Forensic Chemistry最新文献_第4页

Synthesis and isotopic characterization of 1,3,5-trinitroso-1,3,5-triazine (R-Salt) 1,3,5-三硝基-1,3,5-三嗪（R-Salt）的合成及同位素表征

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-12-01 Epub Date: 2025-10-25 DOI: 10.1016/j.forc.2025.100706

Yinghua Wang , Tony Peter , James F. Carter

Hexamine is a precursor chemical for commercial explosives such as RDX and HMX and homemade explosive such as HMTD and R-Salt. Although now controlled in some jurisdictions, hexamine was still available in Australia in the form of solid fuel tablets. The other ingredient of R-Salt, sodium nitrite, was available with few restrictions.

We report the isotopic compositions of hexamine derived from solid fuel tablets and sodium nitrite available in 2024. The isotopic compositions for 18 samples of hexamine spanned wider ranges than previously reported: δ²H from −179 to +104 ‰, δ¹³C from −49.7 to −25.0 ‰ and δ¹⁵N from −6.5 to +3.7 ‰. The nitrogen isotopic compositions of 17 samples of sodium nitrite ranged from −166.9 to +3.1 ‰ representing some of the most ¹⁵N depleted values reported for natural materials.

32 batches of R-Salt were synthesised from selected samples of hexamine and sodium nitrite. Progressing from hexamine to R-Salt, δ²H values became more positive by between +5.2 and + 18 ‰ and δ¹³C values became more positive by between +12.3 and + 14.6 ‰. A combination of these data presents a means to associate samples of R-Salt with precursor hexamine.

The contributions of hexamine and sodium nitrite to the nitrogen isotopic compositions of R-Salt were combined by a simple mass-balance equation. Using this model the δ¹⁵N values of R-Salt were more negative than the combined precursors by between −2.0 and − 1.1 ‰. This presents an additional means to associate samples of R-Salt with both precursor chemicals.

Hexamine是商用炸药（如RDX和HMX）和自制炸药（如HMTD和R-Salt）的前体化学品。虽然现在在一些司法管辖区受到控制，但在澳大利亚仍然可以以固体燃料片剂的形式获得。r -盐的另一种成分亚硝酸钠几乎没有限制。我们报告了2024年从固体燃料片和亚硝酸钠中提取的氢的同位素组成。18个样品的同位素组成范围比以往报道的更宽：δ2H在−179 ~ +104‰，δ13C在−49.7 ~−25.0‰，δ15N在−6.5 ~ +3.7‰。17个亚硝酸钠样品的氮同位素组成范围在- 166.9 ~ +3.1‰之间，代表了一些天然材料中最具15N耗尽值。以亚硝酸钠为原料，合成了32批R-Salt。从hexamine到R-Salt， δ2H值增加了+5.2 ~ + 18‰，δ13C值增加了+12.3 ~ + 14.6‰。这些数据的组合提供了一种将R-Salt样品与前体hexamine相关联的方法。用一个简单的质量平衡方程结合了亚硝酸钠和亚硝酸钠对r -盐氮同位素组成的贡献。在此模型下，R-Salt的δ15N值比组合前驱体负- 2.0 ~ - 1.1‰。这提供了另一种将R-Salt样品与两种前体化学品相关联的方法。

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引用次数: 0

A multifaceted approach to capturing post-blast TATP 捕获爆炸后TATP的多方面方法

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-12-01 Epub Date: 2025-09-08 DOI: 10.1016/j.forc.2025.100694

Ryan M. Bain, Gui-hua Lisa Lang, Cayla See, Shane Kullen, Meghan Kane, Julie Pannuto

Triacetone triperoxide (TATP) is a primary high explosive which is used in improvised explosive devices (IEDs) and represents a challenge for forensic explosive chemists in post-blast scenarios due to its propensity to sublimate under ambient conditions. Herein, two sampling methods for the detection of TATP by gas chromatography mass spectrometry (GC-MS) are demonstrated on both low-resolution and high-resolution mass spectrometry systems. The two GC–MS workflows with headspace sampling were developed with post-blast analysis in mind. The first workflow implemented on-line solid phase microextraction (SPME) with direct headspace desorption. This method was used when samples could fit into a headspace vial. Alternatively, for larger samples, an indirect analysis was performed with an off-line passive sampling technique. This approach was modeled after a common fire debris extraction using an activated charcoal strip. Small scale initiations and post-blast samples using different witness materials were created and analyzed. Some experiments included the use of a sheet explosive in addition to TATP. Finally, the persistence of TATP on a variety of surfaces was investigated. The relationship between collection time, sampling methods and sample matrices to recoverable TATP is presented.

