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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]

In the present work, by means of computer simulation, we studied the adsorption and diffusion of polyelectrolyte macromolecules on oppositely charged surfaces. We considered the surface coverage and the charge of the adsorbed layer depending on the ionization degree of the macromolecules and the charge of the surface and carried out a computer experiment on the polymer diffusion within the adsorbed layers, taking into account its strong dependency on the surface coverage and the macromolecular ionization degree. The different regimes were distinguished that provided maximal mobility of the polymer chains along with a high number of charged groups in the layer, which could be beneficial for the development of the functional coatings. The results were compared with those of previous experiments on the adsorption of polyelectrolyte layers that may be applied as biocidal renewable coatings that can reversibly desorb from the surface. [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]

A single spherical nanoparticle coated with a densely grafted layer of an amphiphilic homopolymer with identical A-graft-B monomer units was studied by means of coarse-grained molecular dynamics. In solvent, selectively poor for mainchain and good for pendant groups; the grafted macromolecules self-assemble into different structures to form a complex pattern on the nanoparticle surface. We distinguish hedgehog, multipetalar, chamomile, and densely structured shells and outline the area of their stability using visual analysis and calculate aggregation numbers and specially introduced order parameters, including the branching coefficient and relative orientation of monomer units. For the first time, the branching effect of splitting aggregates along with the distance to the grafting surface and preferred orientation of the monomer units with rearrangements of the dense compacted shell was described. The results explain the experimental data, are consistent with the analytical theory, and are the basis for the design of stimulus-sensitive matrix-free composite materials. [ABSTRACT FROM AUTHOR]

An analytical theory describing the variety of different morphological structures that spontaneously self-assemble in layers of amphiphilic homopolymers tightly grafted to spherical nanoparticle is proposed. For this purpose, the following structures were identified and outlined: hedgehogs, in which macromolecules are combined into cylindrical aggregates; chamomile, when cylindrical aggregates are connected by their ends into loops; multipetal structure with macromolecules self-assembling into thin lamellae; and unstructured, swollen and uniformly compacted shells. The results are presented in the form of state diagrams and serve as a basis for the directional design of the surface pattern by varying system parameters (particle radius, grafting density and degree of polymerization) and solvent properties (quality and selectivity). [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]

Amphiphilic monomer units contain both hydrophobic and hydrophilic groups. They are characterized by affinity and antagonism simultaneously to both polar and nonpolar solvents, tend to settle themselves at solvent interfaces rather than in the bulk of the solvent and, thus, possess effective surface activity. For this reason, in selective solvents the macromolecules with amphiphilic monomer units self-assemble to complex morphologies with enlarged surface which could be similar to those formed by low-molecular surfactants, lipids and amphiphilic diblock-copolymers. In literature, macromolecules with amphiphilic monomer units are also referred to as polymer amphiphiles. When they consist of identical amphiphilic monomer units, they are called amphiphilic homopolymers. The article aims to review the macromolecular self-assembly driven by amphiphilicity of monomer units containing both solvophobic and solvophilic (hydrophobic and hydrophilic) groups. The particular attention is paid to the situation when such macromolecules assemble into the hollow and vesicle-like particles being especially prospective for different applications. We present the current state of experimental, computational and analytical research in this field and reveal the conditions favoring the formation of vesicles with thin (mono-, bi- or multilayer) membranes. [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.

By means of computer simulation, we have investigated self-organization of a single macromolecule being amphiphilic on the level of an individual monomer unit. It was demonstrated first, that in selective solvent such macromolecules are able to form spontaneously spherical vesicle-like globules having empty cavity in their center and dense shell on their surface. [ABSTRACT FROM AUTHOR]

The influence of the cross-linking agent concentration on the macroscopic properties of hypercrosslinked polystyrene networks was studied by means of computer experiment. The computer experiment includes the consecutive stages molecular dynamics atomistic simulation of a polystyrene solution, the mapping of atomistic structure onto coarse-grained model, the crosslink formation, the reverse mapping, the determination of properties of samples (elastic modulus and specific surface). The measurements of elastic modulus and specific surface were performed in frameworks of coarse-grained and atomistic presentation. It was shown that for both models the elastic modulus increases while the specific surface decreases with increase of the number of crosslinks. Both models give very close values for specific surface whereas the elastic moduli determined from atomistic simulations could be an order of magnitude greater than the values calculated using the coarse-grained representation of the same sample. The calculated values of the elastic modulus and specific surface are in reasonable quantitative correspondence with experimental data. [ABSTRACT FROM AUTHOR]

