Evidence for double valence fluctuation in metallic oxides of lead

The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.

Bond length distortions associated with torsion potentials; ab-initio studies on methanedio

The 4-31G basis set is used to study the bond length variations as functions of dihedral angels in methanediol. This study is compared with O---C---O bond angle optimization studies by Gorenstein and Kar and the possible reason for bond length shorteing in the trans---trans configuration is analysed.

Chemical approaches to penicillin allergy—IV. Binding of carrier receptor protein with penicillin and its analogues

The availability of electrophoretically homogeneous rabbit penicillin carrier receptor protein (CRP) by affinity chromatography afforded an idealin vitro system to calculate the thermodynamic parameters of binding of penicillin and analogues with CRP as well as competitive binding of such analogues with CRP in presence of14C-penicillin G. The kinetics of association of CRP with 7-deoxy penicillin which does not bind covalently with CRP have been studied through equilibrium dialysis with14C-7-deoxybenzyl penicillin and found to be K=2·79×106M−1.−ΔG=8·106 k cal/mole as well as fluorescence quenching studies with exciter λ 280 K=3·573×106M−1,−ΔG=8·239 k cal/mole. The fluorescence quenching studies have been extended to CRP-benzyl penicillin and CRP-6-aminopenicillanic acid (6APA) systems also. The fluorescence data with benzyl penicillin indicate two conformational changes in CRP—a fast change corresponding to the non-covalent binding to CRP with 7-deoxy penicillin and a slower change due to covalent bond formation. With 6-APA the first change is not observed but the conformational change corresponding to covalent binding is only seen. Competitive binding studies indicate that the order of binding of CRP with the analogues of penicillin is as follows: methicillin > 6APA > carbenicillin >o-nitrobenzyl penicillin > cloxacillin ≈ benzyl penicillin ≈ 6-phenyl acetamido penicillanyl alcohol ≈ 7 phenyl acetamido desacetoxy cephalosporanic acid ≈p-amino benzyl penicillin ≈p-nitro benzyl penicillin > ticarcillin >o-amino benzyl penicillin > amoxycillin > 7-deoxy benzyl penicillin > ampicillin.From these data it has been possible to delineate partially the topology of the penicillin binding cleft of the CRP as well as some of the functional groups in the cleft responsible for the binding process.

Shell-model calculation of defect energies in alkali halides employing crystal-independent interionic potential parameters

Shell model calculation of defect energies in alkali halides have been carried out using the ion-dependent, crystal-independent potential parameters of Sangster and Atwood (1978). Results indicate that appreciable differences exist between barrier heights for migration of cations and anions. While barrier heights for cations are generally lower than for anions in alkali halides of NaCl structure, the opposite is true in alkali halides of CsCl structure.

Synthetic peptide models for the redox-active disulfide loop of glutaredoxin. Conformational studies

Two cyclic peptide disulfides Boc-Cys-Pro-X-Cys-NHMe (X = L-Tyr or L-Phe) have been synthesized as models for the 14-membered redox-active disulfide loop of glutaredoxin. 'H NMR studies at 270 MHz in chloroform solutions establish a type I 0-turn conformation for the Pro-X segment in both peptides, stabilized by a 4-1 hydrogen bond between the Cys(1) CO and Cys(4) NH groups. Nuclear Overhauser effects establish that the aromatic ring in the X = Phe peptide is oriented over the central peptide unit. In dimethyl sulfoxide solutions two conformational species are observed in slow exchange on the NMR time scale, for both peptides. These are assigned to type I and type I1 p-turn structures with -Pro-Tyr(Phe)-as the corner residues. The structural assignments are based on correlation of NMR parameters with model 14-membered cyclic cystine peptides with Pro-X spacers. Circular dichroism studies based on the -S-Sn- u* transition suggest a structural change in the disulfide bridge with changing solvent polarity, establishing conformational coupling between the peptide backbone and the disulfide linkage in these systems.

Theoretical Treatment of Interaction Parameters in Multicomponent Metallic Solutions

A new theoretical equation for interaction parameter in multicomponent metallic solutions is developed using the pseudopotential formalism coupled with the free energy of the hard sphere system. The approximate expression for the pseudopotential term is given in terms of the heat of solution at infinite dilution, to allow easy evaluation of the interaction parameter in various multicomponent systems. This theory has been applied to 23 non-ferrous alloys based on Pb, Sn, Bi and indium. Comparison with the results of previous theoretical calculations using only the hard sphere model suggests that the inclusion of the pseudopotential term yields a quantitatively more correct prediction of interaction parameters in multicomponent metallic solutions. Numerical calculations were also made for 320 Fe-base solutions relevant to steelmaking and the agreement between calculation and experimental data appears reasonable, with 90% reliability in predicting the correct sign.

