Metallochlorophylls of magnesium, copper and zinc: evaluation of the influence of the first coordination sphere on their solvatochromism and aggregation properties

In this study the role of different metal centers (magnesium, zinc and copper) on the enhancement of the hydrophilic character of metallochlorophylls, was evaluated. The solvatochromism as well as the aggregation process for these compounds in water/ethanol mixtures at different volume ratios were evaluated using Fluorescence, and Resonant Light Scattering (RLS) measurements, aiming to characterize the behavior of these compounds. Independently on the studied metallochlorophyll, the presence of at least 60% of water results in a considerable increase in the fluorescence emission, probably a direct consequence of a lower aggregation of these compounds, which is confirmed by the results from RLS measurements. Additionally, the results suggest that magnesium and zinc chlorophyll should be promising phototherapeutic agents for Photodynamic Therapy.

Effect of experimental heat treatment on mechanical properties of resin composites

The aim of this study was to verify the influence of an experimental heat treatment (170ºC/10 min) using a casting furnace on the mechanical properties (hardness and flexural strength) of 2 commercial direct resin composites (TPH Spectrum and Filtek P60) compared to a commercial indirect resin system (BelleGlass). Heat treatment temperature was determined after thermal characterization by thermogravimetry (TG) and differential scanning calorimetry (DSC). Data was analyzed by ANOVA and Tukey's test at 5% significance level. There was statistical significance for the main factor heat treatment (p=0.03) and composite (p=0.02), for flexural strength. For Knoop hardness, only the main factor composite was statistically significant (p=0.00). P60 presented higher hardness than TPH. No statistically significant correlation between mechanical properties tested was detected. Based on these results, it was possible to conclude that heat treatment influenced flexural strength of direct composites, while it was not observed for hardness. The association of direct composites with a simple post-cure heat treatment may be an alternative for current indirect composite systems, although more studies are needed to verify other properties of the composites for this application.

Vitaminas e minerais com propriedades antioxidantes e risco cardiometabólico: controvérsias e perspectivas

No processo celular de obtenção de energia, são gerados compostos chamados espécies reativas de oxigênio (ERO) que, em excesso, podem causar danos celulares. Estresse oxidativo resulta do desequilíbrio no estado de óxido-redução a favor da oxidação. Dos mecanismos de defesa antioxidante, participam enzimas endógenas e algumas vitaminas e minerais. A vitamina E encontra-se no plasma e na partícula de LDL, protegendo lipídeos da oxidação. Estudos observacionais relataram associação inversa entre ingestão de vitamina E e risco cardiometabólico (RCM). Entretanto, ensaios clínicos não comprovaram a eficácia de sua suplementação nos desfechos cardiometabólicos. A vitamina C participa do sistema de regeneração da vitamina E, mantendo o potencial antioxidante plasmático. Dados sobre os benefícios de sua suplementação na redução do risco cardiometabólico são inconclusivos. A atividade antioxidante dos carotenoides é responsável, em parte, por seu papel protetor contra doenças cardiovasculares e cânceres. A suplementação desse nutriente também não trouxe resultados consistentes no que se refere à redução do RCM. A participação do zinco e do selênio na defesa antioxidante vem sendo estudada mais recentemente, mas a sua suplementação em indivíduos com níveis séricos normais e ingestão adequada na dieta desses minerais não parece ser necessária. De um modo geral, há muita controvérsia sobre o papel desses micronutrientes no RCM. Estudos epidemiológicos sugerem que o consumo de substâncias antioxidantes provenientes da dieta ou dietas ricas em frutas e hortaliças diminui o RCM. Mais estudos são necessários antes de se recomendar o uso de antioxidantes isolados na forma de suplementos para tal finalidade.

Influence of Annealing Heat Treatment and Cr, Mg, and Ti Alloying on the Mechanical Properties of High-Silicon Cast Iron

The influence of annealing on the mechanical properties of high-silicon cast iron for three alloys with distinct chromium levels was investigated. Each alloy was melted either with or without the addition of Ti and Mg. These changes in the chemical composition and heat treatment aimed to improve the material's mechanical properties by inhibiting the formation of large columnar crystals, netlike laminae, precipitation of coarse packs of graphite, changing the length and morphology of graphite, and rounding the extremities of the flakes to minimize the stress concentration. For alloys with 0.07 wt.% Cr, the annealing reduced the impact resistance and tensile strength due to an enhanced precipitation of refined carbides and the formation of interdendritic complex nets. Annealing the alloys containing Ti and Mg led to a decrease in the mechanical strength and an increase in the toughness. Alloys containing approximately 2 wt.% Cr achieved better mechanical properties as compared to the original alloy. However, with the addition of Ti and Mg to alloys containing 2% Cr, the chromium carbide formation was inhibited, impairing the mechanical properties. In the third alloy, with 3.5 wt.% of Cr additions, the mechanical strength improved. The annealing promoted a decrease in both hardness and amount of iron and silicon complex carbides. However, it led to a chromium carbide formation, which influenced the mechanical characteristics of the matrix of the studied material.

