0000000000121441
AUTHOR
Rosa García
Solution properties of polyelectrolytes—V. Viscometric study of mixed polyanions in pure water
Abstract A viscometric study of sodium polystyrene sulphonate (NaPSS) and sodium poly( l -glutamate) (NaPLG) in salt-free water has been carried out as a function of the total concentration, cm, and the concentration of one polyelectrolyte at fixed concentration of the other. The influences of the molecular weight and concentration are considered in order to establish the degree of compatibility. For the first time, an equation is proposed to define the reduced viscosity of the NaPSS + NaPLG mixture in water. The viscometric interaction parameter, Bm, taking into account the electrostatic and thermodynamic interactions between both polyions, is defined as a geometrical mean of the contribut…
Solution properties of polyelectrolytes XII. Semi-quantitative approach to mixed electrostatic and hydrophobic polymer-gel interactions
Abstract Aqueous size-exclusion chromatography of polyanions, where secondary effects affect the total separation mechanism, was investigated. For elution of polyelectrolytes on inorganic silica-based supports, the electrostatic polymer-gel repulsive interactions were evaluated through the values for a hypothetical repulsion layer, X e , according to the model developed by other workers. Using a similar procedure, the existence of an effective barrier defined as X e − X h is proposed for those systems in which electrostatic repulsion and hydrophobic interactions take place simultaneously as secondary mechanisms. X h can be viewed as a measure of the “enlargement” of the geometrical pore rad…
A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems
Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems…
Macromolecules in ordered media. 6. Effect of the phospholipidic bilayer composition on poly (2-vinyl pyridine) - liposome association
The intrinsic fluorescence emission of poly (2-vinyl pyridine) has been exploited in order to gain insight into the nature of the interaction with artificial membranes. In this contribution, the study has been focused on the effect of the phospholipid bilayer composition on the association to the polymer. Fluorescence data have been converted into association isotherms and then analyzed in terms of both binding and partition models. Results show that the association is enhanced by the presence of negative charged phospholipid as a constituent of the liposomal membrane. The strong surface density dependence of the polymer-liposome association indicatesthe predominantly electrostatic nature o…
A Qualitative Analysis of Secondary Mechanisms in SEC of Polymers Through the Mean Value of the Viscosimetric Exponent
Abstract Size exclusion chromatography (SEC) universal calibration curves for poly(dimethylsiloxane), polybutadiene and poly(2-vinylpyridine) samples have been obtained in columns packed with cross-linked polystyrene gel using cyclohexane, toluene, benzene, dioxane and tetrahydrofuran as eluents at 25°C. The eluents exhibit different thermodynamic quality for the polymeric solutes and for the gel matrix which is reflected in the values of their Mark-Houwink-Sakurada exponents a. The plots of log(hydrodynamic volume) versus retention volume for the polymeric solutes in different eluents are displaced to higher retention volumes than that of THF-polybutadiene (ideal SEC), evidencing the exist…
Theory of Mind Profiles in Children With Autism Spectrum Disorder: Adaptive/Social Skills and Pragmatic Competence
Theory of Mind (ToM) is one of the most relevant concepts in the field of social cognition, particularly in the case of Autism Spectrum Disorders (ASD). Literature showing that individuals with ASD display deficits in ToM is extensive and robust. However, some related issues deserve more research: the heterogeneous profile of ToM abilities in children with ASD and the association between different levels of ToM development and social, pragmatic, and adaptive behaviors in everyday life. The first objective of this study was to identify profiles of children with ASD without intellectual disability (ID), based on explicit and applied ToM knowledge, and compare these profiles with a group of ch…
Porous fractal gels: secondary effects in SEC
Abstract The fractal nature of porous silica gels, Spherosil XOA 200 and of a Lichrospher mixture, has been tested through size exclusion chromatography of polystyrene in pure and mixed eluents. Fractal parameters, D f and L , depend on eluent with D f values close to 2.0 for Spherosil and higher than 2.0 for Lichrospher. D f and L changes with eluent have been related to secondary separation effects and partition and adsorption contributions have been evaluated.
