Exploring the boundaries of vinylogous Mukaiyama aldol processes: stereoselective access to polyunsaturated homoallylic alcohols

Catalytic enantioselective vinylogous aldol reactions using extended enolates are of prominent value in synthetic organic chemistry. Here, we report our advances in the development of enantioselective bis-vinylogous and hyper-vinylogous Mukaiyama aldol reactions between a series of polyenylsilyloxy furans or polyenylsilyoxy indoles and aromatic aldehydes, realized by use of the enabling catalyst combination of silicon tetrachloride and Denmark’s chiral bis-phosphoramide base (R,R)-I. Several crucial issues such as the remote site-, enantio- and geometrical selectivity of the reaction will be highlighted, ultimately focusing on one main question: how far can we push the limits of the vinylogous reactivity transmittal?</i

Gait Pathway in Subcortical Vascular Dementia and in Alzheimer’s Disease

Gait impairment, worse equilibrium scores and falls are associated with leukoaraiosis, as widely recognised [1-6]. In Binswanger\u2019s disease with a severe leukoaraiosis gait disorders are clearly evident while patients with mild periventricular changes may present subclinical forms of gait disorders, as proposed by some authors (see data in [7]). Gait disorders in the elderly are particularly relevant, since they can influence the loss of functional independence and death [8]. As anticipated, cerebral small vessel disease (both white matter lesions and lacunar infarcts) correlates with gait parameters: stride length and a lower gait velocity [8]. Most importantly, subcortical vascular lesions seem to increase the possibility of falls, even if clear evidences are still lacking [9-11]. Walking difficulties in Alzheimer\u2019s disease are well described [12]: patients show slow and irregular steps, difficulties in turning and avoiding obstacles [13, 14]. These disturbances have been described also in patients free from extrapyramidal, ataxic, paretic signs, and clinically relevant musculoskeletal impairments [12, 14]. Moreover, Alzheimer\u2019s disease patients have a worse balance [12, 14, 15] and a higher risk of falls compared with matched controls [16, 17]. The prevalence of gait abnormalities varies widely across the studies (from 8.7% [18] to over 90% [19]); this can be explained because of different inclusion criteria and/or assessment procedures. These observations have been confirmed by studies demonstrating that patients with Alzheimer\u2019s disease walk more slowly compared to healthy controls [12] and these gait problems have been interpreted as manifestations of the extrapyramidal deficits (well-known to affect 12\u201328% of Alzheimer patients), or as side effects of drug treatment (e.g. neuroleptic agents) [20]. Since a overt walking problems and trunk movement alterations can be seen also in absence of extrapyramidal signs, it has been proposed that some Alzheimer\u2019s disease patients may present \u201cfrontal gait disorder\u201d, a syndrome coterminous with gait apraxia [21, 15]. The lack of a standardised instrument to assess gait has been implicated as a possible cause for the low frequency of reports on the topic. Since the walking assessment cannot discriminate between walking disorders caused by gait apraxia and other neurological causes of walking difficulty, there has been the necessity to exclude alternative causes of walking abnormalities in Alzheimer\u2019s disease (overt extrapyramidal impairments or other concurrent neurological diseases); in order to assess gait capacity, a new test has been proposed and a large proportion of the sample (40%) scored below cut off, even if the percentage of severely impaired was smaller. Although the possibility of right\u2013left confusion, working memory deficits, and problems with verbal comprehension was minimised by demonstrating the items, the complexity of some of them might have contributed to inflating the proportion of patients performing poorly. Even though, the presence of associated vascular pathology in a few patients also cannot account for the outcome. Neuroradiological signs of white matter changes were reported in three of the 24 patients (22.5%) in the Della Sala et al.\u2019s study [12], who scored below cut off in the assessment of walking skills. Therefore, in a well-defined population suffering from subcortical vascular dementia and Alzheimer\u2019s disease (standing from a neurological, clinical, and radiological criteria), we tried to explore gait, balance and equilibrium alterations, and a behavioral complex symptom, such as apathy, even considering precipitant factors, such as concomitant pathologies and consequent therapies. We now present an extension of the work, with a speculation on what we observed for a two-year follow-up

Morfologia da plântula de Psychotria hoffmannseggiana (Willd. ex Roem. & Schult.) Müll. Arg. (Rubioideae, Rubiaceae)

