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We report high-level calculations of the excited states of [2,2]-paracyclophane (PCP), which was recently investigated experimentally by ultrafast pump–probe experiments on oriented single crystals [Haggag et al., ChemPhotoChem 6 e202200181 (2022)]. PCP, in which the orientation of the two benzene rings and their range of motion are constrained, serves as a model for studying benzene excimer formation. The character of the excimer state and the state responsible for the brightest transition are similar to those of the benzene dimer. The constrained structure of PCP allows one to focus on the most important degree of freedom, the inter-ring distance. The calculations explain the main features of the transient absorption spectral evolution. This brightest transition of the excimer is polarized along the inter-fragment axis. The absorption of the light polarized in the plane of the rings reveals the presence of other absorbing states of Rydberg character, with much weaker intensities. We also report new transient absorption data obtained by a broadband 8 fs pump, which time-resolve strong modulations of the excimer absorption. The combination of theory and experiment provides a detailed picture of the evolution of the electronic structure of the PCP excimer in the course of a single molecular vibration. [ABSTRACT FROM AUTHOR]

We demonstrate experimentally and numerically the control of magnetization circulation of the closure domain state in thin permalloy squares divided diagonally into four dipolar-coupled isosceles triangles. The control over the magnetization circulation was achieved by the mutual application of a suitable external in-plane magnetic field and interaction with a magnetic force microscopy (MFM) tip. Numerical simulations confirm that the proposed switching protocol is valid for the broad range of MFM tips. Experiments performed on four diagonally cut squares show that this method is robust against slight imperfections in the fabrication process. Moreover, by varying the polarity of the applied field and the direction of the MFM scanning, proper symmetry response of the switching method is observed. [ABSTRACT FROM AUTHOR]

We introduce a new subclass of Fano varieties (Casagrande–Druel varieties) that are 푛-dimensional varieties constructed from Fano double covers of dimension n − 1 . We conjecture that a Casagrande–Druel variety is K-polystable if the double cover and its base space are K-polystable. We prove this for smoothable Casagrande–Druel threefolds, and for Casagrande–Druel varieties constructed from double covers of P n − 1 ramified over smooth hypersurfaces of degree 2 ⁢ d with n > d > n 2 > 1 . As an application, we describe the connected components of the K-moduli space parametrizing smoothable K-polystable Fano threefolds in the families № 3.9 and № 4.2 in the Mori–Mukai classification. [ABSTRACT FROM AUTHOR]

In order to ensure trouble-free operation of offshore oil production and transportation facilities, it is necessary to consider seismic hazard in their design. As part of this work, seismic hazard calculations were performed for the Zhenis oil and gas field facilities located in the Kazakhstan sector of the Middle Caspian. According to this project, the initial seismicity and seismic microzoning were clarified, i.e., accounting for real soil conditions made by different methods. Calculations showed that the intensity of seismic shocks in the Zhenis field can be 8.31 points on the MSK-64 scale, which corresponds of acceleration of a sea bottom ground of 0.253 g. [ABSTRACT FROM AUTHOR]

Cyclodextrins (CDs) are natural cyclic oligosaccharides with the ability to form inclusion complexes with various organic substances. In this paper, we investigate the potential of CD complex formation to enhance the antibacterial activity and antioxidant properties of poorly soluble bioactive agents, such as chalcones, chromenes, stilbenoids and xanthylium derivatives, serving as potential adjuvants, in comparison with standard antiseptics. The interaction of these bioactive agents with the hydrophobic pocket of methyl-β-cyclodextrin (MCD) was confirmed using spectroscopic methods such as UV-vis, FTIR, 1H and 13C NMR, mass-spectrometry. CD-based delivery system allows for combining multiple active agents, improving solubility, antibacterial efficacy by enhancing penetration into target bacterial cells (E. coli selectivity demonstrated via confocal microscopy). Novel compounds of chalcones and stilbenoids derivatives additionally enhance efficacy by inhibiting bacterial efflux pumps, increasing membrane permeability, and inhibiting bacterial enzymes, and showed a synergy when used in combination with metronidazole. The intricate relationship between the structural characteristics and functional properties of chalcones and stilbenoids in terms of their antibacterial and antioxidative capabilities is revealed. The substituents within aromatic rings significantly influence this activity, where position of electron-donating methoxy groups playing a crucial role. Among chalcones, stilbenoids, ana xanthyliums, the compounds caring a benzodioxol ring, analogous to natural bioactive compounds like apiol, dillapiol, and myristicin, emerge as prominent antibacterial activity. To explore the possibility to create theranostic formulations, we used fluorescent markers to visualize target cells, antiseptics to provide antibacterial activity, and bioactive agents as chalcones acting as adjuvants. Additionally, new antioxidant compounds were found such as Xanthylium derivative (R351) and chromene derivative: 1-methyl-3-(2-amino-3-cyano-7-methoxychromene-4-yl)-pyridinium methanesulfate: the pronounced antioxidant properties of these substances are observed comparable to quercetin in the efficiency. Rhodamine 6G, gentian violet, and Congo Red exhibit good antioxidant properties, although their activity is an order of magnitude lower than that of quercetin. However, they have remarkable potential due to their multifaceted nature, including the ability to visualize target cells. The most effective theranostic formulation is the combination of the antibiotic (metronidazole) + dye/fluorophore (methylene blue/rhodamine 6G) for visualization of target cells + adjuvant (chalcones or xanthylium derivatives) for antiinflammation effect. This synergistic combination, results in a promising theranostic formulation for treating bacterial infections, with enhanced efficiency, selectivity and minimizing side effects. [ABSTRACT FROM AUTHOR]

