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Molecular chirality has traditionally been viewed as a binary property where a molecule is classified as either chiral or achiral, yet in recent decades, mathematical methods for quantifying chirality have been explored. Here, we use toy molecular systems to systematically compare the performance of two state-of-the-art chirality measures: (1) the Continuous Chirality Measure (CCM) and (2) the Chirality Characteristic (χ). We find that both methods exhibit qualitatively similar behavior when applied to simple molecular systems such as a four-site molecule or the polymer double-helix, but we show that the CCM may be more suitable for evaluating the chirality of arbitrary molecules or abstract structures such as normal vibrational modes. We discuss a range of considerations for applying these methods to molecular systems in general, and we provide links to user-friendly codes for both methods. We aim for this paper to serve as a concise resource for scientists attempting to familiarize themselves with these chirality measures or attempting to implement chirality measures in their own work. [ABSTRACT FROM AUTHOR]

Recent experiments by Brückner et al. [Science 380, 1357 (2023)] have observed an anomalous chain length dependence of the time of near approach of widely separated pairs of genomic elements on transcriptionally active chromosomal DNA. In this paper, I suggest that the anomaly may have its roots in internal friction between neighboring segments on the DNA backbone. The basis for this proposal is a model of chain dynamics formulated in terms of a continuum scaled Brownian walk (sBw) of polymerization index N. The sBw is an extension of the simple Brownian walk model widely used in path integral calculations of polymer properties, differing from it in containing an additional parameter H (the Hurst index) that can be tuned to produce varying degrees of correlation between adjacent monomers. A calculation using the sBw of the mean time τc for chain closure predicts-under the Wilemski-Fixman approximation for diffusion-controlled reactions-that at early times, τc varies as the 2/3 power of N, in close agreement with the findings of the Brückner et al. study. Other scaling relations of that study, including those related to the probability of loop formation and the mean square displacements of terminal monomers, are also satisfactorily accounted for by the model., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Polymer models describing the statistics of biomolecules under confinement have applications to a wide range of single-molecule experimental techniques and give insight into biologically relevant processes in vivo. In this paper, we determine the transverse position and bending correlation functions for a wormlike chain confined within slits and cylinders (with one and two confined dimensions, respectively) using a mean-field approach that enforces rigid constraints on average. We show the theoretical predictions accurately capture the statistics of a wormlike chain from Monte Carlo simulations in both confining geometries for both weak and strong confinement. We also show that the longitudinal correlation function is accurately computed for a chain confined to a slit and leverages the accuracy of the model to suggest an experimental technique to infer the (often unobservable) transverse statistics from the (directly observable) longitudinal end-to-end distance. [ABSTRACT FROM AUTHOR]

Polymer crystallization has long been a fascinating problem and is still attracting many researchers. Most of the previous simulations are concentrated on clarifying the universal aspects of polymer crystallization using model linear polymers such as polyethylene. We are recently focusing on a nearly untouched but very interesting problem of chiral selecting crystallization in helical polymers. We previously proposed a stepwise approach using two kinds of helical polymers, simple "bare" helical polymers made of backbone atoms only such as polyoxymethylene (POM) and "general" helical polymers containing complicated side groups such as isotactic polypropylene. We have already reported on the crystallization in oligomeric POM-like helix but have observed only weak chiral selectivity during crystallization. In the present paper, we investigate the crystallization of sufficiently long POM-like polymer both from the isotropic melt and from the highly stretched melt. We find in both cases that the polymer shows a clear chiral selecting crystallization. Specifically, the observation of a single crystal growing from the isotropic melt is very illuminating. It shows that the crystal thickness and the crystal chirality are closely correlated; thicker crystals show definite chirality while thinner ones are mostly mixtures of the R- and the L-handed stems. The single crystal is found to have a marked lenticular shape, where the thinner growth front, since being made of the mixture, shows no chiral selectivity. The final chiral crystal is found to be completed through helix reversal processes within thicker regions. [ABSTRACT FROM AUTHOR]

The purpose of this paper is to investigate several analytical methods of solving first passage (FP) problem for the Rouse model, a simplest model of a polymer chain. We show that this problem has to be treated as a multi-dimensional Kramers' problem, which presents rich and unexpected behavior. We first perform direct and forward-flux sampling (FFS) simulations and measure the mean first-passage time t(z) for the free end to reach a certain distance z away from the origin. The results show that the mean FP time is getting faster if the Rouse chain is represented by more beads. Two scaling regimes of t(z) are observed, with transition between them varying as a function of chain length. We use these simulation results to test two theoretical approaches. One is a well known asymptotic theory valid in the limit of zero temperature. We show that this limit corresponds to fully extended chain when each chain segment is stretched, which is not particularly realistic. A new theory based on the well known Freidlin-Wentzell theory is proposed, where dynamics is projected onto the minimal action path. The new theory predicts both scaling regimes correctly, but fails to get the correct numerical prefactor in the first regime. Combining our theory with the FFS simulations leads us to a simple analytical expression valid for all extensions and chain lengths. One of the applications of polymer FP problem occurs in the context of branched polymer rheology. In this paper, we consider the arm-retraction mechanism in the tube model, which maps exactly on the model we have solved. The results are compared to the Milner-McLeish theory without constraint release, which is found to overestimate FP time by a factor of 10 or more. [ABSTRACT FROM AUTHOR]

Motivated by the recent experimental observations of the DNA loop extrusion by protein motors, in this paper, we investigate the statistical properties of the growing polymer loops within the ideal chain model. The loop conformation is characterized statistically by the mean gyration radius and the pairwise contact probabilities. It turns out that a single dimensionless parameter, which is given by the ratio of the loop relaxation time over the time elapsed since the start of extrusion, controls the crossover between near-equilibrium and highly non-equilibrium asymptotics in the statistics of the extruded loop, regardless of the specific time dependence of the extrusion velocity. In addition, we show that two-sided and one-sided loop extruding motors produce the loops with almost identical properties. Our predictions are based on two rigorous semi-analytical methods accompanied by asymptotic analysis of slow and fast extrusion limits. [ABSTRACT FROM AUTHOR]

The external voltage-driven polymer translocation through a conical pore (with a large opening at the entry and a small tip at the exit) is studied by using the Langevin dynamics simulation in this paper. The entire translocation process is divided into an approaching stage and a threading stage. First, the approaching stage starts from the polymer entering the large opening and ends up at a terminal monomer reaching the pore tip. In this stage, the polymer will undergo the conformation adjustment to fit the narrowed cross-sectional area of the pore, leading to three approaching modes: the non-stuck mode with a terminal monomer arriving at the pore tip smoothly, the weak-stuck mode for the polymer stuck inside the pore for a short duration with minor conformational adjustments, and the strong-stuck mode with major conformational changes and a long duration. The approaching times (the duration of the approaching stage) of the three approaching modes show different behavior as a function of the pore apex angle. Second, the threading stage describes that the polymer threads through the pore tip with a linear fashion. In this stage, an increase in the apex angle causes the reduction of the threading time (the duration of the threading stage) due to the increase in the driving force with the apex angle at the tip. Moreover, we also find that with the increase in the apex angle or the polymer length, the polymer threading dynamics will change from the quasi-equilibrium state to the non-equilibrium state. [ABSTRACT FROM AUTHOR]

