Electrochemical and NMR spectroscopic investigations of the influence of the probe molecule Eu(fod)3 on the permeability of lipid membranes to ions.
Investigating the action of the fluorinated europium complex Eu(fod)3 on lipid membranes we found that the complex facilitates the ion transfer through the membrane. Electric measurements on planar lipid membranes showed that the membrane conductivity increases considerably by insertion of the complex into the membrane. The increase in the conductivity was only obtained if both layers of the membrane were modified with the complex. 1H NMR spectroscopic studies using DOPC liposomes gave information about the location of the modifier complex in the lipid membrane. From chemical shift effects we concluded that the complex resides in the choline head group region of the membrane and also in the membrane interior near the -C =C- lipid double bond, but not in the center of the bilayer. For understanding of the mentioned conductivity effect we assume that the europium complex induces defects of yet unknown structure in the lipid matrix which provide paths for the ion transfer through the membrane. As appropriate measurements revealed, these paths seem to conduct cations predominantly. Investigating the current voltage behavior of the modified lipid membranes in dependence on the ion concentration we obtained different shaped current-voltage curves. Calculation showed that a model with only one energy barrier inside the membrane is unable to describe these curves kinetically. However, by assuming two energy barriers--one barrier in each membrane lipid layer--the observed curve can be described satisfactorily.
Institute of Physical and Theoretical Chemistry, University of Leipzig, Germany. kdschulz@sonne.tachemie.uni-leipzig.de
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D004563:Electrochemistry; D004735:Energy Transfer; D005063:Europium / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry*; D008051:Lipid Bilayers / Q000737:chemistry*; D008081:Liposomes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D010539:Permeability; D005466:Fluorocarbons
D005063:Europium; D007202:Indicators and Reagents; D008051:Lipid Bilayers; D008081:Liposomes; D009942:Organometallic Compounds; C009595:tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6- octanedionato)europium(III); D005466:Fluorocarbons