Universal Relation between Entropy and Kinetics.

Relating thermodynamic and kinetic properties is a conceptual challenge with many practical benefits. Here, based on first principles, we derive a rigorous inequality relating the entropy and the dynamic propagator of particle configurations. It is universal and applicable to steady states arbitrarily far from thermodynamic equilibrium. Applying the general relation to diffusive dynamics yields a relation between the entropy and the (normal or anomalous) diffusion coefficient. The relation can be used to obtain useful bounds for the late-time diffusion coefficient from the calculated steady-state entropy or, conversely, to estimate the entropy based on measured diffusion coefficients. We demonstrate the validity and usefulness of the relation through several examples and discuss its broad range of applications, in particular, for systems far from equilibrium.

Detecting and characterizing phase transitions in active matter using entropy.

A major challenge in the study of active matter lies in quantitative characterization of phases and transitions between them. We show how the entropy of a collection of active objects can be used to classify regimes and spatial patterns in their collective behavior. Specifically, we estimate the contributions to the total entropy from correlations between the degrees of freedom of position and orientation. This analysis pin-points the flocking transition in the Vicsek model while clarifying the physical mechanism behind the transition. When applied to experiments on swarming Bacillus subtilis with different cell aspect ratios and overall bacterial area fractions, the entropy analysis reveals a rich phase diagram with transitions between qualitatively different swarm statistics. We discuss physical and biological implications of these findings.

Resolving entropy contributions in nonequilibrium transitions.

We derive a functional for the entropy contributed by any microscopic degrees of freedom as arising from their measurable pair correlations. Applicable both in and out of equilibrium, this functional yields the maximum entropy which a system can have given a certain correlation function. When applied to different correlations, the method allows us to identify the degrees of freedom governing a certain physical regime, thus capturing and characterizing dynamic transitions. The formalism applies also to systems whose translational invariance is broken by external forces and whose number of particles may vary. We apply it to experimental results for jammed bidisperse emulsions, capturing the crossover of this nonequilibrium system from crystalline to disordered hyperuniform structures as a function of mixture composition. We discover that the cross-correlations between the positions and sizes of droplets in the emulsion play the central role in the formation of the disordered hyperuniform states. We discuss implications of the approach for entropy estimation out of equilibrium and for characterizing transitions in disordered systems.

Structured viscoelastic substrates as linear foundations.

The linear (Winkler) foundation is a simple model widely used for decades to account for the surface response of elastic bodies. It models the response as purely local, linear, and perpendicular to the surface. We extend this model to the case in which the foundation is made of a structured material such as a polymer network, which has characteristic scales of length and time. We use the two-fluid model of viscoelastic structured materials to treat a film of finite thickness, supported on a rigid solid and subjected to a concentrated normal force at its free surface. We obtain the foundation modulus (Winkler constant) as a function of the film's thickness, intrinsic correlation length, and viscoelastic moduli, for three choices of boundary conditions. The results can be used to readily extend earlier applications of the Winkler model to more complex, microstructured substrates. They also provide a way to extract the intrinsic properties of such complex materials from mechanical surface measurements.

Parametric excitation of wrinkles in elastic sheets on elastic and viscoelastic substrates.

Thin elastic sheets supported on compliant media form wrinkles under lateral compression. Since the lateral pressure is coupled to the sheet's deformation, varying it periodically in time creates a parametric excitation. We study the resulting parametric resonance of wrinkling modes in sheets supported on semi-infinite elastic or viscoelastic media, at pressures smaller than the critical pressure of static wrinkling. We find distinctive behaviors as a function of excitation amplitude and frequency, including (a) a different dependence of the dynamic wrinkle wavelength on sheet thickness compared to the static wavelength; and (b) a discontinuous decrease in the dominant wrinkle wavelength upon increasing excitation frequency at sufficiently large pressures. In the case of a viscoelastic substrate, resonant wrinkling requires crossing a threshold of excitation amplitude. The frequencies for observing these phenomena in relevant experimental systems are of the order of a kilohertz and above. We discuss experimental implications of the results.

Symmetry properties of nonlinear hydrodynamic interactions between responsive particles.

