Identification of intracellular calcium oxalate crystals in Chamelaucium uncinatum (Myrtaceae)

Intracellular inclusions in the pedicel and calyx-tube tissues of Chamelaucium uncinatum Schauer ( Myrtaceae) flowers are irregular in shape. They were shown, by polarised light and scanning electron microscopy, to be birefringent 8.9-29.5 mum druse (i.e. aggregate) crystals. Energy-dispersive X-ray spectroscopy showed that these crystals were predominantly composed of calcium. Histochemical and acid-solubility tests indicated that the crystals were calcium oxalate. Raman microprobe spectroscopy was used to confirm this chemical identity. The calcium oxalate crystals were located in xylem-vessel lumens and also in parenchyma cells adjacent to vascular tissues. Thus, the crystals may function to regulate soluble calcium concentrations in C. uncinatum tissues near sites where calcium is unloaded from the xylem.

Electron exchange coupling for single-donor solid-state spin qubits

Intervalley interference between degenerate conduction band minima has been shown to lead to oscillations in the exchange energy between neighboring phosphorus donor electron states in silicon [B. Koiller, X. Hu, and S. Das Sarma, Phys. Rev. Lett. 88, 027903 (2002); Phys. Rev. B 66, 115201 (2002)]. These same effects lead to an extreme sensitivity of the exchange energy on the relative orientation of the donor atoms, an issue of crucial importance in the construction of silicon-based spin quantum computers. In this article we calculate the donor electron exchange coupling as a function of donor position incorporating the full Bloch structure of the Kohn-Luttinger electron wave functions. It is found that due to the rapidly oscillating nature of the terms they produce, the periodic part of the Bloch functions can be safely ignored in the Heitler-London integrals as was done by Koiller, Hu, and Das Sarma, significantly reducing the complexity of calculations. We address issues of fabrication and calculate the expected exchange coupling between neighboring donors that have been implanted into the silicon substrate using an 15 keV ion beam in the so-called top down fabrication scheme for a Kane solid-state quantum computer. In addition, we calculate the exchange coupling as a function of the voltage bias on control gates used to manipulate the electron wave functions and implement quantum logic operations in the Kane proposal, and find that these gate biases can be used to both increase and decrease the magnitude of the exchange coupling between neighboring donor electrons. The zero-bias results reconfirm those previously obtained by Koiller, Hu, and Das Sarma.

Composition and quality of harvest residues and soil organic matter under windrow residue management in young hoop pine plantations as revealed by solid-state C-13 NMR spectroscopy

Solid-state C-13 nuclear magnetic resonance (NMR) with cross-polarisation (CP) and magic-angle-spinning (MAS) was used to: (a) examine the changes in carbon (C) composition of windrowed harvest residues during the first 3 years of hoop pine plantations in subtropical Australia; (b) assess the impacts of windrowed harvest residues on soil organic matter (SOM) composition and quality in the 0-10 cm soil layer. Harvest residues were collected from 0-, 1-, 2- and 3-year-old windrows of ca. 2.5 m width (15 m apart for 0-, 1- and 2-year-old sites and 10 m apart for 3-year-old site). Soils from the 0 to 10 cm soil layer were collected from the 1-, 2- and 3-year-old sites. The 13C NMR spectra of the harvest residues indicated the presence of lignin in the hoop pine wood, foliage and newly incorporated organic matter (NIOM). Condensed tannin structures were found in the decay-resistant bark, small wood and foliage, but were absent in other residue components and SOM. The NMR spectra of small wood samples contained condensed tannin structures because the outer layer of bark was not removed. NIOM showed a shift from foliage-like structures (celluloses) to lignin-type structures, indicating an incorporation of woody residues from the decomposing harvest residues. Suberins were also present in the small wood, foliage and bark. The 13C CP NMR spectra of SOM indicated that in areas where windrows were present, SOM did not show compositional changes. However, an increase in SOM quality under the windrows in the second year after their formation as characterised by the alkyl C/O-alkyl C (A/O-A) ratio was mainly due to inputs from the decomposition of the labile, readily available components of the windrowed harvest residues. (C) 2002 Published by Elsevier Science B.V.

