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Hybrid nanosystems based on nanoparticles of zero-valent copper (Cu0), zero-valent silver (Ag0), and zero-valent selenium (Se0) are synthesized. The nanoparticles are stabilized by a water-soluble random copolymer of 2-deoxy-2-methacrylamido-D-glucose with 2-dimethylaminoethyl methacrylate. A comparative study is made using UV–Vis spectroscopy and atomic force microscopy. The effect the nature of the nanoparticles has on the morphological and spectral characteristics of the formed nanosystems is shown. It is found that due to good screening, the reduction of nutrient ions in water in the presence of the indicated copolymer allows spherical nanostructures with diameters of 80 to 250 nm to be obtained.

Copolymers of 2-dimethyl- and 2-diethylaminoethyl methacrylate with 2-deoxy-2-methacryalamido-D-glucose and N-vinyl-N-methylacetamide with 20 – 80 mol% of 2-dialkylaminoethyl methacrylate units and molecular mass (40 – 80)·103 Da were synthesized. Silver nanocomposites based on these copolymers were obtained. The synthesized Ag-containing nanocomposites were found to exhibit antibacterial and antiviral activity.

Luminescent-labeled copolymers of 4-acryloylmorpholine and 2-dialkylaminoethyl methacrylates (2-dimethylaminoethyl methacrylate and 2-diethylaminoethyl methacrylate) of varied compositions and molecular masses were synthesized. Polarized luminescence method was used to study relaxation properties of the polymers in diluted aqueous solutions. The influence of copolymer composition, temperature, pH, ionic strength of solutions on structural and dynamic characteristics of the copolymers in solution was established. The obtained copolymers were used to synthesize silver nanoparticles with an average radius of 7–8 nm. Interaction between the luminescent-labeled copolymers and Ag+ ions was studied. It was demonstrated that reduction of Ag+ by the copolymers and formation of Ag° is accompanied by decrease in mobility of polymer chains due to adsorption of macromolecules on the surface of Ag° nanoparticles and formation of a stabilizing shell.

Copolymers of 4-acryloylmorpholine with 2-dimethyl- and 2-diethylaminoethyl methacrylates of variable composition and molecular mass were prepared by free-radical copolymerization. The reactivity ratios of the comonomers were determined for the first time. The copolymers synthesized are capable to reduce Ag+ ions without using additional agents to form stable nanodispersions of zerovalent silver with spherical nanoparticles of 8–10 nm size.

An original method for the synthesis of copper-containing nanosystems for biomedical applications using hydrazine hydrate as a reducing agent was developed. The process involves intermediate formation of the [Cu(NH3)4]2+ complex ion, which ensures the formation of Cu0 nanoparticles without oxide impurity. The 2-deoxy-2-methacrylamido-D-glucose copolymer with 2-(dimethylamino)ethyl methacrylate or bovine serum albumin was used as a macromolecular hydrophilic stabilizer. The spectral and structure-morphological characteristics of the nanosystems were studied. This stabilization resulted in an almost unimodal distribution of zerovalent copper nanoparticles in aqueous solutions due to their rather good shielding by macromolecules.

Water-soluble random copolymers of N,N-(dimethylamino)ethyl methacrylate or N,N-(diethylamino)ethyl methacrylate with vinylsaccharides (N-methacryloyl aminoglucose, 3-O-methacryloyl glucose, 1-O-methacryloyl sorbose) were synthesized. The copolymers differed in composition, structure of the carbohydrate fragment, and type of carbohydrate–main-polymer-chain bonds. The immunomodulating activity and antitumor properties of the synthesized copolymers were established. Copolymers containing sorbose residues possessed the most pronounced immunodepressant properties.

A method based on the ability of transition-metal ions to quench the fluorescence of labeled polymer molecules is developed to determine the equilibrium stability constants of macromolecular complexes of Ag+, Cu2+, and Ni2+ with the copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated carboxylic acids (methacrylic or acrylic) in aqueous and aqueous–saline media. The stability constants of the complexes strongly depend on the type of transition-metal, the copolymer composition, and the ionic strength of solution, but weakly depend on the type of introduced low-molecular-mass electrolyte and the chemical structure of the carboxyl-containing units.

Polarized luminescence and flow birefringence methods were used in the studies of structural and dynamic characteristics of 2-(diethylamino)ethyl methacrylate and 2-deoxy-2-methacrylamido- d -glucose copolymers with varied content of cationic monomer units while changing temperature, pH and ionic strength of solutions. It was demonstrated that with increasing temperature, nanosecond relaxation times τ IMM (which characterize intramolecular mobility of fragments of copolymer chain in solution) increase over a relatively narrow temperature range. Increase in relaxation times indicates strengthening intramolecular interactions and the formation of intramolecular hydrophobic domains. From the obtained flow birefringence data, it follows that in the vicinity of the lower critical solution temperature (LCST) we have molecular dispersed diluted copolymer solutions. The influence of temperature and ionic strength of solutions on the transition temperature were also studied. The observed changes in intramolecular interactions are accompanied by insignificant changes in root-mean-square dimensions of macromolecular coils; however, coils retain their asymmetry.

