Generic interactions e.g. the Coulomb or other long ranged radially symmetric repulsive interactions between monomers of bead-spring model of a semi-flexible polymer induce instabilities in a initially straight polymer chain to form long lived helical structures. This mechanism can explain the spontaneous emergence of helices in stiff (bio-)polymers as effective charge of the chain increases. The helix formation is independent of the chemistry and torsional potentials are not used. So this method can be used to synthesize helical springs at length scales of nm-10$μ$.
The conformations of semiflexible (bio)polymers are studied in flow through geometrically structured microchannels. Using mesoscale hydrodynamics simulations, we show that the polymer undergoes a rod-to-helix transition as it moves from the narrow high-velocity region into the wide low-velocity region of the channel. The transient helix formation is the result of a non-equilibrium and non-stationary buckling transition of the semiflexible polymer, which is subjected to a compressive force originating from the fluid-velocity variation in the channel. The helix properties depend on the diameter …
Employing Monte Carlo simulations of semiflexible polymer rings in weak spherical confinement a conformational transition to figure eight shaped, writhed configurations is discovered and quantified.
We study the conformations of a semiflexible chain, confined in nano-scaled spherical cavities, under two distinct processes of confinement. Radial contraction and packaging are employed as two confining procedures. The former method is performed by gradually decreasing the diameter of a spherical shell which envelopes a confined chain. The latter procedure is carried out by injecting the chain inside a spherical shell through a hole on the shell surface. The chain is modeled with a rigid body molecular dynamics simulation and its parameters are adjusted to DNA base-pair elasticity. Directiona…
An analytic expression is derived for the distribution $G(\vec{R})$ of the end-to-end distance $\vec{R}$ of semiflexible polymers in external potentials to elucidate the effect of confinement on the mechanical and statistical properties of biomolecules. For parabolic confinement the result is exact whereas for realistic potentials a self-consistent ansatz is developed, so that $G(\vec{R})$ is given explicitly even for hard wall confinement. The theoretical result is in excellent quantitative agreement with fluorescence microscopy data for actin filaments confined in rectangularly shaped microc…
The nematic ordering in semiflexible polymers with contour length $L$ exceeding their persistence length $\ell_p$ is described by a confinement of the polymers in a cylinder of radius $r_{eff}$ much larger than the radius $r_ρ$, expected from the respective concentration of the solution. Large scale Molecular Dynamics simulations combined with Density Functional Theory are used to locate the Isotropic-Nematic ($I-N$)-transition and to validate this cylindrical confinement. Anomalous fluctuations, due to chain deflections from neighboring chains in the nematic phase are proposed. Considering de…
The effect of a finite torque on semiflexible polymers in a confined environment is investigated. It is shown how a new lengthscale appears in the strongly confined limit. The influence of a torque on the extension of biopolymers in nanochannels is also touched upon and it is argued that the presence of a torque has a strong influence on the dimensions of nanochannels needed to prevent hairpins.
Spherical confinement can act either stabilizing or destabilizing on the collapsed state of a semi-flexible polymer. General free-energy arguments suggest that the order of the unconstrained collapse transition is the distinguishing factor: First order implies stabilization, second order causes destabilization. We confirm this conjecture by Monte Carlo simulations of a coarse-grained model for semiflexible polymers whose chain stiffness tunes the transition order. The resulting physical picture is potentially relevant for other systems under strong confinement such as proteins and DNA.
The helix is a ubiquitous motif for biopolymers. We propose a heuristic, entropically based model that predicts helix formation in a system of hard spheres and semiflexible tubes. We find that the entropy of the spheres is maximized when short stretches of the tube form a helix with a geometry close to that found in natural helices. Our model could be directly tested with wormlike micelles as the tubes, and the effect could be used to self-assemble supramolecular helices.
