Role of electrostatics in the binding of charged metallophthalocyanines to neutral and charged phospholipid membranes |
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Authors: | A.A. Pashkovskaya G.P. Shaposhnikov Y.N. Antonenko |
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Affiliation: | a Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Moscow 119992, Russia b Ivanovo State University of Chemical Engineering, Ivanovo, Russia |
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Abstract: | Binding of the cationic tetra(tributylammoniomethyl)-substituted hydroxoaluminum phthalocyanine (AlPcN4) to bilayer lipid membranes was studied by fluorescence correlation spectroscopy (FCS) and intramembrane field compensation (IFC) methods. With neutral phosphatidylcholine membranes, AlPcN4 appeared to bind more effectively than the negatively charged tetrasulfonated aluminum phthalocyanine (AlPcS4), which was attributed to the enhancement of the coordination interaction of aluminum with the phosphate moiety of phosphatidylcholine by the electric field created by positively charged groups of AlPcN4. The inhibitory effect of fluoride ions on the membrane binding of both AlPcN4 and AlPcS4 supported the essential role of aluminum-phosphate coordination in the interaction of these phthalocyanines with phospholipids. The presence of negative or positive charges on the surface of lipid membranes modulated the binding of AlPcN4 and AlPcS4 in accord with the character (attraction or repulsion) of the electrostatic interaction, thus showing the significant contribution of the latter to the phthalocyanine adsorption on lipid bilayers. The data on the photodynamic activity of AlPcN4 and AlPcS4 as measured by sensitized photoinactivation of gramicidin channels in bilayer lipid membranes correlated well with the binding data obtained by FCS and IFC techniques. The reduced photodynamic activity of AlPcN4 with neutral membranes violating this correlation was attributed to the concentration quenching of singlet excited states as proved by the data on the AlPcN4 fluorescence quenching. |
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Keywords: | BLM, bilayer lipid membrane gA, gramicidin A DPhPC, diphytanoylphosphatidylcholine DPhPG, diphytanoylphosphatidylglycerol DGEPC, dipalmitoyl-glycero-ethylphosphocholine AlPcS4, aluminum tetrasulfophthalocyanine AlPcN4, hydroxoaluminum (III) tetra(tributylammoniomethyl)phthalocyanine chloride FCS, fluorescence correlation spectroscopy IFC, intramembrane field compensation method Δφb, difference of boundary potentials CTAB, cetyltrimethylammonium bromide |
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