Role of Different States of Solubilized Water on Solvation Dynamics and Rotational Relaxation of Coumarin 490 in Reverse Micelles of Gemini Surfactants, Water/12-s-12.2Br– (s = 5, 6, 8)/n-Propanol/Cyclohexane

Abstract

The present study demonstrates how the different states of solubilized water viz. quaternary ammonium headgroup-bound, bulklike, counterion-bound, and free water in reverse micelles of a series of cationic gemini surfactants, water/12-s-12 (s = 5, 6, 8).2Br–/n-propanol/cyclohexane, control the solvation dynamics and rotational relaxation of Coumarin 490 (C-490) and microenvironment of the reverse micelles. The relative number of solubilized water molecules of a given state per surfactant molecule decides major and minor components. A rapid increase in the number of bulklike water molecules per surfactant molecule as compared to the slow increase in the number of each of headgroup- and counterion-bound water molecules per surfactant molecule with increasing water content (Wo) in a given reverse micellar system is responsible for the increase in the rate of solvation and rotational relaxation of C-490. The increase in the number of counterion-bound water molecules per surfactant molecule and the concomitant decrease in the number of bulklike water molecules per surfactant molecule with increasing spacer chain length of gemini surfactants at a given Wo are ascribed to the slower rates of both solvation and rotational relaxation. Relative abundances of different states of water have a role on the microenvironment of the reverse micelles as well. Thus, a comprehensive effect of different states of water on dynamics in complex biomimicking systems has been presented here.