Effect of high surface curvature on the main phase transition of supported phospholipid bilayers on SiO2 nanoparticles.

Investigation of the physical properties of highly curved membranes is important in biology, for example, in fusion intermediates, and in pharmaceutical or chromatographic applications, where nanoscale features may affect substrate binding. However, vesicle fusion below 40 nm precludes study of this size regime. In this investigation, the effect of high surface curvature on the adsorption and morphology of phosphotidylcholine lipids with alkyl chain lengths of 14 (DMPC), 16 (DPPC), and 18 (DSPC) onto silica (SiO2) nanobeads was investigated by thermogravimetric analysis (TGA), high sensitivity nanocalorimetry, and vibrational spectroscopy. The SiO2 beads ranged in size from 5 to 100 nm. Stable supported bilayers were formed on all bead sizes by vesicle fusion of the parent MLVs at temperatures above the main phase transition temperature (T(m)) of the lipids. A downward shift in T(m), and a broadening (deltaT1/2) of the transition with respect to the parent MLVs, was observed for the 100 nm beads. With decreasing bead size, T(m) first decreased, but then increased. On the smallest bead size, whose dimensions were comparable to those of the adsorbed lipids, T(m)'s were higher than those of the parent MLVs. The increase in T(m) indicated a stiffening of the supported bilayer, which was confirmed by Raman spectroscopic data. Narrowing of the phase transition or the appearance of peak doublets occurred at the smaller bead sizes. The results were consistent with a model in which the high free volume and increased outer headgroup spacing of lipids on highly curved surfaces induced interdigitation in the supported lipids.