Thermal behavior and decomposition kinetics of rifampicin polymorphs under isothermal and non-isothermal conditions

The thermal behavior of two polymorphic forms of rifampicin was studied by DSC and TG/DTG. The thermoanalytical results clearly showed the differences between the two crystalline forms. Polymorph I was the most thermally stable form, the DSC curve showed no fusion for this species and the thermal decomposition process occurred around 245 ºC. The DSC curve of polymorph II showed two consecutive events, an endothermic event (Tpeak = 193.9 ºC) and one exothermic event (Tpeak = 209.4 ºC), due to a melting process followed by recrystallization, which was attributed to the conversion of form II to form I. Isothermal and non-isothermal thermogravimetric methods were used to determine the kinetic parameters of the thermal decomposition process. For non-isothermal experiments, the activation energy (Ea) was derived from the plot of Log β vs 1/T, yielding values for polymorph form I and II of 154 and 123 kJ mol-1, respectively. In the isothermal experiments, the Ea was obtained from the plot of lnt vs 1/T at a constant conversion level. The mean values found for form I and form II were 137 and 144 kJ mol-1, respectively.

Sintomas vocais e sensações laríngeas em trabalhadores de uma usina de álcool e açúcar expostos a riscos ocupacionais

OBJETIVO: Investigar os sintomas vocais e sensações laríngeas dos trabalhadores de uma usina de álcool e açúcar expostos a ruído e/ou substâncias químicas. MÉTODOS: Participaram 289 trabalhadores de uma usina de álcool e açúcar distribuídos em cinco grupos expostos (I- ruído; II- ruído, óleo, graxa, derivação de petróleo; III- ruído, ácidos, sulfatos, cloretos, nitratos; IV- ruído, poeiras respiráveis e sílica livre cristalizada; V- óleo, graxa, derivação de petróleo) e um grupo controle que responderam o questionário Condições de Produção Vocal - Professor adaptado à categoria profissional. Os grupos foram comparados em relação aos sintomas vocais, sensações laríngeas, tabagismo e riscos físicos e químicos. Esta comparação foi realizada por meio de análise estatística. RESULTADOS: O sintoma vocal e a sensação laríngea mais relatados pelos trabalhadores foram voz grave e tosse com catarro, respectivamente. Considerando o risco físico no ambiente de trabalho, os grupos I e IV foram os que mais citaram presença de ruído. Devido à sua exposição, os mesmos aumentavam a intensidade da voz (Efeito de Lombard-Tarneaud) e, assim, mencionaram sintomas vocais. Em relação aos riscos químicos no ambiente ocupacional, o grupo IV foi o que mais referiu presença de poeira e fumaça, e estas eram compostas por poeiras respiráveis e sílica. Tais exposições ocasionam sintomas vocais e sensações laríngeas e, consequentemente, alterações vocais. CONCLUSÃO: Sintomas vocais e sensações laríngeas podem estar relacionados a atividade profissional em que haja exposição a riscos físicos e/ou químicos.

Evolution of magnetic properties and crystallographic texture in electrical steel with large plastic deformation

Deformation leads to a hardening of steel due to an increase in the density of dislocations and a reduction in their mobility, giving rise to a state of elevated residual stresses in the crystal lattice. In the microstructure, one observes an increase in the contribution of crystalline orientations which are unfavorable to the magnetization, as seen, for example, by a decrease in B(50), the magnetic flux density at a field of 50 A/cm. The present study was carried out with longitudinal strips of fully processed non-oriented (NO) electrical steel, with deformations up to 70% resulting from cold rolling in the longitudinal direction. With increasing plastic deformation, the value of B(50) gradually decreases until it reaches a minimum value, where it remains even for larger deformations. On the other hand, the coercive field H(c) continually increases. Magnetometry results and electron backscatter diffraction results are compared and discussed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3560895]

Functionalized adamantane: Building blocks for nanostructure self-assembly

We report first-principles calculations on the electronic and structural properties of chemically functionalized adamantane molecules, either in isolated or crystalline forms. Boron and nitrogen functionalized molecules, aza-, tetra-aza-, bora-, and tetra-bora-adamantane, were found to be very stable in terms of energetics, consistent with available experimental data. Additionally, a hypothetical molecular crystal in a zincblende structure, involving the pair tetra-bora-adamantane and tetra-aza-adamantane, was investigated. This molecular crystal presented a direct and large electronic band gap and a bulk modulus of 20 GPa. The viability of using those functionalized molecules as fundamental building blocks for nanostructure self-assembly is discussed.

