O. V. Nazarova

Copolymers of 2-Deoxy-2-Methacrylamido-D-Glucose with Aminoacrylates and Allylamine Hydrochloride

New polyvinylsaccharides containing primary or tertiary amino groups were synthesized by radical copolymerization of 2-deoxy-2-methacrylamido-D-glucose (MAG) with 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate (DEAEM), or allylamine hydrochloride. The reactivity ratios of comonomers were determined. The effect of copolymer composition on the conformational properties of macromolecules was detected. For MAG-DEAEM copolymers with DEAEM unit content more than 60 mol-% the increase of degree of ionization causes conformational transition at α = 0.3 to 0.7 from compact polymer coil to loose coil due to the electrostatic repulsion of charged amino groups. The increase of MAG content in copolymers is accompanied by a decrease of their cytotoxicity.

Star‐like Fullerene Containing Poly(Vinylpyrrolydone) Derivatives: Chloroform Solution Properties

Abstract Star‐like fullerene C60 derivatives with different branch number, synthesized by the reaction of fullerene with poly(vinylpyrrolydone) (PVP) macromolecules bearing the terminal amino‐groups, were investigated in solution by the viscometry, dielectric, and electrooptical Kerr‐effect methods in comparison with the ordinary linear PVPs of the same molecular mass. It was shown that covalent linkage of branches to fullerene through amino‐groups leads to appearance of a polar and optically anisotropic nanoparticle (amine‐substituted C60) in the center of the coil of star‐like polymers that radically changes dielectric and electrooptical properties of the initial polymer. Effect of fullerene on the dimension of polymer coil had been detected also.

Model system for multifunctional delivery nanoplatforms based on DNA-Polymer complexes containing silver nanoparticles and fluorescent dye

Creation of multifunctional nanoplatforms is one of the new approaches to complex treatment and diagnosis with the monitoring of the curative process. Inclusion of various components into the drug delivery system may reduce toxicity and enhance or modify the therapeutic effects of medicines. In particular, some properties of metal nanoparticles and nanoclusters provide the ability to create new systems for treatment and diagnosis of diseases, biocatalysis and imaging of objects. For example, the ability of metal nanoparticles to enhance the quantum yield of luminescence can be used in bioimaging and therapy. The aim of the research was to construct and examine a multicomponent system based on DNA-polycation compact structure with the inclusion of silver nanoparticles and luminescent dye as a model system for delivery of genes and drugs with the possibility of modification and enhancement of their action.

Conformational and dynamic characteristics of copolymers of N,N-dimethylaminoethyl methacrylate and 2-deoxy-2-methacrylamido-D-glucose

The conformational and relaxation properties of N,N-dimethylaminoethyl methacrylate and 2-deoxy-2-methacrylamido-D-glucose copolymers in solutions are studied by the methods of molecular hydrodynamics (sedimentation, diffusion, viscometry), polarized luminescence, and flow birefringence. Kuhn-Mark-Houwink equations are obtained, and Kuhn statistical segment lengths at various degrees of protonation of amino groups are estimated. It is found that there is a correlation between the Kuhn statistical segment length and the intramolecular mobility of the copolymers.

Water-soluble polymer derivatives of cholesterol

New cholesterol-containing water-soluble polymers based on N-methacryloyl aminoglucose and N-vinylpyrrolidone are synthesized by free-radical copolymerization and polymer-analogous transformations. Binary and ternary copolymers of various composition containing N-allylamine and N,N,N-trimethylaminoethyl methacrylate methyl sulfate units and cholesterol residues are prepared. Luminescently labeled copolymers of the same composition are obtained. Effects of the nature of polymers and the amount of cholesterol in them on the intramolecular mobility of macromolecules in solution are studied with polarized luminescence. When 2–4 mol % of cholesterol residues are incorporated into the copolymer, the intramolecular mobility of macromolecules decreases, thus indicating formation of intramolecular compact structures via interaction of nonpolar cholesterol groups. In copolymers containing charged groups, these structures are looser than those in neutral copolymers. It is shown that macromolecules of cholesterol-containing polymers of various types can interact with each other. 1 This work was supported by the Russian Foundation for Basic Research (project no. 08-03-00324) and the Council for Grants of the President of the Russian Federation for Support of Leading Institutes of Higher Education (NSh-4391.2008.3).

Relaxation properties and complex formation of copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated acids

With the use of polarized luminescence, relaxation times characterizing the intramolecular mobility of luminescent labeled copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated acids in solutions are determined in both nonionized and ionized states. Elements of the secondary structure typical for poly(methacrylic acid) are formed in copolymers with a high content of methacrylic acid (≥50 mol %) in their nonionized state. This structure is destroyed during ionization. Equilibrium stability constants for complexes of the copolymers with cationic surfactants are determined. Quantitative characteristics of the effects of the surfactant and copolymer structures and the ionic strength of solution on complex formation are estimated.

DNA-polymer complexes for gene therapy

The condensation of DNA induced by vinyl saccharide graft copolymers of N-methacryloy-lamino-D-glucose with N,N-dimethylaminoethyl methacrylate and N-vinylpyrrolidone with N-vinylamine and induced by the linear polycation poly(L-lysine) in solution, as well as the conformational changes of a DNA molecule during its interaction with polycations in solution, is studied by atomic-force microscopy, low-gradient viscometry, dynamic birefringence, spectrophotometry, circular dichroism, and electrophoresis. The differences in the conformational changes of DNA related to the effect of polycations and other agents inducing its condensation are discussed.

Copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated acids

New copolymers of the vinyl saccharide 2-deoxy-2-methacrylamido-D-glucose (M1) with acrylic and methacrylic (M2) acids differing in composition and molecular mass have been synthesized by free-radical copolymerization. The relative activities of the comonomers are determined. It is found that, for acrylic acid, r 1 = 3.03 ± 0.15 and r 2 = 0.5 ± 0.08 and, for methacrylic acid, r 1 = 1.070 ± 0.1 and r 2 = 1.18 ± 0.13. As is evidenced by potentiometric and viscometric measurements, the vinyl saccharide and acid units are capable of interacting, a circumstance that affects the conformational states of macromolecules.

Complexation of N -vinylpyrrolidone– N -allylamine copolymer with perrhenate ion in aqueous solutions

The most common method of metal binding is the introduction of a bifunctional chelating site into natural macromolecules [8]. The direct incorporation of manga nese group metals (technetium 99m, rhenium 188) in the permetallate form into monoclonal antibodies and large proteins has also been reported [9, 10]. This method is accompanied by partial cleavage of the dis ulfide bonds in large proteins, which also leads to loss of their properties.

Conformation properties of poly(N,N-dimethylaminoethyl methacrylate) macromolecules in various solvents

Poly(N,N-dimethylaminoethyl methacrylate) macromolecules in the un-ionized and ionized states were studied by methods of molecular hydrodynamics, optics, and polarized luminescence. The conformation, relaxation, and optical parameters of the macromolecules were determined. The Mark-Kuhn-Houwink equations were obtained for the intrinsic viscosity and diffusion and sedimentation coefficients.