三过氧三丙酮（TATP）是一种用于简易爆炸装置（ied）的初级高爆药，由于其在环境条件下易于升华，因此对爆炸后场景的法医爆炸化学家来说是一个挑战。本文在低分辨率和高分辨率质谱系统上演示了两种气相色谱-质谱（GC-MS）检测TATP的采样方法。顶空取样的两种气相色谱-质谱工作流程是在考虑爆炸后分析的情况下开发的。第一个工作流程实现了直接顶空解吸的在线固相微萃取（SPME）。当样品可以装进顶空小瓶时，使用这种方法。另外，对于较大的样本，使用离线被动采样技术进行间接分析。这种方法是模仿使用活性炭条提取常见的火灾碎片。使用不同的见证材料创建和分析了小尺度的起爆和爆炸后样品。除了TATP，一些实验还包括使用片状炸药。最后，研究了TATP在各种表面上的持久性。给出了采集时间、采样方式和采样矩阵与可恢复TATP的关系。

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引用次数: 0

Determination of the species identity of necrophagous insect puparial casings using field desorption mass spectrometry 用场解吸质谱法测定尸食性昆虫蛹壳的种类

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-12-01 Epub Date: 2025-10-01 DOI: 10.1016/j.forc.2025.100702

Robert B. Cody , Alexa Figueroa , Jennifer Y. Rosati , Rabi A. Musah

Rapid approaches for accurate species identification of necrophagous insect evidence retrieved from decomposing remains is needed because of the importance of this information for the determination of postmortem interval. When the only materials available are the puparial casings from which the adult blow flies emerged, species assignment can very difficult because the casings are similar in appearance across many species. Reported here is a novel and rapid approach utilizing the soft ionization technique of field desorption-mass spectrometry (FD-MS) coupled with multivariate statistical analysis, for species identification of empty puparial cases of the 6 blow fly spp.: Calliphora latifrons, C. livida, C. vicina, Lucilia cuprina, L. sericata and Phormia regina. External validation samples were identified with 100 % accuracy. The chemical basis for the successful differentiation of species was the detection of masses associated with alkanes as large as C₅₅H₁₀₂, and sterols and esters as large as C₅₈H₁₁₈O₂, many of which have yet to be reported in the literature in association with insects. Other compounds were detected that were unique to particular species, such as 3-methyltricosane (C. vicina), 11,11-dimethylhenicosane (C. latifrons), 2-methylhexacosane (C. livida) and 11-decyltetracosane (L. sericata). There were 31 m/z values which were important for discrimination that were observed by FD-MS, but which could not be detected by GC due to their nonvolatility. Observation of these higher molecular weight molecules would enable prediction models to retain higher levels of accuracy even for samples that have undergone significant weathering, because of their resistance to evaporation.

从腐尸中提取的尸食性昆虫证据对于确定死后时间非常重要，因此需要快速准确的物种鉴定方法。当唯一可用的材料是成年吹蝇的羽壳时，物种分配非常困难，因为许多物种的羽壳在外观上是相似的。本文采用场解吸-质谱（FD-MS）软电离技术结合多元统计分析，对6种蝇类（Calliphora latifrons、C. livida、C. vicina、Lucilia cuprina、L. sericata和Phormia regina）的空蛹进行了快速鉴定。外部验证样品的识别准确度为100%。成功区分物种的化学基础是检测到大至C55H102的烷烃和大至C58H118O2的甾醇和酯类物质，其中许多与昆虫相关的物质文献中尚未报道。此外，还检出了3-甲基三糖烷（C. vicina）、11,11-二甲基苯二糖烷（C. latifrons）、2-甲基六糖烷（C. livida）和11-癸基四糖烷（L. sericata）等特有化合物。FD-MS检测到的31个m/z值对鉴别很重要，但GC检测不到，因为它们没有挥发性。对这些高分子量分子的观察将使预测模型保持更高的准确性，即使是那些经历了严重风化的样本，因为它们抵抗蒸发。