Direct electrochemistry of a bacterial sulfite dehydrogenase

Sulfite dehydrogenase from Starkeya novella is an alphabeta heterodimer comprising a 40.6 kDa subunit (containing the Mo cofactor) and a smaller 8.8 kDa heme c subunit. The enzyme catalyses the oxidation of sulfite to sulfate with the natural electron acceptor being cytochrome c(550). Its catalytic mechanism is thought to resemble that found in eukaryotic sulfite oxiclases. Using protein film voltammetry and redox potentiometry, we have identified both Mo- and heme-centered redox responses from the enzyme immobilized on a pyrolytic graphite working electrode: E-m,E-8 (Fe-III/II) +177 mV; E-m,E-8 (Mo-VI/V) +211 mV and E(m,)8 (Mo-V/IV) -118 mV vs NHE; Upon addition of sulfite to the electrochemical cell a steady-state voltammogram is observed and an apparent Michaelis constant (K-m) of 26(l) muM was determined for the enzyme immobilized on the working electrode surface, which is comparable with the value obtained from solution assays.

Intramolecular electron transfer in a bacterial sulfite dehydrogenase

Sulfite dehydrogenase (SDH) from Starkeya novella, a sulfite-oxidizing molybdenum-containing enzyme, has a novel tightly bound αβ-heterodimeric structure in which the Mo cofactor and the c-type heme are located on different subunits. Flash photolysis studies of intramolecular electron transfer (IET) in SDH show that the process is first-order, independent of solution viscosity, and not inhibited by sulfate, which strongly indicates that IET in SDH proceeds directly through the protein medium and does not involve substantial movement of the two subunits relative to each other. The IET results for SDH contrast with those for chicken and human sulfite oxidase (SO) in which the molybdenum domain is linked to a b-type heme domain through a flexible loop, and IET shows a remarkable dependence on sulfate concentration and viscosity that has been ascribed to interdomain docking. The results for SDH provide additional support for the interdomain docking hypothesis in animal SO and clearly demonstrate that dependence of IET on viscosity and sulfate is not an inherent property of all sulfite-oxidizing molybdenum enzymes.

Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

A study of the radiation degradation of styrene/alkane and α-methylstyrene/alkane copolymers

The effects of copolymer composition and microstructure on the radiation chemistry of styrene/alkane and alpha-methylstyrene/alkane copolymers have been studied. The primary radical species formed on radiolysis of the copolymers at 77 K, and identified by ESR spectroscopy, are the same as those formed during radiolysis of the homopolymers. The yields of radicals for the copolymer are as predicted assuming that the cross-section is proportional to the electron density of each component; however, there is some evidence of radical migration to aromatic groups at 77 K. Changes in molecular structure on irradiation were detected by using C-13 NMR spectroscopy. Evidence of the consumption of terminal double bonds, and chain scission in alpha-methylstyrene/alkane copolymers was found. Measurements of viscosity supported the mechanism of cross-linking predominating in styrene/alkane copolymers, while in alpha-methylstyrene/alkane copolymers chain scission was the major result of irradiation. (C) 2003 Society of Chemical Industry.

Electrochemistry of P450cin: new insights into P450 electron transfer

Electrochemistry of bacterial cytochrome P450cin (CYP176A) reveals that, unusually, substrate binding does not affect the heme redox potential, although a marked pH dependence is consistent with a coupled single electron/single proton transfer reaction in the range 6 < pH < 10.

Preparation and characterization of Nickel-and cobalt-doped magnetites

Trabalho apresentado no I Simpósio Mineiro de Ciências dos Materiais, Ouro Preto, Novembro de 2001.

Estudo da corrosão dos aços AISI 1010 e AISI 316L em soluções com elevado teor de cloreto e em ácido naftênico

