Mass spectrometry-based untargeted metabolomics approaches for comprehensive structural annotation of bioactive metabolites from bushy cashew (Anacardium humile) fruits

Funding Information: The authors acknowledge financial support from the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for the institutional and financial support. Publisher Copyright: © 2023Peer reviewedPostprin

NBOMe : perfil de apreensões da Polícia Federal no Brasil

A Polícia Federal (PF) possui informações importantes sobre as apreensões de drogas sintéticas no país que podem ser compiladas e organizadas para descrever o panorama atual das designer drugs no Brasil sob a realidade observada pela PF. Trata-se do Sistema Criminalística, um banco de dados nacional com laudos periciais digitalizados. Neste contexto, este estudo teve como objetivo fazer um levantamento estatístico do perfil de apreensão das drogas sintéticas que contém NBOMe - grupo derivado da feniletilamina com propriedades alucinógenas - seus sais e isômeros, através da análise dos dados contidos nos relatórios periciais emitidos pela Polícia Federal no Brasil nos últimos 5 anos. As seguintes informações foram coletadas: número de laudos, local das apreensões, local de elaboração dos laudos, formas de apresentação, principais drogas apreendidas em conjunto com NBOMe e suas respectivas formas de apresentação, classificação química do NBOMe - de acordo com substituintes - quantidade de unidades apreendidas e principais imagens visualizadas nos materiais apreendidos pelos agentes federais. Foi possível traçar um panorama da situação nacional atual, sob a ótica da PF, sobre drogas sintéticas para o aprofundamento da visão, especialmente em produtos que contenham NBOMe, seus sais e isômeros. Os dados aqui apresentados se destinam a apoiar as políticas de planejamento de ações estratégicas para o controle, supressão e prevenção de uso de drogas e tráfico

Radical Scavenger Capacity of Jabuticaba Fruit ( Myrciaria cauliflora

Jabuticaba is an exotic fruit native to Brazil that has been arousing medicinal interest. Using chemical (HPLC-PDA, resonance mass spectra, and NMR), electroanalytical (differential pulse voltammetry, radical scavenging assay), and pharmacological (in vivo and in vitro) approaches, we have identified its bioactive compounds and hypotensive effects on hypertensive rats. The hydroalcoholic extract of jabuticaba (HEJ) presents a great quantity of phenolic compounds, and several molecules with hydroxyl groups present high efficiency as an antioxidant. The treatment with HEJ (100 and 300 mg/kg/day, for four weeks) presented hypotensive effects on L-NAME-induced hypertensive rats, possibly improving the nitric oxide bioavailability because of its high antioxidant potential. Furthermore, renal and cardiac hypertrophies were also attenuated after the HEJ treatment. Moreover, the vascular responses to contractile and dilating agonists were improved with the HEJ treatment, which is also able to induce nitric oxide production in endothelial cells

Síntese e avaliação da atividade citotóxica de derivados do eugenol contendo núcleos 1,2,3-triazólicos

Eugenol is an aromatic compound found in several plant species. It presents important biological activities including cytotoxicity. In this paper, it is described the synthesis and the evaluation of the cytotoxic activity of eugenol derivatives bearing 1,2,3-triazole functionalities. Eugenol, extracted via hydrodistillation from dried flower buds of Eugenia caryophyllata (=Syzygium aromaticum), was submitted to alkylation reactions to afford two terminal alkynes in good yields. The key reaction involved in the preparation of eugenol derivatives corresponded to the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC), between alkynylated eugenol derivatives and different benzyl azides. The evaluation of the cytotoxicity of twenty seven synthesized derivatives against HL60 leukemia cell line revealed that at 100 µmol L-1, five of them, namely 4-((4-allyl-2-methoxyphenoxy)methyl)-1-(3-bromobenzyl)-1H-1,2,3-triazole (6n), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-benzyl-1H-1,2,3-triazole (7a), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(4-chlorobenzyl)-1H-1,2,3-triazole (7c), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(4-iodobenzyl)-1H-1,2,3-triazole (7e) and 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(3-bromobenzyl)-1H-1,2,3-triazole (7m), were capable of significantly decreasing cell viability. These most active triazolic derivatives were also evaluated against B16F10 melanoma and Nalm6 leukemia cell lines. While only compound 7a was active against the former, compounds 6n, 7a, and 7m displayed activity against the latter. Derivative 7a was active against all cell lines. It is believed that eugenol derivatives bearing triazole functionalities may represent a scaffold to be explored toward the development of new agents against cancer

Paper Spray Ionization Mass Spectrometry as a Potential Tool for Early Diagnosis of Cervical Cancer

