title: Complexation of phospholipids and cholesterol by triterpenic saponins in bulk and in monolayers.
abstract: The interactions between three triterpene saponins: α-hederin, hederacoside C and ammonium glycyrrhizate with model lipids: cholesterol and dipalmitoylphosphatidylcholine (DPPC) are described. The oleanolic acid-type saponins (α-hederin and hederacoside C) were shown to form 1:1 complexes with lipids in bulk, characterized by stability constants in the range (4.0±0.2)·10(3)-(5.0±0.4)·10(4) M(-1). The complexes with cholesterol are generally stronger than those with DPPC. On the contrary, ammonium glycyrrhizate does not form complexes with any of the lipids in solution. The saponin-lipid interactions were also studied in a confined environment of Langmuir monolayers of DPPC and DPPC/cholesterol with the saponins present in the subphase. A combined monolayer relaxation, surface dilational rheology, fluorescence microscopy and neutron reflectivity (NR) study showed that all three saponins are able to penetrate pure DPPC and mixed DPPC/cholesterol monolayers. Overall, the effect of the saponins on the model lipid monolayers does not fully correlate with the lipid-saponin complex formation in the homogeneous solution. The best correlation was found for α-hederin, for which even the preference for cholesterol over DPPC observed in bulk is well reflected in the monolayer studies and the literature data on its membranolytic activity. Similarly, the lack of interaction of ammonium glycyrrhizate with both lipids is evident equally in bulk and monolayer experiments, as well as in its weak membranolytic activity. The combined bulk and monolayer results are discussed in view of the role of confinement in modulating the saponin-lipid interactions and possible mechanism of membranolytic activity of saponins.
authors.affiliation: Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw,Poland. Electronic address: kamil.wojciechowski@ch.pw.edu.pl.
authors.forename: Kamil
authors.initials: K
authors.lastname: Wojciechowski
authors.affiliation: Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw,Poland.
authors.forename: Marta
authors.initials: M
authors.lastname: Orczyk
authors.affiliation: Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Gutberlet
authors.affiliation: Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, WHGA/110, 5232 Villigen - PSI, Switzerland.
authors.forename: Thomas
authors.initials: T
authors.lastname: Geue
mesh_terms: D015060:1,2-Dipalmitoylphosphatidylcholine / Q000737:chemistry*; D002784:Cholesterol / Q000737:chemistry*; D006034:Glycyrrhetinic Acid / Q000737:chemistry*; D008567:Membranes, Artificial; D009828:Oleanolic Acid / Q000031:analogs & derivatives* / Q000737:chemistry; D012503:Saponins / Q000737:chemistry*
chemical_list: D008567:Membranes, Artificial; D012503:Saponins; C010177:beta-hederin; C482302:hederacoside C; D015060:1,2-Dipalmitoylphosphatidylcholine; D009828:Oleanolic Acid; D002784:Cholesterol; D006034:Glycyrrhetinic Acid
keywords: Ammonium glycyrrhizate; Biosurfactant; Dilatational surface rheology; Hederacoside C; Saponin; Surface pressure; α-Hederin