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Indium-Tin-Oxide (ITO) thin films were deposited on glass substrates using DC magnetron reactive sputtering at different bias voltages and substrate temperatures. Some improvements were obtained on film properties, microstructure and other physical characteristics for different conditions. Amorphous and polycrystalline films can be obtained for various deposition conditions. The transmission, absorption, spectral and diffuse reflection of ITO films were measured in some ranges of UV-Vis-NIR. The refractive index (n), Energy band gap Eg and the surface roughness of the film were derived from the measured spectra data. The carrier density (nc) and the carrier mobility (μ) of the film micro conductive properties were discussed. The films exhibited suitable optical transmittance and conductivity for electrochromic applications. © 2002 Elsevier Science B.V. All rights reserved.

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The catalytic step that initiates formation of the ferric oxy-hydroxide mineral core in the central cavity of H-type ferritin involves rapid oxidation of ferrous ion by molecular oxygen (ferroxidase reaction) at a binuclear site (ferroxidase site) found in each of the 24 subunits. Previous investigators have shown that the first detectable reaction intermediate of the ferroxidase reaction is a diferric-peroxo intermediate, F-peroxo, formed within 25 ms, which then leads to the release of H2O2 and formation of ferric mineral precursors. The stoichiometric relationship between F-peroxo, H2O2, and ferric mineral precursors, crucial to defining the reaction pathway and mechanism, has now been determined. To this end, a horseradish peroxidase-catalyzed spectrophotometric method was used as an assay for H2O2. By rapidly mixing apo M ferritin from frog, Fe2+, and O-2 and allowing the reaction to proceed for 70 ms when F-peroxo has reached its maximum accumulation, followed by spraying the reaction mixture into the H2O2 assay solution, we were able to quantitatively determine the amount of H2O2 produced during the decay of F-peroxo. The correlation between the amount of H2O2 released with the amount of F-peroxo accumulated at 70 ms determined by Mossbauer spectroscopy showed that F-peroxo decays into H2O2 with a stoichiometry of 1 F-peroxo:H2O2. When the decay of F-peroxo was monitored by rapid freeze-quench Mossbauer spectroscopy, multiple diferric mu-oxo/mu-hydroxo complexes and small polynuclear ferric clusters were found to form at rate constants identical to the decay rate of F-peroxo. This observed parallel formation of multiple products (H2O2, diferric complexes, and small polynuclear clusters) from the decay of a single precursor (F-peroxo) provides useful mechanistic insights into ferritin mineralization and demonstrates a flexible ferroxidase site.

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For the study of astrophysically relevant capture reactions in the underground laboratory LUNA a new setup of high sensitivity has been implemented. The setup includes a windowless gas target, a 4$π$ BGO summing crystal, and beam calorimeters. The setup has been recently used to measure the d(p,$\gamma$)3He cross-section for the first time within its solar Gamow peak, i.e. down to 2.5keV c.m. energy. The features of the optimized setup are described. © 2002 Elsevier Science B.V. All rights reserved.

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The catalytic step that initiates formation of the ferric oxy-hydroxide mineral core in the central cavity of H-type ferritin involves rapid oxidation of ferrous ion by molecular oxygen (ferroxidase reaction) at a binuclear site (ferroxidase site) found in each of the 24 subunits. Previous investigators have shown that the first detectable reaction intermediate of the ferroxidase reaction is a diferric-peroxo intermediate, F(peroxo), formed within 25 ms, which then leads to the release of H(2)O(2) and formation of ferric mineral precursors. The stoichiometric relationship between F(peroxo), H(2)O(2), and ferric mineral precursors, crucial to defining the reaction pathway and mechanism, has now been determined. To this end, a horseradish peroxidase-catalyzed spectrophotometric method was used as an assay for H(2)O(2). By rapidly mixing apo M ferritin from frog, Fe(2+), and O(2) and allowing the reaction to proceed for 70 ms when F(peroxo) has reached its maximum accumulation, followed by spraying the reaction mixture into the H(2)O(2) assay solution, we were able to quantitatively determine the amount of H(2)O(2) produced during the decay of F(peroxo). The correlation between the amount of H(2)O(2) released with the amount of F(peroxo) accumulated at 70 ms determined by Mossbauer spectroscopy showed that F(peroxo) decays into H(2)O(2) with a stoichiometry of 1 F(peroxo):H(2)O(2). When the decay of F(peroxo) was monitored by rapid freeze-quench Mossbauer spectroscopy, multiple diferric mu-oxo/mu-hydroxo complexes and small polynuclear ferric clusters were found to form at rate constants identical to the decay rate of F(peroxo). This observed parallel formation of multiple products (H(2)O(2), diferric complexes, and small polynuclear clusters) from the decay of a single precursor (F(peroxo)) provides useful mechanistic insights into ferritin mineralization and demonstrates a flexible ferroxidase site.

