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Transient assembled structures play an indispensable role in a wide variety of processes fundamental to living organisms including cellular transport, cell motility, and proliferation. Typically, the formation of these transient structures is driven by the consumption of molecular fuels via dissipative reaction networks. In these networks, building blocks are converted from inactive precursor states to active (assembling) states by (a set of) irreversible chemical reactions. Since the activated state is intrinsically unstable and can be maintained only in the presence of sufficient fuel, fuel depletion results in the spontaneous disintegration of the formed superstructures. Consequently, the properties and behavior of these assembled structures are governed by the kinetics of fuel consumption rather than by their thermodynamic stability. This fuel dependency endows biological systems with unprecedented spatiotemporal adaptability and inherent self-healing capabilities. Fascinated by these unique material characteristics, coupling the assembly behavior to molecular fuel or light-driven reaction networks was recently implemented in synthetic (supra)molecular systems. In this invited feature article, we discuss recent studies demonstrating that dissipative assembly is not limited to the molecular world but can also be translated to building blocks of colloidal dimensions. We highlight crucial guiding principles for the successful design of dissipative colloidal systems and illustrate these with the current state of the art. Finally, we present our vision on the future of the field and how marrying nonequilibrium self-assembly with the functional properties associated with colloidal building blocks presents a promising route for the development of next-generation 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.

We show that a single geometrical rule underlies the stability of “polyoxomolybdates”, the variety of clusters of molybdenum(VI) oxide in (acidified) aqueous solution that are found experimentally. We predict that upon increasing the proton or total molybdenum oxide concentration, the average size of the clusters increases. We compare our predictions with results from ultracentrifugation experiments and with data in the literature. Finally, it is shown that the formation of metal oxide clusters is thermodynamically equivalent to the formation of surfactant micelles.

We report a single step preparation of monodisperse fluorescent poly(methyl)methacrylate (PMMA) lattices cross-linked with ethylene glycol dimethacrylate with radii in the range 150−1000 nm using dispersion polymerization. The particles are applied as fluorescent cores in core−shell PMMA particles for confocal microscopy (Dullens et al. Langmuir 2003, 19, 5963). Contrary to un-cross-linked particles, these cross-linked colloids are stable in good solvents for PMMA as well. Therefore we studied the properties of the cross-linked PMMA particles in the good solvents tetrahydrofuran (THF), chloroform, and toluene using light scattering and confocal scanning laser microscopy. We show that the particles swell instantaneously and that their volume can increase up to more than seven times their volume in poor solvents. Further, it is very likely that the particles are charged in THF.

Monodisperse cross-linked composite PMMA latex particles have been developed. The chemical cross-linking of the PMMA facilitates the preparation of particles consisting of a fluorescent core and a large nonfluorescent shell. These core−shell spheres can be dispersed in a density and refractive index matching mixture. This results in an ideal colloidal hard sphere model system that can be used to study many fundamental problems such as freezing, melting, and the glass transistion using quantitative confocal scanning laser microscopy. Furthermore, precize control over the size and the properties of the core and the shell(s) facilitates other applications of this model system.

Crystallization in suspensions of colloidal hard spheres with a volume fraction of 0.631 ± 0.004, and a polydispersity of less than 3%, is studied experimentally. The mass density of the solvent is almost equal to that of the particles. Normal (1g-like) gravity conditions are simulated by centrifugation. It is shown that there is a limiting density of the quenched hard-sphere fluid, close or equal to the random close-packed density (with a volume fraction of 0.644 ± 0.005), above which crystallization is no longer observed. The results rule out the possibility that gravitational stress in quenched colloidal hard-sphere fluids, with volume fractions lower than the one corresponding to random close packing of spheres, irreversibly induces a packing geometry in which crystallization is suppressed.

We show that coupling between a fast and a slow relaxation time causes the spontaneous formation of protrusions in colloids made of cross-linked polymers. The volume of the protrusions can be controlled by adjusting the ratio between the relaxation times. This, in principle, results in particles with levels of anisotropy that can be made “to order”.