大麻概况及其气相分析方法综述

随着大麻走私的日益猖獗,对大麻进行快速准确的定性定量分析,为司法部门量刑提供准确可靠的依据显得尤为重要。本文对大麻的化学成分、检材种类、滥用方式进行介绍,并对气相色谱分析方法中涉及的检材提取方法、内标物、色谱柱和质谱图等进行综述。     

A preliminary study of the analysis of explosives using packed-column supercritical fluid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection

A packed-column supercritical fluid chromatographic (SFC) separation of explosive compounds hyphenated to atmospheric pressure chemical ionisation (APCI) mass spectrometric (MS) detection has been developed. Nitroaromatics, nitramines and nitrate esters can be resolved and identified, with theoretical limits of detection of approximately 100 ng on column. This represents a development over previously described gas chromatography–thermal energy analysis (GC–TEA), gas chromatography– electron capture detection (GC–ECD) and SFC methods for the analysis of explosives due to the molecular identification afforded by the mass spectrometry. Explosives in the combinations expected in commercially available mixtures can be separated and identified. A successful application to a laboratory trial simulating casework is described.     

The detection of beta-cypermethrin during forensic chemical expertise of biological materials

The optimal conditions for the isolation of beta-cypermethrin from biological materials by means of dioxane extraction have been developed. The possibility to purify beta-cypermethrin from endogenous impurities is demonstrated by combination of liquid-liquid extraction and chromatography through a silica gel column (L 40/100 mcm). It is shown that identification and quantitative determination of beta-cypermethrin extracted from the cadaveric liver tissues are possible using such techniques as thin-layer chromatography, electron spectrometry, and chromato-mass spectrometry. A method for forensic chemical expertise of the presence of beta-cypermethrin in biological materials is described.     

Quantitative analysis of tropane alkaloids in biological materials by gas chromatography-mass spectrometry

A simple and rapid method for quantitation of tropane alkaloids in biological materials has been developed using an Extrelut column with gas chromatography-mass spectrometry (GC-MS). Biological materials (serum and urine) were mixed with a borate buffer and then applied to an Extrelut column. The adsorbed tropane alkaloids were eluted with dichloromethane before a GC-MS analysis. Atropine-d(3) was used as an internal standard. The extracted tropane alkaloids were converted to trimethylsilyl derivatives prior to GC analysis, to improve the instability of tropane alkaloids from heating and the property of them for a GC column. The recoveries of the compounds, which had been spiked to biological materials, were more than 80%. The GC separation of the derivatives from endogenous impurities was generally satisfactory with the use of a semi-polar capillary column. Tropane alkaloids showed excellent linearity in the range of 10-5000 ng/ml and the limit of detection was 5.0 ng/ml for biological materials. The present method is simple and more rapid than those previously reported, and was applied to a poisoning case. It is useful for the routine analysis of tropane alkaloids in cases of suspected tropane alkaloids poisoning.     

尸体脏器中几种镇静药物气相色谱/质谱测定的研究

本文应用气相色谱/质谱(GC/MS)技术,研究了尸体脏器中五种巴比妥酸盐、导眠能、苯妥英的定性和定量分析方法。应用SE-54毛细柱找到了良好分离条件。以安眠酮作内标,建立了定量分析程序。应用这个方法,可在1小时内完成定性分析,检测限为5ng;定量分析的准确度和精密度均为±10％。     

Determination of elemental sulfur in explosives and explosive residues by gas chromatography-mass spectrometry

A new method for the positive identification of elemental sulfur in explosives and explosive residues is developed. Following a carbon disulfide wash of explosives or explosive residues, a sample of the extracted material is injected onto a gas chromatography (GC) column, then analyzed via mass-selective (MS) detection. A positive identification of elemental sulfur is based on both retention time and fragmentation pattern. The GC-MS method is demonstrated to be useful in detecting and positively identifying elemental sulfur from both burned and unburned explosive mixtures. With a detection limit of 2.5 ng (2.5 x 10(-9) grams) of elemental sulfur on the column, it is shown to be 400 times more sensitive than the presumptive chemical color test that is currently the method employed for detection of small amounts of sulfur.     