Recent experiments on the return to equilibrium of solutions of entangled polymers stretched by extensional flows [Zhou and Schroeder, Phys. Rev. Lett. 120, 267801 (2018)] have highlighted the possible role of the tube model's two-step mechanism in the process of chain relaxation. In this paper, motivated by these findings, we use a generalized Langevin equation (GLE) to study the time evolution, under linear mixed flow, of the linear dimensions of a single finitely extensible Rouse polymer in a solution of other polymers. Approximating the memory function of the GLE, which contains the details of the interactions of the Rouse polymer with its surroundings, by a power law defined by two parameters, we show that the decay of the chain's fractional extension in the steady state can be expressed in terms of a linear combination of Mittag-Leffler and generalized Mittag-Leffler functions. For the special cases of elongational flow and steady shear flow, and after adjustment of the parameters in the memory function, our calculated decay curves provide satisfactory fits to the experimental decay curves from the work of Zhou and Schroeder and earlier work of Teixeira et al. [Macromolecules 40, 2461 (2007)]. The non-exponential character of the Mittag-Leffler functions and the consequent absence of characteristic decay constants suggest that melt relaxation may proceed by a sequence of steps with an essentially continuous, rather than discrete, spectrum of timescales. [ABSTRACT FROM AUTHOR]

The loop formation of a single polymer chain has served as a model system for various biological and chemical processes. Theories based on the Smoluchowski equation proposed that the rate constant (kloop) of the loop formation would be inversely proportional to viscosity (η), i.e., kloop ∼ η−1. Experiments and simulations showed, however, that kloop showed the fractional viscosity dependence of kloop ∼ η−β with β < 1 either in glasses or in low-viscosity solutions. The origin of the fractional viscosity dependence remains elusive and has been attributed to phenomenological aspects. In this paper, we illustrate that the well-known failure of classical kinetics of the loop formation results from the breakdown of the local thermal equilibrium (LTE) approximation and that the mutual information can quantify the breakdown of the LTE successfully. [ABSTRACT FROM AUTHOR]

In an extension of earlier studies from this group on the application of the Jarzynski equality to the determination of the elastic properties of a finitely extensible Rouse model of polymers under flow [A. Ghosal and B. J. Cherayil, J. Chem. Phys. 144, 214902 (2016)], we derive several new theoretical results in this paper on the nature of the distribution function P(w) that governs the long-time limit t>>1 of the fluctuations in the work w performed by the polymer during flow-induced stretching. In particular, we show that an expression for the average of the nth power of the work, 〈wn(t)〉, can be obtained in closed form in this limit, making it possible to exactly calculate three important statistical measures of P(w): the mean μ, the skewness γ1, and the kurtosis γ2 (apart from the variance σ²). We find, for instance, that to leading order in t, the mean grows linearly with t at a constant value of the dimensionless flow rate Wi and that the slope of the μ−t curve increases with increasing Wi. These observations are in complete qualitative agreement with data from Brownian dynamics simulations of flow-driven double-stranded DNA by Latinwo and Schroeder [Macromolecules 46, 8345 (2013)]. We also find that the skewness γ1 exhibits an interesting inversion of sign as a function of Wi, starting off at positive values at low Wi and changing to negative values at larger Wi. The inversion takes place in the vicinity of what we interpret as a coil-stretch transition. Again, the finding exactly reproduces behavior seen in other numerical and experimental work by the above group Latinwo et al. [J. Chem. Phys. 141, 174903 (2014)]. Additionally, at essentially the same value of Wi at which this sign inversion takes place, we observe that the kurtosis reaches a minimum, close to 1, providing further evidence of the existence of a coil-stretch transition at this location. Our calculations reproduce another numerical finding: a power law dependence on Wi of the rate of work production that is characterized by two distinct regimes, one lying below the putative coil-stretch transition, where the exponent assumes one value, and the other above, where it assumes a second. [ABSTRACT FROM AUTHOR]

In this paper, molecular dynamics simulations are used to study the effect of molecular water and composition (Si/Al ratio) on the structure and mechanical properties of fully polymerized amorphous sodium aluminosilicate geopolymer binders. The X-ray pair distribution function for the simulated geopolymer binder phase showed good agreement with the experimentally determined structure in terms of bond lengths of the various atomic pairs. The elastic constants and ultimate tensile strength of the geopolymer binders were calculated as a function of water content and Si/Al ratio; while increasing the Si/Al ratio from one to three led to an increase in the respective values of the elastic stiffness and tensile strength, for a given Si/Al ratio, increasing the water content decreased the stiffness and strength of the binder phase. An atomic-scale analysis showed a direct correlation between water content and diffusion of alkali ions, resulting in the weakening of the AlO4 tetrahedral structure due to the migration of charge balancing alkali ions away from the tetrahedra, ultimately leading to failure. In the presence of water molecules, the diffusion behavior of alkali cations was found to be particularly anomalous, showing dynamic heterogeneity. This paper, for the first time, proves the efficacy of atomistic simulations for understanding the effect of water in geopolymer binders and can thus serve as a useful design tool for optimizing composition of geopolymers with improved mechanical properties. [ABSTRACT FROM AUTHOR]

The general theory of the construction of scale-consistent energy terms in the coarse-grained force fields presented in Paper I of this series has been applied to the revision of the UNRES force field for physics-based simulations of proteins. The potentials of mean force corresponding to backbone-local and backbone-correlation energy terms were calculated from the ab initio energy surfaces of terminally blocked glycine, alanine, and proline, and the respective analytical expressions, derived by using the scale-consistent formalism, were fitted to them. The parameters of all these potentials depend on single-residue types, thus reducing their number and preventing over-fitting. The UNRES force field with the revised backbone-local and backbone-correlation terms was calibrated with a set of four small proteins with basic folds: tryptophan cage variant (TRP1; α), Full Sequence Design (FSD; α + β), villin headpiece (villin; α), and a truncated FBP-28 WW-domain variant (2MWD; β) (the NEWCT-4P force field) and, subsequently, with an enhanced set of 9 proteins composed of TRP1, FSD, villin, 1BDC (α), 2I18 (α), 1QHK (α + β), 2N9L (α + β), 1E0L (β), and 2LX7 (β) (the NEWCT-9P force field). The NEWCT-9P force field performed better than NEWCT-4P in a blind-prediction-like test with a set of 26 proteins not used in calibration and outperformed, in a test with 76 proteins, the most advanced OPT-WTFSA-2 version of UNRES with former backbone-local and backbone-correlation terms that contained more energy terms and more optimizable parameters. The NEWCT-9P force field reproduced the bimodal distribution of backbone-virtual-bond angles in the simulated structures, as observed in experimental protein structures. [ABSTRACT FROM AUTHOR]

