We report on a computational study of the statics and dynamics of long flexible linear polymers that spontaneously knot and unknot. Specifically, the equilibrium self-entanglement properties, such as the knotting probability, knot length and position, are investigated with extensive Monte Carlo sampling of chains of up to 15,000 beads. Tens of such equilibrated chains of up to 4, 096 beads are next used as starting points for Langevin dynamics simulations. The complex interplay of chain dynamics and self-knotting is addressed by monitoring the time evolution of various metric and entanglement properties. In particular, the extensive duration of the simulations allows for observing the spontaneous formation and disappearance of prime and composite physical knots in linear chains. Notably, a sizeable fraction of self-knotting and unknotting events is found to involve regions that are far away from the chain termini. To the best of our knowledge this represents the first instance where spontaneous changes in knotting for linear homopolymers are systematically characterized using unbiased dynamics simulations.

The advent of solid state nanodevices allows for interrogating the physicochemical properties of a polyelectrolyte chain by electrophoretically driving it through a nanopore. Salient dynamical aspects of the translocation process have been recently characterized by theoretical and computational studies of model polymer chains free from self-entanglement. However, sufficiently long equilibrated chains are necessarily knotted. The impact of such topological "defects" on the translocation process is largely unexplored, and is addressed in this Letter. By using Brownian dynamics simulations on a coarse-grained polyelectrolyte model we show that knots, despite being trapped at the pore entrance, do not per se cause the translocation process to jam. Rather, knots introduce an effective friction that increases with the applied force, and practically halts the translocation above a threshold force. The predicted dynamical crossover, which is experimentally verifiable, ought to be relevant in applicative contexts, such as DNA nanopore sequencing.

Thermal conformations of semiflexible macromolecules are generically described by the worm-like chain model. The end-to-end distance distribution, a fundamental quantity of the model, is not yet known in closed form. We provide a solution to the practical problem of choosing an appropriate approximation. First, a comprehensive review of existing approximations and exact limiting results is given. We then propose an explicit expression which interpolates between all relevant limiting cases. We show that it accurately reproduces, at no computational cost, high-precision Monte Carlo data, covering a wide range from stiff to flexible chains and from looped to fully stretched configurations. Using this result we quantify the enhancement of short worm-like loop formation by (protein) bridges.

Inspired by experiments that use single-particle tracking to measure the regions of confinement of selected chromosomal regions within cell nuclei, we have developed an analytical approach that takes into account various possible positions and shapes of the confinement regions. We show, in particular, that confinement of a particle into a subregion that is entirely enclosed within a spherical volume can lead to a higher limit of the mean radial square displacement value than the one associated with a particle that can explore the entire spherical volume. Finally, we apply the theory to analyse the motion of extrachromosomal chromatin rings within nuclei of living yeast.

We present results from three-dimensional off-lattice Monte Carlo simulations to investigate the stretching response of a semi-flexible polymer subjected to self-attractive interactions. We employ the quasi-static approximation and consider both the fixed elongation and the fixed force ensemble, which can equally well be reproduced in experiments nowadays. The force vs. elongation curves are in general non-monotonic, and the quantity and height of peaks increase with decreasing temperature, and with increasing stiffness. We finally compute the variation of unfolding force with temperature. Our results should be relevant for stretching experimental studies, and for more refined theoretical modeling, taking non-equilibrium and kinetic effects into account.

We simulate the extension of spatially confined chromatin fibres modelled as polymer chains and examine the effect of the flexibility of the fibre and its degree of freedom. The developed formalism was used to analyse experimental data of telomere–telomere distances in living yeast cells in the absence of confining factors as identified by the proteins Sir4 and yKu70. Our analysis indicates that intrinsic properties of the chromatin fibre, in particular its elastic properties and flexibility, can influence the juxtaposition of the telomeric ends of chromosomes. However, measurements in intact yeast cells showed that the telomeres of chromosomes 3 and 6 come even closer together than the parameters of constraint imposed on the simulations would predict. This juxtaposition was specific to telomeres on one contiguous chromosome and overrode a tendency for separation that is imposed by anchoring.

A new formula for the force vs. extension relation is derived from the discrete version of the so-called Worm-like chain model. This formula correctly fits some recent experimental data on polymer stretching. Moreover, we have compared our formula with a Monte Carlo simulation of a semiflexible polymer.

We study the response to perturbation of non-Poisson dichotomous fluctuations that generate super-diffusion. We adopt the Liouville perspective and with it a quantum-like approach based on splitting the density distribution into a symmetric and an anti-symmetric component. To accomodate the equilibrium condition behind the stationary correlation function, we study the time evolution of the anti-symmetric component, while keeping the symmetric component at equilibrium. For any realistic form of the perturbed distribution density we expect a breakdown of the Onsager principle, namely, of the property that the subsequent regression of the perturbation to equilibrium is identical to the corresponding equilibrium correlation function. We find the directions to follow for the calculation of higher-order correlation functions, an unsettled problem, which has been addressed in the past by means of approximations yielding quite different physical effects.

The scaling of the average gyration radius of polymers as a function of their length can be experimentally determined from ensemble measurements, such as light scattering, and agrees with analytical estimates. Ensemble techniques, yet, do not give access to the full probability distributions. Single molecule techniques, instead, can deliver information on both average quantities and distribution functions. Here we exploit the high resolution of atomic force microscopy over long DNA molecules adsorbed on a surface to measure the average end-to-end distance as a function of the DNA length, and its full distribution function. We find that all the scaling exponents are close to the predicted 3D values (upsilon=0.589+/-0.006 and delta=2.58+/-0.77). These results suggest that the adsorption process is akin to a geometric projection from 3D to 2D, known to preserve the scaling properties of fractal objects of dimension df<2.

