Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

Crystallization of beef heart cytochrome c oxidase

NASA Astrophysics Data System (ADS)

Yoshikawa, Shinya; Shinzawa, Kyoko; Tsukihara, Tomitake; Abe, Toshio; Caughey, Winslow S.

1991-03-01

The three-dimensional structure of cytochrome c oxidase, a complex (multimetal, multisubunit) membrane protein is critical to elucidation of the mechanism of the enzymic reactions and their control. Our recent developments in the crystallization of the enzyme isolated from beef hearts are presented. The crystals appeared more readily at higher protein concentration, lower ionic strength, higher detergent concentration (Brij-35) and lower temperature. Large crystals were obtained by changing one of these parameters to the crystallization point as slowly as possible, keeping the other parameters constant. Increasing the detergent concentration was the most successful method, producing green crystals of the resting oxidized form as hexagonal bipyramids with typical dimensions of 0.6 mm. The usual procedures for crystallization of water soluble proteins, such as increasing ionic strength by vapor diffusion, were not applicable for this enzyme. Crystals of the resting oxidized enzyme belong to a space group of P6 2 or P6 4 with cell dimensions, a = b = 208.7 Å and c = 282.3 Å. The Patterson function shows that the crystal exhibited a non-crystallographic two-fold axis parallel to the c-axis in the asymmetric unit.

Theoretical study of production of unique glasses in space

NASA Technical Reports Server (NTRS)

Larsen, D. C.

1974-01-01

Analytical functional relationships describing homogeneous nucleation and crystallization in various supercooled liquids were developed. The time and temperature dependent relationships of nucleation and crystallization (intrinsic properties) are being used to relate glass forming tendency to extrinsic parameters such as cooling rate through computer simulation. Single oxide systems are being studied initially to aid in developing workable kinetic models and to indicate the primary materials parameters affecting glass formation. The theory and analytical expressions developed for simple systems is then extended to complex oxide systems. A thorough understanding of nucleation and crystallization kinetics of glass forming systems provides a priori knowledge of the ability of a given system to form a glass.

Electrocatalytic Oxidation of Formate by [Ni(P R 2N R' 2) 2(CH 3CN)] 2+ Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galan, Brandon R.; Schöffel, Julia; Linehan, John C.

2011-08-17

[Ni(P R 2N R' 2) 2(CH 3CN)] 2+ complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P R 2N R' 2)(P R" 2N R' 2)(CH 3CN)] 2+ with R = Cy, R' = Ph, R" = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2, protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ~0.04 M (34 equiv). At concentrationsmore » above ~0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s –1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η 1-OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO 2 liberation. Finally, the pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe) 2] 2+ (depe = 1,2-bis(diethylphosphino)ethane) complex.« less

Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ complexes.

PubMed

Galan, Brandon R; Schöffel, Julia; Linehan, John C; Seu, Candace; Appel, Aaron M; Roberts, John A S; Helm, Monte L; Kilgore, Uriah J; Yang, Jenny Y; DuBois, Daniel L; Kubiak, Clifford P

2011-08-17

[Ni(P(R)(2)N(R')(2))(2)(CH(3)CN)](2+) complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P(R)(2)N(R')(2))(P(R''(2))N(R'(2)))(CH(3)CN)](2+) with R = Cy, R' = Ph, R'' = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO(2), protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ∼0.04 M (34 equiv). At concentrations above ∼0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η(1)-OC(O)CH(3) binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO(2) liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.

Beyond the structure-property relationship paradigm: influence of the crystal structure and microstructure on the Li+ conductivity of La2/3Li(x)Ti(1-x)Al(x)O3 Oxides.

PubMed

García-Martín, Susana; Morata-Orrantía, Ainhoa; Alario-Franco, Miguel A; Rodríguez-Carvajal, Juan; Amador, Ulises

2007-01-01

The crystal structures of several oxides of the La(2/3)Li(x)Ti(1-x)Al(x)O(3) system have been studied by selected-area electron diffraction, high-resolution transmission electron microscopy, and powder neutron diffraction, and their lithium conductivity has been by complex impedance spectroscopy. The compounds have a perovskite-related structure with a unit cell radical2 a(p)x2 a(p)x radical2 a(p) (a(p)=perovskite lattice parameter) due to the tilting of the (Ti/Al)O(6) octahedra and the ordering of lanthanum and lithium ions and vacancies along the 2 a(p) axis. The Li(+) ions present a distorted square-planar coordination and are located in interstitial positions of the structure, which could explain the very high ionic conductivity of this type of material. The lithium conductivity depends on the oxide composition and its crystal microstructure, which varies with the thermal treatment of the sample. The microstructure of these titanates is complex due to formation of domains of ordering and other defects such as strains and compositional fluctuations.

Origin of Fe-Ti Oxide Mineralization in the Middle Paleoproterozoic Elet'ozero Syenite-Gabbro Intrusive Complex (Northern Karelia, Russia)

NASA Astrophysics Data System (ADS)

Sharkov, E. V.; Chistyakov, A. V.; Shchiptsov, V. V.; Bogina, M. M.; Frolov, P. V.

2018-03-01

Magmatic oxide mineralization widely developed in syenite-gabbro intrusive complexes is an important Fe and Ti resource. However, its origin is hotly debatable. Some researchers believe that the oxide ores were formed through precipitation of dense Ti-magnetite in an initial ferrogabbroic magma (Bai et al., 2012), whereas others consider them as a product of immiscible splitting of Fe-rich liquid during crystallization of Fe-Ti basaltic magma (Zhou et al., 2013). We consider this problem with a study of the Middle Paleoproterozoic (2086 ± 30 Ma) Elet'ozero Ti-bearing layered intrusive complex in northern Karelia (Baltic Shield). The first ore-bearing phase of the complex is mainly made up of diverse ferrogabbros, with subordinate clinopyroxenites and peridotites. Fe-Ti oxides (magnetite, Ti-magnetite, and ilmenite) usually account for 10-15 vol %, reaching 30-70% in ore varieties. The second intrusive phase is formed by alkaline and nepheline syenites. Petrographical, mineralogical, and geochemical data indicate that the first phase of the intrusion was derived from a moderately alkaline Fe-Ti basaltic melt, while the parental melt of the second phase was close in composition to alkaline trachyte. The orebodies comprise disseminated and massive ores. The disseminated Fe-Ti oxide ores make up lenses and layers conformable to general layering. Massive ores occur in subordinate amounts as layers and lenses, as well as cross-cutting veins. Elevated Nb and Ta contents in Fe-Ti oxides makes it possible to consider them complex ores. It is shown that the Fe-Ti oxide mineralization is related to the formation of a residual (Fe,Ti)-rich liquid, which lasted for the entire solidification history of the first intrusive phase. The liquid originated through multiple enrichment of Fe and Ti in the crystallization zone of the intrusion owing to the following processes: (1) precipitation of silicate minerals in the crystallization zone with a corresponding increase in the Fe and Ti contents in an interstitial melt; and (2) periodic accumulation of the residual melt in front of this zone. Unlike liquid immiscibility leading to melt splitting into two phases, this liquid dissolved the residual components of the melt. Correspondingly, such an Fe-rich liquid has unusual properties and requires further study.

Lattice-cell orientation disorder in complex spinel oxides

DOE PAGES

Chen, Yan; Cheng, Yongqiang; Li, Juchuan; ...

2016-11-07

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Crystal structures of catalytic complexes of the oxidative DNA/RNA repair enzyme AlkB

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu,B.; Edstrom, W.; Benach, J.

2006-01-01

Nucleic acid damage by environmental and endogenous alkylation reagents creates lesions that are both mutagenic and cytotoxic, with the latter effect accounting for their widespread use in clinical cancer chemotherapy. Escherichia coliAlkB and the homologous human proteins ABH2 and ABH3 (refs 5, 7) promiscuously repair DNA and RNA bases damaged by SN2 alkylation reagents, which attach hydrocarbons to endocyclic ring nitrogen atoms (N1 of adenine and guanine and N3 of thymine and cytosine). Although the role of AlkB in DNA repair has long been established based on phenotypic studies, its exact biochemical activity was only elucidated recently after sequence profilemore » analysis revealed it to be a member of the Fe-oxoglutarate-dependent dioxygenase superfamily. These enzymes use an Fe(ii) cofactor and 2-oxoglutarate co-substrate to oxidize organic substrates. AlkB hydroxylates an alkylated nucleotide base to produce an unstable product that releases an aldehyde to regenerate the unmodified base. Here we have determined crystal structures of substrate and product complexes of E. coli AlkB at resolutions from 1.8 to 2.3 Angstroms. Whereas the Fe-2-oxoglutarate dioxygenase core matches that in other superfamily members, a unique subdomain holds a methylated trinucleotide substrate into the active site through contacts to the polynucleotide backbone. Amide hydrogen exchange studies and crystallographic analyses suggest that this substrate-binding 'lid' is conformationally flexible, which may enable docking of diverse alkylated nucleotide substrates in optimal catalytic geometry. Different crystal structures show open and closed states of a tunnel putatively gating O2 diffusion into the active site. Exposing crystals of the anaerobic Michaelis complex to air yields slow but substantial oxidation of 2-oxoglutarate that is inefficiently coupled to nucleotide oxidation. These observations suggest that protein dynamics modulate redox chemistry and that a hypothesized migration of the reactive oxy-ferryl ligand on the catalytic Fe ion may be impeded when the protein is constrained in the crystal lattice.« less

Three-dimensional Bragg coherent diffraction imaging of an extended ZnO crystal.

PubMed

Huang, Xiaojing; Harder, Ross; Leake, Steven; Clark, Jesse; Robinson, Ian

2012-08-01

A complex three-dimensional quantitative image of an extended zinc oxide (ZnO) crystal has been obtained using Bragg coherent diffraction imaging integrated with ptychography. By scanning a 2.5 µm-long arm of a ZnO tetrapod across a 1.3 µm X-ray beam with fine step sizes while measuring a three-dimensional diffraction pattern at each scan spot, the three-dimensional electron density and projected displacement field of the entire crystal were recovered. The simultaneously reconstructed complex wavefront of the illumination combined with its coherence properties determined by a partial coherence analysis implemented in the reconstruction process provide a comprehensive characterization of the incident X-ray beam.

XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robblee, John Henry

A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S 3 → [S 4] → S 0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electronmore » paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S 2 → S 3 transition, in contrast to the S 0 → S 1 and S 1 → S 2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S 2 → S 3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S 0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S 1} state to 2.85 Å in the S 0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn 2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S 0 state have been investigated and a characteristic ''multiline'' signal in the S 0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S 0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S 0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds using XANES and EXAFS spectroscopy. The results from single-crystal Mn complexes show that dramatic dichroism exists in these complexes, and are suggestive of a promising future for single-crystal studies of PS II.« less

The resolution of acyclic P-stereogenic phosphine oxides via the formation of diastereomeric complexes: A case study on ethyl-(2-methylphenyl)-phenylphosphine oxide.

PubMed

Bagi, Péter; Varga, Bence; Szilágyi, András; Karaghiosoff, Konstantin; Czugler, Mátyás; Fogassy, Elemér; Keglevich, György

2018-04-01

As an example of acyclic P-chiral phosphine oxides, the resolution of ethyl-(2-methylphenyl)-phenylphosphine oxide was elaborated with TADDOL derivatives, or with calcium salts of the tartaric acid derivatives. Besides the study on the resolving agents, several purification methods were developed in order to prepare enantiopure ethyl-(2-methylphenyl)-phenylphosphine oxide. It was found that the title phosphine oxide is a racemic crystal-forming compound, and the recrystallization of the enantiomeric mixtures could be used for the preparation of pure enantiomers. According to our best method, the (R)-ethyl-(2-methylphenyl)-phenylphosphine oxide could be obtained with an enantiomeric excess of 99% and in a yield of 47%. Complete racemization of the enantiomerically enriched phosphine oxide could be accomplished via the formation of a chlorophosphonium salt. Characterization of the crystal structures of the enantiopure phosphine oxide was complemented with that of the diastereomeric intermediate. X-ray analysis revealed the main nonbonding interactions responsible for enantiomeric recognition. © 2018 Wiley Periodicals, Inc.

Exhaustive oxidation of a nickel dithiolate complex: some mechanistic insights en route to sulfate formation.

PubMed

Hosler, Erik R; Herbst, Robert W; Maroney, Michael J; Chohan, Balwant S

2012-01-21

A study of the step-wise oxidation of a Ni(II) diaminodithiolate complex through the formation of sulfate, the ultimate sulfur oxygenate, is reported. Controlled oxygenations or peroxidations of a neutral, planar, tetracoordinate, low-spin Ni(II) complex of a N(2)S(2)-donor ligand, (N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-propanediaminato) nickel(ii) (1), led to a series of sulfur oxygenates that have been isolated and characterized by ESI-MS and single-crystal X-ray diffraction. A monosulfenate complex (2) was detected by ESI-MS as a product of oxidation with one equivalent of H(2)O(2). However, this complex proved too unstable to isolate. Reaction of the dithiolate (1) with two equivalents of H(2)O(2) or one O(2) molecule leads to the formation of a monosulfinate complex (3), which was isolated and fully characterized by crystallography. The oxidation product of the monosulfinate (3) produced with either O(2) or H(2)O(2) is an interesting dimeric complex containing both sulfonate and thiolate ligands (4), this complex was fully characterized by crystallography, details of which were reported earlier by us. A disulfonate complex (7) is produced by reaction of 1 in the presence of O(2) or by reaction with exactly six equivalents of H(2)O(2). This complex was isolated and also fully characterized by crystallography. Possible intermediates in the conversion of the monosulfinate complex (3) to the disulfonate complex (7) include complexes with mixed sulfonate/sulfenate (5) or sulfonate/sulfinate (6) ligands. Complex 5, a four-oxygen adduct of 1, was not detected, but the sulfonate/sulfinate complex (6) was isolated and characterized. The oxidation chemistry of 1 is very different from that reported for other planar cis-N(2)S(2) Ni(ii) complexes including N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-ethylenediaminato) nickel(II), (8), and N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane nickel(II). To address the structural aspects of the reactivity differences, the crystal structure of 8 was also determined. A comparison of the structures of planar Ni(II) complexes containing cis-dithiolate ligands, strongly suggests that the differences in reactivity are determined in part by the degree of flexibility that is allowed by the NN' chelate ring.

Neutron diffraction study of the in situ oxidation of UO(2).

PubMed

Desgranges, Lionel; Baldinozzi, Gianguido; Rousseau, Gurvan; Nièpce, Jean-Claude; Calvarin, Gilbert

2009-08-17

This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO(2) into U(3)O(8). The symmetries and the structural parameters of UO(2), beta-U(4)O(9), beta-U(3)O(7), and U(3)O(8) were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO(2) into U(3)O(8) involves a complex modification of the oxygen sublattice and the onset of complex superstructures for U(4)O(9) and U(3)O(7), associated with regular stacks of complex defects known as cuboctahedra, which consist of 13 oxygen atoms. The kinetics of the oxidation process are discussed on the basis of the results of the structural analysis.

Redox chemistry of nickel(II) complexes supported by a series of noninnocent β-diketiminate ligands.

PubMed

Takaichi, June; Morimoto, Yuma; Ohkubo, Kei; Shimokawa, Chizu; Hojo, Takayuki; Mori, Seiji; Asahara, Haruyasu; Sugimoto, Hideki; Fujieda, Nobutaka; Nishiwaki, Nagatoshi; Fukuzumi, Shunichi; Itoh, Shinobu

2014-06-16

Nickel complexes of a series of β-diketiminate ligands ((R)L(-), deprotonated form of 2-substituted N-[3-(phenylamino)allylidene]aniline derivatives (R)LH, R = Me, H, Br, CN, and NO2) have been synthesized and structurally characterized. One-electron oxidation of the neutral complexes [Ni(II)((R)L(-))2] by AgSbF6 or [Ru(III)(bpy)3](PF6)3 (bpy = 2,2'-bipyridine) gave the corresponding metastable cationic complexes, which exhibit an EPR spectrum due to a doublet species (S = 1/2) and a characteristic absorption band in near IR region ascribable to a ligand-to-ligand intervalence charge-transfer (LLIVCT) transition. DFT calculations have indicated that the divalent oxidation state of nickel ion (Ni(II)) is retained, whereas one of the β-diketiminate ligands is oxidized to give formally a mixed-valence complex, [Ni(II)((R)L(-))((R)L(•))](+). Thus, the doublet spin state of the oxidized cationic complex can be explained by taking account of the antiferromagnetic interaction between the high-spin nickel(II) ion (S = 1) and the organic radical (S = 1/2) of supporting ligand. A single-crystal structure of one of the cationic complexes (R = H) has been successfully determined to show that both ligands in the cationic complex are structurally equivalent. On the basis of theoretical analysis of the LLIVCT band and DFT calculations as well as the crystal structure, the mixed-valence complexes have been assigned to Robin-Day class III species, where the radical spin is equally delocalized between the two ligands to give the cationic complex, which is best described as [Ni(II)((R)L(0.5•-))2](+). One-electron reduction of the neutral complexes with decamethylcobaltocene gave the anionic complexes when the ligand has the electron-withdrawing substituent (R = CN, NO2, Br). The generated anionic complexes exhibited EPR spectra due to a doublet species (S = 1/2) but showed no LLIVCT band in the near-IR region. Thus, the reduced complexes are best described as the d(9) nickel(I) complexes supported by two anionic β-diketiminate ligands, [Ni(I)((R)L(-))2](-). This conclusion was also supported by DFT calculations. Substituent effects on the electronic structures of the three oxidation states (neutral, cationic, and anionic) of the complexes are systematically evaluated on the basis of DFT calculations.

Softening non-metallic crystals by inhomogeneous elasticity.

PubMed

Howie, P R; Thompson, R P; Korte-Kerzel, S; Clegg, W J

2017-09-14

High temperature structural materials must be resistant to cracking and oxidation. However, most oxidation resistant materials are brittle and a significant reduction in their yield stress is required if they are to be resistant to cracking. It is shown, using density functional theory, that if a crystal's unit cell elastically deforms in an inhomogeneous manner, the yield stress is greatly reduced, consistent with observations in layered compounds, such as Ti 3 SiC 2 , Nb 2 Co 7 , W 2 B 5 , Ta 2 C and Ta 4 C 3 . The mechanism by which elastic inhomogeneity reduces the yield stress is explained and the effect demonstrated in a complex metallic alloy, even though the electronegativity differences within the unit cell are less than in the layered compounds. Substantial changes appear possible, suggesting this is a first step in developing a simple way of controlling plastic flow in non-metallic crystals, enabling materials with a greater oxidation resistance and hence a higher temperature capability to be used.

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

Generation and characterization of point defects in SrTiO3 and Y3Al5O12

NASA Astrophysics Data System (ADS)

Selim, F. A.; Winarski, D.; Varney, C. R.; Tarun, M. C.; Ji, Jianfeng; McCluskey, M. D.

Positron annihilation lifetime spectroscopy (PALS) was applied to characterize point defects in single crystals of Y3Al5O12 and SrTiO3 after populating different types of defects by relevant thermal treatments. In SrTiO3, PALS measurements identified Sr vacancy, Ti vacancy, vacancy complexes of Ti-O (vacancy) and hydrogen complex defects. In Y3Al5O12 single crystals the measurements showed the presence of Al-vacancy, (Al-O) vacancy and Al-vacancy passivated by hydrogen. These defects are shown to play the major role in defining the electronic and optical properties of these complex oxides.

Copper(II) ion catalytic oxidation of o-phenylenediamine and characterization, X-ray crystal structure and solution studies of the final product [DAPH][H3O][Cu(dipic)2]·3H2O

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Abdul Razak, Ibrahim; Refahi, Masoud; Moghimi, Abolghasem; Rosli, Mohd Mustaqim

2015-09-01

The complex [DAPH][H3O][Cu(dipic)2]·3H2O, (1) (dipicH2 = 2,6-pyridinedicarboxylic acid and DAP = 2,3-diaminophenazine) was prepared from the reaction of Cu(NO3)2·2H2O with mixture of o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid in water. The complex was characterized by FTIR, elemental analysis, UV-Vis and the single-crystal X-ray diffraction. The crystal system is monoclinic with the space group P21/c. This complex is stabilized in the solid state by an extensive network of hydrogen bonds between crystallized water, anionic and cationic fragments, which form a three-dimensional network. Furthermore, hydrogen bonds, π⋯π and Csbnd O⋯π stacking interactions seem to be effective in stabilizing the crystal structures. The protonation constants of dipic (L) and DAP (Q), the equilibrium constants for the dipic-DAP proton transfer system and the stoichiometry and stability constants of binary complexes including each of ligands (dipic, DAP) in presence Cu2+ ion, ternary complexes including, both of ligands (dipic-DAP) in presence of metal ion were calculated in aqueous solutions by potentiometric pH titration method using the Hyperquad2008 program. The stoichiometry of the most complexes species in solution was found to be very similar to the solid-state of cited metal ion complex.

Improvements in serial femtosecond crystallography of photosystem II by optimizing crystal uniformity using microseeding procedures

DOE PAGES

Ibrahim, Mohamed; Chatterjee, Ruchira; Hellmich, Julia; ...

2015-07-01

In photosynthesis, photosystem II (PSII) is the multi-subunit membrane protein complex that catalyzes photo-oxidation of water into dioxygen through the oxygen evolving complex (OEC). To understand the water oxidation reaction, it is important to get structural information about the transient and intermediate states of the OEC in the dimeric PSII core complex (dPSIIcc). In recent times, femtosecond X-ray pulses from the free electron laser (XFEL) are being used to obtain X-ray diffraction (XRD) data of dPSIIcc microcrystals at room temperature that are free of radiation damage. In our experiments at the XFEL, we used an electrospun liquid microjet setup thatmore » requires microcrystals less than 40 μm in size. In this study, we explored various microseeding techniques to get a high yield of monodisperse uniform-sized microcrystals. Monodisperse microcrystals of dPSIIcc of uniform size were a key to improve the stability of the jet and the quality of XRD data obtained at the XFEL. This was evident by an improvement of the quality of the datasets obtained, from 6.5 Å, using crystals grown without the micro seeding approach, to 4.5 Å using crystals generated with the new method.« less

Synthesis, characterization, photoluminescence, and electrochemical studies of novel mononuclear Cu(II) and Zn(II) complexes with the 1-benzylimidazolium ligand

NASA Astrophysics Data System (ADS)

Bibi, Sherino; Mohammad, Sharifah; Manan, Ninie Suhana Abdul; Ahmad, Jimmy; Kamboh, Muhammad Afzal; Khor, Sook Mei; Yamin, Bohari M.; Abdul Halim, Siti Nadiah

2017-08-01

Two new mononuclear coordination complexes [Cu(bim)4Cl2]ṡ2H2O (1) and [Zn(bim)2Cl2] (2) containing the 1-benzylimidazole (bim) ligand were successfully synthesized. Both complexes were characterized by IR, UV-vis, and fluorescence spectroscopies, single crystal and powder X-ray diffraction measurements, and thermogravimetric analysis. Self-assembly during the recrystallization process resulted in the formation of octahedral and tetrahedral Cu(II) and Zn(II) complexes, respectively. The single crystals obtained are representative of the bulk material, as shown by the powder X-ray diffraction patterns. Cyclic voltammetry measurements showed that complex 1 undergoes a quasi-reversible redox reaction, while complex 2 undergoes reduction alone, and no oxidation peak was observed; this is due to the stability of the reduced form of complex 2.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Electrocatalytic Oxidation of Formate by [Ni(P R 2 N R' 2 ) 2 (CH 3 CN)] 2+ Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galan, Brandon R.; Schöffel, Julia; Linehan, John C.

2011-08-17

New [Ni(P R 2N R` 2) 2+(CH 3CN)] 2+ complexes with R = Ph, R` = 4-MeOPh; R = Cy, R` = Ph and a mixed ligand [Ni(P R 2N R` 2)(P R`` 2N R` 2)] 2+ with R = Cy, R` = Ph, R`` = Ph have been synthesized and characterized by single crystal X-ray crystallography. These complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2, protons, and electrons with rates which are first order in catalyst and in formate at formate concentrations below approximately 0.05 M. For the catalysts studied,more » maximum observed turnover frequencies vary from <1.1 s -1 to 12.5 s -1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. A mechanistic scheme is proposed which involves an initial nickel complex bound <1-OC(O)H followed by a rate limiting hydride transfer step. An acetate complex demonstrating the η 1-OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single crystal X-ray crystallography. The pendant amines have been demonstrated to be essential for this electrocatalytic activity as no activity toward formate was found for the similar [Ni(depe) 2][BF 4] 2+ (depe = diethylphosphinoethane) complex. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

PubMed

Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

2005-07-21

The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

Effect of pH on the morphology of kidney stones

NASA Astrophysics Data System (ADS)

Agarwal, Neelesh; Sova, Stacey; Singh, N. B.; Arnold, Brad; Choa, Fow-Sen; Cullum, Brian; Su, Ching-Hua

2016-05-01

The process for the formation of kidney stone is very complex phenomena and has some similarity to the crystal growth from a solution. It is very much dependent on the acidity pH of the fluids. This pH variation affects the content and amount of filtering residue and its morphology. In this study we have performed experiments using carbonate, oxides and urea to simulate and understand the morphologies of the residue filtered and coarsened in different conditions. We observed that different of morphologies of kidney stones can be explained on the basis of acidity and hydration conditions. At lower pH fat prism crystals are observed and as pH increases, long fat needle crystals with large aspect ratio are observed. The coarsening experiments showed further growth of crystals. The remelting experiments showed that during dissolution of kidney stones the joining material breaks first leaving the large faceted crystals undissolved when attempts are made to dissolve into small crystallites. However, the morphology did not change. It was also observed that impurities such as magnesium oxide (MgO) affect the morphology significantly.

Enhanced electric dipole transition in lanthanide complex with organometallic ruthenocene units.

PubMed

Hasegawa, Yasuchika; Sato, Nao; Hirai, Yuichi; Nakanishi, Takayuki; Kitagawa, Yuichi; Kobayashi, Atsushi; Kato, Masako; Seki, Tomohiro; Ito, Hajime; Fushimi, Koji

2015-05-21

Enhanced luminescence of a lanthanide complex with dynamic polarization of the excited state and molecular motion is introduced. The luminescent lanthanide complex is composed of one Eu(hfa)3 (hfa, hexafluoroacetylacetonate) and two phosphine oxide ligands with ruthenocenyl units Rc, [Eu(hfa)3(RcPO)2] (RcPO = diphenylphosphorylruthenocene). The ruthenocenyl units in the phosphine oxide ligands play an important role of switching for dynamic molecular polarization and motion in liquid media. The oxidation states of the ruthenocenyl unit (Rc(1+)/Rc(1+)) are controlled by potentiostatic polarization. Eu(III) complexes attached with bidentate phosphine oxide ligands containing ruthenocenyl units, [Eu(hfa)3(RcBPO)] (RcBPO = 1,1'-bis(diphenylphosphoryl)ruthenocene), and with bidentate phosphine oxide ligands, [Eu(hfa)3(BIPHEPO)] (BIPHEPO =1,1'-biphenyl-2,2'-diylbis(diphenylphosphine oxide), were also prepared as references. The coordination structures and electrochemical properties were analyzed using single crystal X-ray analysis, cyclic voltammetry, and absorption spectroscopy measurements. The luminescence properties were estimated using an optoelectrochemical cell. Under potentiostatic polarization, a significant enhancement of luminescence was successfully observed for [Eu(hfa)3(RcPO)2], while no spectral change was observed for [Eu(hfa)3(RcBPO)]. In this study, the remarkable enhanced luminescence phenomena of Eu(III) complex based on the dynamic molecular motion under potentiostatic polarization have been performed.

Optically-Induced Persistent Magnetization in Oxygen Deficient Strontium Titanate

NASA Astrophysics Data System (ADS)

Crooker, Scott

2015-03-01

Interest in electronics and spintronics based on complex oxide materials has exploded in recent years, fueled by the ability to grow atomically-precise heterostructures of various oxides 1. A foundational material in this burgeoning field is strontium titanate, a (nominally) non-magnetic wide-bandgap semiconductor. Owing to its ubiquity in oxide materials science, studies of SrTiO3's interesting dielectric, lattice, and optical properties represent mature research areas. However, renewed interest in SrTiO3 was recently sparked by observations of unexpected spin and magnetization phenomena at interfaces between SrTiO3 and other nonmagnetic oxides 1. The formation and distribution of oxygen vacancies (VO) in SrTiO3 are widely thought to play an essential but as-yet-incompletely understood role in these emergent phenomena. Here we demonstrate a surprising new aspect to the phenomenology of magnetism in SrTiO3 by reporting the observation of an optically-induced and persistent magnetization in slightly oxygen-deficient SrTiO3-δ bulk crystals, using magnetic circular dichroism spectroscopy and optically-coupled SQUID studies 2. This magnetization appears below 18K, persists for hours below 10K, and is tunable via the polarization and wavelength of sub-bandgap (400-500 nm) light. As such, magnetic patterns can be ``written'' into SrTiO3-δ, and subsequently read out, using light alone. This magnetism occurs only in crystals containing VO, and is consistent with a metastable spin polarization of VO-related defect complexes. These data reveal a detailed interplay between magnetism, lattice defects, and light in an archetypal complex oxide material, which may yield new insights into the recent exciting spin physics observed at oxide interfaces.

Homoleptic nickel(II) complexes of redox-tunable pincer-type ligands.

PubMed

Hewage, Jeewantha S; Wanniarachchi, Sarath; Morin, Tyler J; Liddle, Brendan J; Banaszynski, Megan; Lindeman, Sergey V; Bennett, Brian; Gardinier, James R

2014-10-06

Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)2 complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett σ(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)2](BF4)n (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)2](BF4)2, is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)2](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)2](2+).

Synthesis, structure and catalytic activities of nickel(II) complexes bearing N4 tetradentate Schiff base ligand

NASA Astrophysics Data System (ADS)

Sarkar, Saikat; Nag, Sanat Kumar; Chattopadhyay, Asoke Prasun; Dey, Kamalendu; Islam, Sk. Manirul; Sarkar, Avijit; Sarkar, Sougata

2018-05-01

Two new nickel(II) complexes [Ni(L)Cl2] (1) and [Ni(L)(NCS)2] (2) of a neutral tetradentate mono-condensed Schiff base ligand, 3-(2-(2-aminoethylamino)ethylimino)butan-2-one oxime (L) have been synthesized and characterized using different physicochemical techniques e.g. elemental analyses, spectroscopic (IR, Electronic, NMR) methods, conductivity and molecular measurements. The crystal structure of complex (2) has been determined by using single crystal X-ray diffraction method and it suggests a distorted octahedral geometry around nickel(II) having a NiN6 coordinating atmosphere. The non-coordinated Osbnd H group on the ligand L remain engaged in H-bonding interactions with the S end of the coordinated thiocyanate moiety. These H-bonding interactions lead to Osbnd S separations of 3.132 Å and play prominent role in crystal packing. It is observed that the mononuclear units are glued together with such Osbnd H…S interactions and finally results in an 1D supramolecular sheet-like arrangement. DFT/TDDFT based theoretical calculations were also performed on the ligand and the complexes aiming at the accomplishment of idea regarding their optimized geometry, electronic transitions and the molecular energy levels. Finally the catalytic behavior of the complexes for oxidation of styrene has also been carried out. A variety of reaction conditions like the effect of solvent, effect of temperature and time as well as the effect of ratio of substrate to oxidant were thoroughly studied to judge the catalytic efficiency of the Ni(II) coordination entity.

Solid solutions of gadolinium doped zinc oxide nanorods by combined microwave-ultrasonic irradiation assisted crystallization

NASA Astrophysics Data System (ADS)

Kiani, Armin; Dastafkan, Kamran; Obeydavi, Ali; Rahimi, Mohammad

2017-12-01

Nanocrystalline solid solutions consisting of un-doped and gadolinium doped zinc oxide nanorods were fabricated by a modified sol-gel process utilizing combined ultrasonic-microwave irradiations. Polyvinylpyrrolidone, diethylene glycol, and triethylenetetramine respectively as capping, structure directing, and complexing agents were used under ultrasound dynamic aging and microwave heating to obtain crystalline nanorods. Crystalline phase monitoring, lattice parameters and variation, morphology and shape, elemental analysis, functional groups, reducibility, and the oxidation state of emerged species were examined by PXRD, FESEM, TEM, EDX, FTIR, micro Raman, H2-TPR, and EPR techniques. Results have verified that irradiation mechanism of gelation and crystallization reduces the reaction time, augments the crystal quality, and formation of hexagonal close pack structure of Wurtzite morphology. Besides, dissolution of gadolinium within host lattice involves lattice deformation, unit cell distortion, and angular position variation. Structure related shape and growth along with compositional purity were observed through microscopic and spectroscopic surveys. Furthermore, TPR and EPR studies elucidated more detailed behavior upon exposure to the exerted irradiations and subsequent air-annealing including the formed oxidation states and electron trapping centers, presence of gadolinium, zinc, and oxygen disarrays and defects, as well as alteration in the host unit cell via gadolinium addition.

Antimicrobial activity study of a μ3-oxo bridged [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2] cluster

NASA Astrophysics Data System (ADS)

Pathak, Sayantan; Jana, Barun; Mandal, Manab; Mandal, Vivekananda; Ghorai, Tanmay K.

2017-11-01

Synthesis, characterization and antimicrobial activity of a tri-nuclear μ3-Oxobridged Fe(III) cluster [Fe3O(PhCO2)6(MeOH)3](NO3)(MeOH)2(1) is reported. Cluster 1 is synthesized in a single pot reaction among Fe(NO3)3·9H2O, C6H5COOH, NaN3 (1:4:1) in MeOH. Single crystal X-ray diffraction studies of the isolated crystals show that it is μ3-Oxo bridged trimeric assembly of three Fe atoms via bridging benzoate anions. Furthermore, BVS calculations show that all three Fe atoms in complex 1 are in +3 oxidation state and are surrounded by benzoate anions and methanol in octahedral environment. The oxidation state of iron is also confirmed from the cyclic voltamogram. FT-IR spectroscopy and CHN analysis of the isolated crystals further supports the functional group attached to the periphery of the complex. The nanomolecular size of complex 1 is 1.29 nm. The antimicrobial efficiency studies of the complex 1 show significant inhibition of the growth of the organisms, viz. B. cereus MTCC 1272, S. epidermidis MTCC 3086 and S. typhimurium MTCC 98 and produced 23 ± 1.93 mm, 16 ± 1.77 mm and 12 ± 2.42 mm inhibition zones respectively. However, it shows zero inhibition to the strain of E. coli MTCC 723.

Complexes of cis-dioxomolybdenum(VI) and oxovanadium(IV) with a tridentate ONS donor ligand: Synthesis, spectroscopic properties, X-ray crystal structure and catalytic activity

NASA Astrophysics Data System (ADS)

Fayed, Ahmed M.; Elsayed, Shadia A.; El-Hendawy, Ahmed M.; Mostafa, Mohamed R.

2014-08-01

New cis-dioxomolybdenum(VI) and oxovanadium(IV) complexes of the Schiff base, derived from S-methyl dithiocarbazate and 2,3-dihydroxybenzaldehyde (H2dhsm), have been synthesized. The complexes of the type cis-[MoO2(dhsm)] (1a), cis-[MoO2(dhsm)(D)] (1b-1d) [D = neutral monodentate ligand; EtOH, pyridine (py) or imidazole (imz)], [VO(dhsm)(Nsbnd N)] (2a, 2b) [Nsbnd N = 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)] and [VO(dhsm)] (2c) have been isolated, characterized by 1H NMR, IR, UV-Vis and EPR spectral studies and investigated by cyclic voltammetry. The X-ray crystal structure of cis-[MoO2(dhsm)(EtOH)] (1b) has been determined and shows that the complex has a distorted octahedral geometry in which the H2dhsm behaves as a dianionic ONS tridentate ligand coordinating via phenoxide oxygen, hydrazinic nitrogen and thiolate sulfur. The oxomolybdenum(IV) complex [MoO(dhsm)] (1e) has obtained from dioxomolybdenum(VI) complex (1b) by oxo abstraction with PPh3. The reactivity of the complexes toward catalytic oxidation of alcohols in the presence of H2O2 and t-BuOOH as co-oxidants under solvent free conditions is reported.

Copper and manganese complexes based on 1,4-naphthalene dicarboxylic acid ligand and its derivative: Syntheses, crystal structures, and magnetic properties

NASA Astrophysics Data System (ADS)

Xing, Yubo; Liu, Yuqi; Xue, Xiaofei; Wang, Xinying; Li, Wei

2018-02-01

Three new metal-organic coordination polymers, {[Mn2(1,4-NDC)2 (C2H5OH) (DMF) (H2O)]·CH3OH}n(1), {[Mn(III)(1,4-NDC)(C2H5O)][Mn(II)(1,4-NDC)(DMF)(H2O)]}n(2) and {[Cu2(C13H9O4)4(H2O)2]}n(3) based on1,4-H2NDC and its derivative were hydrothermally synthesized (1,4-H2NDC = 1,4-naphthalene-dicarboxylic acid, C13H10O4 = 4-methyl formate-1-naphthalenecarboxylic acid), and characterized by techniques of single crystal X-ray diffraction, infrared spectra (IR), elemental analysis, powder X-ray diffraction(PXRD) and variable-temperature magnetic susceptibility measurements. X-ray crystal structure analyses reveal that complexes 1 and 2 show a same 3,5-connected fsc 3D topology network with the Schlȁfli symbol of {4·6·8}{4·66·83}. But, the valence of some Mn atom in complex 2 take place transition from the +II oxidation state to the +III oxidation state, which may be the effect of the different solvent ratio. In complex 3, the Cu⋯Cu distance of 2.620(13) Å is significantly shorter than the sum of the van der Waals radii of Cu (1.40 Å), resulting in a strong ferromagnetic interaction between the Cu(II) centers. Furthermore, the temperature-dependent magnetic susceptibility measurements exhibit overall antiferromagnetic interactions between manganese ions for complexes 1 and 2, and a strong ferromagnetic interaction between the Cu(II) centers for complex 3.

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Bulk ZnO: Current Status, Challenges, and Prospects

DTIC Science & Technology

2009-04-01

von Wenckstern, H. Schmidt, M. Lorenz, and M. Grundmann, “Defects in virgin and N+-implanted ZnO single crystals studied by positron annihilation...characterization, and device applications of semiconductor and complex oxide thin films. He is a co-author of more than 50 papers in referred...REPLACE THIS LINE WITH YOUR PAPER IDENTIFICATION NUMBER (DOUBLE-CLICK HERE TO EDIT) < 1 Abstract— Rediscovered in the last decade, zinc oxide

Comparison study of PE epitaxy on carbon nanotubes and graphene oxide and PE/graphene oxide as amphiphilic molecular structure for solvent separation

NASA Astrophysics Data System (ADS)

He, Linghao; Zheng, Xiaoli; Xu, Qun; Chen, Zhimin; Fu, Jianwei

2012-03-01

Carbon nanotubes (CNTs) and graphene nanosheets, as one-dimensional and two-dimensional carbon-based nanomaterials respectively, have different abilities to induce the polymer crystallization. In this study, hybrid materials, polyethylene (PE) decorating on CNTs and graphene oxide (GO), were prepared by a facile and efficient method using supercritical carbon dioxide (SC CO2) as anti-solvent. And the morphology and crystallization behavior of PE on CNTs and GO were investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide angle X-ray diffraction, and differential scanning calorimetry. Although both CNTs and GO could act as nucleating agents to induce PE epitaxial growth, CNTs were decorated by PE lamellar crystals forming nanohybrid "shish-kebab" (NHSK) structure, whereas GO sheets were only decorated with petal-like PE crystals. The varying morphologies of the nanohybrids depend on the PE epitaxy and the interactions between polymer chains and substrates. High surface curvature and the perfect ordered crystal structure of CNTs make PE crystals periodically grow on CNTs. While PE crystals grow and form multiple orientation-lamellae on GO due to the lattice matching and complex interactions between PE chains and GO. In addition, our experimental results show an interesting and evident stratification phenomenon for the PE/GO hybrid material, implying that GO decorated by PE have a screening function for the solvents. We anticipate that this work can widen the area of functionalization of carbon-based nanomaterials with a controlled means by an environmentally benign method, which are important for the functional design in nanodevice applications.

Crystal structures and catalytic performance of three new methoxy substituted salen type nickel(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine

NASA Astrophysics Data System (ADS)

Ghaffari, Abolfazl; Behzad, Mahdi; Pooyan, Mahsa; Amiri Rudbari, Hadi; Bruno, Giuseppe

2014-04-01

Three new nickel(II) complexes of a series of methoxy substituted salen type Schiff base ligands were synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy and elemental analysis. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with n-methoxysalicylaldehyde (n = 3, 4 and 5). Crystal structures of these complexes were determined. Electrochemical behavior of the complexes was studied by means of cyclic voltammetry in DMSO solutions. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant under various conditions to find the optimum operating parameters. Low catalytic activity with moderate epoxide selectivity was observed in in-solvent conditions but in the solvent-free conditions, enhanced catalytic activity with high epoxide selectivity was achieved.

Excellently guarded materials against UV and oxygen in the surfactant molecular complex crystal matrix

NASA Astrophysics Data System (ADS)

Ichikawa, Haruyo; Iimura, Nahoko; Hirata, Hirotaka

2000-07-01

Crystalline surfactant molecular complexes (SCMs) generated between quaternary ammonium cationic surfactants such as CTAB and various additives disclose their excellent protective properties from UV light and oxygen to complex additive materials, which are occluded in the complex crystal matrix. The effects of UV and oxygen were followed by the absorption decay of additive chromophores in comparing that of naked additive specimens with that of those in the complexed state. From the decay profiles, the rate constants and the half-life times were estimated under the assumptions in which the photo and oxidation processes were dominated in accordance with the first-ordered reaction. The results afford us promising prospects in extending the shelf-life of every material, above all medicinal drug, with the consequence that these obtained values evidently demonstrate the remarkably suppressed rate and extremely elongated half-life times.

Characteristics of growth of complex ferroelectric oxide films by plasma-ion sputtering

NASA Astrophysics Data System (ADS)

Mukhortov, V. M.; Golovko, Yu. I.; Mukhortov, Vl. M.; Dudkevich, V. P.

1981-02-01

An experimental investigation was made of the process of growth of a complex oxide film, such as BaTiO3 or (Ba, Sr)TiO3, by plasma-ion sputtering. It was found that ion bombardment of a ceramic target knocked out neutral excited atoms. These atoms lost energy away from the target by collisions and at a certain critical distance hcr they were capable of oxidation to produce BaO, TiO, TiO2, and SrO. Therefore, depending on the distance between the cathode and the substrate, the “construction” material arrived in the form of atoms or molecules of simple oxides. These two (atomic and molecular) deposition mechanisms corresponded to two mechanisms of synthesis and crystallization differing in respect of the dependences of the growth rate, unit cell parameters, and other structural properties on the deposition temperature. The role of re-evaporation and of oxidation-reduction processes was analyzed.

Nanoscale Strontium Titanate Sheets and Crystals

NASA Astrophysics Data System (ADS)

Tilka, Jack Andrew

The physical properties of materials are dominated by their structure and composition. Insight into the structure of complex oxide materials has the potential to improve our understanding and eventually control of their physical properties. This PhD thesis reports the development of characterization and fabrication techniques relevant to improving the scientific understanding of complex oxide materials. The work presented here has two components. I report a way to use ideas that were originally developed in semiconductor processing to control the elastic strain state and crystallization process of the model complex oxide SrTiO3. An additional component is an important series of advances in the analysis of diffraction patterns acquired with focused x-ray nanobeams. The fabrication and characterization of nanoscale SrTiO3 has been experimentally shown to allow the introduction of elastic strain into SrTiO3. The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction experiments show that the SrTiO 3 sheets have rocking curves with angular widths less than 0.02°. These widths are less than a factor of two larger than bulk SrTiO3, which shows that the sheets are suitable substrates for epitaxial thin film growth. A precisely selected elastic strain can be introduced into the SrTiO 3 sheets using a silicon nitride stressor layer. Synchrotron x-ray nanodiffraction studies show that the strain introduced in the SrTiO3 sheets is on the order of 10-4, matching the predictions of an elastic model. This approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect not achievable in heteroepitaxy on rigid substrates. An additional fabrication technique is also evaluated here based on the crystallization of SrTiO3 from initially amorphous thin films. This process is known as solid-phase epitaxy in two-dimensional samples but is just beginning to be explored in more complex geometries. I report experiments in both homoepitaxy and heteroepitaxy including measurements of crystal growth rates and the crystallographic orientations of crystals formed in this way. The lateral growth rates are consistent with previously measured vertical growth. This result indicated that previous work on vertical solid-phase epitaxy could be extended into lateral solid-phase epitaxy, which has the power to be applied to complicated non-planar geometries. The highly coherent and tightly focused x-ray beams produced by hard x-ray light sources enable the nanoscale structural characterization of materials but are accompanied by significant challenges in the interpretation of diffraction and scattering patterns. I report here a series of methods that expand the range of physical problems that can be accurately captured by coherent x-ray optical simulations. My approach has been to expand simulations methods to include arbitrary x-ray incident angles and arbitrary epitaxial heterostructures. I first applied these methods to extract the misorientation of lattice planes and the strain of individual layers of Si/SiGe heterostructures relevant to applications in quantum electronics. Further applications reported in this thesis are in probing defects created in the processing of SrTiO3 and in measuring the change in lattice parameter introduced into strained SrTiO3 sheets. The systematic interpretation of nanobeam diffraction patterns aids in the fabrication of SrTiO3 nanostructures.

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

PubMed

Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

2018-05-01

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Evidence of formation of site-selective inclusion complexation between beta-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers.

PubMed

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M; Graham, Matthew J; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z D

2010-05-28

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with beta-cyclodextrin (beta-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state (13)C NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the beta-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in (13)C solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after beta-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of beta-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that beta-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using (1)H NMR, and a 3:1 (PO unit to beta-CD) was found for all inclusion complexes, which indicated that the number of threaded beta-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the beta-CD in the inclusion complex formed a channel-like structure that is different from the pure beta-CD crystal structure.

Evidence of formation of site-selective inclusion complexation between β-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers

NASA Astrophysics Data System (ADS)

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M.; Graham, Matthew J.; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z. D.

2010-05-01

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with β-cyclodextrin (β-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state C13 NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the β-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in C13 solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after β-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of β-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that β-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using H1 NMR, and a 3:1 (PO unit to β-CD) was found for all inclusion complexes, which indicated that the number of threaded β-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the β-CD in the inclusion complex formed a channel-like structure that is different from the pure β-CD crystal structure.

Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Mousavi, S. Sedighe; Afshari, Sadegh

2016-11-01

New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romano, Christine A.; Zhou, Mowei; Song, Yang

Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase, Mnx, in Bacillus sp. PL-12 is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. However, MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant tomore » crystallization, so its structure is unknown. In this study, native mass spectrometry defines the subunit topology and copper binding of the Mnx complex, while high resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for conceptualizing how Mnx produces nanoparticulate Mn oxides.« less

Oxide perovskite crystals for HTSC film substrates microwave applications

NASA Technical Reports Server (NTRS)

Bhalla, A. S.; Guo, Ruyan

1995-01-01

The research focused upon generating new substrate materials for the deposition of superconducting yttrium barium cuprate (YBCO) has yielded several new hosts in complex perovskites, modified perovskites, and other structure families. New substrate candidates such as Sr(Al(1/2)Ta(1/2))O3 and Sr(Al(1/2)Nb(1/2))O3, Ba(Mg(1/3)Ta(2/3))O3 in complex oxide perovskite structure family and their solid solutions with ternary perovskite LaAlO3 and NdGaO3 are reported. Conventional ceramic processing techniques were used to fabricate dense ceramic samples. A laser heated molten zone growth system was utilized for the test-growth of these candidate materials in single crystal fiber form to determine crystallographic structure, melting point, thermal, and dielectric properties as well as to make positive identification of twin free systems. Some of those candidate materials present an excellent combination of properties suitable for microwave HTSC substrate applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yan; Cheng, Yongqiang; Li, Juchuan

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

PubMed

Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

2015-07-21

Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

Oxidation Chemistry of Inorganic Benzene Complexes.

PubMed

Fleischmann, Martin; Dielmann, Fabian; Balázs, Gábor; Scheer, Manfred

2016-10-17

The oxidation of the 28 VE cyclo-E 6 triple-decker complexes [(Cp R Mo) 2 (μ,η 6 :η 6 -E 6 )] (E=P, Cp R =Cp(2 a), Cp*(2 b), Cp Bn (2 c)=C 5 (CH 2 Ph) 5 ; E=As, Cp R =Cp*(3)) by Cu + or Ag + leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E 6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E 6 ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structures of human thymidylate synthase R163K with dUMP, FdUMP and glutathione show asymmetric ligand binding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, Lydia M.; Celeste, Lesa R.; Lovelace, Leslie L.

Thymidylate synthase (TS) is a well validated target in cancer chemotherapy. Here, a new crystal form of the R163K variant of human TS (hTS) with five subunits per asymmetric part of the unit cell, all with loop 181-197 in the active conformation, is reported. This form allows binding studies by soaking crystals in artificial mother liquors containing ligands that bind in the active site. Using this approach, crystal structures of hTS complexes with FdUMP and dUMP were obtained, indicating that this form should facilitate high-throughput analysis of hTS complexes with drug candidates. Crystal soaking experiments using oxidized glutathione revealed thatmore » hTS binds this ligand. Interestingly, the two types of binding observed are both asymmetric. In one subunit of the physiological dimer covalent modification of the catalytic nucleophile Cys195 takes place, while in another dimer a noncovalent adduct with reduced glutathione is formed in one of the active sites.« less

Crystallographic and spectroscopic snapshots reveal a dehydrogenase in action

DOE PAGES

Huo, Lu; Davis, Ian; Liu, Fange; ...

2015-01-07

Aldehydes are ubiquitous intermediates in metabolic pathways and their innate reactivity can often make them quite unstable. There are several aldehydic intermediates in the metabolic pathway for tryptophan degradation that can decay into neuroactive compounds that have been associated with numerous neurological diseases. An enzyme of this pathway, 2-aminomuconate-6-semialdehyde dehydrogenase, is responsible for ‘disarming’ the final aldehydic intermediate. Here we show the crystal structures of a bacterial analogue enzyme in five catalytically relevant forms: resting state, one binary and two ternary complexes, and a covalent, thioacyl intermediate. We also report the crystal structures of a tetrahedral, thiohemiacetal intermediate, a thioacylmore » intermediate and an NAD +-bound complex from an active site mutant. These covalent intermediates are characterized by single-crystal and solution-state electronic absorption spectroscopy. The crystal structures reveal that the substrate undergoes an E/Z isomerization at the enzyme active site before an sp 3-to-sp 2 transition during enzyme-mediated oxidation.« less

Expression, purification and crystallization of Trypanosoma cruzi dihydroorotate dehydrogenase complexed with orotate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inaoka, Daniel Ken; Takashima, Eizo; Osanai, Arihiro

2005-10-01

The Trypanosoma cruzi dihydroorotate dehydrogenase, a key enzyme in pyrimidine de novo biosynthesis and redox homeostasis, was crystallized in complex with its first reaction product, orotate. Dihydroorotate dehydrogenase (DHOD) catalyzes the oxidation of dihydroorotate to orotate, the fourth step and the only redox reaction in the de novo biosynthesis of pyrimidine. DHOD from Trypanosoma cruzi (TcDHOD) has been expressed as a recombinant protein in Escherichia coli and purified to homogeneity. Crystals of the TcDHOD–orotate complex were grown at 277 K by the sitting-drop vapour-diffusion technique using polyethylene glycol 3350 as a precipitant. The crystals diffract to better than 1.8 Åmore » resolution using synchrotron radiation (λ = 0.900 Å). X-ray diffraction data were collected at 100 K and processed to 1.9 Å resolution with 98.2% completeness and an overall R{sub merge} of 7.8%. The TcDHOD crystals belong to the orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 67.87, b = 71.89, c = 123.27 Å. The presence of two molecules in the asymmetric unit (2 × 34 kDa) gives a crystal volume per protein weight (V{sub M}) of 2.2 Å{sup 3} Da{sup −1} and a solvent content of 44%.« less

Fluorescence kinetics of PSII crystals containing Ca(2+) or Sr(2+) in the oxygen evolving complex.

PubMed

van Oort, Bart; Kargul, Joanna; Maghlaoui, Karim; Barber, James; van Amerongen, Herbert

2014-02-01

Photosystem II (PSII) is the pigment-protein complex which converts sunlight energy into chemical energy by catalysing the process of light-driven oxidation of water into reducing equivalents in the form of protons and electrons. Three-dimensional structures from x-ray crystallography have been used extensively to model these processes. However, the crystal structures are not necessarily identical to those of the solubilised complexes. Here we compared picosecond fluorescence of solubilised and crystallised PSII core particles isolated from the thermophilic cyanobacterium Thermosynechococcus elongatus. The fluorescence of the crystals is sensitive to the presence of artificial electron acceptors (K3Fe(CN)3) and electron transport inhibitors (DCMU). In PSII with reaction centres in the open state, the picosecond fluorescence of PSII crystals and solubilised PSII is indistinguishable. Additionally we compared picosecond fluorescence of native PSII with PSII in which Ca(2) in the oxygen evolving complex (OEC) is biosynthetically replaced by Sr(2+). With the Sr(2+) replaced OEC the average fluorescence decay slows down slightly (81ps to 85ps), and reaction centres are less readily closed, indicating that both energy transfer/trapping and electron transfer are affected by the replacement. Copyright © 2013. Published by Elsevier B.V.

Sonication-assisted synthesis of a new cationic zinc nitrate complex with a tetradentate Schiff base ligand: Crystal structure, Hirshfeld surface analysis and investigation of different parameters influence on morphological properties.

PubMed

Mousavi, S A; Montazerozohori, M; Masoudiasl, A; Mahmoudi, G; White, J M

2018-09-01

A nanostructured cationic zinc nitrate complex with a formula of [ZnLNO 3 ]NO 3 (where L = (N 2 E,N 2' E)-N 1 ,N 1' -(ethane-1,2-diyl)bis(N 2 -((E)-3-phenylallylidene)ethane-1,2-diamine)) was prepared by sonochemical process and characterized by single crystal X-ray crystallography, scanning electron microscopy (SEM), FT-IR and NMR spectroscopy and X-ray powder diffraction (XRPD). The X-ray analysis demonstrates the formation of a cationic complex that metal center is five-coordinated by four nitrogen atom from Schiff base ligand and one oxygen atom from nitrate group. The crystal packing analysis demonstrates the essential role of the nitrate groups in the organization of supramolecular structure. The morphology and size of ultrasound-assisted synthesized zinc nitrate complex have been investigated using scanning electron microscopy (SEM) by changing parameters such as the concentration of initial reactants, the sonication power and reaction temperature. In addition the calcination of zinc nitrate complex in air atmosphere led to production of zinc oxide nanoparticles. Copyright © 2018. Published by Elsevier B.V.

Synthesis and structural studies of two pyridine-armed reinforced cyclen chelators and their transition metal complexes.

PubMed

Wilson, Kevin R; Cannon-Smith, Desiray J; Burke, Benjamin P; Birdsong, Orry C; Archibald, Stephen J; Hubin, Timothy J

2016-08-16

Two novel pyridine pendant-armed macrocycles structurally reinforced by an ethyl bridge, either between adjacent nitrogens (for side-bridged) or non-adjacent nitrogens (for cross-bridged), have been synthesized and complexed with a range of transition metal ions (Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ ). X-ray crystal structures of selected cross-bridged complexes were obtained which showed the characteristic cis-V configuration with potential labile cis binding sites. The complexes have been characterized by their electronic spectra and magnetic moments, which show the expected high spin divalent metal complex in most cases. Exceptions are the nickel side-bridged complex, which shows a mixture of high-spin and low spin, and the cobalt cross-bridged complex which has oxidized to cobalt(III). Cyclic voltammetry in acetonitrile was carried out to assess the potential future use of these complexes in oxidation catalysis. Selected complexes offer significant catalytic potential enhanced by the addition of the pyridyl arm to a reinforced cyclen backbone.

Complexes of horseradish peroxidase with formate, acetate, and carbon monoxide.

PubMed

Carlsson, Gunilla H; Nicholls, Peter; Svistunenko, Dimitri; Berglund, Gunnar I; Hajdu, Janos

2005-01-18

Carbon monoxide, formate, and acetate interact with horseradish peroxidase (HRP) by binding to subsites within the active site. These ligands also bind to catalases, but their interactions are different in the two types of enzymes. Formate (notionally the "hydrated" form of carbon monoxide) is oxidized to carbon dioxide by compound I in catalase, while no such reaction is reported to occur in HRP, and the CO complex of ferrocatalase can only be obtained indirectly. Here we describe high-resolution crystal structures for HRP in its complexes with carbon monoxide and with formate, and compare these with the previously determined HRP-acetate structure [Berglund, G. I., et al. (2002) Nature 417, 463-468]. A multicrystal X-ray data collection strategy preserved the correct oxidation state of the iron during the experiments. Absorption spectra of the crystals and electron paramagnetic resonance data for the acetate and formate complexes in solution correlate electronic states with the structural results. Formate in ferric HRP and CO in ferrous HRP bind directly to the heme iron with iron-ligand distances of 2.3 and 1.8 A, respectively. CO does not bind to the ferric iron in the crystal. Acetate bound to ferric HRP stacks parallel with the heme plane with its carboxylate group 3.6 A from the heme iron, and without an intervening solvent molecule between the iron and acetate. The positions of the oxygen atoms in the bound ligands outline a potential access route for hydrogen peroxide to the iron. We propose that interactions in this channel ensure deprotonation of the proximal oxygen before binding to the heme iron.

Geochemistry of zircons from basic rocks of the Korosten anorthosite-mangerite-charnockite-granite complex, north-western region of the Ukrainian Shield

NASA Astrophysics Data System (ADS)

Shumlyanskyy, Leonid; Belousova, Elena; Petrenko, Oksana

2017-09-01

The concentrations of 26 trace elements have been determined by laser ablation ICP-MS in zircons from four samples of basic rocks of the Korosten anorthosite-mangerite-charnockite-granite plutonic complex, the Ukrainian Shield. Zircons from the Fedorivka and Torchyn gabbroic intrusions and Volynsky anorthosite massif have distinctive abundances of many trace elements (REE, Sr, Y, Mn, Th). Zircons from the gabbroic massifs are unusually enriched in trace elements, while zircons from pegmatites in anorthosite are relatively depleted in trace elements. High concentrations of trace elements in zircons from gabbroic intrusions can be explained by their crystallization from residual interstitial melts enriched in incompatible elements. The zircons studied demonstrate a wide range of Ti concentrations, which reflects their temperature of crystallization: the zircons most enriched in Ti, from mafic pegmatites of the Horbuliv quarry (20-40 ppm), have the highest temperature of crystallization (845 ± 40 °C). Lower (720-770 °C) temperatures of zircon crystallization in gabbroic rocks are explained by its crystallization from the latest portions of the interstitial melt or by simultaneous crystallization of ilmenite. The Ce anomaly in zircons correlates with the degree of oxidation of the coexisting ilmenite.

Highly efficient binuclear ruthenium catalyst for water oxidation.

PubMed

Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

2015-05-22

Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Impact of Fe-Ti Oxide Concentration on the Structural Rigidity of the Lower Oceanic Crust, Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Deans, J. R.; Winkler, D. A.

2017-12-01

Fe-Ti oxides are important components of oceanic core complexes (OCC) formed at slow-spreading ridges, since Fe-Ti oxide phases form throughout the crustal column and are weaker than silicate phases. This study investigated the predicted relationship between the presence and concentration of Fe-Ti oxides and the presence/intensity of crystal-plastic deformation in samples from Atlantis Bank, Southwest Indian Ridge (SWIR). Atlantis Bank is an OCC that formed through the exhumation of lower oceanic crust along a detachment shear zone/fault. OCCs form along slow-spreading ridges and are characterized by the complex interactions between magmatism and crustal extension, thus, making them more susceptible to crystal-plastic deformation at higher temperatures and for weaker phases like Fe-Ti oxides to preferentially partition strain. Atlantis Bank has been the focus of many scientific expeditions to various sites including; Ocean Drilling Program (ODP) Holes 735B and 1105A, and the International Oceanic Discovery Program (IODP) Hole U1473A. A total of 589 thin sections from all three holes were analyzed using the software package Fiji to calculate the Fe-Ti oxide concentration within the thin sections. The Fe-Ti oxide percentage was correlated with the crystal-plastic fabric (CPF) intensity, from 0-5 (no foliation - ultramylonite), for each thin section using the statistical software R. All three holes show a positive correlation between the abundance of Fe-Ti oxides and the CPF intensity. Specifically, 76.3% of samples with a concentration of 5% or more Fe-Ti oxides have a corresponding CPF intensity value of 2 or more (porphyroclastic foliation - ultramylonitic). The positive correlation may be explained by the Fe-Ti oxides preferentially partitioning strain, especially at temperatures below where dry plagioclase can recrystallize. This allows for a mechanism of continued slip along the shear zone or form new shear zones at amphibolite grade conditions while the lower crust is being exhumed. Additionally, IODP U1473A and ODP 1105A had similar correlation values of 0.11 (on a scale of -1 to 1), whereas ODP Hole 735B had double the correlation value of 0.24. Since ODP Hole 735B has older rocks than the other two holes, it may have recorded more deformation comparatively speaking.

U(IV) chalcogenolates synthesized via oxidation of uranium metal by dichalcogenides.

PubMed

Gaunt, Andrew J; Scott, Brian L; Neu, Mary P

2006-09-04

Treatment of uranium metal with dichalcogenides in the presence of a catalytic amount of iodine in pyridine affords molecular U(IV) chalcogenolates that do not require stabilizing ancillary ligands. Oxidation of U(0) by PhEEPh yields monomeric seven-coordinate U(EPh)4(py)3 (E = S(1), Se(2)). The dimeric eight-coordinate complexes [U(EPh)2(mu2-EPh)2(CH3CN)2]2 (E = S(3), Se(4)) are obtained by crystallization from solutions of 1 and 2 dissolved in acetonitrile. Oxidation of U(0) by pySSpy and crystallization from thf yields nine-coordinate U(Spy)4(thf) (5). Incorporation of elemental selenium into the oxidation of U(0) by PhSeSePh results in the isolation of [U(py)2(SePh)(mu3-Se)(mu2-SePh)]4.4py (6), a tetrameric cluster in which each U(IV) ion is eight-coordinate and the U4Se4 core forms a distorted cube. The compounds were analyzed spectroscopically and the single-crystal X-ray structures of 1 and 3-6 were determined. The isolation of 1-6 represents six new examples of actinide chalcogenolates and allows insight into the nature of "hard" actinide ion-"soft" chalcogen donor interactions.

Crystal structure, DNA binding, cleavage, antioxidant and antibacterial studies of Cu(II), Ni(II) and Co(III) complexes with 2-((furan-2-yl)methylimino)methyl)-6-ethoxyphenol Schiff base

NASA Astrophysics Data System (ADS)

Venkateswarlu, Kadtala; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Daravath, Sreenu; Rangan, Krishnan; Shivaraj

2018-05-01

Three novel binary metal complexes; 1 [Cu(L)2], 2 [Ni(L)2] and 3 [Co(L)3] where, L (2-(((furan-2-yl) methylimino)methyl)-6-ethoxyphenol, C14H15NO3), were synthesized and characterized by various spectral techniques. Based on spectral studies square planar geometry is assigned for Cu(II) and Ni(II) complexes, whereas Co(III) owned octahedral geometry. Ligand, [Cu(L)2] and [Ni(L)2] are crystallized and found to be monoclinic crystal systems. CT-DNA absorption binding studies revealed that the complexes show good binding propensity (Kb = 5.02 × 103 M-1, 2.77 × 103 M-1, 1.63 × 104 M-1 for 1, 2 and 3 respectively). The role of these complexes in the oxidative and photolytic cleavage of supercoiled pBR322 DNA was studied and found that the complexes cleave the pBR322 DNA effectively. The catalytic ability of 1, 2 and 3 follows the order: 3 > 1 >2. Antioxidant studies of the new complexes revealed that they exhibit significant antioxidant activity against DPPH radical. The Schiff base and its metal complexes have been screened for antibacterial studies by Minimum Inhibitory Concentration method. It is observed that all metal complexes showed more activity than free ligand.

Synthesis, crystal structure and biological activity of the Schiff base organotin(IV) complexes based on salicylaldehyde-o-aminophenol

NASA Astrophysics Data System (ADS)

Tan, Yu-Xing; Zhang, Zhi-Jian; Liu, Yang; Yu, Jiang-Xi; Zhu, Xiao-Ming; Kuang, Dai-Zhi; Jiang, Wu-Jiu

2017-12-01

Schiff base organotin(IV) complexes C1 ∼ C5b have been synthesized via the reaction of the substituted salicylaldehyde-o-aminophenol Schiff base ligands (L1 ∼ L3) with the dibenzyltin dichloride, n-butyltin trichloride or dibutyltin oxide, respectively. The complexes have been characterized by IR, UV-Vis, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of the Schiff base ligand and complexes C1 ∼ C5b against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCIsbnd H460 were tested respectively, the tests showed that C1 ∼ C5b exhibited significant anticancer activity for the cancer cells in comparison with the ligand, and the activity was greater than carboplatin.

Conformational Changes and Substrate Recognition in Pseudomonas aeruginosa d-Arginine Dehydrogenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Guoxing; Yuan, Hongling; Li, Congran

2010-11-15

DADH catalyzes the flavin-dependent oxidative deamination of D-amino acids to the corresponding {alpha}-keto acids and ammonia. Here we report the first X-ray crystal structures of DADH at 1.06 {angstrom} resolution and its complexes with iminoarginine (DADH{sub red}/iminoarginine) and iminohistidine (DADH{sub red}/iminohistidine) at 1.30 {angstrom} resolution. The DADH crystal structure comprises an unliganded conformation and a product-bound conformation, which is almost identical to the DADH{sub red}/iminoarginine crystal structure. The active site of DADH was partially occupied with iminoarginine product (30% occupancy) that interacts with Tyr53 in the minor conformation of a surface loop. This flexible loop forms an 'active site lid',more » similar to those seen in other enzymes, and may play an essential role in substrate recognition. The guanidinium side chain of iminoarginine forms a hydrogen bond interaction with the hydroxyl of Thr50 and an ionic interaction with Glu87. In the structure of DADH in complex with iminohistidine, two alternate conformations were observed for iminohistidine where the imidazole groups formed hydrogen bond interactions with the side chains of His48 and Thr50 and either Glu87 or Gln336. The different interactions and very distinct binding modes observed for iminoarginine and iminohistidine are consistent with the 1000-fold difference in k{sub cat}/K{sub m} values for D-arginine and D-histidine. Comparison of the kinetic data for the activity of DADH on different D-amino acids and the crystal structures in complex with iminoarginine and iminohistidine establishes that this enzyme is characterized by relatively broad substrate specificity, being able to oxidize positively charged and large hydrophobic D-amino acids bound within a flask-like cavity.« less

A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of Cycloalkanes.

PubMed

Martín-Caballero, Jagoba; San José Wéry, Ana; Reinoso, Santiago; Artetxe, Beñat; San Felices, Leire; El Bakkali, Bouchra; Trautwein, Guido; Alcañiz-Monge, Juan; Vilas, José Luis; Gutiérrez-Zorrilla, Juan M

2016-05-16

The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crystal) techniques. Compound 1 exhibits a POMOF-like supramolecular open-framework built of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross sections of 10.4 × 8.8 Å(2). The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.

Differences between the N·H·O and O·H·O hydrogen bonds in complexes of 2,6-dichloro-4-nitrophenol with pyridines and pyridine N-oxides

NASA Astrophysics Data System (ADS)

Dega-Szafran, Zofia; Kania, Anna; Grundwald-Wyspiańska, Monika; Szafran, Mirosław; Tykarska, Ewa

1996-07-01

Complexes of five pyridines and nine pyridine N-oxides with 2,6-dichloro-4-nitrophenol (DCNP) in solution and the solid state were studied by Fourier transform IR and UV spectroscopy, by quantum-mechanical calculations with the semiempirical parametric method 3 (PM3) and by X-ray analysis. The crystals of the 1 : 1 complex of 4-methoxy-2,6-dimethylpyridine N-oxide with DCNP are monoclinic, space group {P2 1}/{n}, a = 4.5936(5) Å, b = 21.953(3) Å, c = 15.664(2) Å, β = 92.87(1)°, V = 1577.6(8) Å3, Z = 4. The molecules of the complex are joined together by an N +OH⋯O - hydrogen bond with an O⋯O distance of 2.425(3) Å, a CO - distance of 1.286(3) Å and a (N +O)H⋯O - angle of 152.9°. The PM3 method predicts for all the investigated complexes two minima, the deeper one for B⋯HA complexes and the shallower one for the B +H⋯A - forms. For the 4-methylpyridine complex the N +H⋯O - distance is reproduced correctly but for the 4-methoxy-2,6-dimethylpyridine N-oxide complex the N +H⋯O - distance is too long. The predicted hydrogen-bond angles differ from the experimental values by more than 10°. In solid state complexes of pyridines the N⋯O distances and the broad absorption due to a protic vibration are not directly related to Δp Ka. This is due to the crystal packing forces. In solution the broad absorption varies with Δp Ka. A band in the 3500 cm -1 region due to the solvated phenol is present in all investigated complexes in solution. Absorption in the 3000-2000 cm -1 region of pyridine complexes is more intense than that of the pyridine N-oxides, in agreement with the difference in N⋯O and NO⋯O distances. The broad absorption in the spectra of pyridine complexes is more influenced by solvent effects than in the pyridine N-oxide complexes. The UV spectra of the pyridine complexes show two bands due to B⋯HA (305-315 nm) and B +H⋯A - (382-395 nm) forms. The UV spectra of complexes of pyridine N-oxides of intermediate strengths in CH 2Cl 2 are not combinations of the spectra of phenol and phenolate. The band in the intermediate position denotes that neither species close to phenol nor to phenoxide ion is present. In these complexes the proton is probably localized in a single minimum and the minimum moves from the donor to the acceptor or, what is more probable, reorganization of the solvent molecules around the complex is faster than the time range of UV spectroscopy. In acetonitrile the situation is quite different as two bands are present, in agreement with a prototropic equilibrium. Effects of solvent, concentration and stoichiometry on interactions of DCNP with pyridines and pyridine N-oxides are compared and discussed. An extended mechanism of the proton-transfer reaction is proposed.

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest that deformation may have continued after crystallization of the late melt, imposing a weak strain on the oxides. Recent experimental deformation results indicate that magnetite and ilmenite should be weaker than most mafic silicates under anhydrous conditions. However, melt-like oxide morphologies observed in Atlantis Bank shear zones indicate that the redistribution of Fe-Ti-oxide melts may have more influence on the strength and strain localization behavior of oceanic gabbros than their solid-state rheology.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

NASA Astrophysics Data System (ADS)

Frazer, Laszlo; Chang, Kelvin B.; Poeppelmeier, Kenneth R.; Ketterson, John B.

2015-06-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

PubMed Central

Frazer, Laszlo; Chang, Kelvin B; Poeppelmeier, Kenneth R; Ketterson, John B

2015-01-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity. PMID:27877798

Homo- and Heterometallic Bis(Pentafluorobenzoyl)Methanide Complexes of Copper(II) and Cobalt(II)

NASA Astrophysics Data System (ADS)

Crowder, Janell M.

beta-Diketones are well known to form metal complexes with practically every known metal and metalloid. Metal complexes of fluorinated beta-diketones generally exhibit increased volatility and thermal stability compared to the non-fluorinated analogues, and thus are used extensively in various chemical vapor deposition (CVD) processes for the deposition of metal, simple or mixed metal oxides, and fluorine-doped metal oxide thin films. Furthermore, the electron-withdrawing nature of the fluorinated ligand enhances the Lewis acidity of a coordinatively unsaturated metal center which facilitates additional coordination reactions. The physical and structural properties of fluorinated beta-diketonate complexes are discussed in Chapter 1 and a few key application examples are given. The focus of this work is the synthesis and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated metal complexes of bis(pentafluorobenzoyl)- methanide (L, C6F5COCHCOC 6F5-). In Chapter 2, we present the preparation and isolation of the unsolvated complex [Cu(L)2] in pure crystalline form for the first time. We subsequently investigated the reaction of unsolvated [Cu(L)2] with sodium hexafluoroacetylacetonate [Na(hfac)] in a solvent-free environment. This reaction allowed the isolation of the first heterometallic Na-Cu diketonate [Na2Cu2(L) 4(hfac)2] structurally characterized by single crystal X-ray crystallography. Thermal decomposition of [Na2Cu2(L) 4(hfac)2] was investigated for its potential application in MOCVD processes. In the final chapter, we present the first exploration of the anhydrous synthesis of Co(II) complexed with bis(pentafluorobenzoyl)methanide in order to produce a complex without ligated water. Single crystal X-ray crystallographic investigations revealed the isolation of the ethanol adduct, [Co2(L)4(C2H5OH)2], and following the removal of ethanol, a 1,4-dioxane adduct, [{Co 2(L)4}2(C4H8O2)]. In this work, we have provided the first investigation of the synthesis, isolation and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated Cu(II) and Co(II) complexes of bis(pentafluorobenzoyl)methanide ligand. These studies demonstrate how the electrophilicity of a coordinatively unsaturated metal complexed to highly-fluorinated â-diketone ligands can be utilized for the formation of new adducts or new and interesting heterometallic complexes. This body of work provides a basis upon which future research into unsolvated and unligated bis(pentafluorobenzoyl)methanide metal complexes can expand.

Crystal zoning in a large-volume ignimbrite: constraints on the thermal history of a supervolcano magma system

NASA Astrophysics Data System (ADS)

Matthews, N. E.; Pyle, D. M.; Wilson, C. J.

2009-12-01

Chemical zoning of crystals provides an important archive of information that allows for the reconstruction of complex thermal histories and changes in melt composition of the magma reservoir during crystallization. Here we investigate cathodoluminescence (CL) and Ti zonation in quartz crystals extracted from pumices from the Whakamaru and Rangitaiki ignimbrite units (part of the large-volume Whakamaru Group Ignimbrites), New Zealand, to reconstruct the thermal history of the parent magma chamber(s). CL intensity images are taken as a proxy for Ti content and temperature variation during crystal growth, and direct estimates of temperature are made using the TitaniQ geothermometer (Wark & Watson 2006 Cont. Min. Pet.) based on Ti concentration in quartz. These results are reviewed in comparison with temperatures from Fe-Ti oxide geothermometry. Quartz zoning is also compared to zonation in feldspars (using BSE imaging) from the same pumice clasts in order to establish the degree to which different crystal species record similar or contrasting magmatic histories. Quartz crystals in Whakamaru pumice display a variety of CL zoning patterns and resorption boundaries. Overgrowths typically appear to truncate CL growth zoning within the crystal core, indicating periods of resorption and subsequent re-growth - consistent with magma recharge causing a marked change in conditions (temperature and/or volatile saturation) and multi-stage crystallisation. Crystals typically display a dark (lower Ti) resorbed core, with an abrupt change to a CL-bright rim, although irregular textures and complex variations between crystals are observed. Core-to-rim profiles of Ti concentration in analysed quartz crystals show Ti variations within the range 50-225 ppm, corresponding to crystallisation temperatures of 733-935°C (assuming TiO2 activity in the melt of 0.6), with the lowest values recorded in the crystal core, increasing in a step-wise pattern towards the rim. These values are consistent with Fe-Ti oxide temperature data for the same pumice clasts which provide a temperature range of 660-933°C. It is inferred that the major steps in Ti content (and thus CL brightness) represent short-term temperature fluctuations due to magma chamber recharge and rejuvenation of a crystal mush, while rim temperatures are likely to record the magma temperature at the time of eruption.

Biomolecular crystals for material applications and a mechanistic study of an iron oxide nanoparticle synthesis

NASA Astrophysics Data System (ADS)

Falkner, Joshua Charles

The three projects within this work address the difficulties of controlling biomolecular crystal formats (i.e. size and shape), producing 3-D ordered composite materials from biomolecular crystal templates, and understanding the mechanism of a practical iron oxide synthesis. The unifying thread consistent throughout these three topics is the development of methods to manipulate nanomaterials using a bottom-up approach. Biomolecular crystals are nanometer to millimeter sized crystals that have well ordered mesoporous solvent channels. The overall physical dimensions of these crystals are highly dependent on crystallization conditions. The controlled growth of micro- and nanoprotein crystals was studied to provide new pathways for creating smaller crystalline protein materials. This method produced tetragonal hen egg-white lysozyme crystals (250--100,000 nm) with near monodisperse size distributions (<15%). With this degree of control, existing protein crystal applications such as drug delivery and analytical sensors can reach their full potential. Applications for larger crystals with inherently ubiquitous pore structures could extend to materials used for membranes or templates. In this work, the porous structure of larger cowpea mosaic virus crystals was used to template metal nanoparticle growth within the body centered cubic crystalline network. The final composite material was found to have long range ordering of palladium and platinum nonocrystal aggregates (10nm) with symmetry consistent to the virus template. Nanoparticle synthesis itself is an immense field of study with an array of diverse applications. The final piece of this work investigates the mechanism behind a previously developed iron oxide synthesis to gain more understanding and direction to future synthesis strategies. The particle growth mechanism was found to proceed by the formation of a solvated iron(III)oleate complex followed by a reduction of iron (III) to iron (II). This unstable iron(II) nucleates to form a wustite (FeO) core which serves as an epitaxial surface for the magnetite (Fe3O4) shell growth. This method produces spherical particles (6-60nm) with relative size distributions of less than 15%.

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

2006-01-01

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

The mechanism of oxidation in chromophore maturation of wild-type green fluorescent protein: a theoretical study.

PubMed

Ma, Yingying; Sun, Qiao; Smith, Sean C

2017-05-24

Oxidation is viewed as the second and rate-limiting step in the chromophore maturation process of the wild-type green fluorescent protein (GFP) under aerobic conditions. Molecular oxygen is the necessary oxidant for GFP chromophore biosynthesis. In this study, density functional theory (DFT) calculations were employed to study the mechanism of oxidation. Our results indicate that the deprotonation of the Tyr66 α-carbon is probably the rate-limiting step in the oxidation step. Electron transfer from the enolate form of the five-membered heterocycle (EFMH) to molecular oxygen, generating the triplet radical complex [EFMH˙O 2 - ˙] T , is an important step. This complex undergoes intersystem crossing to form an open-shell singlet diradical complex before it forms the closed-shell singlet hydroperoxy adduct. The formation of the hydroperoxy adduct is a proton-coupled electron transfer process. The energy barrier of H 2 O 2 elimination is 16.5 kcal mol -1 . The oxidation product IFMHH 2 O 2 that we discovered is a hydroxylated cyclic imine structure, which is consistent with the crystal structure trapped in the colorless Y66L variant. The relative energy of the oxidation product is -48.7 kcal mol -1 , which is in accordance with the experimental observation that the thermodynamically unfavourable cyclized product is trapped by oxidation. The results herein support the cyclization-oxidation-dehydration mechanism for the chromophore maturation of GFP.

N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

NASA Astrophysics Data System (ADS)

Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

2010-09-01

A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

Syntheses, spectroscopic characterization, SOD-like properties and antibacterial activities of dimer copper (II) and nickel (II) complexes based on imine ligands containing 2-aminothiophenol moiety: X-ray crystal structure determination of disulfide Schiff bases

NASA Astrophysics Data System (ADS)

Bharti, Sulakshna; Choudhary, Mukesh; Mohan, Bharti; Rawat, S. P.; Sharma, S. R.; Ahmad, K.

2018-07-01

A series of new dimer complexes of copper (II) and nickel (II) were designed and synthesized using the Schiff base ligands which was formed by the condensation of 2-aminothiophenol with 2- methoxybenzaldehyde, 3-formylbenzonitrile and 3-bromo-2-hydroxy-5-nitrobenzaldehyde, respectively. The synthesized metallic complexes were characterized by using different physicochemical and spectroscopic methods. The most plausible geometry for the 1:2 complexes appeared to be distorted square-planar or tetrahedral environments. All the synthesized metal complexes are found to be binuclear and confirmed by elemental analyses, magnetic susceptibility measurements and ESR spectroscopy. The Schiff base ligands (HL1/HL2/H2L) were coordinated to the metal ions through the ONS/SNN and/or N, S donor atoms. In order to prevent the oxidation of the thiol group during the formation of Schiff bases and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structures of the Schiff base ligands showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff bases as a new double Schiff base ligands (L1a/L2a/H2La). The L1b ligand is a bicyclic ring system of N, S-containing heterocyclic. The crystal structures of the double Schiff bases were determined by single crystal X-ray diffraction. The molar conductivity values of the complexes in DMSO implied the presence of non-electrolyte species. The SOD-like activity of Schiff bases and its complexes were investigated by NBT-DMSO assay and IC50 values were evaluated. Their biological properties have also been studied. These complexes were also tested for their in vitro antibacterial screening activities against three bacteria (Streptococcus aureus, Salmonella typhi, and Escherichia coli) comparing with the Schiff base ligands. Most of the complexes have higher antibacterial activities than those of the free Schiff bases, double Schiff bases and the control.

Hydrogen-related complexes in Li-diffused ZnO single crystals

NASA Astrophysics Data System (ADS)

Corolewski, Caleb D.; Parmar, Narendra S.; Lynn, Kelvin G.; McCluskey, Matthew D.

2016-07-01

Zinc oxide (ZnO) is a wide band gap semiconductor and a potential candidate for next generation white solid state lighting applications. In this work, hydrogen-related complexes in lithium diffused ZnO single crystals were studied. In addition to the well-known Li-OH complex, several other hydrogen defects were observed. When a mixture of Li2O and ZnO is used as the dopant source, zinc vacancies are suppressed and the bulk Li concentration is very high (>1019 cm-3). In that case, the predominant hydrogen complex has a vibrational frequency of 3677 cm-1, attributed to surface O-H species. When Li2CO3 is used, a structured blue luminescence band and O-H mode at 3327 cm-1 are observed at 10 K. These observations, along with positron annihilation measurements, suggest a zinc vacancy-hydrogen complex, with an acceptor level ˜0.3 eV above the valence-band maximum. This relatively shallow acceptor could be beneficial for p-type ZnO.

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

A Family of A-Site Cation-Deficient Double-Perovskite-Related Iridates: Ln9Sr2Ir4O24 (Ln = La, Pr, Nd, Sm).

PubMed

Ferreira, Timothy; Smith, Mark D; Zur Loye, Hans-Conrad

2018-06-21

The compositions of the general formula Ln 11- x Sr x Ir 4 O 24 (Ln = La, Pr, Nd, Sm; 1.37 ≥ x ≥ 2) belonging to a family of A-site cation-deficient double-perovskite-related oxide iridates were grown as highly faceted single crystals from a molten strontium chloride flux. Their structures were determined by single-crystal X-ray diffraction. On the basis of the single-crystal results, additional compositions, Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm), were prepared as polycrystalline powders via solid-state reactions and structurally characterized by Rietveld refinement. The compositions Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) contain Ir(V) and Ir(IV) in a 1:3 ratio with an average iridium oxidation state of 4.25. The single-crystal compositions La 9.15 Sr 1.85 Ir 4 O 24 and Pr 9.63 Sr 1.37 Ir 4 O 24 contain relatively less Ir(V), with the average iridium oxidation states being 4.21 and 4.09, respectively. The magnetic properties of Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) were measured, and complex magnetic behavior was observed in all cases at temperatures below 30 K.

Crystal structure of a four-copper laccase complexed with an arylamine: insights into substrate recognition and correlation with kinetics.

PubMed

Bertrand, Thomas; Jolivalt, Claude; Briozzo, Pierre; Caminade, Eliane; Joly, Nathalie; Madzak, Catherine; Mougin, Christian

2002-06-11

Laccases are multicopper oxidases that catalyze the oxidation of a wide range of phenols or arylamines, and their use in industrial oxidative processes is increasing. We purified from the white rot fungus Trametes versicolor a laccase that exists as five different isozymes, depending on glycosylation. The 2.4 A resolution structure of the most abundant isozyme of the glycosylated enzyme was solved. The four copper atoms are present, and it is the first crystal structure of a laccase in its active form. The crystallized enzyme binds 2,5-xylidine, which was used as a laccase inducer in the fungus culture. This arylamine is a very weak reducing substrate of the enzyme. The cavity enclosing 2,5-xylidine is rather wide, allowing the accommodation of substrates of various sizes. Several amino acid residues make hydrophobic interactions with the aromatic ring of the ligand. In addition, two charged or polar residues interact with its amino group. The first one is an histidine that also coordinates the copper that functions as the primary electron acceptor. The second is an aspartate conserved among fungal laccases. The purified enzyme can oxidize various hydroxylated compounds of the phenylurea family of herbicides that we synthesized. These phenolic substrates have better affinities at pH 5 than at pH 3, which could be related to the 2,5-xylidine binding by the aspartate. This is the first high-resolution structure of a multicopper oxidase complexed to a reducing substrate. It provides a model for engineering laccases that are either more efficient or with a wider substrate specificity.

Elucidating nitric oxide synthase domain interactions by molecular dynamics.

PubMed

Hollingsworth, Scott A; Holden, Jeffrey K; Li, Huiying; Poulos, Thomas L

2016-02-01

Nitric oxide synthase (NOS) is a multidomain enzyme that catalyzes the production of nitric oxide (NO) by oxidizing L-Arg to NO and L-citrulline. NO production requires multiple interdomain electron transfer steps between the flavin mononucleotide (FMN) and heme domain. Specifically, NADPH-derived electrons are transferred to the heme-containing oxygenase domain via the flavin adenine dinucleotide (FAD) and FMN containing reductase domains. While crystal structures are available for both the reductase and oxygenase domains of NOS, to date there is no atomic level structural information on domain interactions required for the final FMN-to-heme electron transfer step. Here, we evaluate a model of this final electron transfer step for the heme-FMN-calmodulin NOS complex based on the recent biophysical studies using a 105-ns molecular dynamics trajectory. The resulting equilibrated complex structure is very stable and provides a detailed prediction of interdomain contacts required for stabilizing the NOS output state. The resulting equilibrated complex model agrees well with previous experimental work and provides a detailed working model of the final NOS electron transfer step required for NO biosynthesis. © 2015 The Protein Society.

Electron localization in a mixed-valence diniobium benzene complex

DOE PAGES

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; ...

2014-11-11

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

Nitrosoamphetamine binding to myoglobin and hemoglobin: Crystal structure of the H64A myoglobin-nitrosoamphetamine adduct

PubMed Central

Wang, Bing; Powell, Samantha M.; Guan, Ye; Xu, Nan; Thomas, Leonard M.; Richter-Addo, George B.

2017-01-01

N-hydroxyamphetamine (AmphNHOH) is an oxidative metabolite of amphetamine and methamphetamine. It is known to form inhibitory complexes upon binding to heme proteins. However, its interactions with myoglobin (Mb) and hemoglobin (Hb) have not been reported. We demonstrate that the reactions of AmphNHOH with ferric Mb and Hb generate the respective heme-nitrosoamphetamine derivatives characterized by UV-vis spectroscopy. We have determined the X-ray crystal structure of the H64A Mb-nitrosoamphetamine complex to 1.73 Å resolution. The structure reveals the N-binding of the nitroso-d-amphetamine isomer, with no significant H-bonding interactions between the ligand and the distal pocket amino acid residues. PMID:28450187

Crystal Structures of Intermediates in the Nitroalkane Oxidase Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heroux, A.; Bozinovski, D; Valley, M

2009-01-01

The flavoenzyme nitroalkane oxidase is a member of the acyl-CoA dehydrogenase superfamily. Nitroalkane oxidase catalyzes the oxidation of neutral nitroalkanes to nitrite and the corresponding aldehydes or ketones. Crystal structures to 2.2 {angstrom} resolution or better of enzyme complexes with bound substrates and of a trapped substrate-flavin adduct are described. The D402N enzyme has no detectable activity with neutral nitroalkanes. The structure of the D402N enzyme crystallized in the presence of 1-nitrohexane or 1-nitrooctane shows the presence of the substrate in the binding site. The aliphatic chain of the substrate extends into a tunnel leading to the enzyme surface. Themore » oxygens of the substrate nitro group interact both with amino acid residues and with the 2'-hydroxyl of the FAD. When nitroalkane oxidase oxidizes nitroalkanes in the presence of cyanide, an electrophilic flavin imine intermediate can be trapped (Valley, M. P., Tichy, S. E., and Fitzpatrick, P. F. (2005) J. Am. Chem. Soc. 127, 2062-2066). The structure of the enzyme trapped with cyanide during oxidation of 1-nitrohexane shows the presence of the modified flavin. A continuous hydrogen bond network connects the nitrogen of the CN-hexyl-FAD through the FAD 2'-hydroxyl to a chain of water molecules extending to the protein surface. Together, our complementary approaches provide strong evidence that the flavin cofactor is in the appropriate oxidation state and correlates well with the putative intermediate state observed within each of the crystal structures. Consequently, these results provide important structural descriptions of several steps along the nitroalkane oxidase reaction cycle.« less

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

NASA Astrophysics Data System (ADS)

Mudsainiyan, R. K.; Jassal, A. K.; Chawla, S. K.

2015-10-01

A mesoporous 3D polymeric complex (I) having formula {[Zr(IV)O-μ3-(EDTA)Fe(III)OH]·H2O}n has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of -OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (336·454·530)·(36). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and -OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n-π* transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N2 (SBET=8.7693 m2/g) and a maximum amount of H2 (high surface area=1044.86 m2/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. -7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex.

Clathrochelates meet phosphorus. New thio- and phosphorylation reactions of an iron(II) dichloroclathrochelate precursor and preparation of its first phosphorus(III)-containing macrobicyclic derivative.

PubMed

Artyushin, Oleg I; Matveeva, Ekaterina V; Vologzhanina, Anna V; Voloshin, Yan Z

2016-03-28

Phosphorylation reactions of an iron(II) dichloroclathrochelate FeBd2(Cl2Gm)(BF)2 (where Bd(2-) and Cl2Gm(2-) are α-benzildioxime and dichloroglyoxime dianions, respectively) with diphenylphosphine oxide and diethyl thiophosphite were performed under phase-transfer conditions. In the case of diethyl thiophosphite as a P-nucleophile, the best yields were obtained in the dichloromethane-50% NaOH aqueous solution-5 mol% triethylbenzylammonium chloride (TEBAC) system. The use of different molar ratios of a macrobicycle precursor and this thiophosphorylating agent allowed us to obtain both the mono- and the diphosphorylated cage complexes. Nucleophilic substitution with diphenylphosphine oxide was performed in the K2CO3-acetonitrile-5 mol% TEBAC system, giving only the corresponding monophosphorylated iron(II) complex in high yield even in the presence of an excess of this P-nucleophile. The phosphorus(v)-containing clathrochelate product was reduced with an excess of silicoform to give an iron(II) macrobicycle with an inherent diphenylphosphine group in an almost quantitative yield, which was then characterized by (31)P{(1)H} NMR and single-crystal X-ray diffraction; it easily undergoes re-oxidation to the initial clathrochelate. The synthesized phosphorus(v)-containing cage complexes were characterized using elemental analysis, MALDI-TOF mass, IR, UV-Vis, (1)H, (11)B, (13)C{(1)H}, (19)F{(1)H} and (31)P{(1)H} NMR spectra, and by single-crystal X-ray diffraction.

Thermal and oxidative stability of the Ocimum basilicum L. essential oil/β-cyclodextrin supramolecular system.

PubMed

Hădărugă, Daniel I; Hădărugă, Nicoleta G; Costescu, Corina I; David, Ioan; Gruia, Alexandra T

2014-01-01

Ocimum basilicum L. essential oil and its β-cyclodextrin (β-CD) complex have been investigated with respect to their stability against the degradative action of air/oxygen and temperature. This supramolecular system was obtained by a crystallization method in order to achieve the equilibrium of complexed-uncomplexed volatile compounds in an ethanol/water solution at 50 °C. Both the raw essential oil and its β-CD complex have been subjected to thermal and oxidative degradation conditions in order to evaluate the protective capacity of β-CD. The relative concentration of the O. basilicum L. essential oil compounds, as determined by GC-MS, varies accordingly with their sensitivity to the thermal and/or oxidative degradation conditions imposed. Furthermore, the relative concentration of the volatile O. basilicum L. compounds found in the β-CD complex is quite different in comparison with the raw material. An increase of the relative concentration of linalool oxide from 0.3% to 1.1%, in addition to many sesquiterpene oxides, has been observed. β-CD complexation of the O. basilicum essential oil modifies the relative concentration of the encapsulated volatile compounds. Thus, linalool was better encapsulated in β-CD, while methylchavicol (estragole) was encapsulated in β-CD at a concentration close to that of the raw essential oil. Higher relative concentrations from the degradation of the oxygenated compounds such as linalool oxide and aromadendren oxide were determined in the raw O. basilicum L. essential oil in comparison with the corresponding β-CD complex. For the first time, the protective capability of natural β-CD for labile basil essential oil compounds has been demonstrated.