The article provides new data on the structure of the Laptev Sea flank of the Gakkel Ridge. The intensive supply of clastic material from the Laptev Sea shelf leads to the development of a thick alluvial fan at the continental rise, which determines the structure of the bottom topography. In the northwestern direction, the influence of the fan decreases and tectonics becomes the main relief-forming factor. The bathymetric survey traced the asymmetrical rift valley of the Gakkel Ridge, the western flank of which is complicated by terraces. The presence of fault structures, bottom subsidence, extensive sediment supply, and the widespread development of subaqueous slump processes indicate the high neotectonic activity of the Laptev Sea flank of the Gakkel Ridge. For the first time in this region, numerous carbonate rocks have been discovered, the authigenic cement of which is represented by magnesian calcite or aragonite with an admixture of terrigenous material. The palynological and micropaleontological analysis of the carbonate rocks indicates the Quaternary formation of authigenic carbonate cement. An important role in the formation of authigenic carbonates was played by diagenetic solutions coming from the sedimentary cover together with methane and oxidation products of gases and organic matter. The authigenic carbonates were precipitated mainly in an isotopic equilibrium with bottom water at a temperature of about 0°C. The negative correlation between 87Sr/86Sr and δ13C indicates the presence of at least two different sources of carbonate-forming solutions. [ABSTRACT FROM AUTHOR]

This study describes the applicability of the fluorescence polarization assay (FPA) based on the use of FITC-labeled oligosaccharide tracers of defined structure for the measurement of active lysozyme in hen egg white. Depending on the oligosaccharide chain length of the tracer, this method detects both the formation of the enzyme-to-tracer complex (because of lectin-like, i.e., carbohydrate-binding action of lysozyme) and tracer splitting (because of chitinase activity of lysozyme). Evaluation of the fluorescence polarization dynamics enables simultaneous measurement of the chitinase and lectin activities of lysozyme, which is crucial for its detection in complex biological systems. Hen egg white lysozyme (HEWL), unlike human lysozyme (HL), formed a stable complex with the chitotriose tracer that underwent no further transformations. This fact allows for easy measurement of the carbohydrate-binding activity of the HEWL. The results of the lysozyme activity measurement for hen egg samples obtained through the FPA correlated with the results obtained using the traditional turbidimetry method. The FPA does not have the drawbacks of turbidimetry, which are associated with the need to use bacterial cells that cannot be precisely standardized. Additionally, FPA offers advantages such as rapid analysis, the use of compact equipment, and standardized reagents. Therefore, the new express technique for measuring the lysozyme activity is applicable for evaluating the complex biomaterial, including for the purposes of food product quality control. [ABSTRACT FROM AUTHOR]

Activatable fluorescent probes with turn-on emission in response to a biological target can reduce the background signal and improve the detection limit needed for biosensor and bioimaging resolution. Turn-on probes with dual emission (ratiometric probes) have further advantages, as they have self-calibration ability for more reliable detection. Herein, we demonstrate the tunability of the phenolic hemicyanine (HC) scaffold for both DNA biosensing and bioimaging applications using the quinine-binding DNA aptamer (MN4) as a host-guest biosensor platform and live ovarian cancer cells for nuclear imaging. The DNA aptamer MN4 contains a three-way junction (3WJ) consisting of a hydrophobic branch point connecting three double-stranded stems. Phenolic HCs bearing electron-withdrawing halogen substituents (FPhOBtz and Cl2PhOBTz) bind to the 3WJ of MN4 as the phenolate with strong turn-on emission. Subsequent displacement of the phenolate by the quinine target causes a turn-off emission response. In contrast, the parent phenolic HC (PhOBtz) and those bearing electron-donating groups (Me2PhOBtz and (MeO)2PhOBtz) exhibit dual (phenol and phenolate) fluorescence upon MN4 binding. Phenol excitation generates phenolate emission by an excited-state proton transfer (ESPT) process with DNA components serving as the proton acceptor. Quinine displacement of PhOBtz from the 3WJ of MN4 affords a turn-on ratiometric response with preferential light-up of phenol emission. The ability of the phenolic HCs to serve as cellular nuclear stains further highlights the tunability of the phenolic HC probes with the Cl2PhOBtz analog displaying superior staining ability. The simplicity and tunability of phenolic HCs make them attractive fluorescent probes for DNA sensing and bioimaging applications. [ABSTRACT FROM AUTHOR]

The Arctic region, including vast shelf zones, has enormous resource and transport potential and is currently key to Russia's strategic development. This region is promising and attractive for the intensification of global economic activity. When developing this region, it is very important to avoid emergency situations that could result in numerous negative environmental and socio-economic consequences. Therefore, when designing and constructing critical infrastructure facilities in the Arctic, it is necessary to conduct high-quality studies of potential geohazards. This paper reviews and summarizes the scattered information on the main geohazards in the Russian sector of the Arctic Ocean, such as earthquakes, underwater landslides, tsunamis, and focused fluid discharges (gas seeps), and discusses patterns of their spatial distribution and possible relationships with the geodynamic setting of the Arctic region. The study revealed that the main patterns of the mutual distribution of the main geohazards of the Russian sector of the Arctic seas are determined by both the modern geodynamic situation in the region and the history of the geodynamic evolution of the Arctic, namely the formation of the spreading axis and deep-sea basins of the Arctic Ocean. The high probability of the influence of seismotectonic activity on the state of subsea permafrost and massive methane release is emphasized. This review contributes toward better understanding and progress in the zoning of seismic and other geological hazards in the vast Arctic seas of Russia. [ABSTRACT FROM AUTHOR]

