Search

The structure of amphiphilic spherical brushes, consisting of the nano-SiO2 core, the hyperbranched polyamidoamine subshell, and a grafted layer of long hydrophobically modified polyacrylamide (HMPAM) chains, in aqueous solution was analyzed and described in the framework of the original mean-field approach. The scaling estimations of the hydrodynamic radius of such polymer brushes as a function of the number of grafted macromolecules allow concluding that the HMPAM shells are in a globular state and that the region of the stretched chains adjacent to the grafting surface is a minor part of the grafted macromolecules and does not have a significant impact on the self-assembly of the HMPAM shell caused by the complex hydrophobic–hydrophilic composition of their monomer units. In mean-field theory, the amphiphilic nature of HMPAM was taken into account by attaching the hydrophobic side group H to some fraction of monomer units of the hydrophilic P backbone. The strong attraction of H groups causes the aggregation of macromolecules, whereas the affinity of hydrophilic P groups to solvent forces the aggregates to increase their surface. Due to such effective surface activity, in poor solvent, the grafted amphiphilic macromolecules could form a spherical compacted structure around the nanoparticle or self-assemble into a "hedgehog" structure with several "spines" having hydrophobic core and hydrophilic shell. State diagrams, obtained theoretically, reveal that the "hedgehog" structure is preferable for a wide range of energetic parameters. [ABSTRACT FROM AUTHOR]

This article is devoted to the study of polymer layers of amphiphilic homopolymers tightly grafted to a flat surface at the nodes of a square lattice. It was shown that, due to the amphiphilicity of monomer units containing groups with different affinities, in a selective solvent, such layers form lamellae perpendicular to the grafting surface. The period of the lamellae depends on the grafting density and the quality of the solvent. The results are presented in the form of a state diagram in variables "the energy of attraction of the side groups" (effective solvent quality) and "the distance between the grafting points" (inversely proportional to the square root of the grafting density). The diagram contains the regions of stability of lamellae with significantly different periods, and a transitional area with a parking garage structure. The diagram is constructed by calculating the layer-by-layer structure factor and the angle of inclination of the lamellae in the slice. The calculations were performed for different sizes of the simulation box, and the most commensurate size was determined by a special procedure for each grafting density. The results may be interesting not only to specialists in polymer science but also to all those who investigate the processes of self-organization and rearrangement in dense systems. [ABSTRACT FROM AUTHOR]

Impact of mixture composition on self-organization in concentrated solutions of stiff helical and flexible macromolecules was studied by means of molecular dynamics simulation. The macromolecules were composed of identical amphiphilic monomer units but a fraction f of macromolecules had stiff helical backbones and the remaining chains were flexible. In poor solvents the compacted flexible macromolecules coexist with bundles or filament clusters from few intertwined stiff helical macromolecules. The increase of relative content f of helical macromolecules leads to increase of the length of helical clusters, to alignment of clusters with each other, and then to liquid-crystalline-like ordering along a single direction. The formation of filament clusters causes segregation of helical and flexible macromolecules and the alignment of the filaments induces effective liquid-like ordering of flexible macromolecules. A visual analysis and calculation of order parameter relaying the anisotropy of diffraction allow concluding that transition from disordered to liquid-crystalline state proceeds sharply at relatively low content of stiff components. [ABSTRACT FROM AUTHOR]

We performed monomolecular observations on linear and circular giant DNAs (208 kbp) in an aqueous solution by the use of fluorescence microscopy. The results showed that the degree of conformational fluctuation in circular DNA was ca. 40% less than that in linear DNA, although the long-axis length of circular DNA was only 10% smaller than that of linear DNA. Additionally, the relaxation time of a circular chain was shorter than that of a linear chain by at least one order of magnitude. The essential features of this marked difference between linear and circular DNAs were reproduced by numerical simulations on a ribbon-like macromolecule as a coarse-grained model of a long semiflexible, double-helical DNA molecule. In addition, we calculated the radius of gyration of an interacting chain in a circular form on the basis of the mean field model, which provides a better understanding of the present experimental trend than a traditional theoretical equation. [ABSTRACT FROM AUTHOR]