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]

Anomalous thermodynamic properties in ferropericlase throughout its spin crossover transition

The thermodynamics properties of ferropericlase (Mg(1-x)Fe(x)O where x=0.1875) (Fp) throughout its spin crossover were investigated by first principles. Fp was treated as an ideal solid solution of pure high-spin and low-spin states. The Gibbs free energies of the pure states were addressed using the LDA+U method. A vibrational virtual-crystal model was developed to address the vibrational properties of the pure spin cases and used in conjunction with quasiharmonic theory to compute their vibrational free energies. The thermodynamics properties of Fp display significant anomalies that should be typical of spin crossover systems in general. In Fp, in particular, they are fundamental for understanding the state of earth's interior, where the pressure and temperature conditions of the crossover are realized.

Electronic properties and hyperfine fields of nickel-related complexes in diamond

We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.

Rheological Properties of Chocolate Drink from Cupuassu

Flow behavior of chocolate drinks from Cupuassu (Theobroma grandiflorum, Sterculiaceae) from instantised and normal formulation, and enriched with calcium, were studied. Flow behavior was described using common rheological models (Newton, Power Law, and Bingham plastic). Experimental results, obtained at 25 degrees C and 40 degrees C, fitted mostly the Ostwald and Bingham models, with R(2) >= 0.997. The Newtonian model has 0.886 >= R(2) >= 0.991. At 25 degrees C, as expected, viscosity of samples was higher and pseudoplasticity increased (n values were lower than 1). The spray-dryer process lead to differences of rheology of the ""chocolate"" milk drinks. The addition of microcrystalline cellulose plus calcium leads to a lower viscosity.

Anticariogenic Properties of ent-Pimarane Diterpenes Obtained by Microbial Transformation

In the present work, the anticariogenic activities of three pimarane-type diterpenes obtained by fungal biotransformation were investigated. Among these metabolites, ent-8(14), 15-pimaradien-19-ol was the most active compound, displaying very promising MIC values (ranging from 1.5 to 4.0 mu g mL(-1)) against the main microorganisms responsible for dental caries: Streptococcus salivarius, S. sobrinus, S. mutans, S. mitis, S. sanguinis, and Lactobacillus casei. Time kill assays performed with ent-8(14), 15-pimaradien-19-ol against the primary causative agent S. mutans revealed that this compound only avoids growth of the inoculum in the first 12 h (bacteriostatic effect). However, its bactericidal effect is clearly noted thereafter (between 12 and 24 h). The curve profile obtained by combining ent-8(14), 15-pimaradien-19-ol and chlorhexidine revealed a significant reduction in the time necessary for killing S. mutans compared with each of these two chemicals alone. However, no synergistic effect was observed using the same combination in the checkerboard assays against this microorganism. In conclusion, our results point out that ent-8(14), 15-pimaradien-19-ol is an important metabolite in the search for new effective anticariogenic agents.

Electromagnetic energy within a magnetic infinite cylinder and scattering properties for oblique incidence

We analytically calculate the time-averaged electromagnetic energy stored inside a nondispersive magnetic isotropic cylinder that is obliquely irradiated by an electromagnetic plane wave. An expression for the optical-absorption efficiency in terms of the magnetic internal coefficients is also obtained. In the low absorption limit, we derive a relation between the normalized internal energy and the optical-absorption efficiency that is not affected by the magnetism and the incidence angle. This relation, indeed, seems to be independent of the shape of the scatterer. This universal aspect of the internal energy is connected to the transport velocity and consequently to the diffusion coefficient in the multiple scattering regime. Magnetism favors high internal energy for low size parameter cylinders, which leads to a low diffusion coefficient for electromagnetic propagation in 2D random media. (C) 2010 Optical Society of America

Photophysical properties of a photocytotoxic fluorinated chlorin conjugated to four beta-cyclodextrins

