Lateral Diffusion of Molecules Partitioned into Silica-Bound Alkyl Chains: Influence of Chain Length and Bonding Density

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Abstract
Lateral diffusion of a hydrophobic fluorescent molecule partitioned into monomeric alkyl chains bound to a planar silica substrate was measured as a function of chain density and chain length. Measurement of fluorescence recovery after patterned photobleaching was used to observe the diffusional relaxation of a concentration profile of probe molecules over distances of micrometers. The diffusion rate of the probe molecule partitioned into C-18 chains decreased with decreasing chain coverage. As the chain length was reduced from C-18 to C-8 and C-4, the rate of diffusion also decreased. These results, when combined with results from a previous study of the effect of overlaying solvent on diffusion rate (Hansen, R. L.; Harris, J. M. Anal. Chem. 1995, 67, 492−498), are consistent with a domain model for long-range transport of partitioned molecules through the bound ligands. Fluorescence recovery experiments in which diffusion is monitored over a distance of micrometers offer a unique means to probe long-range structure of surface-immobilized alkyl chains.