Corrosion products on steel 20 in aerated hydrazine solutions: Mössbauer study

Composition of corrosion layers on steel 20 in aerated solutions with hydrazine concentrations less than 11 ppm was studied at 50, 60, and 80°C in dynamic conditions by transmission Mössbauer spectroscopy and X-ray diffraction as supplementary technique. Corrosion rates were determined by gravimetric method. A comparison with corrosion in water at 80°C was made. The observed layers have not any protective character. For 0.1 m/s linear velocity, they are composed by nonstoichiometric magnetite, (Fe_3?x O₄,x=0.02–0.04) with lepidocrocite (γ-FeOOH) as secondary phase at 50°C. Haematite (α-Fe₂O₃) is observed at 60 and 80°C with a 19 nm particle size. It becomes smaller for higher velocity (0.7 m/s).     

Banach-stone theorems and separating maps

LetC(X,E) andC(Y,F) denote the spaces of continuous functions on the Tihonov spacesX andY, taking values in the Banach spacesE andF, respectively. A linear mapH:C(X,E)→C(Y,F) isseparating iff(x)g(x)=0 for allx inX impliesHf(y)Hg(y)=0 for ally inY. Some automatic continuity properties and Banach-Stone type theorems (i.e., asserting that isometries must be of a certain form) for separating mapsH between spaces of real- and complex-valued functions have already been developed. The extension of such results to spaces of vector-valued functions is the general subject of this paper. We prove in Theorem 4.1, for example, for compactX andY, that a linear isometryH betweenC(X,E) andC(Y,F) is a “Banach-Stone” map if and only ifH is “biseparating (i.e,H andH ⁻¹ are separating). The Banach-Stone theorems of Jerison and Lau for vector-valued functions are then deduced in Corollaries 4.3 and 4.4 for the cases whenE andF or their topological duals, respectively, are strictly convex. Research supported by the Fundació Caixa Castelló, MI/25.043/92     

Extended X-ray absorption fine structure studies of thulium doped GaN epilayers

The local structure of Tm³⁺ ions incorporated into GaN epilayers was studied by means of Extended X-ray Absorption Fine Structure. The samples were doped either in situ during growth by Molecular Beam Epitaxy or by ion implantation of layers grown by Metal Organic Chemical Vapour Deposition. The implantation was done at ion energy of 300 keV and different nominal fluences of 3×10¹⁵, 4×10¹⁵ cm⁻² and 5×10¹⁵ cm⁻². The concentration of Tm in the samples studied was measured by Wavelength Dispersive X-ray analysis. For the in situ doped sample with concentration of 0.5%, and for all of the implanted samples, Tm was found on the Ga site in GaN. The ion implanted sample and an in situ doped sample with a similar concentration of Tm showed the same local structure, which suggests that the lattice site occupied by Tm does not depend on the doping method. When the average Tm concentration for in situ doped samples is increased to 1.2% and 2.0%, Tm is found to occupy the Ga substitutional site and the presence of a substantial number of Tm ions in the second coordination sphere indicates dopant clustering in the films. The formation of pure TmN clusters was found in an in situ doped sample with a dopant concentration of 3.4%.     

Structural characterization of Acetobacter diazotropicus levansucrase by matrix-assisted laser desorption/ionization mass spectrometry: identification of an N-terminal blocking group and a free-thiol cysteine residue

High-resolution matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was used to characterize the primary structure of the levansucrase (EC 2.4.1.10) secreted by Acetobacter diazotropicus SRT4. The technique permitted not only the reading frame of this enzyme, the amino acid sequence of which was deduced from DNA, but also the elucidation of an N-terminal blocking group and the position of a disulfide bridge between Cys309 and Cys365 among the three Cys residues. A free cysteine (Cys127) was identified by modifying an intact molecule with a sulfhydryl reagent, 5-(octyldithio)-2-nitrobenzoic acid, under non-reducing conditions. In addition, the enzyme obtained by site-directed mutagenesis at Asp279 to Asn279 was also identified by the above methods. Post-source decay analysis of the tryptic peptide containing the mutation site unequivocally revealed an Asn residue at position 279.     

Amperometric sensor for hypoxanthine and xanthine based on the detection of uric acid

The construction and response of an immobilized enzyme modified electrode as an amperometric sensor is described. Xanthine oxidase was adsorbed on a carbon paste electrode and physically entrapped with a semipermeable membrane. Uric acid, the product of the enzymatic reaction, was oxidized electrochemically at +0.4 V vs. Ag/AgCl, yielding a steady-state current directly related to the bulk concentration of the substrate. Hypoxanthine and xanthine were determined in the range 5–100 μM at Ph 7.2 with good precision. Interferences are discussed.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.