We analyse the nature of the confinement of an infinitely long (and finite) linear semiflexible homo-polymer chain confined in between two geometrical constraints (A&B) under good solvent condition in two dimensions. The constraints are stair shaped impenetrable lines. A lattice model of fully directed self avoiding walk is used to list information of walks of the confined chain and the exact enumeration technique is used for the canonical ensemble of conformations of the confined chain to discuss equilibrium statistics of the chain. We obtain the probability of polymerization of the confined …
We analyze static properties of a strongly confined semiflexible polymer, i.e. either trapped in a closed space or compressed by external forces, in an athermal solvent. Like a flexible polymer case, we can resort to an analogy with the semidilute solution, but a complication due to the additional length scale arising from the chain rigidity results in more diverse behaviours depending on system parameters. For each regime, scaling forms of the excess free energy of the confinement are derived. Effects of the confinement geometry and the solvent quality are briefly discussed.
By means of extensive replica-exchange simulations of generic coarse-grained models for helical polymers, we systematically investigate the structural transitions into all possible helical phases for flexible and semiflexible elastic polymers with self-interaction under the influence of torsion barriers. The competing interactions lead to a variety of conformational phases including disordered helical arrangements, single helices, and ordered, tertiary helix bundles. Most remarkably, we find that a bending restraint entails a clear separation and stabilization of the helical phases. This aids …
The properties of semiflexible polymers tethered by one end to an impenetrable wall and exposed to oscillatory shear flow are investigated by mesoscale simulations. A polymer, confined in two dimensions, is described by a linear bead-spring chain, and fluid interactions are incorporated by the Brownian multiparticle collision dynamics approach. At small strains, the polymers follow the applied flow field. However, at high strain, we find a strongly nonlinear response, with major conformational changes. Polymers are stretched along the flow direction and exhibit U-shaped conformations while fol…
The tube model is a central concept in polymer physics, and allows to reduce the complex many-filament problem of an entangled polymer solution to a single filament description. We investigate the probability distribution function of conformations of confinement tubes and single encaged filaments in entangled semiflexible polymer solution. Computer simulations are developed that mimic the actual dynamics of confined polymers in disordered systems with topological constraints on time scales above local equilibration but well below large scale rearrangement of the network. We observe the statist…
We consider a long, semiflexible polymer, with persistence length $P$ and contour length $L$, fluctuating in a narrow cylindrical channel of diameter $D$. In the regime $D\ll P\ll L$ the free energy of confinement $ΔF$ and the length of the channel $R_\parallel$ occupied by the polymer are given by Odijk's relations $ΔF/R_\parallel=A_\circ k_BTP^{-1/3}D^{-2/3}$ and $R_\parallel=L[1-α_\circ(D/P)^{2/3}]$, where $A_\circ$ and $α_\circ$ are dimensionless amplitudes. Using a simulation algorithm inspired by PERM (Pruned Enriched Rosenbluth Method), which yields results for very long polymers, we de…
We discuss the adsorption of semiflexible polymers to a planar attractive wall and focus on the questions of the adsorption threshold for polymers of {\it finite} length and their loop and tail distributions using both Monte-Carlo simulations and analytical arguments. For the adsorption threshold, we find three regimes: (i) a flexible or Gaussian regime if the persistence length is smaller than the adsorption potential range, (ii) a semiflexible regime if the persistence length is larger than the potential range, and (iii) for finite polymers, a novel crossover to a rigid rod regime if the def…
Monte Carlo simulations are used to study the conformational properties of a folded semiflexible polymer confined to a long channel. We measure the variation in the conformational free energy with respect to the end-to-end distance of the polymer, and from these functions we extract the free energy of the hairpin fold, as well as the entropic force arising from interactions between the portions of the polymer that overlap along the channel. We consider the scaling of the free energies with respect to varying the persistence length of the polymer, as well as the channel dimensions for confineme…
