ABSTRACT
Core-level and valence-band x-ray photoemission spectra measured for molecular-beam-epitaxy-grown LaCrO(3)/SrTiO(3)(001) yield band offsets and potential gradients within the LaCrO(3) sufficient to trigger an electronic reconstruction to alleviate the polarity mismatch. Yet, the interface is insulating. Based on first principles calculations, we attribute this unexpected result to interfacial cation mixing combined with charge redistribution within CrO(2) layers, enabled by low-lying d states within LaCrO(3), which suppresses an electronic reconstruction.
ABSTRACT
The outer membrane protein OmcA is an 85 kDa decaheme c-type cytochrome located on the surface of the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1. It is assumed to mediate shuttling of electrons to extracellular acceptors that include solid metal oxides such as hematite (alpha-Fe(2)O(3)). No information is yet available concerning OmcA structure in physiologically relevant conditions such as aqueous environments. We purified OmcA and characterized its solution structure by small angle x-ray scattering (SAXS), and its interaction at the hematite-water interface by neutron reflectometry. SAXS showed that OmcA is a monomer that adopts a flat ellipsoidal shape with an overall dimension of 34 x 90 x 65 A(3). To our knowledge, we obtained the first direct evidence that OmcA undergoes a redox state-dependent conformational change in solution whereby reduction decreases the overall length of OmcA by approximately 7 A (the maximum dimension was 96 A for oxidized OmcA, and 89 A for NADH and dithionite-reduced OmcA). OmcA was also found to physically interact with electron shuttle molecules such as flavin mononucleotide, resulting in the formation of high-molecular-weight assemblies. Neutron reflectometry showed that OmcA forms a well-defined monomolecular layer on hematite surfaces, where it assumes an orientation that maximizes its contact area with the mineral surface. These novel insights into the molecular structure of OmcA in solution, and its interaction with insoluble hematite and small organic ligands, demonstrate the fundamental structural bases underlying OmcA's role in mediating redox processes.
Subject(s)
Cytochromes c/chemistry , Cytochromes c/metabolism , Ferric Compounds/metabolism , Heme , Neutron Diffraction , Scattering, Small Angle , X-Ray Diffraction , Anthraquinones/metabolism , Anthraquinones/pharmacology , Ferric Compounds/pharmacology , Flavins/metabolism , Flavins/pharmacology , Ligands , Models, Molecular , Nitrilotriacetic Acid/analogs & derivatives , Nitrilotriacetic Acid/metabolism , Nitrilotriacetic Acid/pharmacology , Oxidation-Reduction , Protein Conformation/drug effects , Shewanella/enzymology , Solutions , Structure-Activity Relationship , Surface Properties , Water/metabolismABSTRACT
Experimental evidence of the preferential uptake of aluminium by GABAergic neurones and glial cells was provided by synchrotron spectromicroscopy studies. We observed rat cerebellar cultures enriched for GABAergic neurones or glial cells exposed to aluminium ions, detecting the presence and identifying the chemical status of aluminium on cell structures.
Subject(s)
Aluminum/metabolism , Cerebellum/metabolism , Neuroglia/metabolism , Neurons/metabolism , gamma-Aminobutyric Acid/physiology , Absorptiometry, Photon , Animals , Cells, Cultured , Cerebellum/cytology , Cerebellum/ultrastructure , Microscopy, Electron , Neuroglia/ultrastructure , Neurons/ultrastructure , Photons , Rats , SynchrotronsABSTRACT
MnBi has attracted much attention in recent years due to its potential as a rare-earth-free permanent magnet material. It is unique because its coercivity increases with increasing temperature, which makes it a good hard phase material for exchange coupling nanocomposite magnets. MnBi phase is difficult to obtain, partly because the reaction between Mn and Bi is peritectic, and partly because Mn reacts readily with oxygen. MnO formation is irreversible and harmful to magnet performance. In this paper, we report our efforts toward developing MnBi permanent magnets. To date, high purity MnBi (>90%) can be routinely produced in large quantities. The produced powder exhibits 74.6 emu g(-1) saturation magnetization at room temperature with 9 T applied field. After proper alignment, the maximum energy product (BH)max of the powder reached 11.9 MGOe, and that of the sintered bulk magnet reached 7.8 MGOe at room temperature. A comprehensive study of thermal stability shows that MnBi powder is stable up to 473 K in air.
Subject(s)
Bismuth/chemistry , Magnets/chemistry , Manganese/chemistry , Temperature , Magnetic Phenomena , Mechanical PhenomenaABSTRACT
Stoichiometric epitaxial LaAlO(3) grown on TiO(2)-terminated SrTiO(3)(001) by off-axis pulsed laser deposition is shown to exhibit strong cation intermixing. This result is corroborated by classical and quantum mechanical calculations of the relative stabilities of abrupt and intermixed interface configurations. The valence band offset was measured to be 0.16 ± 0.10 eV, and this value cannot be accounted for theoretically without including intermixing in the physical description of the interface.
ABSTRACT
We reexamine the mechanism of ferromagnetism in doped TiO(2) anatase, using epitaxial Cr:TiO(2) with excellent structural quality as a model system. In contrast to highly oriented but defective Cr:TiO(2) (approximately 0.5 micro(b)/Cr), these structurally superior single crystal films exhibit negligible ferromagnetism. Similar results were obtained for Co:TiO(2). We show for the first time that charge-compensating oxygen vacancies alone, as predicted by F-center mediated exchange, are not sufficient to activate ferromagnetism. Instead, the onset of ferromagnetism correlates with the presence of structural defects.
ABSTRACT
Metals deposited in vacuum on metal oxides such as alumina normally grow as three-dimensional clusters because of weak adatom-substrate interactions. This tendency hinders our ability to form interfaces of ultrathin, laminar metal films on oxides for use in microelectronics and other technologies where nanostructural control is desired. We present experimental and theoretical results showing that room temperature Co deposition on fully hydroxylated clean sapphire (alpha-Al2O3) produces a surface chemical reaction that leads to laminar growth, despite a large mismatch in lattice constants. This process should be applicable to a wide range of metals and metal oxides.
ABSTRACT
We analyzed the effects of cold oxygen plasma ashing of neurobiological specimens on different elements with synchrotron spectromicroscopy. Our results demonstrate that while carbon is almost completely removed, phosphorus, calcium, potassium, sulfur, and, to some extent, nitrogen are retained and their relative concentration is enhanced.