O presente trabalho teve por objetivo descrever e ilustrar as características morfológicas das plântulas de Psychotria hoffmannseggiana. O início da germinação ocorreu cerca de 88 dias após a semeadura, com o surgimento da raiz primária. No oitavo dia após a germinação, com o crescimento da raiz, o ápice, a região pilosa e o hipocótilo apresentaram coloração avermelhada. Aos 11 dias, observou-se a emissão de raízes secundárias e o início do alongamento do hipocótilo. Após 21 dias, os cotilédones foram liberados do envoltório seminal, que permaneceu parcialmente aderido a um deles até o 28 dias. Os cotilédones são foliáceos, verdes, peciolados, ovados, opostos com venação pinada. Foi observada a presença de estípulas entre os pecíolos dos cotilédones. Os eofilos surgiram por volta do 26 dias e no 39 dias apresentavam-se expandidos. Os eofilos são simples, verdes, peciolados, elípticos, opostos de venação pinada. A emissão do primeiro par de metafilos ocorreu aos 69 dias após a germinação. A plântula é fanerocotiledonar-epígea com cotilédones foliares verdes

Morfoanatomia foliar de Psychotria hoffmannseggiana (Willd. ex Roem. & Schult.) Müll. Arg. e Psychotria trichophora Müll. Arg. (Rubiaceae)

Psychotria L. é o maior gênero de Rubiaceae, possui cerca de 1.000 espécies, das quais 46 ocorrem no Estado de São Paulo. É considerado taxonomicamente complexo devido ao tamanho e também, à ausência de caracteres morfológicos disponíveis para a definição dos de seus grupos. Foram descritas e analisadas as características morfoanatômicas das folhas de Psychotria hoffmannseggiana e Psychotria trichophora. O material botânico de constou de folhas adultas, coletadas de indivíduos localizados nas áreas de cerrado da Reserva Biológica de Mogi Guaçu, Mogi Guaçu, SP, Brasil. As lâminas foram confeccionadas seguindo as técnicas usuais em anatomia vegetal. A caracterização micromorfológica foi realizada com análise em microscópio eletrônico de varredura. P. hoffmannseggiana e P. trichophora apresentam estípulas interpeciolares, concrescidas na base e com ápice bífido. P. trichophora possui uma bainha delgada e translúcida recobrindo o caule na região das estípulas e acima da inserção dos pecíolos, em P. hoffmannseggiana essa estrutura é ausente. O pecíolo de ambas as espécies é circular. O sistema vascular de P. hoffmannseggiana é composto centralmente por feixes vasculares colaterais em forma de arco, e por dois feixes colaterais posicionados lateralmente. O tecido vascular central de P. trichophora possui as extremidades ligeiramente curvadas e, é acompanhado por dois feixes colaterais menores posicionados nas laterais. O mesofilo, em ambas as espécies é dorsiventral e está representado por uma camada de parênquima paliçádico e de três a quatro camadas de parênquima lacunoso. A organização dos tecidos do bordo foliar reflete a do mesofilo em P. trichophora, e em P. hoffmannseggiana é composto por parênquima aclorofilado. A região cortical da nervura central, em ambas as espécies, é formada por colênquima anelar, seguido por células colapsadas e células parenquimáticas intactas. Em P. trichophora o parênquima paliçádico é descontínuo nessa região. O sistema vascular da nervura central de P. hoffmannseggiana e P. trichophora apresenta-se constituído centralmente por feixes vasculares colaterais em forma de arco e por um feixe vascular colateral disposto lateralmente. Camadas de fibras lignificadas envolvem os feixes vasculares principais, quase que totalmente, nas duas espécies. Idioblastos contendo cristais de oxalato de cálcio aparecem em todas as regiões foliares

Freqüência de inserções Alu autossômicas em duas amostras do Rio Grande do Sul

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Ferricytochrome c Directly Oxidizes Aminoacetone to Methylglyoxal, a Catabolite Accumulated in Carbonyl Stress

