CASPT2 Study of the Potential Energy Surface of the HSO(2) System

The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2) -> H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations:,CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOOs and the HSO(2) minima defining new reaction paths for SH + O(2) -> H + SO(2) and SH + O(2) -> OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.

A theoretical and mass spectrometry study of the fragmentation of mycosporine-like amino acids

In the present study, the mycosporine-like amino acids (MAAs) were isolated from the marine red alga Gracilaria tenuistipitata and analysed by high-resolution accurate-mass sequential mass spectrometry (MSn). In addition to the proposed fragmentation mechanism based on the MSn analysis, it is clearly demonstrated that the elimination of mass 15 is a radical processes taking place at the methoxyl substituent of the double bond. This characteristic loss of a methyl radical was studied by theoretical calculations and the homolytic cleavage of the O-C bond is suggested to be dependent on the bond weakening. The protonation site of the MAAs was indicated by analysis of the Fukui functions and the relative Gibbs energies of the several possible protonated forms. (C) 2008 Elsevier B.V. All rights reserved.

A CASSCF/MRCI Study of the Low-Lying Electronic States of the BeS Molecule

Accurate potential energy curves, dipole moment functions, dissociation energies, and molecular constants for several low-lying singlet and triplet electronic states of BeS were investigated using the CASSCF/MRCI methodology, and the cc-pV5Z basis set for beryllium, and the aug-cc-pV(5+d) Z set for sulfur. Besides presenting improved results for the three lowest lying states, this study presents the first theoretical characterization of another set of nine excited states so far unknown experimentally. Our results are sufficiently accurate to reliably guide the experimental search and characterization of these states, and also to confirm the experimental assignment of the B(1)Sigma(+) excited state. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1694-1700, 2011

Retrospective study of thoracolumbar ventral fenestration through intercostal thoracotomy and paracostal laparotomy in the dog

Foram analisados os resultados da fenestração ventral dos discos toracolombares em 29 cães agrupados segundo a raça, sexo, peso, idade, graus de déficits neurológicos, duração dos sinais, discos intervertebrais envolvidos, tempo para recuperação e porcentagem de sucesso. A raça Dachshund representou 55,18% (n = 16), cães sem raça definida, 13,8% (n = 4), Poodle e Basset Hound e Cocker Spaniel Inglês 6,89% cada (n = 6), e Pastor Alemão, Beagle e Pinscher, 3,45% cada (n = 3), sendo 51,72%, machos e 48,28%, fêmeas, com idade média de 68,03 meses. O grau de déficits neurológicos correspondeu a: 13,8% dos cães pertencentes ao GI (dor), 41,8% ao GII (paresia), 27,6% ao GIII (paraplegia com dor profunda presente) e 17,2% ao GIV (paraplegia com dor profunda ausente). Os sinais clínicos variaram em duração entre 2 e 60 dias, correspondendo às médias de 18,5 (GI), 12,3 (GII), 8,28 (GIII) e 4,2 dias (GIV). A porcentagem de discos intervertebrais acometidos foi: T10/11 (10,81%), T11/12 (24,33%), T12/13 (40,55%), T13/L1 (16,21%) e L1/2, L2/3 e L3/4, 2,7% cada. O tempo médio de recuperação, em dias, foi: 16 (GI), 19,1 (GII), 20,6 (GIII) e 30,6 (GIV), onde 100% dos animais dos grupos I, II e III recuperaram ambas as funções neurológicas e motoras. O grupo IV apresentou 80% de sucesso. Conclui-se que a fenestração ventral produz excelentes resultados pós-operatórios desde que bem selecionados os casos.

Study of postures in sugarcane cutters in the Pontal of Paranapanema-SP, Brazil

The expansion of sugarcane monoculture in Brazil in the last decades has pointed out to the necessity of considering the question of sugarcane cutters occupational health. In this work we present a cross-sectional study aiming to examine the occupational posture of a group of sugarcane cutters, which work in a cane field located in the region of Pontal do Paranapanema-SP, Brazil. The study was made using the Ergonomic Analysis of Work - EAW methodology and the postural analysis method by Win-OWAS. Through the obtained records of postures, it was observed that during a workday the sugarcane cutters remain standing erect on two legs or in one leg 66% of the time and that their trunk remain tilted and in rotation, according to 63% of the positions categorized. It was also observed that the sugarcane cutter trunk performs repetitive and boundless movements during his routine of work, which can expose this individual to additional wear of their musculoskeletal functions. The activities in which the individual engages have favorable or adverse influence on his posture. The repetitive movements involved in specialized occupations are equivalent to repeated exercises, thus may be responsible for the excessive development of certain muscle groups. The study suggests that the postures adopted by sugarcane cutters can overload their musculoskeletal system and predispose the cutters to work-related musculoskeletal diseases.

