Dynamics of meso and thermo citrate synthases with implicit solvation

The dynamics of hydration of meso and thermo citrate synthases has been investigated using the EEF1 methodology implemented with the CHARNM program. The native enzymes are composed of two identical subunits, each divided into a small and large domain. The dynamics behavior of both enzymes at 30 degrees C and 60 degrees C has been compared. The results of simulations show that during the hydration process, each subunit follows a different pathway of hydration, in spite of the identical sequence. The hydrated structures were compared with the crystalline structure, and the root mean square deviation (RMSD) of each residue along the trajectory was calculated. The regions with larger and smaller mobility were identified. In particular, helices belonging to the small domain are more mobile than those of the large domain. In contrast, the residues that constitute the active site show a much lower displacement compared with the crystalline structure. Hydration free energy calculations point out that Thermoplasma acidophilum citrate synthase (TCS) is more stable than chicken citrate synthase (CCS), at high temperatures. Such result has been ascribed to the higher number of superficial charges in the thermophilic homologue, which stabilizes the enzyme, while the mesophilic homologue denatures. These results are in accord with the experimental found that TCS keeps activity at temperatures farther apart from the catalysis regular temperature than the CCS. (c) 2005 Wiley Periodicals, Inc.

Caracterização macro, meso e microscópica das estruturas frágeis do corpo arenítico conglomerático da região de Santana do Acaraú (CE) e seu embasamento circundante

The structural framework of the sedimentary basins usually plays an important role in oil prospects and reservoirs. Geometry, interconectivity and density of the brittle features developed during basin evolution could change the permo-porous character of the rocks involved in generation, migration and entrapment of fluid flow. Once the structural characterization of the reservois using only sub-surface data is not an easy task, many studies are focused in analogous outcrops trying to understand the main processes by which brittle tectonic is archieved. In the Santana do Acaraú region (Ceará state, NE Brazil) a pack of conglomeratic sandstone (here named CAC) has its geometry controlled mainly by NE trending faults, interpreted as related to reactivation of a precambrian Sobral Pedro II Lineament (LSP-II). Geological mapping of the CAC showed a major NE-SW trending synform developed before its complete lithification during a dextral transpression. This region was then selected to be studied in details in order of constrain the cretaceous deformation and so help the understanding the deformation of the basins along the brazilian equatorial margin. In order to characterize the brittle deformation in different scales, I study some attributes of the fractures and faults such as orientation, density, kinematic, opening, etc., through scanlines in satellite images, outcrops and thin sections. The study of the satellite images showed three main directions of the macrostructures, N-S, NE-SW and E-W. Two of theses features (N-S and E-W) are in aggreement with previous geophysical data. A bimodal pattern of the lineaments in the CAC´s basement rocks has been evidenciated by the NE and NW sets of structures obtained in the meso and microscale data. Besides the main dextral transpression two others later events, developed when the sediments were complety lithified, were recognized in the area. The interplay among theses events is responsible for the compartimentation of the CAC in several blocks along within some structural elements display diferents orientations. Based on the variation in the S0 orientation, the CAC can be subdivided in several domains. Dispite of the variations in orientations of the fractures/faults in the diferents domains, theses features, in the meso and microscopic scale, are concentrated in two sets (based on their trend) in all domains which show similar orientation of the S0 surface. Thus the S0 orientation was used to group the domains in three major sets: i) The first one is that where S0 is E-W oriented: the fractures are oriented mainly NE with the development of a secondary NW trending; ii) S0 trending NE: the fractures are concentrated mainly along the trend NW with a secondary concentration along the NE trend; iii) The third set, where S0 is NS the main fractures are NE and the secondary concentration is NW. Another analized parameter was the fault/fracture length. This attribute was studied in diferent scales trying to detect the upscale relationship. A terrain digital model (TDM) was built with the brittlel elements supperposed. This model enhanced a 3D visualization of the area as well as the spatial distribution of the fault/fractures. Finally, I believe that a better undertanding of the brittle tectonic affecting both CAC and its nearby basement will help the future interpretations of the tectonic envolved in the development of the sedimentary basins of the brazilian equatorial margin and their oil reservoirs and prospects, as for instance the Xaréu field in the Ceará basin, which subsurface data could be correlated with the surface ones

Evolução estrutural e termocronológica meso-cenozóica da Zona de Cisalhamento Portalegre, Nordeste do Brasil

