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Hydrophobic polyelectrolytes (HPE) can solubilize bilayer membranes, form micelles or can reversibly aggregate as a function of pH. The transitions are often remarkably sharp. We show that these cooperative transitions occur by a competition between two or more conformational states and can be explained within the framework of Monod - Wymann - Changeux (MWC) theory that was originally formulated for allosteric interactions. Here we focus on the pH-dependent destabilization and permeation of bilayer membranes by HPE. We formulate the general conditions that lead to sharp conformational transitions involving simple macromolecules mediated by concentration variations of molecular ligands. That opens up potential applications ranging from medicine to the development of switchable materials.

There is a large debate on the destabilization mechanism of emulsions. We present a simple technique using mechanical compression to destabilize oil-in-water emulsions. Upon compression of the emulsion, the continuous aqueous phase is squeezed out, while the dispersed oil phase progressively deforms from circular to honeycomb-like shapes. The films that separate the oil droplets are observed to thin and break at a critical oil/water ratio, leading to coalescence events. Electrostatic interactions and local droplet rearrangements do not determine film rupture. Instead, the destabilization occurs like an avalanche propagating through the system, starting at areas where the film thickness is smallest., Comment: 16 pages, 5 figures

The destabilization of emulsions is important for many applications but remains incompletely understood. We perform squeeze flow measurements on oil-in-water emulsions, finding that the spontaneous destabilization of emulsions is generally very slow under normal conditions, with a characteristic time scale given by the drainage of the continuous phase and the coalescence of the dispersed phase. We show that if the emulsion is compressed between two plates, the destabilization can be sped up significantly; on the one hand, the drainage is faster due to the application of the squeezing force. On the other hand, creep processes lead to rearrangements that also contribute to the destabilization., Comment: 8 pages, 6 figures

For biologically relevant macromolecules such as intrinsically disordered proteins, internal degrees of freedom that allow for shape changes have a large influence on both the motion and function of the compound. A detailed understanding of the effect of flexibility is needed in order to explain their behavior. Here, we study a model system of freely-jointed chains of three to six colloidal spheres, using both simulations and experiments. We find that in spite of their short lengths, their conformational statistics are well described by two-dimensional Flory theory, while their average translational and rotational diffusivity follow the Kirkwood-Riseman scaling. Their maximum flexibility does not depend on the length of the chain, but is determined by the near-wall in-plane translational diffusion coefficient of an individual sphere. Furthermore, we uncover shape-dependent effects in the short-time diffusivity of colloidal tetramer chains, as well as non-zero couplings between the different diffusive modes. Our findings may have implications for understanding both the diffusive behavior and the most likely conformations of macromolecular systems in biology and industry, such as proteins, polymers, single-stranded DNA and other chain-like molecules., Comment: 19 pages, 10 figures

Shape changes resulting from segmental flexibility are ubiquitous in molecular and biological systems, and are expected to affect both the diffusive motion and (biological) function of dispersed objects. The recent development of colloidal structures with freely-jointed bonds have now made a direct experimental investigation of diffusive shape-changing objects possible. Here, we show the effect of segmental flexibility on the simplest possible model system, a freely-jointed cluster of three spherical particles, and validate long-standing theoretical predictions. We find that in addition to the rotational diffusion time, an analogous conformational diffusion time governs the relaxation of the diffusive motion, unique to flexible assemblies, and that their translational diffusivity differs by a small but measurable amount. We also uncovered a Brownian quasiscallop mode, where diffusive motion is coupled to Brownian shape changes. Our findings could have implications for molecular and biological systems where diffusion plays an important role, such as functional site availability in lock-and-key protein interactions., Comment: Ruben W. Verweij and Pepijn G. Moerman contributed equally to this work. 22 pages, 11 figures

Chemotactic interactions are ubiquitous in nature and can lead to nonreciprocal and complex emergent behavior in multibody systems. Here we show how chemotactic signaling between microscale oil droplets of different chemistries in micellar surfactant solutions can result in predator-prey-like chasing interactions. The interactions and dynamic self-organization result from the net directional, micelle-mediated transport of oil between emulsion droplets of differing composition and are powered by the free energy of mixing. The nonreciprocal behavior occurs in a wide variety of oil and surfactant conditions, and we systematically elucidate chemical design rules for tuning the interactions between droplets by varying oil and surfactant chemical structure and concentration. Through integration of experiment and simulation, we also investigate the active behavior and dynamic reorganization of multi-droplet clusters. Our findings demonstrate how chemically-minimal systems can be designed with controllable, non-reciprocal chemotactic interactions to generate emergent self-organization and collective behaviors reminiscent of biological systems.

