Copper(II) complexes with pyrazolyl-substituted nitronyl and imino nitroxides

It was established that the reactions of pyrazol-3-yl-substituted nitronyl nitroxide (HL¹) and pyrazol-3-yl-substituted imino nitroxide (HL³) with Cu(II) acetate lead to self-assembly of the Cu₄(OH)₂(OAc)₄(DMF)₂(L¹)₂ tetranuclear and Cu₂(OAc)₂(H₂O)₂(L³)₂ dinuclear complexes, respectively. The reaction of Cu(II) acetate with 5-ethoxycarbonyl-pyrazol-3-yl-substituted nitronyl nitroxide (HL²) gave unexpected solid Cu₂(H₂O)₂(L⁶)₂ · 2DMF, in which L⁶ is a deprotonated 5-carboxy-pyrazol-3-yl-substituted nitronyl nitroxide, formed as a result of cleavage of an ester bond in the starting HL². A similar transformation of the paramagnetic ligand was observed in the reaction of Cu(II) acetate with 5-ethoxycarbonyl-pyrazol-3-yl-substituted imino nitroxide (HL⁴). It led to the formation of Cu₂(DMF)₂(L⁷)₂, where L⁷ is deprotonated 2-(5-carboxy-1H-pyrazol-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide. An X-ray diffraction study indicated that in Cu₄(OH)₂(OAc)₄(DMF)₂(L¹)₂ and Cu₂(OAc)₂(H₂O)₂(L³)₂, the L¹ and L³ paramagnetic ligands perform the bridging cyclic tridentate function, while in Cu₂(H₂O)₂(L⁶)₂ · 2DMF and Cu₂(DMF)₂(L⁷)₂, the paramagnetic L⁶ and diamagnetic L⁷ are bridging bicyclic tetradentate ligands. The magnetic behavior of complexes with coordinated nitronyl nitroxide – Cu₄(OH)₂(OAc)₄(DMF)₂(L¹)₂ and Cu₂(H₂O)₂(L⁶)₂ · 2DMF is dictated by the dominant antiferromagnetic exchange interactions, which is confirmed by quantum-chemical data. The magnetic susceptibility of Cu₂(OAc)₂(H₂O)₂(L³)₂ reflects the competition between the antiferromagnetic and ferromagnetic components, of which the latter is due to electron coupling in the Cu(II) ← N=C–N ? O exchange channels. EPR data confirm the results received from static magnetic measurements for multispin solids.     

Interaction of shock waves with a jet wake during gas injection into supersonic stream

In the present paper, we report the results of an experimental study of the interaction region of a planar compression shock produced by a wedge in stream with the wake formed behind a cocurrent gas jet (H₂, air, or Ar) injected into the flow. Depending on the gas jet parameters, three modes of interaction could be distinguished: a strong interaction, observed when the flow velocity in the wake was subsonic; a moderate interaction, observed when a subsonic flow region, bounded by a shock of almost conical shape, formed in the vicinity of the compression shock; and a neutral interaction. Three-dimensional non-stationary Euler equations were solved to numerically examine the interaction of an axisymmetric jet with an oblique shock wave. The obtained interaction regimes were found to be in a reasonable agreement with experimental data.     

Direct iodination of 3- and 4-nitropyrazoles with a reagent based on iodine monochloride and silver sulfate

The reagent obtained from iodine monochloride and silver sulfate in sulfuric acid easily iodinates I-methyl-3-nitropyrazole under mild conditions to give 4-iodo or 4,5-diiodo derivatives, 1-Methyl-4-nitropyrazole was also directly iodinated with this reagent for the first time. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1482–1484, August, 2000.     

Temperature dependence of pressure broadening of the N = 1− fine structure oxygen line at 118.75 GHz

The absorption profile of the N = 1− fine structure line of oxygen was recorded by a resonator spectrometer at a frequency range of 110-130 GHz at atmospheric pressure and different temperatures ranging from −21 °C up to +22 °C. Analysis of the observed line shape allowed determination of the temperature dependence of the line pressure broadening. The measured value of the temperature exponent is n = 0.74(5) for self-broadening. Consistency of the measurements is supported by simultaneous measurements of the line intensity, the line mixing parameter and the line center frequency, and by comparison of obtained values with previously known data.     

Digital Colorimetry of Indicator Test-Systems Using a Smartphone and Chemometric Analysis in Determination of Quinolones in Pharmaceuticals

Journal of Applied Spectroscopy - A combined approach was developed for the identification and determination of quinolone antibiotics in pharmaceuticals using solid-state fluorescence digital...     

Phase equilibria and thermodynamics of coexisting phases in rare-earth element-iron-oxygen systems. I. The cerium-iron-oxygen system

In the present work it is shown that in the CeFeO system only one ternary compound with a perovskite structure, the orthoferrite CeFeO₃, is formed. We define the crystallographic properties of cerium ferroperovskite more accurately. The thermodynamics of its oxidation and reduction over a temperature range of 900–1200°C are studied using the emf method with a solid electrolyte.It is shown that the free energy of cerium orthoferrite formation from the oxides according to the reaction $\text{1}\text{2}\text{Ce}{}_2\text{O}{}_3\text{+}\text{1}\text{2}\text{Fe}{}_2\text{O}{}_3\text{=}\text{CeFeO}{}_3$, derived from data on the equilibrium oxidation of CeFeO₃, differs very little from the value of ΔG°, calculated from the magnitude of the equilibrium pressure of oxygen over the orthoferrite and reduction products coexisting with it.Phase equilibria and the thermodynamics of coexisting phases in the CeFeO system have been investigated. Equilibrium diagrams are constructed which define the character of the changes taking place in the CeFeO system during changes in partial oxygen pressure, temperature, and composition of the initial oxide mixture. Thus, we have equilibrium diagrams of the type P_O2 = f(composition) with T = constant; with one composition parameter fixed; and T = f(composition) with P_O2 = constant.     

The role of N.S. Kurnakov in creating new generations of researchers

The major milestones in the pedagogic activity of N.S. Kurnakov are listed. The characteristic properties of his teaching activity, his approaches, methods, and his principal ideas as regards the organization of teaching chemistry at a higher school are presented with attracting the memoirs of his disciplines and associated.     

Critical behavior of a random diode network

We study the percolation properties of a random diode network (RDN) which contains two kinds of directed bonds on a square lattice. This network is a special case of the random insulation-resistor-diode network. Both Monte Carlo simulations and series expansion for the percolation probability show that an estimated critical exponent, beta=0.1794+/-0.008, is different from known values for a conventional insulation-resistor-diode network. RDN belongs to neither the isotropic percolation universality class nor to the directed percolation universality, which we attribute to a difference of symmetry breakdown around the critical point.