Phenoxo bridged dinuclear Zn(II) Schiff base complex as new precursor for preparation zinc oxide nanoparticles: Synthesis, characterization, crystal structures and photoluminescence studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saeednia, S., E-mail: sami_saeednia@yahoo.com; Iranmanesh, P.; Ardakani, M. Hatefi

Highlights: • A novel nano-scale Zn(II) complex was synthesized by solvothermal method. • Chemical structure of the nanostructures was characterized as well as bulk complex. • The photoluminescence property of the complex was investigated at room temperature. • The thermogravimetry and differential thermal analysis were carried out. • Thermal decomposition of the nanostructures was prepared zinc oxide nanoparticles. - Abstract: Nanoparticles of a novel Zn(II) Schiff base complex, [Zn(HL)NO{sub 3}]{sub 2} (1), (H{sub 2}L = 2-[(2-hydroxy-propylimino) methyl] phenol), was synthesized by using solvothermal method. Shape, morphology and chemical structure of the synthesized nanoparticles were characterized by scanning electron microscopy (SEM),more » X-ray powder diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR) and UV–vis spectroscopy. Structural determination of compound 1 was determined by single-crystal X-ray diffraction. The results were revealed that the zinc complex is a centrosymmetric dimer in which deprotonated phenolates bridge the two five-coordinate metal atoms and link the two halves of the dimer. The thermal stability of compound 1 was analyzed by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of the initial substrates concentration and reaction time on size and morphology of compound 1 nanostructure was investigated as well. Furthermore, the luminescent properties of the complex 1 were examined. ZnO nanoparticles with diameter between 15 and 20 nm were simply synthesized by solid-state transformation of compound 1 at 700 °C.« less

A Method for Atomic Layer Deposition of Complex Oxide Thin Films

DTIC Science & Technology

2012-12-01

characterization. Fourth, the phase of the crystallized film was analyzed in detail to deter- mine behavior of the films post-annealing. XRD was used extensively for...Schneider. Stacking of ceramic in- verse opals with different lattice constants. Journal of the American Ceramic Society, 95(7):2226–2235, July 2012. [52

Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution

NASA Astrophysics Data System (ADS)

Chang, Seo Hyoung; Danilovic, Nemanja; Chang, Kee-Chul; Subbaraman, Ram; Paulikas, Arvydas P.; Fong, Dillon D.; Highland, Matthew J.; Baldo, Peter M.; Stamenkovic, Vojislav R.; Freeland, John W.; Eastman, Jeffrey A.; Markovic, Nenad M.

2014-06-01

In developing cost-effective complex oxide materials for the oxygen evolution reaction, it is critical to establish the missing links between structure and function at the atomic level. The fundamental and practical implications of the relationship on any oxide surface are prerequisite to the design of new stable and active materials. Here we report an intimate relationship between the stability and reactivity of oxide catalysts in exploring the reaction on strontium ruthenate single-crystal thin films in alkaline environments. We determine that for strontium ruthenate films with the same conductance, the degree of stability, decreasing in the order (001)>(110)>(111), is inversely proportional to the activity. Both stability and reactivity are governed by the potential-induced transformation of stable Ru4+ to unstable Run>4+. This ordered(Ru4+)-to-disordered(Run>4+) transition and the development of active sites for the reaction are determined by a synergy between electronic and morphological effects.

Crystallization of the Na+-translocating NADH:quinone oxidoreductase from Vibrio cholerae

PubMed Central

Casutt, Marco S.; Wendelspiess, Severin; Steuber, Julia; Fritz, Günter

2010-01-01

The Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) from the human pathogen Vibrio cholerae couples the exergonic oxidation of NADH by membrane-bound quinone to Na+ translocation across the membrane. Na+-NQR consists of six different subunits (NqrA–NqrF) and contains a [2Fe–2S] cluster, a noncovalently bound FAD, a noncovalently bound riboflavin, two covalently bound FMNs and potentially Q8 as cofactors. Initial crystallization of the entire Na+-NQR complex was achieved by the sitting-drop method using a nanolitre dispenser. Optimization of the crystallization conditions yielded flat yellow-coloured crystals with dimensions of up to 200 × 80 × 20 µm. The crystals diffracted to 4.0 Å resolution and belonged to space group P21, with unit-cell parameters a = 94, b = 146, c = 105 Å, α = γ = 90, β = 111°. PMID:21139223

Structural transitions and guest/host complexing of liquid crystal helical nanofilaments induced by nanoconfinement.

PubMed

Kim, Hanim; Ryu, Seong Ho; Tuchband, Michael; Shin, Tae Joo; Korblova, Eva; Walba, David M; Clark, Noel A; Yoon, Dong Ki

2017-02-01

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4'- n -pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions.

Structural transitions and guest/host complexing of liquid crystal helical nanofilaments induced by nanoconfinement

PubMed Central

Kim, Hanim; Ryu, Seong Ho; Tuchband, Michael; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Yoon, Dong Ki

2017-01-01

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4′-n-pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions. PMID:28246642

Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations.

PubMed

Andrés, Juan; Gracia, Lourdes; Gouveia, Amanda Fernandes; Ferrer, Mateus Meneghetti; Longo, Elson

2015-10-09

Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and α-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.

Towards precise defect control in layered oxide structures by using oxide molecular beam epitaxy

PubMed Central

Baiutti, Federico; Christiani, Georg

2014-01-01

Summary In this paper we present the atomic-layer-by-layer oxide molecular beam epitaxy (ALL-oxide MBE) which has been recently installed in the Max-Planck Institute for Solid State Research and we report on its present status, providing some examples that demonstrate its successful application in the synthesis of different layered oxides, with particular reference to superconducting La2CuO4 and insulator-to-metal La2− xSrxNiO4. We briefly review the ALL-oxide MBE technique and its unique capabilities in the deposition of atomically smooth single-crystal thin films of various complex oxides, artificial compounds and heterostructures, introducing our goal of pursuing a deep investigation of such systems with particular emphasis on structural defects, with the aim of tailoring their functional properties by precise defects control. PMID:24995148

Influence of complex impurity centres on radiation damage in wide-gap metal oxides

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Popov, A. I.; Schwartz, K.; Shablonin, E.; Vasil'chenko, E.

2016-05-01

Different mechanisms of radiation damage of wide-gap metal oxides as well as a dual influence of impurity ions on the efficiency of radiation damage have been considered on the example of binary ionic MgO and complex ionic-covalent Lu3Al5O12 single crystals. Particular emphasis has been placed on irradiation with ∼2 GeV heavy ions (197Au, 209Bi, 238U, fluence of 1012 ions/cm2) providing extremely high density of electronic excitations within ion tracks. Besides knock-out mechanism for Frenkel pair formation, the additional mechanism through the collapse of mobile discrete breathers at certain lattice places (e.g., complex impurity centres) leads to the creation of complex defects that involve a large number of host atoms. The experimental manifestations of the radiation creation of intrinsic and impurity antisite defects (Lu|Al or Ce|Al - a heavy ion in a wrong cation site) have been detected in LuAG and LuAG:Ce3+ single crystals. Light doping of LuAG causes a small enhancement of radiation resistance, while pair impurity centres (for instance, Ce|Lu-Ce|Al or Cr3+-Cr3+ in MgO) are formed with a rise of impurity concentration. These complex impurity centres as well as radiation-induced intrinsic antisite defects (Lu|Al strongly interacting with Lu in a regular site) tentatively serve as the places for breathers collapse, thus decreasing the material resistance against dense irradiation.

The roles of 4f- and 5f-orbitals in bonding: A magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

DOE PAGES

Lukens, Wayne W.; Speldrich, Manfred; Yang, Ping; ...

2016-05-31

The electronic structures of 4f 3/5f 3 Cp" 3M and Cp" 3M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienylmore » complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. As a result, while interaction with the isocyanide π*-orbitals lowers the energies of the 5f xz2 and 5f yz2-orbitals, spin–orbit coupling greatly reduces the population of 5f xz2 and 5f yz2 in the ground state.« less

Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

PubMed

Bellec, Nathalie; Vacher, Antoine; Barrière, Frédéric; Xu, Zijun; Roisnel, Thierry; Lorcy, Dominique

2015-05-18

Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.

Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition.

PubMed

Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

2015-02-05

A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

Spin filtering through ferromagnetic BiMn O3 tunnel barriers

NASA Astrophysics Data System (ADS)

Gajek, M.; Bibes, M.; Barthélémy, A.; Bouzehouane, K.; Fusil, S.; Varela, M.; Fontcuberta, J.; Fert, A.

2005-07-01

We report on experiments of spin filtering through ultrathin single-crystal layers of the insulating and ferromagnetic oxide BiMnO3 (BMO). The spin polarization of the electrons tunneling from a gold electrode through BMO is analyzed with a counterelectrode of the half-metallic oxide La2/3Sr1/3MnO3 (LSMO). At 3K we find a 50% change of the tunnel resistances according to whether the magnetizations of BMO and LSMO are parallel or opposite. This effect corresponds to a spin-filtering efficiency of up to 22%. Our results thus show the potential of complex ferromagnetic insulating oxides for spin filtering and injection.

Enhancement of polar phase and conductivity relaxation in PIL-modified GO/PVDF composites

NASA Astrophysics Data System (ADS)

Xu, Pei; Fu, Weijia; Cui, Zhaopei; Ding, Yunsheng

2018-02-01

To investigate the effect of graphene oxide (GO) modified by polymerized ionic liquid (PIL) on the crystallization and dielectric relaxation of poly(vinylidene fluoride) (PVDF), a series of PVDF composites have been prepared using the solution casting method. The ion-dipole interaction between PIL and >CF2 and the π-dipole interaction between GO and >CF2 can induce synergistically the polar phase, and the π-ion interaction between GO and PIL can strengthen the induction effect of the polar phase and decrease the degree of crystallization of PVDF. The electric modulus and conductivity relaxation are employed to analyze the experimental complex dielectric permittivity. In the frequency spectra of complex permittivity of PVDF composites, space charge polarization and conductivity lead to a large value of dielectric permittivity. The temperature dependence of relaxation time of conductivity relaxation accords with the Arrhenius equation. A low degree of crystallization, more ion concentration, and polar phase in PVDF/PIL/GO enhance the movement of the polymer chain segment and charge carriers.

Crystal Structure and Antitumor Activity of the Novel Zwitterionic Complex of tri-n-Butyltin(IV) with 2-Thiobarbituric Acid

PubMed Central

Balas, Vasilios I.; Hadjikakou, Sotiris K.; Hadjiliadis, Nick; Kourkoumelis, Nikolaos; Light, Mark E.; Hursthouse, Mike; Metsios, Apostolos K.; Karkabounas, Spyros

2008-01-01

A novel tri-n-butyl(IV) derivative of 2-thiobarbituric acid (HTBA) of formula [(n-Bu)3Sn(TBA) H2O] (1) has been synthesized and characterized by elemental analysis and 119Sn-NMR and FT-IR spectroscopic techniques. The crystal structure of complex 1 has been determined by single crystal X-ray diffraction analysis at 120(2) K. The geometry around Sn(IV) is trigonal bipyramidal. Three n-butyl groups and one oxygen atom from a deprotonated 2-thiobarbituric ligand are bonded to the metal center. The geometry is completed with one oxygen from a water molecule. Compound 1 exhibits potent, in vitro, cytotoxicity against sarcoma cancer cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (PAH, benzo[a]pyrene) carcinogenesis. In addition, the inhibition caused by 1, in the rate of lipoxygenase (LOX) catalyzed oxidation reaction of linoleic acid to hyperoxolinoleic acid, has been also kinetically and theoretically studied. The results are compared to that of cisplatin. PMID:18401456

Crystal structure of bis-(1,3-di-meth-oxy-imidazolin-2-yl-idene)silver(I) hexa-fluorido-phosphate, N-heterocyclic carbene (NHC) complex.

PubMed

Rietzler, Barbara; Laus, Gerhard; Kahlenberg, Volker; Schottenberger, Herwig

2015-12-01

The title salt, [Ag(C5H8N2O2)2]PF6, was obtained by deprotonation and metalation of 1,3-di-meth-oxy-imidazolium hexa-fluorido-phosphate using silver(I) oxide in methanol. The C-Ag-C angle in the cation is 178.1 (2)°, and the N-C-N angles are 101.1 (4) and 100.5 (4)°. The meth-oxy groups adopt an anti conformation. In the crystal, anions (A) are sandwiched between cations (C) in a layered arrangement {C…A…C} n stacked along [001]. Within a C…A…C layer, the hexafluoridophosphate anions accept several C-H⋯F hydrogen bonds from the cationic complex.

Thermal and oxidative stability of the Ocimum basilicum L. essential oil/β-cyclodextrin supramolecular system

PubMed Central

Hădărugă, Nicoleta G; Costescu, Corina I; David, Ioan; Gruia, Alexandra T

2014-01-01

Summary Ocimum basilicum L. essential oil and its β-cyclodextrin (β-CD) complex have been investigated with respect to their stability against the degradative action of air/oxygen and temperature. This supramolecular system was obtained by a crystallization method in order to achieve the equilibrium of complexed–uncomplexed volatile compounds in an ethanol/water solution at 50 °C. Both the raw essential oil and its β-CD complex have been subjected to thermal and oxidative degradation conditions in order to evaluate the protective capacity of β-CD. The relative concentration of the O. basilicum L. essential oil compounds, as determined by GC–MS, varies accordingly with their sensitivity to the thermal and/or oxidative degradation conditions imposed. Furthermore, the relative concentration of the volatile O. basilicum L. compounds found in the β-CD complex is quite different in comparison with the raw material. An increase of the relative concentration of linalool oxide from 0.3% to 1.1%, in addition to many sesquiterpene oxides, has been observed. β-CD complexation of the O. basilicum essential oil modifies the relative concentration of the encapsulated volatile compounds. Thus, linalool was better encapsulated in β-CD, while methylchavicol (estragole) was encapsulated in β-CD at a concentration close to that of the raw essential oil. Higher relative concentrations from the degradation of the oxygenated compounds such as linalool oxide and aromadendren oxide were determined in the raw O. basilicum L. essential oil in comparison with the corresponding β-CD complex. For the first time, the protective capability of natural β-CD for labile basil essential oil compounds has been demonstrated. PMID:25550747

The role of magma mixing/mingling and cumulate melting in the Neapolitan Yellow Tuff caldera-forming eruption (Campi Flegrei, Southern Italy)

NASA Astrophysics Data System (ADS)

Forni, Francesca; Petricca, Eleonora; Bachmann, Olivier; Mollo, Silvio; De Astis, Gianfilippo; Piochi, Monica

2018-06-01

Understanding the mechanisms responsible for the generation of chemical gradients in high-volume ignimbrites is key to retrieve information on the processes that control the maturation and eruption of large silicic magmatic reservoirs. Over the last 60 ky, two large ignimbrites showing remarkable zoning were emplaced during caldera-forming eruptions at Campi Flegrei (i.e., Campanian Ignimbrite, CI, 39 ka and Neapolitan Yellow Tuff, NYT, 15 ka). While the CI displays linear compositional, thermal and crystallinity gradients, the NYT is a more complex ignimbrite characterized by crystal-poor magmas ranging in composition from trachy-andesites to phonolites. By combining major and trace element compositions of matrix glasses and mineral phases from juvenile clasts located at different stratigraphic heights along the NYT pyroclastic sequence, we interpret such compositional gradients as the result of mixing/mingling between three different magmas: (1) a resident evolved magma showing geochemical characteristics of a melt extracted from a cumulate mush dominated by clinopyroxene, plagioclase and oxides with minor sanidine and biotite; (2) a hotter and more mafic magma from recharge providing high-An plagioclase and high-Mg clinopyroxene crystals and (3) a compositionally intermediate magma derived from remelting of low temperature mineral phases (i.e., sanidine and biotite) within the cumulate crystal mush. We suggest that the presence of a refractory crystal mush, as documented by the occurrence of abundant crystal clots containing clinopyroxene, plagioclase and oxides, is the main reason for the lack of erupted crystal-rich material in the NYT. A comparison between the NYT and the CI, characterized by both crystal-poor extracted melts and crystal-rich magmas representing remobilized portions of a "mature" (i.e., sanidine dominated) cumulate residue, allows evaluation of the capability of crystal mushes of becoming eruptible upon recharge.

Water oxidation chemistry of photosystem II.

PubMed

Brudvig, Gary W

2008-03-27

Photosystem II (PSII) uses light energy to split water into protons, electrons and O2. In this reaction, nature has solved the difficult chemical problem of efficient four-electron oxidation of water to yield O2 without significant amounts of reactive intermediate species such as superoxide, hydrogen peroxide and hydroxyl radicals. In order to use nature's solution for the design of artificial catalysts that split water, it is important to understand the mechanism of the reaction. The recently published X-ray crystal structures of cyanobacterial PSII complexes provide information on the structure of the Mn and Ca ions, the redox-active tyrosine called YZ and the surrounding amino acids that comprise the O2-evolving complex (OEC). The emerging structure of the OEC provides constraints on the different hypothesized mechanisms for O2 evolution. The water oxidation mechanism of PSII is discussed in the light of biophysical and computational studies, inorganic chemistry and X-ray crystallographic information.

A review of the antioxidant mechanisms of polyphenol compounds related to iron binding.

PubMed

Perron, Nathan R; Brumaghim, Julia L

2009-01-01

In this review, primary attention is given to the antioxidant (and prooxidant) activity of polyphenols arising from their interactions with iron both in vitro and in vivo. In addition, an overview of oxidative stress and the Fenton reaction is provided, as well as a discussion of the chemistry of iron binding by catecholate, gallate, and semiquinone ligands along with their stability constants, UV-vis spectra, stoichiometries in solution as a function of pH, rates of iron oxidation by O(2) upon polyphenol binding, and the published crystal structures for iron-polyphenol complexes. Radical scavenging mechanisms of polyphenols unrelated to iron binding, their interactions with copper, and the prooxidant activity of iron-polyphenol complexes are briefly discussed.

Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

DOE PAGES

Tilka, J. A.; Park, J.; Ahn, Y.; ...

2018-02-26

A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tilka, J. A.; Park, J.; Ahn, Y.

A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

Crystal-free Formation of Non-Oxide Optical Fiber

NASA Technical Reports Server (NTRS)

Nabors, Sammy A.

2015-01-01

Researchers at NASA Marshall Space Flight Center have devised a method for the creation of crystal-free nonoxide optical fiber preforms. Non-oxide fiber optics are extensively used in infrared transmitting applications such as communication systems, chemical sensors, and laser fiber guides for cutting, welding and medical surgery. However, some of these glasses are very susceptible to crystallization. Even small crystals can lead to light scatter and a high attenuation coefficient, limiting their usefulness. NASA has developed a new method of non-oxide fiber formation that uses axial magnetic fields to suppress crystallization. The resulting non-oxide fibers are crystal free and have lower signal attenuation rates than silica based optical fibers.

Hydrogen-related complexes in Li-diffused ZnO single crystals

DOE PAGES

Corolewski, Caleb D.; Parmar, Narendra S.; Lynn, Kelvin G.; ...

2016-07-21

Zinc oxide (ZnO) is a wide band gap semiconductor and a potential candidate for next generation white solid state lighting applications. In this work, hydrogen-related complexes in lithium diffused ZnO single crystals were studied. In addition to the well-known Li-OH complex, several other hydrogen defects were observed. When a mixture of Li 2O and ZnO is used as the dopant source, zinc vacancies are suppressed and the bulk Li concentration is very high (>10 19 cm -3). In that case, the predominant hydrogen complex has a vibrational frequency of 3677 cm -1, attributed to surface O-H species. When Li 2COmore » 3 is used, a structured blue luminescence band and O-H mode at 3327 cm -1 are observed at 10K. These observations, along with positron annihilation measurements, suggest a zinc vacancy–hydrogen complex, with an acceptor level 0.3 eV above the valence-band maximum. In conclusion, this relatively shallow acceptor could be beneficial for p-type ZnO.« less

Ceruloplasmin: Macromolecular Assemblies with Iron-Containing Acute Phase Proteins

PubMed Central

Samygina, Valeriya R.; Sokolov, Alexey V.; Bourenkov, Gleb; Petoukhov, Maxim V.; Pulina, Maria O.; Zakharova, Elena T.; Vasilyev, Vadim B.; Bartunik, Hans; Svergun, Dmitri I.

2013-01-01

Copper-containing ferroxidase ceruloplasmin (Cp) forms binary and ternary complexes with cationic proteins lactoferrin (Lf) and myeloperoxidase (Mpo) during inflammation. We present an X-ray crystal structure of a 2Cp-Mpo complex at 4.7 Å resolution. This structure allows one to identify major protein–protein interaction areas and provides an explanation for a competitive inhibition of Mpo by Cp and for the activation of p-phenylenediamine oxidation by Mpo. Small angle X-ray scattering was employed to construct low-resolution models of the Cp-Lf complex and, for the first time, of the ternary 2Cp-2Lf-Mpo complex in solution. The SAXS-based model of Cp-Lf supports the predicted 1∶1 stoichiometry of the complex and demonstrates that both lobes of Lf contact domains 1 and 6 of Cp. The 2Cp-2Lf-Mpo SAXS model reveals the absence of interaction between Mpo and Lf in the ternary complex, so Cp can serve as a mediator of protein interactions in complex architecture. Mpo protects antioxidant properties of Cp by isolating its sensitive loop from proteases. The latter is important for incorporation of Fe3+ into Lf, which activates ferroxidase activity of Cp and precludes oxidation of Cp substrates. Our models provide the structural basis for possible regulatory role of these complexes in preventing iron-induced oxidative damage. PMID:23843990

Homeotropic alignment of dendritic columnar liquid crystal induced by hydrogen-bonded triphenylene core bearing fluoroalkyl chains.

PubMed

Ishihara, Shinsuke; Furuki, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Takeoka, Shinji

2014-07-01

A 1:3 molar complex of the fluoroalkyl side chain-substituted 2,6,10-tris-carboxymethoxy-3,7,11-tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyloxy)triphenylene (TPF4) with the second generation dendron 3,5-bis(3,4-bis-dodecyloxybenzyloxy)-N-pyridin-4-yl-benzamide (DN) assembled through complementary hydrogen bonding to form a supramolecular columnar liquid crystal, which exhibited homeotropic alignment when sandwiched between octadecyltrichlorosilane (OTS)-coated or indium tin oxide (ITO)-coated glass plates due to specific interactions between the fluoroalkyl side chains and the substrates.

Biogenic Manganese-Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi-Copper Oxidase, MnxEFG.

PubMed

Tao, Lizhi; Simonov, Alexandr N; Romano, Christine A; Butterfield, Cristina N; Fekete, Monika; Tebo, Bradley M; Bond, Alan M; Spiccia, Leone; Martin, Lisandra L; Casey, William H

2017-01-26

In a natural geochemical cycle, manganese-oxide minerals (MnO x ) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnO x mineralization. Here, the kinetics of MnO x formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near-neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy-terminated monolayer to be in the range 0.36-0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural complexity of simple Fe 2O 3 at high pressures and temperatures

DOE PAGES

Bykova, Elena; Dubrovinsky, L.; Dubrovinskaia, N.; ...

2016-02-11

Although chemically very simple, Fe 2O 3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe 2O 3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described bymore » the homologous series nFeO·mFe 2O 3. Decomposition of Fe 2O 3 and Fe 3O 4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe 5O 7 and Fe 25O 32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.« less

Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx.

PubMed

Romano, Christine A; Zhou, Mowei; Song, Yang; Wysocki, Vicki H; Dohnalkova, Alice C; Kovarik, Libor; Paša-Tolić, Ljiljana; Tebo, Bradley M

2017-09-29

Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase in Bacillus sp. PL-12, Mnx, is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins, MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant to crystallization, so its structure is unknown. Here, we show that native mass spectrometry defines the subunit topology and copper binding of Mnx, while high-resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for understanding Mn biomineralization by such unexplored enzymes.Significant challenges exist for structural characterization of enzymes responsible for biomineralization. Here the authors show that native mass spectrometry and high resolution electron microscopy can define the subunit topology and copper binding of a manganese oxidizing complex, and describe early stage formation of its mineral products.

Copper(II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine

NASA Astrophysics Data System (ADS)

Khattar, Raghvi; Yadav, Anjana; Mathur, Pavan

2015-05-01

Two new mononuclear copper(II) complexes [Cu (L) (NO3)2] (1) and [Cu (L) Br2] (2) where (L = bis(1-(pyridin-2-ylmethyl)-benzimidazol-2-ylmethyl)ether) are synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, UV-Visible, IR spectroscopy, EPR and cyclic voltammetry. The complexes exhibit different coordination structures; the E1/2 value of the complex (1) is found to be relatively more cathodic than that of complex (2). X-band EPR spectra at low temperature in DMF supports a tetragonally distorted complex (1) while complex (2) shows three different g values suggesting a rhombic geometry. These complexes were utilized as a catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine assisted by molecular oxygen. The initial rate of reaction is dependent on the concentration of Cu(II) complex as well as substrate, and was found to be higher for the nitrate bound complex, while presence of acetate anion acts as a mild inhibitor of the reaction, as it is likely to pick up protons generated during the course of reaction. The inhibition suggests that the generated protons are further required in another important catalytic step.

The (oxo)[(2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(4-tolylporphyrinato)]vanadium(IV): Synthesis, UV-visible, Cyclic voltammetry and X-ray crystal structure

NASA Astrophysics Data System (ADS)

Mchiri, Chadlia; Amiri, Nesrine; Jabli, Souhir; Roisnel, Thierry; Nasri, Habib

2018-02-01

The present work is concerned with the oxo vanadium(IV) complex of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(4-tolylporphyrin) with formula [V(Cl8TTP)O] (I), which was prepared by reacting the (oxo)[5,10,15,20-tetrakis(4-tolylporphyrinato)]vanadium(IV) complex ([V(TTP)O]), under aerobic atmosphere, with a large excess of thionyl chloride (SOCl2). The title compound was characterized by UV-visible spectroscopy, cyclic voltammetry and X-ray crystal structure. The electron-withdrawing chlorine substituents at the pyrrole carbons in the vanadyl-Cl8TTP derivative produce remarkable redshifts of the Soret and Q absorption bands and an important anodic shift of the porphyrin ring oxidation and reduction potentials. This is an indication that the porphyrin core of complex (I) is severely nonplanar in solution. The molecular structure of our vanadyl derivative shows a very high saddle distortion and an important ruffled deformation of the porphyrin macrocycle. The crystal structure of (I) is made by one-dimensional chains parallel to the c axis where channels are located between these chains.

Metal-organic chemical vapor deposition of cerium oxide, gallium-indium-oxide, and magnesium oxide thin films: Precursor design, film growth, and film characterization

NASA Astrophysics Data System (ADS)

Edleman, Nikki Lynn

A new class of volatile, low-melting, fluorine-free lanthanide metal-organic chemical vapor deposition (MOCVD) precursors has been developed. The neutral, monomeric cerium, neodymium, gadolinium, and erbium complexes are coordinatively saturated by a versatile, multidentate, ether-functionalized beta-ketoiminate ligand, and complex melting point and volatility characteristics can be tuned by altering the alkyl substituents on the ligand periphery. Direct comparison with lanthanide beta-diketonate complexes reveals that the present precursor class is a superior choice for lanthanide oxide MOCVD. Epitaxial CeO 2 buffer layer films have been grown on (001) YSZ substrates by MOCVD at significantly lower temperatures than previously reported using one of the newly developed cerium precursors. High-quality YBCO films grown on these CeO2 buffer layers by POMBE exhibit very good electrical transport properties. The cerium complex has therefore been explicitly demonstrated to be a stable and volatile precursor and is attractive for low-temperature growth of coated conductor multilayer structures by MOCVD. Gallium-indium-oxide thin films (GaxIn2-xO 3), x = 0.0˜1.1, have been grown by MOCVD using the volatile metal-organic precursors In(dpm)3 and Ga(dpm)3. The films have a homogeneously Ga-substituted, cubic In2O3 microstructure randomly oriented on quartz or heteroepitaxial on (100) YSZ single-crystal substrates. The highest conductivity of the as-grown films is found at x = 0.12. The optical transmission window and absolute transparency of the films rivals or exceeds that of the most transparent conductive oxides known. Reductive annealing results in improved charge transport characteristics with little loss of optical transparency. No significant difference in electrical properties is observed between randomly oriented and heteroepitaxial films, thus arguing that carrier scattering effects at high-angle grain boundaries play a minor role in the film conductivity mechanism. The synthesis and characterization of a new magnesium MOCVD precursor, Mg(dpm)2(TMEDA) is detailed. It is shown that the donating ligand TMEDA prevents oligomerization and subsequent volatility depression as observed in the commonly used [Mg(dpm)2]2. The superiority of Mg(dpm)2(TMEDA) as an MOCVD precursor is explicitly demonstrated by growth of epitaxial MgO thin films on single-crystal SrTiO3 substrates.

PREPARATION OF REFRACTORY OXIDE CRYSTALS

DOEpatents

Grimes, W.R.; Shaffer, J.H.; Watson, G.M.

1962-11-13

A method is given for preparing uranium dioxide, thorium oxide, and beryllium oxide in the form of enlarged individual crystals. The surface of a fused alkali metal halide melt containing dissolved uranium, thorium, or beryllium values is contacted with a water-vapor-bearing inert gas stream at a rate of 5 to 10 cubic centimeters per minute per square centimeter of melt surface area. Growth of individual crystals is obtained by prolonged contact. Beryllium oxide-coated uranium dioxide crystals are prepared by disposing uranium dioxide crystals 5 to 20 microns in diameter in a beryllium-containing melt and contacting the melt with a water-vapor-bearing inert gas stream in the same manner. (AEC)

Structural dissection of Shewanella oneidensis old yellow enzyme 4 bound to a Meisenheimer complex and (nitro)phenolic ligands.

PubMed

Elegheert, Jonathan; Brigé, Ann; Van Beeumen, Jozef; Savvides, Savvas N

2017-10-01

Shewanella oneidensis, a Gram-negative γ-proteobacterium with an extensive redox capacity, possesses four old yellow enzyme (OYE) homologs. Of these, Shewanella yellow enzyme 4 (SYE4) is implicated in resistance to oxidative stress. Here, we present a series of high-resolution crystal structures for SYE4 in the oxidized and reduced states, and in complex with phenolic ligands and the nitro-aromatic explosive picric acid. The structures unmask new features, including the identification of a binding platform for long-chain hydrophobic molecules. Furthermore, we present the first structural observation of a hydride-Meisenheimer complex of picric acid with a flavoenzyme. Overall, our study exposes the binding promiscuity of SYE4 toward a variety of electrophilic substrates and is consistent with a general detoxification function for SYE4. © 2017 Federation of European Biochemical Societies.

Direct monolithic integration of vertical single crystalline octahedral molecular sieve nanowires on silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carretero-Genevrier, Adrian; Oro-Sole, Judith; Gazquez, Jaume

2013-12-13

We developed an original strategy to produce vertical epitaxial single crystalline manganese oxide octahedral molecular sieve (OMS) nanowires with tunable pore sizes and compositions on silicon substrates by using a chemical solution deposition approach. The nanowire growth mechanism involves the use of track-etched nanoporous polymer templates combined with the controlled growth of quartz thin films at the silicon surface, which allowed OMS nanowires to stabilize and crystallize. α-quartz thin films were obtained after thermal activated crystallization of the native amorphous silica surface layer assisted by Sr 2+- or Ba 2+-mediated heterogeneous catalysis in the air at 800 °C. These α-quartzmore » thin films work as a selective template for the epitaxial growth of randomly oriented vertical OMS nanowires. Furthermore, the combination of soft chemistry and epitaxial growth opens new opportunities for the effective integration of novel technological functional tunneled complex oxides nanomaterials on Si substrates.« less

Crystallographic studies of the binding of ligands to the dicarboxylate site of Complex II, and the identity of the ligand in the "oxaloacetate-inhibited" state.

PubMed

Huang, Li-Shar; Shen, John T; Wang, Andy C; Berry, Edward A

2006-01-01

Mitochondrial Complex II (succinate:ubiquinone oxidoreductase) is purified in a partially inactivated state, which can be activated by removal of tightly bound oxaloacetate (E.B. Kearney, et al., Biochem. Biophys. Res. Commun. 49 1115-1121). We crystallized Complex II in the presence of oxaloacetate or with the endogenous inhibitor bound. The structure showed a ligand essentially identical to the "malate-like intermediate" found in Shewanella Flavocytochrome c crystallized with fumarate (P. Taylor, et al., Nat. Struct. Biol. 6 1108-1112) Crystallization of Complex II in the presence of excess fumarate also gave the malate-like intermediate or a mixture of that and fumarate at the active site. In order to more conveniently monitor the occupation state of the dicarboxylate site, we are developing a library of UV/Vis spectral effects induced by binding different ligands to the site. Treatment with fumarate results in rapid development of the fumarate difference spectrum and then a very slow conversion into a species spectrally similar to the OAA-liganded complex. Complex II is known to be capable of oxidizing malate to the enol form of oxaloacetate (Y.O. Belikova, et al., Biochim. Biophys. Acta 936 1-9). The observations above suggest it may also be capable of interconverting fumarate and malate. It may be useful for understanding the mechanism and regulation of the enzyme to identify the malate-like intermediate and its pathway of formation from oxaloacetate or fumarate.

Crystallographic Studies of the Binding of Ligands to theDicarboxylate Site of Complex II, and the Identity of the Ligand in the'Oxaloacetate-Inhibited' State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Li-Shar; Shen, John T.; Wang, Andy C.

2006-07-01

Mitochondrial Complex II (succinate:ubiquinoneoxidoreductase) is purified in a partially innactivated state, which canbe activated by removal of tightly bound oxaloacetate (Kearney, E.B. etal. Biochem Biophys Res Commun 49, 1115-1121). We crystallized Complex IIin the presence of oxaloacetate or with the endogenous inhibitor bound.The structure showed a ligand essentially identical to the "malate-likeintermediate" found in Shewanella Flavocytochrome c crystallized withfumarate (Taylor, P., et al. Nat Struct Biol 6, 1108-1112.)Crystallization of Complex II in the presence of excess fumarate alsogave the malate-like intermediate or a mixture of that and fumarate atthe active site. In order to more conveniently monitor the occupationstate ofmore » the dicarboxylate site, we are developing a library of UV/Visspectral effects induced by binding different ligands to the site.Treatment with fumarate results in rapid development of the fumaratedifference spectrum and then a very slow conversion into a speciesspectrally similar to the OAA liganded complex. Complex II is known to becapable of oxidizing malate to the enol form of oxaloacetate (Belikova,Y.O., et al. Biochim Biophys Acta 936, 1-9). The observations abovesuggest it may also be capable of interconverting fumarate and malate. Itmay be useful for understanding the mechanism and regulation of theenzyme to identify the malate-like intermediate and its pathway offormation from oxaloacetate or fumarate.« less

Oxidative addition of allylic halides to ruthenium(II) compounds. Preparation, reactions, and X-ray crystallographic structure of ruthenium(IV)-allyl complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagashima, Hideo; Mukai, Katsunori; Shiota, Yusuke

1990-03-01

The oxidative addition of allylic halides to (C{sub 5}R{sub 5})RuL{sub 2}X (R = H, Me; L = CO, PPh{sub 3}) gave new Ru(IV)-{eta}{sup 3}-allyl complexes, (C{sub 5}R{sub 5})RuX{sub 2}({eta}{sup 3}-allyl). An X-ray structure determination was carried out on (C{sub 5}Me{sub 5})RuBr{sub 2}({eta}{sup 3}-C{sub 3}H{sub 5}), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-{eta}{sup 3}-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the {pi}-allyl ligands. Crystal data: orthorhombic, space group P2{sub 1}2{sub 1}2{sub 1}, a = 22.738 (1) {angstrom}, b = 13.367 (7) {angstrom}, cmore » = 9.383 (1) {angstrom}, Z = 4., data refined to R = 0.0695. Its {sup 1}H and {sup 13}C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution.« less

O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex.

PubMed

Deville, Claire; Padamati, Sandeep K; Sundberg, Jonas; McKee, Vickie; Browne, Wesley R; McKenzie, Christine J

2016-01-11

A Mn(II) complex, [Mn(dpeo)2](2+) (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn(III) complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn(II) complex of the final ketone ligand, cis-[MnBr2(hidpe)2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H2(18)O and (18)O2 labeling experiments suggest that the inserted O atoms originate from two different O2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-adjusted flux for the traveling solvent floating zone growth of YBaCuFeO5 crystal

NASA Astrophysics Data System (ADS)

Lai, Yen-Chung; Shu, Guo-Jiun; Chen, Wei-Tin; Du, Chao-Hung; Chou, Fang-Cheng

2015-03-01

A modified traveling solvent floating zone (TSFZ) technique was used to successfully grow a large size and high quality single crystal of multiferroic material YBaCuFeO5. This modified TSFZ growth uses a stoichiometric feed rod and pure copper oxide as the initial flux without prior knowledge of the complex phase diagram involving four elements, and the optimal flux for the growth of incongruently melt crystal is self-adjusted after a prolonged stable pulling. The wetting of the feed rod edge that often perturbs the molten zone stability was avoided by adding 2 wt% B2O3. The optimal flux concentration for the YBaCuFeO5 growth can be extracted to be near YBaCuFeO5:CuO=13:87 in molar ratio. The crystal quality was confirmed by the satisfactory refinement of crystal structure of space group P4mm and the two consecutive anisotropic antiferromagnetic phase transitions near 455 K and 170 K.

Investigation on biomolecular interactions of nickel(II) complexes with monoanionic bidentate ligands

NASA Astrophysics Data System (ADS)

Jayamani, Arumugam; Sethupathi, Murugan; Ojwach, Stephen O.; Sengottuvelan, Nallathambi

2018-01-01

Reactions of monoanionic bidentate ligands 5-methylsalicylaldehyde (5-msal), 5-bromosalicylaldehyde (5-brsal), 5-nitrosalicylaldehyde (5-nsal) and 2-hydroxy-1-naphthaldehyde (2-hnap) with nickel perchlorate hexahydrate produced nickel(II) complexes 1-4, respectively. Single crystal X-ray analyses of complexes 1 and 2 confirmed bidentate mode of the ligands with O˄O coordination to give square planar geometry around nickel atoms. Complexes 1-4 showed one quasi-reversible redox peak at cathodic region (-0.67 to -0.80 V) and one redox peak at anodic region (+1.08 to +1.44 V) assignable to the Ni(II)/Ni(I) and Ni(II)/Ni(III) redox couples, respectively. The complexes exhibited good bovine serum albumin (BSA) binding abilities with a maximum binding constant of 1.96 × 105 M-1. The binding of complexes with calf thymus DNA (ctDNA) showed that the binding affinity is consistent with an increase in steric bulk of the ligands. The nuclease activity of the complexes showed efficient oxidative cleavage in the presence of hydrogen peroxide as an oxidizing agent. The complexes showed higher zone of inhibition when screened for antimicrobial activity against bacteria and human pathogenic fungi.

Generalized Ellipsometry on Complex Nanostructures and Low-Symmetry Materials

NASA Astrophysics Data System (ADS)

Mock, Alyssa Lynn

In this thesis, complex anisotropic materials are investigated and characterized by generalized ellipsometry. In recent years, anisotropic materials have gained considerable interest for novel applications in electronic and optoelectronic devices, mostly due to unique properties that originate from reduced crystal symmetry. Examples include white solid-state lighting devices which have become ubiquitous just recently, and the emergence of high-power, high-voltage electronic transistors and switches in all-electric vehicles. The incorporation of single crystalline material with low crystal symmetry into novel device structures requires reconsideration of existing optical characterization approaches. Here, the generalized ellipsometry concept is extended to include applications for materials with monoclinic and triclinic symmetries. A model eigendielectric displacement vector approach is developed, described and utilized to characterize monoclinic materials. Materials are investigated in spectral regions spanning from the far-infrared to the vacuum ultraviolet. Examples are demonstrated for phonon mode determination in cadmium tungstate and yttrium silicate and for band-to-band transitions in gallia (beta-Ga2O3) single crystals. Furthermore, the anisotropic optical properties of an emerging class of spatially coherent heterostructure materials with nanostructure dimensions are investigated. The so-called anisotropic effective medium approximation for slanted columnar thin films is extended to the concept of slanted columnar heterostructure thin films as well as core-shell heterostructure thin films. Examples include the determination of band-to-band transitions, phonon modes and oxidation properties of cobalt-oxide core shell structures and gas-liquid-solid distribution during controlled adsorption of organic solvents in silicon slanted columnar thin films.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

PubMed

Lorenz, Volker; Ehle, Sophie; Liebing, Phil; Engelhardt, Felix; Hashemi-Haeri, Haleh; Oehler, Florian; Hinderberger, Dariush; Busse, Sabine; Urbaschok, Jens; Edelmann, Frank T

2017-12-19

A unique trivalent manganese siloxide complex, blue-violet Mn III Li 2 Cl[(Ph 2 SiO) 2 O] 2 (THF) 4 ·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph 2 SiOH) 2 O (1) followed by reaction with MnCl 2 (THF) 2 gave the structurally remarkable Mn(ii) precursor Mn II Li 4 Cl 2 [(Ph 2 SiO) 2 O] 2 (THF) 5 ·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO 4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

Mononuclear zinc(II) complexes of 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols: Synthesis, structural characterization, DNA binding and cheminuclease activities

NASA Astrophysics Data System (ADS)

Ravichandran, J.; Gurumoorthy, P.; Karthick, C.; Kalilur Rahiman, A.

2014-03-01

Four new zinc(II) complexes [Zn(HL1-4)Cl2] (1-4), where HL1-4 = 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols, have been isolated and fully characterized using various spectro-analytical techniques. The X-ray crystal structure of complex 4 shows the distorted trigonal-bipyramidal coordination geometry around zinc(II) ion. The crystal packing is stabilized by intermolecular NH⋯O hydrogen bonding interaction. The complexes display no d-d electronic band in the visible region due to d10 electronic configuration of zinc(II) ion. The electrochemical properties of the synthesized ligands and their complexes exhibit similar voltammogram at reduction potential due to electrochemically innocent Zn(II) ion, which evidenced that the electron transfer is due to the nature of the ligand. Binding interaction of complexes with calf thymus DNA was studied by UV-Vis absorption titration, viscometric titration and cyclic voltammetry. All complexes bind with CT DNA by intercalation, giving the binding affinity in the order of 2 > 1 ≫ 3 > 4. The prominent cheminuclease activity of complexes on plasmid DNA (pBR322 DNA) was observed in the absence and presence of H2O2. Oxidative pathway reveals that the underlying mechanism involves hydroxyl radical.

Conformational analysis of flavonoids: crystal and molecular structures of morin hydrate and myricetin (1:2) triphenylphosphine oxide complex

NASA Astrophysics Data System (ADS)

Cody, Vivian; Luft, Joseph R.

1994-01-01

The crystal and molecular structures of morin (2',3,4',5,7-pentahydroxyflavone) hydrate ( I), and myricetin (3',4',5',3,5,7-hexahydroxyflavone) triphenylphosphine oxide (TPPO) (1:2) co-crystal complex ( II) have been studied by X-ray analysis and AM1 molecular orbital methods. The molecular conformation of the two flavones described by the torsion angle θ[C(3)-C(2)-C(1t')-C(2')] between the benzopyrone and phenyl ring is -43.3° and 51.0° for molecules A and B of morin, respectively, and -37.0° for myricetin. Minimum energy conformations from AM1 molecular orbital calculations have θ values of -38.2° for morin and -27.0° for myricetin. The energy profile for rotation about θ for morin has a 28 kcal mol -1 barrier at 0° due to steric interactions between the 2'-hydroxy and the 3-hydroxy group. There are two local minima near 30 and 140°, in good agreement with structural results. The profile for myricetin has two equivalent minima near 30 and 150° with a barrier of less than 2 kcal mol -1. In the crystal both flavones form extensive networks of intra- and intermolecular hydrogen bonds. In ( I), each morin conformer packs in alternating layers linked by water molecules, while in ( II), TPPO stabilizes the crystal by formation of short hydrogen bonds (2.58-2.65 Å) of the phosphoryl oxygen to the flavone. Myricetin also forms a two dimensional sheet-like packing in which myricetin molecules hydrogen bond to each other, as well as to TPPO. These conformational and hydrogen bonding patterns provide insight into specific types of ligand-receptor interactions and support structure activity data which suggest the importance of electronic and hydrogen bonding properties in the bioactivity of flavones.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, Roberto

1986-01-01

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10.sup.12 protons per cm.sup.3 and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F.sup.+ luminescence is produced when the crystal is optically excited.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, R.

1985-07-03

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10/sup 12/ protons per cm/sup 3/ and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F/sup +/ luminescence is produced when the crystal is optically excited.

Magnetomechanical effect in silicon (Cz-Si) surface layers

NASA Astrophysics Data System (ADS)

Koplak, O. V.; Dmitriev, A. I.; Morgunov, R. B.

2012-07-01

The mechanical properties of near-surface layers of Czochralski-grown silicon crystals Cz- n-Si(111) have been found to undergo changes in response to an external constant magnetic field ( B ˜ 0.1 T). A magnetically induced variation in the microhardness, Young's modulus, and coefficient of plasticity of silicon crystals correlates with the change in the lattice parameter and internal stresses of the sample. The growth of an oxide film under exposure to a magnetic field plays the principal role in the magnetomechanical effect due to a decrease in the concentration of oxygen complexes in the near-surface layers of the sample. In microstructured silicon, where the surface is considerably more developed, the magnetic field induces more profound changes in the internal stresses as compared to single crystals.

Nephelauxetic effect and 〈r(k)〉₄f radial integrals of Tm³⁺ in crystals.

PubMed

Petrov, Dimitar

2015-12-05

Bonding and covalency parameters have been evaluated from the nephelauxetic ratios βk=Fk (crystal)/Fk (free ion), with k=2, 4, 6, for 24 halide and chalcogenide crystals containing Tm(3+) ions. The radial expectation values for 4f electrons 〈r(k)〉4f of Tm(3+) ion in certain complex oxides, fluorides, and a sulfide have been determined by means of experimental Slater parameter shifts ΔFk relative to the Fk values for the free ion Tm IV. The 〈r(k)〉1f values derived in the dielectric screening model have been compared with those computed by different types of 4f wave functions as well as with other estimates. Copyright © 2015 Elsevier B.V. All rights reserved.

The structure of a one-electron oxidized Mn(iii)-bis(phenolate)dipyrrin radical complex and oxidation catalysis control via ligand-centered redox activity.

PubMed

Lecarme, Laureline; Chiang, Linus; Moutet, Jules; Leconte, Nicolas; Philouze, Christian; Jarjayes, Olivier; Storr, Tim; Thomas, Fabrice

2016-10-18

The tetradentate ligand dppH3, which features a half-porphyrin and two electron-rich phenol moieties, was prepared and chelated to manganese. The mononuclear Mn(iii)-dipyrrophenolate complex 1 was structurally characterized. The metal ion lies in a square pyramidal environment, the apical position being occupied by a methanol molecule. Complex 1 displays two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc + /Fc, which are assigned to ligand-centered processes. The one-electron oxidized species 1+ SbF6- was crystallized, showing an octahedral Mn(iii) center with two water molecules coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that the radical is delocalized over the whole aromatic framework. Complex 1+ SbF6- exhibits an S tot = 3/2 spin state due to the antiferromagnetic coupling between Mn(iii) and the ligand radical. The zero field splitting parameters are D = 1.6 cm -1 , E/D = 0.18(1), g ⊥ = 1.99 and g ∥ = 1.98. The dication 12+ is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a Mn(iii) metal center. Both 1 and 1+ SbF6- catalyze styrene oxidation in the presence of PhIO, but the nature of the main reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed predominantly when using 1+ SbF6-. We examined the ability of complex 1+ SbF6- to catalyze the isomerization of styrene oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case of 1+ SbF6-. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a catalyst based on a redox-active ligand.

