61 research outputs found
Discovering New Ordered Phases of Block Copolymers
We propose a new and general method for discovering novel ordered phases of block copolymer melts. The method involves minimizing a free energy functional in an arbitrary unit cell with respect to the composition profile and the dimensions of the unit cell, without any prior assumption of the microphase symmetry. Varying the initial conditions allows to search for different stable and metastable structures. Application of this method to ABC star and linear triblock copolymers using an approximate free energy reveals new morphologies not yet observed in experiment
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Relaxation Dynamics of Semiflexible Polymers
We study the relaxation dynamics of a semiflexible chain by introducing a time-dependent tension. The chain has one of its ends attached to a large bead, and the other end is fixed. We focus on the initial relaxation of the chain that is initially strongly stretched. Using a tension that is self-consistently determined, we obtain the evolution of the end-to-end distance with no free parameters. Our results are in good agreement with single molecule experiments on double stranded DNA
Forced-unfolding and force-quench refolding of RNA hairpins
Using coarse-grained model we have explored forced-unfolding of RNA hairpin
as a function of and the loading rate (). The simulations and
theoretical analysis have been done without and with the handles that are
explicitly modeled by semiflexible polymer chains. The mechanisms and time
scales for denaturation by temperature jump and mechanical unfolding are vastly
different. The directed perturbation of the native state by results in a
sequential unfolding of the hairpin starting from their ends whereas thermal
denaturation occurs stochastically. From the dependence of the unfolding rates
on and we show that the position of the unfolding transition state
(TS) is not a constant but moves dramatically as either or is
changed. The TS movements are interpreted by adopting the Hammond postulate for
forced-unfolding. Forced-unfolding simulations of RNA, with handles attached to
the two ends, show that the value of the unfolding force increases (especially
at high pulling speeds) as the length of the handles increases. The pathways
for refolding of RNA from stretched initial conformation, upon quenching
to the quench force , are highly heterogeneous. The refolding times, upon
force quench, are at least an order of magnitude greater than those obtained by
temperature quench. The long -dependent refolding times starting from
fully stretched states are analyzed using a model that accounts for the
microscopic steps in the rate limiting step which involves the trans to gauche
transitions of the dihedral angles in the GAAA tetraloop. The simulations with
explicit molecular model for the handles show that the dynamics of force-quench
refolding is strongly dependent on the interplay of their contour length and
the persistence length, and the RNA persistence length.Comment: 42 pages, 15 figures, Biophys. J. (in press
Stretching dynamics of semiflexible polymers
We analyze the nonequilibrium dynamics of single inextensible semiflexible biopolymers as stretching forces are applied at the ends. Based on different (contradicting) heuristic arguments, various scaling laws have been proposed for the propagation speed of the backbone tension which is induced in response to stretching. Here, we employ a newly developed unified theory to systematically substantiate, restrict, and extend these approaches. Introducing the practically relevant scenario of a chain equilibrated under some prestretching force f pre that is suddenly exposed to a different external force f ext at the ends, we give a concise physical explanation of the underlying relaxation processes by means of an intuitive blob picture. We discuss the corresponding intermediate asymptotics, derive results for experimentally relevant observables, and support our conclusions by numerical solutions of the coarse-grained equations of motion for the tension
Tension Dynamics and Linear Viscoelastic Behavior of a Single Semiflexible Polymer Chain
We study the dynamical response of a single semiflexible polymer chain based
on the theory developed by Hallatschek et al. for the wormlike-chain model. The
linear viscoelastic response under oscillatory forces acting at the two chain
ends is derived analytically as a function of the oscillation frequency . We
shall show that the real part of the complex compliance in the low frequency
limit is consistent with the static result of Marko and Siggia whereas the
imaginary part exhibits the power-law dependence +1/2. On the other hand, these
compliances decrease as the power law -7/8 for the high frequency limit. These
are different from those of the Rouse dynamics. A scaling argument is developed
to understand these novel results.Comment: 23 pages, 6 figure
Rapid internal contraction boosts DNA friction
Macroscopic objects are usually manipulated by force and observed with light. On the nanoscale, however, this is often done oppositely: individual macromolecules are manipulated by light and monitored with force. This procedure, which is the basis of single-molecule force spectroscopy, has led to much of our quantitative understanding of how DNA works, and is now routinely applied to explore molecular structure and interactions, DNA–protein reactions and protein folding. Here we develop the technique further by introducing a dynamic force spectroscopy set-up for a non-invasive inspection of the tension dynamics in a taut strand of DNA. The internal contraction after a sudden release of the molecule is shown to give rise to a drastically enhanced viscous friction, as revealed by the slow relaxation of an attached colloidal tracer. Our systematic theory explains the data quantitatively and provides a powerful tool for the rational design of new dynamic force spectroscopy assays
Reversible Association of Telechelic Molecules: An Application of Graph Theory
We develop a method for calculating the exact free energy of tree clusters formed from associating telechelic molecules. The method uses the concept of rooted trees from the graph theory to enumerate all topologically distinct trees having a maximum degree of branching; it recursively separates the trees into different classes based on their connectivity, thus enabling the exact summation of the trees weighted by their respective Boltzmann factors. We apply our method to studying the pregel properties in pure telechelic solutions and in mixed telechelic and single-associating-end polymer solutions. We highlight the effect of energetic tendency for branching in the former and the effect of competitive association in the latter
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