New Publications

N-Silylmethyl-2-(1-Naphthyl)Acetamides: Synthesis, Structure and Computational Screening

Soldatenko, A.S., Molokeev, M.S., Lazareva, N.F.// Current Organic Chemistry//

Synthesis of new hybrid organosilicon compounds based on the amides 1- naphthylacetic acid was described. N-Organyl-2-(1-naphthyl)-N-[(triethoxysilyl)methyl]- acetamides were obtained by the reaction of 1-naphthylacetyl chloride with α-silylamines RNHCH2Si(OEt)3 (R = Me, i-Pr and Ph). Their subsequent interaction with N(CH2CH2OH)3 led to the formation of N-organyl-2-(1-naphthyl)-N-(silatranylmethyl)acetamides. The structure of these hybrid compounds was characterized by 1H, 13C, and 29Si NMR spectroscopy. The structure of N-methyl- and N-isopropyl-2-(1-naphthyl)-N-(silatranylmethy)acetamides was confirmed by X-ray diffraction analysis. Results of computational screening showed that these silatranes are bioavailable and have drug-likeness.

Cherenkov second harmonic generation of femtosecond laser pulses in a homogeneous nonlinear crystal

A M Vyunishev and A S Chirkin// Laser Physics//

DOI 10.1088/1555-6611/ad5156

In experiments on second harmonic (SH) generation (SHG), a conical structure of radiation has been observed. In the present study, a non-stationary theory of SH excitation of ultrashort laser pulses with phase modulation has been developed, which explains the properties of such a structure as Cherenkov radiation. Under phase-mismatched interactions, a maximum of the SH spectrum is observed at the Cherenkov angle, which is determined by the ratio of the SH and laser radiation phase velocities. It is shown that tightly focused laser beams are preferred to observe Cherenkov SHG. The SH spectral width depends on the group velocity mismatch and is more complicated on the excited radiation spectrum. The SH energy can be proportional to the crystal length or group delay length depending on their ratio. We also demonstrate that a complex angular distribution of spectral components (an angular chirp) appears within the SH cross-section.

Crystal structure and thermoelectric properties of mechanically activated LaCoO 3

Vyacheslav A. Dudnikov a, Yuri S. Orlov a b, Leonid A. Solovyov c, Sergey N. Vereshchagin c, Yuri N. Ustyuzhanin a, Sergey M. Zharkov a b, Galina M. Zeer b, Andrey A. Borus a, Vitaly S. Bondarev a b, Sergey G. Ovchinnikov// Journal Of The Taiwan Institute Of Chemical Engineers//

Crystal structure of rare-earth LaCoO3 cobalt oxide subjected to high energy mechanical activation has been studied. In the temperature range of 300–800 K, the electrical conductivity and Seebeck coefficient were measured. Thermal conductivity was measured at 300–480 K.

Bioluminescent aptamer-based microassay for detection of melanoma inhibitory activity protein (MIA)

Bashmakova, E.E., Kudryavtsev, A.N., Tupikin, A.E., (...), Sokolov, A.E., Frank, L.A.// Analytical Methods//


Melanoma inhibitory activity protein (MIA) does obviously offer the potential to reveal clinical manifestations of melanoma. Despite a pressing need for effective diagnosis of this highly fatal disease, there are no clinically approved MIA detection ELISA kits available. A recommended MIA threshold has not yet been defined, mostly by reason of variability in immunoglobulins' affinity and stability, the difference in sample preparation and assay conditions. Here we present a pair of high-affinity DNA aptamers developed as an alternative recognition and binding element for MIA detection. Their stability and reproducible synthesis are expected to ensure this analysis under standard conditions. The devised aptamer-based solid-phase microassay of model standard and control human sera involves luciferase NLuc as a highly sensitive reporter. Bioluminescence dependence on MIA concentration ranges in a linear manner from 2.5 to 250 ng mL−1, providing a MIA detection limit of 1.67 ± 0.57 ng mL

Majorana Modes and Fano Resonances in Aharonov–Bohm Ring with Topologically Nontrivial Superconducting Bridge

Aksenov, S.V., Kagan, M.Y.// Journal of Low Temperature Physics//

We study different resonances (first of all of the Fano type) in the interference device formed by the Aharonov–Bohm ring with superconducting (SC) wire in the topologically nontrivial state playing a role of a bridge between top and bottom arms. We analyze Majorana modes on the ends of the SC wire and show that the collapse of the additional Fano resonance, that is initially induced by transport scheme asymmetry, is connected with the increase of the length of the bridge when the binding energy of the Majorana end modes tends to zero. In local transport regime, the Fano resonances are stable against the change of the transport symmetry. The reasons of both collapse and sustainability are analyzed using a spinless toy model including the Kitaev chain.

