Imidodiphosphate and pyrophosphate: possible biological significance of similar structures

The structure of sodium imidodiphosphate has been determined by single crystal x-ray diffraction. The P-N-P bond angle (127.2 degrees) and P-N bond distance (1.68 angstroms) are remarkably similar to newly refined values for the P-O-P bond angle (128.6 degrees) and the bridging P-O bond distance (1.63 angstroms) of sodium pyrophosphate. This close similarity may explain why P-N-P linkages in algal "polyphosphates" escaped detection until recently and why adenosine triphosphate analogs with this linkage mimic adenosine triphosphate so closely.     

Quantum point contact switches

Switching behavior between electron tunneling and ballistic transport states was induced by repeatedly bringing a sharpened nickel wire into contact with a gold surface. The high-conductivity ballistic state had a quantized conductance of 0.977 +/- 0.015 (2e(2)/h). Switching was accomplished by moving the electrodes with a piezoelectric actuator over a distance of 2 angstroms. The two electrodes and the actuator form a three-terminal device that is demonstrated to be a reliable digital and analog switch; it shows good discrimination between high and low states and possesses the important property of power gain. The conductance channel is most likely only one atom wide and possibly consists of a single atom.     

Oxygen-mediated diffusion of oxygen vacancies on the TiO2(110) surface

Defects such as oxygen vacancies play a crucial role in the surface properties of transition metal oxides. By means of time-resolved, high-resolution scanning tunneling microscopy, we unraveled an adsorbate-mediated diffusion mechanism of oxygen vacancies on rutile TiO2(110). Adsorbed oxygen molecules mediate vacancy diffusion through the loss of an oxygen atom to a vacancy and the sequential capture of an oxygen atom from a neighboring bridging oxygen row, leading to an anisotropic oxygen vacancy diffusion pathway perpendicular to the bridging oxygen rows.     

The Axial Oxygen Atom and Superconductivity in YBa2Cu3O7

Changes in the copper K-edge x-ray absorption spectrum of YBa(2)Cu(3)O(7) across the critical temperature indicate that, accompanying the superconducting transition, the mean square relative displacement of some fraction of the Cu2-O4 bonds becomes smaller or more harmonic (or both), that there may be a slight increase in the associated Cul-O4 distance, and that electronic states involving these atom pairs become more atomic-like. If there is an association between the superconductivity and this lattice instability, then the bridging axial oxygen is of central importnce in determining the high tranition temperature of YBa(2)Cu(3)O(7). Because this structural perturbation will affect the dynamic polrizability of the copper oxygen sublattice, it is consistent with an excitonic pairing mhanism in these materials.     

Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond

Unlike mercury, which has an extensive +1 oxidation state chemistry, zinc usually adopts the +2 oxidation state. Decamethyldizincocene, Zn2(eta5-C5Me5)2, an organometallic compound of Zn(I) formally derived from the dimetallic [Zn-Zn]2+ unit, has been isolated from the low-temperature (-10 degrees C) reaction of Zn(C5Me5)2 and Zn(C2H5)2 in diethyl ether. X-ray studies show that it contains two eclipsed Zn(eta5-C5Me5) fragments with a Zn-Zn distance (+/- standard deviation) of 2.305(+/-3) angstroms, indicative of a metal-metal bonding interaction.     

A short Fe-Fe distance in peroxodiferric ferritin: control of Fe substrate versus cofactor decay?

The reaction of oxygen with protein diiron sites is important in bioorganic syntheses and biomineralization. An unusually short Fe-Fe distance of 2.53 angstroms was found in the diiron (mu-1,2 peroxodiferric) intermediate that forms in the early steps of ferritin biomineralization. This distance suggests the presence of a unique triply bridged structure. The Fe-Fe distances in the mu-1, 2 peroxodiferric complexes that were characterized previously are much longer (3.1 to 4.0 angstroms). The 2.53 angstrom Fe-Fe distance requires a small Fe-O-O angle (approximately 106 degrees to 107 degrees). This geometry should favor decay of the peroxodiferric complex by the release of H2O2 and mu-oxo or mu-hydroxo diferric biomineral precursors rather than by oxidation of the organic substrate. Geometrical differences may thus explain how diiron sites can function either as a substrate (in ferritin biomineralization) or as a cofactor (in O2 activation).     

