Biomedical subjects

A Milchev

Publications and source records attributed to A Milchev.

At least 19 recordsLinked to original sources

PubMed2006

Polymer brushes in cylindrical pores: simulation versus scaling theory.

The structure of flexible polymers endgrafted in cylindrical pores of diameter D is studied as a function of chain length N and grafting density sigma, assuming good solvent conditions. A phenomenological scaling theory, describing the variation of the linear dimensions of the chains with sigma, is developed and tested by molecular dynamics simulations of a bead-spring model. Different regimes are identified, depending on the ratio of D to the size of a free polymer N(3/5). For D>N(3/5) a crossover occurs for sigma=sigma*=N(-6/5) from the "mushroom" behavior (R(gx)=R(gy)=R(gz)=N(35)) to the behavior of a flat brush (R(gz)=sigma(1/3)N,R(gx)=R(gy)=sigma(-1/12)N(1/2)), until at sigma**=(D/N)3 a crossover to a compressed state of the brush, [R(gz)=D,R(gx)=R(gy)=(N(3)D/4sigma)(1/8)<D], occurs. Here coordinates are chosen so that the y axis is parallel to the tube axis, and the z direction normal to the wall of the pore at the grafting site. For D<N(3/5), the coil structure in the dilute regime is a cigar of length R(gy)=ND(-2/3) along the tube axis. At sigma*=(ND(1/3))(-1) the structure crosses over to "compressed cigars," of size R(gy)=(sigmaD)(-1). While for ultrathin cylinders (D<N(1/4)) this regime extends up to the regime where the pore is filled densely (sigma=D/N), for N(1/4)<D<N(1/2) a further crossover occurs at sigma***=D(-9/7)N(-3/7) to a semidilute regime where R(gy)=(N(3)D/4sigma)(1/8) still exceeds D. For moderately wide tubes (N(1/2)<D<N(3/5)) a further crossover occurs at sigma****=N(3)D(-7), where all chain linear dimensions are equal, to the regime of compressed brush. These predictions are compared to the computer simulations. From the latter, extensive results on monomer density and free chain end distributions are also obtained, and a discussion of pertinent theories is given. In particular, it is shown that for large D the brush height is an increasing function of D(-1).

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PubMed2006

Polymer chains in a soft nanotube: a Monte Carlo study.

We study the equilibrium properties of flexible polymer chains confined in a soft tube by means of extensive Monte Carlo simulations. The tube wall is that of a single sheet six-coordinated self-avoiding tethered membrane. Our study assumes that there is no adsorption of the chain on the wall. By varying the length N of the polymer and the tube diameter D we examine the variation of the polymer gyration radius Rg and diffusion coefficient Ddiff in soft and rigid tubes of identical diameter and compare them to scaling theory predictions. We find that the swollen region of the soft tube surrounding the chain exhibits a cigarlike cylindrical shape for sufficiently narrow tubes with D<<Rg. The observed scaling of static conformational properties with chain length N and tube diameter D follows the predictions of scaling theory and displays no significant difference between soft and rigid tubes. The Brownian dynamics of the polymer diffusion in a rigid tube is found to slow down in a tube with soft walls by an amount which depends on the Rg/D ratio albeit the relaxation time tau(parallel) for diffusive motion along the tube still scales as tau(parallel) proportional, N3.

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PubMed2005

Phase transitions in nanosystems caused by interface motion: the Ising bipyramid with competing surface fields.

The phase behavior of a large but finite Ising ferromagnet in the presence of competing surface magnetic fields +/-H(s) is studied by Monte Carlo simulations and by phenomenological theory. Specifically, the geometry of a double pyramid of height 2L is considered, such that the surface field is positive on the four upper triangular surfaces of the bipyramid and negative on the lower ones. It is shown that the total spontaneous magnetization vanishes (for L --> infinity) at the temperature Tf(H), related to the "filling transition" of a semi-infinite pyramid, which can be well below the critical temperature of the bulk. The discontinuous vanishing of the magnetization is accompanied by a susceptibility that diverges with a Curie-Weiss power law, when the transition is approached from either side. A Landau theory with size-dependent critical amplitudes is proposed to explain these observations, and confirmed by finite size scaling analysis of the simulation results. The extension of these results to other nanosystems (gas-liquid systems, binary mixtures, etc.) is briefly discussed.

