Structure of Y and Zr Segregated Grain Boundaries in Alumina

Grain boundary segregation of Y and Zr in -Al₂O₃ and the atomic structural environment around the Y and Zr atoms have been investigated using high resolution STEM and EXAFS. At dilute concentrations, the Y ions in -Al₂O₃ grain boundaries, on average, are coordinated by 4 oxygens, at a distance of 2.30 Å, which corresponds nearly to the Y-O bond length in cubic Y₂O₃, and Zr ions are coordinated by 5 oxygens at a distance of 2.14 Å, which is approximately the same as the average Zr-O bond length in monoclinic ZrO₂. However, in the EXAFS radial distribution function, the Y-cation and Zr-cation next nearest neighbor shell cannot be clearly identified. These results suggest that Y and Zr at dilute concentrations in -Al₂O₃ occupy grain boundary sites with well defined nearest neighbor cation-oxygen bond lengths similar to those in their parent oxides, but with the next nearest neighbor cation-cation distances varying considerably from site to site. Grain growth can cause grain boundaries to become supersaturated by Y. In this case, both the Y-O nearest neighbor coordination number and the ordering of Y with respect to Al ions beyond nearest neighbor O are increased. This Y-Al distance is the same as that expected for the Y-Al distance when Y substitutes for Al while relaxing the Y-O distance to that in Y₂O₃. This may indicate that as the Y concentration increases, Y begins to occupy near-boundary sites in planes on each side of the geometrical boundary. In these near-boundary planes, the nearest neighbor ordering extends at least to nearest neighbor cations. Nucleation of the YAG phase leads to the depletion of these partially ordered layers.     

Synchrotron scanning photoemission microscopy of homogeneous and heterogeneous metal sulfide minerals

Scanning photoemission microscopy (SPEM) has been applied to the investigation of homogeneous and heterogeneous metal sulfide mineral surfaces. Three mineral samples were investigated: homogeneous chalcopyrite, heterogeneous chalcopyrite with bornite, and heterogeneous chalcopyrite with pyrite. Sulfur, copper and iron SPEM images, i.e. surface‐selective elemental maps with high spatial resolution acquired using the signal from the S 2p and Cu and Fe 3p photoemission peaks, were obtained for the surfaces after exposure to different oxidation conditions (either exposed to air or oxidized in pH 9 solution), in addition to high‐resolution photoemission spectra from individual pixel areas of the images. Investigation of the homogeneous chalcopyrite sample allowed for the identification of step edges using the topography SPEM image, and high‐resolution S 2p spectra acquired from the different parts of the sample image revealed a similar rate of surface oxidation from solution exposure for both step edge and a nearby terrace site. SPEM was able to successfully distinguish between chalcopyrite and bornite on the heterogeneous sample containing both minerals, based upon sulfur imaging. The high‐resolution S 2p spectra acquired from the two regions highlighted the faster air oxidation of the bornite relative to the chalcopyrite. Differentiation between chalcopyrite and pyrite based upon contrast in SPEM images was not successful, owing to either the poor photoionization cross section of the Cu and Fe 3p electrons or issues with rough fracture of the composite surface. In spite of this, high‐resolution S 2p spectra from each mineral phase were successfully obtained using a step‐scan approach.     

Self-Assembled Anion-Binding Cryptand for the Selective Liquid–Liquid Extraction of Phosphate Anions

The ligands L¹ and L² form trinuclear self-assembled complexes with Cu²⁺ (i.e. [( L¹ )₂Cu₃]⁶⁺ or [( L² )₂Cu₃]⁶⁺) both of which act as a host to a variety of anions. Inclusion of long aliphatic chains on these ligands allows the assemblies to extract anions from aqueous media into organic solvents. Phosphate can be removed from water efficiently and highly selectively, even in the presence of other anions.     

Pulse EPR Methods for Studying Chemical and Biological Samples Containing Transition Metals

This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double‐resonance (ENDOR), electron‐spin‐echo envelope‐modulation (ESEEM), and double electron–electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model systems, otherwise highly reactive aminyl radicals stabilized with electron‐rich transition metals, and nitroxide–copper–nitroxide clusters. These examples show that multi‐frequency continuous‐wave (CW) and pulse EPR provides detailed information about disordered systems.     

Coenzyme B induced coordination of coenzyme M via its thiol group to Ni(I) of F430 in active methyl-coenzyme M reductase

Methyl-coenzyme M reductase (MCR) catalyzes the reaction of methyl-coenzyme M (CH3-S-CoM) with coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. At the active site, it contains the nickel porphinoid F430, which has to be in the Ni(I) oxidation state for the enzyme to be active. How the substrates interact with the active site Ni(I) has remained elusive. We report here that coenzyme M (HS-CoM), which is a reversible competitive inhibitor to methyl-coenzyme M, interacts with its thiol group with the Ni(I) and that for interaction the simultaneous presence of coenzyme B is required. The evidence is based on X-band continuous wave EPR and Q-band hyperfine sublevel correlation spectroscopy of MCR in the red2 state induced with 33S-labeled coenzyme M and unlabeled coenzyme B.