Mg/Ca partitioning between aqueous solution and aragonite mineral: a molecular dynamics study

We have calculated the concentrations of Mg in the bulk and surfaces of aragonite CaCO3 in equilibrium with aqueous solution, based on molecular dynamics simulations and grand-canonical statistical mechanics. Mg is incorporated in the surfaces, in particular in the (001) terraces, rather than in the bulk of aragonite particles. However, the total Mg content in the bulk and surface of aragonite particles was found to be too small to account for the measured Mg/Ca ratios in corals. We therefore argue that most Mg in corals is either highly metastable in the aragonite lattice, or is located outside the aragonite phase of the coral skeleton, and we discuss the implications of this finding for Mg/Ca paleothermometry.

The role of plasma membrane STIM1 and Ca(2+)entry in platelet aggregation. STIM1 binds to novel proteins in human platelets.

Ca(2+) elevation is essential to platelet activation. STIM1 senses Ca(2+) in the endoplasmic reticulum and activates Orai channels allowing store-operated Ca(2+) entry (SOCE). STIM1 has also been reported to be present in the plasma membrane (PM) with its N-terminal region exposed to the outside medium but its role is not fully understood. We have examined the effects of the antibody GOK/STIM1, which recognises the N-terminal region of STIM1, on SOCE, agonist-stimulated Ca(2+) entry, surface exposure, in vitro thrombus formation and aggregation in human platelets. We also determined novel binding partners of STIM1 using proteomics. The dialysed GOK/STIM1 antibody failed to reduced thapsigargin- and agonist-mediated Ca(2+) entry in Fura2-labelled cells. Using flow cytometry we detect a portion of STIM1 to be surface-exposed. The dialysed GOK/STIM1 antibody reduced thrombus formation by whole blood on collagen-coated capillaries under flow and platelet aggregation induced by collagen. In immunoprecipitation experiments followed by proteomic analysis, STIM1 was found to extract a number of proteins including myosin, DOCK10, thrombospondin-1 and actin. These studies suggest that PM STIM1 may facilitate platelet activation by collagen through novel interactions at the plasma membrane while the essential Ca(2+)-sensing role of STIM1 is served by the protein in the ER.

Genetical and comparative genomics of Brassica under altered Ca supply identifies Arabidopsis Ca-transporter orthologs

Although Ca transport in plants is highly complex, the overexpression of vacuolar Ca2+ transporters in crops is a promising new technology to improve dietary Ca supplies through biofortification. Here, we sought to identify novel targets for increasing plant Ca accumulation using genetical and comparative genomics. Expression quantitative trait locus (eQTL) mapping to 1895 cis- and 8015 trans-loci were identified in shoots of an inbred mapping population of Brassica rapa (IMB211 × R500); 23 cis- and 948 trans-eQTLs responded specifically to altered Ca supply. eQTLs were screened for functional significance using a large database of shoot Ca concentration phenotypes of Arabidopsis thaliana. From 31 Arabidopsis gene identifiers tagged to robust shoot Ca concentration phenotypes, 21 mapped to 27 B. rapa eQTLs, including orthologs of the Ca2+ transporters At-CAX1 and At-ACA8. Two of three independent missense mutants of BraA.cax1a, isolated previously by targeting induced local lesions in genomes, have allele-specific shoot Ca concentration phenotypes compared with their segregating wild types. BraA.CAX1a is a promising target for altering the Ca composition of Brassica, consistent with prior knowledge from Arabidopsis. We conclude that multiple-environment eQTL analysis of complex crop genomes combined with comparative genomics is a powerful technique for novel gene identification/prioritization.

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

Ca(2+)-mediated thiolysis of peptide-resin linkage as an option for preparing protected peptide thioesters

A mild new procedure for preparing protected peptide thioesters, based oil Ca(2+)-assisted thiolysis of peptide-Kaiser oxime resin (KOR) linkage, is described. Ac-Ile-Ser(Bzl)-Asp(OcHx)-SR (Ac: acetyl; Bzl: benzyl; cHx: cyclohexyl), model peptide, was readily released from the resin by incubating the peptide-KOR at 60 degrees C in mixtures of DMF with n-butanethiol [R = (CH(2))(3)CH(3)] or ethyl 3-mercaptopropionate [R = (CH(2))(2)COOCHCH(3)] containing Ca(CH(3)COO)(2). After serine and aspartic acid side-chain deprotection under acid conditions, Ac-Ile-Ser-Asp-S(CH(2))(2)COOCH(2)CH(3) was successfully obtained with good quality and high yield. This type of C-terminal modified peptide may act as an excellent acyl donor in peptide segment condensation by the thioester method, native chemical ligation and enzymatic methods. (c) 2008 Elsevier Ltd. All rights reserved.

