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1.
Med Sci Law ; 64(1): 77-81, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37306159

RESUMO

On 16th June 2022, the first case of lawful 'medically assisted suicide' took place on Italian soil. This event is a result of decade-long debates on informed consent and end-of-life care stimulated by medical jurisprudence. The authors first retrace the crucial moments that allowed this to happen and underline the problems still to be solved. The cases of DJ Fabo, Davide Trentin, Mario and Fabio Ridolfi are discussed, signalling how they influenced the path implemented by Italian jurisprudence.


Assuntos
Suicídio Assistido , Humanos , Itália , Consentimento Livre e Esclarecido
2.
Int J Drug Policy ; 122: 104238, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37890390

RESUMO

BACKGROUND: Since the beginning of the COVID-19 pandemic, several studies have been conducted on the impact of lockdown and containment measures on various aspects of individual and social behaviour, including substance use. The increasing body of literature investigating this phenomenon emphasizes the need for additional studies at the local level. We investigate changes in reported illicit drug consumption following changes in public measures limiting individual mobility in the province of Bergamo, one of the regions that faced the most severe consequences in terms of number of cases and death toll in the early stages of the pandemic. METHODS: The empirical analysis is based on a unique dataset covering all people recorded by police forces as drug users between January 2019 and December 2021 in the province of Bergamo. Data relate to reports for illicit drug consumption and not criminal activities. RESULTS: Estimates show that, during periods when individual mobility was severely limited, the probability of reported cannabis consumption decreased by 8-9%, while that of reported cocaine use increased by 6-12%. No significant changes emerge in the reported consumption of heroin or polysubstance. Furthermore, while reported cannabis use returned to pre-pandemic levels once the restrictive measures were eased, the increased likelihood of reported cocaine use appears to have been more long-lasting. These findings are robust to alternative estimation strategies and different model specifications. Our study also reveals significant gender, age and housing status disparities in reported drug use. CONCLUSION: We provide a novel and distinctive perspective on the topic by using previously unexploited administrative data sources. We show that the relationship between restrictions and reported drug use varies by type of substance. Our methodology and findings can support the design of targeted policies for better resource allocation and improved public health outcomes.


Assuntos
COVID-19 , Cannabis , Cocaína , Drogas Ilícitas , Transtornos Relacionados ao Uso de Substâncias , Humanos , Pandemias , COVID-19/epidemiologia , Controle de Doenças Transmissíveis , Transtornos Relacionados ao Uso de Substâncias/epidemiologia
3.
Forensic Sci Int ; 335: 111282, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35378337

RESUMO

The market of falsified or sub-standard medical products is a global scale phenomenon. This issue affects a wide range of medications, including life-saving medical products. In high-income countries the most falsified products are those defined "lifestyle", which include foremost anabolic steroids and phosphodiesterase 5 inhibitors. The spread of these products in the last years has been possible also because of their online purchase, since they can be bought anonymously and without any medical supervision or prescription. Their use can pose a serious threat for public health, especially because often are manufactured without adherence to quality standards. This leads to final products containing active ingredients different from those declared, at the wrong or unknown dose and contaminated with metals, synthesis by-products and other chemical substances. In this work, we present results on characterisation of illegal pharmaceutical products and doping agents by combining different techniques: chromatography coupled to mass spectrometry for organic analysis and accelerator-based nuclear analytical techniques, such as ion beam analysis (IBA), for elemental analysis. Three IBA techniques, namely PIXE (particle induced X-ray emission), PIGE (particle induced gamma-ray emission) and EBS (elastic backscattering spectrometry) were used in external beam mode to provide an elemental characterisation of the as-is material, placed simply in front of the proton beam, thus avoiding the need of preparing them with pre-analytical steps and greatly enhancing the measurement throughput. Several elements (F, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Br and Sr) were identified in the analysed products. External beam IBA measurements provided the quantitative elemental characterisation of the illegal pharmaceutical products and doping agents under study, complementary to the organic analysis results by chromatography and mass spectrometry thus allowing a rapid (a few minutes) and non-destructive direct assessment of the material for forensic purposes. For the first time IBA results from doping products are reported and further analysis by IBA involving two different accelerator laboratories (one in Italy and one in Brazil) allowed the comparison of results obtained on the same pharmaceutical product. Starting from the results obtained in our study, the actualisation of new research plans should be evaluated, which could lay the foundation for a classification system of illegal pharmaceutical products, doping products. and other substances, based on chromatography, mass spectrometry and IBA measurements; this could allow drawing inferences about the common characteristics of these substances, e.g. provenience of bulk materials, site of production etc. With this purpose, results obtained from two samples of the same pharmaceutical product by IBA in two different accelerator laboratories (one in Italy and one in Brazil) are compared.


