Zharikov, Aleksey Aleksandrovich

Migulin D.A., Rozanova J.V., Zharikov A.A., Feldman V.I., Emelyanova O.V., Zezin A.A.

Zharikov A.A., Zezina E.A., Sybachin A.V., Vasiliev A.L., Emel'yanov A.I., Pozdnyakov A.S., Feldman V.I., Zezin A.A.

Klimov D.I., Zharikov A.A., Zezina E.A., Kotenkova E.A., Zaiko E.V., Bataeva D.S., Semenova A.A., Yushina Y.K., Yaroslavov A.A., Zezin A.A.

In order to control pathogenic microorganisms, three polymer compositions were prepared and tested. First, a water-soluble positively charged polycomplex was synthesized via the electrostatic binding of anionic polyacrylic acid to an excess of polyethylenimine to enhance the biocidal activity of the polycation. Second, an aqueous solution of AgNO3 was added to the polycomplex, thus forming a ternary polycation-polyanion-Ag1+ complex with an additional antimicrobial effect. Third, the resulting ternary complex was subjected to UV irradiation, which ensured the conversion of Ag1+ ions into Ag nanoparticles ranging in size mainly from 10 to 20 nm. Aqueous solutions of the polymer compositions were added to suspensions of the Gram-positive bacteria S. aureus and the Gram-negative bacteria P. aeruginosa, with the following main results: (a) Upon the addition of the binary polycomplex, 30% or more of the cells survived after 20 h. (b) The ternary complex killed S. aureus bacteria but was ineffective against P. aeruginosa bacteria. (c) When the ternary complex with Ag nanoparticles was added, the percentage of surviving cells of both types did not exceed 0.03%. The obtained results are valuable for the development of antibacterial formulations.

Zharikov A.A., Zezina E.A., Vinogradov R.A., Pozdnyakov A.S., Feldman V.I., Chvalun S.N., Vasiliev A.L., Zezin A.A.

Gold nanoparticles (AuNPs) stabilized with poly(1-vinyl-1,2,4-triazole) (PVT) have been synthesized via a one-pot manner in irradiated solutions of 1-vinyl-1,2,4-triazole (VT) and Au(III) ions. The transmission electron microscopy examinations have shown that the sizes of nanoparticles formed range from 1 to 11 nm and are affected by the ratio of VT to gold ions. To study the kinetics peculiarities of the VT polymerization and assembling of AuNPs, UV-Vis spectroscopy was used. The analysis of the data obtained reveals that an inhibition period, influenced by Au(III) concentration, is followed by the polymerization of a monomer. Importantly, the absorbed doses, corresponding to the onset of rapid polymerization, correlate with the doses at which the accelerated formation of AuNPs begins. The kinetics aspects, which could lead to such an effect, are discussed.

Zharikov A.A., Vinogradov R.A., Zezina E.A., Pozdnyakov A.S., Feldman V.I., Vasiliev A.L., Zezin A.A.

Gold nanoparticles (AuNPs) with average sizes of 1.5 nm and 3 nm and narrow size distribution have been prepared in the irradiated aqueous solutions and suspensions of Au(III)-complexes with units of poly(1-vinyl-1,2,4-triazole) (PVT) and poly(1-vinyl-1,2,4-triazole) – poly(acrylic acid) (PAA) respectively. The formation of AuNPs has been studied using UV-VIS spectroscopy and transmission electron microscopy. The effective stabilization of ultrasmall AuNPs is achieved due to the combination of both electrostatic interaction of polymer units and the specific adsorption of functional groups on the nanoparticle surface. The radiation-chemical approach makes it possible to obtain nanoparticles of a controlled size and containing no impurities of chemical reducing agents. • Ultrasmall AuNPs were obtained in the irradiated dispersions of PVT and PVT-PAA. • Radiation-chemical method provides the synthesis of AuNPs with no chemical impurities. • Specific adsorption of PVT groups on Au-surface ensures stabilization of crystal AuNPs. • The smallest amorphous particles are formed in triple PVT-PAA-AuNPs complexes.

Zezin A., Danelyan G., Emel'yanov A., Zharikov A., Prozorova G., Zezina E., Korzhova S., Fadeeva T., Abramchuk S., Shmakova N., Pozdnyakov A.