Squamous intraepithelial lesion is an abnormal growth of epithelial cells on the surface of the cervix that may lead to cervical cancer. Analytical protocols for the determination of squamous intraepithelial lesions are in high demand, since cervical cancer is the fourth most diagnosed cancer among women in the world. Here, paper spray ionization mass spectrometry (PSI-MS) is used to distinguish between healthy (negative for intraepithelial lesion or malignancy) and diseased (high-grade squamous intraepithelial lesion) blood plasmas. A total of 86 blood samples of different women (49 healthy samples, 37 diseased samples) were collected, and the plasmas were prepared. Then, 10 μL of each plasma sample was deposited onto triangular papers for PSI-MS analysis. No additional step of sample preparation was necessary. The interval-successive projection algorithm linear discriminant analysis (iSPA-LDA) was applied to the PSI mass spectra, showing six ions (mostly phospholipids) that were predictive of healthy and diseased plasmas. Values of 77% accuracy, 86% sensitivity, 80% positive predictive value (PPV), and 75% negative predictive value (NPV) were achieved. This study provides evidence that PSI-MS may potentially be used as a fast and simple analytical technique for the early diagnosis of cervical cancer

Petroleomics by FT-ICR MS : revealing the polar composition of crude oil and its derivates

Orientador: Marcos Nogueira EberlinTese (doutorado) - Universidade Estadual de Campinas, Instituto de QuímicaResumo: A ionização por eletrospray (ESI) acoplada com a espectrometria de massas de ressonância ciclotrônica de íons por transformada de Fourrier (FT-ICR MS) permite a detecção de milhares de compostos polares (N, S e O) no petróleo e seus derivados, sem separação cromatográfica. ¿Petroleômica¿ é, portanto, a caracterização do petróleo a nível molecular. Neste trabalho, petróleos de diferentes níveis de evolução térmica, amostras de diesel obtidas por processos diferentes (hidrotratamento e oxitratamento) e cortes de destilação obtidos da destilação molecular de resíduo de petróleo foram analisados usando esta técnica. A primeira parte do trabalho consistiu na análise de petróleos com diferentes níveis de evolução térmica. Com o aumento do estresse térmico, observou-se um aumento da condensação, da aromatização de estruturas cíclicas polares e uma diminuição do número de carbono das classes de compostos identificadas. A intensidade relativa dos compostos pirrólicos foi usada para agrupar os óleos de mesmo nível de evolução térmica usando Análise dos Componentes Principais (PCA), que mostrou bastante eficiente. Na segunda parte, a análise de amostras de diesel obtidas por condições operacionais diferentes (temperatura, pressão e velocidade espacial) do hidrotratamento e pelo processo de oxitratamento, mostrou a produção, respectivamente, de espécies de baixo valores de DBE (do inglês Double Bond Equivalent), devido a hidrogenação dos anéis aromáticos presentes nos compostos polares, e uma variedade de classes contendo mais que um heteroatômo, como Ox ,NOx and SOx, devido a oxidação química dos hidrocarbonetos e compostos polares. A última parte consistiu na análise dos cortes de destilação. Evidenciaram-se com a caracterização de cada corte de destilação as tendências composicionais com aumento da temperatura de destilação. O peso molecular, aromaticidade, o conteúdo de heteroátomos e a distribuição do número de carbono aumentaram proporcionalmente a temperatura de destilação. Os resultados mostraram que é possível a partir dos milhares de compostos, identificados rotineiramente por FT-ICR MS, predizer as propriedades do petróleo e seus derivados, como também na otimização de processos como aqueles que reduzem o nível dos compostos NOSAbstract: Electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) allows the direct detection of thousands of polar compounds (N, S and O) in petroleum and its derivatives, without chromatographic separation. ''Petroleomics¿¿ is therefore the characterization of petroleum at the molecular level. In this work, oils from different levels of thermal maturity, diesel fuel obtained by different processes (hydrotreatment and oxitreatment) and distillate cuts obtained from molecular distillation of petroleum residue were analyzed using this technique. The first part of this study consisted in the analysis of oils of different levels of thermal maturity. With increasing thermal stress, condensation and aromatization of the polar cores increase, and the number of alkyl carbons decreases. The relative intensity of the pyrrolic compounds were used for grouping the oils with same level of thermal maturity by Principal Analysis Components (PCA), that shown to be quite efficient. In a second step, the analysis of different diesel fuel oil samples, obtained from different operational conditions (temperature, pressure and liquid hourly space velocity) of hydrotreatment and by oxitreatment process, showed the production, respectively, of lower DBE (Double Bond Equivalent) species, due the hydrogenation of the aromatic rings present in the polar compounds, and a variety of classes containing more than one heteroatom, such as Ox ,NOx and SOx, due the chemical oxidation of hydrocarbons and heteroatom compounds present in these fuel. The last stage consisted in the analysis of distillate cuts. Each distillate cut was characterized to mark compositional trends with increased distillation temperature. The molecular weight, aromaticity, heteroatom content and carbon number distribution increase proportionately with the temperature. The results show that it is possible from the thousands compounds, identified routinely by FTICR MS analysis, predict the properties of petroleum and its derivatives, as well help improve processes such that used for reduce the level of NSO compoundsDoutoradoQuimica OrganicaDoutor em Ciência