In this paper, we study a system of entangled chains that bear reversible cross-links in a melt state. The cross-links are tethered uniformly on the backbone of each chain. A slip-link type model for the system is presented and solved for the relaxation modulus. The effects of entanglements and reversible cross-linkers are modelled as a discrete form of constraints that influence the motion of the primitive path. In contrast to a non-associating entangled system, the model calculations demonstrate that the elastic modulus has a much higher first plateau and a delayed terminal relaxation. These effects are attributed to the evolution of the entangled chains, as influenced by tethered reversible linkers. The model is solved for the case when the linker survival time τs is greater than the entanglement time τe, but less than the Rouse time τR. [ABSTRACT FROM AUTHOR]

Organic materials with a high index of refraction (RI) are attracting considerable interest due to their potential application in optic and optoelectronic devices. However, most of these applications require an RI value of 1.7 or larger, while typical carbon-based polymers only exhibit values in the range of 1.3–1.5. This paper introduces an efficient computational protocol for the accurate prediction of RI values in polymers to facilitate in silico studies that can guide the discovery and design of next-generation high-RI materials. Our protocol is based on the Lorentz-Lorenz equation and is parametrized by the polarizability and number density values of a given candidate compound. In the proposed scheme, we compute the former using first-principles electronic structure theory and the latter using an approximation based on van der Waals volumes. The critical parameter in the number density approximation is the packing fraction of the bulk polymer, for which we have devised a machine learning model. We demonstrate the performance of the proposed RI protocol by testing its predictions against the experimentally known RI values of 112 optical polymers. Our approach to combine first-principles and data modeling emerges as both a successful and a highly economical path to determining the RI values for a wide range of organic polymers. [ABSTRACT FROM AUTHOR]

In this paper, we focus on the relaxation dynamics of Sierpinski hexagon fractal polymer. The relaxation dynamics of this fractal polymer is investigated in the framework of the generalized Gaussian structure model using both Rouse and Zimm approaches. In the Rouse-type approach, by performing real-space renormalization transformations, we determine analytically the complete eigenvalue spectrum of the connectivity matrix. Based on the eigenvalues obtained through iterative algebraic relations we calculate the averaged monomer displacement and the mechanical relaxation moduli (storage modulus and loss modulus). The evaluation of the dynamical properties in the Rousetype approach reveals that they obey scaling in the intermediate time/frequency domain. In the Zimm-type approach, which includes the hydrodynamic interactions, the relaxation quantities do not show scaling. The theoretical findings with respect to scaling in the intermediate domain of the relaxation quantities are well supported by experimental results. [ABSTRACT FROM AUTHOR]

Morphology of symmetric ABCD tetrablock quaterpolymers in melt was studied by the Monte Carlo (MC) simulation, where the volume fractions of the block chains, f, kept the relationships of fA = fD and fB = fC, and the volume fraction of the two mid-blocks φ was defined as φ = fB + fC. Previous self-consistent field theory for ABCD reported morphological change including several structures; however, the scope was limited within a two-dimensional system. To the contrary, in this paper, MC simulations were carried out in three dimensions with changing the φ value finely, which resulted in finding a tetracontinuous structure in the range of 0.625 ⩽ φ ⩽ 0.75. Moreover the tetracontinuous structure has been found to be the gyroid structure, and the mean curvature of the B/C interface is nearly zero. We concluded that the B/C interface must be the Schoen gyroid surface, one of three-dimensional periodic minimal surfaces. The geometrical nature of the A/B interface should be equivalent to that of the C/D interface, and they stand as level surfaces to the Schoen gyroid surface. [ABSTRACT FROM AUTHOR]

This paper presents a theoretical analysis of the closure kinetics of a polymer with hydrodynamic interactions. This analysis, which takes into account the non-Markovian dynamics of the end-to-end vector and relies on the preaveraging of the mobility tensor (Zimm dynamics), is shown to reproduce very accurately the results of numerical simulations of the complete nonlinear dynamics. It is found that Markovian treatments based on a Wilemski-Fixman approximation significantly overestimate cyclization times (up to a factor 2), showing the importance of memory effects in the dynamics. In addition, this analysis provides scaling laws of the mean first cyclization time (MFCT) with the polymer size N and capture radius b, which are identical in both Markovian and non-Markovian approaches. In particular, it is found that the scaling of the MFCT for large N is given by T - N3/2ln(N/b²), which differs from the case of the Rouse dynamics where T - N². The extension to the case of the reaction kinetics of a monomer of a Zimm polymer with an external target in a confined volume is also presented. [ABSTRACT FROM AUTHOR]

Although the Williams-Landell-Ferry (WLF) equation for the segmental relaxation time T(T) of glass-forming materials is one of the most commonly encountered relations in polymer physics, its molecular basis is not well understood. The WLF equation is often claimed to be equivalent to the Vogel-Fulcher-Tammann (VFT) equation, even though the WLF expression for T(T) contains no explicit dependence on the fragility parameter D of the VFT equation, while the VFT equation lacks any explicit reference to the glass transition temperature Tg, the traditionally chosen reference temperature in the WLF equation. The observed approximate universality of the WLF parameters C1(g) and C2(g) implies that T(T) depends only on T-Tg, a conclusion that seems difficult to reconcile with the VFT equation where the fragility parameter D largely governs the magnitude of T(T). The current paper addresses these apparent inconsistencies by first evaluating the macroscopic WLF parameters C1(g) and C2(g) from the generalized entropy theory of glass-formation and then by determining the dependence of C1(g) and C2(g) on the microscopic molecular parameters (including the strength of the cohesive molecular interactions and the degree of chain stiffness) and on the molar mass of the polymer. Attention in these calculations is restricted to the temperature range (Tg < T < Tg + 100 K), where both the WLF and VFT equations apply. [ABSTRACT FROM AUTHOR]