Age-related diseases are associated with increased production of reactive oxygen and carbonyl species such as methylglyoxal. Aminoacetone, a putative threonine catabolite, is reportedly known to undergo metal-catalyzed oxidation to methylglyoxal, NH4+ ion, and H2O2 coupled with (i) permeabilization of rat liver mitochondria, and (ii) apoptosis of insulin-producing cells. Oxidation of aminoacetone to methylglyoxal is now shown to be accelerated by ferricytochrome c, a reaction initiated by one-electron reduction of ferricytochrome c by aminoacetone without amino acid modifications. the participation of O-2(center dot-) and HO center dot radical intermediates is demonstrated by the inhibitory effect of added superoxide dismutase and Electron Paramagnetic Resonance spin-trapping experiments with 5,5'-dimethyl-1-pyrroline-N-oxide. We hypothesize that two consecutive one-electron transfers from aminoacetone (E-0 values = -0.51 and -1.0 V) to ferricytochrome c (E-0 = 0.26 V) may lead to aminoacetone enoyl radical and, subsequently, imine aminoacetone, whose hydrolysis yields methylglyoxal and NH4+ ion. in the presence of oxygen, aminoacetone enoyl and O-2(center dot-) radicals propagate aminoacetone oxidation to methylglyoxal and H2O2. These data endorse the hypothesis that aminoacetone, putatively accumulated in diabetes, may directly reduce ferricyt c yielding methylglyoxal and free radicals, thereby triggering redox imbalance and adverse mitochondrial responses.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)INCT Processos Redox em Biomedicina (Brazil)Univ São Paulo, Dept Bioquim, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Bioquim & Biol Mol, São Paulo, BrazilUniversidade Federal de São Paulo, Inst Ciencias Ambientais Quim & Farmaceut, São Paulo, BrazilUniv São Paulo, Dept Fis & Informat, São Paulo, BrazilUniv Fed ABC, Ctr Ciencias Nat & Humanas, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Bioquim & Biol Mol, São Paulo, BrazilUniversidade Federal de São Paulo, Inst Ciencias Ambientais Quim & Farmaceut, São Paulo, BrazilWeb of Scienc

Role of T. cruzi exposure in the pattern of T cell cytokines among chronically infected HIV and Chagas disease patients

OBJECTIVES: The impact of Chagas disease (CD) in HIV-infected patients is relevant throughout the world. In fact, the characterization of the adaptive immune response in the context of co-infection is important for predicting the need for interventions in areas in which HIV and Chagas disease co-exist. METHODS: We described and compared the frequency of cytokine-producing T cells stimulated with soluble antigen of Trypanosoma cruzi (T. cruzi) using a cytometric assay for the following groups: individuals with chronic Chagas disease (CHR, n=10), those with Chagas disease and HIV infection (CO, n=11), those with only HIV (HIV, n=14) and healthy individuals (C, n=15). RESULTS: We found 1) a constitutively lower frequency of IL-2+ and IFN-γ+ T cells in the CHR group compared with the HIV, CO and healthy groups; 2) a suppressive activity of soluble T. cruzi antigen, which down-regulated IL-2+CD4+ and IFN-γ+CD4+ phenotypes, notably in the healthy group; 3) a down-regulation of inflammatory cytokines on CD8+ T cells in the indeterminate form of Chagas disease; and 4) a significant increase in IL-10+CD8+ cells distinguishing the indeterminate form from the cardiac/digestive form of Chagas disease, even in the presence of HIV infection. CONCLUSIONS: Taken together, our data suggest the presence of an immunoregulatory response in chronic Chagas disease, which seems to be driven by T. cruzi antigens. Our findings provide new insights into immunotherapeutic strategies for people living with HIV/AIDS and Chagas disease