Ionomers in solution: 1. Viscometric and chromatographic studies in cononsolvent and cosolvent mixtures
Abstract The viscosity and elution behaviour of polystyrene sulfonate ionomers with varying ionic content has been studied in the pure solvents chloroform (CHL), tetrahydrofuran (THF), dioxan (DIO), ethyl acetate (EA) and dimethylformamide (DMF) as well as in their cononsolvent mixtures CHL/THF (50:50), DIO/CHL (75:25) and in the cosolvent mixture EA/DMF (50:50). In the pure solvents with low dielectric constant the reduced viscosities of ionomers are lower at low concentrations and higher at moderate ones than the respective viscosities of the polystyrene precursor. These results can be explained by formation of intramolecular and intermolecular associations. Moreover, differences in visco…
Parasitism of dolfinfhishes, <i>Coryphaena hippurus</i> and <i>Coryphaena equiselis</i>, in the western Mediterranean (Balearic Islands) and central-eastern Atlantic (Canary Islands)
A total of 648 dolphinfishes were examined for internal and external parasites in western Mediterranean (Balearic Islands) and central-eastern Atlantic (Canary Islands) waters in order to make a comparative study between the two areas. The specimens studied from the Mediterranean Sea was Coryphaena hippurus, with 62 large individuals captured from May to September and 497 juveniles captured from August to December. The specimens studied from the central-eastern Atlantic were 39 adult C. hippurus and 49 adult Coryphaena equiselis. Parasites were found in 70% of the fish examined, and represented a total of nine endoparasitic taxa: six digeneans (Class Trematoda, Subclass Digenea; Dinurus tor…
Viscometric study of mixtures of neutral and charged polymers in aqueous solution
The viscosity behaviour of aqueous mixtures formed by a polyelectrolyte (A) and a neutral polymer (B) such as polystyrene sulfonate (PSS)-polyvinylpyrrolidone (PVP) and polylysine (PLL)-PVP has been studied at 25°C. The intrinsic viscosity and viscosity interaction parameter of each polymer in water have been determined and have served us to estimate the compatibility of the different mixtures according to two different methodologies: (i) mixtures of two polymers in water as solvent and (ii) mixtures of either polymer A OFB in a solvent formed by either polymer B or A in water ("polymer solvent method"). By comparing the experimental and theoretical viscosity data it is clearly seen that: m…
Comparative evaluation of the swelling and degrees of cross-linking in three organic gel packings for SEC through some geometric parameters.
Abstract The size exclusion chromatographic (SEC) behavior of five solvent/polymer systems in three organic column packings based on polystyrene/divinylbenzene (PS/DVB) copolymer, TSK-Gel H HR , μ-styragel and TSK-Gel H XL , has been compared. All the packings offer similar characteristics (pore size, particle size and efficiency) but some differences have been found when eluting the same systems. The different elution behavior observed in both polymeric gels has been analyzed in terms of their swelling and cross-linking degrees and of the fractal parameters. From the Universal Calibration plots, values of the chromatographic partition coefficient, K p , have been obtained and using some eq…
A comparative study between cosolvent and cononsolvent ternary polymer systems through the preferential adsorption coefficient
Sorption equilibrium of polystyrene and poly (dimethyl siloxane) in mixed solvents has been monitored by means of the preferential adsorption coefficient experimentally determined from intensity light scattering measurements. The pairs of solvents used to dissolve each polymer sample have been selected for the purpose to perform cosolvent and cononsolvent ternary polymer systems. Flory-Huggins formalism including ternary interactions has been used to predict the sorption equilibrium for the cosolvent system and, for the first time, for cononsolvent ones. Moreover, the proportionality between binary and ternary interactions, recognized by Pouchly, is also corroborated for both ternary polyme…
Macromolecules in ordered media: 4. Poly(2-vinyl pyridine)-liposome association induced by electrostatic interactions
Abstract We have investigated the interaction between vesicles based on dimyristoyl phosphatidic acid (DMPA) and a polymer, such as poly(2-vinyl pyridine) (P2VPy), on the basis of both partition and binding models. The resulting association curves are non monotonous being three regions clearly evidenced. The electrostatic and steric origin of the attractive or repulsive interactions are analyzed as a function of pH, ionic strength and temperature using the fluorescence spectroscopy technique. We emphasize the importance of differentiating the ideal definition of the binding constant from the theoretically evaluated including the activity coefficient, γ, to take into account shifts from the …
