Pub Date : 2025-08-16DOI: 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.
{"title":"Methods to transform illicit drugs: A review and evaluation of drug degradation techniques","authors":"Alexandra L. Mercieca, Morgan Alonzo, Scott Chadwick, Andrew M. McDonagh","doi":"10.1016/j.forc.2025.100689","DOIUrl":"10.1016/j.forc.2025.100689","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"46 ","pages":"Article 100689"},"PeriodicalIF":2.2,"publicationDate":"2025-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145047956","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}
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。
{"title":"Discrimination of Cannabis sativa L. from other similar plant species using solvent extraction, ATR-FTIR and PLS-DA","authors":"Rafaela Dornelas Vieira , Fabiana Casarin , Laíz de Oliveira Magalhães , Ícaro Noé Caixêta , Luciano Chaves Arantes , Jez Willian Batista Braga","doi":"10.1016/j.forc.2025.100690","DOIUrl":"10.1016/j.forc.2025.100690","url":null,"abstract":"<div><div><em>Cannabis sativa</em> 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 <em>Cannabis sativa</em>, 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<sup>−1</sup> for ethanol and petroleum ether; 800–880 cm<sup>−1</sup> 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 <em>Cannabis sativa</em>, effectively addressing the limitations of conventional screening techniques and the complexity of plant-based mixtures.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100690"},"PeriodicalIF":2.2,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144829634","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}
Pub Date : 2025-07-28DOI: 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.
{"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}
Pub Date : 2025-07-20DOI: 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.
{"title":"2D NMR detection and quantification of heroin in a street sample","authors":"Kathryn M. James , Samantha V. Boni , Kayla Gratton , Mallory J. Stopko , Michael Cipoletti , Timothy Gilbert , Alexander K. Goroncy , Takashi L. Suyama","doi":"10.1016/j.forc.2025.100687","DOIUrl":"10.1016/j.forc.2025.100687","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100687"},"PeriodicalIF":2.6,"publicationDate":"2025-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702415","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}
Pub Date : 2025-07-18DOI: 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.
{"title":"Analytical identification of ergot alkaloids in Ipomoea species: Resolving historical, forensic, and legal ambiguities","authors":"Enrico Greco , Andrea Farci , Fiorella Florian , Alberto Pallavicini , Alessandro Miani , Pierluigi Barbieri , Giorgio Samorini","doi":"10.1016/j.forc.2025.100686","DOIUrl":"10.1016/j.forc.2025.100686","url":null,"abstract":"<div><div>This study addresses the longstanding taxonomic confusion between two plant species within the Convolvulaceae family: <em>Ipomoea tricolor</em> Cav. and <em>Ipomoea violacea</em> 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 <em>I. tricolor</em> consistently contain significant levels of psychoactive compounds structurally similar to LSD, while <em>I. violacea</em> seeds lack these alkaloids entirely. This distinction is critical, as current legislative documents frequently misclassify non-psychoactive <em>I. violacea</em> as a controlled substance, inadvertently omitting the psychoactive <em>I. tricolor</em>. 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.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100686"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665694","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}
Pub Date : 2025-07-17DOI: 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.
{"title":"Machine learning-enhanced traceability and particle analysis of pyrotechnic post-explosion residues using SEM/EDS","authors":"Xing Li , Zhen-Wen Sun , Yan-Wu Yu , Gao-Qin Zhang , Guan-Nan Zhang , Yao Liu","doi":"10.1016/j.forc.2025.100685","DOIUrl":"10.1016/j.forc.2025.100685","url":null,"abstract":"<div><div>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 (R<sup>2</sup> > 0.95, Root Mean Squared Error (RMSE) < 0.07), supporting the potential for pyrotechnical traceability from SEM/EDS data of PPERs.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100685"},"PeriodicalIF":2.6,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685991","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}
Pub Date : 2025-07-09DOI: 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.
