An ultraviolet‐visible spectroscopic investigation has been made of the interactions of a specially synthesised series of substituted, model arylazonaphthol dyes with nonionic and anionic surfactants. Changes in spectral features were recorded above the critical micelle concentrations, suggesting specific interactions of dyes with micelles of the respective surfactants. The affinity of the dye for the surfactant micelles increased when various p‐substituent were incorporated in to the dyes. Similarly, there was a shift in azo–hydrazone tautomeric equilibria and an increase in measured dye pKa values. Models are proposed for the location of dyes in nonionic or anionic micelles. Unlike earlier studies, it is concluded that the solubilised dye experiences only one environment in nonionic micelles but the specific location, i.e. whether preferentially incorporated in the hydrophobic micellar interior or in the more hydrophilic, outer polyoxyethylene layer, depends upon the nature of the substituent.
A UV–vis spectroscopic investigation has been made of the interactions of a specially synthesised series of o‐ and p‐substituted, model arylazonaphthol dyes with the cationic and zwitterionic surfactants above and below their critical micelle concentrations at pH 10. Spectra of dyes incorporated in micelles of zwitterionic surfactant or cationic surfactant at pHs < 8 are similar to those found in nonionic micelles, i.e. dye substituents control its location similarly for all the micelle types. However, the common anion is selectively favoured in cationic micelle solutions at pH 10, due to electrostatic interactions within the micellar surface. Introduction of polar groups at either end of the molecule confines the dyes to the surface of either zwitterionic or cationic micelles and are characterised by atypical pKA shifts. Electrostatic complexes between dyes and cationic or zwitterionic surfactants were formed in sub‐micellar regions, those with cationic surfactant being sparingly soluble.
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