Rotaxane Formation of Multicyclic Polydimethylsiloxane in a Silicone Network: A Step toward Constructing "Macro-Rotaxanes" from High-Molecular-Weight Axle and Wheel Components.

Rotaxanes consisting of a high-molecular-weight axle and wheel components (macro-rotaxanes) have high structural freedom, and are attractive for soft-material applications. However, their synthesis remains underexplored. Here, we investigated macro-rotaxane formation by the topological trapping of multicyclic polydimethylsiloxanes (mc-PDMSs) in silicone networks. mc-PDMS with different numbers of cyclic units and ring sizes was synthesized by cyclopolymerization of a α,ω-norbornenyl-functionalized PDMS. Silicone networks were prepared in the presence of 10-60 wt % mc-PDMS, and the trapping efficiency of mc-PDMS was determined. In contrast to monocyclic PDMS, mc-PDMSs with more cyclic units and larger ring sizes can be quantitatively trapped in the network as macro-rotaxanes. The damping performance of a 60 wt % mc-PDMS-blended silicone network was evaluated, revealing a higher tan δ value than the bare PDMS network. Thus, macro-rotaxanes are promising as non-leaching additives for network polymers.

Miscibility and exchange chemical potential of ring polymers in symmetric ring-ring blends.

Generally, differences of polymer topologies may affect polymer miscibility even with the same repeated units. In this study, the topological effect of ring polymers on miscibility was investigated by comparing symmetric ring-ring and linear-linear polymer blends. To elucidate the topological effect of ring polymers on mixing free energy, the exchange chemical potential of binary blends was numerically evaluated as a function of composition ϕ by performing semi-grand canonical Monte Carlo and molecular dynamics simulations of a bead-spring model. For ring-ring blends, an effective miscibility parameter was evaluated by comparing the exchange chemical potential with that of the Flory-Huggins model for linear-linear polymer blends. It was confirmed that in the mixed states satisfying χN > 0, ring-ring blends are more miscible and stable than the linear-linear blends with the same molecular weight. Furthermore, we investigated finite molecular weight dependence on the miscibility parameter, which reflected the statistical probability of interchain interactions in the blends. The simulation results revealed that the molecular weight dependence on the miscibility parameter was smaller in ring-ring blends. The effect of the ring polymers on miscibility was verified to be consistent with the change in the interchain radial distribution function. In ring-ring blends, it was indicated that the topology affected miscibility by reducing the effect of the direct interaction between the components of the blends.

Efficient compressed database of equilibrated configurations of ring-linear polymer blends for MD simulations.

To effectively archive configuration data during molecular dynamics (MD) simulations of polymer systems, we present an efficient compression method with good numerical accuracy that preserves the topology of ring-linear polymer blends. To compress the fraction of floating-point data, we used the Jointed Hierarchical Precision Compression Number - Data Format (JHPCN-DF) method to apply zero padding for the tailing fraction bits, which did not affect the numerical accuracy, then compressed the data with Huffman coding. We also provided a dataset of well-equilibrated configurations of MD simulations for ring-linear polymer blends with various lengths of linear and ring polymers, including ring complexes composed of multiple rings such as polycatenane. We executed 109 MD steps to obtain 150 equilibrated configurations. The combination of JHPCN-DF and SZ compression achieved the best compression ratio for all cases. Therefore, the proposed method enables efficient archiving of MD trajectories. Moreover, the publicly available dataset of ring-linear polymer blends can be employed for studies of mathematical methods, including topology analysis and data compression, as well as MD simulations.

Programmed folding into spiro-multicyclic polymer topologies from linear and star-shaped chains.

The development of precise folding techniques for synthetic polymer chains that replicate the unique structures and functions of biopolymers has long been a key challenge. In particular, spiro-type (i.e., 8-, trefoil-, and quatrefoil-shaped) polymer topologies remain challenging due to their inherent structural complexity. Herein, we establish a folding strategy to produce spiro-type multicyclic polymers via intramolecular ring-opening metathesis oligomerization of the norbornenyl groups attached at predetermined positions along a synthetic polymer precursor. This strategy provides easy access to the desired spiro-type topological polymers with a controllable number of ring units and molecular weight while retaining narrow dispersity (Ɖ < 1.1). This effective strategy marks an advancement in the development of functionalized materials composed of specific three-dimensional nanostructures.

