One-Pot Synthesis of Colloidal Hybrid Au (Ag)/ZnO Nanostructures with the Participation of Maleic Acid Copolymers.

One-pot synthesis of colloidal Au/ZnO and Ag/ZnO nanohybrid structures was carried out. The copolymers of maleic acid-poly(N-vinyl-2-pyrrolidone-alt-maleic acid), poly(ethylene-alt-maleic acid), or poly(styrene-alt-maleic acid) were used as templates for the sorption of cations of metals-precursors and stabilization of the resulting nanoheterostructures. Simultaneous production of two types of nanoparticles has been implemented under mild conditions in an aqueous alkaline medium and without additional reagents. Equimolar ratios of the metal cations and appropriate load on all copolymers were used: molar ratio of maleic acid monomeric units of copolymer/gold (silver)cations/zinc cations was 1/0.15/0.23 (1/0.3/0.15). The process of obtaining the heterostructures was studied using UV-Vis spectroscopy. The kinetics of the formation of heterostructures was influenced by the nature of the maleic acid copolymer and noble metal cations used. A high reaction rate was observed in the case of using zinc and gold cations-precursors and a copolymer of maleic acid with N-vinylpyrrolidone as a stabilizer of nanoparticles. The structure of the synthesized polymer-stabilized heterostructures was studied using instrumental methods of analysis-XPS, FTIR, PXRD, and TEM. Under the conditions used, stable colloidal solutions of heterodimers were obtained, and such structure can be converted to a solid state and back without loss of properties.

Structural Significance of Hydrophobic and Hydrogen Bonding Interaction for Nanoscale Hybridization of Antiseptic Miramistin Molecules with Molybdenum Disulfide Monolayers.

This paper reports an easy route to immobilize the antiseptic drug miramistin (MR) molecules between the sheets of molybdenum disulfide, known for excellent photothermal properties. Two hybrid layered compounds (LCs) with regularly alternating monolayers of MR and MoS2, differing in thickness of organic layer are prepared and studied by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations and quantum theory of atoms in molecules (QTAIM) topological analysis. The obtained structural models elucidate the noncovalent interaction network of MR molecules confined in the two-dimensional spacing surrounded by sulfide sheets. It emerged that the characteristic folded geometry of MR molecule previously evidenced for pure miramistin is preserved in the hybrid structures. Quantification of the energetics of bonding interactions unveils that the most important contribution to structure stabilization of both compounds is provided by the weak but numerous CH…S bonding contacts. They are accompanied by the intra- and inter-molecular interactions within the MR layers, with dominating bonding effect of intermolecular hydrophobic interaction. The results obtained in the models provide a comprehensive understanding of the driving forces controlling the assembly of MR and MoS2 and may lead towards the development of novel promising MoS2-based photothermal therapeutic agents.

Water Saturated with Pressurized CO2 as a Tool to Create Various 3D Morphologies of Composites Based on Chitosan and Copper Nanoparticles.

Methods for creating various 3D morphologies of composites based on chitosan and copper nanoparticles stabilized by it in carbonic acid solutions formed under high pressure of saturating CO2 were developed. This work includes a comprehensive analysis of the regularities of copper nanoparticles stabilization and reduction with chitosan, studied by IR and UV-vis spectroscopies, XPS, TEM and rheology. Chitosan can partially reduce Cu2+ ions in aqueous solutions to small-sized, spherical copper nanoparticles with a low degree of polydispersity; the process is accompanied by the formation of an elastic polymer hydrogel. The resulting composites demonstrate antimicrobial activity against both fungi and bacteria. Exposing the hydrogels to the mixture of He or H2 gases and CO2 fluid under high pressure makes it possible to increase the porosity of hydrogels significantly, as well as decrease their pore size. Composite capsules show sufficient resistance to various conditions and reusable catalytic activity in the reduction of nitrobenzene to aniline reaction. The relative simplicity of the proposed method and at the same time its profound advantages (such as environmental friendliness, extra purity) indicate an interesting role of this study for various applications of materials based on chitosan and metals.

