Efficient Access to Deuterated and Tritiated Nucleobase Pharmaceuticals and Oligonucleotides using Hydrogen‐Isotope Exchange

A general approach for the efficient hydrogen‐isotope exchange of nucleobase derivatives is described. Catalyzed by ruthenium nanoparticles, using mild reaction conditions, and involving either D₂ or T₂ as isotopic sources, this reaction possesses a wide substrate scope and a high solvent tolerability. This novel method facilitates the access to essential diagnostic tools in drug discovery and development: tritiated pharmaceuticals with high specific activities and deuterated oligonucleotides suitable for use as internal standards during LC‐MS quantification.     

Plasma-Catalytic Dry Reforming of CH4 over Calcium Oxide: Catalyst Structural and Textural Modifications

Plasma Chemistry and Plasma Processing - The coupling of catalyst and nonthermal plasma for the dry reforming of methane was investigated with a special attention to the textural and structural...     

Exact relativistic kinetic theory of an electron-beam-plasma system: hierarchy of the competing modes in the system-parameter space

The stability analysis of an electron-beam-plasma system is of critical relevance in many areas of physics. Surprisingly, decades of extensive investigation have not yet resulted in a realistic unified picture of the multidimensional unstable spectrum within a fully relativistic and kinetic framework. All attempts made so far in this direction were indeed restricted to simplistic distribution functions and/or did not aim at a complete mapping of the beam-plasma parameter space. The present Letter comprehensively tackles this problem by implementing an exact linear model. Three kinds of modes compete in the linear phase, which can be classified according to the direction of their wave number with respect to the beam. We determine their respective domain of preponderance in a three-dimensional parameter space and support our results with multidimensional particle-in-cell simulations.     

Measurement of vocal-tract influence during saxophone performance

This paper presents experimental results that quantify the range of influence of vocal tract manipulations used in saxophone performance. The experiments utilized a measurement system that provides a relative comparison of the upstream windway and downstream air column impedances under normal playing conditions, allowing researchers and players to investigate the effect of vocal-tract manipulations in real time. Playing experiments explored vocal-tract influence over the full range of the saxophone, as well as when performing special effects such as pitch bending, multiphonics, and "bugling." The results show that, under certain conditions, players can create an upstream windway resonance that is strong enough to override the downstream system in controlling reed vibrations. This can occur when the downstream air column provides only weak support of a given note or effect, especially for notes with fundamental frequencies an octave below the air column cutoff frequency and higher. Vocal-tract influence is clearly demonstrated when pitch bending notes high in the traditional range of the alto saxophone and when playing in the saxophone's extended register. Subtle timbre variations via tongue position changes are possible for most notes in the saxophone's traditional range and can affect spectral content from at least 800-2000 Hz.     

Unprecedented Reverse Volume Expansion in Spin-Transition Crystals

The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)₂(NCS)₂] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials.     

Benzoxazinone synthesis via Passerini–Smiles couplings

Benzoxazinones are easily prepared using Passerini–Smiles couplings of o-nitrophenol derivatives. Palladium-catalyzed flow-hydrogenation of adducts gives aniline derivatives that cyclize into benzoxazinones on treatment with trifluoroacetic acid.     

Transition Metal Free Cycloamination of Prenyl Carbamates and Ureas Promoted by Aryldiazonium Salts

Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox‐neutral azocycloamination. In general, N‐aryl O‐prenyl carbamates cyclize in a photocatalytic reaction with visible light and an organic dye. With electron‐deficient diazonium salts, electronic matching with an electron‐rich N‐aryl substituent results in a reaction proceeding in the ground state, without either light or photocatalyst. Cyclic voltammetry suggests that this radical reaction is initiated by hydrogen‐atom abstraction mediated by an aryl radical, followed by a radical addition cascade and proton‐coupled hole propagation. The reaction proceeds at room temperature in short reaction times, and a range of functional groups is tolerated.