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.     

Isolation and Identification of Three By‐products Found in Methylamphetamine Synthesized by the Emde Route

This article describes the isolation and structural elucidation of three compounds produced during the synthesis of methylamphetamine by the so‐called “Emde” procedure. The “Emde” procedure involves the preparation of the intermediate chloropseudoephedrine or chloroephedrine from ephedrine or pseudoephedrine, respectively. The intermediates are then reduced to methylamphetamine with hydrogen under pressure in the presence of a catalyst. The by‐product compounds were isolated from methylamphetamine by column chromatography and liquid chromatography (LC). Proton nuclear magnetic resonance spectroscopy (¹H NMR), carbon nuclear magnetic resonance spectroscopy (¹³C NMR), and nanospray quadrupole‐time of flight‐mass spectrometry (Q‐TOF‐MS) were used to identify them as two stereoisomers of the compound N, N′‐dimethyl‐3,4‐diphenylhexane‐2,5‐diamine and N‐methyl‐1‐{4‐[2‐(methylamino)propyl]phenyl}‐1‐phenylpropan‐2‐amine.     

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。     

Positive- and negative-ion mass spectrometry and rapid clean-up of some carbamate pesticides

Positive-ion electron impact (PIEI), positive-ion chemical ionization (PICI) and negative-ion chemical ionization (NICI) mass spectra of 9 carbamate pesticides are presented. In the PIEI mode, the spectra showed small molecular peaks, intense or base peaks due to M - CH3NHCO + H and peaks at m/z 58 due to CH3NHCO. In the PICI mode, peaks due to M + H, M + C2H5, M - CH3NHCO + 2H, CH3NHCO(m/z 58) and M-28 appeared. The cations at m/z 58 found in both PIEI and PICI modes seem very useful for screening of a carbamate. In the NICI mode, the spectra showed peaks due to M - CH3NHCO and characteristic anions appearing at mass numbers higher than molecular ones, which were probably due to dimerization of [M - CH3NHCO]-followed by hydrogen attachment. Carbamates, which had been added to urine, plasma, whole blood, the liver, kidney and brain, could be rapidly isolated by use of Sep-Pak C18 cartridges with chloroform as an elution solvent. They could be detected by wide-bore capillary gas chromatography with a SPB-5 column, with satisfactory separation from impurities in their underivatized forms.     

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.     

Positive and negative ion mass spectrometry of tricyclic antidepressants

Positive electron impact (EI), positive chemical ionization (CI), and negative CI mass spectra of eight tricyclic antidepressants are presented. In the positive EI mode, peak(s) at m/z 193 and/or 195, which corresponded to the tricyclic nucleus, appeared for five compounds; a peak at m/z 58 was common to compounds having a gamma-dimethylaminopropyl group as their side chain. Molecular ions appeared for all compounds though they were very small in some compounds in the positive EI mode. In the positive CI mode, [M + H]+ quasi-molecular peaks appeared together with [M + C2H5]+ peaks in five compounds; the ion at m/z 196, which corresponded to the tricyclic nucleus also appeared in five compounds. In the negative CI mode with 1 Torr chamber pressure, [M - 1]- quasi-molecular ions were observed for all compounds except for lofepramine; [M + 43]- anions, which probably corresponded to [M + C3H4]-, appeared in five compounds; strong [M + Cl]- ions appeared in carpipramine and clocapramine. The anions due to the tricyclic nucleus also appeared in this mode. In the negative CI mode at low pressure (0.01 Torr), the spectra were generally similar to those in the 1 Torr negative CI mode. However, the cluster anions never appeared at the low pressure. Some data on extraction for some antidepressants from human urine and plasma, and their separation by gas chromatography, are also presented.     

The analytical profile of some 4-methylthioamphetamine (4-MTA) homologues

The 4-methylthioamphetamine (4-MTA) is a sulphur-containing amphetamine-type stimulant (ATS), which appeared on the illicit market in Europe at the end of 90s. For the purpose of this study, several N-alkyl homologues of 4-MTA, including 4-methylthiomethamphetamine (4-MTMA), 4-methylthioethylamphetamine (4-MTEA), 4-methylthiodimethamphetamine (4-MTDMA), 4-methylthiopropylamphetamine (4-MTPA) and 4-methylthiobutylamphetamine (4-MTBA) were synthesized. The homologues were characterized by means of gas chromatography/mass spectrometry (GC–MS), infrared (IR) spectroscopy and the magnetic resonance spectroscopy (¹H and ¹³C NMR). The gas chromatography and mass spectrometry properties of their acetyl, trifluoroacyl (TFA), pentafluoropropionyl (PFP) and heptafluorobutyryl (HFB) derivatives were also investigated and discussed.     