Sistema de tração elétrica flexível baseado em veículos trólebus para alimentação com redes CC e ou CA

Este artigo apresenta os principais resultados e o detalhamento da metodologia e equações de controle de um retificador monofásico pré-regulador de 150kW para sistema trólebus. A estrutura proposta possibilita a Correção ativa do Fator de Potência (CFP) com baixos níveis de Distorção Harmônica Total (DHT) na corrente, em conformidade com a norma internacional IEC 61000-3-4. Fruto de um projeto de Pesquisa, Desenvolvimento e Inovação (P) junto à empresa AES Eletropaulo Metropolitana de São Paulo, em parceria com a empresa de transporte Himalaia S.A., o projeto possui como principais objetivos estimular o interesse para a expansão das linhas de trólebus a partir de uma plataforma de alimentação de menor custo de instalação e manutenção, sem a necessidade de subestações retificadoras, e, com vistas a promover a melhoria da qualidade de vida nos grandes centros urbanos. Nessa nova modalidade proposta para o sistema de alimentação, o trólebus pode ser alimentado tanto pelas redes convencionais em corrente contínua (CC) quanto pelas redes de distribuição em corrente alternada (CA), mantendo-se a disposição a dois fios dos sistemas CC, sendo as mudanças de rede de alimentação (CC ou CA) monitoradas e controladas digitalmente. Todo o sistema de gerenciamento e controle do conversor é realizado digitalmente por FPGA XC3S200. Na evolução do sistema proposto, os autores pretendem inclusive eliminar as linhas aéreas de alimentação, através da utilização de postos de alimentação em CA, especialmente desenvolvidos para os pontos de embarque/desembarque de passageiros para este veículo de transporte coletivo, eliminando-se os aspectos visuais negativos das redes de alimentação deste modal, e, reduzindo-se as falhas de operação do sistema.

Fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines, side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm: 202.585 nm; 202.586 nm: 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min(-1) sample flow-rate, calibration curves in the 0.1-0.5 mg L-1 Cu, 0.5-4.0 mg L-1 Fe, 0.5-4.0 mg L-1 Mn, 0.2-1.0 mg L-1 Zn, 10.0-100.0 mg L-1 Ca, 5.0-40.0 mg L-1 Mg and 50.0-250.0 mg L-1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89-103%, 84-107%, 87-103%, 85-105%, 92-106%, 91-114%, 96-114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L-1 Ca, 0.4 mg L-1 Mg, 0.4 mg L-1 K, 7.7 mu g L-1 Cu, 7.7 mu g L-1 Fe, 1.5 mu g L-1 Mn and 5.9 mu g L-1 Zn. (C) 2009 Elsevier B.V. All rights reserved.

Analysis of Ca-PZT powder obtained by the Pechini and partial oxalate methods

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Theoretical study of MgO(001) surfaces: Pure, doped with Fe, Ca, and Al, and with and without adsorbed water

Ab initio calculations of large cluster models have been performed in order to study water adsorption at the five-fold coordinated adsorption site on pure Mg(001) and MgO(001) surfaces doped with Fe, Ca, and Al. The geometric parameters of the adsorbed water molecule have been optimized preparatory to analysis of binding energies, charge transfer, preferential sites of interaction, and bonding distances. We have used Mulliken population analysis methods in order to analyze charge distributions and the direction of charge transfer. We have also investigated energy gaps, HOMO energies, and SCF orbital energies as well as the acid-base properties of our cluster model. Numerical results are compared, where possible, with experiment and interpreted in the framework of various analytical models. (C) 2001 John Wiley & Sons, Inc.