The Portalegre shear zone (ZCPa), which is located in the Rio Grande do Norte and Paraíba states (Northeastern Brazil), is na important right-lateral, northeast-trending lineament formed during the Brazilian Orogenic Cicle). The ZCPa experienced na important brittle reactivation from the Mesozoic until the present. This reactivation led to the formation of the Gangorra, Pau dos Ferros, Coronel João Pessoa, Icozinho and Rio do Peixe basins. The reactivation northern parto f the ZCPa that marks the boundary of the Potiguar Basin is denominated Carnaubais Fault. Several fracture patterns were mapped along the ZCPa. Samples were collected in Neoproterozoic granite outcrops, along the ZCPa. These samples yielded AFT ages from 86±13 to 376±57 Ma, and the mean track length from 10.9±0.8 to 12.9±1.5 mm. Samples from the East block yielded mean ages of 103 Ma, mean track lengtn 12,1mm, and mean altitude 250m, whereas samples from West block yielded mean ages of 150 Ma, which reach 345 Ma and 220 Ma in the Pau dos Ferros and Coronel João Pessoa basins, respectively. Thermal history models were sorted out for each crustal block. Samples from West block recorded a thermal history from Carboniferous Period until the Permiano, when the block experienced gradual uplift until the Cretaceous, when it underwent downfaulting and heating until the Tertiary, and it eventually experienced a rapid uplift movement until recent times. Samples from the East block presented the same cooling and heating events, but at they occurred different times. The East block thermal record started ~140 Ma, when this block experienced cooling until ~75 Ma. Both blocks show a denundacion/erosional history more similar in the Tertiary. The AFT data indicate an important tectonic event ~140 Ma, when the West block experienced downfaulting and the East block experienced uplift. This tectonic process led to the generation of several sedimentary basins in the region, including the Potiguar basin. This tectonic event is also interpreted as a rift process caused by an E-W-trending extension. It the Tertiary, some heating events can be tentatively attributed to the macau volcanic event

A condição das coxas anteriores, do meso-catepímero e do meso-catepisterno dos Tabanidae (Diptera) e sua possível importância na classificação

The condition of certain neglected structures and their possible importance to the classification of the family Tabanidae are studied. The front coxae are considered as belonging to two types: 1) short and robust; 2) long and slender. The posterior edge of the meso-katepimeron presents two conditions: 1) without projection, 2) with backward projection. Similar conditions are found in the meso-Katepisternum, but with intermediate conditions. These characters are discussed in relation to the system proposed for the family by Mackerras. Conditions 1 and 2 of the former two structures separate, respectively, the Pangoniinae and Scepsidinae from the Chrysopsinae and Tabaninae. Condition 2 of the third structure seems to be developing independently in different groups of Tabaninae, with varying degrees of development.

Photodynamic inactivation of biofilms formed by Candida spp., Trichosporon mucoides, and Kodamaea ohmeri by cationic nanoemulsion of zinc 2,9,16,23-tetrakis(phenylthio)-29H, 31H-phthalocyanine (ZnPc)

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

Meso and microhabitat analysis and feeding habits of small nektonic characins (Teleostei: Characiformes) in Neotropical streams

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

Soil loss risk and habitat quality in streams of a meso-scale river basin

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

Characterization and catalytic activity of iron(III) mono(4-N-methyl pyridyl)-tris(halophenyl) porphyrins in homogeneous and heterogeneous systems

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe-imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated (FeP)-P-III and high-spin mono-coordinated (FeP)-P-III species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated (FeP)-P-III. These FePIPG catalysts also contain (FeP)-P-II species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe-O ligation and they are present as high-spin (FeP)-P-III species. The cationic FePs supported on SiSO3- are also high-spin (FeP)-P-III species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3- groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices,both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3- shows that this FeP maintains its activity in a second reaction. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Characterization of electrodes chemically modified with Mn(III) porphyrin/polypyrrole films as catalytic surfaces for an azo dye

In this study we describe the electrochemical behavior of 5,10,15,20-tetrakis(2'-aminophenylporphyrin)manganese(III) chloride supported on a glassy carbon electrode, as well as the electrochemical preparation and characterization of thin films based on pyrrole-3-carboxylic acid. The electrocatalytic action of the electrode modified with the Mn(III) porphyrin toward an azo dye was tested, and the characteristic strong interaction between the incorporated metalloporphyrin and RR120 dye was verified. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.