AbstractPoly‐1‐vinyl‐1,2,4‐triazole (PVT)‐based materials with silver nanoparticles are promising antibacterial products. The metal nanoparticles with controllable sizes were obtained by radiation‐induced reduction of the dispersions of complexes of PVT with silver ions. Formation of the silver nanoparticles in aqueous suspensions irradiated at pH 6.0, 2.5, and 2.0 was studied using methods of UV–VIS spectroscopy and transmission electron microscopy. UV–VIS spectroscopy has detected a change in the efficiency of interaction between protonated or non‐protonated PVT units and the surface of silver nanoparticles. The interaction of macromolecules with the metal surface under different degrees of protonation of PVT functional groups afforded the nanoparticles with a narrow size distribution and an average size from 3 to 10 nm. An increase in the acidity also leads to a decrease in the ratio of the generation/growth of nanoparticles. The radiation approaches both provide the synthesis of the nanoparticles of controlled sizes and permits to obtain the nanocomposites containing no impurities of chemical reducing agents. The nanocomposites obtained exhibit high antibacterial activity against various bacterial strains, which depends on the size of silver nanoparticles.

Zezin A.A., Zharikov A.A., Emel’yanov A.I., Pozdnyakov A.S., Prozorova G.F., Abramchuk S.S., Zezina E.A.

Metal–polymer nanocomposite polyvinyltriazole–silver nanoparticles were obtained using one-pot synthesis in irradiated aqueous solutions of 1-vinyl-1,2,4-triazole (VT) and silver ions. Gel permeation chromatography data show that upon radiation initiation, the molecular weight of poly(1-vinyl-1,2,4-triazole) increases with increasing monomer concentration. To study the kinetics of polymerization and the features of the radiation–chemical formation of nanoparticles, UV-Vis spectroscopy was used. TEM images show a relatively small average size of the forming nanoparticles (2–3 nm) and a narrow size distribution, which shows the effective stabilization of nanoparticles by triazole substituents at a molar ratio of VT and silver ions of 25/1. The addition of ethyl alcohol was used to increase the efficiency of synthesis and suppress the crosslinking of macromolecules in solution. The results of the work show that aqueous–alcoholic solutions of 1 wt.% VT can be used to obtain soluble nanocomposite materials. 10 wt.% monomer solutions have prospects for use in the preparation of polymer gels filled with nanoparticles.

Zharikov A.A., Zezin A.A., Zezina E.A., Emel’yanov A.I., Prozorova G.F.

Abstract The radiational chemical production of silver nanoparticles offers promising prospects for the synthesis of the antibacterial materials in the matrix of the nontoxic poly(vinyltriazole). Use of the optical spectroscopy for the electronic transmission microscopy shows that nanoparticles of the average size of 4 nm are formed in the radiated suspensions of poly(1-vinyl-1,2,4-triazole). The analysis of the data of the optical spectroscopy reveals that nanoparticles are formed in several stages. At the first stage, the formation of clusters is prevalent and the second stage provides the assembly of nanoparticles through the reduction of silver ions on the surface of the clusters.

Prozorova G., Emel'yanov A., Ivanova A., Semenova T., Fadeeva T., Nevezhina A., Korzhova S., Pozdnyakov A.

A novel water-soluble polymer nanocomposite with ultra-small iron oxide nanoparticles intercalated into a biocompatible matrix of 1-vinyl-1,2,4-triazole and N-vinylpyrrolidone copolymer exhibits pronounced antibacterial and antibiofilm activity.

Migulin D.A., Rozanova J.V., Zharikov A.A., Feldman V.I., Emelyanova O.V., Zezin A.A.

Zhang J., Cheng H., Abd-El-Aziz A., Zhang X., Ma N., Abd-El-Aziz A.S.

Although the use of seawater is vital for future water resources, the majority of marine bacteria in seawater pose risks to human and animal health. It is therefore crucial to develop antibacterial membranes with high sterilization efficiency and low cost, especially if the membranes can use sunlight as a renewable source of energy. The composite Ti3C2Tx@PEI/Ag was prepared by in-situ reduction of silver nanoparticles (AgNPs) onto nanosheets of the MXene Ti3C2Tx coated with polyethyleneimine (PEI). The composite exhibits enhanced photothermal conversion efficiency of 22.67% due to roughness of the surface and local plasmon effect of silver nanoparticles (AgNPs) combined with the photothermal properties and thermal conductivity of the Ti3C2Tx nanosheets. The resulting composite Ti3C2Tx@PEI/Ag was then deposited on filter paper to yield the membrane, which was capable of reaching temperatures up to 48.7 °C for 50 s after a single irradiation with sunlight, with stability maintained after four cycles. In antibacterial assays for marine bacteria, the bacterial survival rate in seawater applied to the membrane was 18% in the absence of light and the bacteria were eliminated entirely on exposure to light. The sterilization rate was close to 100% in all five cycles and there was no leakage of silver ions.

Zharikov A.A., Zezina E.A., Bolshakova A.V., Sybachin A.V., Pozdnyakov A.S., Feldman V.I., Zezin A.A.