Assuntos
Oxandrolona , Cromatografia Líquida de Alta Pressão , Cromatografia Gasosa-Espectrometria de Massas , Preparações Farmacêuticas , Citrato de Sildenafila
4.
Annu Rev Anal Chem (Palo Alto Calif) ; 15(1): 173-196, 2022 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-35167323

RESUMO

Surface analysis techniques have rapidly evolved in the last decade. Some of these are already routinely used in forensics, such as for the detection of gunshot residue or for glass analysis. Some surface analysis approaches are attractive for their portability to the crime scene. Others can be very helpful in forensic laboratories owing to their high spatial resolution, analyte coverage, speed, and specificity. Despite this, many proposed applications of the techniques have not yet led to operational deployment. Here, we explore the application of these techniques to the most important traces commonly found in forensic casework. We highlight where there is potential to add value and outline the progress that is needed to achieve operational deployment. We consider within the scope of this review surface mass spectrometry, surface spectroscopy, and surface X-ray spectrometry. We show how these tools show great promise for the analysis of fingerprints, hair, drugs, explosives, and microtraces.


Assuntos
Medicina Legal , Ciências Forenses , Crime , Medicina Legal/métodos , Ciências Forenses/métodos , Espectrometria de Massas , Análise Espectral
5.
Microsc Microanal ; 27(4): 666-677, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-33960287

RESUMO

Inorganic gunshot residue (GSR) analysis is carried out by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) in many forensic laboratories. Characteristic GSR often consists of lead­barium­antimony, commonly associated with sulfur. The strength of forensic GSR evidence increases when unusual elements are found in residues collected both from the suspect and from the discharged firearm. The presence of molybdenum in GSR, due to the use of MoS2 lubricants in firearms, is experimentally demonstrated here for the first time. The most intense molybdenum X-ray emissions are MoL peaks at 2.3 keV which overlap with PbM and SK families due to the poor resolution of EDS detectors. When Pb, S, and Mo are allegedly present in the same particle, the reliability of automatic EDS routines is at risk. Missing identifications or false detections and exclusions may then occur. Molybdenum should be considered as detected only if MoK emissions meet the peak-to-background ratio minimum requirements. A strategy to spot Mo-containing residues is described, based on the automated search of MoS2, using a new "Sulfur only" class added to the classification scheme, followed by careful manual review of all GSR particles at an acceleration voltage of 30 kV. Our proposal improves commonly adopted forensic procedures currently followed in casework.

6.
Talanta ; 224: 121829, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33379047

RESUMO

Illegal trafficking of pharmaceutical products by criminal organisations is a global threat for public health. Drugs for erectile dysfunction such as phosphodiesterase type 5 inhibitors are the most commonly counterfeited medicines in Europe. The search of possible toxic chemical substances in seized products is needed to provide early warning for public health. Furthermore, the elemental profile of the seized products can be useful in criminal investigations. For the first time an ion beam analysis (IBA) procedure to characterise authentic Viagra® tablets and sildenafil-based illegal products is described. Moreover, results are compared with the ones obtained by instrumental neutron activation analysis (INAA) on authentic Viagra® tablets in two reactors. IBA results showed that a combination of particle-induced X-ray emission (PIXE) and secondary ion mass spectrometry using primary ions with energies in the range of several MeV (MeV-SIMS) is a powerful tool to characterise different products in a straightforward manner, allowing discrimination between legal and illegal products. INAA allowed accurate elemental quantification and also showed a great potential for the future implementation of an inter-laboratory classification system.