A rapid and convenient LC/MS method for routine identification of methamphetamine/dimethylamphetamine and their metabolites in urine

A rapid and sensitive LC/MS method was developed for the simultaneous analysis of N,N-dimethylamphetamine (DMA), N,N-dimethylamphetamine N-oxide (DMANO), methylamphetamine (MA) and amphetamine (A) in urine samples. Employing an Alltech C18 column for solid phase extraction followed by LC/MS analysis using an Alltech Platinum EPS C18 column with a mixture of ammonium formate (0.01 M, pH 3) and acetonitrile (77:23, v/v) as mobile phase at a flow rate of 0.2 mL/min, simultaneous identification and quantitation of A, MA, DMA and DMANO in urine can be achieved using a 5-min chromatographic run. The calibration ranges were 0.10-3.0 micro g/mL for DMANO, 0.05-3.0 micro g/mL for DMA and 0.05-5.0 micro g/mL for both MA and A. The intra-, inter-day precision and accuracy for all analytes, spiked at three different concentrations in quality control samples, were in the ranges of 1.7-8.6, 4.1-10.0, -11.6 to 12.9%, respectively. The newly developed method was applied to the analysis of urine samples obtained from 118 suspected MA/DMA abusers, with the presence of MA confirmed in their urine samples under the drug-use surveillance program. Of these 118 samples, 43 were found to contain DMANO and 11 with both DMANO and DMA.     

Chemical signature of ecstasy volatiles by comprehensive two-dimensional gas chromatography

A method for ecstasy volatiles 'signature' analysis based on two-dimensional gas chromatography separation and time-of-flight mass spectrometry detection (GC×GC-TOFMS) is presented. Organic impurity volatiles were extracted by head space solid phase microextraction (HS-SPME). The final column phase choice of the four different column combinations tested was a low-polarity 5% phenyl polysilphenylene-siloxane coupled with a polyethylene glycol phase, which best displayed the complex impurity profile. Second dimension ((2)D) retention time reproducibility was found to be about 1% RSD, and area reproducibility of SPME sampling was just over 5% RSD for compounds with S/N ratio of about 100. High similarity of TOFMS spectra of impurities was obtained against commercial MS libraries. 16 components from the two-dimensional profiles were selected for comparison of the 24 ecstasy tablets, most of which proved to be benzodioxole derived compounds. All tablets were correctly classified in eight groups according to their post-tabletting characteristics, when appropriate data pre-treatment was applied. Principal component analysis revealed clustering of samples according to the country of origin. Samples from Macedonia were elevated in N-formyl-MDMA and N-acetyl-MDMA while samples from Australia were elevated in 3,4-methylenedioxypropane and 3,4-methylenedioxyacetophenone. Furthermore, three components were found to be unique for one of the source countries. The additional separation of components on the (2)D column, increased response due to modulation, high acquisition rate with full mass spectra using TOFMS detection, and MS deconvolution extend the possibility of detecting additional markers and route-specific components, especially of low abundant, polar components.     

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。     

Overview of the seized and examined pharmaceutical in the state of Minas Gerais-Brazil by the Civil Police from 2017 to 2022: A fundamental analysis of the recent impact over the drugs market

This work presents a data survey regarding the qualitative chemical analysis of drugs seized by the Police in the state of Minas Gerais between July 2017 and June 2022, including an evaluation of labeling of 265 samples of anabolic androgenic steroids (AAS) seized in 2020. The Active Pharmaceutical Ingredients (API) present in the samples were identified through chemical analysis and classified by system Anatomical Therapeutic Chemical (ATC) methods. Analysis of the labeling information for 265 samples of AAS followed the guidance of legislation RDC 71 (2009) from ANVISA. For this study 6355 seized pharmaceuticals underwent qualitative chemical analysis that corresponded to 7739 APIs successfully identified and classified. Among the components studied AAS, psychostimulants, anesthetics, and analgesics were the most commonly examined. AAS seized and tested increased by over 100% and for the majority of the samples analyzed were found to not match the labeling on the packaging. In the meantime, anti-obesity drugs presented a prominent increase of 400% from 2020/1 to 2021/2, during covid-19 quarantine. Seized pharmaceuticals and tests can support information in the planning of public health and safety policies.     

