Stability of benzoporphyrin photosensitizers in water/ethanol mixtures: pKa determination and self‐aggregation processes

Benzoporphyrin monoacid derivatives, here named B3A and B3B, are promising new drugs for photodynamic therapy. Although both isomers show interesting characteristics as photosensitizing compounds, they have some distinct physicochemical properties such as the tendency to self‐aggregate in water‐rich media. Because pH drives the presence of each species, the pK_a of these compounds assumes strategic importance. However, traditional micro‐titration methods and UV–Vis absorption techniques fail to give reliable pK_a values due to the characteristics of this highly complex system, such as the precipitation of hydrophobic species, close pK_a values, and high absorption band superposition. In the present work, chemometric tools are employed to evaluate pK_a, and the kinetic tendency of monomers to undergo self‐aggregation is investigated. In solvent mixtures at low water percentage in ethanol, both B3A and B3B are stabilized in a monomeric state. However, in mixtures with a high water content, self‐aggregation takes place, mainly under a mild pH acid condition (3 < pH < 6), in which the prevalent protolytic species of both isomers is the neutral charged form, compounds with carboxylic and porphyrin free‐base groups. It is demonstrated that both isomers can undergo aggregation following a self‐catalytic mechanism, which is 2000 times slower to B3A than B3B. For B3A, the aggregation is manifested by a decrease in the monomer band with the aggregation band probably superposed to that of the monomer. For B3B, together with the decrease in the monomer band, a new band related to self‐aggregates is observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Models for the modern power grid

This article reviews different kinds of models for the electric power grid that can be used to understand the modern power system, the smart grid. From the physical network to abstract energy markets, we identify in the literature different aspects that co-determine the spatio-temporal multilayer dynamics of power system. We start our review by showing how the generation, transmission and distribution characteristics of the traditional power grids are already subject to complex behaviour appearing as a result of the the interplay between dynamics of the nodes and topology, namely synchronisation and cascade effects. When dealing with smart grids, the system complexity increases even more: on top of the physical network of power lines and controllable sources of electricity, the modernisation brings information networks, renewable intermittent generation, market liberalisation, prosumers, among other aspects. In this case, we forecast a dynamical co-evolution of the smart grid and other kind of networked systems that cannot be understood isolated. This review compiles recent results that model electric power grids as complex systems, going beyond pure technological aspects. From this perspective, we then indicate possible ways to incorporate the diverse co-evolving systems into the smart grid model using, for example, network theory and multi-agent simulation.     

Vortices as Degenerate Metrics

We note that the Bogomolny equation for abelian vortices is precisely the condition for invariance of the Hermitian–Einstein equation under a degenerate conformal transformation. This leads to a natural interpretation of vortices as degenerate Hermitian metrics that satisfy a certain curvature equation. Using this viewpoint, we rephrase standard results about vortices and make new observations. We note the existence of a conceptually simple, non-linear rule for superposing vortex solutions, and we describe the natural behaviour of the L ²-metric on the moduli space upon restriction to a class of submanifolds.     

Stationary solutions for the parity-even sector of the CPT-even and Lorentz-covariance-violating term of the standard model extension

In this work, we focus on some properties of the parity-even sector of the CPT-even electrodynamics of the standard model extension. We analyze how the six non-birefringent terms belonging to this sector modify the static and stationary classical solutions of the usual Maxwell theory. We observe that the parity-even terms do not couple the electric and magnetic sectors (at least in the stationary regime). The Green’s method is used to obtain solutions for the field strengths E and B at first order in the Lorentz-covariance-violating parameters. Explicit solutions are attained for point-like and spatially extended sources, for which a dipolar expansion is achieved. Finally, an Earth-based experiment is presented that can lead (in principle) to an upper bound on the anisotropic coefficients as stringent as      

X-ray excited optical luminescence of Ce-doped BaAl2O4

The luminescence properties of Ce³⁺ in BaAl₂O₄ are reported. The results of simultaneous measurements of XEOL and XAS in the X-ray energy range that includes the Ba L_II,III-edges and Ce L_III edge are shown. The XEOL yield increases as the energy of the photons increases. The radioluminescence spectra, taken from 200 to 1100 nm, showed broad emission bands corresponding to 5d¹→²F_5/2, ²F_7/2 transitions of Ce³⁺ when incorporated into two nonequivalent Ba sites. The lifetime of the light emission was also measured using the single bunch operation mode at the Brazilian National Synchrotron Laboratory (LNLS), and BaAl₂O₄:Ce³⁺ showed single exponential decay time component of about 44.3 ns.     

Evaluation of the acoustic performance of classrooms in public schools

This paper presents the results of an evaluation of acoustic comfort of classrooms built according to a standard design. Three constructive designs located in the metropolitan area of Curitiba (Brazil) have been evaluated, two schools built under each of these three designs, in a total of six schools. The acoustic quality of the classrooms have been analyzed based on measurements of the reverberation time, sound pressure level inside and outside the classrooms, and sound insulation. Measurements of ambient noise (external and internal) followed the Brazilian Standards NBR 10151 and NBR 10152. Measurement of reverberation time and sound insulation followed the international Standards ISO 140-4, ISO 140-5, ISO 717-1, and ISO 3382. Results (sound insulation and reverberation time) have been compared with reference values found in the Brazilian Standard NBR 1279, and in the Standards ANSI S12.60 and DIN 18041. Results reveal poor acoustical quality of the surveyed classrooms, for all 3 constructive designs studied. The surveyed designs do not meet the guidelines of either the Brazilian Standards or of the International Standards employed as references.     

Synthesis and Study of the Photophysical Properties of a New Eu<Superscript>3+</Superscript> Complex with 3-Hydroxypicolinamide

This work reports on the synthesis and characterization of a new complex of Eu³⁺ with the 3-hydroxypicolinamide ligand (Hhpa). Here we present an approach for obtaining bis[2-carbamoyl(κO)pyridin-3-olato(κO’)] lanthanide complexes, which were characterized through elemental analysis, thermal analysis, infrared and photoluminescence spectroscopies (emission, excitation, luminescence lifetimes, quantum efficiencies, Judd-Ofelt parameters and quantum yields). Although hpa can act as a bidentate ligand in different conformations, the results attest for the occurrence of a unique coordination site of low symmetry for the Eu³⁺ ions, in which two anionic hpa ligands coordinate the cations through an O/O chelating system. The phosphorescence of the synthesized gadolinium complex provides the energy of the triplet state, which is determined to be at 20,830 cm^-1 over the ground state. This makes the Hhpa ligand very adequate for sensitizing the Eu³⁺ luminescence, which leads to a very efficient antenna effect and opens a wide range of applications for the complex in light emitting organic-inorganic devices.