Forensic Chemistry最新文献_第10页

Portable near-infrared detection to replace color tests in an analytical scheme for forensic drug identification 在法医鉴定毒品的分析方案中，用便携式近红外检测仪取代颜色检测仪

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-11-06 DOI: 10.1016/j.forc.2024.100615

Annique van Beek , Laura I. Stuyver , Henk-Jan Ramaker , Emile M. Mes , Arian C. van Asten , Ruben F. Kranenburg

In the ever-changing drug market the popularity and availability of substances is dynamic. In the Netherlands, ketamine and various cathinones have recently seen increased prevalence. It is crucial for law enforcement to quickly obtain an initial indication of the identity of a substance. This first test also serves as quality control for subsequent confirmation with GC–MS analysis. Traditionally, color tests have been used for these purposes. While these tests are quick and inexpensive, they have the disadvantage of reacting only to a few traditional drugs. Suitable color tests are not available for many new psychoactive substances (NPS). Near-infrared (NIR) spectroscopy is a rapid technique that provides a characteristic spectrum for organic compounds. This technique is more versatile than color tests and can adapt more quickly to market changes by incorporating reference spectra into the library. This study demonstrates the feasibility of obtaining a good quality NIR spectrum from a 20 mg sub-sample in a test tube. This was achieved by scanning the test tube through the glass bottom. In the routine analytical scheme, these test tubes were subsequently batchwise analyzed by GC–MS. From the NIR spectra, 84 % true positive and 100 % true negative results were achieved on 516 casework samples, including identification of substances without available color tests like ketamine. Missed false negatives primarily involved new substances absent from the library, emphasizing the need for continuous library updates. NIR’s adaptability to market changes is crucial, allowing the inclusion of new substances as they emerge. This method enhances law enforcement’s ability to make informed decisions, aiding in the indictment process.

在瞬息万变的毒品市场中，毒品的流行和供应是动态变化的。在荷兰，氯胺酮和各种卡西酮最近越来越流行。对于执法部门来说，快速获得某种物质的初步特征至关重要。首次检测也可作为后续气相色谱-质谱分析确认的质量控制。传统上，这些用途一直使用颜色测试。虽然这些检测方法快速而廉价，但其缺点是只能对少数传统药物产生反应。许多新型精神活性物质 (NPS) 都没有合适的颜色测试。近红外光谱（NIR）是一种快速技术，可提供有机化合物的特征光谱。与颜色测试相比，该技术用途更广，而且通过将参考光谱纳入库，可以更快地适应市场变化。本研究证明了从试管中的 20 毫克子样品中获取高质量近红外光谱的可行性。这是通过玻璃底部扫描试管实现的。在常规分析方案中，这些试管随后通过气相色谱-质谱（GC-MS）进行批量分析。通过近红外光谱分析，516 个案例样本中的阳性结果占 84%，阴性结果占 100%，其中包括对氯胺酮等无法进行颜色测试的物质的鉴定。漏检的假阴性物质主要是库中没有的新物质，这强调了持续更新库的必要性。近红外技术对市场变化的适应性至关重要，可以在新物质出现时将其纳入。这种方法提高了执法部门做出明智决定的能力，有助于起诉过程。

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引用次数: 0

Enhancing Counterfeit Banknote Analysis: Case Studies Using TOF-SIMS 加强伪钞分析：使用 TOF-SIMS 的案例研究

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-11-03 DOI: 10.1016/j.forc.2024.100617

Alice Bejjani , Raymond Tannous , Georges Chalhoub , Mazen Hamdan , Bilal Nsouli

Counterfeiting banknotes poses a significant threat to economies worldwide, particularly in developing countries where cash transactions remain predominant. Despite advancements in security features, counterfeiters continue to adapt, necessitating more sophisticated analysis methods. Time of flight Secondary Ion Mass Spectrometry (TOF-SIMS) offers a powerful approach to surface chemical imaging and depth profiling of counterfeit currencies. Real cases of five different counterfeit Lebanese banknotes are studied, using TOF-SIMS to address specific questions regarding the composition and placement of replicated security features, gaining insights into counterfeit banknote production and the raw materials used. The findings provide essential information to decision-makers at the national bank, supporting the design of future currencies through the selection of security features best suited to the local market, thereby enhancing protection against financial fraud..

