New 7-piperazinylquinolones containing (benzo[<Emphasis Type="BoldItalic">d</Emphasis>]imidazol-2-yl)methyl moiety as potent antibacterial agents

A series of 7-piperazinylquinolones containing a (benzo[d]imidazol-2-yl)methyl moiety were designed and synthesized as new antibacterial agents. The antibacterial activity of title compounds was evaluated against Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis and Bacillus subtilis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa and Klebsiella pneumonia) microorganisms. Among the tested compounds, the N1-cyclopropyl derivative 4a showed the highest activity against S. aureus, S. epidermidis, B. subtilis and E. coli (\(\text {MIC} = 0.097\) \(\upmu \)g/mL), being 2–4 times more potent than reference drug norfloxacin. A structure-activity relationship study demonstrated that the effect of the nitro group on the benzimidazole ring depends on the pattern of substitutions on the piperazinylquinolone.     

Electronic structure of the Np<Emphasis Type="Italic">MT</Emphasis> <Subscript>5</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Fe,Co, Ni; <Emphasis Type="Italic">T</Emphasis> = Ga,In) series of neptunium compounds

Evolution of the electronic structure of the NpMGa₅ (M = Fe, Co, Ni) series of neptunium compounds, whose crystal structure is similar to that of the known family of Pu115 superconductors, was studied by the LDA + U + SO method. The calculations took into account both the strong electron correlations and the spin?orbit coupling in the 5f shell of neptunium. For the first time, the electronic structure was calculated for a hypothetical series of compounds in which gallium is replaced with indium. Parameters of the crystal structure of the given series were obtained using the relationship between the parameters of the crystal structure of the earlier-studied compounds PuCoGa₅ and PuCoIn₅. The analysis of the electronic structure and characteristics of neptunium ions calculated in the framework of the LDA + U + SO method showed that the neptunium ions in NpMIn₅ with M = Fe, Co, and Ni should have an electron configuration closer to f⁴, but a spin and magnetic characteristics close to those in NpMGa₅.     

Synthesis and antimicrobial evaluation of ester-linked 1,4-disubstituted 1,2,3-triazoles with a furyl/thienyl moiety

Twenty ester-linked 1,4-disubstituted 1,2,3-triazoles having a furyl/thienyl moiety have been synthesized from heteroaryl prop-2-yn-1-yl carboxylate and aromatic azides via a Cu(I) catalyzed 1,3-dipolar cycloaddition. All the synthesized compounds were characterized by FTIR, \(^{1}\)H NMR, \(^{13}\)C NMR spectroscopy and HRMS. Synthesized triazoles were tested in vitro for antimicrobial evaluation against Gram-negative bacteria—Escherichia coli, Enterobacter aerogenes and Klebsiella pneumoniae; Gram-positive bacteria—Staphylococcus aureus and two fungal strains—Candida albicans and Aspergillus niger, reflecting moderate to good activity. The structure of compound 6f was also confirmed by X-ray crystallography (CCDC 1469326).     

Nonradiative deactivation of the lowest triplet state of naphthalene and its hydroxy derivatives at 77 K

The validity of an inductive resonance theory of energy transfer from the T ₁→S ₀ transition dipole to overtone vibrations of molecular groups containing H and D atoms is experimentally tested for a series of compounds whose conjugation systems are similar in size. To this end, by using kinetic, spectral, and luminescent methods (measurements of the phosphorescence decay times, phosphorescence spectra, ratios between the quantum yields of phosphorescence and fluorescence at 77 K, total quantum yields of fluorescence at 293 K, and ratios between the quantum yields of fluorescence at 293 and 77 K), the deactivation processes of the lowest excited T ₁ and S ₁ states of seven emitting centers (naphthalene, its hydroxy and dihydroxy derivatives, and their monoanions) in solutions in ethanol-h ₆, ethanol-d ₆, and their 2: 1 mixtures with diethyl ether are studied. For all the compounds studied, the rate constants k _r of the radiative T ₁→S ₀ transition and the changes in the overlap integrals of the spectra of phosphorescence and absorption of overtones of CH stretching vibrations are determined. The rate constants of energy transfer k _dd(CH) from the T ₁→S ₀ transition dipole to the stretching vibrations of the CH bonds are calculated without regard for the changes in the localization and orientation of this transition dipole in the compounds under study. The contribution of an individual CH group k _nr(CH) to the total rate constant of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system is ascertained. A good correlation between the changes in the constants k _nr(CH) and k _dd(CH) in the series of the hydroxy derivatives of naphthalene is found, which is indicative of the inductive resonance mechanism of the energy degradation of the T ₁ state. The deviations from proportionality between the changes in these constants upon passing from naphthalene to its hydroxy derivatives, which correlate with a marked increase in the radiative constant k _nr of the hydroxy derivatives in comparison with naphthalene, indicate changes in the strength and localization of the T ₁→S ₀ transition dipole moment and in its orientation with respect to the plane of the molecule that occur due to introduction of a heteroatom, oxygen, whose lone pair of electrons enters into conjugation with the πelectrons of the naphthalene ring system.     

