Anatoly Yermakov

Carbon-encapsulated nickel nanoparticles (Ni@C) are of considerable interest for catalysis, biotechnology, and hybrid nanostructures. However, the distribution of carbon between the metallic core and the surrounding shell remains difficult to assess. In this work, we apply 13C NMR spectroscopy to directly probe carbon localization in Ni@C nanocomposites, complemented by reference measurements on hollow carbon shells. Two distinct 13C NMR signals are resolved. One line, centered at zero shift, is assigned to glass-like carbon in the shell. The second line, shifted to higher frequency, exhibits a strong temperature dependence and is attributed to carbon atoms dissolved in the ferromagnetic nickel core. The absence of splitting indicates that these carbon atoms occupy crystallographically equivalent positions, most likely octahedral interstitial sites. After annealing at 1273 K, the shifted line disappears while the magnetization increases markedly, confirming carbon migration from the core to the shell. Magnetization measurements reveal a distribution of Curie temperatures among different nanoparticle fractions, reflecting the inhomogeneous distribution of carbon interstitials within the nickel lattice. These results provide direct experimental evidence for a carbon solid solution within the nickel core and demonstrate the capability of 13C NMR to determine carbon localization in core-shell nanocomposites.

In this paper, the electron and magnetic state of iron placed either on the surface or in the core of TiO₂ nanoparticles were investigated using magnetometric methods, electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. It was demonstrated that the EPR spectra of TiO₂ samples with iron atoms localized both on the surface and in the core of specific features depending on the composition and size of the nanoparticles. Theoretical calculations using the density functional theory (DFT) method demonstrated that the localization of Fe atoms on the surface is characterized by a considerably larger set of atomic configurations as compared to that in the core of TiO₂ nanoparticles. Mössbauer spectra of the samples doped with Fe atoms both on the surface and in the core can be described quite satisfactorily using two and three doublets with different quadrupole splitting, respectively. This probably demonstrates that the Fe atoms on particle surface and in the bulk are in different unlike local surroundings. All iron ions, both on the surface and in the core, were found to be in the Fe³⁺ high-spin state.

This work is devoted to the study of the magnetic properties and Electron Paramagnetic Resonance (EPR) spectroscopy of TiO₂:Fe nanoparticles doped with Al in different structural states. The sol-gel methods have been used to obtain the particles in both crystalline (average size from 3 to 20 nm) and X-ray amorphous states. The electron paramagnetic resonance spectra of crystalline samples TiO₂:Fe doped with aluminum besides a resonance line with g-factor ~2 exhibit a small signal with a g-factor of 4.3 from Fe³⁺ ions with rhombohedral distortions. The fraction of Fe³⁺ with rhombohedral distortions increases with increasing aluminum content. For the amorphous state at Al doping, the resonance with a g-factor of 4.3 is completely dominant in the electron paramagnetic resonance spectrum. The density functional theory calculation shows that aluminum prefers to be localized near iron ions, distorting the nearest Fe³⁺ environment. The complex integral electron paramagnetic resonance spectrum of all samples was fitted with sufficient accuracy by three separate resonance lines with different widths and intensities. The temperature behavior of the electron paramagnetic resonance spectrum can be described by the coexistence of paramagnetic centers (isolated Fe³⁺ ions including dipole-dipole interactions) and iron clusters with negative exchange interactions.

The high mortality rate caused by atherosclerosis makes it necessary to constantly search for new and better treatments. In previous reports, chemically modified carbon-coated iron nanoparticles (Fe@C NPs) have been demonstrated a high biocompatibility and promising anti-plaque properties. To further investigate these effects, the interaction of these nanoparticles with the adipose tissue of Wistar rats (in vivo) and human atherosclerotic plaques (ex vivo) was studied. For the in vivo study, cobalt–chromium (CoCr) alloy tubes, which are used for coronary stent manufacturing, were prepared with a coating of polylactic acid (PLA) which contained either modified or non-modified Fe@C NPs in a 5% by weight concentration. The tubes were implanted into an area of subcutaneous fat in Wistar rats, where changes in the histological structure and functional properties of the surrounding tissue were observed in the case of coatings modified with Fe@C NPs. For the ex vivo study, freshly explanted human atherosclerotic plaques were treated in the physiological solution with doses of modified Fe@C NPs, with mass equal to 5% or 25% relative to the plaques. This treatment resulted in the release of cholesterol-like compounds from the surface of the plaques into the solution, thus proving a pronounced destructive effect on the plaque structure. Chemically modified Fe@C NPs, when used as an anti-atherosclerosis agent, were able to activate the activity of macrophages, which could lead to the destruction of atherosclerotic plaques structures. These findings could prove the fabrication of next-generation vascular stents with built-in anti-atherosclerotic agents.

Electron paramagnetic resonance, X‐ray photoelectron spectroscopy, field dependence of magnetization, X‐ray diffraction, and transmission electron microscopy are applied for the characterization of Al‐doped TiO₂ nanopowders with Fe impurities synthesized by the autoclave‐assisted hydrothermal method and annealed in vacuum or in hydrogen. The sizes of the TiO₂:(Al, Fe) nanoparticles are estimated to be about 10–20 nm. It is proposed that Al ions are presumably placed in the TiO₂ lattice in interstitial positions. Moreover, Fe³⁺ ions can occupy tetrahedral positions of Ti⁴⁺ ions as a result of Al‐doping. The results suggest that Al‐doped TiO₂ nanopowders with Fe impurities annealed in vacuum or hydrogen display both intrinsic and extrinsic ferromagnetic properties.

The surface functionalization of magnetic nanoparticles improves their physicochemical properties and applicability in biomedicine. Natural polymers, including proteins, are prospective coatings capable of increasing the stability, biocompatibility, and transverse relaxivity (r2) of magnetic nanoparticles. In this work, we functionalized the nanoclusters of carbon-coated iron nanoparticles with four proteins: bovine serum albumin, casein, and gelatins A and B, and we conducted a comprehensive comparative study of their properties essential to applications in biosensing. First, we examined the influence of environmental parameters on the size of prepared nanoclusters and synthesized protein-coated nanoclusters with a tunable size. Second, we showed that protein coating does not significantly influence the r2 relaxivity of clustered nanoparticles; however, the uniform distribution of individual nanoparticles inside the protein coating facilitates increased relaxivity. Third, we demonstrated the applicability of the obtained nanoclusters in biosensing by the development of a nuclear-magnetic-resonance-based immunoassay for the quantification of antibodies against tetanus toxoid. Fourth, the protein coronas of nanoclusters were studied using SDS-PAGE and Bradford protein assay. Finally, we compared the colloidal stability at various pH values and ionic strengths and in relevant complex media (i.e., blood serum, plasma, milk, juice, beer, and red wine), as well as the heat stability, resistance to proteolytic digestion, and shelf-life of protein-coated nanoclusters.

Nickel nanoparticles coated with few layers of carbon have been embedded into the polydimethylsiloxane (PDMS) matrix in concentrations up to 11 vol %. Dielectric and magnetic properties of composite materials have been studied in wide frequency (20 Hz–1 MHz) and temperature (130–430 K) ranges. It was demonstrated that the temperature behavior of dielectric properties is determined by glass transitions in the PDSM matrix below 200 K and the Maxwell–Wagner relaxation above room temperature. The possibility of using fabricated composites on the basis of the PDMS matrix for producing a wide range of passive electromagnetic components, such as frequency-selective filters, wide-band detectors/sensors of a bolometric type, and even electromagnetic “black holes” is also discussed.