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…

Viscometric behaviour of polymer blends based on poly (vinylidene fluoride)

The viscosity behaviour of dilute dimethylformamide solutions of poly(vinylidene fluoride)-poly (methyl methacrylate) and poly(vinylidene fluoride)-polystyrene has been studied at 25°C. The polymer concentration ranges are such that neither phase separation nor microgel formation occurs, although we are very close to theta conditions. The intrinsic viscosity and viscosity interaction parameter of the ternary mixtures have been calculated. The estimation of the compatibility of the above polymer pairs has been studied based on: a) specific viscosities; b) viscosity interaction parameters, according to Krigbaum and Wall formalism, and c) viscosity interaction parameters of a system formed by …

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…

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.

On the thermodynamic treatment of poly(vinylidene fluoride)/polystyrene blend under liquid—liquid phase separation conditions

Abstract This paper deals with experimental and theoretical investigations on the compatibility of binary of polymer blends in solution. The experimental phase boundary of a crystalline polymer such as poly(vinylidene fluoride) with polystyrene (an amorphous polymer) in dimethylformamide as solvent has been determined by size-exclusion chromatography at 25°C. The composition of the coexisting phases has been used to calculate interaction parameters by means of the Flory—Huggins-type function for the free energy of mixing, including composition dependence of the polymer-polymer interaction parameter and a first correction term denoted as ternary interaction parameter. The calculation of thes…

Ternary Polymer Solutions with Hydrogen Bonds, 1

The Flory Huggins methodology coupled to AET has been extended to ternary polymer systems, in particular to solvent (A)/polymer 1 (B)/polymer 2 (C) systems, with the two polymers displaying H-bonding interactions. Because the H-bonding can perturb the randomness of polymeric conformations, the change in Gibbs free energy of mixing, AG, should arise from changes in combinatorial entropy as well as in interaction energy. The combinatorial part of AG is evaluated through AET as a function of the association constant η between B and C components, the autoassociation constant a between B components, and the independent number m of interaction sites of acceptor C. The enthalpic contribution is ev…

Solution properties of polyelectrolytes

Abstract Chromatographic data for sodium polystyrene sulphonate were obtained on both silica- and polymer-based size-exclusion supports using mobile phases of various pH and ionic strength. Deviations of the elution volume were observed towards both lower and higher values relative to the reference calibration graph obtained with uncharged standards. An empirical correlation is proposed in order to account for all the secondary effects observed. The general applicability of this correlation was further tested for chromatographic data obtained for a series of peptides and proteins on a silica-based support under very different eluent conditions. Deviations from ideal elution behaviour such a…

Cover Picture: Macromol. Theory Simul. 1/2007

Polymer Retention Mechanism in GPC on Active Gels

Abstract The elution behaviour of low molecular weight polystyrene (PS) down to the monomer on spherosil gel in several eluents has been studied. In the medium range of molecular weights the elution behaviour is similar to that followed by high molecular weight PS, the differences in elution volumes among different eluents increasing monotonically with decreasing molecular weight and partition rather than adsorption probably being responsible for the shifts in retention volumes. However, at the total permeation limit, the situation is alike to that found in liquid-solid chromatography, the elution volumes of solutes with molecular sizes very close to that of styrene being determined by solv…

Polymer-polymer interaction parameters in solvent/polymer/polymer ternary systems

Abstract Empirical equations defining the relationships between b23 and χ23 interaction parameters for the ternary systems toluene (1)/poly(dimethylsiloxane), PDMS, (2)/polystyrene, PS, (3) and benzene (1)/PDMS(2)/PS(3) have been determined. The dependences of both interaction parameters on the mean molecular weights of the macromolecular components have also been studied. A single dependence of b23 (or χ23) upon the mean molecular weight is found when both polymeric components have intermediate to high molecular weights. However, that single dependence is not found when the molecular size of polymer (2) is low.

Compatibility between polystyrene copolymers and polymers in solution via hydrogen bonding

Abstract It has been applied the concept of improving miscibility, by introducing and optimizing the extent of intermolecular hydrogen-bonding interactions between two polymers. We select a commodity polymer such as polystyrene, to study the compatibility in chloroform with poly(vinyl pyridine) and poly(vinyl pyrrolidone), both considered as proton acceptors. In order to enhance polymer–polymer miscibility, polystyrene is slightly modified by copolymerization with methacrylic acid, in the first case, and with vinyl-phenol comonomer, in the second one. In this way, two series of polystyrene-based copolymers are synthesized and characterized bearing ca. 8% (w/w) of –OH groups. The miscibility…

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…

Static measurements of refractive index increments at 633 nm with a modified refractive index detector

A R 401 Waters Assoc. differential refractometer has been modified to obtain the variation of refractive index increments, dn/dc, of polymer solutions at 633 nm. The introduced modifications were in the sample injection system and in the light source. The performance of the modified refractometer both with aqueous and organic solutions is analyzed. In order to localize a conformational transition in lysozyme, the dependence of dn/dc on temperature for lysozyme solutions in phosphate buffer is studied. Similarly, (dn/dc)k values for the ternary n-alkane/butanone/poly(dimethyl siloxane) systems over the whole composition range of the binary solvent mixtures are evaluated.

