Effects of compositional and structural features on corrosion behavior of nickel–tungsten alloys

Ni–W alloys were electrodeposited onto copper foil from citrate solution. Coatings containing from 11 to 21 at.% W and having 7–52 μm in thickness were obtained. The structure of these alloys was analyzed by X-ray diffraction and by using electron and light microscopy techniques. Alloys with 11 and 15% W are composed of two phases: solid solution of W in fcc Ni and solid solution of Ni in bcc W. An increase in W content in the Ni–W alloys to ca. 18–19% of W resulted in the grain refinement and the transition to amorphous structure. The corrosion behavior of obtained Ni–W and unalloyed Ni coatings was studied in 0.5 M NaCl solution by means of electrochemical impedance spectroscopy, potentiodynamic polarization and light microscopy. Comparing to pure Ni, the obtained Ni–W coatings exhibited a clearly decreased corrosion resistance (in terms of corrosion current density and polarization or charge transfer resistance at the open circuit potential). Despite of the quite wide range of composition of the alloys under test, the related grain refinement, and the transition to the amorphous structure, no clear relation between the corrosion rate and W content was detected. This behavior can be a result of the interplay of the activating effect of grain refinement or preferential dissolution of W from one side and diffusion barrier action or inhibition provided by the surface film of W oxidation products from the other side. The differences observed in the corrosion resistance of Ni–W coatings are more related to their morphological imperfections arising from various deposition conditions than to the W content. Some samples showed a rather non-uniform nature of corrosion (pronounced attack along cracks). An inversion in the dissolution behavior of Ni–W and unalloyed Ni was observed with increasing anodic potential. Contrary to pure Ni, Ni–W coatings were resistant to pitting corrosion in NaCl solution. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials, Warsaw, 17th–21st September, 2007.     

Low cost prediction of relative stabilities of hydrogen bonded complexes from atomic multipole moments for overly short intermolecular distances

The relative stability of biologically relevant, hydrogen bonded complexes with shortened distances can be assessed at low cost by the electrostatic multipole term alone more successfully than by ab initio methods. These results imply that atomic multipole moments may help improve ligand–receptor ranking predictions, particularly in cases where accurate structural data are not available. © 2013 Wiley Periodicals, Inc.     

Constrained cycloalkyl analogues of glutamic acid: stereocontrolled synthesis of (+)-2-aminobicyclo[3.1.0]hexane-2,6-dicarboxylic acid (LY354740) and its 6-phosphonic acid analogue

A new stereocontrolled synthesis of (+)-2-aminobicyclo[3.1.0]hexane-2.6-dicarboxylic acid (LY354740) 1, a potent and selective 2mGluR agonist, has been accomplished in four steps with an overall yield of 27% starting from the enantiopure (+)-(R)-2-(p-tolylsulfinyl)cyclopent-2-enone 3. The key steps include asymmetric cyclopropanation of 3 with (dimethylsulfuranylidene)acetate (EDSA) and removal of the chiral p-tolylsulfinyl auxiliary from the cycloadduct ent-4c upon treatment with iso-propylmagnesium chloride. The stereoselective hydantoin formation from the bicyclic ketone 6 formed (Bucherer–Bergs reaction) and subsequent hydrolysis completed the synthesis of 1. The same reaction sequence has been applied in the first synthesis of enantiopure (+)-2-amino-6-phosphonobicyclo[3.0.1]hexane-2-carboxylic acid 2, a structural 6-phosphono analogue of 1. The starting bicyclic ketophosphonates 9–11 have been obtained by asymmetric cyclopropanation of (?)-(S)-3 with phosphoryl sulfonium ylides, producing only two endo-isomers. The major endo-isomer (+)-11a containing the 6-diisopropoxyphosphoryl group has been converted in three steps into (+)-endo-2 in 46% overall yield.     

The effects of ion implantation on the anodic oxidation of silicon

The effects of H⁺, C⁺, N⁺, Ne⁺, Al⁺, P⁺, Cl⁺, Ar⁺, Ga⁺, As⁺, Kr⁺, Sb⁺, Xe⁺, Au⁺ and Tl⁺ ion implantation on the anodic oxidation of Si have been investigated as a function of dose and energy, in the as-implanted stage and after heat treatment at temperatures up to 1050°C. It is speculated that the location, in the formed oxide, of agglomerates containing the dopant, and the influence of these agglomerates on oxygen diffusion in SiO₂ and/or oxygen evaluation at the oxide/solution interface are factors which account for the enhancement/retardation of the anodic oxidation.     

