RESUMEN
Fast thermal fluctuations and low frequency phonon modes are thought to play a part in the dynamic mechanisms of many important biological functions in cell membranes. Here we report a detailed far-infrared study of the molecular subpicosecond motions of phospholipid bilayers at various hydrations. We show that these systems sustain several low frequency collective modes and deduce that they arise from vibrations of different lipids interacting through intermolecular van der Waals forces. Furthermore, we observe that the low frequency vibrations of lipid membrane have strong similarities with the subpicosecond motions of liquid water and suggest that resonance mechanisms are an important element to the dynamics coupling between membranes and their hydration water.
Asunto(s)
Membrana Dobles de Lípidos/química , Fosfolípidos/química , Simulación de Dinámica Molecular , Espectrofotometría Infrarroja , Agua/químicaRESUMEN
The effects of hexanol and octanol on the lateral mobility of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) bilayer are investigated by means of pulsed-gradient stimulated-echo NMR spectroscopy. Three distinct diffusions are identified for the DMPC/alcohol systems. They are ascribed to the water, the alcohol, and the lipid. We find that the presence of alcohols promotes the lipid diffusion process both in the liquid and in the interdigitated phases. Furthermore, using the Arrhenius approach, the activation energies are calculated. An explanation in terms of a free volume model, that takes into account also the observed increase of the activation energy in both phases, is proposed. The results obtained here are compared with those presented in our previous work on 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) in order to examine the dependence of the lipid translational diffusion process upon the membrane acyl chain length. A peculiar influence of alcohols on different membranes is found.
Asunto(s)
Hexanoles/metabolismo , Membrana Dobles de Lípidos/metabolismo , Octanoles/metabolismo , Fosfatidilcolinas/metabolismo , Difusión , Dimiristoilfosfatidilcolina/química , Dimiristoilfosfatidilcolina/metabolismo , Membrana Dobles de Lípidos/química , Fluidez de la Membrana , Fosfatidilcolinas/químicaRESUMEN
We have studied the effects of a high concentration of butanol and octanol on the phase behavior and on the lateral mobility of 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) by means of differential scanning calorimetry and pulsed-gradient stimulated-echo (PGSTE) NMR spectroscopy. A lowering of the lipid transition from the gel to the liquid-crystalline state for the membrane-alcohol systems has been observed. NMR measurements reveal three distinct diffusions in the DPPC-alcohol systems, characterized by a high, intermediate, and slow diffusivity, ascribed to the water, the alcohol, and the lipid, respectively. The lipid diffusion process is promoted in the liquid phase while it is hindered in the interdigitated phase due to the presence of alcohols. Furthermore, in the interdigitated phase, lipid lateral diffusion coefficients show a slight temperature dependence. To the best of our knowledge, this is the first time that lateral diffusion coefficients on alcohol with so a long chain, and at low temperatures, are reported. By the Arrhenius plots of the temperature dependence of the diffusion coefficients, we have evaluated the apparent activation energy in both the liquid and in the interdigitated phase. The presence of alcohol increases this value in both phases. An explanation in terms of a free volume model that takes into account also for energy factors is proposed.