Ca2+-mediated interaction between dextran sulfate and dimyristoyl-sn-glycero-3-phosphocholine surfaces studied by 2H nuclear magnetic resonance

Abstract

The binding of dextran sulfates (DSs) with varying chain lengths to phosphatidylcholine multilamellar vesicles was investigated as a function of polyelectrolyte, NaCl, and Ca2+ concentration. Attractive forces between negatively charged polyelectrolytes and zwitterionic phospholipids arise from the assembly of calcium bridges. The formation of calcium bridges between the sulfate groups on the dextran sulfate and the phosphate group of the lipid results in increased calcium binding in mixtures of DS and 1, 2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). At high NaCl concentration, the plateau adsorption of DS 500 is increased. The strength of dextran sulfate binding to DMPC is reflected in the changes of the 2H NMR quadrupolar splittings of the headgroup methylenes. Association forces increase with the number of calcium bridges formed. Low-molecular-weight DS does not bind to DMPC surfaces whereas longer-chain DSs strongly influence headgroup structure as a result of strong association. DS binding increases with increasing concentration; however, further association of the polyelectrolyte can be promoted only if negative charges are sufficiently screened. DS binding to lipid bilayers is a complicated balance of calcium bridging and charge screening. From our data we postulate that the structure of the adsorbed layer resembles a lattice of DS strands sandwiched between the bilayer lamellae.