国外微量物证检验研究进展

本文根据近年来国外法庭微量物证检验方面的研究成果,从检验对象、检验技术及发展趋势三个方面总结了当前国外微量物证的研究现状。介绍了近年来国外法庭科学家在常见的微量物证如油漆、纤维、玻璃等的检测方法和检测技术,尤其重点介绍了一些新技术如电感耦合等离子体原子发射光谱技术(ICP/AES)、微波辅助消融和等离子光谱技术(OES/ICP)、激光等离子质谱联用技术(LA/ICP/MS)等在微量物证中的应用。指出国外微量物证研究相对于国内微量物证研究在技术应用、数据库建立、数据分析、合作研究等方面的优越性。     

LC-MS/MS同时分析尿液中15种安眠镇静药物及其代谢物

目的建立尿液中15种常见安眠镇静药物及代谢物的液相色谱-串联质谱分析方法。方法尿液经酶水解、固相萃取后,用C18液相柱分离,以含甲酸铵和甲酸的水、乙腈为流动相梯度洗脱,质谱采用电喷雾电离（ESI）-正负离子模式同时扫描,采用二级质谱多反应监测（MRM）模式检测目标化合物。结果以化合物的保留时间、两对母离子/子离子对定性,尿中常见安眠镇静药物的检测限为0.01～0.5ng/mL（ESI＋）和10ng/mL（ESI-）;相关系数r在0.994以上;日内及日间精密度均在18%以下;绝对回收率在64.80%～116.20%之间。结论方法快速、灵敏、简便、可靠,能同时分析尿液中的15种安眠镇静药物及其代谢物。     

DART-TOFMS检验红色印油初探

目的研究建立红色印油无损检验的有效鉴定方法。方法应用实时直接分析飞行时间质谱(DART-TOFMS)技术,对12个品种红色印油进行直接无损检测分析,获得样品的质谱信息。结果 2个样品组分相同不能加以区分,其余印油样品质谱区分率为100%。结论本研究建立的检测方法无损、快速、准确、无需样品前处理,可以满足物证鉴定工作对印油的检测需要。     

DESI-HRMS-HDI在添改字迹鉴定中的应用研究

目的通过电喷雾解吸电离(DESI)—高分辨飞行时间质谱(HRMS-HDI)成像技术建立了一种新型添改字迹鉴别技术。方法对10支黑色签字笔书写的“11”被添改成“47”的90个样本用分子成像技术测试。结果该技术可将84个被添改的原始字迹“11”以二维成像方式显现。结论DESI-HRMS-HDI技术无需检材预处理,在大气压下即可进行操作,接近无损检验,操作简便,是一种有效的文件检验技术,适用于文件材料鉴别和篡改文件鉴定。     

HPLC—ESI—MS／MS法测定全血中溴敌隆

目的建立全血中测定溴敌隆的高效液相色谱-电喷雾-质谱联用检测方法。方法血液样品经乙醚提取后，采用Ultra Cl8柱（150mm×2．1mm×5μm）；柱温：23℃；流动相：甲醇；流速：200μl／min；在负离子模式下，通过电喷雾电离（ESI），多反应监测（MRM）测定，外标法定量分析溴敌隆。结果在0．1-50mg／1范围内两者均呈良好的线性关系。溴敌隆的回收率为94．34％（RSD=7．3％），考察了方法的基质抑制作用（matrix effect，ME）（％）=B／A×100％=91．86％（RSD=4．78％）定量检出限为0．028ng。结论本方法简便、灵敏度高、定性定量准确，可以作为检验全血中溴敌隆检验的一种手段。     

