Excited state proton transfer in reverse micelles

Boiko Cohen, Dan Huppert, Kyril M. Solntsev, Yossi Tsfadia, Esther Nachliel, Menachem Gutman

Research output: Contribution to journalArticlepeer-review

Abstract

The aqueous phase of water/AOT reversed micelles having varying diameters was probed by a single free diffusing proton that was released form a hydrophilic photoacid molecule (2-naphthol-6,8-disulfonate). The fluorescence decay signals were reconstructed through the geminate recombination algorithm, accounting for the reversible nature of the proton-transfer reactions at the surface of the excited molecule and at the water/detergent interface. The radial diffusion of the proton inside the aqueous phase was calculated accounting for both the entropy of dilution and the total electrostatic energy of the ion pair, consisting of the pair-energy and self-energy of the ions. The analysis implied that micellar surface must be modeled with atomic resolution, assuming that the sulfono residue protrudes above the water/hydrocarbon interface by ∼2 Å. The analysis of the fluorescence decay curves implies that the molecule is located in a solvent with physical-chemical properties very similar to bulk water, except for the dielectric constant. For reversed micelles with rmax ≥ 16 Å, the dielectric constant of the aqueous phase was ∼70 and for smaller micelles, where ∼60% of the water molecule is in contact with the van der Waals surface of the micelle, it is as low as 60. This reduction is a reflection of the increased fraction of water molecule that is in close interaction with the micelle surface.

Original languageEnglish
Pages (from-to)7539-7547
Number of pages9
JournalJournal of the American Chemical Society
Volume124
Issue number25
DOIs
StatePublished - 26 Jun 2002

Fingerprint

Dive into the research topics of 'Excited state proton transfer in reverse micelles'. Together they form a unique fingerprint.

Cite this