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Equilibrium solubility of flurbiprofen, a nonsteroidal antiinflammatory agent, in supercritical carbon dioxide was measured by a static analytical method in the pressure range from (8.0 to 25.0) MPa, at temperatures of (303.0, 313.0, and 323.0) K. The cosolvent effect of ethanol in the solubility of the bioactive compound in supercritical carbon dioxide was investigated at 18 MPa and 313 K. The results obtained have a potential application in supercritical processes for this drug. Experimental solubility data were correlated with an empirical density-based Chrastil model.

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[M(CpBz)(CO)3CH3] (M=Mo, 2a, W, 2b; CpBz=C5(CH2Ph)5) have been prepared and reacted with PCl5 and PhI · Cl2. Depending on the metal and on the chlorinating reagent used [Mo(CpBz) ($η$2-COCH3)Cl3], 3, [W(CpBz)Cl4], 4, [Mo(CpBz)(CO)3Cl], 5 and [Mo(CpBz)Cl4], 6 have been obtained. The molecular structures of all compounds are reported and two conformations have been characterised for the benzyl substituents. In complexes 2a, 2b and 5 one phenyl ring bends towards the metals while in 3 and 4 the five phenyls point opposite to the metals. © 2004 Elsevier B.V. All rights reserved.

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This paper is a draft contribution for a definition of the concept of divestment. This topic is still very influenced by definitions from the fields of economics or management. Thus, from a group of definitions and approaches developed by different authors we try to elaborate on this divestment concept, searching for indicators and variables related to this practice. The founded indicators allow us to identify the main consequences and the potential social impacts due to divestment situations. Also we try to develop a methodology of research for analysis and impact framework that come from divestment action of companies.

According to the model proposed in previous papers [Pettigrew, G. W., Prazeres, S., Costa, C., Palma, N., Krippahl, L., and Moura, J. J. (1999) The structure of an electron-transfer complex containing a cytochrome c and a peroxidase, J. Biol. Chem. 274, 11383-11389; Pettigrew, G. W., Goodhew, C. F., Cooper, A., Nutley, M., Jumel, K., and Harding, S. E. (2003) Electron transfer complexes of cytochrome c peroxidase from Paracoccus denitrificans, Biochemistry 42, 2046-2055], cytochrome c peroxidase of Paracoccus denitrificans can accommodate horse cytochrome c and Paracoccus cytochrome c(550) at different sites on its molecular surface. Here we use H-1 NMR spectroscopy, analytical ultracentrifugation, molecular docking simulation, and microcalorimetry to investigate whether these small cytochromes can be accommodated simultaneously in the formation of a ternary complex. The pattern of perturbation of heme methyl and methionine methyl resonances in binary and ternary solutions shows that a ternary complex can be formed, and this is confirmed by the increase in the sedimentation coefficient upon addition of horse cytochrome c to a solution in which cytochrome c(550) fully occupies its binding site on cytochrome c peroxidase. Docking experiments in which favored binary solutions of cytochrome, c(550) bound to cytochrome c peroxidase act as targets for horse cytochrome c and the reciprocal experiments in which favored binary solutions of horse cytochrome c bound to cytochrome c peroxidase act as targets for cytochrome c(550) show that the enzyme can accommodate both cytochromes at the same time on adjacent sites. Microcalorimetric titrations are difficult to interpret but are consistent with a weakened binding of horse cytochrome c to a binary complex of cytochrome c peroxidase and cytochrome c(550) and binding of cytochrome c(550) to the cytochrome c peroxidase that is affected little by the presence of horse cytochrome c in the other site. The presence of a substantial capture surface for small cytochromes on the cytochrome c peroxidase has implications for rate enhancement mechanisms which ensure that the two electrons required for re-reduction of the enzyme after reaction with hydrogen peroxide are delivered efficiently.