Ultrastructural study of the follicular epithelium in oocytes of Pachycondyla (Neoponera) villosa ants (Hymenoptera : Ponerinae)

Insect oocytes are surrounded by the follicular epithelium which is simple and cuboidal, wih the mainly functions of: synthesis of vitellin membrane and chorion and synthesis and transport of hemolymph products (proteins). In Pachycondyla (Neoponera) villosa ants workers aged less than 10 days do not present the formation of ovarian follicles (oocytes, nurse cells and follicular cells) indicating that vitellogenesis starts at approximately 10 days of age. Studies of participation of the follicular epithelium in Pachycondyla (Neoponera) villosa showed that in stage I oocytes the epithelium does not present the opening of intercellular spaces. In stage II these spaces begin to be observed together with separation of the follicular epithelium from the oocyte surface. In stage III two types of material were observed in the intercellular spaces: electrodense material in the basal region and compacted material in apical one as well as follicular epithelium/oocytes interface suggesting that the extraovarian material that reach oocytes undergoes some type of modification during passage through the intercellular spaces. The follicular epithelium spaces in queen are bigger than in workers oocytes.

Study of acrosome formation, interspecific and intraspecific, in the testicular lobes of some pentatomid species

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

Study of the (D)over-barN Interaction in a QCD Coulomb Gauge Quark Model

We study the (D) over barN interaction at low energies with a quark model inspired in the QCD Hamiltonian in Coulomb gauge. The model Hamiltonian incorporates a confining Coulomb potential extracted from a self-consistent quasiparticle method for the gluon degrees of freedom, and transverse-gluon hyperfine interaction consistent with a finite gluon propagator in the infrared. Initially a constituent-quark mass function is obtained by solving a gap equation and baryon and meson bound-states are obtained in Fock space using a variational calculation. Next, having obtained the constituent-quark masses and the hadron waves functions, an effective meson-nucleon interaction is derived from a quark-interchange mechanism. This leads to a short range meson-baryon interaction and to describe long-distance physics vector- and scalar-meson exchanges described by effective Lagrangians are incorporated. The derived effective (D) over barN potential is used in a Lippmann-Schwinger equation to obtain phase shifts. The results are compared with a recent similar calculation using the nonrelativistic quark model.

A theoretical study of the A(2)Sigma(+)-X-2 Pi system of the SiP molecule

The A (2)Sigma(+) and X(2)Pi electronic states of the SiP species have been investigated theoretically at a very high level of correlation treatment (CASSCF/MRSDCI). Very accurate potential energy curves are presented for both states, as well as the associated spectroscopic constants as derived from the vib-rotational energy levels determined by means of the numerical solution of the radial Schrodinger equation. Electronic transition moment function, oscillator strengths, Einstein coefficients for spontaneous emission, and Franck-Condon factors for the A(2)Sigma(+)-X(2)Pi system have been calculated. Dipole moment functions and radiative lifetimes for both states have also been determined. Spin-orbit coupling constants are also reported. The radiative lifetimes for the A(2)Sigma(+) state, taking into account the spin-orbit diagonal correction to the X(2)Pi state, decrease from a value of 138 ms at v' = 0 to 0.48 ms at v' = 8, and, for the X(2)Pi state, from 2.32 s at v = 1 to 0.59 s at v = 5. Vibrational and rotational transitions are expected to be relatively strong.

GCHF basis sets and their application in the electronic structure study of PrMnO3

The approach called generator coordinate Hartree-Fock (GCHF) method is used in the selection of Gaussian basis set [25s18p for O ((3)p), 31s21p14d for Mn (S-6), and 33s22p16d9f for Pr ((4)J)] for atoms. The role of the weight functions in the assessment of the numerical integration range of the GCHF equations is shown. These basis sets are contracted to (25s18p/9s5p), (31s21p14d/9s6p4d), and (33s22pl6d9f118sl2p5d3f) by segmented contraction scheme of Dunning and they are utilized in calculations of Restricted-Open-HF (ROHF) Total and Orbital energies of the (MnO+1)-Mn-3 and (PrO+1)-Pr-1 fragments, to evaluate their quality in molecular studies. The addition of one d polarization function in the contracted (9s5p) basis set for O(P-3) atom and their application with the contracted (9s6p4d), (18s21p5d3f) basis sets for Mn (S-6) and Pr-Pr ((4)j) atoms lead to the electronic structure study of PrMnO3. The dipole moment, the total energy, and total atomic charges properties were calculated and were carried out at ROHF level with the [PrMnO3](2) fragment. The calculated values show that PrMnO3 does not present piezoelectric properties. (C) 2004 Elsevier B.V. All rights reserved.

