Alkylphosphate self-assembled monolayers (SAMs) were prepared on Nb-doped SrTiO(3) (Nb-STO) conducting metal oxide substrates. Unlike thiols on gold, the alkylphosphate SAMs on Nb-STO exhibited an electrochemical stability over a wide voltage range from -2 to 2 V. Cyclic voltammetry showed that the SAM modification inhibited the electrochemical activity of the underlying conducting substrate with an efficiency dependent on the chain length. Impedance spectroscopy showed that SAM-modified Nb-STO substrates have a significantly higher resistance than bare substrates. 相似文献
The iron (Fe) proteins of molybdenum (Mo)-, vanadium (V)-, and iron (Fe)-only nitrogenases are encoded by nifH, vnfH, and anfH, respectively. While the nifH-encoded Fe protein has been extensively studied over recent years, information regarding the properties of the vnfH- and anfH-encoded Fe proteins has remained scarce. Here, we present a combined biochemical, electron paramagnetic resonance (EPR) and X-ray absorption spectroscopy (XAS) analysis of the [Fe(4)S(4)] clusters of NifH, VnfH, and AnfH of Azotobacter vinelandii . Our data show that all three Fe proteins contain [Fe(4)S(4)] clusters of very similar spectroscopic and geometric structural properties, although NifH differs more from VnfH and AnfH with regard to the electronic structure. These observations have an interesting impact on the theory of the plausible sequence of evolution of nitrogenase Fe proteins. More importantly, the results presented herein provide a platform for future investigations of the differential activities of the three Fe proteins in nitrogenase biosynthesis and catalysis. 相似文献
The impedance is derived for a dense layer electrode of a mixed conducting oxide, assuming that the electronic resistance may be ignored. The influence of layer thickness, oxygen diffusion and surface exchange rate on the ‘General Finite Length Diffusion’ expression is evaluated. The thickness dependence is tested for a series of thin, dense layer electrodes of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) deposited on a Ce0.9Gd0.1O1.95 electrolyte by pulsed laser deposition (PLD). A minimum thickness is required to avoid the influence of contact points of the contacting Pt-gauze and sheet resistance, which is about 1 μm for the studied LSCF electrodes. LEISS surface analysis indicates that PLD deposition process easily leads to a significant Cr contamination of the LSCF surface. Electrochemical impedance spectroscopy analysis indicates that the influence on the exchange rate of this Cr-contamination is still negligible. 相似文献
The linear and nonlinear elastic properties of B4C boron carbide ceramics have been studied. The second-order elastic constants and other parameters of the theory of elasticity in the linear approximation have been calculated based on the experimentally measured density and velocity values of longitudinal and shear bulk acoustic waves in the samples. The Thurston-Brugger method has been used to determine the third-order elastic constants of B4C. To achieve this, we have measured the relative changes of the longitudinal and shear bulk acoustic wave velocities depending on the uniaxial compression applied to the sample. 相似文献
[Structure: see text] The reduction of aryl diazonium salts in the presence of nonactivated olefins provides rapid entry to carbodiazenylation products. The regioselective functionalization of double bonds is achieved in a one-pot process starting from aniline derivatives. Carboamination of olefins is possible via a two-step carbodiazenylation-hydrogenation sequence in which one aniline equivalent is recovered. 相似文献
Powder X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and molecular dynamics have been employed
to investigate structural transformations in hexagonal and cubic modifications of fullerite C60 after the action of high pressure (4 GPa) within the temperature range 20–1450°C. It has been found that fullerene molecules
polymerize to afford polymer structures only in the case of face-centered cubic samples. Under the effect of high pressure
and temperature, fullerite C60 with a hexagonal close-packed structure is initially transformed into the cubic modification and, then, forms polymerized
structures, which, during an increase in the treatment temperature, become less stable and ordered than the same polymerized
structures obtained directly from cubic fullerite C60. X-ray photoelectron spectroscopy measurements suggest deformation of the cages of fullerene molecules in the polymerized
structures. 相似文献
Two in one : The simultaneous formation of bimetallic μ‐methylene bridged RhIII complexes as well as dimeric RhIII complexes with terminal chloromethyl groups is observed for P,N‐ligand stabilized RhI complexes by C? Cl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed.
The continuous spectrum of analytical toroidally rotating magnetically confined plasma equilibria is investigated analytically and numerically. In the presence of purely toroidal flow, the ideal magnetohydrodynamic equations leave the freedom to specify which thermodynamic quantity is constant on the magnetic surfaces. Introducing a general parametrization of this quantity, analytical equilibrium solutions are derived that still posses this freedom. These equilibria and their spectral properties are shown to be ideally suited for testing numerical equilibrium and stability codes including toroidal rotation. Analytical expressions are derived for the low-frequency continuous Alfvén spectrum. These expressions still allow one to choose which quantity is constant on the magnetic surfaces of the equilibrium, thereby generalizing previous results. The centrifugal convective effect is shown to modify the lowest Alfvén continuum branch to a buoyancy frequency, or Brunt–Väisälä frequency. A comparison with numerical results for the case that the specific entropy, the temperature, or the density is constant on the magnetic surfaces yields excellent agreement, showing the usefulness of the derived expressions for the validation of numerical codes. 相似文献