Crystal structures of two 1,2-bis-(1-aryl-3-methyltriazene-3-yl-)ethanes with aryl substituents of opposite polarity

The crystal and molecular structure of 1,2-bis-{1-(2-cyanophenyl)-3-methyltriazen-3-yl-}ethane (1) and 1,2-bis-{1-(2-methoxyphenyl)-3-methyltriazen-3-yl-}ethane (2) have been determined by single crystal X-ray diffraction analysis. Bis-triazene (1) exists as the staggered conformation in the solid state, with an anti-anti configuration around the N2–N3 bond of the triazene units, whereas 2 assumes a gauche conformation with the syn-syn configuration in the triazene units. Crystal data: 1 C₁₈H₁₈N₈, triclinic, space group P –1, a = 6.108(2), b = 8.118(3), c = 9.600(4)Å, = 101.37(7)°, = 96.47(7)°, = 102.71(5)°, V = 449.1(3)ų, Z = 2; 2 C₁₈H₂₄N₆O₂, monoclinic, space group P 2₁/n, a = 13.119(5), b = 7.745(2), c = 19.201(2)Å, = 96.47(7)°, V = 1910.3(9)ų, Z = 4.     

X-Ray crystal structure determination of a series of 1-aryl- 2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1, 3-diazepan-1-yl]-1-diazenes obtained from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1-(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(1), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]-1,3-di azepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(2), and 1-(p-methoxyphenyl)-2-[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene(3) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3-diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 5, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type 6, which exemplify the general cage structure of type 4. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue 8a(X=CN); compounds 2 and 8a(X=CN) are homologous with respect to the alkane spacer moiety. The structures of 2 and 8a(X=CN) are very different in one respect; in 2 the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in 8a(X=CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.Crystal data: 1 C₂₃H₃₀N₈Br₂, triclinic, space group P-1, a=8.3979(2), b=10.7828(3), c=14.4692(5) ?, α=83.670(1), β=78.662(1), γ=78.758(1)°, V=1256.48(6) ?³, for Z=2. 2 C₂₅H₃₀N₁₀, monoclinic, space group P2 ₁ /n, a=13.4046(6), b=9.4482(4), c=10.6913(4)?, β=103.239(2)°, V=2490.5(2) ?³, for Z=4. 3 C₂₅H₃₆N₈O₂, triclinic, space group P-1, a=8.5223(3), b=10.6913(4), c=14.4034(7)?, α=85.657(2), β=78.731(2), γ=80.153(1)°, V=1266.88(9) ?³, for Z=2.     

Electron-rich heteroaroylphosphonates and their reaction with trimethyl phosphite

Dialkyl heteroaroylphosphonates based on thiophene, pyrrole or furan have been prepared and their reactions with trimethyl phosphite investigated. Deoxygenation of the carbonyl groups in these heteroaroylphosphonates occurs to give carbene intermediates, which then undergo further reaction. In the case of the furan-3-oylphosphonates and those systems containing a thiophene or pyrrole ring, the major reaction pathway involves intermolecular trapping of the carbene intermediates by the trimethyl phosphite, leading to the formation of ylidic phosphonates that can be readily converted into the corresponding 1,1-bisphosphonates. However, in some furan-2-oylphosphonates the carbenes generated undergo ring-opening to initially give acyclic alkynylphosphonates which may react further to give other novel phosphorus compounds. The effects of substituents on the extent to which intermolecular trapping of the initially formed carbene competes with intramolecular rearrangement has been investigated. The latter process appears to be suppressed by a substituent at the 5-position of the furan ring, the resulting ylidic phosphonates being a rare example of an efficient intermolecular trapping of a furan-2-yl carbene.     

Sulfur based self-assembled monolayers (SAM’s) on piezoelectric crystals for immunosensor development

Self-assembled monolayers (SAM’s) of different thiols and sulfides with various structures were tested. They were investigated as a method to covalently bind antibodies to the surface of piezoelectric crystals. A capture assay using a Mouse IgG test system was performed. All tests were performed in solution. The reduction in frequency observed as binding occurred was monitored in real time. The SAM’s were activated with 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (NHS) prior to antibody immobilisation. Ethanolamine was used to block any available activated sizes after antibody immobilisation. The potential of this technique for immunosensor development is demonstrated. Received: 19 January 1999 / Revised: 1 March 1999 / Accepted: 4 March 1999     

Reduction potential tuning of the blue copper center in Pseudomonas aeruginosa azurin by the axial methionine as probed by unnatural amino acids

The conserved axial ligand methionine 121 from Pseudomonas aeruginosa azurin (Az) has been replaced by isostructural unnatural amino acid analogues, oxomethionine (OxM), difluoromethionine (DFM), trifluoromethionine (TFM), selenomethionine (SeM), and norleucine (Nle) using expressed protein ligation. The replacements resulted in < 6 nm shifts in the S(Cys)-Cu charge transfer (CT) band in the electronic absorption spectra and < 8 gauss changes in the copper hyperfine coupling constants (AII) in the X-band electron paramagnetic resonance spectra, suggesting that isostructural replacement of Met resulted in minimal structural perturbation of the copper center. The slight blue shifts of the CT band follow the trend of stronger electronegativity of the ligands. This trend is supported by 19F NMR studies of the fluorinated methionine analogues. However, the order of AII differs, suggesting additional factors influencing AII. In contrast to the small changes in the UV-vis and EPR spectra, a large variation of > 227 mV in reduction potential was observed for the series of variants reported here. Additionally, a linear correlation was established between the reduction potentials and hydrophobicity of the variants. Extension of this analysis to other type 1 copper-containing proteins reveals a linear correlation between change in hydrophobicity and change in reduction potential, independent of the protein scaffold, experimental conditions, measurement techniques, and steric modifications. This analysis has also revealed for the first time high and low potential states for type 1 centers, and the difference may be attributable to destabilization of the protein fold by disruption of hydrophobic or hydrogen bonding interactions that stabilize the type 1 center.     