{"title":"Electron ionization fragmentation studies of ethoxy and methoxymethyl substituted phenylacetones","authors":"C. Randall Clark , Younis Abiedalla","doi":"10.1016/j.forc.2025.100684","DOIUrl":"10.1016/j.forc.2025.100684","url":null,"abstract":"<div><div>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.</div><div>The methoxymethylbenzaldehydes yield a major fragment at <em>m/z</em> 135 via loss of the methyl radical. The ethoxy substituted isomers however have a base peak at <em>m/z</em> 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 <em>m/z</em> 135 via loss of the acetyl radical and the <em>m/z</em> 107 cation via elimination of ethene from the ethoxybenzyl cation. The EI mass spectra of methoxymethylphenylacetones are dominated by the radical cation at <em>m/z</em> 104 [C<sub>8</sub>H<sub>8</sub>]<sup>+•</sup>. Unique <em>meta</em>- specific radical cations at <em>m/z</em> 136 and <em>m/z</em> 108 were observed in 3-ethoxyphenylacetone. An <em>ortho</em> effect in methoxymethylphenylacetones yielded the unique fragments at <em>m/z</em> 121, <em>m/z</em> 146 and <em>m/z</em> 145. The results of this study identify <em>m/z</em> 107 and <em>m/z</em> 104 as unique marker ions for the differentiation of the regioisomeric ethoxy and methoxymethyl substituted phenylacetones.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100684"},"PeriodicalIF":2.6,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144623866","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}
Pub Date : 2025-07-01DOI: 10.1016/j.forc.2025.100683
Thomas D. Ledergerber , Liliana Barbosa , Kourtney Dalzell , Luis Arroyo , Tatiana Trejos
This study encompasses the detection, characterization, and classification of organic gunshot residue (OGSR) through the analysis of three forensically relevant sample types, including neat smokeless powders recovered from live ammunition, extracts from fired cartridge cases, and the hands of known shooters. Liquid chromatography-tandem mass spectrometry is used as an analytical tool for five manufacturer-grade ammunition brands. The relative detection and quantification of Akardite II, ethyl centralite, methyl centralite, diphenylamine, 2-nitrodiphenylamine, and 4-nitrodiphenylamine is used for chemical characterization and to reveal main chemical changes during deflagration. Classification via discriminant analysis methods is effective for neat smokeless powders and spent cartridge cases, reaching correct classification rates as high as 83.7 %. Alternative chemometric techniques, including k-nearest neighbors and support vector machine algorithms, are more appropriate for residues recovered from the shooter's hands that exhibit greater inter-sample variability. The more challenging traces of hand residues yield correct classification rates of up to 62.7 %, partly due to significant changes in the formation of nitro-diphenylamines and Akardite II in some organic gunshot residue. The findings presented in this study demonstrate that analyzing OGSR can offer valuable insights into the discrimination of manufacturer-spent cartridges and, to some extent, hand residues, assisting in forensic investigations and shooting reconstructions when limited evidence is available.
{"title":"Characterization and classification of organic gunshot residue from neat smokeless powder, cartridge cases, and the hands of known shooters","authors":"Thomas D. Ledergerber , Liliana Barbosa , Kourtney Dalzell , Luis Arroyo , Tatiana Trejos","doi":"10.1016/j.forc.2025.100683","DOIUrl":"10.1016/j.forc.2025.100683","url":null,"abstract":"<div><div>This study encompasses the detection, characterization, and classification of organic gunshot residue (OGSR) through the analysis of three forensically relevant sample types, including neat smokeless powders recovered from live ammunition, extracts from fired cartridge cases, and the hands of known shooters. Liquid chromatography-tandem mass spectrometry is used as an analytical tool for five manufacturer-grade ammunition brands. The relative detection and quantification of Akardite II, ethyl centralite, methyl centralite, diphenylamine, 2-nitrodiphenylamine, and 4-nitrodiphenylamine is used for chemical characterization and to reveal main chemical changes during deflagration. Classification via discriminant analysis methods is effective for neat smokeless powders and spent cartridge cases, reaching correct classification rates as high as 83.7 %. Alternative chemometric techniques, including k-nearest neighbors and support vector machine algorithms, are more appropriate for residues recovered from the shooter's hands that exhibit greater inter-sample variability. The more challenging traces of hand residues yield correct classification rates of up to 62.7 %, partly due to significant changes in the formation of nitro-diphenylamines and Akardite II in some organic gunshot residue. The findings presented in this study demonstrate that analyzing OGSR can offer valuable insights into the discrimination of manufacturer-spent cartridges and, to some extent, hand residues, assisting in forensic investigations and shooting reconstructions when limited evidence is available.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100683"},"PeriodicalIF":2.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144534856","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}
Pub Date : 2025-06-29DOI: 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.
{"title":"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","authors":"Jennifer K. Field , Benjamin S. Barrett , Erika Sitch , Ryan E. Mewis , William H. Campbell , Melvin R. Euerby , Oliver B. Sutcliffe","doi":"10.1016/j.forc.2025.100682","DOIUrl":"10.1016/j.forc.2025.100682","url":null,"abstract":"<div><div>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 <em>ortho-</em>, <em>meta-</em> and <em>para</em>-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 (<em>n</em> = 10); fentanyl analogues (n = 10), despropionyl precursors (<em>n</em> = 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.</div></div>","PeriodicalId":324,"journal":{"name":"Forensic Chemistry","volume":"45 ","pages":"Article 100682"},"PeriodicalIF":2.6,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633796","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}
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