Recent intriguing experimental observations of atomic scale friction enhancement, that takes place at scanning velocities correspondent with the cantilever frequency and/or its fractions (1/n, n = 1, 2, 3, ...), can be explained as the manifestation of an autoparametric resonance. Taking explicitly into account high flexibility of AFM tips, the developed theory reveals the autoparametric resonance to be a natural consequence of the rich dynamics of the combined tip–cantilever system. Besides the explanation of the observed friction force peaks, the theory predicts a dense multiplicity of smaller peaks to appear when the washboard frequency coincides with a rational part (m/n, with integer m and n) of the cantilever frequency. An important conclusion is made that the resonance enhancement of friction is independent of frequency of excited phonons, and it should manifest itself for any possible mechanism of frictional energy dissipation in the substrate, phononic, electronic, or any other. [ABSTRACT FROM AUTHOR]

In this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro-NNO-azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro-NNO-azoxy compounds involving two chemical steps (formation of azoxy group containing a leaving group and its nitration) and demanding expensive, corrosive, and hygroscopic nitronium salts, the presented electrochemical method consists of a single step and is based solely on nitrosoarenes and ammonium dinitramide. The dinitramide salt plays the roles of both the electrolyte and reactant for the coupling. Despite the fact that many side reactions can be expected due to the redox-activity of both the reagents and target products, under optimized conditions the synthesis is performed in an undivided cell under constant current conditions with high current density and can be easily scaled up without a reduction in the product yield. Moreover, the synthesized nitro-NNO-azoxy compounds are discovered to be potent fungicides active against a broad range of phytopathogenic fungi. [ABSTRACT FROM AUTHOR]

The data obtained on the qualitative and quantitative composition of summer phyto- and zooplankton of two lakes of the Taimyr Peninsula indicate a higher trophic status of the water body, which is under pressure from hydrophilic birds. Compared to the background water body, statistically significantly higher phytoplankton abundance (134 600 ± 16 300 cells/L vs. 60 400 ± 11 800 cells/L), zooplankton biomass (134 600 ± 16 300 cells/L vs. 60 400 ± 11 800 cells/L), zooplankton biomass (349.0 ± 170.2 mg/L vs. 64.5 ± 19.5 mg/L), and rotifer biomass (15.6 ± 3.5 mg/L vs. 1.6 ± 0.4 mg/L) and their dominance, as well as saprobic index (1.71 ± 0.09 vs. 1.48 ± 0.06), are registered. At the same time, specific features of community organization are revealed—higher species richness of phyto- and zooplankton and the absence of Cyanobacteria in phytoplankton composition and statistically a significantly higher abundance of Bacillariophyta (80 700 ± 11 800 kl./L vs. 31 700 ± 650 kl./L) and number of species (4 vs. 2) and biomass (326.6 mg/L vs. 60.6 ± 18.8 mg/L) of copepods, which may be determined by the peculiarities of hydrobionts reaction to the products of bird activity. This allows us to speak about the prospects of guanotrophication to improve the trophic status of water bodies without the significant deterioration of environmental quality and biodiversity of hydrobiont communities. [ABSTRACT FROM AUTHOR]

This study focuses on the synthesis of a series of oligo- α -(1→6)-D-galactopyranosides bearing β -D-galactofuranosyl residues at O-2 and/or O-3, which relate structurally to fragments of glucuronoxylomannogalactan (GXMGal) from the fungal pathogen Cryptococcus neoformans that causes severe diseases in immunocompromised patients. The preparation of target compounds is based on the use of a selectively O-protected N-phenyltrifluoroacetimidoyl galactopyranoside donor with an allyl group at O-2, levulinoyl group (Lev) at O-3, pentafluorobenzoyl (PFB) group at O-4, and fluorenylmethoxycarbonyl (Fmoc) group at O-6. The choice of protecting groups for this donor ensures the stereospecific formation of α- (1→6)-glycosidic bonds due to the stereodirecting effect of acyls at O-3, O-4, and O-6. At the same time, this combination of O-substituents permits the selective recovery of free OH groups at O-2, O-3, and O-6 for chain elongation via the introduction of β- D-galactofuranosyl and α- D-galactopyranosyl residues. The reported compounds are obtained as aminopropyl glycosides, which are transformed into biotinylated conjugates for further use as coating antigens in immunological studies. The obtained oligosaccharides were subjected to detailed 13C NMR analysis to show the spatial similarity of the obtained hexasaccharide with the corresponding fragment in the GXMGal chain, making this compound suitable for further immunological studies of C. neoformans. [ABSTRACT FROM AUTHOR]

Self-decomposition of phthalimide-N-oxyl radical (PINO), a catalytically active species in N-hydroxyphthalimide (NHPI) catalyzed aerobic oxidation and oxidative coupling reactions, is one of the key reasons limiting its use. However, the literature data do not provide unambiguous information about either the mechanism or the PINO decomposition products. In this work, based on operando IR spectroscopy a new model of PINO self-decomposition was proposed, which in particular explains the contradictions in earlier works on this topic. The kinetics of PINO self-decomposition is complex, consisting of several simultaneous processes characterized by different rates and yielding the different products, making the concept of an effective rate constant impractical for PINO decay. In summary, as the PINO decomposition progresses and its concentration decreases the dominant decomposition pathway switches from the initial formation of the PINO "trimer" to the production of NHPI. The crucial role of medium acidity in determining the path of PINO radical decomposition was discovered. Under highly acidic conditions, the formation of the "trimer" product is suppressed. For the first time, the characteristic vibration frequencies of PINO have been experimentally determined. Operando IR spectroscopy has proven to be a useful tool for studying reactions involving nitroxyl radicals, offering simultaneous monitoring of reactants, intermediates, and products. [ABSTRACT FROM AUTHOR]