A Heterobimetallic W-Ni Complex Containing a Redox-Active W[SNS]2 Metalloligand.

PubMed

Rosenkoetter, Kyle E; Ziller, Joseph W; Heyduk, Alan F

2016-07-05

The tungsten complex W[SNS]2 ([SNS]H3 = bis(2-mercapto-4-methylphenyl)amine) was bound to a Ni(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane] fragment to form the new heterobimetallic complex W[SNS]2Ni(dppe). Characterization of the complex by single-crystal X-ray diffraction revealed the presence of a short W-Ni bond, which renders the complex diamagnetic despite formal tungsten(V) and nickel(I) oxidation states. The W[SNS]2 unit acts as a redox-active metalloligand in the bimetallic complex, which displays four one-electron redox processes by cyclic voltammetry. In the presence of the organic acid 4-cyanoanilinium tetrafluoroborate, W[SNS]2Ni(dppe) catalyzes the electrochemical reduction of protons to hydrogen coincident with the first reduction of the complex.

From bis(imidazole-2-thion-4-yl)phosphane to a flexible P-bridged bis(NHC) ligand and its silver complex.

PubMed

Majhi, Paresh Kumar; Schnakenburg, Gregor; Streubel, Rainer

2014-11-28

Synthesis of the first P(V)-bridged bis(NHC) ligand 7 was achieved via deprotonation of P(V)-functionalized bis(imidazolium) salt 6, which was obtained via oxidative desulfurization of bis(imidazole-2-thion-4-yl)phosphane 2. Bis(imidazolium) salt 6 was also employed to synthesize the corresponding silver complex 8. All new products were firmly established by spectroscopic and spectrometric methods as well as elemental analysis and, in addition, X-ray crystal structure analysis in the case of 3.

Reflection spectra and their angular dependences of one-dimensional photonic crystals based on aluminium oxide

NASA Astrophysics Data System (ADS)

Gorelik, V. S.; Yashin, M. M.; Pudovkin, A. V.; Vodchits, A. I.

2017-11-01

The article considers optical properties (transmission and reflection) of one-dimensional photonic crystals based on mesoporous anodic aluminum oxide, with periods of crystal lattices 188 and 194 nm. A comparison of the experimentally measured reflection spectrum in the spectral region of the first stop-zone with the theoretical dependence obtained from the dispersion relation for one-dimensional photonic crystal is carried out. The angular dependence of the first stop-zone spectral positions of one-dimensional photonic crystal is established. The authors analyze the possibility of applications of mesoporous one-dimensional photonic crystals based on aluminum oxide as the selective narrowband filters and mirrors.

Uranium(iii) complexes supported by hydrobis(mercaptoimidazolyl)borates: synthesis and oxidation chemistry.

PubMed

Maria, Leonor; Santos, Isabel C; Santos, Isabel

2018-05-23

The reaction of [UI3(thf)4] with the sodium or lithium salts of hydrobis(2-mercapto-1-methylimidazolyl)borate ligands ([H(R)B(timMe)2]-) in a 1 : 2 ratio, in tetrahydrofuran, gave the U(iii) complexes [UI{κ3-H,S,S'-H(R)B(timMe)2}2(thf)2] (R = H (1), Ph (2)) in good yields. Crystals of [UI{κ3-H,S,S'-H(Ph)B(timMe)2}2(thf)2] (2) were obtained by recrystallization from a tetrahydrofuran/acetonitrile solution, and the ion-separated uranium complex [U{κ3-H,S,S'-H(Ph)B(timMe)2}2(CH3CN)3][I] (3-I) was obtained by dissolution of 2 in acetonitrile followed by recrystallization. One-electron oxidation of 2 with AgBPh4 or I2 resulted in the formation of the cationic U(iv) complexes [U{κ3-H,S,S'-H(Ph)B(timMe)2}3][X] (X = BPh4 (6-BPh4), I (6-I)), due to a ligand redistribution process. These complexes are the first examples of homoleptic poly(azolyl)borate U(iv) complexes. Treatment of complex 2 with azobenzene led to the isolation of crystals of the U(iv) compound [UI{κ3-H(Ph)B(timMe)2}2(κ2-timMe)] (7). Treatment of 2 with pyridine-N oxide (pyNO) led to the formation of the uranyl complex [UO2{κ2-S,S'-H(Ph)B(timMe)2}2] (8) and of complex 6-I, while from the reaction of [U{κ3-H(Ph)B(timMe)2}2(thf)3][BPh4] (5) with pyNO, the oxo-bridged U(iv) complex [{U{κ3-H(Ph)B(timMe)2}2(pyNO)}2(μ-O)][BPh4]2 (9) was also obtained. In the U(iii) and U(iv) complexes, the bis(azolyl)borate ligands bind to the uranium center in a κ3-H,S,S' coordination mode, while in the U(vi) complex the ligands bind to the metal in a κ2-S,S' mode. The presence of UH-B interactions in the solid-state, for the nine-coordinate complexes 1, 2, 3, 6 and 7 and for the eight-coordinate complex 9, was supported by IR spectroscopy and/or X-ray diffraction analysis.

A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

PubMed

Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2016-05-11

At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

Characterization of Heavy Oxide Inorganic Scintillator Crystals for Direct Detection of Fast Neutrons Based on Inelastic Scattering

DTIC Science & Technology

2015-03-01

HEAVY OXIDE INORGANIC SCINTILLATOR CRYSTALS FOR DIRECT DETECTION OF FAST NEUTRONS BASED ON INELASTIC SCATTERING by Philip R. Rusiecki...HEAVY OXIDE INORGANIC SCINTILLATOR CRYSTALS FOR DIRECT DETECTION OF FAST NEUTRONS BASED ON INELASTIC SCATTERING 6. AUTHOR(S) Philip R. Rusiecki 7...ABSTRACT (maximum 200 words) Heavy oxide inorganic scintillators may prove viable in the detection of fast neutrons based on the mechanism of

Syntheses and molecular structures of novel Ru(II) complexes with bidentate benzimidazole based ligands and their catalytic efficiency for oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Dayan, Osman; Tercan, Melek; Özdemir, Namık

2016-11-01

Five bidentate ligands derived from quinoline-2-carboxylic acid, i.e. 2-(1H-benzimidazol-2-yl)quinoline (L1), 2-(1-benzyl-1H-benzimidazol-2-yl)quinoline (L2), 2-[1-(2,3,5,6-tetramethylbenzyl)-1H-benzimidazol-2-yl]quinoline (L3), 2-[1-(4-chlorobenzyl)-1H-benzimidazol-2-yl]quinoline (L4), and 2-[1-(4-methylbenzyl)-1H-benzimidazol-2-yl]quinoline (L5) were synthesized. Treatment of L1-5 with [RuCl2(p-cymene)]2 and KPF6 afforded six-coordinate piano-stool Ru(II) complexes, namely, [RuCl(L1)(p-cymene)]PF6 (C1), [RuCl(L2)(p-cymene)]PF6 (C2), [RuCl(L3)(p-cymene)]PF6 (C3), [RuCl(L4)(p-cymene)]PF6 (C4), and [RuCl(L5)(p-cymene)]PF6 (C5). Synthesized compounds were characterized with different techniques such as 1H and 13C NMR, FT-IR, and UV-vis spectroscopy. The solid state structure of L1 and C3 was confirmed by single-crystal X-ray diffraction analysis. The single crystal structure of C3 verified coordination of L3 to the Ru(II) center. The Ru(II) center has a pseudo-octahedral three legged piano stool geometry. The complexes C1-5 were tested as catalysts for the catalytic oxidation of benzyl alcohol to benzaldehyde in the presence of periodic acid (H5IO6) (Substrate/Catalyst/Oxidant = 1/0.01/0.5). The best result was obtained with C2 (3 h→90%).

Crystallisation and crystal forms of carbohydrate derivatives

NASA Astrophysics Data System (ADS)

Lennon, Lorna

This thesis is focused on the synthesis and solid state analysis of carbohydrate derivatives, including many novel compounds. Although the synthetic chemistry surrounding carbohydrates is well established in the literature, the crystal chemistry of carbohydrates is less well studied. Therefore this research aims to improve understanding of the solid state properties of carbohydrate derivatives through gaining more information on their supramolecular bonding. Chapter One focuses on an introduction to the solid state of organic compounds, with a background to crystallisation, including issues that can arise during crystal growth. Chapter Two is based on glucopyranuronate derivatives which are understudied in terms of their solid state forms. This chapter reports on the formation of novel glucuronamides and utilising the functionality of the amide bond for crystallisation. TEMPO oxidation was completed to form glucopyranuronates by oxidation of the primary alcohol groups of glucosides to the carboxylic acid derivatives, to increase functionality for enhanced crystal growth. Chapter Three reports on the synthesis of glucopyranoside derivatives by O-glycosylation reactions and displays crystal structures, including a number of previously unsolved acetate protected and deprotected crystal structures. More complex glycoside derivatives were also researched in an aim to study the resultant supramolecular motifs. Chapter Four contains the synthesis of aryl cellobioside derivatives including the novel crystal structures that were solved for the acetate protected and deprotected compounds. Research was carried out to determine if 1-deoxycellodextrins could act as putative isostructures for cellulose. Our research displays the presence of isostructural references with 1-deoxycellotriose shown to be similar to cellulose III11, 1-deoxycellotetraose correlates with cellulose IV11 and 1-deoxycellopentose shows isostructurality similar to that of cellulose II. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project and relevant crystallographic information.

Nondestructive method for chemically machining crucibles or molds from their enclosed ingots and castings

DOEpatents

Stout, Norman D.; Newkirk, Herbert W.

1991-01-01

An inventive method is described for chemically machining rhenium, rhenium and tungsten alloy, and group 5b and 6b crucibles or molds from included ingots and castings comprised of oxide crystals including YAG and YAG based crystals, garnets, corundum crystals, and ceramic oxides. A mixture of potassium hydroxide and 15 to 90 weight percent of potassium nitrate is prepared and maintained at a temperature above melting and below the lower of 500 degrees centigrade or the temperature of decomposition of the mixture. The enveloping metal container together with its included oxide crystal object is rotated within the heated KOH-KNO.sub.3 mixture, until the container is safely chemically machined away from the included oxide crystal object.

Transport Properties of Complex Oxides: New Ideas and Insights from Theory and Simulation

NASA Astrophysics Data System (ADS)

Benedek, Nicole

Complex oxides are one of the largest and most technologically important materials families. The ABO3 perovskite oxides in particular display an unparalleled variety of physical properties. The microscopic origin of these properties (how they arise from the structure of the material) is often complicated, but in many systems previous research has identified simple guidelines or `rules of thumb' that link structure and chemistry to the physics of interest. For example, the tolerance factor is a simple empirical measure that relates the composition of a perovskite to its tendency to adopt a distorted structure. First-principles calculations have shown that the tendency towards ferroelectricity increases systematically as the tolerance factor of the perovskite decreases. Can we uncover a similar set of simple guidelines to yield new insights into the ionic and thermal transport properties of perovskites? I will discuss recent research from my group on the link between crystal structure and chemistry, soft phonons and ionic transport in a family of layered perovskite oxides, the Ln2NiO4+δ Ruddlesden-Popper phases. In particular, we show how the lattice dynamical properties of these materials (their tendency to undergo certain structural distortions) can be correlated with oxide ion transport properties. Ultimately, we seek new ways to understand the microscopic origins of complex transport processes and to develop first-principles-based design rules for new materials based on our understanding.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, XS; Michaelis, VK; Ong, TC

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building unitsmore » (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+O2- ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7m(2)g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.« less

A novel copper (II) complex containing a tetradentate Schiff base: Synthesis, spectroscopy, crystal structure, DFT study, biological activity and preparation of its nano-sized metal oxide

NASA Astrophysics Data System (ADS)

Tohidiyan, Zeinab; Sheikhshoaie, Iran; Khaleghi, Mouj; Mague, Joel T.

2017-04-01

A new nano-sized copper (II) complex, [Cu(L)] with a tetra dentate Schiff base ligand, 2-((E)-(2-(E-5- bromo-2-hydroxybezenylideneamino) methyl)-4-bromophenol [H2L] was prepared by the reaction between of Cu (CH3COO)2·2H2O and (H2L) ligand with the ratio of 1:1, at the present of triethylamine by sonochemical method. The structure of [Cu (L)] complex was determined by FT-IR, UV-Vis, FESEM and molar conductivity. The structure of [Cu (L)] complex was characterized by single crystal X-ray diffraction. The geometry of [Cu (L)] complex was optimized using density functional theory (DFT) method with the B3LYP/6-31(d) level of theory. The calculated bond lengths and bond angles are in good agreement with the X-ray data. This complex was used as a novel precursor for preparing of CuO nano particles by the thermal decomposition method. The antibacterial activities of [H2L] ligand, nano-sized [Cu (L)] complex and nano-sized CuO have been screened against various strains of bacteria. According to the results, nano-sized CuO can be considered as an appropriate antibiotic agent.

Effect of dipolar fields, surface termination, and surface orientation on photochemical reactions on transition metal oxides

NASA Astrophysics Data System (ADS)

Giocondi, Jennifer Lynn

Experiments have been conducted to determine the effects of dipolar fields, surface termination, and surface orientation on the photochemical reactivity of several transition metal oxides. These compounds include BaTiO3, SrTiO3, BaTi4O9, Sr2Nb2O 7, and Sr2Ta2O7 which were studied as polycrystalline ceramics, single crystals, micron-sized faceted particles, or some combination of these forms. The reduction of Ag+ from an aqueous AgNO3 solution (Ag0 product) and the oxidation of Pb2+ from an aqueous lead acetate solution (PbO 2 product) were selected as probe reactions because they leave insoluble products on the oxide surfaces. The reactivity of ferroelectric BaTiO3 was dominated by the effect of dipolar fields on the transport of photogenerated charge carriers. Silver was reduced on domains with a positive surface charge while lead was oxidized on domains with a negative surface charge. This reactivity implies that the dipolar field in individual domains drives photogenerated charge carriers to oppositely charged surfaces. This reaction mechanism results in a physical separation of the photogenerated charge carriers and the locations of the oxidation and reduction half reactions on the catalyst surface. Experiments performed on polycrystalline ceramics, single crystals, and micron-sized particles all showed this domain specific reactivity. SrTiO3 has the ideal cubic perovskite structure from which the tetragonally distorted ferroelectric BaTiO3 phase is derived. Polished and annealed surfaces of randomly oriented grain surfaces were bound by some combination of the following three planes: {110}, {111}, and a complex facet inclined approximately 24° from {100}. Surfaces with the complex {100} facet were found to be the most active for Ag reduction. Single crystal studies also showed that the nonpolar (100) surface is the most reactive and that the composition of the termination layer does not influence this reaction. However, the polar (111) and (110) surfaces had a non-uniform distribution of reaction products. For these orientations, the location of the reduction and oxidation reactions is determined by the chemical and charge terminations of the different terraces or facets. The reactivity for silver reduction on the faceted particles is ranked as (100) > (111) > (110) while the (100) surface was least reactive for lead oxidation. Overall, these results show that the photochemical reactivity of SrTiO3 is anisotropic and that on polar surfaces, dipolar fields arising from charged surface domains influence the transport of photogenerated charge carriers and promote spatially selective oxidation and reduction reactions. (Abstract shortened by UMI.)

Metal ion binding to iron oxides

NASA Astrophysics Data System (ADS)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toczydlowska, Diana; Kedra-Krolik, Karolina; Nejbert, Krzysztof

The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) duemore » to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.« less

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

DOE PAGES

Balasekaran, Samundeeswari Mariappan; Sattelberger, Alfred P.; Hagenbach, Adelheid; ...

2017-12-08

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp –); 2, L = diphenyl formamidinate (dpf –)) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoesmore » two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.« less

Crystal Structure of the ERp44-Peroxiredoxin 4 Complex Reveals the Molecular Mechanisms of Thiol-Mediated Protein Retention.

PubMed

Yang, Kai; Li, De-Feng; Wang, Xi'e; Liang, Jinzhao; Sitia, Roberto; Wang, Chih-Chen; Wang, Xi

2016-10-04

ERp44 controls the localization and transport of diverse proteins in the early secretory pathway. The mechanisms that allow client recognition and the source of the oxidative power for forming intermolecular disulfides are as yet unknown. Here we present the structure of ERp44 bound to a client, peroxiredoxin 4. Our data reveal that ERp44 binds the oxidized form of peroxiredoxin 4 via thiol-disulfide interchange reactions. The structure explains the redox-dependent recognition and characterizes the essential non-covalent interactions at the interface. The ERp44-Prx4 covalent complexes can be reduced by glutathione and protein disulfide isomerase family members in the ER, allowing the two components to recycle. This work provides insights into the mechanisms of thiol-mediated protein retention and indicates the key roles of ERp44 in this biochemical cycle to optimize oxidative folding and redox homeostasis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balasekaran, Samundeeswari Mariappan; Sattelberger, Alfred P.; Hagenbach, Adelheid

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp –); 2, L = diphenyl formamidinate (dpf –)) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoesmore » two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.« less

A Review of In Situ Observations of Crystallization and Growth in High Temperature Oxide Melts

NASA Astrophysics Data System (ADS)

Wang, Zhanjun; Sohn, Il

2018-05-01

This review summarizes the significant results of high-temperature confocal laser scanning microscopy (CLSM) and single hot thermocouple technology (SHTT) and its application in observing the crystallization and growth in high-temperature oxide melts from iron- and steel-making slags to continuous casting mold fluxes. Using in situ observations of CLSM and SHTT images of high-temperature molten oxides with time, temperature, and composition, the crystallization behavior, including crystal morphology, crystallization temperature, initial nucleation and growth rate, could be obtained. The broad range of applications using in situ observations during crystallization have provided a wealth of opportunities in pyrometallurgy and is provided in this review.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The main mineralized zone is located in the upper part of this unit, about 70 m above this discontinuity. The highly differentiated Fe-Ti-P facies of the Lanjanina series in the Itsindro Gabbro Complex have been interpreted as corresponding to the Fe-Ti-P rich, Si-poor member remaining after an immiscible segregation of an evolved mafic magma. The granite dykes and the overlying granite unit represent the second, Si-rich member of the immiscibility process. The presence of large amounts of sulphide is attributed to sulphur contamination of the Fe-Ti-rich liquid. Fe-Ti oxides will tend to crystallize on the sulphide droplets and the accumulation of dense Fe-sulphides (liquid) and associated Fe-Ti oxides (solid) will result in this complex and unusual association taking the form of a net texture.

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

PubMed

Harris, Caleb F; Bayless, Michael B; van Leest, Nicolaas P; Bruch, Quinton J; Livesay, Brooke N; Bacsa, John; Hardcastle, Kenneth I; Shores, Matthew P; de Bruin, Bas; Soper, Jake D

2017-10-16

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO] 2- dianions, of the general formula [(OCO)Co II L] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)Co II L] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc + /Fc, corresponding to generation of formally Co(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [( S OCO)Co III (THF) 2 ] + containing a closed-shell [ S OCO] 2- diphenolate ligand bound to a S = 1 Co(III) center, or [( S OCO • )Co II (THF) 2 ] + with a low-spin Co(II) ion ferromagnetically coupled to monoanionic [ S OCO • ] - containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [( S OCO 0 )Co II (THF) 3 ] 2+ , with a single unpaired electron localized on the d 7 Co(II) center and a doubly oxidized, charge-neutral, closed-shell S OCO 0 ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed.

Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Dell, William B.; Agarwal, Pratul K.; Meilleur, Flora

Lytic polysaccharide monooxygenases have attracted vast attention owing to their abilities to disrupt glycosidic bonds via oxidation instead of hydrolysis and to enhance enzymatic digestion of recalcitrant substrates including chitin and cellulose. Here, we determined the high-resolution X-ray crystal structures of an enzyme from Neurospora crassa in the resting state and of a copper(II) dioxo intermediate complex formed in the absence of substrate. X-ray crystal structures also revealed “pre-bound” molecular oxygen adjacent to the active site. An examination of protonation states enabled by neutron crystallography and density functional theory calculations identified a role for a conserved histidine in promoting oxygenmore » activation. Our results provide a new structural description of oxygen activation by substrate free lytic polysaccharide monooxygenases and provide insights that can be extended to reactivity in the enzyme–substrate complex.« less

Oxygen Activation at the Active Site of a Fungal Lytic Polysaccharide Monooxygenase

DOE PAGES

O'Dell, William B.; Agarwal, Pratul K.; Meilleur, Flora

2016-12-22

Lytic polysaccharide monooxygenases have attracted vast attention owing to their abilities to disrupt glycosidic bonds via oxidation instead of hydrolysis and to enhance enzymatic digestion of recalcitrant substrates including chitin and cellulose. Here, we determined the high-resolution X-ray crystal structures of an enzyme from Neurospora crassa in the resting state and of a copper(II) dioxo intermediate complex formed in the absence of substrate. X-ray crystal structures also revealed “pre-bound” molecular oxygen adjacent to the active site. An examination of protonation states enabled by neutron crystallography and density functional theory calculations identified a role for a conserved histidine in promoting oxygenmore » activation. Our results provide a new structural description of oxygen activation by substrate free lytic polysaccharide monooxygenases and provide insights that can be extended to reactivity in the enzyme–substrate complex.« less

Analytical studies on the crystal melt interface shape in the Czochralski process for oxide single crystals

NASA Astrophysics Data System (ADS)

Jeong, Ja Hoon; Kang, In Seok

2000-09-01

Effects of the operating conditions on the crystal-melt interface shape are analytically investigated for the Czochralski process of the oxide single crystals. The ideas, which were used for the silicon single-crystal growth by Jeong et al. (J. Crystal Growth 177 (1997) 157), are extended to the oxide single-crystal growth problem by considering the internal radiation in the crystal phase and the melt phase heat transfer with the high Prandtl number. The interface shape is approximated in the simplest form as a quadratic function of radial position and an expression for the deviation from the flat interface shape is derived as a function of operating conditions. The radiative heat transfer rate between the interface and the ambient is computed by calculating the view factors for the curved interface shape with the assumption that the crystal phase is completely transparent. For the melt phase, the well-known results from the thermal boundary layer analysis are applied for the asymptotic case of high Prandtl number based on the idea that the flow field near the crystal-melt interface can be modeled as either a uniaxial or a biaxial flow. Through this work, essential information on the interface shape deformation and the effects of operating conditions are brought out for the oxide single-crystal growth.

Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-Coordinate Silicon Alcoholate Complexes

PubMed Central

Li, Xiansen; Michaelis, Vladimir K.; Ong, Ta-Chung; Smith, Stacey J.; Griffin, Robert G.; Wang, Evelyn N.

2014-01-01

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. We report the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes via a novel transesterification mechanism. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+-O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counterions as a result of unique atomic arrangement in its structure. On the other hand, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. PMID:24737615

Graphene chiral liquid crystals and macroscopic assembled fibres

PubMed Central

Xu, Zhen; Gao, Chao

2011-01-01

Chirality and liquid crystals are both widely expressed in nature and biology. Helical assembly of mesophasic molecules and colloids may produce intriguing chiral liquid crystals. To date, chiral liquid crystals of 2D colloids have not been explored. As a typical 2D colloid, graphene is now receiving unprecedented attention. However, making macroscopic graphene fibres is hindered by the poor dispersibility of graphene and by the lack of an assembly method. Here we report that soluble, chemically oxidized graphene or graphene oxide sheets can form chiral liquid crystals in a twist-grain-boundary phase-like model with simultaneous lamellar ordering and long-range helical frustrations. Aqueous graphene oxide liquid crystals were continuously spun into metres of macroscopic graphene oxide fibres; subsequent chemical reduction gave the first macroscopic neat graphene fibres with high conductivity and good mechanical performance. The flexible, strong graphene fibres were knitted into designed patterns and into directionally conductive textiles. PMID:22146390

Crystal Structure of Mistletoe Lectin I (ML-I) from Viscum album in Complex with 4-N-Furfurylcytosine at 2.85 Å Resolution.

PubMed

Ahmad, Malik Shoaib; Rasheed, Saima; Falke, Sven; Khaliq, Binish; Perbandt, Markus; Choudhary, M Iqbal; Markiewicz, Wojciech T; Barciszewski, Jan; Betzel, Christian

2018-05-23

Viscum album (the European mistletoe) is a semi-parasitic plant, which is of high medical interest. It is widely found in Europe, Asia and North America. It contains at least three distinct lectins (i.e. ML-I, II, and III), varying in molecular mass and specificity. Among them ML-I is in focus of medical research for various activities, including anti-cancer activities. To understand the molecular basis for such medical applications a few studies have already addressed the structural and functional analysis of ML-I in complex with ligands. In continuation of these efforts, we are reporting the crystal structure of ML from Viscum album in complex with the nucleic acid oxidation product 4-N-furfurylcytosine (FC) refined to 2.85 Å resolution. FC is known to be involved in different metabolic pathways related to oxidative stress and DNA modification. X-ray suitable hexagonal crystals of the ML-I/FC complex were grown within four days at 294 K using the hanging drop vapor diffusion method. Diffraction data were collected up to a resolution of 2.85 Å. The ligand affinity was verified via in-silico docking. The high-resolution structure was refined subsequently to analyze particularly the active site conformation and binding epitope of 4-N-furfurylcytosine. A distinct 2Fo-Fc electron density at the active site was interpreted as a single FC molecule. The specific binding of FC is achieved also through hydrophobic interactions involving Tyr76A, Tyr115A, Glu165A, and Leu157A of the ML-I A-chain. The binding energy of FC to the active site of ML-I was calculated as well to be -6.03 kcal mol-1. In comparison to other reported ML-I complexes we observed distinct differences in the vicinity of the nucleic acid base binding site upon interaction with FC. Therefore, data obtained will provide new insights in understanding the specificity, inhibition and cytotoxicity of the ML-I A-chain and related RIPs. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Multistep Oxidation of Diethynyl Oligophenylamine-Bridged Diruthenium and Diiron Complexes.

PubMed

Zhang, Jing; Guo, Shen-Zhen; Dong, Yu-Bao; Rao, Li; Yin, Jun; Yu, Guang-Ao; Hartl, František; Liu, Sheng Hua

2017-01-17

Homo-dinuclear nonlinear complexes [{M(dppe)Cp*} 2 {μ-(-C≡C) 2 X}] (dppe = 1,2-bis(diphenylphosphino)ethane; Cp* = η 5 -C 5 Me 5 ; X = triphenylamine (TPA), M = Ru (1a) and Fe (1b); X = N,N,N',N'-tetraphenylphenylene-1,4-diamine (TPPD), M = Ru (2a)) were prepared and characterized by 1 H, 13 C, and 31 P NMR spectroscopy and single-crystal X-ray diffraction (1a, 2a). Attempts to prepare the diiron analogue of 2a were not successful. Experimental data obtained from cyclic voltammetry, square wave voltammetry, UV-vis-NIR (NIR = near-infrared) spectro-electrochemistry, and very informative IR spectro-electrochemistry in the C≡C stretching region, combined with density functional theory calculations, afford to make an emphasizing assessment of the close association between the metal-ethynyl termini and the oligophenylamine bridge core as well as their respective involvement in sequential one-electron oxidations of these complexes. The anodic behavior of the homo-bimetallic complexes depends strongly both on the metal center and the length of the oligophenylamine bridge core. The poorly separated first two oxidations of diiron complex 1b are localized on the electronically nearly independent Fe termini. In contrast, diruthenium complex 1a exhibits a significantly delocalized character and a marked electronic communication between the ruthenium centers through the diethynyl-TPA bridge. The ruthenium-ethynyl halves in 2a, separated by the doubly extended and more flexible TPPD bridge core, show a lower degree of electronic coupling, resulting in close-lying first two anodic waves and the NIR electronic absorption of [2a] + with an indistinctive intervalence charge transfer character. Finally, the third anodic waves in the voltammetric responses of the homo-bimetallic complexes are associated with the concurrent exclusive oxidation of the TPA or TPPD bridge cores.

Electrochemistry of 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene ligands: free phosphines, metal complexes, and chalcogenides.

PubMed

Mandell, Chelsea L; Kleinbach, Shannon S; Dougherty, William G; Kassel, W Scott; Nataro, Chip

2010-10-18

The oxidative electrochemistries of a series of chiral bisphosphinoferrocene ligands, 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene (FerroTANE) and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene (FerroLANE), were examined. The reversibility of the oxidation is sensitive to the steric bulk of the alkyl groups. New transition metal compounds and phosphine chalcogenides of these ligands were prepared and characterized. X-ray crystal structures of 10 of these compounds are reported. The percent buried volume (%V(bur)) is a recently developed measurement based on crystallographic data that examines the steric bulk of N-heterocyclic carbene and phosphine ligands. The %V(bur) for the FerroTANE and FerroLANE structures with methyl or ethyl substituents suggests these ligands are similar in steric properties to 1,1'-bis(diphenylphosphino)ferrocene (dppf). In addition the %V(bur) has been found to correlate well with the Tolman cone angle for phosphine chalcogenides. The oxidative electrochemistries of the transition metal complexes occur at more positive potentials than the free ligands. While a similar positive shift is seen for the oxidative electrochemistries of the phosphine chalcogenides, the oxidation of the phosphine selenides does not occur at the iron center, but rather oxidation occurs at the selenium atoms.

The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

NASA Astrophysics Data System (ADS)

Platt, Andrew W. G.; Singh, Kuldip

2016-05-01

The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

The effect factors of potassium dihydrogen phosphate crystallization in aqueous solution

NASA Astrophysics Data System (ADS)

Zhou, Cun; Sun, Fei; Liu, Xuzhao

2017-01-01

The effects of cooling rate and pH on the potassium dihydrogen phosphate crystallization process were studied by means of batch crystallization process. The experiment shows that with the increase of cooling rate, the metastable zone width increase and the induction period decrease. When the pH is 3.0, the metastable zone width and induction period are both the minimum, while the crystallization rate is the highest. The crystallization products were characterized by scanning election microscope. Potassium Dihydrogen Phosphate (KDP) is a kind of excellent nonlinear optical materials, and belongs to tetragonal system, and ideal shape is aggregate of tetragonal prism and tetragonal dipyramid, the (100) cone is alternating accumulation by double positive ions and double negative ions [1-4]. The crystals of aqueous solution method to grow have large electro-optical nonlinear coefficient and high loser-damaged threshold, and it is the only nonlinear optical crystal could be used in inertial confinement fusion (ICF), KDP crystals are the ideal system to study the native defects of complex oxide insulating material [5-7]. With the development of photovoltaic technology, KDP crystals growth and performance have become a research focus worldwide [8, 9]. The merits of the crystallization process directly affect the quality of KDP products, so the study of the effect of crystallization conditions has an important significance on industrial production. This paper studied the change rule of metastable zone width, induction period, crystallization rate and particle size distribution in crystal process, and discussed the technical condition of KDP crystallization.

Synthesis, selected coordination chemistry and extraction behavior of a (phosphinoylmethyl)pyridyl N-oxide-functionalized ligand based upon a 1,4-diazepane platform

DOE PAGES

Ouizem, Sabrina; Rosario Amorin, Daniel; Dickie, Diane A.; ...

2015-05-09

For syntheses of new multidentate chelating ligands ((6,6'4(1,4-diazepane-1,4-diyl)bis(methylene))bis(pyridine-6,2-diyl))bis(methylene))bis(diphenylphosphine oxide) (2) and 6,6'-((1,4-diazepane1,4-diyl)bis(methylene))bis(2-((diphenylphosphoryl)methyl)pyridine 1-oxide) (3), based upon a 1,4-diazepane platform functionalized with 2-(diphenylphosphinoylmethyl)pyridine P-oxide and 2-(diphenylphosphinoylmethyl)pyridine NP-dioxide fragments, respectively, the results are reported. Our results from studies of the coordination chemistry of the ligands with selected lanthanide nitrates and Cu(BF 4)(2) are outlined, and crystal structures for two complexes, [Cu(2)](BF 4) 2 and [Cu(3)](BF 4) 2, are described along with survey Eu(III) and Am(III) solvent extraction analysis, for 3.

Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

PubMed

Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

2013-01-07

We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

Optical monitoring of gases with cholesteric liquid crystals.

PubMed

Han, Yang; Pacheco, Katherine; Bastiaansen, Cees W M; Broer, Dirk J; Sijbesma, Rint P

2010-03-10

A new approach to optical monitors for gases is introduced using cholesteric liquid crystals doped with reactive chiral compounds. The approach is based on cholesteric pitch length changes caused by a change in helical twisting power (HTP) of the chiral dopants upon reaction with the analyte. The concept is demonstrated for monitoring carbon dioxide via reversible carbamate formation and for oxygen using the irreversible oxidation of a chiral dithiol to a disulfide. Monitoring of CO(2) was achieved by doping a commercial cholesteric liquid crystalline mixture (E7) with 1.6% mol of the 1:1 complex of an optically pure diamine with a TADDOL derivative. Upon exposure to carbon dioxide, the reflection band of a thin film of the mixture shifted from 637 to 495 nm as a consequence of dissociation of the complex after carbamate formation of the diamine. An O(2) monitor was obtained by doping E7 with a chiral binaphthyl dithiol derivative and a nonresponsive codopant. The reflection band of the oxygen monitor film changed from 542 to 600 nm, due to the conformational change accompanying oxidation of the dithiol to disulfide. These monitoring mechanisms hold promise for application in smart packaging, where carbon dioxide and oxygen are of special interest because of their roles in food preservation.

Damage and recovery of skin barrier function after glycolic acid chemical peeling and crystal microdermabrasion.

PubMed

Song, Ji Youn; Kang, Hyun A; Kim, Mi-Yeon; Park, Young Min; Kim, Hyung Ok

2004-03-01

Superficial chemical peeling and microdermabrasion have become increasingly popular methods for producing facial rejuvenation. However, there are few studies reporting the skin barrier function changes after these procedures. To evaluate objectively the degree of damage visually and the time needed for the skin barrier function to recover after glycolic acid peeling and aluminum oxide crystal microdermabrasion using noninvasive bioengineering methods. Superficial chemical peeling using 30%, 50%, and 70% glycolic acid and aluminum oxide crystal microdermabrasion were used on the volar forearm of 13 healthy women. The skin response was measured by a visual observation and using an evaporimeter, corneometer, and colorimeter before and after peeling at set time intervals. Both glycolic acid peeling and aluminum oxide crystal microdermabrasion induced significant damage to the skin barrier function immediately after the procedure, and the degree of damage was less severe after the aluminum oxide crystal microdermabrasion compared with glycolic acid peeling. The damaged skin barrier function had recovered within 24 hours after both procedures. The degree of erythema induction was less severe after the aluminum oxide crystal microdermabrasion compared with the glycolic acid peeling procedure. The degree of erythema induced after the glycolic acid peeling procedure was not proportional to the peeling solution concentration used. The erythema subsided within 1 day after the aluminum oxide crystal microdermabrasion procedure and within 4 days after the glycolic acid peeling procedure. These results suggest that the skin barrier function is damaged after the glycolic acid peeling and aluminum oxide crystal microdermabrasion procedure but recovers within 1 to 4 days. Therefore, repeating the superficial peeling procedure at 2-week intervals will allow sufficient time for the damaged skin to recover its barrier function.

DFT study of the active site of the XoxF-type natural, cerium-dependent methanol dehydrogenase enzyme.

PubMed

Bogart, Justin A; Lewis, Andrew J; Schelter, Eric J

2015-01-19

Rare-earth metal cations have recently been demonstrated to be essential co-factors for the growth of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV. A crystal structure of the rare-earth-dependent methanol dehydrogenase (MDH) includes a cerium cation in the active site. Herein, the Ce-MDH active site has been analyzed through DFT calculations. The results show the stability of the Ce(III)-pyrroloquinoline quinone (PQQ) semiquinone configuration. Calculations on the active oxidized form of this complex indicate a 0.81 eV stabilization of the PQQ(0) LUMO at cerium versus calcium, supporting the observation that the cerium cation in the active site confers a competitive advantage to Methylacidiphilum fumariolicum SolV. Using reported aqueous electrochemical data, a semi-empirical correlation was established based on cerium(IV/III) redox potentials. The correlation allowed estimation of the cerium oxidation potential of +1.35 V versus saturated calomel electrode (SCE) in the active site. The results are expected to guide the design of functional model complexes and alcohol-oxidation catalysts based on lanthanide complexes of biologically relevant quinones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Various

This report covers the following titles: (1) Fertility and litter size of normally ovulated and artificially ovulated mice; (2) Further studies on sterility produced in male mice by deuterium oxide; (3) Planarian disaggregation; (4) Uptake of organic compounds by planarians. II; (5) Effects of environmental complexity and training on acetylcholinesterase and cholinesterase activity in rat brain; (6) Effects of environmental complexity and training on brain chemistry and anatomy among mature rats; (7) Improvements in paper chromatographic techniques for labeled cell extracts; (8) measurement and adjustment of pH in small volumes of solutions; (9) Carbon-14 and Nitrogen-15 tracer studies of aminomore » acid synthesis during photosynthesis by Chlorella Pyrenoidosa; (10) Photosynthesis of {sup 14}C-labeled protein from {sup 14}CO{sub 2} by Chlorella; (11) Further studies on carboxydismutase; (12) Electron microscopy of chlorophyll a crystals; (13) The possible role of chromanyl phosphates in oxidative and photosynthetic phosphorylation; (14) Oxidation-reductions of some coenzymes; (15) Preparation of some [{sup 14}C] labeled substances: glucose-6-phosphate, fructose-6-phosphate, 6-phosphogluconic acid, pyruvic acid, and succinic acid; (16) attempt to synthesize high molecular weight polynucleotides using Schramm's purely chemical method; and (17) Optical properties of some dye-polyanion complexes.« less

Metastable electronic states in uranium tetrafluoride

DOE PAGES

Miskowiec, Andrew J.

2018-04-03

Here, the DFT+ U approach, where U is the Hubbard-like on-site Coulomb interaction, has successfully been used to improve the description of transition metal oxides and other highly correlated systems, including actinides. The secret of the DFT+ U approach is the breaking of d or f shell orbital degeneracy and adding an additional energetic penalty to non-integer occupation of orbitals. A prototypical test case, UO 2, benefits from the + U approach whereby the bare LDA method predicts UO 2 to be a ferromagnetic metal, whereas LDA+ U correctly predicts UO 2 to be insulating. However, the concavity of themore » energetic penalty in the DFT+ U approach can lead to a number of convergent “metastable” electronic configurations residing above the ground state. Uranium tetrafluoride (UF 4) represents a more complex analogy to UO 2 in that the crystal field has lower symmetry and the unit cell contains two symmetrically distinct U atoms. We explore the metastable states in UF 4 using several different methods of selecting initial orbital occupations. Two methods, a “pre-relaxation” method wherein an initial set of orbital eigenvectors is selected via the self-consistency procedure and a crystal rotation method wherein the x, y, z axes are brought into alignment with the crystal field, are explored. We show that in the case of UF 4, which has non-collinearity between its crystal axes and the U atoms' crystal field potentials, the orbital occupation matrices are much more complex and should be analyzed using a novel approach. In addition to demonstrating a complex landscape of metastable electronic states, UF 4 also shows significant hybridization in U–F bonding, which involves non-trivial contributions from s, p, d, and f orbitals.« less

Metastable electronic states in uranium tetrafluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miskowiec, Andrew J.

Here, the DFT+ U approach, where U is the Hubbard-like on-site Coulomb interaction, has successfully been used to improve the description of transition metal oxides and other highly correlated systems, including actinides. The secret of the DFT+ U approach is the breaking of d or f shell orbital degeneracy and adding an additional energetic penalty to non-integer occupation of orbitals. A prototypical test case, UO 2, benefits from the + U approach whereby the bare LDA method predicts UO 2 to be a ferromagnetic metal, whereas LDA+ U correctly predicts UO 2 to be insulating. However, the concavity of themore » energetic penalty in the DFT+ U approach can lead to a number of convergent “metastable” electronic configurations residing above the ground state. Uranium tetrafluoride (UF 4) represents a more complex analogy to UO 2 in that the crystal field has lower symmetry and the unit cell contains two symmetrically distinct U atoms. We explore the metastable states in UF 4 using several different methods of selecting initial orbital occupations. Two methods, a “pre-relaxation” method wherein an initial set of orbital eigenvectors is selected via the self-consistency procedure and a crystal rotation method wherein the x, y, z axes are brought into alignment with the crystal field, are explored. We show that in the case of UF 4, which has non-collinearity between its crystal axes and the U atoms' crystal field potentials, the orbital occupation matrices are much more complex and should be analyzed using a novel approach. In addition to demonstrating a complex landscape of metastable electronic states, UF 4 also shows significant hybridization in U–F bonding, which involves non-trivial contributions from s, p, d, and f orbitals.« less

Effects of Pedogenic Fe Oxides on Soil Aggregate-Associated Carbon

NASA Astrophysics Data System (ADS)

Asefaw Berhe, A.; Jin, L.

2017-12-01

Carbon sequestration is intimately related to the soil structure, mainly soil aggregate dynamics. Carbon storage in soil aggregates has been recognized as an important carbon stabilization mechanism in soils. Organic matter and pedogenic Fe oxides are major binding agents that facilitate soil aggregate formation and stability. However, few studies have investigated how different forms of pedogenic Fe oxides can affect soil carbon distribution in different aggregate-size fractions. We investigated sequentially extracted pedogenic Fe oxides (in the order of organically complexed Fe extracted with sodium pyrophosphate, poorly-crystalline Fe oxides extracted with hydroxylamine hydrochloride, and crystalline Fe oxides extracted with dithionite hydrochloride) and determined the amount and nature of C in macroaggregates (2-0.25mm), microaggregates (0.25-0.053mm), and two silt and clay fractions (0.053-0.02mm, and <0.02mm) in Musick soil from Sierra Nevada mountain in California. We also determined how pedogenic Fe oxides affect soil carbon distribution along soil depth gradients. Findings of our study revealed that the proportion of organic matter complexed Fe decreased, but the proportion of crystalline Fe increased with increasing soil depths. Poorly crystalline Fe oxides (e.g. ferrihydrite) was identified as a major Fe oxide in surface soil, whereas crystalline Fe oxides (e.g. goethite) were found in deeper soil layers. These results suggest that high concentration of organic matter in surface soil suppressed Fe crystallization. Calcium cation was closely related to the pyrophosphate extractable Fe and C, which indicates that calcium may be a major cation that contribute to the organic matter complexed Fe and C pool. Increasing concentrations of extractable Fe and C with decreasing aggregate size fractions also suggests that Fe oxides play an important role in formation and stability of silt and clay fractions, and leading to further stabilization of carbon in soil. Our findings provide mechanistic understanding of how pedogenic Fe oxides play important role in carbon stabilization in different aggregate-size fractions in soil.

Heat-shock properties in yttrium-oxide films synthesized from metal-ethylenediamine tetraacetic acid complex through flame-spray apparatus

NASA Astrophysics Data System (ADS)

Xin, D. Y.; Komatsu, Keiji; Abe, Keita; Costa, Takashi; Ikeda, Yutaka; Nakamura, Atsushi; Ohshio, Shigeo; Saitoh, Hidetoshi

2017-03-01

Recently, a new deposition technique using a metal-ethylenediamine tetraacetic acid (EDTA) complex has been developed. In this study, the heat-shock properties of metal-oxide films synthesized from a metal-EDTA complex were investigated. Y2O3 films were synthesized on stainless-steel (SUS) substrate from EDTA•Y•H through the combustion of H2-O2 gas. A cyclic heat-shock test was conducted on the fabricated Y2O3 films through exposure to the H2-O2 flame. The existence of Y2O3 crystals was confirmed. Surface cracks or damages were not observed in the samples after the cyclic thermal test. Although the number of cross-sectional cracks, crack lengths, and cracks per unit area was increased by the heat shock, delaminations were not observed in the Y2O3 films. The results show that the prepared Y2O3 films have high thermal-shock resistance and are suitable for use as thermal barrier coatings.

Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center.

PubMed

Chu, Terry; Boyko, Yaroslav; Korobkov, Ilia; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

2016-09-06

The aluminum(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis(phenyl sulfide) complex NacNacAl(SPh)2 (2) and alkyl thiolate aluminum complex NacNacAlEt(SEt) (3). As well, reaction of 1 with tetraphenyl diphosphine furnishes the bis(diphenyl phosphido) complex NacNacAl(PPh2)2 (4). Production of 3 and 4 are the first examples of C(sp(3))-S and R2P-PR2 activation by a main-group element complex. All three complexes were characterized by multinuclear NMR spectroscopy and X-ray crystal structure analysis. Furthermore, a variable-temperature NMR spectroscopic study was undertaken on 4 to study its dynamic behavior in solution.

Plagioclase zonation styles in hornblende gabbro inclusions from Little Glass Mountain, Medicine Lake volcano, California: Implications for fractionation mechanisms and the formation of composition gaps

USGS Publications Warehouse

Brophy, J.G.; Dorais, M.J.; Donnelly-Nolan, J.; Singer, B.S.

1997-01-01

The rhyolite of Little Glass Mountain (73-74% SiO2) is a single eruptive unit that contains inclusions of quenched andesite liquid (54-61% SiO2) and partially crystalline cumulate hornblende gabbro (53-55% SiO2). Based on previous studies, the quenched andesite inclusions and host rhyolite lava are related to one another through fractional crystallization and represent an example of a fractionation-generated composition gap. The hornblende gabbros represent the cumulate residue associated with the rhyolite-producing and composition gap-forming fractionation event. This study combines textural (Nomarski Differential Interference Contrast, NDIC, imaging), major element (An content) and trace element (Mg, Fe, Sr, K, Ti, Ba) data on the style of zonation of plagioclase crystals from representative andesite and gabbro inclusions, to assess the physical environment in which the fractionation event and composition gap formation took place. The andesite inclusions (54-61% SiO2) are sparsely phyric with phenocrysts of plagioclase, augite and Fe-oxide??olivine, +/-orthopyroxene, +/-hornblende set within a glassy to crystalline matrix. The gabbro cumulates (53-55% SiO2) consist of an interconnected framework of plagioclase, augite, olivine, orthopyroxene, hornblende and Fe-oxide along with highly vesicular interstitial glass (70-74% SiO2). The gabbros record a two-stage crystallization history of plagioclase + olivine + augite (Stage I) followed by plagioclase+orthopyroxene + hornblende + Fe-oxide (Stage II). Texturally, the plagioclase crystals in the andesite inclusions are characterized by complex, fine-scale oscillatory zonation and abundant dissolution surfaces. Compositionally (An content) the crystals are essentially unzoned from core-to-rim. These features indicate growth within a dynamic (convecting?), reservoir of andesite magma. In contrast, the plagioclase crystals in the gabbros are texturally smooth and featureless with strong normal zonation from An74 at the core to around An30, K, and Ba abundances increase and Mg abundances decrease steadily towards the rim. Ti, Fe, and Sr abundances increase and then decrease towards the rim. The trace element variations are fully consistent with the two-stage crystallization sequence inferred from the gabbro mineralogy. These results indicate progressive closed-system in situ crystallization in a quiescent magmatic boundary layer environment located along the margins of the andesite magma body. The fractional crystallization that generated the host rhyolite lava is one of inward solidification of a crystallizing boundary layer followed by melt extraction and accumulation of highly evolved interstitial liquid. This mechanism explains the formation of the composition gap between parental andesite and rhyolite magma compositions.

