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The rational design of composites based on graphene/metal oxides is one of the pillars for advancing their application in various practical fields, particularly gas sensing. In this study, a uniform distribution of ZnO nanoparticles (NPs) through the graphene layer was achieved, taking advantage of amine functionalization. The beneficial effect of amine groups on the arrangement of ZnO NPs and the efficiency of their immobilization was revealed by core-level spectroscopy, pointing out strong ionic bonding between the aminated graphene (AmG) and ZnO. The stability of the resulting Am-ZnO nanocomposite was confirmed by demonstrating that its morphology remains unchanged even after prolonged heating up to 350 °C, as observed by electron microscopy. On-chip multisensor arrays composed of both AmG and Am-ZnO were fabricated and thoroughly tested, showing almost tenfold enhancement of the chemiresistive response upon decorating the AmG layer with ZnO nanoparticles, due to the formation of p-n heterojunctions. Operating at room temperature, the fabricated multisensor chips exhibited high robustness and a detection limit of 3.6 ppm and 5.1 ppm for ammonia and ethanol, respectively. Precise identification of the studied analytes was achieved by employing the pattern recognition technique based on linear discriminant analysis to process the acquired multisensor response.

During operation, cables of overhead power lines (OPLs) are exposed to the impact that differs in separate parts of the OPL span due to the different responses of cables near the clamps and far from them. This paper presents the results of a study of aluminum and steel wires cut from such separate parts of ACSR cables before and after exploitation. Structural, microstructural, and elastic–microplastic properties of wires and their changes during operation were studied through optical microscopy, energy-dispersive X-ray microanalysis, electron backscattering diffraction, X-ray diffraction, densitometry, and acoustic measurements. The characteristics of the properties of the wires along the span were found to change in a coordinated manner. Numerical estimates of the influence of the steel core on aging the ACSR cable were obtained. Changes in the properties of the wires, as well as oxidization and corrosion of their near-surface layers, were studied in detail. Quantitative values of the characteristics of properties, the most distant from those observed in the new wires, were revealed for samples of aluminum and steel wires cut from the cable at 1/4 span and near clamps. It is assumed that these cable parts should be the most crucial for cable durability.

The facile synthesis of biografted 2D derivatives complemented by a nuanced understanding of their properties are keystones for advancements in biosensing technologies. Herein, we thoroughly examine the feasibility of aminated graphene as a platform for the covalent conjugation of monoclonal antibodies towards human IgG immunoglobulins. Applying core-level spectroscopy methods, namely X-ray photoelectron and absorption spectroscopies, we delve into the chemistry and its effect on the electronic structure of the aminated graphene prior to and after the immobilization of monoclonal antibodies. Furthermore, the alterations in the morphology of the graphene layers upon the applied derivatization protocols are assessed by electron microscopy techniques. Chemiresistive biosensors composed of the aerosol-deposited layers of the aminated graphene with the conjugated antibodies are fabricated and tested, demonstrating a selective response towards IgM immunoglobulins with a limit of detection as low as 10 pg/mL. Taken together, these findings advance and outline graphene derivatives’ application in biosensing as well as hint at the features of the alterations of graphene morphology and physics upon its functionalization and further covalent grafting by biomolecules.

Single Al wires from unused AAAC (A50) cables were studied after laboratory fatigue testing, which simulated processes arising in these wires during their operation in the cables of overhead power lines (OPLs) and are valuable for predicting the lifespan of cables of OPLs. These wires, which were either fractured during testing (maximum loads—149.4–155.9 MPa; number of cycles till rupture—83,656–280,863) or remained intact, were examined by X-ray diffraction, electron backscatter diffraction, densitometry, and acoustic methods. An analysis of the structural, microstructural, and elastic-microplastic properties of the wires revealed common characteristics inherent in the samples after operation in OPLs and after fatigue tests, namely a decrease in the integral and near-surface layer (NSL) densities of the wires, a decrease in their Young’s modulus and microplastic stress, and an increase in the decrement. However, the tests did not fully reproduce the environmental influence, since in contrast to the natural conditions, no aluminum-oxide crystallites were formed in NSLs in tests and the microstructure was different. A comparison of the characteristics of the broken and unbroken wires allows us to suggest that the fastening locations of the wires are crucial for their possible failure.