Most theories of the binding of molecules to surfaces or for the association between molecules treat the binding species as structureless entities and neglect their rigidity and the changes in their stiffness induced by the binding process. The binding species are also taken to be "ideal," meaning that the existence of van der Waals interactions and changes in these interactions upon molecular binding are also neglected. An understanding of the thermodynamics of these multifunctional molecular binding processes has recently come into focus in the context of the molecular binding of complex molecules, such as dendrimers and DNA grafted nanoparticles, to surfaces where the degree of binding cooperativity and selectivity, as well as the location of the binding transition, are found to be sensitive to the number of binding units constrained to a larger scale polymeric scaffold. We address the fundamental problem of molecular binding by extending classical Langmuir theory to describe the particular example of the reversible binding of semiflexible polymer chains to a solid substrate under melt conditions. The polymer chains are assumed to have a variable number N of binding units (segments) and to exhibit variable bending energies and van der Waals interactions in the bulk and on the surface, in addition to strong directional interactions with the surface. The resulting generalized Langmuir theory is applied to the examination of the influence of the chain connectivity of ideal polymers on the surface coverage Θ, transition binding temperature T 1/2 at which Θ = 1/2, and on the derivative |dΘ/dT| T=T 1/2 and the constant volume specific heat of binding, C v , measures of the cooperativity and "sharpness" of the binding transition, respectively. Paper II is devoted to the impact of the van der Waals attractive interactions and chain stiffness on the reversible binding of nonideal polymer chains to a solid surface, including the enthalpy-entropy compensation phenomenon observed experimentally in many molecular and particle binding processes.bind , measures of the cooperativity and "sharpness" of the binding transition, respectively. Paper II is devoted to the impact of the van der Waals attractive interactions and chain stiffness on the reversible binding of nonideal polymer chains to a solid surface, including the enthalpy-entropy compensation phenomenon observed experimentally in many molecular and particle binding processes.

The presence of gradient softer outer layers, commonly observed in biological systems (such as cartilage and ocular tissues), as well as synthetic crosslinked hydrogels, profoundly influences their interactions with opposing surfaces. Our prior research demonstrated that gradient-stiffness hydrogel layers, characterized by increasing elasticity with depth, control contact mechanics, particularly in proximity to the layer thickness. We postulate that the distribution of polymers within these gradient layers imparts extraordinary stretch and adhesion characteristics due to network adaptability and stress-induced reorganization. To investigate this phenomenon, we utilized Atomic Force Microscopy nanoindentation to assess the depth-dependent adhesion behavior of polyacrylamide hydrogels with varying gradient layer thicknesses. Two gradient layer thicknesses were achieved by employing different molding materials: glass and polyoxymethylene (POM). Glass-molded hydrogels exhibited a thinner gradient layer alongside a stiffer bulk layer compared to their POM-molded counterparts. In indentation experiments, the POM-molded hydrogel had larger adhesion compared to glass-molded hydrogel. We find that indenting within the gradient layer engenders increased load-unload hysteresis due to heightened fluid transport in the sparse outer polymer network. Consequently, this led to augmented adhesion and work of separation at shallow depths. We suggest that the prominent stretching capability of the sparse outer polymer network during probe retraction contributes to enhanced adhesion. The Maugis–Dugdale adhesive model only fits well to indentations on the thin layer or indentations which engage significantly with the bulk. These results facilitate a comprehensive characterization of adhesion mechanics in gradient-stiffness hydrogels, which could foster their application across emerging contexts in health science and environmental domains. [ABSTRACT FROM AUTHOR]

Mastering the manipulation of the electron spin plays a crucial role in comprehending the behavior of organic materials in several applications, such as asymmetric catalysis, chiroptical switches, and electronic devices. A promising avenue for achieving such precise control lies in the Chiral Induced Spin Selectivity (CISS) effect, where electrons with a favored spin exhibit preferential transport through chiral assemblies of specific handedness. Chiral supramolecular polymers emerge as excellent candidates for exploring the CISS effect due to their ability to modulate their helical structure through noncovalent interactions. In this context, systems capable of responding to external stimuli are particularly intriguing, sometimes even displaying chirality inversion. This study unveils spin selectivity in chiral supramolecular polymers, derived from single enantiomers, through scanning tunneling microscopy conducted in scanning tunneling spectroscopy mode. Following two distinct sample preparation protocols for each enantiomer, we generate supramolecular polymers with opposite handedness and specific spin transport characteristics. Our primary focus centers on chiral π-conjugated building blocks, with the aim of advancing novel systems that can inspire the organic spintronics community from a supramolecular chemistry level. [ABSTRACT FROM AUTHOR]

Comb-like polymers have shown potential as advanced materials for a diverse palette of applications due to the tunability of their polymer architecture. To date, however, it still remains a challenge to understand how the conformational properties of these polymers arise from the interplay of their architectural parameters. In this work, extensive simulations were performed using dissipative particle dynamics to investigate the effect of grafting density, backbone length, and sidechain length on the conformations of comb-like polymers immersed in a good solvent. To quantify the effect of these architectural parameters on polymer conformations, we computed the asphericity, radius of gyration, and backbone and sidechain end-to-end distances. Bond–bond correlation functions and effective Kuhn lengths were computed to quantify the topological stiffness induced by sidechain–sidechain interactions. Simulation results reveal that the effective Kuhn length increases as grafting density and sidechain length increase, in agreement with previous experimental and theoretical studies. This increase in stiffness results in comb-like polymers adopting extended conformations as grafting density and sidechain length increase. Simulation results regarding the radius of gyration of comb-like polymers as a function of grafting density are compared with scaling theory predictions based on a free energy proposed by Morozova and Lodge [ACS Macro Lett. 6, 1274–1279 (2017)] and scaling arguments by Tang et al. [Macromolecules 55, 8668–8675 (2022)]. [ABSTRACT FROM AUTHOR]

We analyze the shear response of grafted polymer chains in shear flow via coarse-grained molecular dynamics simulations with an explicit solvent. We find that the solvent flow penetrates into almost the whole brush for "mushroom"-type brushes but only a few bond distances for dense brushes. In all cases, the external stress on the wall equals the entropic stress associated with the distorted polymer conformations. We find that the external stress increases linearly with shear rate at low rates and sublinearly at high rates. The transition from linear to sublinear scaling occurs where chains react to flow by reorienting. Sublinear scaling with shear rate disappears if the shear rate is nondimensionalized with the effective relaxation time of chain subsegments located in the outer part of the brush that experiences flow. [ABSTRACT FROM AUTHOR]

Micelles of anionic or zwitterionic surfactants produced depletion interactions between nanofibrils leading to weak gels, while cationic surfactants adsorbed to the nanofibrils, screening repulsions leading to tough gels or phase separation. Are fundamentally and technologically interesting due to their diverse building blocks, network-supporting attractive forces, and gelation pathways. As described below, the 29 articles that appear in this issue shed new light on a wide variety of related topics, including limited valence networks, bridged colloidal networks and coagulant gels, depletant-mediated gels, I in situ i structural characterization of gel aging, mechanical and rheological properties of colloidal networks, hybrid and deformable particle assemblies, and nanocrystal gels with tunable optical response. Bridged networks and coagulant gels Colloidal networks formed by nonspecific bridging polymers represent another interesting class of gel formers, although it can be challenging to design dispersible systems with tunable polymer-colloid interactions. [Extracted from the article]

