Geminate proton recombination at the surface of SDS and CTAC micelles probed with a micelle-anchored anthocyanin.
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).
Rodrigues
Rita
R
Centro de Química Estrutural, Departamento Engenharia Química, IST/UTL, Lisboa, Portugal.
Vautier-Giongo
Carolina
C
Silva
Palmira F
PF
Fernandes
Ana C
AC
Cruz
Rui
R
Maçanita
António L
AL
Quina
Frank H
FH
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
D000872:Anthocyanins; D008823:Micelles; D011522:Protons; D000644:Quaternary Ammonium Compounds; C514921:hexadecyltrimethylammoniumchloride; D012967:Sodium Dodecyl Sulfate