The oxalic acid catalysed oxidation of bis(2,4,6-tripyridyl-1,3,5-triazine)-iron(II) by chromium(VI) in acetate buffer

Summary The reaction between bis(2,4,6-tripyridyl-1,3,5-triazine)-iron(II), Fe(TPTZ) _inf2 ^sup2+ and chromium(VI) in acetate buffers is very slow. However, in the presence of oxalic acid (catalyst) it is very fast and is completed within 10s. The reaction was studied in the 3.6–5.6 pH range using stopped-flow spectrophotometry. The reaction is first order in the substrate and zero order in the oxidant. The rate of the reaction increases with the increase in pH. Kinetic evidence for complexation between the substrate and the catalyst was obtained and a mechanism involving the formation of an ion-pair between Fe(TPTZ) _inf2 ^sup2+ and the oxalate ion is proposed.     

Robust M-estimation of a dispersion matrix with a structure

An iterative algorithm for the robust M-estimation of the dispersion matrix of the form + ² I _p has been given. This algorithm converges after some steps and reduces the effect of outliers on the covariance matrix. The consistency and asymptotic normality of the estimator are established.     

An Imidazolylidene-Based Mesoionic Carbene–Mn(I) Complex and Its Catalytic Potential in N-Heteroarene Hydrogenation

Herein we report the first mesoionic carbene (MIC)-Mn(I) complex Mn-bim-MIC^imz derived from imidazolylidene motif. Structurally the octahedral Mn(I) complex Mn-bim-MIC^imz was assembled with an anionic benzimidazolato-anchored imidazolylidene MIC-based bidentate ligand ( bim-MIC^imz ) and four CO ligands, as supported by detailed characterization using NMR and FTIR spectroscopy, mass spectrometry, and single crystal X-ray diffraction study. We reckoned that the bim-MIC^imz ligand would provide a robust and stable bonding with the Mn(I) centre, and also enhance electron density at the Mn(I) centre through its stronger σ-donating/weaker π-accepting property. These structural and electronic attributes triggered to exploit Mn-bim-MIC^imz in catalytic hydrogenation of N-heteroarenes, where efficient hydride (Mn−H) delivery is a key step.     

Photolytic metallization of au nanoclusters and electrically conducting micrometer long nanostructures on a DNA scaffold

An electroless, photolytic method is described to synthesize Au nanoclusters and electrically conductive, micronmeter long nanostructures on DNA. Electrical characterization indicates that the Au nanostructures are continuous, exhibiting Ohmic behavior with very low contact resistance with the electrodes. The nanoclusters have a size of 10-40 nm, and the nanostructure have a diameter of 40-70 nm with resistivity comparable to that of pure metal. The method is highly selective with deposition confined to the DNA template.     

Quantum noise measurements in a continuous-wave laser-diode-pumped Nd:YAG saturated amplifier

We present measurements of the power noise due to optical amplification in a Nd:YAG free-space traveling-wave amplifier as the amplifier transitions from the linear regime into the heavily saturated regime. The quantum noise behavior is demonstrated by saturating the gain of a 100-W class zigzag slab amplifier with a high-power beam and measuring the power noise detected by a single-spatial-mode probe beam traversing the same optical path through the amplifier.     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Stabilization of ZnMnO<Subscript>3</Subscript> phase from sol–gel synthesized nitrate precursors

The stabilization and analysis of pure ZnMnO₃ phase may help to understand the solubility limits of Mn in ZnO in wurtzite and cubic structures. In this report, synthesis and characterization of stable ZnMnO₃ phase is discussed which is extracted from sol–gel synthesis of zinc and manganese nitrate precursors. The reflections at higher diffraction angles for this known cubic system with space group Fd3 m were calculated with the help of JADE 8.0 program. The reliability factor for ZnMnO₃ calculated from Rietveld refinement was 2%. A narrow phase pure ZnMnO₃ stabilization region was identified with the help of energy dispersive spectroscopy mapping. High resolution X-ray photoelectron spectroscopy measurements of Mn^3p position of ZnMnO₃ compared with ZnMn₂O₄ showed a higher binding energy shift ~0.85 eV indicating Mn⁴⁺ valence state in ZnMnO₃.     

Selective metal cation capture by soft anionic metal-organic frameworks via drastic single-crystal-to-single-crystal transformations

Flexible anionic metal-organic frameworks (MOFs) are transformed into neutral heterobimetallic systems via single-crystal-to-single-crystal processes invoked by cation insertion. These transformations are directed by cooperative bond breakage and formation, resulting in expansion or contraction of the 3D framework by up to 33% due to the flexible nature of the organic linker. These MOFs displays highly selective uptake of divalent transition-metal cations (e.g., Co(2+) and Ni(2+)) over alkali-metal cations (Li(+) and Na(+)).     

Determination of gold and silver in dross using EDXRF technique

Gold and silver in dross were determined by energy‐dispersive X‐ray fluorescence technique. Sample was prepared by pressed pellet method using microcrystalline cellulose powder as binder, and a method of standard additions was used for quantification. L_β X‐ray of gold (11.4 keV) and K_β X‐ray of silver (24.9 keV) were used for analysis. The measured concentrations of gold and silver were 132 ± 8 and 1181 ± 84 mg kg^?1, respectively. The results were validated by instrumental neutron activation analysis technique. The t‐test indicated that there was no significant difference between results obtained by the two techniques. Energy‐dispersive X‐ray fluorescence is a simple, precise and accurate technique for the determination of gold and silver in dross. Copyright © 2014 John Wiley & Sons, Ltd.