ABSTRACT
Pyrogallol red (PGR) presents high reactivity toward reactive (radical and nonradical) species (RS). This property of PGR, together with its characteristic spectroscopic absorption in the visible region, has allowed developing methodologies aimed at evaluating the antioxidant capacity of foods, beverages, and human fluids. These methods are based on the evaluation of the consumption of PGR induced by RS and its inhibition by antioxidants. However, at present, there are no reports regarding the degradation mechanism of PGR, limiting the extrapolation to how antioxidants behave in different systems comprising different RS. In the present study, we evaluate the kinetics of PGR consumption promoted by different RS (peroxyl radicals, peroxynitrite, nitrogen dioxide, and hypochlorite) using spectroscopic techniques and detection of product by HPLC mass spectrometry. The same pattern of oxidation and spectroscopic properties of the products is observed, independently of the RS employed. Mass analysis indicates the formation of only one product identified as a quinone derivative, excluding the formation of peroxides or hydroperoxides and/or chlorinated compounds, in agreement with FOX's assays and oxygen consumption experiments. Cyclic voltammetry, carried out at different pH's, shows an irreversible oxidation of PGR, indicating the initial formation of a phenoxy radical and a second charge transfer reaction generating an ortho-quinone derivative. Spectroelectrochemical oxidation of PGR shows oxidation products with identical UV-visible absorption properties to those observed in RS-induced oxidation.
Subject(s)
Antioxidants/chemistry , Free Radicals/chemistry , Pyrogallol/analogs & derivatives , Reactive Oxygen Species/chemistry , Chromatography, High Pressure Liquid , Electrochemical Techniques , Humans , Hydrogen Peroxide/chemistry , Hydrogen Peroxide/metabolism , Hydrogen-Ion Concentration , Kinetics , Oxidation-Reduction , Pyrogallol/chemistry , Pyrogallol/metabolism , Spectrophotometry, Ultraviolet , Tandem Mass SpectrometryABSTRACT
Multiparameter linear energy-density relationships to model solvent effects in room temperature ionic liquids (RTILs) are introduced and tested. The model incorporates two solvent dependent and two specific solute-solvent parameters represented by a set of electronic indexes derived from the conceptual density functional theory. The specific solute-solvent interactions are described in terms of the electronic chemical potential for proton migration between the anion or cation and the transition state structure of a specific reaction. These indexes provide a quantitative estimation of the hydrogen bond (HB) acceptor basicity and the hydrogen bond donor acidity of the ionic solvent, respectively. A sound quantitative scale of HB strength is thereby obtained. The solvent dependent contributions are described by the global electrophilicity of the cation and nucleophilicity of the anion forming the ionic liquid. The model is illustrated for the kinetics of cycloaddition of cyclopentadiene towards acrolein. In general, cation HB acidity outweighs the remaining parameters for this reaction.
Subject(s)
Acrolein/chemical synthesis , Cyclopentanes/chemistry , Ionic Liquids/chemistry , Quantum Theory , Acrolein/chemistry , Hydrogen Bonding , Kinetics , Molecular Structure , Solvents/chemistryABSTRACT
33 polycyclic derivatives have been studied and tested on Leishmania donovani and L. major promastigotes. Their antileishmanial activity was assessed in vitro and an assay of their cytotoxicity was realized on human myelomonocytic cell line. The reference molecules used in the assays were amphotericin B and pentamidine. Among the compounds tested, 29 possess an antileishmanial activity; 25 of those were more active against L. donovani than amphotericin B, and nine were as effective as amphotericin B against L. major. Many synthesized derivatives were more active against L. donovani than against L. major. The cytotoxicity studies have shown that among the thirty-three derivatives tested, 12 molecules have an IC50 towards THP-1 cells about equal than that reference drugs, the 21 other derivatives are much less toxic. A 3D QSAR study was undertaken and has permitted to predict activity against L. donovani and L. major and to highlight critical area to optimize activity against the two species.
Subject(s)
Amphotericin B/pharmacology , Antiprotozoal Agents/pharmacology , Leishmania/drug effects , Pentamidine/pharmacology , Polycyclic Compounds/pharmacology , Animals , Cell Line , Cell Survival/drug effects , Humans , Quantitative Structure-Activity RelationshipABSTRACT
Se revisan 203 casos de cirrosis hepática atendidos en el Servicio de Medicina. A. El 89.1% tiene antecedentes alcohólicos. B. Los pacientes ingresan al hospital en etapa avanzada de su enfermedad. C. La mortalidad es del 54%. D. La hemorragia digestiva alta, insuficiencia hepática y coma son las complicaciones predominantes
Subject(s)
Humans , Male , Female , Liver Cirrhosis, Alcoholic/epidemiology , Liver Cirrhosis/epidemiology , BiopsyABSTRACT
Primary leiomyoma and leiomyosarcoma of the appendix are extremely rare, and most often the diagnosis is histopathologic. We have reported the largest leiomyoma of the appendix known to date.