Scaling behavior of knotted random polygons and self-avoiding polygons: Topological swelling with enhanced exponent.

We show that the average size of self-avoiding polygons (SAPs) with a fixed knot is much larger than that of no topological constraint if the excluded volume is small and the number of segments is large. We call it topological swelling. We argue an "enhancement" of the scaling exponent for random polygons with a fixed knot. We study them systematically through SAP consisting of hard cylindrical segments with various different values of the radius of segments. Here we mean by the average size the mean-square radius of gyration. Furthermore, we show numerically that the topological balance length of a composite knot is given by the sum of those of all constituent prime knots. Here we define the topological balance length of a knot by such a number of segments that topological entropic repulsions are balanced with the knot complexity in the average size. The additivity suggests the local knot picture.

Knotting probability of self-avoiding polygons under a topological constraint.

We define the knotting probability of a knot K by the probability for a random polygon or self-avoiding polygon (SAP) of N segments having the knot type K. We show fundamental and generic properties of the knotting probability particularly its dependence on the excluded volume. We investigate them for the SAP consisting of hard cylindrical segments of unit length and radius rex. For various prime and composite knots, we numerically show that a compact formula describes the knotting probabilities for the cylindrical SAP as a function of segment number N and radius rex. It connects the small-N to the large-N behavior and even to lattice knots in the case of large values of radius. As the excluded volume increases, the maximum of the knotting probability decreases for prime knots except for the trefoil knot. If it is large, the trefoil knot and its descendants are dominant among the nontrivial knots in the SAP. From the factorization property of the knotting probability, we derive a sum rule among the estimates of a fitting parameter for all prime knots, which suggests the local knot picture and the dominance of the trefoil knot in the case of large excluded volumes. Here we remark that the cylindrical SAP gives a model of circular DNA which is negatively charged and semiflexible, where radius rex corresponds to the screening length.

Statistical and Dynamical Properties of Topological Polymers with Graphs and Ring Polymers with Knots.

We review recent theoretical studies on the statistical and dynamical properties of polymers with nontrivial structures in chemical connectivity and those of polymers with a nontrivial topology, such as knotted ring polymers in solution. We call polymers with nontrivial structures in chemical connectivity expressed by graphs "topological polymers". Graphs with no loop have only trivial topology, while graphs with loops such as multiple-rings may have nontrivial topology of spatial graphs as embeddings in three dimensions, e.g., knots or links in some loops. We thus call also such polymers with nontrivial topology "topological polymers", for simplicity. For various polymers with different structures in chemical connectivity, we numerically evaluate the mean-square radius of gyration and the hydrodynamic radius systematically through simulation. We evaluate the ratio of the gyration radius to the hydrodynamic radius, which we expect to be universal from the viewpoint of the renormalization group. Furthermore, we show that the short-distance intrachain correlation is much enhanced for real topological polymers (the Kremer⁻Grest model) expressed with complex graphs. We then address topological properties of ring polymers in solution. We define the knotting probability of a knot K by the probability that a given random polygon or self-avoiding polygon of N vertices has the knot K. We show a formula for expressing it as a function of the number of segments N, which gives good fitted curves to the data of the knotting probability versus N. We show numerically that the average size of self-avoiding polygons with a fixed knot can be much larger than that of no topological constraint if the excluded volume is small. We call it "topological swelling".

Statistical and hydrodynamic properties of topological polymers for various graphs showing enhanced short-range correlation.

For various polymers with different structures in chemical connectivity expressed by graphs, we numerically evaluate the mean-square radius of gyration and the hydrodynamic radius systematically through simulation. We call polymers with nontrivial structures in chemical connectivity and those of nontrivial topology of spatial graphs as embeddings in three dimensions topological polymers. We evaluate the two quantities both for ideal and real chain models and show that the ratios of the quantities among different structures in chemical connectivity do not depend on the existence of excluded volume if the topological polymers have only up to trivalent vertices, as far as the polymers investigated. We also evaluate the ratio of the gyration radius to the hydrodynamic radius, which we expect to be universal from the viewpoint of renormalization group. Furthermore, we show that the short-distance intrachain correlation is much enhanced for real topological polymers (the Kremer-Grest model) expressed with complex graphs.

