title: Geminate proton recombination at the surface of SDS and CTAC micelles probed with a micelle-anchored anthocyanin.
abstract: The functionalized flavylium salt 6-hexyl-7-hydroxy-4-methyflavylium chloride (HHMF) was employed to probe some of the fundamental features of proton transfer reactions at the surface of anionic sodium dodecyl sulfate (SDS) and cationic hexadecyltrimethylammonium chloride (CTAC) micelles. In contrast to most ordinary flavylium salts, HHMF is insoluble in water, but readily incorporates into SDS and CTAC micelles. In the ground state, the rate constant for deprotonation of the acid form (AH+) of HHMF decreases 100-fold upon going from CTAC (kd = 3.0 x 10(6) s(-1)) to SDS (kd = 1.4 x 10(4) s(-1)), consistent with the presence of an activation barrier for proton transfer in the ground state and reflecting, respectively, stabilization or destabilization of the AH+ cation by the micelle. Reprotonation of A is diffusion-controlled in both micelles (kp(SDS) = (2.1 x 10(11))[H+]aq s(-1) and kp(CTAC) = (3.7 x 10(8))[H+]aq s(-1)), the difference reflecting the rate of proton entry into the micelles. In the excited singlet state, the rate constants for deprotonation of the AH+* form of HHMF are similar in the two micelles (2.4 x 10(10) s(-1)), consistent with activationless proton transfer. Reprotonation of the excited A is dominated by fast geminate recombination of the photogenerated (A*-H+) pair at the micelle surface (k(rec)(SDS) = 6.1 x 10(9) s(-1) and k(rec)(CTAC) = 3.4 x 10(10) s(-1)) and the net efficiencies of geminate recombination are quite similar in SDS (0.89) and CTAC (0.86).
authors.affiliation: Centro de Química Estrutural, Departamento Engenharia Química, IST/UTL, Lisboa, Portugal.
authors.forename: Rita
authors.initials: R
authors.lastname: Rodrigues
authors.forename: Carolina
authors.initials: C
authors.lastname: Vautier-Giongo
authors.forename: Palmira F
authors.initials: PF
authors.lastname: Silva
authors.forename: Ana C
authors.initials: AC
authors.lastname: Fernandes
authors.forename: Rui
authors.initials: R
authors.lastname: Cruz
authors.forename: António L
authors.initials: AL
authors.lastname: Maçanita
authors.forename: Frank H
authors.initials: FH
authors.lastname: Quina
mesh_terms: D000872:Anthocyanins / Q000737:chemistry*; D008823:Micelles; D011522:Protons; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D013499:Surface Properties
chemical_list: D000872:Anthocyanins; D008823:Micelles; D011522:Protons; D000644:Quaternary Ammonium Compounds; C514921:hexadecyltrimethylammoniumchloride; D012967:Sodium Dodecyl Sulfate