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.     

Arithmetic families of smooth surfaces and equisingularity of embedded schemes

This article deals with the foundations of a theory of equisingularity for families of zero-dimensional sheaves of ideals on smooth algebraic surfaces, in the arithmetic context, i.e., where one works with schemes defined over Dedekind rings. Here, different equisingularity conditions are analyzed and compared, based on one of the following requirements: 1) each member of the the family has the same desingularization tree, 2) the family admits a simultaneous desingularization, 3) a naturally associated family of curves is equisingular. Similar conditions had been investigated, in the context of Complex Local Analytic Geometry, by J. J. Risler. Received: 17 November 1997 / Revised version: 19 April 1999     

Olive milling wastewater as a medium for growth of fourPleurotus species

Four species of Pleurotus were adapted to grow on olive milling wastewater, and in certain conditions produced high yield of fruit bodies. Some biochemical transformations were observed in the olive milling wastewater owing to the growth of Pleurotus. In particular, the fungi actively excreted large amounts of laccase in the medium, and at the same time the concentration of phenolics and other toxic compounds significantly decreased, as revealed by HPLC analysis and toxicity tests on standard cultures of human cell lines.     

Market Power Issues in Bid-Based Hydrothermal Dispatch

The objective of this work is to investigate market power issues in bid-based hydrothermal scheduling. Initially, market power was simulated with a single stage Cournot–Nash equilibrium model. In this static model the equilibrium was calculated analytically. It was shown that the total production of N strategic agents is smaller than the least-cost solution by a factor of (N/(N+1)). Market power analysis for multiple stages was then carried through a stochastic dynamic programming scheme, where the decision in each stage and state is the Cournot–Nash equilibrium of a multi-agent game. Case studies with data taken from the Brazilian system are presented.     

Quantitative analysis by comprehensive two-dimensional gas chromatography using interval Multi-way Partial Least Squares calibration

A new approach for target quantitative analysis for comprehensive two-dimensional gas chromatography (GC × GC), interval Multi-way Partial Least Square (iNPLS) is presented and evaluated in this paper. In iNPLS, the two-dimensional chromatogram is split in small sections; each of these pieces is treated as an independent new chromatogram. Separated conventional NPLS calibration models for the concentration of the target analyte are built for each of the pieces of the whole chromatogram, and the best model is selected for quantitative analysis. An algorithm for iNPLS running on MatLab platform was written, preliminarily evaluated with using solutions of model compounds with different chemical properties and subsequently applied to quantify some allergens in perfume samples. The results were found to be adequate, and good precision and accuracy was obtained even for poorly resolved peaks.     

Synthesis and characterization of new porphyrin/4-quinolone conjugates

New porphyrin/4-quinolone conjugates were synthesized from the Suzuki-Miyaura coupling reaction of a β-borylated porphyrin with bromo-4-quinolones containing N-ethyl and N-d-ribofuranosyl substituents. The use of electrospray ionization tandem mass spectrometry showed important information about the fragmentation pathways of the new compounds. It was possible to distinguish between those compounds with the porphyrin moiety linked at the 6-position of the quinolone unit from their 7-substituted isomers. The new compounds showed to be good singlet oxygen generators.     

Thermal Behavior of Sr(II) and Ba(II)‐Diclofenac Complexes in Solid State: Study of the Dehydration and Thermal Decomposition

Solid state compounds of general formula Sr(Diclof)₂·5.7H₂O and Ba(Diclof)₂·4.8H₂O were obtained. Thermogravimetry (TG), differential scanning calorimetry (DSC), X‐ray diffraction powder patterns and microscopy analysis were used to characterize these compounds. Details concerning the dehydration and thermal decomposition as well as data of kinetic parameters have been described here. The kinetic behaviors of these stages were evaluated from several heating rates with samples masses of 2 and 5 mg in open crucibles under a nitrogen atmosphere. The results of the present study improve the knowledge on these compounds including their dehydration and thermal stability. The obtained data depend on the mass of the sample which results in two kinetic behavior patterns.     

Pharmaceutical composition of hydrochlorothiazide:β-cyclo-dextrin: preparation by three different methods, physico-chemical characterization and in vivo diuretic activity evaluation

Hydrochlorothiazide is a common diuretic antihypertensive drug of the thiazide family. Its poor aqueous solubility is one of the reasons for its limited bioavailability after oral administration. This work aimed at the development of a hydrochlorothiazide:β-cyclodextrin (HTZ:β-CD) pharmaceutical composition in order to improve water solubility and bioavailability of the drug. The HTZ:β-CD complexes were prepared by three different methods: spray-drying, freeze-drying and fluid bed. Complexes were characterized by thermal analysis, Fourier transform-infrared (FTIR) spectroscopy, powder X-ray diffractometry, NMR (2D-ROESY), scanning electron microscopy (SEM), particle analysis and intrinsic dissolution. The findings reveal that three binary systems prepared presented better solubility results in comparison with free HTZ. Increased diuretic effect was observed to HTZ:β-CD obtained by fluid bed in comparison to free drug in rats. Results taken together suggest that pharmacological effect of HTZ in complex was increased by solubility improvement promoted by cyclodextrin.