Assuntos
Medicamentos Falsificados , Inibidores da Fosfodiesterase 5 , Europa (Continente) , Humanos , Íons , Masculino , Análise de Ativação de Nêutrons , Citrato de Sildenafila
7.
Int J Legal Med ; 134(3): 1083-1094, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32052122

RESUMO

The aim of this work was to characterise three non-toxic ammunition (NTA) from the GECO and Fiocchi brands, which are available in the Italian market. Characterisation was carried out by considering both the elemental chemical composition and morphology, using scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDS). Particles were collected from both the cartridge cases and the shooters' hands after shooting tests. Six volunteers fired two shots for each ammunition. Several elements, such as aluminium, potassium, silicon, sulphur, titanium and zinc were found in gunshot residue (GSR) particles from different ammunition. We also studied the persistence of these types of GSR on the hands of the shooters in a range between 1 and 6 h after shooting. The GSR particles from the three NTA tested were found on the hands of shooters until 6 h after the shots. The characterisations undertaken in this work will be useful for specialists in forensic science and legal medicine to evaluate trace evidence from these new NTA in casework, as such formulations are in growth.


Assuntos
Armas de Fogo , Metaloides/análise , Metais Leves/análise , Pele/química , Zinco/análise , Balística Forense/métodos , Medicina Legal , Mãos , Humanos , Fatores de Tempo
8.
J Forensic Sci ; 64(6): 1658-1667, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31211876

RESUMO

Gunshot residue (GSR) from the discharge of ammunition can provide crucial information in reconstructing criminal cases. Traditional primers create particles of heavy metals such as lead, barium, and antimony. In forensic laboratories, automatic inorganic particle detection is performed by scanning electron microscopy (SEM), using the backscattered electron signal to search for bright residues among the many darker environmental particles, due to higher electron density of the former. Some innovative primers, indicated as heavy metal-free (HMF), produce a residue of elements with atomic numbers below 21, urgently demanding new detecting solutions. For the first time, residues from Sellier & Bellot Nontox HMF primer are demonstrated to emit visible light under electron beam stimulation in a SEM. Cathodoluminescence is then proposed as a promising tool to both detect and characterize residues in forensic cases involving HMF primers, with minor changes to traditional analytical apparatus used for inorganic GSR analysis.

9.
Sci Justice ; 59(2): 181-189, 2019 03.
Artigo em Inglês | MEDLINE | ID: mdl-30798867

RESUMO

Gunshot Residue (GSR) produced by the discharge of a firearm often provides very useful information in criminal investigations in cases involving the use of firearms. Scanning Electron Microscopy equipped with an Energy Dispersive X-ray Spectrometer (SEM-EDS) is typically used worldwide to visualize micrometric particles constituting GSR and to analyse their elemental composition. The 2017 ASTM Standard guide for gunshot residue analysis by scanning electron microscopy/energy dispersive X-ray spectroscopy specifies that "Particles classified as characteristic of GSR will have one of the following elemental compositions: Lead, antimony, barium; Lead, barium, calcium, silicon, tin". For the first time, the presence of an additional element, such as Sn, plays a key role in ASTM particle classification. It is known that some ammunitions, used for pistols, revolvers and rifles, contain tin foil discs for sealing the primer mixture into the cup, resulting in GSR particles containing Sn. The authors faced some cases in which Sn was unexpectedly found in GSR particles from a 0.22 Long Rifle derringer and from some 12 gauge shotguns. No tin foil discs are used in rimfire ammunitions and there is no published evidence of tin foil discs in shotshell ammunitions. Following a "case by case" approach, experimental research has been carried out to explain how Sn can be present in GSR particles when the last discharged cartridge also does not contain any Sn either in components and in the explosive charges. Moreover, the use of Particle Induced X-ray Emission (PIXE) showed the capability to overcome overlap ambiguity of Sb and Sn peaks in the X-ray spectra, being a possible key issue in real shooting cases if Sn quantities are below the lower limit of SEM detection, especially when Sb is also present.

