Molybdenum(ii) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study.

New complexes [Mo(η3-C3H5)X(CO)2(4-Y-BIAN)] (4-Y-BIAN = bis(4-Y-phenyl)-acenaphthenequinonediimine), with X = Br and Y = H, Me, OMe, COOH and X = Cl, Y = OMe, as well as the cation with X = NCMe and Y = OMe were synthesized, expanding the scope of this family. Two single crystal X-ray structures (X = Br, Y = Me, OMe) display a less symmetric arrangement (axial isomer), where one N donor atom is trans to the allyl group and the second to one CO. DFT studies showed similar energies for the two possible isomers of the complexes, with a very small preference for the observed axial isomer. The HOMO of the complexes is localized in the metal and the HOMO-1 of the oxidized species has a contribution from the BIAN ligand, while the LUMO is fully localized in BIAN. Electrochemical studies showed one process corresponding to the oxidation of Mo(ii) to Mo(iii) for complexes with X = Br, Y = H, Me, and two oxidation reactions for those with X = Br, Y = Cl, OMe, while the COOH derivative exhibited no oxidation wave. The antitumor effect of the complexes with X = Br was tested in cancer lines, and the H and OMe complexes were particularly active, with EC50 values below 8 µM in HeLa cell lines. The DNA binding constants determined by titration experiments were comparable with those of doxorubicin and ethidium bromide, suggesting a mechanism of action based on intercalation in DNA.

New Molybdenum(II) Complexes with α-Diimine Ligands: Synthesis, Structure, and Catalytic Activity in Olefin Epoxidation.

Three new complexes [Mo(η³-C3H5)Br(CO)2{iPrN=C(R)C5H4N}], where R = H (IMP = N-isopropyl 2-iminomethylpyridine), Me, and Ph, were synthesized and characterized, and were fluxional in solution. The most interesting feature was the presence, in the crystal structure of the IMP derivative, of the two main isomers (allyl and carbonyls exo), namely the equatorial isomer with the Br trans to the allyl and the equatorial with the Br trans to one carbonyl, the position trans to the allyl being occupied by the imine nitrogen atom. For the R = Me complex, the less common axial isomer was observed in the crystal. These complexes were immobilized in MCM-41 (MCM), following functionalization of the diimine ligands with Si(OEt)3, in order to study the catalytic activity in olefin epoxidation of similar complexes as homogeneous and heterogeneous catalysts. FTIR, 13C- and 29Si-NMR, elemental analysis, and adsorption isotherms showed that the complexes were covalently bound to the MCM walls. The epoxidation activity was very good in both catalysts for the cis-cyclooctene and cis-hex-3-en-1-ol, but modest for the other substrates tested, and no relevant differences were found between the complexes and the Mo-containing materials as catalysts.

Modos de viver e fazer arte de pessoas em situação de rua / Ways of living and making art of people in homeless situation / Modos de vida y arte de personas que viven en las calles

Resumo Este é um estudo acerca da arte de viver das pessoas em situação de rua. Trata-se de um recorte de uma pesquisa-intervenção realizada por meio de cartografias nômades, objetivando analisar processos de subjetivação em saúde mental que se configuram na produção desse modo de existência. Utiliza-se observação participante e diário de rua para a produção de dados, compondo, pesquisadores e sujeitos, as paisagens psicossociais para tensionar os dispositivos da rede de atenção psicossocial. Conclui-se que a vivência em situação de rua é um modo de fazer arte, ainda quando não se trata de resistência política ativa, haja vista a capacidade de sobrevir em extrema condição de vulnerabilidade social.(AU)

Abstract This is a study about the art of living of the people in homeless situation. It is part of a research-intervention done through the nomads' cartography method, aiming to analyze the subjective processes in mental health that are configured in the production of this way of existence. It used participant and daily observation and street notes to the production of data, composing, researchers and subjects, psychosocial landscapes to tension the psychosocial care network devices. In conclusion, the experience of living on the streets is a way of making art, even when it is not active political resistance, given their ability to survive in extreme condition of social vulnerability.(AU)

Resumen Este es un estudio sobre el arte de vivir de personas en la calle. Se trata de una investigación realizada por medio de cartografías nómadas, cuyo objetivo es analizar los procesos subjetivación en salud mental que se configuran en la producción de este modo de existencia. Se utiliza la observación participativa y el diario de calle, componiendo, investigadores y sujetos, los paisajes psicosociales para la producción de datos y para activar los dispositivos de la red de atención psicosocial. Se concluye que la vivencia en la calle es un modo de hacer arte, aun cuando no se trate de resistencia política activa, haya vista la capacidad de supervivencia en extrema condición de vulnerabilidad social.(AU)

Modos de viver e fazer arte de pessoas em situação de rua / Ways of living and making art of people in homeless situation / Modos de vida y arte de personas que viven en las calles

Resumo Este é um estudo acerca da arte de viver das pessoas em situação de rua. Trata-se de um recorte de uma pesquisa-intervenção realizada por meio de cartografias nômades, objetivando analisar processos de subjetivação em saúde mental que se configuram na produção desse modo de existência. Utiliza-se observação participante e diário de rua para a produção de dados, compondo, pesquisadores e sujeitos, as paisagens psicossociais para tensionar os dispositivos da rede de atenção psicossocial. Conclui-se que a vivência em situação de rua é um modo de fazer arte, ainda quando não se trata de resistência política ativa, haja vista a capacidade de sobrevir em extrema condição de vulnerabilidade social.

