Crystallization of concentrated colloidal suspensions was studied in real space with laser scanning confocal microscopy. Direct imaging in three dimensions allowed identification and observation of both nucleation and growth of crystalline regions, providing an experimental measure of properties of the nucleating crystallites. By following their evolution, we identified critical nuclei, determined nucleation rates, and measured the average surface tension of the crystal-liquid interface. The structure of the nuclei was the same as the bulk solid phase, random hexagonal close-packed, and their average shape was rather nonspherical, with rough rather than faceted surfaces.

Despite progress in the understanding of crystal nucleation and crystal growth since the first theories for nucleation were developed, an exact quantitative prediction of the nucleation rates in most systems has remained an unsolved problem. Colloidal suspensions show a phase behavior that is analogous to atomic or molecular systems and serve accordingly as ideal model systems for studying crystal nucleation with an accuracy and depth on a microscopic scale that is hard to reach for atomic or molecular systems. Due to the mesoscopic size of colloidal particles they can be studied in detail on the single-particle level and their dynamics is strongly slowed down in comparison with atomic or molecular systems, such that the formation of a crystal nucleus can be followed in detail. In this review, recent progress in the study of homogeneous and heterogeneous crystal nucleation in colloids and the controlled growth of crystalline colloidal structures is reviewed. All this work has resulted in unprecedented insights into the early stage of nucleation and it is also relevant for a deeper understanding of soft matter materials in general as well as for possible applications based on colloidal suspensions.

Impurities in crystals generally cause point defects and can even suppress crystallization. This general rule, however, does not apply to colloidal crystals formed by soft microgel particles [Iyer ASJ, Lyon LA (2009) Angew Chem Int Ed 48:4562-4566], as, in this case, the larger particles are able to shrink and join the crystal formed by a majority of smaller particles. Using small-angle X-ray scattering, we find the limit in large-particle concentration for this spontaneous deswelling to persist. We rationalize our data in the context of those counterions that are bound to the microgel particles as a result of the electrostatic attraction exerted by the fixed charges residing on the particle periphery. These bound counterions do not contribute to the suspension osmotic pressure in dilute conditions, as they can be seen as internal degrees of freedom associated with each microgel particle. In contrast, at sufficiently high particle concentrations, the counterion cloud of each particle overlaps with that of its neighbors, allowing these ions to freely explore the space outside the particles. We confirm this scenario by directly measuring the osmotic pressure of the suspension. Because these counterions are then no longer bound, they create an osmotic pressure difference between the inside and outside of the microgels, which, if larger than the microgel bulk modulus, can cause deswelling, explaining why large, soft microgel particles feel the squeeze when suspended with a majority of smaller particles. We perform small-angle neutron scattering measurements to further confirm this remarkable behavior.oint defects in crystalline materials disrupt the crystal structure and often prevent crystallization. This is the case, for instance, when large particles are introduced in a crystal of smaller particles. Bragg illustrated the consequences of this disruption using soap bubbles (1). In metal melts, a size mismatch of 15% between the atoms suppresses crystallization (2), and, in hard spheres, which constitute an important model system for condensed matter, a polydispersity above 12% also prevents crystallization (3). Furthermore, the polydispersity in hard sphere crystals does not exceed 5.7%, due to local segregation of dissimilar particles during crystallization (4, 5).Remarkably, these restrictions do not necessarily apply to suspensions of soft microgels, which are cross-linked polymer particles immersed in a solvent that can exist in either swollen or deswollen states, depending on external conditions like temperature (6) and pH (7). Indeed, microgel suspensions containing a small fraction of larger particles can crystallize without defects by shrinking the larger particles to a size that is identical to that of the smaller and more abundant microgel particles (8). This deswelling was hypothesized to result either from the direct interaction between large and small particles or from the osmotic pressure exerted by the small microgels on the larger ones (2). Here, we show that none of these effects drive this proces...

ABSTRACT:The development of simple, efficient and robust strategies affording the facile construction of biomimetic organocatalytic nano-objects is currently a subject of great interest. Herein, a new pathway to artificial organocatalysts based on partially collapsed individual soft nano-objects displaying useful and diverse biomimetic catalytic functions is reported. Single-chain polymer nanoparticles endowed with enzyme-mimetic activity synthesized following this new route display: i) a relatively extended morphology under good solvent conditions, as revealed by small angle neutron scattering and coarse-grained molecular dynamics simulation results, ii) multiple, compartmentalized and accessible catalytic sites in which borane catalytic units are retained via B ... O interactions, and iii) unprecedented reductase and polymerase enzyme-mimetic properties.