Ambient mass spectrometry application in forensic chemistry : identification of markers for ANFO explosive detection and characterization of inorganic oxidizing agents

Orientador: Marcos Nogueira EberlinDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de QuímicaResumo: Os estudos com explosivos, de modo geral, tem se intensificado nos últimos anos devido ao grande interesse que esta classe representa na área forense. No entanto, ainda são poucos os trabalhos que se dedicam ao estudo de caracterização e detecção de resíduos de explosivos inorgânicos. Este tipo de explosivo se caracteriza pela presença de um agente oxidante inorgânico - geralmente um sal - e, devido à grande facilidade de obtenção destes materiais comercialmente - já que são substâncias sem controle legal - seu uso em ações criminosas é cada vez mais intenso. Como exemplo podemos citar o explosivo ANFO (ammonium nitrate fuel oil), o mais utilizado em pedreiras e na construção civil no Brasil, assim como nos crimes de explosão de caixas eletrônicos. Considerando este contexto, foram avaliadas amostras de explosivo ANFO padrão para gerar perfis característicos por espectrometria de massas com ionização por eletrospray (ESI(±)-MS). Ambos os modos foram caracterizados também por espectrometria de massas de alta resolução a fim de se obter mais informações a respeito das classes de compostos. Após a elucidação dos possíveis marcadores, a técnica EASI (easy ambient sonic-spray ionization) foi aplicada no modo negativo, inclusive em amostras reais de perícia, na tentativa de identificar resíduos de ANFO em notas de real verdadeiras. Por fim, alguns agentes oxidantes inorgânicos ¿ mais especificamente da classe dos nitratos - comumente utilizados em formulações caseiras foram caracterizados por espectrometria de massas ambiente a fim de verificar o perfil apresentado conjuntamente com a elucidação das fórmulas moleculares por espectrometria de massas de alta resolução no modo negativoAbstract: Research on explosive compounds has intensified over the last years due to the great importance of this area to forensic science. Despite this, few are the works related to the characterization and detection of inorganic explosive residues. This kind of explosive has an inorganic oxidizing agent as the main component - generally a salt ¿ and due to the ease of being commercially available ¿ once they have no legal restrictions ¿ its use on criminal actions has been increasing. The most used inorganic explosive in the world ¿ as well as in Brazil ¿ is ANFO (ammonium nitrate fuel oil), applied for civil construction and quarrying and also for a recent form of crime: the explosion of automated teller machines. Against this background, samples of commercial ANFO were analyzed using electrospray mass spectrometry (ESI(±)-MS) in order to obtain characteristic profiles. High resolution mass spectrometry (HR-MS) was applied for molecular composition elucidation. Once the possible markers were selected, easy ambient sonic-spray ionization (EASI-MS) set for negative mode analysis was used for identification of ANFO residues on Brazilian real bills, including on a sample collected from a real crime scene. Finally, the profile of inorganic oxidizing agents ¿ more specifically nitrate salts ¿ commonly employed on homemade explosive formulations was obtained via EASI-MS with later molecular elucidation with HR-MSMestradoQuimica AnaliticaMestre em Químic

Metabolic Signature of Arrhythmogenic Cardiomyopathy

Arrhythmogenic cardiomyopathy (ACM) is a genetic-based cardiac disease accompanied by severe ventricular arrhythmias and a progressive substitution of the myocardium with fibro-fatty tissue. ACM is often associated with sudden cardiac death. Due to the reduced penetrance and variable expressivity, the presence of a genetic defect is not conclusive, thus complicating the diagnosis of ACM. Recent studies on human induced pluripotent stem cells-derived cardiomyocytes (hiPSC-CMs) obtained from ACM individuals showed a dysregulated metabolic status, leading to the hypothesis that ACM pathology is characterized by an impairment in the energy metabolism. However, despite efforts having been made for the identification of ACM specific biomarkers, there is still a substantial lack of information regarding the whole metabolomic profile of ACM patients. The aim of the present study was to investigate the metabolic profiles of ACM patients compared to healthy controls (CTRLs). The targeted Biocrates AbsoluteIDQ® p180 assay was used on plasma samples. Our analysis showed that ACM patients have a different metabolome compared to CTRLs, and that the pathways mainly affected include tryptophan metabolism, arginine and proline metabolism and beta oxidation of fatty acids. Altogether, our data indicated that the plasma metabolomes of arrhythmogenic cardiomyopathy patients show signs of endothelium damage and impaired nitric oxide (NO), fat, and energy metabolism

