Non-equilibrium structural and dynamic behaviors of active polymers in complex and crowded environments.

Active matter systems, which convert internal chemical energy or energy from the environment into directed motion, are ubiquitous in nature and exhibit a range of emerging non-equilibrium behaviors. However, most of the current works on active matter have been devoted to particles, and the study of active polymers has only recently come into the spotlight due to their prevalence within living organisms. The intricate interplay between activity and conformational degrees of freedom gives rise to novel structural and dynamical behaviors of active polymers. Research in active polymers remarkably broadens diverse concepts of polymer physics, such as molecular architecture, dynamics, scaling and so on, which is of significant importance for the development of new polymer materials with unique performance. Furthermore, active polymers are often found in strongly interacting and crowded systems and in complex environments, so that the understanding of this behavior is essential for future developments of novel polymer-based biomaterials. This review thereby focuses on the study of active polymers in complex and crowded environments, and aims to provide insights into the fundamental physics underlying the adaptive and collective behaviors far from equilibrium, as well as the open challenges that the field is currently facing.

Programmable Potentials Choreograph Defects in a Colloidal Crystal Shell.

Crystallization on spherical surfaces is obliged by topology to induce lattice defects. But controlling the organization of such defects remains a great challenge due to the long-range constraints of the curved geometry. Here, we report on DNA-coated colloids whose programmable interaction potentials can be used to regulate the arrangement of defects and even achieve perfect icosahedral order on a sphere. Combined simulations and theoretical analysis show how the potential can be tuned by changing the temperature, thereby controlling the number of defects. An explicit expression for the effective potential is derived, allowing us to distinguish the effects of entropic repulsion and enthalpic attraction. Altogether, the present findings provide insights into the physics of crystallization on curved spaces and may be used for designing desired crystal geometries.

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.

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.

"Shutter" Effects Enhance Protein Diffusion in Dynamic and Rigid Molecular Networks.

Hydrogels have been widely applied to understand the fundamental functions and mechanism of a natural extracellular matrix (ECM). However, revealing the high permeability of ECM through synthetic hydrogels is still challenged by constructing analogue networks with rigid and dynamic properties. Here, in this study, taking advantage of the rigidity and dynamic binding of DNA building blocks, we have designed a model hydrogel system with structural similarity to ECM, leading to enhanced diffusion for proteins compared with a synthetic polyacrylamide (PAAm) hydrogel. The molecular diffusion behaviors in such a rigid and dynamic network have been investigated both in experiments and simulations, and the dependence of diffusion coefficients with respect to molecular size exhibits a unique transition from a power law to an exponential function. A "shutter" model based on the rigid and dynamic molecular network has been proposed, which has successfully revealed how the rigidity and dynamic bond exchange determine the diffusion mechanism, potentially providing a novel perspective to understand the possible mechanism of enhanced diffusion behaviors in ECM.

Studies on the Synergistic Effect of Tandem Semi-Stable Complementary Domains on Sequence-Defined DNA Block Copolymers.

Tandem semi-stable complementary domains play an important role in life, while the role of these domains in the folding process of nucleic acid molecules has not been systematically studied. Here, we designed a clean model system by synthesizing sequence-defined DNA-OEG copolymers composed of ssDNA fragments with palindromic sequences and orthogonal oligo(tetraethylene glycol) (OEG) linkers. By altering the lengths of DNA units (6-12 nt) and OEG linkers (Xn = 0-4) separately, we systematically studied how stabilities of tandem complementary domains and connecting flexibilities affect the assembly topology. Combining experimental methods and coarse-grained molecular simulation analysis, distributions of multiple assembled conformations (mainly monomers, dimers, and clusters) were characterized. Both results indicated that tandem semi-stable complementary domains tend to form homogeneous closed circular dimers instead of larger clusters due to the synergistic enhancement effect, and the distributions of each conformation highly depend on flexibilities.

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.

Entropy-Driven Unconventional Crystallization of Spherical Colloidal Nanocrystals Confined in Wide Cylinders.