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 …

Association Equilibria Theory for Polymers in Mixed Solvents with Specific Interactions

Hydrogen bonding plays an important role in determining the physical and thermodynamic properties of polar fluids. Theoretical and experimental aspects of polymers, in mixed solvents with hydrogen-bonding-specific interactions, are investigated using a simple association model based on the theory of association equilibria developed by Pouchly et al. The thermodynamic non-idealities are accounted for using a modified Flory-Huggins theory with effective g ij parameters. The entropic term of the above formalism has been formulated taking into account the pplymer segment-solvent as well as the solvent-solvent hydrogen-bond formation. Four equilibrium constants are introduced to make a realistic…

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…

Treatment of poly(styrene-co-methacrylic acid)/poly(4-vinylpyridine) blends in solution under liquid–liquid phase-separation conditions. A new method for phase-separation data attainment from viscosity measurements

Phase diagrams are contributed for polymer mixture systems in solution. One polymer has proton-acceptor character and the other has growing proton-donor nature, which is reflected in the phase diagrams. Usually, these diagrams are obtained from size-exclusion chromatographic (SEC) measurements. A totally novel application, which is exposed in this report, is the construction of the phase diagram from the viscometric experiments of polymer mixtures. The evaluated binodal or cloud-point isotherms so built agree well with those from SEC. The results indicate an augmentation in the dimensions of donor polymer B, in the presence of acceptor polymer C, intensifying with the concentration of C, wh…

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.

Elution curves on spherosil gels in pure and mixed eluents of poly(dimethylsiloxane), PDMS, and poly(methyl methacrylate), PMMA, as well as those of polystyrene, PS, just for comparison, have been determined. In a general way, PDMS elution volumers fit to those of PS, whereas PMMA elution curves shift to higher retention volumes. The differences in retention volumes between the different polymeric solutes have been interpreted in terms of differences in polymer-gel and polymer-solvent interactions. Hydrogen-bonding seems to be the main contribution to solute-substrate interactions.

Ternary Polymer Solutions with Hydrogen Bonds, 2

Experimental ternary phase diagrams for ternary systems CHL/PS-MAA/PVPy with diverse MAA contents have been determined by GPC. The presence of MAA in the copolymers gives rise to specific interactions, by hydrogen bond formation between both polymeric components, so strong that the isotherm for the system with the highest MAA content so far studied, CHL/PS-MAA(8%)/PVPy, is representative of a complex coacervation situation. By applying the theoretical background deduced by coupling the Flory-Huggins lattice model to the AET developed for ternary polymeric systems SPP with specific intermolecular interactions (via hydrogen bonds), free energy surfaces for the CHL/PS-MAA/PVPy systems are cons…

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…

Synthesis and characterization of bisulfonated poly(vinyl alcohol)/graphene oxide composite membranes with improved proton exchange capabilities

Abstract Composite membranes based on poly(vinyl alcohol) (PVA) and graphene oxide (GO) were prepared by solution-casting method to be used as proton exchange membranes (PEMs) in fuel cell (FC) applications. Bisulfonation was employed as a strategy to enhance the proton conductivity of these membranes. First, a direct sulfonation of the polymer matrix was accomplished by intra-sulfonation of the polymer matrix with propane sultone, followed by the inter-sulfonation of the polymer chains using sulfosuccinic acid (SSA) as a crosslinking agent. Furthermore, the addition of graphene oxide (GO) as inorganic filler was also evaluated to enhance the proton-conducting of the composite membranes. Th…

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 …

Study of the molecular origin of the mechanical and dielectric β relaxation of methyl methacrylate/isopropenyl methyl ketone copolymers

Resultats de l'etude dielectrique, mecanique et par TSC en faveur d'une combinaison d'une barriere intra- et intermoleculaire dans la relaxation beta

Quantitative Prediction of Concentration Effects in Steric Exclusion Chromatography

Abstract A semiempirical model, based on a previous one quantitatively describing the dependence of the elution volume, V(cA), on the concentration of injected polymer, cA, in exclusion chromatography (SEC) at dilute solutions, has been developed. In the derived equation, concentration effects are mainly governed by the Huggins' coefficient, kA, and by the quadratic coefficient in the polynomial expansion of the reduced specific viscosity, kA. Because of the incertitudes on reliable kA and kA' values, these are respectively removed from the model through she Imai's equation and the empirical correlation kA' + 0.122=kA, here obtained. Thus, A predicted elution volumes besides polymer concent…

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 …

Macromolecules in ordered media. II. A fluorescence study of the polymer-liposome association

The interactions of poly (4-vinyl pyridine) with dimyristoylphosphatidic acid-based liposomes were studied in heterogeneous solution systems. The polymer was dispersed in aqueous buffer solutions of small unilamellar vesicles and after a suitable period of incubation to raise the equilibrium, the experiments has been conducted as a function of polymer concentration and temperature. According to the measurements of the steady-state fluorescence spectra, changes in the intensities as well as shifts in the emission peak wavelength, has served as raw data to accounting for the polymer-vesicle interactions. Quantitative evaluation of the interaction has been done using a simple associating model…

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…

Correlation between transport and equilibrium properties through the ternary interaction parameter for cosolvent and cononsolvent polymeric systems

A study of the ternary polymer systems dimethyl formamide-ethyl acetate-polystyrene, chloroform-1,4 dioxane-polystyrene and tetrahydrofuran-chloroform-polystyrene was carried out by viscosity and light scattering at 298 K. A good correlation has been found between the excess intrinsic viscosity, unperturbed polymer dimensions, second virial coefficient and the excess Gibbs free energy by using a ternary interaction parameter, dependent on molecular weight. This modification enables the conversion between transport and equilibrium properties.

Relative strength of H-bonding groups on biodegradable polymer-based blends in solution

The intermolecular hydrogen bonding interactions between poly(3-hydroxybutyrate) and poly(styrene-co-vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady-state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly-(3-hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3-hydroxybutyrate) and poly(styrene-co-4-vi…