伪造钞票对全球经济构成重大威胁，尤其是在现金交易仍占主导地位的发展中国家。尽管防伪功能不断进步，但伪造者仍在不断调整，因此需要更复杂的分析方法。飞行时间二次离子质谱法（TOF-SIMS）为伪造货币的表面化学成像和深度剖析提供了一种强大的方法。研究了五种不同的黎巴嫩伪钞的真实案例，利用 TOF-SIMS 解决了有关复制防伪特征的成分和位置的具体问题，深入了解了伪钞的生产和所使用的原材料。研究结果为国家银行的决策者提供了重要信息，通过选择最适合当地市场的防伪特征来支持未来货币的设计，从而加强对金融欺诈的防范。

引用次数: 0

Halogen-bond mediated charge transfer for visual competitive colorimetric detection of fentanyl 卤素键介导的电荷转移用于芬太尼的视觉竞争性比色检测

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-11-03 DOI: 10.1016/j.forc.2024.100618

Boyan Li , Qiongyao Ning , Wenyou Ye , Qianxi Wang , Haili Yu , Xuecheng Chen , Yi He

Colorimetric assays are inexpensive and attractive tools for the detection of fentanyl (FTN), yet further enhancing their sensitivity remains a major challenge. Herein, we develop a halogen-bond mediated visual competitive colorimetric assay for FTN using Erythrosine B (EB) as a probe. The addition of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide (F-127) induces the EB aggregation, strongly suppressing the background signal. Upon the introduction of FTN, the subsequent competitive reaction displaces F-127 to generate EB-FTN charge-transfer complexes via N^…I halogen bonds between electron-rich amine groups and electron-deficient iodine sites, accompanying a significant absorbance wavelength shift and pink-to-purple color change. The limits of detection of this approach for FTN are 2 mg·L⁻¹ by the naked eye and 0.19 mg·L⁻¹ by UV–vis spectroscopy, which are approximately 3.7-fold to 4 orders of magnitude more sensitive than the reported colorimetric assays. Meanwhile, the present method is well applied for FTN-spiked domestic sewage samples, and an easy-to-use smartphone-based digital image colorimetry is also fabricated. It is expected that such an assay can play a key role in alleviating the worldwide opioid overdose crisis.

比色测定法是检测芬太尼（FTN）的廉价而有吸引力的工具，但进一步提高其灵敏度仍是一项重大挑战。在此，我们以赤藓红 B（EB）为探针，开发了一种卤素键介导的视觉竞争比色法检测 FTN。加入聚（环氧乙烷）-块状-聚（环氧丙烷）-块状-聚（环氧乙烷）（F-127）可诱导 EB 聚合，从而强烈抑制背景信号。引入 FTN 后，随后的竞争反应会置换 F-127，通过富电子胺基团和缺电子碘位点之间的 N...I 卤素键生成 EB-FTN 电荷转移复合物，伴随着显著的吸光波长偏移和粉红色到紫色的颜色变化。这种方法对芴甲氧羰基的检测限为肉眼 2 mg-L-1，紫外可见光谱 0.19 mg-L-1，比已报道的比色法灵敏度高出约 3.7 倍至 4 个数量级。同时，本方法还能很好地应用于添加了 FTN 的生活污水样品，并制作了一种易于使用的基于智能手机的数字图像比色法。这种检测方法有望在缓解全球阿片类药物过量危机方面发挥关键作用。

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引用次数: 0

Use of optimized 1H selTOCSY for identification and individualization of petrol samples from fire debris 使用优化的 1H selTOCSY 对火灾残骸中的汽油样本进行识别和个性化处理

