Classical simulation of deposition of thiophene oligomers on TiO(2)-anatase: Relevance of long-range electrostatic interactions

We performed classical molecular dynamics simulations of the vapor-deposition of alpha-T4 oligomers on the TiO(2)-anatase (101) surface, comparing different sets of charges associated with the atoms of the model. The potential energy surfaces for alpha-T4 and TiO(2) were described by re-parametrizations of the Universal force field with charges given by the charge equilibration (QEq) scheme, or with fixed charges obtained by an ab initio method using the Hirshfeld partition. The two sets of charges lead to completely different results for the interface formation, and for the characteristics of the organic film, with a clearly defined alpha-T4 contact layer in the QEq case, and a more homogeneous molecular distribution when using Hirshfeld charges. The main reason for the discrepancy was found to be the incorrect charge assignment given by QEq to the sulfur and alpha-carbon atoms in thiophenes, and highlight the relevance of long-range interactions in the organization of molecular films. (C) 2009 Elsevier B.V. All rights reserved.

Ground-state energy of a classical artificial molecule

We study the ground-state energy of a classical artificial molecule formed by two-dimensional clusters (artificial atoms) of N/2 charged particles separated by a distance d. For the small molecules of N = 2 and 4, we obtain analytical expressions for this energy. For the larger ones, we calculate the ground-state energy using molecular dynamics simulation for N up to 128. From our numerical results, we are able to find out a function to approximate the ground-state energy of the molecules covering the range from atoms to molecules for any inter-atom distance d and for particle number from N = 8 to 128 within a difference less than one percent from the MD data.

Mapping the Intramolecular Vibrational Energy Flow in Proteins Reveals Functionally Important Residues

Unveiling the mechanisms of energy relaxation in biomolecules is key to our understanding of protein stability, allostery, intramolecular signaling, and long-lasting quantum coherence phenomena at ambient temperatures. Yet, the relationship between the pathways of energy transfer and the functional role of the residues involved remains largely unknown. Here, we develop a simulation method of mapping out residues that are highly efficient in relaxing an initially localized excess vibrational energy and perform site-directed mutagenesis functional assays to assess the relevance of these residues to protein function. We use the ligand binding domains of thyroid hormone receptor (TR) subtypes as a test case and find that conserved arginines, which are critical to TR transactivation function, are the most effective heat diffusers across the protein structure. These results suggest a hitherto unsuspected connection between a residue`s ability to mediate intramolecular vibrational energy redistribution and its functional relevance.

Measurement of the energy spectrum of cosmic rays above 10(18) eV using the Pierre Auger Observatory

We report a measurement of the flux of cosmic rays with unprecedented precision and Statistics using the Pierre Auger Observatory Based on fluorescence observations in coincidence with at least one Surface detector we derive a spectrum for energies above 10(18) eV We also update the previously published energy spectrum obtained with the surface detector array The two spectra are combined addressing the systematic uncertainties and, in particular. the influence of the energy resolution on the spectral shape The spectrum can be described by a broken power law E(-gamma) with index gamma = 3 3 below the ankle which is measured at log(10)(E(ankle)/eV) = 18 6 Above the ankle the spectrum is described by a power law with index 2 6 followed by a flux suppression, above about log(10)(E/eV) = 19 5, detected with high statistical significance (C) 2010 Elsevier B V All rights reserved

Modeling and simulation of the anode in direct ethanol fuels cells

Mathematical modeling has been extensively applied to the study and development of fuel cells. In this work, the objective is to characterize a mechanistic model for the anode of a direct ethanol fuel cell and perform appropriate simulations. The software Comsol Multiphysics (R) (and the Chemical Engineering Module) was used in this work. The software Comsol Multiphysics (R) is an interactive environment for modeling scientific and engineering applications using partial differential equations (PDEs). Based on the finite element method, it provides speed and accuracy for several applications. The mechanistic model developed here can supply details of the physical system, such as the concentration profiles of the components within the anode and the coverage of the adsorbed species on the electrode surface. Also, the anode overpotential-current relationship can be obtained. To validate the anode model presented in this paper, experimental data obtained with a single fuel cell operating with an ethanol solution at the anode were used. (C) 2008 Elsevier B.V. All rights reserved.

Docking and molecular dynamics simulation of quinone compounds with trypanocidal activity

In this work, two different docking programs were used, AutoDock and FlexX, which use different types of scoring functions and searching methods. The docking poses of all quinone compounds studied stayed in the same region in the trypanothione reductase. This region is a hydrophobic pocket near to Phe396, Pro398 and Leu399 amino acid residues. The compounds studied displays a higher affinity in trypanothione reductase (TR) than glutathione reductase (GR), since only two out of 28 quinone compounds presented more favorable docking energy in the site of human enzyme. The interaction of quinone compounds with the TR enzyme is in agreement with other studies, which showed different binding sites from the ones formed by cysteines 52 and 58. To verify the results obtained by docking, we carried out a molecular dynamics simulation with the compounds that presented the highest and lowest docking energies. The results showed that the root mean square deviation (RMSD) between the initial and final pose were very small. In addition, the hydrogen bond pattern was conserved along the simulation. In the parasite enzyme, the amino acid residues Leu399, Met400 and Lys402 are replaced in the human enzyme by Met406, Tyr407 and Ala409, respectively. In view of the fact that Leu399 is an amino acid of the Z site, this difference could be explored to design selective inhibitors of TR.