The densest packings of identical spherical colloidal nanocrystals in a thin cylinder generally give rise to confinement-induced chiral ordering. Here, we demonstrate that entropy can invalidate Pauling's packing rules for the nanocrystals confined in wide cylinders and novel ordered phases, where chiral ordering is broken, emerge. The nucleation and growth of spherical colloidal nanocrystals in the wide cylinders exhibit unique mechanisms which are distinctly different from that of thin ones. Furthermore, theoretical models which capture the essential physics of the ordering transitions are developed to reproduce the achiral ordering and reveal that the ordered phases are thermodynamically stable and stabilized through confinement-mediated entropic effect. These findings demonstrate that entropy arising from thermal motion can invalidate Pauling's packing rules of spherical colloidal nanocrystals confined in cylinders, which provides new insights into confinement physics of colloidal particles and might inspire nonintuitive design rules for the fabrication of novel ordered phases through confinement.

De Novo Design of Entropy-Driven Polymers Resistant to Bacterial Attachment via Multicomponent Reactions.

Nonbactericidal polymers that prevent bacterial attachment are important for public health, environmental protection, and avoiding the generation of superbugs. Here, inspired by the physical bactericidal process of carbon nanotubes and graphene derivatives, we develop nonbactericidal polymers resistant to bacterial attachment by using multicomponent reactions (MCRs) to introduce molecular "needles" (rigid aliphatic chains) and molecular "razors" (multicomponent structures) into polymer side chains. Computer simulation reveals the occurrence of spontaneous entropy-driven interactions between the bacterial bilayers and the "needles" and "razors" in polymer structures and provides guidance for the optimization of this type of polymers for enhanced resistibility to bacterial attachment. The blending of the optimized polymer with commercially available polyurethane produces a film with remarkably superior stability of the resistance to bacterial adhesion after wear compared with that of commercial mobile phone shells made by the Sharklet technology. This proof-of-concept study explores entropy-driven polymers resistant to bacterial attachment via a combination of MCRs, computer simulation, and polymer chemistry, paving the way for the de novo design of nonbactericidal polymers to prevent bacterial contamination.

Entropy at Bio-Nano Interfaces.

Entropy, one of the central concepts of thermodynamics, can be a predominant contribution to structural formation and transition. Although it is well-known that diverse forces and energies can significantly contribute to the structures and activities at bio-nano interfaces, the potential entropic contribution remains less well understood. Therefore, this review article seeks to provide a conceptual framework demonstrating that entropy can be exploited to shape the physicochemical properties of bio-nano interfaces and thereby regulate the structures, responses, and functions of biological systems. We introduce the typical types of entropy that matter at bio-nano interfaces. Moreover, some key characteristics featuring entropy at bio-nano interfaces, such as the difference between entropic force and energetic interaction and the associated implications for biomimetic research, are discussed. We expect that this review could stimulate further effort in the fundamental research of entropy in biology and in the biological applications of entropic effects in designer biomaterials.

Selective Permeable Lithium-Ion Channels on Lithium Metal for Practical Lithium-Sulfur Pouch Cells.

Lithium metal batteries are considered a promising candidate for high-energy-density energy storage. However, the strong reducibility and high reactivity of lithium lead to low Coulombic efficiency when contacting oxidants, such as lithium polysulfide caused by the serious "shuttle effect" in lithium-sulfur batteries. Herein we design selectively permeable lithium-ion channels on lithium metal surface, which allow lithium ions to pass through by electrochemical overpotential, while the polysulfides are effectively blocked due to the much larger steric hindrance than lithium ions. The selective permeation of lithium ions through the channels is further elucidated by the molecular simulation and visualization experiment. Consequently, a prolonged cycle life of 75 cycles and high Coulombic efficiency of 99 % are achieved in a practical Li-S pouch cell with limited amounts of lithium and electrolyte, confirming the unique role the selective ion permeation plays in protecting highly reactive alkali metal anodes in working batteries.

Cellular Uptake of Active Particles.

Active particles are widely recognized to potentially revolutionize technologies in numerous biomedical applications. However, the physical origin behind cellular uptake of these particles in the nonequilibrium state remains scarcely understood. Here we combine Brownian dynamics simulation as well as theoretical analysis to provide the criterion for cellular uptake of active particles, related to various physical attributes. Upon enhancing the activity, the uptake efficiency for the active particles with tilted orientation is examined to be nonmonotonic, in stark contrast to the monotonic dependence for active particles orientated normally to the membrane. This can be attributed to the interplay between membrane adhesion energy and kinetic energy of active particles, resulting in unique kinetic pathways. Furthermore, a theoretical model that captures the essential physics of the cellular endocytosis process is developed to reproduce this nonmonotonic feature. The results are of immediate interest to understand and tune activity-mediated cellular interaction and internalization of such emerging colloids.

