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Composition and properties of complexes between anionic liposomes and diblock copolymers with cationic and poly(ethylene oxide) blocks
Authors:Oleg V Ivashkov  Andrey V Sybachin  Anna A Efimova  Viktor N Orlov  Dmitry V Pergushov  Holger Schmalz  Alexander A Yaroslavov
Affiliation:1. Department of Chemistry, MV Lomonosov Moscow State University, Moscow, Russia;2. Research Institute of Physico‐Chemical Biology, MV Lomonosov Moscow State University, Moscow, Russia;3. Makromolekulare Chemie II, Universit?t Bayreuth, Bayreuth, Germany
Abstract:A series of cationic diblock copolymers were synthesized via sequential anionic polymerization of 2‐vinylpyridine and ethylene oxide and further quaternization of the resulting diblock copolymers with dimethyl sulfate. Diblock copolymers with a degree of polymerization (DP) of the cationic block equal to 40 and DP of the poly(ethylene oxide) (PEO) block equal to 45, 210 and 450, as well as a cationic homopolymer with DP = 40 (control), were adsorbed on the surface of anionic liposomes of 40–60 nm in diameter. The liposomes were constructed with egg lecithin admixed with 0.1 mole fraction of a doubly anionic lipid, cardiolipin. The liposome–polymer complexes were characterized using electrophoretic mobility measurements, dynamic light scattering, conductivity, fluorescence and UV spectroscopy, and differential scanning calorimetry. Adsorption of the polymers causes the liposomes to aggregate; the only exception is the diblock copolymer with DP of the PEO block of 450, which shows an aggregation‐preventing effect. In all cases, the integrity of liposomes is retained upon their complexation with polymers. The diblock copolymer with a short PEO block induces clustering of anionic lipid in the outer leaflet of the membrane; this effect becomes less pronounced with increasing DP of the PEO block. The differences in behaviour of the diblock copolymers are explained in terms of copolymer cluster formation via hydrogen bonding between neighbouring PEO blocks. These observations are important for interpretation of biological effects produced by cationic polymers and selection of cationic polymers for biomedical applications. © 2017 Society of Chemical Industry
Keywords:liposomes  block copolymers  flip‐flop  lateral lipid segregation  complexes
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