Background: Regenerative medicine and transplantation science continuously seek methods to circumvent immune-mediated rejection and promote tissue regeneration. Sertoli cells, with their inherent immunoprotective properties, emerge as pivotal players in this quest. However, whether Sertoli cells can play immunomodulatory role in tadpole tail regeneration and can thus benefit the regeneration process are needed to be discovered. Methods: Immature Sertoli cells from Xenopus tropicalis (XtiSCs) were transplanted into X. tropicalis tadpoles, followed by the amputation of the final third of their tails. We assessed the migration of XtiSCs, tail regeneration length, muscle degradation and growth, and macrophage counts across various regions including the entire tail, tail trunk, injection site, and regeneration site. The interactions between XtiSCs and macrophages were examined using a confocal microscope. To deplete macrophages, clodronate liposomes were administered prior to the transplantation of XtiSCs, while the administration of control liposomes acted as a negative control. Student's t-test was used to compare the effects of XtiSCs injection to those of a 2/3PBS injection across groups with no liposomes, control liposomes, and clodronate liposomes. Results: XtiSCs have excellent viability after transplantation to tadpole tail and remarkable homing capabilities to the regeneration site after tail amputation. XtiSCs injection increased macrophage numbers at 3 days post-amputation and 5 days post-amputation in the tail trunk, specifically at the injection site and at the regenerated tail, in a macrophage depleted environment (clodronate-liposome injection). What's more, XtiSCs injection decreased muscle fibers degradation significantly at 1 day post-amputation and facilitated new muscle growth significantly at 3 days post-amputation. In addition, whole-mount immunostaining showed that some XtiSCs co-localized with macrophages. And we observed potential mitochondria transport from XtiSCs to macrophages using MitoTracker staining in tadpole tail. Conclusions: Our study delineates the novel role of XtiSCs in facilitating muscle regeneration post tadpole tail amputation, underscoring a unique interaction with macrophages that is crucial for regenerative success. This study not only highlights the therapeutic potential of Sertoli cells in regenerative medicine but also opens avenues for clinical translation, offering insights into immunoregulatory strategies that could enhance tissue regeneration and transplant acceptance. [ABSTRACT FROM AUTHOR]

Aquatic ecosystems are increasingly affected by anthropogenic pollution, including heavy metals like mercury, which accumulate in organisms and cause harmful effects. At the same time, human activities such as industrial operations and the use of electric power lines also alter the magnetic background in natural water bodies. However, the interaction between mercury exposure and magnetic fields remains poorly understood. This study aimed to investigate the combined effects of mercury and magnetic fields on the digestive enzyme activity of common carp (Cyprinus carpio), focusing on the relevance of magnetic fields due to their increasing presence in industrialized environments. Two groups of fish were fed diets with low (0.02 mg/kg) or high (0.27 mg/kg) mercury content for 6 months and exposed to extremely low-frequency magnetic fields or hypomagnetic conditions. Results showed significant differences in mercury accumulation between groups, with higher levels in carps fed with high-mercury content diets. These fish also exhibited increased body length and weight compared to those on a low-mercury diet. The amylolytic activity (total activity of enzymes hydrolyzing starch: α-amylase, glucoamylase, and maltase) and proteolytic activity (total activity of serine proteinases) in the fish intestine were assessed. Magnetic exposure had contrasting effects on enzyme activity, depending on mercury levels in the diet. Fish fed the low-mercury diet exhibited decreased amylolytic activity following magnetic field exposure, while fish on the high-mercury diet showed increased activity. Proteolytic activity followed a similar pattern, with opposite effects observed between the two dietary groups. These findings suggest that mercury accumulation alters the biological response to magnetic fields, possibly through compensatory biochemical mechanisms. Understanding the interactions between toxic substances and magnetic fields is critical for improving environmental risk assessments. [ABSTRACT FROM AUTHOR]

The authors study the parameters of the electromagnetic field when heating ferromagnetic steels in induction-resistive heating devices. New ways of calculating are obtained, and characteristics of electromagnetic fields in multilayer systems are determined. An estimate is made of the effect an internal copper layer of a heater, an air gap between layers, and the inductor current have on the parameters of the electromagnetic field. [ABSTRACT FROM AUTHOR]

Parallel factor analysis (PARAFAC) is widely used in relation to fluorescence excitation/emission spectra to track the movement of water masses and to study seasonal changes in the composition and content of dissolved organic matter. The stage of selecting the number of components is one of the most difficult when using factor analysis. The widely used method of analyzing loads when splitting the original set into halves in many cases does not allow a determination of the best model because of the closeness of their statistical estimates. Because the use of regularization with a penalty for the sum of parameter modules tends to lead to sparse solutions in which some of the coefficients are equal to zero, the use of this approach allows one to select those variables that carry useful information. A procedure is proposed for selecting the number of components when performing parallel factor analysis of fluorescence spectra using a penalty for the 1- and 2-norms of the solution. [ABSTRACT FROM AUTHOR]

On the one hand, Ni3-xCoxB2O6 solid solutions are promising anode materials for lithium batteries, and on the other hand, they have antiferromagnetic properties. This study examines the lattice dynamics of Ni3-xCoxB2O6 solid solutions for x = 0, 1, 2, 3 by means of quantum chemistry and Raman spectroscopy. The vibrational spectra of the compound NiCo2B2O6 have been studied using the polarized Raman spectroscopy method. Good agreement was found between the theoretical and experimental results. As expected, the largest change in frequencies was observed in the modes where the vibrations of the metal ion had a large amplitude. The substitution of cobalt by nickel does not lead to the appearance of soft modes. This fact indicates that the structures of the solid solutions are stable. [ABSTRACT FROM AUTHOR]

