Detection of polymer compatibility by means of self-organization: poly(ethylene oxide) and poly(sodium 4-styrenesulfonate).

Information on the miscibility of different polymers A and B on a molecular level is important in many ways. However, along the traditional lines this knowledge is difficult and time consuming to achieve. The current study presents a simple alternative, based on the determination of the intrinsic viscosities (specific hydrodynamic volume of isolated coils) for blend solutions in a common solvent. In the case of incompatible polymers, isolated coils contain one macromolecule only, either A or B. In contrast, compatible polymers form mixed isolated coils, because of favorable interactions. The present investigation was carried out for the system water/poly(ethylene oxide)/poly(sodium 4-polystyrenesulfonate), for which the reason of compatibility lies in the formation Na+ bridges between the sulfonate groups of the polyelectrolyte and the OH groups of the poly(ethylene oxide). Zero shear viscosities were measured as a function of polymer concentration for blends of different compositions and modeled quantitatively by means of relations yielding the excess intrinsic viscosities ε (zero in the case of incompatibility) and viscometric interaction parameters. Particular attention is being paid to the role the molar masses of the polymers play for the resulting ε values.

Associative behaviour of κ-carrageenan in aqueous solutions and its modification by different monovalent salts as reflected by viscometric parameters.

The viscometric behaviour of κ-carrageenan in aqueous solutions and in the presence of monovalent salts was investigated at 25 °C. Coil, helix or double helix conformations were induced by cooling hot κ-carrageenan solutions under appropriate ionic conditions. A new viscometric approach was used for modeling the behaviour of κ-carrageenan solutions. The intrinsic viscosity, [η], is markedly changed by the presence of different monovalent salts (NaCl, NaI and CsI). In pure water, the intrinsic viscosity amounts to 48 dL·g-1. In 0.1 M NaCl solutions (single helix state) [η] is 6.2 dL·g-1, whereas in 0.1 M NaI (double helix conformation) it is approximately twice as large. In 0.1 M CsI (dissimilar cation and counter-ion) the intrinsic viscosity is three times larger, suggesting the formation of the associated κ-carrageenan helices. Stepwise association of κ-carrageenan helices was followed in presence of NaI/CsI mixtures of different compositions. The value of Smidsrød-Haug stiffness parameter (B) measured for κ-carrageenan in NaCl solutions is 4.47 × 10-2, higher than that of DNA (5.5 × 10-3), but lower than those reported for carboxymethyl cellulose (6.3 × 10-2), indicating that the chain conformation is moderately rigid.

Self-assembling of poly(aspartic acid) with bovine serum albumin in aqueous solutions.

Macromolecular co-assemblies built up in aqueous solutions, by using a linear polypeptide, poly(aspartic acid) (PAS), and a globular protein, bovine serum albumin (BSA), have been studied. The main interest was to identify the optimum conditions for an interpenetrated complex formation in order to design materials suitable for biomedical applications, such as drug delivery systems. BSA surface possesses several amino- and carboxylic groups available for covalent modification, and/or bioactive substances attachment. In the present study, mixtures between PAS and BSA were investigated at 37°C in dilute aqueous solution by viscometry, dynamic light scattering and zeta potential determination, as well as in solid state by AFM microscopy and dielectric spectroscopy. The experimental data have shown that the interpolymer complex formation occurs for a PAS/BSA molar ratio around 0.541.

Dependence of solvent quality on the composition of copolymers: experiment and theory for solutions of P(MMA-ran-t-BMA) in toluene and in chloroform.

The interaction of toluene with P(MMA-ran-t-BMA) and with the corresponding homopolymers was determined via vapor pressure measurements at 30, 50 and 70 °C. A unified thermodynamic approach served for the modeling of the results. It is capable of describing the behavior of the different solutions by means of two adjustable parameters, one representing the effective number of solvent segments and the other accounting for the interactions between the components. The solvent quality of toluene passes a maximum, a minimum and another maximum upon an increase of the t-BMA content of the copolymer at all temperatures. A similar behavior is discernable from vapor pressure data of chloroform published for the same copolymers. The heats of mixing for toluene depend strongly on temperature; at 50 °C they are all endothermal with the exception of PMMA, for which the value obtained from vapor pressures at 30 °C agrees very well with published caloric data.