Ekaterina A Skomorokhova,1,2 Tatiana P Sankova,3 Iurii A Orlov,1 Andrew N Savelev,3 Daria N Magazenkova,3 Mikhail G Pliss,4,5 Alexey N Skvortsov,3 Ilya M Sosnin,1 Demid A Kirilenko,1,6 Ivan V Grishchuk,3 Elena I Sakhenberg,7 Elena V Polishchuk,1,8 Pavel N Brunkov,1,6 Alexey E Romanov,1,6 Ludmila V Puchkova,1– 3 Ekaterina Yu Ilyechova1,2 1International Research Center of Functional Materials and Devices of Optoelectronics, ITMO University, St. Petersburg, Russia; 2Department of Molecular Genetics, Research Institute of Experimental Medicine, St. Petersburg, Russia; 3Higher Engineering Physics School of the Institute of Physics, Nanotechnology and Telecommunications, Peter the Great St. Petersburg Polytechnic University, St. Petersburg, Russia; 4Department of Experimental Physiology and Pharmacology, Almazov National Medical Research Centre, St. Petersburg, Russia; 5Laboratory of Blood Circulation Biophysics, Pavlov First Saint Petersburg State Medical University, St. Petersburg, Russia; 6Center of Nanoheterostructures Physics, Ioffe Institute, Russian Academy of Sciences, St. Petersburg, Russia; 7Laboratory of Cell Protection Mechanisms, Institute of Cytology, Russian Academy of Sciences, St. Petersburg, Russia; 8Telethon Institute of Genetics and Medicine, Pozzuoli, Naples, ItalyCorrespondence: Ekaterina Yu Ilyechova Department of Molecular GeneticsResearch Institute of Experimental Medicine, Acad. Pavlov Street, 12, St. Petersburg 197376, RussiaTel +79217605274Fax +78122322307Email ilichevaey@itmo.ruPurpose: The ability of silver nanoparticles (AgNPs) of different sizes to influence copper metabolism in mice is assessed.Materials and Methods: AgNPs with diameters of 10, 20, and 75 nm were fabricated through a chemical reduction of silver nitrate and characterized by UV/Vis spectrometry, transmission and scanning electronic microscopy, and laser diffractometry. To test their bioactivity, Escherichia coli cells, cultured A549 cells, and C57Bl/6 mice were used. The antibacterial activity of AgNPs was determined by inhibition of colony-forming ability, and cytotoxicity was tested using the MTT test (viability, %). Ceruloplasmin (Cp, the major mammalian extracellular copper-containing protein) concentration and enzymatic activity were measured using gel-assay analyses and WB, respectively. In vitro binding of AgNPs with serum proteins was monitored with UV/Vis spectroscopy. Metal concentrations were measured using atomic absorption spectrometry.Results: The smallest AgNPs displayed the largest dose- and time-dependent antibacterial activity. All nanoparticles inhibited the metabolic activity of A549 cells in accordance with dose and time, but no correlation between cytotoxicity and nanoparticle size was found. Nanosilver was not uniformly distributed through the body of mice intraperitoneally treated with low AgNP concentrations. It was predominantly accumulated in liver. There, nanosilver was included in ceruloplasmin, and Ag-ceruloplasmin with low oxidase activity level was formed. Larger nanoparticles more effectively interfered with the copper metabolism of mice. Large AgNPs quickly induced a drop of blood serum oxidase activity to practically zero, but after cancellation of AgNP treatment, the activity was rapidly restored. A major fraction of the nanosilver was excreted in the bile with Cp. Nanosilver was bound by alpha-2-macroglobulin in vitro and in vivo, but silver did not substitute for the copper atoms of Cp in vitro.Conclusion: The data showed that even at low concentrations, AgNPs influence murine copper metabolism in size-dependent manner. This property negatively correlated with the antibacterial activity of AgNPs.Keywords: silver nanoparticles, copper status, ceruloplasmin, alpha-2-macroglobulin, bile, urine

The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene’s electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core-level methods and reveal the modification of their valence band (VB) upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X-ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene’s VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core-level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical properties.