Zharikov A.A., Zezina E.A., Sybachin A.V., Vasiliev A.L., Emel'yanov A.I., Pozdnyakov A.S., Feldman V.I., Zezin A.A.

Płaza-Altamer A., Kołodziej A.

Ali A.A., Al-Jorani K.R., Merza M.M.

The divalent transition metal ions Co, Ni, and Cu coordination compounds with unusual bidentate mixed Schiff base-based 1,2,4-triazole-3-thione ligand in a protonated specific coordination stoichiometry and structures forms were synthesized. The structural composition of the ligand 5-(1-naphthylmethyl)-4-{(Z)-[(2E)-3-phenyl-2-propen-1-ylidene]amino}-2,4-dihydro-3H-1,2,4-triazole-3-thione (LH) was fully identified by 1H and 13C NMR, FTIR, UV-Vis, mass spectrometry as well elemental analysis. The UV-Vis, FTIR spectroscopy, magnetic susceptibility measurements, molar conductance, flame atomic absorption, and elemental analysis (CHNS) techniques were used to characterize the synthesized complexes. Three complexes of Ni(II), Co(II), and Cu(II), in addition to the ligand LH, were the subject of computational investigations. Benchmark analyses were carried out to determine the best degree of calculation for the complexes under the study. The B3LYP approach was chosen as the computation method. The B3LYP/6-31G (d,p) (LANL2DZ) was the best calculation rank. IR spectra and structural studies were carried out. Furthermore, a thorough investigation and examination of biological characteristics were conducted. Complex (Cu) was determined to be the most excellent choice for biological applications based on calculation findings.

Goncharova D., Salaev M., Volokitina A., Magaev O., Svetlichnyi V., Vodyankina O.

Gold-based catalysts occupy one of the largest segments in catalysis science and technology. (Ultra)small Au nanoparticles (

Emel’yanov A., Korzhova S., Ivanova A., Semenova T., Chepenko D., Usmanov R., Pozdnyakov A.

New water-soluble nanocomposites with cobalt oxide nanoparticles (Co3O4NPs) in a poly(1-vinyl-1,2,4-triazole) (PVT) matrix have been synthesized. The PVT used as a stabilizing polymer matrix was obtained by radical polymerization of 1-vinyl-1,2,4-triazole (VT). The polymer nanocomposites with Co3O4 nanoparticles were characterized by ultraviolet–visible, Fourier-transform infrared spectroscopy, atomic absorption spectroscopy, transmission electron microscopy, dynamic light scattering, gel permeation chromatography, and simultaneous thermogravimetric analysis. The resulting polymer nanocomposites consist of spherical isolated cobalt nanoparticles with a diameter of 1 to 13 nm. The average hydrodynamic diameters of macromolecular coils are 15–112 nm. The cobalt content in nanocomposites ranges from 1.5 to 11.0 wt.%. The thermal stability of nanocomposites is up to 320 °C.

Zhmurova A.V., Prozorova G.F., Korzhova S.A., Pozdnyakov A.S., Zvereva M.V.

In this work, the structural characteristics and DC electrical conductivity of firstly synthesized organic–inorganic nanocomposites of thermoelectric Te0 nanoparticles (1.4, 2.8, 4.3 wt%) and poly(1-vinyl-1,2,4-triazole) (PVT) were analyzed. The composites were characterized by high-resolution transmission electron microscopy, X-ray diffractometry, UV-Vis spectroscopy, and dynamic light scattering analysis. The study results showed that the nanocomposite nanoparticles distributed in the polymer matrix had a shape close to spherical and an average size of 4–18 nm. The average size of the nanoparticles was determined using the Brus model relation. The optical band gap applied in the model was determined on the basis of UV-Vis data by the Tauc method and the 10% absorption method. The values obtained varied between 2.9 and 5.1 nm. These values are in good agreement with the values of the nanoparticle size, which are typical for their fractions presented in the nanocomposite. The characteristic sizes of the nanoparticles in the fractions obtained from the Pesika size distribution data were 4.6, 4.9, and 5.0 nm for the nanocomposites with percentages of 1.4, 2.8, and 4.3%, respectively. The DC electrical conductivity of the nanocomposites was measured by a two-probe method in the temperature range of 25–80 °C. It was found that the formation of an inorganic nanophase in the PVT polymer as well as an increase in the average size of nanoparticles led to an increase in the DC conductivity over the entire temperature range. The results revealed that the DC electrical conductivity of nanocomposites with a Tellurium content of 2.8, 4.3 wt% at 80 °C becomes higher than the conventional boundary of 10−10 S/cm separating dielectrics and semiconductors.