Concentration gradients play a critical role in embryogenesis, bacterial locomotion, as well as the motility of active particles. Particles develop concentration profiles around them by dissolution, adsorption, or the reactivity of surface species. These gradients change the surface energy of the particles, driving both their self-propulsion and governing their interactions. Here we uncover a regime in which solute-gradients mediate interactions between slowly dissolving droplets without causing autophoresis. This decoupling allows us to directly measure the steady-state, repulsive force, which scales with interparticle distance as $F\sim {1/r^{2}}$. Our results show that the process is diffusion rather than reaction rate limited, and the theoretical model captures the dependence of the interactions on droplet size and solute concentration, using a single fit parameter, $l=16\pm 3$~nm, which corresponds to the lengthscale of a swollen micelle. Our results shed light on the out-of-equilibrium behavior of particles with surface reactivity., Comment: 5 pages, 4 figures

Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable due to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy, and deformability have---to the best of our knowledge---not been realized. Here, we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogous to the simplest chemical bond, where two isotropic orbitals hybridize into the molecular orbital of H2, these flexible groups redistribute upon binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, while anisotropic snowman-like particles self-assemble into hollow monolayer microcapsules. A modest change of the building blocks thus results in a significant leap in the complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into dramatically more complex structures than similar particles that are isotropic or non-deformable.

The self-assembly of anisotropic patchy particles with triangular shape was studied by experiments and computer simulations. The colloidal particles were synthesized in a two-step seeded emulsion polymerization process, and consist of a central smooth lobe connected to two rough lobes at an angle of $\sim$90$^{\circ}$, resembling the shape of a "Mickey Mouse" head. Due to the difference in overlap volume, adding an appropriate depletant induces an attractive interaction between the smooth lobes of the colloids only, while the two rough lobes act as steric constraints. The essentially planar geometry of the "Mickey Mouse" particles is a first geometric deviation of dumbbell shaped patchy particles. This new geometry is expected to form one-dimensional tube-like structures rather than spherical, essentially zero-dimensional micelles. At sufficiently strong attractions, we indeed find tube-like structures with the sticky lobes at the core and the non-sticky lobes pointing out as steric constraints that limit the growth to one direction, providing the tubes with a well-defined diameter but variable length both in experiments and simulations. In the simulations, we found that the internal structure of the tubular fragments could either be straight or twisted into so-called Bernal spirals.

We report on the differences between colloidal systems left to evolve in the earth's gravitational field and the same systems for which a slow continuous rotation averaged out the effects of particle sedimentation on a distance scale small compared to the particle size. Several systems of micron-sized colloidal particles were studied: a hard sphere fluid, colloids interacting via long-range electrostatic repulsions above the freezing volume fraction, an oppositely charged colloidal system close to either gelation and/or crystallization, colloids with a competing short-range depletion attraction and a long-range electrostatic repulsion, colloidal dipolar chains, and colloidal gold platelets under conditions where they formed stacks. Important differences in the structure formation were observed between the experiments where the particles were allowed to sediment and those where sedimentation was averaged out. For instance, in the case of colloids interacting via long-range electrostatic repulsions, an unusual sequence of dilute-Fluid/dilute-Crystal/dense-Fluid/dense-Crystal phases was observed throughout the suspension under the effect of gravity, related to the volume fraction dependence of the colloidal interactions, whereas the system stayed homogeneously crystallized with rotation. For the oppositely charged colloids, a gel-like structure was found to collapse under the influence of gravity with a few crystalline layers grown on top of the sediment, whereas when the colloidal sedimentation was averaged out, the gel completely transformed into crystallites that were oriented randomly throughout the sample. Rotational averaging out gravitational sedimentation is an effective and cheap way to estimate the importance of gravity for colloidal self-assembly processes., Comment: 13 pages, 13 figures