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-11-01 DOI: 10.1016/j.forc.2024.100614

Yanita Yankova , John Warren , Michael D. Cole , Silvia Cirstea

Detection and identification of ignitable liquids in fire investigation is ongoing challenge for forensics investigators. This study uses the analytical power of NMR analysis and permits the identification of trace amounts of olefinic compounds the complex mixture of petrol that aids the individualization of petrol sources. The ¹H selTOCSY NMR method has proven to be successful in the investigation of the four sets of alkenes namely: 3-methyl-1-butene (set 1), a mixture of 3-methyl-1-butene and 1-pentene (set 2), 2-methyl-2-butene (set 3) and a mixture of cis and trans-2-pentene (set 4) in petrol samples evaporated to different extents, simulating the action of weathering of actual casework samples, and still achieved significant discrimination of petrol brands at 25 % and 50 % evaporation. Discrimination of burned samples also proved possible, both of burnt petrol its own and then petrol burned on different substrates including wood, carpet, fabric, and paper materials representing common household fire debris residues. ¹H selTOCSY NMR experiments on these alkene signals remove most of the non-alkene-related signals from the spectra and thus provide additional clarity in heavily burnt and contaminated samples, increasing the capacity to discriminate between samples using the four alkene markers.

在火灾调查中检测和识别可燃液体是法医调查人员一直面临的挑战。本研究利用核磁共振分析的分析能力，对汽油复杂混合物中的痕量烯烃化合物进行鉴定，从而帮助确定汽油来源。事实证明，1H selTOCSY NMR 方法在研究以下四组烯烃方面取得了成功：在汽油样品中，3-甲基-1-丁烯（第 1 组）、3-甲基-1-丁烯和 1-戊烯的混合物（第 2 组）、2-甲基-2-丁烯（第 3 组）以及顺式和反式-2-戊烯的混合物（第 4 组）的蒸发程度不同，模拟了实际案例样品的风化作用，在蒸发 25% 和 50% 的情况下，仍能显著区分汽油品牌。事实证明，还可以对燃烧过的样品进行区分，包括燃烧过的汽油本身和在不同基质上燃烧过的汽油，这些基质包括木材、地毯、织物和代表常见家庭火灾残留物的纸质材料。对这些烯信号进行的 1H selTOCSY NMR 实验消除了光谱中大部分与烯无关的信号，从而使严重燃烧和污染的样品更加清晰，提高了使用四个烯标记对样品进行鉴别的能力。

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引用次数: 0

Detection of synthetic cathinones in seized drugs using surface-enhanced Raman spectroscopy (SERS) 利用表面增强拉曼光谱（SERS）检测缉获药物中的合成卡西酮类化合物

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-10-28 DOI: 10.1016/j.forc.2024.100613

Mario O. Vendrell-Dones, Emily Hernandez, Sevde Dogruer Erkok, Bruce McCord

There is need for a screening method to assist authorities in detecting cathinone analogs in a rapid, reliable, and sensitive fashion. This work describes the development of Ag colloidal systems for use as SERS-enhancing substrates to detect six synthetic cathinone analogs. Furthermore, specific interactions between the analyte and metal surface were probed by determining the effect of functional groups attached to the core synthetic cathinone. Initial work involved Density Functional Theory (DFT) calculations at B3LYP/6-311G** level to predict Raman frequencies of the studied compounds. Normal Raman measurements on dried solid residues of synthetic cathinone standards were next examined, and the resulting scaled spectra were used to ensure concordance of the DFT-predicted frequencies with experimental values. Subsequent work focused on the development of a SERS protocol, which included the selection of nanoparticles in solution, followed by the addition of aggregating agents such as MgCl₂ and KBr to produce high-density hot-spots on the nanometallic surface. Sample treatment conditions necessary to detect the selected synthetic cathinone analogs were also optimized. Once completed, the characterization and identification of the main peaks that make up the synthetic cathinone core structure were assigned and unique functional groups for each of the analogs were identified. Overall, the analytical process takes less than a minute, making the procedure useful for field screening. Ultimately, this procedure can aid law enforcement and first responders by providing a more specific method for rapid and sensitive on-site analysis of seized drugs.