Smyslov R., Emel’yanov A., Nekrasova T., Prozorova G., Korzhova S., Trofimova O., Pozdnyakov A.

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.

Pascual L.M., Boudesocque S., Dupont L., Michel J., Plantier-Royon R., GATARD S.

Prozorova G.F., Pozdnyakov A.S.

In this review, a comparative analysis of the literature and our own results obtained in the study of the physicochemical, dielectric, and proton-conducting properties of composite polymer materials based on 1H-1,2,4-triazole has been carried out. It has been established that 1H-1,2,4-triazole and homopolymers and copolymers of 1-vinyl-1,2,4-triazole are promising for the development of proton-conducting fuel cell membranes. They significantly improve the basic characteristics of electrolyte membranes, increase their film-forming ability, increase thermal stability up to 300–330 °C, increase the electrochemical stability region up to 3–4 V, promote high mechanical strength and morphological stability of membranes, and provide high ionic conductivity (up to 10−3–10−1 S/cm) under anhydrous conditions at temperatures above 100 °C. There is also an improvement in the solubility and a decrease in the glass transition temperature of polymers based on 1-vinyl-1,2,4-triazole, which facilitates the processing and formation of membrane films. The results obtained demonstrate the uniqueness of 1H-1,2,4-triazole and (co)polymers based on 1-vinyl-1,2,4-triazole and the promise of their use for the creation of heat-resistant plastic and electrochemically stable, mechanically strong proton-conducting membranes with high ionic conductivity under anhydrous conditions and at high temperatures.

Fatemi M., Bahrami Z.

The application of nanomaterials in different fields totally depends on their characteristics. Considering the impact of the synthesis method on the final product’s characteristics such as size and morphology, selection of the proper method is critical. In general, the nanomaterial synthesis methods can be classified into two main categories: top-down and bottom-up. In the top-down methods, bulk materials are converted into nanomaterials using specific techniques such as mechanical milling. In the bottom-up methods, following the selection of a suitable precursor and creation of adequate conditions, atoms and molecules will lie next to each other and make nanomaterials consequently. Although most of the top-down synthesis methods are capable of mass production of nanomaterials, the diversity and ease of the bottom-up synthesis methods have made this category more interesting. Different types of nanomaterials can be used as carriers for cancer therapy, including zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) nanomaterials. This chapter investigates the most important synthesis methods for the abovementioned nanomaterials and evaluates the corresponding effective parameters.

Ghazy A.R., Shalaby M.G., Ibrahim A., ElShaer A., Mahmoud Y.A., Al-Hossainy A.F.

• Biosynthesize CuO 2 nanoparticles from Fusarium oxysporum at 100 ppm and hybrid nanocomposite [P(AN-co-MMA)/Cu 2 O] HNC • The structural properties of the [P(AN-co-MMA)/Cu 2 O] HNC films are studied by different characterization techniques such as X-Ray Diffraction XRD, UV-Vis optical properties, and laser photoluminescence PL. • Simulated data TD-(DFT) of the hybrid nanocomposite are made and compared with Experimental data. • A geometric study and energy gap of nanocomposite was made by Using DMOl 3 /TD-DFT designs. • The crystallite size (D) value average is 112.39 nm for [P(AN-co-MMA)/0.1-0.25Cu 2 O] HNC hybrid nanocomposite thin film. • The investigated large optical energy bandgap and PL analysis for hybrid nanocomposite is advantageous for some energy storage applications. A fungal mycelium-free extract was used to biosynthesize CuO 2 nanoparticles from Fusarium oxysporum at 100 ppm of copper sulfate. A poly(acrylonitrile-co-methylmethacrylate) (P(AN-co-MMA)) was prepared by a precipitation polymerization method. A Cu 2 O nanoparticle was added by ratios of 0.25, 0.20, 0.15, and 0.10 to copolymer weight and then deposited on glass substrates by using the dip-casting method to form hybrid nanocomposite thin film [P(AN-co-MMA)/Cu 2 O] HNC . The structural properties of the [P(AN-co-MMA)/Cu 2 O] HNC films are studied by different characterization techniques such as X-Ray Diffraction XRD, UV-Vis optical properties, and laser photoluminescence PL. Additionally, using density functional theory (DFT), optimization via TD-DFTD/Mol 3 and Cambridge Serial Total Energy Bundle (TD-FDT/CASTEP) was developed. The TD-DFT calculations accurately matched the observed XRD, and optical properties and validated the molecular structure of the examined materials. XRD pattern of the copolymer film shows that an amorphous structure is obtained. While a peak appeared at 2θ equal to 35.8º is for Cu 2 O nanoparticles. The average crystallite size of Cu 2 O nanocrystals and [P(AN-co-MMA)/Cu 2 O] HNC are about 78 nm and nm. Optical properties of the [P(AN-co-MMA)/Cu 2 O] HNC films at normal incidence of light in the wavelength range of 200–1100 nm are studied. The calculations of the direct energy gap show that it has changed from 4.15 eV for P(An-co-MMA) copolymer to 3.98 eV for 0.25 Cu 2 O nanocrystals loading. PL technique analyses indicated four emission peaks appeared at 398 nm, 455 nm, 518 nm, and 702 nm for the hybrid nanocomposites while only one peak at 398 nm appeared for P(An-co-MMA) copolymer. The optical characteristics predicted by CASTEP in TD-DFT are in good agreement with the experimental values. The obtained results indicate that the [P(An-co-MMA)/Cu 2 O] HNC film is a good candidate in electronic devices to block UV radiations based on its band gap and optical characteristics.