Lithium cobalt oxide is a convenient model material for the vast family of cathode materials with a layered structure and still retains some commercial perspectives for microbatteries and some other applications. In this work, we have used ab initio calculations, x-ray diffraction, Raman spectroscopy, and a theoretical physical model, based on quasi-harmonic approximation with anharmonic contributions of the three-phonon and four-phonon processes, to study a temperature-induced change of Raman spectra for LiCoO2. The obtained values of shift and broadening for Eg and A1g bands can be used for quantitative characterization of temperature change, for example, due to laser-induced heating during Raman spectra measurements. The theoretical analysis of the experimental results lets us conclude that Raman spectra changes for LiCoO2 can be explained by the combination of thermal expansion of the crystal lattice and phonon damping by anharmonic coupling with comparable contributions of the three-phonon and four-phonon processes. The obtained results can be further used to develop Raman-based quality control tools. [ABSTRACT FROM AUTHOR]

Exciplexes are excited-state complexes formed as a result of partial charge transfer from the donor to the acceptor species when one moiety of the donor–acceptor pair is electronically excited. The arene–amine exciplex formed between oligo-(p-phenylene) (OPP) and triethylamine (TEA) is of interest in the catalytic photoreduction of CO2 because it can compete with complete electron transfer to the OPP catalyst. Therefore, formation of the exciplex can hinder the generation of a radical anion OPP·− necessary for subsequent CO2 reduction. We report an implementation of a workflow automating quantum-chemistry calculations that generate and characterize an ensemble of structures to represent this exciplex state. We use FireWorks, Pymatgen, and Custodian Python packages for high-throughput ensemble generation. The workflow includes time-dependent density functional theory optimization, verification of excited-state minima, and exciplex characterization with natural transition orbitals, exciton analysis, excited-state Mulliken charges, and energy decomposition analysis. Fluorescence spectra computed for these ensembles using Boltzmann-weighted contributions of each structure agree better with experiment than our previous calculations based on a single representative exciplex structure [Kron et al., J. Phys. Chem. A 126, 2319–2329 (2022)]. The ensemble description of the exciplex state also reproduces an experimentally observed red shift of the emission spectrum of [OPP-4–TEA]* relative to [OPP-3–TEA]*. The workflow developed here streamlines otherwise labor-intensive calculations that would require significant user involvement and intervention. [ABSTRACT FROM AUTHOR]

Phthalimide‐N‐oxyl radicals (PINO) are catalytically active hydrogen abstracting species generated from N‐hydroxyphthalimide (NHPI) – one of the most efficient and widely used organocatalysts for free‐radical oxidative CH‐functionalization processes. The self‐decay of PINO is one of the main limiting factors of NHPI usage, but currently there is no consensus on the mechanism of this important process. In the present work, quantitative EPR and NMR monitoring of PINO generation and degradation along with decay product analysis and control experiments allowed us to build a consistent picture of PINO decay chemistry and put together previously contradictory results. PINO yields achievable employing various oxidants were measured and compared for the first time. At least two PINO decay pathways were revealed: "trimerization" (with partial fragmentation, favored by high PINO concentrations at initial stage of decay), and medium oxidation favored by low PINO concentrations. The main PINO decomposition product, the "trimer" can easily be recycled back to NHPI. [ABSTRACT FROM AUTHOR]

A possible molecular mechanism of the ligand–receptor binding of Ac-Lys-Lys-Lys-NH2 (Ac-KKK-NH2) to the NaV1.8 channel that is responsible for nociceptive signal coding in the peripheral nervous system is investigated by a number of experimental and theoretical techniques. Upon Ac-KKK-NH2 application at 100 nM, a significant decrease in the effective charge carried by the NaV1.8 channel activation gating system Zeff is demonstrated in the patch-clamp experiments. A strong Ac-KKK-NH2 analgesic effect at both the spinal and supraspinal levels is detected in vivo in the formalin test. The distances between the positively charged amino groups in the Ac-KKK-NH2 molecule upon binding to the NaV1.8 channel are 11–12 Å, as revealed by the conformational analysis. The blind docking with the NaV1.8 channel has made it possible to locate the Ac-KKK-NH2 binding site on the extracellular side of the voltage-sensing domain VSDI. The Ac-KKK-NH2 amino groups are shown to form ionic bonds with Asp151 and Glu157 and a hydrogen bond with Thr161, which affects the coordinated movement of the voltage sensor up and down, thus modulating the Zeff value. According to the results presented, Ac-KKK-NH2 is a promising candidate for the role of an analgesic medicinal substance that can be applied for pain relief in humans. [ABSTRACT FROM AUTHOR]

In 1990 F. Chiarenza and M. Frasca published a paper in which they generalized a result of C. Fefferman on estimates of the integral of |bu|^{p} through the integral of |Du|^{p} for p>1. Formally their proof is valid only for d\geq 3. We present here further generalization with a different proof in which D is replaced with the fractional power of the Laplacian for any dimension d\geq 2. [ABSTRACT FROM AUTHOR]

