Spatial patterns and factors associated with the incidenceof tuberculosis-diabetes in Brazil.

OBJECTIVES: The aim of this study was to analyse the spatial patterns and factors associated with the incidence of tuberculosis-diabetes (TB-DM) in Brazil, from 2001 to 2019. STUDY DESIGN: Ecological study. METHODS: Brazilian municipalities were used as the units of analysis. The local empirical Bayesian rate and the spatial autocorrelation test were calculated. Moran and Getis-Ord Gi∗ were used to identify spatial clusters, and spatially weighted regression was conducted. RESULTS: In total, 75,021 new cases of TB associated with DM were reported in Brazil during the study period. Most Brazilian municipalities had an average TB-DM incidence of 1.0-2.0/100,000 inhabitants. The regression showed that the Gini index (ß = 0.85) and family health strategy coverage (ß = -0.26) were the two indicators that had the most influence on TB-DM incidence in Brazil. CONCLUSIONS: This study identified spatial clusters of TB-DM in Brazil. The results also indicated that social inequalities played a key role in the incidence of TB.

Circulating microRNAs associated with liver fibrosis in chronic hepatitis C patients.

A major challenge in hepatitis C research is the detection of early potential for progressive liver disease. MicroRNAs (miRNAs) are small RNAs that regulate gene expression and can be biomarkers of pathological processes. In this study, we compared circulating miRNAs identified in hepatitis C virus (HCV)-infected patients presenting two extremes of liver disease: mild/moderate fibrosis and cirrhosis. The patients in the cirrhosis group subsequently developed hepatocellular carcinoma (HCC). We identified 163 mature miRNAs in the mild/moderate fibrosis group and 171 in the cirrhosis group, with 144 in common to both groups. Differential expression analysis revealed 5 upregulated miRNAs and 2 downregulated miRNAs in the cirrhosis group relative to the mild/moderate fibrosis group. Functional analyses of regulatory networks (target gene and miRNA) identified gene categories involved in cell cycle biological processes and metabolic pathways related to cell cycle, cancer, and apoptosis. These results suggest that the differentially expressed circulating miRNAs observed in this work (miR-215-5p, miR-483-5p, miR-193b-3p, miR-34a-5p, miR-885-5p, miR-26b-5p and miR -197-3p) may be candidates for biomarkers in the prognosis of liver disease.

mRNA structure regulates protein expression through changes in functional half-life.

Messenger RNAs (mRNAs) encode information in both their primary sequence and their higher order structure. The independent contributions of factors like codon usage and secondary structure to regulating protein expression are difficult to establish as they are often highly correlated in endogenous sequences. Here, we used 2 approaches, global inclusion of modified nucleotides and rational sequence design of exogenously delivered constructs, to understand the role of mRNA secondary structure independent from codon usage. Unexpectedly, highly expressed mRNAs contained a highly structured coding sequence (CDS). Modified nucleotides that stabilize mRNA secondary structure enabled high expression across a wide variety of primary sequences. Using a set of eGFP mRNAs with independently altered codon usage and CDS structure, we find that the structure of the CDS regulates protein expression through changes in functional mRNA half-life (i.e., mRNA being actively translated). This work highlights an underappreciated role of mRNA secondary structure in the regulation of mRNA stability.

Analysis of RNA nearest neighbor parameters reveals interdependencies and quantifies the uncertainty in RNA secondary structure prediction.

RNA secondary structure prediction is often used to develop hypotheses about structure-function relationships for newly discovered RNA sequences, to identify unknown functional RNAs, and to design sequences. Secondary structure prediction methods typically use a thermodynamic model that estimates the free energy change of possible structures based on a set of nearest neighbor parameters. These parameters were derived from optical melting experiments of small model oligonucleotides. This work aims to better understand the precision of structure prediction. Here, the experimental errors in optical melting experiments were propagated to errors in the derived nearest neighbor parameter values and then to errors in RNA secondary structure prediction. To perform this analysis, the optical melting experimental values were systematically perturbed within the estimates of experimental error and alternative sets of nearest neighbor parameters were then derived from these error-bounded values. Secondary structure predictions using either the perturbed or reference parameter sets were then compared. This work demonstrated that the precision of RNA secondary structure prediction is more robust than suggested by previous work based on perturbation of the nearest neighbor parameters. This robustness is due to correlations between parameters. Additionally, this work identified weaknesses in the parameter derivation that makes accurate assessment of parameter uncertainty difficult. Considerations for experimental design are provided to mitigate these weaknesses are provided.