Reaction of 5,5-diphenyl-2-thiohydantoin with 1,2-dibromoethane.crystal and molecular structures of 2,3-dihydro-6,6-diphenylimi-dazo-[2,1-b]-thiazol-5(6h)-one and 2,3-dihydro-5,5-diphenylimi-dazo-[2,-1-b]-thiazol-6(5h)-one and their reactivity

The crystal and molecular structures of the title isomeric compounds $\text{1}$ and $\text{2}$, obtained by intramolecular N,S--dialkylation of 5,5-diphenyl-2-thiohydantoin with 1,2-dibro-moethane, have been determined from X-ray diffractometer data. 2,3-Dihydro-6,6-diphenylimidazo-[2,1-b]-thiazol-5(6H)-one $\text{1}$ crystallizes in space group P2₁2₁2₁ with a=11.376(3), b=12,255(5), c=8.434(3) Å and Z=4. Crystals of $\text{2}$, containing one molecule of benzene, are monoclinic,space group P2₁/c with a=11.539(6), b=10.242(3), c=16.353(5) Å, β=95.45(5)° and Z=4. In both cases a planar geometry of the two fused five-membered heterocyclic rings was found. The selected bond lengths in $\text{1}$ and $\text{2}$, as well as those analogous imidazothiazinones $\text{3}$ and $\text{4}$, were used to calculate E_HOSE (Harmonic Oscillation Stabilization Energy). The problem of stability and chemical reactivity of compounds $\text{1}$ to $\text{4}$ is also discussed.     

Parallel Optimization of Synthetic Pathways within the Network of Organic Chemistry

Finding a needle in a haystack: The number of possible synthetic pathways leading to the desired target of a synthesis can be astronomical (10(19) within five synthetic steps). Algorithms are described that navigate through the entire known chemical-synthetic knowledge to identify optimal synthetic pathways. Examples are provided to illustrate single-target optimization and parallel optimization of syntheses leading to multiple targets.     

The first nonempirical circular dichroism determination of the absolute configuration of N-phthalimidosulfoximines based on exciton coupling mechanism and a correlation with the absolute configuration of chiral sulfoxides

A simple nonempirical method for the assignment of absolute configuration of N-phthalimidosulfoximines and related S-chiral sulfoxides, based on exciton-coupled circular dichroism, is presented.     

Thermolysis of complex cyanides,XV

The thermal decompositions of K₂[Fe(CN)₄ L]·4 H₂O, H₂[Fe(CN)₄ L] and H[Fe(CN)L](L=1,1-bipyridine, of 1,10-phenanthroline) were studied. The experimental results showed that the protonated ferrous complexes decompose with formation of HCN at lower temperature than the corresponding potassium salts. The decomposition of K₂[Fe(CN)₄ L] starts by removal of the ligand L. HCN elimination is followed by a redox reaction with formation of cyanogen in the case of H[Fe^III(CN)₄ L].

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Zusammenfassung Die thermische Zersetzung von K₂ [Fe(CN)₄ Z]·4H₂O, H₂[Fe(CN)₄ L] und H[Fe(CN)₄ L] (L=1,1'-Dipyridin, 1,10-Phenantrolin) wurde untersucht. Die Versuchsergebnisse zeigten, dass die protonierten Ferrokomplexe unter Bildung von HCN bei niedrigeren Temperaturen zersetzt werden, als die entsprechenden Kaliumsalze. Die Zersetzung von K₂ [Fe(CN)₄ L] beginnt durch die Abspaltung des LigandenL. Nach Eliminierung des HCN folgt eine Redox-Reaktion unter Bildung von Dizyan im Falle von H[Fe^III(CN)₄ Z].

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K₂[Fe(CN)₄ L]·4₂, H₂[Fe(CN)₄ L] H[Fe(CN)₄ L] L=1,1- 1.10-. , , . K₂[Fe(CN)₄ L] L. H[Fe¹¹¹(CN)₄ L] HCN - .

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XIV. A. Hantshmann, J. Salvetter, H. Hennig and B. Mohai, Thermochim. Acta. 25 (1978) 341

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The authors thank I. Ötvös for mass-spectroscopic investigations, and Mrs. Csukás, Mrs. Csiszár and Mrs. Haeffner for experimental assistance.     

Synthesis of mono- and 1,4-dicarbonyl compounds based on the oxygenation of phosphonate carbanions. Synthesis of dihydrojasmone,allethrone and methylenomycin b

Oxidation of the α-alkylthio-substituted phosphonate carbanions was found to give the corresponding carbonyl compounds. A new synthesis of 1,4-dicarbonyl systems involving the oxygenation of phosphonate carbanions as a key step is described. Total synthesis of dihydrojasmone and allethrone and formal synthesis of methylenomycin B is reported.     

Determination of the intershell conductance in multiwalled carbon nanotubes

We report on the intershell electron transport in multiwalled carbon nanotubes (MWNTs). To do this, local and nonlocal four-point measurements are used to study the current path through the different shells of a MWNT. For short electrode separations less, similar 1 mum the current mainly flows through the two outer shells, described by a resistive transmission line with an intershell conductance per length of approximately (10 kOmega)(-1)/microm. The intershell transport is tunnel type and the transmission is consistent with the estimate based on the overlap between pi orbitals of neighboring shells.