Location of spectroscopic probes in self-aggregating assemblies. II. The location of pyrene and other probes in sodium dodecyl sulfate micelles.

The location of pyrene in sodium dodecyl sulfate (SDS) micelles is determined as a function of the aggregation number, N, by exploiting the fact that spin probes 5- and 16-doxyl stearic acid methyl esters (5DSE and 16DSE, respectively) are effective quenchers of pyrene fluorescence. The locations of the two spin probes are known from Part 1 of this series (J. Phys. Chem. B 2006, 110, 9791) and the distance between the probes and pyrene is determined by using a hydrodynamic theory to predict the quenching rate constant. The hydrodynamic theory requires the microviscosity of the regions through which the probe and pyrene diffuse. The same spin probe that serves as quencher provides a measure of the microviscosity; thus, all the information needed to locate pyrene is available from each spin probe. Employing 5DSE, at N = 53, pyrene is found to diffuse through a zone 67% of which lies within the Stern layer and 33% in the core. As the micelle grows, due to increasing either the surfactant or added-salt concentration, this diffusion zone moves outward such that, at N = 130, near the sphere-rod transition, it lies approximately 75% within the Stern layer and 25% in the core. Employing 16DSE, the location of pyrene is within 0.4 A of that found from 5DSE at low values of N and within 0.8 A at high values. Full information required to locate pyrene by using the currently developed method is not yet available for other spin probes and other commonly employed quenchers; nevertheless, using a variety of strategies and reasonable assumptions leads to the same location of pyrene within the uncertainties of the method. All of the spectroscopic probes employed in this study are largely located within the polar shell of the micelles, the largest departure being about 4% of the diameter of the micelle.