High-strength composite hydrogels “cellulose–polyacrylamide” were synthesized by free-radical polymerization of acrylamide conducted inside the previously formed physical network of regenerated plant cellulose. Partial hydrolysis of the amide groups of these hydrogels yielded their ionic forms with a degree of hydrolysis of 0.1 and 0.25. The cylindrical hydrogel samples of three compositions were implanted in the preformed osteochondral defects of the rabbit’s femoral knee joints. No signs of migration or disintegration of the tested implants were revealed in the course of in vivo tests as long as 90 and 120 days after the implantation. The mechanical behavior of hydrogel samples-implants before implantation and after their removal from the joints of laboratory animals was studied in detail. The morphology and chemical composition of the removed implants were studied by SEM combined with the EDX method. The results showed that the mechanical characteristics of hydrogel implants remained practically unchanged after in vivo tests. The removed implants, as well as the initial hydrogels, endured cyclic compression loading at the amplitude up to 50
N-Methyl-N-vinylacetamide–N-methyl-N-vinylamine copolymer of 85 : 15 mol
Radical copolymerization has been used to synthesize copolymers of coumarin and N-vinylpyrrolidone with a wide range of molecular mass and composition. Molecular and hydrodynamic characteristics of the prepared copolymers and their dependence on the conditions of their synthesis in bulk and in ethanolic solution have been investigated by means of dynamic and static light scattering.
New copolymers of vinylphosphonic and p-methacrylamidobenzoic acids of varying compositions were synthesized via free radical copolymerization. The structure of the obtained polymers was confirmed by NMR and FTIR spectroscopy. As the proportion of vinylphosphonic acid in the initial reaction mixture increased, the yield of the copolymer and its molecular mass both decreased. The synthesized copolymers were found to form stable soluble luminescent complexes in dilute aqueous solutions, with a concentration range of 0.002 to 0.02 mg/ml. An increase in the concentration of vinylphosphonic acid moieties in copolymers was accompanied by a noticeable decrease in the luminescence intensity. The new copolymers' ability to bind efficiently with lanthanide ions renders them a promising material for the design of polymeric contrast agents, preparations for radioimmunotherapy and photodynamic therapy.
Water-soluble copolymers of p-methacrylamidobenzoic acid (MABA) with neutral comonomers ( N -vinylpyrrolidone (VP), N -methyl- N -vinylacetamide (MVAA), N -methacryloyl glucosamine (MAG)) and anionic comononer sodium styrene sulfonate (NaSS) were synthesized by radical copolymerization. The interactions between the prepared copolymers and Tb 3+ ions in aqueous solutions were studied; the significant influence of chemical structure of a comonomer on luminescence intensity of Tb 3+ complexes with the copolymers was revealed. The luminescence intensity of Tb 3+ complexes with the copolymers containing N -vinylamide units (VP, MVAA) is three times more intense than that observed for the complexes between Tb 3+ and MAG-containing copolymers. In the case of NaSS-containing copolymers, the luminescence intensity is controlled by the values of binding constants between Tb 3+ and MABA and the content of MABA units in a copolymer. The studied copolymers and their complexes with Tb 3+ have low cytotoxicity and a pronounced antiviral activity against human respiratory syncytial virus.
Исследована радикальная сополимеризация в воде стиролсульфоната натрия с винилсахаридом 2-деокси-2-метакриламидо-D-глюкозой. Определены константы относительной активности, которые составили для стиролсульфоната натрия r 1 = 1.58 ± 0.05, для 2-деокси-2-метакриламидо-D-глюкозы r 2 = 0.18 ± 0.01. Синтезированы водорастворимые сополимеры разного состава с варьируемой молекулярной массой, обладающие высокой противовирусной активностью.
Planar chromatography is used to develop methods for the analytical control of processes of the synthesis of biomedical polymers and their complexes with biologically active substances, which made it possible to create a number of long-acting antiviral, antitumor, antimicrobial, and antiseptic preparations.
