Interactions between Methylene Blue and Sodium Dodecyl Sulfate in Aqueous Solution Studied by Molecular Spectroscopy

The interactions of methylene blue (MB, a cationic redox indicator and biological stain) and sodium dodecyl sulfate (SDS, a micelle-forming, anionic surfactant) in aqueous solution have been examined by using Rayleigh scattering, UV-visible absorption, and fluorescence spectroscopy. At SDS concentrations significantly below the critical micelle concentration (cmc), MB forms noncovalent dimers and aggregates with SDS that scatter light but do not fluoresce. For solutions containing 1 μM MB and < 3–5 mM SDS, shifts in the absorption spectrum characteristic of the formation of MB H-aggregates are noted. There appears to be little effect on the fluorescence emission spectrum, indicating that these MB aggregates do not fluoresce appreciably. At and above the known SDS cmc, MB is observed to interact with the micelles. The MB excited-state fluorescence lifetime (380 ps) remains constant until SDS micelles form, then increases to 615 ps. The MB rotational reorientation time similarly increases from 105 to 500 ps between 6 and 8 mM SDS. This finding suggests that the MB is encountering, on average, a microenvironment in the SDS micelles that is 5-fold more viscous than liquid water or the molar volume of the MB/SDS species that is reorienting is 5-fold larger than MB in water.