Technetium complexes with arylselenolato and aryltellurolato ligands.

Reactions of (NBu4)[TcOCl4] or [TcCl3(PPh3)2(CH3CN)] with in situ-prepared lithium arylselenolates and -tellurolates give (NBu4)[TcVO(ArE)4] (E = Se, Te; Ar = phenyl) and [TcIII(ArE)3(PPh3)(CH3CN)] (E = Se, Te; Ar = phenyl, 2,6-Me2phenyl, mesityl) complexes, respectively. The products contain square-pyramidal (TcV compounds) and trigonal bipyramidal (TcIII complexes) coordinated technetium atoms. Density functional theory calculations indicate that the Tc-chalcogen bonds in the TcIII compounds have a greater bond order than those in the TcV compounds.

Oak kombucha protects against oxidative stress and inflammatory processes.

Black tea infusion is the common substrate for preparing kombucha; however other sources such as oak leaves infusions can be used for the same purpose. Almost any white oak species have been used for medicinal applications by some ethnic groups in Mexico and could be also suitable for preparing kombucha analogues from oak (KAO). The objective of this research was to investigate the antioxidant activity and anti-inflammatory effects of KAO by examining its modulation ability on macrophage-derived TNF-alpha and IL-6. Herbal infusions from oak and black tea were fermented by kombucha consortium during seven days at 28 °C. Chemical composition was determined by LC-ESI-MS/MS. The antioxidant activity of samples against oxidative damage caused by H2O2 in monocytes activated (macrophages) was explored. Additionally, it was determined the anti-inflammatory activity using lipopolysaccharide (LPS) - stimulated macrophages; in particular, the nitric oxide (NO), TNF-alpha, and IL-6 production was assessed. Levels of pro-inflammatory cytokines IL-6 and TNF-alpha were significantly reduced by the sample treatment. Likewise, NO production was lower in treatment with kombucha and KAO compared with LPS-stimulated macrophages. Fermented beverages of oak effectively down-regulated the production of NO, while pro-inflammatory cytokines (TNF-alpha and IL-6) in macrophages were stimulated with LPS. Additionally, phytochemical compounds present in KAO decrease oxidative stress.

Electronic properties of hydrogen-bonded complexes of benzene(HCN)(1-4): comparison with benzene(H2O)(1-4).

The electronic properties, specifically, the dipole and quadrupole moments and the ionization energies of benzene (Bz) and hydrogen cyanide (HCN), and the respective binding energies, of complexes of Bz(HCN)(1-4), have been studied through MP2 and OVGF calculations. The results are compared with the properties of benzene-water complexes, Bz(H(2)O)(1-4), with the purpose of analyzing the electronic properties of microsolvated benzene, with respect to the strength of the CH/π and OH/π hydrogen-bond (H-bond) interactions. The linear HCN chains have the singular ability to interact with the aromatic ring, preserving the symmetry of the latter. A blue shift of the first vertical ionization energies (IEs) of benzene is observed for the linear Bz(HCN)(1-4) clusters, which increases with the length of the chain. NBO analysis indicates that the increase of the IE with the number of HCN molecules is related to a strengthening of the CH/π H-bond, driven by cooperative effects, increasing the acidity of the hydrogen cyanide H atom involved in the π H-bond. The longer HCN chains (n ≥ 3), however, can bend to form CH/N H-bonds with the Bz H atoms. These cyclic structures are found to be slightly more stable than their linear counterparts. For the nonlinear Bz(HCN)(3-4) and Bz(H(2)O)(2-4) complexes, an increase of the binding energy with the number of solvent molecules and a decrease of the IE of benzene, relative to the values for the Bz(HCN) and Bz(H(2)O) complexes, respectively, are observed. Although a strengthening of the CH/π and OH/π H-bonds, with increasing n, also takes place for the Bz(H(2)O)(2-4) and Bz(HCN)(3-4) nonlinear complexes, Bz proton donor, CH/O, and CH/N interactions are at the origin of this decrease. Thus CH/π and OH/π H-bonds lead to higher IEs of Bz, whereas the weaker CH/N and CH/O H-bond interactions have the opposite effect. The present results emphasize the importance of both aromatic XH/π (X = C, O) and CH/X (X = N, O) interactions for understanding the structure and electronic properties of Bz(HCN)(n) and Bz(H(2)O)(n) complexes.