Positive identification of the principal component of a white powder as scopolamine by quantitative one-dimensional and two-dimensional NMR techniques

An unidentified white powder collected as evidence in an intelligence investigation was characterized exclusively by nuclear magnetic resonance (NMR) analysis. A small fraction of the powder dissolved in D2O was subjected to a series of one- and two-dimensional techniques which were used to elucidate the molecular structure of the powder's major component and positively identify it as the scopolamine biotoxin. Quantitative one-dimensional experiments identified individual proton and carbon atom sites, and conventional 14N spectroscopy detected a single nitrogen atom site. Heteronuclear single quantum coherence data correlated all protons to their directly bonded carbon atom, and together with the quantitative spectra, were used to determine the number of protons directly bonded to each carbon atom. The presence of a methyl, carboxyl, and a benzyl group was also identified from these data. Correlation spectroscopy detected a three proton and a nine proton JH,H network, representing a CH2CH moiety and seven carbon atom ring, respectively. These five elements were assembled into an almost complete molecular structure by using long-range, J-coupled, 1H-13C pairs detected by heteronuclear multiple bond correlation (HMBC) spectroscopy and 1H-1H dipolar-coupled pairs found from nuclear Overhauser effect spectroscopy (NOESY) data. Additional oxygen atom sites were inferred from 1H-13C correlation intensities in the HMBC spectra along with 1H and 13C chemical shift values, or directly from NOESY correlations. Only a single oxygen atom site could not be inferred from NMR data, but its presence was inferred from comparisons to target analyte structures to complete the structure of the scopolamine molecule. To confirm these results, an ethanol/H2O solution of the powder was analyzed by direct infusion into an ion trap mass spectrometer. A prominent base signal was observed at m/z 304.1 amu, corresponding to the protonated molecular ion of scopolamine. Subsequently, the ion was selected and subjected to collision-induced dissociation, producing characteristic major MS/MS fragments at m/z 138.1 and 156.1. Comparisons of 1H and 13C chemical shift values and JH,H values measured from our NMR data were found to agree very favorably with previously reported values for scopolamine in D2O.     

Quantitative Analysis of Gamma‐Hydroxybutyrate at Endogenous Concentrations in Hair using Liquid Chromatography Tandem Mass Spectrometry

Abstract: A method capable of quantifying endogenous concentrations of gamma‐hydroxybutyrate (GHB) in human head hair was developed and validated using liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS). Hair was digested under alkaline conditions, and GHB was isolated using liquid–liquid extraction. LC/MS/MS was performed using atmospheric pressure chemical ionization in the negative mode, multiple reaction monitoring, and deuterated internal standard (GHB‐D₆). Linearity was observed between 0.1 and 100 ng/mg GHB (R² = 1.000). The limits of detection and quantitation in human hair were 0.2 and 0.4 ng/mg, respectively. Accuracy at 2 ng/mg and 10 ng/mg was determined to be 97% and 94%, and intra‐assay CVs at these concentrations were 5.2% and 7.4% (n = 4). Beta‐hydroxybutyrate (BHB), alpha‐hydroxybutyrate, gamma‐butyrolactone, and 1,4‐butanediol did not produce an interference, and there was negligible ion suppression or enhancement from the matrix.     

Characterization and Differentiation of Geometric Isomers of 3‐methylfentanyl Analogs by Gas Chromatography/Mass Spectrometry,Liquid Chromatography/Mass Spectrometry,and Nuclear Magnetic Resonance Spectroscopy

The cis and trans isomers of 3‐methylfentanyl and its three analogs were chemically synthesized, and these compounds were characterized and differentiated by gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), and nuclear magnetic resonance (NMR) spectroscopy. The cis and trans isomers of the 3‐methylfentanyl analogs were completely separated by GC/MS. Although the high temperature of the GC injection port caused thermal degradation of β‐hydroxy‐3‐methylfentanyl, the degradation was completely suppressed by trimethylsilyl derivatization. The isomers were also well separated by LC/MS on an octadecylsilyl column with 10 mM ammonium acetate and methanol as the mobile phase. The proton NMR signals were split when the hydrochloride salts of the 3‐methylfentanyl analogs were dissolved in deuterated chloroform because stereoisomers were formed by the coordination of the hydrochloride proton to the nitrogen of the piperidine ring of the 3‐methylfentanyl analogs.     