10.
Drug Test Anal ; 11(1): 33-44, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29962002

RESUMO

Synthetic cathinones are a type of drug belonging to group of new psychoactive substances (NPSs). The illicit market for these substances is characterized by the continuous introduction to the market of new analogs to evade legislation and to avoid detection. New screening and confirmation assays are therefore needed, mainly in forensic/clinical samples. In the current development, a porous membrane-protected, micro-solid-phase extraction (µ-SPE) has been developed for the assessment of several cathinones in urine. The µ-SPE device consisted of a cone-shaped polypropylene (PP) porous membrane containing the adsorbent (molecularly imprinted polymers, MIPs, synthesized for the first time for this class of drugs). MIPs were prepared using ethylone and 3-methylmethcathinone (3-MMC) as templates, ethylene glycol dimethacrylate (EGDMA) as a functional monomer, divinylbenzene (DVB) as a cross-linker, and 2,2´-azobisisobutyronitrile (AIBN) as an initiator. The prepared ethylone-based MIP and 3-MMC-based MIP have been fully characterized and evaluated as new selective adsorbents for µ-SPE. Cathinones separation/determination was performed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Optimum loading conditions (pH 5.0, loading for 4.0 minutes under orbital-horizontal shaking at 200 rpm) and elution conditions [2.0 mL of 75:20:5 heptane/2-propanol/ammonium hydroxide and ultrasounds assistance (37 kHz, 325 W) for 4.0 minutes] were found for ethylone-based MIP. Validation (intra-day and inter-day precision and analytical recovery) showed RSD values lower than 9 and 10% for intra-day and inter-day precision, and within the 88%-101% range for intra-day and inter-day analytical recovery.


Assuntos
Alcaloides/urina , Impressão Molecular/métodos , Polímeros/análise , Psicotrópicos/urina , Microextração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida de Alta Pressão/normas , Humanos , Impressão Molecular/normas , Microextração em Fase Sólida/normas , Espectrometria de Massas em Tandem/normas
11.
Forensic Sci Int Synerg ; 1: 126-136, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-32411964

RESUMO

The commerce of illegal and counterfeit medicinal products on internet is a serious criminal problem. Drugs for erectile dysfunction such as phosphodiesterase type 5 inhibitor are the most commonly counterfeited medicines in Europe. The search of possible toxic chemical substances in seized products is needed. Moreover, the profiling of the material can be the source of relevant forensic information. For the first time a combined approach based on liquid chromatography (LC) coupled to high resolution mass spectrometry (HRMS) and instrumental neutron activation analysis (INAA) is proposed and tested, allowing characterisation of both authentic and illegal pharmaceuticals containing sildenafil seized in Italy. LC-HRMS allowed the detection and identification of unknown impurities not reported on labels in illegal products and the quantitation of the sildenafil. INAA showed to be suitable to provide both qualitative and quantitative information for forensic purposes on 23 elements, allowing discrimination between legal and illegal products.

12.
Analyst ; 143(18): 4394-4399, 2018 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-30137067

RESUMO

Using a miniaturized near infrared spectrometer associated to chemometrics we developed a rapid and non destructive procedure to characterise paper and investigate its aging with the aim of solving dating problems. Two sets of paper were considered in this study (books and sheets) in order to ensure the results are not dependent of the storage conditions. The MicroNIR has the ability to distinguish paper according to the chemical composition of the surface as a function of the period of manufacturing. The optimized analytical platform is fast and simple, avoiding sample pre-treatment procedures. As a consequence, the approach may be considered as the optimal technology to carry out analysis of ancient paper or other similar materials for diagnostic or forensic purposes as it is entirely portable and non-destructive.

