Structural models of lipid surface monolayers from X-ray and neutron reflectivity measurements.
Structural investigations of phospholipid monolayers on aqueous subphases on the submolecular level using X-ray and neutron reflectivity measurements are reviewed. While such investigations have been limited in the past by a relatively restricted accessible momentum transfer range, recent developments in synchrotron technology--almost doubling this range--have considerably improved the capabilities of the technique. Until recently, data interpretation has entirely relied on 'box models' which describe the structures as molecularly homogeneous slabs--one hydrophobic and one hydrophilic. It is shown that box models of phospholipid monolayers are rather inadequate to model data at the high momentum transfer available nowadays in X-ray measurements. As an alternative, a hybrid data inversion strategy is proposed that treats the hydrophobic alkane phase as a homogeneous slab and describes the position of submolecular fragments of the lipid headgroups by means of distribution functions along the interface. Within this approach, composition-space refinement--enabling the coupling of data sets from various X-ray and neutron contrasts--in connection with volumetric constraints enables structural characterization of lipid monolayers in unprecedented detail. Extending a recent characterization of dimyristoylphosphatidic acid (DMPA) monolayers on pure water [Schalke et al., Biochim. Biophys. Acta 1464 (2000) 113-126] it is shown that stoichiometric binding of the divalent cations--DMPA-:Cat2+= 2:1--occurs only at exceedingly low areas per molecule, A lipid. At low surface pressure pi, both cations and anions are incorporated into the headgroup in significant amounts, approximately 0.68 Ba2+ and approximately 0.35 Cl- per PA molecule at pi = 2 mN m(-1). They are continuously squeezed out upon compression, until upon approaching Alipid = 41 A2, the stoichiometric ratio between bound cations and acidic headgroups is observed. The average inclination angle alpha of the headgroups as well as their water content is constant along the whole isotherm. The intrinsic contribution to the distribution width--i.e. the spread that is due to a distribution of the fragments within the headgroup without the action of capillary waves--increases with compression up to pi approximately 30 mN m(-1) and drops sharply thereafter in a regime of the isotherm where Alipid approaches its limiting value. The same general picture is observed for DMPA on subphases with 10 mM Ca2+, although the lower electron density of that cation limits the precision of the results.
Schalke
M
M
Leipzig University, Institute of Experimental Physics I, Germany.
Lösche
M
M
D000814:Aniline Compounds / Q000737:chemistry; D002413:Cations, Divalent; D008081:Liposomes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009502:Neutrons; D010743:Phospholipids / Q000737:chemistry*; D013329:Structure-Activity Relationship; D014961:X-Ray Diffraction
D000814:Aniline Compounds; D002413:Cations, Divalent; D008081:Liposomes; D010743:Phospholipids; C050795:N,N-dimethyl-4-anisidine