title: Molecular restructuring of water and lipids upon the interaction of DNA with lipid monolayers.
abstract: Understanding the molecular mechanism of DNA/lipid interaction is critical in optimizing the use of lipid cofactors in gene therapy. Here, we address this question by employing label-free vibrational sum frequency (VSF) spectroscopy to study the interaction of DNA with lipid monolayers of the cationic lipids DPTAP(1,2-dipalmitoyl-3-trimethylammonium-propane) and diC14-amidine as well as the zwitterionic lipid DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) in the presence and absence of calcium. Our approach has the advantage both of allowing us to explicitly probe intermolecular interactions and of providing insight into the structure of water and lipids around DNA at the lipid interface. We find, by examination of the OD stretch of interfacial D(2)O, that water structure differs markedly between systems containing DNA adsorbed to cationic and those that contain DNA adsorbed to zwitterionic lipid monolayers (in the presence or absence of Ca(2+)). The spectral response of interfacial water in the cationic system is consistent with a highly structured, undercoordinated, structural 'type' of water. Further, by investigation of CH stretch modes of the diC14-amidine lipid tails, we demonstrate that the adsorption of DNA to this lipid leads to increased ordering of lipid tails.
authors.affiliation: FOM Institute for Atomic and Molecular Physics [AMOLF], 104 Science Park, 1098 XG Amsterdam, The Netherlands. campen@amolf.nl
authors.forename: R Kramer
authors.initials: RK
authors.lastname: Campen
authors.forename: Thuy T M
authors.initials: TT
authors.lastname: Ngo
authors.forename: Maria
authors.initials: M
authors.lastname: Sovago
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Ruysschaert
authors.forename: Mischa
authors.initials: M
authors.lastname: Bonn
mesh_terms: D004247:DNA / Q000737:chemistry / Q000378:metabolism*; D007834:Lasers; D050356:Lipid Metabolism; D008055:Lipids / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D055620:Optical Phenomena; D013057:Spectrum Analysis; D014732:Vibration; D014867:Water / Q000737:chemistry* / Q000378:metabolism*
chemical_list: D008055:Lipids; D014867:Water; D004247:DNA