Cy3 in AOT Reverse Micelles I. Dimer Formation Revealed through Steady-State and Time-Resolved Spectroscopy

Cyanine-3 (Cy3) fluorescent dye molecules confined in sodium di-2-ethylhexyl sulfosuccinate (AOT) reverse micelles were examined using steady-state absorption and emission as well as time-resolved fluorescence spectroscopy to understand the effect of confinement on the spectroscopic properties of the dye. This study explored a wide range of reverse micelle sizes, with hydrodynamic radii ranging from similar to 1.7 to similar to 5 nm. The relative concentrations of Cy3 and AOT reverse micelles were such that, on average, one dye molecule was present for every 2 x 10(4) to 9 x 10(5) reverse micelles. In the smallest reverse micelles examined, observed changes in the absorption and emission spectra and fluorescence lifetime of the dye molecules indicated H-aggregation of Cy3 into side-by-side dimers. It is hypothesized that this dimerization is governed by the high local concentrations that result from the confinement of the Cy3 in the reverse micelles. What is notable about this study is that this dimer occurs even at overall dye concentrations in the nanomolar range. Such concentrations are too low for aggregation to occur in bulk solution. Hence, the reverse micelles serve as nanocatalysts for this aggregation process.