A polymer model given in terms of beads, interacting through Hookean springs and hydrodynamic forces, is studied. A Brownian dynamics description of this bead-spring polymer model is extended to multiple resolutions. Using this multiscale approach, a modeller can efficiently look at different regions of the polymer in different spatial and temporal resolutions with scalings given for the number of beads, statistical segment length, and bead radius in order to maintain macro-scale properties of the polymer filament. The Boltzmann distribution of a Gaussian chain for differing statistical segment lengths gives a diffusive displacement equation for the multi-resolution model with a mobility tensor for different bead sizes. Using the pre-averaging approximation, the translational diffusion coefficient is obtained as a function of the inverse of a matrix and then in closed form in the long-chain limit. This is then confirmed with numerical experiments. [ABSTRACT FROM AUTHOR]

To examine the conventional idea that the gauche conformation of the OCCO dihedral angle promotes the dissolution of polyethylene glycol (PEG) in water through strong hydration, the thermodynamic properties of liquid mixtures of PEG and water were studied by means of polymer reference interaction site model (PRISM) theory. The intramolecular correlation functions required as input for PRISM theory were calculated by the generator matrix method, accompanied by changes in the distribution of dihedral angles. In the infinite dilution limit, the increased probability of gauche conformation of the OCCO dihedral angles stabilizes the hydration of PEG through enhanced hydrogen bonding between the ether oxygen of PEG and water. The mixing Gibbs energies of the liquid mixtures were also calculated in the whole concentration range based on the Gibbs–Duhem equation, as per our recent proposal. A liquid–liquid phase separation was observed when all the dihedral angles of PEG were in the trans conformation; for the liquid mixture to be miscible in the whole concentration range, the introduction of the OCCO gauche conformation was found to be indispensable. The above theoretical results support the conventional idea that the OCCO gauche conformation is important for the high miscibility of PEG and water. [ABSTRACT FROM AUTHOR]

The scattering functions of nine generations of ideal tri-functional comb and dendrimer polymers are computed by novel graph techniques. The properties of polymers having from 9 to 3069 branches are explored. The g-ratios and the scattering functions indicate that as the number of branches increases, comb polymers behave more and more like linear polymers with half the number of branches, whereas dendrimers become more like spherical objects. [ABSTRACT FROM AUTHOR]

Contemporary graph learning algorithms are not well-suited for large molecules since they do not consider the hierarchical interactions among the atoms, which are essential to determining the molecular properties of macromolecules. In this work, we propose Multiresolution Graph Transformers (MGT), the first graph transformer architecture that can learn to represent large molecules at multiple scales. MGT can learn to produce representations for the atoms and group them into meaningful functional groups or repeating units. We also introduce Wavelet Positional Encoding (WavePE), a new positional encoding method that can guarantee localization in both spectral and spatial domains. Our proposed model achieves competitive results on three macromolecule datasets consisting of polymers, peptides, and protein-ligand complexes, along with one drug-like molecule dataset. Significantly, our model outperforms other state-of-the-art methods and achieves chemical accuracy in estimating molecular properties (e.g., highest occupied molecular orbital, lowest unoccupied molecular orbital, and their gap) calculated by Density Functional Theory in the polymers dataset. Furthermore, the visualizations, including clustering results on macromolecules and low-dimensional spaces of their representations, demonstrate the capability of our methodology in learning to represent long-range and hierarchical structures. Our PyTorch implementation is publicly available at https://github.com/HySonLab/Multires-Graph-Transformer. [ABSTRACT FROM AUTHOR]

Following recent molecular dynamic simulations [M. Dinpajooh and A. Nitzan, J. Chem. Phys. 153, 164903 (2020)], we theoretically analyze how the phonon heat transport along a single polymer chain may be affected by varying the chain configuration. We suggest that phonon scattering controls the phonon heat conduction in strongly compressed (and tangled) chain when multiple random bends act as scattering centers for vibrational phonon modes, which results in the diffusive character of heat transport. As the chain is straightening up, the number of scatterers decreases, and the heat transport acquires nearly ballistic character. To analyze these effects, we introduce a model of a long atomic chain made out of identical atoms where some atoms are put in contact with scatterers and treat the phonon heat transfer through such a system as a multichannel scattering problem. We simulate the changes in the chain configurations by varying the number of the scatterers and mimic a gradual straightening of the chain by a gradual reducing of the number of scatterers attached to the chain atoms. It is demonstrated, in agreement with recently published simulation results, that the phonon thermal conductance shows a threshold-like transition from the limit where nearly all atoms are attached to the scatterers to the opposite limit where the scatterers vanish, which corresponds to a transition from the diffusive to the ballistic phonon transport. [ABSTRACT FROM AUTHOR]

Formation of base pairs between the nucleotides of a ribonucleic acid (RNA) sequence gives rise to a complex and often highly branched RNA structure. While numerous studies have demonstrated the functional importance of the high degree of RNA branching—for instance, for its spatial compactness or interaction with other biological macromolecules—RNA branching topology remains largely unexplored. Here, we use the theory of randomly branching polymers to explore the scaling properties of RNAs by mapping their secondary structures onto planar tree graphs. Focusing on random RNA sequences of varying lengths, we determine the two scaling exponents related to their topology of branching. Our results indicate that ensembles of RNA secondary structures are characterized by annealed random branching and scale similarly to self-avoiding trees in three dimensions. We further show that the obtained scaling exponents are robust upon changes in nucleotide composition, tree topology, and folding energy parameters. Finally, in order to apply the theory of branching polymers to biological RNAs, whose length cannot be arbitrarily varied, we demonstrate how both scaling exponents can be obtained from distributions of the related topological quantities of individual RNA molecules with fixed length. In this way, we establish a framework to study the branching properties of RNA and compare them to other known classes of branched polymers. By understanding the scaling properties of RNA related to its branching structure, we aim to improve our understanding of the underlying principles and open up the possibility to design RNA sequences with desired topological properties. [ABSTRACT FROM AUTHOR]

Mesogens, which are typically stiff rodlike or disklike molecules, are able to self-organize into liquid crystal (LC) phases in a certain temperature range. Such mesogens, or LC groups, can be attached to polymer chains in various configurations including within the backbone (main-chain LC polymers) or at the ends of side-chains attached to the backbone in an end-on or side-on configuration (side-chain LC polymers or SCLCPs), which can display synergistic properties arising from both their LC and polymeric character. At lower temperatures, chain conformations may be significantly altered due to the mesoscale LC ordering; thus, when heated from the LC ordered state through the LC to isotropic phase transition, the chains return from a more stretched to a more random coil conformation. This can cause macroscopic shape changes, which depend significantly on the type of LC attachment and other architectural properties of the polymer. Here, to study the structure–property relationships for SCLCPs with a range of different architectures, we develop a coarse-grained model that includes torsional potentials along with LC interactions of a Gay–Berne form. We create systems of different side-chain lengths, chain stiffnesses, and LC attachment types and track their structural properties as a function of temperature. Our modeled systems indeed form a variety of well-organized mesophase structures at low temperatures, and we predict higher LC-to-isotropic transition temperatures for the end-on side-chain systems than for analogous side-on side-chain systems. Understanding these phase transitions and their dependence on polymer architecture can be useful in designing materials with reversible and controllable deformations. [ABSTRACT FROM AUTHOR]