Do Reuss and Voigt bounds really bound in high-pressure rheology experiments?

Energy dispersive synchrotron x-ray diffraction is carried out to measure differential lattice strains in polycrystalline Fe(2)SiO(4) (fayalite) and MgO samples using a multi-element solid state detector during high-pressure deformation. The theory of elastic modelling with Reuss (iso-stress) and Voigt (iso-strain) bounds is used to evaluate the aggregate stress and weight parameter, α (0≤α≤1), of the two bounds. Results under the elastic assumption quantitatively demonstrate that a highly stressed sample in high-pressure experiments reasonably approximates to an iso-stress state. However, when the sample is plastically deformed, the Reuss and Voigt bounds are no longer valid (α becomes beyond 1). Instead, if plastic slip systems of the sample are known (e.g.?in the case of MgO), the aggregate property can be modelled using a visco-plastic self-consistent theory.     

Effect of particle size distribution on particle based composite anode models

Particle based models of composite anodes are useful tools for exploring the behavior of SOFC systems. As part of our efforts to develop models for understanding fuel cells, we have been building models of Ni-YSZ composite anodes using experimentally measured particle size distributions. The objectives of this study were to characterize the percolation threshold and conductivity of these models in comparison to simpler mono dispersed and biphasic particle size distributions from the literature. We found that the average values for the onset of percolation and the measured conductivity of the models with experimentally measured particle size distributions are similar to those for the simple distributions and the experimentally measured distributions. For all of the configurations evaluated, the onset of percolation in the Nickel phase occurred at a solid fraction of Nickel between 20% and 25%. This corresponded almost exactly to the point at which the coordination number between Nickel phase particles reached 2.2. The significant finding was that the variation in the value for the conductivity, as measured by the standard deviation of the results, was several orders of magnitude higher than for the simpler systems. We explored the validity of our assumptions, specifically the assumption of random particle placement, by building a particle model directly from FIB-SEM data. In this reconstruction, it was clear that the location of particles was not random. Particles of the same type and size had much likelihood of contact higher than would indicated by random location.     

A solution method for the sub-surface stresses and local deflection of a semi-infinite inhomogeneous elastic medium

This paper proposes analytical Fourier series solutions (based on the Airy stress function) for the local deflection and subsurface stress field of a two-dimensional graded elastic solid loaded by a pre-determined pressure distribution. We present a selection of numerical results for a simple sinusoidal pressure which indicates how the inhomogeneity of the solid affects its behaviour. The model is then adapted and used to derive an iterative algorithm which may be used to solve for the contact half width and pressure induced from contact with a rigid punch. Finally, the contact of a rigid cylindrical stamp is studied and our results compared to those predicted by Hertzian theory. It is found that solids with a slowly varying elastic modulus produce results in good agreement with those of Hertz whilst more quickly varying elastic moduli which correspond to solids that become stiffer below the surface give rise to larger maximum pressures and stresses whilst the contact pressure is found to act over a smaller area.     

Adsorption of sulfur dioxide by CoFe2O4 spinel ferrite nanoparticles and corresponding changes in magnetism

Adsorption of sulfur dioxide on 10 nm CoFe(2)O(4) spinel ferrite nanoparticles was examined. Adsorption loadings of sulfur dioxide at breakthrough conditions were determined to be approximately 0.62 mol/kg, which is significant given the 150 m(2)/g surface area of the nanoparticles. Adsorption proceeds through a chemisorption mechanism with sulfur dioxide forming a sulfate upon adsorption on the particle surface, which leads to a 23% decrease in the remnant magnetization, a 20% decrease in the saturation magnetization, and a 9% decrease in the coercivity of the magnetic nanoparticles. Adsorbent materials that provide a magnetic signal when adsorption occurs could have broad implications on adsorption-based separations.     

Influence of the Native Oxide Layer on the Silicon Surface During Initial Stages of Nitridation

 Thin SiO₂ layers were produced by thermal oxidation of Si wafer material. To study the effect of nitridation on the oxide layers, the specimens were nitrided in a furnace at high temperature. Non-destructive ion beam analysis was performed to determine changes in the elemental concentrations and depth profiles of the major components. In particular, N and O concentrations were measured using the non-resonant nuclear reactions ¹⁴N(d, α)¹²C and ¹⁶O(d, p)¹⁷O, respectively. To obtain depth profiles of the as-prepared and nitrided specimens, the samples were measured with RBS and heavy ion elastic recoil detection analysis. The ion beam analyses revealed an increase in thickness of the SiO₂ layers with temperature. The specimens nitrided at 1200 °C were almost free of N. Surface topology investigations with scanning electron microscopy revealed concentric annular artificial patterns at the surfaces. In the centre of the pattern, only silicon was measured. Additionally, a band consisting of Si, O, and N surrounding the pattern was discovered. The findings are in agreement with specimens prepared at higher temperatures. Received June 19, 2000. Revision December 9, 2000.