Effect of repeated disinfections by microwave energy on the physical and mechanical properties of denture base acrylic resins

The present study evaluated the effect of repeated simulated microwave disinfection on physical and mechanical properties of Clássico, Onda-Cryl and QC-20 denture base acrylic resins. Aluminum patterns were included in metallic or plastic flasks with dental stone following the traditional packing method. The powder/liquid mixing ratio was established according to the manufacturer's instructions. After water-bath polymerization at 74ºC for 9 h, boiling water for 20 min or microwave energy at 900 W for 10 min, the specimens were deflasked after flask cooling and finished. Each specimen was immersed in 150 mL of distilled water and underwent 5 disinfection cycles in a microwave oven set at 650 W for 3 min. Non-disinfected and disinfected specimens were subjected to the following tets: Knoop hardness test was performed with 25 g load for 10 s, impact strength test was done using the Charpy system with 40 kpcm, and 3-point bending test (flexural strength) was performed at a crosshead speed of 0.5 mm/min until fracture. Data were analyzed statistically by ANOVA and Tukey's test (α= 0.05%). Repeated simulated microwave disinfections decreased the Knoop hardness of Clássico and Onda-Cryl resins and had no effect on the impact strength of QC-20. The flexural strength was similar for all tested resins.

Influence of intrapulpal pressure simulation on the bond strength of adhesive systems to dentin

The purpose of this study was to evaluate the influence of intrapulpal pressure simulation on the bonding effectiveness of etch & rinse and self-etch adhesives to dentin. Eighty sound human molars were distributed into eight groups, according to the permeability level of each sample, measured by an apparatus to assess hydraulic conductance (Lp). Thus, a similar mean permeability was achieved in each group. Three etch & rinse adhesives (Prime & Bond NT - PB, Single Bond -SB, and Excite - EX) and one self-etch system (Clearfil SE Bond - SE) were employed, varying the presence or absence of an intrapulpal pressure (IPP) simulation of 15 cmH2O. After adhesive and restorative procedures were carried out, the samples were stored in distilled water for 24 hours at 37°C, and taken for tensile bond strength (TBS) testing. Fracture analysis was performed using a light microscope at 40 X magnification. The data, obtained in MPa, were then submitted to the Kruskal-Wallis test ( a = 0.05). The results revealed that the TBS of SB and EX was significantly reduced under IPP simulation, differing from the TBS of PB and SE. Moreover, SE obtained the highest bond strength values in the presence of IPP. It could be concluded that IPP simulation can influence the bond strength of certain adhesive systems to dentin and should be considered when in vitro studies are conducted.

Effects of dietary energy and nitrogen supplements on rumen fermentation and protozoa population in buffalo and zebu cattle

The effects were assessed of two energy sources in concentrate (ground grain corn vs. citrus pulp) and two nitrogen sources (soybean meal vs. urea) on rumen metabolism in four buffaloes and four zebu cattle (Nellore) with rumen cannula and fed in a 4 × 4 Latin square design with feeds containing 60% sugar cane. Energy supplements had no effect on the rumen ammonia concentration in cattle, but ground grain corn promoted higher ammonia level than citrus pulp in buffalo. Urea produced higher ammonia level than soybean meal in both animal species. On average, the buffaloes maintained a lower rumen ammonia concentration (11.7 mg/dL) than the cattle (14.5 mg/dL). Buffaloes had lower production of acetic acid than cattle (58.7 vs. 61.6 mol/100 mol) and higher of propionic acid (27.4 vs. 23.6 mol/100 mol). There was no difference in the butyric acid production between the buffaloes (13.6 mol/100 mol) and cattle (14.8 mol/100 mol) and neither in the total volatile fatty acids concentration (82.5 vs. 83.6 mM, respectively). The energy or nitrogen sources had no effect on rumen protozoa count in either animal species. The zebu cattle had higher rumen protozoa population (8.8 × 10(5)/mL) than the buffaloes (6.1 × 10(5)/mL). The rumen protozoa population differed between the animal species, except for Dasytricha and Charonina. The buffaloes had a lower Entodinium population than the cattle (61.0 vs 84.9%, respectively) and a greater percentage of species belonging to the Diplodiniinae subfamily than the cattle (28.6 vs. 1.4%, respectively). In cattle, ground corn is a better energy source than citrus pulp for use by Entodinium and Diplodiniinae. In the buffaloes, the Entodinium are favored by urea and Diplodiniinae species by soybean meal.