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引用次数: 0

Electron ionization fragmentation studies of ethoxy and methoxymethyl substituted phenylacetones 乙氧基和甲氧基甲基取代苯丙酮的电子电离破碎研究

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-07-09 DOI: 10.1016/j.forc.2025.100684

C. Randall Clark , Younis Abiedalla

The EI mass spectral fragmentation pathways and products were compared for substituted benzaldehydes and phenylacetones containing ethoxy and methoxymethyl substituents. The methoxymethylbenzene group is the only ether regioisomeric possibility with the ethoxybenzene group (and each have an isobaric relationship with the methylenedioxybenzene group) and are substituted in all three aromatic ring positions relative to the aldehyde and acetone moieties. The phenylacetones were synthesized from the corresponding precursor benzaldehydes. Stable isotope deuterium labeling in the ether substituents as well as product ion spectra and accurate mass time-of-flight analysis confirmed the structure of major fragments and allowed for prediction of the mechanisms of formation.

The methoxymethylbenzaldehydes yield a major fragment at m/z 135 via loss of the methyl radical. The ethoxy substituted isomers however have a base peak at m/z 121 via rearrangement loss of ethene followed by elimination of the aldehyde hydrogen radical. The EI mass spectra of ethoxyphenylacetones show the major ethoxybenzyl cation at m/z 135 via loss of the acetyl radical and the m/z 107 cation via elimination of ethene from the ethoxybenzyl cation. The EI mass spectra of methoxymethylphenylacetones are dominated by the radical cation at m/z 104 [C₈H₈]^+•. Unique meta- specific radical cations at m/z 136 and m/z 108 were observed in 3-ethoxyphenylacetone. An ortho effect in methoxymethylphenylacetones yielded the unique fragments at m/z 121, m/z 146 and m/z 145. The results of this study identify m/z 107 and m/z 104 as unique marker ions for the differentiation of the regioisomeric ethoxy and methoxymethyl substituted phenylacetones.

比较了含乙氧基和甲氧基取代基的苯甲醛和苯丙酮的EI质谱裂解途径和产物。甲氧基甲苯是唯一可能与乙氧基形成乙醚区域异构体的基团（两者都与亚二氧基有等重关系），并且在相对于醛和丙酮的三个芳香环位置上都被取代。苯丙酮是由相应的前体苯甲醛合成的。稳定同位素氘在醚取代基上的标记以及产物离子谱和精确的质量飞行时间分析证实了主要碎片的结构，并允许预测形成机制。甲氧基甲基苯甲醛通过甲基自由基的损失在m/z 135处产生一个主要片段。然而，乙氧基取代异构体在m/z 121处有一个碱基峰，这是由于乙烯的重排损失，然后是醛氢自由基的消除。乙氧基苯丙酮的EI质谱表明，在m/z 135处，乙氧基苯基阳离子因乙酰自由基的损失而形成；在m/z 107处，乙氧基苯基阳离子因乙烯的消除而形成。甲氧基甲基苯丙酮的EI质谱以m/z 104 [C8H8]+•自由基阳离子为主。在3-乙氧基苯丙酮中观察到m/z 136和m/z 108特异的自由基阳离子。甲氧基甲基苯丙酮的邻位效应在m/z 121， m/z 146和m/z 145处产生了独特的片段。本研究鉴定m/ z107和m/ z104是区分区域异构体乙氧基和甲氧基甲基取代苯丙酮的唯一标记离子。

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引用次数: 0

Correlation of compositional change with visualization enhancement results and morphology evolution of blood based on thermal performance analysis 基于热性能分析的血液成分变化与可视化增强结果及形态演变的相关性研究

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-05-26 DOI: 10.1016/j.forc.2025.100669

Junyi Di , Jing Jin , Zirui Lu , Xinyu Yan , Peibin Wang , Jinzhuan Zhang , Chaoyi Shi