Thermodynamics of copolymer solutions: how the pair interactions contribute to the overall effect.

Vapor pressure measurements were performed for solutions of poly(methyl methacrylate-ran-tert-butyl methacrylate) with different weight fractions of tert-butyl methacrylate units, and their parental homopolymers in chloroform at 323 K, over a large domain of concentrations. The Flory-Huggins interaction parameters obtained from these experimental investigations show complex dependences of the Flory-Huggins interaction parameter on concentration and copolymer composition. This behavior can be modeled by taking into account an approach which considers the ability of the polymers to rearrange in a response to changes in their molecular surroundings [Adv. Polym. Sci. 2011, 238, 1-66]. According to this concept, the mixing process is subdivided into two clearly separable steps and accounts for the specific interactions between the solvent and copolymer segments.

Joint aqueous solutions of dextran and bovine serum albumin: coexistence of three liquid phases.

The phase diagram of the system water/dextran (DEX)/BSA was measured as well as modeled. On the experimental side, cloud points were determined and the coexisting phases were analyzed. The theoretical calculations use an approach capable of describing solutions of chain polymers and of globular proteins with the same formalism. The required thermodynamic input comes from experiments concerning the binary subsystems, except for the polymer blend for which one interaction parameter had to be adjusted. Both sources of information yield the same essential features: the existence of a large composition area of immiscibility, starting from the subsystem DEX/BSA and extending well into the region of dilute polymer solutions. This range is subdivided into three sections: one two-phase area at high polymer content, a two-phase area at low polymer content, and a three-phase region located in between. Measured and calculated phase diagrams match qualitatively; the reasons for the quantitative discrepancies are being discussed.

Intrinsic viscosities of polyelectrolytes: specific salt effects and viscometric master curves.

Dilute solutions of the sodium salt of polystyrene sulfonic acid (PSS-Na) were measured viscometrically as a function of composition in aqueous solvents of different salinity, where the extra salt was either NaCl or CaCl2. Such experiments yield {η}, the generalized intrinsic viscosities (hydrodynamic specific volume) of the polyelectrolyte for arbitrary polymer concentrations, c. In the limit of infinite dilution {η} becomes identical to the intrinsic viscosity [η]. For NaCl {η} decreases monotonously with rising c, whereas maxima are passed in the case of CaCl2. Condensing c and the concentration of extra salt in the mixed solvent into a single variable enables the establishment of predictive master curves. The viscometrically observed changes in the spatial extension of the individual polymer coils are discussed in light of the corresponding thermodynamic information.

Liquid/gas and liquid/liquid phase equilibria of the system water/bovine serum albumin.

The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adjustable parameters and describes the vapor pressures quantitatively; it also forecasts the existence of a miscibility gap.

Synergistic behavior of poly(aspartic acid) and Pluronic F127 in aqueous solution as studied by viscometry and dynamic light scattering.

Pluronic F127/poly(aspartic acid) mixtures were investigated in dilute solutions by viscometry and dynamic light scattering. The two polymers were chosen due to well known applications in biomedical field, taking into account the final purpose (the use of the complex structure as drug delivery systems). The central item was to identify the possibility of complexation between the poly(carboxylic acid) and a non-ionic polymer and to investigate the conditions of the interpolymer complex formation. The ability of Pluronic F127 to form micelle is well known. Poly(aspartic acid), as a polycarboxylic acid with resemblance with polyacrylic acid, can act as dispersant, antiscalant, superabsorber, being also able to form micelles. Due to its functional groups, -COOH and -NH(2), poly(aspartic acid) can make physical and/or chemical bonds with other macromolecular compounds. The intrinsic viscosity and the dynamic light scattering data obtained for PLU/PAS mixtures at 25 °C have shown that interpolymer complex formation occurs around 1/1 wt. ratio between the two polymers.

Intrinsic viscosities of polyelectrolytes in the absence and in the presence of extra salt: Consequences of the stepwise conversion of dextran into a polycation.