13.
J Chromatogr A ; 1550: 8-20, 2018 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-29605179

RESUMO

Several molecularly imprinted polymers (MIPs) have been synthesized for the first time using various synthetic cannabinoids (JWH007, JWH015 and JWH098) as template molecules. Ethylene dimethacrylate (EDMA) was used as a functional monomer for all cases. Similarly, divinylbenzene (DVB) and 2,2'-azobisisobutyronitrile (AIBN) were used as cross-linker and initiator, respectively. The prepared MIPs have been fully characterized and evaluated as new selective adsorbents for micro-solid phase extraction (µ-SPE) of synthetic cannabinoids in urine. The developed MIP-µ-SPE devices consisted of a polypropylene (PP) porous membrane containing the adsorbent (novel porous membrane protected micro-solid phase extraction based on a cone-shaped device) for operating in batch mode, which allowed a fast and integrated extraction-cleanup procedure. High performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used for quantifying the analytes after MIP-µ-SPE. The best performances were obtained for MIPs prepared from JWH015 as a template. Optimum loading conditions were found to be urine pH of 5.0 and adsorption time of 8.0 min under mechanical (orbital-horizontal) stirring at 100 rpm. The composition of the eluting solution consisted of 75:20:5 heptane/2-propanol/ammonium hydroxide. The elution was assisted by ultrasounds (37 kHz, 325 W) for 8.0 min. In addition, studies regarding selectivity have also been addressed for several drugs of abuse under optimized loading/adsorption conditions. Validation of the method showed good precision and analytical recovery by intra-day and inter-day assays (RSD values lower than 7 and 10% for intra-day and inter-day precision, and within the 83-100% range for intra-day and inter-day analytical recovery).


Assuntos
Canabinoides/urina , Cromatografia Líquida/métodos , Impressão Molecular/métodos , Polímeros/química , Microextração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Adsorção , Hidróxido de Amônia/química , Calibragem , Cromatografia Líquida de Alta Pressão/métodos , Humanos , Concentração de Íons de Hidrogênio , Limite de Detecção , Nitrilas/química , Reprodutibilidade dos Testes , Fatores de Tempo , Compostos de Vinila/química
14.
J Forensic Leg Med ; 52: 35-39, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-28850861

RESUMO

Death due to inhalation of aliphatic hydrocarbons such as butane and propane is a particularly serious problem worldwide, resulting in several fatal cases of sniffing these volatile substances in order to "get high". Despite the number of cases published, there is not a unique approach to case management of fatal sniffing. In this paper we illustrate the volatile lipophilic substances management in a case of a prisoner died after sniffing a butane-propane gas mixture from prefilled camping stove gas canisters, discussing the comprehensive approach of the crime scene, the autopsy, histology and toxicology. A large set of accurate values of both butane and propane was obtained by gas chromatography-mass spectrometry analyzing the following post-mortem biological samples: peripheral blood, heart blood, vitreous humor, liver, lung, heart, brain/cerebral cortex, fat tissue, kidney, and allowed an in depth discussion about the cause of death. A key role is played by following the proper sampling approach during autopsy.


Assuntos
Butanos/análise , Butanos/intoxicação , Abuso de Inalantes , Propano/análise , Propano/intoxicação , Tecido Adiposo/química , Tecido Adiposo/patologia , Adulto , Análise Química do Sangue , Química Encefálica , Patologia Legal , Toxicologia Forense , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Rim/química , Rim/patologia , Fígado/química , Fígado/patologia , Pulmão/química , Pulmão/patologia , Masculino , Miocárdio/química , Miocárdio/patologia , Púrpura/patologia , Mucosa Respiratória/patologia , Corpo Vítreo/química , Corpo Vítreo/patologia
15.
Talanta ; 160: 15-20, 2016 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-27591582

RESUMO

The analytical capability to detect hydrogen peroxide vapour can play a key role in localizing a site where a H2O2 based Improvised Explosive (IE) is manufactured. In security activities it is very important to obtain information in a short time. For this reason, an analytical method to be used in security activity needs portable devices. The authors have developed the first analytical method based on a portable luminometer, specifically designed and validated to locate IE manufacturing sites using quantitative on-site vapour analysis for H2O2. The method was tested both indoor and outdoor. The results demonstrate that the detection of H2O2 vapours could allow police forces to locate the site, while terrorists are preparing an attack. The collected data are also very important in developing new sensors, able to give an early alarm if located at a proper distance from a site where an H2O2 based IE is prepared.

