Dendron brushes and dendronized polymers: a theoretical outlook.

Dendron brushes are molecular structures built up of treelike macromolecules, with multiple generations of branches, grafted with a root segment to a surface (particle) or to a backbone chain (dendronized polymer) with a sufficiently high grafting density so that the dendrons interact laterally. Recent advances in the theory of dendron brushes are highlighted and complemented by insights from numerical self-consistent field modelling. Our focus is on controversial issues, which are still under debate, such as, the strain distribution in individual dendrons and the appearance of distinct populations with a different extent of stretching for dendrons in planar brushes. We anticipate that dendritic brushes (i) show a strong resistance against bending, which may manifest in a high apparent persistence length of dendronized polymers, and (ii) have an unusually large beneficial effect on the colloidal stability due to the sharp steric repulsive interaction observed when these surface layers are pushed towards the overlap.

Persistence Length of Dendritic Molecular Brushes.

On the basis of mean-field theory, we predict that molecular brushes with dendritic side chains ("dendronized polymers") may exhibit the behavior of semirigid polymers capable of lyotropic odering. The apparent persistence length of these molecular brushes is governed by the interactions between dendritic grafts and may significantly exceed the characteristic brush thickness. Compared to bottle-brushes with linear grafts, manifestation of the induced rigidity in molecular brushes with dendritic branches is expected at smaller degrees of polymerization of the grafts. Under good solvent conditions, the induced rigidity depends solely on the number of side chain monomers per unit length of backbone and the second virial coeffcient of monomer-monomer interactions, irrespective of graft topology.

Modeling of charged amphiphilic copolymer stars near hydrophobic surfaces.

Numerical self-consistent field theory has been applied to amphiphilic copolyelectrolyte stars in the solution and at interfaces both in one- and two-gradient coordinate systems. Our focus is on polymer stars for which the solvent is poor for the short blocks in the center and good for the longer charged chain parts at the periphery of the star. Both in solution as well as near an interface, the structure of the core is influenced by the hydrophobic interactions that tend to form a compact globule with size Rc and the forces exerted by the charged peripheral chain parts that like to expand the core. When the distance H of the center of the star to the surface becomes smaller than the total size R, the interaction force becomes significant; it is positive for Rc

Wetting phase diagrams of a polyacid brush with a triple point.

The (pre)wetting behavior of an annealed polyelectrolyte (PE) brush by an electrolyte solution that is strongly segregated from an apolar phase is analyzed. In this complex interface, there are interactions on various length scales. There are short-range interactions with the (uncharged) surface, and there are interactions on the length scale of the brush height. Using either the ionic strength or the water-surface interaction strength as the control parameters, it is possible to approach and induce a wetting transition in this system. The first-order wetting transition, promoted by favorable short-range substrate interactions with the surface, is in competition with the wetting transition controlled by the detachment of the fluid interface from the periphery of the PE brush. The electric double layer on top of the PE brush contributes with a repulsive forces to the disjoining pressure that tends to thicken the wetting film, and therefore, the transition in all cases is first order. Various phase portraits of the wetting phase diagram are envisioned. One of these features the crossing of two prewetting lines. At the crossing point three surface states coexist. This triple point is analyzed in some detail with the help of a molecular-level self-consistent field model.

Curved polymer and polyelectrolyte brushes beyond the Daoud-Cotton model.

We revise the classical Daoud-Cotton (DC) model to describe conformations of polymer and polyelectrolyte chains end-grafted to convex spherical and cylindrical surfaces. In the framework of the DC model, local stretching of chains in the brush does not depend on the degree of polymerization of grafted chains, and the polymer density profile follows a single-exponent power law. This model, however, does not correspond to a minimum in free energy of the curved brush. The nonlocal (NL) approximation exploited in the present paper implies the minimization of the overall free energy of the brush and predicts that the polymer density profile does not follow a single-exponent power law. In the limit of large surface curvature the NL approximation provides the same scaling laws for brush thickness and free energy as the local DC model. Numerical prefactors are however different. Extra extension of chains in the brush interior region leads to larger equilibrium brush thickness and lower free energy per chain. A significant difference between outcomes of the two models is found for brushes formed by ionic polymers, particularly for weakly dissociating (p H-sensitive) polyelectrolytes at low solution salinity.