Enhancement of the magnetoelectric effect in the Bi2Fe4O9/BiFeO3 composite as a result of dipole and migration polarization in mullite

Udod, L.V., Aplesnin, S.S., Zelenov, F.V., (...), Molokeev, M.S., Romanova, O.B.// Journal of Materials Science//

The effect of the size of Bi2Fe4O9 and BiFeO3 nanoparticles on the magnetoelectric interaction in the Bi2Fe4O9/BiFeO3 composite with a percentage ratio of 67/33 has been studied. The electrostriction and electric polarization on electric and magnetic field in wide temperature range has been measured. The hysteresis of the polarization and I‒V characteristics has been found. Temperature ranges with activation and hopping types of conductivity have been found. The mechanism of electric polarization and the crossover temperature from dipole polarization to migration polarization at 260 K have been established. Linear and quadratic contributions to the magnetoelectric effect have been found. Below 120 K the linear contribution is an order of magnitude greater than the quadratic contribution and above 240 K the quadratic contribution to the ME effect prevails. Models have been proposed to explain the enhancement of the magnetoelectric effect as a result of the migration polarization in mullite and linear magnetoelectric effect in bismuth ferrite. The correlation of temperatures of the extremum of the temperature coefficient of the electrical resistance and the magnetic phase transition in mullite at 260 K indicates a polaron-type conductivity and a strong electron‒phonon interaction. A change in the sign of the electrostriction coefficient upon heating and the compression temperature of the composite in an electric field was found.

Kondo effects in variable-valence manganese-substituted thulium selenide

Romanova, O.B., Aplesnin, S.S., Sitnikov, M.N., (...), Zhivulko, A.M., Yanushkevich, K.I.// Ceramics International//

The MnXTm1‒XSe (0 ≤ Х ≤ 0.2) solid solutions have been first synthesized and their structural, magnetic, and transport properties have been studied in the temperature range of 80–1000 K and magnetic fields of up to 12 kOe. The surface morphology of the samples has been examined and the chemical analysis has been carried out. It is shown that the valence change with the increasing substitution concentration is accompanied by a change in the lattice parameter and a decrease in the magnetic moment of the samples. The Kondo temperatures caused by the manganese and thulium subsystem have been found in the low- and room-temperature regions. The temperature of localization of small-radius polarons has been determined. A drastic decrease in the relaxation time in the range of the manganese ion percolation through the lattice in the MnXTm1‒XSe system has been established. The change of the current carrier type upon variation in the temperature and substitution concentration was determined from the Seebeck coefficient. A high-temperature extremum of thermopower was revealed, which is explained within the framework of the Anderson model.

Resistive switching properties of a nanostructured layer of mixed ZrO2 phases obtained in low-pressure arc discharge plasma

Karpov, I.V., Fedorov, L.Y., Abkaryan, A.K., (...), Nemtsev, I.V., Irtyugo, L.A.// Vacuum//

The controlled vacuum-arc synthesis of zirconium dioxide (ZrO2) nanoparticles is considered, which makes it possible to regulate the percentage ratio of the monoclinic and tetragonal phases. The samples were characterized using XRD analysis, SEM, HRTEM analysis, FT-IR analysis, TG/DTA analysis and EPR spectroscopy. It has been established that the formation of the tetragonal phase is associated with the formation of a large number of oxygen vacancies formed due to high-speed quenching of nanoparticles. Reducing the operating gas pressure in a vacuum chamber from 180 Pa to 30 Pa makes it possible to obtain nanoparticles up to 2 nm in size. The synthesized ZrO2 nanoparticles do not contain foreign impurities and when heated, the weight loss is up to 7 %. The process of local resistive switching in the contact of an atomic force microscope (AFM) probe to a nanostructured ZrO(2-x) layer on a conducting substrate has been studied. Cyclic current-voltage characteristics demonstrate the existence of stable states of high and low resistance, switched by changing the polarity of the applied voltage. The coexistence of the m- and t-ZrO2 phases (and the resulting oxygen nonstoichiometry in the interboundary regions) provides conditions for the formation/destruction of a filament from oxygen vacancies, which determine the conductivity of the dielectric in the LRS state

Temperature/Component-Dependent Luminescence in Lead-Free Hybrid Metal Halides for Temperature Sensor and Anti-Counterfeiting

Zhou, G., Wang, Y., Mao, Y., (...), Xia, Z., Zhang, X.-M.// Advanced Functional Materials//