Anionic Polymerization of Para-Diethynylbenzene: Synthesis of a Strictly Linear Polymer.

Anionic homo- and copolymerization of p-diethynylbenzene in the presence of n-BuLi in polar solvents was carried out. The use of hexamethylphosphortriamide (HMPA) makes it possible to synthesize a completely linear soluble polymer that does not have branching and phenylene fragments. A copolymer of p-diethynylbenzene with diphenyldiacetylene was synthesized. Homo- and copolymers of p-diethynylbenzene have high thermo- and thermo-oxidative stability. By the interaction of side reactive ethynylphenylene groups with various reagents, it is proposed to synthesize clusters along the conducting chain of poly-p-diethynylbenzene. Due to presenting C≡CH side groups, boron, copper, and cobalt derivatives were synthesized. It is shown that not all theoretically possible stereoisomers can be formed as a result of the polymerization. The application of p-diethynylbenzene polymers for the modification of industrial samples of epoxy novolac resin, oligoester acrylates, and carbon fibers has been demonstrated.

Green approach for fabrication of bacterial cellulose-chitosan composites in the solutions of carbonic acid under high pressure CO2.

The functionalization of the bacterial cellulose (BC) surface with a chitosan biopolymer to expand the areas of possible applications of the modified BC is an important scientific task. The creation of such composites in the carbonic acid solutions that were performed in this work has several advantages in terms of being biocompatible and eco-friendly. Quantitative analysis of chitosan content in the composite was conducted by tritium-labeled chitosan radioactivity detection method and this showed three times increased chitosan loading. Different physicochemical methods showed successful incorporation of chitosan into the BC matrix and interaction with it through hydrogen bonds. Microscopy results showed that the chitosan coating with a thickness of around 10 nm was formed in the bulk of BC, covering each microfibril. It was found that the inner specific surface area increased 1.5 times on deposition of chitosan from the solutions in carbonic acid.

New Carbon Nanofiber Composite Materials Containing Lanthanides and Transition Metals Based on Electrospun Polyacrylonitrile for High Temperature Polymer Electrolyte Membrane Fuel Cell Cathodes.

Electrospinning of polyacrylonitrile/DMF dopes containing salts of nickel, cobalt, zirconium, cerium, gadolinium, and samarium, makes it possible to obtain precursor nanofiber mats which can be subsequently converted into carbon nanofiber (CNF) composites by pyrolysis at 1000-1200 °C. Inorganic additives were found to be uniformly distributed in CNFs. Metal states were investigated by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). According to XPS in CNF/Zr/Ni/Gd composites pyrolyzed at 1000 °C, nickel exists as Ni0 and as Ni2+, gadolinium as Gd3+, and zirconium as Zr4+. If CNF/Zr/Ni/Gd is pyrolyzed at 1200 °C, nickel exists only as Ni0. For CNF/Sm/Co composite, samarium is in Sm3+ form when cobalt is not found on a surface. For CNF/Zr/Ni/Ce composite, cerium exists both as Ce4+ and as Ce3+. Composite CNF mats were platinized and tested as cathodes in high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC). Such approach allows to introduce Pt-M and Pt-MOx into CNF, which are more durable compared to carbon black under HT-PEMFC operation. For CNF/Zr/Ni/Gd composite cathode, higher performance in the HT-PEMFC at I >1.2 A cm-2 is achieved due to elimination of mass transfer losses in gas-diffusion electrode compared to commercial Celtec®P1000.

Silver/Chitosan Nanocomposites: Preparation and Characterization and Their Fungicidal Activity against Dairy Cattle Toxicosis Penicillium expansum.

