Hydrodynamic Anisotropy of Depletion in Nonequilibrium.

Active colloids in a bath of inert particles of smaller size cause anisotropic depletion. The active hydrodynamics of this nonequilibrium phenomenon, which is fundamentally different from its equilibrium counterpart and passive particles in an active bath, remains scarcely understood. Here we combine mesoscale hydrodynamic simulation as well as theoretical analysis to examine the physical origin for the active depletion around a self-propelled noninteractive colloid. Our results elucidate that the variable hydrodynamic effect critically governs the microstructure of the depletion zone. Three characteristic states of anisotropic depletion are identified, depending on the strength and stress of activity. This yields a state diagram of depletion in the two-parameter space, captured by developing a theoretical model with the continuum kinetic theory and leading to a mechanistic interpretation of the hydrodynamic anisotropy of depletion. Furthermore, we demonstrate that such depletion in nonequilibrium results in various clusters with ordered organization of squirmers, which follows a distinct principle contrary to that of the entropy scenario of depletion in equilibrium. The findings might be of immediate interest to tune the hydrodynamics-mediated anisotropic interactions and active nonequilibrium organizations in the self-propulsion systems.

The entropy-controlled strategy in self-assembling systems.

Self-assembly of various building blocks has been considered as a powerful approach to generate novel materials with tailorable structures and optimal properties. Understanding physicochemical interactions and mechanisms related to structural formation and transitions is of essential importance for this approach. Although it is well-known that diverse forces and energies can significantly contribute to the structures and properties of self-assembling systems, the potential entropic contribution remains less well understood. The past few years have witnessed rapid progress in addressing the entropic effects on the structures, responses, and functions in the self-assembling systems, and many breakthroughs have been achieved. This review provides a framework regarding the entropy-controlled strategy of self-assembly, through which the structures and properties can be tailored by effectively tuning the entropic contribution and its interplay with the enthalpic counterpart. First, we focus on the fundamentals of entropy in thermodynamics and the entropy types that can be explored for self-assembly. Second, we discuss the rules of entropy in regulating the structural organization in self-assembly and delineate the entropic force and superentropic effect. Third, we introduce the basic principles, significance and approaches of the entropy-controlled strategy in self-assembly. Finally, we present the applications where this strategy has been employed in fields like colloids, macromolecular systems and nonequilibrium assembly. This review concludes with a discussion on future directions and future research opportunities for developing and applying the entropy-controlled strategy in complex self-assembling systems.

Configurational Entropy-Enabled Thermostability of Cell Membranes in Extremophiles: From Molecular Mechanism to Bioinspired Design.

Understanding physicochemical interactions and mechanisms related to the cell membranes of lives under extreme conditions is of essential importance but remains scarcely explored. Here, using a combination of computer simulations and experiments, we demonstrate that the structural integrity and controllable permeability of cell membranes at high temperatures are predominantly directed by configurational entropy emerging from distorted intermolecular organization of bipolar tethered lipids peculiar to the extremophiles. Detailed simulations across multiple scales─from an all-atom exploration of molecular mechanism to a mesoscale examination of its universal nature─suggest that this configurational entropy effect can be generalized to diverse systems, such as block copolymers. This offers biomimetic inspiration for designing heat-tolerant materials based on entropy, as validated by our experiments of synthetic polymers. The findings provide new insight into the basic nature of the mechanism underlying the adaptation of organisms to extreme conditions and might open paths for designed materials inspired by entropic effects in biological systems.

Understanding Interfacial Nanoparticle Organization through Simulation and Theory: A Review.

