We show that the equilibrium size of single-layer shells composed of polyoxometalate macroions is inversely proportional to the dielectric constant of the medium in which they are dispersed. This behavior is consistent with a stabilization mechanism based on Coulomb repulsion combined with charge regulation. We estimate the cohesive energy per bond between macroions on the shells to be approximately ÿ6kT. This number is extracted from analysis based on a charge regulation model in combination with a model for defects on a sphere. The value of the cohesive bond energy is in agreement with the model-independent critical aggregate concentration. This observation points to a new class of thermodynamically stable shell-like objects. We point out the possible relevance our findings have for certain surfactant systems.

By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of near field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as in the kinetics of growth. In microgravity purely diffusive aggregation is observed. By using the continuously variable particle interaction potential we can for the first time experimentally relate the strength of attraction between the particles and the structure of the aggregates.

Abstract:As-grown single-crystal InP nanowires, covered with a surface oxide, show a photoluminescence efficiency that strongly varies from wire to wire. We show that the luminescence efficiency of single-crystal InP nanowires can be improved by photoassisted wet chemical etching in a butanol solution containing HF and the indium-coordinating ligand trioctylphosphine oxide. Electron-hole photogeneration, electron scavenging, and oxidative dissolution combined with surface passivation by the indium-coordinating ligand are essential elements to improve the luminescence efficiency. Time traces of the luminescence of surfacepassivated wires show strong oscillations resembling the on-off blinking observed with single quantum dots. These results reflect the strong influence of a single or a few nonradiative recombination center(s) on the luminescence properties of an entire wire.

The formation of a noncovalent triblock copolymer based on a coiled-coil peptide motif is demonstrated in solution. A specific peptide pair (E and K) able to assemble into heterocoiled coils was chosen as the middle block of the polymer and conjugated to poly(ethylene glycol) (PEG) and polystyrene (PS) as the outer blocks. Mixing equimolar amounts of the polymer-peptide block copolymers PS-E and K-PEG resulted in the formation of coiled-coil complexes between the peptides and subsequently in the formation of the amphiphilic triblock copolymer PS-E/K-PEG. Aqueous self-assembly of the separate peptides (E and K), the block copolymers (PS-E and K-PEG), and equimolar mixtures thereof was studied by circular dichroism, dynamic light scattering, and cryogenic transmission electron microscopy. It was found that the noncovalent PS-E/K-PEG copolymer assembled into rodlike micelles, while in all other cases, spherical micelles were observed. Temperature-dependent studies revealed the reversible nature of the coiled-coil complex and the influence of this on the morphology of the aggregate. A possible mechanism for these transitions based on the interfacial free energy and the free energy of the hydrophobic blocks is discussed. The self-assembly of the polymer-peptide conjugates is compared to that of polystyrene-b-poly(ethylene glycol), emphasizing the importance of the coiled-coil peptide block in determining micellar structure and dynamic behavior.