A meso-tetrakis(pentafluorophenyl)-chlorin with the reduced pyrrole ring linked to an isoxazolidine ring (FC) has been conjugated to four beta-cyclodextrins (CDFC). The CDFC exhibits excellent water solubility and is a potent photosensitizer towards proliferating NCTC 2544 human keratinocytes. The study by conventional steady state absorption and fluorescence spectroscopies and by time-resolved femto- and nanosecond laser flash spectroscopies suggests that in ethanol and pH 7 buffer the beta-cyclodextrins embed the highly hydrophobic tetrakis(pentafluorophenyl)-chlorin macrocycle and strongly interact with the chlorin rings in the singlet and triplet manifolds. In these solvents, femtosecond spectroscopy suggests that the conjugate undergoes a rapid relaxation in the upper excited singlet states induced by photochemical and/or conformation change(s) at a rate of about 5 ps(-1) to fluorescent states whose lifetime is similar to 8 ns. This interaction is destroyed upon addition of Triton X100 to buffer. Both FC and CDFC strongly fluoresce (Phi(F) similar to 0.5) in micelles. Similar behavior is observed at the triplet level. In ethanol and water, the initial transient triplet state absorbance decays within 1-3 mu s yielding a longer lived triplet with spectral properties indistinguishable from that of original difference absorbance spectra. The determination of the molar absorbance in the 440-460 nm region (similar to 35 000 M(-1) cm(-1)) leads to an estimate of similar to 0.2 for the triplet formation quantum yield of FC in toluene and of FC and CDFC in Triton X100 micelles. Quenching of the CDFC triplets by dioxygen in buffer produces (1)O(2) in a good yield consistent with the effective photocytotoxicity of the chlorin-cyclodextrins conjugate towards cultured NCTC 2544 human keratinocytes. By contrast, FC which aggregates in buffer produces little if any (1)O(2).

Psychometric properties of the Child Health Assessment Questionnaire (CHAQ) applied to children and adolescents with cerebral palsy

Background: Cerebral palsy (CP) patients have motor limitations that can affect functionality and abilities for activities of daily living (ADL). Health related quality of life and health status instruments validated to be applied to these patients do not directly approach the concepts of functionality or ADL. The Child Health Assessment Questionnaire (CHAQ) seems to be a good instrument to approach this dimension, but it was never used for CP patients. The purpose of the study was to verify the psychometric properties of CHAQ applied to children and adolescents with CP. Methods: Parents or guardians of children and adolescents with CP, aged 5 to 18 years, answered the CHAQ. A healthy group of 314 children and adolescents was recruited during the validation of the CHAQ Brazilian-version. Data quality, reliability and validity were studied. The motor function was evaluated by the Gross Motor Function Measure (GMFM). Results: Ninety-six parents/guardians answered the questionnaire. The age of the patients ranged from 5 to 17.9 years (average: 9.3). The rate of missing data was low(< 9.3%). The floor effect was observed in two domains, being higher only in the visual analogue scales (<= 35.5%). The ceiling effect was significant in all domains and particularly high in patients with quadriplegia (81.8 to 90.9%) and extrapyramidal (45.4 to 91.0%). The Cronbach alpha coefficient ranged from 0.85 to 0.95. The validity was appropriate: for the discriminant validity the correlation of the disability index with the visual analogue scales was not significant; for the convergent validity CHAQ disability index had a strong correlation with the GMFM (0.77); for the divergent validity there was no correlation between GMFM and the pain and overall evaluation scales; for the criterion validity GMFM as well as CHAQ detected differences in the scores among the clinical type of CP (p < 0.01); for the construct validity, the patients' disability index score (mean: 2.16; SD: 0.72) was higher than the healthy group ( mean: 0.12; SD: 0.23)(p < 0.01). Conclusion: CHAQ reliability and validity were adequate to this population. However, further studies are necessary to verify the influence of the ceiling effect on the responsiveness of the instrument.

Probing the Galactic thick disc vertical properties and interfaces

Aims. This work investigates the properties (metallicity and kinematics) and interfaces of the Galactic thick disc as a function of height above the Galactic plane. The main aim is to study the thick disc in a place where it is the main component of the sample. Methods. We take advantage of former astrometric work in two fields of several square degrees in which accurate proper motions were measured down to V-magnitudes of 18.5 in two directions, one near the north galactic pole and the other at a galactic latitude of 46 degrees and galactic longitude near 0 degrees. Spectroscopic observations have been acquired in these two fields for a total of about 400 stars down to magnitude 18.0, at spectral resolutions of 3.5 to 6.25 angstrom. The spectra have been analysed with the code ETOILE, comparing the target stellar spectra with a grid of 1400 reference stellar spectra. This comparison allowed us to derive the parameters effective temperature, gravity, [Fe/H] and absolute magnitude for each target star. Results. The Metallicity Distribution Function (MDF) of the thin-thick-disc-halo system is derived for several height intervals between 0 and 5 kpc above the Galactic plane. The MDFs show a decrease of the ratio of the thin to thick disc stars between the first and second kilo-parsec. This is consistent with the classical modelling of the vertical density profile of the disc with 2 populations with different scale heights. A vertical metallicity gradient, partial derivative[Fe/H]/partial derivative z = -0.068 +/- 0.009 dex kpc(-1), is observed in the thick disc. It is discussed in terms of scenarios of formation of the thick disc.