Understanding the behaviors of nanoparticles at interfaces is crucial not only for the design of novel nanostructured materials with superior properties but also for a better understanding of many biological systems where nanoscale objects such as drug molecules, viruses, and proteins can interact with various interfaces. Theoretical studies and tailored computer simulations offer unique approaches to investigating the evolution and formation of structures as well as to determining structure-property relationships regarding the interfacial nanostructures. In this feature article, we summarize our efforts to exploit computational approaches as well as theoretical modeling in understanding the organization of nanoscale objects at the interfaces of various systems. First, we present the latest research advances and state-of-the-art computational techniques for the simulation of nanoparticles at interfaces. Then we introduce the applications of multiscale modeling and simulation methods as well as theoretical analysis to explore the basic science and the fundamental principles in the interfacial nanoparticle organization, covering the interfaces of polymer, nanoscience, biomacromolecules, and biomembranes. Finally, we discuss future directions to signify the framework in tailoring the interfacial organization of nanoparticles based on the computational design. This feature article could promote further efforts toward fundamental research and the wide applications of theoretical approaches in designing interfacial assemblies for new types of functional nanomaterials and beyond.

Heterogeneous Dynamics of Polymer Melts Exerted by Chain Loops Anchored on the Substrate: Insights from Molecular Dynamics Simulation.

Understanding polymer-substrate interfacial dynamics at the molecular level is crucial for tailoring the properties of polymer ultrathin films (PUFs). Herein, through coarse-grained molecular dynamics simulation, the effect of length (Nloop) and rigidity (Kloop) of loop chains on the dynamics of linear chains is systematically explored, in which the loop chains are adsorbed on a solid substrate and the linear chains are covered on the loop chains. It is found that there is an optimal Kloop, which strongly confines the motion of the linear chains. Meanwhile, compared to increasing the rigidity of the loop chains, increasing the length of the loop chains can more effectively confine the motion of the linear chains. More interestingly, we observe that the mismatch of the length (ΔN) and rigidity (ΔK) between the loop and linear chains leads to dynamic asymmetry (ΔDc). The relationship between the ΔN, ΔK, and ΔDc are found to follow the mathematical expression of ΔDc ∼ (ΔN)α(ΔK)ß, in which the values of α and ß are around 4.58 and 0.83, separately. Remarkably, using the Gaussian process regression model, we construct a master curve of diffusion coefficient on the segmental and chain length scales of the linear chains as a function of Nloop and Kloop, which is further validated by our simulated prediction. In general, this work provides a fundamental understanding of polymer interfacial dynamics at the molecular level, enlightening some rational principles for manipulating the physical properties of PUFs.

Bimodal Polymer End-Linked Nanoparticle Network Design Strategy to Manipulate the Structure-Mechanics Relation.

A kind of bimodal polymer end-linked network employing nanoparticles (NPs) as net points has been designed and constructed through coarse-grained molecular dynamics simulation. We systematically explore the effects of the molecular weight (length of the long polymer chains), chain flexibility, and temperature on the accurate distribution of the spherical NPs and the resulting mechanical properties of the bimodal network. It is found that the NPs can be dispersed well, and a larger average distance between the NPs is realized with the increase of the length of the long polymer chains, the rigidity of short and long chains, and the temperature. There is a linear relationship between the average interparticle distance of NPs and the arithmetical average of the root-mean-square end-to-end distance of long and short chains. By adopting the uniaxial deformation, the stress-strain behavior and the bond orientation are examined. The results illustrate that introducing the short chains into the uniform long chains network can notably improve the tensile stress-strain performance. The bond orientation behaviors present that short chains are more prone to be oriented and stretched, contributing to more stress during the stretching process. Furthermore, enhanced stress-strain behaviors can be observed by manipulating the chain stiffness and temperature. Interestingly, the bimodal end-linked network reveals a distinctively enhanced stress-strain behavior versus the temperature, which is opposite to that of traditional physically mixed polymer nanocomposites (PNCs), attributed to a higher entropic elasticity and the uniform dispersion of NPs of the end-linked system at high temperatures. The network exhibits a linear relationship for the stress at a fixed strain versus the temperature. Notably, it is indicated that the contribution of entropy accounts for most of the total stress, while the change of internal energy only accounts for a small part, which is consistent with the experimental observation of the classic rubber elastic theory. In general, our study demonstrates a rational route to precisely control the spatial dispersion of the NPs and effectively tailor the mechanical properties of PNCs.