Ag0 nanoparticles are prepared via the reduction of silver ions by copolymers of N,N-dimethylaminoethyl methacrylate and 2-deoxy-2-methacrylamido-D-glucose of various compositions in water at room temperature. It is found that an insignificant part of the macromolecules is involved in the reduction of Ag+ to Ag0 and stabilization of the resulting nanoparticles. As shown by flow-birefringence studies, the optical properties of solutions of stabilized silver nanoparticles change abruptly relative to the optical properties of the solutions of the initial copolymers.

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.

Hydrodynamic properties of the homologous series of the homopolymer 2-deoxy-2-methacryla-mido-D-glucose and the copolymers of 2-deoxy-2-methacrylamido-D-glucose with unsaturated acids in 0.2 M NaCl are studied via static and dynamic light scattering, viscometry, refractometry, and translational diffusion. The copolymers synthesized via the free-radical copolymerization of 2-deoxy-2-methacrylamido-D-glucose with acrylic acid or methacrylic acid contain ∼20 mol % acid units. At this amount of acid units, the equilibrium rigidity of copolymer chains corresponds to that of homopolymer chains. The copolymers are distinguished by the hydrodynamic characteristics of molecules. The copolymer with methacrylic acid is similar to the homopolymer, whereas the copolymer with acrylic acid features substantially different parameters of relationships relating the hydrodynamic characteristics of homologs to their molecular masses.

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.

On the basis of hydrophilic copolymers of N-vinylamides—N-vinylpyrrolidone and N-methyl-N-vinylacetamide—that contain carboxylic or activated ester groups, new polymeric β-cyclodextrin derivatives are synthesized via polymer-analogous transformations. Their solubility in water depends on the content of β-cyclodextrin and the types of hydrophilic and reactive comonomers.

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).

The formation of DNA complexes with polycations of different structure (homopolymers: N,N-dimethylaminoethyl and methylsulfate salt of N,N,N-trimethylaminoethylmethacrylate, along with a copolymer of N,N-dimethylaminoethyl methacrylate with N-methacryloylaminoglucose) in water-salt solutions, was studied by the method of static and dynamic light scattering. It was shown that, depending on the value of ϕ = [mol polycation]/[mole of DNA], complexes of different structure are formed: in field ϕ 6 in the presence of a large excess of polycations, loose structures are formed. The extreme dependence of the molecular weight of formed supramolecular structures on the values of ϕ was established.

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.

Method for synthesis of graft-copolymers of a vinyl saccharide, 2-deoxy-2-methylacrylamido-D-glucose, and N,N-dimethylaminoethyl methacrylate was developed. Statistical copolymers with a controllable hydrophobic-hydrophilic balance were synthesized by alkylation of a statistical copolymer with various alkyl iodides.

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.

In this study the methods of synthesis of hydrophilic aldehyde-bearing polymers and copolymers based on 2-deoxy-2-methacrylamido-D-glucose have been developed. Polymers with controllable aldehyde group content were synthesized via free-radical polymerization and subsequent polymeranalogous modification. The water-soluble polymers obtained were investigated in view of their capacity to be adsorbed on two commercial mineral supports used in bone tissue engineering. Besides, cytotoxicity of synthesized polymers was tested. 2008 Wiley Periodicals, Inc. J Appl Polym Sci 108: 2386-2397, 2008

Copolymers of N-methacryloylaminodeoxyglucose with acrylic and methacrylic acids were prepared by radical copolymerization. The reactions of these copolymers with p-nitrophenol, N-hydroxysuccinimide, and N-hydroxyphthalimide in the presence of N,N'-dicyclohexylcarbodiimide were studied.

The copolymerizations of N-vinylpyrrolidone with N-hydroxyphthalimide and N-hydroxysuccinimide esters of acrylic, methacrylic and crotonic acids have been investigated. The reactivity ratios were determined, and kinetic investigations of the copolymerizations were carried out. It was shown that, by varying the acid component of the monomeric ester, it is possible to obtain reactive copolymers greatly differing in structure.

The dynamic light scattering method was used to study the process of complex formation of cholesterol-containing polymers of vinylsaccharide 2-deoxy-2-methacrylamido-D-glucose (double and ternary copolymers) in water solutions in the different polymer mole ratio. Compared to the initial ternary cholesterol-containing copolymer the conditions of compaction of the complex formed are found.