Interfacial charging phenomena of aluminum (hydr)oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiemstra, T.; Yong, H.; Van Riemsdijk, W.H.

1999-08-31

The interfacial charging of Al(OH){sub 3} (gibbsite and bayerite) and Al{sub 2}O{sub 3} has been studied. For Al(OH){sub 3} it can be shown that the very strong variation in charging behavior for different preparations is related to the relative presence of differently reacting crystal planes. The edge faces of the hexagonal gibbsite crystals are proton reactive over the whole pH range, in contrast to the 001 plane, which is mainly uncharged below pH = 10. On this 001 face only doubly coordinated surface groups are found, in contrast to the edges which also have singly coordinated surface groups. The resultsmore » are fully in agreement with the predictions of the Multi site complexation (MUSIC) model. The proton adsorption, electrolyte ion adsorption, and shift of the IEP of gibbsite and aluminum oxide have been modeled simultaneously. For gibbsite, the ion pair formation of Na is larger than that of Cl, as is evidenced by modeling the experimentally observed upward shift on the IEP and charge reversal at high electrolyte concentrations. All these experimental results can be satisfactorily modeled with the MUSIC model, including the experimental surface potential of aluminum oxide (ISFET).« less

Superconductivity in Russia: Update and prospects

NASA Technical Reports Server (NTRS)

Ozhogin, V.

1995-01-01

The research projects and new technological developments that have occured in Russia are highlighted in this document. Some of the research discussed includes: x-ray structure analysis of YBCO superconducting single crystals and accompanying phase transformations; the role of electron-electron interaction in High Temperature Superconductors (HTSC); the formation of Cooper pairs in crystals; the synthesis and research on a new family of superconductors based on complex copper and mercury oxides (HgBa2CuO4 + alpha and HgBa2CaCu2O6 + alpha); methods for the extraction of higher (up to C200) fullerenes and metalfullerenides has been developed; and process of production of Josephson junctions and development of SQUID's.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corbey, Jordan F.; Rapko, Brian M.; Wang, Zheming

Abstract The crystal structures of americium species containing a common multi-functional phosphine oxide ligand, reported for its ability to extract f elements from acidic solutions, namely 2,6-[Ph2P(O)CH2]2C5H3-NO, L, have finally been determined after over three decades of separations studies involving these species and their surrogates. The molecular compounds Am(L)(NO3)3, Am 1:1, and [Am(L)2(NO3)][NO3]2, Am 2:1, along with their neodymium and europium analogs were synthesized and characterized using single-crystal X-ray crystallography, attenuated total reflectance Fourier transform infrared (ATR) spectroscopy and luminescence spectroscopy to provide a comprehensive comparison with new and known analogous complexes.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

Radiative heat transport during the vertical Bridgman growth of oxide single crystals: slabs versus cylinders

NASA Astrophysics Data System (ADS)

Virozub, Alexander; Brandon, Simon

1998-10-01

Internal radiative heat transport in oxide crystals during their growth via the vertical Bridgman technique is known to promote severely deflected melt/crystal interface shapes. These highly curved interfaces are likely to encourage unwanted phenomena such as inhomogeneous distribution of impurities in the solidified crystalline material. Past computational analyses of oxide growth systems have mostly been confined to cylindrical geometries. In this letter a two-dimensional finite-element model, describing the growth of slab-shaped oxide crystals via the vertical Bridgman technique, is presented; internal radiative heat transport through the transparent crystalline phase is accounted for in the formulation. Comparison with calculations of cylindrical-shaped crystal growth systems shows a strong dependence of thermal fields and of melt/crystal interface shapes on the crystal geometry. Specifically, the interface position is strongly shifted toward the hot zone and its curvature dramatically increases in slab-shaped systems compared to what is observed in cylindrical geometries. This significant qualitative difference in interface shapes is shown to be linked to large quantitative differences in values of the viewing angle between the hot melt/crystal interface and the cold part of the crucible.

Oxidation and reduction in irradiated binary crystals of resorcinol and progesterone

NASA Astrophysics Data System (ADS)

Box, Harold C.; Budzinski, Edwin E.

1985-12-01

The binary single crystals of resorcinol and progesterone were x-irradiated at 4.2 K. The semiquinone of resorcinol was generated by radiation induced oxidation. The oxidation and reduction products were identified from ESR and ENDOR measurements. (AIP)

Control of optical properties of YAG crystals by thermal annealing

NASA Astrophysics Data System (ADS)

Tkachenko, S.; Arhipov, P.; Gerasymov, I.; Kurtsev, D.; Vasyukov, S.; Nesterkina, V.; Shiran, N.; Mateichenko, P.; Sidletskiy, O.

2018-02-01

Optical properties of YAG crystals grown and annealed under different atmosphere conditions have been compared. Simultaneously we have registered the surface composition of crystals and content of basic admixtures in the crystals grown under the reducing conditions. Unlike YAG grown under weakly oxidizing conditions in Ir crucibles and bleached under oxidizing annealing, YAGMo crystals grown in Mo crucibles under reducing Ar + CO atmosphere can be bleached by both oxidizing and reducing thermal annealing. The bleaching of YAGMo is not reversed by further annealing under any available conditions. Mechanisms of this phenomenon have been discussed, including a possible role of admixtures in elimination of color centers in YAG grown under the reducing conditions.

Thermal Shock Behavior of Single Crystal Oxide Refractive Concentrators for High Temperatures Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Choi, Sung R.; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium-aluminum-garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) have been considered as refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermal mechanical reliability of the oxide components in severe thermal environments during space mission sun/shade transitions is of great concern. In this paper, critical mechanical properties of these oxide crystals are determined by the indentation technique. Thermal shock resistance of the oxides is evaluated using a high power CO, laser under high temperature-high thermal gradients. Thermal stress fracture behavior and failure mechanisms of these oxide materials are investigated under various temperature and heating conditions.

Method for enhancement of useful luminescence from vacancy defects in refractory oxides for tunable lasers

DOEpatents

Chen, Yok

1990-01-01

Refractory oxide crystals suitable for use in tunable lasers and a method for preparing the same are provided. The crystals are characterized by high quantum efficiency, high thermal stability, good crystal transparency, and a high percentage of useful luminescence. The method for preparation of the crystals involves removing substantially all the hydrogen, thermochemically reducing the crystal's oxygen content to produce oxygen (anion) vacancy defects, and subsequently irradiating the crystal with electrons to inactivate trace H.sup.- ions so that an increased amount of short lived F.sup.+ luminescence is produced when the crystal is optically excited.

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

NASA Astrophysics Data System (ADS)

Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

2015-01-01

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln2(phen)2(SO4)3(H2O)2]n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO4 2 - anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic-inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.

X-ray photoelectron spectroscopic evidence for bacteria-enhanced dissolution of hornblende

NASA Astrophysics Data System (ADS)

Kalinowski, B. E.; Liermann, L. J.; Brantley, S. L.; Barnes, A.; Pantano, C. G.

2000-04-01

An Arthrobacter species capable of extracting Fe from hornblende was isolated from a soil from the Adirondacks, NY (USA). This bacteria isolate, used in batch experiments with hornblende, accelerated the release of Fe from hornblende without measurably affecting Al release. The isolate produces both low molecular weight organic acids (LMWOA) and a catecholate siderophore. Polished hornblende (glass and crystal) discs were analyzed with X-ray photoelectron spectroscopy (XPS) before and after incubation with growing Arthrobacter sp. to investigate whether the bacteria caused a distinguishable chemical signature on the upper 100 Å of mineral surface. After removal of the arthrobacter grown on hornblende crystal or glass substrates using lysozyme, XPS revealed surface depletion of Fe for samples grown for several days in buffered (crystal) and unbuffered (crystal and glass) media. Fe/Si ratios of hornblende surfaces dissolved under biotic conditions are significantly lower than Fe/Si ratios on surfaces dissolved under abiotic conditions for similar amounts of time. Enhanced Fe release and the formation of Fe-depleted surfaces is inferred to be caused by catechol complexation at the mineral surface. Because natural siderophore was not isolated in sufficient quantities to run bacteria-free leaching experiments, parallel investigations were run with a commercially available siderophore (desferrioxamine B). Desferrioxamine B was observed to enhance release of Fe, Si, and Al from hornblende both with and without added bacteria. Formation of desferrioxamine-Fe surface complexes were probed by studying the multiple splitting and shift in intensities of the N 1s line analyzed by XPS on siderophore ± Fe on gold surfaces and siderophore + hornblende crystal surfaces. Based upon the observed formation of an hydroxamate (desferrioxamine) surface complex on hornblende, we infer that catecholate siderophores, such as those produced by the arthrobacter, also complex on the hornblende surface. Surface complexation is favored because of the extremely high association constants for siderophore + Fe(III). X-ray photoelectron spectroscopic data is therefore consistent with a model wherein enhanced Fe release by these bacteria or desferrioxamine B is caused by Fe-siderophore complexation at the silicate surface. Such complexation presumably weakens bonds between the Fe and the oxide lattice, causing enhanced Fe leaching and an Fe-depleted surface. Some leaching may also be due to LMWOA, although this is interpreted to be of secondary importance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ulin, V. P.; Ulin, N. V.; Soldatenkov, F. Yu., E-mail: f.soldatenkov@mail.ioffe.ru

The interaction of heavily doped p- and n-type Si crystals with hydrofluoric acid in the dark with and without contact with metals having greatly differing work functions (Ag and Pd) is studied. The dependences of the dissolution rates of Si crystals in HF solutions that contain oxidizing agents with different redox potentials (FeCl{sub 3}, V{sub 2}O{sub 5} and CrO{sub 3}) on the type and level of silicon doping are determined. Analysis of the experimental data suggests that valence-band holes in silicon are not directly involved in the anodic reactions of silicon oxidation and dissolution and their generation in crystals doesmore » not limit the rate of these processes. It is also shown that the character and rate of the chemical process leading to silicon dissolution in HF-containing electrolytes are determined by the interfacial potential attained at the semiconductor–electrolyte interface. The mechanism of electrochemical pore formation in silicon crystals is discussed in terms of selfconsistent cooperative reactions of nucleophilic substitution between chemisorbed fluorine anions and coordination- saturated silicon atoms in the crystal subsurface layer. A specific feature of these reactions for silicon crystals is that vacant nonbonding d{sup 2}sp{sup 3} orbitals of Si atoms, associated with sixfold degenerate states corresponding to the Δ valley of the conduction band, are involved in the formation of intermediate complexes. According to the suggested model, the pore-formation process spontaneously develops in local regions of the interface under the action of the interfacial potential in the adsorption layer and occurs as a result of the detachment of (SiF{sub 2}){sub n} polymer chains from the crystal. Just this process leads to the preferential propagation of pores along the <100> crystallographic directions. The thermodynamic aspects of pore nucleation and the effect of the potential drop across the interface, conduction type, and free-carrier concentration in the crystal on the pore size and structure are discussed. The concepts developed in the study can consistently account for experimental facts characterizing the etching of silicon crystals with various electrical parameters under various conditions providing the anodic polarization of crystals in HF-containing solutions.« less

Development of Host Crystals for Ce(+3) Blue and Blue-Green Solid-State Lasers.

DTIC Science & Technology

1982-07-01

oxides ............ 9 Syntheses of LaA1O3 and Lal-xScxO3 . . . . . . . . . . . . . .. . . . . . 10 Syntheses of Oxides from Oxalates ...oxidation of Ce+ 3 . The crystal growth of LaA1O3 has been reported from the melt, hydrothermally , and both LaA103 and Th0 2 from fluxes. ’Va Fa...temperature and/or flux composition may be necessary to produce this oxide. Syntheses of Oxides from Oxalates Syntheses of oxides by the oxidative

Cleavage of nicotinamide adenine dinucleotide by the ribosome-inactivating protein from Momordica charantia.

PubMed

Vinkovic, M; Dunn, G; Wood, G E; Husain, J; Wood, S P; Gill, R

2015-09-01

The interaction of momordin, a type 1 ribosome-inactivating protein from Momordica charantia, with NADP(+) and NADPH has been investigated by X-ray diffraction analysis of complexes generated by co-crystallization and crystal soaking. It is known that the proteins of this family readily cleave the adenine-ribose bond of adenosine and related nucleotides in the crystal, leaving the product, adenine, bound to the enzyme active site. Surprisingly, the nicotinamide-ribose bond of oxidized NADP(+) is cleaved, leaving nicotinamide bound in the active site in the same position but in a slightly different orientation to that of the five-membered ring of adenine. No binding or cleavage of NADPH was observed at pH 7.4 in these experiments. These observations are in accord with current views of the enzyme mechanism and may contribute to ongoing searches for effective inhibitors.

Hibonite: Crystal Chemistry and Origin of Blue Coloration in Meteoritic Assemblages

NASA Technical Reports Server (NTRS)

Burns, R. G.; Burns, V. M.

1985-01-01

The blue color and optical spectra of hibonite, a common constituent of refractory inclusions in carbonaceous chondrites, are discussed. Because they may be manifestations of exotic cation species stabilized in unusual coordination sites in the hibonite crystalstructure. Hibonite, ideally CaAl12O19, is conducive to atomic substitution of host Ca2+ and Al3+ ions by a variety of lanthanide and first series transition elements. The latter cations are responsible for the colors of many rock-forming minerals as a result of intraelectronic or intervalence transitions. The visible-region spectra of most oxide and silicate minerals are generally well understood. Assignments of absorption bands in meteoritic hibonite optical spectra due to uncertainties of cation valencies and complexities in the crystal structure are examined. The crystal chemistry of hibonite is reviewed, Mossbauer spectral measurements of iron-bearing hibonite and electronic transitions that may be responsible for the blue coloration of meteoritic hibonites are discussed.

Spatially resolved ultrafast magnetic dynamics initiated at a complex oxide heterointerface

DOE PAGES

Forst, M.; Wilkins, S. B.; Caviglia, A. D.; ...

2015-07-06

Static strain in complex oxide heterostructures 1,2 has been extensively used to engineer electronic and magnetic properties at equilibrium 3. In the same spirit, deformations of the crystal lattice with light may be used to achieve functional control across heterointerfaces dynamically 4. Here, by exciting large-amplitude infrared-active vibrations in a LaAlO 3 substrate we induce magnetic order melting in a NdNiO 3 film across a heterointerface. Femtosecond resonant soft X-ray diffraction is used to determine the spatiotemporal evolution of the magnetic disordering. We observe a magnetic melt front that propagates from the substrate interface into the film, at a speedmore » that suggests electronically driven motion. Lastly, light control and ultrafast phase front propagation at heterointerfaces may lead to new opportunities in optomagnetism, for example by driving domain wall motion to transport information across suitably designed devices.« less

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

Late-stage magmatic to deuteric/metasomatic accessory minerals from the Cerro Boggiani agpaitic complex (Alto Paraguay Alkaline Province)

NASA Astrophysics Data System (ADS)

Comin-Chiaramonti, Piero; Renzulli, Alberto; Ridolfi, Filippo; Enrich, Gaston E. R.; Gomes, Celso B.; De Min, Angelo; Azzone, Rogério G.; Ruberti, Excelso

2016-11-01

This work describes rare accessory minerals in volcanic and subvolcanic silica-undersaturated peralkaline and agpaitic rocks from the Permo-Triassic Cerro Boggiani complex (Eastern Paraguay) in the Alto Paraguay Alkaline Province. These accessory phases consist of various minerals including Th-U oxides/silicates, Nb-oxide, REE-Sr-Ba bearing carbonates-fluorcarbonates-phosphates-silicates and Zr-Na rich silicates. They form a late-stage magmatic to deuteric/metasomatic assemblage in agpaitic nepheline syenites and phonolite dykes/lava flows made of sodalite, analcime, albite, fluorite, calcite, ilmenite-pyrophanite, titanite and zircon. It is inferred that carbonatitic fluids rich in F, Na and REE percolated into the subvolcanic system and metasomatically interacted with the Cerro Boggiani peralkaline and agpaitic silicate melts at the thermal boundary layers of the magma chamber, during and shortly after their late-stage magmatic crystallization and hydrothermal deuteric alteration.

Magnesium oxide doping reduces acoustic wave attenuation in lithium metatantalate and lithium metaniobate crystals

NASA Technical Reports Server (NTRS)

Croft, W.; Damon, R.; Kedzie, R.; Kestigian, M.; Smith, A.; Worley, J.

1970-01-01

Single crystals of lithium metatantalate and lithium metaniobate, grown from melts having different stoichiometries and different amounts of magnesium oxide, show that doping lowers temperature-independent portion of attenuation of acoustic waves. Doped crystals possess optical properties well suited for electro-optical and photoelastic applications.

Expression, purification, crystallization and preliminary X-ray crystallographic analysis of L-lactate dehydrogenase and its H171C mutant from Bacillus subtilis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanfeng; Gao, Xiaoli

2012-08-31

L-Lactate dehydrogenase (LDH) is an important enzyme involved in the last step of glycolysis that catalyzes the reversible conversion of pyruvate to L-lactate with the simultaneous oxidation of NADH to NAD{sup +}. In this study, wild-type LDH from Bacillus subtilis (BsLDH-WT) and the H171C mutant (BsLDH-H171C) were expressed in Escherichia coli and purified to near-homogeneity. BsLDH-WT was crystallized in the presence of fructose 1,6-bisphosphate (FBP) and NAD{sup +} and the crystal diffracted to 2.38 {angstrom} resolution. The crystal belonged to space group P3, with unit-cell parameters a = b = 171.04, c = 96.27 {angstrom}. BsLDH-H171C was also crystallized asmore » the apoenzyme and in complex with NAD{sup +}, and data sets were collected to 2.20 and 2.49 {angstrom} resolution, respectively. Both BsLDH-H171C crystals belonged to space group P3, with unit-cell parameters a = b = 133.41, c = 99.34 {angstrom} and a = b = 133.43, c = 99.09 {angstrom}, respectively. Tetramers were observed in the asymmetric units of all three crystals.« less

Platinum(II) diimine complexes with catecholate ligands bearing imide electron-acceptor groups: synthesis, crystal structures, (spectro)electrochemical and EPR studies, and electronic structure.

PubMed

Shavaleev, Nail M; Davies, E Stephen; Adams, Harry; Best, Jonathan; Weinstein, Julia A

2008-03-03

A series of catechols with attached imide functionality (imide = phthalimide PHT, 1,8-naphthalimide NAP, 1,4,5,8-naphthalenediimide NDI, and NAP-NDI) has been synthesized and coordinated to the Pt (II)(bpy*) moiety, yielding Pt(bpy*)(cat-imide) complexes (bpy* = 4,4'-di- tert-butyl-2,2'-bipyridine). X-ray crystal structures of PHT and NAP complexes show a distorted square-planar arrangement of ligands around the Pt center. Both complexes form "head-to-tail" dimers in the solid state through remarkably short unsupported Pt...Pt contacts of 3.208 (PHT) and 3.378 A (NAP). The Pt(bpy*)(cat-imide) complexes are shown to combine optical (absorption) and electrochemical properties of the catecholate (electron-donor) and imide (electron-acceptor) groups. The complexes show a series of reversible reduction processes in the range from -0.5 to -1.9 V vs Fc (+)/Fc, which are centered on either bpy* or imide groups, and a reversible oxidation process at +0.07 to +0.14 V, which is centered on the catecholate moiety. A combination of UV-vis absorption spectroscopy, cyclic voltammetry, UV-vis spectroelectrochemistry, and EPR spectroscopy has allowed assignment of the nature of frontier orbitals in Pt(bpy*)(cat-imide) complexes. The HOMO in Pt(bpy*)(cat-imide) is centered on the catechol ligand, while the LUMO is localized either on bpy* or on the imide group, depending on the nature of the imide group involved. Despite the variations in the nature of the LUMO, the lowest-detectable electronic transition in all Pt(bpy*)(cat-imide) complexes has predominantly ligand-to-ligand (catechol-to-diimine) charge-transfer nature (LLCT) and involves a bpy*-based unoccupied molecular orbital in all cases. The LLCT transition in all Pt(bpy*)(cat-imide) complexes appears at 530 nm in CH2Cl2 and is strongly negatively solvatochromic. The energy of this transition is remarkably insensitive to the imide group present, indicating lack of electronic communication between the imide and the catechol moieties within the cat-imide ligand. The high extinction coefficient, approximately 6 x 10(3) L mol(-1) cm(-1) of this predominantly LLCT transition is the result of the Pt orbital contribution, as revealed by EPR spectroscopy of the complexes in various redox states. The CV profile of the oxidation process of Pt(bpy*)(cat-imide) in CH2Cl2 and DMF is concentration dependent, as was shown for NDI and PHT complexes as typical examples. Oxidation appears as a simple diffusion-limited process at low concentrations, with an increasing anodic-to-cathodic peak separation eventually resolving as two independent consecutive waves as the concentration of the complex increases. It is suggested that aggregation of the complexes in the diffusion layer in the course of oxidation is responsible for the observed concentration dependence. Overall, the Pt(bpy*)(cat-imide) complexes are electrochromic compounds in which a series of stepwise reversible redox processes in the potential range from 0.2 to -2 V (vs Fc (+)/Fc) leads to tuneable absorbencies between 300 and 850 nm.

Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

NASA Astrophysics Data System (ADS)

Al-Rashdi, Kamelah S.; Babgi, Bandar A.; Sahin, Cigdem; Eltayeb, Naser E.; Moxey, Graeme J.; Humphrey, Mark G.; Basaleh, Amal S.

2018-04-01

The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV-vis absorption spectra of the complexes 2-5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1-5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1-5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

Crystal structure of CotA laccase complexed with 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonate) at a novel binding site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhongchuan; Xie, Tian; Key Laboratory of Environmental Microbiology of Sichuan Province, Chengdu 610041, People’s Republic of

2016-03-24

The crystal structure of CotA complexed with 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonate) in a hole motif has been solved; this novel binding site could be a potential structure-based target for protein engineering of CotA laccase. The CotA laccase from Bacillus subtilis is an abundant component of the spore outer coat and has been characterized as a typical laccase. The crystal structure of CotA complexed with 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonate) (ABTS) in a hole motif has been solved. The novel binding site was about 26 Å away from the T1 binding pocket. Comparison with known structures of other laccases revealed that the hole is a specific feature ofmore » CotA. The key residues Arg476 and Ser360 were directly bound to ABTS. Site-directed mutagenesis studies revealed that the residues Arg146, Arg429 and Arg476, which are located at the bottom of the novel binding site, are essential for the oxidation of ABTS and syringaldazine. Specially, a Thr480Phe variant was identified to be almost 3.5 times more specific for ABTS than for syringaldazine compared with the wild type. These results suggest this novel binding site for ABTS could be a potential target for protein engineering of CotA laccases.« less

Synthesis, crystal structure and properties of a new 3D supramolecular unsymmetrical tetradentate Schiff bases copper (II) framework with stable tunnels

NASA Astrophysics Data System (ADS)

Al-Noaimi, Mousa; Awwadi, Firas F.; Al-Razagg, Raiid; Esmadi, Fatima T.

2016-12-01

Flexible unsymmetrical Schiff base ligand (L) which is derived from the half unit Y = C6H5COCH2C(Ndbnd CH2C6H4NH2)CH3 (obtained from the reaction of benzoylacetone and 2-aminobenzylamine) and 2- quinolinecarboxaldehyde have been successfully co-assembled with Cu(ClO4)2 to give out the [Cu(L)]ClO4 complex. The complex crystallizes in two different space groups; P21/n and P-1. The crystal structure of the P-1 phase indicates the presence of tunnels; the volume of these tunnels is 157 Å3 which is big enough to accommodate solvent molecules. The X-ray data indicates that these tunnels are most probably filled by highly disordered solvent molecules or solvent molecules with partial occupancy. The tunneled structure is stabilized via π-π stacking interactions to give a supramolecular MOF with 1D rhomboidal tunnels array. The copper(II) atom assumes a distorted-square pyrimidal coordination geometry where the perchlorate is located on the apex of the pyramide. In addition, this work presents and discusses the spectroscopic (IR, UV/vis), electro-chemical (cyclic voltammetry) behavior of the Cu(II) complexes. The Cu(II) oxidation state is stabilized by the novel tetradentate ligands, showing Cu(I/II) couple around 0.1 vs. Cp2Fe/Cp2Fe+.

The crystal structures of native hydroquinone 1,2-dioxygenase from Sphingomonas sp. TTNP3 and of substrate and inhibitor complexes.

PubMed

Ferraroni, Marta; Da Vela, Stefano; Kolvenbach, Boris A; Corvini, Philippe F X; Scozzafava, Andrea

2017-05-01

The crystal structure of hydroquinone 1,2-dioxygenase, a Fe(II) ring cleaving dioxygenase from Sphingomonas sp. strain TTNP3, which oxidizes a wide range of hydroquinones to the corresponding 4-hydroxymuconic semialdehydes, has been solved by Molecular Replacement, using the coordinates of PnpCD from Pseudomonas sp. strain WBC-3. The enzyme is a heterotetramer, constituted of two subunits α and two β of 19 and 38kDa, respectively. Both the two subunits fold as a cupin, but that of the small α subunit lacks a competent metal binding pocket. Two tetramers are present in the asymmetric unit. Each of the four β subunits in the asymmetric unit binds one Fe(II) ion. The iron ion in each β subunit is coordinated to three protein residues, His258, Glu264, and His305 and a water molecule. The crystal structures of the complexes with the substrate methylhydroquinone, obtained under anaerobic conditions, and with the inhibitors 4-hydroxybenzoate and 4-nitrophenol were also solved. The structures of the native enzyme and of the complexes present significant differences in the active site region compared to PnpCD, the other hydroquinone 1,2-dioxygenase of known structure, and in particular they show a different coordination at the metal center. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of Phosphate on the Oxidation of Hydroxysulfate Green Rust

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benali, Omar; Abdelmoula, Mustapha; Genin, Jean-Marie R.

During Hydroxysulfate green rust GR(SO{sub 4}{sup 2}) oxidation, lepidocrocite and goethite were formed. The oxidation of GR(SO{sub 4}{sup 2-}) in the presence of phosphate ions, also involved the formation of poorly crystallized lepidocrocite but not that of goethite. The dissolution of lepidocrocite is inhibited by adsorption of phosphate ions as confirmed by X-ray photoelectron spectroscopy. The formation of the poorly crystallized protective layer against corrosion is effectively due to the phosphate ions which adsorb on the surface of lepidocrocite, and prevents it to turn into a well crystallized oxide.

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Thermodynamic investigations on the growth of CuAlO2 delafossite crystals

NASA Astrophysics Data System (ADS)

Wolff, Nora; Klimm, Detlef; Siche, Dietmar

2018-02-01

Simultaneous differential thermal analysis (DTA) and thermogravimetric (TG) measurements with copper oxide/aluminum oxide mixtures were performed in atmospheres with varying oxygen partial pressures and with crucibles made of different materials. Only sapphire and platinum crucibles proved to be stable under conditions that are useful for the growth of CuAlO2 delafossite single crystals. Then the ternary phase diagram Al2O3-CuO-Cu and its isopleth section Cu2O-Al2O3 were redetermined. Millimeter sized crystals could be obtained from copper oxide melts with 1-2 mol% addition of aluminum oxide that are stable in platinum crucibles held in oxidizing atmosphere containing 15-21% oxygen.

The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

PubMed

Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

2018-06-13

The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural basis of redox-dependent substrate binding of protein disulfide isomerase

PubMed Central

Yagi-Utsumi, Maho; Satoh, Tadashi; Kato, Koichi

2015-01-01

Protein disulfide isomerase (PDI) is a multidomain enzyme, operating as an essential folding catalyst, in which the b′ and a′ domains provide substrate binding sites and undergo an open–closed domain rearrangement depending on the redox states of the a′ domain. Despite the long research history of this enzyme, three-dimensional structural data remain unavailable for its ligand-binding mode. Here we characterize PDI substrate recognition using α-synuclein (αSN) as the model ligand. Our nuclear magnetic resonance (NMR) data revealed that the substrate-binding domains of PDI captured the αSN segment Val37–Val40 only in the oxidized form. Furthermore, we determined the crystal structure of an oxidized form of the b′–a′ domains in complex with an undecapeptide corresponding to this segment. The peptide-binding mode observed in the crystal structure with NMR validation, was characterized by hydrophobic interactions on the b′ domain in an open conformation. Comparison with the previously reported crystal structure indicates that the a′ domain partially masks the binding surface of the b′ domain, causing steric hindrance against the peptide in the reduced form of the b′–a′ domains that exhibits a closed conformation. These findings provide a structural basis for the mechanism underlying the redox-dependent substrate binding of PDI. PMID:26350503

Single Crystal Membranes

NASA Technical Reports Server (NTRS)

Stormont, R. W.; Morrison, A.

1974-01-01

Single crystal a- and c-axis tubes and ribbons of sodium beta-alumina and sodium magnesium beta-alumina were grown from sodium oxide rich melts. Additional experiments grew ribbon crystals containing sodium magnesium beta, beta double prime, beta triple prime, and beta quadruple prime. A high pressure crystal growth chamber, sodium oxide rich melts, and iridium for all surfaces in contact with the melt were combined with the edge-defined, film-fed growth technique to grow the single crystal beta-alumina tubes and ribbons. The crystals were characterized using metallographic and X-ray diffraction techniques, and wet chemical analysis was used to determine the sodium, magnesium, and aluminum content of the grown crystals.

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mudsainiyan, R.K., E-mail: mudsainiyanrk@gmail.com; Jassal, A.K.; Chawla, S.K., E-mail: sukhvinder.k.chawla@gmail.com

2015-10-15

A mesoporous 3D polymeric complex (I) having formula ([Zr(IV)O-μ{sup 3}-(EDTA)Fe(III)OH]·H{sub 2}O){sub n} has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and onemore » oxygen atom of –OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and –OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n–π⁎ transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N{sub 2} (S{sub BET}=8.7693 m{sup 2}/g) and a maximum amount of H{sub 2} (high surface area=1044.86 m{sup 2}/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. −7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex. - Graphical abstract: The complex (I) crystallized with unexpected coordination modes of EDTA having 4-c, 16-c net with new topology and point symbol is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern proved its stability with high preference of H{sub 2} uptake by complex. - Highlights: • 3D complex having unexpected coordination modes of EDTA with Zr(IV) and Fe(III). • The structure consists of 4-c and 16-c (2-nodal) net with new topology. • Reasonable S{sub BET} (8.7693 m{sup 2}/g) but high H{sub 2} uptake (1044.86 m{sup 2}/g) due to limited pore size. • Quenching behavior due to n–π⁎ transition by complexation with transition metal ions. • From DLS study, zeta potential value is −7.94.« less

Selective oxidation of aliphatic C-H bonds in alkylphenols by a chemomimetic biocatalytic system.

PubMed

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Feng, Yingang; Liu, Shuang-Jiang; Li, Shengying

2017-06-27

Selective oxidation of aliphatic C-H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C-H bonds of p - and m -alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.

Selective oxidation of aliphatic C–H bonds in alkylphenols by a chemomimetic biocatalytic system

PubMed Central

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Liu, Shuang-Jiang; Li, Shengying

2017-01-01

Selective oxidation of aliphatic C–H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum. The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C–H bonds of p- and m-alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity. PMID:28607077

Pre-eruptive rejuvenations of crystalline mush by reservoir heating: the case of trachy-dacitic lavas of Quetrupillán Volcanic Complex, Chile (39º30' lat. S)

NASA Astrophysics Data System (ADS)

Brahm, R.; Parada, M. Á.; Morgado, E. E.; Contreras, C.

2015-12-01

The Southern Volcanic Zone of the Andes is dominated by mainly basaltic to andesitic products, as is the case of the Villarrica 2015 eruption. An exception is the case of the nearby Quetrupillán Volcanic Complex (QVC). The QVC forms part of the NW-SE Villarrica-Quetrupillán-Lanín active volcanic chain and contains products of mainly trachy-dacitic composition that differs from the basaltic and basaltic-andesite composition of the neighboring stratovolcanoes. The studied Holocene QVC trachy-dacites exhibit similar geochemical, mineralogical features. They are crystal-poor (<12% phenocrysts) with phenocrysts occurring as isolated crystals or forming crystal clots within a glass-rich groundmass. Two groups of plagioclase phenocrysts were found: Group 1 plagioclases are commonly associated with pyroxene in crystal clots and with oscillatory zoning of An40-50, and Group 2 plagioclases occur as isolated crystals of variable composition (An70-85), with rims of similar composition to Group 1. Some Group 2 crystals have cores with compositions similar to the rims with resorption features. Clinopyroxenes within clots have compositions of En40-46Fs11-21Wo39-43 similar to the isolated clinopyroxenes. Orthopyroxene phenocrysts have composition of En36-68Fs15-34Wo03-04. Microphenocrysts of magnetite-ilmenite pairs (Mt14-36-Il90-94) were identified. Pyroxene phenocrysts are in disequilibrium with the whole-rock composition, suggesting that they are antecrysts. Two-pyroxene thermometry gives temperatures of 911-980ºC, while the Mt-Il equilibrium gives higher temperatures of 963-1114ºC, for the later stages of lava crystallization. The presence of a crystalline mush is suggested by the abundance of crystal clots in disequilibrium with the host rock composition whose calculated formation conditions of 0.5-1.5 kbar, 950-990ºC and 2.1-3.1 wt% of H2O, were obtained from a Rhyolite-MELTS simulation. Rejuvenation of a crystal mush by reservoir heating events is suggested due to resorption, regrowth and complex zonation of plagioclases and the higher temperatures obtained from the late stage of Fe-Ti oxide equilibrium. These events would generate the opening of the mush at the bottom of the magma chamber, allowing the interstitial melt extraction prior to eruption.

Synthesis, reactivity, and properties of N-fused porphyrin rhenium(I) tricarbonyl complexes.

PubMed

Toganoh, Motoki; Ikeda, Shinya; Furuta, Hiroyuki

2007-11-12

The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the rhenium(I) tricarbonyl complexes bearing N-fused porphyrinato ligands (4) in moderate to good yields. The rhenium complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes 4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4 proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives (19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible reduction waves are observed. Their redox potentials imply narrow HOMO-LUMO band gaps of 4 and are consistent with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton. Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations.

Prototypes of newly conceived inorganic and biological sensors for health and environmental applications.

PubMed

Nicolini, Claudio; Adami, Manuela; Sartore, Marco; Bragazzi, Nicola Luigi; Bavastrello, Valter; Spera, Rosanna; Pechkova, Eugenia

2012-12-12

This paper describes the optimal implementation of three newly conceived sensors for both health and environmental applications, utilizing a wide range of detection methods and complex nanocomposites. The first one is inorganic and based on matrices of calcium oxide, the second is based on protein arrays and a third one is based on Langmuir-Blodgett laccase multi-layers. Special attention was paid to detecting substances significant to the environment (such as carbon dioxide) and medicine (drug administration, cancer diagnosis and prognosis) by means of amperometric, quartz crystal microbalance with frequency (QCM_F) and quartz crystal microbalance with dissipation monitoring (QCM_D) technologies. The resulting three implemented nanosensors are described here along with proofs of principle and their corresponding applications.

Azide and acetate complexes plus two iron-depleted crystal structures of the di-iron enzyme delta9 stearoyl-acyl carrier protein desaturase. Implications for oxygen activation and catalytic intermediates.

PubMed

Moche, Martin; Shanklin, John; Ghoshal, Alokesh; Lindqvist, Ylva

2003-07-04

Delta9 stearoyl-acyl carrier protein (ACP) desaturase is a mu-oxo-bridged di-iron enzyme, which belongs to the structural class I of large helix bundle proteins and that catalyzes the NADPH and O2-dependent formation of a cis-double bond in stearoyl-ACP. The crystal structures of complexes with azide and acetate, respectively, as well as the apoand single-iron forms of Delta9 stearoyl-ACP desaturase from Ricinus communis have been determined. In the azide complex, the ligand forms a mu-1,3-bridge between the two iron ions in the active site, replacing a loosely bound water molecule. The structure of the acetate complex is similar, with acetate bridging the di-iron center in the same orientation with respect to the di-iron center. However, in this complex, the iron ligand Glu196 has changed its coordination mode from bidentate to monodentate, the first crystallographic observation of a carboxylate shift in Delta9 stearoyl-ACP desaturase. The two complexes are proposed to mimic a mu-1,2 peroxo intermediate present during catalytic turnover. There are striking structural similarities between the di-iron center in the Delta9 stearoyl-ACP desaturase-azide complex and in the reduced rubrerythrin-azide complex. This suggests that Delta9 stearoyl-ACP desaturase might catalyze the formation of water from exogenous hydrogen peroxide at a low rate. From the similarity in iron center structure, we propose that the mu-oxo-bridge in oxidized desaturase is bound to the di-iron center as in rubrerythrin and not as reported for the R2 subunit of ribonucleotide reductase and the hydroxylase subunit of methane monooxygenase. The crystal structure of the one-iron depleted desaturase species demonstrates that the affinities for the two iron ions comprising the di-iron center are not equivalent, Fe1 being the higher affinity site and Fe2 being the lower affinity site.

Igneous stratigraphy and rock-types from a deep transect of the gabbroic lower crust of the Atlantis Bank core complex (SW Indian Ridge): preliminary results from IODP Expedition 360

NASA Astrophysics Data System (ADS)

Sanfilippo, A.; France, L.; Ghosh, B.; Liu, C. Z.; Morishita, T.; Natland, J. H.; Dick, H. J.; MacLeod, C. J.; Expedition 360 Scientists, I.

2016-12-01

International Ocean Discovery Program (IODP) Expedition 360 represents the first leg of a multi-phase drilling programme ('SloMo' project) aimed at investigating the nature of the lower crust and Moho at slow spreading ridges. As an initial phase of the SloMo project, IODP Exp. 360 intended to recover a representative transect of the lower oceanic crust formed at Atlantis Bank, an oceanic core complex on the SW Indian Ridge. During this expedition, 89 cores of gabbroic rocks were recovered at Hole U1473A, drilled to 789.7 m below seafloor. This hole was subsequently deepened to 809.4 mbsf during transit Expedition 362T, which recovered additional 7 cores. The gabbroic section recovered at Hole U1473A consists of several types of gabbro, diabase, and felsic veins. The main lithology is dominated by olivine gabbro (76.5% in abundance), followed by gabbro containing 1-2% oxide (9.5%), gabbro with >2% oxide (7.4%), gabbro sensu stricto (5.1%), felsic veins (1.5%) and diabase (<0.5%). The different lithologies appear randomly distributed throughout the section, although oxide abundance seems to decrease slightly downhole, except for the lowermost intervals where oxide gabbros are more abundant. Based on changes in rock types, grain size, texture, and the occurrence of felsic material, we identified eight lithologic units, which locally define separate geochemical trends. Each unit is characterized by meter-scale heterogeneity which classically characterizes gabbros formed at slow spreading ridges. Reaction textures in olivine gabbros, crosscutting relationships between oxide gabbros and host rocks, the presence of intrusive to sutured contacts, igneous layering and the widespread occurrence of felsic veins and segregations indicate that the evolution of this section was controlled by complicated interactions of magmatic processes, e.g., fractional crystallization, melt-rock reaction, late-stage melt migration, which were active in a crystal mush formed by multiple injections of magma. This contribution describes the main features of these rocks and discusses the complexity of the igneous processes producing this 800 m-long transect of oceanic crust that was formed in a robust magmatic segment of an ultraslow spreading ridge.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Yuanyuan; Sushko, Peter V.; Melzer, Daniel

A novel pathway of increasing the surface density of catalytically active oxygen radical sites on a MoVTeNb oxide (M1 phase) catalyst during alkane oxidative dehydrogenation is reported. The novel sites form when a fraction of Te4+ is reduced and emitted from the M1 crystals under catalytic operating conditions, without compromising structural integrity of the catalyst framework. Density functional theory calculations show this Te reduction induces multiple inter-related electron transfers, and the associated cooperative effects lead to the formation of O- radicals. The in situ observations identify complex dynamic changes in the catalyst on an atomistic level, highlighting a new waymore » to tailor structure and dynamics for highly active catalysts.« less

Inosine Can Increase DNA's Susceptibility to Photo-oxidation by a RuII Complex due to Structural Change in the Minor Groove.

PubMed

Keane, Páraic M; Hall, James P; Poynton, Fergus E; Poulsen, Bjørn C; Gurung, Sarah P; Clark, Ian P; Sazanovich, Igor V; Towrie, Michael; Gunnlaugsson, Thorfinnur; Quinn, Susan J; Cardin, Christine J; Kelly, John M

2017-08-01

Key to the development of DNA-targeting phototherapeutic drugs is determining the interplay between the photoactivity of the drug and its binding preference for a target sequence. For the photo-oxidising lambda-[Ru(TAP) 2 (dppz)] 2+ (Λ-1) (dppz=dipyridophenazine) complex bound to either d{T 1 C 2 G 3 G 4 C 5 G 6 C 7 C 8 G 9 A 10 } 2 (G9) or d{TCGGCGCCIA} 2 (I9), the X-ray crystal structures show the dppz intercalated at the terminal T 1 C 2 ;G 9 A 10 step or T 1 C 2 ;I 9 A 10 step. Thus substitution of the G 9 nucleobase by inosine does not affect intercalation in the solid state although with I9 the dppz is more deeply inserted. In solution it is found that the extent of guanine photo-oxidation, and the rate of back electron-transfer, as determined by pico- and nanosecond time-resolved infrared and transient visible absorption spectroscopy, is enhanced in I9, despite it containing the less oxidisable inosine. This is attributed to the nature of the binding in the minor groove due to the absence of an NH 2 group. Similar behaviour and the same binding site in the crystal are found for d{TTGGCGCCAA} 2 (A9). In solution, we propose that intercalation occurs at the C 2 G 3 ;C 8 I 9 or T 2 G 3 ;C 8 A 9 steps, respectively, with G 3 the likely target for photo-oxidation. This demonstrates how changes in the minor groove (in this case removal of an NH 2 group) can facilitate binding of Ru II dppz complexes and hence influence any sensitised reactions occurring at these sites. No similar enhancement of photooxidation on binding to I9 is found for the delta enantiomer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supernucleation and Orientation of Poly(butylene terephthalate) Crystals in Nanocomposites Containing Highly Reduced Graphene Oxide

PubMed Central

2017-01-01

The ring-opening polymerization of cyclic butylene terephthalate into poly(butylene terephthalate) (pCBT) in the presence of reduced graphene oxide (RGO) is an effective method for the preparation of polymer nanocomposites. The inclusion of RGO nanoflakes dramatically affects the crystallization of pCBT, shifting crystallization peak temperature to higher temperatures and, overall, increasing the crystallization rate. This was due to a supernucleating effect caused by RGO, which is maximized by highly reduced graphene oxide. Furthermore, combined analyses by differential scanning calorimetry (DSC) experiments and wide-angle X-ray diffraction (WAXS) showed the formation of a thick α-crystalline form pCBT lamellae with a melting point of ∼250 °C, close to the equilibrium melting temperature of pCBT. WAXS also demonstrated the pair orientation of pCBT crystals with RGO nanoflakes, indicating a strong interfacial interaction between the aromatic rings of pCBT and RGO planes, especially with highly reduced graphene oxide. PMID:29296028

Effects of protonation and metal coordination on intramolecular charge transfer of tetrathiafulvalene compound.

PubMed

Zhu, Qin-Yu; Liu, Yu; Lu, Wen; Zhang, Yong; Bian, Guo-Qing; Niu, Gai-Yan; Dai, Jie

2007-11-26

A protonated bifunctional pyridine-based tetrathiafulvalene (TTF) derivative (DMT-TTF-pyH)NO3 and a copper(II) complex Cu(acac)2(DMT-TTF-py)2 have been obtained and studied. Electronic spectra of the protonated compound show a large ICT (intramolecular charge transfer) band shift (Deltalambda=136 nm) compared with that of the neutral compound. Cyclic voltammetry also shows a large shift of the redox potentials (DeltaE1/2(1)=77 mV). Theoretical calculation suggests that the pyridium substituent is a strong pi-electron acceptor. Crystal structures of the protonated compound and the metal complex have been obtained. The dihedral angle between least-squares planes of the pyridyl group and the dithiole ring might reflect the intensity of the ICT effect between the TTF moiety and the pyridyl group. It is also noteworthy that the TTF moiety could be oxidized to TTF2+ dication by Fe(ClO4)(3).6H2O when forming a metal complex, while the protonated TTF derivative can only be oxidized to the TTF*+ radical cation by Fe(ClO4)(3).6H2O even with an excess amount of the Fe(III) salt, which can be used to control the oxidation process to obtain neutral TTF, TTF*+ radical cation, or TTF2+ dication.

Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory.

PubMed

Alonso, Ester; Casas, José M.; Cotton, F. Albert; Feng, Xuejung; Forniés, Juan; Fortuño, Consuelo; Tomas, Milagros

1999-11-01

The electrolytic behavior of the dinuclear complexes [NBu(4)](2)[MM'(&mgr;-PPh(2))(2)(C(6)F(5))(4)] (M = M' = Pt (1), Pd (1a); M = Pt, M' = Pd (1b)) has been studied, showing electrochemically irreversible oxidation and related reduction processes. The chemical oxidation of the binuclear compound for M = M' = Pt, results in the formation of the binuclear Pt(III) compound [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]. The crystal structure analysis of both complexes has been carried out, showing very similar structures with similar Pt-C and Pt-P distances and analogous skeletons. However the Pt-Pt distances are very different, 3.621(1) Å for the Pt(II) compound and 2.7245(7) Å for the Pt(III) derivative (as are the parameters geometrically related to this Pt-Pt distance), suggesting that, in the Pt(III) compound, there is a strong Pt-Pt bond. Results of DFT calculations on [Pt(2)(&mgr;-PH(2))(2)(C(6)F(5))(4)](n)()(-) (n = 2, 0) agree very well with the crystallographic data and indicate that, in the Pt(III) compound, there is approximately a single sigma bond between the metal atoms.