The cytochrome c nitrite reductase is isolated from the membranes of the sulfate-reducing bacterium Desulfovibrio desulfuricans ATCC 27774 as a heterooligomeric complex composed by two subunits (61 kDa and 19 kDa) containing c-type hemes, encoded by the genes nrfA and nrfH, respectively. The extracted complex has in average a 2NrfA:1NrfH composition. The separation of ccNiR subunits from one another is accomplished by gel filtration chromatography in the presence of SDS. The amino-acid sequence and biochemical subunits characterization show that NrfA contains five hemes and NrfH four hemes. These considerations enabled the revision of a vast amount of existing spectroscopic data on the NrfHA complex that was not originally well interpreted due to the lack of knowledge on the heme content and the oligomeric enzyme status. Based on EPR and Mossbauer parameters and their correlation to structural information recently obtained from X-ray crystallography on the NrfA structure {[}Cunha, C. A., Macieira, S., Dias, J.M., Almeida, M.G., Goncalves, L. M. L., Costa, C., Lampreia, J., Huber, R., Moura, J. J. G., Moura, I. & Romano, M. (2003) J. Biol. Chem. 278, 17455-17465], we propose the full assignment of midpoint reduction potentials values to the individual hemes. NrfA contains the high-spin catalytic site (-80 mV) as well as a quite unusual high reduction potential (+150 mV)/low-spin bis-His coordinated heme, considered to be the site where electrons enter. In addition, the reassessment of the spectroscopic data allowed the first partial spectroscopic characterization of the NrfH subunit. The four NrfH hemes are all in a low-spin state (S = 1/2). One of them has a g(max) at 3.55, characteristic of bis-histidinyl iron ligands in a noncoplanar arrangement, and has a positive reduction potential.

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The gene encoding cytochrome c nitrite reductase (NrfA) from Desulfovibrio desulfuricans ATCC 27774 was sequenced and the crystal structure of the enzyme was determined to 2.3-Angstrom resolution. In comparison with homologous structures, it presents structural differences mainly located at the regions surrounding the putative substrate inlet and product outlet, and includes a well defined second calcium site with octahedral geometry, coordinated to propionates of hemes 3 and 4, and caged by a loop non-existent in the previous structures. The highly negative electrostatic potential in the environment around hemes 3 and 4 suggests that the main role of this calcium ion may not be electrostatic but structural, namely in the stabilization of the conformation of the additional loop that cages it and influences the solvent accessibility of heme 4. The NrfA active site is similar to that of peroxidases with a nearby calcium site at the heme distal side nearly in the same location as occurs in the class II and class III peroxidases. This fact suggests that the calcium ion at the distal side of the active site in the NrfA enzymes may have a similar physiological role to that reported for the peroxidases.

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A lot has been written over the last decade with regard to Toyota and the productive model associated to it (toyota-ism). And more specifically concerning the "(…) best-seller that changed the... sociological world" (Castillo, 1998: 31). But the case of Salvador Caetano’s Ovar Industrial Division (OID), that assembles Toyota light commercial vehicles in Portugal, allows us to put forward a sub-hypothesis that fits into the analysis schema proposed in the First GERPISA International Program – "In short, GERPISA members considered that the plurality of models was much a plausible hypothesis deserving testing as that of the diffusion of a unique model (…)" (Boyer, Freyssenet, 2001: 42). So we add: and within Toyota itself, is it not true that different productive models co-exist – especially when delocalised – depending, amongst other factors, on the degree of Toyota participation – in terms of capital and technology transfer – in the local company (strong or weak) and on the markets to be reached (internal or external)? If so, what work system can we expect to find in a plant that presents such peculiar characteristics as this one?

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Functionally graded materials (FGM’s), particularly in the form of Al-Si metal matrix composites (MMC’s) selectively reinforced at the surface with SiC particles, are advanced materials, combining high wear resistance with high bulk toughness or even a thermal barrier at the surface. Centrifugal casting is one of the most effective methods for processing this type of MMC, but accurate control of the ceramic particles distribution/gradient in the metallic matrix has not yet been completely attained. In this work, precursor Al/SiC composites were prepared by rheocasting, using SiC particles and an Al-10Si–2.2 Mg alloy. Morphology of the SiC particles was previously characterized by laser interpherometry and SEM. Differing grain sizes were selected as reinforcing elements. The MMC’s were then molten and centrifugally cast in order to produce the FGM composites, whose structure and properties were investigated by XRD, quantitative image analysis of optical micrographs and longitudinal hardness profiles. Therefore, it was possible to evaluate the influence of the particle grain size on the structure and properties of the FGM. Apart from the evaluation of the effects of particle grain size per se, its influence when combined with differing casting conditions are reported as well.