16.
Forensic Sci Int ; 265: 116-20, 2016 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-26874736

RESUMO

The diffusion of New Psychoactive Substances (NPS) in the illicit drug market is a worldwide problem. The aim of the study is to describe the qualitative distribution of drugs of abuse in seized materials confiscated in the Italian territory over the last two years. Between 2013 and 2015 162 seizures of substances purchased through the Internet and confiscated by police authorities were analyzed: 35 seizures (22%) were crystals of 3-methylmethcathinone (3-MMC). Although 3-MMC is subject to the relevant legislation in Italy, it is not controlled in other countries such as the Netherlands, from which the shipments originated. 33 seizures (20%) were crystals of 4-methylethcathinone (4-MEC), 19 seizures (12%) were powders containing methylenedioxypyrovalerone (MDPV). N,N-diallyl-5-methoxytryptamine (5-MeO-DALT) was identified in 5 powders, whereas ethylphenidate in six and pyrrolidinophenones in fourteen seized powders: 6 α-PVP (alpha-pyrrolidinovalerophenone), 6 α-PHP (alpha-pyrrolidinohexiophenone) and 1 α-PVT (alpha-pyrrolidinopentiothiophenone). Other substances identified were cathinones such as pentedrone, methylone, buthylone, ethylone, methedrone, 3-CMC (3-chloromethcathinone), 3,4-dimethylmethcathinone (3,4-DMMC), flephedrone (4-fluoromethcathinone or 4-FMC), 2-FMC and 3-FMC (2- and 3-fluoromethcathinone), MPPP (4-methyl-alpha-pyrrolidinopropiophenone), bk-2C-B (2-amino-1-(4-bromo-2,5-dimethoxyphenyl)ethan-1-one). Other compounds were NM2AI (N-methyl-2-aminoindane), MPA (1-(thiophen-2-yl)-2-methylaminopropane), MTTA (mephtetramine), 4-APB and 6-APB (4- and 6- (2-aminopropyl)benzofuran), 2-fluoromethamphetamine, 1mCPP (1-meta-chlorophenylpiperazine) and diphenidine, detected for the first time in Europe. Only three seizures contained synthetic cannabinoids, consisting of herbal blends soaked in N-(1-adamantyl)-1-pentyl-1H-indazole-3-carboxamide (AKB48), or a mixture of 5-F-AKB48 and BB-22 (1-(cyclohexylmethyl)-8-quinolinyl ester-1H-indole-3-carboxylic acid). In some mixtures of drugs - such as granules - 4-MEC and pentedrone were detected, also with traces of diphenidine on one occasion. In other cases 5-MeO-DALT, ethylphenidate and caffeine were mixed together. In one batch, the mixture was flephedrone and methoxethamine, whereas in another one the sample contained methylone, ethylone, methedrone, 4-fluoroamphetamine, 5-MeO-DALT and 5MeO-MiPT (N-methyl-N-isopropyl-5-methoxytryptamine). In 9 seizures, tablets shipped together with NPS were also found to contain sildenafil. The analyses performed on these seizures showed the presence of a wide number of NPS within the Italian boundaries coming from abroad, therefore this study confirms the threat for the public health, especially when the content of NPS being sold is not reported on the label or misleading.


Assuntos
Crime/estatística & dados numéricos , Psicotrópicos/análise , Transtornos Relacionados ao Uso de Substâncias/epidemiologia , Crime/legislação & jurisprudência , Toxicologia Forense , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Itália/epidemiologia , Detecção do Abuso de Substâncias/métodos
17.
Rapid Commun Mass Spectrom ; 29(13): 1196-204, 2015 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-26395784