In modern economic infrastructure, Al cables of overhead power transmission lines are used both without and with a steel core (respectively, all aluminum alloy conductor (AAAC) and aluminum conductor steel reinforced (ACSR) cables). In this article, the changes in structural, microstructural, and elastic-microplastic properties have been analyzed for the outer wires of the AAAC (A50) and ACSR cables (AC50/8 cables with a steel core of ~8 mm2 cross-section, hereinafter referred to as AC50) with the cross-section of the stranded conductor of ~50 mm2, which were in operation for 0–20 years in the Volgograd region of Russia. Using the techniques of X-ray diffraction, electron backscattered diffraction, densitometry, and the acoustic method, the structural and microstructural features of the wires have been compared and found to be correlated with their elastic-microplastic properties. It has been ascertained that the presence of a steel core in AC50 leads to a decrease in the defectiveness of the near-surface layer of their aluminum wires. Compared with A50 cables, the development of void defects in the near-surface layer of Al-wires of AC50 cables slows down (by ~1 year with a service life of ~10 years and by ~3 years with a service life of ~20 years).

Overhead power-transmission lines are one of the most important components of modern infrastructure. Their service life is determined by the state of the near-surface defect layers (NSDLs) of wires constituting these lines. Both the structure and microstructure of the NSDLs of wires of the AAAC type (All Aluminum Alloy Conductor), which were in operation during 0 (new) to 62 years, were investigated by methods of the X-ray (XRD) and electron back-scattering diffraction, optical microscopy, and resistivity measurements, as well as by means of densitometric and acoustic measurements with layer-by-layer removal of the near-surface material by etching. Two characteristic thicknesses of the NSDLs were obtained, different methods providing close results, namely, ~30–50 μm and ~56–140 μm. According to the mass-density distribution (XRD), these characteristic thicknesses correspond to the depths from the surface where they occur, respectively, ~70% and ~99% of the density drop in comparison with the bulk density value. The rate of increase in NSDL thickness is ~4 μm/year in the interval from 0 to 18 years. Results of investigation of elastic and microplastic properties of wires after removal of ~35 μm of the upper layer are also presented.

The health of the components that make up the cables of power lines, and hence their service life, is governed at the micro level by changes in their structure and microstructure. In this paper, the structure and microstructure of aluminum wires of overhead power transmission lines (without a steel core) of different service life from 0 to 62 years have been investigated by quantitative techniques of X-ray diffraction, diffraction of back-scattered electrons, and the densitometric method. Elastoplastic properties of the wires have been tested by the acoustic-resonance method. A decrease in the Al material density Δρ/ρ∼−0.165% was found in the near-surface layer of ∼36 μm depth and in the bulk of the wires with an increase in the service life from 0 to 18 years. The density decrease is associated with the accumulation of microcracks. The following density increase (Δρ/ρ∼−0.06%) in wires with a service life of 62 years is attributed to the formation of ∼0.7 vol.% of crystalline Al oxides in the near-surface layers of the wires. The nature of the change in the elastic modulus, microplastic flow stress, and decrement indicates complex structural changes correlating with the results obtained by diffraction methods.

Graphene derivatization to either engineer its physical and chemical properties or overcome the problem of the facile synthesis of nanographenes is a subject of significant attention in the nanomaterials research community. In this paper, we propose a facile and scalable method for the synthesis of thiolated graphene via a two-step liquid-phase treatment of graphene oxide (GO). Employing the core-level methods, the introduction of up to 5.1 at.% of thiols is indicated with the simultaneous rise of the C/O ratio to 16.8. The crumpling of the graphene layer upon thiolation without its perforation is pointed out by microscopic and Raman studies. The conductance of thiolated graphene is revealed to be driven by the Mott hopping mechanism with the sheet resistance values of 2.15 kΩ/sq and dependable on the environment. The preliminary results on the chemiresistive effect of these films upon exposure to ethanol vapors in the mix with dry and humid air are shown. Finally, the work function value and valence band structure of thiolated graphene are analyzed. Taken together, the developed method and findings of the morphology and physics of the thiolated graphene guide the further application of this derivative in energy storage, sensing devices, and smart materials.