Migulin D.A., Rozanova J.V., Meshkov I.B., Milenin S.A., Shitikov E.A., Muzafarov A.M.

AbstractNowadays the most common gastrointestinal related gram‐negative H. pylori and E. coli pathogen bacteria that are considered to be the main causes for the development of various gastric diseases and bloodstream infections are rapidly developing resistance against the standard antibiotics, commonly used in the clinical practices. One of the alternative high potential approaches for solving problems of bacterial resistance includes applications of silver‐based materials and silver nanoparticles (AgNPs). In the present study two types of amine‐ and triazol‐ functional polyorganosilsesquioxane nanocomposite sorbent hydrogels with narrowly dispersed AgNPs were developed. In vitro antibacterial activity and cytotoxicity tests showed concentration‐ and time‐dependent activity of the prepared nanocomposites against gram‐negative E. coli and H. pylori bacteria and a reduced cytotoxicity towards Caco‐2 human colon epithelial cells. Molecular structures and chemical compositions of the synthesized composites elucidated with transmission and scanning electron microscopy and UV‐Vis spectroscopy revealed spherical and narrowly dispersed along the polymer matrices AgNPs with average sizes of 3–5 nm. It was estimated that the chemical composition and particularly the zeta‐potentials values that were found to be dependent on the molecular structures of the synthesized nanocomposites had a high influence on the AgNPs antibacterial activity and cytoxicity profiles.

Filippov S.K., Khusnutdinov R., Murmiliuk A., Inam W., Zakharova L.Y., Zhang H., Khutoryanskiy V.

In this focus article, we provide a scrutinizing analysis of transmission electron microscopy and dynamic light scattering as the two common methods to study the sizes of nanoparticles with focus on the application in pharmaceutics and drug delivery.

Meltonyan A.V., Poghosyan A.H., Sargsyan S.H.

The adsorption of 1-vinyl-1,2,4-triazole monomers on Au(111) surface was investigated via molecular dynamics method. Our results indicate that the surface coverage varied depending on the concentration of the monomers. Specifically, as the concentration of the monomers increased, the surface coverage also increased. At the highest concentrations, we observed up to 73% coverage of the metal surface. We show that the 1-vinyl-1,2,4-triazole monomers display a strong adsorption on gold surface, and the monomer binds to metal surface via heterocyclic pyridine-like nitrogen, and the distance between near nitrogen to gold is estimated to be 0.25 nm. Note that upon the concentration increase, we track the different layers of adsorption. The 1-vinyl-1,2,4-triazole (VT) molecule was created using online resources of MOLVIEW. The Au {111} facet was taken from our previous simulation, and as a force field, the CHARMM-GOIP concept was used. As a water model, the SPC approach was used. The latest version of GROMACS with GPU support was used. The snapshots were generated with the VMD package.

Vasil’kov A., Migulin D., Naumkin A., Volkov I., Butenko I., Golub A., Sadykova V., Muzafarov A.

New hybrid materials based on Ag nanoparticles stabilized by a polyaminopropylalkoxysiloxane hyperbranched polymer matrix were prepared. The Ag nanoparticles were synthesized in 2-propanol by metal vapor synthesis (MVS) and incorporated into the polymer matrix using metal-containing organosol. MVS is based on the interaction of extremely reactive atomic metals formed by evaporation in high vacuum (10−4–10−5 Torr) with organic substances during their co-condensation on the cooled walls of a reaction vessel. Polyaminopropylsiloxanes with hyperbranched molecular architectures were obtained in the process of heterofunctional polycondensation of the corresponding AB2-type monosodiumoxoorganodialkoxysilanes derived from the commercially available aminopropyltrialkoxysilanes. The nanocomposites were characterized using transmission (TEM) and scanning (SEM) electron microscopy, X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD) and Fourier-transform infrared spectroscopy (FTIR). TEM images show that Ag nanoparticles stabilized in the polymer matrix have an average size of 5.3 nm. In the Ag-containing composite, the metal nanoparticles have a “core-shell” structure, in which the “core” and “shell” represent the M0 and Mδ+ states, respectively. Nanocomposites based on silver nanoparticles stabilized with amine-containing polyorganosiloxane polymers showed antimicrobial activity against Bacillus subtilis and Escherichia coli.

