19F multipulse nuclear magnetic resonance study of lithium perfluoro-octanoate + water liquid crystal systems
Abstract
Two modified MREV8 sub-cycles forming a partially pertially permuted cycle (PP16) have been used in a multipulse study of the mesophases formed by the lithium perfluoro-octanoate (LiPFO)+ water system. The lineshapes show characteristic axially symmetric chemical shift tensors which have been measured over a range of temperature (20-68°C) and concentration (47.8-72% LiPFO).
The shift anisotropy in the hexagonal phase is halved in magnitude and opposite in sign to that observed in the lamellar phase, indicating the presence of rapid rotational diffusion. A rotational study of an aligned hexagonal sample (47.8 % LiPFO:52.2 % H2O) is used to demonstrate the effects of two dimensional averaging on a chemical shift tensor.
The observed shift tensors are used to estimate values for the order parameter based on the known values of the 19F chemical shift tensor elements for CF2 groups in Teflon at liquid nitrogen temperatures. When compared with chain dimensions estimated from X-ray data, the values of S indicate the existence of rotational isomerisation for the surfactant chain. The molecular order generally increases with increasing concentration, but a decrease is observed at the hexagonal/lamellar boundary.