Geochemical studies of abyssal lavas recovered by DSRV Alvin from Eastern Galapagos Rift, Inca Transform, and Ecuador Rift: 2. Phase chemistry and crystallization history

NASA Astrophysics Data System (ADS)

Perfit, Michael R.; Fornari, Daniel J.

1983-12-01

A diverse suite of lavas recovered by DSRV Alvin from the eastern Galapagos rift and Inca transform includes mid-ocean ridge tholeiitic basalts (MORB), iron- and titanium-enriched basalts (FeTi basalts), and abyssal andesites. Rock types transitional in character (ferrobasalts and basaltic andesites) were also recovered. The most mafic glassy basalts contain plagioclase, augite, and olivine as near-liquidus phases, whereas in more fractionated basalts, pigeonite replaces olivine and iron-titanium oxides crystallize. Plagioclase crystallizes after pyroxenes and iron-titanium oxides in andesites, possibly due to increased water contents or cooling rates. Apatite phenocrysts are present in some andesitic glasses. Ovoid sulfide globules are also common in many lavas. Compositional variations of phenocrysts in glassy lavas reflect changes in magma chemistry, temperature of crystallization, and cooling rate. The overall chemical variations parallel the chemical evolution of the lava suite and are similar to those in other fractionated tholeiitic complexes. Elemental partitioning between plagioclase-, pyroxene-, and olivine-glass pairs suggests that equilibration occurred at low pressure in a rather restricted temperature range. Various geothermometers indicate that the most primitive MORB began to crystallize between 1150° and 1200°C with fo2 < 10-7 atm. Coexisting iron-titanium oxides in more evolved lavas yield temperatures ˜1025°C to as low as 910°C withfo2 from 10-8 to 10-12 atm. PH 2 o could have been as high as 1 kbar during andesite crystallization. Compositions of the lavas from the Galapagos rift follow the experimentally determined (1 atm-QFM) liquid line of descent. Least squares calculations for the major elements indicate that the entire suite of lavas can be produced by fractional crystallization of successive residual liquids from a MORB parent magma. FeTi basalts represent 30-65 cumulative weight percent crystallization of plagioclase, augite, and olivine. An additional 30-50% fractionation of pyroxenes, plagioclase, titanomagnetite, and possible apatite is required to generate andesite from FeTi basalt liquids. The presence of partially resorbed mafic xenocrysts in some andesites, FeTi basalt inclusions in these xenocrysts, high-silica glass inclusions in basaltic andesites, and the transitional chemistry of basaltic andesites are evidence that some magma mixing occurred during crystal fractionation. The diversity of lava types recovered at single dive sites suggests that low-pressure fractional crystallization is a very efficient process beneath the eastern Galapagos rift and that isolated magma bodies must be present at shallow levels beneath the accretionary locus. Voluminous FeTi basalts erupted at the rift-transform intersection are genetically related to the rift lavas, but their restricted chemistry reflects different thermal and tectonic controls on their petrogenesis.

Modeling Czochralski growth of oxide crystals for piezoelectric and optical applications

NASA Astrophysics Data System (ADS)

Stelian, C.; Duffar, T.

2018-05-01

Numerical modeling is applied to investigate the impact of crystal and crucible rotation on the flow pattern and crystal-melt interface shape in Czochralski growth of oxide semi-transparent crystals used for piezoelectric and optical applications. Two cases are simulated in the present work: the growth of piezoelectric langatate (LGT) crystals of 3 cm in diameter in an inductive furnace, and the growth of sapphire crystals of 10 cm in diameter in a resistive configuration. The numerical results indicate that the interface shape depends essentially on the internal radiative heat exchanges in the semi-transparent crystals. Computations performed by applying crystal/crucible rotation show that the interface can be flattened during LGT growth, while flat-interface growth of large diameter sapphire crystals may not be possible.

Structure and Reactivity of a Thermostable Prokaryotic Nitric-oxide Synthase That Forms a Long-lived Oxy-Heme Complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sudhamsu,J.; Crane, B.

2006-01-01

In an effort to generate more stable reaction intermediates involved in substrate oxidation by nitric-oxide synthases (NOSs), we have cloned, expressed, and characterized a thermostable NOS homolog from the thermophilic bacterium Geobacillus stearothermophilus (gsNOS). As expected, gsNOS forms nitric oxide (NO) from L-arginine via the stable intermediate N-hydroxy L-arginine (NOHA). The addition of oxygen to ferrous gsNOS results in long-lived heme-oxy complexes in the presence (Soret peak 427 nm) and absence (Soret peak 413 nm) of substrates L-arginine and NOHA. The substrate-induced red shift correlates with hydrogen bonding between substrate and heme-bound oxygen resulting in conversion to a ferric heme-superoxymore » species. In single turnover experiments with NOHA, NO forms only in the presence of H4B. The crystal structure of gsNOS at 3.2 A Angstroms of resolution reveals great similarity to other known bacterial NOS structures, with the exception of differences in the distal heme pocket, close to the oxygen binding site. In particular, a Lys-356 (Bacillus subtilis NOS) to Arg-365 (gsNOS) substitution alters the conformation of a conserved Asp carboxylate, resulting in movement of an Ile residue toward the heme. Thus, a more constrained heme pocket may slow ligand dissociation and increase the lifetime of heme-bound oxygen to seconds at 4 degC. Similarly, the ferric-heme NO complex is also stabilized in gsNOS. The slow kinetics of gsNOS offer promise for studying downstream intermediates involved in substrate oxidation.« less

Effect of Surface Preparation on the 815°C Oxidation of Single-Crystal Nickel-Based Superalloys

NASA Astrophysics Data System (ADS)

Sudbrack, Chantal K.; Beckett, Devon L.; MacKay, Rebecca A.

2015-11-01

A primary application for single-crystal superalloys has been jet engine turbine blades, where operation temperatures reach well above 1000°C. The NASA Glenn Research Center is considering use of single-crystal alloys for future, lower temperature application in the rims of jet engine turbine disks. Mechanical and environmental properties required for potential disk rim operation at 815°C are being examined, including the oxidation and corrosion behavior, where there is little documentation at intermediate temperatures. In this study, single-crystal superalloys, LDS-1101+Hf and CMSX-4+Y, were prepared with different surface finishes and compared after isothermal and cyclic oxidation exposures. Surface finish has a clear effect on oxide formation at 815°C. Machined low-stress ground surfaces after exposure for 440 h produce thin Al2O3 external scales, which is consistent with higher temperature oxidation, whereas polished surfaces with a mirror finish yield much thicker NiO external scales with subscale of Cr2O3-spinel-Al2O3, which may offer less reliable oxidation resistance. Additional experiments separate the roles of cold-work, localized deformation, and the extent of polishing and surface roughness on oxide formation.

Structural characterization of oxidized titanium surfaces

NASA Astrophysics Data System (ADS)

Jobin, M.; Taborelli, M.; Descouts, P.

1995-05-01

Oxidized titanium surfaces resulting from various processes have been structurally characterized by means of scanning force microscopy, x-ray photoemission spectroscopy (XPS), x-ray diffraction, and electron energy-loss spectroscopy (EELS) with losses in the 0-100 eV range. It has been found that the surface morphology has a granular structure for electropolished titanium and for titanium evaporated on mica at low substrate temperature (570 K), but changes to flat terraces for the films evaporated at higher temperature (770 K). Angular-dependent XPS has revealed the presence of a Ti2O3 suboxide at the Ti/TiO2 interface for electropolished titanium. Dry oxidation has been performed at 770 and 970 K on both weakly and highly crystallized evaporated titanium films oriented along (0001). In the case of underlying crystallized metallic titanium, the resulting TiO2 films are crystallized with the anatase (004) orientation for oxidation at 770 K and with rutile (200) orientation for oxidation at 970 K. EELS spectra interpreted in terms of the molecular orbitals of a (TiO6)8- cluster show that the local octahedral environment of titanium atoms is preserved on native oxides, even if these oxides are not crystallized.

Tuning the structure and habit of iron oxide mesocrystals

DOE PAGES

Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; ...

2016-07-11

A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and themore » quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.« less

Inorganic and organic structures as interleavers among [bis(1-methyl-3-(p-carboxylatephenyl)triazenide 1-oxide)Ni(II)] complexes to form supramolecular arrangements

NASA Astrophysics Data System (ADS)

Santos, Aline Joana Rolina Wohlmuth Alves; dos Santos Hackbart, Helen Cristina; Giacomini, Gabriela Xavier; Bersch, Patrícia; Paraginski, Gustavo Luiz; Hörner, Manfredo

2016-12-01

Alternative compounds to capture metal ions are triazenes 1-oxide since they are basic compounds O(N) with negative charge in the deprotonated form. The proximity of both coordination sites (O and N) enables these compounds to have good chelating ability and a tendency to stabilize in the formation of rings with soft and hard transition metal ions. The structure analysis by single crystal X-ray diffraction of compounds (1) and (2) demonstrate the formation of 3D supramolecular arrangements through ion-ion, ion-dipolo and dipolo-dipolo interactions. In one of them, there are [(H2O)2(CH3CH3SO)K2]2+ as linkers of polymerization and, in another complex, there are [(H2O)(CH3CH3SO)Ni(H2O)6]2+ as a linker of polymerization. These linkers act in the polymerization of the novel mononuclear complex [bis(1-methyl (p-carboxylatephenyl) triazenide 1-oxide) NiII] (3). The crystallography analysis of (1) and (2) showed distorted quadratic geometry for Ni (II), thus, there are two axial positions available in Ni (II) to be used in catalysis studies and as sensor or biosensor. In addition, this study shows the support of this novel mononuclear complex of Ni (II) (3) on protonated chitosan chains (4). The compounds (3) and (4) were characterized by spectroscopic analysis, infrared (IR) and energy dispersive X-ray detector (EDS), and by differential scanning calorimetry analysis (DSC). The specificity of ligand 1-methyl (p-carboxyphenyl) triazene 1-oxide to capture potassium and nickel ions will be tested at different pH values, as well as the capacity of the triazenide 1-oxide of Ni (II) complex, supported on chitosan polymer, or not, to act as a catalyst for organic reactions and biomimetic organic reactions.

Supramolecular interactions between triphenylphosphine oxide and benzamide evaluated by positron annihilation lifetime spectroscopy

NASA Astrophysics Data System (ADS)

Oliveira, F. C.; Denadai, A. M. L.; Fulgêncio, F.; Oliveira, A. M.; Andrade, A. C. A.; Melo, A. C. A.; Yoshida, M. I.; Windmöller, D.; Magalhães, W. F.

2017-04-01

In the present work, intermolecular interactions between triphenylphosphine oxide (TPPO) and benzamide (BZM) has been studied in solid state by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques (in solid state and in solution) and by computational modeling (in gaseous phase). Isothermal Titration Calorimetry (ITC) in ethyl acetate solvent showed that complexation is a stepwise process, with 2:1 and 1:1 TPPO/BZM stoichiometries, both driven by entropy. HPLC analysis of isolated single crystal confirmed the existence of a 2:1 TPPO/BZM crystalline complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complexes are relatively weaker than those found in pure precursors. Finally, PALS showed higher positronium formation probability (I3) at [TPPO0.62·BZM0.38] and [TPPO0.25·BZM0.75] molar fractions, corroborating the existence of two stoichiometries for the TPPO/BZM system and suggesting greater electronic availability of n- and π-electrons in heterosynton complexes, as resulting of interactions, bring forward new evidences of the participation of electronic excited states on the positronium formation mechanism.

Structural studies of Proteus mirabilis catalase in its ground state, oxidized state and in complex with formic acid.

PubMed

Andreoletti, Pierre; Pernoud, Anaïs; Sainz, Germaine; Gouet, Patrice; Jouve, Hélène Marie

2003-12-01

The structure of Proteus mirabilis catalase in complex with an inhibitor, formic acid, has been solved at 2.3 A resolution. Formic acid is a key ligand of catalase because of its ability to react with the ferric enzyme, giving a high-spin iron complex. Alternatively, it can react with two transient oxidized intermediates of the enzymatic mechanism, compounds I and II. In this work, the structures of native P. mirabilis catalase (PMC) and compound I have also been determined at high resolution (2.0 and 2.5 A, respectively) from frozen crystals. Comparisons between these three PMC structures show that a water molecule present at a distance of 3.5 A from the haem iron in the resting state is absent in the formic acid complex, but reappears in compound I. In addition, movements of solvent molecules are observed during formation of compound I in a cavity located away from the active site, in which a glycerol molecule is replaced by a sulfate. These results give structural insights into the movement of solvent molecules, which may be important in the enzymatic reaction.

Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

PubMed

Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

2015-06-28

Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

Method for surface treatment of a cadmium zinc telluride crystal

DOEpatents

James, Ralph; Burger, Arnold; Chen, Kuo-Tong; Chang, Henry

1999-01-01

A method for treatment of the surface of a CdZnTe (CZT) crystal that reduces surface roughness (increases surface planarity) and provides an oxide coating to reduce surface leakage currents and thereby, improve resolution. A two step process is disclosed, etching the surface of a CZT crystal with a solution of lactic acid and bromine in ethylene glycol, following the conventional bromine/methanol etch treatment, and after attachment of electrical contacts, oxidizing the CZT crystal surface.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

NASA Astrophysics Data System (ADS)

Yamaura, Kazunari

2016-04-01

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

Crystal structure of a trapped catalytic intermediate suggests that forced atomic proximity drives the catalysis of mIPS.

PubMed

Neelon, Kelly; Roberts, Mary F; Stec, Boguslaw

2011-12-07

1-L-myo-inositol-phosphate synthase (mIPS) catalyzes the first step of the unique, de novo pathway of inositol biosynthesis. However, details about the complex mIPS catalytic mechanism, which requires oxidation, enolization, intramolecular aldol cyclization, and reduction, are not fully known. To gain further insight into this mechanism, we determined the crystal structure of the wild-type mIPS from Archaeoglobus fulgidus at 1.7 Å, as well as the crystal structures of three active-site mutants. Additionally, we obtained the structure of mIPS with a trapped 5-keto-glucose-6-phosphate intermediate at 2 Å resolution by a novel (to our knowledge) process of activating the crystal at high temperature. A comparison of all of the crystal structures of mIPS described in this work suggests a novel type of catalytic mechanism that relies on the forced atomic proximity of functional groups. The lysine cluster is contained in a small volume in the active site, where random motions of these side chains are responsible for the progress of the complex multistep reaction as well as for the low rate of catalysis. The mechanism requires that functional groups of Lys-274, Lys-278, Lys-306, and Lys-367 assume differential roles in the protonation/deprotonation steps that must occur during the mIPS reaction. This mechanism is supported by the complete loss of activity of the enzyme caused by the Leu-257 mutation to Ala that releases the lysine containment. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Scintillation properties of selected oxide monocrystals activated with Ce and Pr

NASA Astrophysics Data System (ADS)

Wojtowicz, Andrzej J.; Drozdowski, Winicjusz; Wisniewski, Dariusz; Lefaucheur, Jean-Luc; Galazka, Zbigniew; Gou, Zhenhui; Lukasiewicz, Tadeusz; Kisielewski, Jaroslaw

2006-01-01

In the last 10-15 years there has been a significant effort toward development of new, more efficient and faster materials for detection of ionizing radiation. A growing demand for better scintillator crystals for detection of 511 keV gamma particles has been due mostly to recent advances in modern imaging systems employing positron emitting radionuclides for medical diagnostics in neurology, oncology and cardiology. While older imaging systems were almost exclusively based on BGO and NaI:Tl crystals the new systems, e.g., ECAT Accel, developed by Siemens/CTI, are based on recently discovered and developed LSO (Lu 2SiO 5:Ce, Ce-activated lutetium oxyorthosilicate) crystals. Interestingly, despite very good properties of LSO, there still is a strong drive toward development of new scintillator crystals that would show even better performance and characteristics. In this presentation we shall review spectroscopic and scintillator characterization of new complex oxide crystals, namely LSO, LYSO, YAG, LuAP (LuAlO 3, lutetium aluminate perovskite) and LuYAP activated with Ce and Pr. The LSO:Ce crystals have been grown by CTI Inc (USA), LYSO:Ce, LuAP:Ce and LuYAP:Ce crystals have been grown by Photonic Materials Ltd., Scotland (PML is the only company providing large LuAP:Ce crystals on a commercial scale), while YAG:Pr and LuAP:Pr crystals have been grown by Institute of Electronic Materials Technology (Poland). All these crystals have been characterized at Institute of Physics, N. Copernicus University (Poland). We will review and compare results of measurements of radioluminescence, VUV spectroscopy, scintillation light yields, scintillation time profiles and low temperature thermoluminescence performed on these crystals. We will demonstrate that all experiments clearly indicate that there is a significant room for improvement of LuAP, LuYAP and YAG. While both Ce-activated LSO and LYSO perform very well, we also note that LuYAP:Ce, LuAP:Ce and YAG:Pr offer some advantages and, after a likely improvement of some parameters, may also present a viable and desired alternative in applications that require high counting rates or better time resolution. Unfortunately, LuAP:Pr, although the fastest among all the materials studied, may be seriously limited in its achievable light yield by inherent physical processes that are responsible for nonradiative quenching of scintillation light in this material.

Insights into Metal Oxide and Zero-Valent Metal Nanocrystal Formation on Multiwalled Carbon Nanotube Surfaces during Sol-Gel Process.

PubMed

Das, Dipesh; Sabaraya, Indu V; Sabo-Attwood, Tara; Saleh, Navid B

2018-06-05

Carbon nanotubes are hybridized with metal crystals to impart multifunctionality into the nanohybrids (NHs). Simple but effective synthesis techniques are desired to form both zero-valent and oxides of different metal species on carbon nanotube surfaces. Sol-gel technique brings in significant advantages and is a viable technique for such synthesis. This study probes the efficacy of sol-gel process and aims to identify underlying mechanisms of crystal formation. Standard electron potential (SEP) is used as a guiding parameter to choose the metal species; i.e., highly negative SEP (e.g., Zn) with oxide crystal tendency, highly positive SEP (e.g., Ag) with zero-valent crystal-tendency, and intermediate range SEP (e.g., Cu) to probe the oxidation tendency in crystal formation are chosen. Transmission electron microscopy and X-ray diffraction are used to evaluate the synthesized NHs. Results indicate that SEP can be a reliable guide for the resulting crystalline phase of a certain metal species, particularly when the magnitude of this parameter is relatively high. However, for intermediate range SEP-metals, mix phase crystals can be expected. For example, Cu will form Cu₂O and zero-valent Cu crystals, unless the synthesis is performed in a reducing environment.

Wide-band-gap, alkaline-earth-oxide semiconductor and devices utilizing same

DOEpatents

Abraham, Marvin M.; Chen, Yok; Kernohan, Robert H.

1981-01-01

This invention relates to novel and comparatively inexpensive semiconductor devices utilizing semiconducting alkaline-earth-oxide crystals doped with alkali metal. The semiconducting crystals are produced by a simple and relatively inexpensive process. As a specific example, a high-purity lithium-doped MgO crystal is grown by conventional techniques. The crystal then is heated in an oxygen-containing atmosphere to form many [Li].degree. defects therein, and the resulting defect-rich hot crystal is promptly quenched to render the defects stable at room temperature and temperatures well above the same. Quenching can be effected conveniently by contacting the hot crystal with room-temperature air.

Synthesis of Oxides Containing Transition Metals

DTIC Science & Technology

1990-07-09

metal oxide single crystals by the electrolysis of molten salts containing mixtures of the appropriate oxides. Andreiux and Bozon (33-34) were able to...examples of unusual transition metal oxides which can be prepared (usually as single crystals) by electrolysis of fused salts . Summary The methods of...ferrites with the composition MFe 204 involved the thermal decomposition of oxalate (3) or pyridinate salts (1). The synthesis of ferrites from mixed

Bimetallic Platinum-Rhodium Alloy Nanodendrites as Highly Active Electrocatalyst for the Ethanol Oxidation Reaction.

PubMed

Bai, Juan; Xiao, Xue; Xue, Yuan-Yuan; Jiang, Jia-Xing; Zeng, Jing-Hui; Li, Xi-Fei; Chen, Yu

2018-06-13

Rationally designing and manipulating composition and morphology of precious metal-based bimetallic nanostructures can markedly enhance their electrocatalytic performance, including selectivity, activity, and durability. We herein report the synthesis of bimetallic PtRh alloy nanodendrites (ANDs) with tunable composition by a facile complex-reduction synthetic method under hydrothermal conditions. The structural/morphologic features, formation mechanism, and electrocatalytic performance of PtRh ANDs are investigated thoroughly by various physical characterization and electrochemical methods. The preformed Rh crystal nuclei effectively catalyze the reduction of Pt 2+ precursor, resulting in PtRh alloy generation due to the catalytic growth and atoms interdiffusion process. The Pt atoms deposition distinctly interferes in Rh atoms deposition on Rh crystal nuclei, resulting in dendritic morphology of PtRh ANDs. For the ethanol oxidation reaction (EOR), PtRh ANDs display the chemical composition and solution pH co-dependent electrocatalytic activity. Because of the alloy effect and particular morphologic feature, Pt 1 Rh 1 ANDs with optimized composition exhibit better reactivity and stability for the EOR than commercial Pt nanocrystals electrocatalyst.

Crystallization of bFGF-DNA Aptamer Complexes Using a Sparse Matrix Designed for Protein-Nucleic Acid Complexes

NASA Technical Reports Server (NTRS)

Cannone, Jaime J.; Barnes, Cindy L.; Achari, Aniruddha; Kundrot, Craig E.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

The Sparse Matrix approach for obtaining lead crystallization conditions has proven to be very fruitful for the crystallization of proteins and nucleic acids. Here we report a Sparse Matrix developed specifically for the crystallization of protein-DNA complexes. This method is rapid and economical, typically requiring 2.5 mg of complex to test 48 conditions. The method was originally developed to crystallize basic fibroblast growth factor (bFGF) complexed with DNA sequences identified through in vitro selection, or SELEX, methods. Two DNA aptamers that bind with approximately nanomolar affinity and inhibit the angiogenic properties of bFGF were selected for co-crystallization. The Sparse Matrix produced lead crystallization conditions for both bFGF-DNA complexes.

Enhancement radiative cooling performance of nanoparticle crystal via oxidation

NASA Astrophysics Data System (ADS)

Jia, Zi-Xun; Shuai, Yong; Li, Meng; Guo, Yanmin; Tan, He-ping

2018-03-01

Nanoparticle-crystal is a promising candidate for large scale metamaterial fabrication. However, in radiative cooling application, the maximum blackbody radiation wavelength locates far from metal's plasmon wavelength. In this paper, it will be shown if the metallic nanoparticle crystal can be properly oxidized, the absorption performance within room temperature blackbody radiation spectrum can be improved. Magnetic polariton and surface plasmon polariton have been explained for the mechanism of absorption improvement. Three different oxidation patterns have been investigated in this paper, and the results show they share a similar enhancing mechanism.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

PubMed

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

Structural characterization of ferric hemoglobins from three antarctic fish species of the suborder notothenioidei.

PubMed

Vergara, Alessandro; Franzese, Marisa; Merlino, Antonello; Vitagliano, Luigi; Verde, Cinzia; di Prisco, Guido; Lee, H Caroline; Peisach, Jack; Mazzarella, Lelio

2007-10-15

Spontaneous autoxidation of tetrameric Hbs leads to the formation of Fe (III) forms, whose physiological role is not fully understood. Here we report structural characterization by EPR of the oxidized states of tetrameric Hbs isolated from the Antarctic fish species Trematomus bernacchii, Trematomus newnesi, and Gymnodraco acuticeps, as well as the x-ray crystal structure of oxidized Trematomus bernacchii Hb, redetermined at high resolution. The oxidation of these Hbs leads to formation of states that were not usually detected in previous analyses of tetrameric Hbs. In addition to the commonly found aquo-met and hydroxy-met species, EPR analyses show that two distinct hemichromes coexist at physiological pH, referred to as hemichromes I and II, respectively. Together with the high-resolution crystal structure (1.5 A) of T. bernacchii and a survey of data available for other heme proteins, hemichrome I was assigned by x-ray crystallography and by EPR as a bis-His complex with a distorted geometry, whereas hemichrome II is a less constrained (cytochrome b5-like) bis-His complex. In four of the five Antartic fish Hbs examined, hemichrome I is the major form. EPR shows that for HbCTn, the amount of hemichrome I is substantially reduced. In addition, the concomitant presence of a penta-coordinated high-spin Fe (III) species, to our knowledge never reported before for a wild-type tetrameric Hb, was detected. A molecular modeling investigation demonstrates that the presence of the bulkier Ile in position 67beta in HbCTn in place of Val as in the other four Hbs impairs the formation of hemichrome I, thus favoring the formation of the ferric penta-coordinated species. Altogether the data show that ferric states commonly associated with monomeric and dimeric Hbs are also found in tetrameric Hbs.

Oxygen regime of Siberian alkaline-ultramafic magmas

NASA Astrophysics Data System (ADS)

Ryabchikov, Igor; Kogarko, Liya

2017-04-01

Regimes of S2 and O2 are decisive factors controlling behavior of chalcophile and siderophile elements in magmatic processes. These parameters play important role during magmagenesis and in the course of crystallization and fluid mass transfer in magma chamber. Alkaline-ultramafic magmatism in Maymecha-Kotuy Province (Polar Siberia) is represented by giant intrusive complexes as well as by volcanics and dyke rocks, which include a well-known variety - meimechites. The latter are considered primary magmas of alkaline-ultramafic plutons in the region like for instance Guli intrusive complex. Sulfur content in primitive magmas estimated from the analyses of melt inclusions in olivine megacrysts from meimechites is close to 0.1 %. fO2 values calculated using olivine+clinopyroxene+spinel and spinel+melt oxygen barometers (1, 2) are 2-3 log units above QFM buffer. The relatively high oxygen potential at the early magmatic stage of alkaline-ultramafic Guli pluton provide predominance of sulfates among other forms of sulfur in the melt. This leads to the almost complete absence of sulfides in highly magnesian rocks. The oxidizing conditions exert important effect on behavior of many ore metals. At the stage of magma generation absence of sulfides in mantle materialresults in the presence of siderophile elements in metallic form and saturation of primary magmas in respect of metallic phases at an early stage of injection of the melt into the magma chamber. Later, under favorable circumstances during magma crystallization nuggets of precious metals may be formed. During further evolution of magmatic system fO2 and activity of oxidized sulfur decrease due to intensive crystallization of magnetite during the formation of koswites, then oxygen fugacity becomes even lower as a result serpentinization at a postmagmatic stage. These serpentization processes are caused by the displacement of reactions in the aqueous phase due to cooling towards the formation of methane and other reduced components and, possibly, with their concentration in the gas phase due to boiling at lowered pressure. This leads to the appearance of late sulfides in the intergranular space of the investigated rocks. Sulfides are represented by pentlandite, monosulfide solid solution and heazlewoodite. Thermodynamic analysis of equilibria involving these minerals has shown that the oxygenpotential in the later stages is significantly reduced (up to three logarithmic units below QFM buffer at 300 ° C). The transition from an oxidizing to a reducing environment will contribute to the mobilization of many ore metals by aqueous fluids and then theirconcentrated deposition. This may be particularly important factor for gold, which is mobilized by fluid under oxidizing environment and precipitated due to the decreasing fO2. Au is present in placers on the territory of the Guli complex. Highly oxidized nature of the early phases of alkaline-ultramafic magmatic systems (high magnetite component of chrome spinel, high concentrations of ferric iron in pyroxene), and signs of the transition to a more reducing environment at a late stage (intensive crystallization of magnetite, occurrence of sulfur-deficient sulfides) can be considered as a potential prognostic signs of gold mineralization. Russian Science Foundation (grant 15-17-30019) has supported this work. 1. I. D. Ryabchikov, Oxygen potential of high-magnesium magmas. Doklady Earth Sciences 448, 149 (Jan, 2013). 2. I. D. Ryabchikov, L. N. Kogarko, A new version of the spinel-olivine-pyroxene oxybarometer and extreme redox differentiation in magmatic systems of mantle sources. Doklady Earth Sciences 430, 248 (Feb, 2010).

Remarkable lowering in the synthesis temperature of LiMn2O4via citrate solution-gel synthesis facilitated by ethanol.

PubMed

Maino, G; Carleer, R; Marchal, W; Bonneux, G; Hardy, A; Van Bael, M K

2017-11-07

LiMn 2 O 4 (LMO) is interesting from the viewpoint of its energy storage applications as it is a cathode in lithium ion batteries (LIB), which contains no rare, toxic or expansive elements, while it provides a high theoretical capacity (148 mA h g -1 ) at a reasonable voltage (4 V region) and a higher thermal stability compared to cobalt based cathodes and has a good rechargeability and cycling stability due to its spinel structure. Low temperature synthesis routes for cathode materials are currently gaining attention, in order to decrease the ecological footprint of the final LIB. Here, the crystallization temperature of LMO by a citrate based solution-gel synthesis was significantly lowered, to as low as 250 °C by the addition of ethanol to the precursor. The role of ethanol in this synthesis process was explored. It was found to lead to a considerable increase in the oxidation rate of the redox couple Mn 2+ /Mn 3+ , a lowering of the precursor decomposition temperature by 200 °C, besides a drastic decrease in the crystallization temperature (reaching 250 °C). Moreover, the main cause was identified to be an esterification reaction of ethanol with the carboxylic acid in the precursor complexes, taking place before the oxide formation. The insights obtained strengthen the knowledge regarding citrato-Mn 2+ /Mn 3+ complexes present in aqueous solution-gel synthesis routes and are relevant for the preparation of various manganese containing oxides. Moreover, the precursor developed opens up a new possibility for the low temperature synthesis of LMO powders and thin films for application in LIB. In the case of thin film batteries, the low temperature processing provides compatibility with other materials in the thin film battery stack, avoiding undesired oxidations or interfacial reactions.

Chemical variations in the Triple Group of the Skaergaard intrusion: insights for the mineralization and crystallization process

NASA Astrophysics Data System (ADS)

Nielsen, T. F.; Bernstein, S.

2009-12-01

The 54 Ma. old Skaergaard intrusion ( East Greenland) is a type example for fractionation of basaltic melt along the Fenner Trend. The Triple Group is the upper most 100 m of the Middle Zone and consists of FeTi-oxide rich layered gabbro with three distinct leugabbro layers 2-5 m thick ( L-layers; L1-L3, 2-5m thick) and a less marked layer (L0) c.20 m below L1. These are the most marked of many such layers. Apart from the pronounced layering the lower part of the Triple Group also hosts a world class Au-PGE mineralization. The mineralization is perfectly concordant with the L-layers, and the Triple Group invites investigation of the relationship between host and mineralization. The mineralization includes 5 main levels defined by palladium concentration. The chemical variation across the mineralization is covered by ca. 250 bulk major and trace element compositions, each representing 25cm of stratigraphy giving a continuum of ca. 60m. Proportions of normative plagioclase (plag) and pyroxene (px, including cpx and opx) are complementary, except in mineralized gabbro which is rich in FeTi-oxides. Cumulus ilmenite (ilm) is strongly enriched in layers (7m apart). They occur in both plag- and px-rich gabbro, whereas magnetite (mt) shows no simple correlation with ilm and is mainly a poikilitic intercumulus phase. The L-layers are composed of an upper part rich in plag and px and poor in FeTi-oxides, and a lower part rich in plag and FeTi-oxides and poor in px. The marked breaks in the mineralogy in the L-layers separate one layered succession from the next. The layered successions consist of a lower oxide-poor px-plag adcumulate, followed by complex mesocratic orthocumulate with poikilitic interstitial FeTi-oxide, and an upper part of increasingly simple plag-rich adcumulate with decreasing content of interstitial mt. The Au-PGE mineralized levels are found in the complex FeTi-rich gabbros at and in the base of the leucogabbro layers. The stratigraphic variation in density and densities of melt and liquidus phases suggest plag to have neutral buoyancy (floating), whereas all other phases would sink. The repeated successions are suggested to be the result of repeated “self-stratification” in the mush zone at the crystallization front, characterized by separation of px and plag leaving a transitional zone enriched in Fe-rich melt. In this melt, crystallization of mt led to S-saturation and formation of immiscible sulfide globules (30µm) in which PGE-minerals crystallize. During solidification, residual or immiscible Si-rich melt and volatiles rose from the transitional zone and took Au, Ag, Pt, Te, As, Pb, Sb, Sn, a.o. along to the main magma above and at late stage to granophyric veins. The Fe-enriched gabbros in the transitional zone are commonly accepted as average gabbros, but are in the Triple Group mixes of cumulus phases and evolved Fe-rich melt and should be used with care in the modeling of lines of liquid descent.

Method for surface treatment of a cadmium zinc telluride crystal

DOEpatents

James, R.; Burger, A.; Chen, K.T.; Chang, H.

1999-08-03

A method for treatment of the surface of a CdZnTe (CZT) crystal is disclosed that reduces surface roughness (increases surface planarity) and provides an oxide coating to reduce surface leakage currents and thereby, improve resolution. A two step process is disclosed, etching the surface of a CZT crystal with a solution of lactic acid and bromine in ethylene glycol, following the conventional bromine/methanol etch treatment, and after attachment of electrical contacts, oxidizing the CZT crystal surface. 3 figs.

Surface characteristics of anodized and hydrothermally treated titatnium with an increasing concentration of calcium ion

NASA Astrophysics Data System (ADS)

Park, Il Song; Bae, Tae Sung; Seol, Kyeong Won

2006-10-01

Titanium is widely used as an implant material due to its good mechanical properties and the excellent biocompatibility of the oxide film on the surface. To modify the unstable oxide surface of pure titanium, plasma electrolytic oxidation was applied in this study. The electrolyte used for anodizing was a mixture of GP (glycerophosphate disodium salt) and CA (calcium acetate). In addition, a hydrothermal treatment was performed to precipitate a calcium phosphate crystal on the titanium oxide layer for bioactivity. The effect of the CA concentration of the electrolyte on the surface of titanium was investigated, with CA concentrations at 0.1 M, 0.2 M, and 0.3 M. A high concentration of CA results in a low breakdown voltage; hence many large micropores were formed on the anodized surface. Moreover, the size of the HA crystals was more minute in proportion to the increasing concentration of CA. The crystal phase of titanium dioxide was mainly anatase, and a rutile phase was also observed. As the size and/or amount of HA crystals increased, the surface roughness increased. However, the surface roughness could be decreased by fully and uniformly covering the surface with HA crystals. The corrosion resistance in the saline solution was increased by anodic spark oxidation. In addition, it was slightly increased by a hydrothermal treatment. It is considered that a more stable and thicker titanium oxide layer is formed by anodic oxidation and a hydrothermal treatment.

Rheological Characterization of Molten Polymer-Drug Dispersions as a Predictive Tool for Pharmaceutical Hot-Melt Extrusion Processability.

PubMed

Van Renterghem, Jeroen; Vervaet, Chris; De Beer, Thomas

2017-11-01

The aim of this study was to investigate (i) the influence of drug solid-state (crystalline or dissolved in the polymer matrix) on the melt viscosity and (ii) the influence of the drug concentration, temperature and shear rate on polymer crystallization using rheological tests. Poly (ethylene oxide) (PEO) (100.000 g/mol) and physical mixtures (PM) containing 10-20-30-40% (w/w) ketoprofen or 10% (w/w) theophylline in PEO were rheologically characterized. Rheological tests were performed (frequency and temperature sweeps in oscillatory shear as well as shear-induced crystallization experiments) to obtain a thorough understanding of the flow behaviour and crystallization of PEO-drug dispersions. Theophylline did not dissolve in PEO as the complex viscosity (η*) of the drug-polymer mixture increased as compared to that of neat PEO. In contrast, ketoprofen dissolved in PEO and acted as a plasticizer, decreasing η*. Acting as a nucleating agent, theophylline induced the crystallization of PEO upon cooling from the melt. On the other hand, ketoprofen inhibited crystallization upon cooling. Moreover, higher concentrations of ketoprofen in the drug-polymer mixture increasingly inhibited polymer crystallization. However, shear-induced crystallization was observed for all tested mixtures containing ketoprofen. The obtained rheological results are relevant for understanding and predicting HME processability (e.g., barrel temperature selection) and downstream processing such as injection moulding (e.g., mold temperature selection).

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Crystal Growth Technology

NASA Astrophysics Data System (ADS)

Scheel, Hans J.; Fukuda, Tsuguo

2004-06-01

This volume deals with the technologies of crystal fabrication, of crystal machining, and of epilayer production and is the first book on industrial and scientific aspects of crystal and layer production. The major industrial crystals are treated: Si, GaAs, GaP, InP, CdTe, sapphire, oxide and halide scintillator crystals, crystals for optical, piezoelectric and microwave applications and more. Contains 29 contributions from leading crystal technologists covering the following topics:

General aspects of crystal growth technology Silicon Compound semiconductors Oxides and halides Crystal machining Epitaxy and layer deposition Scientific and technological problems of production and machining of industrial crystals are discussed by top experts, most of them from the major growth industries and crystal growth centers. In addition, it will be useful for the users of crystals, for teachers and graduate students in materials sciences, in electronic and other functional materials, chemical and metallurgical engineering, micro-and optoelectronics including nanotechnology, mechanical engineering and precision-machining, microtechnology, and in solid-state sciences.

• Crystal growth of triphenylphosphine oxide 4-nitrophenol (TP4N) for nonlinear optical (NLO) applications

  NASA Astrophysics Data System (ADS)

  Pandian, Muthu Senthil; Karuppasamy, P.; Kamalesh, T.; Ramasamy, P.; Verma, Sunil

  2018-04-01

  The optically good quality organic single crystals of triphenylphosphine oxide 4-nitrophenol (TP4N) were successfully grown by slow evaporation solution technique (SEST) using methanol as solvent. The lattice parameters of the grown crystal were confirmed by single crystal X-ray diffraction analysis. The optical transmittance, cut-off wavelength and band gap of the TP4N crystal were obtained by UV-Vis NIR spectrum analysis. The photoluminescence studies were carried out to find out the luminesce properties of TP4N single crystal. The photoconductivity studies reveal that the TP4N crystal has negative photoconductive nature. The third order nonlinear susceptibility (χ(3)) of TP4N crystal was evaluated using the Z-scan technique at 640 nm.

• Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

  PubMed

  Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

  2015-01-05

  Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.

• Effects of Borax on the Reduction of Pre-oxidized Panzhihua Ilmenite

  NASA Astrophysics Data System (ADS)

  Guo, Yufeng; Zheng, Fuqiang; Jiang, Tao; Chen, Feng; Wang, Shuai; Qiu, Guanzhou

  2018-01-01

  The effects of borax (sodium borate) on the enhancement reduction of pre-oxidized Panzhihua ilmenite were investigated. The effects of borax on the mineral phase transformation, microstructures, crystal cell parameter, melting point and Mg distribution were studied to reveal the mechanism of enhancement reduction. Under the constant reduction conditions, the borax could reduce the reduction activation energy of pre-oxidized ilmenite. The reduction kinetics analysis indicated that the reduction rate was controlled by interfacial chemical reaction. The reduction activation energy of the pre-oxidized ilmenite with 4% borax was 80.263 kJ/mol, which was 28.585 kJ/mol less than that of the pre-oxidized ilmenite without borax. Borax could eliminate the migration of Mg into the reduced particle center. The crystal cell parameter of the reduced product was increased by adding borax. Borax could improve the growth of dendritic crystals in the pre-oxidized ilmenite.

• A convenient synthetic route to benz[cd]azulenes: versatile ligands with the potential to bind metals in an eta5, eta6, or eta7 fashion.

  PubMed

  Balduzzi, Sonya; Müller-Bunz, Helge; McGlinchey, Michael J

  2004-10-25

  A facile method for preparing the 2H-benz[cd]azulene system, based upon an elaboration of the guaiazulene framework, is presented. Aerial oxidation to the corresponding 8-(2-propylidene)-benz[cd]azulene, and also cycloaddition reactions with tetracyanoethylene (TCNE), are described. The first X-ray crystal structure of a 2H-benz[cd]azulene, as an eta6-coordinated Cr(CO)3 complex, is reported.

Advanced Organic Solid States Materials. Volume 173. Materials Research Society Symposium Proceedings

DTIC Science & Technology

1990-08-08

for their collaboration in synthetic study. We also thank Prof. N. Kasai and Dr. Y. Kai for their collaboration in X - ray crystallographic study. We...substantially with the increasing amount of doping as monitored by the powder x - ray diffraction. After doping the sample was kept for at least one day...physical properties at different oxidation states in solution and in the solid state of tEDTB complexed with TCNQF4. The X ray crystal structure of

Polymer-bound oxidovanadium(IV) and dioxidovanadium(V) complexes as catalysts for the oxidative desulfurization of model fuel diesel.

PubMed

Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Kuznetsov, Maxim L; Avecilla, Fernando; Costa Pessoa, João

2010-07-19

The Schiff base (Hfsal-dmen) derived from 3-formylsalicylic acid and N,N-dimethyl ethylenediamine has been covalently bonded to chloromethylated polystyrene to give the polymer-bound ligand, PS-Hfsal-dmen (I). Treatment of PS-Hfsal-dmen with [V(IV)O(acac)(2)] in the presence of MeOH gave the oxidovanadium(IV) complex PS-[V(IV)O(fsal-dmen)(MeO)] (1). On aerial oxidation in methanol, complex 1 was oxidized to PS-[V(V)O(2)(fsal-dmen)] (2). The corresponding neat complexes, [V(IV)O(sal-dmen)(acac)] (3) and [V(V)O(2)(sal-dmen)] (4) were similarly prepared. All these complexes are characterized by various spectroscopic techniques (IR, electronic, NMR, and electron paramagnetic resonance (EPR)) and thermal as well as field-emission scanning electron micrographs (FE-SEM) studies, and the molecular structures of 3 and 4 were determined by single crystal X-ray diffraction. The EPR spectrum of the polymer supported V(IV)O-complex 1 is characteristic of magnetically diluted V(IV)O-complexes, the resolved EPR pattern indicating that the V(IV)O-centers are well dispersed in the polymer matrix. A good (51)V NMR spectrum could also be measured with 4 suspended in dimethyl sulfoxide (DMSO), the chemical shift (-503 ppm) being compatible with a VO(2)(+)-center and a N,O binding set. The catalytic oxidative desulfurization of organosulfur compounds thiophene, dibenzothiophene, benzothiophene, and 2-methyl thiophene (model of fuel diesel) was carried out using complexes 1 and 2. The sulfur in model organosulfur compounds oxidizes to the corresponding sulfone in the presence of H(2)O(2). The systems 1 and 2 do not loose efficiency for sulfoxidation at least up to the third cycle of reaction, this indicating that they preserve their integrity under the conditions used. Plausible intermediates involved in these catalytic processes are established by UV-vis, EPR, (51)V NMR, and density functional theory (DFT) studies, and an outline of the mechanism is proposed. The (51)V NMR spectra recorded for solutions in methanol confirm that complex 4, on treatment with H(2)O(2), is able to generate peroxo-vanadium(V) complexes, including quite stable protonated peroxo-V(V)-complexes [V(V)O(O)(2)(sal-dmen-NH(+))]. The (51)V NMR and DFT data indicate that formation of the intermediate hydroxido-peroxo-V(V)-complex [V(V)(OH)(O(2))(sal-dmen)](+) does not occur, but instead protonated [V(V)O(O)(2)(sal-dmen-NH(+))] complexes form and are relevant for catalytic action.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, Edith D.

1992-01-01

A method for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B.sub.x O.sub.y are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T.sub.m1 of the oxide of boron (T.sub.m1 =723.degree. K. for boron oxide B.sub.2 O.sub.3), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T.sub.m2 of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm.sup.2. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 .mu.m.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, E.D.

1992-07-21

A method is disclosed for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B[sub x]O[sub y] are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T[sub m1] of the oxide of boron (T[sub m1]=723 K for boron oxide B[sub 2]O[sub 3]), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T[sub m2] of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm[sup 2]. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 [mu]m. 7 figs.

New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Daria L.; Beltrán-Suito, Rodrigo; Thomsen, Julianne M.

2016-02-05

This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation processmore » requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.« less

Effect of surface site interactions on potentiometric titration of hematite (α-Fe2O3) crystal faces.

PubMed

Chatman, Shawn; Zarzycki, P; Preočanin, T; Rosso, K M

2013-02-01

Time dependent potentiometric pH titrations were used to study the effect of atomic scale surface structure on the protonation behavior of the structurally well-defined hematite/electrolyte interfaces. Our recently proposed thermodynamic model [1,25] was applied to measured acidimetric and alkalimetric titration hysteresis loops, collected from highly organized (001), (012), and (113) crystal face terminations using pH equilibration times ranging from 15 to 30 min. Hysteresis loop areas indicate that (001) faces equilibrate faster than the (012) and (113) faces, consistent with the different expected ensembles of singly-, doubly-, and triply-coordinated surface sites on each face. Strongly non-linear hysteretic pH-potential relationships were found, with slopes exceeding Nernstian, collectively indicating that protonation and deprotonation is much more complex than embodied in present day surface complexation models. The asymmetrical shape of the acidimetric and alkalimetric titration branches were used to illustrate a proposed steric "leaky screen" repulsion/trapping interaction mechanism that stems from high affinity singly-coordinated sites electrostatically and sterically screening lower affinity doubly- and triply-coordinated sites. Our data indicate that site interaction is the dominant phenomenon defining surface potential accumulation behavior on single crystal faces of metal oxide minerals. Copyright © 2012 Elsevier Inc. All rights reserved.

Computational insights on crystal structures of the oxygen-evolving complex of photosystem II with either Ca²⁺ or Ca²⁺ substituted by Sr²⁺

DOE PAGES

Vogt, Leslie; Ertem, Mehmed Z.; Pal, Rhitankar; ...

2015-01-15

The oxygen-evolving complex of photosystem II can function with either Ca²⁺ or Sr²⁺ as the heterocation, but the reason for differing turnover rates remains unresolved despite reported X-ray crystal structures for both forms. Using quantum mechanics/molecular mechanics (QM/MM) calculations, we optimize structures with each cation in both the resting state (S₁) and in a series of reduced states (S₀, S₋₁, and S-₂). Through comparison with experimental data, we determine that X-ray crystal structures with either Ca²⁺ or Sr²⁺ are most consistent with the S-₂ state, Mn₄[III,III,III,II] with O4 and O5 protonated. As expected, the QM/MM models show that Ca²⁺/Sr²⁺ substitutionmore » results in elongation of the heterocation bonds and displaces terminal waters W3 and W4. The optimized structures also show that hydrogen-bonded W5 is displaced in all S states with Sr²⁺ as the heterocation, suggesting that this water may play a critical role during water oxidation.« less

Experimental and Numerical Study of Ammonium Perchlorate Counterflow Diffusion Flames

NASA Technical Reports Server (NTRS)

Smooke, M. D.; Yetter, R. A.; Parr, T. P.; Hanson-Parr, D. M.; Tanoff, M. A.