A fatal poisoning involving Bromo-Dragonfly

This paper reports a fatal overdose case involving the potent hallucinogenic drug Bromo-Dragonfly (1-(8-bromobenzo[1,2-b; 4,5-b′]difuran-4-yl)-2-aminopropane). In the present case, an 18-year-old woman was found dead after ingestion of a hallucinogenic liquid. A medico-legal autopsy was performed on the deceased, during which liver, blood, urine and vitreous humour were submitted for toxicological examination. Bromo-Dragonfly was identified in the liver blood using UPLC–TOFMS, and was subsequently quantified in femoral blood (0.0047 mg/kg), urine (0.033 mg/kg) and vitreous humour (0.0005 mg/kg) using LC–MS/MS. Calibration standards were prepared from Bromo-Dragonfly isolated from a bottle found next to the deceased. The structure and purity of the isolated compound were unambiguously determined from analysis of UPLC–TOFMS, GC–MS, HPLC–DAD, ¹H and ¹³C NMR data and by comparison to literature data.The autopsy findings were non-specific for acute poisoning. However, based on the toxicological findings, the cause of death was determined to be a fatal overdose of Bromo-Dragonfly, as no ethanol and no therapeutics or other drugs of abuse besides Bromo-Dragonfly were detected in the liver, blood or urine samples from the deceased. To our knowledge, this is the first report of quantification of Bromo-Dragonfly in a biological specimen from a deceased person. This case caused the drug to be classified as an illegal drug in Denmark on 5th December 2007.     

THCVA-A - a new additional marker for illegal cannabis consumption

The aim of the present investigations was to find markers for differentiating between the consumption of illegal cannabis products and legal medication containing fully synthetic Δ9-tetrahydrocannabinol (Δ9-THC), e.g., Marinol capsules. Δ9-Tetrahydrocannabinolic acid A (Δ9-THCA-A) and Δ9-tetrahydrocannabivarinic acid A (Δ9-THCVA-A) were taken into consideration for analysis, because these substances are the precursors of Δ9-THC and Δ9-tetrahydrocannabivarin (Δ9-THCV) in plant material of Cannabis sativa and are not contained in medical THC formulations. Whereas Δ9-THCA-A is an already well investigated substance, there is little analytical data on Δ9-THCVA-A. The reason for the presented investigations was a case in which a man was tested positive for Δ9-THC during a routine traffic control claiming that the positive serum sample resulted from the intake of a THC medication (Marinol) and not from consuming illegal cannabis products. Sample preparation consisted of a protein precipitation with acetonitrile. Analysis was carried out on a Thermo Fisher LCQ Deca ion trap LC-MS-MS-system using electron spray ionization (ESI) in negative mode. MS(2)- and MS(3)-full scan spectra were recorded for Δ9-THCA-A and Δ9-THCVA-A starting from [M-H](-). Reference spectra were obtained by measuring a Δ9-THCA-A reference solution and an ethanolic cannabis extract for Δ9-THCVA-A as there is no reference material for this cannabinoid available on the market yet. Main transitions for Δ9-THCA-A were m/z 357→313 and 339 in the MS(2)-spectrum and m/z 313→245 and 191 in the MS(3)-spectrum. Fragmentation pattern of Δ9-THCVA-A was identical with a difference of 28 amu less for the precursor ion as well as the fragments due to a shorter alkyl side chain in the molecule (MS(2): m/z 329→285 and 311; MS(3): m/z 285→217 and 163). The two plant cannabinoids Δ9-THCA-A and Δ9-THCVA-A could be detected in the serum sample by LC-MS-MS which proved the intake of illegal cannabis products derived from plant material of C. sativa in the described case.     

Differentiation of regioisomeric ring-substituted fluorophenethylamines with product ion spectrometry

The electron ionization (EI) of aromatic ring-substituted isomers gives virtual identical mass spectra which seriously affects their analysis. Especially regioisomeric meta- and para-ring-substituted compounds cannot show any ortho-effect reactions making their differentiation by mass spectrometry impossible. Furthermore o-, m- and p-substituted compounds can only be separated insufficiently by chromatography due to their very similar retention that do not allow univocal identification. Product ion mass spectrometry has proved to be a useful tool to differentiate structurally closely related fluorophenethylamines even in the case of the meta- and para-isomers. A series of N-alkylated o-, m- and p-fluoroamphetamines and 1-(4-fluorophenyl)butan-2-amines have been synthesized in microscale and studied by product ion spectrometry. The combination of chemical ionization (CI) and product ion spectrometry of hydrogen fluoride loss ions [M+H?HF]⁺ allows a univocal differentiation of all studied fluoro-substituted phenethylamines without prior derivatization. This method with submicrogram detection limits provides great advantages for the differentiation between aromatic regioisomeric fluorophenethylamine designer drugs where other methods such as nuclear magnetic resonance (NMR) spectrometry lack sufficient sensitivity or might fail because complex mixtures have to be analyzed.     