Transport properties of phosphomolybdate and phosphotungstate glasses

The d.c. conductivity of phosphomolybdate and phosphotungstate glasses is discussed. The conductivity of these glasses is due to the hopping of electrons between two valence states (Mo5+ to Mo6+ or W5+ W6+). In some of the glasses, the activation energy itself is found to be a function of temperature. This appears to be due to thermally activated and variable-range hopping mechanisms operating in different temperature regimes. The relation between conductivity and the [M5+]/[Mtotal](M ≡ Mo, W) ratio does not show any systematic variation. This anomaly can be understood using the structural models of these glasses. In contrast, Mott's theory and the Triberis and Friedman model have been used to obtain conductivity parameters such as the percolation distance Rij and 2agrRij (agr is the tunnelling probability). The conductivity parameter 2agrRij is quite useful to resolve the controversy regarding the tunnelling term exp(2agrRij) existing in the literature. For low values of 2agrRij, it is shown that the exp (2agrRij) term is very significant.

Droplet Epitaxy of InN Quantum Dots on Si(111) by RF Plasma-Assisted Molecular Beam Epitaxy

InN quantum dots (QDs) were fabricated on Si(111) substrate by droplet epitaxy using an RF plasma-assisted MBE system. Variation of the growth parameters, such as growth temperature and deposition time, allowed us to control the characteristic size and density of the QDs. As the growth temperature was increased from 100 C to 300 degrees C, an enlargement of QD size and a drop in dot density were observed, which was led by the limitation of surface diffusion of adatoms with the limited thermal energy. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to assess the QDs size and density. The chemical bonding configurations of InN QDs were examined by X-ray photo-electron spectroscopy (XPS). Fourier transform infrared (FTIR) spectrum of the deposited InN QDs shows the presence of In-N bond. Temperature-dependent photoluminescence (PL) measurements showed that the emission peak energies of the InN QDs are sensitive to temperature and show a strong peak emission at 0.79 eV.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Exact static polarizabilities of correlated finite model systems

A finite-field method for calculating exact polarizabilities of correlated conjugated model systems within the valence bond (VB) framework is presented. The correlations reduce the polarizabilities from their noninteracting values and extend the range of linearity to higher external fields. The large nonlinear polarizabilities observed in strongly correlated conjugated organic molecules cannot be directly attributed to electron correlations. The method described can be employed to calculate static polarizabilities for any desired state of a correlated system.

Equivalent circuit parameters of the film-covered magnesium/electrolyte interface in Mg/MnO2 dry cells from transient and ac impedance measurements

The electrochemical properties of the film-covered anode/solution interface in the magnesium/ manganese dioxide dry cell have been evaluated. The most plausible electrical equivalent circuit description of the Mg/solution interface with the passive film intact, has been identified. These results are based on the analysis of ac impedance and voltage transient measurements made on the dry cell under conditions which cause no damage to the protective passive film on the anode. The study demonstrates the complementary character of impedance and transient measurements when widely different frequency ranges are sampled in each type of investigation. The values and temperature dependence of the anode-film resistance, film capacitance, double-layer capacitance and charge-transfer resistance of the film-covered magnesium/solution interface have been determined. The magnitude of these values and its implications in understanding the important performance aspects of the magnesium/manganese dioxide dry cell are discussed. The study may be extended, in principle, to Li, Al and Ca batteries.

Variational calculation for the spin-(1/2 Heisenberg antiferromagnet on a square lattice

The ground-state properties of the spin-(1/2 Heisenberg antiferromagnet on a square lattice are studied by using a simple variational wave function that interpolates continuously between the Néel state and short-range resonating-valence-bond states. Exact calculations of the variational energy for small systems show that the state with the lowest energy has long-range antiferromagnetic order. The staggered magnetization in this state is approximately 70% of its maximum possible value. The variational estimate of the ground-state energy is substantially lower than the value obtained for the nearest-neighbor resonating-valence-bond wave function.