Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes

Summary [RuCl₂(PPh₃)₃], [{RuCl₂(TPPMS)₂}₂] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids. In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared traditionally in a more complicated way.     

Mechanism of hydrogenolysis and isomerization of oxacyloalkanes on metals, V. Selectivities of metal catalysts in ring-opening reactions of oxiranes

The deoxygenation of methyloxirane to propene and its isomerization to oxo compounds on a Ni/SiO₂ catalyst were studied in a pulse microreactor, in the presence of H₂ as carrier gas, at 473 K. It was found that the deoxigenation leads to the creation of new types of active centers (Lewis acid site-basic site), which cause a change in the direction of ring opening. The differences in regioselectivity observed between Ni and Cu, and Pt and Pd, can be explained by the different affinities of the metals for oxygen. This finding can be generalized to other oxygen-containing compounds.

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=qa Ni/SiO₂ 473 . , - - , . Ni Cu, Pt Pd . .

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Part IV: J. Catal. (to be published)     

Conformational properties of propargyloxy-calix[4]arene tricarboxamides: NMR and DFT studies on the O-through-the-annulus rotation

The size limit of substituents allowing O-through-the-annulus rotation of substituted calix[4]arenes was further extended to the propargyloxy group in 24-propargyloxy-25,26,27-tris(N,N-dimethylcarbamoylmethoxy)-p-tert-butylcalix[4]arene by demonstrating its free but slow motion affording equilibrium between the partial cone and 1,2-alternate conformers. The effect of solvent and upper rim substituents R¹ on the conformational inversion was investigated by means of ¹H NMR. The rotational isomerisation of the parent (R¹ = H) analogue could not unambiguously be detected. The experimental results were supported by comprehensive density functional theory studies.     

Direct experimental limit on neutron-mirror-neutron oscillations

In case a mirror world with a copy of our ordinary particle spectrum would exist, the neutron n and its degenerate partner, the mirror neutron n', could potentially mix and undergo nn' oscillations. The interaction of an ordinary magnetic field with the ordinary neutron would lift the degeneracy between the mirror partners, diminish the n' amplitude in the n wave function and, thus, suppress its observability. We report an experimental comparison of ultracold neutron storage in a trap with and without superimposed magnetic field. No influence of the magnetic field is found and, assuming negligible mirror magnetic fields, a limit on the oscillation time taunn' > 103 s (95% C.L.) is derived.     

First observation of trapped high-field seeking ultracold neutron spin states

Ultracold neutrons were stored in a volume, using a magnetic dipole field shutter. Radial confinement was provided by material walls. Low-field seeking neutrons were axially confined above the magnetic field. High-field seeking neutrons are trapped inside the magnetic field. They can systematically shift the measured neutron lifetime to lower values in experiments with magnetic confinement.     

On the square root of a positive selfadjoint operator

We provide a short, elementary proof of the existence and uniqueness of the square root in the context of unbounded positive selfadjoint operators on real or complex Hilbert spaces.     

Decays of heavy Higgs Bosons into vector Bosons

The decays Higgs → Higgs + V (V = W, Z) are studied in the Weinberg-Salam model with two Higgs doublets and are shown to exceed the usual fermion decay mode with known fermions and the mode V$\text{V}$ in a large region of Higgs masses and mixing angles. Higgs-Higgs final states and the role of the heavy Higgs decays are briefly discussed.     

Experimental study of 199Hg spin anti-relaxation coatings

We report on a comparison of spin relaxation rates in a ¹⁹⁹Hg magnetometer using different wall coatings. A compact mercury magnetometer was built for this purpose. Glass cells coated with fluorinated materials show longer spin coherence times than if coated with their hydrogenated homologues. The longest spin relaxation time of the mercury vapor was measured with a fluorinated paraffin wall coating.