Hybrid metal halides (HMHs) have emerged as a promising platform for optically functional crystalline materials, but it is extremely challenging to thoroughly elucidate the electron transition coupled to additional ligand emission. Herein, to discover sequences of lead-free HMHs with distinct optically active metal cations are aimed, that is, Sb3+ (5s2) with the lone-pair electron configuration and In3+ (4d10) with the fully-filled electron configuration. (Me2NH2)4MCl6·Cl (Me = −CH3M = Sb, In) exhibits the superior temperature/component-dependent luminescence behaviors resulting from the competition transition between triplet-states (Tn-S0) self-trapped excitons (STEs) of inorganic units and singlet-state (S1-S0) of organic cations, which is manipulated by the optical activity levels of [SbCl6]3− and [InCl6]3−. The bonding differences between Sb3+/In3+ and Cl in terms of electronic excitation and hybridization are emphasized, and the different electron-transition mechanisms are established according to the PL spectra at the extreme temperature of 5 to 305 K and theoretical calculations. By fine-tuning the B-site Sb3+/In3+ alloying, the photoluminescence quantum yield (PLQY = 81.5%) and stability are optimized at 20% alloying of Sb3+. This research sheds light on the rules governing PL behaviors of HMHs, as well as exploring the optical-functional application of aviation temperature sensors and access-control systems.

Near-unity PLQY and high anti-thermal quenching red luminescence from one-dimensional hybrid manganese chloride for efficient and stable white light-emitting diodes

Su, B., Molokeev, M.S., Chen, R., Zhang, T.// Journal of Materials Chemistry C//

The discovery of novel Mn2+-based metal halides with excellent luminescence properties and thermostability is particularly of great importance for solid-state lighting (SSL). Herein, a novel one-dimensional hybrid manganese chloride (TMA)MnCl3 of a hexagonal system with a P63/m space group is synthesized via a simple saturation crystallization method. Under 443 nm excitation, (TMA)MnCl3 single crystals exhibit a strong broad-band red emission peak at 645 nm originating from the 4T1 → 6A1 transition of Mn2+ ions with a full width at half maximum of 99 nm and a photoluminescence quantum yield (PLQY) of 98.6%. Moreover, (TMA)MnCl3 shows a high anti-thermal quenching behavior, and the integrated PL intensity still retains 100% of the initial intensity measured at 300 °C, caused by the high structural rigidity. Benefiting from its strong blue light excitation, high PLQY, and excellent thermal stability, a stable white light-emitting diode device is fabricated by combining a 465 nm blue LED chip, green-emitting Lu3Al5O12:Ce3+ and the (TMA)MnCl3 red phosphor with a high color rendering index of 94.3% and a correlated color temperature of 3995 K. This work develops a novel hybrid manganese chloride red-emitter and paves a new path to explore high-performance phosphors excited by blue light for SSL.

Unraveling dynamic Jahn-Teller effect and magnetism in FeTiF6×6H2O single crystal

Platunov, M.S., Fedorova, N.A., Pyastolova, Y.V., (...), Tomilin, F.N., Dubrovskiy, A.A.// Journal of Alloys and Compounds//

Hydrated iron fluoridotitanate (FeTiF6 × 6 H2O) single crystals are fascinating magnetic materials with unique properties. To understand the underlying mechanisms, this study combines X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) techniques, complemented by density functional theory (DFT) calculations. Polarization-dependent X-ray absorption spectroscopy, encompassing XANES and XMCD, is a powerful technique for probing the local structures and magnetic properties of materials. It is element-selective, bulk-sensitive, and compatible with a wide range of experimental conditions. In this study, we used XANES and XMCD spectroscopies to investigate the local structures and magnetic properties of Fe and Ti in FeTiF6 × 6 H2O single crystals. XANES analysis revealed distinct local environments around Fe and Ti, providing insights into their coordination environments. Element-selective magnetization measurement at the Fe K-edge demonstrated that iron sites in the oxidation state Fe2+ have an unambiguous paramagnetic contribution to the magnetization along the b-axis. Notably, the absence of an XMCD signal at the Ti K-edge confirmed the absence of a magnetic moment in Ti atoms within the crystal. DFT calculations corroborate the experimental findings and provide insights into the electronic structure and magnetic interactions. The combined results provide a comprehensive understanding of the dynamic Jahn-Teller effect in FeTiF6 × 6 H2O single crystals, highlighting the significance of polarization-dependent X-ray absorption spectroscopy in unraveling the intricate magnetic behavior of such materials. This study contributes to the fundamental understanding of magnetism in these materials and paves the way for the development of novel magnetic materials with tailored properties.