Characterization Of Anfo Explosive By High Accuracy Esi(+/-)-ftms With Forensic Identification On Real Samples By Easi(-)-ms

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Ammonium nitrate fuel oil (ANFO) is an explosive used in many civil applications. In Brazil, ANFO has unfortunately also been used in criminal attacks, mainly in automated teller machine (ATM) explosions. In this paper, we describe a detailed characterization of the ANFO composition and its two main constituents (diesel and a nitrate explosive) using high resolution and accuracy mass spectrometry performed on an FT-ICR-mass spectrometer with electrospray ionization (ESI(+/-)-FTMS) in both the positive and negative ion modes. Via ESI(-)-MS, an ion marker for ANFO was characterized. Using a direct and simple ambient desorption/ionization technique, i.e., easy ambient sonic-spray ionization mass spectrometry (EASI-MS), in a simpler, lower accuracy but robust single quadrupole mass spectrometer, the ANFO ion marker was directly detected from the surface of banknotes collected from ATM explosion theft. (C) 2015 Elsevier Ireland Ltd. All rights reserved.249156164Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CAPES [23038.006844/2014-46

Forensic application of X-ray fluorescence spectroscopy for the discrimination of authentic and counterfeit revenue stamps

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Energy-dispersive X-ray fluorescence (ED-XRF) spectroscopy with data treatment via chemometric tools was explored as an analytical protocol to discriminate between authentic and counterfeit revenue stamps. Untreated samples were directly analyzed, and the discrimination was based on the characterization of constituent elements present in the inks and paper. Authentic samples and samples that were suspected of being counterfeit were analyzed at three different areas on their surfaces: the ink-printed area, the non-printed area, and the holographic area. Principal component analysis (PCA) was applied to the data to discriminate between authentic and counterfeit revenue stamps. Major differences in the elemental composition were noted (according to chemometrics and t-test, p < 0.05), and ED-XRF spectroscopy plus PCA protocol is proposed for use by non-specialist operators to screen for counterfeit stamps.Energy-dispersive X-ray fluorescence (ED-XRF) spectroscopy with data treatment via chemometric tools was explored as an analytical protocol to discriminate between authentic and counterfeit revenue stamps. Untreated samples were directly analyzed, and the701119101915CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)23038.006844/2014-46This work was supported by CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (grant number 23038.006844/2014-46

Ayahuasca and Kambo intoxication after alternative natural therapy for depression, confirmed by mass spectrometry

CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOWe present a case report about an acute intoxication episode after an oral administration of Ayahuasca and dermal exposure of Kambo for treatment of depression. The clinical features observed were hallucination, agitation, tremors of extremities, oral par36212221CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO23038.006844/2014-46830525/1999-82015/10650-82016/23157-

Characterization Of Anfo Explosive By High Accuracy Esi(±)-ftms With Forensic Identification On Real Samples By Easi(-)-ms.

Ammonium nitrate fuel oil (ANFO) is an explosive used in many civil applications. In Brazil, ANFO has unfortunately also been used in criminal attacks, mainly in automated teller machine (ATM) explosions. In this paper, we describe a detailed characterization of the ANFO composition and its two main constituents (diesel and a nitrate explosive) using high resolution and accuracy mass spectrometry performed on an FT-ICR-mass spectrometer with electrospray ionization (ESI(±)-FTMS) in both the positive and negative ion modes. Via ESI(-)-MS, an ion marker for ANFO was characterized. Using a direct and simple ambient desorption/ionization technique, i.e., easy ambient sonic-spray ionization mass spectrometry (EASI-MS), in a simpler, lower accuracy but robust single quadrupole mass spectrometer, the ANFO ion marker was directly detected from the surface of banknotes collected from ATM explosion theft.249C156-16