Ring expansion in perfluorooxiranes under electrophilic catalysis conditions

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, p. 2183, September, 1990.     

The electrochemical behaviour of the altenuene mycotoxin and its acidic properties

The electrooxidation of altenuene (ALT), one of the mycotoxins of the Alternaria alternata genus, on a glassy carbon disk electrode is studied for the first time by using cyclic and square wave voltammetry. From the electrochemical responses, a complex reaction mechanism could be inferred. Values of 1.06×10⁻⁵ cm² s⁻¹, 1.116 V and 2 were determined for the diffusion coefficient, the apparent formal potential and the electron number, respectively, for the overall electrode process by convolution analysis of linear scan voltammograms. Square wave voltammetry was used to generate I_p versus c_ALT* calibration curves for this fungal metabolite. A detection limit of 4.0×10⁻⁷ M was determined for a 2:1 signal to noise ratio. The acid dissociation constant for ALT was determined from conventional UV–vis spectrophotometric measurements. Experimental variations of absorbance as a function of pH at a given wavelength were fitted by using the exact equation that describes the system. Good agreement between the experimental absorbance versus pH plots and the curves generated by the fitting process was found.     

Local Rings of Rings of Quotients

The aim of this paper is to characterize those elements in a semiprime ring R for which taking local rings at elements and rings of quotients are commuting operations. If Q denotes the maximal ring of left quotients of R, then this happens precisely for those elements if R which are von Neumann regular in Q. An intrinsic characterization of such elements is given. We derive as a consequence that the maximal left quotient ring of a prime ring with a nonzero PI-element is primitive and has nonzero socle. If we change Q to the Martindale symmetric ring of quotients, or to the maximal symmetric ring of quotients of R, we obtain similar results: an element a in R is von Neumann regular if and only if the ring of quotients of the local ring of R at a is isomorphic to the local ring of Q at a. Partially supported by the Ministerio de Educación y Ciencia and Fondos Feder, jointly, trough projects MTM2004-03845, MTM2007-61978 and MTM2004-06580-C02-02, MTM2007-60333, by the Junta de Andalucía, FQM-264, FQM336 and FQM02467 and by the Plan de Investigación del Principado de Asturias FICYT-IB05-017.     

ChemInform Abstract: Explaining Stability of Transition Metal Carbides — and Why TcC Does Not Exist.

The formation of transition metal (M) carbides M_xC_y and trends of their stability are systematically investigated using the USPEX code within the DFT.     

Composition assessment of ferric oxide by accurate peak fitting of the Fe 2p photoemission spectrum

A quantitative study of the surface composition of ferric oxide employing photoemission spectra is presented. It was possible to accurately reproduce the expected composition (Fe_2.00±0.05O₃) by modeling the background as a combination of Shirley‐type (Shirley–Vegh–Salvi–Castle) and slope backgrounds through the active approach. The line‐shape employed to fit apparent peak asymmetries was the double‐Lorentzian. It was possible to resolve a previously unreported satellite located at ~729 eV. Copyright © 2016 John Wiley & Sons, Ltd.     

Additive Differential Pulse Voltammetry for the Study of Slow Charge Transfer Processes at Spherical Electrodes

The application of additive differential pulse voltammetry to the study of the kinetics of a charge transfer process is studied. A simple analytical solution is presented, valid for spherical electrodes of any size and for electrode processes of any reversibility. From this solution, valuable diagnostic criteria for the elucidation of the electrochemical reversibility are established based on the variation of the ADPV signal with the duration of the potential pulses, the electrode radius and the pulse height. Working curves for the determination of the kinetic parameters are also given. The value of the ADPV technique is experimentally demonstrated by studying the kinetics of the reduction of 3‐nitrophenolate^? and europium³⁺ at mercury hemispherical microelectrodes.     

Distribution of copper- and nickel-containing modifier components in the pore space of HZSM-5 zeolite

The distribution of copper- and nickel-containing components in the pore space of HZSM-5 zeolite was quantitatively studied. It was found that the detailed distribution of a modifier in the micropore and mesopore volumes of the zeolite depends on both the chemical nature of the modifier and the conditions of supporting and the regime of M²⁺ polycondensation in the pore space of the zeolite. The experimental data on the low-temperature adsorption of nitrogen on Cu(n)ZSM-5 catalysts can be interpreted as the result of the partial filling of the zeolite micropore space (10 vol %) and the finest mesopores with D < 3 nm with the modifier. In the case of Ni(n)ZSM-5 catalysts, the penetration of the modifier into zeolite channels (micropores) in detectable amounts was not found, and it was arranged in mesopores on the surface of zeolite crystallites. The reason for differences between modifier distributions in the pore structure of the zeolite was explained from the standpoint of different structures of copper and nickel polyhydroxo complexes in impregnating solutions after polycondensation. It was found that, in the Cu(n)ZSM-5 and Ni(n)ZSM-5 catalysts, the modifier component contained copper and nickel only in a doubly charged state and mainly octahedral oxygen environments. In this case, three-dimensional nanoparticles or coarsely dispersed particles of CuO were not detected in the pore space of the support, whereas the presence of a small amount of sufficiently large NiO crystals with a coherent-scattering region of 80–100 nm was detected in Ni(n)ZSM-5, and these crystals occurred on the surface of zeolite crystals. It was found that the apparent density of a copper-or nickel-containing component arranged in the pore space of the zeolite was lower than the density of the bulk CuO and NiO phases by a factor of ～3 and 4, respectively, because of the size effect.     

Tracking protein electrodenaturation fronts in the electrochemical treatment of tumors

Electrochemical reactions in the electrochemical treatment of tumors (EChT) induce extreme pH changes and, consequently, protein electrodenaturation fronts intimately related to tumor destruction. Here we introduce a new in vitro EChT collagen–macronutrient gel (CMG) model to study protein electrodenaturation fronts as a mean of assessing EChT effectiveness. Our CMG model shows that from an initial uniform condition two electrodenaturation fronts evolve expanding towards each other until collision. Moreover, electrodenaturation front tracking reveals that the front grows under a diffusion-controlled regime. Based on this evidence it is possible, in principle, to predict the time needed for tumor destruction without compromising healthy tissue. These results are consistent with those previously obtained with in vivo and in vitro EChT modeling. In contrast to previous simpler in vitro models, our CMG model represents a better structural and chemical approximation to a real tissue thus providing a better tool for validation of new in silico EChT models aimed at a more accurate prediction of tissue destruction level.