V. G. Rostiashvili

Driven polymer translocation through a nanopore: A manifestation of anomalous diffusion

We study the translocation dynamics of a polymer chain threaded through a nanopore by an external force. By means of diverse methods (scaling arguments, fractional calculus and Monte Carlo simulation) we show that the relevant dynamic variable, the translocated number of segments s(t), displays an anomalous diffusive behavior even in the presence of an external force. The anomalous dynamics of the translocation process is governed by the same universal exponent α=2/(2ν+2−γ1), where ν is the Flory exponent and γ1 the surface exponent, which was established recently for the case of non-driven polymer chain threading through a nanopore. A closed analytic expression for the probability distribution function W(s, t), which follows from the relevant fractional Fokker-Planck equation, is derived in terms of the polymer chain length N and the applied drag force f. It is found that the average translocation time scales as . Also the corresponding time-dependent statistical moments, and reveal unambiguously the anomalous nature of the translocation dynamics and permit direct measurement of α in experiments. These findings are tested and found to be in perfect agreement with extensive Monte Carlo (MC) simulations.

Polymer translocation through a nanopore: A showcase of anomalous diffusion

The translocation dynamics of a polymer chain through a nanopore in the absence of an external driving force is analyzed by means of scaling arguments, fractional calculus, and computer simulations. The problem at hand is mapped on a one-dimensional anomalous diffusion process in terms of the reaction coordinate s (i.e., the translocated number of segments at time t ) and shown to be governed by a universal exponent alpha=2(2nu+2-gamma(1), where nu is the Flory exponent and gamma(1) is the surface exponent. Remarkably, it turns out that the value of alpha is nearly the same in two and three dimensions. The process is described by a fractional diffusion equation which is solved exactly in the interval 0<s<N with appropriate boundary and initial conditions. The solution gives the probability distribution of translocation times as well as the variation with time of the statistical moments <s(t) and <s2(t)-<s(t)>2, which provide a full description of the diffusion process. The comparison of the analytic results with data derived from extensive Monte Carlo simulations reveals very good agreement and proves that the diffusion dynamics of unbiased translocation through a nanopore is anomalous in its nature.

Forced translocation of a polymer: Dynamical scaling versus molecular dynamics simulation

We suggest a theoretical description of the force-induced translocation dynamics of a polymer chain through a nanopore. Our consideration is based on the tensile (Pincus) blob picture of a pulled chain and the notion of a propagating front of tensile force along the chain backbone, suggested by Sakaue [Phys. Rev. E 76, 021803 (2007); Phys. Rev. E 81, 041808 (2010); Eur. Phys. J. E 34, 135 (2011)]. The driving force is associated with a chemical potential gradient that acts on each chain segment inside the pore. Depending on its strength, different regimes of polymer motion (named after the typical chain conformation: trumpet, stem-trumpet, etc.) occur. Assuming that the local driving and drag forces are equal (i.e., in a quasistatic approximation), we derive an equation of motion for the tensile front position X(t). We show that the scaling law for the average translocation time 〈τ〉 changes from ∼ N2ν/f1/ν to ∼ N^1+ν/f (for the free-draining case) as the dimensionless force f[over ̃]R=aNνf/T (where a, N, ν, f, and T are the Kuhn segment length, the chain length, the Flory exponent, the driving force, and the temperature, respectively) increases. These and other predictions are tested by molecular-dynamics simulation. Data from our computer experiment indicate indeed that the translocation scaling exponent α grows with the pulling force f[over ̃]R, albeit the observed exponent α stays systematically smaller than the theoretically predicted value. This might be associated with fluctuations that are neglected in the quasistatic approximation.

Structure and dynamics of a polymer melt at an attractive surface

AbstractWe study the structural and dynamic properties of a polymer melt in the vicinity of an adhesive solid substrate by means of Molecular Dynamics simulation at various degrees of surface adhesion. The properties of the individual polymer chains are examined as a function of the distance to the interface and found to agree favorably with theoretical predictions. Thus, the adsorbed amount at the adhesive surface is found to scale with the macromolecule length as

Polymer chain in a quenched random medium: slow dynamics and ergodicity breaking

\Gamma \propto \sqrt N

Forced-Induced Desorption of a Polymer Chain Adsorbed on an Attractive Surface: Theory and Computer Experiment

, regardless of the adsorption strength. For chains within the range of adsorption we analyze in detail the probability size distributions of the various building blocks: loops, tails and trains, and find that loops and tails sizes follow power laws while train lengths decay exponentially thus confirming some recent theoretical results. The chain dynamics as well as the monomer mobility are also investigated and found to depend significantly on the proximity of a given layer to the solid adhesive surface with onset of vitrification for sufficiently strong adsorption.

Thermal breakage and self-healing of a polymer chain under tensile stress

We suggest a governing equation that describes the process of polymer-chain translocation through a narrow pore and reconciles the seemingly contradictory features of such dynamics: (i) a Gaussian probability distribution of the translocated number of polymer segments at time t after the process has begun, and (ii) a subdiffusive increase of the distribution variance Δ(t) with elapsed time Δ(t)∝t(α). The latter quantity measures the mean-squared number s of polymer segments that have passed through the pore Δ(t)=([s(t)-s(t=0)](2)), and is known to grow with an anomalous diffusion exponent α<1. Our main assumption [i.e., a Gaussian distribution of the translocation velocity v(t)] and some important theoretical results, derived recently, are shown to be supported by extensive Brownian dynamics simulation, which we performed in 3D. We also numerically confirm the predictions made recently that the exponent α changes from 0.91 to 0.55 to 0.91 for short-, intermediate-, and long-time regimes, respectively.

Localization of a multiblock copolymer at a selective interface: Scaling predictions and Monte Carlo verification

Abstract:The Langevin dynamics of a self-interacting chain embedded in a quenched random medium is investigated by making use of the generating functional method and one-loop (Hartree) approximation. We have shown how this intrinsic disorder causes different dynamical regimes. Namely, within the Rouse characteristic time interval the anomalous diffusion shows up. The corresponding subdiffusional dynamical exponents have been explicitly calculated and thoroughly discussed. For the larger time interval the disorder drives the center of mass of the chain to a trap or frozen state provided that the Harris parameter, (Δ/bd)N2 - νd≥1, where Δ is a disorder strength, b is a Kuhnian segment length, N is a chain length and ν is the Flory exponent. We have derived the general equation for the non-ergodicity function f (p) which characterizes the amplitude of frozen Rouse modes with an index p = 2πj/N. The numerical solution of this equation has been implemented and shown that the different Rouse modes freeze up at the same critical disorder strength Δc ∼ N- γ where the exponent γ ≈ 0.25 and does not depend from the solvent quality.