María Luisa Moyá

Radical scavenging ability of polyphenolic compounds towards DPPH free radical.

Free radical scavenging activity of different polyphenolic compounds commonly present in wine has been evaluated using DPPH method. The experiments were performed with different amounts of phenols within the linear interval of response and with an excess of DPPH in all cases. In these conditions, for most of the compounds tested, the reaction was biphasic. Total stoichiometry values n confirm the implication of more than one step in the process. Flavan-3-ol compounds showed the highest values, especially procyanidins B1 (9.8) and B2 (9.1). In this family, n values coincide with the number of hydroxyl groups available. EC(50) and TEC(50) parameters have been calculated. EC(50) values are extremely diverse, being the procyanidins B1 and B2 the most potent scavenging compounds and resveratrol the less one. TEC(50) considers the rate of reaction towards the free radical. (+)-Catechin and (-)-epicatechin are the phenolic compounds that need more time to react. In contrast, caftaric and caffeic acids are the phenolic acids that react more rapidly. Antioxidant efficacy (AE) is a parameter that combines both factors. Compounds as kaempferol, with a high EC(50) value, could be considered as an antioxidant with low relevance, but instead shows the highest AE value of the phenolic compounds tested, due to its fast rate of reaction, what is of great biological importance.

Effects of Addition of Polar Organic Solvents on Micellization

Micellization of several surfactants in water-organic solvent mixtures has been investigated. Only solvents localized mainly in the bulk phase of the micellar solutions (they do not incorporate into the micelles) were studied, with either higher or lower permittivity than that of pure water. Results show that the influence of organic solvent addition on the aggregation process can be approximately accounted for by considering the changes in the bulk phase cohesive energy density, described by the Gordon parameter, G. To our knowledge, this is the first time that, for a given surfactant, the Gibbs energies of micellization, Delta G M degrees , obtained in several water-organic solvent mixtures have been fitted together. It is worth noting that data from different research groups have been considered. The Delta G M degrees versus G correlation will permit the estimation of the variations in the Gibbs energy of micellization upon addition of known quantities of a given polar organic solvent. Speaking in a general way, organic solvent addition results in the bulk phase becoming a better solvent for the surfactant molecules. This would make the hydrophobic tail transfer from the bulk phase into the micelles less favorable and, as a consequence, Delta G M degrees increases (becomes less negative), making the aggregation process less spontaneous.

Water−Ethylene Glycol Cationic Dimeric Micellar Solutions: Aggregation, Micellar Growth, and Characteristics As Reaction Media

Effects of ethylene glycol (EG) addition on the micellization and on the micellar growth in two aqueous didodecyl dicationic dibromide surfactant, 12-s-12,2Br- (s=2, 6) solutions, with the weight percentage of EG up to 50%, have been investigated. An increment in the amount of EG makes the aggregation process less spontaneous due to the water-EG mixtures being better solvents for the cationic dimeric surfactant molecules than pure water (solvophobic effect). Results show that C*, the surfactant concentration where the sphere-to-rod transition occurs, increases when EG content in the bulk phase increases. The amount of the organic solvent influences C* principally through the decrease in the hydrocarbon/bulk phase interfacial tension (air/bulk phase surface tension) caused by its presence. Changes in the aggregation number, in the micropolarity, in the microviscosity, and in the rheological behavior accompanying micellar growth were studied in the water-EG micellar solutions. Kinetic studies provide information about the characteristics of the dimeric micelles as microreactors. Kinetic data also show that an increase in the surfactant concentration leads to micellar growth.

Mixtures of monomeric and dimeric surfactants: hydrophobic chain length and spacer group length effects on non ideality.

Critical micelle concentrations of the Cm TAB+12- s-12 (s=3, 4, 5 and m=10, 12, 14, 16) binary systems have been determined, through conductivity and fluorescence measurements, at 298 K. Application of different theoretical approaches to explain mixed micellization shows that non-ideality of the binary systems follows the trend C16TAB+12-3-12<C14TAB+12-3-12<C12TAB+12-3-12<C10TAB+12-3-12, and C12TAB+12-5-12 approximately C12TAB+12-4-12<C12TAB+12-3-12. Literature data corresponding to the C12TAB+12-2-12, C12TAB+ m-s-m (s=2, 4, 6 and m=12, 14, 16) and TritonX-100+12-s-12 (with s=3, 6, 12) mixtures were considered in order to investigate the hydrophobic chain length and the spacer group length roles on the observed non ideal behavior. It was found that the capacity of the mixture components to form micelles of similar or different shapes plays a major role in non-ideality.

Effects of glycols on the thermodynamic and micellar properties of TTAB in water.