Mechanistic insights of organic reactions catalyzed by palladium : Heck, oxa-Heck and Buchwald-Hartwig coupling by ESI-MS/MS

Orientador: Marcos Nogueira EberlinDissertação (mestrado)- Universidade Estadual de Campinas, Instituto de QuimicaResumo: A espectrometria de Massas por eletronspray (ESI-MS) tornou-se um método prático para o estudo de mecanismos reacionais em solução. Neste trabalho importantes reações catalisadas por paládio: reação de Heck-Mizoroki, oxa-Heck e o acoplamento de Buchwald-Hartwig foram monitoradas por ESI-MS visando interceptar espécies que comprovam as atuais propostas mecanísticas ou que abram caminho para novas propostas para estas reações. O monitoramento das reações foi realizado no modo off-line, acompanhamento da reação em intervalos pré-definidos de tempo, no qual alíquotas das soluções reacionais foram retiradas e diluídas em solventes apropriados e injetados por infusão direta no QTOF. Importantes intermediários reacionais destas reações foram interceptados por ESI-MS e caracterizados por ESI-MS/MS, o que possibilitou confirmar as espécies catalíticas responsáveis pela formação da ligação carbono-carbono na reação de Heck-Mizoroki, os principais intermediários para proposta mecanística desta reação e as atuais propostas da reação oxa-Heck e do acoplamento de Buchwald-Hartwig. No caso da reação oxa-Heck, os paladaciclos interceptados são os primeiros indícios experimentais para atual proposta mecanística desta interessante transformaçãoAbstract: Eletronspray ionization mass spectrometry (ESI-MS) has become a practical tool to study reaction mechanisms in solution. In this work important reactions catalyzed by palladium: Heck-Mizoroki reaction, oxa-Heck reaction and Buchwald-Hartwig coupling were monitored by ESI-MS to intercept transient intermediates that show the current mechanistic proposals or to open the way for new proposals for these reactions. These reaction was monitored in offline mode, whereas aliquots of the reaction solutions were withdrawn and diluted in appropriate solvents and injected by direct infusion at the Q-TOF in pre-defined intervals of time. Important intermediates from these reactions were intercepted by ESI-MS and characterized by its tandem version ESI-MS/MS, which allowed confirming the catalytic species responsible for the formation of carbon-carbon bond in the Heck-Mizoroki reaction, the main intermediaries mechanistic proposal from this reaction and the current proposals of oxa-Heck reaction and the Buchwald-Hartwig coupling. In oxa-Heck reaction, the intercepted palladacycles are the first experimental evidence for this current mechanistic proposal for this interesting transformationMestradoQuimica OrganicaMestre em Químic

Characterization and differentiation of ballpoint pen ink strokes on paper using orbitrap mass spectrometry and multivariate statistic

In criminal expertise routine, the expert is confronted by the challenge of detecting fraud in several important documents. One kind of forgery is the change of a document date of emission by one type of fraud is the adulteration of the date of emission of a document through the erasure and addition of another date with ballpoint pen of color similar to original. The forgery can be detected by characterization of colorant substances of each ink formulation. This could be done by using Orbitrap mass spectrometry. This study performed analysis in ESI-Orbitrap mass spectrometer to obtain the colorants and additives pattern of each brand of blue and black ballpoint pen tested, and after differentiated the pens by multivariate statistic (PCA and HCA). The analysis of ballpoint pen samples in a Q-Exactive® Orbitrap mass analyser was able to differentiate the samples, even for inks of very similar color, and the method proved to be very sensitive. The exact mass spectra were submitted to multivariate statistical analysis and the Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) was able to characterize the variables that were responsible for the variation and similarity of the samples. The HCA and PCA were able to group pens from the same brand and also to approximate pens of different brands but similar formulations. At the same time, multivariate analysis could identify pens that were very dissimilar from the others