Biocompatible Systems for Controlled Delivery of Antiseptics for Topical Application

Vladimirova, A.V., Murueva, A.V., Shershneva, A.M., (...), Shabanov, A.V., Shishatskaya, E.I.// Journal of Siberian Federal University - Biology//

Controlled drug delivery is one of the frontier areas of science, which uses an interdisciplinary approach. The delivery systems offer numerous advantages over conventional dosage forms, such as improved efficacy and patient compatibility, reduced toxicity, and ease of use. Such systems often use micro- and nanoparticles as carriers for drugs, the prolonged effect of which is achieved due to the controlled slow release of the encapsulated drug. This study investigated the effects of encapsulation of various antiseptics (brilliant green, miramistin, and furacilin) and the chemical composition of the polymer on the yield, structure, size, drug release kinetics, and antibacterial activity of microparticles produced from resorbable polyesters of microbiological origin, polyhydroxyalkanoates. Microparticles with a 5.6–94.8 μm diameter were produced. The form of the active substance molecule has been found to be the most significant factor affecting the characteristics of polyhydroxyalkanoate microparticles. The surface structure of particles is rather determined by the chemical composition of the polymer, and the release kinetics to the model medium depends on the encapsulated drug. Microparticles based on PHAs loaded with brilliant green and furacilin showed antibacterial effects in S. aureus and E. coli cultures. The study demonstrated that microparticles with antiseptics encapsulated in them have potential as prolonged drug delivery systems and are of interest for further research

Structure, magnetic and magnetocaloric properties of the Mn5Ge3 thin film grown on Si(111)

Tarasov, A.S., Komogortsev, S.V., Lukyanenko, A.V., (...), Varnakov, S.N., Volkov, N.V.// Journal of Materials Science//

Mn5Ge3 is a ferromagnetic hexagonal crystal promising for spintronics and magnetocalorics. A systematic study and analysis of the magnetic properties of the Mn5Ge3 thin film grown on Si(111) were performed. The magnetic anisotropy of the film is determined by the shape anisotropy and the easy magnetization axis aligned along the c axis of the crystal. The uniaxial anisotropy constant Ku fully corresponds to that for a bulk single crystal, which indicates that c axis coincides with film normal. Mn5Ge3 film demonstrates high saturation magnetization MS = 900 emu/cm3 (900 kA/m) at T = 100 K and magnetocaloric effect ΔS = 3.16 ± 0.22 J kg−1 K−1 at 300 K and B = 1.5 T. ΔS is comparable to that for multicomponent or Gd rare earth films. Furthermore, a different anisotropy of the magnetocaloric effect compared to bulk Mn5Ge3 was found, which may be related to the anisotropy of the film shape and, possibly, to the domain structure. The results obtained are promising for the design and development of magnetocaloric, spintronic, and spin-caloritronic devices on a silicon platform.

Fe3O4/Au nanocomposites: Characterization and cytotoxicity effects in vitro

Yaroslavtsev, R.N., Tyumentseva, A.V., Velikanov, D.A., (...), Volochaev, M.N., Stolyar, S.V.// Materials Chemistry and Physics//

Magnetic nanocomposites containing iron oxide and gold components take great attention last years because of their relative biocompatibility and the ability to combine the magnetic properties of iron and the chemical bonding properties of gold for the possible drug delivery or diagnostics for various diseases. However, such particles have some toxicity to living cells, and the effect depends on many factors, including size, shape, the ratio of components in the composites, and the type of cells affected. And thus, the search for compositions and technologies for producing iron-gold particles with improved properties and reduced cytotoxicity remains relevant. The aim of the study was to synthesize and characterize Fe3O4/Au nanocomposites and evaluate their influence on living cells using the example of cell line HEK293.

Fe3O4 nanoparticles (NPs) were synthesized by co-precipitation of Fe2+/Fe3+ water solution in alkaline conditions and then boiled with HAuCl4 in 0.1 M sodium citrate. The NPs properties were estimated by transmission electron microscopy (TEM), vibration magnetometry and ferromagnetic resonance (FMR).

According to magnetometric measurements, nanoparticles are mainly in a superparamagnetic state. By fitting magnetization curves, the magnetic characteristics of nanoparticles were determined: saturation magnetization (59.3 emu/g) and magnetic anisotropy constant ( = 0.86·105 erg/cm3). The average particle size estimated from magnetic measurements was 8.7 nm. Considering the presence of a magnetically dead layer, this is in good agreement with the TEM results. The temperature dependence of the FMR linewidth was analyzed using two models. As a result, the parameters ��� and �/�� were determined. The models used showed good agreement. The values of the anisotropy constant ( = 1.06·105 erg/cm3) and the average particle size (6.8 nm) are estimated.

