ABSORPTION SPECTRA AND ACID‐BASE DISSOCIATION OF THE 4‐ALKYL DERIVATIVES OF 7‐HYDROXYCOUMARIN IN SELF‐ASSEMBLED SURFACTANT SOLUTION: COMMENTS ON THEIR USE AS ELECTROSTATIC SURFACE POTENTIAL PROBES

Abstract

Abstract— The absorption spectra of the un‐ionized and ionized forms of 4‐heptadecyl‐7‐hydroxycoumarin (HHC) in aqueous self‐assembled surfactant solution have been investigated. From a comparison with the absorption spectra of 7‐hydroxycoumarin, 7‐hydroxy‐4‐methylcoumarin (MHC) and HHC in neat organic solvents and organic solvent/water mixtures it is shown that the 7‐hydroxycoumarin chromophore of HHC in self‐assembled surfactant solution resides, on average, in an interfacial microenvironment which has a lower effective dielectric constant than that of the bulk aqueous solution. The absorption spectrum of the ionized form of HHC in aggregates of self‐assembled surfactant molecules with cationic quaternary ammonium headgroups is found to be consistent with there being specific molecular interaction between the anionic chromophore and the quaternary ammonium headgroup. pH titrations performed with MHC in pure water and in four molar aqueous solutions of sodium chloride and tetra‐methylammonium chloride indicate that the acid‐base dissociation of HHC in charged micelles and vesicles should not be substantially influenced by any interfacial salt‐effects, and that the acid‐base dissociation of HHC in cationic micelles and vesicles with quaternary ammonium headgroups should not be markedly affected by the specific molecular interaction that exists. Estimates of the electrostatic surface potentials of a number of self‐assembled surfactant aggregates are made by utilising the acid‐base dissociation of HHC and assuming that the nonionic micelles of n‐dodecyl octaoxyethylene glycol monoether (C12E8) can serve as a reference state of zero surface potential. The validity of this assumption in relation to both micelles and vesicles is discussed in detail.