需要一种筛选方法来协助有关部门以快速、可靠和灵敏的方式检测卡西酮类似物。这项工作描述了开发银胶体系统作为 SERS 增强底物来检测六种合成卡西酮类似物的情况。此外，还通过确定附着在核心合成卡西酮上的官能团的影响，探究了分析物与金属表面之间的特定相互作用。最初的工作包括在 B3LYP/6-311G** 水平上进行密度泛函理论（DFT）计算，以预测所研究化合物的拉曼频率。接下来，对合成卡西酮标准的干燥固体残留物进行了正常拉曼测量，并使用由此产生的缩放光谱来确保 DFT 预测频率与实验值一致。随后的工作重点是开发 SERS 方案，包括选择溶液中的纳米粒子，然后加入 MgCl2 和 KBr 等聚集剂，在纳米金属表面产生高密度热点。此外，还对检测所选合成卡西酮类似物所需的样品处理条件进行了优化。完成后，对构成合成卡西酮核心结构的主峰进行了特征描述和鉴定，并确定了每种类似物的独特官能团。总体而言，分析过程耗时不到一分钟，因此可用于现场筛选。最终，该程序可以帮助执法人员和急救人员，为快速灵敏地现场分析缉获的毒品提供更具体的方法。

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引用次数: 0

Development and validation of a forensic workflow for the complete profiling of illicit drugs and excipients 开发和验证用于非法药物和辅料完整特征分析的法医工作流程

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.forc.2024.100612

Mikaela J. Radke, Alan White, Wendy A. Loughlin, Sarah L. Cresswell

The development of a complete understanding of the societal harms of illicit drug mixtures requires a greater emphasis on the complete identification of illicit and excipient compounds. To increase the feasibility of this in practice, common and emerging analytical techniques were examined in the context of developing a non-targeted forensic workflow. The purpose of this workflow was to increase the identification of excipient compounds without compromising the quality of illicit drug identification as required for admissibility of evidence in court. This incorporated the testing of simulated compound mixtures to develop the principal avenues of analysis. These pathways were then validated through the testing of unknown compound mixtures. The techniques of focus included GCMS, FTIR, LC-HRMS for identification, and LC-HRMS for quantitation. These techniques were organised into their respective categories of techniques, according to the SWGDRUG guidelines, to produce a workflow that would ensure the admissibility of evidence no matter the pathway taken. HRMS was examined as an emerging technique not currently used in illicit drug analysis facilitating non-targeted analysis pathways. From this, and in combination with GCMS, all organic components were identifiable in simulated and unknown mixtures. Partial identification was also achieved for insoluble compounds using FTIR analysis. Identification by HRMS was facilitated by comparison to reference standards and MS/MS spectra matching to the high-resolution database MzCloud. This demonstrated the applicability of HRMS, specifically the Exploris 120 Orbitrap, to the identification and quantitation of both illicit and organic excipient compounds within Forensic Chemistry.

要全面了解非法药物混合物的社会危害，就必须更加重视非法化合物和辅料化合物的全面鉴定。为了提高这种做法在实践中的可行性，在开发非目标法医学工作流程的背景下，对常见的和新兴的分析技术进行了研究。该工作流程的目的是在不影响非法药物鉴定质量的情况下，提高辅料化合物的鉴定率，这也是法庭采纳证据的要求。其中包括对模拟化合物混合物进行测试，以开发主要的分析途径。然后通过测试未知化合物混合物来验证这些途径。重点技术包括 GCMS、FTIR、用于鉴定的 LC-HRMS 和用于定量的 LC-HRMS。根据 SWGDRUG 指南，这些技术被归入各自的技术类别，以形成一个工作流程，确保无论采用哪种途径，证据都具有可采性。HRMS 作为一种目前尚未用于非法药物分析的新兴技术，为非目标分析途径提供了便利。由此，结合 GCMS，可以识别模拟和未知混合物中的所有有机成分。利用傅立叶变换红外分析法还对不溶性化合物进行了部分鉴定。通过与参考标准的比较以及与高分辨率数据库 MzCloud 的 MS/MS 光谱匹配，促进了 HRMS 的鉴定。这表明 HRMS（特别是 Exploris 120 Orbitrap）适用于法医化学中非法和有机辅料化合物的鉴定和定量。