Rapid and specific diagnosis is necessary for both the treatment and prevention of infectious diseases. Bacteria and viruses that enter the bloodstream can trigger a strong immune response in infected animals and humans. The fluorescence polarization assay (FPA) is a rapid and accurate method for detecting specific antibodies in the blood that are produced in response to infection. One of the first examples of FPA is the non-competitive test for detecting brucellosis in animals, which was followed by the development of other protocols for detecting various infections. Fluorescently labeled polysaccharides (in the case of brucellosis and salmonellosis) or specific peptides (in the case of tuberculosis and salmonellosis, etc.) can be used as biorecognition elements for detecting infections. The availability of new laboratory equipment and mobile devices for fluorescence polarization measurements outside the laboratory has stimulated the development of new fluorescence polarization assays (FPAs) and the emergence of commercial kits on the market for the detection of brucellosis, tuberculosis, and equine infectious anemia viruses. It has been shown that, in addition to antibodies, the FPA method can detect both viruses and nucleic acids. The development of more specific and sensitive biomarkers is essential for the diagnosis of infections and therapy monitoring. This review summarizes studies published between 2003 and 2023 that focus on the detection of infections using FPA. Furthermore, it demonstrates the potential for using new biorecognition elements (e.g., aptamers, proteins, peptides) and the combined use of FPA with new technologies, such as PCR and CRISPR/Cas12a systems, for detecting various infectious agents. [ABSTRACT FROM AUTHOR]

Background: Inflammation-induced testicular damage is a significant contributing factor to the increasing incidence of infertility. Traditional treatments during the inflammatory phase often fail to achieve the desired fertility outcomes, necessitating innovative interventions such as cell therapy. Methods: We explored the in vivo properties of intravenously administered Sertoli cells (SCs) in an acute lipopolysaccharide (LPS)-induced inflammatory mouse model. Infiltrating and resident myeloid cell phenotypes were assessed using flow cytometry. The impact of SC administration on testis morphology and germ cell quality was evaluated using computer-assisted sperm analysis (CASA) and immunohistochemistry. Results: SCs demonstrated a distinctive migration pattern, importantly they preferentially concentrated in the testes and liver. SC application significantly reduced neutrophil infiltration as well as preserved the resident macrophage subpopulations. SCs upregulated MerTK expression in both interstitial and peritubular macrophages. Applied SC treatment exhibited protective effects on sperm including their motility and kinematic parameters, and maintained the physiological testicular morphology. Conclusion: Our study provides compelling evidence of the therapeutic efficacy of SC transplantation in alleviating acute inflammation-induced testicular damage. These findings contribute to the expanding knowledge on the potential applications of cell-based therapies for addressing reproductive health challenges and offer a promising approach for targeted interventions in male infertility. [ABSTRACT FROM AUTHOR]

The present study is devoted to the analysis of extreme sea level oscillations of the Laptev Sea using the ADCIRC model. The numerical modeling is performed on a high-resolution grid and verified for sea level observations from three tide gauges. We have revealed regional characteristics of extreme sea level oscillations for different parts of the Laptev Sea coast. The maximum total sea level range was 544 cm in Ebelyakh Bay, while the minimum was 267 cm in Khatanga Bay, where maximum tidal ranges were obtained. Some areas in Khatanga Bay and Anabar Bay had maximum tidal ranges exceeding 200 cm. The study provided an estimation of the possible magnitude of coastal flooding by calculating the extreme total and residual sea levels for different return periods: 1, 2, 5, 10, 20, 50, and 100 years. The amplitude of extreme surges calculated for the 100-year return period can exceed 300 cm for several sections of the Laptev Sea coast, with the maximum sea level range being about 680 cm for Anabar and Ebelyakh Bays. [ABSTRACT FROM AUTHOR]

To design hydrosteam turbines of the Segner-wheel type, it is necessary to have reliable characteristics of a Laval nozzle with a large expansion ratio when water strongly subcooled to a saturation temperature is fed to the nozzle. The authors have given a review of a number of works on determining the flow-rate coefficient μ and the coefficient of velocity ϕ when water subcooled to a saturation temperature flows out of Laval nozzles. The complexity of the process of outflow of a steam–water mixture has been noted, which is dependent on the relation of the temperature and pressure at entry into the nozzle, pressure behind the nozzle and the nozzle expansion ratio, and the configuration of the entrance region. Experimental data have been given on blowdowns of geometrically similar nozzles with measuring the jet thrust and determining the flow-rate and velocity coefficients. It has been shown that the linear dimensions of the nozzle throat do not influence μ when a constant relation of the length of the throat to its diameter is observed. The velocity coefficient during the outflow of a boiling liquid depends on the linear dimensions of the expanding section of the nozzle, i.e., testing of geometrically similar nozzles do not ensure a correct determination of φ. It has been shown that the nozzles' efficiency must be compared in the design regime when the pressure on the exit section is equal to the pressure in the chamber where the steam–water mixture flows. Analysis results will be useful for calculating and designing a reaction hydrosteam turbine. [ABSTRACT FROM AUTHOR]

In unbounded media, the acoustic attenuation as function of frequency is related to the frequency-dependent sound velocity (dispersion) via Kramers–Kronig dispersion relations. These relations are fundamentally important for better understanding of the nature of attenuation and dispersion and as a tool in physical acoustics measurements, where they can be used for control purposes. However, physical acoustic measurements are frequently carried out not in unbounded media but in acoustic waveguides, e.g., inside liquid-filled pipes. Surface acoustic waves are also often used for physical acoustics measurements. In the present work, the applicability of Kramers–Kronig relations to guided and surface waves is investigated using the approach based on the theory of functions of complex variables. It is demonstrated that Kramers–Kronig relations have limited applicability to guided and surface waves. In particular, they are not applicable to waves propagating in waveguides characterised by the possibility of wave energy leakage from the waveguides into the surrounding medium. For waveguides without leakages, e.g., those formed by rigid walls, Kramers–Kronig relations remain valid for both ideal and viscous liquids. Examples of numerical calculations of wave dispersion and attenuation using Kramers–Kronig relations, where applicable, are presented for unbounded media and for waveguides formed by two rigid walls. [ABSTRACT FROM AUTHOR]

