Forensic Chemistry最新文献_第4页

Headspace detection and characterization of erythritol tetranitrate 四硝酸赤藓糖醇的顶空检测与表征

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-08 DOI: 10.1016/j.forc.2025.100693

Janet Crespo-Cajigas , Dawn M. Mills , Melissa J. Clinard

Erythritol Tetranitrate (ETN) is an improvised explosive that has been recently integrated into explosive detector canine (EDC) training in the United States. The odor profile for ETN has not been well characterized, preventing the development of representative training aids and best training practices. Here, the headspace composition of ETN was characterized for the first time using thermal desorption gas chromatography–mass spectrometry (TD-GC–MS). The TD parameters, sorbent materials, and microchamber settings used for headspace sampling were optimized. The odor profile of ETN under ambient conditions was determined from two separately synthesized ETN samples to contain ETN, nonanoic acid, and an unidentified compound attributed to the erythritol precursor. A Tenax degradation product (2,4-ditertbutyl-6-nitro-phenol) was also detected in each sample indicating the likely release of NO₂ from ETN and contribution to its headspace composition. Furthermore, various chemicals unrelated to the synthetic preparation of ETN were detected and identified as contaminants due to storage conditions of each sample, indicating the tendency of the ETN samples tested to absorb volatiles from its surroundings. Additional compounds were detected in the headspace of ETN (triethyl phosphate, nonanoic acid, 2-ethyl hexanoic acid) but were unable to be attributed to a source. The odor profile reported herein can serve as a baseline to evaluate ETN EDC standards and generalization while the TD-GC–MS methods presented can be used by other laboratories to characterize newly synthesized ETN samples, develop and validate of alternative ETN K9 training aids, and assess contamination of ETN K9 training aids due to storage or frequent use.

四硝酸赤藓糖醇（ETN）是一种简易爆炸物，最近被纳入美国的爆炸物探测犬（EDC）训练中。ETN的气味特征还没有很好地表征，这阻碍了代表性培训辅助工具和最佳培训实践的发展。本文首次利用热解吸气相色谱-质谱（TD-GC-MS）对ETN的顶空成分进行了表征。优化了TD参数、吸附剂材料和用于顶空取样的微室设置。通过两个单独合成的ETN样品，测定了环境条件下ETN的气味特征，其中包含ETN、壬酸和一种归属于赤藓糖醇前体的未识别化合物。每个样品中还检测到Tenax降解产物（2,4-二叔丁基-6-硝基苯酚），表明ETN可能释放NO2及其顶空成分的贡献。此外，由于每个样品的储存条件，检测到与ETN合成制备无关的各种化学物质并将其识别为污染物，这表明所测试的ETN样品有从周围环境中吸收挥发物的倾向。在ETN的顶空中检测到其他化合物（磷酸三乙酯、壬酸、2-乙基己酸），但无法归因于来源。本文报告的气味特征可以作为评估ETN EDC标准和泛化的基线，而提出的TD-GC-MS方法可以被其他实验室用于表征新合成的ETN样品，开发和验证替代ETN K9训练辅助工具，并评估由于储存或频繁使用而导致的ETN K9训练辅助工具的污染。

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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 : 2025-09-08 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

Corrigendum to “Revealing novel ionic species and key forensic insights: comparative analysis of non-extracted seized tablets vs. corresponding extracts by DART-HRMS” [Forensic Chem. 44 (2025) 100665 “揭示新的离子种类和关键的法医见解：用DART-HRMS对未提取的缉获片剂和相应的提取物进行比较分析”[法医化学，44(2025)100665]的更正

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-09-01 DOI: 10.1016/j.forc.2025.100673

Alexandre Narcelli Pestana de Aguiar , Diego Rissi Carvalhosa , Francisco Radler de Aquino Neto , Gabriela Vanini

引用次数: 0

Methods to transform illicit drugs: A review and evaluation of drug degradation techniques 转化非法药物的方法：药物降解技术综述与评价

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-08-16 DOI: 10.1016/j.forc.2025.100689

Alexandra L. Mercieca, Morgan Alonzo, Scott Chadwick, Andrew M. McDonagh

The disposal of seized illicit drugs is highly dependent on incineration methods. Accessible alternatives for the destruction and disposal of illicit drugs may be required due to operational or risk management strategies. In this review, alternative methods of illicit drug disposal are evaluated, highlighting thermal, chemical, biological and miscellaneous degradation techniques. Chemical degradation of illicit drugs offers the most promising alternative to incineration. Oxidative processes utilise commercially available reagents and are accessible, with some methods already established as industry processes. Advanced oxidation processes have short run times (<24 h) and can completely mineralise organic compounds, overcoming the limitation of forming undesired transformation products. Other feasible methods for drug degradation include bacterial growth and gamma irradiation. It is apparent, however, that there is currently no universal alternative method for drug degradation, as diverse classes of drugs exhibit different degradation characteristics. In some instances, harmful compounds can be produced from the degradation of the illicit drugs although if the transformation products are not illicit, they can be integrated into existing chemical waste procedures using appropriate hazardous waste protocols.

