Unconcatenated Rings Research Articles

Unexpected Slow Relaxation Dynamics in Pure Ring Polymers Arise from Intermolecular Interactions.

Ring polymers have fascinated scientists for decades, but experimental progress has been challenging due to the presence of linear chain contaminants that fundamentally alter dynamics. In this work, we report the unexpected slow stress relaxation behavior of concentrated ring polymers that arises due to ring-ring interactions and ring packing structure. Topologically pure, high molecular weight ring polymers are prepared without linear chain contaminants using cyclic poly(phthalaldehyde) (cPPA), a metastable polymer chemistry that rapidly depolymerizes from free ends at ambient temperatures. Linear viscoelastic measurements of highly concentrated cPPA show slow, non-power-law stress relaxation dynamics despite the lack of linear chain contaminants. Experiments are complemented by molecular dynamics (MD) simulations of unprecedentedly high molecular weight rings, which clearly show non-power-law stress relaxation in good agreement with experiments. MD simulations reveal substantial ring-ring interpenetrations upon increasing ring molecular weight or local backbone stiffness, despite the global collapsed nature of single ring conformation. A recently proposed microscopic theory for unconcatenated rings provides a qualitative physical mechanism associated with the emergence of strong inter-ring caging which slows down center-of-mass diffusion and long wavelength intramolecular relaxation modes originating from ring-ring interpenetrations, governed by the onset variable N/ND, where the crossover degree of polymerization ND is qualitatively predicted by theory. Our work overcomes challenges in achieving ring polymer purity and by characterizing dynamics for high molecular weight ring polymers. Overall, these results provide a new understanding of ring polymer physics.

Computer simulations of melts of ring polymers with nonconserved topology: A dynamic Monte Carlo lattice model.

We present computer simulations of a dynamic Monte Carlo algorithm for polymer chains on a fcc lattice which explicitly takes into account the possibility to overcome topological constraints by controlling the rate at which nearby polymer strands may cross through each other. By applying the method to systems of interacting ring polymers at melt conditions, we characterize their structure and dynamics by measuring, in particular, the amounts of knots and links which are formed during the relaxation process. In comparison with standard melts of unknotted and unconcatenated rings, our simulations demonstrate that the mechanism of strand crossing makes polymer dynamics faster provided the characteristic timescale of the process is smaller than the typical timescale for chain relaxation in the unperturbed state, in agreement with recent experiments employing solutions of DNA rings in the presence of the type II topoisomerase enzyme. In the opposite case of slow rates the melt is shown to become slower, and this prediction may be easily validated experimentally.

Theory of Transient Localization, Activated Dynamics, and a Macromolecular Glass Transition in Ring Polymer Liquids.

We construct a segmental scale force level theory for the center-of-mass diffusion constant and corresponding relaxation time for globally compact unconcatenated ring polymer solutions and melts (degree of polymerization N). The approach is based on slowly decaying macromolecular scale intermolecular force dynamic correlations as the origin of their unusual dynamics. Unentangled Rouse, weakly caged, and activated regimes are predicted. The barrier of the activated regime scales linearly with N and as a power law of concentration, which drives a kinetic glass transition on the radius-of-gyration scale. The values of N at the two dynamic crossovers (Rouse to weakly caged, weakly caged to activated) are proportional, with nonuniversality entering mainly via macromolecular volume fraction and dimensionless compressibility. Quantitative comparisons with simulation data reveal good agreement. Aspects of intermediate time dynamics are analyzed, and predictions are made for the conditions required to observe a macromolecular glass transition in the laboratory and on the computer.

Intramolecular relaxation of ring polymers in dilute solutions

The intramolecular relaxation dynamics of unconcatenated ring polymers in dilute solutions is theoretically investigated within the framework of the Rouse–Zimm theory. The excluded volume interactions (EVIs) between the nonbonded monomers are modeled by a harmonic potential, where the interaction parameter is evaluated from Flory’s mean-field approach. The hydrodynamic interactions (HIs) between the pairs of monomers are approximated by a preaveraged Oseen tensor. The mechanical moduli are dominated by the smaller relaxation rates corresponding to the collective relaxation modes in the low frequency regime, while they are governed by the higher relaxation rates corresponding to the local relaxation modes in the high frequency regime. EVI decreases the relaxation rates of the normal modes where the decrease for the collective modes is larger than that for the local modes, which consequently expands the width of the relaxation spectrum. The characteristic overall relaxation time is evaluated from the inverse of the crossover frequency, which is the same for rings of various sizes with HI and with both HI and EVI, while it shifts to lower frequencies with increasing ring size for the Rouse rings.