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引用次数: 0

Recovery and detection of ignitable liquid residues from the substrates by solid phase microextraction – direct analysis in real time mass spectrometry 通过固相微萃取--实时质谱直接分析--回收和检测底物中的可燃液体残留物

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.forc.2024.100611

Shruthi Perna , Ngee Sing Chong , Mengliang Zhang

In this study, direct analysis in real time mass spectrometry (DART-MS) was coupled to the solid phase microextraction (SPME) to extract and analyze the ignitable liquid residues (ILR) present in the sample matrices. The SPME extraction parameters, such as extraction temperature and extraction time, were optimized using a two-factor central composite design. The SPME-DART-MS setup was utilized to analyze the substrates and fire debris matrices spiked with gasoline. The results indicate that the less volatile marker compounds from gasoline were recovered from the substrates and fire debris, and their profiles matched well with the gasoline liquid samples analyzed directly by DART-MS. As expected, the effective extraction of marker compounds in gasoline required a relatively high temperature, i.e., 150 ℃. In the presence of a matrix, a higher extraction temperature and longer extraction time could benefit the extraction efficiency. The desorption of ILR on SPME fiber was performed by inserting the fiber into the DART-MS helium gas stream at 300 ℃ for 1 min with no carry-over residues being observed between successive samples. The chemical information attained with this method is typically not observed in the current GC/MS-based practice. The SPME-DART-MS was also extended to reanalyze less volatile components of ILR on substrates after the ASTM E1412 activated charcoal method, which indicates its possible application subsequent to the traditional GC/MS ILR analysis. The SPME-DART-MS has shown promise in ILR detection as an important complementary tool.

本研究将直接分析实时质谱法（DART-MS）与固相微萃取法（SPME）相结合，对样品基质中的可燃液体残留物（ILR）进行萃取和分析。采用双因素中心复合设计优化了 SPME 的萃取参数，如萃取温度和萃取时间。利用 SPME-DART-MS 装置对添加了汽油的基质和火灾残骸基质进行了分析。结果表明，从基质和火灾残骸中回收到了挥发性较低的汽油标记化合物，而且其特征与直接用 DART-MS 分析的汽油液体样品十分吻合。正如预期的那样，有效萃取汽油中的标记化合物需要相对较高的温度，即 150 ℃。在存在基质的情况下，更高的萃取温度和更长的萃取时间会提高萃取效率。将 SPME 纤维插入 300 ℃ 的 DART-MS 氦气流中 1 分钟，即可解吸 SPME 纤维上的 ILR，且在连续样品之间观察不到携带残留物。这种方法所获得的化学信息通常是目前基于气相色谱/质谱法所无法观察到的。在使用 ASTM E1412 活性炭法之后，SPME-DART-MS 还可用于重新分析基质上挥发性较低的 ILR 成分，这表明它可以在传统的 GC/MS ILR 分析之后继续使用。作为一种重要的补充工具，SPME-DART-MS 在检测 ILR 方面已显示出良好的前景。

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引用次数: 0

High-throughput LC-PDA method for determination of Δ9-THC and related cannabinoids in Cannabis sativa 测定大麻中 Δ9-THC 和相关大麻素的高通量 LC-PDA 方法

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-10-09 DOI: 10.1016/j.forc.2024.100610

