Modern approaches for determination and identification of barrenwort (<Emphasis Type="Italic">Epimedium</Emphasis>) flavonoids

The modern methods of analysis of the main active substances barrenwort (Epimedium)—flavonoids—are considered. Various types of extraction are used to isolate these components from plant raw materials. Flavonoids are separated by capillary electrophoresis, thin layer chromatography, and high performance liquid chromatography (HPLC) in combination with UV and mass spectrometric detection.     

Crystal structure of modular sodium-rich and low-iron eudialyte from Lovozero alkaline massif

The structure of the sodium-rich representative of the eudialyte group found by A.P. Khomyakov at the Lovozero massif (Kola Peninsula) is studied by X-ray diffraction. The trigonal cell parameters are: a = 14.2032(1) and c = 60.612(1) Å, V = 10589.13 Å3, space group R3m. The structure is refined to the final R = 5.0% in the anisotropic approximation of atomic displacement parameters using 3742|F| > 3σ(F). The idealized formula (Z = 3) is Na₃₇Ca₁₀Mn₂FeZr₆Si₅₀(Ti, Nb)₂O₁₄₄(OH)₅Cl₃ · H₂O. Like other 24-layer minerals of the eudialyte group, this mineral has a modular structure. Its structure contains two modules, namely, “alluaivite” (with an admixture of “eudialyte”) and “kentbrooksite,” called according to the main structural fragments of alluaivite, eudialyte, and kentbrooksite. The mineral found at the Lovozero alkaline massif shows some chemical and symmetry-structural distinctions from the close-in-composition labyrinthite modular mineral from the Khibiny massif. The difference between the minerals stems from different geochemical conditions of mineral formation in the two regions.     

Gas-phase reactions of the bis(η-cyclopentadienyl)methylzirconium cation with imines

The reactions of the bis(η⁵-cyclopentadienyl)methylzirconium cation (1) with four imines have been studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. Reactivity of the bis(η⁵-cyclopentadienyl)methylzirconium cation is governed by the availability of a labile hydrogen in the corresponding imine. The products observed differ from those that might be expected in analogy with earlier work on ketones, aldehydes and alkenes (e.g., zirconocene η³-enolate and η³-allyl complexes): azomethyne/benzylidene species are found instead of enamines; however, the general reaction mechanism resembles that proposed for ketones and alkenes. An elimination reaction leading to final products was shown to be preceded by a fast migratory insertion/deinsertion equilibrium for alkyl-substituted imines. Such an equilibrium is not possible for aryl-substituted imines due to lack of lability of the aryl groups and thus only methane elimination was observed for these imines.     

Synthesis of new functionalized 3,7-diazabicyclo[3.3.1]nonanes by aminomethylation of the Guareschi imides

The aminomethylation of 4,4-dialkyl-2,6-dioxopiperidine-3,5-dicarbonitriles (Guareschi imides) was studied for the first time. When the Guareschi imides were treated with primary aliphatic amines and an excess of formaldehyde, 2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitriles were obtained in varying yields (15–67%). The structure of 9,9-dimethyl-7-(2-methylpropyl)-2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitrile was studied by X-ray diffraction analysis.     

Influence of Al3Ni crystallisation origin particles on hot deformation behaviour of aluminium based alloys

Abstract

Binary Al–Ni, Al–Mg and ternary Al–Mg–Ni alloys containing various dispersions and volume fraction of second-phase particles of crystallisation origin were compressed in a temperature range of 200–500 °C and at strain rates of 0.1, 1, 10, 30 s^?1 using the Gleeble 3800 thermomechanical simulator. Verification of axisymmetric compression tests was made by finite-element modelling. Constitutive models of hot deformation were constructed and effective activation energy of hot deformation was determined. It was found that the flow stress is lowered by decreasing the Al₃Ni particle size in case of a low 0.03 volume fraction of particles in binary Al–Ni alloys. Intensive softening at large strains was achieved in the alloy with a 0.1 volume fraction of fine Al₃Ni particles. Microstructure investigations confirmed that softening is a result of the dynamic restoration processes which were accelerated by fine particles. In contrast, the size of the particles had no influence on the flow stress of ternary Al–Mg–Ni alloy due to significant work hardening of the aluminium solid solution. Atoms of Mg in the aluminium solid solution significantly affect the deformation process and lead to the growth of the effective activation energy from 130–150 kJ/mol in the binary Al–Ni alloys to 170–190 kJ/mol in the ternary Al–Mg–Ni alloy.