Direct determination of ionic solvation from neutron diffraction

Much information on ionic solvation in electrolyte solutions has been inferred from macroscopic thermodynamic and transport properties and from spectroscopy. These ion-water interactions can now be probed directly and unambiguously by neutron diffraction. Such measurements have been done with neodymium trichloride solutions in heavy water that are identical in every respect except the isotopic state of the neodymium ions; these experiments yield in a straightforward manner the distribution of oxygen and deuterium atoms from the water molecules in the first hydration sphere of the neodymium ion. Each ion is surrounded by 8.6 oxygen atoms at a distance of 2.48 angstroms and 16.7 deuterium atoms at 3.13 angstroms indicating a well-defined first hydration sphere of water molecules, the deuterium atoms pointing away from the cation.     

Structural aspects of reversible molecular oxygen uptake

The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.     

Rocket ultraviolet spectrophotometry of comet kohoutek (1973f)

Observations of Comet Kohoutek (1973f) in the spectral region between 1200 and 3200 angstroms were made from an Aerobee rocket on 5.1 January 1974 universal time. The strongest features observed were the Lyman alpha line of neutral atomic hydrogen at 1216 angstroms and the hydroxyl (OH) bands at 3090 and 3142 angstroms. Atomic oxygen and atomic carbon were also detected, and their luminosity implies a production rate (of carbon monoxide or carbon dioxide) commensurate with that of water vapor.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

The manganese site of the photosynthetic water-splitting enzyme

As the originator of the oxygen in our atmosphere, the photosynthetic water-splitting enzyme of chloroplasts is vital for aerobic life on the earth. It has a manganese cluster at its active site, but it is poorly understood at the molecular level. Polarized synchrotron radiation was used to examine the x-ray absorption of manganese in oriented chloroplasts. The manganese site, in the "resting" (S1) state, is an asymmetric cluster, which probably contains four manganese atoms, with interatomic separations of 2.7 and 3.3 angstroms; the vector formed by the 3.3-angstrom manganese pair is oriented perpendicular to the membrane plane. Comparisons with model compounds suggest that the cluster contains bridging oxide or hydroxide ligands connecting the manganese atoms, perhaps with carboxylate bridges connecting the 3.3-angstrom manganese pair.     

Flocculation mechanism: charge neutralization and bridging

Electrophoresis measurements and electron-microscope observations with two model colloids and a polymeric flocculant show zeta-potential changes and details of floc structure. Fibers of the flocculant extend radially from the particle surface and vary in thickness from 20 to 300 angstroms. Both charge neutralization and bridging may function simultaneously.     

In Situ X-ray Absorption Study of Surface Complexes: Selenium Oxyanions on agr-FeOOH

A novel application of x-ray absorption spectroscopy has provided structural information for ions sorbed at oxide-water interfaces. As an example, in situ extended x-ray absorption fine structure (EXAFS) measurements of adsorbed selenate and selenite ions at ah alpha-FeOOH(goethite)-water interface have been performed; these measurements show that selenate forms a weakly bonded, outer-sphere complex and that selenite forms a strongly bonded, inner-sphere complex. The selenite ion is bonded directly to the goethite surface in a bidentate fashion with two iron atoms 3.38 angstroms from the selenium atom. Adsorbed selenate has no iron atom in the second coordination shell of selenium, which indicates retention of its hydration sphere upon sorption. This method provides direct structural information for adsorbed species at solid-liquid interfaces.     