The morphology evolution and compositional change of blood during heating are crucial for understanding the results of visualization enhancement when using chemical reagents. Given the complexity of blood composition, human and two other mammalian blood samples were initially centrifuged and prepared as dried whole blood, dried erythrocytes, and dried plasma for further TG-IR analysis. The results indicated that the decomposition process of blood could be divided into four distinct stages: 35-190 °C, 190-430 °C, 430-610 °C, and 610-800 °C. In the second stage, lipids and proteins underwent thermal decomposition, resulting in an approximately 50 % mass loss of blood with the release of NH₃ and CO₂, and obvious bulges presented with a black metallic appearance due to the rapid release of gases. The bloodstains could be visualized by the luminol test after heating at 310 °C for 5 min. Also, a positive reaction could be obtained by using tetramethylbenzidine (TMB) after heating at 400 °C for 5 min. In the third stage, the mass loss was further reduced by approximately 40 %. The streaks or block-like fractures appeared on the surface, with the metallic luster largely disappearing. Negative visualization results were obtained from bloodstains after heating at 480 °C for 5 min, suggesting that the hemoglobin was completely decomposed. The thermal decomposition process was gradually decreased when heating above 610 °C and completed around 880 °C, with minimal fibrous residues left. The compositional changes of blood during heating were correlated with morphology evolution and visualization enhancement, providing the evidence for blood detection in fire scenes.

在使用化学试剂时，血液在加热过程中的形态演变和成分变化对于理解可视化增强的结果至关重要。考虑到血液成分的复杂性，人类和其他两种哺乳动物的血液样本首先进行离心处理，制备成干燥的全血、干燥的红细胞和干燥的血浆，用于进一步的TG-IR分析。结果表明，血液的分解过程可分为35 ~ 190℃、190 ~ 430℃、430 ~ 610℃和610 ~ 800℃四个阶段。在第二阶段，脂质和蛋白质进行热分解，随着NH3和CO2的释放，血液质量损失约50%，由于气体的快速释放，出现明显的凸起，呈现黑色金属外观。在310°C加热5分钟后，通过鲁米醇测试可以看到血迹。在400°C加热5分钟后，使用四甲基联苯胺（TMB）可以获得正反应。在第三阶段，质量损失进一步降低了约40%。表面出现条状或块状断裂，金属光泽基本消失。在480℃下加热5 min后，血迹可见阴性，说明血红蛋白已完全分解。在610℃以上加热时，热分解过程逐渐减少，在880℃左右完成，纤维残留物最少。加热过程中血液成分的变化与形态进化和可视化增强相关，为火灾现场血液检测提供了依据。

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引用次数: 0

2D NMR detection and quantification of heroin in a street sample 街头样本中海洛因的二维核磁共振检测与定量

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-07-20 DOI: 10.1016/j.forc.2025.100687

Kathryn M. James , Samantha V. Boni , Kayla Gratton , Mallory J. Stopko , Michael Cipoletti , Timothy Gilbert , Alexander K. Goroncy , Takashi L. Suyama

Two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy was evaluated for the identification and quantification of compounds in an unknown street drug sample. Using 2D COSY and HSQC techniques, heroin was successfully quantified, and the presence of 6-monoacetylmorphine (6-MAM), xylazine, and caffeine was confirmed through partial structural elucidation. These methods demonstrated the ability to differentiate structurally similar opioid analogues without reliance on reference library databases. While gas chromatography–mass spectrometry (GC–MS) remains the standard in forensic laboratories, it has limitations in de novo structural analysis and in detecting emerging analogues absent from spectral libraries. In this study, heroin and fentanyl were quantified in both simulated and actual street samples at concentrations ranging from 0.97 to 1.80 mg/mL, with errors between 0 % and 34 % using a 400 MHz NMR instrument. A benchtop 60 MHz NMR system also detected and quantified 56 mg/mL of heroin with a 24 % error in a simulated sample. These findings support the complementary role of 2D NMR spectroscopy in forensic drug analysis in light of the opioid epidemic and the evolving drug market.

