Jens Glaser

Metastable orientational order of colloidal discoids

The interplay between phase separation and kinetic arrest is important in supramolecular self-assembly, but their effects on emergent orientational order are not well understood when anisotropic building blocks are used. Contrary to the typical progression from disorder to order in isotropic systems, here we report that colloidal oblate discoids initially self-assemble into short, metastable strands with orientational order—regardless of the final structure. The model discoids are suspended in a refractive index and density-matched solvent. Then, we use confocal microscopy experiments and Monte Carlo simulations spanning a broad range of volume fractions and attraction strengths to show that disordered clusters form near coexistence boundaries, whereas oriented strands persist with strong attractions. We rationalize this unusual observation in light of the interaction anisotropy imparted by the discoids. These findings may guide self-assembly for anisotropic systems in which orientational order is desired, such as when tailored mechanical properties are sought.

Using depletion to control colloidal crystal assemblies of hard cuboctahedra.

Depletion interactions arise from entropic forces, and their ability to induce aggregation and even ordering of colloidal particles through self-assembly is well established, especially for spherical colloids. We vary the size and concentration of penetrable hard sphere depletants in a system of cuboctahedra, and we show how depletion changes the preferential facet alignment of the colloids and thereby selects different crystal structures. Moreover, we explain the cuboctahedra phase behavior using perturbative free energy calculations. We find that cuboctahedra can form a stable simple cubic phase, and, remarkably, that the stability of this phase can be rationalized only by considering the effects of both the colloid and depletant entropy. We corroborate our results by analyzing how the depletant concentration and size affect the emergent directional entropic forces and hence the effective particle shape. We propose the use of depletants as a means of easily changing the effective shape of self-assembling anisotropic colloids.

A parallel algorithm for implicit depletant simulations

We present an algorithm to simulate the many-body depletion interaction between anisotropic colloids in an implicit way, integrating out the degrees of freedom of the depletants, which we treat as an ideal gas. Because the depletant particles are statistically independent and the depletion interaction is short-ranged, depletants are randomly inserted in parallel into the excluded volume surrounding a single translated and/or rotated colloid. A configurational bias scheme is used to enhance the acceptance rate. The method is validated and benchmarked both on multi-core processors and graphics processing units for the case of hard spheres, hemispheres, and discoids. With depletants, we report novel cluster phases in which hemispheres first assemble into spheres, which then form ordered hcp/fcc lattices. The method is significantly faster than any method without cluster moves and that tracks depletants explicitly, for systems of colloid packing fraction ϕc < 0.50, and additionally enables simulation of the fluid-solid transition.

Test of a scaling hypothesis for the structure factor of disordered diblock copolymer melts

Coarse-grained theories of dense polymer liquids such as block copolymer melts predict a universal dependence of equilibrium properties on a few dimensionless parameters. For symmetric diblock copolymer melts, such theories predict a universal dependence on only χN and , where χ is an effective interaction parameter, N is the degree of polymerization, and is a measure of overlap. We test whether simulation results for the structure factor S(q) obtained from several different simulation models are consistent with this two-parameter scaling hypothesis. We compare results from three models: (1) a lattice Monte Carlo model, the bond-fluctuation model, (2) a bead–spring model with harsh repulsive interactions, similar to that of Kremer and Grest, and (3) a bead–spring model with very soft repulsion between beads, and strongly overlapping beads. We compare results from pairs of simulations of different models that have been designed to have matched values of , over a range of values of χN and N, and devise methods to test the scaling hypothesis without relying on any prediction for how the phenomenological interaction parameter χ depends on more microscopic parameters. The results strongly support the scaling hypothesis, even for rather short chains, confirming that it is indeed possible to give an accurate universal description of simulation models that differ in many details.

Supercharging enables organized assembly of synthetic biomolecules

There are few methods for the assembly of defined protein oligomers and higher order structures that could serve as novel biomaterials. Using fluorescent proteins as a model system, we have engineered novel oligomerization states by combining oppositely supercharged variants. A well-defined, highly symmetrical 16-mer (two stacked, circular octamers) can be formed from alternating charged proteins; higher order structures then form in a hierarchical fashion from this discrete protomer. During SUpercharged PRotein Assembly (SuPrA), electrostatic attraction between oppositely charged variants drives interaction, while shape and patchy physicochemical interactions lead to spatial organization along specific interfaces, ultimately resulting in protein assemblies never before seen in nature.