1999-01-01

Many solid rocket propellants are based on a composite mixture of ammonium perchlorate (AP) oxidizer and polymeric binder fuels. In these propellants, complex three-dimensional diffusion flame structures between the AP and binder decomposition products, dependent upon the length scales of the heterogeneous mixture, drive the combustion via heat transfer back to the surface. Changing the AP crystal size changes the burn rate of such propellants. Large AP crystals are governed by the cooler AP self-deflagration flame and burn slowly, while small AP crystals are governed more by the hot diffusion flame with the binder and burn faster. This allows control of composite propellant ballistic properties via particle size variation. Previous measurements on these diffusion flames in the planar two-dimensional sandwich configuration yielded insight into controlling flame structure, but there are several drawbacks that make comparison with modeling difficult. First, the flames are two-dimensional and this makes modeling much more complex computationally than with one-dimensional problems, such as RDX self- and laser-supported deflagration. In addition, little is known about the nature, concentration, and evolution rates of the gaseous chemical species produced by the various binders as they decompose. This makes comparison with models quite difficult. Alternatively, counterflow flames provide an excellent geometric configuration within which AP/binder diffusion flames can be studied both experimentally and computationally.

The crystal structure of xanthine oxidoreductase during catalysis: Implications for reaction mechanism and enzyme inhibition

PubMed Central

Okamoto, Ken; Matsumoto, Koji; Hille, Russ; Eger, Bryan T.; Pai, Emil F.; Nishino, Takeshi

2004-01-01

Molybdenum is widely distributed in biology and is usually found as a mononuclear metal center in the active sites of many enzymes catalyzing oxygen atom transfer. The molybdenum hydroxylases are distinct from other biological systems catalyzing hydroxylation reactions in that the oxygen atom incorporated into the product is derived from water rather than molecular oxygen. Here, we present the crystal structure of the key intermediate in the hydroxylation reaction of xanthine oxidoreductase with a slow substrate, in which the carbon–oxygen bond of the product is formed, yet the product remains complexed to the molybdenum. This intermediate displays a stable broad charge–transfer band at ≈640 nm. The crystal structure of the complex indicates that the catalytically labile Mo—OH oxygen has formed a bond with a carbon atom of the substrate. In addition, the Mo⋕S group of the oxidized enzyme has become protonated to afford Mo—SH on reduction of the molybdenum center. In contrast to previous assignments, we find this last ligand at an equatorial position in the square-pyramidal metal coordination sphere, not the apical position. A water molecule usually seen in the active site of the enzyme is absent in the present structure, which probably accounts for the stability of this intermediate toward ligand displacement by hydroxide. PMID:15148401

The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation

DOE PAGES

Matheu, Roc; Ertem, Mehmed Z.; Pipelier, Muriel; ...

2018-01-19

A family of Ru complexes based on the pentadentate ligand t5a 3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {Ru II(Ht5a-κ-N 2O)(py) 3} (1H II(κ-N 2O)), {Ru III(t5a-κ-N 3O 1.5)(py) 2} (2 III(κ-N 3O 1.5)), and {Ru IV(t5a-κ-N 3O 2)(py) 2}+ ({2 IV(κ-N3O 2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N 2O), 2 III(κ-N 3O 1.5), and {2 IV(κ-N 3O 2)}+ have been investigated in solution by spectroscopic methods (NMR, UV–vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2 III(κ-N 3O 1.5) have beenmore » studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a 3– ligand. Under neutral to basic conditions complex {2 IV(κ-N3O 2)}+ undergoes aquation, generating {Ru IV(OH)(t5a-κ-N 2O)(py) 2} (2 IV(OH)(κ-N 2O)). Further oxidation of the complex forms {Ru V(O)(t5a-κ-N 2O)(py) 2} (2 V(O)(κ-N 2O)), which is a very efficient water oxidation catalyst, reaching a TOF MAX value of 9400 s –1 at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2 V(O)(κ-N 2O) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.« less

The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matheu, Roc; Ertem, Mehmed Z.; Pipelier, Muriel

A family of Ru complexes based on the pentadentate ligand t5a 3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {Ru II(Ht5a-κ-N 2O)(py) 3} (1H II(κ-N 2O)), {Ru III(t5a-κ-N 3O 1.5)(py) 2} (2 III(κ-N 3O 1.5)), and {Ru IV(t5a-κ-N 3O 2)(py) 2}+ ({2 IV(κ-N3O 2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N 2O), 2 III(κ-N 3O 1.5), and {2 IV(κ-N 3O 2)}+ have been investigated in solution by spectroscopic methods (NMR, UV–vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2 III(κ-N 3O 1.5) have beenmore » studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a 3– ligand. Under neutral to basic conditions complex {2 IV(κ-N3O 2)}+ undergoes aquation, generating {Ru IV(OH)(t5a-κ-N 2O)(py) 2} (2 IV(OH)(κ-N 2O)). Further oxidation of the complex forms {Ru V(O)(t5a-κ-N 2O)(py) 2} (2 V(O)(κ-N 2O)), which is a very efficient water oxidation catalyst, reaching a TOF MAX value of 9400 s –1 at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2 V(O)(κ-N 2O) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.« less

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

NASA Astrophysics Data System (ADS)

Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

2016-05-01

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet and magnesium oxide.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

Crystal Structure Characterization of Thin Layer Zinc Oxide

NASA Astrophysics Data System (ADS)

Doyan, Aris; Susilawati; Azizatul Fitri, Siti; Ahzan, Sukainil

2017-05-01

In this research the characterization of the crystal structure of a thin layer of ZnO (zinc oxide) were synthesized by sol - gel method and spin coating deposited on a glass substrate. The samples were divided into three sol concentrations of 0.1, 0.3, 0.5 Molar and two deposition temperature is 350 °C, and 550 °C. UV-Vis. spectrophotometer results showed that in the spectrum of visible light (wavelength range 300-800 nm) has a transmittance value of which increases with increasing concentration and temperature deposition of zinc oxide, otherwise the value of the absorption and the band gap energy decreases with the addition of concentration and deposition temperature. The transmittances value of the highest and lowest absorption was 93.5% and 0.03 is at a concentration of 0.1 M and zinc oxide deposition temperature of 550 °C, with a value of band gap energy of 2.98 eV. The XRD results showed that the zinc oxide crystal orientation in the field of 013 with a crystal grain size 14.4472 nm. SEM results showed the surface morphology of zinc oxide such as rod-like.

Uranium metallogenesis of the peraluminous leucogranite from the Pontivy-Rostrenen magmatic complex (French Armorican Variscan belt): the result of long-term oxidized hydrothermal alteration during strike-slip deformation

NASA Astrophysics Data System (ADS)

Ballouard, C.; Poujol, M.; Mercadier, J.; Deloule, E.; Boulvais, P.; Baele, J. M.; Cuney, M.; Cathelineau, M.

2018-06-01

In the French Armorican Variscan belt, most of the economically significant hydrothermal U deposits are spatially associated with peraluminous leucogranites emplaced along the south Armorican shear zone (SASZ), a dextral lithospheric scale wrench fault that recorded ductile deformation from ca. 315 to 300 Ma. In the Pontivy-Rostrenen complex, a composite intrusion, the U mineralization is spatially associated with brittle structures related to deformation along the SASZ. In contrast to monzogranite and quartz monzodiorite (3 < U < 9 ppm; Th/U > 3), the leucogranite samples are characterized by highly variable U contents ( 3 to 27 ppm) and Th/U ratios ( 0.1 to 5) suggesting that the crystallization of magmatic uranium oxide in the more evolved facies was followed by uranium oxide leaching during hydrothermal alteration and/or surface weathering. U-Pb dating of uranium oxides from the deposits reveals that they mostly formed between ca. 300 and 270 Ma. In monzogranite and quartz monzodiorite, apatite grains display magmatic textures and provide U-Pb ages of ca. 315 Ma reflecting the time of emplacement of the intrusions. In contrast, apatite grains from the leucogranite display textural, geochemical, and geochronological evidences for interaction with U-rich oxidized hydrothermal fluids contemporaneously with U mineralizing events. From 300 to 270 Ma, infiltration of surface-derived oxidized fluids leached magmatic uranium oxide from fertile leucogranite and formed U deposits. This phenomenon was sustained by brittle deformation and by the persistence of thermal anomalies associated with U-rich granitic bodies.

Tirandamycin biosynthesis is mediated by co-dependent oxidative enzymes

NASA Astrophysics Data System (ADS)

Carlson, Jacob C.; Li, Shengying; Gunatilleke, Shamila S.; Anzai, Yojiro; Burr, Douglas A.; Podust, Larissa M.; Sherman, David H.

2011-08-01

Elucidation of natural product biosynthetic pathways provides important insights into the assembly of potent bioactive molecules, and expands access to unique enzymes able to selectively modify complex substrates. Here, we show full reconstitution, in vitro, of an unusual multi-step oxidative cascade for post-assembly-line tailoring of tirandamycin antibiotics. This pathway involves a remarkably versatile and iterative cytochrome P450 monooxygenase (TamI) and a flavin adenine dinucleotide-dependent oxidase (TamL), which act co-dependently through the repeated exchange of substrates. TamI hydroxylates tirandamycin C (TirC) to generate tirandamycin E (TirE), a previously unidentified tirandamycin intermediate. TirE is subsequently oxidized by TamL, giving rise to the ketone of tirandamycin D (TirD), after which a unique exchange back to TamI enables successive epoxidation and hydroxylation to afford, respectively, the final products tirandamycin A (TirA) and tirandamycin B (TirB). Ligand-free, substrate- and product-bound crystal structures of bicovalently flavinylated TamL oxidase reveal a likely mechanism for the C10 oxidation of TirE.

Reactions of copper macrocycles with antioxidants and HOCl: potential for biological redox sensing.

PubMed

Sowden, Rebecca J; Trotter, Katherine D; Dunbar, Lynsey; Craig, Gemma; Erdemli, Omer; Spickett, Corinne M; Reglinski, John

2013-02-01

A series of simple copper N(2)S(2) macrocycles were examined for their potential as biological redox sensors, following previous characterization of their redox potentials and crystal structures. The divalent species were reduced by glutathione or ascorbate at a biologically relevant pH in aqueous buffer. A less efficient reduction was also achieved by vitamin E in DMSO. Oxidation of the corresponding univalent copper species by sodium hypochlorite resulted in only partial (~65 %) recovery of the divalent form. This was concluded to be due to competition between metal oxidation and ligand oxidation, which is believed to contribute to macrocycle demetallation. Electrospray mass spectrometry confirmed that ligand oxidation had occurred. Moreover, the macrocyclic complexes could be demetallated by incubation with EDTA and bovine serum albumin, demonstrating that they would be inappropriate for use in biological systems. The susceptibility to oxidation and demetallation was hypothesized to be due to oxidation of the secondary amines. Consequently these were modified to incorporate additional oxygen donor atoms. This modification led to greater resistance to demetallation and ligand oxidation, providing a better platform for further development of copper macrocycles as redox sensors for use in biological systems.

Synthesis, crystal, and biological activity of a novel carbene silver(I) complex with imidazole derivative

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiu-Fu, Lu, E-mail: jiufulu@163.com; Hong-Guang, Ge; Juan, Shi

2015-12-15

Reaction of 2-(1-methyl-1,2-dihydroimidazol-3-yl)acetonitrile tetrafluoroborate with silver oxide in dichloromethane readily yields [Ag(DIM){sub 2}]BF{sub 4}, where DIM is 2-(1-methyl-1, 2-dihydroimidazol-3-yl)acetonitrile, representing a carbene organic ligand. The title compound was characterized by elemental analysis, IR, MS and single crystal X-ray diffraction. The crystal is of monoclinic system, space group C2/c with a = 14.010(18), b = 8.303(11), c = 14.936(20) Å, β = 93.910(4)°, V = 1639(4) Å{sup 3}, Z = 4, D{sub x} = 1.771 g/cm{sup 3}, F (000) = 864, µ(MoK{sub α}) = 1.278 mm{sup –1}. The final R{sup 1} = 0.0711 and wR{sup 2} = 0.1903 for reflections withmore » I > 2σ(I). In addition, the preliminary biological test showed that the title compound had anti-fungus yeast activity.« less

The Effect of Hydrogen Annealing on the Oxidation Resistance of Four EPM Single Crystal Superalloys

NASA Technical Reports Server (NTRS)

Smialek, James L.; Barrett, Charles A.; Garlick, Ralph G.

2001-01-01

Four single crystal EPM (enabling propulsion materials) developmental airfoil superalloys were hydrogen annealed at 1300 C for up to 100 hours to remove sulfur and improve oxidation resistance. Although the 1100 and 1150 C cyclic oxidation resistance was remarkably improved by annealing for 24 or 100 hours, the behavior was still considerably inferior to that of commercially available single crystal superalloys, especially those that are either Y-doped or hydrogen annealed. Excessive degradation in the developmental alloys appeared to be correlated with low Cr contents and, to a lesser extent, high Co and Re contents.

X-ray Crystal Truncation Rod Studies of Surface Oxidation and Reduction on Pt(111)

DOE PAGES

Liu, Yihua; Barbour, Andi; Komanicky, Vladimir; ...

2016-02-26

Here, we present X-ray crystal truncation rods measurements of Pt(111) surface under electrochemical conditions. Analyses of crystal truncation rods reveal that surface oxide formation buckles the top surface layer of platinum to two different heights at the potential (0.95 V vs RHE) below the so-called place-exchange potential. While the anti-Bragg intensity, sensitive to the top surface layer, drops in response to the anodic charge transfers, its responses to the cathodic charge transfers are significantly delayed. Implications to the surface oxidation and reduction behaviors are discussed.

Influence of Oxidation in Starting Material Sn on Electric Transport Properties of SnSe Single Crystals

NASA Astrophysics Data System (ADS)

Yamashita, Aichi; Ogiso, Osamu; Matsumoto, Ryo; Tanaka, Masashi; Hara, Hiroshi; Tanaka, Hiromi; Takeya, Hiroyuki; Lee, Chul-Ho; Takano, Yoshihiko

2018-06-01

We found that the electronic transport property of SnSe single crystals was sensitively affected by oxidation in raw Sn. Semiconducting SnSe single crystals were obtained by using Sn of grain form as a starting material while powder Sn resulted in metallic SnSe. X-ray photoelectron spectroscopy analysis revealed that the surfaces of raw Sn were oxidized, which volume fraction is lower in grain Sn. This indicates that the amount of oxygen in raw Sn is the key factor for the electronic transport property of SnSe.

Effect of polar surfaces on organic molecular crystals

NASA Astrophysics Data System (ADS)

Sharia, Onise; Tsyshevskiy, Roman; Kuklja, Maija; University of Maryland College Park Team

Polar oxide materials reveal intriguing opportunities in the field of electronics, superconductivity and nanotechnology. While behavior of polar surfaces has been widely studied on oxide materials and oxide-oxide interfaces, manifestations and properties of polar surfaces in molecular crystals are still poorly understood. Here we discover that the polar catastrophe phenomenon, known on oxides, also takes place in molecular materials as illustrated with an example of cyclotetramethylene tetranitramine (HMX) crystals. We show that the surface charge separation is a feasible compensation mechanism to counterbalance the macroscopic dipole moment and remove the electrostatic instability. We discuss the role of surface charge on degradation of polar surfaces, electrical conductivity, optical band-gap closure and surface metallization. Research is supported by the US ONR (Grants N00014-16-1-2069 and N00014-16-1-2346) and NSF. We used NERSC, XSEDE and MARCC computational resources.

A combined experimental and DFT study of active structures and self-cycle mechanisms of mononuclear tungsten peroxo complexes in oxidation reactions

NASA Astrophysics Data System (ADS)

Jin, Peng; Wei, Donghui; Wen, Yiqiang; Luo, Mengfei; Wang, Xiangyu; Tang, Mingsheng

2011-04-01

Tungsten peroxo complexes have been widely used in olefin epoxidation, alcohol oxidation, Baeyer-Villiger oxidation and other oxidation reactions, however, there is still not a unanimous viewpoint for the active structure of mononuclear tungsten peroxo complex by now. In this paper, the catalysis of mononuclear tungsten peroxo complexes 0- 5 with or without acidic ligands for the green oxidation of cyclohexene to adipic acid in the absence of organic solvent and phase-transfer catalyst has been researched in experiment. Then we have suggested two possible kinds of active structures of mononuclear tungsten peroxo complexes including peroxo ring ( nA, n = 0-1) and hydroperoxo ( nB, n = 0-1) structures, which have been investigated using density functional theory (DFT). Moreover, the calculations on self-cycle mechanisms involving the two types of active structures of tungsten peroxo complexes with and without oxalic acid ligand have also been carried out at the B3LYP/[LANL2DZ/6-31G(d, p)] level. The highest energy barrier are 26.17 kcal/mol ( 0A, peroxo ring structure without oxalic acid ligand), 23.91 kcal/mol ( 1A, peroxo ring structure with oxalic acid ligand), 18.19 kcal/mol ( 0B, hydroperoxo structure without oxalic acid ligand) and 13.10 kcal/mol ( 1B, hydroperoxo structure with oxalic acid ligand) in the four potential energy profiles, respectively. The results indicate that both the energy barriers of active structure self-cycle processes with oxalic acid ligands are lower than those without oxalic acid ligands, so the active structures with oxalic acid ligands should be easier to recycle, which is in good agreement with our experimental results. However, due to the higher energy of product than that of the reactant, the energy profile of the self-cycle process of 1B shows that the recycle of 1B could not occur at all in theory. Moreover, the crystal data of peroxo ring structure with oxalic acid ligand could be found in some experimental references. Thus, the viewpoint that the peroxo ring active structure should be the real active structure has been proved in this paper.

Assessment of ligand binding at a site relevant to SOD1 oxidation and aggregation.

PubMed

Manjula, Ramu; Wright, Gareth S A; Strange, Richard W; Padmanabhan, Balasundaram

2018-05-01

Cu/Zn superoxide dismutase-1 (SOD1) mutations are causative for a subset of amyotrophic lateral sclerosis (ALS) cases. These mutations lead to structural instability, aggregation and ultimately motor neuron death. We have determined crystal structures of SOD1 in complex with a naphthalene-catechol-linked compound which binds with low micro-molar affinity to a site important for oxidative damage-induced aggregation. SOD1 Trp32 oxidation is indeed significantly inhibited by ligand binding. Our work shows how compound linking can be applied successfully to ligand interactions on the SOD1 surface to generate relatively good binding strength. The ligand, positioned in a region important for SOD1 fibrillation, offers the possibility that it, or a similar compound, could prevent the abnormal self-association that drives SOD1 toxicity in ALS. © 2018 Federation of European Biochemical Societies.

High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

PubMed Central

Rivas-Murias, Beatriz; Manuel Vila-Fungueiriño, José; Rivadulla, Francisco

2015-01-01

Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures. PMID:26153533

Resolution of 1-n-butyl-3-methyl-3-phospholene 1-oxide with TADDOL derivatives and calcium salts of O,O'-Dibenzoyl-(2R,3R)- or O,O'-di-p-toluoyl-(2R,3R)-tartaric acid.

PubMed

Bagi, Péter; Fekete, András; Kállay, Mihály; Hessz, Dóra; Kubinyi, Miklós; Holczbauer, Tamás; Czugler, Mátyás; Fogassy, Elemér; Keglevich, György

2014-03-01

The resolution methods applying (-)-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane ("TADDOL"), (-)-(2R,3R)-α,α,α',α'-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol ("spiro-TADDOL"), as well as the acidic and neutral Ca(2+) salts of (-)-O,O'-dibenzoyl- and (-)-O,O'-di-p-toluoyl-(2R,3R)-tartaric acid were extended for the preparation of 1-n-butyl-3-methyl-3-phospholene 1-oxide in optically active form. In one case, the intermediate diastereomeric complex could be identified by single-crystal X-ray analysis. The absolute P-configuration of the enantiomers of the phospholene oxide was also determined by comparing the experimentally obtained and calculated CD spectra. © 2014 Wiley Periodicals, Inc.

Structural insights into enzymatic degradation of oxidized polyvinyl alcohol.

PubMed

Yang, Yu; Ko, Tzu-Ping; Liu, Long; Li, Jianghua; Huang, Chun-Hsiang; Chan, Hsiu-Chien; Ren, Feifei; Jia, Dongxu; Wang, Andrew H-J; Guo, Rey-Ting; Chen, Jian; Du, Guocheng

2014-09-05

The ever-increasing production and use of polyvinyl alcohol (PVA) threaten our environment. Yet PVA can be assimilated by microbes in two steps: oxidation and cleavage. Here we report novel α/β-hydrolase structures of oxidized PVA hydrolase (OPH) from two known PVA-degrading organisms, Sphingopyxis sp. 113P3 and Pseudomonas sp. VM15C, including complexes with substrate analogues, acetylacetone and caprylate. The active site is covered by a lid-like β-ribbon. Unlike other esterase and amidase, OPH is unique in cleaving the CC bond of β-diketone, although it has a catalytic triad similar to that of most α/β-hydrolases. Analysis of the crystal structures suggests a double-oxyanion-hole mechanism, previously only found in thiolase cleaving β-ketoacyl-CoA. Three mutations in the lid region showed enhanced activity, with potential in industrial applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and synthesis of a tetradentate '3-amine-1-carboxylate' ligand to mimic the metal binding environment at the non-heme iron(II) oxidase active site.

PubMed

Dungan, Victoria J; Ortin, Yannick; Mueller-Bunz, Helge; Rutledge, Peter J

2010-04-07

Non-heme iron(II) oxidases (NHIOs) catalyse a diverse array of oxidative chemistry in Nature. As part of ongoing efforts to realize biomimetic, iron-mediated C-H activation, we report the synthesis of a new 'three-amine-one-carboxylate' ligand designed to complex with iron(II) and mimic the NHIO active site. The tetradentate ligand has been prepared as a single enantiomer in nine synthetic steps from N-Cbz-L-alanine, pyridine-2,6-dimethanol and diphenylamine, using Seebach oxazolidinone chemistry to control the stereochemistry. X-Ray crystal structures are reported for two important intermediates, along with variable temperature NMR experiments to probe the hindered interconversion of conformational isomers of several key intermediates, 2,6-disubstituted pyridine derivatives. The target ligand and an N-Cbz-protected precursor were each then complexed with iron(II) and tested for their ability to promote alkene dihydroxylation, using hydrogen peroxide as the oxidant.

Dynamic defect correlations dominate activated electronic transport in SrTiO3

PubMed Central

Snijders, Paul C.; Şen, Cengiz; McConnell, Michael P.; Ma, Ying-Zhong; May, Andrew F.; Herklotz, Andreas; Wong, Anthony T.; Ward, T. Zac

2016-01-01

Strontium titanate (SrTiO3, STO) is a critically important material for the study of emergent electronic phases in complex oxides, as well as for the development of applications based on their heterostructures. Despite the large body of knowledge on STO, there are still many uncertainties regarding the role of defects in the properties of STO, including their influence on ferroelectricity in bulk STO and ferromagnetism in STO-based heterostructures. We present a detailed analysis of the decay of persistent photoconductivity in STO single crystals with defect concentrations that are relatively low but significantly affect their electronic properties. The results show that photo-activated electron transport cannot be described by a superposition of the properties due to independent point defects as current models suggest but is, instead, governed by defect complexes that interact through dynamic correlations. These results emphasize the importance of defect correlations for activated electronic transport properties of semiconducting and insulating perovskite oxides. PMID:27443503

Dynamic defect correlations dominate activated electronic transport in SrTiO 3

DOE PAGES

Snijders, Paul C.; Sen, Cengiz; McConnell, Michael P.; ...

2016-07-22

Strontium titanate (SrTiO 3, STO) is a critically important material for the study of emergent electronic phases in complex oxides, as well as for the development of applications based on their heterostructures. Despite the large body of knowledge on STO, there are still many uncertainties regarding the role of defects in the properties of STO, including their influence on ferroelectricity in bulk STO and ferromagnetism in STO-based heterostructures. In this paper, we present a detailed analysis of the decay of persistent photoconductivity in STO single crystals with defect concentrations that are relatively low but significantly affect their electronic properties. Themore » results show that photo-activated electron transport cannot be described by a superposition of the properties due to independent point defects as current models suggest but is, instead, governed by defect complexes that interact through dynamic correlations. In conclusion, these results emphasize the importance of defect correlations for activated electronic transport properties of semiconducting and insulating perovskite oxides.« less

Oxygen isotope trajectories of crystallizing melts: Insights from modeling and the plutonic record

NASA Astrophysics Data System (ADS)

Bucholz, Claire E.; Jagoutz, Oliver; VanTongeren, Jill A.; Setera, Jacob; Wang, Zhengrong

2017-06-01

Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ18O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ18O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ18O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ18O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO2 content, and high temperature stability of low δ18O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ18O at degrees of crystallization greater than 80%. Total calculated increases in melt δ18O of 1.0-1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc-related Dariv Igneous Complex (Mongolia). These two sequences were chosen as their major and trace element compositions appear to have been predominantly controlled by closed-system fractional crystallization and their LLDs have been modeled in detail. We calculated equilibrium melt δ18O values using the measured mineral δ18O values and calculated mineral-melt fractionation factors. Increases of 2-3‰ and 1-1.5‰ in the equilibrium melts are observed for the Dariv Igneous Complex and the UUMZ of the Bushveld Complex, respectively. Closed-system fractional crystallization model results reproduce the 1‰ increase observed in the equilibrium melt δ18O for the Bushveld UUMZ, whereas for the Dariv Igneous Complex assimilation of high δ18O material is necessary to account for the increase in melt δ18O values. Assimilation of evolved supracrustal material is also confirmed with Sr and Nd isotope analyses of clinopyroxene from the sequence. Beginning with a range of mantle-derived basalt δ18O values of 5.7‰ ("pristine" mantle) to ∼7.0‰ (heavily subduction-influenced mantle), our model results demonstrated that high-silica melts (i.e. granites) with δ18O of up to 8.5‰ can be produced through fractional crystallization alone. Lastly, we model the zircon-melt δ18O fractionations of different LLDs, emphasizing their dependence on the specific SiO2-T relationships of a given crystallizing melt. Wet, relatively cool granitic melts will have larger zircon-melt fractionations, potentially by ∼1.5‰, compared to hot, dry granites. Therefore, it is critical to constrain zircon-melt fractionations specific to a system of interest when using zircon δ18O values to calculate melt δ18O.

New constraints on the origin of the Skaergaard intrusion Cu-Pd-Au mineralization: Insights from high-resolution X-ray computed tomography

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Rudashevsky, Nikolay S.; Nielsen, Troels F. D.; Barnes, Stephen J.; Rudashevsky, Vladimir N.

2014-03-01

This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe-Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu-Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu-Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe-Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe-Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide + PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe-Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

Amphorous hydrated Fe(III) sulfate: metastable product and bio-geochemical marker of iron oxidizing thiobacilli

NASA Astrophysics Data System (ADS)

Lazaroff, Norman; Jollie, John; Dugan, Patrick R.

1998-07-01

Chemolithotrophic iron oxidation by Thiobacillus ferrooxidans and other iron oxidizing thiobacilli produce an Fe(III) sulfato complex that polymerizes as x-ray amorphous filaments approximately 40 nm in diameter. The precursor complex in solutionis seen by ATR-FTIR spectroscopy to have a sulfate spectrum resembling the v(subscript 3) and v(subscript 1) vibrational modes of the precipitated polymer. Chemically similar precipitates prepared by oxidation of acid ferrous sulfate with hydrogen peroxide have a different micromorphology, higher iron/sulfur ratio and acid solubility than the bacterial product. They possess coalescing globular microstructures composed of compacted micro-fibrils. Scanning electron microscopy and diffuse reflectance FTIR show the formation of iron polymer on the surface of immobilized cells of T. ferrooxidans, oxidizing iron during the corrosion of steel. Although spatially separated form the steel coupons by a membrane filter, the cell walls become covered with tufts of amorphous hydrated Fe(III) sulfate. The metastable polymer is converted to crystalline goethite, lepidocrocite, and magnetite in that order, as the pH rises due to proton reduction at cathodic sites on the steel. The instability of the iron polymer to changes in pH is also evidenced by the loss of sulfate when washed with lithium hydroxide solution at pH 8. Under those conditions there is little change in micromorphology, but restoration of sulfate with sulfuric acid at pH 2.5, fails to re-establish the original chemical structure. Adding sulfate salts of appropriate cations to solutions of the Fe(III) sulfato complex or suspensions of its precipitated polymer in dilute sulfuric acid, result in dissociation of the metastable complex followed by crystallization of ferric ions and sulfate in jarosites. Jarosites and other derivatives of iron precipitation by iron oxidizing thiobacilli, form conspicuous deposits in areas of natural pyrite leaching. The role of iron oxidizing thiobacilli in pyrite leaching, biohydrometallurgy, acid mine drainage, and the cycle of iron and sulfur in nature, has been studied for nearly 50 years. The manifestation of those activities, so widespread on Earth, can be a clue for seeking evidence of life elsewhere.

Dye sensitized solar cell applications of CdTiO3-TiO2 composite thin films deposited from single molecular complex

NASA Astrophysics Data System (ADS)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy; Huang, Nay Ming; Arifin, Zainudin; Mazhar, Muhammad

2015-10-01

A heterobimetallic complex [Cd2Ti4(μ-O)6(TFA)8(THF)6]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO3-TiO2 composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO3-TiO2 composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application.

Synthesis, crystal growth, structural and physicochemical studies of novel binary organic complex: 4-chloroaniline-3-hydroxy-4-methoxybenzaldehyde

NASA Astrophysics Data System (ADS)

Sharma, K. P.; Reddi, R. S. B.; Bhattacharya, S.; Rai, R. N.

2012-06-01

The solid-state reaction, which is solvent free and green synthesis, has been adopted to explore the novel compound. The phase diagram of 4-chloroaniline (CA) and 3-hydroxy-4-methoxybenzaldehyde (HMB) system shows the formation of a novel 1:1 molecular complex, and two eutectics on either sides of complex. Thermochemical studies of complex and eutectics have been carried out for various properties such as heat of fusion, entropy of fusion, Jackson's parameters, interfacial energy and excess thermodynamic functions. The formation of molecular complex was also studied by IR, NMR, elemental analysis and UV-Vis absorption spectra. The single crystal of molecular complex was grown and its XRD study confirms the formation of complex and identifies the crystal structure and atomic packing of crystal of complex. Transmission spectra of grown crystal of the complex show 70% transmittance efficiency with cut off wavelength 412 nm. The band gap and refractive index of the crystal of complex have also been studied.

The Pyruvate and α-Ketoglutarate Dehydrogenase Complexes of Pseudomonas aeruginosa Catalyze Pyocyanin and Phenazine-1-carboxylic Acid Reduction via the Subunit Dihydrolipoamide Dehydrogenase*

PubMed Central

Glasser, Nathaniel R.; Wang, Benjamin X.; Hoy, Julie A.; Newman, Dianne K.

2017-01-01

Phenazines are a class of redox-active molecules produced by diverse bacteria and archaea. Many of the biological functions of phenazines, such as mediating signaling, iron acquisition, and redox homeostasis, derive from their redox activity. Although prior studies have focused on extracellular phenazine oxidation by oxygen and iron, here we report a search for reductants and catalysts of intracellular phenazine reduction in Pseudomonas aeruginosa. Enzymatic assays in cell-free lysate, together with crude fractionation and chemical inhibition, indicate that P. aeruginosa contains multiple enzymes that catalyze the reduction of the endogenous phenazines pyocyanin and phenazine-1-carboxylic acid in both cytosolic and membrane fractions. We used chemical inhibitors to target general enzyme classes and found that an inhibitor of flavoproteins and heme-containing proteins, diphenyleneiodonium, effectively inhibited phenazine reduction in vitro, suggesting that most phenazine reduction derives from these enzymes. Using natively purified proteins, we demonstrate that the pyruvate and α-ketoglutarate dehydrogenase complexes directly catalyze phenazine reduction with pyruvate or α-ketoglutarate as electron donors. Both complexes transfer electrons to phenazines through the common subunit dihydrolipoamide dehydrogenase, a flavoprotein encoded by the gene lpdG. Although we were unable to co-crystallize LpdG with an endogenous phenazine, we report its X-ray crystal structure in the apo-form (refined to 1.35 Å), bound to NAD+ (1.45 Å), and bound to NADH (1.79 Å). In contrast to the notion that phenazines support intracellular redox homeostasis by oxidizing NADH, our work suggests that phenazines may substitute for NAD+ in LpdG and other enzymes, achieving the same end by a different mechanism. PMID:28174304

The Pyruvate and α-Ketoglutarate Dehydrogenase Complexes of Pseudomonas aeruginosa Catalyze Pyocyanin and Phenazine-1-carboxylic Acid Reduction via the Subunit Dihydrolipoamide Dehydrogenase.

PubMed

Glasser, Nathaniel R; Wang, Benjamin X; Hoy, Julie A; Newman, Dianne K

2017-03-31

Phenazines are a class of redox-active molecules produced by diverse bacteria and archaea. Many of the biological functions of phenazines, such as mediating signaling, iron acquisition, and redox homeostasis, derive from their redox activity. Although prior studies have focused on extracellular phenazine oxidation by oxygen and iron, here we report a search for reductants and catalysts of intracellular phenazine reduction in Pseudomonas aeruginosa Enzymatic assays in cell-free lysate, together with crude fractionation and chemical inhibition, indicate that P. aeruginosa contains multiple enzymes that catalyze the reduction of the endogenous phenazines pyocyanin and phenazine-1-carboxylic acid in both cytosolic and membrane fractions. We used chemical inhibitors to target general enzyme classes and found that an inhibitor of flavoproteins and heme-containing proteins, diphenyleneiodonium, effectively inhibited phenazine reduction in vitro , suggesting that most phenazine reduction derives from these enzymes. Using natively purified proteins, we demonstrate that the pyruvate and α-ketoglutarate dehydrogenase complexes directly catalyze phenazine reduction with pyruvate or α-ketoglutarate as electron donors. Both complexes transfer electrons to phenazines through the common subunit dihydrolipoamide dehydrogenase, a flavoprotein encoded by the gene lpdG Although we were unable to co-crystallize LpdG with an endogenous phenazine, we report its X-ray crystal structure in the apo-form (refined to 1.35 Å), bound to NAD + (1.45 Å), and bound to NADH (1.79 Å). In contrast to the notion that phenazines support intracellular redox homeostasis by oxidizing NADH, our work suggests that phenazines may substitute for NAD + in LpdG and other enzymes, achieving the same end by a different mechanism. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Structures, physicochemical and cytoprotective properties of new oxidovanadium(IV) complexes -[VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O

NASA Astrophysics Data System (ADS)

Drzeżdżon, Joanna; Jacewicz, Dagmara; Wyrzykowski, Dariusz; Inkielewicz-Stępniak, Iwona; Sikorski, Artur; Tesmar, Aleksandra; Chmurzyński, Lech

2017-09-01

New oxidovanadium(IV) complexes with a modification of the ligand in the VO2+ coordination sphere were synthesized. [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O were obtained as dark green crystals and grey-green powder, respectively (mIDA = N-methyliminodiacetic anion, IDA = iminodiacetic anion, dmbipy = 4,4‧-dimethoxy-2,2‧-dipyridyl). The crystal structure of [VO(mIDA)(dmbipy)]·1.5H2O has been determined by the X-ray diffraction method. The studies of structure of [VO(mIDA)(dmbipy)]•1.5H2O have shown that this compound occurs in the crystal as two rotational conformers. Furthermore, the stability constants of [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O complexes in aqueous solutions were studied by using the potentiometric titration method and, consequently, determined using the Hyperquad2008 program. Moreover, the title complexes were investigated as antioxidant substances. The impact of the structure modification in the VO2+ complexes on the radical scavenging activity has been studied. The ability to scavenge the superoxide radical by two complexes - [VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O was studied by cyclic voltammetry (CV) and nitrobluetetrazolium (NBT) methods. The title complexes were also examined by the spectrophotometric method as scavengers of neutral organic radical - 1,1-diphenyl-2-picrylhydrazyl (DPPH•) and radical cation - 2,2'-azinobis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS•+). Furthermore, the biological properties of two oxidovanadium(IV) complexes were investigated in relation to its cytoprotective properties by the MTT and LDH tests based on the hippocampal HT22 neuronal cell line during the oxidative damage induced by hydrogen peroxide. Finally, the results presented in this paper have shown that the both new oxidovanadium(IV) complexes with the 4,4‧-dimethoxy-2,2‧-dipyridyl ligand can be treated as the cytoprotective substances.

Human heme oxygenase oxidation of 5- and 15-phenylhemes.

PubMed

Wang, Jinling; Niemevz, Fernando; Lad, Latesh; Huang, Liusheng; Alvarez, Diego E; Buldain, Graciela; Poulos, Thomas L; de Montellano, Paul R Ortiz

2004-10-08

Human heme oxygenase-1 (hHO-1) catalyzes the O2-dependent oxidation of heme to biliverdin, CO, and free iron. Previous work indicated that electrophilic addition of the terminal oxygen of the ferric hydroperoxo complex to the alpha-meso-carbon gives 5-hydroxyheme. Earlier efforts to block this reaction with a 5-methyl substituent failed, as the reaction still gave biliverdin IXalpha. Surprisingly, a 15-methyl substituent caused exclusive cleavage at the gamma-meso-rather than at the normal, unsubstituted alpha-meso-carbon. No CO was formed in these reactions, but the fragment cleaved from the porphyrin eluded identification. We report here that hHO-1 cleaves 5-phenylheme to biliverdin IXalpha and oxidizes 15-phenylheme at the alpha-meso position to give 10-phenylbiliverdin IXalpha. The fragment extruded in the oxidation of 5-phenylheme is benzoic acid, one oxygen of which comes from O2 and the other from water. The 2.29- and 2.11-A crystal structures of the hHO-1 complexes with 1- and 15-phenylheme, respectively, show clear electron density for both the 5- and 15-phenyl rings in both molecules of the asymmetric unit. The overall structure of 15-phenylheme-hHO-1 is similar to that of heme-hHO-1 except for small changes in distal residues 141-150 and in the proximal Lys18 and Lys22. In the 5-phenylheme-hHO-1 structure, the phenyl-substituted heme occupies the same position as heme in the heme-HO-1 complex but the 5-phenyl substituent disrupts the rigid hydrophobic wall of residues Met34, Phe214, and residues 26-42 near the alpha-meso carbon. The results provide independent support for an electrophilic oxidation mechanism and support a role for stereochemical control of the reaction regiospecificity.

Preparation and guest-uptake protocol for a porous complex useful for 'crystal-free' crystallography.

PubMed

Inokuma, Yasuhide; Yoshioka, Shota; Ariyoshi, Junko; Arai, Tatsuhiko; Fujita, Makoto

2014-02-01

We recently reported a new method for single-crystal X-ray diffraction (SCD) analysis that does not require the crystallization of the target compound. In this 'crystal-free' crystallography, a tiny crystal of a porous complex is soaked in the solution of the target guest. The guest molecules are absorbed and oriented in the crystal pores and can be analyzed by X-ray diffraction. We describe here a detailed synthetic protocol for the preparation of uniform single crystals of the porous host complex and for the subsequent guest uptake. The protocol describes our most versatile porous complex, which is prepared from commercially available ZnI2 and 2,4,6-tri(4-pyridyl)-1,3,5-triazine. The host complex has large pores with a cross-section of 8 × 5 Å(2). Single crystals of the complex are grown from layered solutions of the two components. The pores of the as-synthesized complex are filled with nitrobenzene, which is replaced with the inert solvent cyclohexane. This solvent exchange is essential for the rapid and effective inclusion of target compounds. The most crucial and delicate step is the selection of high-quality single crystals from the mixture of crystals of various shapes and sizes. We suggest using the facial indices of the single crystals as a criterion for crystal selection. Single-crystal samples for X-ray analysis can be prepared by immersing the selected crystals in a cyclohexane/dichloromethane solution of target compound. After a very slow evaporation of the solvent, typically over 2 d, the final crystal can be picked and directly subjected to SCD analysis. The protocol can be completed within ∼16 d.

Synthesis, characterization and properties of copper(I) complexes with bis(diphenylphosphino)-ferrocene ancillary ligand

NASA Astrophysics Data System (ADS)

Liu, Xinfang; Zhang, Songlin; Ding, Yuqiang

2012-06-01

Three copper(I) complexes (2-4) containing dppf ancillary ligand (dppf = bis(diphenylphosphino)-ferrocene) were synthesized when chloride-bridged copper(I) complex 1 reacted with acetanilide and characterized by IR, element analysis and NMR spectrum. And the crystal structures of complexes 2 and 4 have been determined by X-ray diffraction method. Complex 2, an acetate-bridged copper(I) complex, was obtained under N2 atmosphere in un-dried solvent; the acetate ion came from the hydrolysis reaction of acetanilide due to residual water in solvent. Acetanilide was deprotonated and coordinated with the copper(I) centre to form a copper(I) amidate complex 3 when reacted in pre-dried solvent. In addition, a known complex 4, the oxidation product of dppf, was isolated from the same reaction system when reacted in air atmosphere. CV and TG experiments were carried out to check the electron transfer properties and thermal stabilities of complexes 2-3. Finally, the arylation reaction of complex 3 with iodobenzene was performed to study the reaction mechanism of copper(I) catalyzed Goldberg reaction.

The inner workings of the hydrazine synthase multiprotein complex.

PubMed

Dietl, Andreas; Ferousi, Christina; Maalcke, Wouter J; Menzel, Andreas; de Vries, Simon; Keltjens, Jan T; Jetten, Mike S M; Kartal, Boran; Barends, Thomas R M

2015-11-19

Anaerobic ammonium oxidation (anammox) has a major role in the Earth's nitrogen cycle and is used in energy-efficient wastewater treatment. This bacterial process combines nitrite and ammonium to form dinitrogen (N2) gas, and has been estimated to synthesize up to 50% of the dinitrogen gas emitted into our atmosphere from the oceans. Strikingly, the anammox process relies on the highly unusual, extremely reactive intermediate hydrazine, a compound also used as a rocket fuel because of its high reducing power. So far, the enzymatic mechanism by which hydrazine is synthesized is unknown. Here we report the 2.7 Å resolution crystal structure, as well as biophysical and spectroscopic studies, of a hydrazine synthase multiprotein complex isolated from the anammox organism Kuenenia stuttgartiensis. The structure shows an elongated dimer of heterotrimers, each of which has two unique c-type haem-containing active sites, as well as an interaction point for a redox partner. Furthermore, a system of tunnels connects these active sites. The crystal structure implies a two-step mechanism for hydrazine synthesis: a three-electron reduction of nitric oxide to hydroxylamine at the active site of the γ-subunit and its subsequent condensation with ammonia, yielding hydrazine in the active centre of the α-subunit. Our results provide the first, to our knowledge, detailed structural insight into the mechanism of biological hydrazine synthesis, which is of major significance for our understanding of the conversion of nitrogenous compounds in nature.

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

USGS Publications Warehouse

Henneberry, Yumiko K.; Kraus, Tamara E.C.; Nico, Peter S.; Horwath, William R.

2012-01-01

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

On stoichiometry and intermixing at the spinel/perovskite interface in CoFe2O4/BaTiO3 thin films.

PubMed

Tileli, Vasiliki; Duchamp, Martial; Axelsson, Anna-Karin; Valant, Matjaz; Dunin-Borkowski, Rafal E; Alford, Neil McN

2015-01-07

The performance of complex oxide heterostructures depends primarily on the interfacial coupling of the two component structures. This interface character inherently varies with the synthesis method and conditions used since even small composition variations can alter the electronic, ferroelectric, or magnetic functional properties of the system. The focus of this article is placed on the interface character of a pulsed laser deposited CoFe2O4/BaTiO3 thin film. Using a range of state-of-the-art transmission electron microscopy methodologies, the roles of substrate morphology, interface stoichiometry, and cation intermixing are determined on the atomic level. The results reveal a surprisingly uneven BaTiO3 substrate surface formed after the film deposition and Fe atom incorporation in the top few monolayers inside the unit cell of the BaTiO3 crystal. Towards the CoFe2O4 side, a disordered region extending several nanometers from the interface was revealed and both Ba and Ti from the substrate were found to diffuse into the spinel layer. The analysis also shows that within this somehow incompatible composite interface, a different phase is formed corresponding to the compound Ba2Fe3Ti5O15, which belongs to the ilmenite crystal structure of FeTiO3 type. The results suggest a chemical activity between these two oxides, which could lead to the synthesis of complex engineered interfaces.

The molecular origins of specificity in the assembly of a multienzyme complex.

PubMed

Frank, René A W; Pratap, J Venkatesh; Pei, Xue Y; Perham, Richard N; Luisi, Ben F

2005-08-01

The pyruvate dehydrogenase (PDH) multienzyme complex is central to oxidative metabolism. We present the first crystal structure of a complex between pyruvate decarboxylase (E1) and the peripheral subunit binding domain (PSBD) of the dihydrolipoyl acetyltransferase (E2). The interface is dominated by a "charge zipper" of networked salt bridges. Remarkably, the PSBD uses essentially the same zipper to alternately recognize the dihydrolipoyl dehydrogenase (E3) component of the PDH assembly. The PSBD achieves this dual recognition largely through the addition of a network of interfacial water molecules unique to the E1-PSBD complex. These structural comparisons illuminate our observations that the formation of this water-rich E1-E2 interface is largely enthalpy driven, whereas that of the E3-PSBD complex (from which water is excluded) is entropy driven. Interfacial water molecules thus diversify surface complementarity and contribute to avidity, enthalpically. Additionally, the E1-PSBD structure provides insight into the organization and active site coupling within the approximately 9 MDa PDH complex.

