A planar chiral non-metallocenic analogue of the most popular N,N-dimethylbenzylaminate palladacycle

A racemic planar chiral tertiary amine pCp-CH₂NMe₂ (HL¹, pCp = [2.2]paracyclophane-4-yl) was prepared by aminomethylation of the bromide pCp-Br with Eschenmoser’s salt. Direct cyclopalladation of this new ligand with palladium(II) acetate results in the formation of the racemic CN-dimer rac-3 in a moderate yield of 64%. The enantiomerically pure dimer (S_pl, S_pl)-3 was obtained by the standard procedure of racemic palladacycle resolution using (S_C)-prolinate as a chiral derivatising agent. The ortho-palladated structure, absolute configuration of the chiral plane and stereochemical peculiarities of the new CN-palladacycle were established by means of NMR spectroscopy and an X-ray diffraction study of its (S_C)-prolinate derivative.     

High-Energy Proton-Beam-Induced Polymerization/Oxygenation of Hydroxynaphthalenes on Meteorites and Nitrogen Transfer from Urea: Modeling Insoluble Organic Matter?

Formation and structural modification of oxygenated polycyclic aromatic hydrocarbons (oxyPAHs) by UV irradiation on minerals have recently been proposed as a possible channel of PAH transformation in astrochemical and prebiotic scenarios of possible relevance for the origin of life. Herein, it is demonstrated that high-energy proton-beam irradiation in the presence of various meteorites, including stony iron, achondrite, and chondrite types, promotes the conversion of two representative oxyPAH compounds, 1-naphthol and 1,8-dihydroxynaphthalene, to complex mixtures of oxygenated and oligomeric derivatives. The main identified products include polyhydroxy derivatives, isomeric dimers encompassing benzofuran and benzopyran scaffolds, and, notably, a range of quinones and perylene derivatives. Addition of urea, a prebiotically relevant chemical precursor, expanded the range of identified species to include, among others, quinone diimines. Proton-beam irradiation of oxyPAH modulated by nitrogen-containing compounds such as urea is proposed as a possible contributory mechanism for the formation and processing of insoluble organic matter in meteorites and in prebiotic processes.     

Dynamical systems on quantum tori Lie algebras

We use quantum tori Lie algebras (QTLA), which are a one-parameter family of sub-algebras ofgl , to describe local and non-local versions of the Toda systems. It turns out that the central charge of QTLA is responsible for the non-locality. There are two regimes in the local systems-conformal for irrational values of the parameter and non-conformal and integrable for its rational values. We also consider infinite-dimensional analogs of rigid tops. Some of these systems give rise to quantized (magneto-)hydrodynamic equations of an ideal fluid on a torus. We also consider infinite dimensional versions of the integrable Euler and Clebsch cases.     

Selective Ruthenium Labeling of the Tryptophan Residue in the Bee Venom Peptide Melittin

Melittin is a membrane‐active peptide from bee venom with promising antimicrobial and anticancer activity. Herein we report on a simple and selective method for labeling of the tryptophan residue in melittin by the organometallic fragment [(C₅H₅)Ru]⁺ in aqueous solution and in air. Ruthenium coordination does not disturb the secondary structure of the peptide (as verified by 2D NMR spectroscopy), but changes the pattern of its intermolecular interactions resulting in an 11‐fold decrease of hemolytic activity. The high stability of the organometallic conjugate allowed the establishment of the biodistribution of the labeled melittin in mice by inductively coupled plasma MS analysis of ruthenium.     

Electrochemical method for the preparation nanocomposites based on carbon nanotubes and chromium oxides for oxygen electrodes

An electrochemical method for the preparation of nanostructured composites based on multiwalled carbon nanotubes and chromium oxide is proposed. The method involves electrodeposition of chromium oxides from a solution of hexavalent chromium oxide in sulfuric acid on carbon nanotubes. By varying the electrolysis conditions one can obtain deposited—catalyst particles of different size and vary the amount of catalyst. Oxygen electrodes have been made from the materials obtained for fuel cells with alkaline electrolyte, which showed good electrocatalytic properties.     

Validation of reducing-difference procedure for the interpretation of non-polarized infrared spectra of n-component solid mixtures

Validation of reducing-difference procedure based on subtracting of non-polarized infrared (IR) spectra of n-component solid mixtures is presented. The accuracy and precision are established. The limits of detection are 3.0, 2.5, 1.5 and 1.0 wt.% for 5-, 4-, 3-and 2-component mixtures, respectively. Smoothing procedures for IR spectral analysis, based on Savitzky-Golay or Fourier methods are applied as well. The mean values and relative standard deviations for peak position (ν_i) and integral absorbance (A_i) obtained by this data processing approach have been examined using Student's t-test.     

Stereoselective electrocatalytic transformation of arylidenemalononitriles and malononitrile into (1R,5S,6R)-6-aryl-2-amino-4,4-dialkoxy-1,5-dicyano-3-azabicyclo[3.1.0]hex-2-enes

Electrolysis of arylidenemalononitriles and malononitrile in alcohols in an undivided cell in the presence of sodium bromide as mediator results in the stereoselective formation of (1R,2S,6R)^*-6-aryl-2-amino-4,4-dialkoxy-1,5-dicyano-3-azabicyclo[3.1.0]hex-2-enes in 60-80% yields.