Two identical particles driven by the same steady force through a viscous fluid may move relative to one another due to hydrodynamic interactions. The presence or absence of this relative translation has a profound effect on the dynamics of a driven suspension consisting of many particles. We consider a pair of particles which, to linear order in the force, do not interact hydrodynamically. If the system possesses an intrinsic property (such as the shape of the particles, their position with respect to a boundary, or the shape of the boundary) which is affected by the external forcing, hydrodynamic interactions that depend nonlinearly on the force may emerge. We study the general properties of such nonlinear response. Analysis of the symmetries under particle exchange and under force reversal leads to general conclusions concerning the appearance of relative translation and the motion's time reversibility. We demonstrate the applicability of the conclusions in three specific examples: (a) two spheres driven parallel to a wall; (b) two deformable objects driven parallel to their connecting line; and (c) two spheres driven along a curved path. The breaking of time reversibility suggests a possible use of nonlinear hydrodynamic interactions to disperse or assemble particles by an alternating force.

Persistent collective motion of a dispersing membrane domain.

We study the Brownian motion of an assembly of mobile inclusions embedded in a fluid membrane. The motion includes the dispersal of the assembly, accompanied by the diffusion of its center of mass. Usually, the former process is much faster than the latter because the diffusion coefficient of the center of mass is inversely proportional to the number of particles. However, in the case of membrane inclusions, we find that the two processes occur on the same timescale, thus significantly prolonging the lifetime of the assembly as a collectively moving object. This effect is caused by the quasi-two-dimensional membrane flows, which couple the motions of even the most remote inclusions in the assembly. The same correlations also cause the diffusion coefficient of the center of mass to decay slowly with time, resulting in weak subdiffusion. We confirm our analytical results by Brownian dynamics simulations with flow-mediated correlations. The effect reported here should have implications for the stability of nanoscale membrane heterogeneities.

A review of shaped colloidal particles in fluids: anisotropy and chirality.

This review treats asymmetric colloidal particles moving through their host fluid under the action of some form of propulsion. The propulsion can come from an external body force or from external shear flow. It may also come from externally-induced stresses at the surface, arising from imposed chemical, thermal or electrical gradients. The resulting motion arises jointly from the driven particle and the displaced fluid. If the objects are asymmetric, every aspect of their motion and interaction depends on the orientation of the objects. This orientation in turn changes in response to the driving. The objects' shape can thus lead to a range of emergent anisotropic and chiral motion not possible with isotropic spherical particles. We first consider what aspects of a body's asymmetry can affect its drift through a fluid, especially chiral motion. We next discuss driving by injecting external force or torque into the particles. Then we consider driving without injecting force or torque. This includes driving by shear flow and driving by surface stresses, such as electrophoresis. We consider how time-dependent driving can induce collective orientational order and coherent motion. We show how a given particle shape can be represented using an assembly of point forces called a Stokeslet object. We next consider the interactions between anisotropic propelled particles, the symmetries governing the interactions, and the possibility of bound pairs of particles. Finally we show how the collective hydrodynamics of a suspension can be qualitatively altered by the particles' shapes. The asymmetric responses discussed here are broadly relevant also for swimming propulsion of active micron-scale objects such as microorganisms.

Inferring entropy from structure.

The thermodynamic definition of entropy can be extended to nonequilibrium systems based on its relation to information. To apply this definition in practice requires access to the physical system's microstates, which may be prohibitively inefficient to sample or difficult to obtain experimentally. It is beneficial, therefore, to relate the entropy to other integrated properties which are accessible out of equilibrium. We focus on the structure factor, which describes the spatial correlations of density fluctuations and can be directly measured by scattering. The information gained by a given structure factor regarding an otherwise unknown system provides an upper bound for the system's entropy. We find that the maximum-entropy model corresponds to an equilibrium system with an effective pair interaction. Approximate closed-form relations for the effective pair potential and the resulting entropy in terms of the structure factor are obtained. As examples, the relations are used to estimate the entropy of an exactly solvable model and two simulated systems out of equilibrium. The focus is on low-dimensional examples, where our method, as well as a recently proposed compression-based one, can be tested against a rigorous direct-sampling technique. The entropy inferred from the structure factor is found to be consistent with the other methods, superior for larger system sizes, and accurate in identifying global transitions. Our approach allows for extensions of the theory to more complex systems and to higher-order correlations.

Surface Response of a Polymer Network: Semi-infinite Network.

We study theoretically the surface response of a semi-infinite viscoelastic polymer network using the two-fluid model. We focus on the overdamped limit and on the effect of the network's intrinsic length scales. We calculate the decay rate of slow surface fluctuations, and the surface displacement in response to a localized force. Deviations from the large-scale continuum response are found at length scales much larger than the network's mesh size. We discuss implications for surface scattering and microrheology. We provide closed-form expressions that can be used for surface microrheology: the extraction of viscoelastic moduli and intrinsic length scales from the motions of tracer particles lying on the surface without doping the bulk material.

