Magnetic structure of single-domain antiferromagnetic FCT γ-Mn-Cu and γ-Mn-Fe alloys

Detailed neutron diffraction studies both by double axis and triple axis spectrometer are reported for the first time for fct single-domain single crystals of γ-Mn-Cu and γ-Mn-Fe. The main purpose of these studies was to elucidate further the nature of the diffuse (001) peak, forbidden by the AF1 magnetic structure, established earlier in this group of γ-Mn alloys. Line shapes and their temperature dependence were measured for (001), (100) and (010) reflections in Mn-Fe and in Mn—Cu, in the latter case both for homogeneous (quenched) and chemically decomposed (aged) samples. Only (001) reflection was found in Mn-Fe, while in Mn-Cu samples diffuse peaks were also observed at (100) and (010). Together with their temperature dependence and the results of energy analysis the data suggest a new model of the magnetic structure of these alloys. In Mn-Fe the spins deviate by a fixed angle from the c axis and this perturbation has an infinite correlation range and life time. In Mn-Cu a more complex set of perturbations is required to interpret the data.     

New catalytic route to functionalized vinylboronates

Vinylsubstituted boronates i.e. vinyldioxaborolane and vinyldioxaborinane react regioselectively with olefins in the presence of RuHCl(CO)(PCy3)2 with the formation of functionalized vinylboron derivatives. The reaction opens a new catalytic route for preparation of organoboranes.     

Kansa-RBF algorithms for elliptic problems in regular polygonal domains

We propose matrix decomposition algorithms for the efficient solution of the linear systems arising from Kansa radial basis function discretizations of elliptic boundary value problems in regular polygonal domains. These algorithms exploit the symmetry of the domains of the problems under consideration which lead to coefficient matrices possessing block circulant structures. In particular, we consider the Poisson equation, the inhomogeneous biharmonic equation, and the inhomogeneous Cauchy-Navier equations of elasticity. Numerical examples demonstrating the applicability of the proposed algorithms are presented.     

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.     

EPR spectra of gamma-irradiated DL-alpha-alanine supported on molecular sieves

The aim of the work was to collect information concerning boundary effects which are suspected in alpha-alanine dosimeters consisted of powdered microcrystalline alpha-alanine and binders. In our experiments the conventional binders were replaced by molecular sieves (MS). MS are inorganic porous materials (host structures) with well organized and uniform intra-crystalline pore systems of nano-scale size. The guest molecules can be either physically adsorbed on very large inner MS surface, or chemically bound to the active sites. They can be also encapsulated inside the intracrystalline cavities. The EPR spectra of gamma irradiated DL-alpha-alanine supported on NaY, CeY, SOD, mordenite, ZSM-5 and ALPO(4)-5 were very similar to that one observed for irradiated microcrystalline DL-alpha-alanine. In the case of alanine supported on HY an initial EPR spectrum was different and only after some weeks it made resemble to the well known quintet observed in microcrystalline samples. In sodalites synthesized in the presence of DL-alpha-alanine EPR signal appeared in non-irradiated sample was very low and structureless. The irradiated sample showed a distinct spectrum which was quite different from that one observed for crystalline DL-alpha-alanine.     

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.     

Behaviour of selected pesticide residues in blackcurrants (<Emphasis Type="Italic">Ribes nigrum</Emphasis>) during technological processing monitored by liquid-chromatography tandem mass spectrometry

In this experiment, the behaviour of ten pesticides on field-sprayed blackcurrants (Ribes nigrum) after washing, juicing and cooking was investigated. The concentration level changes in two acaricides (fenazaquin, propargite), three insecticides (alpha-cypermethrin, deltamethrin and lambdacyhalothrin) and five fungicides (boscalid, bupirimate, difenoconazole, pyraclostrobin, thiophanate-methyl) were quantified. Analysis was carried out using the QuEChERS method followed by chromatographic analysis based on LC-MS/MS. The matrix effects ranged from —(17.4 ± 8.1) % to (15.9 ± 7.8) %. The limits of detection and limits of quantification were 0.003 mg kg^?1 and 0.01 mg kg^?1, respectively. The mean recoveries of the analytes ranged between 71 % and 109 %. The processing factors of all the blackcurrant products were determined. Washing reduced the pesticide residues up to 71 %. Juicing significantly reduced all the pesticide residues (processing factors (PFs) ranged 0.14–0.47). Cooking resulted in a decrease in residues up to 82 %. The residue levels of alpha-cypermethrin, deltamethrin and lambda-cyhalothrin in blackcurrant jam increased, and PFs > 1 were noted as PF = 1.38, 1.66 and 1.04, respectively. Cluster analysis was performed to find any similarity in the behaviour of pesticides after processing. The results confirmed that solubility, polarity and mode of action could be used to explain differences in the behaviour of pesticides.     

Sulfur radicals embedded in various cages of ultramarine analogs prepared from zeolites

The colored (greenish) products analogous to ultramarine obtained from zeolite A, cancrinite and erionite by means of high-temperature (500-800 °C) treatment of zeolites mixed with elemental sulfur and alkalis can maintain the original structure of the parent zeolite under certain preparation conditions. The ESR spectra of samples recorded at room temperature always indicate the presence of radicals S₃⁻ (the blue chromophore). The spectra of samples prepared from zeolites recorded at 77 K exhibit additional signals that could be assigned to the yellow chromophore (the radical S₂⁻) encapsulated inside the β or ε-cages. It is remarkable that in the case of products with preserved cancrinite structure, where the S₂⁻ radicals are encapsulated inside the ε-cages, the above signals are visible already at room temperature. It may result from retarded mobility of these species in small cancrinite cages.     

Photophysics of Schiff Bases: Theoretical Study of Salicylidene Methylamine

The proton‐transfer reaction in a model aromatic Schiff base, salicylidene methylamine (SMA), in the ground and in the lowest electronically‐excited singlet states, is theoretically analyzed with the aid of second‐order approximate coupled‐cluster model CC2, time‐dependent density functional theory (TD‐DFT) using the Becke, three‐parameter Lee–Yang–Parr (B3LYP) functional, and complete active space perturbation theory CASPT2 electronic structure methods. Computed vertical‐absorption spectra for the stable ground‐state isomers of SMA fully confirm the photochromism of SMA. The potential‐energy profiles of the ground and the lowest excited singlet state are calculated and four photophysically relevant isomeric forms of SMA; α, β, γ, and δ are discussed. The calculations indicate two S₁/S₀ conical intersections which provide non‐adiabatic gates for a radiationless decay to the ground state. The photophysical scheme which emerges from the theoretical study is related to recent experimental results obtained for SMA and its derivatives in the low‐temperature argon matrices (J. Grzegorzek, A. Filarowski, Z. Mielke, Phys. Chem. Chem. Phys. 2011 , 13, 16596–16605). Our results suggest that aromatic Schiff bases are potential candidates for optically driven molecular switches.     

Interval methods of Adams-Bashforth type with variable step sizes

Numerical Algorithms - In a number of our previous papers, we have proposed interval versions of multistep methods (explicit and implicit), including interval predictor-corrector methods, in which...