气相色谱/质谱检验合成大麻素K3中AKB48

目的建立较为快速准确的合成大麻素K3中AKB48的气相色谱/质谱检验方法。方法对进样口温度、初始柱温、柱流速及质谱采样率等4项色谱及质谱实验参数进行考察优化。结果 GC/MS检验合成大麻素K3中AKB48的优化条件为:进样口温度280℃,柱初始温度80℃,柱流速为2.0ml/min,质谱采样率为2。结论该方法具有快速、准确、灵敏等优点,可用于K3中AKB48的定性检验鉴定。     

Semi-automatic analysis of fire debris

Automated analysis of fire residues involves a strategy which deals with the wide variety of received criminalistic samples. Because of unknown concentration of accelerant in a sample and the wide range of flammable products, full attention from the analyst is required. Primary detection with a photoionisator resolves the first problem, determining the right method to use: the less responsive classical head-space determination or absorption on active charcoal tube, a better fitted method more adapted to low concentrations can thus be chosen. The latter method is suitable for automatic thermal desorption (ATD400), to avoid any risk of cross contamination. A PONA column (50 mx0.2 mm i.d.) allows the separation of volatile hydrocarbons from C(1) to C(15) and the update of a database. A specific second column is used for heavy hydrocarbons. Heavy products (C(13) to C(40)) were extracted from residues using a very small amount of pentane, concentrated to 1 ml at 50 degrees C and then placed on an automatic carousel. Comparison of flammables with referenced chromatograms provided expected identification, possibly using mass spectrometry. This analytical strategy belongs to the IRCGN quality program, resulting in analysis of 1500 samples per year by two technicians.     

Determination of dimethoate in blood and hemoperfusion cartridge following ingestion of formothion: a case study

A 57-year-old male who had ingested not more than 22 g of formothion was semicomatose on admission to hospital, approximately 1.5 h after ingestion. Dimethoate, a hydrolyzed formothion, was found in blood samples collected from the patient and in the charcoal column in the direct hemoperfusion cartridge which was used 6 to 7.5 h after ingestion. It was extracted and purified by Extrelut column extraction. A gas chromatograph, equipped with a flame photometric detector and a gas chromatograph-mass spectrometer, were used to detect and confirm the presence of dimethoate. The blood dimethoate concentrations which were taken approximately 1.5 and 6 h after ingestion were 21.4 and 12.7 micrograms/g, respectively. A blood dimethoate concentration of 21.4 micrograms/g would appear to indicate a high level of formothion intoxication. The total amount of dimethoate found in the charcoal column used was 15 mg.     

An analysis of a prehistoric homicide from northern California

An analysis was performed on a prehistoric human vertebral column recovered during an archaeological excavation in the Sierra of northern California. Fifteen burials believed to represent the Maidu culture of 400 to 700 years ago were recovered. The vertebral column from one of the individuals is particularly significant because of three embedded projectile points. The analysis attempts to recreate the trajectory of each point; to determine the possible extent of damage done by each with emphasis upon which could have been fatal; and by employing available ethnographic and archaeological data, to suggest the possible circumstances surrounding the violent event. The conclusion suggests that death may have resulted from any of the three wounds and was probably the result of an intratribal dispute.     