Diffusive transport of nanoscale objects through cell membranes: a computational perspective.

Diffusion is an essential and fundamental means of transport of substances on cell membranes, and the dynamics of biomembranes plays a crucial role in the regulation of numerous cellular processes. The understanding of the complex mechanisms and the nature of particle diffusion have a bearing on establishing guidelines for the design of efficient transport materials and unique therapeutic approaches. Herein, this review article highlights the most recent advances in investigating diffusion dynamics of nanoscale objects on biological membranes, focusing on the approaches of tailored computer simulations and theoretical analysis. Due to the presence of the complicated and heterogeneous environment on native cell membranes, the diffusive transport behaviors of nanoparticles exhibit unique and variable characteristics. The general aspects and basic theories of normal diffusion and anomalous diffusion have been introduced. In addition, the influence of a series of external and internal factors on the diffusion behaviors is discussed, including particle size, membrane curvature, particle-membrane interactions or particle-inclusion, and the crowding degree of membranes. Finally, we seek to identify open problems in the existing experimental, simulation, and theoretical research studies, and to propose challenges for future development.

Tailoring Interfacial Nanoparticle Organization through Entropy.

The ability to tailor the interfacial behaviors of nanoparticles (NPs) is crucial not only for the design of novel nanostructured materials with superior properties and of interest for many promising applications such as water purification, enhanced oil recovery, and innovative energy transduction, but also for a better insight into many biological systems where nanoscale particles such as proteins or viruses can interact and organize at certain interfaces. As a class of emerging building blocks, Janus NPs consisting of two compartments of different chemistry or polarity are ideal candidates to generate tunable and stable interfacial nanostructures because of the asymmetric nature. However, precise control over such interfacial nanostructures toward a controllable order and even responses to various external stimuli still remains a great challenge as the interfaces do not simply serve as a scaffold but rather induce complex enthalpic and entropic interactions. In this Account, we focus on our efforts on exploiting entropy strategies based on computational design to tailor the spatial distribution and ordering of NPs at the interfaces of various systems. First, we introduce the physical principle of entropic ordering, being the theoretical basis of entropy-directed interfacial self-assembly. The typical types of entropy, which have been harnessed to manipulate the interfacial NP organization, are then summarized, including conformational entropy, shape entropy, and rotational and vibrational entropy. Next, we describe the emerging pathways in the development of novel environmentally responsive systems which involve the use of entropy to access the stimuli-responsive behaviors of interfacial nanostructures. Taking one step further, how molecular architectures can be tailored to tune the entropic contributions to the interfacial self-assembly is demonstrated, through identifying the effects of various intrinsic properties of block segments, such as chain length and stiffness, on entropy-governed precise organization of Janus NPs at block copolymer interfaces. Finally, we detail some key factors for tailoring interfacial organization through entropy. In summary, entropy strategies offer a promising and abundant framework for precisely programming the structural organization of NPs at interfaces. We discuss future directions to signify the framework in tailoring the interfacial organization of NPs. We hope that this Account will promote further efforts toward fundamental research and the wide applications of designed interfacial assemblies in new types of functional nanomaterials and beyond.

Plastic Crystal-to-Crystal Transition of Janus Particles under Shear.

Colloidal Janus spheres in the bulk typically spontaneously assemble into plastic crystalline phases, while particle orientations exhibit glasslike dynamics without long-range order. Through Brownian dynamics simulations, we demonstrate that shear can trigger a phase transition from an isotropic crystal with orientational disorder to an orientationally ordered crystal with lamellae along the shear direction. This nonequilibrium transition is accompanied with the orientational ordering following a nucleation and growth mechanism. By performing a phenomenological extension of free energy analysis, we reveal that the nucleation originates from the orientation fluctuations induced by shear. The growth of the orientationally crystalline cluster is examined to be disklike, captured by developing a lattice model with memoryless state functions. These findings bring new insights into the mechanisms for the ordering transition of anisotropic particles at nonequilibrium states.

Entropic Effects in Polymer Nanocomposites.