Regeneration of the palladium catalyst of acetylene hydrogenation in modified supercritical CO<Subscript>2</Subscript>

The results of the regeneration of the deactivated palladium catalyst of acetylene hydrogenation using supercritical fluid extraction (T = 130°C, P = 250 bar) were reported. The activity of the catalyst regenerated in supercritical carbon dioxide is comparable to the activity of the catalyst regenerated by the conventional procedure.     

On the calculation of the two-point function for the thirring-model by the method of functional integration

By the method of functional integration the two-point functionS _F for the spinor model with the interaction\( - \lambda (\bar \psi \psi )^2 \) is calculated in a two-dimensional space-time. After Fourier-transformationS _F (p) results as a power series with respect to 1/√λ. If we change the order of terms, we get a series in powers of γp. Each coefficient is a series in powers of 1/√λ. The first terms of this series are considered as a good approximation for bigλ. By reasons of convergence of the integrals we must displace the expansion centre of the series in powers ofγ p fromp ²=0 top ²=a ².     

Charge state of a transition metal impurity in II–VI semiconductors

The results of calculating the electronic structure of semiconductor compounds A^IIB^VI: 3d(A = Zn; B = S, Se, Te; 3d = Sc-Cu) at a low content of 3d impurities are discussed. The excess charge of an impurity ion with respect to the charge of the zinc ion is determined for the whole series of 3d impurities. It is found that the excess charge gradually varies from +0.6|e| for the scandium impurity to ?0.2|e| for the copper impurity. Photoionization of an impurity ion is simulated by adding a hole or an electron to the impurity center. The added charge is redistributed between the impurity ion and its nearest neighbors, thus decreasing or increasing the total excess charge of the impurity center by a magnitude of ～ 0.2|e|.     

Anomalous thermopower in heavy-fermion compounds CeB<Subscript>6</Subscript>, CeAl<Subscript>3</Subscript>, and CeCu<Subscript>6 − <Emphasis Type="Italic">x</Emphasis></Subscript>Au<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

High-precision measurements of thermopower have been performed in a wide temperature range (2–300 K) for a series of cerium-based heavy-fermion compounds, including CeB₆, CeAl₃, CeCu₆, and substitutional solid solutions of the CeCu_{6 ? x} Au _x system (x = 0.1, 0.2). All compounds exhibit an unusual (logarithmic) asymptotic behavior of the temperature dependence of the Seebeck coefficient: S ∝ ?lnT. In the case of cerium hexaboride, this anomalous behavior of S(T) is accompanied by the appearance of weak-carrier-localization-mode asymptotics in the conductivity (σ(T) ∝ T ^0.39), while the paramagnetic susceptibility χ(T) and the effective mass of charge carriers m _eff(T) vary according to a power law (χ(T), m _eff(T) ∝ T ^?0.8) in the temperature interval T = 10–80 K. This behavior corresponds to renormalization of the density of states at the Fermi level. The observed anomalous behavior of thermopower in CeB₆ and other cerium-based intermetallic compounds is attributed to the formation of heavy fermions (many-body states in the metal matrix) at low temperatures.     

Behavior of the excitation cross sections of the perturbed series of the xenon atom

Behavior of the excitation cross sections of the perturbed 6s[3/2]_n°?np[1/2]₀ spectral series of the xenon atom is experimentally studied. By using the methods of extended electron beam and optical spectroscopy, the cross sections are measured and the optical excitation functions are recorded for the transitions of this series with n=6–13. A deviation of the dependence Q=f(n) from a power-law function is revealed, as well as changes in the form of optical excitation functions and in the nature of the branching caused by perturbation of the 7p[1/2]₀ level by levels of the 5p ⁵(² P _1/2°)6p configuration.     

Ab initio calculations of B<Subscript>2</Subscript> type RHg (R = Ce,Pr, Eu and Gd) intermetallic compounds

Spin polarized ab initio calculations have been carried out to study the structural, electronic, elastic and thermal properties of RHg (R = Ce, Pr, Eu and Gd) intermetallic compounds in B₂ structure. The calculations have been performed by using both generalized gradient approximation (GGA) and local spin density approximation (LSDA). The calculated value of lattice constant (a ₀) for these compounds with GGA is in better agreement with the experimental data than those with LSDA. Bulk modulus (B), first-order pressure derivative of bulk modulus and magnetic moment (μ _B ) are also presented. The energy band structure and electron density of states show the occupancy of 4f states for light as well as heavy rare earth atom. The elastic constants are predicted from which all the related mechanical properties like Poisson’s ratio (σ), Young’s modulus (E), shear modulus (G _H ) and anisotropy factor (A) are calculated. The ductility or brittleness of these compounds is predicted from Pugh’s rule (B/G _H ) and Cauchy pressure (C ₁₂ ? C ₄₄). The Debye temperature (θ _D ) is estimated from the average sound velocity, which have not been calculated and measured yet.     