利用二维核磁共振（2D NMR）技术对一种未知街头毒品样品中的化合物进行鉴定和定量。利用2D COSY和HSQC技术，成功定量了海洛因，并通过部分结构解析证实了6-单乙酰吗啡（6-MAM）、噻嗪和咖啡因的存在。这些方法证明了在不依赖参考图书馆数据库的情况下区分结构相似的阿片类药物类似物的能力。虽然气相色谱-质谱（GC-MS）仍然是法医实验室的标准，但它在新生结构分析和检测光谱库中缺失的新兴类似物方面存在局限性。在这项研究中，海洛因和芬太尼在模拟和实际街道样本中被量化，浓度范围为0.97至1.80 mg/mL，使用400 MHz核磁共振仪器，误差在0%至34%之间。台式60 MHz核磁共振系统也检测和定量56毫克/毫升的海洛因在模拟样品24%的误差。鉴于阿片类药物流行和不断发展的药物市场，这些发现支持二维核磁共振波谱在法医药物分析中的补充作用。

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引用次数: 0

Development and comparison of reversed-phase ultra high-performance liquid chromatography (RP-UHPLC) and hydrophilic interaction liquid chromatography (HILIC) approaches to the analysis of regioisomeric fluorofentanyl derivatives and related compounds 反相高效液相色谱法（RP-UHPLC）与亲水性相互作用液相色谱法（HILIC）在氟芬太尼区域异构体衍生物及相关化合物分析中的应用及比较

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-06-29 DOI: 10.1016/j.forc.2025.100682

Jennifer K. Field , Benjamin S. Barrett , Erika Sitch , Ryan E. Mewis , William H. Campbell , Melvin R. Euerby , Oliver B. Sutcliffe

This study describes the development and comparison of low, intermediate and high pH gradient RP-UHPLC-MS/MS with that of gradient HILIC-MS/MS analysis for a range of fluorofentanyl derivatives including four families of ortho-, meta- and para-regioisomers. High pH RP-UHPLC-MS/MS using an ammonium hydroxide and methanol gradient on a high pH stable SuperC18 column at low temperature was demonstrated to be the most successful chromatographic mode for separating 26 analytes including: regioisomeric fluorofentanyls (n = 10); fentanyl analogues (n = 10), despropionyl precursors (n = 4) and two commonly encountered related substances (heroin and xylazine). Low and intermediate pH RP-UHPLC failed to afford separation of many of the fluorofentanyl regioisomers on stationary phases possessing complementary selectivity with either acetonitrile or methanol over a wide temperature range. HILIC on a bare silica column using an acetonitrile and ammonium acetate / acetic acid gradient provided good separation of fluorofentanyl regiosiomers except for the despropionyl series. High pH gradient RP-UHPLC was demonstrated to provide orthogonal chromatographic selectivity to that of HILIC in the gradient analysis of 18 fentanyl and related substances. Seven isobaric fluorofentanyl structural isomers could be readily discriminated from the unique fragmentation ions obtained using positive electrospray ionization MS/MS. The optimum high pH RP-UHPLC chromatographic conditions for the separation of the fluorofentanyls was equally successful for the rapid separation of a wide range of fentanyl regio- and structural isomers.

本研究描述了低、中、高pH梯度RP-UHPLC-MS/MS与梯度HILIC-MS/MS分析的发展和比较，用于一系列氟芬太尼衍生物，包括四个家族的邻位异构体、间位异构体和准区域异构体。高pH RP-UHPLC-MS/MS使用氢氧化铵和甲醇梯度在高pH稳定的SuperC18柱在低温下被证明是分离26种分析物的最成功的色谱模式，包括：区域异构体氟芬太尼（n = 10）；芬太尼类似物（n = 10），地丙酰前体（n = 4）和两种常见的相关物质（海洛因和噻嗪）。在较宽的温度范围内，低pH和中等pH的RP-UHPLC无法在与乙腈或甲醇具有互补选择性的固定相上分离许多氟芬太尼区域异构体。在裸硅柱上使用乙腈和乙酸铵/乙酸梯度的HILIC可以很好地分离氟芬太尼区域异构体，但地丙基系列除外。高pH梯度RP-UHPLC对18种芬太尼及其相关物质的梯度分析具有较好的正交选择性。利用正电喷雾电离质谱联用技术可以很容易地从分离得到的独特的碎片离子中区分出7种氟芬太尼结构异构体。高pH反相高效液相色谱法分离氟芬太尼的最佳条件同样成功地快速分离了广泛的芬太尼区域和结构异构体。

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引用次数: 0

Discovery of selective markers for chlorine gas exposure in concrete 发现混凝土中氯气暴露的选择性标记物

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-06-18 DOI: 10.1016/j.forc.2025.100680

Mirjam de Bruin-Hoegée , Bence Dallos , Tomas van Groningen , Jelle de Koning , Latifa Lamriti , Marcel J. van der Schans , Arian C. van Asten