Iurii A Orlov,1,2 Tatiana P Sankova,1,2 Polina S Babich,3 Ilya M Sosnin,1,4 Ekaterina Yu Ilyechova,1,5 Demid A Kirilenko,1,6 Pavel N Brunkov,1,6 Gennadii L Ataev,3 Alexey E Romanov,1,4,6 Ludmila V Puchkova1,2,5 1International Research and Education Center “Functional materials and devices of optoelectronics and microelectronics”, ITMO University, 2Department of Biophysics, Peter the Great St Petersburg Polytechnic University, 3Department of Zoology, Herzen State Pedagogical University of Russia, St Petersburg, 4Nanocatalysts and Functional Materials Laboratory, Togliatti State University, Togliatti, 5Department of Molecular Genetics, Research Institute of Experimental Medicine, 6Ioffe Institute, St Petersburg, Russia Abstract: Silver nanoparticles (SNPs) are new functional materials that are widely used in biomedical and industrial technologies. Two main features that make SNPs valuable are their strong antibacterial effects and low toxicity to eukaryotes. In this study, SNPs were synthesized using a modified method of reducing the metal ions to their atomic state followed by crystallization. SNPs were characterized by UV/vis spectroscopy, X-ray diffractometry, atomic force microscopy, and transmission electron microscopy (TEM). The SNPs were spherically shaped with an average linear dimension of 20 nm. In aqueous solution, the SNPs were beige-yellow in color, and they formed a black color in bacteria-rich growth media. The toxicity and bioavailability of the SNPs were tested using Escherichia coli cells and C57Bl/6 mice. Although the SNPs displayed bactericidal activity, an E. coli cell strain transformed with an expression plasmid carrying a human CTR1 ectodomain with three motives that bind Cu(II), Cu(I), and Ag(I) demonstrated increased resistance to treatment with SNPs. TEM showed that the SNPs were absorbed by the E. coli cell, and flow cytometry showed that the SNPs induced apoptosis-like death. In mice treated with SNPs (daily intraperitoneal injection of 10 µg SNPs/g body weight over 4 days), the ceruloplasmin (Cp) oxidase activity in the blood serum decreased. However, level of Cp gene expression, the relative contents of the Cp protein in the Golgi complex and in the serum did not change. Treatment with SNPs did not influence the activity of superoxide dismutase 1 in the liver and had no apparent toxic effects in mice. These findings expand the scope of application for the use of new SNPs. The data are discussed in a paradigm, in which the effects of SNPs are caused by the interference of silver ions with copper metabolism. Keywords: silver nanoparticles, bioavailability, apoptosis-like death, mammalian copper metabolism, copper status

New single crystals, based on 2-methylbenzimidazole (MBI), of MBI-phosphite (C16H24N4O7P2), MBI-phosphate-1 (C16H24N4O9P2), and MBI-phosphate-2 (C8H16N2O9P2) were obtained by slow evaporation method from a mixture of alcohol solution of MBI crystals and water solution of phosphorous or phosphoric acids. Crystal structures and chemical compositions were determined by single crystal X-ray diffraction (XRD) analysis and confirmed by XRD of powders and elemental analysis. Raman spectroscopy of new crystals evidences the presence in crystals of MBI-, H3PO3-, or H3PO4- and water molecules. Dielectric properties of crystals reveal strong increase and low frequency dispersion of dielectric constant and losses at heating, indicating the appearance of proton conductivity. At low temperatures in MBI-phosphate-2, an increase of dielectric constant analogous to quantum paraelectric state is observed.

There is much interest in effective copper chelators to correct copper dyshomeostasis in neurodegenerative and oncological diseases. In this study, a recombinant fusion protein for expression in Escherichia coli cells was constructed from glutathione-S-transferase (GST) and the N-terminal domain (ectodomain) of human high affinity copper transporter CTR1 (hNdCTR1), which has three metal-bound motifs. Several biological properties of the GST-hNdCTR1 fusion protein were assessed. It was demonstrated that in cells, the protein was prone to oligomerization, formed inclusion bodies and displayed no toxicity. Treatment of E. coli cells with copper and silver ions reduced cell viability in a dose- and time-dependent manner. Cells expressing GST-hNdCTR1 protein demonstrated resistance to the metal treatments. These cells accumulated silver ions and formed nanoparticles that contained AgCl and metallic silver. In this bacterial population, filamentous bacteria with a length of about 10 µm were often observed. The possibility for the fusion protein carrying extracellular metal binding motifs to integrate into the cell’s copper metabolism and its chelating properties are discussed.