Synthesis and antifungal activity of dehydroabietic acid-based 1,3,4-thiadiazole-thiazolidinone compounds

In an attempt to search for new natural products-based antifungal agents, a series of novel dehydroabietic acid derivatives bearing a 1,3,4-thiadiazole-thiazolidinone moiety were designed and synthesized. The primary bioassay used showed that at a concentration of \(50\,\upmu \hbox {g}/\hbox {mL}\), the target compounds 3c, 3f, and 3n exhibited excellent antifungal activity (91.3 % inhibition) against Gibberella zeae, which was equivalent to the commercial antifungal drug azoxystrobin (positive control).     

A new method for measuring the solubility of slightly soluble substances in supercritical carbon dioxide

A self-consistent approach to the measurement of the solubility of biologically active compounds in supercritical (SC) media based on infrared spectroscopy is exemplified by paracetamol in supercritical CO₂. According to this approach, the integral extinction coefficient for a chosen analytical spectral band is determined from additional spectroscopic measurement of the compound under study dissolved in an inert solvent at known concentrations in the considered range of the parameters of state (pressure and temperature, p and T). The values of solubility of the compound under study in the SC medium are calculated based on the above-obtained values of the extinction coefficient and the analytical values of the integral intensity of the chosen spectral band for saturated solutions in the p,T-range of interest. The method allows one to determine the solubility with a high accuracy even if the measured values are as low as 10^–4–10^–1 mol %.     

Spin-glass-like transition in the majority-vote model with anticonformists

Majority-vote model on scale-free networks and random graphs is investigated in which a randomly chosen fraction p of agents (called anticonformists) follows an antiferromagnetic update rule, i.e., they assume, with probability governed by a parameter q (0 < q < 1∕2), the opinion opposite to that of the majority of their neighbors, while the remaining 1 ? p fraction of agents (conformists) follows the usual ferromagnetic update rule assuming, with probability governed by the same parameter q, the opinion in accordance with that of the majority of their neighbors. For p = 1 it is shown by Monte Carlo simulations and using the Binder cumulants method that for decreasing q the model undergoes second-order phase transition from a disordered (paramagnetic) state to a spin-glass-like state, characterized by a non-zero value of the spin-glass order parameter measuring the overlap of agents’ opinions in two replicas of the system, and simultaneously by the magnetization close to zero. In the case of the model on scale-free networks the critical value of the parameter q weakly depends on the details of the degree distribution. As p is decreased, the critical value of q falls quickly to zero and only the disordered phase is observed. On the other hand, for p close to zero for decreasing q the usual ferromagnetic transition is observed.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Polarization of phosphorescence transitions and probabilities of intramolecular nonradiative deactivation of the lowest triplet state of aromatic molecules

This study continues the experimental testing of the validity of the inductive resonance theory of dipole-dipole energy transfer from the T ₁→S ₀ transition dipole to stretching vibrations of intramolecular CH bonds of naphthalene and its hydroxy derivatives. To this end, in the series of compounds under study, the range of variation of the geometrical parameter [Φ(CH)]² of the Förster theory, which accounts for the mutual orientation of the energy donor and acceptor, is estimated. Preliminarily, the angles between the transition dipole moments of the radiative and absorptive electronic transitions (T ₁→S ₀ and S ₀→S ₁; T ₁→S ₀ and S ₀→S ₂; S ₁→S ₀ and S ₀ →S ₁; and S ₁→S ₀ and S ₀→S ₂) are measured at 77 K by the method of polarization photoselection. From the polarization measurements, the angles between the phosphorescence transition dipole moment and the plane of a molecule are determined. It was found that, upon passage from naphthalene to its β derivatives, the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule markedly changes, with the in-plane component of the dipole moment being increased by an order of magnitude. The experimentally determined rate constants of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system, k _nr(CH), are compared with the rate constants [Φ(CH)]² of the inductive resonance energy transfer from the dipole of the T ₁→S ₀ transition to the dipole of the CH vibrations polarized in the plane of a molecule, calculated with regard to the orientational factor [Φ(CH)]². This comparison showed that, in the series of compounds under study, a change in the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule does not affect the rate of the nonradiative T ₁?S ₀ transition. This inference is confirmed by the absence of a correlation between the rate constants k _dd(CH) calculated by us (with regard to [Φ(CH)]²) and the well-known rate constants k _nr(CH) of individual sublevels of the T ₁ state measured at T≤1.35 K for a number of organic molecules. The possible sources of discrepancy between the experimental data that k _nr(CH) is independent of [Φ(CH)]² and the predictions of the theory are considered. A conclusion is made that the electronic-vibrational energy transfer between electric dipoles is the most probable mechanism of the T ₁?S ₀ transitions, but the rate constant of the dipole-dipole energy transfer upon interaction of the electronic and vibrational dipoles in a molecule does not depend on their orientations.     

