Thermal coefficient of linear expansion of non-crystalline chalcogenides in the As-S-Se-Te-I system

The object of the paper is an investigation of the glasses of the (As₂S₃)_x(AsSe_0.5Te_0.5I)_100-x. type for 65≤;x≤;95, using methods of thermomechanical analysis. Values of the thermal coefficients of linear expansion in solid and visco-plastic phase were determined. it was shown that introducing arsenic-sulfide in glass-matrix AsChI, i.e. (AsSe_0.5Te_0.5I), leads to an increasing stability of these glasses. The characteristic temperatures of softening Tg and the temperature of the beginning of deformation t_w increase by increasing content of As₂S₃. The analytical forms of dependence of four significant physical values α_g, α_l, Tg, Tw, as a function of As₂S₃ content in the structure of glasses were fitted. This revised version was published online in July 2006 with corrections to the Cover Date.     

Infrared absorption and electron paramagnetic resonance studies of vinyl radical in noble-gas matrices

Vinyl radicals produced by annealing-induced reaction of mobilized hydrogen atoms with acetylene molecules in solid noble-gas matrices (Ar, Kr, and Xe) were characterized by Fourier transform infrared and electron paramagnetic resonance (EPR) spectroscopies. The hydrogen atoms were generated from acetylene by UV photolysis or fast electron irradiation. Two vibrational modes of the vinyl radical (nu7 and nu5) were assigned in IR absorption studies. The assignment is based on data for various isotopic substitutions (D and 13C) and confirmed by comparison with the EPR measurements and density-functional theory calculations. The data on the nu7 mode is in agreement with previous experimental and theoretical results whereas the nu5 frequency agrees well with the computational data but conflicts with the gas-phase IR emission results.     

An efficient approach to isoindolo[2,1-b][2]benzazepines via intramolecular [4+2] cycloaddition of maleic anhydride to 4-α-furyl-4-N-benzylaminobut-1-enes

Acylation of 4-α-furyl-4-N-benzylaminobut-1-enes with maleic anhydride gave 4-oxo-3-aza-10-oxatricyclo[5.2.1.0^1,5]dec-8-ene-6-carboxylic acid via amide formation followed by intramolecular Diels-Alder reaction of furan (IMDAF). The cycloaddition proceeded under mild reaction conditions (25 °C) and provided only the exo-adduct in quantitative yield. Treatment of this compound with PPA gave isoindolo[2,1-b][2]benzazepine derivatives via ring opening, aromatization and intramolecular electrophilic alkylation. In order to extend the scope of the reaction sequence, 7-oxo-5,11b,12,13-tetrahydro-7H-isoindolo[2,1-b][2]benzazepine-8-carboxylic acids were further transformed into useful synthetic intermediates.     

From microscopic to macroscopic nuclear collective dynamics

We apply smoothing procedures to response functions for isoscalar vibrations. For collective motion, we find a transition from a structured strength distribution to one corresponding to one incoherent, strongly overdamped mode. It is argued that the latter may be interpreted as macroscopic motion exhibiting, to some extent, features of the hydrodynamical model. We discuss the physical origin of this behaviour, in particular its relation to the disappearance of shell structure.Supported in part by the Deutsche Forschungsgemeinschaft     

Synthesis,Characterization and DFT Study of a New Family of High-Energy Compounds Based on s-Triazine,Carborane and Tetrazoles

An efficient one-pot synthesis of carborane-containing high-energy compounds was developed via the exploration of carbon–halogen bond functionalization strategies in commercially available 2,4,6-trichloro-1,3,5-triazine. The synthetic pathway first included the substitution of two chlorine atoms in s-triazine with 5-R-tetrazoles (R = H, Me, Et) units to form disubstituted tetrazolyl 1,3,5-triazines followed by the sequential substitution of the remaining chlorine atom in 1,3,5-triazine with carborane N- or S-nucleophiles. All new compounds were characterized by IR- and NMR spectroscopy. The structure of four new compounds was confirmed by single crystal X-ray diffraction analysis. The density functional theory method (DFT B3LYP/6-311 + G*) was used to study the geometrical structures, enthalpies of formation (EOFs), energetic properties and highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies and the detonation properties of synthesized compounds. The DFT calculation revealed compounds processing the maximum value of the detonation velocity or the maximum value of the detonation pressure. Theoretical terahertz frequencies for potential high-energy density materials (HEDMs) were computed, which allow the opportunity for the remote detection of these compounds.     

Synthesis of Functionalized Isoquinolone Derivatives via Rh(III)-Catalyzed [4+2]-Annulation of Benzamides with Internal Acetylene-Containing α-CF3-α-Amino Carboxylates

A convenient pathway to a new series of α-CF₃-substituted α-amino acid derivatives bearing pharmacophore isoquinolone core in their backbone has been developed. The method is based on [4+2]-annulation of N-(pivaloyloxy) aryl amides with orthogonally protected internal acetylene-containing α-amino carboxylates under Rh(III)-catalysis. The target annulation products can be easily transformed into valuable isoquinoline derivatives via a successive aromatization/cross-coupling operation.     

Synthesis,In Silico and In Vivo Toxicity Assessment of Functionalized Pyridophenanthridinones via Sequential MW-Assisted Intramolecular Friedel-Crafts Alkylation and Direct C–H Arylation

A rapid, efficient, and original synthesis of novel pyrido[3,2,1-de]phenanthridin-6-ones is reported. First, the key cinnamamide intermediates 8a–f were easily prepared from commercial substituted anilines, cinnamic acid, and 2-bromobenzylbromide in a tandem amidation and N-alkylation protocol. Then, these N-aryl-N-(2-bromobenzyl) cinnamamides 8a–f were subjected to a TFA-mediated intramolecular Friedel-Crafts alkylation followed by a Pd-catalyzed direct C–H arylation to obtain a series of potentially bioactive 4-phenyl-4,5-dihydro-6H,8H-pyrido[3,2,1-de]phenanthridin-6-one derivatives 4a–f in good yields. Finally, the toxicological profile of the prepared final compounds, including their corresponding intermediates, was explored through in silico computational methods, while the acute toxicity toward zebrafish embryos (96 hpf-LC₅₀, 50% lethal concentration) was also determined in the present study.     

A Water Molecule Triggers Guest Exchange at a Mono-Zinc Centre Confined in a Biomimetic Calixarene Pocket: a Model for Understanding Ligand Stability in Zn Proteins

In this study, the ligand exchange mechanism at a biomimetic Zn^II centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate Zn^II intermediates, and inversion of the pyramid at the Zn^II centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of Zn^II in proteins.