I. M. Zorin

Dilational surface viscoelasticity of polymer solutions

A review of recent results on the dilational surface viscoelastic properties of aqueous solutions of non-ionic polymers is given. In the frequency range from 0.001 up to 1000 Hz the methods of transverse and longitudinal surface waves and the oscillating barrier method were applied. Viscoelastic behavior of adsorbed polymer films significantly differs from the behavior of films formed by only conventional surfactants of low molecular weight. For example, the dynamic surface elasticity of the former systems is low and almost constant in a broad concentration range. One can observe the increase of the surface elasticity only at extremely low concentrations and/or in the range of semi-dilute solutions. If the surface stress relaxation in conventional surfactant solutions is usually determined by the diffusional exchange between the surface layer and the bulk phase, the relaxation processes in the polymer systems proceed mainly inside the surface layer. Possible mechanism of the latter relaxation is discussed.

Synthesis, hydrodynamic, and conformational properties of poly(N-acryloyl-11-aminoundecanoic acid) in solutions

Poly(N-acryloyl-11-aminoundecanoic acid) samples are synthesized in monomer solutions occurring in both micellar and nonmicellar states. It is shown that polymeric ionogenic surfactants of various molecular masses can be prepared through variation in the concentration of a polymerizable surfactant or in the ionic strength of a solution. The polymer of interest is investigated in detail via the methods of molecular hydrodynamics (viscometry, isothermal diffusion, and velocity sedimentation), dynamic light scattering, GPC, and scanning probe microscopy. The solubility of the polymer in various solvents is examined in detail, and the tendency of this polymer toward association in DMF solutions is discovered. The equilibrium rigidity of macromolecules, which is characterized by the Kuhn segment length A = 100 × 10−8 cm, and the effective hydrodynamic radius are determined in a dioxane-cyclohexanol mixed solvent.

Scanning probe microscopy of adsorption layers of sodium polystyrenesulfonate/dodecyltrimethylammonium bromide complexes

Scanning probe microscopy is used to study adsorption films of sodium polystyrenesulfonate/dodecyltrimethylammonium bromide complexes, which are transferred from aqueous solution surfaces to the mica surface by the Langmuir-Blodgett method. It is established that the results obtained at surfactant concentrations below critical micelle concentration agree with the conclusions on the structure of the films dased on the data of the dilatational surface rheology (Noskov, B.A., Loglio, G., Miller, R., J. Phys. Chem. B, 2004, vol. 108, p. 18615). At low concentrations of the low-molecular-mass surfactant, a thin adsorption film containing a large number of holes is formed on the surface of an aqueous solution. As the surfactant concentration is increased to reach the region of a dramatic reduction in the dynamic surface elasticity, the morphology of the film drastically changes; i.e., dense three-dimensional aggregates are formed on the solution surface.

Preliminary communication - The effect of a substituent in the central ring on the liquid crystalline properties of di(4-alkoxycarbonylphenyl) terephthalates

Four series of di(4-alkoxycarbonylphenyl) terephthalates with different lateral substituents in the central ring and lengths of the terminal alkyl groups were synthesized. The influence of the lateral substituent on thermodynamical parameters of the phase transitions and elastic properties of the nematic phases (ratio of bend elastic constant to diamagnetic anisotropy K3/Delta chi) were studied by polarizing optical microscopy, differential scanning calorimetry and observations of the Freedericksz transition. It was found that increasing the alkyl chain length and the substituent size in the sequence H, Cl, Br, NO2 results in reduction in stability of the crystal and (as frequently observed in other cases) the liquid crystal phases. The changes in the bend elastic constant and the melting enthalpy caused by the substituent variation are correlated with each other, a fact that is explained by the dependence of short-range lamellar packing on size and polarity of substituent.

Novel surfactant-selective membrane electrode based on polyelectrolyte-surfactant complex.

Novel class of active ionophores for surfactant selective electrodes is proposed. PVC membrane doped with polyelectrolyte-surfactant stoichiometric complex is used for ion-selective electrode construction responsive to cetyltrimethyl ammonium bromide and related surfactants. New ionophore is quite stable and completely insoluble in aqueous media in wide range of pH. The electrode displays nearly Nernstian slope in CTAB concentration range 10(-6)-10(-3)M. Polyelectrolyte platform allows to design wide range of different ionophores responsive to cationic organic substances.

n-Alkyl ammonium 2-acrylamido-2-methylpropanesulfonates: Synthesis, properties, and polymerization