Ab initio study of high tridymite by the formalism generator coordinate Hartree-Fock

The Generator Coordinate Hartree-Fock (GCHF) Method is applied to generate extended 14s 8p and 17s 11p Gaussian basis sets for the atoms O and Si, respectively. The role of the weight functions in the assessment of the numerical integration range of the GCHF is shown. The Gaussian basis sets are contracted to [6s4p] O atom and [8s5p] Si atom by the Dunning's segmented contraction scheme. To evaluate the quality of our contracted [6s4p] and [8s5p] bases in molecular calculations we accomplish calculations of total and orbital energies in the Hartree-Fock-Roothaan method for O-2 and SiO molecules. We compare the results obtained with the our (14s 8p) and (17s 11p) bases sets with the of 6-311G basis and with values from the literature. The addition of one d polarization function in the silicon basis and its utilization with the basis for oxygen leads to the calculation of electronic properties and IR Spectrum of high tridymite in space group D-3d. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Gaussian basis sets to the theoretical study of the electronic structure of perovskite (LaMnO3)

The Generator Coordinate Hartree-Fock (GCHF) method is applied to generate extended (20s14p), (30s19p13d), and (31s23p18d) Gaussian basis sets for the 0, Mn, and La atoms, respectively. The role of the weight functions (WFs) in the assessment of the numerical integration range of the GCHF equations is shown. These basis sets are then contracted to [5s3p] and [11s6p6d] for 0 and Mn atoms, respectively, and [17s11p7d] for La atom by a standard procedure. For quality evaluation of contracted basis sets in molecular calculations, we have accomplished calculations of total and orbital energies in the Hartree-Fock-Roothaan (HFR) method for (MnO1+)-Mn-5 and (LaO1+)-La-1 fragments. The results obtained with the contracted basis sets are compared with values obtained with the extended basis sets. The addition of one d polarization function in the contracted basis set for 0 atom and its utilization with the contracted basis sets for Mn and La atoms leads to the calculations of dipole moment and total atomic charges of perovskite (LaMnO3). The calculations were performed at the HFR level with the crystal [LaMnO3](2) fragment in space group C-2v the values of dipole moment, total energy, and total atomic charges showed that it is reasonable to believe that LaMnO3 presents behaviour of piezoelectric material. (C) 2003 Elsevier B.V. All rights reserved.

Small-angle X-ray scattering study of gelation and aging of Eu3+-doped sol-gel-derived siloxane-poly(oxyethylene) nanocomposites

The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.

The generator coordinate Hartree-Fock method as strategy for building Gaussian basis sets to ab initio study of the process of adsorption of sulfur on platinum (200) surface

The scheme named generator coordinate Hartree-Fock method (GCHF) is used to build (22s14p) and (33s22p16d9f) gaussian basis sets to S ((3)P) and Pt ((3)D) atoms, respectively. Theses basis sets are contracted to [13s10p] and [19s13p9d5f] through of Dunning's segmented contraction scheme and are enriched with d and g polarization functions, [13s10p1d] and [19s13p9d5flg]. Finally, the [19s13p9d5f1g] basis Set to Pt ((3)D) was supplemented with s and d diffuse functions, [20s13p10d5flg], and used in combination with [13s10p1d] to study the effects of adsorption of S ((3)D) atom on a pt ((3)D) atom belonged to infinite Pt (200) surface. Atom-atom overlap population, bond order, and infrared spectrum of [pt(_)S](2 -) were calculated properties and were carried out at Hartree-Fock-Roothaan level. The results indicate that the process of adsorption of S ((3)P) on pt ((3)D) in the infinite Pt (200) surface is mainly caused by a strong contribution of sigma between the 3p(z) orbital of S ((3)P) and the 6s orbital of pt ((3)D). (c) 2004 Elsevier B.V. All rights reserved.

DBMODELING - A database applied to the study of protein targets from genome projects

Genome sequencing efforts are providing us with complete genetic blueprints for hundreds of organisms. We are now faced with assigning, understanding, and modifying the functions of proteins encoded by these genomes. DBMODELING is a relational database of annotated comparative protein structure models and their metabolic pathway characterization, when identified. This procedure was applied to complete genomes such as Mycobacteritum tuberculosis and Xylella fastidiosa. The main interest in the study of metabolic pathways is that some of these pathways are not present in humans, which makes them selective targets for drug design, decreasing the impact of drugs in humans. In the database, there are currently 1116 proteins from two genomes. It can be accessed by any researcher at http://www.biocristalografia.df.ibilce.unesp.br/tools/. This project confirms that homology modeling is a useful tool in structural bioinformatics and that it can be very valuable in annotating genome sequence information, contributing to structural and functional genomics, and analyzing protein-ligand docking.