The production of cytochrome c peroxidase (CCP) from Pseudomonas ( Ps.) stutzeri (ATCC 11607) was optimized by adjusting the composition of the growth medium and aeration of the culture. The protein was isolated and characterized biochemically and spectroscopically in the oxidized and mixed valence forms. The activity of Ps. stutzeri CCP was studied using two different ferrocytochromes as electron donors: Ps. stutzeri cytochrome c(551) (the physiological electron donor) and horse heart cytochrome c. These electron donors interact differently with Ps. stutzeri CCP, exhibiting different ionic strength dependence. The CCP from Paracoccus ( Pa.) denitrificans was proposed to have two different Ca(2+) binding sites: one usually occupied (site I) and the other either empty or partially occupied in the oxidized enzyme (site II). The Ps. stutzeri enzyme was purified in a form with tightly bound Ca(2+). The affinity for Ca(2+) in the mixed valence enzyme is so high that Ca(2+) returns to it from the EGTA which was added to empty the site in the oxidized enzyme. Molecular mass determination by ultracentrifugation and behavior on gel filtration chromatography have revealed that this CCP is isolated as an active dimer, in contrast to the Pa. denitrificans CCP which requires added Ca(2+) for formation of the dimer and also for activation of the enzyme. This is consistent with the proposal that Ca(2+) in the bacterial peroxidases influences the monomer/dimer equilibrium and the transition to the active form of the enzyme. Additional Ca(2+)does affect both the kinetics of oxidation of horse heart cytochrome c (but not cytochrome c(551)) and higher aggregation states of the enzyme. This suggests the presence of a superficial Ca(2+)binding site of low affinity.

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The concept of functionally graded material (FGM), may be considered as a model particularly interesting to be applied in components for the automotive industry, if reliability and cost can be controlled in an advantageous way. In fact, coupling superior superficial wear resistance with a significant bulk toughness, without compromising important weight savings, by using Al-Si metal matrix composites (MMC’s) selectively reinforced at the surface with SiC particles, is likely to be considered as a innovative advance to that industrial field, if adequate production techniques are developed. Casting under a centrifugal force may well be considered as one of the most effective methods for processing Al-based FGM´s. A primary problem to be faced when producing MMC´s reinforced with ceramic particles is related with the imperfect wetting of the ceramic particles by the molten matrix alloy. A first consequence of defective wetting may be the formation of ceramic-ceramic, ceramic-gas and/or metal-gas interfaces, instead of the desired metal-ceramic interface. Secondly, wetting phenomena play an essential role regarding the physical, chemical and mechanical characteristics of the metal/ceramic interface. A general consequence of these aspects may be related with the degradation of the material properties, be it mechanical, chemical, or thermal in nature. The present work refers to an X-ray microtomography experiment aiming at the elucidation of some aspects regarding particle distribution in SiCp-reinforced functionally graded aluminium composites. Precursor composites were produced by rheocasting. These were then molten and centrifugally cast in order to produce the FGM composites. From these, small cylindrical samples were extracted and observed by X-ray microtomography at the European Synchrotron Radiation Facility (ESRF). The 3D tomographic images were obtained in edge-detection mode (phase-contrast mode), and an adequate segmentation procedure was employed to isolate the pores and SiC particles from the Al matrix. This has allowed a study of the relations between the matrix, the SiC particles, and locally intervening porosities of varying shapes, aiming at a better understanding of the mechanisms involved.

A novel iron(III) porphyrin disulphide derivative have been successfully immobilised on gold surfaces by self-assembly. The redox response of the modified electrodes was compared with the obtained for a similar iron porphyrin in solution, confirming the immobilisation of the metalloporphyrin. The gravimetric data obtained by electrochemical quartz crystal microbalance (EQCM) during adsorption allowed an estimation of the electrode coverage, providing further evidence for the formation of the porphyrin SAM. The modified electrodes were also measured by conventional and imaging ellipsometry. The electrocatalytic activity of the two modified electrodes was tested for the reduction of the molecular oxygen. (C) 2002 Elsevier Science B.V. All rights reserved.

The present work refers to an X-ray microtomography experiment aiming at the elucidation of some aspects regarding particle distribution in SiC-particle-reinforced functionally graded aluminium composites.
Precursor composites were produced by rheocasting. These were then molten and centrifugally cast to obtain the
functionally graded composites. From these, cylindrical samples, around 1 mm in diameter, were extracted, which were then irradiated with a X-ray beam produced at the European Synchrotron Radiation Facility.
The 3-D images were obtained in edge-detection mode. A segmentation procedure has been adapted in order to
separate the pores and SiC particles from the Al matrix. Preliminary results on the particle and pore distributions are presented.