Nanostructured Polymeric Micelles Carrying Xanthene Dyes for Photodynamic Evaluation

It was evaluated the properties of the xanthene dyes Erythrosin B, Eosin Y and theirs Methyl, Butyl and Decyl ester derivatives as possible photosensitizers (PS) for photodynamic treatments. The more hydrophobic dyes self‐aggregate in water/ethanol solutions above 70% water (vol/vol) in the mixture. In buffered water, these PS were encapsulated in Pluronic polymeric surfactants of P‐123 and F‐127 by two methodologies: direct addition and the thin‐film solid dispersion methods. The thin‐film solid method provided formulations with higher stabilities besides effective encapsulation of the PS as monomers. Size measurements demonstrated that Pluronic forms self‐assembled micelles with uniform size, which present slightly negative surface potential and a spherical form detected by TEM microscopy. The ester length modulates xanthene localization in the micelle, which is deeper with the increase in the alkyl chain. Moreover, some PS are distributed into two populations: one on the corona micelle interface shell (PEO layer) and the other into the core (PPO region). Although all PS formulations show high singlet oxygen quantum yield, promising results were obtained for Erythrosin B esters with the hydrophobic P‐123, which ensures their potential as drug for clinical photodynamic applications.     

Compatibility of activity coefficients estimated experimentally and by Pitzer equations for the assessment of seawater pH

Calibration of pH meters is usually performed with reference pH buffer solutions of low ionic strength, I ≤ 0.1 mol kg^?1. For seawater pH measurements (I ≈ 0.7 mol kg^?1), calibration buffers in high ionic strength matrix are required. The Harned cell, in association with the Nernst equation and a model for estimating the chloride ion activity coefficient, \(\gamma_{{{\text{Cl}}^{ - } }} ,\) is the basis of the primary method for pH assignment to reference pH buffers. The semi-empirical Pitzer model is, in principle, adequate to estimate \(\gamma_{{{\text{Cl}}^{ - } }}\) of complex solutions, namely seawater. Nevertheless, no assessment of the validity of the model for this matrix is known to the authors. This work aims at estimating the adequacy of the Pitzer model by assessing the metrological compatibility of mean activity coefficients, in this case \(\gamma_{ \pm } = \sqrt {\gamma_{{{\text{H}}^{ + } }} \gamma_{{{\text{Cl}}^{ - } }} }\) estimated experimentally with the Harned cell, \(\gamma_{ \pm }^{\text{Exp}} ,\) and using the Pitzer model, \(\gamma_{ \pm }^{\text{Ptz}}\). The measurement uncertainty considered in the compatibility test was estimated using the bottom-up approach, where components were combined by the numerical Kragten method after checking its adequacy. The compatibility of the estimated \(\gamma_{ \pm }\) was assessed for solutions with increasing complexity and an ionic strength of 0.67 mol kg^–1. \(\gamma_{ \pm }^{\text{Exp}}\) and \(\gamma_{ \pm }^{Ptz}\) are metrologically compatible for a confidence level of 95 % where the relative standard uncertainty of their difference ranged from 1.1 % to 3.1 % in all chloride solutions to approximately 6.3 % when sodium sulfate was also present. This led to assume the validity of the Pitzer model equations to estimate \(\gamma_{{{\text{Cl}}^{ - } }} ,\) required to define reference pH values of buffer solutions with high ionic strength.     

Krause's model of opinion dynamics on isolated time scales

We analyze a bounded confidence model, introduced by Krause, on isolated time scales. In this model, each agent takes into account only the assessments of the agents whose opinions are not too far away from its own opinion. We show that the behavior of the model depends strongly on the graininess function μ: If μ takes values in the interval ]0,1], then our discrete time scale model behaves similarly to the classical one, but if μ takes values in ]1,+∞[, then the model has different properties. Simulations are performed to validate the theoretical results. Copyright © 2016 John Wiley & Sons, Ltd.     

Multivariate optimization and HS-SPME/GC-MS analysis of VOCs in red, yellow and purple varieties of Capsicum chinense sp. peppers

Peppers are used not only in cookery, but also in many other applications, like cosmetic, pharmaceutical and nourishing industry. The chemical composition of peppers is quite complex and several volatile and non-volatile substances contribute to their flavor, which is an important sensorial propriety. In this work a headspace/solid phase microextraction/gas chromatography coupled to mass spectrometry method was developed to evaluate the profiles of volatile compounds that contribute to the aroma of red, yellow and purple varieties of Capsicum chinense sp. peppers. The optimization of the extraction conditions was carried out using multivariate strategies such as factorial design and response surface methodology. The GC-MS analysis allowed the tentative identification of 34 compounds, with similarities higher than 85%, in accordance with the NIST mass spectral library. The data obtained by the analysis of volatile compounds, according to the proposed method, were treated with PCA chemometrics tool in order to group different varieties of C. chinense sp. peppers with similar VOC profiles. Amongst the most abundant VOCs, hexyl ester of pentanoic acid, dimethylcyclohexanols, humulene and esters of butanoic acid were found. Principal component analysis turned possible to visualize the grouping tendencies of the studied varieties of pepper, as well as the identification of the volatile compounds responsible for discriminating the three groups. Considering the fact that many species of peppers are used as human food, the significance of this work is further emphasized by its applicability to the study of food quality indicators, and as a tool for investigations on the composition of the pepper sources.     

First principles calculation of the dipole moments of small mixed Ge/Te semiconductor clusters

We investigate the structural and electronic properties of the small mixed semiconductor clusters GeTe, Ge₂Te, GeTe₂ and Ge₂Te₂ by means of first principles supercell calculations using the local density approximation and the pseudopotential plane wave method. The cluster geometry is optimized using a conjugate gradient method. For GeTe₂ we confirm the linear structure (D_∞h ) suggested by recent experiments. For Ge₂Te we obtain an equilateral triangle as the equilibrium structure. For Ge₂Te₂ we obtain a deformed tetrahedrom (butterfly C_2v symmetry). For each of these molecules we compute the dipole moment in the equilibrium geometry and in selected geometries near to equilibrium corresponding to states higher in energy by a few tens of meV. For the equilibrium state of Ge₂Te and Ge₂Te₂ we obtain permanent dipole moments smaller than those estimated from recent experiments at room temperature. For selected low lying excited states of these clusters, which have elongated Ge-Te bond length, we obtain enhanced dipole moments, improving the agreement with the ones estimated from experiments.     

Centrifugation equilibrium for spheres and spherocylinders

The centrifugation equilibrium problem is formulated and solved using a new procedure in which the specified variables are the temperature, system volume, particle dimensions and concentrations, angular speed, cell length, and cell distance from the rotation axis. As a result, we obtain the concentration profiles for all types of particles present in the system, which are considered to be immersed in a fluid. The particles are modeled as hard nonattractive spherocylinders using an equation of state, but the procedure is not restricted to any geometrical shape, and can be used with any equation of state available. The fluid is treated as a continuous medium, responsible for centrifugal buoyancy. We make calculations for colloidal suspensions of silica, often used for separations in biotechnology. Results are in good agreement with experiments and show excellent agreement in comparison with Monte Carlo simulations. Our calculations also predict focusing and shifting phenomena that have been experimentally observed in separations of fine particles.