Novel O‐propyl,S‐propyl,and N‐propyl substituted 1,4‐naphthoquinones and 1,4‐anthraquinones as potential fingermark development reagents for porous surfaces

Lawsone is a 2‐substituted‐1,4‐naphthoquinone derivative, which has been proposed as an alternative to the reagents currently used for fingermark detection on porous surfaces. 2‐substituted‐anthraquinones, which contain an additional conjugated benzene ring, have a similar chemical structure to that of lawsone. In this study, a new series of 2‐substituted‐1,4‐naphthoquinones and 2‐substituted‐1,4‐anthraquinones were synthesized and completely characterized by¹H NMR,¹³C NMR, IR, and HPLC‐TOF/MS analyses. All newly synthesized 2‐substituted‐1,4‐quinones were investigated for their ability to develop latent fingermarks on porous surfaces, and this ability was compared with that of lawsone. Each fingermark developed was graded using an established method; thus, quantitative data were attributed to each fingermark. It has been demonstrated that the 1,4 ‐ quinones react with amino acids present in latent fingermarks on selected paper surfaces to produce faint yellow‐orange impressions, which exhibit strong photoluminescence when illuminated with a forensic light source at 440 nm and observed through a red filter. None of the compounds caused background darkening. The results obtained were generally similar to those of lawsone, however, 8‐dibromo‐2‐(propylamino)naphthalene‐1,4‐dione and 5,8‐dibromo‐2‐(propylthio)naphthalene‐1,4‐dione yielded better results for copier paper and colored (blue) copier paper used in this analysis. To the best of our knowledge, this is the first study to examine the role of 1,4‐anthraquinone derivatives as potential fingermark development reagents. The results indicate that 1,4‐quinones have a potential to be used as reagents for enhancement of latent fingermarks.     

Positive- and negative-ion mass spectrometry and rapid clean-up of 19 phenothiazines

Positive-ion electron impact (PIEI), positive-ion chemical ionization (PICI) and negative-ion chemical ionization (NICI) mass spectra of 19 phenothiazines are presented. In the PIEI mode, peaks due to M, M minus side chain (M - R1), M - R1 + H, and side chain itself (R1) appeared for most compounds. The M - R1 and R1 ions were very useful for drug screening. In the PICI mode, most spectra showed base or intense peaks due to M + H, and small peaks due to M + C2H5; peaks due to M - R1 + 2H and R1 also appeared in many compounds. In the NICI mode, fragmentation modes were different in different compound groups; molecular or [M - H]- quasi-molecular anions appeared in many compounds with aliphatic side chains. Anions at m/z 98 and 115 were characteristic for compounds with (N-methylpiperazinyl)propyl side chains. Selected ion monitoring in the PIEI mode generally gave much higher sensitivity than in the PICI and NICI modes. Phenothiazines present in urine or plasma could be rapidly isolated by use of Sep-Pak C18 cartridges. Thirteen of 19 phenothiazines could be detected by HP-17 wide-bore capillary gas chromatography with satisfactory separation from impurities in their underivatized forms.     

Analysis of Δ-tetrahydrocannabinol in oral fluid samples using solid-phase extraction and high-performance liquid chromatography–electrospray ionization mass spectrometry

An analytical method using solid-phase extraction (SPE) and high-performance liquid chromatography–mass spectrometry (LC–MS) has been developed and validated for the confirmation of Δ⁹-tetrahydrocannabinol (THC) in oral fluid samples. Oral fluid was extracted using Bond Elut LRC-Certify solid-phase extraction columns (10 cm³, 300 mg) and elution performed with n-hexane/ethyl acetate. Quantitation made use of the selected ion-recording mode (SIR) using the most abundant characteristic ion [THC + H⁺], m/z 315.31 and the fragment ion, m/z 193.13 for confirmation, and m/z 318.00 for the protonated internal standard, [d₃-THC + H⁺]. The method proved to be precise for THC, in terms of both intra-day and inter-day analyses, with coefficients of variation less than 10%, and the calculated extraction efficiencies for THC ranged from 76 to 83%. Calibration standards spiked with THC between 2 and 100 ng/mL showed a linear relationship (r² = 0.999). The method presented was applied to the oral fluid samples taken from the volunteers during the largest music event in Portugal, named Rock in Rio-Lisboa. Oral fluid was collected from 40 persons by expectoration and with Salivette^®. In 55% of the samples obtained by expectorating, THC was detected with concentration ranges from 1033 to 6552 ng/mL and in 45% of cases THC was detected at concentrations between 51 and 937 ng/mL. However, using Salivette^® collection, 26 of the 40 cases had an undetectable THC.     