41种抗生素LC/MS联合测定的谱图库建立

目的建立常见41种抗生素LC/MS联合测定谱图库。方法采用ZORBAX sb-aq,2.1mm×150mm×3.5μm（带预柱）;柱温：30℃;流动相：甲酸（0.1%）甲醇和甲酸（0.1%）水溶液梯度条件;流速：0.4mL/min;通过电喷雾电离（ESI）,自动三级质谱检测。结果应用液质联用仪通用检测方法,得到了含有41种常见抗生素的自用质谱谱库和保留时间参数谱图库。通过谱图解卷积和保留时间锁定软件方法实现数据自动处理。结论该方法具有不易漏检和减少假阳性的优点,完全可替代手工检索质谱,可用于实际案件检验。     

生物质谱技术在法医遗传学中的应用展望

随着基质辅助激光解吸电离质谱 (MALDI MS)和电喷雾离子化质谱 (ESI MS)两种技术的迅速发展 ,生物质谱技术已经成为生命科学研究中的重要工具。由于直接检测分子的质量 ,质谱技术同其他方法相比更加准确。生物质谱技术在核酸序列分析中具有快速性、微量化、和高通量的特点。利用MALDI TOF MS技术可以分析降解检材的SNP遗传标记 ,这在法医学中将有着重要的意义。本文对生物质谱技术的原理、进展、面临的困难以及在法医遗传学中的应用前景作了评述     

检验ABH血型物质红细胞的研制——检验B血型物质红细胞的制备

<正> 目前,在法医物证检验中,ABH 血型物质的检验占物证检验的大部分。为寻求一个灵敏度高,操作简便的方法,我们将抗 B单克隆抗体结合在醛化人“O”型红细胞表面(红细胞致敏),利用该红细胞检验 B 血型物质获得了初步成功。经反复试验,证明此方法具有灵敏、快速、准确、简便而易于掌握等优点。现将其制备方法及特点报告如下.     

国外微量物证检验研究进展

本文根据近年来国外法庭微量物证检验方面的研究成果,从检验对象、检验技术及发展趋势三个方面总结了当前国外微量物证的研究现状。介绍了近年来国外法庭科学家在常见的微量物证如油漆、纤维、玻璃等的检测方法和检测技术,尤其重点介绍了一些新技术如电感耦合等离子体原子发射光谱技术（ICP/AES）、微波辅助消融和等离子光谱技术（OES...     

液相色谱-质谱联用测定血中氟乙酸类鼠药

目的建立血中氟乙酸类鼠药液相色谱-电喷雾离子阱质谱分析方法。方法血样经甲醇沉淀蛋白后离心,上清液用氮气吹干,流动相定容过滤膜,滤液直接进行液相色谱-电喷雾离子阱质谱联用分析。结果血中氟乙酸根在0.050μg/mL-2.0μg/mL之间具有良好的线性关系,最低检出限为0.020μg/mL。结论本文建立的方法快速、灵敏、操作简便,适用于刑事案件中该类氟乙酸类鼠药的快速检验,具有一定的实用价值。     

Validation of thin layer chromatography with AccuTOF-DART™ detection for forensic drug analysis

Abstract: Thin layer chromatography (TLC) is a technique that is commonly employed in the forensic drug analysis of pharmaceutical preparations. Detection is typically accomplished using various visualization spray reagents. Conventional gas chromatography–mass spectrometry (GC‐MS) analysis is typically performed to confirm the TLC results. Depending on the drugs tested and the instrument conditions required, this confirmation can take up to an hour to complete. Direct analysis in real time (DART?) is an ionization source, coupled to an accurate‐mass time‐of‐flight mass spectrometer that has the capability to ionize materials under ambient conditions. To streamline analysis, the combination of TLC with DART? detection is proposed to screen and subsequently identify drug compounds, all from the same TLC plate. DART? confirmations of TLC analyses take <10 min to complete and compare favorably to GC‐MS in sensitivity and selectivity. This study validates the use of TLC‐DART in the forensic identification of the components of several pharmaceutical preparations.     

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.     

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.     

