Spectral and voltammetric studies on titanium substituted Keggin-type heteropolyanions

Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [Ti^IIITi^IVW₁₀PO₄₀]⁸⁻ is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K₅M^II[Ti₂W₁₀PO₄₀].xH₂O(M^II = Cu or Mn) are isomorphous with K₇[Ti₂W₁₀PO₄₀].6H₂O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K₅M^II[Ti₂W₁₀PO₄₀].xH₂O complexes. This high symmetry is confirmed in K₅Cu[Ti₂W₁₀PO₄₀] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K.     

Sliding spark spectroscopy

Summary A new analytical radiation source combined with fiber optics linked to a diode array detection device with modified software is described. The direct-reading spectrometer simultaneously covers the wavelength range 185–510 nm with a spectral resolution of <1.5 nm. Intense optical emission is observed when positionally stable high-current surface sparks supplied by a pulse-generator with definite discharge parameters (max. 800 Ampere/pulse) are sliding over compact non-conductive materials such as plastics, glasses, quartz filters or powder pellets. Substrate vaporization, ionization and excitation processes in the surface discharge plasma channel generate emission corresponding to neutral and ionic states. The spectra are essentially composed of lines emitted by the electrode material (e.g. copper, silver), from the substrate under investigation, radiation continuum as well as structured background from the surrounding air atmosphere. Due to the occurrence of emission lines of reactive fillers, inorganic pigments and stabilizers, a rapid multi-element screening method is demonstrated. A rapid identification system (mix-up test) of PVC or fire-retardant thermoplastics within one second has been realized from the atomic emission line intensity originating from the sputtered copper electrode material according to its increased volatility in the presence of chlorine (modified Beilstein test).Puls-Plasma-Technik GmbH, Dortmund     

Chiroptical properties of steroid 1,3-diaxial diols in the presence of [Mo2(OAc)4]

Summary Bidentate complexes of dimolybdenum tetraacetate with 1,3-diaxial diols show Cotton effects around 490–540 nm (CD band I), 400–440 nm (II), 350–380 nm (III), 320 nm (IV) and 280 nm (V). The sign of the Cotton effect II can be predicted by a proposed sector rule. It seems that from the Cotton effects for cyclic 1,3-diols the absolute configurations or conformations can be obtained.A part of this material was presented at III-rd International Conference on CD Spectroscopy [1]     

Spectral shift function and trace formula

The complete proofs of Krein’s theorem on the spectral shift function and the trace formula are given for a pair of self-adjoint operators such that either (i) their difference is trace-class or (ii) the difference of their resolvents is trace-class. The proofs, essentially due to Krein, is based on Herglotz’s theorem on the boundary value of the analytic functions whose imaginary part is non-negative on the upper half plane, and an almost optimal class of functions are obtained for which the trace formula is valid. Also an alternative method based on Weyl-von Neumann’s theorem for self-adjoint operators, avoiding the complex function theory and inspired by Voiculescu’s work, is given for the first case. Furthermore, some applications of the spectral shift function have been discussed.     

Trimode ladar/radar transponder systems for tracking long range cooperative targets

Detection and tracking of cooperative airborne targets are very important for military and also for civilian purposes. Previous research has shown that detection and tracking LASER offer high precision but their operation range is limited to less than 40 km even in good visibility propagation conditions. For long operation ranges, high power and bulky RADAR are required which can be significantly reduced by using active transponders on the cooperative target. A trimode LADAR/RADAR/Transponder system is investigated providing optimum performances. A L band Radar with active transponder is operated for all weather long ranges up to Low Earth Orbit satellites. The L mode is switched to a Mm wave mode RADAR for operation distances lower than 350 km and to an accurate LASER mode for the final tracking steps.     

Electrooxidation of carbo/thiocarbohydrazide and their hydrazone derivatives at a glassy carbon electrode

Electrochemical oxidation of thio/carbohydrazide and their hydrazone derivatives Benzaldehyde thiocarbohydrazone [BTCH] diacetylene thiocarbohydrazone [DATCH] have been studied in Brit-ton Robinson buffer in aqueous and nonaqueous media at a glassy carbon electrode. The effects of pH, sweep rate, concentration, temperature and surfactants have been studied. The complex bis (carbo/thiocabohydrazide) Zn(II) chloride was also subjected to voltammetric analysis in order to understand the reactivity both in free and metal bound states. The reaction conditions were optimized for the determination of above compounds in micrograms quantities by differential pulse voltammetry, analytical utility of this investigation is also highlighted.     

Tuning size and catalytic activity of nano-clusters of cobalt oxide

Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4–6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.     

Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from¹H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.