The radical copolymerization of sodium styrene sulfonate with vinyl saccharide 2-deoxy-2-methacrylamido-D-glucose in water is studied. For sodium styrene sulfonate and 2-deoxy-2-methacrylamido-D-glucose the reactivity ratios are found to be r1 = 1.58 ± 0.05 and r2 = 0.18 ± 0.01, respectively. Water-soluble copolymers of varying compositions and molecular weights demonstrating high antiviral activity are synthesized.
Selenium (Se 0 ) nanoparticles are stabilized with water-soluble polymers containing ionogenic groups of the different signs, namely, poly( N,N,N -trimethylammonium)ethyl methacrylate iodide (polycation) and sodium polystyrenesulfonate (polyanion). A comprehensive comparative study of the resulting selenium-containing nanodispersions by the UV–visible spectroscopy, atomic force and transmission electron microscopy, and dynamic and electrophoretic light-scattering methods is conducted. The effect of the charge sign of the polymer stabilizer on the structural–morphological, dimensional, electrochemical, and spectral characteristics of selenium-containing nanodispersions is shown.
Organic-inorganic composite systems for biomedical applications with zero-valent copper nanoparticles were synthesized. Hydrazine hydrate was used as a reducing agent; ionogenic water-soluble copolymers (polyelectrolytes) were used as hydrophilic polymeric stabilizers. Small-angle X-ray and neutron scattering methods were used to evaluate the size distribution of zero-valent copper nanoparticles stabilized by the copolymer. Transmission electron microscopy and atomic force microscopy were used to visualize this distribution. It was shown that using a copolymer of 2-deoxy-2-methacrylamido-D-glucose with 2-dimethylaminoethyl methacrylate or acrylic acid with N,N,N,N-trimethyl [methacryloyloxyethyl] ammonium methyl sulfate facilitated the preparation of zero-valent copper nanoparticles with the sizes of less than 5 nm. The maximum size of nanoparticles in their distribution was less than 60 nm. This effect is due to the relatively good shielding of nanoparticles in solution.
Radical copolymerization of coumarin with N-vinylamides (N‑vinylpyrrolidone, N-methyl-N-vinylacetamide, N-vinylformamide) has been used to prepare copolymers of various composition with variable molecular weights. Subsequent reactions in their polymer chains affords water-soluble copolymers of salts of hydroxycinnamic acid and its hydrazides. The synthesized copolymers of hydroxycinnamic acid salts and hydrazides with N-vinylamides have low cytotoxicity and demonstrate the pronounced antiviral activity against human respiratory syncytial virus (strain A2).
Water-soluble random copolymer of N -vinylformamide with sodium 4-styrenesulfonate is synthesized by free radical copolymerization. Copolymer fractions are studied by the methods of molecular hydrodynamics: viscometry, translational diffusion, and sedimentation velocity in dilute aqueous solutions. Molecular characteristics and scaling relations are obtained. Considerable differences in the conformational behavior of molecules of the copolymer and N -vinylformamide and sodium 4-styrenesulfonate homopolymers are discussed.
A series of water-soluble comb-like copolymers of N -methyl- N -vinylacetamide and N -methyl- N -vinylamine (MVAA‒ со ‒MVA) bearing hydrophobic dodecyl side groups С 12 Н 25 has been investigated by means of molecular hydrodynamics (viscometry, translational diffusion, and analytical ultracentrifugation) in dilute solutions in 0.1 M NaCl, under conditions of suppression of the polyelectrolyte effects. The issues of homology of these amphiphilic copolymers have been considered. The viscometry data plotted as lnη r as function of c [η] have allowed to distinguish between macromolecules of the copolymers according to their hydrophobicity. Positive values of the second derivative B 2 determined from the initial parts of these curves have served as a measure of hydrophobicity of the amphiphilic copolymers. The noticeable differences in the B 2 values for different copolymers have shown that they do not form true homologous series. For the quasi-homologous series of the MVAA– со –MVAC 12 H 25 ·HI copolymers with close values of B 2 , the Kuhn–Mark–Houwink–Sakurada relationships have been obtained and the equilibrium rigidity of the chains has been assessed using the modified Gray–Bloomfield–Hearst equation.