Comparison of some theoretical models for fittings of the temperature dependence of the fundamental energy gap in GaAs

In this work we report on a comparison of some theoretical models usually used to fit the dependence on temperature of the fundamental energy gap of semiconductor materials. We used in our investigations the theoretical models of Viña, Pässler-p and Pässler-ρ to fit several sets of experimental data, available in the literature for the energy gap of GaAs in the temperature range from 12 to 974 K. Performing several fittings for different values of the upper limit of the analyzed temperature range (Tmax), we were able to follow in a systematic way the evolution of the fitting parameters up to the limit of high temperatures and make a comparison between the zero-point values obtained from the different models by extrapolating the linear dependence of the gaps at high T to T = 0 K and that determined by the dependence of the gap on isotope mass. Using experimental data measured by absorption spectroscopy, we observed the non-linear behavior of Eg(T) of GaAs for T > ΘD.

Photophysical properties and quantum chemical studies of poly(2,7-9,9'-dihexylfluorene-dyil)

This work reports the photophysical properties (excitation and fluorescence spectra, fluorescence quantum yield, fluorescence lifetimes) of the poly(2,7-9,9'-dihexylfluorene-dyil) in dilute solutions of four solvents (toluene, tetrahydrofuran, chloroform and ethyl acetate) as well as the properties in solid state. Photoluminescence showed spectra characteristic of disordered α-backbone chain conformation. Simulation of the electronic absorption spectra of oligomers containing 1 to 11 mers showed that the critical conjugation length is between 6 and 7 mers. We also estimated the theoretical dipole moments which indicated that a coil conformation is formed with 8 repeating units per turn. We also showed that some energy transfer process appears in solid state which decreases the emission lifetime. Furthermore, based on luminescent response of the systems herein studied and electroluminescent behavior reported on literature, both photo and electroluminescence emissions arise from the same emissive units.

High-energy events and short-term changes in superficial beach sediments

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Diet quality index adjusted for energy requirements in adults

This study aimed to develop a diet quality index (DQI-a) adjusted for energy requirement. Dietary intake of adults was assessed using 24-hour food recall. The DQI was developed for scores evenly distributed across ten items characterizing different aspects of diet: food groups, nutrients, and variety. The components categorized under the food groups from the Dietary Guide for Brazilians were adjusted according to the estimated energy requirements of the population studied. Index consistency and correlation with nutrients of the diet was analyzed by Cronbach's alpha. A total of 737 individuals were assessed and energy requirements ranged from 1,800 to 2,500kcal among women and 2,500 to 3,400kcal in men. The food group with greatest variation in total portions was cereals and tubers. Cronbach's alpha of the DQI-a was 0.643 and the index correlated with most of the nutrients. The DQI-a can be considered a valuable instrument for assessing diet quality of the Brazilian population.

Sources of variation of energy and nutrient intake among adolescents in São Paulo, Brazil

The aim of the current study was to describe the sources of variation of energy and nutrient intake and to calculate the number of repetitions of diet measurements to estimate usual intake in adolescents from São Paulo, Brazil. Data was collected using 24-hour dietary recalls (24hR) in 273 adolescents between 2007 and 2008. Individuals completed a repeat 24hR around two months later. The sources of variation were estimated using the random effect model. Variance ratios (within-person to between-person variance ratio) and the number of repetitions of 24hR to estimate usual intake were calculated. The principal source of variation was due to within-person variance. The contribution of day of week and month of year was less than 8%. Variations ranged from 1.15 for calcium to 7.31 for vitamin E. The number of 24hR repeats required to estimate usual intake varied according to nutrient and gender, numbering 15 for males and 8 for females.

Effect of an energy-deficient diet on populations of ciliate protozoans in bovine rumen

Ten young rumen-cannulated crossbred steers were randomly divided into two groups: a control group (C; n=4), which was fed a balanced diet for daily weight gain of 900g; and a pronounced energy-deprived group (PED; n=6), receiving 30% less of the required energy for maintenance. After 140 days of these alimentary regimes, rumen fluid and urine samples were collected for biochemical and functional tests, before feeding and at 1, 3, 6, and 9 hours after feeding. The energy-deprivation diet caused a significant reduction in the number of Entodinium, Eodinium, Isotricha, Dasytricha, Eremoplastron, Eudiplodinium, Metadinium, Charonina, Ostracodinium, and Epidinium protozoa. There was no effect of the time of sampling in both groups on the total number of ciliates in rumen fluid. A higher number of protozoan forms in binary division were recorded in the control group, at the 6th and 9th hours after feeding (P<0.019). There was a high positive correlation between the total count of protozoans in rumen fluid and glucose fermentation, ammonia, and urinary allantoin excretion index; and a negative correlation between the total count of protozoa and metilene blue reduction, and a medium correlation between the total count of protozoa and total volatile fatty acids concentration. The determination of the protozoa populations does not imply in the use of complex and hard-to-execute techniques, although it is time consuming and needs practice. This exam particularly helps in clinical expected diagnosis.