Oscillatory Force Autocorrelations in Equilibrium Odd-Diffusive Systems.

The force autocorrelation function (FACF), a concept of fundamental interest in statistical mechanics, encodes the effect of interactions on the dynamics of a tagged particle. In equilibrium, the FACF is believed to decay monotonically in time, which is a signature of slowing down of the dynamics of the tagged particle due to interactions. Here, we analytically show that in odd-diffusive systems, which are characterized by a diffusion tensor with antisymmetric elements, the FACF can become negative and even exhibit temporal oscillations. We also demonstrate that, despite the isotropy, the knowledge of FACF alone is not sufficient to describe the dynamics: the full autocorrelation tensor is required and contains an antisymmetric part. These unusual properties translate into enhanced dynamics of the tagged particle quantified via the self-diffusion coefficient that, remarkably, increases due to particle interactions.

Kinetically Controlled Site-Specific Self-assembly of Hairy Colloids.

The solvophobicity-driven directional self-assembly of polymer-coated gold nanorods is a well-established phenomenon. Yet, the kinetics of this process, the origin of site-selectivity in the self-assembly, and the interplay of (attractive) solvophobic brush interactions and (repulsive) electrostatic forces are not fully understood. Herein, we use a combination of time-resolved (vis/NIR) extinction spectroscopy and finite-difference time-domain (FDTD) simulations to determine conversion profiles for the assembly of gold nanorods with polystyrene shells of distinct thicknesses into their (tip-to-tip) self-assembled structures. In particular, we demonstrate that the assembly process is highly protracted compared with diffusion-controlled rates, and we find that the assembly rate varies for different thickness values of the polymer shell. Our findings were rationalized using coarse-grained molecular dynamics simulations, which also corroborated the tip-to-tip preference in the self-assembly process, albeit with a uniform polymer coating. Utilizing the knowledge of quantified conversion rates for distinct colloidal species, we designed coassembling systems with different brush thicknesses, featuring "narcissistic" self-sorting behavior. This provides new perspectives for high-level supracolloidal self-assembly.

Entropic repulsion of cholesterol-containing layers counteracts bioadhesion.

Control of adhesion is a striking feature of living matter that is of particular interest regarding technological translation1-3. We discovered that entropic repulsion caused by interfacial orientational fluctuations of cholesterol layers restricts protein adsorption and bacterial adhesion. Moreover, we found that intrinsically adhesive wax ester layers become similarly antibioadhesive when containing small quantities (under 10 wt%) of cholesterol. Wetting, adsorption and adhesion experiments, as well as atomistic simulations, showed that repulsive characteristics depend on the specific molecular structure of cholesterol that encodes a finely balanced fluctuating reorientation at the interface of unconstrained supramolecular assemblies: layers of cholesterol analogues differing only in minute molecular variations showed markedly different interfacial mobility and no antiadhesive effects. Also, orientationally fixed cholesterol layers did not resist bioadhesion. Our insights provide a conceptually new physicochemical perspective on biointerfaces and may guide future material design in regulation of adhesion.

Analysis of the Binding of Cytokines to Highly Charged Polymer Networks.

A model describing the binding of biological signaling proteins to highly charged polymer networks is presented. The networks are formed by polyelectrolyte chains for which the distance between two charges at the chain is smaller than the Bjerrum length. Counterion condensation on such highly charged chains immobilizes a part of the counterions. The Donnan-equilibrium between the polymer network and the aqueous solution with salt concentration c s b $c_s^b$ is used to calculate the salt concentration of the co- and counterions c s g $c_s^g$ entering the network. Two factors are decisive: i) The electrostatic interaction between the network and the protein is given by the Donnan-potential of the network and the net charge of the protein. In addition to this leading term, a second term describes the change in the Born-energy of the proteins when entering the network. ii) The interaction of the protein with the highly charged chains within the network is governed by counterion release: Patches of positive charge at the protein become multivalent counterions of the polyelectrolyte chains thus releasing a concomitant number of condensed counterions. The model compares favorably to experimental data obtained on a set of biohybrid polymer networks composed of crosslinked glycosaminoglycan chains that interact with a mixture of key signaling proteins.