Ab initio approach to the electronic properties of sodium-ammonia clusters: comparison with ammonia clusters.

Ab initio results for the electronic properties of sodium-ammonia [Na(NH(3))(n);n=1-8] and the corresponding ionized structures [Na(+)(NH(3))(n)] are reported and compared with those for neutral ammonia clusters [(NH(3))(n)]. Emphasis was placed on the analysis of polarization effects and calculation of vertical and adiabatic ionization potentials. The theoretical discussion is based on second order Møller-Plesset perturbation theory and Green's function or electron propagator theory calculations. Our results for the ionization energies (IEs) of Na(NH(3))(n) clusters are in very good agreement with experimental information. The relationship between the dependence of the IEs on the number of ammonia molecules (n), polarization effects, and hydrogen bond formation is investigated. The presence of a hydrogen bond acceptor-only ammonia molecule that binds a delocalized excess electron in Na(NH(3))(6-7) clusters is discussed.

Born-Oppenheimer molecular dynamics of the hydration of Na+ in a water cluster.

The hydration of Na(+) in a water cluster is studied through all-electron Born-Oppenheimer molecular dynamics. The structure, dipole moment, and vibrational spectrum of the sodium cation hydration shells are examined. Emphasis is placed on the extent of the effect of the hydrated cation on the cluster properties. Our results show that hydration of Na(+) takes place in the interior of the cluster leading to significant changes in the hydrogen-bond (H-bond) network beyond the first hydration shell. In particular, we find that single acceptor-only H-bond arrangements increase significantly at the surface of the cluster relative to a neat water cluster. The vibrational spectrum of the first hydration shell of the cation, comprised mostly of H-bond double donor-single acceptor water molecules, is similar to that found for water molecules in the interior of a neat water cluster, although a small blue shift of the OH stretching band is observed. Further, a small reduction of the dipole moment of water molecules in the first hydration shell of the cation relative to a neat water cluster is also observed, and this persists to a minor extent when we move from the interior to the surface of the cluster. The present results indicate that the effect of the Na(+) on the cluster properties, although not pronounced, is not constrained to the first hydration shell. The reason appears to lie mostly in the specific orientation of the water molecules in the first coordination sphere, inducing modifications on the H-bond network topology of the cluster.

A Simple One-Body Approach to the Calculation of the First Electronic Absorption Band of Water.

A one-body decomposition approach for investigating the electronic absorption spectra of molecular systems was proposed and applied to water clusters (H2O)N including up to N = 80 water molecules. Two specific aspects of the present implementation are the inclusion of the coupling between excited states and a simplified representation for the N-body Coulombic effects. For smaller clusters, the results based on the one-body decomposition scheme are in good agreement with full EOM-CCSD calculations. Two different regimes can be identified in the electronic absorption profile of larger water clusters. The first low-energy regime is dominated by local excitonic states on the cluster surface, whereas the higher-energy excitations associated with the second one are of delocalized nature.

The changing hydrogen-bond network of water from the bulk to the surface of a cluster: a born-oppenheimer molecular dynamics study.