The effect of the NPs on the HEK293 cells was studied by MTT-assay, flow cytometry and RT-PCR. The exposure with the NPs lead to a significant decrease of cell metabolic activity in HEK293 cell culture, but this effect was not accompanied by cell death. It was shown that the expression of antioxidant enzymes SOD1 and GPX1 was reduced at the mRNA stage. So the NPs synthesized may affect gene expression and metabolism of HEK293 cells, but this does not have fatal consequences for cell viability.

Spontaneous rotation of magnets levitating above high-Tc superconductor

Gokhfeld, D. M.; Shalomov, S. Yu.; Sultimov, D. B.; Petrov, M. I.//, e-Print Archive, Condensed Matter//

The levitation of a cylindrical permanent magnet over a high-temperature superconductor cooled by liquid nitrogen can be accompanied by spontaneous oscillations and rotation. The reason for spontaneous rotation of the magnet is magnetization inhomogeneity induced by the temperature gradient. An experiment was carried out on the levitation of Nd-Fe-B magnets over a composite high-temperature superconductor. The experimental results confirm that the rotation frequency depends on the difference in the magnetization values in the upper and lower halves of the magnet. Methods for controlling the rotation frequency of a levitating magnet are proposed.

Impact of nano-biomaterials on the world

Edelman, I., Ovchinnikov, S., Thakur, A., Thakur, P.// Integrated Nanomaterials and their Applications//

People have been exposed to airborne nanosized materials (100 nm) for thousands of years, but since the industrial revolution, particularly with regard to combustion operations, the level of exposure has significantly increased. Since the advent of nanotechnology, two decades ago, the danger of exposure to nanomaterials by ingestion, absorption through the skin, absorption through the dermis, and medication administration utilizing designed nanoparticles, has grown. Nanomaterials acquire new mechanical, electrical, optical, catalytic, and, last but not least, biological capabilities when they shrink from bulk to nanoscale. The creation, usage, and disposal of the product, as well as the toxicological impacts of nanomaterials, must all be studied. Basic multidisciplinary research including materials scientists, toxicologists, medical professionals, and environmental engineers is necessary to better understand the health risks and safety concerns of nanoparticles.

On Linear Cellular Automata

Kulikov, V.R., Kytmanov, A.A., Poroshin, A.O., Timofeev, I.V., Fedchenko, D.P.// Programming and Computer Software//

wolfram cellular automata are considered and their operation is demonstrated using an example of traffic flow simulation. For the class of one-dimensional elementary cellular automata, the concept of linearity is introduced in the language of Zhegalkin operators. An algorithm for finding linear Zhegalkin operators with multipliers of three variables is presented. The algorithm is implemented in Python.

Analyzing the Symmetry of the Raman Spectra of Crystals According to Angular Dependences

Golovkina, E.V., Krylova, S.N., Vtyurin, A.N., Krylov, A.S.// Bulletin of the Russian Academy of Sciences: Physics//

The authors propose a way of reconstructing the Raman tensor by studying the angular dependences of the intensities of the Raman lines of unoriented microcrystals. The technique is verified using familiar calomel Hg2Cl2 crystals. It is shown that the lines on DUT-8 (Ni) crystals indicating phases with open and closed pores have different types of symmetries. The technique can be used to reconstruct the Raman tensor for any unoriented crystalline sample.

Crystal structure and thermoelectric properties of mechanically activated LaCoO3

Dudnikov, V.A., Orlov, Y.S., Solovyov, L.A., (...), Bondarev, V.S., Ovchinnikov, S.G.// Journal of the Taiwan Institute of Chemical Engineers//

Crystal structure of rare-earth LaCoO3 cobalt oxide subjected to high energy mechanical activation has been studied. In the temperature range of 300–800 K, the electrical conductivity and Seebeck coefficient were measured. Thermal conductivity was measured at 300–480 K.

Influence of Dielectric Relaxations of Soil Water on the Temperature Dependence of Soil Permittivity

Karavayskiy, A. Yu.; Lukin, Yu. I.// Optics and Spectroscopy//

Using a generalized refractive mixture dielectric model, the influence of the relative permittivity spectra of bound and unbound water in mineral soil on the nature of the temperature dependence of the relative permittivity of natural mineral soil, with a clay fraction content of 41.3%, was studied in the electromagnetic field frequency range from 50 MHz to 15 GHz. The causes of the emergence of intersections in the relative permittivity spectra of mineral soil, obtained at different temperatures but for a sample of the same moisture content, have been studied. It has been proved that the emergence of such an intersection point in the frequency range up to 1.5 GHz is due to the Maxwell–Wagner effect in bound water. The dependences of the frequency of the intersection point of the relative permittivity spectra of mineral soil on the temperature and volumetric content of bound and unbound water have been studied.