RESUMO

RATIONALE: We describe the analytical characterization of the designer drug bk-2C-B, a cathinone derivative, contained in a seized tablet, in the absence of an analytical standard. METHODS: The analytical techniques employed include gas chromatography/mass spectrometry (GC/MS), without and with derivatization with 2,2,2-trichloroethyl chloroformate, liquid chromatography/high-resolution-MS (LC/HRMS) with an Orbitrap® analyzer, and nuclear magnetic resonance (NMR). LC/HRMS measurements consisted of accurate mass measurements of MH(+) ionic species under full scan conditions; comparison of experimental and calculated MH(+) isotopic patterns; examination of the isotopic fine structure (IFS) of the M+1, M+2, M+3 isotopic peaks relative to the monoisotopic M+0 peak; study of MH(+) collision-induced dissociation (CID) product ions obtained in fragmentation experiments. RESULTS: GC/MS analysis gave highly informative EI mass spectra, particularly after the derivatization of bk-2C-B with 2,2,2-trichloroethyl chloroformate. The application of LC/HRMS, allowing for accurate mass measurements at 100,000 resolving power, greatly enhanced analytical capabilities in structural characterization of this new designer drug. HRMS allowed us to obtain the accurate mass measurements of bk-2C-B MH(+) ionic species, with a mass accuracy of 2.19 ppm; fully superimposable experimental and calculated MH(+) isotopic patterns, with RIA1 and RIA2 values <4%; the IFS of the M+1, M+2, M+3 isotopic peaks relative to the monoisotopic M+0 peak completely in accordance with theoretical values. These findings enabled us to obtain the elemental composition formula of the seized drug. Furthermore, characteristic MH(+) CID product ions enabled the characterization of the bk-2C-B molecular structure. The presence of (79)Br and (81)Br isotopes in the substance molecule produced a characteristic isotopic pattern in most MS spectra. Lastly, NMR spectra allowed us to obtain useful information about the position of substituents in the designer drug. CONCLUSIONS: The combination of all the analytical techniques employed allowed the characterization of the seized psychoactive substance, in spite of the lack of a reference standard.


Assuntos
Acetofenonas/análise , Drogas Desenhadas/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Espectroscopia de Ressonância Magnética/métodos , Espectrometria de Massas/métodos , Bromo/análise , Cromatografia Líquida/métodos , Isótopos/análise , Fosgênio/análogos & derivados , Fosgênio/química , Comprimidos/análise
18.
Artigo em Inglês | MEDLINE | ID: mdl-26209771

RESUMO

The increasing number of new psychoactive substances (NPS) present in the illicit market render their identification in biological fluids/tissues of great concern for clinical and forensic toxicology. Analytical methods able to detect the huge number of substances that can be used are sought, considering also that many NPS are not detected by the standard immunoassays generally used for routine drug screening. The aim of this work was to develop a method for the screening of different classes of NPS (a total of 78 analytes including cathinones, synthetic cannabinoids, phenethylamines, piperazines, ketamine and analogues, benzofurans, tryptamines) from blood samples. The simultaneous extraction of analytes was performed by Dispersive Liquid/Liquid Microextraction DLLME, a very rapid, cheap and efficient extraction technique that employs microliters amounts of organic solvents. Analyses were performed by a target Ultrahigh Performance Liquid Chromatography tandem Mass Spectrometry (UHPLC-MS/MS) method in multiple reaction monitoring (MRM). The method allowed the detection of the studied analytes with limits of detection (LODs) ranging from 0.2 to 2ng/mL. The proposed DLLME method can be used as an alternative to classical liquid/liquid or solid-phase extraction techniques due to its rapidity, necessity to use only microliters amounts of organic solvents, cheapness, and to its ability to extract simultaneously a huge number of analytes also from different chemical classes. The method was then applied to 60 authentic real samples from forensic cases, demonstrating its suitability for the screening of a wide number of NPS.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Microextração em Fase Líquida/métodos , Psicotrópicos/sangue , Espectrometria de Massas em Tandem/métodos , Humanos , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes
19.
Curr Neuropharmacol ; 13(1): 26-46, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26074742

