Tracer diffusion in silica inverse opals.

We employed fluorescence correlation spectroscopy (FCS) to study the diffusion of small fluorescence tracers in liquid filled silica inverse opals. The inverse opals consisted of a nanoporous silica scaffold spanning a hexagonal crystal of spherical voids of 360 nm diameter connected by circular pores of 70 nm diameter. The diffusion of Alexa Fluor 488 in water and of perylene-3,4,9,10-tetracarboxylic diimide (PDI) in toluene was studied. Three diffusion modes could be distinguished: (1) Free diffusion limited by the geometric constraints given by the inverse opal, where, as compared to the free solution, this diffusion is slowed down by a factor of 3-4, (2) slow diffusion inside the nanoporous matrix of the silica scaffold, and (3) diffusion limited by adsorption. On the length scale of the focus of a confocal microscope of roughly 400 nm diffusion was non-Fickian in all cases.

Diffusion in polymer solutions studied by fluorescence correlation spectroscopy.

We employed fluorescence correlation spectroscopy (FCS) to study the diffusion of molecular and macromolecular tracers in polystyrene solutions over a broad range of concentrations (c) and molecular weights (M(w,m)) of the matrix polymer. Molecular tracer diffusion scales only with the matrix concentration and superimposes on a single, nonpolymer specific, curve. On the contrary, the diffusion of macromolecular tracers in solutions of matrix polymers with M(w,m) sufficiently larger than the tracer molecular weight scales with c/c(p)*, where c(p)* is the tracer overlap concentration. We further demonstrate that FCS can address local and global dynamics simultaneously.