The arising of ferromagnetism in Al-doped Mn2(Ga1-xAlx)C MAX phases

Zhandun, Vyacheslav S.; Zamkova, Natalia G.; Draganyuk, Oksana N.// JMMM//

The magnetic properties of ordered MAX phases Mn2(AlxGa1−x)C (x = 0.125, 0.25, 0.5, 0.75 and 0.875) have been studied within the DFT-GGA. We have found that increase of Al atom at A-site leads to the formation of the ferromagnetic phase with large magnetization of about 3.6 μB/f.u. The investigation of the phase stability is performed by comparing the total energy of the MAX phases with that of a set of competitive phases for calculation of the phase formation enthalpy. Up to a concentration of Al atoms x = 0.7 the compound remains thermodynamically stable. The exchange constants analysis shows the crucial role of exchange interactions between manganese atoms along the c-axis in forming of ferromagnetism. The magnetic transition temperature of Mn2(AlxGa1−x)C alloys increases with increase of the aluminum concentration.

Mn-Mn Magnetic Coupling Interaction-Induced Red Emission in a Tetra-Coordinated Lattice

Wang, W., Wei, Y., Qiu, L., (...), Tu, D., Li, G.// Chemistry of Materials

Strong magnetic coupling interactions originating from a short Mn–Mn distance in some heavy Mn2+-doped matrices have important effects on luminescence of single Mn2+ ions and close-knit Mn2+–Mn2+ pairs. However, the intrinsic mechanism of controlling spectral regulation remains elusive since the underlying relationship among Mn–Mn distances, magnetic coupling interactions, and optical properties is unclear. Herein, we create an unusual red emission (620 nm) of Mn2+ in a typical tetra-coordinated lattice of Li2CdGeO4 by simply enhancing the Mn2+-doped level in addition to regular green emission (528 nm). Although the dual emission peaks occupy the same tetra-coordinated crystallographic lattice of CdO4, different temperature-dependent emission behaviors are observed, which expands a possibility in optical thermometry sensors. Detailed Mn–Mn distances are calculated via Rietveld refinement analysis, and their effects on the Mn–Mn coupling interactions are evaluated. Furthermore, the Mn–Mn coupling interaction types are identified through electron spin resonance and magnetic measurements. The continuously decreasing distances between Mn2+ ions strengthen the dipole–dipole coupling effect, resulting in the atypical red emission in a tetra-coordinated lattice environment. These findings elucidate the spectral regulation mechanism from the perspective of magnetic coupling interactions, providing a new pathway to regulate Mn2+-related emission.

Microbially mediated synthesis of vivianite by Desulfosporosinus on the way to phosphorus recovery

Knyazev, Y.V., Platunov, M.S., Ikkert, O.P., (...), Balaev, D.A., Karnachuk, O.V.// Environmental Science: Advances//

DOI: 10.1039/D4VA00040D 

We explored the role of biomineralization in industrial waste sludge formation, using the laboratory cultivation of Desulfovibrio sp. OL sulfate reducing species isolated from the Komsomolsky waste sludge (Russia). The most frequently reported sulfate-reducing bacteria (SRB) biomineralization products are various iron sulfides. Here we present first studies of the products of Desulfosporosinus metallidurans, acidophilic SRB from acid mine drainage. We analyzed the biomineralized sample using X-ray diffraction, electron microscopy, X-ray absorption and Mössbauer spectroscopies, and magnetization measurements via First-Order Reversal Curve (FORC) diagram analysis. Our findings show that the biomineralization occurring under pure culture conditions leads to the formation of greigite (Fe3S4) nanorods, along with larger microbially mediated crystals of vivianite (Fe3(PO4)2·8H2O) and siderite (FeCO3). Energy dispersive X-ray spectroscopy revealed that the crystal sizes of vivianite and siderite were comparatively larger than those of the nanorod-shaped greigite. Transmission electron microscopy and Mössbauer spectroscopy detected ultrafine ferrihydrite (Fe2O3·nH2O) superparamagnetic nanoparticles with an average size of 2.5 nm. FORC analysis showed significant magnetic interactions among these nanoparticles, suggesting their potential for magnetic separation applications. The current study demonstrates that ferrihydrite nanoparticles have a strong magnetic affinity for other crystal phases produced by Desulfosporosinus metallidurans. Therefore, we believe that the investigated bacterial species can be exploited in advanced magnetic separation techniques. This offers a cost-effective and environmentally friendly method for purifying sediments in industrial waste sludge.