A comparative study of newly synthesized copper- and selenium-containing nanosystems based on a wide range of water-soluble polymer stabilizers is carried out using atomic force and transmission electron microscopy. Bovine serum albumin, poly-4-acryloylmorpholine, water-soluble statistical copolymers of 2-deoxy-2-methacrylamido-D-glucose or 4-acryloylmorpholine with 2-dimethylaminoethyl methacrylate) are used as polymer stabilizers. The effect of the stabilizer and nanoparticle nature on the structural and morphological characteristics of the nanostructures/nanoparticles and the mechanism of their formation is revealed using copper- and selenium-containing nanosystems as an example. In an aqueous solution of the studied nanosystems, mainly spherical nanostructures/nanoparticles are formed, the size of which is primarily determined by the nature of the nanoparticles: copper-containing nanostructures/nanoparticles have a smaller size than selenium-containing ones.
A comparative study of the spectral and structural-morphological characteristics of a metal (copper, silver) and a metalloid (selenium) containing nanodispersions based on biocompatible water-soluble stabilizers (bovine serum albumin, random copolymers of 2-deoxy-2-methacrylamide-D-glucose or 4-acryloyl-morpholine with 2-dimethylaminoethyl-methacrylate) is carried out by means of the UV-spectroscopy as well as the atomic-force and transmission electron microscopy. Effect of the nature of the nanoparticle as well as polymeric stabilizer on the spectral and structural-morphological characteristics and mechanism of formation of the nanostructures/nanoparticles is demonstrated. It is established that structures with different organizations of the organic phase around nanoparticles are formed in the studied nanodispersions. It is shown that for the studied polymer carriers, metal-containing nanostructures/nanoparticles have smaller dimensions than metalloid-containing systems.
Water-soluble complexes of N-vinylpyrrolidone/N-vinylamine copolymers with lactones of D-glucuronic acid were obtained and characterized by chromatographic, spectral, and hydrodynamic methods. The complexes efficiently inhibited the enzyme β-glucuronidase that causes the appearance of bladder tumors. The products demonstrated prolonged action and were stable during storage.
Water-soluble copolymers of sodium styrene sulfonate and 4-methacrylamidosalicylic acid of 93.7 mol % composition have been synthesized, and their interaction with terbium and gadolinium ions has been investigated to fabricate luminescent probes promising for their visualization in biomedical research. It has been shown that, in aqueous solutions in the copolymer concentration range 0.15–1.7 mg mL–1 and at the ratio [Tb3+]/[COO–] = 1, water-soluble luminescent metal polymer complexes with a luminescence lifetime of 823 µs are formed. When Tb3+ ions are partially replaced in the complex by Gd3+ ions, bimetallic complexes with intense luminescence are formed.
New copolymers of vinylphosphonic acid (VPA) with 2-deoxy-2-methacrylamido-D-glucose, 4-acryloylmorpholine (4-AM), and acrylamide have been synthesized, and their antiviral activity against influenza virus has been studied in in vitro and in vivo experiments. Optimal antiviral characteristics and low cytotoxicity were exhibited by the copolymer of VPA with 4-AM, composition 56 : 44 mol %, molecular weight 33 000. The polymer exhibited virus-inhibiting properties with an IC50 = 1 µg/mL and a selectivity index of 302. Prophylactic intranasal administration of the polymer in a murine model of influenza pneumonia completely prevented the virus-induced death of animals, whereas the level of mortality in the placebo group was 90%. The results of this study indicate a high antiviral potential of polymeric compounds based on VPA.
Poly(methacryloylamino galactose) has been synthesized by a modified method, which enables one to increase the yield of the polymer substance. Samples and fractions have been studied by molecular hydrodynamics methods. Molecular masses, scaling relations, and data on equilibrium rigidity of macromolecules have been estimated from the hydrodynamic characteristics.