The effect of the environment on the properties of water in the bulk and at the surface of a cluster is studied by all-electron Born-Oppenheimer molecular dynamics. The vibrational spectrum of surface and bulk water is interpreted in terms of the molecular orientation and the local changes in the H-bond network of the cluster. Our results show that, in spite of the presence of a surface moiety of "acceptor-only" molecules, the H-bond network is significantly more labile at the surface than in the bulk part of cluster, and single donor-acceptor arrangements are largely dominant at the interface. Further, although surface water molecules depict in average a single H atom protruding into the vapor, molecules exhibit significant orientational freedom. These results explain the apparently opposite experimental observations from infrared sum frequency generation and X-ray spectroscopy of the liquid-vapor interface. The dipole moment, intramolecular geometry and surface relaxation are also analyzed at light of the different H-bond regions in the cluster.

First principles molecular dynamics of molten NaI: structure, self-diffusion, polarization effects, and charge transfer.

The structure and self-diffusion of NaI and NaCl at temperatures close to their melting points are studied by first principles Hellmann-Feynman molecular dynamics (HFMD). The results are compared with classical MD using rigid-ion (RI) and shell-model (ShM) interionic potentials. HFMD for NaCl was reported before at a higher temperature [N. Galamba and B. J. Costa Cabral, J. Chem. Phys. 126, 124502 (2007)]. The main differences between the structures predicted by HFMD and RI MD for NaI concern the cation-cation and the anion-cation pair correlation functions. A ShM which allows only for the polarization of I- reproduces the main features of the HFMD structure of NaI. The inclusion of polarization effects for both ionic species leads to a more structured ionic liquid, although a good agreement with HFMD is also observed. HFMD Green-Kubo self-diffusion coefficients are larger than those obtained from RI and ShM simulations. A qualitative study of charge transfer in molten NaI and NaCl was also carried out with the Hirshfeld charge partitioning method. Charge transfer in molten NaI is comparable to that in NaCl, and results for NaCl at two temperatures support the view that the magnitude of charge transfer is weakly state dependent for ionic systems. Finally, Hirshfeld charge distributions indicate that differences between RI and HFMD results are mainly related to polarization effects, while the influence of charge transfer fluctuations is minimal for these systems.

First principles molecular dynamics of molten NaCl.

First principles Hellmann-Feynman molecular dynamics (HFMD) results for molten NaCl at a single state point are reported. The effect of induction forces on the structure and dynamics of the system is studied by comparison of the partial radial distribution functions and the velocity and force autocorrelation functions with those calculated from classical MD based on rigid-ion and shell-model potentials. The first principles results reproduce the main structural features of the molten salt observed experimentally, whereas they are incorrectly described by both rigid-ion and shell-model potentials. Moreover, HFMD Green-Kubo self-diffusion coefficients are in closer agreement with experimental data than those predicted by classical MD. A comprehensive discussion of MD results for molten NaCl based on different ab initio parametrized polarizable interionic potentials is also given.

The Kohn-Sham density of states and band gap of water: from small clusters to liquid water.

Electronic properties of water clusters (H2O)(n), with n=2, 4, 8, 10, 15, 20, and 30 molecules were investigated by sequential Monte Carlo/density-functional theory (DFT) calculations. DFT calculations were carried out over uncorrelated configurations generated by Monte Carlo simulations of liquid water with a reparametrized exchange-correlation functional that reproduces the experimental information on the electronic properties (first ionization energy and highest occupied molecular orbital-lowest unoccupied molecular orbital gap) of the water dimer. The dependence of electronic properties on the cluster size (n) shows that the density of states (DOS) of small water clusters (n>10) exhibits the same basic features that are typical of larger aggregates, such as the mixing of the 3a1 and 1b1 valence bands. When long-ranged polarization effects are taken into account by the introduction of embedding charges, the DOS associated with 3a1 orbitals is significantly enhanced. In agreement with valence-band photoelectron spectra of liquid water, the 1b1, 3a1, and 1b2 electron binding energies in water aggregates are redshifted by approximately 1 eV relative to the isolated molecule. By extrapolating the results for larger clusters the threshold energy for photoelectron emission is 9.6+/-0.15 eV (free clusters) and 10.58+/-0.10 eV (embedded clusters). Our results for the electron affinity (V0=-0.17+/-0.05 eV) and adiabatic band gap (E(G,Ad)=6.83+/-0.05 eV) of liquid water are in excellent agreement with recent information from theoretical and experimental works.

