A Silsesquioxane Organically Modified with 4-Amino-5-(4-pyridyl)-4H-1,2,4-triazole-3-thiol: Thermal Behavior and Its Electrochemical Detection of Sulfhydryl Compounds

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo do metamorfismo de rochas de alto grau do grupo Araxá na região de São Sebastião do Paraíso - MG

This study focuses on metasedimentary rocks from the Passos Nappe in São Sebastião do Paraíso, southern Minas Gerais, Brazil. These rocks belong to the Internal Domain (Araxa Group) of the Southern Brasilia Belt, a Neproterozoic orogenic belt associated to the formation of the Gondwana Supercontinent. Rocks from the studied area are characterized by an inverted metamorphic gradient. Previously calculated metamorphic conditions show an increasing from geenschist facies at the base (450°C, 6 kbar), to upper amphibolite facies (750°C, 11 Kbar) at the top of the sequence. However, most of these estimates are based on Fe-Mg exchange thermometers and peak temperatures may be underestimated due to Fe-Mg exchange from cooling after peak metamorphism. In this study, we present new PT results for these rocks, based on metamorphic mineral assemblage LA-ICP-MS analyses. In the studied area, rocks from the top of the sequence have a typical granulite facies mineral assemblage: Grt+Ky+Kfs+/-Pl+liq. These rocks lack muscovite and have only minor amounts of Ti-rich, dark brown biotite. In a simplified NaKFMASH system the stability field for this mineral assemblage is bounded by the reactions Sil = Ky on the low pressure side, Ms+Ab = Ky+Kfs+liq on the low temperature side and for high-Mg bulk compositions Bt + Grt = Opx + Ky + liq on the high-temperature side. Minimum temperatures (considering post-peak reequilibration) of ca. 750°C are obtained by Fe/(Fe+Mg) values of 0.7 in garnets from a Grt+Ky+Kfs bearing sample. LA-ICP-MS results obtained for three samples show that rutiles included in garnets have up to 1847 ppm of Zr, which would translate into temperatures up to 830°C for a pressure between 12 to 15 kbar. Also for retroeclogite sample, the results indicate the contents of Zr in the garnet 537 ppm at a temperature of 708 ° C. It is noteworthy that several occurrences of retroeclogites occur in the upper part of the sequence and pressures...

Avaliação da membrana P81 como agente ligante da técnica de difusão em filmes finos por gradiente de concentração (DGT) para determinação de mercúrio em sistemas aquáticos

Worldwide environmental degradation is an undesirable byproduct resulting from the increasing demand for natural resources. Water sources are suffering intense contamination since they usually receive a huge amount of domestic and industrial effluents - which are mostly wasted without proper treatment - inserting a large number of pollutants in the environment, heavy metals included. Mercury holds great toxicological importance because, under some physicochemical conditions in a water environment, Hg (II) ion turns into methylated compounds stemming from this element, such as methylmercury CH3Hg, which is highly toxic for the aquatic community in which bioaccumulation occurs. Nowadays passive sampling techniques are being developed to enable the analytical procedures which are applied in environmental monitoring. Diffusive gradients in thin-films technique (DGT) has been proven an interesting tool for the determination of labile metal species due to its in situ application. The DGT technique consists of a piston-like device on which the following series of agents is disposed: a binding agent (conventionally Chelex 100 resin), a diffusive agent, usually a polyacrylamide gel, and a membrane filter. Nevertheless, the agents conventinally used for this technique don't usually show satisfactory results in mercury sampling. The main goal of this study was to evaluate the phosphate-treated cellulose membrane (Whatman P 81), an alternative material, as binding agent in the DGT to determine labile mercury fractions in aquatic systems. In this context, we conducted a study of the behavior of this material in relation with system variables, pH and ionic strength. Afterwards we performed immersions of the DGT devices in real and enriched samples and in situ aiming the determination of mercury

O papel da proteína TET2 no enriquecimento do DNA genômico em 5-hidroximetilcitosina em lesões elanocíticas pré-malignas e pré-metastáticas com fenótipo stem cell-like