Many variants of RNA, DNA, and even proteins can be considered semiflexible polymers, where bending stiffness, as a type of energetic penalty, competes with attractive van der Waals forces in structure formation processes. Here, we systematically investigate the effect of the bending stiffness on ground-state conformations of a generic coarse-grained model for semiflexible polymers. This model possesses multiple transition barriers. Therefore, we employ advanced generalized-ensemble Monte Carlo methods to search for the lowest-energy conformations. As the formation of distinct versatile ground-state conformations, including compact globules, rod-like bundles, and toroids, strongly depends on the strength of the bending restraint, we also performed a detailed analysis of contact and distance maps. [ABSTRACT FROM AUTHOR]

Nonsolvent-induced phase separation (NIPS) is a popular method for creating polymeric particles with internal microstructure, but many fundamental questions remain surrounding the kinetics of the complex coupled mass transfer and phase separation processes. In this work, we use simulations of a phase-field model to examine how (i) finite domain boundaries of a polymer droplet and (ii) solvent/nonsolvent miscibility affect the NIPS process. To isolate the effects of phase separation kinetics and solvent/nonsolvent mass transfer on the NIPS process, we study two different cases. First, we investigate droplet concentrations that originate inside the two-phase region, where phase separation kinetics alone governs the microstructure. Second, we investigate the effects of solvent/nonsolvent mass transfer by studying droplet concentrations that begin outside the two-phase region, where both phase separation kinetics and mass transfer play a role. In both cases, we find that qualitative NIPS behavior is a strong function of the relative location of the initial droplet composition with respect to the phase diagram. We also find that polymer/nonsolvent miscibility competes with solvent/nonsolvent miscibility in driving NIPS kinetic behavior. Finally, we examine polymer droplets undergoing solvent/nonsolvent exchange and find that the model predicts droplets that shrink with nearly Fickian diffusion kinetics. We conclude with a brief perspective on the state of simulations of NIPS processes and some recommendations for future work. [ABSTRACT FROM AUTHOR]

Polymer cation exchange membranes (CEMs) are widely used in water treatment processes. The fundamental factors that control the separation and selectivity of cations with different valences in CEMs are not fully understood. In this study, we use atomistic molecular dynamics simulations to investigate the underlying molecular mechanisms that control the mobility of cations with different valences in Nafion membranes. Our results indicate structural differences in binding of monovalent and divalent cations, which gives rise to differences in ion diffusion in Nafion. Monovalent cations are shown to be "territorially" bound, i.e., bound while partially hydrated, to the fixed charge groups whereas divalent cations are shown to be "site" bound, i.e., bound while fully dehydrated, to the charge groups on the polymer. This difference in binding structure gives rise to differences in transport characteristics of cations in Nafion. [ABSTRACT FROM AUTHOR]

We present a theory of adsorption of flexible polyelectrolytes on the interior and exterior surfaces of a charged vesicle in an electrolyte solution. The criteria for adsorption and the density profiles of the adsorbed polymer chain are derived in terms of various characteristics of the polymer, vesicle, and medium, such as the charge density and length of the polymer, charge density and size of the vesicle, electrolyte concentration and dielectric constant of the medium. For adsorption inside the vesicle, the competition between the loss of conformational entropy and gain in adsorption energy results in two kinds of encapsulated states, depending on the strength of the polymer-vesicle interaction. By considering also the adsorption from outside the vesicle, we derive the entropic and energy contributions to the free energy change to transfer an adsorbed chain in the interior to an adsorbed chain on the exterior. In this paper, we have used the Wentzel-Kramers-Brillouin (WKB) method to solve the equation for the probability distribution function of the chain. The present WKB results are compared with the previous results based on variational methods. The WKB and variational results are in good agreement for both the interior and exterior states of adsorption, except in the zero-salt limit for adsorption in the exterior region. The adsorption criteria and density profiles for both the interior and exterior states are presented in terms of various experimentally controllable variables. Calculation of the dependencies of free energy change to transfer an adsorbed chain from the interior to the exterior surface on salt concentration and vesicle radius shows that the free energy penalty to expel a chain from a vesicle is only of the order of thermal energy. [ABSTRACT FROM AUTHOR]

We develop a theory for the motion of a particle grafted with inhomogeneous bead-spring Rouse chains via the generalized Langevin equation (GLE), where individual grafted polymers are allowed to take different bead friction coefficients, spring constants, and chain lengths. An exact solution of the memory kernel K(t) is obtained for the particle in the time (t) domain in the GLE, which depends only on the relaxation of the grafted chains. The t-dependent mean square displacement g(t) of the polymer-grafted particle is then derived as a function of the friction coefficient γ0 of the bare particle and K(t). Our theory offers a direct way to quantify the contributions of the grafted chain relaxation to the mobility of the particle in terms of K(t). This powerful feature enables us to clarify the effect on g(t) of dynamical coupling between the particle and grafted chains, leading to the identification of a relaxation time of fundamental importance in polymer-grafted particles, namely, the particle relaxation time. This timescale quantifies the competition between the contributions of the solvent and grafted chains to the friction of the grafted particle and separates g(t) into the particle- and chain-dominated regimes. The monomer relaxation time and the grafted chain relaxation time further divide the chain-dominated regime of g(t) into subdiffusive and diffusive regimes. Analysis of the asymptotic behaviors of K(t) and g(t) provides a clear physical picture of the mobility of the particle in different dynamical regimes, shedding light on the complex dynamics of polymer-grafted particles. [ABSTRACT FROM AUTHOR]

Polymers contain functional groups that participate in hydrogen bond (H-bond) with water molecules, establishing a robust H-bond network that influences bulk properties. This study utilized molecular dynamics (MD) simulations to examine the H-bonding dynamics of water molecules confined within three poly(meth)acrylates: poly(2-methoxyethyl acrylate) (PMEA), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(1-methoxymethyl acrylate) (PMC1A). Results showed that H-bonding dynamics significantly slowed as the water content decreased. Additionally, the diffusion of water molecules and its correlation with H-bond breakage were analyzed. Our findings suggest that when the H-bonds between water molecules and the methoxy oxygen of PMEA are disrupted, those water molecules persist in close proximity and do not diffuse on a picosecond time scale. In contrast, the water molecules H-bonded with the hydroxy oxygen of PHEMA and the methoxy oxygen of PMC1A diffuse concomitantly with the breakage of H-bonds. These results provide an in-depth understanding of the impact of polymer functional groups on H-bonding dynamics. [ABSTRACT FROM AUTHOR]