This work aimed to evaluate the fungicide activity of chitosan-silver nanocomposites (Ag-Chit-NCs) against Penicillium expansum from feed samples. The physicochemical properties of nanocomposites were characterized by X-ray fluorescence analysis (XRF), small-angle X-ray scattering (SAXS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The morphological integrity of the nanohybrid was confirmed by electron transmission. By the data of RFA (X-ray fluorescent analysis), the contents of Ag in Ag-chitosan composite were 5.9 w/w%. The size distribution of the Ag nanoparticles incorporated in the chitosan matrix was investigated by SAXS. The main part of the size heterogeneity distribution in the chitosan matrix corresponds to the portion of small particles (3-4 nm). TEM analysis revealed a spherical morphology in the form of non-agglomerated caps, and 72% of the nanoparticles measured up to 4 nm. The minimum inhibitory concentration of NCs was evaluated in petri dishes. Three different concentrations were tested for antifungal activity against the mycotoxigenic P. expansum strain. Changes in the mycelium structure of P. expansum fungi by scanning electron microscopy (SEM) were observed to obtain information about the mode of action of Ag-Chit-NCs. It was shown that NC-Chit-NCs with sizes in the range from 4 to 10 nm have internalized sizes in cells, form agglomerates in the cytoplasm, and bind to cell organelles. Besides, their ability to influence protein and DNA fragmentation was examined in P. expansum. SDS-PAGE explains the apparent cellular protein response to the presence of various Ag-Chit-NCs. The intensity of P. expansum hyphal cell protein lines treated with Ag-Chit-NCs was very thin, indicating that high molecular weight proteins are largely prevented from entering the electrophoretic gel, which reflects cellular protein modification and possible damage caused by the binding of several protein fragments to Ag-Chit-NCs. The current results indicate that Ag-Chit-NCs <10 nm in size have significant antifungal activity against P. expansum, the causative agent of blue mold-contaminated dairy cattle feed.

Plasmon Resonance of Silver Nanoparticles as a Method of Increasing Their Antibacterial Action.

In this article, a series of silver-containing dressings are prepared by metal-vapor synthesis (MVS), and their antibacterial properties are investigated. The antibacterial activity of the dressings containing silver nanoparticles (AgNPs) against some Gram-positive, and Gram-negative microorganisms (Staphylococcus aureus, Staphylococcus haemolyticus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Moraxella spp.) has been determined. Based on the plasmon resonance frequency of these nanoparticles, the frequency of laser irradiation of the dressing was chosen. The gauze bandage examined showed pronounced antibacterial properties, especially to Staphylococcus aureus strain. When 470 nm laser radiation, with a power of 5 mW, was applied for 5 min, 4 h after inoculating the Petri dish, and placing a bandage containing silver nanoparticles on it, the antibacterial effect of the latter significantly increased-both against Gram-positive and Gram-negative microorganisms. The structure and chemical composition of the silver-containing nanocomposite were studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). The synthesized AgNPs demonstrate narrow and monomodal particle size distribution with an average size of 1.75 nm. Atoms of metal in Ag/bandage system are mainly in Ag° state, and the oxidized atoms are in the form of Ag-Ag-O groups.

Probing of complex carbon nanofiber paper as gas-diffusion electrode for high temperature polymer electrolyte membrane fuel cell.

The development of fuel cells is an important part of alternative energy studies. High-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) is a very promising and commercialized type of fuel cell since it allows the use of hydrogen contaminated with CO. However, current advances in HT-PEMFC are based on searching for more sustainable materials for the membrane electrode assembly. The key issue is to find new, more stable carbonaceous Pt-electrocatalyst supports instead of the traditional carbon black powder. In the present study, we primarily demonstrate a new electrode design concept. Complex carbon nanofiber paper (CNFP) electrodes, obtained by polyacrylonitrile (PAN) electrospinning with further pyrolysis at 900-1200 °C, are suitable for platinum deposition and were probed as the gas-diffusion electrode for HT-PEMFC. Complex composite electrodes were obtained by introducing zirconium and nickel salts into the electrospinning PAN solution. After pyrolysis, ZrO x and Ni(0) nanoparticles were distributed in the CNFP throughout the whole nanofiber volume, as it is seen in the high-resolution transmission electron microscopy images. The samples were thoroughly studied by X-ray photoelectron, Raman and impedance spectroscopy, cyclic voltammetry, and elemental analysis. The MEAs designed on platinized composite CNFPs demonstrate higher performance at 180 °C compared to non-composite ones and are comparable with commercial Celtec® P1000.