The synthesis, spectroscopic properties and X-ray structure of Zn(II) complexes with amino derivatives of chromone

Three new Zn(II) complexes containing the ligands 5-amino-8-methyl-4H-chromen-4-one (1), 6- or 7-amino-2-phenyl-4H-chromen-4-one (2, 3) were prepared. The new synthesised compounds were characterised by IR, ¹H NMR and MS spectroscopy. The crystal structure of complex 4 was determined with the use X-ray diffraction. The Zn(II) centre of 4 is linked by two chlorido and two N-bound aminochromone ligands, 1, in a strongly distorted tetrahedral configuration with the dissymetric point group C₂. The protonation constants of the ligands 1, 2 and 3 corresponded to 3.68, 3.88 and 6.83, respectively. The stability constants of the Zn(II) complexes were calculated from the potentiometric titration data. The complexes were found to have the formulae ML and ML₂ for ligands 1 and 2, and ML for ligand 3. Fluorescence spectroscopic properties were also studied; the strongest fluorescence in solution was exhibited by complex 6.     

Correlation of hydrogen capacity in carbon material with the parameters of electrosorption

Electrochemical storage of hydrogen in activated carbon material has been investigated using different parameters of cathodic polarization. It has been proven that application of short galvanostatic pulses could be efficient for hydrogen storage in microporous carbon material. Charging current loads from 50 mA g⁻¹ to 32 A g⁻¹ have been used showing correlation between hydrogen capacity, time of charging and electrical efficiency. The anodic charge equivalent to electrooxidation of 1.0 wt% of hydrogen can be already reached after 90 s of cathodic polarization. Temperature effect has been also evaluated and a gradual increase of hydrogen capacity with a better pronounced oxidation plateau was obtained at higher temperatures. Reversible electrosorption of hydrogen is a useful reaction in supercapacitor performance and it might have a potential application for a negative electrode of supercapacitor as well as reversibly operating electrode in the secondary cell.      

Conjugated Schiff bases. VII—Decarbonylation of some 1,3-hetrodienes under electron impact

The mass spectra of some 1,3- heterodienes containing the 1-oxa-4-aza-butadiene system have been determined and the characteristic fragmentation pathways are discussed. The pathways suggested are supported by the appropriate metastables, the spectra of model compounds and by deuterium labelling. The 1, 3-heterodienes substituted by the thioarylamide group from ions involving participation of the sulphur atom.     

Ferrioxamine B analogues: targeting the FoxA uptake system in the pathogenic Yersinia enterocolitica

A series of ferrioxamine B analogues that target the bacterium Yersinia enterocolitica were prepared. These iron carriers are composed of three hydroxamate-containing monomeric units. Two identical monomers consist of N-hydroxy-3-aminopropionic acid coupled with beta-alanine, and a third unit at the amino terminal is composed of N-hydroxy-3-aminopropionic acid and one of the following amino acids: beta-alanine (1a), phenylalanine (1b), cyclohexylalanine (1c), or glycine (1d). Thermodynamic results for representatives of the analogues have shown a strong destabilization (3-4 orders of magnitude) of the ferric complexes with respect to ferrioxamine B, probably due to shorter spacers and a more strained structure around the metal center. No significant effect of the variations at the N-terminal has been observed on the stability of the ferric complexes. By contrast, using in vivo radioactive uptake experiments, we have found that these modifications have a substantial effect on the mechanism of iron(III) uptake in the pathogenic bacteria Yersinia enterocolitica. Analogues 1a and 1d were utilized by the ferrioxamine B uptake system (FoxA), while 1b and 1c either used different uptake systems or were transported to the microbial cell nonspecifically by diffusion via the cell membrane. Transport via the FoxA system was also confirmed by uptake experiments with the FoxA deficient strain of Yersinia enterocolitica. A fluorescent marker, attached to 1a in a way that did not interfere with its biological activity, provided additional means to monitor the uptake mechanism by fluorescence techniques. Of particular interest is the observation that 1a was utilized by the uptake system of ferrioxamine B in Yersinia enterocolitica (FoxA) but failed to use the ferrioxamine uptake route in Pseudomonas putida. Here, we present a case in which biomimetic siderophore analogues deliberately designed for a particular bacterium can distinguish between related uptake systems of different microorganisms.     

Construction of a side pumped double-clad fiber using polished couplers

The paper presents a new way of side pumping double-clad fibers. Elaborated asymmetric polished couplers are presented. By using these couplers in pumping power set-ups of double-clad fiber very good pumping efficiency a very good efficiency was attained. The experimental and numerical optimizations of designed couplers are presented.     

Mechanochemical synthesis and thermal stability of phases in the Y2O3–Yb2O3 system

Substitutional, continuous solid solution of the general formula Y_2–xYb_xO₃ was obtained from the mixture of Y₂O₃ and Yb₂O₃ oxides, for the first time by the mechanochemical method in a high-energy ball milling. The monophasic samples of nanocrystalline solid solution for x?>?0.00 and x?<?2.00 were examined by the methods: XRD, DTA, SEM, IR and UV–Vis–DR. As follows from the results, the solid solution crystallizes in cubic system and is isostructural with Y₂O₃ and Yb₂O₃. The solution is stable in the air atmosphere up to at least 900°C, and its decomposition temperature decreases with the increase in x, that is, with decreasing number of Yb³⁺ ions replacing Y³⁺ ions in the crystal lattice of Y₂O₃. The energy band gap estimated for the solid solution varies from?~?5.30 eV for x?=?0.50 to?~?4.90 eV for x?=?1.50, which means that it is an insulator.

     

NMR studies of the Zn2+ interactions with rat and human beta-amyloid (1-28) peptides in water-micelle environment

Alzheimer's disease is a fatal neurodegenerative disorder involving the abnormal accumulation and deposition of peptides (amyloid-beta, Abeta) derived from the amyloid precursor protein. Here, we present the structure and the Zn2+ binding sites of human and rat Abeta(1-28) fragments in water/sodium dodecyl sulfate (SDS) micelles by using 1H NMR spectroscopy. The chemical shift variations measured after Zn2+ addition at T>310 K allowed us to assign the binding donor atoms in both rat and human zinc complexes. The Asp-1 amine, His-6 Ndelta, Glu-11 COO-, and His-13 Nepsilon of rat Abeta28 all enter the metal coordination sphere, while His-6 Ndelta, His-13, His-14 Nepsilon, Asp-1 amine, and/or Glu-11 COO- are all bound to Zn2+ in the case of human Abeta28. Finally, a comparison between the rat and human binding abilities was discussed.     

Zn(II) ions bind very efficiently to tandem repeat region of "prion related protein" (PrP-rel-2) of zebra-fish. MS and potentiometric evidence

Multi-histidine peptide fragments of zebra-fish prion protein are effective ligands for Zn(II) ions. Moreover the formation of a dinuclear complex species with a longer peptide can suggest the existence of the cooperative effect in the metal ion binding.     

Reductive cleavage of O-, S-, and N-organonitroso compounds by nickel(I) beta-diketiminates

An electron-rich nickel(I) beta-diketiminate cleaves the E-NO bond of O-, S-, and N-organonitroso species to give the nickel nitrosyl [Me 3NN]NiNO along with dimeric nickel(II) alkoxide or thiolate complexes {[Me 3NN]Ni} 2(mu-E) 2 or the mononuclear nickel(II) amide [Me 3NN]NiNPh 2. This diamagnetic three-coordinate amide exhibits temperature-dependent NMR spectra due to a low-lying triplet state.