Geochronology of the lpanema layered mafic-ultramafic complex, Minas gerais, Brazil: Evidence of extension at the meso-neoproterozoic time boundary

The mafic/ultramafic Ipanema Layered Complex (ILC), Minas Gerais Brazil, consists of seven individual bodies. These units crosscut polyphase orthogneisses and interlayered paragneisses of the Paleoproterozoic Juiz de Fora Complex. Intrusive granitoids tectonically related to [lie Neoproterozoie Aracuai orogen are also present in the study area.A Sm-Nd whole-rock linear array for seven samples metapyoxenites, metaperidotiles, metagabbro. and meta-anorthosite) from the Santa Cruz massif, the largest body of the ILC. suggest that it was emplaced at 1104 +/- 78 Ma the original magma was derived from a depleted mantle source (epsilon(Ndt)= +3.8). U-Pb single-grain zircon stud of a meta-anorthosite yields all upper intercept age of 1719 +/- 4 Ma, which is interpreted to represent inheritance. The lower intercept at 630+/-3 Ma indicates (hat a Neoproterozoic tectonothermal episode overprinted the ILC, this event occurred under upper-amphiolite-, to granulite-facies conditions. The 630 Ma episode is consistent with the timing of regional metamorphism and deformation of the adjacent Aracuai orogen (Brasiliano collage). Emplacement of the ILC and other coeval metamafies and meta-ultramafics (of alkaline affinity) in the re, oil is attributed to early extension tectonics, accompanying accretion of the Rodinia super- continent during the Mesoproterozoic-Neoproterozoic time boundary.

Manganese(III) porphyrins: Catalytic activity and intermediate studies in homogeneous systems

We studied how solvent, stirring method, PhIO/MnP molar ratio, presence of water and axial ligand affect the catalytic activities of Mn(TPP)Cl, Mn(MNPP)Cl, Mn(TDCPP)Cl and Mn(TFPP)Cl in the oxidation of cyclohexane by PhIO. A study of the catalytic intermediates in the reaction between Mn(TPP)Cl or Mn(TDCPP)Cl and PhIO was also carried out by UV-Vis and EPR spectroscopies. The reaction of Mn(TPP)Cl with PhIO showed the formation of a mixture of species Mn-IV(OP+ and Mn-V(O)P as intermediates, which were confirmed by the deconvolution of the UV-Vis spectra. Addition of imidazole as cocatalyst favoured the formation of the intermediate species Mn-V(O)P, evidenced by the UV-Vis band at 408 nm. The corresponding EPR spectra gave evidence that in the presence of imidazole, Mn-IV(OP+ species are formed only in very low amounts. For Mn(TDCPP)Cl the dominating intermediate species is Mn-IV(OP+. Addition of imidazole to halogen-substituted MnP systems does not result in increase of the C-ol yields because very stable bis-imidazole-MnP complexes are formed. Anchoring of such MnP on imidazole propyl gel (IPG) results in better catalytic activity because in this case, the catalyst is mono-coordinated to the support and imidazole favours the formation of the intermediate species Mn-V(O)P.

A tectônica meso-cenozóica de parte da borda nordeste da Bacia do Paraná: traços de fissão em apatita

The possible development of thermal events in the central portion of São Paulo state was described based on apatite fission track analysis. Using apatites of sedimentary rocks of the Paraná Basin, modeling the thermal history was made possible due to the homogeneity of the data. Every thermal history begins with a total annealing of fission tracks, related to the Serra Geral magmatism, evolving into a cooling period. In addition to cooling after the magmatism (Early Cretaceous) two other periods of cooling were also detected, registered in the Late Cretaceous/ Paleocene and Eocene, driven as much by uplift with tectonic denudation as by faulting. The nearest portion of the edge of the basin (external to the Dome of Pitanga), registered a period of warming over the Paleocene that can be attributed to the increase in the geothermal gradient. The periods of cooling have a regional and temporal relationship with the tectonic events that occurred in the southeastern Brazil and were described in the crystalline basement. The period of warming, registered in the Late Cretaceous/ Paleocene, has local occurrence and can be found only in the southern portion of the studied area.

Cuentas de producción y análisis de insumo-producto: hacia la integración de los datos micro, meso y macroeconómicos

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