Slow dynamics in a liquid crystal: 1H and 19F NMR relaxometry

Abstract

Spin-lattice relaxation rates (R(1H) and R(1F)) of two nuclear species ((1)H and (19)F) are measured at different temperatures in the isotropic phase of a liquid crystal (4(')-butoxy-3(')-fluoro-4-isothiocyanatotolane-4OFTOL), over a wide range of Larmor frequency (10 kHz-50 MHz). Their dispersion profiles are found to be qualitatively very different, and the R(1F) in particular shows significant dispersion (varying over two orders of magnitude) in the entire isotropic range, unlike R(1H). The proton spin-lattice relaxation, as has been established, is mediated by time modulation of magnetic dipolar interactions with other protons (case of like spins), and the discernable dispersion in the mid-frequency range, observed as the isotropic to nematic transition is approached on cooling, is indicative of the critical slowing of the time fluctuations of the nematic order. Significant dispersion seen in the R(1F) extending to very low frequencies suggests a distinctly different relaxation path which is exclusively sensitive to the ultra slow modes apparently present in the system. We find that under the conditions of our experiment at low Zeeman fields, spin-rotation coupling of the fluorine with the molecular angular momentum is the dominant mechanism, and the observed dispersion is thus attributed to the presence of slow torques experienced by the molecules, arising clearly from collective modes. Following the arguments advanced to explain similar slow processes inferred from earlier detailed ESR measurements in liquid crystals, we propose that slowly relaxing local structures representing such dynamic processes could be the likely underlying mechanism providing the necessary slow molecular angular momentum correlations to manifest as the observed low frequency dispersion. We also find that the effects of the onset of cross-relaxation between the two nuclear species when their resonance lines start overlapping at very low Larmor frequencies (below ~400 kHz), provide an additional relaxation contribution.

Concepts and Methods of Solid-State NMR Spectroscopy Applied to Biomembranes

“…Let us next introduce a more general formulation that is capable of dealing with the various possible types of motions in a more unified way. In the liquid-crystalline state, a hierarchy of motions of the molecules occurs within the bilayer, as manifested by the frequency dependence of the 1 H, 2 H, and 13 C nuclear relaxation rates. ,− Evidently, one can expect contributions from segmental motions as well as molecular motions and possibly collective fluctuations of the bilayer itself. The general types of motional models that can be considered are illustrated by Figure .…”

Solid-State 2H NMR Studies of Water-Mediated Lipid Membrane Deformation

“…Many biological membranes are in the liquid-crystalline phase with a hierarchy of motions of the molecules within the bilayer, as manifested by the frequency dependence of the 1 H, 2 H, and 13 C nuclear relaxation rates [41,[70][71][72][73][74][75][76]. The energy landscape includes fast segmental motions at short length scales, individual lipid molecular diffusion and collective bilayer fluctuations at intermediate length scales, and collective undulations of larger patches of the membrane at larger length scales (Fig.…”