Tuning of the [Cu3(mu-O)]4+/5+ redox couple: spectroscopic evidence of charge delocalization in the mixed-valent [Cu3(mu-O)]5+ species

Trinuclear Cu (II)-complexes of formula [Cu (II) 3(mu 3-E)(mu-4-R-pz) 3X 3] (+/- n ), E = O and OH; R = H, Cl, Br, CH(O) and NO 2; X = Cl, NCS, CH 3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu 3 (7+)-complex [Cu 3(mu 3-O)(mu-pz) 3Cl 3] (-) revealed an intervalence charge transfer band at 9550 cm (-1) (epsilon = 2600 cm (-1) M (-1)), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, H ab, of 4775 cm (-1).     

Effects of MHD free convection and mass transfer on the flow past an oscillating infinite coaxial vertical circular cylinder

The effects of MHD free convection and mass transfer are taken into account on the flow past oscillating infinite coaxial vertical circular cylinder. The analytical expressions for velocity, temperature and concentration of the fluid are obtained by using perturbation technique.

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Einwirkungen von freier MHD-Konvektion und Stoffübertragung auf eine Strömung nach einem schwingenden unendlichen koaxialen vertikalen Zylinder

Zusammenfassung Die Einwirkungen der freien MHD-Konvektion und Stoffübertragung auf eine Strömung nach einem schwingenden, unendlichen, koaxialen, vertikalen Zylinder wurden untersucht. Die analytischen Ausdrücke der Geschwindigkeit, Temperatur und Fluidkonzentration sind durch die Perturbationstechnik erhalten worden.

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Nomenclature C _p Specific heat at constant temperature - C the species concentration near the circular cylinder - C _w the species concentration of the circular cylinder - C the species concentration of the fluid at infinite - * dimensionless species concentration - D chemical molecular diffusivity - g acceleration due to gravity - Gr Grashof number - Gm modified Grashof number - K thermal conductivity - Pr Prandtl number - r _a ,r _b radius of inner and outer cylinder - a, b dimensionless inner and outer radius - r,r coordinate and dimensionless coordinate normal to the circular cylinder - Sc Schmidt number - t time - t dimensionless time - T temperature of the fluid near the circular cylinder - T _w temperature of the circular cylinder - T temperature of the fluid at infinite - u velocity of the fluid - u dimensionless velocity of the fluid - U ₀ reference velocity - z,z coordinate and dimensionless coordinate along the circular cylinder - coefficient of volume expansion - * coefficient of thermal expansion with concentration - dimensionless temperature - H ₀ magnetic field intensity - coefficient of viscosity - _e permeability (magnetic) - kinematic viscosity - electric conductivity - density - M Hartmann number - dimensionless skin-friction - frequency - dimensionless frequency     

Combinatory-Algebraic Perspective on Multipartiteness,Entanglement and Quantum Localization

We claim that both multipartiteness and localization of subsystems of compound quantum systems are of an essentially relative nature crucially depending on the set of operationalistically available states. In a more general setting, to capture the relativity and variability of our structures with respect to the observation means, sheaves of algebras may need be introduced. We provide the general formalism based on algebras which exhibits the relativity of multipartiteness and localization.     

Structural architectures of charge-assisted,hydrogen-bonded, 2D layered amine⋯tetraphosphonate and zinc⋯tetraphosphonate ionic materials

The synthesis, characterization and structural analyses of ionic amine-phosphonate and hydrated metal ion-phosphonate compounds are reported. These are (en)(HDTMP), (NH₄)(EDTMP), Zn(H₂O)₆(TDTMP) (en = ethylenediamine, HDTMP = hexamethylenediamine-tetrakis(methylenephosphonate), EDTMP = diethylenediamine-tetrakis(methylenephosphonate), TDTMP = tetramethylenediamine-tetrakis(methylenephosphonate)). All three compounds are composed of discrete anions and cations, stabilized by intricate networks of hydrogen bonds, and form 2D layered architectures.     

Etherates and pyridinium compounds of mixed complex iodoacids of gallium(III)

The preparationof etherates and pyridinium compounds of mixed complex iodoacids of Ga(III) is reported together with some physical and chemical properties, as well as conductometric measurements and the ultraviolet and infrared spectra of the new compounds. From the analytical, conductometric, stability and spectral data, some information is gained about the probable structure of the complexes.

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Etherate und Pyridin-Verbindungen von gemischtkomplexen Jodosäuren von Gallium(III)

Zusammenfassung Es wird über die Darstellung von Ether- und Pyridiniumverbindungen gemischter komplexer Jodosäuren von Ga(III), sowie über einige physikalische und chemische Eigenschaften, konduktometrische Daten und die UV- und IR-Spektren dieser neuen Verbindungen berichtet. Auf Grund von analytischen, konduktometrischen, spektroskopischen und Stabilitätsbefunden wurden Informationen über die wahrscheinliche Struktur dieser Komplexe gewonnen.

     

Microfabricated disposable lab-on-a-chip sensors with integrated bismuth microelectrode arrays for voltammetric determination of trace metals

This work reports the fabrication of disposable three-electrode cells with integrated metal-film electrodes. The devices were fabricated by a multi-step micro-fabrication approach combining sputtering for the deposition of metals and the dielectric material (SiO₂) on the surface of a silicon wafer and photolithography for the definition of the geometry of the sensors. The working electrode was a microelectrode array consisting of bismuth microdisks while the reference and counter electrode strips were made of Ag and Pt, respectively. The utility of these devices was tested for the trace determination of Pb(II) and Cd(II) by anodic stripping voltammetry and Ni(II) by adsorptive stripping voltammetry. The detection of these trace metals was carried out in unstirred and undeoxygenated solutions exhibiting sub-μg L⁻¹ limits of detection and enhanced analytical characteristics compared to conventional bismuth-film electrodes.     

Palladium nanostructures and nanoparticles from molecular precursors on highly ordered pyrolytic graphite

Nanostructures and nanoparticles of palladium assembled on highly ordered pyrolytic graphite (HOPG) by the adsorption of palladium molecular precursors (MPs), in dichloromethane solutions, have been prepared. Self-assemblies of palladium nanostructures on HOPG were characterized by scanning electron microscopy (SEM), Auger electron spectroscopy (AES), transmission electron microscopy (TEM), and atomic force microscopy (AFM) techniques. In this work, palladium rings had a wide variety of sizes in the nanometer range, and the ring/tube structures were preserved after a reductive process in which palladium metallic nanoparticles were formed. Noncircular structures were observed at HOPG defects and atomic step sites, as well. It is proposed that the observed ring formation of the palladium molecular precursors on HOPG substrates is related to the functional groups in the MPs, van der Waals interactions between particles and between particle-substrate, as well as the wetting properties of the solvent. In the present work, we illustrate several examples of the formation and characterization of palladium complex tubes and the resulting palladium rings, via the reduction process.