trans-Bis(azido-κN)bis(pyridine-2-carboxamide-κ2N1,O2)nickel(II)

In the title compound, [Ni(N₃)₂(C₆H₆N₂O)₂], the Ni^II atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N—H...N hydrogen bonds.     

Energetics of radical transfer in DNA photolyase

Charge separation and radical transfer in DNA photolyase from Escherichia coli is investigated by computing electrostatic free energies from a solution of the Poisson-Boltzmann equation. For the initial charge separation 450 meV are available. According to recent experiments [Aubert et al. Nature 2000, 405, 586-590] the flavin receives an electron from the proximal tryptophan W382, which consequently forms a cationic radical WH(*)(+)382. The radical state is subsequently transferred along the triad W382-W359-W306 of conserved tryptophans. The radical transfer to the intermediate tryptophan W359 is nearly isoenergetic (58 meV uphill); the radical transfer from the intermediate W359 to the distal W306 is 200 meV downhill in energy, funneling and stabilizing the radical state at W306. The resulting cationic radical WH(*)(+)306 is further stabilized by deprotonation, yielding the neutral radical W(*)306, which is 214 meV below WH(*)(+)306. The time scale of the charge recombination process yielding back the resting enzyme with FADH(*) is governed by reprotonation of W306, with a calculated lifetime of 1.2 ms that correlates well with the measured lifetime of 17 ms. In photolyase from Anacystis nidulans the radical state is partially transferred to a tyrosine [Aubert et al. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 5423-5427]. In photolyase from Escherichia coli, there is a tyrosine (Y464) close to the distal tryptophan W306 that could play this role. We show that this tyrosine cannot be involved in radical transfer, because the electron transfer from tyrosine to W306 is much too endergonic (750 meV) and a direct hydrogen transfer is likely too slow. Coupling of specific charge states of the tryptophan triad with protonation patterns of titratable residues of photolyase is small.     

Composite Ferric Oxyhydroxide-Containing Phases Formed in Neutral Aqueous Solutions of Tryptophan and Indole-3-Acetic Acid

Mössbauer, FTIR and XRD analyses showed that in aqueous medium in air in the presence of L-tryptophan (Trp) or indole-3-acetic acid (IAA) the ambient-temperature ageing of the precipitates formed from ferrous sulphate at pH7 gave composite phases with varying proportions of -FeOOH (a dominating crystalline phase), -FeOOH (both fine-grained, showing superparamagnetic behaviour at 298 K, and relatively better crystallized) and amorphous ferric hydroxide. The experimental data suggested a competition for adsorption sites at the oxyhydroxide surface in the suspension during phase transformations, as well as the transformation of -FeOOH (and/or amorphous ferric hydroxide) to -FeOOH via the dissolution-reprecipitation mechanism. The formation of certain ferric oxyhydroxide phases in the presence of Trp and IAA — released e.g., in the course of bacterial and plant metabolism — can contribute to the regulation of soil mineral composition.     

Mössbauer spectroscopic and X-ray diffraction study of the thermal decomposition of natural siderite and goethite

Thermal decomposition of natural siderite and goethite has been studied using Mössbauer spectroscopy and X-ray diffraction. Hematite and magnetite were the principal compounds formed during high temperature treatment of siderite. Natural goethite transformed to hematite at high temperatures. The crystal structures, stoichiometry and the nuclear magnetic properties of Fe-oxides formed are discussed.     

Mercury(II) complex with terpyridine: structure of the 2∶1 solvate of [Hg(terpy)2](CF3SO3)2 with acetone

[Hg(terpy)₂](CF₃SO₃)₂·0.5(CH₃)₂CO crystallizes in the triclinic space group witha=14.631(6),b=15.258(4),c=18.785(7) Å, =69.66(2), =70.72(1), =88.55(1)°. The crystal structure consists of two independent [Hg(terpy)₂]²⁺ cations, four trifluoromethanesulfonate anions and an acetone molecule in the asymmetric unit. Each mercury atom is coordinated by two tridentate terpyridine ligands forming an irregular six-coordination polyhedron. The Hg–N bond lengths range from 2.27(2) to 2.53(2) Å.     