The Effects of Commercially Available Preservative-Free FDA-Approved Triamcinolone (Triesence (R)) on Retinal Cells in Culture

Purpose: To evaluate the effects of Triesence (R) (TRI), a new preservative-free triamcinolone approved by the U. S. Food and Drug Administration (FDA) for intraocular use, on human retina pigment epithelial (ARPE-19) and rat neurosensory (R28) cells in culture. Methods: ARPE-19 and R28 cell cultures were treated 24 h with 1,000, 500, 200, or 100 mu g/mL of crystalline (cTRI) or 1,000, 500, or 200 mu g/mL of solubilized (sTRI). TRI was solubilized by centrifuging the drug, discarding the supernatant containing the vehicle and then resuspending the drug pellet in an equivalent amount of Dimethyl sulfoxide to achieve the same concentration as the commercial preparation. Percentage of cell viability (CV) was evaluated by a trypan blue dye-exclusion assay. The mitochondrial membrane potential (Delta Psi m) was analyzed with the JC-1 assay. The caspase-3/7 activity was measured by a fluorochrome assay. Results: In the ARPE-19 cultures, the cTRI caused a decrease in CV at 1,000 mg/mL (13.03 +/- 6.51; P < 0.001), 500 mu g/mL (28.87 +/- 9.3; P < 0.001), 200 mu g/mL (54.93 +/- 5.61; P < 0.001), and 100 mu g/mL (82.53 +/- 0.65; P < 0.005) compared with the untreated controls (96.98 +/- 0.16). In R28 cultures, the cTRI treatment also reduced CV values significantly (P < 0.001) for the 1,000 mu g/mL (22.73 +/- 2.44), 500 mu g/mL (34.63 +/- 1.91), 200 mu g/mL (58.70 +/- 1.39), and 100 mu g/m (75.33 +/- 2.47) compared with the untreated controls (86.08 +/- 3.54). Once the TRI was solubilized (sTRI), the CV and Delta Psi m remained similar to the untreated controls for both ARPE-19 and R28 cells. The sTRI treatment with 1,000, 500, and 200 mu g/mL increased in caspase-3/7 activity in ARPE-19 cells (P < 0.01) and in R28 cells (P < 0.05) compared with dimethyl sulfoxide equivalent controls. Conclusion: The crystalline form of TRI (cTRI) can cause a significant decrease in CV to cultured retinal cells. Once the TRI is solubilized (sTRI), at the same concentrations, the cells remain viable with no decrease in CV or Delta Psi m. The sTRI can, however, increase caspase-3/7 activity, thus suggesting some degree of apoptosis.

Relationship Between Surface Topography and Energy Density Distribution of Er,Cr:YSGG Beam on Irradiated Dentin: An Atomic Force Microscopy Study

Objective: The aim of this study was to assess by atomic force microscopy (AFM) the effect of Er,Cr:YSGG laser application on the surface microtopography of radicular dentin. Background: Lasers have been used for various purposes in dentistry, where they are clinically effective when used in an appropriate manner. The Er, Cr: YSGG laser can be used for caries prevention when settings are below the ablation threshold. Materials and Methods: Four specimens of bovine dentin were irradiated using an Er, Cr:YSGG laser (lambda = 2.78 mu m), at a repetition rate of 20 Hz, with a 750-mu m-diameter sapphire tip and energy density of 2.8 J/cm(2) (12.5 mJ/pulse). After irradiation, surface topography was analyzed by AFM using a Si probe in tapping mode. Quantitative and qualitative information concerning the arithmetic average roughness (Ra) and power spectral density analyses were obtained from central, intermediate, and peripheral areas of laser pulses and compared with data from nonirradiated samples. Results: Dentin Ra for different areas were as follows: central, 261.26 (+/- 21.65) nm; intermediate, 83.48 (+/- 6.34) nm; peripheral, 45.8 (+/- 13.47) nm; and nonirradiated, 35.18 (+/- 2.9) nm. The central region of laser pulses presented higher ablation of intertubular dentin, with about 340-760 nm height, while intermediate, peripheral, and nonirradiated regions presented no difference in height of peritubular and interperitubular dentin. Conclusion: According to these results, we can assume that even when used at a low-energy density parameter, Er, Cr: YSGG laser can significantly alter the microtopography of radicular dentin, which is an important characteristic to be considered when laser is used for clinical applications.

