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.
In this study, a series of new chelating copolymers containing 20% azomethine groups, poly(N-vinylpyrrolidone-co-vinylsalicylideneimine) (poly[VP-co-VSalI]), poly(N-vinylpyrrolidone-co-vinylpicolinideneimine) (poly[VP-co-VPicI]), poly(N-vinylpyrrolidone-co-vinylpyridoxylideneimine) (poly[VP-co-VPyrI]) with M = 63000 Da and their vanadium(IV) complexes - poly(VP-co-VSalI)-VO, poly(VP-co-VPicI)-VO, poly(VP-co-VPyrI)-VO, were designed and synthesized. These are intended for the delivery and pH-dependent release of vanadium species in the intestine environment. The chelating polymers were obtained from poly(N-vinylpyrrolidone-co-N-vinylamine) (poly[VP-VAm]) by polymer-analogous transformations with the corresponding aldehydes. The vanadium content, determined by ICP-AES and spectrophotometric methods, was 5.36%, 4.99%, and 9.1% of the dry mass for poly(VP-co-VSalI)-VO, poly(VP-co-VPyrI)-VO, and poly(VP-co-VPicI)-VO, respectively. XPS data confirmed that only vanadium(IV) is presented in the complexes. All complexes demonstrated a pH-dependent release of low molecular weight vanadium species, making them promising candidates for the development of vanadium-containing systems for oral administration. These systems protect the main vanadium content in the stomach but can release biologically active ions in the intestine.
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.
Methods were developed for the synthesis of water-soluble metal–polymer nanocomposites of vanadium citrate complex with vinylphosphonic acid copolymers with acrylamide or 2-dimethylaminoethyl methacrylate. It was shown that the vanadium complex binds to the copolymer in an acid medium, while in a neutral medium, the nanocomposite dissociates to release the free complex. With a molar excess of the vanadium complex, intramolecular cross-linkings occurs, which leads to compaction of macromolecules.
It was revealed that the neutral hydrophilic comonomer nature affects the reduction of silver ions by copolymers of 2-dimethylaminoethyl methacrylate and the formation of Ag-0 nanocomposites based on them. The kinetic of silver reduction was investigated, and rate constants of pseudo first-order reactions were determined. It was shown that the rate constants increase in series 4-acryloyl morpholine <N-methyl-N-vinylacetamide < 2-deoxy-2-methacrylamido-d-glucose. The optimal molar ratio [polymer unit] : [Ag+] and polymer concentration were established. It was established that spherical silver nanoparticles have the mean radius of 7-9 nm. A decrease in the pH of aqueous dispersions of nanocomposites leads to narrowing of the surface plasmon resonance band and to shifting to shorter wavelengths. In this case, the hydrodynamic radius increases. It is assumed that the observed effect is caused both by a change in the distance between nanoparticles and by their mutual arrangement in the associate.
We use atomic-force microscopy, transmission electron microscopy, ultraviolet (UV)/visible spectroscopy, and dynamic light scattering to perform a comparative study of new hybrid bioactive nanosystems based on nanoparticles of various natures: zero-valent copper (Cu-0), zero-valent selenium (Se-0), and zero-valent silver (Ag-0) stabilized with a water-soluble homopolymer poly-4-acryloylmorpholine (PAM). We demonstrate the possibility of regulating the structural and morphological parameters and the dimensional and spectral characteristics of bioactive nanosystems by varying the nature of nanoparticles. The reduction of ions of biogenic elements in water in the presence of poly-4-acryloylmorpholine, due to sufficiently good screening, yields spherical nanostructures with a diameter not exceeding 180 nm (PAM/Se-0). The most probable sizes of nanoparticles do not exceed 12 nm.
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.
For grafted copolyimides with variable length and grafting density of polymethylmethacrylate side chains, the molecular masses were determined using three modes of SEC analysis, which differ in the detectors set. The results were compared with the values obtained (i) using H-1 NMR spectra, (ii) those calculated by summing the molecular masses of homopolymer linear blocks that make up the copolymer, as well as (iii) with the absolute values of molecular masses determined by sedimentation-diffusion analysis. It is shown that for branched grafted copolyimides the use of only a refractometric detector or its combination with a viscometric detector in the SEC analysis did not allow for obtaining reliable molecular masses. On the contrary, the combination of refractometric and viscometric detectors with a light scattering detector provided for the determination of the molecular masses close to the respective absolute values. It is also shown that for linear block copolymers, unlike branched copolymers, the molecular masses close to the absolute values can be obtained using any of the three modes of SEC analysis. For the first time, a concept of the critical molecular mass of the side chains of grafted copolyimides is introduced as a quantitative criterion that takes into account the total length and also the density of grafting of the side chains.
Water-soluble terpolymers of 2-deoxy-N-methacryloylamidoglucose, methacryloylacetone, and methacrylic acid have been synthesized by the of radical copolymerization method. It has been shown that they form luminescent complexes with terbium ions in aqueous solutions. The luminescence intensity depends on the ratio of the components and remains constant in the presence of CaCl2 and NaCl. These terbium-binding terpolymers can be the basis for the creation of both luminescent probes and radioactive pharmaceuticals where a short-lived γ-emitter 161Tb is used for cancer ratiotherapy.
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 degrees is accompanied by decrease in mobility of polymer chains due to adsorption of macromolecules on the surface of Ag degrees nanoparticles and formation of a stabilizing shell.
Controlled atom-transfer radical polymerization and ring-opening polymerization methods are used for the first time to synthesize symmetric pentablock copolymers with a central block, which is a polymer brush with the polyimide backbone and poly(methyl methacrylate) side chains, and outer linear block copolymers of poly(ε-caprolactone) with poly(methyl methacrylate). The chemical structure of the polymers is studied by 1H NMR spectroscopy. The molecular weight characteristics of the synthesized pentablock copolymers are determined by multidetector size exclusion liquid chromatography. It is shown that these characteristics are in good agreement with the absolute molecular weights obtained by sedimentation-diffusion analysis.
Chromatographic methods of analysis of the products of the radical copolymerization of random copolymers of N-vinyl-2-pyrrolidone and 6-crotonoyl aminohexanoic acid are developed and molecular characteristics of the copolymers are determined. A method is proposed for the purification of the obtained carboxylated water-soluble copolymers of monomeric hydrophobic acid impurities by low-pressure gel-permeation chromatography.
Синтезированы сополимеры 2-диметиламиноэтилметакрилата и 2-диэтиламиноэтилметакрилата с 2-деокси-2-метакриламидо-D-глюкозой и N-винил-N-метилацетамидом, содержащие 20 – 80 мол. % звеньев 2-диалкиламиноэтилметакрилата с молекулярной массой (40 – 80) · 103. Получены нанокомпозиции серебра на основе указанных сополимеров. Найдено, что синтезированные серебросодержащие нанокомпозиты обладают антимикробной и противовирусной активностью.