Danischewski J., Donelson D., Farzansyed M., Jacoski E., Kato H., Lucin Q., Roca M.

The interpretation of color change in sensors and tests can be linked to incorrect conclusions if the intrinsic color changes are not accounted for. In this work, we study the intrinsic color change associated with the process of embedding nanoparticles in a polymer to create nanocomposite films. We present a safer, faster method to coat silver nanoparticles with silica and employ a seven-factor Plackett-Burman design to identify critical factors in the synthesis. Silver nanodisks with increasing thicknesses of the silica shell showed a decreasing sensitivity of their localized surface plasmon resonance (LSPR) toward changes in the refractive index surrounding the nanoparticle. A color shift of up to 72 nm was observed when bare nanoparticles were embedded in poly(vinyl alcohol), but no color change was perceived when nanoparticles were coated with a 25-nm-thick silica shell. Understanding the origin of color changes intrinsic to the preparation of polymeric nanocomposites aids in the design and correct use of plasmonic sensors.

Zharikov A.A., Zezina E.A., Vinogradov R.A., Pozdnyakov A.S., Feldman V.I., Chvalun S.N., Vasiliev A.L., Zezin A.A.

Gold nanoparticles (AuNPs) stabilized with poly(1-vinyl-1,2,4-triazole) (PVT) have been synthesized via a one-pot manner in irradiated solutions of 1-vinyl-1,2,4-triazole (VT) and Au(III) ions. The transmission electron microscopy examinations have shown that the sizes of nanoparticles formed range from 1 to 11 nm and are affected by the ratio of VT to gold ions. To study the kinetics peculiarities of the VT polymerization and assembling of AuNPs, UV-Vis spectroscopy was used. The analysis of the data obtained reveals that an inhibition period, influenced by Au(III) concentration, is followed by the polymerization of a monomer. Importantly, the absorbed doses, corresponding to the onset of rapid polymerization, correlate with the doses at which the accelerated formation of AuNPs begins. The kinetics aspects, which could lead to such an effect, are discussed.

Mkrtchyan K.V., Pigareva V.A., Zezina E.A., Kuznetsova O.A., Semenova A.A., Yushina Y.K., Tolordava E.R., Grudistova M.A., Sybachin A.V., Klimov D.I., Abramchuk S.S., Yaroslavov A.A., Zezin A.A.

Due to the presence of cationic units interpolyelectrolyte complexes (IPECs) can be used as a universal basis for preparation of biocidal coatings on different surfaces. Metallopolymer nanocomposites were successfully synthesized in irradiated solutions of polyacrylic acid (PAA) and polyethylenimine (PEI), and dispersions of non-stoichiometric IPECs of PAA–PEI containing silver ions. The data from turbidimetric titration and dynamic light scattering showed that pH 6 is the optimal value for obtaining IPECs. Metal polymer complexes based on IPEC with a PAA/PEI ratio equal to 3/1 and 1/3 were selected for synthesis of nanocomposites due to their aggregative stability. Studies using methods of UV–VIS spectroscopy and TEM have demonstrated that the size and spatial organization of silver nanoparticles depend on the composition of polymer systems. The average sizes of nanoparticles are 5 nm and 20 nm for complexes with a molar ratio of PAA/PEI units equal to 3/1 and 1/3, respectively. The synthesized nanocomposites were applied to the glass surface and exhibited high antibacterial activity against both gram-positive (Staphylococcus aureus) and gram-negative bacteria (Salmonella). It is shown that IPEC-Ag coatings demonstrate significantly more pronounced biocidal activity not only in comparison with macromolecular complexes of PAA–PEI, but also coatings of PEI and PEI based nanocomposites.

Yu. Vasil'kov A., Migulin D.A., Muzalevskiy V.M., Naumkin A.V., Yu. Pereyaslavtsev A., Zubavichus Y.V., Nenajdenko V.G., Muzafarov A.M.