[The effect of external restrictions on the stability of the globular state]. / Vliianie vneshnikh ogranichenii na stabil'nost' globuliarnogo sostoianiia.

The delta Td changes of heat denaturation temperature for globule proteins were estimated, for a globule inserted into pores of a inert carrier, that limits the conformational set of the denatured chain. Based on calculations for a grated selfintercepted chain in a slit-like pore, with no interactions with the pore walls, functions of delta Td depending on the rigidity of the unfolded chain, its length and pore sizes were determined. For alpha-chymotrypsin in polyacrylamide gels the estimated delta Td was of several degrees. The possible influence of the pore form and intramolecular interactions for a denatured chain on the value of the stabilizing effect is discussed.

[Studies on the coil-globule transition by the Monte-Carlo method]. / Izuchenie perekhoda klubok - globula metodom Monte-Karlo.

The results of a dynamical Monte-Carlo study on the coil-globule and globule-coil transitions are presented. Self-avoiding chains of lengths N = 32 and 64 are investigated. The kinetic model included two- and three-bonds flips. The relaxation of the chain was induced by the abrupt change of the interaction between the monomers. The time evolution of the radius of gyration and the number of intramolecular contacts was obtained. It is established that the transition to the compact state occurs due to the contacts between the monomers close to each other along the chain. The results obtained are compared with the predictions of analytical theories.

[Helix-globule transitions of polypeptides selectively reacting with the interface]. / Perekhody spiral'--klubok v polipeptidakh, izbiratel'no vzaimodeistvuiushchikh s poverkhnost'iu razdela faz.

An analytical theory of helix-coil transitions for polypeptides in a solution near a flat and homogeneous interface is given. The following cases were considered: a) only the helical parts are absorbtively active; b) only the coiled sections of the chain are active in adsorption. It has been shown that the binding of the polymer chain to the surface is a result of a phase transition of a second order, moreover in case a) the presence of a secondary structure abruptly increases the ability of the macromolecules to bind to the interface. This largely increases the stability of the helical structure of the chain and leads to a practically complete spiralization of the macromolecule. The profile of the conformational transitions was strictly asymmetrical which is typical for the phase transitions. In case b) the process of binding resembles the adsorbtion of the Gaussian coils. In this case the rate of spiralization of the chain decreases in the course of binding and the degradation of the secondary structure is significant even if the helical state in volume is stable. The profile of the transition remains qualitatively similar to the helix-coil transition in volume but is displaced to the region of larger equilibrium constants.

On conformations of the superhelix structure.

The slight deformation of a helical macromolecule leading to the superhelical structure is considered. General equations which connect "internal" stereochemical parameters of the backbone of a helical macromolecule with "external" parameters of the superhelix are obtained; they are analogous to those of Shimanouchi and Mizushima. The case when the radius of the major helix is much greater than the radius of the minor helix is treated. Assuming that all conformational changes are due to small distortions of the rotation angles (bond angles and bond lengths are kept constant) the general equations reduce to a set of nonhomogeneous linear algebraic equations. Its solution (in the case of the DNA double-helix in B-form) shows that the DNA backbone can form a coiled-coil with parameters close to those estimated from experimental data on DNP in chromatine from nuclei of cells.

[Conformational transitions in adsorbed macromolecules with secondary structure]. / Konformatsionnye perekhody v adsorbirovannykh makromolekulakh s vtorichnoi strukturoi.

An analytical theory is presented taking into account the effects of the flat adsorbing surface on the equilibrium properties of the long single-stranded macromolecule possessing a secondary structure. Change of the secondary structure is described in terms of Zimm--Bragg theory; adsorbtion properties are calculated for the lattice model without taking into account the 3-dimensional interactions. It is shown that the presence of the adsorbing surface sharpens helix-coil transition, displacing it towards the lower constants of equilibrium (s). A relation of the critical energy of adsorbtion (--epsilonkappa) on s is obtained at different values of the cooperativity factor sigma. This relationship represents a phase diagram of the system. Various sections of this phase diagram corresponding to different dependence of s and --epsilon on the external factors are considered. It is shown that the process of adsorbtion may occur in different manners: either cooperatively or by the phase transition of type II with jumps in one or in three points.