Polymerizable surfactant organic salts based on n-alkylamines and 2-acrylamido-2-methylpropanesulfonic acid—n-dodecyl ammonium 2-acrylamido-2-methylpropane sulfonate and n-cetyl ammonium 2-acrylamido-2-methylpropane sulfonate—are synthesized, characterized, and studied for the first time. Their critical micelle concentrations in water are estimated by the methods of conductometry and viscometry. The appearance of micelles in water is confirmed by atomic-force microscopy. As evidenced by some features, cetyl ammonium 2-acrylamido-2-methylpropanesulfonate forms reverse micelles in xylene. The polymerization of n-alkyl ammonium 2-acrylamido-2-methylpropane sulfonates that gives rise to stoichiometric polyelectrolyte-colloid complexes is performed in systems based on solvents of various polarities: from low-polarity xylene and dioxane to water. In low- and high-polarity systems, the features of polymerization are typical for micellar polymerization. (It is completed within several minutes.) In dioxane-water mixtures having intermediate polarities, the rate of polymerization is much lower. The polymerization of the monomers in xylene affords stable organic gels. The resulting polymers are water-insoluble, but are soluble in several alcohols and chloroform. Films cast from chloroform solutions demonstrate a well-defined layer structure.

Molecular, conformational, and optical characteristics of poly(dodecylammonium-2-acrylamido-2-methylpropanesulfonate) in organic solvents

A number of samples of poly(dodecylammonium-2-acrylamido-2-methylpropanesulfonate)—a comb-like polymer with ionically bound side chains—are obtained by the polymerization of dodecylammonium-2-acrylamido-2-methylpropanesulfonate in an aqueous medium. The samples are obtained in a wide molecular-mass range. Molecular, hydrodynamic, and optical characteristics of the samples are determined by the methods of sedimentation-diffusion analysis, viscometry, and flow birefringence in dilute polymer solutions in chloroform and dimethyl sulfoxide containing small amounts of 0.1 M LiCl. It is shown that conformational and optical characteristics based on hydrodynamic and dynamo-optic investigations agree with the data available for acrylic and methacrylic polymers with the same lengths of side groups. In other words, the character of attachment (covalent or ionic) of long side chains to the backbone has no effect on the conformational and optical characteristics of macromolecules.

Optical, dynamic, and electro-optical properties of poly(N-acryloyl-11-aminoundecanoic acid) in solutions

The optical, electro-optical, and dynamic characteristics of poly(N-acryloyl-11-aminoundecanoic acid) in organic solvents and of the sodium salt of its monomer in water were studied via the methods of flow birefringence, equilibrium and nonequilibrium electric birefringence, and dynamic light scattering. It is shown that, in aqueous solutions, the monomer forms coarse particles of both symmetric and asymmetric shapes. The linear dimensions of these particles are estimated from the data of translational and rotational diffusion. Polymer macromolecules in organic solvents feature negative anisotropy of optical polarizability. Contributions of optical microform and macroform effects to the observed flow birefringence are analyzed in detail. The intrinsic optical anisotropy of the monomer unit of the polymer, which correlates well with the corresponding values for comb-shaped polymers of a similar structure, is estimated. It is shown that polymer molecules lack marked intrinsic permanent macromolecular dipoles and that electric birefringence in their solutions is associated with macroscopic induced dipole moments that appear during orientation of the dipole moments of polar groups in side chains of the polymer under application of an electric field.

Photocurrent in Multilayered Assemblies of Porphyrin-Fullerene Covalent Dyads: Evidence for Channels for Charge Transport.

Specially designed porphyrin-fullerene dyads have been synthesized to verify literature predictions based on quantum chemistry calculations that certain porphyrin-fullerene dyads are able to self-arrange into specific structures providing channels for charge transport in a bulk mass of organic compound. According to AFM and SEM data, the newly synthesized compounds were indeed prone to some kind of self-arrangement, although to a lesser degree than was expected. A dispersion corrected DFT study of the molecular non-covalent interactions performed at the DFT-D3 (B3LYP, 6-31G*) level of theory showed that the least energy corresponded to head-to-head dimers, with close contacts of porphyrin-porphyrin and fullerene-fullerene fragments, thus providing a unit building block of the channel for charge transport. Experimental proof for the existence of channels for charge transport was obtained by observing a photocurrent in a simple photovoltaic cell.

Fixation of micelle structure by monomer polymerization: Hydrodynamic properties of polymerized micelles

Polymerized and nonpolymerized micelles of N-acryloyl-11-aminoundecanoic acid and its sodium salt in water and dimethylformamide are studied by viscometry, isothermal diffusion, and dynamic light scattering. It is revealed that the hydrodynamic sizes of polymerized micelles (PMs) obtained via polymerization of the surfactants in aqueous solutions at low concentrations of the latter are significantly larger than those of the starting surfactant micelles. In dimethylformamide, as the surfactant concentration at which the synthesis is carried out is increased, the hydrodynamic size of PMs, which is calculated in terms of the cylindrical particle model, rises from 25 to 220 nm. The formation of additional internal crosslinks reduces the equilibrium rigidity of the PM chains by a factor of 1.5–2.