Extraction and isolation of cannabinoids from marijuana seizures and characterization by 1H NMR allied to chemometric tools

Marijuana, a drug derived from the Cannabis sativa L. plant, is the world's most consumed illicit drug. In this paper, a total of 156 marijuana samples seized in the state of Espírito Santo (ES), Brazil were studied and analysed by proton nuclear magnetic resonance (¹H NMR) spectroscopy to identify the major cannabinoids present. A crude extract of all samples was purified using high performance liquid chromatography so that these compounds could serve as reference substances. Nine fractions were obtained and analysed by ¹H NMR and gas chromatography–mass spectrometry (GC–MS), with five presented cannabinoids. ?⁹-THC (Δ⁹-trans-tetrahydrocannabinol), ?⁹-THCA (?⁹-tetrahydrocannabinolic acid), ?⁸-THC (?⁸-tetrahydrocannabinol), 11-hydroxycannabinol, CBV (cannabivarin), and CBN (cannabinol) were found, and their chemical structures were confirmed by GC–MS. The latter compound was obtained with high purity (≈100%), while the others were obtained as less complex mixtures with purity higher than 75% (except for Δ⁸-THC). Principal component analysis (PCA) was used on the ¹H NMR spectra of the 156 samples, and it was found that the samples were grouped according to the months, differentiating into two groups (from July 2014 to January 2015 and from February 2015 to July 2015), where non-grouping was observed from four macro-regions of the ES state (North, Central, Metropolitan, and South). The chemical profile of the seized samples was correlated to the ¹H NMR spectrum of an isolated CBN sub-fraction, in which the group formed by samples seized in the year 2015 presented lower CBN content in the chemical composition. From the PCA score plot, two groups of samples were confirmed using the partial least squares discriminant analysis and orthogonal projections to latent structures classification methods.     

Detection of trace drugs of abuse in baby formula using solid‐phase microextraction direct analysis in real‐time mass spectrometry (SPME‐DART‐MS)

The intentional or unintentional adulteration of baby formula with drugs of abuse is one of the many increasingly complex samples forensic chemists may have to analyze. This sample type presents a challenge because of a complex matrix that can mask the detection of trace drug residues. To enable screening of baby formula for trace levels of drugs, the use of solid‐phase microextraction (SPME) coupled with direct analysis in real‐time mass spectrometry (DART‐MS) was investigated. A suite of five drugs was used as adulterants and spiked into baby formula. Samples were then extracted using SPME fibers which were analyzed by DART‐MS. Development of a proof‐of‐concept method was completed by investigating the effects of the DART gas stream temperature and the linear speed of the sample holder. Optimal values of 350°C and 0.2 mm/s were found. Once the method was established, representative responses and sensitivities for the five drugs were measured and found to be in the range of single ng/mL to hundreds ng/mL. Additional studies found that the presence of the baby formula matrix increased analyte signal (relative to methanolic solutions) by greater than 200%. Comparison of the SPME‐DART‐MS method to a traditional DART‐MS method for trace drug detection found at least a factor of 13 improvement in signal for the drugs investigated. This work demonstrates that SPME‐DART‐MS is a viable technique for the screening of complex matrices, such as baby formula, for trace drug residues and that development of a comprehensive method is warranted.     

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.     

Analytical Characterization of Erythritol Tetranitrate,an Improvised Explosive

Erythritol tetranitrate (ETN), an ester of nitric acid and erythritol, is a solid crystalline explosive with high explosive performance. Although it has never been used in any industrial or military application, it has become one of the most prepared and misused improvise explosives. In this study, several analytical techniques were explored to facilitate analysis in forensic laboratories. FTIR and Raman spectrometry measurements expand existing data and bring more detailed assignment of bands through the parallel study of erythritol [¹⁵N₄] tetranitrate. In the case of powder diffraction, recently published data were verified, and ¹H, ¹³C, and ¹⁵N NMR spectra are discussed in detail. The technique of electrospray ionization tandem mass spectrometry was successfully used for the analysis of ETN. Described methods allow fast, versatile, and reliable detection or analysis of samples containing erythritol tetranitrate in forensic laboratories.