Polymers conjugated with active agents have applications in biomedicine, anticorrosion, and smart agriculture. When the active agent is used as a drug, corrosion inhibitor, or pesticide, it can be released upon a specific stimulus. The efficiency and the sustainability of active agents are determined by the released kinetics. In this work, we study the fast-release kinetics of 8-hydroxyquinoline (8HQ) from a pH-responsive, random copolymer of methyl methacrylate and 8-quinolinyl-sulfide-ethyl acrylate [P(MMA-co-HQSEA)] by hydrolysis of the β-thiopropionate groups. We used contact angle measurements of sliding drops as an elegant way to characterize the release kinetics. Based on the results gained from 1H nuclear magnetic resonance measurement, fluorescent intensity measurement, and velocity-dependent contact angle measurement, we found that both the hydrolysis rate and polymer conformation affect the release kinetics of 8HQ from a P(MMA-co-HQSEA) film. Polymer chains collapse and further suppress the release from the inner layer in acidic conditions, while polymer chains in a stretched condition further facilitate the release from the inner layer. As a result, the cumulative release rate of 8HQ is higher in the basic condition than in the acidic condition. [ABSTRACT FROM AUTHOR]

We derive the non-adiabatic ring polymer molecular dynamics (RPMD) approach in the phase space of the SU(N) Lie Group. This method, which we refer to as the spin mapping non-adiabatic RPMD (SM-NRPMD), is based on the spin-mapping formalism for the electronic degrees of freedom (DOFs) and ring polymer path-integral description for the nuclear DOFs. Using the Stratonovich–Weyl transform for the electronic DOFs and the Wigner transform for the nuclear DOFs, we derived an exact expression of the Kubo-transformed time-correlation function (TCF). We further derive the spin mapping non-adiabatic Matsubara dynamics using the Matsubara approximation that removes the high frequency nuclear normal modes in the TCF and derive the SM-NRPMD approach from the non-adiabatic Matsubara dynamics by discarding the imaginary part of the Liouvillian. The SM-NRPMD method has numerical advantages compared to the original NRPMD method based on the Meyer–Miller–Stock–Thoss (MMST) mapping formalism due to a more natural mapping using the SU(N) Lie Group that preserves the symmetry of the original system. We numerically compute the Kubo-transformed position auto-correlation function and electronic population correlation function for three-state model systems. The numerical results demonstrate the accuracy of the SM-NRPMD method, which outperforms the original MMST-based NRPMD. We envision that the SM-NRPMD method will be a powerful approach to simulate electronic non-adiabatic dynamics and nuclear quantum effects accurately. [ABSTRACT FROM AUTHOR]

The Jarzynski relation (and its variants) has provided a route to the experimental evaluation of equilibrium free energy changes based on measurements conducted under arbitrary non-equilibrium conditions. Schroeder and co-workers [Soft Matter 10, 2178 (2014) and J. Chem. Phys. 141, 174903 (2014)] have recently exploited this fact to determine the elastic properties of model DNA from simulations and experiments of chain extension under elongational flow, bypassing the need to make these measurements mechanically using sophisticated optical trapping techniques. In this paper, motivated by these observations, we investigate chain elasticity analytically, using the Jarzynski relation and a finitely extensible nonlinear elastic-type Rouse model within a path integral formalism to calculate (essentially exactly) both the flow-induced free energy change between chain conformations of definite average end-to-end distance, as well as the force-extension curve that follows from it. This curve, based on a new analytic expression, matches the trends in the corresponding curve obtained from a model of chain stretching developed by Marko and Siggia [Macromolecules 28, 8759 (1995)], which itself is in very satisfactory agreement with the numerical and experimental data from the work of Schroeder et al.

Polymer density functional theory (PDFT) is a computationally efficient and robust statistical mechanics theory for capturing the interfacial microstructure of grafted polymer brushes (PBs). Undoubtedly, the intramolecular and intermolecular interactions in PDFT (e.g., hard-core interactions and direct Coulomb interactions) are greatly affected by the grafting behavior of PBs. However, the combination of these interactions with the physical constraints on grafting behavior remains unclear and there is a remarkable difference in the density profile of grafted PB between PDFT and simulation. Herein, we propose a PDFT to study neutral and charged grafted PBs by incorporating the physical constraints of end-grafted PBs into the excess free energies due to intramolecular and intermolecular interactions. This PDFT has been successfully validated where the density distributions of neutral and weakly charged PBs predicted by the PDFT are in excellent agreement with the results of the Monte Carlo and molecular dynamics simulations. In addition, the significant contribution of grafting behavior to the free energy of PB systems is presented. Consequently, this work provides a powerful and accurate theoretical method to reveal the interfacial microstructure of grafted PBs. [ABSTRACT FROM AUTHOR]

Similarly charged polyelectrolytes are known to attract each other and aggregate into bundles when the charge density of the polymers exceeds a critical value that depends on the valency of the counterions. The dynamics of aggregation of such rigid polyelectrolytes are studied using large scale molecular dynamics simulations. We find that the morphology of the aggregates depends on the value of the charge density of the polymers. For values close to the critical value, the shape of the aggregates is cylindrical with height equal to the length of a single polyelectrolyte chain. However, for larger values of charge, the linear extent of the aggregates increases as more and more polymers aggregate. In both the cases, we show that the number of aggregates decrease with time as power laws with exponents that are not numerically distinguishable from each other and are independent of charge density of the polymers, valency of the counterions, density, and length of the polyelectrolyte chain. We model the aggregation dynamics using the Smoluchowski coagulation equation with kernels determined from the molecular dynamics simulations and justify the numerically obtained value of the exponent. Our results suggest that once counterions condense, effective interactions between polyelectrolyte chains short-ranged and the aggregation of polyelectrolytes are diffusion-limited. [ABSTRACT FROM AUTHOR]

We investigate the rheo-mechanical properties of Mebiol Gel®, a thermosensitive gel-forming polymer extensively used as a medium for cellular culture, using passive microrheology made either by standard dynamic light scattering or by photon correlation imaging. In the dilute limit, Mebiol displays a Newtonian behavior with an effective viscosity that decreases with temperature, consistent with a peculiar aggregation mechanism characterized by an increase of the molecular weight with a simultaneous reduction of the aggregate size. By increasing concentration and approaching gelation, both the storage and loss moduli show a nonmonotonic dependence with temperature, with a pronounced maximum around Tm ≃ 28–30 °C, the value above which, in the dilute limit, the individual Mebiol chains are fully compacted. Such a distinctive trend of the elastic and viscous properties persists within the gel, which, therefore, becomes "softer" above Tm. Although when temperature changes are performed adiabatically, the transition from the fluid to the gel phase takes place without any apparent discontinuity, a rapid T-jump leads to the formation of a hard gel at a concentration where a low heating rate conversely yields a fluid phase. This is a visible manifestation of the nonequilibrium nature of these physical gels. [ABSTRACT FROM AUTHOR]