Viscosities of dilute polymer solutions were measured in capillary viscometers for samples varying in their fraction f of charged units from 0.00 to 0.90. The dependence of the logarithm of the relative viscosity on polymer concentration c is in all cases reproduced quantitatively by three characteristic parameters: [η], the intrinsic viscosity; B, a viscometric interaction parameter (related to the Huggins constant); [η], a parameter required only for polyelectrolytes at low concentrations of extra salt. In pure water [η] increases more than 80 times as the fraction f rises from zero to 0.90 and [η] starts from zero and goes up to ≈71mL/g. Upon the addition of NaCl [η] decreases by at least one order of magnitude (depending on the value of f). The observed dependences of log [η] on logcsalt can be modeled quantitatively by Boltzmann sigmoids.

Intrinsic viscosities of polyelectrolytes: determination and modeling of the effects of extra salt.

Based on early measurements of J. J. Hermans and co-workers (D. T. F. Pals, J. J. Hermans, Recl. Trav. Chim. Pays-Bas 1952, 71, 513-520; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1950, 5, 733-734; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1948, 3, 897-898), the present contribution demonstrates how primary data should be evaluated in order to obtain reliable intrinsic viscosities. This procedure yields detailed information on the changes of the intrinsic viscosities and of the corresponding viscometric interaction parameters caused by an increasing salinity of water. Both quantities decline from a maximum value in the pure solvent to a minimum value, which is approached in the limit of sufficiently high salt concentrations, and can be modeled quantitatively by means of a Boltzmann sigmoid. Particular attention is paid to the significance of results obtained by means of the method of isoionic dilution, proposed by J. J. Hermans and co-workers.

Pullulan and dextran: uncommon composition dependent Flory-Huggins interaction parameters of their aqueous solutions.

Vapor pressure measurements were performed for aqueous solutions of pullulan ( M w 280 kg/mol) and dextran ( M w 60 and 2100 kg/mol, respectively) at 25, 37.5, and 50 degrees C. The Flory-Huggins interaction parameters obtained from these measurements, plus information on dilute solutions taken from the literature, show that water is a better solvent for pullulan than for dextran. Furthermore, they evince uncommon composition dependencies, including the concurrent appearance of two extrema, a minimum at moderate polymer concentration and a maximum at high polymer concentration. To model these findings, a previously established approach, subdividing the mixing process into two clearly separable steps, was generalized to account for specific interactions between water and polysaccharide segments. Three adjustable parameters suffice to describe the results quantitatively; according to their numerical values, the reasons for the solubility of polysaccharides in water, as compared with that of synthetic polymers in organic solvents, differ in a principal manner. In the former case, the main driving force comes from the first step (contact formation between the components), whereas it is the second step (conformational relaxation) that is advantageous in the latter case.

Thermodynamic interaction parameters for the system water/NMMO hydrate.

Vapor pressures of water were measured for aqueous solutions of N-methyl-morpholine N-oxide (NMMO) at 80, 90 and 100 degrees C. The Flory-Huggins interaction parameters, chi, calculated from these data as a function of phi, the volume fraction of NMMO, are negative at all concentrations; at low phi, they decrease by more than a factor of 2 as T is raised, whereas they remain almost unchanged as phi approaches unity. Accordingly, the heat of mixing is pronouncedly endothermal at low NMMO concentrations but close to athermal at low water content. The composition dependence of chi can be equally well described by the Redlich-Kister equation and by an approach subdividing the mixing process into two separate steps. The opportunities of the latter modeling for a better molecular understanding of the mixing processes are discussed.

Cellulose/water: liquid/gas and liquid/liquid phase equilibria and their consistent modeling.

Liquid/liquid and liquid/gas equilibria were measured for the water/cellulose system at 80 degrees C using three different polymer samples. For these experiments we prepared cellulose films of approximately 20-25 microm in thickness and determined their equilibrium swelling in water. Thereafter the polymer concentration in the mixed phase was increased by means of a stepwise removal of the volatile component, and the equilibrium vapor pressures were measured using an automated combination of head space sampling and gas chromatography. Contrary to the usual behavior of polymers, the swelling of cellulose increases as its molar mass becomes larger. The Flory-Huggins interaction parameters calculated from the measured vapor pressures pass a pronounced minimum as a function of composition; for high cellulose contents they are negative, whereas they become positive for water-rich mixtures. All experimental findings are consistently interpreted by means of an approach accounting explicitly for the effects of chain connectivity and for the ability of macromolecules to respond to environmental changes by conformational rearrangement.

Rheology of sodium hyaluronate saline solutions for ophthalmic use.