固根萃取技术在系统药、毒物分析中的应用

根据反相色谱法及离子交换色谱法的原理,研制了一种固相萃取小柱,建立了筛分系统,可以同时完成对复杂体系中酸性、中性及碱性药、毒物的一次革取净化及富集,适应于系统毒物及药物筛分工作的需要。并对筛分柱的草取机理进行了初步的实验论证。     

毛细管气相色谱法测定酱油中4-甲基咪唑的含量

目的建立毛细管气相色谱法定量分析酱油中有毒成分4-甲基咪唑的方法。方法酱油样品在层析柱中用二氯甲烷洗脱,洗脱液浓缩后加入N,N-二甲基苯胺作为内标,采用DB-FFAP毛细管柱分离样品,氮磷检测器测定4-甲基咪唑含量。结果方法线性范围为4.9~1.5×102μg/L;检测限为0.16μg/L;标准加入0.0102mg和0.0602mg 4-甲基咪唑的平均回收率为97.25%和99.44%。结论本文方法具有操作简便、快速、准确等优点,可用于检验酱油中的4-甲基咪唑。     

兔尿中敌鼠及其代谢物的HPLC-DAD分析

目的 尿中敌鼠及其代谢物的HPLC分析方法研究。方法 用CN柱和SAX柱的固相萃取(SPE)技术分离提取兔尿中的敌鼠及其代谢物,用香豆素作内标,用HPLC-DAD方法进行fenxi。色谱柱:Hypersil BDSC_(18)(150×4.6mm):保护柱:Phenomenex C_(18) (ODS,4×3.0mm,Octadecyl;流动相A:0.5％离子对A水溶液,B:0.5%离子对A甲醇液,梯度程序洗脱;DAD检测波长为311nm。结果 在中毒的兔尿中检出11种敌鼠代谢物。结论 此方法简单、准确、快速。     

体液中微量士的宁的富集及同时检测

目的将分子印迹技术运用到法医毒物分析中,建立一种全新的测定体液中微量士的宁的方法。方法运用分子印迹原位聚合技术,在色谱柱中一步合成了对士的宁具有专属识别能力的分子印迹聚合物,以此聚合物为介质,装填一厘米的小柱,建立体液中微量士的宁的富集及同时检测方法。结果以士的宁分子印迹聚合物作为尿液和血浆中微量士的宁的富集和检测介质,方法的检出限为4.9ng,样品回收率均大于92%,相对标准偏差小于6.59%,工作曲线的线性相关系数分别为0.9991和0.9966。运用此方法对中毒家兔血浆和尿液中的士的宁进行了测定。结论建立的新方法可以实现对士的宁专属的、灵敏的检测,适合于法医学毒物分析运用。     

Visualization and LC/MS analysis of colorless pepper sprays

Pepper sprays are used in a variety of circumstances, including criminal activity, self-defense, and law enforcement. As such, the presence or absence of pepper sprays on evidentiary materials is often important when determining the facts of an incident. When no visible stains are present on evidentiary materials, ascertaining the presence or absence of pepper spray can be a challenge to the forensic analyst. A method, based on a chemical derivatization of capsaicinoids using a diazonium salt, has been developed for the visualization of colorless, ultraviolet (UV) activated fluorescent dye-free pepper sprays on textiles. Identification of both the capsaicinoids and their derivatives is confirmed via extraction of the derivatized capsaicinoids followed by liquid chromatography/mass spectrometry (LC/MS) analysis. LC/MS analysis is conducted using a YMC Basic column and elution of the compounds using a gradient of 10 mM ammonium formate, pH 4.2 and methanol at 0.35 mL/min. Full-scan MS data are collected for the full 6.5 min LC analysis. Although this method is qualitative in nature, visual detection of as little as 50 microL of a 0.2% pepper spray (equivalent to approximately 0.1 mg) on a variety of garments is possible, and more than adequate signal-to-noise is obtained for reconstructed ion chromatograms on LC/MS analysis at these levels.     

气相色谱-负化学源质谱法检测生物样品中佐匹克隆

目的建立气相色谱-负化学源质谱检验生物样品中佐匹克隆的方法。方法采用OasisHLB柱进行固相萃取,NCI-GC／MS检验。结果生物样品中佐匹克隆平均萃取回收率达75．8％,最低检出限0．01μg·mL^-1,线性良好,相关系数R^2=0．9989。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。