A VLT/FLAMES survey for massive binaries in Westerlund 1 III. The WC9d binary W239 and implications for massive stellar evolution

Context. There is growing evidence that a treatment of binarity amongst OB stars is essential for a full theory of stellar evolution. However the binary properties of massive stars - frequency, mass ratio & orbital separation - are still poorly constrained. Aims. In order to address this shortcoming we have undertaken a multiepoch spectroscopic study of the stellar population of the young massive cluster Westerlund 1. In this paper we present an investigation into the nature of the dusty Wolf-Rayet star and candidate binary W239. Methods. To accomplish this we have utilised our spectroscopic data in conjunction with multi-year optical and near-IR photometric observations in order to search for binary signatures. Comparison of these data to synthetic non-LTE model atmosphere spectra were used to derive the fundamental properties of the WC9 primary. Results. We found W239 to have an orbital period of only similar to 5.05 days, making it one of the most compact WC binaries yet identified. Analysis of the long term near-IR lightcurve reveals a significant flare between 2004-6. We interpret this as evidence for a third massive stellar component in the system in a long period (> 6 yr), eccentric orbit, with dust production occuring at periastron leading to the flare. The presence of a near-IR excess characteristic of hot (similar to 1300 K) dust at every epoch is consistent with the expectation that the subset of persistent dust forming WC stars are short (< 1 yr) period binaries, although confirmation will require further observations. Non-LTE model atmosphere analysis of the spectrum reveals the physical properties of the WC9 component to be fully consistent with other Galactic examples. Conclusions. The simultaneous presence of both short period Wolf-Rayet binaries and cool hypergiants within Wd 1 provides compelling evidence for a bifurcation in the post-Main Sequence evolution of massive stars due to binarity. Short period O+OB binaries will evolve directly to the Wolf-Rayet phase, either due to an episode of binary mediated mass loss - likely via case A mass transfer or a contact configuration - or via chemically homogenous evolution. Conversely, long period binaries and single stars will instead undergo a red loop across the HR diagram via a cool hypergiant phase. Future analysis of the full spectroscopic dataset for Wd 1 will constrain the proportion of massive stars experiencing each pathway; hence quantifying the importance of binarity in massive stellar evolution up to and beyond supernova and the resultant production of relativistic remnants.

The merging cluster Abell 1758 revisited: multi-wavelength observations and numerical simulations

Context. Cluster properties can be more distinctly studied in pairs of clusters, where we expect the effects of interactions to be strong. Aims. We here discuss the properties of the double cluster Abell 1758 at a redshift z similar to 0.279. These clusters show strong evidence for merging. Methods. We analyse the optical properties of the North and South cluster of Abell 1758 based on deep imaging obtained with the Canada-France-Hawaii Telescope (CFHT) archive Megaprime/Megacam camera in the g' and r' bands, covering a total region of about 1.05 x 1.16 deg(2), or 16.1 x 17.6 Mpc(2). Our X-ray analysis is based on archive XMM-Newton images. Numerical simulations were performed using an N-body algorithm to treat the dark-matter component, a semi-analytical galaxy-formation model for the evolution of the galaxies and a grid-based hydrodynamic code with a parts per million (PPM) scheme for the dynamics of the intra-cluster medium. We computed galaxy luminosity functions (GLFs) and 2D temperature and metallicity maps of the X-ray gas, which we then compared to the results of our numerical simulations. Results. The GLFs of Abell 1758 North are well fit by Schechter functions in the g' and r' bands, but with a small excess of bright galaxies, particularly in the r' band; their faint-end slopes are similar in both bands. In contrast, the GLFs of Abell 1758 South are not well fit by Schechter functions: excesses of bright galaxies are seen in both bands; the faint-end of the GLF is not very well defined in g'. The GLF computed from our numerical simulations assuming a halo mass-luminosity relation agrees with those derived from the observations. From the X-ray analysis, the most striking features are structures in the metal distribution. We found two elongated regions of high metallicity in Abell 1758 North with two peaks towards the centre. In contrast, Abell 1758 South shows a deficit of metals in its central regions. Comparing observational results to those derived from numerical simulations, we could mimic the most prominent features present in the metallicity map and propose an explanation for the dynamical history of the cluster. We found in particular that in the metal-rich elongated regions of the North cluster, winds had been more efficient than ram-pressure stripping in transporting metal-enriched gas to the outskirts. Conclusions. We confirm the merging structure of the North and South clusters, both at optical and X-ray wavelengths.