By means of molecular dynamics computer simulation, the conformational space of polyampholyte macromolecules with various distributions of the charged groups along the chain is studied. A coarse‐grained model where each monomer unit of the chain is presented as a non‐charged group in the backbone of the macromolecule connected with a charged side pendant is considered. A limiting case of fully charged chains in the isoelectric point is investigated. The oppositely charged monomer units are distributed in various patterns: regular alternating, multiblock, or random sequences. It is found that the chains with random unit distribution adopt much more compacted conformations than the chains with regular distributions with comparable block lengths. Calculating the chain size and its fluctuation along with the spatial density distribution, coil, and globular conformations are distinguished and arranged on the diagrams in terms of chain length, block length, and Bjerrum length. [ABSTRACT FROM AUTHOR]

A coarse-grained model is used to study the conformational properties of semiflexible polymers with amphiphilic monomer units containing both hydrophilic and hydrophobic interaction sites. The hydrophobically driven conformational transitions are studied using molecular dynamics simulations for the chains of varying stiffness, as characterized by intrinsic Kuhn segment lengths that vary over a decade. It is shown that the energy of hydrophobic attraction required for the realization of the coil-to-globule transition increases with increasing chain stiffness. For rather stiff backbone, the coil-to-globule transition corresponds to a first order phase transition. We find that depending on the chain stiffness, a variety of thermodynamically stable anisometric chain morphologies are possible in a solvent selectively poor for hydrophobic sites of amphiphilic monomer units. For flexible chains, the amphiphilic polymer forms a cylindrical globule having blob structure with nearly spherical blobs. With increasing stiffness, the number of blobs composing the globule decreases and the shape of blobs transforms into elongated cylinder. Further increase in stiffness leads to compaction of macromolecules into a collagenlike structure when the chain folds itself several times and different strands wind round each other. In this state, the collagenlike structures coexist with toroidal globules, both conformations having approximately equal energies. [ABSTRACT FROM AUTHOR]

"Swiss-cheese" polyelectrolyte gels (i.e., gels containing a regular set of closed spherical pores) are considered as a suitable system for modeling of a medium with extremely inhomogeneous distribution of charged species. It is shown that the inhomogeneous distribution of ions in Swiss-cheese polyelectrolyte gels can he reached simply by immersion of the gels in an aqueous solution of charged species (e.g., low-molecular 1 -1 salt or multivalent ions and macroions charged likely to the gel chains). If a polymer gel is kept in such a solution for a long time, the concentration of ions within relatively big voids becomes equal to that in external solution. On the other hand, due to the Donnan effect the ion's concentration in polymer matrix is always lower than that in external solution. As a result the multivalent ions distribute between water voids and polymer matrix. The extent of this distribution is characterized by partition coefficient kD (determined as ratio kD =nsvoid/nsmat of the concentrations nsvoid and nsmat of ions in water voids and in polymer matrix, correspondingly). It is shown that the partition coefficient kD can be larger than 10 for low-molecular salt, reaches 103 for bivalent ions, and is higher than 106 for tetravalent ions. In the case of polymer macroions the partition coefficient kD tends to infinity. Our calculations show that the lower limit of characteristic scales of heterogeneity (determined by water voids size starting from which the condition of total electroneutrality is fulfilled and effect of partition is the most pronounced) can he equal to tens of nanometers. [ABSTRACT FROM AUTHOR]

Part II. Examines the conformational behavior of a two-dimensional single flexible-chain polymer dissolved in a monoatomic solvent. Contraction of the polymer chain at the solvent critical region; Use of Monte Carlo calculations in the study; Importance of polymer segment and solvent particle attraction in the induction of changes.

Part I. Examines the conformation of polymer chain in monoatomic solvent based on site-site Ornstein-Zernike integral equation in the solvent critical region. Prediction of intrachain attraction between monomeric chains; Induction of conformational changes by strong fluctuating solvent; Possibility of collapse transition in solvent point.