Machine learning of an implicit solvent for dynamic Monte Carlo simulations.

The Bond Fluctuation Model (BFM) is a highly efficient and versatile method for simulating polymers, membranes, and soft matter. Due to its coarse-grained nature, the BFM is employed to understand the universal properties of polymers. Solvent effects are often mediated by explicit solvent particles, while implicit solvent models have had limited use as they may lead to frozen states and, thus, ergodicity-related problems. In simulation setups, such as coagulated multiple homopolymers chains, explicit solvent models are computationally expensive because the region of interest can be localized in a small space compared to the dimension of the periodic box. We introduce an implicit solvent model based on an artificial neural network (NN) that was trained with BFM simulation data for single homopolymers in an explicit solvent. We demonstrate that NN-based simulations that take into account only the information of the local environment of monomers reproduce the expected universal macroscopic properties of the polymer under varying solvent conditions. The homopolymer chains simulated using the NN reproduce the coil-globule transition, the static and dynamic bond autocorrelation, and the mean square displacement of chain monomers. We show that the learned parameters from a single chain system can be transferred to a system containing multiple homopolymers, indicating that the learned parameters are transferable to considerably different systems.

Influence of the Atmosphere on the Wettability of Polymer Brushes.

Polymer brushes, i.e., end-tethered polymer chains on substrates, are sensitive to adaptation, e.g., swelling, adsorption, and reorientation of the surface molecules. This adaptation can originate from a contacting liquid or atmosphere for partially wetted substrates. The macroscopic contact angle of the aqueous drop can depend on both adaptation mechanisms. We analyze how the atmosphere around an aqueous droplet determines the resulting contact angle of the wetting droplet on polymer brush surfaces. Poly(N-isopropylacrylamide) (PNiPAAm)-based brushes are used due to their exceptional sensitivity to solvation and liquid mixture composition. We develop a method that reliably measures wetting properties when the drop and the surrounding atmosphere are not in equilibrium, e.g., when evaporation and condensation tend to contaminate the liquid of the drop and the atmosphere. For this purpose, we use a coaxial needle in the droplet, which continuously exchanges the wetting liquid, and in addition, we constantly exchange the almost saturated atmosphere. Depending on the wetting history, PNiPAAm can be prepared in two states, state A with a large water contact angle (∼65°) and state B with a small water contact angle (∼25°). With the coaxial needle, we can demonstrate that the water contact angle of a sample in state B significantly increases by ∼30° when a water-free atmosphere is almost saturated with ethanol, compared to an ethanol-free atmosphere at 50% relative humidity. For a sample in state A, the relative humidity has little influence on the water contact angle.

Active chiral molecules in activity gradients.

While the behavior of active colloidal molecules is well studied now for constant activity, the effect of activity gradients is much less understood. Here, we explore one of the simplest molecules in activity gradients, namely active chiral dimers composed of two particles with opposite active torques of the same magnitude. We show analytically that with increasing torque, the dimer switches its behavior from antichemotactic to chemotactic. The origin of the emergent chemotaxis is the cooperative exploration of an activity gradient by the two particles. While one of the particles moves into higher activity regions, the other moves towards lower activity regions, resulting in a net bias in the direction of higher activity. We do a comparative study of chiral active particles with charged Brownian particles under a magnetic field and show that despite the fundamental similarity in terms of their odd-diffusive behavior, their dynamics and chemotactic behavior are generally not equivalent. We demonstrate this explicitly in a dimer composed of oppositely charged active particles, which remains antichemotactic to any magnetic field.

Collisions Enhance Self-Diffusion in Odd-Diffusive Systems.

It is generally believed that collisions of particles reduce the self-diffusion coefficient. Here we show that in odd-diffusive systems, which are characterized by diffusion tensors with antisymmetric elements, collisions surprisingly can enhance the self-diffusion. In these systems, due to an inherent curving effect, the motion of particles is facilitated, instead of hindered by collisions leading to a mutual rolling effect. Using a geometric model, we analytically predict the enhancement of the self-diffusion coefficient with increasing density. This counterintuitive behavior is demonstrated in the archetypal odd-diffusive system of Brownian particles under Lorentz force. We validate our findings by many-body Brownian dynamics simulations in dilute systems.