A key goal of organic chemistry is to develop new principles for the control of reactions, which can be used to create promising materials demanded in all fields of scientific research and industry. This review is an overview of the scientific advances, which have been made by the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences in the past decade within the framework of current trends in organic chemistry. The review covers the results, which are significant for fundamental research and hold great promise for the application in different areas, from the production of materials, petrochemistry, and chemical ecology to medicine, agriculture, and food industry. [ABSTRACT FROM AUTHOR]

This commentary documents how federal funding agencies are changing the criteria by which they distribute taxpayer money intended for scientific research. Increasingly, STEMM (Science, Technology, Engineering, Mathematics, and Medicine) funding agencies are requiring applicants for funding to include a plan to advance DEI (“Diversity, Equity, and Inclusion”) in their proposals and to dedicate a part of the research budget to its implementation. These mandates undermine the academic freedom of researchers and the unbiased generation of knowledge needed for a well-functioning democracy. Maintaining excellence in science is fundamental to the continuation of the U.S. as a global economic leader. Science provides a basis for solving important global challenges such as security, energy, climate, and health. Diverting funding from science into activities unrelated to the production of knowledge undermines science’s ability to serve humankind. When funding agencies politicize science by using their power to further a particular ideological agenda, they contribute to public mistrust in science. Hijacking science funding to promote DEI is thus a threat to our society. [ABSTRACT FROM AUTHOR]

We classify non-factorial nodal Fano threefolds with 1 node and class group of rank 2. [ABSTRACT FROM AUTHOR]

Brucellosis in animals is an infectious disease caused by bacteria of the genus Brucella. Known methods for diagnosing brucellosis face some challenges, due to the difficulties in isolating and standardizing the natural brucellosis antigen. In this work, we investigated the possibility of using the fluorescence polarization assay (FPA) with synthetic glycoconjugate biosensing tracers to detect antibodies against Brucella as a new methodology for diagnosing brucellosis. Based on the received results, the synthetic fluorescein-labeled trisaccharide tracer is most effective for Brucellosis detection. This tracer is structurally related to the immune determinant fragment of the Brucella LPS buildup of N-formyl-d-perosamine units, connected via α-(1→3)-linkage at the non-reducing end and α-(1→2)-linkage at the reducing end. The sensitivity and specificity in the case of the use of trisaccharide tracer 3b were 71% and 100% (Yuden's method) and 87% and 88% (Euclidean method), respectively, which is comparable with the diagnostic efficiency of traditionally used serological methods, such as the agglutination test (AT), complement fixation test (CFT), and Rose Bengal test (RBT). Given the known advantages of FPA (e.g., speed, compactness of the equipment, and standard reagents) and the increased specificity of the developed test system, it would be appropriate to consider its widespread use for the diagnosis of brucellosis in animals, including rapid testing in the field. [ABSTRACT FROM AUTHOR]

We present an ab initio computational study of the Auger electron spectrum of benzene. Auger electron spectroscopy exploits the Auger–Meitner effect, and although it is established as an analytic technique, the theoretical modeling of molecular Auger spectra from first principles remains challenging. Here, we use coupled-cluster theory and equation-of-motion coupled-cluster theory combined with two approaches to describe the decaying nature of core-ionized states: (i) Feshbach–Fano resonance theory and (ii) the method of complex basis functions. The spectra computed with these two approaches are in excellent agreement with each other and also agree well with experimental Auger spectra of benzene. The Auger spectrum of benzene features two well-resolved peaks at Auger electron energies above 260 eV, which correspond to final states with two electrons removed from the 1e1g and 3e2g highest occupied molecular orbitals. At lower Auger electron energies, the spectrum is less well resolved, and the peaks comprise multiple final states of the benzene dication. In line with theoretical considerations, singlet decay channels contribute more to the total Auger intensity than the corresponding triplet decay channels. [ABSTRACT FROM AUTHOR]

The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is capable of computing reliable energies, wave functions, and first-order properties of excited states in diradicals and polyenes that have a significant doubly excited character with respect to the ground state, without the need for including the computationally expensive triple excitations. Here, we extend the capabilities of the EOM-DEA-CCSD method to the calculations of a multiphoton property, two-photon absorption (2PA) cross sections. Closed-form expressions for the 2PA cross sections are derived within the expectation-value approach using response wave functions. We analyze the performance of this new implementation by comparing the EOM-DEA-CCSD energies and 2PA cross sections with those computed using the CC3 quadratic response theory approach. As benchmark systems, we consider transitions to the states with doubly excited character in twisted ethene and in polyenes, for which EOM-EE-CCSD (EOM-CCSD for excitation energies) performs poorly. The EOM-DEA-CCSD 2PA cross sections are comparable with the CC3 results for twisted ethene; however, the discrepancies between the two methods are large for hexatriene. The observed trends are explained by configurational analysis of the 2PA channels. [ABSTRACT FROM AUTHOR]

