Interaction of Polylysines with the Surface of Lipid Membranes

Marukovich, Natalia; McMurray, Mark; Finogenova, O.A.; Nesterenko, Alexey M.; Batishchev, Oleg V.; Ermakov, Yury A.

doi:10.1016/b978-0-12-411516-3.00006-1

Cited by 19 publications

(28 citation statements)

References 61 publications

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“…Accord ing to our studies this component may indicate alter ations of membrane structure in this area being directly connected with their lipid composition and hydration of phospholipids polar heads [8]. Previously [9] we report about two phases in boundary potential changes of opposite signs observed in adsorption kinetics of polylysines with various molecular mass. Interpretation of this fact was based on the assumption that these phases correspond to the surface and dipole potentials.…”

Section: Introductionsupporting

confidence: 72%

“…Initial zeta potential values had the same value of about -100 mV for both lipids. Lysine adsorption became detectable at nega tively charged membranes only and was completely reversible [9]. So, this case can be treated by the well known theory of Gouy-Chapman model developed for the electrical double layer (EDL) and combined with binding isotherm for the ions forming the Stern layer [16].…”

Section: Resultsmentioning

confidence: 99%

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Structural factors of lysine and polylysine interaction with lipid membranes

Marukovich

Nesterenko

Ermakov

2015

Biochem. Moscow Suppl. Ser. A

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Electrostatic effects in lysine and polylysine adsorption at lipid membrane surface were studied. Electrokinetic measurements demonstrated that lysine induces similar dose dependent changes of zeta potential in suspensions of liposomes made from cardiolipin (CL) and phosphatidylserine (PS). These changes correlate well with numerical description of diffuse part of electric double layer by Gouy-Chap man-Stern model in assumption that both potassium cation and lysine molecules determine the ionic strength of the media. Good agreement with the electrokinetic data was found with the isotherm constructed for lysine distribution between bilayer and water with low constant (K d = 1.2 × 10 -3 M -1 ) independently of potassium adsorption (K = 1 M -1 ) on lipid molecules or for their competitive adsorption with the same con stants. Lysine adsorption induces total boundary potential changes of planar bilayer lipid membranes (BLM) from the same lipids registered by the method of intramembranous field compensation. In contrast to surface potential of liposomes in electrokinetic experiments the total boundary potential of BLM remains unchanged up to concentration of lysine that is about 1.5 orders of magnitude higher. This fact corresponds to changes in opposite directions of surface and dipole components of boundary potential. They compensate each other to some extent when lysine adsorbs at the surface. This explanation was supported by molecular dynamic sim ulation of bilayers from DOPS in the presence of lysine. According to the MD simulations, the compensation effect can be attributed to lysine effect on hydrogen bonds of water molecules with phosphate groups of lipids but not with carboxylic groups. A similar "compensation effect" was expected and observed with membranes from CL and PS. The amplitude of dipole effect was about 40 mV due to the lysine-lipid interactions and corresponded well to the amplitude of the slow phase in the boundary potential changes induced by polylysine adsorption on planar BLM. This phase can be attributed to polypeptide conformational changes and/or lipid bilayer restructuring phenomena.

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Section: Introductionsupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Structural factors of lysine and polylysine interaction with lipid membranes

Marukovich

Nesterenko

Ermakov

2015

Biochem. Moscow Suppl. Ser. A

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“…Boundary potential shifted to negative direction (figure 6) indicates the dipole effect. This idea is qualitatively supported by comparison data of two electrostatic methods applied to mono-lysine solutions (figure 7) [14]. Surface and boundary potentials measured at different lysine concentration in liposome suspension and by IFC method applied to planar BLM composed from PS or Cl (left panel).…”

Section: Inera Workhopsupporting

confidence: 49%

“…The similar phenomena are responsible for electrostatic effects induced by adsorption of charged organic molecules -lysine and linear chains of polylysine -to the lipid surface [14]. Two principal facts are important to mention in this aspect (figure 6).…”

Section: Inera Workhopmentioning

confidence: 99%

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Boundary potential of lipid bilayers: methods and interpretations

Ermakov

Nesterenko

2017

J. Phys.: Conf. Ser.

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Abstract. The electric field distribution at the boundaries of cell membrane consists of diffuse part of the electrical double layer and the potential drop over polar area inside the membrane itself. The latter is generally attributed to the dipole effect, which depends on the lipid hydration and phase state. This report focuses on the experimental approaches developed to detect the relation between dipole effects and the bilayer structure, and to study their molecular nature. The total boundary potential (BP) of planar bilayer lipid membranes (BLM) can be controlled by Intramembranous Field Compensation (IFC) method developed in our laboratory. When combined with electrokinetic measurements in liposome suspension it allows detecting the changes of the dipole potential due to adsorption of inorganic cations and charged molecules. Multivalent inorganic cations increase the dipole potential up to 100-150 mV and make the membrane rigid. Most of these observations were simulated by Molecular Dynamics (MD) in order to visualize the relationship of electric field with the different structural factors (lipid structure, water orientation, ion adsorption etc.) responsible for its dipole component. Two principal contributors to BP -water and lipid molecules -create the opposite effects. The negative contribution with respect to the bulk is due to lipid itself and the inorganic cation penetration into the polar area of membrane. The positive contribution is caused by water orientation. Particularly, in the case of lysine adsorption, the contribution of water includes the rearrangement of H-bonds with the lipid phosphate group. This fact explains well the unusual kinetic phenomena registered by IFC in the case of polylysine adsorption at the BLM surface.The electric field distribution at the boundaries of phospholipid membrane was intensively studied in many different aspects concerning its biological importance. Naturally, this field is sensitive to the ionic composition of the media and becomes essential for any membrane transport of ionized substances. In other hand, many water-soluble drugs primary interact with the outer surface of cells by electrostatic forces. Model lipid systems -liposomes, planar bilayer lipid membranes (BLM) and monolayers -are commonly used to study the electrostatic phenomena and their relation to structure of membrane interfaces. Our presentation focuses on the experimental approaches developed in our laboratory to differ two components of the boundary potential -the electric field in the water solution that corresponds to the diffuse part of the electrical double layer, and the electric potential drop over polar area at the lipid/water interface [1]. The first one, named here as the surface potential, ϕs, is related to screening of surface charge by ionic media as it well defined by the classic Gouy-Chapman model. To describe the ion equilibrium at the membrane surface the classic model was supplemented with Langmuir-type isotherms. We do not present details of this classic theory, known as Go...

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Composition and properties of complexes between anionic liposomes and diblock copolymers with cationic and poly(ethylene oxide) blocks

et al. 2017

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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.

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Interaction of Polylysines with the Surface of Lipid Membranes

Cited by 19 publications

References 61 publications

Structural factors of lysine and polylysine interaction with lipid membranes

Structural factors of lysine and polylysine interaction with lipid membranes

Boundary potential of lipid bilayers: methods and interpretations

Composition and properties of complexes between anionic liposomes and diblock copolymers with cationic and poly(ethylene oxide) blocks

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