New copper-containing organosilicon hybrid materials were synthesized by the reaction of branched polymethyl- silsesquioxane with copper nanoparticles prepared by the metal-vapor synthesis. Hybrid materials showed a high activity in the catalytic olefination of p -chlorobenzaldehyde hydrazone with polyhaloalkanes such as CBrCl 3 , CBr 4 and CF CBr to afford the corresponding halostyrenes in the yields above 80%. The structure and composition of the prepared nanocomposites were studied by X-ray using synchrotron radiation to show that the active sites of the catalysts are mixed copper(I)–copper(II) oxides (Cu–Cu 2 O–CuO) in nature.

Zhang X., Qu Q., Cheng W., Zhou A., Deng Y., Ma W., Zhu M., Xiong R., Huang C.

Prussian blue (PB) with distinct hollow mesoporous structure and favorable properties has captured the attention of extensive biomaterial researchers. However, there is an unmet need for biocompatible PB microparticles with recyclability fabricated by a facile method. Herein, a size-controlled PB alginate microparticles (PBAMs) generated by a one-step and large batch production gas-shearing strategy. With the characteristic of porous and surface-modifiable, PBAMs used as vehicles may effectively load and release drug to improve the therapeutic efficacy. Meanwhile, Fe2+ in PBAMs exerts a catalyze for chemodynamic therapy (CDT) to produce reactive oxygen species (ROS), which synergizes with the photothermal therapy (PTT) induced by PB particles with effective photothermal conversion, achieving active tri-modality combination antitumor and antibacterial. The new concept for the low-cost and facile preparation of biocompatible PBAMs here illustrated opens a novel pathway toward the effective multifunctional platform.

Shevtsova T., Cavallaro G., Lazzara G., Milioto S., Donchak V., Harhay K., Korolko S., Budkowski A., Stetsyshyn Y.

New temperature-responsive hybrid nanomaterials based on modified halloysite nanotubes (HNTs) containing grafted polymer brushes with silver nanoparticles have been successfully fabricated. We used a three steps process including synthesis of the initiating coatings onto HNTs surface, fabrication of the POEGMA – poly(oligo(ethylene glycol)ethyl ether methacrylate) grafted brushes and synthesis of the silver nanoparticles (AgNPs). The synthesis and properties of hybrid nanomaterials were studied by FT-IR, TGA and DLS methods. It is shown that the introduction of AgNPs, formed from 0.005 M AgNO 3 solution leads to a significant reduction of low critical solution temperature (LCST) of the polymer layer from 29.7 to 21.6 °C. The samples fabricated from 0.05 M AgNO 3 solution did not evidence a temperature-induced transition, despite of the contents of AgNPs obtained for both solutions are almost identical (≈ 4%w). The presence of AgNPs with sizes of ca. 20 nm was confirmed in the hybrids prepared from both AgNO 3 concentrations by UV–vis spectroscopy, and electron microscopy. These temperature-responsive hybrid nanomaterials may be used for conservation of solid substrates, production of advanced medical facemasks, photothermal therapy against microorganisms and tumors etc. • AgNPs are integrated into polymer matrix of hybrid nanomaterial. • Hybrid nanomaterial shows temperature-responsive properties. • Hybrid nanomaterial with AgNPs has significantly reduced LCST.

Shiryaeva E.S., Baranova I.A., Sanochkina E.V., Dement'eva O.V., Kartseva M.E., Shishmakova E.M., Rudoy V.M., Belousov A.V., Morozov V.N., Feldman V.I.

In this study we have probed the role of different enhancement mechanisms of the nanosensitizers in the X-ray irradiated oxygen-free model aqueous organic systems containing “bare” gold nanoparticles (AuNPs) using the spin-trapping technique with electron paramagnetic resonance detection. The observed enhancement effect was found to be ca. 1.67 wp −1 for the AuNPs with an average diameter of 18 nm and 45 kVp X-rays. The comparison with Monte Carlo simulation shows that the sensitizing effect of AuNPs in the X-ray irradiated oxygen-free aqueous organic systems could be attributed to the increasing absorbed dose due to high absorption cross-section of gold atoms. It implies that the radiation-chemical yield of hydroxyl radicals responsible for the oxidative damage in the absence of oxygen remains virtually unchanged in the presence of AuNPs. Also, no clear evidence was found for the dose rate effects upon variation of this parameter by more than an order of magnitude (0.06–1.21 Gy/s). In practical sense, these results urge the development of new efficient approaches for the radiation treatment of hypoxic media using nanoparticles. • The sensitizing effect of gold NPs under X-ray irradiation in oxygen-free environment was studied. • The effect is reasonably explained by the physical enhancement mechanism. • The experimental results are in agreement with the Monte Carlo simulations. • No evidence for chemical enhancement was found under the hypoxic conditions.

