[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.

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.

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.

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.

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.

Crystals of cytochrome c peroxidase from Pseudomonas stutzeri were obtained using sodium citrate and PEG 8000 as precipitants. A complete data set was collected to a resolution of 1.6 A under cryogenic conditions using synchrotron radiation at the ESRF. The crystals belong to space group P2(1), with unit-cell parameters a = 69.29, b = 143.31, c = 76.83 A, beta = 100.78 degrees. Four CCP molecules were found in the asymmetric unit, corresponding to a pair of dimers related by local dyads. The crystal packing in the structure shows that the functional dimers can dimerize, as suggested by previous biochemical studies.

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