Theoretical analysis of the elastic free energy contributions to polymer brushes in poor solvent: A refined mean-field theory.

We consider polymer brushes in poor solvent that are grafted onto planar substrates and onto the internal and external surfaces of a cylinder using molecular dynamics simulation, self-consistent field (SCF), and mean-field theory. We derive a unified expression for the mean field free energy for the three geometrical classes. While for low grafting densities, the effect of chain elasticity can be neglected in poor solvent conditions, it becomes relevant at higher grafting densities and, in particular, for concave geometries. Based on the analysis of the end monomer distribution, we introduce an analytical term that describes the elasticity as a function of grafting density. The accuracy of the model is validated with molecular dynamics simulations as well as SCF computations and shown to yield precise values for the layer thickness over a wide range of system parameters. We further apply this model to analyze the gating behavior of switchable brushes inside nanochannels.

Tunable Brownian magneto heat pump.

We propose a mesoscopic Brownian magneto heat pump made of a single charged Brownian particle that is steered by an external magnetic field. The particle is subjected to two thermal noises from two different heat sources. When confined, the particle performs gyrating motion around a potential energy minimum. We show that such a magneto-gyrator can be operated as both a heat engine and a refrigerator. The maximum power delivered by the engine and the performance of the refrigerator, namely the rate of heat transferred per unit external work, can be tuned and optimised by the applied magnetic field. Further tunability of the key properties of the engine, such as the direction of gyration and the torque exerted by the engine on the confining potential, is obtained by varying the strength and direction of the applied magnetic field. In principle, our predictions can be tested by experiments with colloidal particles and complex plasmas.

Active colloidal molecules in activity gradients.

We consider a rigid assembly of two active Brownian particles, forming an active colloidal dimer, in a gradient of activity. We show analytically that depending on the relative orientation of the two particles the active dimer accumulates in regions of either high or low activity, corresponding to, respectively, chemotaxis and antichemotaxis. Certain active dimers show both chemotactic and antichemotactic behavior, depending on the strength of the activity. Our coarse-grained Fokker-Planck approach yields an effective potential, which we use to construct a nonequilibrium phase diagram that classifies the dimers according to their tactic behavior. Moreover, we show that for certain dimers a higher persistence of the motion is achieved similar to the effect of a steering wheel in macroscopic devices. This work could be useful for designing autonomous active colloidal structures which adjust their motion depending on the local activity gradients.

A nanofluidic system based on cylindrical polymer brushes: how to control the size of nanodroplets.

In molecular dynamics simulations we investigate the self-organized formation of droplets from a continuous flow of incoming nanoparticles. This transformation is facilitated by a cylindrical channel that is decorated with a polymer brush in a marginally poor solvent. We analyze droplet formation and propagation by means of simple scaling arguments which are tested in the simulations. Polymer brushes in marginally poor solvents serve as a pressure feedback system, exhibit a collapse transition under the moderate pressure of the incident flow, without the need for additional external stimuli, and finally close spontaneously after droplet passage. Our results qualitatively demonstrate the control of polymer brushes over continuous fluids and droplet formation, and its effectiveness as a means of fluid control can be used to design nanofluidic rectification devices that operate reliably under moderate pressure.

Mechanofluorescent Polymer Brush Surfaces that Spatially Resolve Surface Solvation.

Polymer brushes, consisting of densely end-tethered polymers to a surface, can exhibit rapid and sharp conformational transitions due to specific stimuli, which offer intriguing possibilities for surface-based sensing of the stimuli. The key toward unlocking these possibilities is the development of methods to readily transduce signals from polymer conformational changes. Herein, we report on single-fluorophore integrated ultrathin (<40 nm) polymer brush surfaces that exhibit changing fluorescence properties based on polymer conformation. The basis of our methods is the change in occupied volume as the polymer brush undergoes a collapse transition, which enhances the effective concentration and aggregation of the integrated fluorophores, leading to a self-quenching of the fluorophores' fluorescence and thereby reduced fluorescence lifetimes. By using fluorescence lifetime imaging microscopy, we reveal spatial details on polymer brush conformational transitions across complex interfaces, including at the air-water-solid interface and at the interface of immiscible liquids that solvate the surface. Furthermore, our method identifies the swelling of polymer brushes from outside of a direct droplet (i.e., the polymer phase with vapor above), which is controlled by humidity. These solvation-sensitive surfaces offer a strong potential for surface-based sensing of stimuli-induced phase transitions of polymer brushes with spatially resolved output in high resolution.

