Ionic binding of phospholipids to interfaces: dependence on metal ion identity.

We report on the deposition of 1,2-dimyristoyl-sn-glycero-3-phosphatidic acid (DMPA) on selected metal-phosphate-terminated self-assembled monolayers (SAMs) constructed on Au. The phosphate-terminated SAMs were reacted with Zr(4+), Cu(+), Cu(2+), Fe(3+), Zn(2+), Ni(2+), Ca(2+), and Mg(2+), with subsequent exposure of the resulting interface to DMPA unilamellar vesicles. The resulting interface was characterized using X-ray photoelectron spectroscopy (XPS), optical ellipsometry, water contact angle measurements, and cyclic voltammetry (CV). The strongest lipid-metal ion interfacial interactions are with Zr(4+) and Fe(3+), with Ca(2+), Cu(+), Ni(2+), Zn(2+), and Mg(2+) producing somewhat less well organized adlayers. Cu(2+) did not bind strongly to the interfacial phosphate moiety, yielding a lipid bilayer structure. These results can be understood in the context of the strength of the metal bisphosphate complex that forms between the phospholipid and the chemically modified interface.