The aim of this work was to investigate the rheological properties of different saline solutions of sodium hyaluronate (NaHA) with special interest for medical applications. The experimental results were compared with literature data for commercial ophthalmic viscosurgical devices (OVDs) used in cataract surgery. We offer some tools to tailor the rheological behavior of OVDs for different purposes. We have investigated to which extent surgical requirements can be fulfilled by adjusting either the molecular weight of NaHA or its concentration, parameters that are in some respects equivalent but not in others. Furthermore, we demonstrate that moduli and complex viscosities of NaHA saline solutions are adequately falling on master curves, using either empirical or calculated shift factors, the latest ones being based on a modified Rouse model.

Phase behavior of aqueous solutions of bovine serum albumin in the presence of dextran, at rest, and under shear.

The demixing conditions for aqueous solutions of bovine serum albumin (BSA, fraction V) and for joint solutions of BSA plus dextran (DEX, M(w) = 2000 kg/mol) were determined by turbidimetric measurements as a function of composition, temperature, and shear rate. Aqueous solutions of BSA phase separate upon heating. Within the region of BSA concentrations between 0.05 and 32 wt %, the demixing temperature, T1, falls from ca. 65 degrees C to an almost constant value of 45 degrees C. Adding DEX to the BSA solutions reduces the homogeneous region of the mixture drastically where the amount of DEX required to lower T1 to 25 degrees C decreases rapidly as the concentration of BSA is raised. Experiments concerning the influences of shear have been performed for the ternary system up to 500 s(-1). They demonstrate that the content of dextran determines the sign of the effect. At low DEX concentrations, the mechanical field favors the homogeneous state (shear-induced mixing), whereas the opposite effect (shear-induced demixing) is observed at high DEX concentrations. Possible reasons for this observation are discussed.

Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures.

Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70 degrees C) or cyclohexane (CH) (32-60 degrees C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite composition interval at constant vapor pressure; with CH this phenomenon is either absent or too insignificant to be detected. For PS solutions in TL the DSC traces look as usual, whereas these curves may become bimodal for solutions in CH. The implications of the vitrification of the polymer solutions for the determination of Flory-Huggins interaction parameters from vapor pressure data are discussed. A comparison of the results for TL/PS with recently published data on the same system demonstrates that the experimental method employed for the determination of vapor pressures plays an important role at high polymer concentrations and low temperatures.

Continuous spin fractionation and characterization by size-exclusion chromatography for styrene-butadiene block copolymers.

Linear and star-shaped styrene-butadiene block copolymers synthesized by anionic polymerization of butadiene and styrene were fractionated by applying a newly developed large-scale fractionation technique, named continuous spin fractionation (CSF). Their molecular weight and polydispersity index (d=M(w)/M(n)) were measured with size-exclusion chromatography and static light scattering. For the linear triblock copolymer a fractionation via temperature variation turned out to be better suited than the usual isothermal procedure. The star-shaped polymer with the d value of 1.33 was fractionated in two CSF steps to get the targeted sample, which has a considerably more uniform structure and a narrower molecular weight distribution (d=1.11). The corresponding starting linear diblock copolymer was fractionated in one step reducing d from 1.68 to 1.17. With one set of simple laboratory equipment, 1kg polymer can be fractionated per day. Utilizing CSF, for the first time, we fractionated successfully the block copolymers.

Thermal diffusion of dextran in aqueous solutions in the absence and the presence of urea.

The Ludwig-Soret effect was studied for aqueous solutions of dextran in the temperature range 15 < T < 55 degrees C taking into account the effect of the addition of urea. In the absence of urea, the Soret coefficient S(T) changes sign; it is positive for T > 45.0 degrees C but negative for T < 45.0 degrees C. The positive sign of S(T) means that the dextran molecules migrate toward the cold side of the fluid; this behavior is typical for polymer solutions, whereas a negative sign indicates the macromolecules move toward the hot side. The addition of urea to the aqueous solution of dextran rises S(T) and reduces the inversion temperature. For 2 M urea the change in the sign of S(T) is observed at T = 29.7 degrees C and beyond that value S(T) is always positive in the studied temperature range. To rationalize these observations, it is assumed that the addition of urea leads to an opening of hydrogen bonds similar to that induced by an increase in temperature.