Membrane fluidity and the surface properties of the lipid bilayer: ESR experiment and computer simulation

Penetration of the liposome membranes formed in the gel phase from DPPC (DPPC liposomes) and in the liquid-crystalline phase from egg yolk lecithin (EYL liposomes) by the TEMPO (2,2,6,6-tetramethylpiperidine- 1-oxyl) and 16 DOXYL (2-ethyl-2-(15-methoxy-oxopentadecyl)-4,4-dimethyl-3-oxazolidinyloxy) spin probes has been investigated. The penetration process was followed by 120 hours at 240 degrees C, using the electron spin resonance (ESR) method. The investigation of the kinetics of the TEMPO probe building into the membranes of both types of liposomes revealed differences appearing 30 minutes after the start of the experiment. The number of TEMPO particles built into the EYL liposome membranes began to clearly rise, aiming asymptotically to a constant value after about 100 minutes, whereas the number of the TEMPO particles built into the DPPC liposome membranes was almost constant in time. The interpretation of the obtained experimental results was enriched with those of computer simulation, following the behavior of the polar heads (dipoles) of the lipid particles forming a lipid layer due to the change in the value of the model parameter, k, determining the mobility of the dipoles. The possibility of the formation of an irregular ordering of the polar part of lipid membranes was proved, which leads to the appearance of spaces filled with of water for k > 0.4. The appearance of these defects enables the penetration of the bilayer by the TEMPO particles. The limited mobility of lipid polar heads (k < 0.2) prevents the appearance of such areas facilitating the penetration of the lipid membrane by alien particles in the gel phase.