Durante a transformação maligna dos melanócitos, padrões de metilação do DNA encontram-se alterados, afetando a expressão gênica. As citosinas metiladas (5mC) podem ser hidroxiladas pelas dioxigenases dependentes de 2-oxoglutarato e Fe(II), Tet1, 2 e 3, resultando na formação de 5-hidroximetilcitosina (5hmC) (Globisch et al., 2010; Ko et al., 2010). A 5hmC pode agir tanto como um produto intermediário na desmetilação ativa do DNA quanto na desmetilação passiva ao longo de sucessivas replicações, o que pode contribuir com a dinâmica da metilação do DNA (Tahiliani et al., 2009). Além disso, demonstrou-se que Tet1 e Tet2 são expressas em células tronco embrionárias (Ito et al., 2010) e que 5hmC desempenha importante papel na manutenção e diferenciação destas células (Koh et al., 2011). No entanto, o papel da 5hmC e das proteínas Tet tanto na fisiologia normal quanto em doenças como o câncer ainda não está claro. Utilizando um modelo linear de progressão do melanoma, observamos aumento na expressão gênica de Tet1 nas linhagens celulares correspondendo a melanócitos pré-malignos (4C) e células de melanoma não metastático (4C11-), comparado a melanócitos não tumorigênicos (melan-a) e células de melanoma metastático (4C11+). Em relação à expressão proteica, há um aumento da expressão de Tet1 nas linhagens 4C e 4C11+, o que pode ser relacionado às fases de transição epitélio-mesênquima (EMT) e mesênquima-epitélio (MET), respectivamente. Além disso, constatamos aumento na expressão gênica e proteica de Tet2 na linhagem metastática 4C11+, o que pode indicar diferenças funcionais entre as proteínas Tet1 e Tet2. Também verificamos aumento significativo do conteúdo de 5hmC na linhagem 4C11+, o que se correlaciona com maior expressão gênica e proteica de Tet2. Por fim, linhagens humanas de melanoma metastático menos agressivas apresentaram aumento significativo na expressão dos genes TET1 ...

Preparação e Modificação Química de Nanoestruturas de Octa(aminopropil) silsesquioxano para Aplicações Analíticas

Pós-graduação em Ciência dos Materiais - FEIS

Direct preparation and characterization of copper pentacyanonitrosylferrate nanoparticles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Voltammetric Behavior of a Chemically Modified Silsesquioxane with 4-Amino-5-Phenyl-4h-[1,2,4]-Triazole-3-Thiol and its Application for Detection of L-Dopamine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo comparativo das características bioquímicas funcionais e especificidade catalítica de aspartil, cisteíno e serino peptidases fúngicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de procedimentos e métodos analíticos no campo forense aplicando os princípios da química verde

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

DESENVOLVIMENTO E AVALIAÇÃO DE ELETRODOS DE DIFUSÃO GASOSA (EDG) PARA GERAÇÃO DE H2O2 IN SITU E SUA APLICAÇÃO NA DEGRADAÇÃO DO CORANTE REATIVO AZUL 19

DEVELOPMENT AND EVALUATION OF GAS DIFFUSION ELECTRODES (GDE) FOR GENERATION OF H2O2 IN SITU AND THEIR APPLICATION IN THE DEGRADATION OF REACTIVE BLUE 19 DYE. This work reports the development of GDE for electrogeneration of H2O2 and their application in the degradation process of Reactive Blue 19 dye. GDE produced by carbon black with 20% polytetrafluoroethylene generated up to 500 mg L-1 of H2O2 through the electrolysis of acidic medium at -0.8 V vs Ag/AgCl. Reactive Blue 19 dye was degraded most efficiently with H2O2 electrogenerated in the presence of Fe(II) ions, leading to removal of 95% of the original color and 39% of TOC at -0.8 V vs Ag/AgCl.

The density of metastatic lymph node as prognostic factor in squamous cell carcinoma of the tongue and floor of the mouth

The presence of metastatic lymph nodes is a relevant prognostic factor in oral cancer. Objective: This paper aims to assess metastatic lymph node density (pN+) in patients with tongue and floor-of-mouth squamous cell carcinoma (SCC) and the association of this parameter with disease-free survival (DFS). Materials and Methods: A group of 182 patients seen between 1985 and 2007 was included, 169 of which were males. Five were on stage I, 35 on stage II, 56 on stage III, and 85 on stage IV. Median values were considered in lymph node density assessment, and the Kaplan-Meier curve was used to evaluate DFS; survival differences within the group were elicited through the log-rank test. Results: An average 3.2 metastatic lymph nodes were excised from the patients in the group. Density ranged from 0.009 to 0.4, with a mean value of 0.09. Five-year DFS rates were of 44% and 28% for the groups with lymph node densities below and above the median respectively (p = 0.006). Two-year local/regional control was achieved for 71% and 49% for the patients below and above the median density respectively (p = 0.01). In terms of pN staging, local/regional control was achieved in 70% and 54% of pN1 and pN2 patients respectively, albeit without statistical significance (0.20%). Conclusion: Lymph node density may be used as a prognostic indicator for tongue and floor-ofmouth SCC.

