Application of Thin Titanium/Titanium Oxide Layers Deposited on Gold for Infrared Reflection Absorption Spectroscopy: Structural Studies of Lipid Bilayers

Ultrathin titanium layers when deposited on the surface of gold can be successfully applied for infrared reflection absorption spectroscopy (IRRAS) investigations. It was shown that the reflectivity, the phase shift, and the mean square electric field of the p- and s-polarized IR radiation in up to 20 nm thick titanium layers covered with a 3−4 nm thick layer of native oxide are comparable to those of the air/gold interface. The surface selection rule is fulfilled. Thus, qualitative and quantitative analysis of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayers transferred in liquid expanded (LE) and liquid condensed (LC) states can be performed. Differences are found in the hydration state and molecular arrangement of the two investigated bilayers. In the DMPC bilayer in the LE state, the C−N bond in the positively charged choline moiety is inclined by 70° toward the surface of the negatively charged titanium substrate. In the phosphate moiety, the in-plane vector of the O−P−O group makes a small angle of 15° to the surface normal. This open structure of the lipid molecule corresponds to the B crystal structure of the DMPC molecule and provides space for strong hydration of the polar headgroup. In the DMPC bilayer in the LC state, the intermolecular distances are reduced; the C−N bond of the choline group makes a smaller angle to the surface normal, and the in-plane vector of the O−P−O group in the phosphate moiety displays a larger tilt. The degree of hydration is reduced. The arrangement of the polar headgroup region corresponds to the A crystal structure of the DMPC molecule.