Polarization effects and charge separation in AgCl-water clusters.

Structural, energetic, vibrational, and electronic properties of salt ion pairs (AgCl and NaCl) in water (W) clusters were investigated by density functional theory. In agreement with recent theoretical studies of NaCl-water clusters, structures where the salt ion pair is separated by solvent molecules or solvent separated ion pair (SSIP) were found in AgCl-W(6) and AgCl-W(8) aggregates. Our results indicate that for small AgCl-water clusters, contact ion pair (CIP) structures are energetically more stable than SSIP, whereas an opposite tendency was observed for NaCl-water clusters. In comparison with CIP, SSIP are characterized by extensive electronic density reorganization, reflecting enhanced polarization effects. A major difference between AgCl-water and NaCl-water CIP aggregates concerns charge transfer. In AgCl-water CIP clusters, charge is transferred from the solvent (water) to the ion pair. However, in NaCl-water CIP clusters charge is transferred from the ion pair to the water molecules. The electronic density reorganization in the aggregates was also discussed through the analysis of electronic density difference isosurfaces. Time dependent density functional theory calculations show that upon complexation of AgCl and NaCl with water molecules, excitation energies are significantly blueshifted relative to the isolated ion pairs ( approximately 2 eV for AgCl-W(8) SSIP). In keeping with results for NaI-water clusters [Peslherbe et al., J. Phys. Chem. A 104, 4533 (2000)], electronic oscillator strengths of transitions to excited states are weaker for SSIP than for CIP structures. However, our results also suggest that the difference between excitation energies and oscillator strengths of CIP and SSIP structures may decrease with increasing cluster size.

A seleção brasileira de voleibol infanto-juvenil feminina e o seu perfil dermatoglífico / The Brazilian volleyball juvenile female team and its dermatoglyphic characteristics

OBJECTIVE: To identify the dermatoglypical caracteristics by the digital impressions. METHODS: The study was descriptive and 19 female athletics were included. They were 15.9 +/- 0.36 years old, there weight was 67.4 +/- 8.73kg, and thad 181.6 +/- 6.11cm, from the juvenile 2004 Brazilian voleybol juvenile selection team. The Cummins & Midlo (1942), method was used to identify the dermatoglyphical caracteristics by the digital impressions from 10 hand digits of athletes. RESULTS: The study showed the following model of digital impressions: A = 0.42 +/- 0.69; L = 6.89 +/- 2.89; W = 2.74 +/- 3.14; D10 = 12.32 +/- 3.51 e SQTL = 119.37 +/- 28.99. CONCLUSIONS: The present study confirmed that the dermatoglyphical characteristics of the female voleybol athletes of the juvenile Brazilian team are similar to that of the adult male team. Its necessary to compare these data with the adult female voley team, in order to stablish parameters to evaluate the potencial of future athletes.

Effect of angiotensin-(1-7) on jejunal absorption of water in rats.

The effect of angiotensin-(1-7) on jejunal water absorption in rats was investigated. The jejunal sac of anesthetized rats was filled with two ml of tyrode solution containing 3.7 MBq of tritiated water. A femoral vein was cannulated for administration of peptides and drugs. Infusion of Ang-(1-7) at the dose of 0.7 ng/kg.min produced a significant increase in jejunal water absorption compared to control (32% increase). The Ang-(1-7) antagonist A-779 abolished the effect of Ang-(1-7) on water absorption. A reduction of the Ang-(1-7) effect was also produced by treatment with the AT(1) receptor antagonist, losartan or the AT(2) receptor antagonist, PD123.177. The increase in jejunal water absorption produced by Ang-(1-7) was blocked by the nitric oxide synthase inhibitor, L-NAME and by indomethacin. These data suggest that the effect of Ang-(1-7) on the jejunal loop is mediated by activation of a multiple angiotensin receptors and/or by an atypical angiotensin receptor. Furthermore, the effect of Ang-(1-7) on jejunal water absorption is mediated by nitric oxide and by a cyclooxygenase-dependent mechanism.