RESUMO

UNLABELLED: The definition New psychoactive substances (NPS) refers to emerging drugs whose chemical structures are similar to other psychoactive compounds but not identical, representing a "legal" alternative to internationally controlled drugs. There are many categories of NPS, such as synthetic cannabinoids, synthetic cathinones, phenylethylamines, piperazines, ketamine derivatives and tryptamines. Tryptamines are naturally occurring compounds, which can derive from the amino acid tryptophan by several biosynthetic pathways: their structure is a combination of a benzene ring and a pyrrole ring, with the addition of a 2-carbon side chain. Tryptamines include serotonin and melatonin as well as other compounds known for their hallucinogenic properties, such as psilocybin in 'Magic mushrooms' and dimethyltryptamine (DMT) in Ayahuasca brews. AIM: To review the scientific literature regarding tryptamines and their derivatives, providing a summary of all the available information about the structure of these compounds, their effects in relationship with the routes of administration, their pharmacology and toxicity, including articles reporting cases of death related to intake of these substances. METHODS: A comprehensive review of the published scientific literature was performed, using also non peer-reviewed information sources, such as books, government publications and drug user web fora. CONCLUSIONS: Information from Internet and from published scientific literature, organized in the way we proposed in this review, provides an effective tool for specialists facing the emerging NPS threat to public health and public security, including the personnel working in Emergency Department.


Assuntos
Drogas Ilícitas/toxicidade , Psicotrópicos/toxicidade , Transtornos Relacionados ao Uso de Substâncias/epidemiologia , Triptaminas/toxicidade , Drogas Desenhadas , Humanos , Intoxicação/patologia , Relação Estrutura-Atividade , Transtornos Relacionados ao Uso de Substâncias/mortalidade , Triptaminas/química , Triptaminas/classificação
20.
Forensic Sci Int ; 246: 25-30, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25460104

RESUMO

The capability to collect timely information about the substances employed on-site at a crime scene is of fundamental importance during scientific investigations in crimes involving the use of explosives. TNT (2,4,6-trinitrotoluene) is one of the most employed explosives in the 20th century. Despite the growing use of improvised explosives, criminal use and access to TNT is not expected to decrease. Immunoassays are simple and selective analytical tests able to detect molecules and their immunoreactions can occur in portable formats for use on-site. This work demonstrates the application of three immunochemical assays capable of detecting TNT to typical forensic samples from experimental tests: an indirect competitive ELISA with chemiluminescent detection (CL-ELISA), a colorimetric lateral flow immunoassay (LFIA) based on colloidal gold nanoparticles label, and a chemiluminescent-LFIA (CL-LFIA). Under optimised working conditions, the LOD of the colorimetric LFIA and CL-LFIA were 1 µg mL(-1) and 0.05 µg mL(-1), respectively. The total analysis time for LFIAs was 15 min. ELISA proved to be a very effective laboratory approach, showing very good sensitivity (LOD of 0.4 ng mL(-1)) and good reproducibility (CV value about 7%). Samples tested included various materials involved in controlled explosions of improvised explosive devices (IEDs), as well as hand swabs collected after TNT handling tests. In the first group of tests, targets covered with six different materials (metal, plastic, cardboard, carpet fabric, wood and adhesive tape) were fixed on top of wooden poles (180 cm high). Samples of soil from the explosion area and different materials covering the targets were collected after each explosion and analysed. In the second group of tests, hand swabs were collected with and without hand washing after volunteers simulated the manipulation of small charges of TNT. The small amount of solution required for each assay allows for several analyses. Results of immunoassays confirmed that they were suitable to detect post-blast residues in soil and target materials and post transfer residues on hands, allowing further confirmation by more selective techniques. ELISA and LFIAs results obtained from the same solution were consistently in good agreement, and were confirmed by gas chromatography coupled to mass spectrometry (GC-MS). The reported immunoassays data demonstrates the suitability of LFIAs as on-site rapid and effective assays to detect TNT traces. The CL-ELISA proved useful in obtaining very sensitive detection in forensic investigations and testing, while CL-LFIA had performances in between LFIA and CL-ELISA.


Assuntos
Colorimetria , Ensaio de Imunoadsorção Enzimática/métodos , Substâncias Explosivas/análise , Imunoensaio/métodos , Medições Luminescentes/métodos , Trinitrotolueno/análise , Explosões , Ciências Forenses/métodos , Cromatografia Gasosa-Espectrometria de Massas , Mãos , Humanos , Reprodutibilidade dos Testes , Pele/química , Solo/química
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