A. M. Wasserman

Some EPR spin probe and spin label studies of polymer systems

The application of EPR spin probe and spin label technique for solving the two problems of polymer physical chemistry is considered. The first problem is the determination of conformational state and chain sizes in amorphous solid polymers. This determination is based on the analysis of the intramolecular dipolar broadening of EPR spectra of spin labelled macromolecules in glassy solvents or in the bulk of unlabeled polymers at 77 K. The second problem is the determination of molecular mobility and structure of two polymer colloid systems: (a) the complex of colloidal silica and synthetic polycation macromolecule and (b) polymer-surfactant micellar organized systme.

Macromolecular and morphological evolution of poly(styrene sulfonate) complexes with tetradecyltrimethylammonium bromide.

Macromolecular characteristics and morphology of water-soluble complexes between sodium poly(styrene sulfonate) (PSS) and tetradecyltrimethylammonium bromide have been followed as a function of surfactant-to-polymer charge ratio (S/P) to elicit possible changes in the complexation mechanism. As revealed by light scattering, shorter PSS (30 and 150 repeat units) yield multichain complexes while longer PSS (450 and 5000 repeat units) form single-chain species throughout 0 < S/P < 0.9. Irrespective of PSS chain length, the complexes exist in solution in a swollen coil conformation and undergo a compaction with S/P but never collapse into a globule. Even when the free PSS chain is too short to coil (30 repeat units), the complexes adopt a coiled conformation due to multichain aggregation. Morphological changes (manifested by a hypochromic shift in UV spectra of the complexes at S/P < 0.5 and an increase in the local surfactant mobility observed at S/P > 0.5 by ESR) strongly suggest a change in the formation mechanism of the complexes with a transition near S/P = 0.5.

Mobility of the spin probe TEMPO in glassy metathesis polymers with substituents containing flexible Si-O-Si groups

Glassy metathesis polymers (glass-transition temperatures of 110–236°C) containing substituents with flexible Si-O-Si groups are studied by the spin-probe method with the use of the stable nitroxyl radical TEMPO. A high mobility of the spin probe not correlating with the free volume of polymers is reported. These results and the earlier discovered thermodynamic selectivity of the indicated polymers (high permeability coefficients of higher hydrocarbons) make it possible to infer that Si-O-Si groups are responsible for the observed behavior similarly to that in siloxane rubbers.

Molecular mobility in micellar complexes of a nonionic surfactant and the poly(acrylic acid)-based hydrogel

The interaction between the polyelectrolyte gel of crosslinked poly(acrylic acid) (PAA) and nonionic surfactant Brij 58 based on poly(ethylene glycol) (C16H33(CH2CH2O)20OH) is studied. It is established that poly(acrylic acid)-surfactant complexes are formed. Nondissociated carboxyl groups of poly(acrylic acid) and oxygen atoms of the surfactant are involved in the complexation. Surfactant micelles are a kind of bridge that connects polymer chains. The presence of the surfactant decreases the equilibrium swelling of the hydrogel. The spin probe method is employed to determine the local mobility of the hydrocarbon core of a micelle in the complex. It was shown that the local mobility is independent of the hydrogel crosslink density and is much lower in acidic than in alkaline media. In acidic media, much more surfactant molecules of micelles are involved in the complexation than in alkaline media. However, even in alkaline media, surfactant micelles cannot leave the hydrogel, while the spin probes located in micelles are at equilibrium with the spin probes present in the external aqueous medium. The prospects for applying the considered systems as carriers for controlled release drugs are discussed.

Spin probes in micellar and polymer self-associating systems

The results of studies of micellar and self-associating polymer systems by spin probe ESR spectroscopy are summarized. The local dynamics and structures of low-molecular-weight micelles built of cationic surfactants bearing long alkyl chains (from C16 to C22), gels of hydrophobically modified polymers, polymer micelles, micellar complexes of nonionic surfactant (Brij58) with hydrogels based on polyacrylic acid, and associates formed in aqueous solutions of poly(diphenylenesulfophthalide) are discussed. Interest in these systems is caused by prospects of their practical use as carriers in drug delivery, in biotechnology, for the enhancement of oil production, and in other purposes.