Prediction of maxima and minima in the curve of total sorption parameter in ternary polymer systems. Influence of ternary interaction parameter
Flory-Huggins theory modified by Pouchly has been applied to predict maxima and minima in the curve of total sorption in ternary polymer systems formed by a polymer and two liquids. In this work, different diagrams based on experimental magnitudes easily obtained such as the difference in affinities of liquids, solvents and non solvents, and the solvent molar volume ratio. Total sorption parameter has been considered to be the decisive magnitude to define extrema conditions in both cosolvent and cononsolvent ternary polymer systems. The theoretical prediction is not altered by the inclusion of ternary interactions. Different examples of ternary systems dealing with vinyl polymers and polydi…
Solution properties of polyelectrolytes. III. Effect of sodium polystyrene sulfonate concentration on viscometric and size exclusion chromatographic behavior at different ionic strengths
The effect of sodium polystyrene sulfonate concentration on the shape of its molecules in aqueous solution at different NaNO3 ionic strengths has been analyzed by viscometry and size-exclusion chromatography (s.e.c). An equation has been developed which predicts the intrinsic viscosity, [η] p.cp.cs, at finite concentration of both polyion (cp) and electrolyte (cs). The experimental results obtained by both techniques can be accounted for in terms of the theory. Several factors involved in the elution mechanism have been considered and the variation of the slopes of s.e.c. calibration curves with cp and cs has been discussed in terms of polyion conformation changes.
Macromolecules in ordered media: 7. Influence of ionic strength and bilayer composition on the association of polyelectrolytes to mixed liposomes
The effect of both the phospholipid composition of the bilayer and the ionic strength of the medium on the association between poly(2-vinyl pyridine) and mixed liposomes based on dimyristoyl phosphatidic acid and dimyristoyl phosphatidil choline was investigated using fluorescence spectroscopy. Intensity changes upon addition of vesicles have allowed us to estimate the extent of the association and data have been processed as association isotherms. We found that the association is enhanced by increasing both the ionic strength and the anionic phospholipid fraction. However, whereas the negative net charge of the bilayer strongly enhances the interaction, the presence of more and more electr…
Macromolecules in ordered media: 5. Poly(4-vinyl pyridine)—liposome association induced by electrostatic interactions
Abstract The association of water-soluble vinyl polymers to dimyristoyl phosphatidic acid unilamellar vesicles as a function of pH, temperature and salt content using steady-state fluorescence and viscometry has been investigated. Poly(4-vinyl pyridine) fluorescence data were converted to association isotherms and discussed in terms of binding and partition models. The results of this report support previous suggestions: (1) in the case of polyions the inclusion of the activity coefficient in both models is essential; (2) the parameters calculated using the two different theoretical approaches can be directly compared by the relating equation proposed for us. Finally, the excellent agreemen…
Viscometric study on the compatibility of polymer–polymer mixtures in solution
Abstract The viscosity behaviour of mixtures formed by two uncharged polymers in dilute solution has been studied at 25°C. The ternary systems assayed, and denoted solvent (1)/ polymer (2)/ polymer (3), have in common the poly(ether sulphone) (PES) as polymer 2, and poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA) or poly(styrene) (PS) as polymer 3. The intrinsic viscosity and the viscometric interaction parameters have been experimentally measured for the binary (solvent/polymer) as well as for the ternary systems, and also theoretically evaluated for the latter. The estimation of the compatibility degree of the above polymer pairs have been done by means of three criteri…
Solution properties of polyelectrolytes
