title: Ionic strength and composition govern the elasticity of biological membranes. A study of model DMPC bilayers by force- and transmission IR spectroscopy.
abstract: Infrared (IR) spectroscopy was used to quantify the ion mixture effect of seawater (SW), particularly the contribution of Mg(2+) and Ca(2+) as dominant divalent cations, on the thermotropic phase behaviour of 1,2-dimyristoyl-sn-glycero-3-posphocholine (DMPC) bilayers. The changed character of the main transition at 24 °C from sharp to gradual in films and the 1 °C shift of the main transition temperature in dispersions reflect the interactions of lipid headgroups with the ions in SW. Force spectroscopy was used to quantify the nanomechanical hardness of a DMPC supported lipid bilayer (SLB). Considering the electrostatic and ion binding equilibrium contributions while systematically probing the SLB in various salt solutions, we showed that ionic strength had a decisive influence on its nanomechanics. The mechanical hardness of DMPC SLBs in the liquid crystalline phase linearly increases with the increasing fraction of all ion-bound lipids in a series of monovalent salt solutions. It also linearly increases in the gel phase but almost three times faster (the corresponding slopes are 4.9 nN/100 mM and 13.32 nN/100 mM, respectively). We also showed that in the presence of divalent ions (Ca(2+) and Mg(2+)) the bilayer mechanical hardness was unproportionally increased, and that was accompanied with the decrease of Na(+) ion and increase of Cl(-) ion bound lipids. The underlying process is a cooperative and competitive ion binding in both the gel and the liquid crystalline phase. Bilayer hardness thus turned out to be very sensitive to ionic strength as well as to ionic composition of the surrounding medium. In particular, the indicated correlation helped us to emphasize the colligative properties of SW as a naturally occurring complex ion mixture.
authors.affiliation: Division for Marine and Environmental Research, Ruđer Bošković Institute, POB 180, Zagreb, Croatia. Electronic address: ssegota@irb.hr.
authors.forename: Suzana
authors.initials: S
authors.lastname: Šegota
authors.affiliation: Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, POB 180, Zagreb, Croatia.
authors.forename: Danijela
authors.initials: D
authors.lastname: Vojta
authors.affiliation: Division for Marine and Environmental Research, Ruđer Bošković Institute, POB 180, Zagreb, Croatia.
authors.forename: Galja
authors.initials: G
authors.lastname: Pletikapić
authors.affiliation: Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, POB 180, Zagreb, Croatia.
authors.forename: Goran
authors.initials: G
authors.lastname: Baranović
mesh_terms: D002118:Calcium / Q000737:chemistry*; D002413:Cations, Divalent / Q000737:chemistry; D004134:Dimyristoylphosphatidylcholine / Q000737:chemistry*; D004548:Elasticity; D008051:Lipid Bilayers / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D008560:Membrane Fluidity; D018625:Microscopy, Atomic Force; D009994:Osmolar Concentration; D044367:Phase Transition; D012623:Seawater / Q000737:chemistry; D013055:Spectrophotometry, Infrared
chemical_list: D002413:Cations, Divalent; D008051:Lipid Bilayers; D008274:Magnesium; D002118:Calcium; D004134:Dimyristoylphosphatidylcholine
keywords: AFM; Force spectroscopy; IR spectroscopy; Ion binding; Ion mixture; Lipid bilayers; Nanomechanics; Seawater