The constraints imposed by nano- and microscale confinement on the conformational degrees of freedom of thermally fluctuating biopolymers are utilized in contemporary nano-devices to specifically elongate and manipulate single chains. A thorough theoretical understanding and quantification of the statistical conformations of confined polymer chains is thus a central concern in polymer physics. We present an analytical calculation of the radial distribution function of harmonically confined semiflexible polymers in the weakly bending limit. Special emphasis has been put on a proper treatment of…
A variational framework is developed to examine the equilibrium states of a semi-flexible polymer that is constrained to lie on a fixed surface. As an application the confinement of a closed polymer loop of fixed length $2πR$ within a spherical cavity of smaller radius, $R_0$, is considered. It is shown that an infinite number of distinct periodic completely attached equilibrium states exist, labeled by two integers: $n=2,3,4,...$ and $p=1,2,3,...$, the number of periods of the polar and azimuthal angles respectively. Small loops oscillate about a geodesic circle: $n=2$, $p=1$ is the stable gr…
The longitudinal response of single semiflexible polymers to sudden changes in externally applied forces is known to be controlled by the propagation and relaxation of backbone tension. Under many experimental circumstances, realized, e.g., in nano-fluidic devices or in polymeric networks or solutions, these polymers are effectively confined in a channel- or tube-like geometry. By means of heuristic scaling laws and rigorous analytical theory, we analyze the tension dynamics of confined semiflexible polymers for various generic experimental setups. It turns out that in contrast to the well-kno…
Equilibrium states of a closed semiflexible polymer binding to a cylinder are described. This may be either by confinement or by constriction. Closed completely bound states are labeled by two integers: the number of oscillations, $n$, and the number of times it winds the cylinder, $p$, the latter a topological invariant. We examine the behavior of these states as the length of the loop is increased by evaluating the energy, the conserved axial torque and the contact force. The ground state for a given $p$ is the state with $n=1$; a short loop with $p=1$ is an elliptic deformation of a paralle…
By means of computer simulations, we investigate the relaxation of the Rouse modes in a simple bead-spring model for non-entangled polymer blends. Two different models are used for the fast component, namely fully-flexible and semiflexible chains. The latter are semiflexible in the meaning that static intrachain correlations are strongly non-gaussian at all length scales. The dynamic asymmetry in the blend is strongly enhanced by decreasing temperature, inducing confinement effects on the fast component. The dynamics of the Rouse modes show very different trends for the two models of the fast …
We develop an analytical method for studying the properties of a non-interacting Wormlike Chain (WLC) in confined geometries. The mean field-like theory replaces the rigid constraints of confinement with average constraints, thus allowing us to develop a tractable method for treating a WLC wrapped on the surface of a sphere, and fully encapsulated within it. The efficacy of the theory is established by reproducing the exact correlation functions for a WLC confined to the surface of a sphere. In addition, the coefficients in the free energy are exactly calculated. We also describe the behavior …
Monte Carlo computer simulations are used to study the conformational free energy of a folded polymer confined to a long cylindrical tube. The polymer is modeled as a hard-sphere chain. Its conformational free energy $F$ is measured as a function of $λ$, the end-to-end distance of the polymer. In the case of a flexible linear polymer, $F(λ)$ is a linear function in the folded regime with a gradient that scales as $f\equiv |dF/dλ| \sim N^0 D^{-1.20\pm 0.01}$ for a tube of diameter $D$ and a polymer of length $N$. This is close to the prediction $f \sim N^0 D^{-1}$ obtained from simple scaling a…
The statistical mechanics of a ribbon polymer made up of two semiflexible chains is studied using both analytical techniques and simulation. The system is found to have a crossover transition at some finite temperature, from a type of short range order to a fundamentally different sort of short range order. In the high temperature regime, the 2-point correlation functions of the object are identical to worm-like chains, while in the low temperature regime they are different due to a twist structure. The crossover happens when the persistence length of individual strands becomes comparable to t…