Characteristic length of the knotting probability revisited.

We present a self-avoiding polygon (SAP) model for circular DNA in which the radius of impermeable cylindrical segments corresponds to the screening length of double-stranded DNA surrounded by counter ions. For the model we evaluate the probability for a generated SAP with N segments having a given knot K through simulation. We call it the knotting probability of a knot K with N segments for the SAP model. We show that when N is large the most significant factor in the knotting probability is given by the exponentially decaying part exp(-N/NK), where the estimates of parameter NK are consistent with the same value for all the different knots we investigated. We thus call it the characteristic length of the knotting probability. We give formulae expressing the characteristic length as a function of the cylindrical radius rex, i.e. the screening length of double-stranded DNA.

Statistical and hydrodynamic properties of double-ring polymers with a fixed linking number between twin rings.

For a double-ring polymer in solution we evaluate the mean-square radius of gyration and the diffusion coefficient through simulation of off-lattice self-avoiding double polygons consisting of cylindrical segments with radius rex of unit length. Here, a self-avoiding double polygon consists of twin self-avoiding polygons which are connected by a cylindrical segment. We show numerically that several statistical and dynamical properties of double-ring polymers in solution depend on the linking number of the constituent twin ring polymers. The ratio of the mean-square radius of gyration of self-avoiding double polygons with zero linking number to that of no topological constraint is larger than 1, in particular, when the radius of cylindrical segments rex is small. However, the ratio is almost constant with respect to the number of vertices, N, and does not depend on N. The large-N behavior of topological swelling is thus quite different from the case of knotted random polygons.

Exact relaxation dynamics of a localized many-body state in the 1D Bose gas.

Through an exact method, we numerically solve the time evolution of the density profile for an initially localized state in the one-dimensional bosons with repulsive short-range interactions. We show that a localized state with a density notch is constructed by superposing one-hole excitations. The initial density profile overlaps the plot of the squared amplitude of a dark soliton in the weak coupling regime. We observe the localized state collapsing into a flat profile in equilibrium for a large number of particles such as N=1000. The relaxation time increases as the coupling constant decreases, which suggests the existence of off-diagonal long-range order. We show a recurrence phenomenon for a small number of particles such as N=20.

Quantum phase transition in a pseudo-Hermitian Dicke model.

We show that a Dicke-type non-Hermitian Hamiltonian admits entirely real spectra by mapping it to the "dressed Dicke model" through a similarity transformation. We find a positive-definite metric in the Hilbert space of the non-Hermitian Hamiltonian so that the time evolution is unitary and allows a consistent quantum description. We then show that this non-Hermitian Hamiltonian describing nondissipative quantum processes undergoes quantum phase transition. The exactly solvable limit of the non-Hermitian Hamiltonian has also been discussed.

Level statistics of a pseudo-Hermitian Dicke model.

A non-Hermitian operator that is related to its adjoint through a similarity transformation is defined as a pseudo-Hermitian operator. We study the level statistics of a pseudo-Hermitian Dicke Hamiltonian that undergoes quantum phase transition (QPT). We find that the level-spacing distribution of this Hamiltonian near the integrable limit is close to Poisson distribution, while it is Wigner distribution for the ranges of the parameters for which the Hamiltonian is nonintegrable. We show that the assertion in the context of the standard Dicke model that QPT is a precursor to a change in the level statistics is not valid in general.

Dimension of ring polymers in bulk studied by Monte-Carlo simulation and self-consistent theory.

We studied equilibrium conformations of ring polymers in melt over the wide range of segment number N of up to 4096 with Monte-Carlo simulation and obtained N dependence of radius of gyration of chains R(g). The simulation model used is bond fluctuation model (BFM), where polymer segments bear excluded volume; however, the excluded volume effect vanishes at N-->infinity, and linear polymer can be regarded as an ideal chain. Simulation for ring polymers in melt was performed, and the nu value in the relationship R(g) proportional to N(nu) is decreased gradually with increasing N, and finally it reaches the limiting value, 1/3, in the range of N>or=1536, i.e., R(g) proportional to N(1/3). We confirmed that the simulation result is consistent with that of the self-consistent theory including the topological effect and the osmotic pressure of ring polymers. Moreover, the averaged chain conformation of ring polymers in equilibrium state was given in the BFM. In small N region, the segment density of each molecule near the center of mass of the molecule is decreased with increasing N. In large N region the decrease is suppressed, and the density is found to be kept constant without showing N dependence. This means that ring polymer molecules do not segregate from the other molecules even if ring polymers in melt have the relationship nu=1/3. Considerably smaller dimensions of ring polymers at high molecular weight are due to their inherent nature of having no chain ends, and hence they have less-entangled conformations.