Conversor CA-CA de elevado fator de potência para aplica��ões com geradores de Ímã permanente

This paper proposes and describes a high power factor AC-AC converter for naval applications using Permanent Magnet Generator (PMG). The three-phase output voltages of the PMG vary from 260 Vrms (220 Hz) to 380 Vrms (360 Hz), depending on load conditions. The proposed converter consists of a Y-/ΔY power transformer, which provides electrical isolation between the PMG and remaining stages, and a twelve-pulse uncontrolled rectifier stage directly connected to a single-phase inverter stage, without the use of an intermediary DC-DC topology. This proposal results in more simplicity for the overall circuitry, assuring robustness, reliability and reduced costs. Furthermore, the multipulse rectifier stage is capable to provide high power factor and low total harmonic distortion for the input currents of the converter. The single-phase inverter stage was designed to operate with wide range of DC bus voltage, maintaining 120 Vrms, 60 Hz output. The control philosophy, implemented in a digital signal processor (DSP) which also contains protection routines, alows series connections between two identical converters, achieving 240 Vrms, 60 Hz total output voltage. Measured total harmonic distortion for the AC output voltage is lower than 2% and the input power factor is 0.93 at 3.6kW nominal load. © 2010 IEEE.

Mini-inversores para aproveitamento de energia fotovoltaica, com técnicas de MPPT, sincronismo e conexão com a rede de CA em BT, proteção de ilhamento, gerenciamento da energia e da operação

Pós-graduação em Engenharia Elétrica - FEIS

Influência dos defeitos cristalinos nas propriedades dielétricas e não-ôhmicas do 'CA' 'CU IND.3' 'TI IND.4' 'O IND.12'(CCTO)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dinâmica do carbono dissolvido no Rio Acre: variações espaciais e sazonais

Este trabalho teve como principal objetivo estudar a dinâmica do carbono dissolvido ao longo de um trecho do rio Acre, avaliando a influência da área urbana da cidade de Rio Branco, e da descarga de três de seus tributários (Riozinho do Rola, igarapé Judia, igarapé São Francisco), bem como a influência das mudanças hidrológicas sazonais. Foram realizadas campanhas de campo mensais, entre dezembro de 2006 e setembro de 2007, em cinco sítios no rio Acre e um sítio na foz de cada um dos três tributários. A cada amostragem 1 litro de amostra de água era submetida a filtração e dividida em alíquotas para as análises de carbono orgânico dissolvido (COO), carbono inorgânico dissolvido (CIO) e íons maiores (Ca�� + , Mg² + , K + , Na + , NH 4 + , HCO 3 -, Cl¯, SO 4 ²¯, NO 3 - , NO 2 - , e PO 4 3-) . Além das coletas foram medidos in situ os parâmetros físico-químicos pH, condutividade elétrica, oxigênio dissolvido e temperatura da água. O pH médio anual no rio Acre variou de 6,46 a 6,54 entre os sítios e a condutividade elétrica apresentou valores médios anuais entre os sítios que variam de 69,93 a 77,84 µS cm¯¹. Nos tributários, os valores médios anuais de pH variaram de 6,10 a 6,51 e a condutividade elétrica apresentou valores médios anuais que variaram entre 54,08 e 153,03 S cm¯¹. Os cátions predominantes no rio Acre e nos tributários foram o Na + e o Ca 2+ e os ânions foram o cr e o sol-. A concentração média anual de COD no rio Acre variou de 4,62 a 5,17 mg l¯¹, sem diferenças significativas entre os sítios de amostragem. Nos tributários as médias anuais, de COD variaram de 3,55 a 6,55 mg r1. As concentrações foram, significativamente maiores no período de cheia, com médias que variaram de 6,26 a 6,39 mg l¯¹ nos sítios do rio Acre. O igarapé São Francisco foi o único tributário que não apresentou diferenças entre os períodos sazonais. O CID teve uma concentração média anual no rio Acre que variou de 527,91 a 598,18 µM, sem diferenças significativas entre os sítios de amostragem. As maiores concentrações foram observada na seca, quando as concentrações médias variaram de 816,31 a 998,52 µM. Nos tributários as concentrações médias anuais de CID variaram de 248,54 a 986,50 µM.Quanto a pressão parcial do CO2 (pCO 2 ) , os sítios no rio Acre apresentam valores médios anuais variando entre 3559 e 4059 ppm, sem diferenças entre os sítios e com os maiores valores ocorrendo no período de cheia. Com base nos resultados, pode-se concluir que a dinâmica do carbono dissolvido no rio Acre não apresenta variações significativas decorrentes das descargas dos tributários nem do lançamento de esgotos. Por outro lado, as mudanças hidrológicas sazonais são os maiores responsáveis pelas alterações nesta dinâmica.