Synthesis and characterization of [Ru(eta(6)-C10H14)(dppf)X][PF6] (X = Cl, Br, I, SnF3) compounds: The X-ray structure of [Ru(eta(6)-C10H14)(dppf)Cl][SnCl3]center dot 0.45CH(2)Cl(2)

The arene-ruthenium complex [Ru(eta(6)-C10H14)(dppf)Cl]PF6 (1) was used as a precursor for the syntheses of the [Ru(eta(6)-C10H14)(dppf)Br]PF6 (2), [Ru(eta(6)-C10H14)(dppf)I]PF6 (3). [Ru(eta(6)-C10H14)(dppf)SnF3]PF6 (4) and [Ru(eta(6)-C10H14)(dppf)Cl][SnCl3]center dot 0.45CH(2)Cl(2) (5) complexes by its reactions with KBr, Kl, SnF2 and SnCl2. respectively. All of the compounds were characterized by NMR, IR, Fe-57 and Sn-119-Mossbauer spectroscopy, and cyclic voltammetry. The single-crystal X-ray structure analysis of the [Ru(eta(6)-C10H14)(dppf)Cl] [SnCl3]center dot 0.45CH(2)Cl(2) complex revealed the expected piano-stool geometry. Cyclic voltammograms of the complexes showed only one quasi-reversible electrochemical process, involving the oxidation of Fe(II) and Ru(II) at the same potential, which was confirmed by exhaustive electrolysis experiments. Fe-57-Mossbauer parameters obtained for the complexes (1-5) were fitted with one doublet corresponding to a site of one iron(II). The Sn-119-Mossbauer parameters of the complex (4) indicate that tin is tetra covalent. (c) 2012 Elsevier Ltd. All rights reserved.

Descriptions of Thereza murutinga sp. nov. and Pristocnemis caipira sp. nov., and new records of Caelopyginae (Opiliones: Laniatores: Gonyleptidae)

Two new species of Caelopyginae are described: Pristocnemis caipira sp. nov. from Parque Nacional da Serra da Canastra, Minas Gerais, Brazil, and Thereza murutinga sp. nov., from Parati, Rio de Janeiro, Brazil. Pristocnemis caipira sp. nov. is diagnosed by shallow grooves on the dorsal scutum, a lower number of tarsal segments, presence of a spine on the anal operculum, large, pointed tubercles on the lateral margins of the dorsal scutum, and an absence of white patches on the dorsal scutum. Thereza murutinga sp. nov. is diagnosed by the combination of the following characters: incomplete median longitudinal groove on area III and absent on area II, prosoma much smaller than opisthosoma, and a large white patch covering the prosoma and whole areas of the opisthosomal scutum. A cladistic analysis including the two new species was performed to investigate their relationship within the subfamily. We obtained 927 trees of 185 steps (CI=0.4, RI=0.74), which corroborated the generic assignments of the new species, but infrageneric relationships remained unsolved. In addition, male genitalia of Ampheres luteus (Giltay) and genera Pristocnemis and Thereza are redescribed, new distribution records for Caelopyginae species are presented, and biogeographical implications are discussed.

Desenvolvimento e avaliação de eletrodos de difusão gasosa (EDG) para geração de H2O2 in situ e sua aplicação na degradação do corante reativo azul 19

This work reports the development of GDE for electrogeneration of H2O2 and their application in the degradation process of Reactive Blue 19 dye. GDE produced by carbon black with 20% polytetrafluoroethylene generated up to 500 mg L-1 of H2O2 through the electrolysis of acidic medium at -0.8 V vs Ag/AgCl. Reactive Blue 19 dye was degraded most efficiently with H2O2 electrogenerated in the presence of Fe(II) ions, leading to removal of 95% of the original color and 39% of TOC at -0.8 V vs Ag/AgCl.

Speciazione del cromo nei sedimenti di una laguna costiera

Il presente lavoro di tesi ha affrontato le problematiche legate alla speciazione del cromo in particolare i rischi legati alla forma esavalente che risulta particolarmente tossica per gli organismi acquatici. Sono state svolte diverse prove per la messa appunto di una metodica standar dell’US EPA “Method 3060A” indicata per l’estrazione selettiva del Cr(VI) in campioni di sedimento e suolo. Un set di campioni provenienti da sedimenti della laguna costiera della Pialassa della Baiona sono stati analizzati per quantificare i livelli cromo environmentally available, previa dissoluzione in acqua regia, e livelli di cromo esavalente per valutare l’eventuale rischio per il biota acquatico. Sia i livelli di concentrazione di cromo environmentally available confrontati con le linee guida internazionali che i livelli di cromo e Cr(VI) paragonati ai livelli di effetto ritrovati in letteratura non mostrano un potenziale rischio per gli organismi bentonici. I bassi valori di cromo esavalente sono in accordo con le condizioni riducenti tipiche di ambienti di transizione come quello di studio dove la forma chimica del cromo predominante sembra essere quella trivalente. La metodica seguita per la determinazione del cromo esavalente ha diversi limiti rappresentati dall’azione di interferenti quali AVS, Fe(II) e materia organica naturalmente presenti nei sedimenti, per questo procede ancora la ricerca di analisi di speciazione più selettive.