Axial oxygen-centered lattice instabilities and high-temperature superconductivity

Copper K-edge x-ray absorption data indicate that an axial oxygen-centered lattice instability accompanying the 93 K superconducting transition in YBa(2)Cu(3)O(7) is of a pseudo-(anti)ferroelectric type, in that it appears to involve the softening of a double potential well into a structure in which the difference between the two copper-oxygen distances and the barrier height have both decreased. This softer structure is present only at temperatures within a fluctuation region around the transition. A similar process involving the analogous axial oxygen atom also accompanies the superconducting transition in T1Ba(2)Ca(3)Cu(4)O(11), where the superconducting transition temperature T(c) is ~120 K. The mean square relative displacement of this oxygen atom in YBa(2)Cu(3)O(7) is also specifically affected by a reduction in the oxygen content and by the substitution of cobalt for copper, providing further evidence for the sensitivity of the displacement to additional factors that also influence the superconductivity. On the basis of the implied coupling of this ionic motion to the superconductivity, a scenario for high-temperature superconductivity is presented in which both phonon and electronic (charge transfer) channels are synergistically involved.     

Comet kohoutek: ultraviolet images and spectrograms

Emissions of atomic oxygen (1304 angstroms), atomic carbon (1657 angstroms), and atomic hydrogen (1216 angstroms) from Comet Kohoutek were observed with ultraviolet cameras carried on a sounding rocket on 8 January 1974. Analysis of the Lyman alpha halo at 1216 angstroms gave an atomic hydrogen production rate of 4.5 x 10(29) atoms per second.     

Crystal Structure of Krypton Difluoride at -80{degrees}C

Krypton difluoride is tetragonal, space group P4(2)/ mnm, with two linear molecules per unit cell aligned in planes perpendicular to the tetrad axes. The alignment alternates by 90 degrees between successive planes. The kryptonfluorine bond distance is 1.89 +/- 0.02 angstroms.     

In Situ Determination of the NiAs Phase of FeO at High Pressure and Temperature

In situ synchrotron x-ray diffraction measurements of FeO at high pressures and high temperatures revealed that the high-pressure phase of FeO has the NiAs structure (B8). The lattice parameters of this NiAs phase at 96 gigapascals and 800 kelvin are a = 2.574(2) angstroms and c = 5.172(4) angstroms (the number in parentheses is the error in the last digit). Metallic behavior of the high-pressure phase is consistent with a covalently and metallically bonded NiAs structure of FeO. Transition to the NiAs structure of FeO would enhance oxygen solubility in molten iron. This transition thus provides a physiochemical basis for the incorporation of oxygen into the Earth's core.     

The Framework Topology of ZSM-18, a Novel Zeolite Containing Rings of Three (Si,Al)-O Species

ZSM-18 is the first known aluminosilicate zeolite to contain rings of three (Si,Al)-O species (3-rings). Its framework topology has been determined by hypothetical model building, subsequent constrained distance and angle least-squares refinements of atomic coordinates, and x-ray powder diffraction pattern simulations. Its channel structure is characterized by a linear unidimensional 12-ring channel, with an approximate pore opening of 7.0 angstroms. In addition, the channels are lined with pockets that are capped by 7-rings with dimensions of 2.8 angstroms by 3.5 angstroms. An intraframework packing model of the organic moiety used in the synthesis suggests that a strong templating effect may be responsible for the formation of this unusual zeolite structure.     

A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-

Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.     

Atmospheric Absorption Anomalies in the Ultraviolet near an Altitude of 50 Kilometers

Rocket-borne radiometer determinations of ozone distributions by absorption of ultraviolet sunlight show anomalous eflects near 3000 angstroms. The instrument uses four 40-angstrom filters in the spectral region between 2650 and 3300 angstroms. At altitudes below 40 kilometers, signals from filters centered near 3000 angstroms appear reduced at least 25 percent below calculated values. However, at higher altitudes an unpredicted sharp increase in signals is observed. These effects are inconsistent with ozone absorption and cannot be ascribed to instrument characteristics. A previously unobserved absorption band of an atmospheric constituent, possibly the metastable excited states of molecular oxygen O(2)((1)Delta(g)) or O(2)((1)Sigma(g)+) can account for the anomalous effects.