Tetra-crowned porphyrin as P450 biomimetic model for carbamazepine oxidation

A substituted porphyrin bearing four crown ether units, H(2)(TCP), was synthesized from the reaction between (5,10,15,20-tetra(o-aminophenyl) porphyrin) and the acyl derivative of the ether (4-carboxy-18-crown-6). The free-base porphyrin was characterized by C, N, and H elemental analysis; UV-vis and IR spectroscopies; and (1)H NMR. The corresponding ironporphyrin, Fe(TCP)Cl, was obtained via iron insertion into H(2)(TCP). Fe(TCP)Cl was employed as catalyst for carbamazepine (CBZ) oxidation by iodosylbenzene (PhIO), 3-chloroperoxybenzoic acid (m-CPBA) or sodium hypochlorite (NaOCl), in methanol or in a biphasic water/dichloroethane system. The crowned ironporphyrin proved to be a highly efficient and selective catalyst for CBZ epoxidation even in the biphasic dichloroethane /H(2)O system, with no need for an additional phase transfer agent.FAPESPCNPqCAPE

Protomers : formation, separation and characterization via travelling wave ion mobility mass spectrometry

Travelling wave ion mobility mass spectrometry (TWIM‐MS) with post‐TWIM and pre‐TWIM collision‐induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM‐MS. CID performed after TWIM separation (post‐TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N‐protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH3, whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co‐existing protomers of two isomeric porphyrins were also separated and characterized via post‐TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO2 loss, but a CID‐resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups476712719CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPNão temNão temNão temWe thank FAPESP, CNPq, FINEP and CAPES for financial suppor

Protomers: Formation, Separation And Characterization Via Travelling Wave Ion Mobility Mass Spectrometry.

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH(3) , whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO(2) loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups.47712-

VIII Congresso Estadual Paulista sobre Formação de Educadores

O tema proposto para discussão durante o VIII Congresso Estadual Paulista sobre a Formação de Educadores – Modos de ser Educador: Artes e Técnicas – Ciências e Políticas envolve a busca de integração entre as diferentes dimensões que compõem a formação do profissional da educação. O trabalho e o sentido da intervenção social desse profissional se constituem em objeto em torno do qual as análises e interpretações vão recolher os fundamentos de debate sobre cultura como totalidade, incluindo: Artes e Técnicas – Ciências e Políticas. A dinâmica que caracteriza a formação de educadores requer a interpretaçãodesses fundamentos para o constante redimensionamento e definição dos objetivos visando aperfeiçoar o papel do profissional educador na sociedade. Por meio de discussões entrediferentes setores ligados à educação é que podem ser avaliados, preservados ou transformados os móveis que norteiam a formação do educador dentro de contextos culturais/sociais específicos, nos diversos campos, artes, técnicas, ciências e políticas. A disponibilidade de um espaço como o VIII Congresso Estadual Paulista sobre a Formação de Educadores para que estudiosos do tema - Educação - se congreguem e debatam a produção de conhecimento sob diversos ângulos, insere e qualifica esse evento como um processo de contribuição para o aprofundamento de estudos na área educacional. Os Congressos Estaduais Paulistas sobre a Formação de Educadores (CEPFE) vêm acontecendo desde 1990 e têm dedicado ênfase especial à formação de profissionais da educação, nos níveis de ensino fundamental, médio e universitário. Tal conformação do Congresso procura extrapolar questões próprias do padrão formal, para a abordagem de formação do profissional da educação embasada na crítica constante, capaz de dinamizar processos e resultados. Essa pretensão ressalta a importância do envolvimento de diferentes áreas do saber numa discussão sobre significados da produção de conhecimento. Daí poderão provir os resultados esperados a partir das atividades programadas para o VIII Congresso dentre os quais está esse caderno de resumos que ora apresentamos.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Diminishing benefits of urban living for children and adolescents’ growth and development

Optimal growth and development in childhood and adolescence is crucial for lifelong health and well-being1–6. Here we used data from 2,325 population-based studies, with measurements of height and weight from 71 million participants, to report the height and body-mass index (BMI) of children and adolescents aged 5–19 years on the basis of rural and urban place of residence in 200 countries and territories from 1990 to 2020. In 1990, children and adolescents residing in cities were taller than their rural counterparts in all but a few high-income countries. By 2020, the urban height advantage became smaller in most countries, and in many high-income western countries it reversed into a small urban-based disadvantage. The exception was for boys in most countries in sub-Saharan Africa and in some countries in Oceania, south Asia and the region of central Asia, Middle East and north Africa. In these countries, successive cohorts of boys from rural places either did not gain height or possibly became shorter, and hence fell further behind their urban peers. The difference between the age-standardized mean BMI of children in urban and rural areas was <1.1 kg m–2 in the vast majority of countries. Within this small range, BMI increased slightly more in cities than in rural areas, except in south Asia, sub-Saharan Africa and some countries in central and eastern Europe. Our results show that in much of the world, the growth and developmental advantages of living in cities have diminished in the twenty-first century, whereas in much of sub-Saharan Africa they have amplified