Universality in the diffusion of knots.

We have evaluated a universal ratio between diffusion constants of the ring polymer with a given knot K and a linear polymer with the same molecular weight in solution through the Brownian dynamics under hydrodynamic interaction. The ratio is found to be constant with respect to the number of monomers, N , and hence the estimate at some N should be valid practically over a wide range of N for various polymer models. Interestingly, the ratio is determined by the average crossing number (N{AC}) of an ideal conformation of knotted curve K , i.e., that of the ideal knot. The N{AC} of ideal knots should therefore be fundamental in the dynamics of knots.

Scattering functions of knotted ring polymers.

We discuss the scattering function of a Gaussian random polygon with N nodes under a given topological constraint through simulation. We evaluate the form factor PK(q) of a Gaussian polygon of N = 200 having a fixed knot K for some different knots such as the trivial, trefoil, and figure-eight knots. Here the Gaussian polygons with different knots K have distinct values of the mean-square radius of gyration, R2(G,K). We obtain the Kratky plots of the form factors--i.e., the plots of (qR(G,K))2PK(q) versus qR(G,K)--for the different topological constraints and discuss nontrivial large-q behavior as well as small-q behavior for the scattering functions. We also find that the distinct values of R2(G,K) play an important role in the large-q and small-q properties of the Kratky plots.

Average size of random polygons with fixed knot topology.

We have evaluated by numerical simulation the average size R(K) of random polygons of fixed knot topology K=,3(1),3(1) musical sharp 4(1), and we have confirmed the scaling law R(2)(K) approximately N(2nu(K)) for the number N of polygonal nodes in a wide range; N=100-2200. The best fit gives 2nu(K) approximately 1.11-1.16 with good fitting curves in the whole range of N. The estimate of 2nu(K) is consistent with the exponent of self-avoiding polygons. In a limited range of N (N greater, similar 600), however, we have another fit with 2nu(K) approximately 1.01-1.07, which is close to the exponent of random polygons.

Geometrical complexity of conformations of ring polymers under topological constraints.

One measure of geometrical complexity of a spatial curve is the average of the number of crossings appearing in its planar projection. The mean number of crossings averaged over some directions have been numerically evaluated for N-noded ring polymers with a fixed knot type. When N is large, the average crossing number of ring polymers under the topological constraint is smaller than that of no topological constraint. The decrease of the geometrical complexity is significant when the thickness of polymers is small. It is also suggested from the simulation that the relation between the average crossing number and the average size of ring polymers should depend on whether they are under a topological constraint or not.

Knot complexity and the probability of random knotting.

The probability of a random polygon (or a ring polymer) having a knot type K should depend on the complexity of the knot K. Through computer simulation using knot invariants, we show that the knotting probability decreases exponentially with respect to knot complexity. Here we assume that some aspects of knot complexity are expressed by the minimal crossing number C and the "rope length" of K, which is defined by the smallest length of rope with unit diameter that can be tied to make the knot K.

Finite-size and asymptotic behaviors of the gyration radius of knotted cylindrical self-avoiding polygons.

Several nontrivial properties are shown for the mean-square radius of gyration R2(K) of ring polymers with a fixed knot type K. Through computer simulation, we discuss both finite size and asymptotic behaviors of the gyration radius under the topological constraint for self-avoiding polygons consisting of N cylindrical segments with radius r. We find that the average size of ring polymers with the knot K can be much larger than that of no topological constraint. The effective expansion due to the topological constraint depends strongly on the parameter r that is related to the excluded volume. The topological expansion is particularly significant for the small r case, where the simulation result is associated with that of random polygons with the knot K.