Nonlinear Shear Rheology of Entangled Polymer Rings

Steady-state shear viscosity η(γ) of unconcatenated ring polymer melts as a function of the shear rate γ is studied by a combination of experiments, simulations, and theory. Experiments using pol...

Many-body contacts in fractal polymer chains and fractional Brownian trajectories.

We calculate the probabilities that a trajectory of a fractional Brownian motion with arbitrary fractal dimension d_{f} visits the same spot n≥3 times, at given moments t_{1},...,t_{n}, and obtain a determinant expression for these probabilities in terms of a displacement-displacement covariance matrix. Except for the standard Brownian trajectories with d_{f}=2, the resulting many-body contact probabilities cannot be factorized into a product of single-loop contributions. Within a Gaussian network model of a self-interacting polymer chain, which we suggested recently [K. Polovnikov et al., Soft Matter 14, 6561 (2018)1744-683X10.1039/C8SM00785C], the probabilities we calculate here can be interpreted as probabilities of multibody contacts in a fractal polymer conformation with the same fractal dimension d_{f}. This Gaussian approach, which implies a mapping from fractional Brownian motion trajectories to polymer conformations, can be used as a semiquantitative model of polymer chains in topologically stabilized conformations, e.g., in melts of unconcatenated rings or in the chromatin fiber, which is the material medium containing genetic information. The model presented here can be used, therefore, as a benchmark for interpretation of the data of many-body contacts in genomes, which we expect to be available soon in, e.g., Hi-C experiments.

Threading of Unconcatenated Ring Polymers at High Concentrations: Double-Folded vs Time-Equilibrated Structures.

Unconcatenated ring polymers in concentrated solutions and melt are remarkably well described as double-folded conformations on randomly branched primitive trees. This picture though contrasts recent evidence for extensive intermingling between close-by rings in the form of long-lived topological constraints or threadings. Here, we employ the concept of ring minimal surface to quantify the extent of threadings in polymer solutions of the double-folded rings vs rings in equilibrated molecular dynamics computer simulations. Our results show that the double-folded ring polymers are significantly less threaded compared to their counterparts at equilibrium. Second, threadings form through a slow process whose characteristic time-scale is of the same order of magnitude as that of the diffusion of the rings in solution. These findings are robust, being based on universal (model-independent) observables as the average fraction of threaded length or the total penetrations between close-by rings and the corresponding distribution functions.

Nanoprobe diffusion in entangled polymer solutions: Linear vs. unconcatenated ring chains.

We employ large-scale molecular dynamics computer simulations to study the problem of nanoprobe diffusion in entangled solutions of linear polymers and unknotted and unconcatenated circular (ring) polymers. By tuning both the diameter of the nanoprobe and the density of the solution, we show that nanoprobes of diameter smaller than the entanglement distance (tube diameter) of the solution display the same (Rouse-like) behavior in solutions of both polymer architectures. Instead, nanoprobes with larger diameters appear to diffuse markedly faster in solutions of rings than in solutions of linear chains. Finally, by analysing the distribution functions of spatial displacements, we find that nanoprobe motion in rings' solutions shows both Gaussian and ergodic behaviors, in all regimes considered, while, in solutions of linear chains, nanoprobes exceeding the size of the tube diameter show a transition to non-Gaussian and non-ergodic motion. Our results emphasize the role of chain architecture in the motion of nanoprobes dispersed in polymer solutions.

Intermolecular structural correlations in model globular and unconcatenated ring polymer liquids.

