Search

The present work highlights the effect of urea on solvation dynamics and the rotational relaxation of Coumarin 480 (C-480) in the Stern layer of aqueous micelles of cationic gemini surfactants, 12-4(OH) n -12 ( n = 0, 1, 2). UV-visible absorption, steady-state fluorescence and fluorescence anisotropy, time-resolved fluorescence and fluorescence anisotropy, and dynamic light scattering measurements have been carried out for this study. The formation of micelles becomes disfavored in the presence of urea at high concentration. Solvation dynamics is bimodal in nature with fast solvation as a major component. The average solvation time increases, reaches a maximum, and then decreases with increasing concentration of urea because the degree of counterion dissociation also follows the same order with the addition of urea in the micellar solution. With increased degree of counterion dissociation, the extent of clustering of water molecules is increased, resulting in slower solvation process. The -OH group present in the spacer group of gemini surfactant controls the rate of solvation by shielding the water molecules from the probe molecules forming hydrogen bond. The microviscosity of micelles is decreased with increasing concentration of urea, as a result of which the rotational relaxation process becomes faster. In the presence of the -OH group in the spacer group, the microviscosity of micelles is enhanced, resulting in longer rotational relaxation time. Rotational relaxation process is bimodal in nature with the major contribution from the fast component to the fluorescence depolarization. Slow rotational relaxation is mainly due to the lateral diffusion of C-480 molecules along the surface of the micelle. The tumbling motion of the micelle as a whole is much slower than the lateral diffusion of C-480. Wobbling motion of C-480 becomes faster with increasing concentration of urea as a result of decreased microviscosity of micelles. The alignment of C-480 molecules in micelles might change with changing microviscosity., Competing Interests: The authors declare no competing financial interest.

Solvation dynamics and rotational relaxation of coumarin 480 in aqueous micelles of cationic gemini surfactants with diethyl ether (EE) spacer group ( m -EE- m ) and tails with varying tail lengths ( m = 12, 14, and 16) have been studied. Studies have been carried out by measuring UV-visible absorption, steady-state fluorescence and fluorescence anisotropy, time-resolved fluorescence and fluorescence anisotropy, 1 H NMR spectroscopy, and dynamic light scattering. Effects of hydrocarbon tail length and hydrophilicity of spacer group on solvation dynamics and rotational relaxation processes at inner side of the Stern layer of micelles have been studied. With increasing hydrophobicity of tails of surfactants, water molecules in the Stern layer become progressively more rigid, resulting in a decrease in the rate of solvation process with slow solvation as a major component. With increasing hydrophilicity of the spacer group of gemini surfactant, the extent of free water molecules is decreased, thereby making the duration of the solvation process longer. Solvation times in the micelles of gemini surfactants with hydrophilic spacer are almost 4 times longer compared to those in the micelles of their conventional counterpart. Rotational relaxation time increases with increasing tail length of surfactant as a result of increasing microviscosity of micelles with fast relaxation as a major component. With increasing hydrophilicity of the spacer group, the anisotropy decay becomes slower due to the formation of more compact micelles. Rotational relaxation in gemini micelles is also slower compared to that in their conventional counterpart. The anisotropy decay is found to be biexponential with lateral diffusion of the probe along the surface of the micelle as a slow component. Rotational motion of micelle as a whole is a very slow process, and the motion becomes further slower with increasing size of the micelle. The time constants for wobbling motion and lateral diffusion of the probe become longer with increasing microviscosity of micelles., Competing Interests: The authors declare no competing financial interest.