Photochemical behavior of some substituted benzophenoxazinones

Irradiation of some substituted benzophenoxazinones in methanol solution by visible light yields dimerization and substitution products. A possible radical mechanism is proposed and validated by quantum mechanical computations.     

Correlation spectroscopy as a tool for detecting losses of ligand elements in laser welding of aluminium alloys

The plasma plume induced during laser welding of metals is a mixture of metal vapour, coming from the vaporised weld pool surface and shielding gas. The influence of the shielding gas on the welded joints quality is not yet well understood and very few investigations, to the best of our knowledge, were addressed to study its role in case of welding of aluminium–magnesium alloys. In this paper we present a study of the dynamics of plasma plume produced in laser welding of 5xxx aluminium alloys by means of correlation spectroscopy. By our results we can correlate the influence of the welding speed, in case of ineffective gas shielding, to the loss of alloying elements. Finally, the results obtained are consistent with the EDX analysis performed in post-processing on the welded joints.     

Volumetric and transport properties of aerosol-OT reversed micelles containing light and heavy water

Densities and viscosities of sodium bis(2-ethylhexyl) sulfosuccinate (AOT in-heptane system containing light and heavy water, as a function of the molar ratio R (R=[H₂O or D₂O]/[AOT]) were measured at 0, 5, 25 and 40°C. At low R values, the apparent molar volume of deuterium oxide is smaller than that of light water. The difference is related to the strength of the hydrogen bonding H₂O and D₂O. The viscosities of both H₂O-AOT-n-heptane and D₂O-AOT-n-heptane systems were explained in terms of intermicellar interactions mainly governed by hydration of the head groups of AOT.     

Characteristic Features of Gravitational Wave Lensing as Probe of Lens Mass Model

To recognize gravitational wave lensing events and being able to differentiate between similar lens models will be of crucial importance once one will be observing several lensing events of gravitational waves per year. In this work, the lensing of gravitational waves is studied in the context of LISA sources and wave-optics regime. While different papers before the studied microlensing effects enhanced by simultaneous strong lensing, the focus is on frequency (time) dependent phase effects produced by one lens that will be visible with only one lensed signal. It is shows how, in the interference regime (i.e., when interference patterns are present in the lensed image), one is able to i) distinguish a lensed waveform from an unlensed one, and ii) differentiate between different lens models. In pure wave-optics, on the other hand, the feasibility of the study depends on the signal-to-noise ratio of the signal and/or the amplitude of the lensing effect. To achieve these goals, the phase of the amplification factor of the different lens models and its effect on the unlensed waveform is studied, and the signal-to-noise calculation to provide some quantitative examples is exploited.     

A Riemann-Hilbert boundary value problem in neutron transport theory

Summary A Riemann-Hilbert boundary value problem, occurring in neutron transport theory, is presented and solved in this note for the case of an infinite straight line and zero index.

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Sommario Viene presentato e risolto in questa nota un problema al contorno di Riemann-Hilbert di indice zero e relativo ad un intervallo infinito. Esso ha origine da un problema di diffusione di neutroni, studiato nell'ambito della teoria del trasporto.

     

Probing the Coordinative Unsaturation and Local Environment of Ti3+ Sites in an Activated High‐Yield Ziegler–Natta Catalyst

The typical activation of a fourth generation Ziegler–Natta catalyst TiCl₄/MgCl₂/phthalate with triethyl aluminum generates Ti³⁺ centers that are investigated by multi‐frequency continuous wave and pulse EPR methods. Two families of isolated, molecule‐like Ti³⁺ species have been identified. A comparison of the experimentally derived g tensors and ^35,37Cl hyperfine and nuclear‐quadrupole tensors with DFT‐computed values suggests that the dominant EPR‐active Ti³⁺ species is located on MgCl₂(110) surfaces (or equivalent MgCl₂ terminations with tetra‐coordinated Mg). O₂ reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization.     

Organocatalytic,Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene‐Embedding Linear and Angular Polycycles

A direct aminocatalytic synthesis has been developed for the chemo‐, regio‐, diastereo‐, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable π‐extended allylidenemalononitriles as electron‐rich 1,3‐diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β‐unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6‐, 5,6‐, 7,6‐, 6,6,6‐, and 6,5,6‐fused ring systems, as well as biorelevant steroid‐like 6,6,6,6,5‐ and 6,6,6,5,6‐rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bis‐vinylogous Michael/Michael/retro‐Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.