Delayed nucleation in lipid particles.

Metastable states in first-order phase-transitions have been traditionally described by classical nucleation theory (CNT). However, recently an increasing number of systems displaying such a transition have not been successfully modelled by CNT. The delayed crystallization of phospholipids upon super-cooling is an interesting case, since the extended timescales allow access into the dynamics. Herein, we demonstrate the controllable behavior of the long-lived metastable liquid-crystalline phase of dilauroyl-phosphatidylethanolamine (DLPE), arranged in multi-lamellar vesicles, and the ensuing cooperative transition to the crystalline state. Experimentally, we find that the delay in crystallization is a bulk phenomenon, which is tunable and can be manipulated to span two orders of magnitude in time by changing the quenching temperature, solution salinity, or adding a secondary phospholipid. Our results reveal the robust persistence of the metastability, and showcase the apparent deviation from CNT. This distinctive suppression of the transition may be explained by the resistance of the multi-lamellar vesicle to deformations caused by nucleated crystalline domains. Since phospholipids are used as a platform for drug-delivery, a programmable design of cargo hold and release can be of great benefit.

Screening length for finite-size ions in concentrated electrolytes.

The classical Debye-Hückel (DH) theory clearly accounts for the origin of screening in electrolyte solutions and works rather well for dilute electrolyte solutions. While the Debye screening length decreases with the ion concentration and is independent of ion size, recent surface-force measurements imply that for concentrated solutions, the screening length exhibits an opposite trend; it increases with ion concentration and depends on the ionic size. The screening length is usually defined by the response of the electrolyte solution to a test charge but can equivalently be derived from the charge-charge correlation function. By going beyond DH theory, we predict the effects of ion size on the charge-charge correlation function. A simple modification of the Coulomb interaction kernel to account for the excluded volume of neighboring ions yields a nonmonotonic dependence of the screening length (correlation length) on the ionic concentration, as well as damped charge oscillations for high concentrations.

Light-Controlled Selective Collection-and-Release of Biomolecules by an On-Chip Nanostructured Device.

The analysis of biosamples, e.g., blood, is a ubiquitous task of proteomics, genomics, and biosensing fields; yet, it still faces multiple challenges, one of the greatest being the selective separation and detection of target proteins from these complex biosamples. Here, we demonstrate the development of an on-chip light-triggered reusable nanostructured selective and quantitative protein separation and preconcentration platform for the direct analysis of complex biosamples. The on-chip selective separation of required protein analytes from raw biosamples is performed using antibody-photoacid-modified Si nanopillars vertical arrays (SiNPs) of ultralarge binding surface area and enormously high binding affinity, followed by the light-controlled rapid release of the tightly bound target proteins in a controlled liquid media. Two important experimental observations are presented: (1) the first demonstration on the control of biological reaction binding affinity by the nanostructuring of the capturing surface, leading to highly efficient protein collection capabilities, and (2) the light-triggered switching of the highly sticky binding surfaces into highly reflective nonbinding surfaces, leading to the rapid and quantitative release of the originally tightly bound protein species. Both of these two novel behaviors were theoretically and experimentally investigated. Importantly, this is the first demonstration of a three-dimensional (3D) SiNPs on-chip filter with ultralarge binding surface area and reversible light-controlled quantitative release of adsorbed biomolecules for direct purification of blood samples, able to selectively collect and separate specific low abundant proteins, while easily removing unwanted blood components (proteins, cells) and achieving desalting results, without the requirement of time-consuming centrifugation steps, the use of desalting membranes, or affinity columns.

Spontaneous and directed symmetry breaking in the formation of chiral nanocrystals.

Symmetry plays a crucial part in our understanding of the natural world. Mirror symmetry breaking is of special interest as it is related to life as we know it. Studying systems which display chiral amplification, therefore, could further our understanding of symmetry breaking in chemical systems, in general, and thus also of the asymmetry in Nature. Here, we report on strong chiral amplification in the colloidal synthesis of intrinsically chiral lanthanide phosphate nanocrystals, measured via circularly polarized luminescence. The amplification involves spontaneous symmetry breaking into either left- or right-handed nanocrystals below a critical temperature. Furthermore, chiral tartaric acid molecules in the solution direct the amplified nanocrystal handedness through a discontinuous transition between left- and right-handed excess. We analyze the observations based on the statistical thermodynamics of critical phenomena. Our results demonstrate how chiral minerals with high enantiopurity can form in a racemic aqueous environment.