We revisit a model of semiflexible Gaussian chains proposed by Winkler et al., solve the dynamics of the discrete description of the model, and derive exact algebraic expressions for some of the most relevant dynamical observables, such as the mean-square displacement of individual monomers, the dynamic structure factor, the end-to-end vector relaxation, and the shear stress relaxation modulus. The mathematical expressions for the dynamic structure factor are verified by comparing them with results from Brownian dynamics simulations, reporting an excellent agreement. Then, we generalize the model to linear polymer chains with arbitrary stiffness. In particular, we focus on the case of a linear polymer with stiffness that changes linearly from one end of the chain to the other, and we study the same dynamical functions previously presented. We discuss different approaches to check whether a polymer has constant or heterogeneous stiffness along its contour. Finally, we provide expressions for the Lagrangian multipliers for Gaussian chains with variable stiffness and bond length, as well as for chains with torsion-like interactions. Overall, this work presents a new insight into a well-known model for semiflexible chains and provides tools that can be exploited to explore a much broader class of polymers or compare the predictions of the model with simulations of coarse-grained semiflexible polymers. [ABSTRACT FROM AUTHOR]

We study the collective elastic behavior of semiflexible polymer solutions in a nematic liquid-crystalline state using polymer field theory. Our polymer field-theoretic model of semiflexible polymer solutions is extended to include second-order fluctuation corrections to the free energy, permitting the evaluation of the Frank elastic constants based on orientational order fluctuations in the nematic state. Our exact treatment of wormlike chain statistics permits the evaluation of behavior from the nematic state, thus accurately capturing the impact of single-chain behavior on collective elastic response. Results for the Frank elastic constants are presented as a function of aligning field strength and chain length, and we explore the impact of conformation fluctuations and hairpin defects on the twist, splay, and bend moduli. Our results indicate that the twist elastic constant Ktwist is smaller than both bend and splay constants (Kbend and Ksplay, respectively) for the entire range of polymer rigidity. Splay and bend elastic constants exhibit regimes of dominance over the range of chain stiffness, where Ksplay > Kbend for flexible polymers (large-N limit) while the opposite is true for rigid polymers. Theoretical analysis also suggests the splay modulus tracks exactly to that of the end-to-end distance in the transverse direction for semiflexible polymers at intermediate to large-N. These results provide insight into the role of conformation fluctuations and hairpin defects on the collective response of polymer solutions. [ABSTRACT FROM AUTHOR]

We present a simple mean-field theory to describe the polymer-mediated depletion attraction between colloidal particles that accounts for the polymer's chain stiffness. We find that for fixed polymer radius of gyration and volume fraction, the strength of this attraction increases with increasing chain stiffness in both dilute and semidilute concentration regimes. In contrast, the range of attraction monotonically decreases with chain stiffness in the dilute regime, while it attains a maximum in the semidilute regime. The obtained analytical expressions for the depletion interaction were compared with numerical self-consistent field lattice computations and shown to be in quantitative agreement. From the interaction potential between two spheres, we calculated the second osmotic virial coefficient B2, which appears to be a convex function of chain stiffness. A minimum of B2 as a function of chain stiffness was observed both in the numerical self-consistent field computations and the analytical theory. These findings help explain the general observation that semiflexible polymers are more effective depletants than flexible polymers and give insight into the phase behavior of mixtures containing spherical colloids and semiflexible polymers. [ABSTRACT FROM AUTHOR]

There are a variety of complementary descriptions of the temperature dependence of the structural relaxation time τ in glass-forming materials, which we interpret positively as suggesting an underlying unified description. We examine the inter-relation between the string model, an outgrowth of the Adam and Gibbs approach that emphasizes collective particle exchange motion, and the localization model, which emphasizes the volume explored by particles in their caged states, a kind of dynamic "free volume." Each model of liquid dynamics is described by a limited set of parameters that must be interrelated if both descriptions simultaneously describe the relaxation behavior. We pursue the consequences of this idea by performing coarse-grained molecular simulations of polymer melts with additives of variable size and interaction strength with the polymer matrix, thereby significantly altering the relaxation of the composite material. Both the string and localization models describe our relaxation time data well, and a comparison of the model parameters allows us to relate the local caging scale ⟨u2⟩ (the Debye-Waller parameter) to the entropy of activation for molecular rearrangements in the string model, thereby developing a bridge between these seemingly disparate approaches to liquid dynamics. [ABSTRACT FROM AUTHOR]

We report a colloid–polymer model system with tunable bridging interactions for microscopic studies of structure and dynamics using confocal imaging. The interactions between trifluoroethyl methacrylate-co-tert-butyl methacrylate copolymer particles and poly(acrylic acid) (PAA) polymers were controllable via polymer concentration and pH. The strength of adsorption of PAA on the particles, driven by pH-dependent interactions with polymer brush stabilizers on the particle surfaces, was tuned via solution pH. Particle–polymer suspensions formulated at low pH, where polymers strongly adsorbed to the particles, contained clusters or weak gels at particle volume fractions of ϕ = 0.15 and ϕ = 0.40. At high pH, where the PAA only weakly adsorbed to the particle surface, particles largely remained dispersed, and the suspensions behaved as a dense fluid. The ability to visualize the suspension structure is likely to provide insight into the role of polymer-driven bridging interactions in the behavior of colloidal suspensions. [ABSTRACT FROM AUTHOR]

Depletion attraction induced by non-adsorbing polymers or small particles in colloidal solutions has been widely used as a model colloidal interaction to understand aggregation behavior and phase diagrams, such as glass transitions and gelation. However, much less attention has been paid to study the effective colloidal interaction when small particles/molecules can be reversibly attracted to large colloidal particles. At the strong attraction limit, small particles can introduce bridging attraction as it can simultaneously attach to neighbouring large colloidal particles. We use Baxter's multi-component method for sticky hard sphere systems with the Percus-Yevick approximation to study the bridging attraction and its consequence to phase diagrams, which are controlled by the concentration of small particles and their interaction with large particles. When the concentration of small particles is very low, the bridging attraction strength increases very fast with the increase of small particle concentration. The attraction strength eventually reaches a maximum bridging attraction (MBA). Adding more small particles after theMBA concentration keeps decreasing the attraction strength until reaching a concentration above which the net effect of small particles only introduces an effective repulsion between large colloidal particles. These behaviors are qualitatively different from the concentration dependence of the depletion attraction on small particles and make phase diagrams very rich for bridging attraction systems. We calculate the spinodal and binodal regions, the percolation lines, the MBA lines, and the equivalent hard sphere interaction line for bridging attraction systems and have proposed a simple analytic solution to calculate the effective attraction strength using the concentrations of large and small particles. Our theoretical results are found to be consistent with experimental results reported recently. [ABSTRACT FROM AUTHOR]