Energetics of C-Cl, C-Br, and C-I bonds in haloacetic acids: enthalpies of formation of XCH2COOH (X=CI, Br, I) compounds and the carboxymethyl radical.

The standard molar enthalpies of formation of chloro-, bromo-, and iodoacetic acids in the crystalline state, at 298.15 K, were determined as deltafH(o)m(C2H3O2Cl, cr alpha)=-(509.74+/- 0.49) kJ x mol(-1), deltafH(o)m(C2H3O2Br, cr I)-(466.98 +/- 1.08) kJ x mol(-1), and deltafH(o)m (C2H3O2I, cr)=-(415.44 +/- 1.53) kJ x mol(-1), respectively, by rotating-bomb combustion calorimetry. Vapor pressure versus temperature measurements by the Knudsen effusion method led to deltasubH(o)m(C2H3O2Cl)=(82.19 +/- 0.92) kJ x mol(-1), deltasubH(o)m(C2H3O2Br)=(83.50 +/- 2.95) kJ x mol(-1), and deltasubH(o)m-(C2H3O2I) = (86.47 +/- 1.02) kJ x mol(-1), at 298.15 K. From the obtained deltafH(o)m(cr) and deltasubH(o)m values it was possible to derive deltafH(o)m(C2H3O2Cl, g)=-(427.55 +/- 1.04) kJ x mol(-1), deltafH(o)m (C2H3O2Br, g)=-(383.48 +/- 3.14) kJ x mol(-1), and deltafH(o)m(C2H3O2I, g)=-(328.97 +/- 1.84) kJ x mol(-1). These data, taken with a published value of the enthalpy of formation of acetic acid, and the enthalpy of formation of the carboxymethyl radical, deltafH(o)m(CH2COOH, g)=-(238 +/- 2) kJ x mol(-1), obtained from density functional theory calculations, led to DHo(H-CH2COOH)=(412.8 +/- 3.2) kJ x mol(-1), DHo(Cl-CH2COOH)=(310.9 +/- 2.2) kJ x mol(-1), DHo(Br-CH2COOH)=(257.4 +/- 3.7) kJ x mol(-1), and DHo(I-CH2COOH)=(197.8 +/- 2.7) kJ x mol(-1). A discussion of the C-X bonding energetics in XCH2COOH, CH3X, C2H5X, C2H3X, and C6H5X (X=H, Cl, Br, I) compounds is presented.

Lepidopteran caterpillar fauna on lactiferous host plants in the central Brazilian cerrado.

Nine lactiferous plants of five families were examined for caterpillars in a 4 ha cerrado sensu stricto (savanna-like vegetation) area of the University of Brasília Experimental Farm (DF, Brazil), from August 1995 to May 1997. In 5,540 censuses, less than 5% of the plants hosted caterpillars. All the caterpillars found, a total of 55 species in 15 families were reared under laboratory conditions. Pyralidae, Geometridae, Elachistidae, Megalopygidae, and Limacodidae were the richest caterpillar families recorded. Of the 55 species, more than 40% were polyphagous, feeding on different host plant families, while 21 were considered rare species with less than four records during the study period. The species' rareness did not permit any analysis of diet breadth. The presence of latex in the host plants seems to affect both the proportion of host plants with caterpillars (abundance) and the caterpillar species richness. The habit of eating plants that characteristically produce latex occurs in several distantly-related lepidopteran families. The results support the argument that specific behaviors to circumvent plant latex defense may have arisen independently many times in the Lepidoptera.