Investigations of oxide superconductors by x-ray absorption, photoemission and cognate spectroscopies

X-ray absorption spectra, X-ray photoelectron spectra and Auger spectra of cuprate superconductors are discussed. The studies establish the absence of Cu3+ for all practical purposes, but point out the importance of oxygen holes. X-ray photoelectron spectra of BaBi0.25Pb0.75O3 and related compounds are also examined.

Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Electronic-Transitions In Hydrogen-Bonded Dimers Of Carboxylic-Acids In The Vapor-Phase - An Electron-Energy Loss Spectroscopic Study

An electron energy loss spectroscopic study of the formic acid dimer has shown bands centred around 7.2, 8.5, 9.8, and 11.1 eV, of which the first and the third bands are assigned to n- rc* transitions and the other two to n-n* transitions; similar transitions are found in the acetic acid dimer.

A core-level photoemission spectroscopic study of the electron-doped superconductor, Nd2-xCexCuO4-δ

A photoemission study of superconducting Nd1.85Ce0.15CuO4-δ shows that Ce in the cuprate is essentially in the 4+ state. While the electron donated by Ce does not appear to affect the Cu 3d band, we still find evidence for the presence of considerable Cu1+ - related configurations due to covalency effects. A role for oxygen holes and Cu1+ species is indicated just as in other cuprate superconductors.

An ultraviolet photoelectron spectroscopic study of BF3–donor complexes

He i spectra of strong n–v type adducts of BF3 with H2O, CH3OH, (C2H5)2O, and CH3CN as well as of weak complexes of BF3 with NO and H2S are reported along with assignments based on MO calculations. The energy of the fluorine orbitals of BF3 is shown to be shifted in proportion to the strength of the donor–acceptor interaction. BF3 seems to form a contact pair with CS2.

High-pressure NMR investigations of the protonic conductor (NH4)4Fe(CN)6.1.5H2O

The effect of high hydrostatic pressure up to 1.5 GPa on ionic motion in (NH4)4Fe(CN)6.1.5H2O has been studied by wide-line 1H NMR experiments performed in the temperature range from room temperature to 77 K. The experiments at room temperature have shown a large increase in the second moment at 0.45 GPa as a result of a pressure-induced phase transition. The temperature dependence study up to 0.425 GPa has shown a gradual increase in the values of activation energy and attempt frequency with increase in pressure. The activation volume for motion at 300 K has been estimated to be 6% of molar volume. Vacancy-assisted ionic jumps are concluded to be the mode of charge transport. Second moments estimated at 77 K show evidence for tunnelling reorientation of at least one of the two NH4+ groups in the compound.

A spectroscopic study of the interaction of isoflavones with human serum albumin

Genistein and daidzein, the major isoflavones present in soybeans, possess a wide spectrum of physiological and pharmacological functions. The binding of genistein to human serum albumin (HSA) has been investigated by equilibrium dialysis, fluorescence measurements, CD and molecular visualization. One mole of genistein is bound per mole of HSA with a binding constant of 1.5 +/- 0.2 X 10(5) m(-1). Binding of genistein to HSA precludes the attachment of daidzein. The ability of HSA to bind genistein is found to be lost when the tryptophan residue of albumin is modified with N-bromosuccinimide. At 27 degrees C (pH 7.4), van't Hoff's enthalpy, entropy and free energy changes that accompany the binding are found to be -13.16 kcal.mol(-1), -21 cal.mol(-1)K(-1) and -6.86 kcal.mol(-1), respectively. Temperature and ionic strength dependence and competitive binding measurements of genistein with HSA in the presence of fatty acids and 8-anilino-1-naphthalene sulfonic acid have suggested the involvement of both hydrophobic and ionic interactions in the genistein-HSA binding. Binding measurements of genistein with BSA and HSA, and those in the presence of warfarin and 2,3,5-tri-iodobenzoic acid and Forster energy transfer measurements have been used for deducing the binding pocket on HSA. Fluorescence anisotropy measurements of daidzein bound and then displaced with warfarin, 2,3,5-tri-iodobenzoic acid or diazepam confirm the binding of daidzein and genistein to subdomain IIA of HSA. The ability of HSA to form ternery complexes with other neutral molecules such as warfarin, which also binds within the subdomain IIA pocket, increases our understanding of the binding dynamics of exogenous drugs to HSA.

Investigations on Bi2CuO4: a quasi-one-dimensional oxide system

The potential of Bi2CuO4 as the first oxide system to show a linear-chain magnetic behaviour is examined. Electron diffraction studies do not resolve the previously reported ambiguity regarding its space group. The magnetic susceptibility data at high temperatures are best fitted to a uniform antiferromagnetic spin-1/2 Heisenberg chain. At low temperatures, however, neither the uniform nor the alternating Heisenberg antiferromagnetic model fits the data. Magnetic susceptibility data over the entire temperature range can be fitted if one assumes dimeric units with a nearly degenerate second singlet state close to the ground state, these states being separated from an excited triplet state by an energy gap. A simple heuristic model of a dimer that gives such an energy level spectrum is examined.

Proton NMR investigations of ferroelectricity in ammonium sulphate

Results of cw wide-line proton magnetic resonance investigations on ammonium sulphate and rubidium ammonium sulphate are presented. The pressure and temperature dependence of some of the properties of ammonium sulphate are explained stressing the importance of the role of the ammonium ions.