Interaction between cationic monomer and sodium dodecyl sulfate in concentrated aqueous solutions: EPR spectroscopy and rotational viscometry

The interaction of a cationic monomer, trimethyl[methacryloxyethyl]ammonium methyl sulfate, with sodium dodecyl sulfate (SDS) has been studied in relatively concentrated solutions containing SDS (70–500 mM) and the monomer (from 7 mM to 2.5 M). The high concentrations of the components do not prevent the monomer from bonding to oppositely charged SDSs, which confirms the possibility in principle to polymerize ionic monomers through a template mechanism using micelles of oppositely charged surfactants as templates. The range of component ratios 0.5 ≤ [monomer]/[SDS] ≤ 2 is most promising for realization of the template mechanism of polymerization. The effect of SDS on the macroscopic and microscopic properties of the system significantly and to a maximum extent decreases upon a further rise in the relative concentration of the monomer.

Structuring in aqueous solutions of polydiphenylenesulfophthalide: dimensions of associates and their local mobility

The dimensions of associates formed in aqueous solutions of polydiphenylenesulfophthalide (PDPSP) and products of its treatment with alkali-metal hydroxides are measured by light scattering. As shown by EPR spin-probe spectroscopy, the associates are hydrophobic structures. The local mobility of polydiphenylenesulfophthalide associates is lower than that of associates of the polymer treated with alkalimetal hydroxides, but, in all cases, this value is commensurable with the local mobility of solid polystyrene.

Local mobility of micelles of new cationic surfactants and their interactions with hydrophobically modified polyacrylamides

The local dynamics and organization of micelles of new long-chain cationic surfactants with saturated hydrocarbon fragments (from C16 to C22) are investigated via the EPR spin-probe technique. The local mobility of spin probes in the hydrocarbon core of a micelle changes insignificantly, while the order parameter noticeably increases with lengthening of the hydrocarbon fragment of the surfactant molecule. The specific features of the interaction of the surfactants with network junctions of the gels formed by two types of hydrophobically modified polyacrylamides—either containing charged groups (sodium acrylate) in the backbone or lacking these groups—are studied. In both cases, the local mobility of network junctions of the gel increases after the introduction of the surfactant (C18). Moreover, for surfactant with a long alkyl group (C2), the microscopic viscosity of the gel based on the uncharged polymer decreases, although the local mobility of the network junctions increases. Possible causes of the observed specific features are discussed.

Local mobility and rheological characteristics of gels based on hydrophobically modified poly(acrylamides)

For hydrophobically modified poly(acryl amide), we analyze the effect of various parameters of the macromolecular structure (number and length of side hydrophobic groups, content of charged groups, type of bonding between side chains and the polymer backbone, and the degree of blocking of hydrophobic groups distributed along the chain) on the local mobility of physical network junctions and rheological characteristics of gels. We have found that the local mobility measured by the method of spin-probe EPR spectroscopy is either independent or it slightly depends on the above parameters. At the same time, these parameters exert a strong effect on the rheological characteristics of gels. This disagreement can be explained by the fact that local mobility of junctions is primarily controlled by the intermolecular interactions of hydrophobic groups and by the covalent bonding between these groups and a macromolecule. However, the rheological characteristics depend on the number of junctions, their dimensions, and other parameters.

Local dynamics of micelles of new long-chain surfactants in aqueous media

The molecular dynamics, organization, and phase state of aqueous solutions of new long-chain cationic surfactants with saturated hydrocarbon radicals (from C16 to C22) containing one or two hydroxyl groups in their polar heads are studied by the spin-probe EPR spectroscopy. In the region of micellar solutions, local mobility of surfactant molecules slightly changes with an increase in the length of hydrocarbon radical, whereas the order parameter of micelles increases notably. The addition of two hydroxyl groups to the polar part of long-chain (C22) surfactant molecule considerably decreases local mobility and increases the ordering of micellar system compared to the micelles of analogous surfactant with one hydroxyl group. Phase transition from micellar to a solid state is observed in this system with a decrease in temperature. The addition of KCl to aqueous surfactant solution lowers the local mobility, increases the order parameter of micelles, and can cause changes in the phase state of a system. In the presence of salt, the correlation time of probe rotation and its order parameter depend on surfactant concentration. Apparently, this is explained by changes in the shape of micelles upon variations in surfactant concentration.