Polymer nanocomposite materials, consisting of a polymer matrix embedded with nanoscale fillers or additives that reinforce the inherent properties of the matrix polymer, play a key role in many industrial applications. Understanding of the relation between thermodynamic interactions and macroscopic morphologies of the composites allow for the optimization of design and mechanical processing. This review article summarizes the recent advancement in various aspects of entropic effects in polymer nanocomposites, and highlights molecular methods used to perform numerical simulations, morphologies and phase behaviors of polymer matrices and fillers, and characteristic parameters that significantly correlate with entropic interactions in polymer nanocomposites. Experimental findings and insight obtained from theories and simulations are combined to understand how the entropic effects are turned into effective interparticle interactions that can be harnessed for tailoring nanostructures of polymer nanocomposites.

Mesoscale Graphene-like Honeycomb Mono- and Multilayers Constructed via Self-Assembly of Coclusters.

Honeycomb structure endows graphene with extraordinary properties. But could a honeycomb monolayer superlattice also be generated via self-assembly of colloids or nanoparticles? Here we report the construction of mono- and multilayer molecular films with honeycomb structure that can be regarded as self-assembled artificial graphene (SAAG). We construct fan-shaped molecular building blocks by covalently connecting two kinds of clusters, one polyoxometalate and four polyhedral oligomeric silsesquioxanes. The precise shape control enables these complex molecules to self-assemble into a monolayer 2D honeycomb superlattice that mirrors that of graphene but on the mesoscale. The self-assembly of the SAAG was also reproduced via coarse-grained molecular simulations of a fan-shaped building block. It revealed a hierarchical process and the key role of intermediate states in determining the honeycomb structure. Experimental images also show a diversity of bi- and trilayer stacking modes. The successful creation of SAAG and its stacks opens up prospects for the preparation of novel self-assembled nanomaterials with unique properties.

How Implementation of Entropy in Driving Structural Ordering of Nanoparticles Relates to Assembly Kinetics: Insight into Reaction-Induced Interfacial Assembly of Janus Nanoparticles.

The ability to understand and exploit entropic contributions to ordering transition is of essential importance in the design of self-assembling systems with well-controlled structures. However, much less is known about the role of assembly kinetics in entropy-driven phase behaviors. Here, by combining computer simulations and theoretical analysis, we report that the implementation of entropy in driving phase transition significantly depends on the kinetic process in the reaction-induced self-assembly of newly designed nanoparticle systems. In particular, such systems comprise binary Janus nanoparticles at the fluid-fluid interface and undergo phase transition driven by entropy and controlled by the polymerization reaction initiated from the surfaces of just one component of nanoparticles. Our simulations demonstrate that the competition between the reaction rate and the diffusive dynamics of nanoparticles governs the implementation of entropy in driving the phase transition from randomly mixed phase to intercalated phase in these interfacial nanoparticle mixtures, which thereby results in diverse kinetic pathways. At low reaction rates, the transition exhibits abrupt jump in the mixing parameter, in a similar way to first-order, equilibrium phase transition. Increasing the reaction rate diminishes the jumps until the transitions become continuous, behaving as a second-order-like phase transition, where a critical exponent, characterizing the transition, can be identified. We finally develop an analytical model of the blob theory of polymer chains to complement the simulation results and reveal essential scaling laws of the entropy-driven phase behaviors. In effect, our results allow for further opportunities to amplify the entropic contributions to the materials design via kinetic control.

Optimal Reactivity and Improved Self-Healing Capability of Structurally Dynamic Polymers Grafted on Janus Nanoparticles Governed by Chain Stiffness and Spatial Organization.

Structurally dynamic polymers are recognized as a key potential to revolutionize technologies ranging from design of self-healing materials to numerous biomedical applications. Despite intense research in this area, optimizing reactivity and thereby improving self-healing ability at the most fundamental level pose urgent issue for wider applications of such emerging materials. Here, the authors report the first mechanistic investigation of the fundamental principle for the dependence of reactivity and self-healing capabilities on the properties inherent to dynamic polymers by combining large-scale computer simulation, theoretical analysis, and experimental discussion. The results allow to reveal how chain stiffness and spatial organization regulate reactivity of dynamic polymers grafted on Janus nanoparticles and mechanically mediated reaction in their reverse chemistry, and, particularly, identify that semiflexible dynamic polymers possess the optimal reactivity and self-healing ability. The authors also develop an analytical model of blob theory of polymer chains to complement the simulation results and reveal essential scaling laws for optimal reactivity. The findings offer new insights into the physical mechanism in various systems involving reverse/dynamic chemistry. These studies highlight molecular engineering of polymer architecture and intrinsic property as a versatile strategy in control over the structural responses and functionalities of emerging materials with optimized self-healing capabilities.