenylpiperazines were synthesized and evaluated using GC‐MS and FT‐IR. The EI mass spectra show fragments characteristic of both the dimethoxyphenyl and the piperazine portions of the molecules including the dimethoxyphenylaziridinium cation (m/z 180) and dimethoxyphenyl cation (m/z 137). The ion at m/z 56 for the C₃H₆N⁺ fragment is characteristic of the piperazine ring and was observed in all the spectra. The perfluoroacyl derivatives were resolved by GC, and their mass spectra showed some differences in relative abundance of ions. FTIR provides direct confirmatory data for differentiation between the regioisomeric dimethoxyphenylpiperazines, and GC separation was accomplished on an Rtx‐200 phase.     

Positive and negative ion mass spectrometry and rapid isolation with Sep-Pak C18 cartridges of ten local anaesthetics.

The positive ion electron impact (PIEI), positive ion chemical ionization (PICI) and negative ion chemical ionization (NICI) mass spectra and a rapid isolation procedure using Sep-Pak C18 cartridges are presented for ten local anaesthetics. In the PIEI mode, molecular peaks were very small or missing for most compounds. Peaks at m/z 86 due to the diethylaminoethyl or propylaminoethyl group constituted base peaks in six compounds. In the PICI mode, peaks due to M + H and M + C2H5 appeared. The cation at m/z 86 was also observed for the six compounds. This ion seems useful for the screening of local anaesthetics. In the NICI mode, anions at m/z M - H constituted base peaks for all compounds, peaks at m/z M + 12 appeared in many compounds. The total ion current in the PIEI and PICI modes generally gave higher sensitivity than in the NICI mode. Local anaesthetics present in whole blood or cerebrospinal fluid (CSF) could be rapidly isolated by use of Sep-Pak C18 cartridges with chloroform/methanol as an elution solvent. Their detection was possible using wide-bore capillary gas chromatography with SPB-1 and HP-17 wide-bore capillary columns with satisfactory separation from impurities.     

A detailed mechanistic fragmentation analysis of methamphetamine and select regioisomers by GC/MS

A novel ring-substituted methamphetamine regioisomer, N,alpha,4-trimethyl phenmethylamine, was synthesized in order to study the validity of proposed structures for various mass spectrometry (MS)-derived peaks in a methamphetamine fragmentation pattern. While other research efforts have studied aspects of methamphetamine in detail, a full fragmentation study has not been reported previously. In addition to showing molecular structures represented by fragment peaks, mechanisms for selected processes are detailed. An empirically derived procedure to easily determine by simple spectral peak pattern recognition the geometry of dimethyl- or ethyl-substituted immonium ions (RRC = N+ RR) where m/z = 58 is outlined. These results are platform independent for electron ionization (EI) instruments, but have also proven to be helpful in explaining spectral peaks observed in spectra from ion trap systems. The spectrum for the synthesized methamphetamine regioisomer was accurately predicted using this methodology. While this approach is useful in some casework, the converse may be more useful: when an unexpected or unusual peak pattern arises in a spectrum, being able to analyze it to determine the structure of the molecule. This paper gives an analyst the means to begin such retro-synthetic analyses.     

Qualitative and quantitative analysis of seized street drug samples and identification of source

In this paper we describe the identification of constituents of the illicit drugs seized from different regions of eastern India by GC-MS. The constituents were identified to be heroin, acetyl morphine, morphine and acetyl codeine. Quantitative estimation of the constituents were made by GC-MS and HPTLC. In view of non-availability of the authentic samples of drugs of different origin, nothing positive can be said about the origin of illicit drug samples. The possibility of isotopic substitution, an important method for identification of source, was examined from the comparison of the intensity of different (ion) peaks 369 (heroin, m/z=369), 370, 371 and 372 using selective ion monitoring mode. No isotopic substitution in the constituents was observed. Attempts were made to identify the source of the illicit samples from heroin/acetylcodeine ratios in the way described in the literature.