PADRONIZAÇÃO E ANÁLISE DE ILHA DE CALOR URBANO: COLETA DE DADOS COM SISTEMA MÓVEL EM GOIÂNIA-GO

Research into the urban microclimate is important in the area of urban planning, helping to create resilient cities in the face of current climate change conditions. The article aims to present a methodology for collecting mobile data to analyze the possibility of the urban heat island phenomenon occurring in the Itatiaia district of Goiânia - GO, using mobile transects. The research methodology has three stages: definition of the object of study; data collection; and systematization of data and analysis of results.&nbsp; The analysis revealed that densely urbanized areas, with little vegetation, have a higher heat island intensity, reaching&nbsp; peak temperatures due to heat retention in materials such as asphalt and concrete. In contrast, places along the linear park showed lower temperatures, related to the vegetation that provides shade and evapotranspiration. Thus, it can be seen that the standardization of the mobile transect is essential in order to obtain reliable data.As pesquisas sobre o do microclima urbano são importantes na área de planejamento urbano, auxiliando na criação de cidades resilientes diante das atuais condições de mudanças climáticas. O artigo objetiva apresentar uma metodologia de coleta de dados móveis para analisar a possibilidade de ocorrência do fenômeno de ilha de calor urbana no Bairro Itatiaia, em Goiânia – GO, utilizando transectos móveis. A metodologia da pesquisa possui 3 etapas: definição do objeto de estudo; coleta de dados; e sistematização de dados e análise de resultados.&nbsp; A análise revelou que áreas densamente urbanizadas, com pouca vegetação, apresentam maior intensidade na ilha de calor, atingindo picos de temperaturas devido à retenção de calor em materiais como asfalto e concreto. Em contraponto, locais ao longo do parque linear exibiram temperaturas mais baixas, relacionado com a vegetação que oferece sombreamento e evapotranspiração. Assim, nota-se que a padronização do transecto móvel é essencial para obter dados confiáveis

Application of the focus group technique in research with the SANS network on procedures in food and nutrition in basic health care

Focus groups are seen as important tools in qualitative research for evaluating projects aimed at articulating social networks and movements. Six focus groups were held as one of the stages in research as part of the Food Safety and Sustainable Nutrition Project (SANS). This social network articulates the academic world with social movements and government in defense of the human right to suitable nutrition. This report is aimed at discussing the experience of applying focus groups to the investigation of perceptions by health professionals of activities related to food and nutrition in basic health care. These groups made it possible to bring together 52 professionals from 13 municipalities in the State of São Paulo, Brazil, and they exchanged experiences and debated issues related to food safety in the area of health care. The group discussions identified eating, nutrition vigilance and intersectoriality as emerging topics. The focus group technique proved to be a suitable tool for investigating the topic quickly and in depth, with a large number of professionals working in different contexts. In fact, the discussions went beyond the objectives of the research, since the group work made it possible to strengthen the process of articulation carried out by a network that promoting local measures in food safety and sustainable nutrition.Grupo focal como recurso da pesquisa qualitativa é importante ferramenta na avaliação propositiva de projetos de articulação de redes e movimentos sociais. Seis grupos focais foram aplicados como uma das etapas de pesquisa do Projeto Rede de Segurança Alimentar e Nutricional Sustentável (Rede-SANS), rede social de articulação da academia com os movimentos populares e poder público, em defesa do Direito Humano à Alimentação Adequada. Este relato teve como objetivo discutir a experiência da aplicação da referida técnica para investigar as percepções de profissionais de saúde sobre as ações de alimentação e nutrição na Atenção Básica. Os grupos focais permitiram aproximação e troca de experiências de 52 profissionais de 13 municípios de diferentes regiões do Estado de São Paulo para debater questões de segurança alimentar no contexto da área da saúde e promoveu reflexões sobre a alimentação, vigilância nutricional e intersetorialidade, como temas emergentes nos grupos. A técnica aplicada se demonstrou adequada para investigar o tema em profundidade, em pouco tempo, com um número grande de profissionais de distintos contextos para além dos objetivos da pesquisa. A realização dos grupos focais possibilitou o fortalecimento do processo de articulação de rede para a promoção de ações locais de segurança alimentar e nutricional sustentável.40741

Real-Time PCR in HIV/Trypanosoma cruzi Coinfection with and without Chagas Disease Reactivation: Association with HIV Viral Load and CD4+ Level

Chagas disease is endemic in Latin America and is caused by the flagellate protozoan T. cruzi. The acute phase is asymptomatic in the majority of the cases and rarely causes inflammation of the heart or the central nervous system. Most infected patients progress to a chronic phase, characterized by cardiac or digestive involvement when not asymptomatic. However, when patients are also exposed to an immunosuppressant (such as chemotherapy), neoplasia, or other infections such as HIV, T. cruzi infection may develop into a severe disease (Chagas disease reactivation) involving the heart and central nervous system. The current microscopic methods for diagnosing Chagas disease reactivation are not sensitive enough to prevent the high rate of death observed in these cases. Therefore, we propose a quantitative method to monitor blood levels of the parasite, which will allow therapy to be administered as early as possible, even if the patient has not yet presented symptoms