Melting and freezing of spherical bismuth nanoparticles confined in a homogeneous sodium borate glass

The melting temperature and the crystallization temperature of Bi nanoclusters confined in a sodium borate glass were experimentally determined as functions of the cluster radius. The results indicate that, on cooling, liquid Bi nanodroplets exhibit a strong undercooling effect for a wide range of radii. The difference between the melting temperature and the freezing temperature decreases for decreasing radius and vanishes for Bi nanoparticles with a critical radius R = 1.9 nm. The magnitude of the variation in density across the melting and freezing transitions for Bi nanoparticles with R = 2 nm is 40% smaller than for bulk Bi. These experimental results support a basic core-shell model for the structure of Bi nanocrystals consisting of a central crystalline volume surrounded by a structurally disordered shell. The volume fraction of the crystalline core decreases for decreasing nanoparticle radius and vanishes for R = 1.9 nm. Thus, on cooling, the liquid nanodroplets with R < 1.9 nm preserve, across the liquid-to-solid transformation, their homogeneous and disordered structure without crystalline core.

Supramolecular polymorphism of DNA in non-cationic L(alpha) lipid phases

The structure of a complex between hydrated DNA and a non-cationic lipid is studied, including its phase diagram. The complex is spontaneously formed by adding DNA fragments (ca. 150 base pairs in length) to non-cationic lipids and water. The self-assembly process often leads to highly ordered structures. The structures were studied by combining X-ray scattering, fluorescence and polarized microscopy, as well as freeze-fracture experiments with transmission electron microscopy. We observe a significant increase of the smectic order as DNA is incorporated into the water layers of the lamellar host phase, and stabilization of single phase domains for large amounts of DNA. The effect of confinement on DNA ordering is investigated by varying the water content, following three dilution lines. A rich polymorphism is found, ranging from weakly correlated DNA-DNA in-plane organizations to highly ordered structures, where transmembrane correlations lead to the formation of columnar rectangular and columnar hexagonal superlattices of nucleotides embedded between lipid lamellae. From these observations, we suggest that addition of DNA to the lamellar phase significantly restricts membrane fluctuations above a certain concentration and helps the formation of the lipoplex. The alteration of membrane steric interactions, together with the appearance of interfacial interactions between membranes and DNA molecules may be a relevant mechanism for the emergence of highly ordered structures in the concentrated regime.

Elastic Maier-Saupe-Zwanzig model and some properties of nematic elastomers

We introduce a simple mean-field lattice model to describe the behavior of nematic elastomers. This model combines the Maier-Saupe-Zwanzig approach to liquid crystals and an extension to lattice systems of the Warner-Terentjev theory of elasticity, with the addition of quenched random fields. We use standard techniques of statistical mechanics to obtain analytic solutions for the full range of parameters. Among other results, we show the existence of a stress-strain coexistence curve below a freezing temperature, analogous to the P-V diagram of a simple fluid, with the disorder strength playing the role of temperature. Below a critical value of disorder, the tie lines in this diagram resemble the experimental stress-strain plateau and may be interpreted as signatures of the characteristic polydomain-monodomain transition. Also, in the monodomain case, we show that random fields may soften the first-order transition between nematic and isotropic phases, provided the samples are formed in the nematic state.

Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI center dot NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI center dot PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 degrees C, 200 degrees C and 250 degrees C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 degrees C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.

