The challenge of C-H activation in organic synthesis

This review aims at to the presentation and discussion of the principal aspects of the C-H activation by transition metals. Representative examples were selected from the recent literature to illustrate these principles beginning with somewhat simple examples and moving up to more complex ones. The synthetic potential of the C-H activation, as well as the potential advantages and disadvantages of the methodology are highlighted with relevant recent examples, along with brief insights on the mechanism aspects of these reactions.1779179

O desafio da ativação das ligações C-H em síntese orgânica

This review aims at to the presentation and discussion of the principal aspects of the C-H activation by transition metals. Representative examples were selected from the recent literature to illustrate these principles beginning with somewhat simple examples and moving up to more complex ones. The synthetic potential of the C-H activation, as well as the potential advantages and disadvantages of the methodology are highlighted with relevant recent examples, along with brief insights on the mechanism aspects of these reactions

Pandemia de Influenza A (N1H1): O Que Aprender com Ela?

Influenza pandemics are natural events that occur periodically. The pandemic’s current agent, Influenza virus A (H1N1) was first identified in Mexico in April 2009, spread rapidly and has caused deaths mainly among young adults. The objective of this manuscript is to present the biological aspects involved in the outbreak of this pandemic, as well as population-control strategies for pandemic influenza. In addition to the population mitigation measures, whose efficacy has been described by theoretical models, today we also have drugs with efficacy valued in some patient groups. These drugs reduce moderately the duration and severity of symptoms, as long as they are started early. This pandemic, with a large number of cases, but caused by a virus of low lethality, could be managed preferably in Units of Primary Health Care, that would treat the wild cases and forward the severe ones to the hospitals. However, what occurred in numerous cities was the burden on emergency care with triage situations, forcing managers to improvise field hospitals, tents and containers to house the extra work in services that were already at the limit of physical infrastructure and human resources. Pandemic Influenza exposed the fragility of our network of primary care and lack of ICU beds.Pandemias de gripe são eventos naturais que ocorrem periodicamente. O agente da pandemia atual, o vírus Influenza A (H1N1), foi identificado primeiramente no México em abril de 2009, disseminou-se rapidamente e tem causado óbitos principalmente entre adultos jovens. O objetivo deste manuscrito é apresentar os aspectos biológicos envolvidos na eclosão desta pandemia, bem como as estratégias de contenção populacional da pandemia de Influenza. Além das medidas populacionais, cuja eficácia tem sido descrita através de modelos teóricos, atualmente também dispomos de medicamentos com eficácia avaliada em alguns grupos de pacientes. Estes medicamentos reduzem moderadamente o tempo de duração e a gravidade dos sintomas, desde que iniciados precocemente. Esta pandemia, com um grande número de casos, mas causada por um vírus de baixa letalidade, poderia ser manejada preferentemente em Unidades de Atenção Primária à Saúde, que tratariam os casos leves e encaminhariam os graves aos hospitais. Contudo, o que ocorreu em inúmeras cidades foi a sobrecarga das emergências com situações de triagem, forçando os gestores a improvisar hospitais de campanha, containeres e tendas para abrigar o trabalho extra em serviços que já operavam no limite de estrutura física e de recursos humanos. A pandemia de Influenza expôs a fragilidade da nossa rede de atenção básica e a falta de leitos de UTI

Alkaloids with Activity against the Zika Virus Vector Aedes aegypti (L.)—Crinsarnine and Sarniensinol, Two New Crinine and Mesembrine Type Alkaloids Isolated from the South African Plant Nerine sarniensis

Two new Amaryllidaceae alkaloids, belonging to the mesembrine- and crinine-types, named crinsarnine (1) and sarniensinol (2), were isolated from the dried bulbs of Nerine sarniensis together with bowdensine (3), sarniensine (4), hippadine (5) and 1-O-acetyl-lycorine (6). Crinsarnine (1) and sarniensinol (2) were characterized using spectroscopic and chiroptical methods as (1S,2S,4aR,10bS)-2,7-dimethoxy-1,2,3,4,4a,6-hexahydro-5,11b-ethano[1,3]dioxolo-[4,5-j]phenanthridin- 1-yl acetate and (6-(3aR,4Z,6S,7aS)-6-methoxy-1-methyl-2,3,3a,6,7,7a-hexa-hydro-1H-indol-3a-yl)benzo [d][1,3]dioxol-5-yl)methanol, respectively. Furthermore, the complete spectroscopic characterization of bowdensine (3) is reported for the first time. Compounds 1–6 were evaluated against the Orlando reference strain of Aedes aegypti. None of compounds showed mortality against 1st instar Ae. aegypti larvae at the concentrations tested. In adult topical bioassays, only 1 displayed adulticidal activity with an LD50 = 2.29 ± 0.049 μg/mosquito. As regards the structure-activity relationship, the pretazettine and crinine scaffold in 2 and 4 and in 1 and 3 respectively, proved to be important for their activity, while the pyrrole[de]phenanthridine scaffold present in 5 and 6 was important for their reactivity. Among the pretazettine group compounds, opening of the B ring or the presence of a B ring lactone as well as the trans-stereochemistry of the A/B ring junction, appears to be important for activity, while in crinine-type alkaloids, the substituent at C-2 seems to play a role in their activity

Regioselective protein oxidative cleavage enabled by enzyme-like recognition of an inorganic metal oxo cluster ligand

