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.
Functional copolymers of 1-vinyl-1,2,4-triazole (VT) and N-vinylcarbazole (VK) were synthesized using a free-radical polymerization. The content of hole-conducting N-vinylcarbazole units was found to be 9, 16, and 37 mol. %. Fourier transform infrared spectroscopy, 1H-NMR spectroscopy, gel permeation chromatography, thermogravimetric analysis, and differential scanning were applied to characterize the poly(VT–co–VK). Based on a polymer ligand, metal−polymer complexes with Tb³⁺ ions were obtained in a polymethyl methacrylate matrix, and their luminescent properties were studied. The maximum photoluminescence of the complex can be achieved when using 16 mol. % of N-vinylcarbazole units. This is because two photoprocesses (excimer formation and excitation energy transfer) occur simultaneously and competitively.
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.
It has been shown that macromolecules of poly(methacryloyloxyethyl phosphorylcholine) can form hydrogen bonded interpolymer complexes with homo- and copolymers of carboxylic acids and with poly(vinylphosphonic) acid in aqueous solutions. Polarized luminescence and IR spectroscopy were applied in the investigation. Nanosecond relaxation times characterizing the mobility of the chain fragments for the initial luminescent labeled polymers were determined and their changes by a factor of 2–50 were established during the formation of an interpolymer complex. Hydrogen bonds play a dominant role in the formation of these complexes. Hydrophobic interactions serve as an additional stabilizing factor. It is established that poly(methacryloyloxyethyl phosphorylcholine)/poly(vinylphosphonic acid) complex forms a looser structure in comparison with those for polycarboxylic acids as result of electrostatic repulsion between charged groups.
Radical polymerization was used to synthesize and characterize (co)polymers with sodium styrenesulfonate (NaSS), 4-methacryloylamidosalicylic acid (MASA), and N-vinylpyrrolidone, which have a low cytotoxicity and a high antiviral activity against the human respiratory syncytial virus. The interaction of copolymers with Tb3+ ions was studied. The complexes formed in dilute aqueous solutions at a concentration of MASA units c ⩽ 1 · 10−4 mol L−1 demonstrate a strong luminescence. The luminescence intensity is independent of copolymer composition, but increases when the NaSS units are substituted with uncharged N-vinylpyrrolidone units. The obtained Tb3+ polymer complexes are promising luminescent sensors for the visualization of biological objects interacting with copolymers.
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.
2-Methacryloyloxyethyleniminodiacetic acid and its new water-soluble copolymers with N-vinylpyrrolidone have been synthesized. The interaction of the copolymers in dilute aqueous solutions with lanthanide ions has been studied. The study has revealed the 25-fold amplification of Eu3+ luminescence in the polymer complex has been revealed as compared with a low-molecular-weight analog upon the formation of both heteroligand complexes with thenoyltrifluoroacetone and Eu3+ and Gd3+ heterometallic (bimetallic) complexes.
Star-shaped polymers with the calix[8]arene core and poly(2-isopropyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline)–poly[3-(2-oxazoline)propionic acid] block copolymer arms at various ways of attaching blocks to the core are synthesized by ring-opening cationic polymerization. Luminescent labels are introduced by the esterification of carboxyl groups by diazomethane derivatives. In order to obtain interpolymer complexes luminescently labeled poly(methacrylic acid) and poly(acrylic acid) are synthesized. The resulting polymers are characterized by the methods of molecular hydrodynamics and optics. Interpolymer complex formation in the aqueous solutions of the polymers is studied by polarized luminescence. It is shown that the chemical structure of the polyoxazoline fragment and the way of its addition to the core influence the structural and dynamic characteristics of the interpolymer complexes with polycarboxylic acids and their stability.
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.
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.
Reducing and stabilizing abilities of three poly(ethylene glycol) (PEG) samples modified with primary amino groups in one or two terminal positions of the polymer chains, as well as with dendrons based on L-aspartic acid in both terminal positions of the polymer chains, have been studied. Stable dispersions of silver nanoparticles have been formed at room temperature in aqueous solutions of AgNO3 in the presence of the modified PEGs without additional reducing agents. Spectrophotometric examinations have shown that an increase in the number of amino groups per polymer molecule results in accelerating the formation of nanoparticles and improving the stabilizing ability of the modified PEGs. Molecular hydrodynamic methods (analytical centrifugation and dynamic light scattering) have been used to determine the absolute values of the molecular mass of silver nanoparticles stabilized with dendronized PEGs and the hydrodynamic sizes of the particles. Molecular hydrodynamics and electron microscopy have yielded interconsistent estimates of silver nanoparticle sizes.
The interaction of a molecular brush consisting of a polyimide backbone and luminescence-labeled poly(methacrylic acid) side chains with poly-N-vinylamides (poly-N-vinylpyrrolidone and poly-N-vinylcaprolactam) with different molecular weights is studied via polarized luminescence under stationary excitation in organic solvents with different thermodynamic qualities in relation to the chain blocks of the polymers, namely, selective (methanol) and common (dimethylformamide). The decrease in the mobility of the grafted poly(methacrylic acid) chains with the growth in the molecular weight of poly-N-vinylamide observed in both selective and common solvents gives evidence of the transition from a “loose” structure to a more compact structure of the interpolymer complex. It is shown on the basis of the analysis of the nanosecond relaxation times characterizing the mobility of the sections of the grafted poly(methacrylic acid) chains and reflecting the change in the intra- and intermolecular interactions that the formation of interpolymer complexes in dimethylformamide leads to a looser structure.
Water-soluble polymeric complexones, N -vinylpyrrolidone- N -allyl- p -aminosalicylic acid copolymers with low content of chelating units, were synthesized. The formation of Eu 3+ heteroligand complexes containing these complexones was studied. The complexation of Eu 3+ with the polymeric complexone and low-molecular-mass organic coligand, thenoyltrifluoroacetone (TTA), ensures efficient energy transfer from molecular orbitals of the polymeric ligand to Eu 3+ , allowing the Eu 3+ luminescence intensity in aqueous solutions to be enhanced by more than 1–1.5 orders of magnitude. The maximal intensity of the Eu 3+ luminescence in the heteroligand complex is observed at the [Eu 3+ ]:[COO − ] ratio of ∼1 and [Eu 3+ ]/[TTA] = 1.2−1.5. In the presence of univalent metal salts, the Eu 3+ luminescence intensity does not noticeably change up to their concentration of 0.4 M. Addition of Ca 2+ or Mg 2+ salts leads to a drastic decrease in the Eu 3+ luminescence intensity in the solution.