Confinement is a versatile and well-established tool to study the properties of polymers either to understand biological processes or to develop new nano-biomaterials. We investigate the conformations of a semiflexible polymer ring in weak spherical confinement imposed by an impenetrable shell. We develop an analytic argument for the dominating polymer trajectory depending on polymer flexibility considering elastic and entropic contributions. Monte Carlo simulations are performed to assess polymer ring conformations in probability densities and by the shape measures asphericity and nature of a…
We study equilibrium shapes and shape transformations of a confined semiflexible chain inside a soft lipid tubule using simulations and continuum theories. The deformed tubular shapes and chain conformations depend on the relative magnitude of their bending moduli. We characterise the collapsed macromolecular shapes by computing statistical quantities that probe the polymer properties at small length scales and report a prolate to toroidal coil transition for stiff chains. Deformed tubular shapes, calculated using elastic theories, agree with simulations. In conjunction with scattering studies…
The interplay of geometrical and topological entanglement in semiflexible knotted polymer rings confined inside a spherical cavity is investigated using advanced numerical methods. By using stringent and robust algorithms for locating knots, we characterize how the knot length lk depends on the ring contour length, Lc and the radius of the confining sphere, Rc . In the no- and strong- confinement cases we observe weak knot localization and complete knot delocalization, respectively. We show that the complex interplay of lk, Lc and Rc that seamlessly bridges these two limits can be encompassed …
We have studied structure formation in a confined block copolymer melt by means of dynamic density functional theory (DDFT). The confinement is two-dimensional, and the confined geometry is that of a cylindrical nanopore. Although the results of this study are general, our coarse-grained molecular model is inspired by an experimental lamellae-forming PS-PBD diblock copolymer system (Shin et al, Science, 306, 76 (2004)), in which an exotic toroidal structure was observed upon confinement in alumina nanopores. Our computational study shows that a zoo of exotic structures can be formed, although …
We study cholesteric order in liquid crystal shells with planar degenerate anchoring. We observe that the bipolar and radial configurations intensively reported for bulk droplets have a higher degree of complexity when the liquid crystal is confined to a spherical shell. The bipolar configuration is replaced by a structure where the boojums are linked to a stack of disclination rings that spans the shell, while the radial configuration exhibits a double helix structure where two disclinations wind around each other. Our results confirm recent numerical simulations and highlight the complexity …
Using an algorithm for simulating equilibrium configurations, we study a fluctuating helical polymer either (i) contained in a cylindrical pore or (ii) wound around a cylindrical rod. We work in the regime where both the contour length and the persistence length of the helical polymer are much larger than the diameter of the cylinder. In case (i) we calculate the free energy of confinement and interpret it in terms of a worm-like chain in a pore with an effective diameter that depends on the parameters of the helix. In case (ii) we consider the possibility that one end of the helical polymer e…
Motivated by bacterial transport through porous media, here we study the swimming of an actuated, flexible helical filament in both three-dimensional free space and within a cylindrical tube whose diameter is much smaller than the length of the helix. The filament, at rest, has a native helical shape modeled after the geometry of a typical bacterial flagellar bundle. The finite length filament is a free swimmer, and is driven by an applied torque as well as a counter-torque (of equal strength and opposite direction) that represents a virtual cell body. We use a regularized Stokeslet framework …
This paper extends on a recent work where it was shown that forces dependent on the helical structure may cause two DNA molecules to spontaneously braid [R. Cortini et Al, Biophys. J. 101, 875 (2011)]. Here, bending fluctuations of DNA centre lines about the braid axis are incorporated into the braiding theory. The free energy of the pair of molecules is recalculated and compared to its value without incorporating undulations. We find that the loss of configurational entropy due to confinement of the molecules in the braid is rather high. This contribution to the Free Energy pushes up the amou…
Engineering Tunable Synthetic Su-Schrieffer-Heeger Chains in Liquid Crystal Microcavities
Institute of Experimental Physics, Faculty of Physics, University of Warsaw（华沙大学物理学院实验物理研究所）；Institute of Applied Physics, Military University of Technology（军事理工大学应用物理研究所）；Institute of Chemistry, Military University of Technology（军事理工大学化学研究所）