Walter B. Wilson, Aaron A. Urbas, Haley Jensen, Lane C. Sander

Before the passage of the Agriculture Improvement Act of 2018, more commonly referred to as the 2018 Farm Bill, forensic laboratories were only required to perform qualitative measurements to confirm the identity of seized plant samples as Cannabis sativa (hemp or marijuana). The new law defines hemp at a federal level as Cannabis sativa containing 0.3 % or less Δ⁹-THC. Because forensic laboratories were not adequately equipped with the proper methods or training to meet these requirements, significant backlogs in casework resulted. The National Institute of Standards and Technology (NIST) responded by providing analytical tools to the forensic community. An accurate and precise method was previously developed to determine Δ⁹-THC, Δ⁹-THCA, and total Δ⁹-THC in botanical samples based on liquid chromatography with photodiode array detection (LC-PDA). Cannabis plant samples were ground and extracted with methanol using routine laboratory equipment. The original sample preparation procedure was time-consuming, taking over 70 min. The method described here has been optimized with the time required for sample preparation and LC-PDA analysis has been reduced to less than 30 min.

在《2018 年农业改进法案》（通常称为《2018 年农业法案》）通过之前，法医实验室只需进行定性测量，以确认查获的植物样本是否为大麻（Cannabis sativa）。新法律在联邦层面将大麻定义为含有 0.3% 或更少 Δ9-THC 的大麻。由于法医实验室没有充分配备适当的方法或培训来满足这些要求，导致案件工作严重积压。美国国家标准与技术研究院（NIST）通过向法医界提供分析工具做出了回应。此前已开发出一种准确而精确的方法，基于液相色谱法和光电二极管阵列检测法 (LC-PDA)，测定植物样本中的Δ9-THC、Δ9-THCA 和总Δ9-THC。使用常规实验室设备将大麻植物样本研磨并用甲醇提取。最初的样品制备过程耗时超过 70 分钟。本文介绍的方法经过优化，将样品制备和 LC-PDA 分析所需的时间缩短至 30 分钟以内。

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引用次数: 0

Validation of a rapid GC–MS method for forensic seized drug screening applications 验证用于法医缉获药物筛查的快速气相色谱-质谱法

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-09-13 DOI: 10.1016/j.forc.2024.100609

Briana A. Capistran , Edward Sisco

With the lack of standardized validation protocols across the forensic chemistry community, validation of instrumentation can be a challenging and time-consuming task. However, this process is crucial to understanding the associated capabilities and limitations, especially for nascent technologies. Rapid GC–MS is one such emerging analytical technique being increasingly implemented in forensic laboratories due to its fast and informative screening capabilities. However, a full validation for forensic samples has yet to be published since its debut. This work presents the results of a comprehensive validation of a rapid GC–MS system for seized drug screening through the assessment of nine components: selectivity, matrix effects, precision, accuracy, range, carryover/contamination, robustness, ruggedness, and stability. Single- and/or multi-compound test solutions of commonly encountered seized drug compounds were used to assess method and system performance. Results met the designated acceptance criteria for a majority of components. For example, retention time and mass spectral search score % RSDs were ≤10 % for precision and robustness studies. Limitations were identified for components that did not meet the acceptance criteria (e.g., inability to differentiate some isomers). The study design is part of a larger validation package developed for rapid GC–MS that includes a validation plan and automated workbook. The template, available for adoption by laboratories, ultimately aims to reduce the barrier of implementation for rapid GC–MS technology.