Abstract This is a study about the art of living of the people in homeless situation. It is part of a research-intervention done through the nomads' cartography method, aiming to analyze the subjective processes in mental health that are configured in the production of this way of existence. It used participant and daily observation and street notes to the production of data, composing, researchers and subjects, psychosocial landscapes to tension the psychosocial care network devices. In conclusion, the experience of living on the streets is a way of making art, even when it is not active political resistance, given their ability to survive in extreme condition of social vulnerability.

Resumen Este es un estudio sobre el arte de vivir de personas en la calle. Se trata de una investigación realizada por medio de cartografías nómadas, cuyo objetivo es analizar los procesos subjetivación en salud mental que se configuran en la producción de este modo de existencia. Se utiliza la observación participativa y el diario de calle, componiendo, investigadores y sujetos, los paisajes psicosociales para la producción de datos y para activar los dispositivos de la red de atención psicosocial. Se concluye que la vivencia en la calle es un modo de hacer arte, aun cuando no se trate de resistencia política activa, haya vista la capacidad de supervivencia en extrema condición de vulnerabilidad social.

Psoriasis and metabolic syndrome.

Psoriasis is a chronic, systemic inflammatory disease associated with several cardiometabolic comorbidities, such as obesity, insulin resistance, dyslipidemia, and hypertension, and with clinically significant increased risk of cardiovascular disease and cardiovascular mortality. These comorbidities are components of the metabolic syndrome. Multiple epidemiologic studies have revealed a high prevalence of metabolic syndrome in patients with psoriasis compared with other skin diseases. Genetic susceptibility and overlapping inflammatory pathways may be potential biologic links underlying this association. Understanding the interrelationship between these conditions is important for the management of psoriasis and its associated comorbidities. This review will focus on the range of these comorbidities, with emphasis on the metabolic syndrome, aiming to encourage physicians to screen patients with psoriasis for cardiometabolic disorders and risk factors.

[Psoriasis and cardiovascular disease]. / Psoríase e doença cardiovascular.

Psoriasis is a common, chronic and systemic inflammatory disease associated with several comorbidities, such as obesity, hypertension, diabetes, dyslipidaemia and metabolic syndrome, but also with an increased risk of cardiovascular disease, like myocardial infarction or stroke. The chronic inflammatory nature of psoriasis has been suggested to be a contributing and potentially independent risk factor for the development of cardiovascular comorbidities and precocious atherosclerosis. Aiming at alerting clinicians to the need of screening and monitoring cardiovascular diseases and its risk factors in psoriatic patients, this review will focus on the range of cardiometabolic comorbidities and increased risk of cardiovascular disease associated with psoriasis.

A psoríase é uma doença inflamatória sistémica crónica, frequente, associada a várias comorbilidades, destacando-se a obesidade, a hipertensão arterial, a diabetes, a dislipidemia e síndrome metabólico. Adicionalmente associa-se também a aumento do risco de doença cardiovascular ­ enfarte agudo do miocárdio e acidente vascular cerebral. A inflamação sistémica crónica presente na psoríase tem sido sugerida como um factor de risco independente para estas comorbilidades e para o aparecimento de aterosclerose precoce. Esta revisão das várias comorbilidades cardio-metabólicas e do risco de doença cardiovascular associado à psoríase tem como objectivopromover o conhecimento e alertar os clínicos para a necessidade de rastreio, monitorização e tratamento dos factores de risco de doença cardiovascular nestes doentes.

Framingham Risk Score underestimates cardiovascular disease risk in severe psoriatic patients: implications in cardiovascular risk factors management and primary prevention of cardiovascular disease.

Severe psoriasis has been associated with increase cardiovascular mortality, due to a higher prevalence of traditional cardiovascular risk factors and premature atherosclerosis, as a consequence of its systemic inflammation. Recently, it has been estimated that severe psoriasis may confer an increased 6.2% on long-term risk of cardiovascular disease based on Framingham Risk Score, which can have practical implications in the treatment of cardiovascular risk factors and primary prevention of cardiovascular disease, as treatment guidelines account for the risk of cardiovascular disease in treatment goals. The aim of this study was to analyze the influence of the attributable risk of severe psoriasis on long-term risk of cardiovascular disease and its implication on the correct treatment of cardiovascular risk factors and primary prevention of cardiovascular disease on a real-world cohort of patients. One hundred severe psoriasis patients without psoriatic arthritis or previous cardiovascular disease were evaluated and it was found that more than half of the patients were reclassified to a higher cardiovascular risk category with important clinical implications on the correct management of their cardiovascular risk factors and primary prevention of cardiovascular disease, as a considerable proportion of patients with hypertension, hypercholesterolemia and coronary heart disease equivalent risk were not being correctly managed.