Prozorova G.F., Pozdnyakov A.S.

The review summarizes the data on the synthesis, physicochemical properties, and biological activity of poly(1-vinyl-1,2,4-triazole) and its nanocomposites with silver nanoparticles. The results of studying the antibacterial and antitumor activity of the polymers and nanocomposites and their immunomodulatory ability, toxicity, and interaction with body cells, as well as the prospects for their use in the development of medical materials, are presented.

Zharikov A.A., Vinogradov R.A., Zezina E.A., Pozdnyakov A.S., Feldman V.I., Vasiliev A.L., Zezin A.A.

Gold nanoparticles (AuNPs) with average sizes of 1.5 nm and 3 nm and narrow size distribution have been prepared in the irradiated aqueous solutions and suspensions of Au(III)-complexes with units of poly(1-vinyl-1,2,4-triazole) (PVT) and poly(1-vinyl-1,2,4-triazole) – poly(acrylic acid) (PAA) respectively. The formation of AuNPs has been studied using UV-VIS spectroscopy and transmission electron microscopy. The effective stabilization of ultrasmall AuNPs is achieved due to the combination of both electrostatic interaction of polymer units and the specific adsorption of functional groups on the nanoparticle surface. The radiation-chemical approach makes it possible to obtain nanoparticles of a controlled size and containing no impurities of chemical reducing agents. • Ultrasmall AuNPs were obtained in the irradiated dispersions of PVT and PVT-PAA. • Radiation-chemical method provides the synthesis of AuNPs with no chemical impurities. • Specific adsorption of PVT groups on Au-surface ensures stabilization of crystal AuNPs. • The smallest amorphous particles are formed in triple PVT-PAA-AuNPs complexes.

Migulin D.A., Rozanova J.V., Migulin V.A., Cherkaev G.V., Meshkov I.B., Zezin A.A., Muzafarov A.M.

In this study, using the "click-chemistry" azide-alkyne cycloaddition reaction, two new types of polymers, namely, water-soluble amine-functional and water-insoluble pyridine-functional hyperbranched 1,2,3-triazoleorganoethoxysiloxane polymers, capable of stabilizing ultra-small silver nanoparticles and efficient for chemical surface modification were synthesized and characterized by 1H-NMR, 13C-NMR, 29Si-NMR and FT-IR spectroscopy, MALDI and GPC. Coordinatively active hetero-organic polymers with a flexible branched polyethoxysiloxane backbone bearing chelating 1,2,3-triazolyl-dimethylamine and -pyridine conjugated functional groups were exploited towards coordination with Ag+ metal ions, and formation and stabilization of narrowly dispersed silver nanoparticles (Ag-NPs) obtained in the process of radiation induced metal ion reduction. The influence of the chemically assisted radiation process on the Ag-NP size and size distribution was investigated. Hyperbranched polyorganoethoxysiloxanes loaded with Ag-NPs were covalently cross-linked on a Stöber silica surface, demonstrating the efficiency of the developed hetero-organic functional polymers in the preparation of functional nanocomposite coatings for various applications (heterogeneous catalytic systems, antibacterial materials, nanoparticle-based optical sensing devices, etc.). The nanocomposites were investigated and characterized by TEM-EDS, DLS, UV-Vis spectroscopy and 29Si MAS NMR spectroscopy.

Zezin A., Danelyan G., Emel'yanov A., Zharikov A., Prozorova G., Zezina E., Korzhova S., Fadeeva T., Abramchuk S., Shmakova N., Pozdnyakov A.

AbstractPoly‐1‐vinyl‐1,2,4‐triazole (PVT)‐based materials with silver nanoparticles are promising antibacterial products. The metal nanoparticles with controllable sizes were obtained by radiation‐induced reduction of the dispersions of complexes of PVT with silver ions. Formation of the silver nanoparticles in aqueous suspensions irradiated at pH 6.0, 2.5, and 2.0 was studied using methods of UV–VIS spectroscopy and transmission electron microscopy. UV–VIS spectroscopy has detected a change in the efficiency of interaction between protonated or non‐protonated PVT units and the surface of silver nanoparticles. The interaction of macromolecules with the metal surface under different degrees of protonation of PVT functional groups afforded the nanoparticles with a narrow size distribution and an average size from 3 to 10 nm. An increase in the acidity also leads to a decrease in the ratio of the generation/growth of nanoparticles. The radiation approaches both provide the synthesis of the nanoparticles of controlled sizes and permits to obtain the nanocomposites containing no impurities of chemical reducing agents. The nanocomposites obtained exhibit high antibacterial activity against various bacterial strains, which depends on the size of silver nanoparticles.