The objective of the present study is development of novel surface-active block, comb-like, and branched copolymers with peroxide-containing chains, as well as derived functional luminescent and magnetic nanoparticles. The main experimental approaches are based on tailored synthesis of the oligoperoxide surfactants of desired structures and derived coordinating complexes of transitional and rare earth elements. Oligoperoxide-based synthesis of luminescent, magnetic, and other functional nanocomposites with controlled size distribution, functionality, reactivity, and biocompatibility is described. Developed methods provide combining the formation of polymeric, metal, and metal-oxide nanoparticles with irreversible modification of their surface by functional fragments capable of radical and other reactions, including binding of physiologically active substances. Novel nanoparticles were studied by chemical, colloidal-chemical, and rheological methods, X-ray diffraction technique, luminescent spectroscopy, and transmission and scanning electronic microscopy. The availability of ditertiary peroxide fragments on the nanoparticle surface provides a possibility of radical grafting functional polymer chains. The developed functional nanoparticles have been used for phagocytosis measurement, as well as markers of pathological cells, antimicrobial remedies, and nanocarriers for targeted drug delivery.
It is revealed that chain ordering strongly affects optical and electrochromic properties of polyaniline. Polyaniline film with 70% crystalline phase combines the remarkable ability to modulate the light transmittance (coloration efficiency of 150 cm 2 /C with a contrast ratio approaching 10 at λ = 633 nm) with an unprecedented "bright-cool" bleached state, where the polymer is highly transparent to light but has low transmittance for the most intense near-infrared irradiation. Compared to the recently developed dual-band electrochromic materials in which modulation of the near-infrared absorption is realized through plasmonic electrochromism of WO 3−x nanoparticles, the highly crystalline polyaniline film demonstrates in the "bright-cool" regime a 10 times lower transmittance at 900 nm (1.6 vs 16%) with the same level (≈60%) of transmittance in the visible region. The coloration efficiency found here is almost 3-fold higher than commonly communicated for polyaniline.
The grafted copolymerization of 2-hydroxyethyl methacrylate to polyvinylpyrrolidone in the presence of mineral fillers (hydroxyapatite, montmorillonite and wollastonite) under ultrasound has been investigated. The effect of ultrasound, nature and amount of mineral filler on the polymerization rate and composition of copolymers has been determined. Ultrasound substantially intensifies the polymerization process and actively affects the formation of the copolymer composition. Under its action, a porous structure of composites is formed, even without adding special foaming agents. The obtained results were used to improve the technology of obtaining osteoplastic porous composites.
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