Abstract
The electrophoretic mobility of silica-encapsulated semiconductor nanocrystals (quantum dots) dependent on the pH and the ionic strength of the separation electrolyte has been determined by CE. Having shown the viability of the approach, the electrophoretic mobility μ of the nanoparticles investigated is calculated for varied zeta potential ζ, particle radius r, and ionic strength I employing an approximate analytical expression presented by Ohshima (J. Colloid Interface Sci. 2001, 239, 587–590). The comparison of calculated with measured data shows that the experimental observations exactly follow what would be expected from theory. Within the parameter range investigated at fixed ζ and I there is an increase in μ with r which is a nonlinear function. This dependence of μ on size parameters can be used for the size-dependent separation of particles. Modeling of μ as function of I and ζ makes it possible to calculate the size distribution of nanoparticles from electrophoretic data (using the peak shape of the particle zone in the electropherogram) without the need for calibration provided that ζ is known with adequate accuracy. Comparison of size distributions calculated via the presented method with size histograms determined from transmission electron microscopy (TEM) micrographs reveals that there is an excellent matching of the size distribution curves obtained with the two independent methods. A comparison of calculated with measured distributions of the electrophoretic mobility showed that the observed broad bands in CE studies of colloidal nanoparticles are mainly due to electrophoretic heterogeneity resulting from the particle size distribution.