Lattice Boltzmann simulation of two-sided lid-driven flow in a staggered cavity

In this article, the lattice Boltzmann method is employed in order to explore incompressible fluid flow inside a two-sided lid-driven staggered cavity. Results of the lattice Boltzmann simulation for antiparallel motion of lids are compared with the data from existing literature. For parallel motion of lids, the characteristics of flow pattern for a variety of Re numbers (50–3200) are presented. An asymmetric steady-state flow pattern for parallel motion of lids is obtained.     

Characterization analysis of raw and pyrolyzed plane tree seed (Platanus orientalis L.) samples for its application in carbon capture and storage (CCS) technology

Journal of Thermal Analysis and Calorimetry - Raw and pyrolyzed samples of the plane tree seeds (PTS) were tested by various advanced analytical techniques including simultaneous TG-DSC technique,...     

Interpretative optimization and artificial neural network modeling of the gas chromatographic separation of polycyclic aromatic hydrocarbons

An interpretative strategy (factorial design experimentation+total resolution analysis+chromatogram simulation) was employed to optimize the separation of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene) in temperature-programmed gas chromatography (GC). Also, the retention behavior of PAHs in the same GC system was studied by a feed-forward artificial neural network (ANN). GC separation was investigated as a function of one (linear temperature ramp) or two (linear temperature ramp+the final hold temperature) variables. The applied interpretative approach resulted in rather good agreement between the measured and the predicted retention times for PAHs in both one and two variable modeling. The ANN model, strongly affected by the number of input experiments, was shown to be less effective for one variable used, but quite successful when two input variables were used. All PAHs, including difficult to separate peak pairs (benzo(k)fluoranthene/benzo(b)fluoranthene and indeno(1,2,3-c,d)pyrene/dibenzo(a,h)anthracene), were separated in a standard (5% phenyl-95% dimethylpolysiloxane) capillary column at an optimum temperature ramp of 8.0 degrees C/min and final hold temperature in the range of 260-320 degrees C.     

10.1007/s10973-006-8123-z

This work presents preparation and thermal characterization of three novel organomercurials: Hg₂(CF₃COCHCOCF₃)₂-μ₂-(CF₃COCCOCF₃)μ₂(CF₃C(OH)₂CH₂C(OH)₂CF₃) (I), Hg₂(CF₃COCHCOCF₃)₂-μ₂-(CF₃COCCOCF₃) (II) and Hg₂(CH₃COCHCOCF₃)₂-μ₂-(CH₃COCCOCF₃) (III) which means that they contain at least one direct mercury-to-carbon bond among the carbonyl groups of β-diketone molecules which are capable for chelating of metal ions. IR-spectra support the conclusion that mercury is most probably bound to the γ-carbon of fluorinated derivatives of acetylacetone and is not chelated through oxygen in any of the isolated compounds. The thermal decomposition of mercurated hexafluoro- and trifluoroacetylacetone in nitrogen occurs in a few steps. Each step was identified and studied by simultaneous DTA/TG analyzer. On the basis of dynamic heating experiments by TG applying Flynn-Wall method the activation energy for each of them was determined.     

Ising quantum Hall ferromagnet in magnetically doped quantum wells

We report on the observation of the Ising quantum Hall ferromagnet with Curie temperature T(C) as high as 2 K in a modulation-doped (Cd,Mn)Te heterostructure. In this system field-induced crossing of Landau levels occurs due to the giant spin-splitting effect. Magnetoresistance data, collected over a wide range of temperatures, magnetic fields, tilt angles, and electron densities, are discussed taking into account both Coulomb electron-electron interactions and s-d coupling to Mn spin fluctuations. The critical behavior of the resistance "spikes" at T-->T(C) corroborates theoretical suggestions that the ferromagnet is destroyed by domain excitations.