Microelectrophoresis of Silica Rods Using Confocal Microscopy.

The electrophoretic mobility and the zeta potential (ζ) of fluorescently labeled colloidal silica rods, with an aspect ratio of 3.8 and 6.1, were determined with microelectrophoresis measurements using confocal microscopy. In the case where the colloidal particles all move at the same speed parallel to the direction of the electric field, we record a xyz-stack over the whole depth of the capillary. This method is faster and more robust compared to taking xyt-series at different depths inside the capillary to obtain the parabolic flow profile, as was done in previous work from our group. In some cases, rodlike particles do not move all at the same speed in the electric field, but exhibit a velocity that depends on the angle between the long axis of the rod and the electric field. We measured the orientation-dependent velocity of individual silica rods during electrophoresis as a function of κa, where κ-1 is the double layer thickness and a is the radius of the rod associated with the diameter. Thus, we determined the anisotropic electrophoretic mobility of the silica rods with different sized double layers. The size of the double layer was tuned by suspending silica rods in different solvents at different electrolyte concentrations. We compared these results with theoretical predictions. We show that even at already relatively high κa when the Smoluchowski limiting law is assumed to be valid (κa > 10), an orientation dependent velocity was measured. Furthermore, we observed that at decreasing values of κa the anisotropy in the electrophoretic mobility of the rods increases. However, in low polar solvents with κa < 1, this trend was reversed: the anisotropy in the electrophoretic mobility of the rods decreased. We argue that this decrease is due to end effects, which was already predicted theoretically. When end effects are not taken into account, this will lead to strong underestimation of the experimentally determined zeta potential.

Phase diagram of binary colloidal rod-sphere mixtures from a 3D real-space analysis of sedimentation-diffusion equilibria.

Self-assembly of binary particle systems offers many new opportunities for materials science. Here, we studied sedimentation equilibria of silica rods and spheres, using quantitative 3D confocal microscopy. We determined not only pressure, density and order parameter profiles, but also the experimental phase diagram exhibiting a stable binary smectic liquid-crystalline phase (Sm2). Using computer simulations we confirmed that the Sm2-phase can be stabilized by entropy alone, which opens up the possibility of combining new materials properties at a wide array of length scales.

Shape-Dependent Multiexciton Emission and Whispering Gallery Modes in Supraparticles of CdSe/Multishell Quantum Dots.

Semiconductors are indispensable as the active light-emitting element in many optoelectronic devices. However, even the purest bulk semiconductors suffer from considerable nonradiative recombination leading to low photoluminescence efficiencies. Zero-dimensional quantum dots show a much better carrier-to-photon conversion caused by confinement of the excitons but suffer from nonradiative recombination when assembled into a solid, due to exciton energy transfer. Here, we report on the shape-dependent optical properties of self-assembled supraparticles composed of CdSe/multishell nanocrystals. All supraparticles show stable and bright photoluminescence in ambient up to high excitation intensities. When the supraparticles are deposited on a silicon surface their spherical shape is deformed due to drying. In addition to single-exciton emission, we observe bright emission from multiexciton states at high excitation powers. In contrast, supraparticles that retain their perfectly spherical shape show a spectrum with sharp Mie whispering gallery modes, while multiexciton emission is absent.

Pores with longitudinal irregularities distinguish objects by shape.

The resistive-pulse technique has been used to detect and size objects which pass through a single pore. The amplitude of the ion current change observed when a particle is in the pore is correlated with the particle volume. Up to date, however, the resistive-pulse approach has not been able to distinguish between objects of similar volume but different shapes. In this manuscript, we propose using pores with longitudinal irregularities as a sensitive tool capable of distinguishing spherical and rod-shaped particles with different lengths. The ion current modulations within resulting resistive pulses carry information on the length of passing objects. The performed experiments also indicate the rods rotate while translocating, and displace an effective volume that is larger than their geometrical volume, and which also depends on the pore diameter.

Geometry- and rate-dependent adhesive failure of micropatterned surfaces.

The dynamic nature of adhesive interface failure remains poorly understood, especially when the contact between the two surfaces is localized in microscopic points of adhesion. Here, we explore the dynamic failure of adhesive interfaces composed of a large number of micron-sized pillars against glass. Surprisingly, we find a large influence of the microcontact geometry; ordered arrays of these pillars exhibit significantly stronger adhesive properties than equivalent surfaces in which the pillars are disordered. This can be understood with a simple geometric argument that accounts for the number of adhesive bonds that needs to be broken simultaneously to propagate the crack front. Moreover, the adhesive strength in both cases depends largely on the velocity with which the surfaces are separated. This rate dependence is explained on the basis of a semi-phenomenological model that describes macroscopic failure as a consequence of microscopic bond-rupture events. Our results suggest that the dynamics of adhesive failure, in the limit explored here, is predominantly stress-driven and highly sensitive to local geometry effects.