Tatiana Nekrasova

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.

Free radical copolymerization is used for the synthesis of novel water-soluble copolymers of vinylphosphonic acid with 2-deoxy-2-methacrylamido-D-glucose or 4-acryloylmorpholine, with varied compositions and molecular masses, as well as for the synthesis of copolymers of vinylphosphonic acid with acrylamide. The obtained copolymers contain 6–97 mol.% of vinylphosphonic acid units, and their molecular masses vary from 5 × 10³ to 310 × 10³. The monomer reactivity ratios of vinylphosphonic acid and 2-deoxy-2-methacrylamido-D-glucose in copolymerization are determined for the first time, and their values are 0.04 and 9.02, correspondingly. It is demonstrated that the synthesized copolymers form luminescent mixed-ligand complexes with Eu³⁺, thenoyltrifluoroacetone, and phenanthroline. The influence of the comonomer’s nature on the intensity of the luminescence of complex solutions is revealed.

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.