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Remains of dinosaurian embryos, hatchlings and early juveniles are currently the subject of increasing interest, as new discoveries and techniques now allow to analyse palaeobiological subjects such as growth and life history strategies of dinosaurs. So far, available ‘embryonic’ material mainly involved Ornithopods and some Theropods of Upper Cretaceous age. We describe here the histology of several bones (vertebrae, limb bones) from the tiny but exceptionally well preserved in ovo remains of Upper Jurassic Theropod dinosaurs from the Paimogo locality near Lourinhã (Portugal). This Jurassic material allows to extend in time and to considerably supplement in great details our knowledge of early phases of growth in diameter and in length of endoskeletal bones of various shape, as well as shape modelling among carnivorous dinosaurs. Endochondral ossification in both short and long bones involves extensive pads of calcified cartilages permeated by marrow buds. We discuss the likely occurrence of genuine cartilage canals in dinosaurs and of an avian-like ‘medullary cartilaginous cone’ in Theropods. Patterns of periosteal ossification suggest high initial growth rates (20 μ m·day−1 or more), at once modulated by precise and locally specific changes in rates of new bone deposition. The resulting very precise shape modelling appears to start early and to involve at once some biomechanical components.

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The periplasmic hydrogenase of Desulfovibrio vulgaris (Hildenbourough) is an all Fe-containing hydrogenase. It contains two ferredoxin type [4Fe-4S] clusters, termed the F clusters, and a catalytic H cluster. Recent X-ray crystallographic studies on two Fe hydrogenases revealed that the H cluster is composed of two sub-clusters, a [4Fe-4S] cluster ([4Fe-4S]H) and-a binuclear Fe cluster ([2Fe]H), bridged by a cysteine sulfur. The aerobically purified D. vulgaris hydrogenase is stable in air. It is inactive and requires reductive activation. Upon reduction, the enzyme becomes sensitive to O-2 indicating that the reductive activation process is irreversible. Previous EPR investigations showed that upon reoxidation (under argon) the H cluster exhibits a rhombic EPR signal that is not seen in the as-purified enzyme, suggesting a conformational change in association with the reductive activation. For the purpose of gaining more information on the electronic properties of this unique H cluster and to understand further the reductive activation process, variable-temperature and variable-field Mossbauer spectroscopy has been used to characterize the Fe-S clusters in D. vulgaris hydrogenase poised at different redox states generated during a reductive titration, and in the GO-reacted enzyme. The data were successfully decomposed into spectral components corresponding to the F and H clusters,and characteristic parameters describing the electronic and magnetic properties of the F and H clusters were obtained. Consistent with the X-ray crystallographic results, the spectra of the H cluster can be understood as originating from an exchange coupled [4Fe-4S] - [2Fe] system. In particular, detailed analysis of the data reveals that the reductive activation begins with reduction of the [4Fe-4S]H cluster from the 2+ to the If state, followed by transfer of the reducing equivalent from the [4Fe-4S]H subcluster to the binuclear [2Fe]H subcluster. The results also reveal that binding of exogenous CO to the H cluster affects significantly the exchange coupling between the [4Fe-4S]H and the [2Fe]H subclusters. Implication of such a CO binding effect is discussed.

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