Electron spin resonance (ESR) spectroscopy was used to measure the rotational mobility of an uncharged nitroxide spin probe (4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy) in hectorite gels of variable water content. Physical adsorption segregated the probe molecules into two populations: probes in the solution or a solution-like phase, and motionally restricted probes in the adsorbed phase. Although the spectra of these two populations were discrete, indicating that exchange between them was slow on the time scale relevant to ESR, their overlap prevented a straightforward determination of mobility of the adsorbed probes. Even though adsorption was weak, effects of the adsorbed population on the spectral lineshape were detectable for suspensions containing as little as 20 grams clay per liter of water. Orientation of the adsorbed probes on the fully hydrated hectorite surfaces was similar to that of a positively charged nitroxide probe, suggesting that steric factors rather than electrostatic forces control short-range organic molecule interaction with the silicate. The possibility of reaching false conclusions about probe mobility and interlamellar water viscosity when using a weakly adsorbing probe is discussed.

The outer layer of the skin, stratum corneum (SC) is an efficient transport barrier and it tolerates mechanical deformation. At physiological conditions, the majority of SC lipids are solid, while the presence of a small amount of fluid lipids is considered crucial for SC barrier and material properties. Here we use solid-state and diffusion nuclear magnetic resonance to characterize the composition and molecular dynamics of the fluid lipid fraction in SC model lipids, focusing on the role of the essential SC lipid CER EOS, which is a ceramide esterified omega-hydroxy sphingosine linoleate with very long chain. We show that both rigid and mobile structures are present within the same CER EOS molecule, and that the linoleate segments undergo fast isotropic reorientation while exhibiting extraordinarily slow self-diffusion. The characterization of this unusual self-assembly in SC lipids provides deepened insight into the molecular arrangement in the SC extracellular lipid matrix and the role of CER EOS linoleate in the healthy and diseased skin.

Molecular mobility is hypothesised to be a key factor influencing storage stability of seeds because it may control the rate of deteriorative reactions responsible for reduced shelf life. The relationship between the longevity of lettuce seeds and the molecular mobility was investigated in the cytoplasm of lettuce radicles. Longevity of lettuce seeds was predicted using the viability equation of Ellis and Roberts, and the molecular mobility was determined by saturation transfer electron paramagnetic resonance spectroscopy measurements of rotational motion of a polar spin probe inserted into the cytoplasm. Increasing the temperature resulted in faster rotational motion and shorter longevity. There was a linear relationship between the logarithms of rotational motion and estimated seed longevity for temperatures above 5°C. Below 5°C, there was a deviation from linearity. Based on the hypothesis that the molecular mobility in the cytoplasm determines the rate of detrimental reactions, seed longevity at sub-zero temperatures was predicted by extrapolation of the rotational motion using the linear relationship. Predictions of longevity at sub-zero temperatures based on rotational motion indicated longer survival times than those based on the viability equation. A kinetic approach to ageing using molecular mobility measurements is expected to improve our understanding of seed storage stability and might eventually lead to realistic predictions of longevity at low temperatures.