Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Isolation of Bisphenol A-Tolerating/degrading Shewanella haliotis Strain MH137742 from an Estuarine Environment

Applied Biochemistry and Biotechnology - The human exposure to bisphenol A (BPA) occurs frequently. Once, this compound was one of the highest volume chemicals produced worldwide and used as a...     

On the role of the interface charge in non-ideal metal–semiconductor contacts

The bias dependent interface charge is considered as the origin of the observed non-ideality in current–voltage and capacitance–voltage characteristics. Using the simplified model for the interface electronic structure based on defects interacting with the continuum of interface states, the microscopic origin of empirical parameters describing the bias dependent interface charge function is investigated. The results show that in non-ideal metal–semiconductor contacts the interface charge function depends on the interface disorder parameter, density of defects, barrier pinning parameter and the effective gap center. The theoretical predictions are tested against several sets of published experimental data on bias dependent ideality factor and excess capacitance in various metal–semicoductor systems.     

Evolution of the Alfvénic correlation in the solar wind

Summary The radial evolution of Alfvénic correlation is such that its value decreases with increasing heliocentric distance. So far this behaviour has been interpreted as an increase in the local production of ?inward? modes interacting destructively with the ?outward? modes. This work, which deals with largescale turbulence, shows that local generation phenomena are not commonly found in the solar wind and that the Alfvénic character of the fluctuations mainly depend on the ?outward? modes alone. The interaction of these modes with density and/or magnetic-field structures convected by the wind causes their destruction and a consequent depletion of the Alfvénic correlation. The same effect would be obtained if ?inward? modes were really present. Our conclusions are that large-scale ?inward? modes are the spectral counterpart of non-propagating field and plasma structures convected by the solar wind and identified as both compression regions and pressure balance structures. Paper presented at the V Cosmic Physics National Conference, S. Miniato, November 27–30, 1990.     

Finite Groups Acting on Homology 3-Spheres: On a Result of M. Reni

 We give a list including all finite groups G which admit smooth orientation preserving actions on homology 3-spheres (arbitrary actions, i.e. possibly with fixed points; if the action is free then the group G has periodic cohomology and the classification of such groups is well known). The main work in this direction is due to M. Reni. In the present paper, we complete and extend his results for the case of nonsolvable groups G. Received 19 March 2001; in revised form 15 September 2001     

Nonlinear effects in optical fibers

The basic differential equations necessary to represent nonlinear propagation of short and ultrashort optical pulses in dielectric waveguides are derived. After introducing fundamental and higher-order soliton solutions of the nonlinear Schroedinger equations, the possibilities of realizing soliton-based communication systems are discussed. Higher-order nonlinear effects associated with selj-Raman gain and optical amplification in connection with the use of active fibers are also described.     

Measurement of acoustic particle velocities in enclosed sound field: Assessment of two Laser Doppler Velocimetry measuring systems

The performances of two Laser Doppler Velocimetry (LDV) systems adapted for measuring the acoustic particle velocities are assessed in enclosed sound field. This assessment is performed by comparing the acoustic velocities measured by means of LDV to reference acoustic velocities estimated from sound pressure measurements. The two LDV systems are based on a single optical bench which delivers an optical signal called Doppler signal. The Doppler signal, which is frequency modulated, is analyzed by means of two signal processing systems, the BSA (Burst Spectrum Analyser from Dantec) on the one hand, and a system specifically developed for the estimation of the acoustic velocity on the other hand. Once the experimental setup has been optimized for minimizing the errors made on the reference velocities, the assessment is performed and shows that both systems can measure the acoustic velocity in enclosed field in two the frequency ranges [0-4 kHz] and [0-2 kHz] respectively for acoustic velocity amplitudes of 10 mm/s and 1 mm/s.