查获的非法药物的处置高度依赖焚化方法。由于业务或风险管理战略，可能需要销毁和处置非法药物的可获得的替代办法。在本综述中，对非法药物处置的替代方法进行了评价，重点介绍了热、化学、生物和各种降解技术。化学降解非法药物是最有希望替代焚烧的方法。氧化过程利用商业上可用的试剂，并且易于获得，其中一些方法已经建立为工业过程。高级氧化工艺运行时间短（24小时），可以完全矿化有机化合物，克服了形成不需要的转化产物的限制。其他可行的药物降解方法包括细菌生长和伽马射线照射。然而，很明显，由于不同类别的药物表现出不同的降解特征，目前还没有通用的替代药物降解方法。在某些情况下，可以通过非法药物的降解产生有害化合物，但如果转化产物不是非法的，则可以使用适当的危险废物议定书将其纳入现有的化学废物程序。

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引用次数: 0

Discrimination of Cannabis sativa L. from other similar plant species using solvent extraction, ATR-FTIR and PLS-DA 溶剂提取、ATR-FTIR和PLS-DA鉴别大麻与其他类似植物

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-08-09 DOI: 10.1016/j.forc.2025.100690

Rafaela Dornelas Vieira , Fabiana Casarin , Laíz de Oliveira Magalhães , Ícaro Noé Caixêta , Luciano Chaves Arantes , Jez Willian Batista Braga

Cannabis sativa L. is a plant with diverse applications, but remains the most widely used illicit substance worldwide. Its classification as a drug of abuse, along with socio-economic concerns, has led to its prohibition in numerous countries, including Brazil, where its consumption, cultivation, and sale are strictly prohibited. This regulatory context highlights the need for reliable and accurate methods for cannabis identification. In this study, three straightforward and efficient analytical methods were developed for the identification of Cannabis sativa, using simple extraction procedures followed by ATR-FTIR spectroscopy. Three solvents were evaluated: chloroform and petroleum ether, both combined with Fast Blue B salt, and ethanol, employed as a standalone solvent. Optimized spectral regions (1550–1650 cm⁻¹ for ethanol and petroleum ether; 800–880 cm⁻¹ for chloroform) and preprocessing techniques, such as Standard Normal Variate (SNV) and mean centering, resulted in a robust PLS-DA model. The method exhibited a low incidence of outliers (0.4 %–1.6 %), minimal false-negative and false-positive error rates (1.1 %–2.8 % and 0.0 %–3.0 %, respectively). Ethanol performed as the best and greener method, with an efficiency of 99.4 %, no residual generation, and eliminating the need for bonding agents like Fast Blue B salt. It also aligns with green chemistry principles, making it safer for analysts and the environment. Overall, the proposed method offers a reliable, accurate, and sustainable alternative for the forensic identification of Cannabis sativa, effectively addressing the limitations of conventional screening techniques and the complexity of plant-based mixtures.

大麻是一种具有多种用途的植物，但仍然是世界上使用最广泛的非法物质。它被归类为滥用药物，加上社会经济问题，导致包括巴西在内的许多国家禁止它，在那里它的消费、种植和销售是严格禁止的。这种监管背景强调需要可靠和准确的大麻识别方法。在本研究中，开发了三种简单有效的分析方法来鉴定大麻，使用简单的提取程序和ATR-FTIR光谱。评估了三种溶剂：氯仿和石油醚，两者都与Fast Blue B盐结合，乙醇作为独立溶剂。优化的光谱区域(1550-1650 cm−1乙醇和石油醚；800-880 cm−1（氯仿）和预处理技术，如标准正态变量（SNV）和均值定心，产生了稳健的PLS-DA模型。该方法的异常值发生率低（0.4% ~ 1.6%），假阴性和假阳性错误率最小（分别为1.1% ~ 2.8%和0.0% ~ 3.0%）。乙醇是最好的和更环保的方法，效率为99.4%，没有残留的产生，并且不需要粘合剂，如Fast Blue B盐。它还符合绿色化学原则，使分析人员和环境更安全。总的来说，该方法为大麻的法医鉴定提供了一种可靠、准确和可持续的替代方法，有效地解决了传统筛选技术的局限性和植物基混合物的复杂性。

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引用次数: 0

SPME–GC–MS analysis of fire debris: assessing sample transfer viability for automated analysis and the influence of sooty materials 火灾碎片的SPME-GC-MS分析：评估自动分析的样品转移可行性和煤烟材料的影响

IF 2.2 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-07-28 DOI: 10.1016/j.forc.2025.100688