Motivated by recent experimental data on DNA stretching in presence of polyvalent counterions, we study the force-induced unfolding of a homopolymer on and off lattice. In the fixed force ensemble the globule unravels via a series of steps due to surface effects which play an important role for finite-size chains. This holds both for flexible and stiff polymers. We discuss in a qualitative way how this result may impact on the interpretation of DNA stretching experiments showing peaks in the characteristic curves, by extracting from the raw data the corresponding elongation-versus-force characteristic curves. Furthermore, approximate analytical and numerical calculations, valid in a quasi-equilibrium fixed stretch ensemble, and if the initial low-temperature state is ordered in a spool, show that the average force versus elongation displays peaks related to the geometry of the initial configuration. We finally argue how the proposed mechanisms identified for the arising of peaks may couple in the experiments, and comment on the role of dynamic effects.

We study the thermodynamics of an exactly solvable model of a self-interacting, partially directed self-avoiding walk in two dimensions when a force is applied on one end of the chain. The critical force for the unfolding is determined exactly, as a function of the temperature, below the Theta transition. The transition is of second order and is characterized by new critical exponents that are determined by a careful numerical analysis. The usual polymer critical index nu on the critical line, and another one which we call zeta, takes a nontrivial value that is numerically close to 2/3.

A new formula for the force vs extension relation is derived from the discrete version of the so called worm like chain model. This formula correctly fits some recent experimental data on polymer stretching and some numerical simulations with pairwise repulsive potentials. For a more realistic Lennard-Jones potential the agreement with simulations is found to be good when the temperature is above the θ temperature. For lower temperatures a plateau emerges, as predicted by some recent experimental and theoretical results, and our formula gives good results only in the high force regime. We briefly discuss how other kinds of self-interactions are expected to affect the elasticity of the polymer.

We discuss the problem of the equivalence between Continuous Time Random Walk (CTRW) and Generalized Master Equation (GME). The walker, making instantaneous jumps from one site of the lattice to another, resides in each site for extended times. The sojourn times have a distribution psi(t) that is assumed to be an inverse power law. We assume that the Onsager principle is fulfilled, and we use this assumption to establish a complete equivalence between GME and the Montroll-Weiss CTRW. We prove that this equivalence is confined to the case when psi(t) is an exponential. We argue that is so because the Montroll-Weiss CTRW, as recently proved by Barkai [E. Barkai, Phys. Rev. Lett. 90, 104101 (2003)], is non-stationary, thereby implying aging, while the Onsager principle, is valid only in the case of fully aged systems. We consider the case of a dichotomous fluctuation, and we prove that the Onsager principle is fulfilled for any form of regression to equilibrium provided that the stationary condition holds true. We set the stationary condition on both the CTRW and the GME, thereby creating a condition of total equivalence, regardless the nature of the waiting time distribution. As a consequence of this procedure we create a GME that it is a"bona fide"master equation, in spite of being non-Markovian. We note that the memory kernel of the GME affords information on the interaction between system of interest and its bath. The Poisson case yields a bath with infinitely fast fluctuations. We argue that departing from the Poisson form has the effect of creating a condition of infinite memory and that these results might be useful to shed light into the problem of how to unravel non-Markovian master equations.

We consider a toy model of pointer interacting with a 1/2-spin system, whose σx variable is measured by the environment, according to the prescription of decoherence theory. If the environment measuring the variable σx yields ordinary statistical mechanics, the pointer sensitive to the 1/2-spin system undergoes the same, exponential, decoherence regardless of whether real collapses or an entanglement with the environment, mimicking the effect of real collapses, occur. In the case of non-ordinary statistical mechanics the occurrence of real collapses make the pointer still relax exponentially in time, while the equivalent picture in terms of reduced density matrix generates an inverse power law decoherence.

We show that the widely accepted conviction that a connection can be established between the probability density entropy and the Kolmogorov-Sinai (KS) entropy is questionable. We adopt the definition of density entropy as a functional of a distribution density whose time evolution is determined by a transport equation, conceived as the only prescription to use for the calculation. Although the transport equation is built up for the purpose of affording a picture equivalent to that stemming from trajectory dynamics, no direct use of trajectory time evolution is allowed, once the transport equation is defined. With this definition in mind we prove that the detection of a time regime of increase of the density entropy with a rate identical to the KS entropy is possible only in a limited number of cases. The proposals made by some authors to establish a connection between the two entropies in general, violate our definition of density entropy and imply the concept of trajectory, which is foreign to that of density entropy.

We address the study of sporadic randomness by means of the Manneville map. We point out that the Manneville map is the generator of fluctuations yielding the Lévy processes, and that these processes are currently regarded by some authors as statistical manifestations of a nonextensive form of thermodynamics. For this reason we study the sensitivity to initial conditions with the help of a nonextensive form of the Lyapunov coefficient. The purpose of this research is twofold. The former is to assess whether a finite diffusion coefficient might emerge from the nonextensive approach. This property, at first sight, seems to be plausible in the nonstationary case, where conventional Kolmogorov-Sinai analysis predicts a vanishing Lyapunov coefficient. The latter purpose is to confirm or reject conjectures about the nonextensive nature of Lévy processes. We find that the adoption of a nonextensive approach does not serve any predictive purpose: It does not even signal a transition from a stationary to a nonstationary regime. These conclusions are reached by means of both numerical and analytical calculations that shed light on why the Lévy processes do not imply any need to depart from the adoption of traditional complexity measures.