Effect of Cosurfactants on the Interfacial Hydration of CTAB Quaternary Reverse Micelle Probed Using Excited State...

It has been proven previously that the negatively charged photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) resides at the interface of the cationic reverse micelle (RM) cetyltrimethylammonium bromide (CTAB)/octanol/water/cyclohexane and is a potential reporter of hydration through the excited state proton transfer (ESPT) process. However, the ESPT dynamics monitored by the pump-probe study was limited to the ultrafast timescale and hence did not report any discernible ESPT signature. Herein, we reinvestigate the ESPT behavior using fluorescence spectroscopy in the nanosecond timescale and at different values of w₀ (=[water]/[surfactant]). We clearly observed distinct w₀-dependent ESPT signatures analogous to conventional ternary cationic RMs implying considerable interfacial hydration. The results agree with a recent molecular simulation study, where significant penetration of water molecules into the interface was predicted for the CTAB quaternary RM. Moreover, we also found that the ESPT dynamics and the fluorescence anisotropy decay of HPTS depend differentially on the octanol/CTAB ratio (p₀). The ESPT process was found to be disfavored, whereas the anisotropy decay accelerates upon the increase in p₀ values. Our analysis indicates that with the increase in the octanol concentration, dehydrated regions enrich gradually at the interface. However, the increase in octanol concentration may reduce the effective electrostatic potential experienced by the probe and thus may result in faster rotational relaxation.