Abstract Aqueous size-exclusion chromatography was used to analyse the elution behaviour of several standard ionic polymers, including poly( l -glutamic acid), sodium poly(styrene sulphonate) and poly(acrylic acid), different in nature and chain flexibility, as a function of the pH and ionic strength of the eluent. Two organic-based hydrophilic packings, Spherogel TSK PW4000 and Ultrahydrogel 250, were tested in order to select the optimal conditions of macromolecular separation, and the results obtained for each column were compared. A set of calibration graphs for the above polyions as a function of eluent pH and ionic strength were obtained and compared with those obtained for uncharged …
Solution Properties of Polyelectrolytes. VI. Secondary Effects in Aqueous Size-Exclusion Chromatography
Abstract An independent analysis of different operational variables in aqueous size exclusion chromatography of poly electrolytes has been carried out using a silica-based support. The effect of polyion concentration, pH and ionic strength on sodium polystyrenesulfonate calibration plots has been investigated. Finally, a novel semi-empirical model has been developed from thermodynamic considerations which relates the support effective pore volume to the polyelectrolyte molecular weight and qualitatively describes secondary effects.
Solution properties of polyelectrolytes. II. Comparison of the effects of both polyion and eluent salt concentrations on the calibrations in aqueous exclusion chromatography
The elution behaviour of charged water-soluble polymers (sodium polystyrene sulphonate) in both salt-free and NaCl-containing aqueous mobile phases has been investigated by size-exclusion chromatography. A comparative analysis has been established between the results as a function of polyion and salt concentrations, which demonstrates that the chromatographic behaviour is similar in both cases. The variation of the slopes of the different concentration-dependent calibration curves is discussed in terms of polyelectrolyte conformational changes. Finally, a semi-empirical model has been developed to predict the dependence of the elution volume in either polyion or salt concentration, and its …
Solution Properties of Poly-Electrolytes. XI. Adsorption Effects in Aqueous Size-Exclusion Chromatog-Raphy of Polyanions
Abstract Elution profiles of a series of polymer standards such as sodium poly(styrene sulphonate), poly(acrylic acid) and poly(L-glutamic acid) have been obtained from size-exclusion chromatography experiments using separately two types of hydrophilic supports. A variety of mobile phase compositions have been performed to enhance adsorption effects in order to study how this phenomenon can affect to the chromatographic separation mechanism of polyanions. Distribution coefficient values, in general greater than unity, have served to quantify the adsorption effect, as well as to analyze their dependence on eluent ionic strength, on the ionic groups of the support and on the chemical nature a…
Solution properties of polyelectrolytes. I. Exclusion chromatography of sodium polystyrene sulphonate in salt-free water as eluent
The effect of concentration of sodium polystyrene sulphonate on the elution volume in exclusion chromatography has been investigated using salt-free water as eluent. A non-linear increase in the elution volume has been observed with increasing injected sample concentration. Concentration-dependent calibrations have been obtained which approach the universal calibration for uncharged polymers (dextrans) as polyelectrolyte concentration increases. The separation mechanisms are interpreted in terms of electrostatic and hydrodynamic interactions. A semi-empirical model is proposed to predict concentration effects of linear polyions in exclusion chromatography and good agreement has been found b…
Macromolecules in ordered media III. A fluorescence study on the association of poly-2-vinylpyridine with a phospholipid bilayer
Association of low molecular weight poly-2-vinylpyridine taken as a polycation model with unilamellar vesicles based on dimirystoylphosphatidic acid has been experimentally investigated by means of fluorescence energy transfer experiments. The conventional profiles for the binding isotherms were obtained, confirming strong deviations from the ideality of these complex fluid composites. Two approaches, named binding and partitioning equilibrium, respectively, were used to obtain the association constant, K A; the number of phospholipids that form a binding site, N; the partition coefficient, Λ; the activity coefficient, γ; and the effective charge, v. Analysis of these parameters as a functi…