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Electrolytes are known to impart considerable disorder to lipid assemblies, including monolayers at the air-water interface, bilayers, and vesicles. In the present work, we have investigated the disordering effect of sodium salts of monovalent anions that span the lyotropic series on the monolayers of 1,2-dipalmitoyl-sn-glycero-phosphocholine (DPPC) at 12 C. Pressure-area isotherms, Brewster-angle microscopy (BAM), grazing-incidence X-ray diffraction (GIXD), and infrared absorption-reflection spectroscopy (IRRAS) were used to investigate in complementary ways the salt effects on lipid monolayers. At 12 C these effects were found to be quite dramatic, a major finding being that the liquid-expanded phase, which is not present at this temperature on a pure water subphase, reappears and dominates in the presence of electrolytes. Salts expand the monolayer, destroy the ordered phase that exists at zero pressure, and affect the ordering of the lipid chains and their tilt angle in the liquid condensed phase. Finally, very chaotropic anions force DPPC lipids to adopt an untilted conformation in the condensed phase, an unprecedented finding for nonmixed Langmuir monolayers of this phospholipid. A distinctly different behavior of very chaotropic anions from that of normal chaotropic ones thus emerges. The effect of the former is not just a limited perturbation of the lipid assembly but a major disruption of the structure, which arises from competition between the lipids and the ions for interfacial sites. © 2012 American Chemical Society. 116 50 14602 14612 Cited By :15

In this work, we use Langmuir monolayers of dipalmitoyl phosphatidylcholine (DPPC) as model systems to enhance the understanding of specific anion effects in physicochemical and biological systems. The 298 K isotherms (equation of state, EOS) of DPPC over solutions of a range of sodium salts depend strongly on the type and concentration of the salt in the subphase. We focus in particular on the liquid expanded phase region of the DPPC EOS and assume that the deviation of the isotherms over electrolyte solutions from that over pure water is due entirely to the charging of the lipid monolayer by the ions. We then examine the ability of a range of phenomenological continuum models to explain the pressure increase in the presence of electrolytes. The important finding is that insoluble lipid monolayers allow the discrimination between possible modes of ion-lipid interaction. Chemical binding models, simple or modified, cannot fit the range of data presented in this work. Both dispersion interaction and partitioning models fit most of the experimental isotherms and provide unique values for dispersion coefficients or ionic partitioning constants, respectively, even though the nature of these models is completely different (the former concentrates on the potential of mean force that acts on an ion in the double layer, while the latter concentrates on the treatment of interactions at the interface). Surprisingly, the respective fitting parameters are very highly correlated, reflecting, we believe, the effect of ion size on ionic properties and interactions. With sodium fluoride (NaF) as the subphase electrolyte, it is demonstrated that sodium exhibits a weak complexation-type interaction with the zwitterionic lipids. The simple dispersion and partitioning models cannot account for the NaF results, highlighting the need for more complex salt-lipid interaction models that account both for sodium binding and anion partitioning. This realization sets the stage for the companion paper. © 2009 American Chemical Society. 113 5 1447 1459 Cited By :43

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 (π-AL) 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 π-?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. © 2009 American Chemical Society. 113 44 14816 14823 Cited By :24