Forced to line up for perfect order

Physical confinement and magnetic fields are used to align organic molecules that self-assemble into large-size single crystals with perfect positional order

Entropic patchiness:effects of colloid shape and depletion

\u3cp\u3eThis paper reviews ‘entropic patchiness’ of colloidal particles. On the one hand this may be due to their intrinsic tendency to form certain shape-dependent configurations in crowded suspensions, on the other hand this can be strongly enhanced by using depletion interactions that are also of purely entropic origin. A brief account of the Onsager theory and its consequences for the formation of colloidal liquid crystals of highly anisometric particles is presented. It is further supplemented by a recap of the description of depletion attraction between colloids and the effects of their shape. A number of recent examples exploiting entropic patchiness are discussed.\u3c/p\u3

Study of petrolatum structure:explaining its variable rheological behavior

\u3cp\u3eThe rheological properties of petrolatum are dependent on both temperature and thermal history. How this thermal dependency can be explained is unclear. In the past it has been suggested that the structure of petrolatum consists of a three-dimensional crystalline network. This has been established using old microscopic techniques only. Therefore a study on the microstructure of petrolatum was conducted using rheometry, DSC, pulsed NMR, polarized light microscopy and synchrotron X-ray. The combination of these techniques show that petrolatum is composed of 21% solid material at room temperature. This consists of partly crystalline lamellar sheets which are packed in stacks. The occurrence of these lamellar sheets is temperature dependent and the number of lamellar stacks is dependent on thermal history. It was shown that rheological differences in petrolatum can be explained by the number of lamellar stacks present, where more lamellar stacks result in more rigid petrolatum.\u3c/p\u3

Observation of solid-solid transitions in 3D crystals of colloidal superballs

\u3cp\u3eSelf-organization in anisotropic colloidal suspensions leads to a fascinating range of crystal and liquid crystal phases induced by shape alone. Simulations predict the phase behaviour of a plethora of shapes while experimental realization often lags behind. Here, we present the experimental phase behaviour of superball particles with a shape in between that of a sphere and a cube. In particular, we observe the formation of a plastic crystal phase with translational order and orientational disorder, and the subsequent transformation into rhombohedral crystals. Moreover, we uncover that the phase behaviour is richer than predicted, as we find two distinct rhombohedral crystals with different stacking variants, namely hollow-site and bridge-site stacking. In addition, for slightly softer interactions we observe a solid-solid transition between the two. Our investigation brings us one step closer to ultimately controlling the experimental self-assembly of superballs into functional materials, such as photonic crystals.\u3c/p\u3

Scattering from colloidal cubic silica shells:Part I, particle form factors and optical contrast variation

\u3cp\u3eHypothesis: Colloidal cubic silica shells, prepared from cuprous oxide cubes, with a typical size of 100 nm are promising model particles for scattering studies on dilute, as well as concentrated fluids, of non-spherical colloids. Experiments: Small angle X-ray scattering, and static light scattering are employed to determine form factors of cubic silica shells and silica covered cuprous oxide cubes. Contrast variation experiments are performed to assess the refractive index and optical homogeneity of the cubic silica shells, which is important for the extension of the scattering study to concentrated dispersions of cubic shells in Part II (Dekker, submitted for publication). Results: The experimental form factors, which compare well to theoretical form factors, manifest cubic silica shells that are dispersed as single stable colloids with a shape intermediate between a sphere and a perfect cube. Contrast variation demonstrates that the silica shells are optically homogeneous, with a refractive index that is independent of the shell thickness. The results presented here open up the possibility to extract structure factors from light scattering measurements on concentrated cube dispersions in Part II.\u3c/p\u3

High-resolution SAXS setup with tuneable resolution in direct and reciprocal space:a new tool to study ordered nanostructures

\u3cp\u3eA novel compact small-angle X-ray scattering (SAXS) setup with tuneable resolution in both direct and reciprocal space has been designed and tested for the study of nanostructured materials with a hierarchical structure. The setup exploits a set of compound refractive lenses that focus the X-ray beam at the detector position. Anodic alumina membranes with a self-ordered porous structure were chosen as test samples. The setup allows patterns to be collected with a minimum scattering vector value of 0.001 14;nm\u3csup\u3e-1\u3c/sup\u3e and gives the possibility for an easy continuous switch between taking high-resolution statistically averaged diffraction data of macroscopically large sample volumes and lower-resolution diffraction on a small single domain of the anodic aluminium oxide film. It is revealed that the pores are longitudinal and their ordering within each domain tends towards the ideal hexagonal structure, whereas the in-plane orientation of the pore arrays changes from domain to domain. The possible advantages and disadvantages of the proposed compact SAXS scheme are discussed.\u3c/p\u3

Wet-chemical synthesis of chiral colloids

\u3cp\u3eWe disclose a method for the synthesis of chiral colloids from spontaneously formed hollow sugar-surfactant microtubes with internally confined mobile colloidal spheres. Key feature of our approach is the grafting of colloid surfaces with photoresponsive coumarin moieties, which allow for UV-induced, covalent clicking of colloids into permanent chains, with morphologies set by the colloid-to-tube diameter ratio. Subsequent dissolution of tube confinement yields aqueous suspensions that comprise bulk quantities of a variety of linear chains, including single helical chains of polystyrene colloids. These colloidal equivalents of chiral (DNA) molecules are intended for microscopic study of chiral dynamics on a single-particle level.\u3c/p\u3

Inward growth by nucleation:Multiscale self-assembly of ordered membranes

\u3cp\u3eStriking morphological similarities found between superstructures of a wide variety of seemingly unrelated crystalline membrane systems hint at the existence of a common formation mechanism. Resembling systems such as multiwalled carbon nanotubes, bacterial protein shells, or peptide nanotubes, the self-assembly of SDS/b-cyclodextrin complexes leads to monodisperse multilamellar microtubes. We uncover the mechanism of this hierarchical self-assembly process by time-resolved small- and ultrasmall-angle x-ray scattering. In particular, we show that symmetric crystalline bilayers bend into hollow cylinders as a consequence of membrane line tension and an anisotropic elastic modulus. Starting from single-walled microtubes, successive nucleation of new cylinders inside preexisting ones drives an inward growth. As both the driving forces that underlie the self-assembly behavior and the resulting morphologies are common to systems of ordered membranes, we believe that this formation mechanism has a similarly general applicability.\u3c/p\u3

Giant capsids from lattice self-assembly of cyclodextrin complexes

\u3cp\u3eProteins can readily assemble into rigid, crystalline and functional structures such as viral capsids and bacterial compartments. Despite ongoing advances, it is still a fundamental challenge to design and synthesize protein-mimetic molecules to form crystalline structures. Here we report the lattice self-assembly of cyclodextrin complexes into a variety of capsid-like structures such as lamellae, helical tubes and hollow rhombic dodecahedra. The dodecahedral morphology has not hitherto been observed in self-assembly systems. The tubes can spontaneously encapsulate colloidal particles and liposomes. The dodecahedra and tubes are respectively comparable to and much larger than the largest known virus. In particular, the resemblance to protein assemblies is not limited to morphology but extends to structural rigidity and crystallinity - A well-defined, 2D rhombic lattice of molecular arrangement is strikingly universal for all the observed structures. We propose a simple design rule for the current lattice self-assembly, potentially opening doors for new protein-mimetic materials.\u3c/p\u3