Unveiling the Mechanism of the Location of the Grafted Nanoparticles in a Lamellar-Forming Block Copolymer.

Through coarse-grained molecular dynamics simulation of polymer-grafted nanoparticles (NPs) in a lamellar-forming diblock copolymer (BCP), we systematically study the effects of the grafting density (Ng), the compatibility between the grafted chains and the A-block of BCPs (εgA), and the NP number (N) on the distance (D) of the NPs from the interface by proposing novel characterization parameters of the orientation and distribution of the grafted chains. The NP gradually migrates away from the interface and into the A-block region with the increase of εgA for all studied Ng, while slightly returning toward the interface at high εgA and great Ng, which is the first observation of nonmonotonic migration at the molecular level. We ascribe the reason of this to the behavior of the grafted chains that are near the interface. Furthermore, we classify the grafted chains into three types along the normal direction of the interface and the migration process is illustrated by the distribution and orientation of the different types of grafted chains, together with the radial distribution function between the NP and the A-block chains. We observe the formation of the NP layers parallel to the interface for N < 20, and a similar nonmonotonic migration of the layers is as well observed. The D is the largest for a small N because of the excluded volume effects between the NPs. Increasing Ng and N pushes the neighboring NP layers toward the interface due to the mutual repulsion. Generally, this study may shed some light on how to better understand and design high-performance polymer nanocomposites with a tunable location of NPs.

Tailoring the mechanical properties by molecular integration of flexible and stiff polymer networks.

Designing a multiple-network structure at the molecular level to tailor the mechanical properties of polymeric materials is of great scientific and technological importance. Through the coarse-grained molecular dynamics simulation, we successfully construct an interpenetrating polymer network (IPN) composed of a flexible polymer network and a stiff polymer network. First, we find that there is an optimal chain stiffness for a single network (SN) to achieve the best stress-strain behavior. Then we turn to study the mechanical behaviors of IPNs. The result shows that the stress-strain behaviors of the IPNs appreciably exceed the sum of that of the corresponding single flexible and stiff network, which highlights the advantage of the IPN structure. By systematically varying the stiffness of the stiff polymer network of the IPNs, optimal stiffness also exists to achieve the best performance. We attribute this to a much larger contribution of the non-bonded interaction energy. Last, the effect of the component concentration ratio is probed. With the increase of the concentration of the flexible network, the stress-strain behavior of the IPNs is gradually enhanced, while an optimized concentration (around 60% molar ration) of the stiff network occurs, which could result from the dominant role of the enthalpy rather than the entropy. In general, our work is expected to provide some guidelines to better tailor the mechanical properties of the IPNs made of a flexible network and a stiff network, by manipulating the stiffness of the stiff polymer network and the component concentration ratio.

Formation mechanism of bound rubber in elastomer nanocomposites: a molecular dynamics simulation study.

Bound rubber plays a key role in the mechanical reinforcement of elastomer nanocomposites. In the present work, we reveal the formation mechanism of bound rubber in elastomer nanocomposites, using the coarse-grained molecular dynamics simulations. For the polymer-nanoparticle system, the "chain bridge" connected with neighboring nanoparticles forms, once the gap between two neighboring nanoparticles is less than the polymer size. The polymer-nanoparticle-solvent systems, mimicking the oil-swollen rubber in the experiment, are simulated with three models. From the analysis of the potential energy, the static structure and dynamic diffusing processes, all the models indicate that the increase of the volume fraction of the nanoparticles and the polymer-nanoparticle interaction strength could promote the formation of the bound rubber. The existence of solvent disrupts the bound rubber, and eventually deteriorates the mechanical properties. These simulations could provide some theoretical guidance for a better understanding of the formation mechanism of the bound rubber, which is helpful for designing the elastomer materials with excellent mechanical properties.