Absence of ferromagnetic order in high quality bulk Co-doped ZnO samples

Bulk Zn(1-x)Co(x)O samples were synthesized via standard solid-state reaction route with different Co molar concentrations up to 21%. A detailed microstructural analysis was carried out to investigate alternative sources of ferromagnetism, such as secondary phases and nanocrystals embedded in the bulk material. Conjugating different techniques we confirmed the Zn replacement by Co ions in the wurtzite ZnO structure, which retains, however, a high crystalline quality. No segregated secondary phases neither Co-rich nanocrystals were detected. Superconducting quantum interference device magnetometry demonstrates a paramagnetic Curie-Weiss behavior with antiferromagnetic interactions. We discuss the observed room temperature paramagnetism of our samples considering the current models for the magnetic properties of diluted magnetic semiconductors. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3459885]

Unraveling effects of disorder on the electronic structure of SiO(2) from first principles

We present a first-principles systematic study of the electronic structure of SiO(2) including the crystalline polymorphs alpha quartz and beta cristobalite, and different types of disorder leading to the amorphous phase. We start from calculations within density functional theory and proceed to more sophisticated quasiparticle calculations according to the GW scheme. Our results show that different origins of disorder have also different impact on atomic and electronic-density fluctuations, which affect the electronic structure and, in particular, the size of the mobility gap in each case.

Defect-induced effects on carrier migration through one-dimensional poly(para-phenylenevinylene) chains

Defects in one-dimensional (1D) systems can be intrinsically distinct from its three-dimensional counterparts, and polymer films are good candidates for showing both extremes that are difficult to individuate in the experimental data. We study theoretically the impact of simple hydrogen and oxygen defects on the electron transport properties of one-dimensional poly(para-phenylenevinylene) chains through a multiscale technique, starting from classical structural simulations for crystalline films to extensive ab initio calculations within density functional theory for the defects in single crystalline-constrained chains. The most disruptive effect on carrier transport comes from conjugation breaking imposed by the overcoordination of a carbon atom in the vinyl group independently from the chemical nature of the defect. The particular case of the [C=O] (keto-defect) shows in addition unexpected electron-hole separation, suggesting that the experimentally detected photoluminescence bleaching and photoconductivity enhancement could be due to exciton dissociation caused by the 1D characteristics of the defect.

Magnetoelastic and thermal effects in the BiMn(2)O(5) lattice: A high-resolution x-ray diffraction study

High-resolution synchrotron x-ray diffraction measurements were performed on single crystalline and powder samples of BiMn(2)O(5). A linear temperature dependence of the unit cell volume was found between T(N)=38 and 100 K, suggesting that a low-energy lattice excitation may be responsible for the lattice expansion in this temperature range. Between T(*)similar to 65 K and T(N), all lattice parameters showed incipient magnetoelastic effects, due to short-range spin correlations. An anisotropic strain along the a direction was also observed below T(*). Below T(N), a relatively large contraction of the a parameter following the square of the average sublattice magnetization of Mn was found, indicating that a second-order spin Hamiltonian accounts for the magnetic interactions along this direction. On the other hand, the more complex behaviors found for b and c suggest additional magnetic transitions below T(N) and perhaps higher-order terms in the spin Hamiltonian. Polycrystalline samples grown by distinct routes and with nearly homogeneous crystal structure above T(N) presented structural phase coexistence below T(N), indicating a close competition amongst distinct magnetostructural states in this compound.

Internal Strain Distribution in Freestanding Porous Silicon

Elastic properties of freestanding porous silicon layers fabricated by electrochemical anodization were studied by Raman scattering. Different anodization currents provided different degrees of porosity in the nanometer scale. Raman lines corresponding to the longitudinal optical phonons of crystalline and amorphous phases were observed. The amorphous volume fraction increased and the phonon frequencies for both phases decreased with increasing porosity. A strain distribution model is proposed whose fit to the experimental results indicates that the increasing nanoscale porosity causes strain relaxation in the amorphous domains and strain buildup in the crystalline ones. The present analysis has significant implications on the estimation of the crystalline Si domain's characteristic size from Raman scattering data. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3225832] All rights reserved.