We employ the field theoretic polymer integral equation theory to construct a segment-level theory for the thermodynamics and pair structure of dense liquids of interpenetrating ring polymers and a simple globule model. The latter is defined by a fractal mass distribution on all internal length scales with an exponent equal to the spatial dimension (dF = ds = 3). In an isochoric ensemble the dimensionless compressibility and pressure is predicted to vary exponentially with macromolecular volume fraction. An intermolecular correlation hole exists down to small length scales. This model appears to be useful for a recently studied experimental soft nanoparticle suspension, and also serves as a reference system for our analysis of ring liquids. Motivated by simulations, a two-fractal exponent ring model is adopted for the intramolecular structure factor. At smaller lengths it describes chain-like macromolecules, while on larger scales it corresponds to a space-filling object in the sense that dF = ds = 3. The crossover between these two regimes is of order the entanglement length of the linear chain analog. Based on a constant compressibility ensemble, the effective volume fraction grows at intermediate values of degree of polymerization (N), and crosses over to a very slow logarithmic growth at large N. A weaker intermolecular correlation hole is predicted. The number of nearest neighbor rings increases dramatically at small N, akin to linear chain melts, but then tends to saturate at large N, in accord with simulations. The tools developed may be relevant for other partially interpenetrating soft objects such as core-shell nanogels or microgels.

Nonequilibrium molecular dynamics study of ring polymer melts under shear and elongation flows: A comparison with their linear analogs

We present detailed results for the structural and rheological properties of unknotted and unconcatenated ring polyethylene (PE) melts under shear and elongation flows via direct atomistic nonequilibrium molecular dynamics simulations. Short (C78H156) and long (C400H800) ring PE melts were subjected to planar Couette flow (PCF) and planar elongational flow (PEF) across a wide range of strain rates from linear to highly nonlinear flow regimes. The results are analyzed in detail through a direct comparison with those of the corresponding linear polymers. We found that, in comparison to their linear analogs, ring melts possess rather compact chain structures at or near the equilibrium state and exhibit a considerably lesser degree of structural deformation with respect to the applied flow strength under both PCF and PEF. The large structural resistance of ring polymers against an external flow field is attributed to the intrinsic closed-loop configuration of the ring and the topological constraint of nonconcatenation between ring chains in the melt. As a result, there appears to be a substantial discrepancy between ring and linear systems in terms of their structural and rheological properties such as chain orientation, the distribution of chain dimensions, viscosity, flow birefringence, hydrostatic pressure, the pair correlation function, and potential interaction energies. The findings and conclusions drawn in this work would be a useful guide in future exploration of the characteristic dynamical and relaxation mechanisms of ring polymers in bulk or confined systems under flowing conditions.

Scale-Dependent Viscosity in Polymer Fluids.

In this communication, we use simple physical arguments to construct a "phase diagram" of various frequency and wave vector-dependent regimes of effective viscosity for polymer fluids, including nonentangled and entangled melts, semidilute solutions without and with hydrodynamic interactions, as well as the more exotic case of a melt of unconcatenated ring polymers.

Understanding the dynamics of rings in the melt in terms of the annealed tree model

The dynamical properties of a long polymer ring in a melt of unknotted and unconcatenated rings are calculated. We re-examine and generalize the well known model of a ring confined to a lattice of topological obstacles in light of the recently developed Flory theory of untangled rings which maps every ring on an annealed branched polymer and establishes that the backbone associated with each ring follows self-avoiding rather than Gaussian random walk statistics. We find the scaling of the ring relaxation time and diffusion coefficient with ring length, as well as the time dependence of stress relaxation modulus, zero shear viscosity and the mean square averaged displacements of both individual monomers and the ring's mass centre. Our results agree within error bars with all available experimental and simulation data of the ring melt, although the quality of the data so far is insufficient to make a definitive judgement for or against the annealed tree theory. At the end we review briefly the relation between our findings and experimental data on chromatin dynamics.

Conjectures on the statistics of ring polymers

We present some conjectures concerning the equilibrium statistics and dynamics of ring polymers. We argue that unconcatenated ring polymers in the melt may have statistics intermediate between those of collapsed and Gaussian chains. An extremely crude (Flory-like) treatment suggests that the radius R of such a ring scales with its polymerization index N as R ∼ N 2/5. In contrast, a ring in a melt of long linear chains (of the same chemical species) should be swollen. Moreover, rings of one chemical species (A) can be compatible with linear chains of another (B), even when linear chains of A and B are not compatible. Rings in a network of fixed obstacles are also discussed. A simple analysis of their dynamics shows that the diffusion constant D of such a ring (in three dimensions) scales with its polymerization index N as D ∼ N-2. This prediction is confirmed by computer simulations. Finally, we consider a knotted ring formed irreversibly in a theta solvent, and argue that, under appropriate formation conditions, such a ring may remain Gaussian when placed in a good solvent.