On the low-temperature onset of molecular flexibility in lipid bilayers seen by Raman scattering

For dipalmitoylphosphatidylcholine (DPPC) lipid/water bilayers, a detailed temperature dependence of the Raman scattering spectra at the spectral range of the CH 2-stretching modes was investigated. Below 150 K the ratio of intensities of the 2880 cm (-1) antisymmetric vibration line and the 2850 cm (-1) symmetric one was found to be nearly temperature-independent. Between 150 and 230 K it decreases slightly as temperature increases; and above 230 K it decreases remarkably. This decrease is accompanied with broadening of the antisymmetric line, from 4.2 cm (-1) at 100 K to 5.7 cm (-1) at 296 K. According to literature, the decrease of the antisymmetric line may be interpreted in two ways: (i) the appearance of a static conformational disorder (or of a disorder fluctuating at the time scale larger than picoseconds) and (ii) relaxation at the ps time scale, which is induced by coupling with temperature-activated librational-torsional motion of the lipid chain. Both these interpretations imply that obtained data evidence the appearance of molecular flexibility of lipids around approximately 200 K. The observed effect is to be compared with low-temperature dynamical transition found in disordered media with neutron scattering, Mossbauer absorption, molecular dynamics simulations and other techniques. This transition implies that with temperature increase harmonic atomic motions are transformed to large-amplitude anharmonic (or stochastic) ones. The characteristic times of these motions lay at the ps time scale. The closeness of the temperature of the transition and of the time scale of motions with those found in this work by Raman scattering for lipid bilayers supports the dynamic nature of the 2880 cm (-1) antisymmetric vibration line decrease (i.e., that it is induced by coupling with libration-torsion). To prove that the observed onset of flexibility is a property of a disordered state, Langmuir-Blodgett films of behenic acid were studied. These films contain, like lipids, long CH 2-tails, but, in opposite to bilayers, they have a well-ordered crystalline-like structure. The relative intensity of the antisymmetric/symmetric CH 2-stretching lines was found in these films to be temperature-independent in the whole temperature range studied, between 60 and 296 K.