Phase Transitions and Nonlinear Optical Property Modifications in BaGa4Se7

Isaenko, L., Dong, L., Melnikova, S.V., (...), Belousov, R.A., Lin, Z.// Inorganic Chemistry//

Phase transitions can change the crystal structure and modify the physical properties of crystals. In this work, we investigate the phase transition behavior in BaGa4Se7, an important middle infrared (mid-IR) nonlinear optical (NLO) crystal, in the temperature range from room temperature to 1173 K. Interestingly, the BaGa4Se7 crystal undergoes a reversible ferroelastic phase transition at T = 528 K, resulting in the presence of a newly discovered phase (γ-phase) at the higher temperature. The experimental temperature dependence of optical birefringence, as well as the first-principles birefringence and NLO coefficients, reveals that the γ-phase exhibits larger birefringence and better NLO properties compared with those of the low-temperature phase (α-phase). This work demonstrates that phase-transition-induced structural modification can improve the mid-IR NLO properties, which would provide an effective avenue to obtain materials with good optoelectronic performance.

Regularity of thermal characteristics, thermoelectric properties of EuLnCuSe3 compounds (Ln = La–Lu)

Habibullayev, N.N., Burkov, A.T., Novikov, S.V., (...), Denisenko, Y.G., Andreev, O.V.// European Physical Journal Plus//

The temperatures and enthalpies of the decomposition of EuLnCuSe3 compounds (Ln = La–Lu) are determined for the first time as functions of the Ln3+ ionic radius (rLn3+). The EuLnCuSe3 compounds with Ln = La and Ce decompose in the course of a solid-phase reaction to form EuSe, Ln2Se3, and Cu2−xSe, whereas those with Ln = Tb, Dy, Ho, Tm, and Lu melt incongruently to form EuSe and a melt, for example, Tdecay = 1175 K and ΔHdecay = 2.66 kJ/mol for EuLaCuSe3, while Tmelt = 1576 K and ΔHmelt = 2.69 kJ/mol for EuTbCuSe3. When plotted as functions of rLn3+, the temperatures of thermal effects of these compounds exhibit a periodic dependence and a tetrad effect. The temperature dependence of electrical resistivity and that of the Seebeck coefficient are measured from 300 to 600 K. It is shown that the studied compounds are p-type semiconductors with bandgaps ranging from 0.4 to ~ 1 eV.

Biodegradation of microbial plastic poly(3-hydroxybutyrate) in soil ecosystems at different latitudes

Prudnikova, S.V., Kiselev, E.G., Demidenko, A.V., (...), Thomas, S., Volova, T.G.// Giant//

The features of the degradation of the "green" plastic poly(3-hydroxybutyrate) [P(3HB)] in the soil of various geographical regions were studied: in red ferralitic soil under tropical conditions (Kerala, India) and in chernozem soil under conditions of a sharply continental climate (Eastern Siberia, Russia). Significant differences in the chemical composition, temperature, and humidity of the studied soils were revealed. The number of bacteria and mycelial fungi in the Siberian chernozem was higher than in the red soil of India, from 2-3 to 10 or more times. The degradation of P(3HB) films in the chernozem occurred faster than in the red soil, which was drier, with a low content of humus and minerals, and fewer microorganisms than the chernozem. The half-life of polymer samples in Siberia and India was 64.8 and 126.4 days, respectively. During degradation, a decrease in the molecular weight and an increase in the degree of crystallinity of polymer samples were revealed, which indicates a more active biodegradation of the amorphous phase of the polymer by soil microorganisms. The primary degraders of the polymer have been isolated and identified, and it has been shown that the complexes of degrading bacteria and fungi in different types of soils did not have common species. Despite the presence of species with pronounced depolymerase activity, the rate of film degradation in red ferralitic soils was slowed down by unfavorable environmental conditions. The obtained results confirm the importance of studying the process of PHA degradation in natural conditions.

Adsorption properties and catalytic activity of Fe3O4-Ag nanostructures

Ivanova, O.S., Lin, C.-R., Edelman, I.S., (...), Petrov, D.A., Lin, E.-S.// Applied Surface Science//

The morphology and magnetic properties as well as adsorption capacity and catalytic activity of Fe3O4-Ag nanoparticles synthesized by the solvothermal method were studied in dependence on the duration of the thermolysis process (3, 6, and 8 h). X-ray diffraction, transmission electron microscopy, and energy-dispersive spectroscopy measurements showed that the morphology of nanoparticles changed strongly as the duration of thermolysis increased. At 6 and 8 h duration, Fe3O4 nanocrystals grow and assemble into porous spherical globules with an Ag core (samples 2 and 3). These samples demonstrate high magnetization value and very low coercivity. The adsorption capacity of nanoparticles was studied with respect to two organic dyes: cationic methylene blue (MB) and anionic Congo red (CR). The particles showed preferential adsorption of the cationic dye. High catalytic activity towards four dyes: MB, methyl orange (MO), CR, and Rhodamine C (RhC) at the presence of NaBH4 is the remarkable property of these samples. The rate constant of the catalytic reaction was 1.4 min−1. Simultaneous exposure of CR and MO dyes to nanoparticles and NaBH4 caused their irreversible 100 % degradation while in the case of MB and RhC, a transition to their leuco form occurred.