Oxidative modifications of proteins are key to many applications in biotechnology. Metal-catalyzed oxidation reactions efficiently oxidize proteins but with low selectivity, and are highly dependent on the protein surface residues to direct the reaction. Herein, we demonstrate that discrete inorganic ligands such as polyoxometalates enable an efficient and selective protein oxidative cleavage. In the presence of ascorbate (1 mM), the Cu-substituted polyoxometalate K8[Cu2+(H2O)(α2-P2W17O61)], (CuIIWD, 0.05 mM) selectively cleave hen egg white lysozyme under physiological conditions (pH =7.5, 37 °C) producing only four bands in the gel electropherogram (12.7, 11, 10, and 5 kDa). Liquid chromatography/mass spectrometry analysis reveals a regioselective cleavage in the vicinity of crystallographic CuIIWD/lysozyme interaction sites. Mechanistically, polyoxometalate is critical to position the Cu at the protein surface and limit the generation of oxidative species to the proximity of binding sites. Ultimately, this study outlines the potential of discrete, designable metal oxo clusters as catalysts for the selective modification of proteins through radical mechanisms under non-denaturing conditions

Information perception, wishes, and satisfaction in ambulatory cancer patients under active treatment: Patient-reported outcomes with QLQ-INFO25

Background: Information is vital to cancer patients. Physician-patient communication in oncology presents specific challenges. The aim of this study was to evaluate self-reported information of cancer patients in ambulatory care at a comprehensive cancer centre and examine its possible association with patients' demographic and clinical characteristics. Patients and methods: This study included adult patients with solid tumours undergoing chemotherapy at the Institute Jules Bordet's Day Hospital over a ten-day period. EORTC QLQ-C30 and QLQ-INFO25 questionnaires were administered. Demographic and clinical data were collected. Descriptive and inferential statistics were used. Results: 101 (99%) fully completed the questionnaires. They were mostly Belgian (74.3%), female (78.2%), with a mean age of 56.9 ± 12.8 years. The most frequent tumour was breast cancer (58.4%). Patients were well-informed about the disease and treatments, but presented unmet information domains. The Jules Bordet patients desired more information on treatment side effects, long-term outcome, nutrition, and recurrence symptoms. Patients on clinical trials reported having received less information about their disease and less written information than patients outside clinical trials. Higher information levels were associated with higher quality of life (QoL) scores and higher patient satisfaction. Conclusion: Patients were satisfied with the information they received and this correlated with higher QoL, but they still expressed unmet information wishes. Additional studies are required to investigate the quality of the information received by patients enrolled in clinical trials. © the authors; licensee ecancermedicalscience

Criação de ambiente interativo e complexo para animais cativos: Creating an interactive and complex environment for captive animals

O professor dos nativos digitais transforma os estudantes, em ouvintes ativos e produtores de conhecimentos, dispondo das metodologias ativas, para a promoção do “aluno protagonista”, incentivando a autonomia e participação, a partir de problemas e situações reais centralizando-o no processo de aprendizagem, responsabilizando-o pela construção do conhecimento. Propiciando esse processo dinâmico, a disciplina de clínica de animais silvestres implementa a partir de aula expositiva inicial; bibliografias; discussões; visitas guiadas à zoológicos, refúgios, CETAS; elaboração de projetos e confecção de enriquecimentos ambientais; implantação e avaliação in loco dos enriquecimentos produzidos, culminando em iniciação científica. Pois, coleções de animais com fins de exibição, preservação, reprodução, manutenção e educação ambiental, que estão alocadas em zoológicos, criatórios conservacionistas, e, refúgios ecológicos, são avaliadas quanto ao “bem estar psicológico” dos animais, o qual é melhorado pelo enriquecimento ambiental que permite ajustes fisiológicos e comportamentais, frente as adversidades de ambiente e manejo, fundamentado em conhecimentos científicos. Promovendo assim ao aluno protagonista a construção do conhecimento, com a promoção da homeostasia dos animais cativos através da redução do estresse

Cefepime-induced encephalopathy

A cefepima é um antimicrobiano da classe das cefalosporinas de quarta geração, prescrita para muitas infecções consideradas graves. Os efeitos adversos que mais chamam a atenção são os que envolvem o sistema nervoso central, relatados como encefalopatia por cefepima. O diagnóstico dessa enfermidade deve ser rápido, e a interrupção da droga, imediata.Cefepime is a fourth-generation cephalosporin antibiotic commonly prescribed for severe infections. Its most serious adverse effects, known as cefepime-induced encephalopathy, involve the central nervous system. This disorder must be quickly diagnosed and the drug suspended immediately

Synthesis of beta-phenylchalcogeno-alpha, beta-unsaturated esters, ketones and nitriles using microwave and solvent-free conditions

A simple, clean and efficient solvent-free protocol was developed for hydrochalcogenation of alkynes containing a Michael acceptor (ester, ketone and nitrile) with phenylchalcogenolate anions generated in situ from the respective diphenyl dichalcogenide (Se, Te, S), using alumina supported sodium borohydride. This efficient and improved method is general and furnishes the respective (Z)-beta-phenylchalcogeno-<FONT FACE=Symbol>a,b</FONT>-unsaturated esters, ketones and nitriles, in good yield and higher selectivity, compared with those that use organic solvent and inert atmosphere. The use of microwave (MW) irradiation facilitates the procedure and accelerates the reaction