Structural and electronic properties of PbTiO3 slabs: a DFT periodic study

Structural and electronic properties of the bulk and relaxed surfaces (TiO2 and PbO terminated) of cubic PbTiO3 are investigated by means of periodic quantum-mechanical calculations based on density functional theory. It is observed that the difference in surface energies is small and relaxations effects are most prominent for Ti and Ph surface atoms. The electronic structure shows a splitting of the lowest conduction bands for the TiO2 terminated surface and of the highest valence bands for the PbO terminated slab. The calculated indirect band gap is: 3.18, 2.99 and 3.03 eV for bulk, TiO2 and PbO terminations, respectively. The electron density maps show that the Ti-O bond has a partial covalent character, whereas the Pb-O bonds present a very low covalency. (C) 2004 Elsevier B.V. All rights reserved.

Effects of the magnesium and chloride ions and shikimate on the structure of shikimate kinase from Mycobacterium tuberculosis

Bacteria, fungi and plants can convert carbohydrate and phosphoenolpyruvate into chorismate, which is the precursor of various aromatic compounds. The seven enzymes of the shikimate pathway are responsible for this conversion. Shikimate kinase (SK) is the fifth enzyme in this pathway and converts shikimate to shikimate-3-phosphate. In this work, the conformational changes that occur on binding of shikimate, magnesium and chloride ions to SK from Mycobacterium tuberculosis (MtSK) are described. It was observed that both ions and shikimate influence the conformation of residues of the active site of MtSK. Magnesium influences the conformation of the shikimate hydroxyl groups and the position of the side chains of some of the residues of the active site. Chloride seems to influence the affinity of ADP and its position in the active site and the opening length of the LID domain. Shikimate binding causes a closing of the LID domain and also seems to influence the crystallographic packing of SK. The results shown here could be useful for understanding the catalytic mechanism of SK and the role of ions in the activity of this protein.

Effects of cardiomyopathic mutations on the biochemical and biophysical properties of the human alpha-tropomyosin

Mutations in the protein alpha-tropomyosin (Tm) can cause a disease known as familial hypertrophic cardiomyopathy. In order to understand how such mutations lead to protein dysfunction, three point mutations were introduced into cDNA encoding the human skeletal tropomyosin, and the recombinant Tms were produced at high levels in the yeast Pichia pastoris. Two mutations (A63V and K70T) were located in the N-terminal region of Tm and one (E180G) was located close to the calcium-dependent troponin T binding domain. The functional and structural properties of the mutant Tms were compared to those of the wild type protein. None of the mutations altered the head-to-tail polymerization, although slightly higher actin binding was observed in the mutant Tm K70T, as demonstrated in a cosedimentation assay. The mutations also did not change the cooperativity of the thin filament activation by increasing the concentrations of Ca2+. However, in the absence of troponin, all mutant Tms were less effective than the wild type in regulating the actomyosin subfragment 1 Mg2+ ATPase activity. Circular dichroism spectroscopy revealed no differences in the secondary structure of the Tms. However, the thermally induced unfolding, as monitored by circular dichroism or differential scanning calorimetry, demonstrated that the mutants were less stable than the wild type. These results indicate that the main effect of the mutations is related to the overall stability of Tm as a whole, and that the mutations have only minor effects on the cooperative interactions among proteins that constitute the thin filament.

Vascular effects and electrolyte homeostasis of the natriuretic peptide isolated from Crotalus oreganus abyssus (North American Grand Canyon rattlesnake) venom

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Raman spectroscopy analysis of structural photoinduced changes in GeS2 + Ga2O3 thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS2 + Ga2O3 (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds' breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Photoexpansion and photobleaching effects in oxysulfide thin films of the GeS2+Ga2O3 system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, structural refinement and optical behavior of CaTiO3 powders: A comparative study of processing in different furnaces

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electronic and structural properties of the (10(1)over-bar0) and (11(2)over-bar0) ZnO surfaces

The structural and electronic properties of ZnO (10 (1) over bar0) and (11 (2) over bar0) surfaces were investigated by means of density functional theory applied to periodic calculations at B3LYP level. The stability and relaxation effects for both surfaces were analyzed. The electronic and energy band properties were discussed on the basis of band structure as well as density of states. There is a significant relaxation in the (10 (1) over bar0) as compared to the (11 (2) over bar0) terminated surfaces. The calculated direct gap is 3.09, 2.85, and 3.09 eV for bulk, (10 (1) over bar0), and (11 (2) over bar0) surfaces, respectively. The band structures for both surfaces are very similar.

Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Functional and Structural Adaptations in the Pancreatic alpha-Cell and Changes in Glucagon Signaling During Protein Malnutrition

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Effects of N Helix Deletion and Mutant F29W on the Ca2+ Binding and Functional Properties of Chicken Skeletal Muscle Troponin C

To assess the structural and functional significance of the N helix (residues 3-13) of avian recombinant troponin C (rTnC), we have constructed NHdel, in which residues 1-11 have been deleted, both in rTnC and in the spectral probe mutant F29W (Pearlstone, J. R., Borgford, T., Chandra, M., Oikawa, K., Kay, C. M., Herzberg, O., Moult, J., Herklotz, A., Reinach, F. C., and Smillie, L.B. (1992) Biochemistry 31, 6545-6553). Comparison of the far- and near-UV CD spectra (±Ca2+) of F29W and F29W/ NHdel and titration of the Ca2+-induced ellipticity and fluorescence changes indicates that the deletion has little effect on the global fold of the molecule but reduces the Ca2+ affinity of the N domain, but not the C domain, by 1.6-1.8-fold. Comparisons of the mutants NHdel, F29W, and F29W/NHdel with rTnC have been made using several functional assays. In reconstituted troponin-tropomyosin actomyosin subfragment 1 and myofibrillar ATPase systems, both F29W and NHdel have significantly reduced Ca2+-activated enzymic activities. These effects are cumulative in the double mutant F29W/ NHdel. On the other hand, maximal isometric tension development in Ca2+-activated reconstituted skinned fibers is not affected with F29W and NHdel, although the Ca2+ sensitivity of NHdel in this system is markedly reduced. We conclude that both mutations, NHdel and F29W, are functionally deleterious, possibly affecting interactions of the N domain with troponin I and/or T.

Cycloactive, aneugenic and clastogenic effects of Paracoccidioides brasiliensis exoantigen in human lymphocyte cultures

The in vitro effect of Paracoccidioides brasiliensis exoantigen on the human lymphocytes cell cycle and chromosomes was studied. Human peripheral blood lymphocyte cultures from ten healthy, white, non-smoking, non-related adult males (mean age 31·3 ± 8·2 years) were studied. Blood cultures were treated with three exoantigen concentrations (0·25, 2·50 and 10·00 μg ml -1). At least 1000 metaphases were analysed at each concentration, for evaluation of numerical and structural chromosome aberrations (cA) and 30 000 for mitotic index (MI). Among the treated cultures, statistically significant differences in the frequencies of MI and cA were not observed. Nevertheless, when compared with control cultures, they all showed a significantly lower frequency of MI and higher frequency of cA. It is suggested that the detected alterations were caused by the exoantigen, its fractions or its metabolites. © 1996 Informa UK Ltd All rights reserved.

Effects of tunicamycin on glycoprotein antigens of Aspergillus fumigatus

Tunicamycin, which inhibits N-glycosylation of proteins, was used as a tool to determine the type of linkage which occurs in glycoprotein antigens of Aspergillus fumigatus. When A. fumigatus extracts were electrophoretically separated and blotted then probed with anti-Aspergillus patients' sera, differences in antigenic profiles were noted when tunicamycin-treated samples were compared with controls. Tunicamycin had no detectable effect on the cellular proteinases of A. fumigatus, most of which are glycosylated. Some enzymatic components were lacking when extracellular proteinases were compared with those of control samples. The major catalase component of A. fumigatus is a concanavalin A (Con A)-binding glycoprotein. In cultures grown in the presence of tunicamycin, partiallydeglycosylated catalase components were obtained which could be distinguished from the native catalase by their altered mobilities in polyacrylamide gels. The effect of deglycosylation on catalase antigens was monitored using an antiserum raised to a ConA-binding fraction of A fumigatus mycelium. These antibodies bound both to the native glycoprotein and the partially deglycosylated material. These latter two were largely unaffected when incubated with an antiserum raised to a non-ConA-binding fraction of A. fumigatus which is essentially carbohydrate free. The ability to produce partially-glycosylated antigens of A. fumigatus offers a model to study the effect of basic structural modifications on both the enzymatic and antigenic activities of these molecules.

Structural changes induced by ultrasound during aging of the boehmite phase

Structural changes induced by ultrasound during the aging of the aluminum monohydroxide (boehmite) were studied by means of X-ray diffraction (XRD) and nitrogen adsorption. The BET surface area and the pore volume of the ultrasound stimulated hydroxide (HU) are about 40% less than those of the non-stimulated one (HS). The mean pore size practically does not change, while the mean crystallite size (L) is about 25% greater in the HU system. The increase of L alone is not enough to account for the surface area diminution, suggesting that the sonication also induces compaction by elimination of some porosity. The sonication of the precursor hydroxide does not seem to play an apparent role in the structural properties of the resulting calcinated γ-alumina. © 1997 Elsevier Science B.V.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.