Vibrational Sum Frequency Generation Spectroscopic Investigation of the Interaction of Thiocyanate Ions with Zwitterionic Phospholipid Monolayers at the Air−Water Interface

Abstract

Thiocyanate (SCN(-)) is a highly chaotropic anion of considerable biological significance, which interacts quite strongly with lipid interfaces. In most cases it is not exactly known if this interaction involves direct binding to lipid groups, or some type of indirect association or partitioning. Since thiocyanate is a linear ion, with a considerable dipole moment and nonspherical polarizability tensor, one should also consider its capability to adopt different or preferential orientations at lipid interfaces. In the present work, the interaction of thiocyanate anions with zwitterionic phospholipid monolayers in the liquid expanded (LE) phase is examined using surface pressure-area per molecule (pi-A(L)) isotherms and vibrational sum frequency generation (VSFG) spectroscopy. Both dipalmitoyl phosphatidylcholine (DPPC) and dimyristoyl phosphatidylethanolamine (DMPE) lipids, which form stable monolayers, have been used in this investigation, since their headgroups may be expected to interact with the electrolyte solution in different ways. The pi-A(L) isotherms of both lipids indicate a strong expansion of the monolayers when in contact with SCN(-) solutions. From the C-H stretch region of the VSFG spectra it can be deduced that the presence of the anion perturbs the conformation of the lipid chains significantly. The interfacial water structure is also perturbed in a complex way. Two distinct thiocyanate populations are detected in the CN stretch spectral region, proving that SCN(-) associates with zwitterionic phospholipids. Although this is a preliminary investigation of this complex system and more work is necessary to clarify certain points made in the discussion, a potential identification of the two SCN(-) populations and a molecular-level explanation for the observed effects of the SCN(-) on the VSFG spectra of the lipids is provided.