Dynamical features in cationic micelles of varied chain length.

Chain length is one of the parameters controlling the structural arrangement of micelle monomers, such that one can tailor the monomers for different applications, but the effect of chain length on the dynamical behavior of micelles is unknown. In this article, we report a study on the effect of varying chain length on the dynamical behavior of alkyltrimethylammonium bromide (C(n)TAB) micelles (n = 10, 12, 14, and 16) using incoherent quasielastic neutron scattering (QENS). The data analysis clearly shows the presence of two distinct motions: global motion of whole micelles and faster internal motions of the C(n)TAB monomers. The global diffusion is Fickian in nature, whereas the internal motions can be described with a model that considers the motions of the headgroup and the hydrophobic alkyl chain separately. Methyl groups in the headgroup undergo 3-fold jump rotations, and the hydrogen atoms belonging to the alkyl chain undergo localized translational diffusion. The hydrogen atoms belonging to the alkyl chain are confined within spherical volumes that increase linearly along the C(n)TAB chain: the hydrogen atoms closer to the headgroup move within smaller spheres with lower diffusion coefficients than those farther from the headgroup. The main result is that, with increasing chain length, the dynamics of the C(n)TAB monomer is greatly affected: diffusion is reduced and occurs in smaller spheres, and residence times are increased. Global motion is also hindered with increased chain length.