Chlorine gas (Cl₂) is still being used as a chemical weapon in modern war zones. After an attack with this toxic chemical, verifying its use is challenging due to its reactivity and rapid evaporation. Additionally, only a limited number of selective markers relating to the use of chlorine gas are found. For forensic purposes it is necessary to discriminate Cl₂ from other chlorine containing chemicals. Therefore, the current study aims to use gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS) together with machine learning methods to discover selective markers for chlorine gas exposure. Four types of concrete originating from Europe or the Middle East were exposed to various levels of Cl₂ as well as to some commonly used chlorine containing chemicals. After extraction with various solvents, the samples were analyzed. Based on the tentative identification of 32 chlorinated markers with GC–MS and 146 markers with LC-HRMS/MS, principal component analysis (PCA) and linear discriminant analysis (LDA) models were constructed. A clear distinction between concrete samples exposed to bleach and chlorine gas was apparent. For forensic classification, a Bayesian likelihood ratio (LR) model was applied that showed limited rates of misleading evidence and maximum LRs of 0.038 to 93. The markers chloroacetone, dichloroacetone, tetrachlorophenol, and 5-chloro-8-quinolinol were found to be selective for chlorine gas exposure. Their identity was verified by GC–MS/MS and LC-MS/MS in comparison with commercially available reference standards. In conclusion, this study demonstrates the feasibility of chemical profiling in concrete to differentiate among various chlorinating agents.

氯气（Cl2）在现代战区仍被用作化学武器。在受到这种有毒化学物质的攻击后，由于其反应性和快速蒸发，验证其使用是具有挑战性的。此外，只发现了数量有限的与氯气使用有关的选择性标记。为了法医的目的，有必要将Cl2与其他含氯化学品区分开来。因此，本研究旨在利用气相色谱-质谱（GC-MS）和液相色谱-高分辨率串联质谱（LC-HRMS/MS）结合机器学习方法发现氯气暴露的选择性标记物。来自欧洲或中东的四种混凝土暴露在不同水平的二氧化氯以及一些常用的含氯化学品中。用各种溶剂提取后，对样品进行分析。在对32个氯代标记物进行GC-MS和146个标记物进行LC-HRMS/MS初步鉴定的基础上，建立了主成分分析（PCA）和线性判别分析（LDA）模型。暴露于漂白剂和氯气的混凝土样品之间的明显区别是显而易见的。对于法医分类，贝叶斯似然比（LR）模型显示误导证据率有限，最大似然比为0.038 ~ 93。氯丙酮、二氯丙酮、四氯苯酚和5-氯-8-喹啉酚标记物对氯气暴露具有选择性。用GC-MS /MS和LC-MS/MS与市售标准品进行了鉴别。总之，本研究证明了在混凝土中进行化学分析以区分不同氯化剂的可行性。

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引用次数: 0

Exploiting a gold leaf-based voltammetric sensor for the estimation of firing distance 利用金箔伏安传感器估算射击距离

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-06-21 DOI: 10.1016/j.forc.2025.100681

Thinnapong Wongpakdee , Supatana Buking , Prapin Wilairat , Kanchana Uraisin , Nuanlaor Ratanawimarnwong , Duangjai Nacapricha

In this study, we present a novel electrochemical approach for firing distance estimation using a gold leaf-based sensor integrated with screen-printed electrodes. This is the first report of employing a gold leaf-based sensor for the voltammetric estimation of firing distance by detecting Pb in gunshot residue (GSR) on fabric targets. The sensor consists of a gold leaf sheet as the working electrode, with carbon and silver/silver chloride screen-printed electrodes serving as the counter and reference electrodes, respectively. Pb(II), a key component of GSR, was extracted from 15 mm fabric discs using manual shaking in nitric acid for 3 min. The extracted solution was analyzed by anodic stripping voltammetry (ASV) with a portable electrochemical system. The Pb(II) signal was then correlated with the firing distance to construct an analytical curve for estimation of shooting distance in the range of 5–60 cm. The resulting mathematical model enables accurate distance estimation. This cost-effective, reagent-free, and field-deployable electrochemical sensor offers a rapid and accessible alternative for forensic firearm investigations.