由于法医化学界缺乏标准化的验证协议，仪器验证可能是一项具有挑战性且耗时的任务。然而，这一过程对于了解相关能力和局限性至关重要，尤其是对于新兴技术而言。快速气相色谱-质谱（GC-MS）就是这样一种新兴的分析技术，因其快速、信息量大的筛选能力而越来越多地应用于法医实验室。然而，自其问世以来，针对法医样本的全面验证尚未公布。本研究通过对选择性、基质效应、精确性、准确性、范围、携带/污染、稳健性、坚固性和稳定性等九个方面的评估，展示了用于缉获毒品筛查的快速气相色谱-质谱系统的全面验证结果。使用常见缉获毒品化合物的单化合物和/或多化合物测试溶液来评估方法和系统性能。大多数成分的结果都符合指定的验收标准。例如，在精确度和稳健性研究中，保留时间和质谱搜索得分 RSD ≤10 %。对于不符合验收标准的成分（如无法区分某些异构体），则确定了其局限性。该研究设计是为快速气相色谱-质谱（GC-MS）开发的大型验证包的一部分，其中包括验证计划和自动工作手册。该模板可供实验室采用，最终目的是减少快速气相色谱-质谱技术的实施障碍。

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引用次数: 0

Structural characterization of nitazene analogs using electron ionization-mass spectrometry (EI-MS) 利用电子电离质谱法（EI-MS）确定硝氮类似物的结构特征

IF 2.6 3区医学 Q2 CHEMISTRY, ANALYTICAL

Forensic Chemistry

Pub Date : 2024-09-01 DOI: 10.1016/j.forc.2024.100605

Emma K. Hardwick, J. Tyler Davidson

Nitazene analogs are among the most recent and potent additions to the novel synthetic opioid (NSO) market, and new analogs continue to emerge. Seized drug analysis commonly utilizes gas chromatography-electron ionization-mass spectrometry (GC-EI-MS), so it is therefore imperative to understand how nitazene analogs behave under EI-MS conditions, and how substitution at various sites on the molecule may impact the resulting EI mass spectra. This study characterizes the EI fragmentation behavior of 20 representative nitazene analogs that contain differing substitutions and proposes rational mechanisms to explain the observed behavior.

A general EI fragmentation pathway for nitazene analogs was proposed, with the most common nitazene fragment ions being observed at m/z 86, m/z 107, m/z 58, and m/z 77. Characteristic ions were determined for different substitution groups, enabling the identification of diethyl, desethyl, pyrrolidine, and piperidine substitutions at the amine moiety, and different alkoxy chain lengths at the aromatic ring of the benzyl group. Mechanisms for the formation of these characteristic ions were proposed with the aid of isotopically labeled standards and high-resolution mass spectrometry measurements. To help with the interpretation of EI mass spectra for nitazene analogs, decision trees were developed that encompass the characteristic fragment ions observed for substitutions to the amine moiety and benzyl group, with additional criteria provided for substitutions to the benzimidazole moiety. This study summarizes the fragmentation patterns and characteristic fragment ions in the EI mass spectra of 20 representative nitazene analogs, which will aid the seized drug community in identifying novel nitazene analogs.

硝氮类似物是新型合成阿片（NSO）市场上最新出现的强效新药，而且新的类似物还在不断涌现。缉获药物分析通常使用气相色谱-电子电离质谱法（GC-EI-MS），因此必须了解硝氮类似物在 EI-MS 条件下的表现，以及分子上不同位点的取代如何影响所产生的 EI 质谱。本研究描述了含有不同取代位点的 20 种具有代表性的硝氮类似物的电离碎片行为，并提出了解释所观察到的行为的合理机制。针对不同的取代基团确定了特征离子，从而确定了胺分子上的二乙基、去乙基、吡咯烷和哌啶取代基，以及苄基芳香环上的不同烷氧基链长。借助同位素标记标准和高分辨率质谱测量，提出了这些特征离子的形成机制。为了帮助解释硝氮类似物的电离质谱，研究人员开发了决策树，其中包括观察到的胺分子和苄基取代的特征碎片离子，并为苯并咪唑分子的取代提供了额外的标准。本研究总结了 20 种具有代表性的硝基苯类似物的电离质谱中的碎片模式和特征碎片离子，这将有助于缉毒界鉴定新型硝基苯类似物。

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引用次数: 0