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PubMed2003

Interface localization-delocalization in a double wedge: a new universality class with strong fluctuations and anisotropic scaling.

Using Monte Carlo simulations and finite-size scaling methods we study "wetting" in Ising systems in a LxLxL(y) pore with quadratic cross section. Antisymmetric surface fields H(s) act on the free LxL(y) surfaces of the opposing wedges, and periodic boundary conditions are applied along the y direction. In the limit L--> infinity, L(y)/L(3)=const, the system exhibits a new type of phase transition, which is the analog of the "filling transition" that occurs in a single wedge. It is characterized by critical exponents alpha=3/4, beta=0, and gamma=5/4 for the specific heat, order parameter, and susceptibility, respectively.

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PubMed2002

The electrostatic persistence length of polymers beyond the OSF limit.

We use large-scale Monte Carlo simulations to test scaling theories for the electrostatic persistence length l(e) of isolated, uniformly charged polymers with Debye-Hückel intrachain interactions in the limit where the screening length kappa(-1) exceeds the intrinsic persistence length of the chains. Our simulations cover a significantly larger part of the parameter space than previous studies. We observe no significant deviations from the prediction l(e) proportional to kappa(-2) by Khokhlov and Khachaturian which is based on applying the Odijk-Skolnick-Fixman theories of electrostatic bending rigidity and electrostatically excluded volume to the stretched de Gennes-Pincus-Velasco-Brochard polyelectrolyte blob chain. A linear or sublinear dependence of the persistence length on the screening length can be ruled out. We show that previous results pointing into this direction are due to a combination of excluded-volume and finite chain length effects. The paper emphasizes the role of scaling arguments in the development of useful representations for experimental and simulation data.

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PubMed2002

Polymer depletion interaction between parallel walls--a Monte Carlo study.

An off-lattice bead-spring model of self-assembling equilibrium ("living") polymers is used to study the polymer-induced interaction between parallel walls immersed in polydisperse solutions of different concentration by means of Monte Carlo simulation. The two walls form an open slit in contact with an external reservoir so that the confined system may exchange monomers with the surrounding phase and adapt its polydispersity in order to relax the confinement constraint. We find that the properties of the polymers in the constrained system as well as the net force deltaF acting on the walls depend essentially on the polymer concentration in the reservoir which leads to qualitative differences in their behavior with changing inter-planar distance H: In a dilute polymer solution at concentration phi below the semi-dilute threshold phi* the force between the walls is attractive and decreases steadily with growing wall separation H, so that deltaF approximately 0 at H/ Rg> or =3 if H is measured in gyration radii Rg of the unperturbed polymers. The total monomer concentration within the slit is smaller than the concentration in the reservoir and decreases monotonically with H/Rg-->0. The ratio Nin/Nout of mean chain length Nin in the slit to that in the reservoir, Nout, decreases from unity at H-->infinity, goes through a minimum at H/Rg approximately 1, and then rises again to Nin/Nout>1 for wall separations H/Rg<1. In contrast, in a dense solution of equilibrium polymers at phi>phi* one detects no indirect wall-wall interaction, deltaF approximately 0, for H larger than the monomer size. Thus, earlier speculations about the existence of possible depletion interaction between parallel walls even in a dense polymer system cannot be confirmed. Inside the slit the monomer density is found to be always larger than in the reservoir while Nin/Nout<1 and decreases steadily as H/Rg-->0. The depletion force between parallel plates has been determined also in a monodisperse solution of conventional polymers. Qualitatively the force behavior does not differ from that of living polymers.

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PubMed2000

Conformations of random polyampholytes

We study the size R(g) of random polyampholytes (i.e., polymers with randomly charged monomers) as a function of their length N. All results of our extensive Monte Carlo simulations can be rationalized in terms of the scaling theory we develop for the Kantor-Kardar necklace model, although this theory neglects the quenched disorder in the charge sequence along the chain. We find approximately N1/2. The elongated globule model, the initial predictions of both Higgs and Joanny ( approximately N1/3) and Kantor and Kardar ( approximately N), and previous numerical estimates are ruled out.

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PubMed1995