Molecular Accessibility and Diffusion of Resorufin in Zeolite Crystals

Abstract

We have used confocal laser scanning microscopy on the small, fluorescent resorufin dye molecule to visualize molecular accessibility and diffusion in the hierarchical, anisotropic pore structure of large (similar to 10 mu m-sized) zeolite-beta crystals. The resorufin dye is widely used in life and materials science, but only in its deprotonated form because the protonated molecule is barely fluorescent in aqueous solution. In this work, we show that protonated resorufin is in fact strongly fluorescent when confined within zeolite micropores, thus enabling fluorescence microimaging experiments. We find that J-aggregation guest-guest interactions lead to a decrease in the measured fluorescence intensity that can be prevented by using non-fluorescent spacer molecules. We characterized the pore space by introducing resorufin from the outside solution and following its diffusion into zeolite-beta crystals. The eventual homogeneous distribution of resorufin molecules throughout the zeolite indicates a fully accessible pore network. This enables the quantification of the diffusion coefficient in the straight pores of zeolite-beta without the need for complex analysis, and we found a value of 3x10(-15) m(2) s(-1). Furthermore, we saw that diffusion through the straight pores of zeolite-beta is impeded when crossing the boundaries between zeolite subunits.