title: Photooxidation of diglycine in confined media. Application of the microreactor model for spin-correlated radical pairs in reverse micelles and water-in-oil microemulsions.
abstract: Time-resolved electron paramagnetic resonance spectra (X-band) of correlated radical pairs created in AOT reverse micelles and microemulsions are presented, simulated, and discussed using the microreactor model. The radicals are formed inside the water pool using photooxidation of diglycine by the excited triplet states of two different anthraquinone sulfonate salts. Water pool size and temperature effects on the spectra are reported, and the simulations allow for extraction of the diffusion coefficient in the interior, which monotonically increases with water pool size. The data directly correlate with the diffusional properties of correlated radical pairs in regular aqueous micelle solutions studied previously by similar methods. Competition between H-atom abstraction and electron transfer is observed with anthraquinone sulfonate, but electron transfer is the only reaction pathway observed when anthraquinone disulfonate triplet state is the sensitizing species.
authors.affiliation: Venable and Kenan Laboratories, Department of Chemistry, CB #3290, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
authors.forename: Ryan C
authors.initials: RC
authors.lastname: White
authors.forename: Valery F
authors.initials: VF
authors.lastname: Tarasov
authors.forename: Malcolm D E
authors.initials: MD
authors.lastname: Forbes
mesh_terms: D000880:Anthraquinones / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D004655:Emulsions / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D006033:Glycylglycine / Q000737:chemistry*; D008823:Micelles; D008956:Models, Chemical; D015394:Molecular Structure; D009821:Oils / Q000737:chemistry*; D010084:Oxidation-Reduction; D010777:Photochemistry; D013455:Sulfur / Q000737:chemistry; D013696:Temperature; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D000880:Anthraquinones; D004655:Emulsions; D005609:Free Radicals; D008823:Micelles; D009821:Oils; D014867:Water; D006033:Glycylglycine; D013455:Sulfur