Lúcio Paulo Lima Logrado , Jez Willian Batista Braga

Abstract

Arson investigation poses unique challenges in forensic science due to the destructive nature of fires, which can compromise physical evidence. It is one of the most challenging areas of forensic chemistry, frequently applied to identify flammable liquids in fire debris. SPME–GC–MS is one of the most applied techniques for this purpose. Automated SPME–GC–MS systems offer various advantages over manual versions, such as increased efficiency, reproducibility, precision, and reduced analysis time. However, samples are often not sent to the laboratory in vials appropriate for automated SPME, raising questions about the feasibility of transferring them to these headspace vials in the laboratory to take advantage of this automation. Another significant issue with this analytical technique is how highly adsorbent materials in the sample, such as sooty materials, can hinder SPME analyses by affecting analyte desorption and subsequent detection. This study addresses these crucial questions by evaluating sample losses and assessing the impact of sooty materials on results. It demonstrates that transferring fire debris samples is feasible, with minimal impact on chromatographic profiles even for unburned gasoline when exposed to the atmosphere for short periods. Burned gasoline can still be identified, despite some losses, even after more than 24 h. The study also demonstrated that the presence of sooty material can hinder analyte detection in direct SPME analysis, but this can be mitigated using nonpolar solvent extractions followed by analyses of the dried extract using the same analytical technique.

摘要：火灾具有破坏物证的破坏性，火灾调查对法医学提出了独特的挑战。这是法医化学中最具挑战性的领域之一，经常用于识别火灾碎片中的易燃液体。SPME-GC-MS是这方面应用最广泛的技术之一。与手动版本相比，自动化SPME-GC-MS系统具有各种优势，例如提高效率、再现性、精度和缩短分析时间。然而，样品通常不是装在适合自动化SPME的小瓶中送到实验室的，这就提出了将样品转移到实验室中利用这种自动化的顶空小瓶中的可行性问题。该分析技术的另一个重要问题是样品中的高吸附性材料，如煤烟材料，如何通过影响分析物的解吸和随后的检测来阻碍SPME分析。本研究通过评估样品损失和评估煤烟材料对结果的影响来解决这些关键问题。这表明，转移火灾碎片样品是可行的，即使是短时间暴露在大气中未燃烧的汽油，对色谱剖面的影响也很小。即使在超过24小时后，仍然可以识别出燃烧的汽油，尽管有一些损失。该研究还表明，在直接SPME分析中，煤烟物质的存在会阻碍分析物的检测，但可以使用非极性溶剂萃取，然后使用相同的分析技术分析干燥的提取物，从而减轻这种影响。

{"title":"SPME–GC–MS analysis of fire debris: assessing sample transfer viability for automated analysis and the influence of sooty materials","authors":"Lúcio Paulo Lima Logrado , Jez Willian Batista Braga","doi":"10.1016/j.forc.2025.100688","DOIUrl":"10.1016/j.forc.2025.100688","url":null,"abstract":"<div><div>Abstract</div><div>Arson investigation poses unique challenges in forensic science due to the destructive nature of fires, which can compromise physical evidence. It is one of the most challenging areas of forensic chemistry, frequently applied to identify flammable liquids in fire debris. SPME–GC–MS is one of the most applied techniques for this purpose. Automated SPME–GC–MS systems offer various advantages over manual versions, such as increased efficiency, reproducibility, precision, and reduced analysis time. However, samples are often not sent to the laboratory in vials appropriate for automated SPME, raising questions about the feasibility of transferring them to these headspace vials in the laboratory to take advantage of this automation. Another significant issue with this analytical technique is how highly adsorbent materials in the sample, such as sooty materials, can hinder SPME analyses by affecting analyte desorption and subsequent detection. This study addresses these crucial questions by evaluating sample losses and assessing the impact of sooty materials on results. It demonstrates that transferring fire debris samples is feasible, with minimal impact on chromatographic profiles even for unburned gasoline when exposed to the atmosphere for short periods. Burned gasoline can still be identified, despite some losses, even after more than 24 h. The study also demonstrated that the presence of sooty material can hinder analyte detection in direct SPME analysis, but this can be mitigated using nonpolar solvent extractions followed by analyses of the dried extract using the same analytical technique.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100688"},"PeriodicalIF":2.2,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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 : 2025-07-20 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

Analytical identification of ergot alkaloids in Ipomoea species: Resolving historical, forensic, and legal ambiguities 麦角生物碱的分析鉴定：解决历史、法医和法律上的歧义

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-07-18 DOI: 10.1016/j.forc.2025.100686

Enrico Greco , Andrea Farci , Fiorella Florian , Alberto Pallavicini , Alessandro Miani , Pierluigi Barbieri , Giorgio Samorini