A mudança no mercado global do petróleo nos últimos anos, com o declínio das reservas de óleo leve, têm forçado a busca por novos campos petrolíferos em ambientes mais remotos, como nos campos localizados na camada pré-sal, e a exploração de óleos pesados que possuem elevado teor de ácidos naftênicos. Isso acarreta em grandes desafios para a previsão do desempenho de materiais frente às novas condições ambientais em que estão inseridos. No presente trabalho, o comportamento da corrosão do aço carbono AISI 1010 e do aço inoxidável AISI 316L foi estudado em soluções aquosas com elevado teor de cloreto e em solução de ácido naftênico ciclopentanóico a fim de ter melhor entendimento da ação dessas espécies no processo de corrosão e simular a corrosão pela água de produção na indústria petrolífera. Foram aplicadas as técnicas de potencial de circuito aberto, polarização potenciodinâmica, voltametria cíclica, espectroscopia de impedância eletroquímica, espectroscopia Raman, microscopia eletrônica de varredura e microscopia de força atômica, usadas, em cada caso, de acordo com a conveniência. O aumento da [Cl-] na faixa de 1,2–2,8 mol.L-1 não altera os processos catódicos e anódicos perto do Ecorr para os aços AISI 1010 e AISI 316L. Em condições de sobrepotenciais afastados do Ecorr, o aumento de [Cl-] aumenta os processos oxidativos de corrosão, o que é expresso pelas maiores densidades de corrente e carga anódica e aumento da perda de massa sofrida pelos eletrodos de ambos os aços. Portanto, os danos da corrosão são mais intensos quando se aumenta a [Cl-]. O aço AISI 1010 é ativo nas soluções de NaCl e a corrosão se propaga livremente de forma uniforme. Para o aço AISI 316L, uma ampla faixa de passividade pode ser vista nas soluções de NaCl; no Epit ocorre a ruptura do filme passivo e o crescimento de pites estáveis. Após 24 h de imersão em soluções de sulfato de sódio (branco) e de ácido naftênico ciclopentanóico ocorre crescimento de filme de óxido e as fases α-Fe2O3, Fe3O4 e δ-FeO(OH) foram identificadas nos espécimes de aço AISI 1010 e Fe3O4 foi identificado nos defeitos do filme prévio presente na superfície do aço AISI 316L. Os filmes formados em solução de ácido ciclopentanóico possuem menor resistência à polarização, maior rugosidade e maior taxa de corrosão quando comparado aos filmes crescidos na solução branco, para ambos os aços. A presença do ácido naftênico muda a forma como a reação de corrosão se procede e contribui para o aumento da corrosão. A corrosão naftênica foi mais pronunciada no aço carbono porque a presença dos elementos de liga no aço inox reduzem o número de sítios ativos ricos em Fe e tornam menos oportuna a ligação do Fe com o naftenato.

Estudo da corrosão e inibição dos aços carbono AISI 1010, inoxidável AISI 316 e duplex UNS S31803 em meio de solução de íons cloreto

O comportamento da corrosão e inibição à corrosão dos aços carbono AISI 1010, inox AISI 316 e duplex UNS S31803 foi estudado em meio de solução de íons cloreto à 3,0% (m/v), na ausência e presença do benzimidazol e imidazol como inibidores. A caracterização química e morfológica dos aços foi realizada por meio das técnicas de espectrometria de emissão ótica, difração de raios X (DRX), microscopia ótica, microscopia eletrônica de varredura (MEV) e energia dispersiva de raios X (EDX). As análises eletroquímicas foram realizadas através das técnicas de polarização potenciodinâmica e espectroscopia de impedância eletroquímica. As análises de DRX e de metalografia mostraram as fases presentes em cada aço, sendo o aço AISI 1010 composto pela fase ferrita, o aço AISI 316 pelas fases de FeNi e Cr e o aço UNS S31803 pelas fases austenita e ferrita. Além disso, a metalografia e as análises de MEV e EDX permitiram identificar regiões e certos elementos presentes nos aços que propiciam à ocorrência da corrosão, tais como inclusões. Os inibidores foram testados em diferentes concentrações (25 ppm, 50 ppm, 100 ppm, 500 ppm e 1000 ppm) para os três aços, através das curvas de polarização e impedância eletroquímica, e verificou-se que para todas as concentrações houve aumento da resistência à corrosão dos aços. Pelas curvas de polarização verificou-se que o benzimidazol proporcionou aos aços AISI 1010, AISI 316 e UNS S31803, eficiências de inibição de cerca de 51%, 71% e 75%, respectivamente. Enquanto que o imidazol apresentou eficiência de cerca de 73%, 95% e 86%, respectivamente. Os resultados de impedância eletroquímica mostraram que as eficiências de inibição do benzimidazol foram de aproximadamente 52%, 73% e 71%, respectivamente, para os aços AISI 1010, AISI 316 e UNS S31803. E por sua vez, o imidazol apresentou eficiências de aproximadamente 96% para os aços AISI 1010 e AISI 316 e 85% para o aço UNS S31803. O teste de perda de massa mostrou que para o aço AISI 1010 tanto o benzimidazol quanto e o imidazol inibiram a corrosão, sendo que reduziram a corrosão em cerca de 17% e 24%, respectivamente. Nas análises das curvas de polarização em estudos com a água do mar observou-se que os inibidores foram menos eficientes do que em meio de solução de cloreto. O benzimidazol obteve eficiências de cerca de 14%, 50% e 33%, respectivamente, para os aços AISI 1010, AISI 316 e UNS S31803. Enquanto que o imidazol apresentou eficiências de aproximadamente 21%, 59% e 34%, respectivamente. Em todas as análises eletroquímicas e análise de perda de massa, o imidazol se mostrou o melhor inibidor para os aços estudados.

Cristalização de Biomateriais Vitrocerâmicos e Mineralização em Meio Fisiológico Simulado

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.