Permeability of immobile rings of membrane inclusions to in-plane flow.

We study the flow of membranal fluid through a ring of immobile particles mimicking, for example, a fence around a membrane corral. We obtain a simple closed-form expression for the permeability coefficient of the ring as a function of the particles' line fraction. The analytical results agree with those of numerical calculations and are found to be robust against changes in particle number and corral shape. From the permeability results, we infer the collective diffusion coefficient of lipids through the ring and discuss possible implications for collective lipid transport in a crowded membrane.

Many-particle mobility and diffusion tensors for objects in viscous sheets.

We derive a mobility tensor for many cylindrical objects embedded in a viscous sheet. This tensor guarantees a positive dissipation rate for any configuration of particles and forces, analogous to the Rotne-Prager-Yamakawa tensor for spherical particles in a three-dimensional viscous fluid. We test our result for a ring of radially driven particles, demonstrating the positive-definite property at all particle densities. The derived tensor can be utilized in Brownian dynamics simulations with hydrodynamic interactions for such systems as proteins in biomembranes and inclusions in free-standing liquid films.

Membrane undulations in a structured fluid: Universal dynamics at intermediate length and time scales.

The dynamics of membrane undulations inside a viscous solvent is governed by distinctive, anomalous, power laws. Inside a viscoelastic continuous medium these universal behaviors are modified by the specific bulk viscoelastic spectrum. Yet, in structured fluids the continuum limit is reached only beyond a characteristic correlation length. We study the crossover to this asymptotic bulk dynamics. The analysis relies on a recent generalization of the hydrodynamic interaction in structured fluids, which shows a slow spatial decay of the interaction toward the bulk limit. For membranes which are weakly coupled to the structured medium we find a wide crossover regime characterized by different, universal, dynamic power laws. We discuss various systems for which this behavior is relevant, and delineate the time regime over which it may be observed.

Correlations in suspensions confined between viscoelastic surfaces: Noncontact microrheology.

We study theoretically the velocity cross-correlations of a viscous fluid confined in a slit between two viscoelastic media. We analyze the effect of these correlations on the motions of particles suspended in the fluid. The compliance of the confining boundaries gives rise to a long-ranged pair correlation, decaying only as 1/r with the interparticle distance r. We show how this long-ranged effect may be used to extract the viscoelastic properties of the confining media without embedding tracer particles in them. We discuss the remarkable robustness of such a potential technique with respect to details of the confinement, and its expected statistical advantages over standard two-point microrheology.

Strain tensor selection and the elastic theory of incompatible thin sheets.

The existing theory of incompatible elastic sheets uses the deviation of the surface metric from a reference metric to define the strain tensor [Efrati et al., J. Mech. Phys. Solids 57, 762 (2009)JMPSA80022-509610.1016/j.jmps.2008.12.004]. For a class of simple axisymmetric problems we examine an alternative formulation, defining the strain based on deviations of distances (rather than distances squared) from their rest values. While the two formulations converge in the limit of small slopes and in the limit of an incompressible sheet, for other cases they are found not to be equivalent. The alternative formulation offers several features which are absent in the existing theory. (a) In the case of planar deformations of flat incompatible sheets, it yields linear, exactly solvable, equations of equilibrium. (b) When reduced to uniaxial (one-dimensional) deformations, it coincides with the theory of extensible elastica; in particular, for a uniaxially bent sheet it yields an unstrained cylindrical configuration. (c) It gives a simple criterion determining whether an isometric immersion of an incompatible sheet is at mechanical equilibrium with respect to normal forces. For a reference metric of constant positive Gaussian curvature, a spherical cap is found to satisfy this criterion except in an arbitrarily narrow boundary layer.

Pattern transitions in a compressible floating elastic sheet.

Thin rigid sheets floating on a liquid substrate appear, for example, in coatings and surfactant monolayers. Upon uniaxial compression the sheet undergoes transitions from a compressed flat state to a periodic wrinkled pattern to a localized folded pattern. The stability of these states is determined by the in-plane elasticity of the sheet, its bending rigidity, and the hydrostatics of the underlying liquid. Wrinkles and folds, and the wrinkle-to-fold transition, were previously studied for incompressible sheets. In the present work we extend the theory to include finite compressibility. We analyze the details of the flat-to-wrinkle transition, the effects of compressibility on wrinkling and folding, and the compression field associated with pattern formation. The state diagram of the floating sheet including all three states is presented.