Ab initio calculations of Born charges in ferroelectrics with a perovskite structure

A method has been proposed for calculating Born effective charges in compounds with a cubic perovskite structure. The method is based on the first-principles calculation of individual contributions from the short-range interaction and the intercell dipole-dipole interaction to the Born tensor Z _ii (s) for crystalline dielectrics. It has been shown that the contribution from the short-range interaction Z _ii ^sr (s) to the Born tensor components can be derived from ab initio calculations performed for polyatomic clusters. The results of the calculations of the short-range interactions Z _ii ^sr (s) for the cubic phases of the BaTiO₃, SrTiO₃, CaTiO₃, PbTiO₃, BaZrO₃, PbZrO₃, KNbO₃, and KTaO₃ compounds with the use of the electronic structure calculations within the Hartree-Fock approximation and the density functional theory are presented. For the BaTiO₃, SrTiO₃, CaTiO₃, PbTiO₃, KNbO₃, and KTaO₃ compounds, the components of the complete Born tensor have been also calculated. The obtained values of Z _ii (s) are in good agreement with the results of the calculations in terms of the linear response theory and the Berry phase approach.     

Variation in the energy spectra of primary cosmic rays for 2007–2015, according to data from the URAGAN muon hodoscope

Simulations of how secondary components of cosmic rays are generated and pass through the atmosphere are performed using the CORSIKA software package. The relationship between the vertical projection of the local anisotropy vector A _Z and the index of primary particle spectrum γ is calculated. The time series of A _Z for 2007–2015 are obtained using data from the URAGAN muon hodoscope. Matrix data corrected for barometric and temperature effects are used to estimate A _Z . Using the A _Z time series, the average annual daily variations Δγ are estimated. Annual and daily variations in the slope of the energy spectrum of primary protons are observed.     

Gamow Vectors and Borel Summability in a Class of Quantum Systems

We analyze the detailed time dependence of the wave function ψ(x,t) for one dimensional Hamiltonians \(H=-\partial_{x}^{2}+V(x)\) where V (for example modeling barriers or wells) and ψ(x,0) are compactly supported.We show that the dispersive part of ψ(x,t) is the Borel sum of its asymptotic series in powers of t ^?1/2, t→∞. The remainder, the difference between ψ and the Borel sum, i.e., the exponential part of the transseries of ψ, is a convergent expansion of the form \(\sum_{k=0}^{\infty}g_{k}\Gamma_{k}(x)e^{-\gamma_{k} t}\), where Γ _k are the Gamow vectors of H, and iγ _k are the associated resonances; generically, all g _k are nonzero. For large k, γ _k ～const?klog?k+k ² π ² i/4. The effect of the Gamow vectors is visible when time is not very large, and the decomposition defines rigorously resonances and Gamow vectors in a nonperturbative regime, in a physically relevant way.The decomposition allows for calculating ψ for moderate and large t, to any prescribed exponential accuracy, using optimal truncation of power series plus finitely many Gamow vectors contributions.The analytic structure of ψ is perhaps surprising: in general (even in simple examples such as square wells), ψ(x,t) turns out to be C ^∞ in t but nowhere analytic on ?⁺. In fact, ψ is t-analytic in a sector in the lower half plane and has the whole of ?⁺ a natural boundary. In the dual space, we analyze the resurgent structure of ψ.     

Thermodynamic properties of water–aliphatic alcohol systems in a wide range of parameters

The results of thermal and thermodynamic (phase diagram) property calculations of water–aliphatic alcohol (methanol, ethanol, n-propanol) systems in liquid and vapor phases, as well as supercritical fluid water–methanol systems have been presented. The calculations are based on the polynomial equation of state, represented by expansion of the compressibility factor into a power series of reduced density (ω = ρ/ρ_cr and reduced temperature (τ = T/T _cr)

$$Z = \frac{p}{{RT{\rho _m}}} = 1 + \sum\limits_{i = 1}^m {\sum\limits_{j = 0}^{{n_i}} {\frac{{{a_{ij}}{\omega ^i}}}{{{\tau ^j}}}} } $$

, which describes experimental p,ρ,T,x-dependencies with an average relative error of 1.2%.