Monte Carlo simulations are employed in order to analyze the structure of polyelectrolyte complexes consisting of two identical but oppositely charged macroions with varying chain stiffness. It is shown that two complex structures can arise depending on the stiffness of the constituent chains. Stiff chains are organized into a 'ladder' structure in which chains are located parallel to each other and monomeric units are arranged into ionic pairs according to their position in the chain. Flexible chains form a globular 'scrambled-egg' structure with a disordered position of monomer units. The conformational transition between the two structures proceeds as a phase transition. [ABSTRACT FROM AUTHOR]

The paper aims to study the mechanical properties of epoxy resin filled with clay nanoparticles (NPs), depending on their shapes and content on the surface of a modifying agent capable of forming covalent bonds with a polymer. The cylindrical clay nanoparticles with equal volume and different aspects ratios (disks, barrel, and stick) are addressed. The NPs' bonding ratio with the polymer (RGC) is determined by the fraction of reactive groups and conversion time and varies from RGC = 0 (non-bonded nanoparticles) to RGC = 0.65 (more than half of the surface groups are linked with the polymer matrix). The performed simulations show the so-called load-bearing chains (LBCs) of chemically cross-linked monomers and modified nanoparticles to determine the mechanical properties of the simulated composites. The introduction of nanoparticles leads to the breaking of such chains, and the chemical cross-linking of NPs with the polymer matrix restores the LBCs and strengthens the composite. At small values of RGC, the largest value of the elastic modulus is found for systems filled with nanoparticles having the smallest surface area, and at high values of RGC, on the contrary, the systems containing disk-shaped particles with the largest surface area have a larger elastic modulus than the others. All calculations are performed within the framework of a mesoscopic model based on accurate mapping of the atomistic structures of the polymer matrix and nanoparticles into coarse-grained representations, which, if necessary, allow reverse data mapping and quantitative assessment of the state of the filled epoxy resin. On the other hand, the obtained data can be used to design the functional materials with specified mechanical properties based on other practically significant polymer matrices and nanofillers. [ABSTRACT FROM AUTHOR]

The composition, structure and localization of neutral glycosphingolipids of human aorta taken from subjects who had died after myocardial infarction were studied. Individual glycosphingolipids were purified by high-performance liquid chromatography and were characterized on the basis of their chromatographic mobility, carbohydrate composition, methylation analysis and by 1H-NMR spectroscopy. The main aortic glycosphingolipids were identified as glucosylceramide, lactosylceramide, globotriaosylceramide and globotetraosylceramide. Significant differences in the neutral glycosphingolipid composition of intima and media were detected. The neutral glycosphingolipid profile of medial plaques resembled that of unaffected media; however, significant differences were detected between intimal plaques and unaffected intima. Whereas the latter contained trihexosylceramide and globoside as the only neutral glycolipids, the intimal plaque glycolipids consisted mainly of glucosylceramide and also contained appreciable amounts of lactosylceramide which were completely absent in the unaffected intima. In comparison to intimal plaques, unaffected intima is characterized by a much higher content of cerebrosides terminating by β-galactosyl residues which are known to interact with growth factors and other external stimuli. It thus seems possible that the proliferative activity of smooth muscle cells in atherosclerotic diseases is to some extent associated with their neutral glycolipid profile. [ABSTRACT FROM AUTHOR]

By means of computer modeling, the self-organization of densely grafted macromolecules with amphiphilic monomer units as a function of macromolecular polymerization degree and solvent quality was studied and a diagram of state was constructed. The diagram contains fields of disordered distribution of monomer units and of prolonged aggregates, regions of lamellae with small and big domain spacing, and transition region. Within the transition region, the lamellae with different spacing coexist: the lamellae with big domain spacing are on the top of the grafting layer and the lamellae with small domain spacing are close to the grafting surface. The lamellae are connected with each other and form bicontinuous parking garage structure joining all side groups into a single cluster. The domain spacing of lamellae does not depend on the macromolecular length, but the width of the transition region decreases with the decrease of polymerization degree until total vanishing at relatively short macromolecules. The sharp switch between lamellae and bicontinuous structure opens the perspective for practical applications of densely grafted layers with amphiphilic monomer units., Competing Interests: The authors declare no competing financial interest.

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.