This study addresses the longstanding taxonomic confusion between two plant species within the Convolvulaceae family: Ipomoea tricolor Cav. and Ipomoea violacea L., historically mistaken as synonymous. Employing advanced analytical methods including LC-MS/MS (Orbitrap), coupled with genetic barcoding, we provide clear biochemical differentiation between the two species based on the presence or absence of psychoactive ergoline alkaloids. Our analyses confirm that seeds of I. tricolor consistently contain significant levels of psychoactive compounds structurally similar to LSD, while I. violacea seeds lack these alkaloids entirely. This distinction is critical, as current legislative documents frequently misclassify non-psychoactive I. violacea as a controlled substance, inadvertently omitting the psychoactive I. tricolor. The analytical method is robust and precise, providing an effective forensic tool for the accurate identification of these botanically similar but chemically distinct species. Correct taxonomic and biochemical identification of these plants is essential to law enforcement and policy-makers for accurate legal scheduling and preventing regulatory misinterpretation regarding plant-derived psychoactive substances.

本研究解决了旋花科两种植物之间长期存在的分类混淆：三色旋花。和紫牡丹，历史上被误认为是同义词。采用先进的分析方法，包括LC-MS/MS (Orbitrap)，结合遗传条形码，我们基于是否存在精神活性麦角碱生物碱，提供了两个物种之间明确的生化区分。我们的分析证实，三色堇种子始终含有显著水平的与LSD结构相似的精神活性化合物，而紫堇种子完全缺乏这些生物碱。这种区别是至关重要的，因为目前的立法文件经常错误地将非精神活性堇菜归类为受控物质，无意中遗漏了精神活性三色堇菜。该分析方法可靠、准确，为准确鉴定这些植物相似但化学成分不同的物种提供了有效的法医工具。对这些植物进行正确的分类和生化鉴定，对于执法和政策制定者准确的法律安排和防止对植物源性精神活性物质的监管误解至关重要。

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引用次数: 0

Machine learning-enhanced traceability and particle analysis of pyrotechnic post-explosion residues using SEM/EDS 机器学习增强了烟火爆炸后残留物的可追溯性和颗粒分析

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2025-07-17 DOI: 10.1016/j.forc.2025.100685

Xing Li , Zhen-Wen Sun , Yan-Wu Yu , Gao-Qin Zhang , Guan-Nan Zhang , Yao Liu

Mordern techniques such as spectroscopic and chromatographic techniques have advanced pyrotechnic precursor analysis, yet the forensic investigation methods of post-detonation residues remains limited, thereby constraining the identification of explosive sources. Pyrotechnic post-explosion residues (PPERs) retain stoichiometric signatures that can be linked to precursor formulations through machine learning-enhanced scanning electron microscopy / energy-dispersive X-ray spectroscopy (SEM/EDS) analysis, offering a foundation for further forensic study. This study presents a systematic approach to PPERs analysis with three key components: (1) the development of a test vessel and particles collection system for PPERs; (2) the employment of an automated SEM/EDS protocol incorporating the Particle X Perception System for high-throughput elemental and morphological characterization (15,000–38,000 particles per sample), and a data pretreatment analytical protocol that included morphometric screening criteria and multivariate statistical methods; (3) the construction of a machine learning framework integrating t-distributed Stochastic Neighbor Embedding (t-SNE) for dimensionality reduction and Random Forest Regression (RFR) for predictive modeling. The hybrid model demonstrated excellent clustering performance (Normalized Mutual Information (NMI) > 0.80) and high predictive accuracy (R² > 0.95, Root Mean Squared Error (RMSE) < 0.07), supporting the potential for pyrotechnical traceability from SEM/EDS data of PPERs.

光谱学和色谱学等现代技术使烟火前体分析技术得到了发展，但对爆炸后残留物的法医调查方法仍然有限，从而制约了爆炸源的鉴定。烟火爆炸后残留物（PPERs）保留了化学计量特征，可以通过机器学习增强的扫描电子显微镜/能量色散x射线光谱（SEM/EDS）分析将其与前体配方联系起来，为进一步的法医研究提供基础。本研究提出了一种系统的PPERs分析方法，包括三个关键组成部分：(1)开发一个测试容器和PPERs颗粒收集系统；(2)采用包含粒子X感知系统的自动化SEM/EDS方案进行高通量元素和形态表征（每个样品15,000-38,000个粒子），以及包括形态测定筛选标准和多元统计方法的数据预处理分析方案；(3)构建融合t分布随机邻居嵌入（t-SNE）降维和随机森林回归（RFR）预测建模的机器学习框架。混合模型显示了优异的聚类性能(归一化互信息（NMI） >；0.80)，预测精度高(R2 >；0.95，均方根误差（RMSE） <；0.07)，支持从扫描电镜/能谱仪数据的烟火可追溯性的潜力。

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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 : 2025-07-09 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