在这项研究中，我们提出了一种新的电化学方法来估计发射距离，该方法使用基于金箔的传感器集成了丝网印刷电极。本文首次报道了利用金箔传感器通过检测织物目标上的枪弹残余物（GSR）中的铅来伏安估计射击距离。该传感器由金箔片作为工作电极，碳和银/氯化银丝网印刷电极分别作为计数电极和参比电极。从15 mm的织物圆盘中提取GSR的关键成分Pb(II)，在硝酸中手动振荡3 min，提取液采用便携式电化学系统阳极溶出伏安法（ASV）进行分析。将Pb（II）信号与发射距离进行关联，构建了估算5 ~ 60 cm范围内发射距离的解析曲线。由此产生的数学模型可以进行精确的距离估计。这种低成本、无试剂、可现场部署的电化学传感器为法医枪支调查提供了一种快速、方便的替代方案。

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引用次数: 0

Development of a semi-preparative LC method for the purification of synthetic cannabinoids impregnated in herbal products for chemical characterization by NMR and HRMS 建立一种半制备液相色谱法，用于纯化浸渍在草药产品中的合成大麻素，并通过NMR和HRMS进行化学表征

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 Epub Date: 2025-06-10 DOI: 10.1016/j.forc.2025.100678

Karen Rafaela Gonçalves de Araújo , Gabriela de Paula Meirelles , Daniel Pecoraro Demarque , Fabiane Dorr , Luiz Ferreira Neves Júnior , Alexandre Learth Soares , Camila Delanesi Guedes , José Luiz da Costa , Mauricio Yonamine

Synthetic cannabinoids (SCs) now encompass over 360 compounds under international control. Identifying these substances is a significant challenge for law enforcement, as they are new drugs found in herbal fragments, and reference standards are not available for traditional chemical analysis. To address this, substances can be identified using type A analytical techniques, according to the Scientific Working Group for the Analysis of Seized Drugs which are those with the highest level of selectivity and provide structural information, such as nuclear magnetic resonance and mass spectrometry. However, these methods require compound purification for proper characterization. This study aimed to develop a purification method for SCs in herbal fragments to enable chemical analysis. Seized samples were first analyzed using gas chromatography-electron ionization-mass spectrometry (GC-EI-MS). Then, a semi-preparative liquid chromatography (LC) method was applied, successfully isolating SCs and allowing their structural determination through NMR and high-resolution mass spectroscopy. In the first sample, MDMB-CHMINACA was identified as the sole SC. In the second sample, GC-EI-MS analysis revealed a mass spectrum that did not match any library entry. After purification, the substance was identified as ADB-INACA. In the third sample, the method facilitated the separation and structural determination of four SCs (MDMB-INACA, ADB-BUTINACA, MDMB-4en-PINACA, and 5F-ADB) in a mixture from an herbal sample. In conclusion, the method developed for purification using semi-preparative LC for subsequent chemical characterization proved to be effective for the structural determination of new SCs present in herbal drugs seized by the police.

合成大麻素（SCs）目前包括360多种受国际管制的化合物。确定这些物质对执法来说是一项重大挑战，因为它们是在草药碎片中发现的新药，而传统的化学分析没有参考标准。为了解决这个问题，根据分析缉获药物科学工作组的说法，可以使用A类分析技术来识别物质，这些技术具有最高的选择性并提供结构信息，例如核磁共振和质谱。然而，这些方法需要化合物纯化以进行适当的表征。本研究旨在建立一种纯化草药片段中SCs的方法，用于化学分析。首先使用气相色谱-电子电离-质谱（GC-EI-MS）对检获样品进行分析。然后，采用半制备液相色谱（LC）方法，成功分离出SCs，并通过核磁共振和高分辨率质谱对其结构进行测定。在第一个样本中，MDMB-CHMINACA被鉴定为唯一的SC。在第二个样本中，GC-EI-MS分析显示其质谱与任何文库条目都不匹配。纯化后鉴定为ADB-INACA。在第三个样品中，该方法有助于从草药样品混合物中分离和测定四种SCs （MDMB-INACA, ADB-BUTINACA， MDMB-4en-PINACA和5F-ADB）的结构。总之，利用半制备LC进行纯化并进行后续化学表征的方法被证明对警方查获的草药中存在的新SCs的结构测定是有效的。

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