We present the synthesis of monodisperse cone-shaped silica colloids and their fluorescent labeling. Rod-like silica colloids prepared by ammonia-catalyzed hydrolysis and condensation of tetraethyl orthosilicate in water droplets containing polyvinylpyrrolidone cross-linked by citrate ions in pentanol were found to transform into cone-shaped particles upon mild etching by NaOH in water. The diameter and length of the resulting particles were determined by those of the initial rod-like silica colloids. The mechanism responsible for the cone-shape involves silica etching taking place with a varying rate along the length of the particle. Our experiments thus also lead to new insights into the variation of the local particle structure and composition. These are found to vary gradually along the length of the rod, as a result of the way the rod grows out of a water droplet that keeps itself attached to the flat end of the bullet-shaped particles. Subtle differences in composition and structure could also be resolved by high-resolution stimulated emission depletion confocal microscopy on fluorescently labeled particles. The incorporation of a fluorescent dye chemically attached to an amine-based silane coupling agent resulted in a distribution of fluorophores mainly on the outside of the rod-shaped particles. In contrast, incorporation of the silane coupling agent alone resulted in a homogeneous distribution. Additionally, we show that etching rods, where a silane coupling agent alone was incorporated and subsequently coupled to a fluorescent dye, resulted in fluorescent silica cones, the orientation of which can be discerned using super-resolution confocal microscopy.

We present experimental and theoretical results on suspensions of silica rods in DMSO-water, subjected to an applied electric field. The experimental results indicate that, if the electrode used for generating the electric field is in direct contact with the suspension, a fraction of the rods close to the electrode surface does not stand parallel to the field but instead lies flat on the electrode when the field is switched on. To explain these results theoretically, we modify the coupled dipole method to include “image dipoles”, and find that a rod close to the electrode experiences not only the expected global potential energy minimum at an orientation parallel to the electric field, but also a local minimum several times the thermal energy in depth for orientations parallel to the electrode surface. Additionally, we indicate how the magnitude of the potential energy depends on the electric field strength and include results not only for negatively polarizable (which correspond to the aforementioned experimental system), but also for positively polarizable rods.

We describe a facile method to synthesize sterically stabilized monodisperse fluorescent poly(methyl methacrylate) (PMMA) colloids in the polar solvent mixture water/methanol with either a core-shell or a homogeneously cross-linked structure by dispersion polymerization. The particles were sterically stabilized by the polymer poly(vinylpyrrolidone) (PVP). The morphology of the particles was controlled by varying the moment at which the gradual addition of cross-linker and dye was started. The absence of these extra agents at a time when the particle nuclei formed reduced the negative effects on this important process to a minimum and produced a core-shell structure, whereas an essentially homogeneously cross-linked fluorescent polymer colloid structure could be obtained by reducing the starting time of the addition of dye and cross-linker to zero. Three different dyes were chemically incorporated into the polymer network. Such dyes are important for the use of the particles in confocal scanning laser microscopy studies aimed at characterizing concentrated dispersions quantitatively in real space. A series of PMMA particles with different sizes were obtained through the variation of the weight ratio of solvents and the content of cross-linker. Furthermore, the swelling properties of the cross-linked PMMA particles in a good solvent (tetrahydrofuran) were investigated. The particles were stable in polar solvents (water and formamide) but could also successfully be transferred to apolar solvents such as decahydronaphthalene (decalin). The PVP stabilizer also allowed the particles to be permanently bonded in flexible strings by the application of an external electric field.