Strongly enhanced dynamics of a charged Rouse dimer by an external magnetic field.

While the dynamics of dimers and polymer chains in a viscous solvent is well understood within the celebrated Rouse model, the effect of an external magnetic field on the dynamics of a charged chain is much less understood. Here, we generalize the Rouse model for a charged dimer to include the effect of an external magnetic field. Our analytically solvable model allows a fundamental insight into the magneto-generated dynamics of the dimer in the overdamped limit as induced by the Lorentz force. Surprisingly, for a dimer of oppositely charged particles, we find an enormous enhancement of the dynamics of the dimer center, which exhibits even a transient superballistic behavior. This is highly unusual in an overdamped system for there is neither inertia nor any internal or external driving. We attribute this to a significant translation and rotation coupling due to the Lorentz force. We also find that magnetic field reduces the mobility of a dimer along its orientation and its effective rotational diffusion coefficient. In principle, our predictions can be tested by experiments with colloidal particles and complex plasmas.

Crystallization of Polymers under the Influence of an External Force Field.

We simulated the crystallization and melting behavior of entangled polymer melts using molecular dynamics where each chain is subject to a force dipole acting on its ends. This mimics the deformation of chains in a flow field but represents a well-defined equilibrium system in the melt state. Under weak extension within the linear response of the chains, the mechanical work done on the system is about two orders of magnitude smaller as compared with the heat of fusion. As a consequence, thermodynamic and simple arguments following the secondary nucleation model predict only small changes of the crystalline phase. By contrast, an increase of the stem length up to a factor of two is observed in our simulations. On the other hand, the lamellar thickening induced by the external force is proportional to the increase of the entanglement length in the melt prior to crystallization as measured by the primitive path method. While the mechanical work done on the system is only a small perturbation for thermodynamics of polymer crystallization, the change of the primitive path is large. This suggests that a strong increase in the lamellar thickness induced, by external deformation, a topological rather than a thermodynamic origin.

Chemotaxis of Cargo-Carrying Self-Propelled Particles.

Active particles with their characteristic feature of self-propulsion are regarded as the simplest models for motility in living systems. The accumulation of active particles in low activity regions has led to the general belief that chemotaxis requires additional features and at least a minimal ability to process information and to control motion. We show that self-propelled particles display chemotaxis and move into regions of higher activity if the particles perform work on passive objects, or cargo, to which they are bound. The origin of this cooperative chemotaxis is the exploration of the activity gradient by the active particle when bound to a load, resulting in an average excess force on the load in the direction of higher activity. Using a new theoretical model, we capture the most relevant features of these active-passive dimers, and in particular we predict the crossover between antichemotactic and chemotactic behavior. Moreover, we show that merely connecting active particles to chains is sufficient to obtain the crossover from antichemotaxis to chemotaxis with increasing chain length. Such an active complex is capable of moving up a gradient of activity such as provided by a gradient of fuel and to accumulate where the fuel concentration is at its maximum. The observed transition is of significance to protoforms of life, enabling them to locate a source of nutrients even in the absence of any supporting sensomotoric apparatus.

Memory effects in polymer brushes showing co-nonsolvency effects.

Densely packed polymer chains grafted to a substrate, especially polymer brushes, have been studied intensively. Of special interest are systems that react to changes in external conditions or"remember" previous conditions. With this focus, we explore the properties of PNiPAAm brushes and relate published work to own results. The co-nonsolvency effect leads to a collapse of a PNiPAAm brush for a certain mixing ratio of ethanol in water. This also influences the wetting behavior of PNiPAAm brushes. We show that through prewetting of a brush with different liquids (water and ethanol), the contact angle of subsequent water drops changes significantly. To explain this change, the swelling of the brush was investigated with spectroscopic ellipsometry and the orientation of the molecules at the surface with sum-frequency generation (SFG). Only little change in swelling was found. The SFG measurements reveal in the ethanol prewetted case a well ordered hydrophobic methyl layer at the interface, which is consistent with the contact angle measurement.

