New Amphiphilic Terpolymers of N-Vinylpyrrolidone with Acrylic Acid and Triethylene Glycol Dimethacrylate as Promising Drug Delivery: Design, Synthesis and Biological Properties In Vitro.

The terpolymers of N-vinylpyrrolidone (VP) with acrylic acid and triethylene glycol methacrylate were synthesized with more than 90% yield by radical copolymerization in ethanol from monomeric mixtures of different molar composition (98:2:2, 95:5: 2 and 98:2:5) and their monomer composition, absolute molecular masses and hydrodynamic radii in aqueous media were determined. Using the MTT test, these terpolymers were established to be low toxic for non-tumor Vero cells and HeLa tumor cells. Polymer compositions of hydrophobic dye methyl pheophorbide a (MPP) based on studied terpolymers and linear polyvinylpyrrolidone (PVP) were obtained and characterized in water solution. Quantum-chemical modeling of the MPP-copolymer structures was conducted, and the possibility of hydrogen bond formation between terpolymer units and the MPP molecule was shown. Using fluorescence microscopy, the accumulation and distribution of polymer particles in non-tumor (FetMSC) and tumor (HeLa) cells was studied, and an increase in the accumulation of MPP with both types of particles was found.

Macromolecular Design and Engineering of New Amphiphilic N-Vinylpyrrolidone Terpolymers for Biomedical Applications.

New amphiphilic VP-(di)methacrylate terpolymers of different monomer compositions and topologies have been synthesized by radical polymerization in toluene without any growth regulator of polymer chains. Their structures and properties in solid state and water solution were studied by double-detector size-exclusion chromatography; IR-, 1H, and 13C NMR-spectroscopy; DLS, TEM, TG, and DSC methods. The composition of the VP-AlkMA-TEGDM monomer mixture has been established to regulate the topology of the resulting macromolecules. The studied terpolymers presented on TEM images as individual low-contrast particles and their conglomerates of various sizes with highly ordered regions; in general, they are amorphous structures. None of the terpolymers demonstrated cytotoxic effects for noncancerous Vero and tumor HeLa cells. Hydrophobic D-α-tocopherol (TP) was encapsulated in terpolymer nanoparticles (NPs), and its antioxidant activity was evaluated by ABTS (radical monocation 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid)) or DPPH (2,2'-diphenyl-1-picrylhydrazyl) methods. The reaction efficiency depends on the TP-NP type. The IC50 values for the decolorization reaction of ABTS•+ and DPPH inhibition in the presence of initial and encapsulated TP were obtained.

Novel Push-Pull Benzodithiophene-Containing Polymers as Hole-Transport Materials for Efficient Perovskite Solar Cells.

Donor-acceptor conjugated polymers are considered advanced semiconductor materials for the development of thin-film electronics. One of the most attractive families of polymeric semiconductors in terms of photovoltaic applications are benzodithiophene-based polymers owing to their highly tunable electronic and physicochemical properties, and readily scalable production. In this work, we report the synthesis of three novel push-pull benzodithiophene-based polymers with different side chains and their investigation as hole transport materials (HTM) in perovskite solar cells (PSCs). It is shown that polymer P3 that contains triisopropylsilyl side groups exhibits better film-forming ability that, along with high hole mobilities, results in increased characteristics of PSCs. Encouraging a power conversion efficiency (PCE) of 17.4% was achieved for P3-based PSCs that outperformed the efficiency of devices based on P1, P2, and benchmark PTAA polymer. These findings feature the great potential of benzodithiophene-based conjugated polymers as dopant-free HTMs for the fabrication of efficient perovskite solar cells.