We present a new implementation for computing spin–orbit couplings (SOCs) within a time-dependent density-functional theory (TD-DFT) framework in the standard spin-conserving formulation as well in the spin–flip variant (SF-TD-DFT). This approach employs the Breit–Pauli Hamiltonian and Wigner–Eckart's theorem applied to the reduced one-particle transition density matrices, together with the spin–orbit mean-field treatment of the two-electron contributions. We use a state-interaction procedure and compute the SOC matrix elements using zero-order non-relativistic states. Benchmark calculations using several closed-shell organic molecules, diradicals, and a single-molecule magnet illustrate the efficiency of the SOC protocol. The results for organic molecules (described by standard TD-DFT) show that SOCs are insensitive to the choice of the functional or basis sets, as long as the states of the same characters are compared. In contrast, the SF-TD-DFT results for small diradicals (CH2, NH 2 + , SiH2, and PH 2 + ) show strong functional dependence. The spin-reversal energy barrier in a Fe(III) single-molecule magnet computed using non-collinear SF-TD-DFT (PBE0, ωPBEh/cc-pVDZ) agrees well with the experimental estimate. [ABSTRACT FROM AUTHOR]

We report a combined experimental and theoretical investigation of electron–molecule interactions using pyrrole as a model system. Experimental two-dimensional electron energy loss spectra (EELS) encode information about the vibrational states of the molecule as well as the position and structure of electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features. We confirm the two previously described π resonances at about 2.5 and 3.5 eV (the calculations place these two states at 2.92 and 3.53 eV vertically and 2.63 and 3.27 eV adiabatically). The calculations also predict a low-lying resonance at 0.46 eV, which has a mixed character—of a dipole-bound state and σ* type. This resonance becomes stabilized at one quanta of the NH excitation, giving rise to the sharp feature at 0.9 eV in the corresponding EELS. Calculations of Franck–Condon factors explain the observed variations in the vibrational excitation patterns. The ability of theory to describe EELS provides a concrete illustration of the utility of non-Hermitian quantum chemistry, which extends such important concepts as potential energy surfaces and molecular orbitals to states embedded in the continuum. [ABSTRACT FROM AUTHOR]

Sensitivity and selectivity of modern electrochemical genotyping methods are insufficient to detect a single-oligonucleotide mismatch in low-concentration native DNA samples. Novel methods of tuning, controlling, and monitoring plasmon modes are necessary to achieve attomolar and higher sensitivity for the modern graphene-based transducers of molecular signals. The electrochemical DNA assay is promising one for applications in the molecular diagnostics of tumors with the genome single-nucleotide polymorphism (SNP) for simultaneously discriminating both wild-type and mutant alleles of the gene in very small concentrations. We offer the plasmon-associated DNA-genotyping method based on the screening effects in assemblies of Raman-optically active conjugates comprising DNA and metallic carbon nanotubes. The impedimetric DNA sensors of non-Faradaic type based on the plasmonic screening effect can be more sensitive than the Raman optical transducer based on Raman DNA optical activity resulting in the plasmon resonance due to liability of the Raman transducer parameters to environmental influence. [ABSTRACT FROM AUTHOR]

Brucellosis is a dangerous zoonotic disease caused by bacteria of the genus Brucella. Diagnosis of brucellosis is based on the detection in animal and human sera of antibodies to the O-polysaccharide of Brucella lipopolysaccharide. The currently employed serodiagnosis of brucellosis relies on the use of the Brucella O-polysaccharide as a diagnostic antigen. However, the existence of bacterial species, which also express O-polysaccharides structurally similar to that of Brucella, may decrease the specificity of the brucellosis detection due to false-positive test results. It has been shown that the efficiency of the test can be significantly improved by using synthetic oligosaccharides that correspond to the so-called M epitope of the Brucella O-antigen. This epitope is characterized by an a-(1^3)-linkage between D-perosamine units and is unique to Brucella. Here we report on an efficient approach to the synthesis of oligosaccharides that model the M epitope of the Brucella O-polysaccharide. The approach is based on the use of the a-(1^3)-linked disaccharide thioglycoside as the key donor block. Its application allowed the straightforward assembly of a set of four protected oligosaccharides, which includes a disaccharide, two trisaccharides, and a tetrasaccharide, in five glycosylation steps. The synthesized oligosaccharides are planned to be used in the development of diagnostic tools for identifying brucellosis in humans and domestic animals, as well as a potential vaccine against it. [ABSTRACT FROM AUTHOR]

The $4 n^2$ -inequality for smooth points plays an important role in the proofs of birational (super)rigidity. The main aim of this paper is to generalize such an inequality to terminal singular points of type $cA_1$ , and obtain a $2 n^2$ -inequality for $cA_1$ points. As applications, we prove birational (super)rigidity of sextic double solids, many other prime Fano 3-fold weighted complete intersections, and del Pezzo fibrations of degree $1$ over $\mathbb {P}^1$ satisfying the $K^2$ -condition, all of which have at most terminal $cA_1$ singularities and terminal quotient singularities. These give first examples of birationally (super)rigid Fano 3-folds and del Pezzo fibrations admitting a $cA_1$ point which is not an ordinary double point. [ABSTRACT FROM AUTHOR]

We report on the piezoresistive method for detecting stability loss events in microelectromechanical sensors based on bifurcation. The method involves measuring the resistivity changes of an entire beam to detect snap-through transitions in an electrostatically actuated, bistable double-clamped crystalline silicon (Si) microbeam. The applicability of the suggested approach in two types of sensors—an ambient air temperature sensor or a mean air velocity sensor, is demonstrated. In both cases, the bistable beam, serving as the sensing element, is affected by the electrothermal Joule's heating and air cooling. The measured signal is obtained by monitoring the critical voltages of the snap-through transitions. Piezoresistive sensing is especially suitable for the response monitoring of the exposed to the environment, free-standing heated microbeam sensors, where optical, piezoelectric, or electrostatic interrogation methods are not applicable. The approach can be implemented in various bifurcation microsensors and for response monitoring of bistable actuators. [ABSTRACT FROM AUTHOR]