Biological Activity of Flavonoids Copper Complexes

Three flavonoid copper(II) complexes Cu₂(quercetin)(CH₃COO)₃(CH₃OH) ( 1 ), Cu(anthrarufin)(CH₃COO)·1/2H₂O ( 2 ) and Cu(naringin)(OCH₃)(CH₃OH)₂ ( 3 ) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X‐band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H₂O₂ or the superoxide‐generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A probably mechanism of the DNA damage is proposed.     

The modulating possibilities of dicarbollide clusters: optimizing the Kharasch catalysts

exo-Cluster dicarbollides substitution has allowed tuning of the E degrees (Ru(II)/Ru(III)) potential to obtain the best-performing Kharasch catalyst. We postulate that this is possible through the to-and-fro electron movement between the boron cluster and the sulfonium moieties.     

Silylation partielle et réduction de composés gem-polychlorés fonctionnels

The trimethylchlorosilane/magnesium/hexamethylphosphoric triamide (HMPT) system reacts with some functional polychlorinated compounds (chloral, hexachloroacetone, acetone chloroform) affording a partial reduction accompanied by silylation and leads to new functional silylated derivatives.These reactions exhibit reductive properties of magnesium, in HMPT, towards the CCl bond.     

Determination of the pH of binary mobile phases for reversed-phase liquid chromatography

The measurement of pH in chromatographic mobile phases has been a constant subject of discussion during many years. The pH of the mobile phase is an important parameter that determines the chromatographic retention of many analytes with acid-base properties. In many instances a proper pH measurement is needed to assure the accuracy of retention-pH relationships or the reproducibility of chromatographic procedures. Three different methods are common in pH measurement of mobile phases: measurement of pH in the aqueous buffer before addition of the organic modifier, measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with standard solutions prepared in the same mobile phase solvent, and measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with aqueous standard solutions. This review discusses the different pH measurement and calibration procedures in terms of the theoretical and operational definitions of the different pH scales that can be applied to water-organic solvent mixtures. The advantages and disadvantages of each procedure are also presented through chromatographic examples. Finally, practical recommendations to select the most appropriate pH measurement procedure for particular chromatographic problems are given.     

Quantum-chemical gas-phase calculations on the protonation forms oftrans- andcis-urocanic acid

The neutral, cationic, and anionic structures of both prototropic tautomers oftrans- andcis-urocanic acid [(E)- and (Z)-3-(1H-imidazol-4(5)-yl)propenoic acid, respectively] were studied by using semiempirical andab initio gas-phase calculations. Potential energy surfaces of the structures were calculated by using the semiempirical AM1 method, and the geometries corresponding to global minima on these surfaces were optimized up to the MP2/6-31G^* level of theory. The calculated protonation forms of each urocanic acid isomer have a planar molecular structure due to a delocalized -electron system, and all of them prefer thes-trans conformation with respect to the bond between the imidazole and the propenoic acid moieties. Thecis-urocanic acid structures are stabilized by an intramolecular hydrogen bond. The chargedcis-urocanic acid isomers have a lower molecular energy than the correspondingtrans-isomers, whereas the neutral molecules have, after inclusion of thermodynamic corrections, approximately the same energy. The cationic urocanic acid structures have about 2500 kJ mol^–1 lower energy than the anionic ones and about 1000 kJ mol^–1 lower energy than the neutral ones. The nonzwitterionic forms of the neutral urocanic acid isomers have about 200 kJ mol^–1 lower energy than the zwitterionic ones. These energy differences are explained by the proton affinities of the imidazole and the propenoic acid moieties of the urocanic acid structures.     

Dissociation constants of phenols in methanol--water mixtures

A preferential solvation model that relates solute properties with solvent composition in binary mixtures has been applied to the dissociation pKa values of a set of 28 substituted phenols in methanol-water mixtures. The parameters of the model allow estimation of the pKa value of each phenol for any methanol-water composition. Moreover, it is demonstrated that the pKa values of the whole set of phenols at any methanol-water composition are linearly related to the pKa values of the phenols in water. Equations that relate the correlations' slope and intercept values with the solvent composition have been derived and tested with the set of phenols. The general parameters obtained for these equations allow an accurate calculation of the pKa value of any phenol, even of those not included in the original set, at any methanol-water composition solely from the pKa value of the phenol in water. These calculated pKa values can be used for quantitative structure-HPLC retention relationships. The method is tested by comparison of the calculated pKa values with the HPLC determined pKa values of 26 phenols in a polymeric column with a 50% methanol as mobile phase.     

Size evolution of the vibrational predissociation process in Br2...Nen clusters: simulation and kinetic study

A hybrid quantum-classical simulation of the vibrational predissociation of Br2...Nen, (n = 2-11) clusters in the B electronic state is carried out. The time-evolution of the reactants, products, and intermediates is analyzed by a kinetic mechanism consisting of three elementary steps: direct vibrational predissociation (VP), intramolecular vibrational redistribution (IVR), and evaporative cooling (EC). The importance of intramolecular vibrational redistribution followed by evaporative cooling relative to direct vibrational predissociation is shown to increase rapidly with increasing cluster size. Final product state distributions reveal that only one or less Br2 stretching quantum per neon atom is required in order to achieve complete dissociation (n quanta for n < or = 9 and n - 1 for n = 10 and 11). The proportion of available energy going into translation is proposed as a parameter to study the statistical behavior of the Van der Waals clusters. It is shown to depend only on the number of remaining degrees of freedom, a characteristic of a statistical behavior, for n > or = 3.     

Synthesis and conformational analysis of novel N(OCH3)-linked disaccharide analogues

N(OMe)-linked disaccharide analogues, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy-6-methoxyamino-alpha-D-glucopyranoside in an aqueous environment. The coupling reactions were found to be chemo- and stereoselective affording beta-(1-->6) disaccharide mimics when using Glc and GlcNAc; in the case of Gal, the beta-anomer was prevalent (beta:alpha=7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogues was demonstrated, based on the use of an unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds was carried out by using NMR spectroscopy, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe)-linked disaccharide analogues exhibit a slightly different conformational behavior to their parent natural disaccharides.     

Reactivity of benzoyl chlorides in nonionic microemulsions: potential application as indicators of system properties

The solvolysis reactivity of benzoyl chlorides entails a high sensitivity on medium properties. A systematic study of the reaction of a series of these substrates, varying the electron-withdrawing character of the substituent, has been performed in nonionic microemulsions. The kinetic effects due to variation of microemulsion compositions can be assigned to modifications in system properties, to be precise, to modifications in interface properties. Microemulsion properties that are obtained from kinetic analysis of solvolysis show a good agreement with the characterization of the microemulsion that was made via 1H NMR and solvatochromic fluorescence probes. Benzoyl chlorides with electron-donating groups react through a dissociative mechanism, whereas electron-withdrawing groups favor an associative mechanism. A comparative analysis of reactivity between the different substrates at the interface shows a variation in the contributions of both reaction pathways, associative and dissociative, to the whole reaction mechanism. The confined media shift the point where the mechanism changes from an associative to a dissociative pathway, far away from the turning point in water. Furthermore, the change in mechanism can be modulated by modification of the microemulsion composition.