Aggregation of tetradecyltrimethylammonium bromide, TTAB, in mixed solvent systems containing ethylene glycol, EG, 1,2-propylene glycol, 1,2-PROP, 1,3-propylene glycol, 1,3-PROP, and tetraethylene glycol, TEG, has been investigated by employing conductivity and fluorescence methods. Gibbs energies of micellization were determined in order to evaluate the effects of the co-solvent on the aggregation process. Information about the influence of the organic solvent on the surfactant adsorption at the air-solution interface, on the micellar size and on the polarity of the micellar interfacial region was obtained by means of surface tension and fluorescence measurements. The study of the reaction methyl naphthalene-2-sulfonate + Br(-) in the water-glycol TTAB micellar solutions provided information about the characteristics of TTAB micelles as microreactors in the water-solvent binary mixtures.

Micellization and micellar growth of alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) surfactants in the presence of medium-chain linear alcohols

Micellization and micellar growth of cationic dimeric surfactants of the alkanedyil-alpha,omega-bis(dimethyldodecylammonium) bromide type, 12-s-12,2Br(-) (s=3, 4, 6), in the presence of various amounts of 1-butanol, 1-pentanol, and 1-hexanol have been investigated. The influence of the nature and concentration of alcohol on the cmc, on the micellar ionization degree, on the average micellar aggregation number, and on the polarity of the micellar interfacial region was investigated by using conductivity and fluorescence measurements. Subsequently, effects of alcohol addition on the surfactant concentration range where sphere to rod transitions occur were examined and information about changes in the micropolarity and in the microviscosity accompanying the morphological transition was obtained. The experimental results were explained by considering the variations in the different contributions to the Gibbs energy of micellization caused by the presence of alcohols. The study of the reaction methyl naphthalene-2-sulfonate+Br(-) in some water-alcohol 12-6-12,2Br(-) micellar solutions provided information about the characteristics of the dimeric micelles as microreactors and show the complexity of the microheterogeneous systems studied.

SOLVENT EFFECTS ON THE DISSOCIATION OF ALIPHATIC CARBOXYLIC ACIDS IN WATER-N,N-DIMETHYLFORMAMIDE MIXTURES : CORRELATION BETWEEN ACIDITY CONSTANTS AND SOLVATOCHROMIC PARAMETERS

The acid dissociation constants of nine aliphatic carboxylic acids in several N,N-dimethylformamide-water mixtures were subjected to factor analysis (FA) and two solvent factors emerged. A further target factor analysis (TFA) indicated that the Kamlet and Taft general equation is reduced in these mixtures to two terms: the independent one and that related to the hydrogen bond acceptor (HBA) basicity β solvatochromic parameter. Accordingly, an excellent correlation is found between the logarithmic values of the acidity constants of each acid in the binary mixtures and their corresponding β values.

Substitution reactions at pentacyanoferrate(II) complexes: linear free-energy relationships in mixed solvents

The kinetics of replacement of 4-phenylpyridine (4-phpy) by cyanide in Fe(CN)5(4-phpy)3– have been studied in various isodielectric water–cosolvent mixtures at 298 K. The experimental data are well correlated through the following equation: δΔG#exp=aδAm+bδBm+cGexc where Am, Bm and Gexc are the acidity parameter, the basicity parameter and the excess Gibbs free energy of the mixture, respectively. This multiparameter regression was also applied to data, taken from the literature, of substitution reactions at different pentacyanoferrate(II) complexes in order to show its general validity for explaining the effect of the medium on these types of processes in binary aqueous mixtures.

Oxidation of Fe(CN)4–6 by S2O2–8 in AOT–oil–water microemulsions

The Oxidation of hexacyanoferrat (II) by peroxodisulfate has been studied in sodium bis(2-ethylhexyl) sulfosuccinate (aerosol-OT or AOT)–oil–water microemulsions at 298.2 K. The rate of this reaction is appreciably higher in a microemulsion than when it takes place in a conventional aqueous solution. The dependence of the rate constants on the surfactant concentration, on the nature of the oil phase and on the molar ratio w=[H2O]/[AOT] has been investigated. Results show that when the AOT concentration remains constant, the reaction rate increases by decreasing the molar ratio, w. For a given [H2O]/[AOT] value, the reaction rate shows no dependence on the surfactant concentration or on the nature of the oil phase.

Study of the ligand substitution reaction Fe (CN)5H2O3? + pyrazine in micellar solutions

The ligand substitution reaction Fe(CN)5H2O3− + pyrazine Fe(CN)5 pyrazine3− + H2O has been studied in sodium dodecyl sulfate SDS, hexadecyltrimethylammonium bromide, CTAB, and salt aqueous solutions at 298.2 K. Kinetics were studied in dilute and concentrated salt solutions and in SDS and CTAB solutions at surfactant concentrations below and above the critical micelle concentration. Experimental results show that salt effects can be explained by considering the interaction between the cations present in the working media which come from the background electrolyte, and the Fe(CN)5H2O3− species in the vicinity of the cyanide ligands. This interaction makes the release of the aqua ligand from the inner-coordination shell of the iron(II) complex to the bulk more difficult resulting in a decrease of the reaction rate when the electrolyte concentration increases. Kinetic data in surfactant solutions show that not only micellized surfactants are operative kinetically, but also nonmicellized surfactants are influencing the reactivity.