Identification of two cannabimimetic compounds WIN48098 and AM679 in illegal products

Two synthetic cannabinoids have been identified, during a survey, as new adulterants; they might have been intended to be used as ingredients for smart drugs. The characterization of these compounds has been made by gas chromatography–mass spectrometry (GC–MS), Orbitrap high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR), leading to the identification of WIN48098, a compound disclosed as a new adulterant in herbal and powder products, and AM679, identified in Italy for the first time.Taking into account the high number of synthetic cannabinoids seized during the last year in Italy, how quickly they appear on the illegal market and the rapidity required for analytical results, a method was developed for the simultaneous quantitation of several synthetic cannabinoids, using gas chromatography–flame ionization detection (GC–FID).     

Evaluation of laser desorption mass spectrometry and UV accelerated aging of dyes on paper as tools for the evaluation of a questioned document

Laser desorption mass spectrometry (LDMS) may be used for the detection and identification of dyes found in inks. Naturally-aged and artificially-aged blue and black ballpoint pen inks containing the cationic dye methyl violet were analyzed on paper. The average molecular weight of the dye sample was calculated from LD mass spectral data and plotted versus time. The resulting aging curves demonstrate that, as dye degradation increases, the average molecular weight of the dye decreases. Typical variables involved in ink aging, such as the type of paper and ink formulation, were investigated. Results show that these variables influence the rate of dye degradation. Furthermore, UV accelerated aging has been developed and tested as an alternative to thermal approaches.     

Detection of counterfeit antiviral drug Heptodin™ and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS)

Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated.An extensive study for the antiviral drug Heptodin™ has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range.The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.     

液相电喷雾离子质谱技术在法医DNA中的应用

生物质谱技术是近年来发展较为迅速的生物分析技术之一,在对大分子生物质量测定中,其以快速、准确、灵敏等优点受到研究者的青睐。其中,液相电喷雾离子电离质谱(LC-ESI-MS)在法医DNA分析中对STR以及SNP遗传标记的检测具有独特的应用价值和广阔的应用前景。本文对ESI-MS的现状和在法医DNA分析中的应用等方面进行了综述,分析了LC-ESI-MS技术在法医学DNA分析中的优缺点,以促进其在国内法医DNA分析中的应用与发展。     

Discriminating red spray paints by optical microscopy, Fourier transform infrared spectroscopy and X-ray fluorescence

Red spray paints from different European suppliers were characterised to determine the discriminating power of a sequence of analysing techniques. A total of 51 red spray paints were analysed with the help of three techniques: (1) optical microscopy, (2) Fourier transform infrared spectrometry and (3) X-ray fluorescence. Infrared spectra were classified according to binder type, filler and pigment composition and a searchable spectral library was created. Due to the difference in the elemental composition of spray paints, a further discrimination was possible. The microscopic analysis was not taken into consideration for classification purposes. The structure of the substrate under a paint coating strongly affects the surface characteristics of this spray paint. Together with the spectral library, a database of information of spray paints was build.     

Analysis of biofluids for flunitrazepam and metabolites by electrospray liquid chromatography/mass spectrometry

A rapid and sensitive liquid chromatography/electrospray ionization mass spectrometry (LC/MS) procedure has been developed for the analysis of biofluids containing flunitrazepam and its metabolites. Specimens were spiked with deuterated analogs of the analytes. Urine specimens were enzymatically hydrolyzed and blood specimens were untreated. Extractions were carried out using CleanScreen DAU SPE cartridges. The drugs were separated on a C18 column using a methanol-water-ammonium hydroxide (60:40: 0.03 v/v) mobile phase. After determination of base peaks using full scan mass spectrometry, the mass spectrometry method was optimized to operate in selected-ion monitoring (SIM) mode for the base peak of each analyte. Positive findings were confirmed by LC/MS/MS using the same mobile phase and column. This analytical procedure allows for the detection of low levels of flunitrazepam and metabolites in biofluids. It is useful for ascertaining the role of flunitrazepam in cases of drug-facilitated sexual assault.