Magnetic ordering and the role of superexchange Ni–O–B–O–Ni upon the formation of magnetic order in ludwigite Ni2MnBO5 from first-principal calculations

Sofronova, S., Chernyshev, A.// Computational Condensed Matter//

The energies of various magnetically ordered structures for ludwigite Ni2MnBO5 have been calculated in the framework of the first-principles approach using the Wien2K program package, with the parameters of exchange interactions being determined. Two subsystems can be distinguished in the magnetic system, which are associated with the triads 4-2-4 and 3-1-3. The magnetic moments of the ions in both triads are antiferromagnetically oriented. The analysis of the exchange contribution to the energy shows that there occurs an increase of the magnetic cell relative to the crystallographic one due to antiferromagnetic ordering of the magnetic moments along the c axis in three-legged ladders formed by 4-2-4 triads. However, in three-legged ladders formed by 3-1-3 triads, the magnetic moments of the ions are ordered along the c-axis ferromagnetically. The predicted type of magnetic ordering in Ni2MnBO5 is similar to magnetic ordering in Fe3BO5. Non-collinear ordering of the magnetic moments of the subsystems at different temperatures is also likely to be observed in Ni2MnBO5, as is the case in Fe3BO5. Superexchange (indirect) interactions (No-O-B-O-Ni) influence the orientation of the magnetic moments of two 3-1-3 (4-2-4) triads within the unit cell. It is these interactions that may be responsible for the formation of long-range magnetic order in Co3BO5 and ferrimagnetic-antiferromagnetic spin-reorientation transition in Fe3BO5.

Yellow-Orange Emission in Sb3+-Doped Hexakis(thiocarbamidium) Hexabromoindium(III) Tribromide

Golovnev, N.N., Gerasimova, M.A., Belash, I.M., Zolotov, A.O., Molokeev, M.S.// Inorganic Chemistry//

A luminescent zero-dimensional organic–inorganic hybrid indium halide (TUH)6[In1–xSbxBr6]Br3 (TU = thiourea, 0 ≤ x ≤ 0.0998) was synthesized via the solvothermal method. In structures, resolved by single-crystal X-ray diffraction, isolated distorted [InBr6]3– and [SbBr6]3– octahedra are linked to organic TUH+ cations by intermolecular N–H···Br and N–H···S hydrogen bonds. The crystals were characterized by elemental analysis, TG-DSC, powder X-ray diffraction, FTIR analysis, and steady-state absorption and photoluminescence spectroscopy. (TUH)6[In1–xSbxBr6]Br3 exhibits a broadband yellow-orange emission centered at 595–602 nm with a half-width of 141–149 nm (0.48–0.52 eV) and a large Stokes shift of 232–238 nm (1.33–1.35 eV). This emission can be attributed to the self-trapped exciton emission of triplet states of the octahedral anion [SbBr6]3– or [InBr6]3–. Two possible emission mechanisms were discussed. Doping with Sb3+ leads to a significant increase in photoluminescence quantum yield from 25.7 at x = 0 to 48.4% at x = 0.0065, when excited at 365 nm, indicating the potential use of (TUH)6[In1–xSbxBr6]Br3 compounds in the field of photonics.

Ceramic Substrates for Filtration Membranes Based on Fine Fly Ash Microspheres

Fomenko, E.V., Akimochkina, G.V., Anshits, A.G., (...), Maksimova, A.A., Ryzhkov, I.I.// Membranes and Membrane Technologies//

A procedure has been proposed for producing ceramic substrates for filtration membranes based on a narrow fraction of fine fly ash microspheres using cold uniaxial pressing followed by high-temperature firing. It has been shown that increasing the sintering temperature from 1000 to 1150°C leads to a decrease in open porosity from 40 to 24%, a decrease in the average pore size from 1.60 to 0.34 μm, and an increase in the compressive strength from 9.5 to 159 MPa. The resulting substrates are characterized by water permeability values of 1210, 310, 240, 170 L m−2 h−1 bar−1 at sintering temperatures of 1000, 1050, 1100 and 1150°C, respectively. Experiments on filtration of aqueous suspensions of fine microspheres (dav = 2.5 µm) and microsilica (dav = 1.9 μm) through a substrate produced at a sintering temperature of 1150°C have shown the rejection close to 100%. The proposed methodology for using ash waste in the production of membrane materials promotes the development of technologies for the integrated processing of thermal energy waste.

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