FRET-Integrated Polymer Brushes for Spatially Resolved Sensing of Changes in Polymer Conformation.

Polymer brush surfaces that alter their physical properties in response to chemical stimuli have the capacity to be used as new surface-based sensing materials. For such surfaces, detecting the polymer conformation is key to their sensing capabilities. Herein, we report on FRET-integrated ultrathin (<70 nm) polymer brush surfaces that exhibit stimuli-dependent FRET with changing brush conformation. Poly(N-isopropylacrylamide) polymers were chosen due their exceptional sensitivity to liquid mixture compositions and their ability to be assembled into well-defined polymer brushes. The brush transitions were used to optically sense changes in liquid mixture compositions with high spatial resolution (tens of micrometers), where the FRET coupling allowed for noninvasive observation of brush transitions around complex interfaces with real-time sensing of the liquid environment. Our methods have the potential to be leveraged towards greater surface-based sensing capabilities at intricate interfaces.

Searching for Aquamelt Behavior among Silklike Biomimetics during Fibrillation under Flow.

In this paper, we elucidate a generic mechanism behind strain-induced phase transition in aqueous solutions of silk-inspired biomimetics by atomistic molecular dynamics simulations. We show the results of modeling of homopeptides polyglycine Gly30 and polyalanine Ala30 and a heteropeptide (Gly-Ala-Gly-Ala-Gly-Ser)5, i.e., the simplest and yet relevant sequences that could mimic the behavior of natural silk under stress conditions. First, we analyze hydrophobicities of the sequences by calculating the Gibbs free energy of hydration and inspecting the interchain hydrogen bonding and hydration by water. Second, the force-extension profiles are scanned and compared with the results for poly(ethylene oxide), the synthetic polymer for which the aquamelt behavior has been proved recently. Additionally, the conformational transitions of oligopeptides from coiled to extended states are characterized by a generalized order parameter and by the dependence of the solvent-accessible surface area of the chains on applied stretching. Fibrillation itself is surveyed using both the two-dimensional interchain pair correlation function and the SAXS/WAXS patterns for the aggregates formed under stress. These are compared with experimental data found in the literature on fibril structure of silk composite materials doped with oligoalanine peptides. Our results show that tensile stress introduced into aqueous oligopeptide solutions facilitates interchain interactions. The oligopeptides display both a greater resistance to extension as compared to poly(ethylene oxide) and a reduced ability for hydrogen bonding of the stretched chains between oligomers and with water. Fiber formation is proved for all simulated objects, but the most structured one is made of a heteropeptide (Gly-Ala-Gly-Ala-Gly-Ser)5: For this sequence, we obtain the highest degree of the secondary structure motifs in the fiber. We conclude that this is the most promising candidate among considered sequences to find the aquamelt behavior in further experimental studies.

Flow-Induced Formation of Thin PEO Fibers in Water and Their Stability After the Strain Release.

Recently, we have shown that a tensile stress applied to chains of poly(ethylene oxide) (PEO) in water reduces the solubility and leads to phase separation of PEO chains from water with the formation of a two-phase region. In this work, we further elucidate the generic mechanism behind strain-induced phase transitions in aqueous PEO solutions with concentrations of 50-60 wt % by performing all-atom molecular dynamics simulations. In particular, we study the stability of oriented PEO fibers after removing stretching forces. We found that the size of the PEO bundle increased with time, which is associated with the dissolution of PEO chains on the fiber surface due to the reformation of hydrogen bonds between the outer PEO molecules and water. For precise characterization of the fibers, the scattering patterns (small- and wide-angle X-ray spectra) for configurations taken at different relaxation times are calculated. The tendency of the oligomer chains to be peeled off from the surface of the bundle eventually might lead to a complete dissolution of the PEO fiber. We conclude that either entanglement constraints or a quick drying process are necessary to conserve the fiber structure in a quiescent state. The scattering results show that external strain induced a liquid-liquid phase separation first. On long time scales, this can be a precursor for crystallization of the fiber.