Electron-irradiation-induced crystallization at metallic amorphous/silicon oxide interfaces caused by electronic excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagase, Takeshi, E-mail: t-nagase@uhvem.osaka-u.ac.jp; Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1, Yamada-Oka, Suita, Osaka 565-0871; Yamashita, Ryo

2016-04-28

Irradiation-induced crystallization of an amorphous phase was stimulated at a Pd-Si amorphous/silicon oxide (a(Pd-Si)/SiO{sub x}) interface at 298 K by electron irradiation at acceleration voltages ranging between 25 kV and 200 kV. Under irradiation, a Pd-Si amorphous phase was initially formed at the crystalline face-centered cubic palladium/silicon oxide (Pd/SiO{sub x}) interface, followed by the formation of a Pd{sub 2}Si intermetallic compound through irradiation-induced crystallization. The irradiation-induced crystallization can be considered to be stimulated not by defect introduction through the electron knock-on effects and electron-beam heating, but by the electronic excitation mechanism. The observed irradiation-induced structural change at the a(Pd-Si)/SiO{sub x} and Pd/SiO{sub x}more » interfaces indicates multiple structural modifications at the metal/silicon oxide interfaces through electronic excitation induced by the electron-beam processes.« less

Redox process catalysed by growing crystal-strengite, FePO4,2H2O, crystallizing from solution with iron(II) and hydroxylamine

NASA Astrophysics Data System (ADS)

Lundager Madsen, Hans Erik

2014-09-01

In an attempt to grow pure crystals of the iron(II) phosphate vivianite, Fe3(PO4)2,8H2O, from a solution of Mohr's salt, Fe(NH4)2(SO4)2,6H2O, added to a solution of ammonium phosphate, hydroxylammonium chloride, NH3OHCl, was added to the iron(II) stock solution to eliminate oxidation of iron(II) by oxygen from the air. However, the effect turned out to be the opposite of the expected: whereas hydroxylamine reduces iron(III) in bulk solution, it acted as a strong oxidant in the presence of growing iron phosphate crystals, causing the crystallization of the iron(III) phosphate strengite, FePO4,2H2O, as the only solid phase. Evidently the crystal surface catalyses oxidation of iron(II) by hydroxylamine. The usual composite kinetics of spiral growth and surface nucleation was found. The surface-nucleation part yielded edge free energy λ in the range 12-45 pJ/m, virtually independent of temperature and in the range typical for phosphates of divalent metals. The scatter of values for λ presumably arises from contributions from different crystal forms to the overall growth rate. The low mean value points to strong adsorption of iron(II), which is subsequently oxidized at the crystal surface, forming strengite. The state of the system did not tend to thermodynamic equilibrium, but to a metastable state, presumably controlled by the iron(II) rich surface layer of the crystal. In addition to crystal growth, it was possible to measure nucleation kinetics by light scattering (turbidimetry). A point of transition from heterogeneous to homogeneous nucleation was found, and from the results for the homogeneous domain a rather precise value of crystal surface free energy γ=55 mJ/m2 was found. This is a relatively low value as well, indicating that the redox process plays a role already at the nucleation stage.

Molecular basis of crystal morphology-dependent adhesion behavior of mefenamic acid during tableting.

PubMed

Waknis, Vrushali; Chu, Elza; Schlam, Roxana; Sidorenko, Alexander; Badawy, Sherif; Yin, Shawn; Narang, Ajit S

2014-01-01

The molecular basis of crystal surface adhesion leading to sticking was investigated by exploring the correlation of crystal adhesion to oxidized iron coated atomic force microscope (AFM) tips and bulk powder sticking behavior during tableting of two morphologically different crystals of a model drug, mefenamic acid (MA), to differences in their surface functional group orientation and energy. MA was recrystallized into two morphologies (plates and needles) of the same crystalline form. Crystal adhesion to oxidized iron coated AFM tips and bulk powder sticking to tablet punches was assessed using a direct compression formulation. Surface functional group orientation and energies on crystal faces were modeled using Accelrys Material Studio software. Needle-shaped morphology showed higher sticking tendency than plates despite similar particle size. This correlated with higher crystal surface adhesion of needle-shaped morphology to oxidized iron coated AFM probe tips, and greater surface energy and exposure of polar functional groups. Higher surface exposure of polar functional groups correlates with higher tendency to stick to metal surfaces and AFM tips, indicating involvement of specific polar interactions in the adhesion behavior. In addition, an AFM method is identified to prospectively assess the risk of sticking during the early stages of drug development.

Eliminating Crystals in Non-Oxide Optical Fiber Preforms and Optical Fibers

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; LaPointe, Michael R.

2012-01-01

Non ]oxide fiber optics such as heavy metal fluoride and chalcogenide glasses are extensively used in infrared transmitting applications such as communication systems, chemical sensors, and laser fiber guides for cutting, welding and medical surgery. The addition of rare earths such as erbium, enable these materials to be used as fiber laser and amplifiers. Some of these glasses however are very susceptible to crystallization. Even small crystals can lead to light scatter and a high attenuation coefficient, limiting their usefulness. Previously two research teams found that microgravity suppressed crystallization in heavy metal fluoride glasses. Looking for a less expensive method to suppress crystallization, ground based research was performed utilizing an axial magnetic field. The experiments revealed identical results to those obtained via microgravity processing. This research then led to a patented process for eliminating crystals in optical fiber preforms and the resulting optical fibers. In this paper, the microgravity results will be reviewed as well as patents and papers relating to the use of magnetic fields in various material and glass processing applications. Finally our patent to eliminate crystals in non ]oxide glasses utilizing a magnetic field will be detailed.

Effect of zinc oxide nanoparticles on dielectric behavior of nematic liquid crystal

NASA Astrophysics Data System (ADS)

Sharma, Amit; Kumar, Pankaj; Malik, Praveen

2018-05-01

In this work, phase transition and dielectric behavior of nematic liquid crystal (NLC), E7 and zinc oxide (ZnO) nanoparticles (NPs) doped nematic liquid crystals are investigated. Effect of nano-particles dispersion is analyzed and compared with the dielectric behavior of E7 and E7-ZnO. Frequency dependent dielectric permittivity at various temperatures in nematic phase for E7 and E7-ZnO sample is also studied.

Mapping the Binding Interface of VEGF and a Monoclonal Antibody Fab-1 Fragment with Fast Photochemical Oxidation of Proteins (FPOP) and Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Ying; Wecksler, Aaron T.; Molina, Patricia; Deperalta, Galahad; Gross, Michael L.

2017-05-01

We previously analyzed the Fab-1:VEGF (vascular endothelial growth factor) system described in this work, with both native top-down mass spectrometry and bottom-up mass spectrometry (carboxyl-group or GEE footprinting) techniques. This work continues bottom-up mass spectrometry analysis using a fast photochemical oxidation of proteins (FPOP) platform to map the solution binding interface of VEGF and a fragment antigen binding region of an antibody (Fab-1). In this study, we use FPOP to compare the changes in solvent accessibility by quantitating the extent of oxidative modification in the unbound versus bound states. Determining the changes in solvent accessibility enables the inference of the protein binding sites (epitope and paratopes) and a comparison to the previously published Fab-1:VEGF crystal structure, adding to the top-down and bottom-up data. Using this method, we investigated peptide-level and residue-level changes in solvent accessibility between the unbound proteins and bound complex. Mapping these data onto the Fab-1:VEGF crystal structure enabled successful characterization of both the binding region and regions of remote conformation changes. These data, coupled with our previous higher order structure (HOS) studies, demonstrate the value of a comprehensive toolbox of methods for identifying the putative epitopes and paratopes for biotherapeutic antibodies.

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

NASA Technical Reports Server (NTRS)

Ritzert, F. J.; Yun, H. M.; Miner, R. V.

1997-01-01

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

Crystallization Behavior of Copper Smelter Slag During Molten Oxidation

NASA Astrophysics Data System (ADS)

Fan, Yong; Shibata, Etsuro; Iizuka, Atsushi; Nakamura, Takashi

2015-10-01

Copper slag is composed of iron silicate obtained by smelting copper concentrate and silica flux. One of the most important criteria for the utilization of this secondary resource is the recovery of iron from the slag matrix to decrease the volume of dumped slag. The molten oxidation process with crushing magnetic separation appears to be a more sustainable approach and is based on directly blowing oxidizing gas onto molten slag after the copper smelting process. In the current study, using an infrared furnace, the crystallization behavior of the slag during molten oxidation was studied to better understand the trade-off between magnetite and hematite precipitations, as assessed by X-ray diffraction (using an internal standard). Furthermore, the crystal morphology was examined using a laser microscope and Raman imaging system to understand the iron oxide transformation, and the distribution of impurities such as Cu, Zn, As, Cr, and Pb were complemented with scanning electron microscopy and energy dispersive spectroscopy. In addition, the reaction mechanism was investigated with a focus on the oxidation processes.

Oxide Thermoelectric Materials: A Structure-Property Relationship

NASA Astrophysics Data System (ADS)

Nag, Abanti; Shubha, V.

2014-04-01

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity ( ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure-property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron-phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.

Dynamics of metal-induced crystallization of ultrathin Ge films by rapid thermal annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Yuanxun; Huang, Shujuan; Shrestha, Santosh

2015-12-07

Though Ge crystallization has been widely studied, few works investigate metal-induced crystallization of ultrathin Ge films. For 2 nm Ge films in oxide matrix, crystallization becomes challenging due to easy oxidation and low mobility of Ge atoms. Introducing metal atoms may alleviate these problems, but the functions and the behaviours of metal atoms need to be clarified. This paper investigates the crystallization dynamics of a multilayer structure 1.9 nm Ge/0.5 nm Al/1.5 nm Al{sub 2}O{sub 3} under rapid thermal annealing (RTA). The functions of metal atoms, like effective anti-oxidation, downshifting Raman peaks, and incapability to decrease crystallization temperature, are found and explained. The metalmore » behaviours, such as inter-diffusion and defect generation, are supported with direct evidences, Al-Ge nanobicrystals, and Al cluster in Ge atoms. With these understandings, a two-step RTA process achieves high-quality 2 nm nanocrystal Ge films with Raman peak at 298 cm{sup −1} of FWHM 10.3 cm{sup −1} and atomic smooth interfaces.« less

Selective tuning of high-Q silicon photonic crystal nanocavities via laser-assisted local oxidation.

PubMed

Chen, Charlton J; Zheng, Jiangjun; Gu, Tingyi; McMillan, James F; Yu, Mingbin; Lo, Guo-Qiang; Kwong, Dim-Lee; Wong, Chee Wei

2011-06-20

We examine the cavity resonance tuning of high-Q silicon photonic crystal heterostructures by localized laser-assisted thermal oxidation using a 532 nm continuous wave laser focused to a 2.5 μm radius spot-size. The total shift is consistent with the parabolic rate law. A tuning range of up to 8.7 nm is achieved with ∼ 30 mW laser powers. Over this tuning range, the cavity Qs decreases from 3.2×10(5) to 1.2×10(5). Numerical simulations model the temperature distributions in the silicon photonic crystal membrane and the cavity resonance shift from oxidation.

A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes

PubMed Central

Artesani, Alessia; Gherardi, Francesca; Nevin, Austin; Valentini, Gianluca; Comelli, Daniela

2017-01-01

It is known that oil paintings containing zinc white are subject to rapid degradation. This is caused by the interaction between the active groups of binder and the metal ions of the pigment, which gives rise to the formation of new zinc complexes (metal soaps). Ongoing studies on zinc white paints have been limited to the chemical mechanisms that lead to the formation of zinc complexes. On the contrary, little is known of the photo-physical changes induced in the zinc oxide crystal structure following this interaction. Time-resolved photoluminescence spectroscopy has been applied to follow modifications in the luminescent zinc white pigment when mixed with binder. Significant changes in trap state photoluminescence emissions have been detected: the enhancement of a blue emission combined with a change of the decay kinetic of the well-known green emission. Complementary data from molecular analysis of paints using Fourier transform infrared spectroscopy confirms the formation of zinc carboxylates and corroborates the mechanism for zinc complexes formation. We support the hypothesis that zinc ions migrate into binder creating novel vacancies, affecting the photoluminescence intensity and lifetime properties of zinc oxide. Here, we further demonstrate the advantages of a time-resolved photoluminescence approach for studying defects in semiconductor pigments. PMID:28772700

Zinc oxide crystal whiskers as a novel sorbent for solid-phase extraction of flavonoids.

PubMed

Wang, Licheng; Shangguan, Yangnan; Hou, Xiudan; Jia, Yong; Liu, Shujuan; Sun, Yingxin; Guo, Yong

2017-08-15

As a novel solid-phase extraction material, zinc oxide crystal whiskers were used to extract flavonoid compounds and showed good extraction abilities. X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and surface area/pore volume characterized the sorbent. The zinc oxide was packed into a solid-phase extraction micro-column and its extraction ability was evaluated by four model flavonoid compounds. The sample loading and elution parameters were optimized and the zinc oxide based analytical method for flavonoids was established. It showed that the method has wide linearities from 1 to 150μg/L and low limits of detection at 0.25μg/L. The relative standard deviations of a single column repeatability and column to column reproducibility were less than 6.8% and 10.6%. Several real samples were analyzed by the established method and satisfactory results were obtained. The interactions between flavonoids and zinc oxide were calculated and proved to be from the Van der Waals' forces between the 4p and 5d orbitals from zinc atom and the neighboring π orbitals from flavonoid phenyl groups. Moreover, the zinc oxide crystal whiskers showed good stability and could be reused more than 50 times under the operation conditions. This work proves that the zinc oxide crystal whiskers are a good candidate for flavonoids enrichment. Copyright © 2017. Published by Elsevier B.V.

Autophagy inhibition attenuates hyperoxaluria-induced renal tubular oxidative injury and calcium oxalate crystal depositions in the rat kidney.

PubMed

Duan, Xiaolu; Kong, Zhenzhen; Mai, Xin; Lan, Yu; Liu, Yang; Yang, Zhou; Zhao, Zhijian; Deng, Tuo; Zeng, Tao; Cai, Chao; Li, Shujue; Zhong, Wen; Wu, Wenqi; Zeng, Guohua

2018-06-01

Hyperoxaluria-induced oxidative injury of renal tubular epithelial cell is a casual and essential factor in kidney calcium oxalate (CaOx) stone formation. Autophagy has been shown to be critical for the regulation of oxidative stress-induced renal tubular injury; however, little is known about its role in kidney CaOx stone formation. In the present study, we found that the autophagy antagonist chloroquine could significantly attenuate oxalate-induced autophagy activation, oxidative injury and mitochondrial damage of renal tubular cells in vitro and in vivo, as well as hyperoxaluria-induced CaOx crystals depositions in rat kidney, whereas the autophagy agonist rapamycin exerted contrasting effects. In addition, oxalate-induced p38 phosphorylation was significantly attenuated by chloroquine pretreatment but was markedly enhanced by rapamycin pretreatment, whereas the protective effect of chloroquine on rat renal tubular cell oxidative injury was partly reversed by a p38 protein kinase activator anisomycin. Furthermore, the knockdown of Beclin1 represented similar effects to chloroquine on oxalate-induced cell oxidative injury and p38 phosphorylation in vitro. Taken together, our results revealed that autophagy inhibition could attenuate oxalate-induced oxidative injury of renal tubular cell and CaOx crystal depositions in the rat kidney via, at least in part, inhibiting the activation of p38 signaling pathway, thus representing a novel role of autophagy in the regulation of oxalate-induced renal oxidative injury and CaOx crystal depositions for the first time. Copyright © 2018. Published by Elsevier B.V.

The use of trimethylamine N-oxide as a primary precipitating agent and related methylamine osmolytes as cryoprotective agents for macromolecular crystallography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Haley; Venkat, Murugappan; Hti Lar Seng, Nang San

2012-01-01

The stabilizing osmolyte trimethylamine N-oxide (TMAO) is shown to be an efficient primary precipitant for protein crystal growth. In addition to TMAO, two other methylamine osmolytes, sarcosine and betaine, are shown to be effective cryoprotective agents for protein crystal cooling. Both crystallization and cryoprotection are often bottlenecks for high-resolution X-ray structure determination of macromolecules. Methylamine osmolytes are known stabilizers of protein structure. One such osmolyte, trimethylamine N-oxide (TMAO), has seen occasional use as an additive to improve macromolecular crystal quality and has recently been shown to be an effective cryoprotective agent for low-temperature data collection. Here, TMAO and the relatedmore » osmolytes sarcosine and betaine are investigated as primary precipitating agents for protein crystal growth. Crystallization experiments were undertaken with 14 proteins. Using TMAO, seven proteins crystallized in a total of 13 crystal forms, including a new tetragonal crystal form of trypsin. The crystals diffracted well, and eight of the 13 crystal forms could be effectively cryocooled as grown with TMAO as an in situ cryoprotective agent. Sarcosine and betaine produced crystals of four and two of the 14 proteins, respectively. In addition to TMAO, sarcosine and betaine were effective post-crystallization cryoprotective agents for two different crystal forms of thermolysin. Precipitation reactions of TMAO with several transition-metal ions (Fe{sup 3+}, Co{sup 2+}, Cu{sup 2+} and Zn{sup 2+}) did not occur with sarcosine or betaine and were inhibited for TMAO at lower pH. Structures of proteins from TMAO-grown crystals and from crystals soaked in TMAO, sarcosine or betaine were determined, showing osmolyte binding in five of the 12 crystals tested. When an osmolyte was shown to bind, it did so near the protein surface, interacting with water molecules, side chains and backbone atoms, often at crystal contacts.« less

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations.

PubMed

Zhang, Ning; Chen, Chen; Mei, Zongwei; Liu, Xiaohe; Qu, Xiaolei; Li, Yunxiang; Li, Siqi; Qi, Weihong; Zhang, Yuanjian; Ye, Jinhua; Roy, Vellaisamy A L; Ma, Renzhi

2016-04-27

Exploring surface-exposed highly active crystal facets for photocatalytic oxidations is promising in utilizing monoclinic WO3 semiconductor. However, the previously reported highly active facets for monoclinic WO3 were mainly toward enhancing photocatalytic reductions. Here we report that the WO3 with {100} facet orientation and tuned surface electronic band structure can effectively enhance photocatalytic oxidation properties. The {100} faceted WO3 single crystals are synthesized via a facile hydrothermal method. The UV-visible diffuse reflectance, X-ray photoelectron spectroscopy valence band spectra, and photoelectrochemical measurements suggest that the {100} faceted WO3 has a much higher energy level of valence band maximum compared with the normal WO3 crystals without preferred orientation of the crystal face. The density functional theory calculations reveal that the shift of O 2p and W 5d states in {100} face induce a unique band structure. In comparison with the normal WO3, the {100} faceted WO3 exhibits an O2 evolution rate about 5.1 times in water splitting, and also shows an acetone evolution rate of 4.2 times as well as CO2 evolution rate of 3.8 times in gaseous degradation of 2-propanol. This study demonstrates an efficient crystal face engineering route to tune the surface electronic band structure for enhanced photocatalytic oxidations.

Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sezer, Güneş Günay; Department of Chemistry, Eskişehir Osmangazi University, Eskişehir; Yeşilel, Okan Zafer

ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology withmore » the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.« less

Structures of the Porphyromonas gingivalis OxyR regulatory domain explain differences in expression of the OxyR regulon in Escherichia coli and P. gingivalis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svintradze, David V.; Virginia Commonwealth University, Richmond, VA 23219-1540; Peterson, Darrell L.

Differences in OxyR regulated expression of oxidative stress genes between Escherichia coli and Porphyromonas gingivalis are explained by very minor differences in structure and amino-acid sequence of the respective oxidized and reduced OxyR regulatory domains. These differences affect OxyR quaternary structures and are predicted from model building of full length OxyR–DNA complexes to confer distinct modes of DNA binding on this transcriptional regulator. OxyR transcriptionally regulates Escherichia coli oxidative stress response genes through a reversibly reducible cysteine disulfide biosensor of cellular redox status. Structural changes induced by redox changes in these cysteines are conformationally transmitted to the dimer subunit interfaces,more » which alters dimer and tetramer interactions with DNA. In contrast to E. coli OxyR regulatory-domain structures, crystal structures of Porphyromonas gingivalis OxyR regulatory domains show minimal differences in dimer configuration on changes in cysteine disulfide redox status. This locked configuration of the P. gingivalis OxyR regulatory-domain dimer closely resembles the oxidized (activating) form of the E. coli OxyR regulatory-domain dimer. It correlates with the observed constitutive activation of some oxidative stress genes in P. gingivalis and is attributable to a single amino-acid insertion in P. gingivalis OxyR relative to E. coli OxyR. Modelling of full-length P. gingivalis, E. coli and Neisseria meningitidis OxyR–DNA complexes predicts different modes of DNA binding for the reduced and oxidized forms of each.« less

The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

2016-05-01

Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

Inheritance of Crystallographic Orientation during Lithiation/Delithiation Processes of Single-Crystal α-Fe2O3 Nanocubes in Lithium-Ion Batteries.

PubMed

Ma, Xiaowei; Zhang, Manyu; Liang, Chongyun; Li, Yuesheng; Wu, Jingjing; Che, Renchao

2015-11-04

Iron oxides are very promising anode materials based on conversion reactions for lithium-ion batteries (LIBs). During conversion processes, the crystal structure and composition of the electrode material are drastically changed. Surprisingly, in our study, inheritance of a crystallographic orientation was found during lithiation/delithiation processes of single-crystal α-Fe2O3 nanocubes by ex situ transmission electron microscopy. Single-crystal α-Fe2O3 was first transformed into numerous Fe nanograins embedded in a Li2O matrix, and then the conversion between Fe and FeO nanograins became the main reversible electrochemical reaction for energy storage. Interestingly, these Fe/FeO nanograins had almost the same crystallographic orientation, indicating that the lithiated/delithiated products can inherit the crystallographic orientation of single-crystal α-Fe2O3. This finding is important for understanding the detailed electrochemical conversion processes of iron oxides, and this feature may also exist during lithiation/delithiation processes of other transition-metal oxides.

Purification, crystallization and preliminary crystallographic studies of the TLDc domain of oxidation resistance protein 2 from zebrafish

PubMed Central

Alsarraf, Husam M. A. B.; Laroche, Fabrice; Spaink, Herman; Thirup, Søren; Blaise, Mickael

2011-01-01

Cell metabolic processes are constantly producing reactive oxygen species (ROS), which have deleterious effects by triggering, for example, DNA damage. Numerous enzymes such as catalase, and small compounds such as vitamin C, provide protection against ROS. The TLDc domain of the human oxidation resistance protein has been shown to be able to protect DNA from oxidative stress; however, its mechanism of action is still not understood and no structural information is available on this domain. Structural information on the TLDc domain may therefore help in understanding exactly how it works. Here, the purification, crystallization and preliminary crystallographic studies of the TLDc domain from zebrafish are reported. Crystals belonging to the orthorhombic space group P21212 were obtained and diffracted to 0.97 Å resolution. Selenomethionine-substituted protein could also be crystallized; these crystals diffracted to 1.1 Å resolution and the structure could be solved by SAD/MAD methods. PMID:22102041

A liquid crystal microlens array with aluminum and graphene electrodes for plenoptic imaging

NASA Astrophysics Data System (ADS)

Lei, Yu; Tong, Qing; Luo, Jun; Zhang, Xinyu; Sang, Hongshi; Xie, Changsheng

2015-12-01

Currently, several semiconducting oxide materials such as typical indium tin oxide are widely used as the transparent conducting electrodes (TCEs) in liquid crystal microlens arrays. In this paper, we fabricate a liquid crystal microlens array using graphene rather than semiconducting oxides as the TCE. Common optical experiments are carried out to acquire the focusing features of the graphene-based liquid crystal microlens array (GLCMLA) driven electrically. The acquired optical fields show that the GLCMLA can converge incident collimating lights efficiently. The relationship between the focal length and the applied voltage signal is presented. Then the GLCMLA is deployed in a plenoptic camera prototype and the raw images are acquired so as to verify their imaging capability. Our experiments demonstrate that graphene has already presented a broad application prospect in the area of adaptive optics.

Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding† †Electronic supplementary information (ESI) available: General procedures, synthetic details, spectroscopic data, X-ray crystallographic data. CCDC 1524162–1524166. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00034k Click here for additional data file. Click here for additional data file.

PubMed Central

Dutkiewicz, Michał S.; Apostolidis, Christos

2017-01-01

Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(iii) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], and its KCp adduct K[Np(Cp)4] and [Np(Cp′)3] (Cp′ = C5H4SiMe3) have been made and characterised providing the first single crystal X-ray analyses of NpIII Cp complexes. In all NpCp3 derivatives there are three Cp rings in η5-coordination around the NpIII centre; additionally in [Np(Cp)3] and K[Np(Cp)4] one Cp ring establishes a μ-η1-interaction to one C atom of a neighbouring Np(Cp)3 unit. The solid state structure of K[Np(Cp)4] is unique in containing two different types of metal–Cp coordination geometries in the same crystal. NpIII(Cp)4 units are found exhibiting four units of η5-coordinated Cp rings like in the known complex [NpIV(Cp)4], the structure of which is now reported. A detailed comparison of the structures gives evidence for the change of ionic radii of ca. –8 pm associated with change in oxidation state between NpIII and NpIV. The rich redox chemistry associated with the syntheses is augmented by the reduction of [Np(Cp′)3] by KC8 in the presence of 2.2.2-cryptand to afford a neptunium(ii) complex that is thermally unstable above –10 °C like the UII and ThII complexes K(2.2.2-cryptand)[Th/U(Cp′)3]. Together, these spontaneous and controlled redox reactions of organo-neptunium complexes, along with information from structural characterisation, show the relevance of organometallic Np chemistry to understanding fundamental structure and bonding in the minor actinides. PMID:28553487

DC electrical conductivity measurements for pure and titanium oxide doped KDP Crystals grown by gel medium

NASA Astrophysics Data System (ADS)

Mareeswaran, S.; Asaithambi, T.

2016-10-01

Now a day's crystals are the pillars of current technology. Crystals are applied in various fields like fiber optic communications, electronic industry, photonic industry, etc. Crystal growth is an interesting and innovative field in the subject of physics, chemistry, material science, metallurgy, chemical engineering, mineralogy and crystallography. In recent decades optically good quality of pure and metal doped KDP crystals have been grown by gel growth method in room temperature and its characterizations were studied. Gel method is a very simple and one of the easiest methods among the various crystal growth methods. Potassium dihydrogen phosphate KH2PO4 (KDP) continues to be an interesting material both academically and technologically. KDP is a delegate of hydrogen bonded materials which possess very good electrical and nonlinear optical properties in addition to interesting electro-optic properties. We made an attempt to grow pure and titanium oxide doped KDP crystals with various doping concentrations (0.002, 0.004, 0.006, 0.008 and 0.010) using gel method. The grown crystals were collected after 20 days. We get crystals with good quality and shaped crystals. The dc electrical conductivity (resistance, capacitance and dielectric constant) values of the above grown crystals were measured at two different frequencies (1KHz and 100 Hz) with a temperature range of 500C to 1200C using simple two probe setup with Q band digital LCR meter present in our lab. The electrical conductivity increases with the increase of temperature. Dielectric constants value of titanium oxide doped KDP crystal was slightly decreased compared with pure KDP crystals. Results were discussed in details.

Fast optical switch having reduced light loss

NASA Technical Reports Server (NTRS)

Nelson, Bruce N. (Inventor); Cooper, Ronald F. (Inventor)

1992-01-01

An electrically controlled optical switch uses an electro-optic crystal of the type having at least one set of fast and slow optical axes. The crystal exhibits electric field induced birefringence such that a plane of polarization oriented along a first direction of a light beam passing through the crystal may be switched to a plane of polarization oriented along a second direction. A beam splitting polarizer means is disposed at one end of the crystal and directs a light beam passing through the crystal whose plane of polarization is oriented along the first direction differently from a light beam having a plane of polarization oriented along the second direction. The electro-optic crystal may be chosen from the crystal classes 43m, 42m, and 23. In a preferred embodiment, the electro-optic crystal is a bismuth germanium oxide crystal or a bismuth silicon oxide crystal. In another embodiment of the invention, polarization control optics are provided which transmit substantially all of the incident light to the electro-optic crystal, substantially reducing the insertion loss of the switch.

Morphological Control of Co3O4 and Its Photocatalytic Properties

EPA Science Inventory

Cobaltosic oxide (Co3O4), a p-type semiconductor, belongs to the normal spinel crystal structure based on a cubic close packing array of oxide ions. The size, surface, geometry, and crystal phase of catalysts are important parameters for controlling their chemical, optical, and ...

Alkaline igneous rocks of Magnet Cove, Arkansas: Mineralogy and geochemistry of syenites

USGS Publications Warehouse

Flohr, M.J.K.; Ross, M.

1990-01-01

Syenites from the Magnet Cove alkaline igneous complex form a diverse mineralogical and geochemical suite. Compositional zoning in primary and late-stage minerals indicates complex, multi-stage crystallization and replacement histories. Residual magmatic fluids, rich in F, Cl, CO2 and H2O, reacted with primary minerals to form complex intergrowths of minerals such as rinkite, fluorite, V-bearing magnetite, F-bearing garnet and aegirine. Abundant sodalite and natrolite formed in pegmatitic segregations within nepheline syenite where Cl- and Na-rich fluids were trapped. During autometasomatism compatible elements such as Mn, Ti, V and Zr were redistributed on a local scale and concentrated in late-stage minerals. Early crystallization of apatite and perovskite controlled the compatible behavior of P and Ti, respectively. The formation of melanite garnet also affected the behaviour of Ti, as well as Zr, Hf and the heavy rare-earth elements. Pseudoleucite syenite and garnet-nepheline syenite differentiated along separate trends, but the two groups are related to the same parental magma by early fractionation of leucite, the presumed precursor of intergrowths of K-feldspar and nepheline. The Diamond Jo nepheline syenite group defines a different differentiation trend. Sphene-nepheline syenite, alkali syenite and several miscellaneous nepheline syenites do not consistently plot with the other syenite groups or each other on element and oxide variation diagrams, indicating that they were derived from still other parental syenite magmas. Mineral assemblages indicate that relatively high f{hook};O2, at or above the fayalite-magnetite-quartz buffer, prevailed throughout the crystallization history of the syenites. ?? 1990.

Chloroquine Binding Reveals Flavin Redox Switch Function of Quinone Reductase 2*

PubMed Central

Leung, Kevin K. K.; Shilton, Brian H.

2013-01-01

Quinone reductase 2 (NQO2) is an FAD-linked enzyme and the only known human target of two antimalarial drugs, primaquine (PQ) and chloroquine (CQ). The structural differences between oxidized and reduced NQO2 and the structural basis for inhibition by PQ and CQ were investigated by x-ray crystallography. Structures of oxidized NQO2 in complex with PQ and CQ were solved at 1.4 Å resolution. CQ binds preferentially to reduced NQO2, and upon reduction of NQO2-CQ crystals, the space group changed from P212121 to P21, with 1-Å decreases in all three unit cell dimensions. The change in crystal packing originated in the negative charge and 4–5º bend in the reduced isoalloxazine ring of FAD, which resulted in a new mode of CQ binding and closure of a flexible loop (Phe126–Leu136) over the active site. This first structure of a reduced quinone reductase shows that reduction of the FAD cofactor and binding of a specific inhibitor lead to global changes in NQO2 structure and is consistent with a functional role for NQO2 as a flavin redox switch. PMID:23471972

Effect of temperature on the adsorption of sulfanilamide onto aluminum oxide and its molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Ji, Ying-xue; Wang, Feng-he; Duan, Lun-chao; Zhang, Fan; Gong, Xue-dong

2013-11-01

The effect of temperature on the adsorption of sulfanilamide (SA) onto aluminum oxide was researched through batch adsorption experiments, and was then simulated using the molecular dynamics (MD) method. The results show that SA can be adsorbed effectively by the adsorbent of aluminum oxide due to their interactions between SA molecule and the surface of aluminum oxide crystal, and temperature is a key factor which influences the adsorption efficiency obviously. The removal ratio of SA at 298 K is the highest among the selected temperatures (293 K, 298 K, 303 K). MD simulations revealed the interactions between SA molecules and (0 1 2) surface of aluminum oxide crystal at molecular level. The SA molecule has clung to the (0 1 2) face of aluminum oxide crystal, and its structure is deformed during its combining process with the surface. Both binding energies (Eb) and deformation energies (ΔEdeform) in the SA-aluminum oxide system follow the same order as: SA-Al2O3 (298 K) > SA-Al2O3 (293 K) > SA-Al2O3 (303 K). Their deformation energies are far less than their non-bonding energies. Analysis of radial distribution functions (RDFs) indicates that SA can be adsorbed effectively by aluminum oxide crystal mainly through non-bond interactions. The simulation results agree well with the experimental results, which verify the rationality and reliability of the MD simulation. The further MD simulations provide theoretically optimal temperature (301 K) for the adsorption of SA onto aluminum oxide. The molecular dynamics simulation will be useful for better understanding the adsorption mechanism of antibiotics onto metal oxides, which will also be helpful for optimizing experimental conditions to improve the adsorptive removal efficiency of antibiotics.

Iron crystallization in a fluidized-bed Fenton process.

PubMed

Boonrattanakij, Nonglak; Lu, Ming-Chun; Anotai, Jin

2011-05-01

The mechanisms of iron precipitation and crystallization in a fluidized-bed reactor were investigated. Within the typical Fenton's reagent dosage and pH range, ferric ions as a product from ferrous ion oxidation would be supersaturated and would subsequently precipitate out in the form of ferric hydroxide after the initiation of the Fenton reaction. These precipitates would simultaneously crystallize onto solid particles in a fluidized-bed Fenton reactor if the precipitation proceeded toward heterogeneous nucleation. The heterogeneous crystallization rate was controlled by the fluidized material type and the aging/ripening period of the crystallites. Iron crystallization onto the construction sand was faster than onto SiO(2), although the iron removal efficiencies at 180 min, which was principally controlled by iron hydroxide solubility, were comparable. To achieve a high iron removal rate, fluidized materials have to be present at the beginning of the Fenton reaction. Organic intermediates that can form ferro-complexes, particularly volatile fatty acids, can significantly increase ferric ion solubility, hence reducing the crystallization performance. Therefore, the fluidized-bed Fenton process will achieve exceptional performance with respect to both organic pollutant removal and iron removal if it is operated with the goal of complete mineralization. Crystallized iron on the fluidized media could slightly retard the successive crystallization rate; thus, it is necessary to continuously replace a portion of the iron-coated bed with fresh media to maintain iron removal performance. The iron-coated construction sand also had a catalytic property, though was less than those of commercial goethite. Copyright © 2011 Elsevier Ltd. All rights reserved.

Synthesis and molecular structure of a zinc complex of the vitamin K3 analogue phthiocol

NASA Astrophysics Data System (ADS)

Kathawate, Laxmi; Sproules, Stephen; Pawar, Omkar; Markad, Ganesh; Haram, Santosh; Puranik, Vedavati; Salunke-Gawali, Sunita

2013-09-01

The complex [Zn(phthiocol)2(H2O)2]; 1, where phthiocol is 2-hydroxy-3-methyl-1,4-naphthoquinone, has been synthesized and characterized by elemental analysis, FT-IR, 1H NMR, UV-vis spectroscopy, thermogravimetric (TG) analysis, electrochemical and single crystal X-ray diffraction studies. The νCO stretch shifts to lower frequencies upon complexation of phthiocol to Zn2+. 1H NMR spectra show an upfield shift of the benzenoid ring protons in 1. There is a bathochromic shift of the LMCT band in the UV-vis spectra of 1. Single crystal X-ray structure of 1 show distorted octahedral geometry around Zn2+. Two phthiocol ligands are in plane with the metal, while water molecules are trans to this plane. Coordination of deprotonated phthiocol ligands is 'trans, trans' to Zn2+. Intra as well as intermolecular interactions are observed in 1. Molecules of 1 show three dimensional network through CH⋯O and OH⋯O interactions. Additional anodic peaks are observed in cyclic voltammogram of phthiocol ligand due to oxidation of reduced species formed during reduction. One-electron reduction of 1 is shown to be reversible and DFT studies define this redox event as ligand-centered.

Structures of plutonium coordination compounds: A review of past work, recent single crystal x-ray diffraction results, and what we're learning about plutonium coordination chemistry

NASA Astrophysics Data System (ADS)

Neu, M. P.; Matonic, J. H.; Smith, D. M.; Scott, B. L.

2000-07-01

The compounds we have isolated and characterized include plutonium(III) and plutonium(IV) bound by ligands with a range of donor types and denticity (halide, phosphine oxide, hydroxamate, amine, sulfide) in a variety of coordination geometries. For example, we have obtained the first X-ray structure of Pu(III) complexed by a soft donor ligand. Using a "one pot" synthesis beginning with Pu metal strips and iodine in acetonitrile and adding trithiacyclononane we isolated the complex, PuI3(9S3)(MeCN)2 (Figure 1). On the other end of the coordination chemistry spectrum, we have obtained the first single crystal structure of the Pu(IV) hexachloro anion (Figure 2). Although this species has been used in plutonium purification via anion exchange chromatography for decades, the bond distances and exact structure were not known. We have also characterized the first plutonium-biomolecule complex, Pu(IV) bound by the siderophore desferrioxamine E.In this presentation we will review the preparation, structures, and importance of previously known coordination compounds and of those we have recently isolated. We will show the coordination chemistry of plutonium is rich and varied, well worth additional exploration.

CO oxidation studies over supported noble metal catalysts and single crystals: A review

NASA Technical Reports Server (NTRS)

Boecker, Dirk; Gonzalez, Richard D.

1987-01-01

The catalytic oxidation of CO over noble metal catalysts is reviewed. Results obtained on supported noble metal catalysts and single crystals both at high pressures and under UHV conditions are compared. The underlying causes which result in surface instabilities and multiple steady-state oscillations are considered, in particular, the occurrence of hot spots. CO islands of reactivity, surface oxide formation and phase transformations under oscillatory conditions are discussed.

Age and petrogenesis of the Diana Complex, Adirondack Mountains, New York

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grant, N.; Yang, Yingping; Cliff, R.

1992-01-01

U-Pb zircon data show that the Diana Complex was emplaced 1152[plus minus]12 Ma ago along the Carthage-Colton Mylonite Zone (CCMZ), that marks the boundary between the Adirondack Highlands and the Lowlands. The tectonic setting of the Complex is uncertain because granitoid plutons of the same age were emplaced under syntectonic conditions in the Lowlands, while in the Highlands the same plutons have been viewed as anorogenic. Deformation focused on the CCMZ is reflected in whole-rock Rb-Sr isochron age of 1038[plus minus]97 Ma for the Complex. This resetting is typical of granitoid plutons within a 10 km-wide zone across the CCMZ,more » but is absent outside this zone elsewhere in the Lowlands. Although the chemical continuity of the Complex with Adirondack mafic rocks of the same presumed age demonstrates that crystal fractionation from a basic parent was a likely origin for the Complex, it is probable the magmas were modified by crustal assimilation. For example, the initial [sup 87]Sr/[sup 86]Sr[sub 1152] values for the Complex (0.7042[plus minus]3) are higher than the same ratios for Adirondack mafic rocks (0.7033[plus minus]6), and one zircon fraction lies to the right of the discordia defined by the other four analyzed fractions. The nature and age of the assimilant may be constrained by a metasedimentary xenolith with a whole-rock Rb-Sr isochron age of 1318[plus minus]15 Ma. Changes in TiO[sub 2] and P[sub 2]O[sub 5] abundances and La/Yb values indicate that the crystallization of both accessory (e.g., Fe-Ti oxides, apatite and zircon) and silicate phases were important in the fractionation of the Diana Complex syenites.« less

Structure-Function of the Cytochrome b 6f Complex of Oxygenic Photosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cramer, W. A.; Yamashita, E.; Baniulis, D.

2014-03-20

Structure–function of the major integral membrane cytochrome b 6f complex that functions in cyanobacteria, algae, and green plants to transfer electrons between the two reaction center complexes in the electron transport chain of oxygenic photosynthesis is discussed in the context of recently obtained crystal structures of the complex and soluble domains of cytochrome f and the Rieske iron–sulfur protein. The energy-transducing function of the complex, generation of the proton trans-membrane electrochemical potential gradient, centers on the oxidation/reduction pathways of the plastoquinol/plastoquinone (QH 2/Q), the proton donor/acceptor within the complex. These redox reactions are carried out by five redox prosthetic groupsmore » embedded in each monomer, the high potential two iron–two sulfur cluster and the heme of cytochrome f on the electropositive side (p) of the complex, two noncovalently bound b-type hemes that cross the complex and the membrane, and a covalently bound c-type heme (c n) on the electronegative side (n). These five redox-active groups are organized in high- (cyt f/[2Fe–2S] and low-potential (hemes b p, b n, c n) electron transport pathways that oxidize and reduce the quinol and quinone on the p- and n-sides in a Q-cycle-type mechanism, while translocating as many as 2 H + to the p-side aqueous side for every electron transferred through the high potential chain to the photosystem I reaction center. The presence of heme c n and the connection of the n-side of the membrane and b 6f complex to the cyclic electron transport chain indicate that the Q cycle in the oxygenic photosynthetic electron transport chain differs from those connected to the bc 1 complex in the mitochondrial respiratory chain and the chain in photosynthetic bacteria. Inferences from the structure and C2 symmetry of the complex for the pathway of QH 2/Q transfer within the complex, problems posed by the presence of lipid in the inter-monomer cavity, and the narrow portal for QH2 passage through the p-side oxidation site proximal to the [2Fe–2S] cluster are discussed.« less

Low temperature synthesis of Ru-Cu alloy nanoparticles with the compositions in the miscibility gap

NASA Astrophysics Data System (ADS)

Martynova, S. A.; Filatov, E. Yu.; Korenev, S. V.; Kuratieva, N. V.; Sheludyakova, L. A.; Plusnin, P. E.; Shubin, Yu. V.; Slavinskaya, E. M.; Boronin, A. I.

2014-04-01

A complex salt [Ru(NH3)5Cl][Cu(C2O4)2H2O]-the precursor of nanoalloys combining ruthenium and copper was prepared. It crystallizes in the monoclinic space group P21/n. Thermal properties of the prepared salt were examined in different atmospheres (helium, hydrogen, oxygen). Thermal decomposition of the precursor in inert atmosphere was thoroughly examined and the intermediate products were characterized. Experimental conditions for preparation of copper-rich (up to 12 at% of copper) metastable solid solution CuxRu1-x (based on Ru structure) were optimized, what is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range. Catalytic properties of copper-ruthenium oxide composite were tested in catalytic oxidation of CO.

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

PubMed

Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

2007-12-14

The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

Cyclometalated platinum(ii) complexes of 2,2'-bipyridine N-oxide containing a 1,1'-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies.

PubMed

Shahsavari, Hamid R; Fereidoonnezhad, Masood; Niazi, Maryam; Mosavi, S Talaat; Habib Kazemi, Sayed; Kia, Reza; Shirkhan, Shima; Abdollahi Aghdam, Siamak; Raithby, Paul R

2017-02-14

The preparation and characterization of new heteronuclear-platinum(ii) complexes containing a 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ 2 N,C-bipyO-H)(SMe 2 )], A, in which bipyO-H is a cyclometalated rollover 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of the corresponding binuclear complex [Pt 2 Me 2 (κ 2 N,C-bipyO-H) 2 (μ-dppf)], 1, or the mononuclear complex [PtMe(κ 1 C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelating ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by the single-crystal X-ray diffraction method and it was shown that the chelating dppf ligand in this complex was arranged in a "synclinal-staggered" conformation. Also, the occurrence of intermolecular C-H Cp O bipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.

Synthesis and spectral and redox properties of three triply bridged complexes of ruthenium

USGS Publications Warehouse

Llobet, A.; Curry, M.E.; Evans, H.T.; Meyer, T.J.

1989-01-01

Syntheses are described for the ligand-bridged complexes [(tpm)RuIII(??-O)(??-L)2RuIII(tpm) n+ (L = O2P(O)(OH), n = 0 (1); L = O2CO, n = 0 (2); L = O2CCH3, n = 2 (3); tpm is the tridentate, facial ligand tris(1-pyrazolyl)methane. The X-ray crystal structure of [(tpm)Ru(??-O)(??-O2P(O)(OH))2Ru(tpm)]??8H 2O was determined from three-dimensional X-ray counter data. The complex crystallizes in the trigonal space group P3221 with three molecules in a cell of dimensions a = 18.759 (4) A?? and c = 9.970 (6) A??. The structure was refined to a weighted R factor of 0.042 based on 1480 independent reflections with I ??? 3??(I). The structure reveals that the complex consists of two six-coordinate ruthenium atoms that are joined by a ??-oxo bridge (rRU-O = 1.87 A??; ???RuORu = 124.6??) and two ??-hydrogen phosphato bridges (average rRu-O = 2.07 A??) which are capped by two tpm ligands. The results of cyclic voltammetric and coulometric experiments show that the complexes undergo both oxidative and reductive processes in solution. Upon reduction, the ligand-bridged structure is lost and the monomer [(tpm)Ru(H2O)3]2+ appears quantitatively. All three complexes are diamagnetic in solution. The diamagnetism is a consequence of strong electronic coupling between the low-spin d5 Ru(III) metal ions through the oxo bridge and the relatively small Ru-O-Ru angle. ?? 1989 American Chemical Society.

Invisible defects in complex crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longhi, Stefano, E-mail: stefano.longhi@fisi.polimi.it; Della Valle, Giuseppe

2013-07-15

We show that invisible localized defects, i.e. defects that cannot be detected by an outside observer, can be realized in a crystal with an engineered imaginary potential at the defect site. The invisible defects are synthesized by means of supersymmetric (Darboux) transformations of an ordinary crystal using band-edge wavefunctions to construct the superpotential. The complex crystal has an entire real-valued energy spectrum and Bragg scattering is not influenced by the defects. An example of complex crystal synthesis is presented for the Mathieu potential. -- Highlights: •We show the existence of invisible localized defects in complex crystals. •They turn out tomore » be fully invisible to Bloch waves belonging to any lattice band. •An example of invisible defect is presented for a PT-symmetric Mathieu crystal.« less

Effect of doping with nickel ions on the structural state of a zinc oxide crystal

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Maksimov, V. I.; Gruzdev, N. B.

2009-10-01

The fine structure of a hexagonal zinc oxide crystal doped with nickel ions of the composition Zn1 - x Ni x O has been studied using neutron diffraction and magnetic measurements. It is established that even at very low doping levels ( x = 0.0004), the crystal undergoes local distortions in basal planes of the initial hexagonal lattice. The local distortions are assumed to be sources of the formation of ferromagnetism in compounds of this class.

Low temperature production of large-grain polycrystalline semiconductors

DOEpatents

Naseem, Hameed A [Fayetteville, AR; Albarghouti, Marwan [Loudonville, NY

2007-04-10

An oxide or nitride layer is provided on an amorphous semiconductor layer prior to performing metal-induced crystallization of the semiconductor layer. The oxide or nitride layer facilitates conversion of the amorphous material into large grain polycrystalline material. Hence, a native silicon dioxide layer provided on hydrogenated amorphous silicon (a-Si:H), followed by deposited Al permits induced crystallization at temperatures far below the solid phase crystallization temperature of a-Si. Solar cells and thin film transistors can be prepared using this method.

Crystallization of Mitochondrial Respiratory Complex II from Chicken Heart: a Membrane Protein Complex Diffracting to 2.0 Å.

PubMed Central

Huang, Li-shar; Borders, Toni M.; Shen, John T.; Wang, Chung-Jen; Berry, Edward

2006-01-01

Synopsis A multi-subunit mitochondrial membrane protein complex involved in the Krebs Cycle and respiratory chain has been crystallized in a form suitable for near-atomic resolution structure determination. A procedure is presented for preparation of diffraction-quality crystals of a vertebrate mitochondrial respiratory Complex II. The crystals have the potential to diffract to at least 2.0 Å with optimization of post-crystal-growth treatment and cryoprotection. This should allow determination of the structure of this important and medically relevant membrane protein complex at near-atomic resolution and provide great detail of the mode of binding of substrates and inhibitors at the two substrate-binding sites. PMID:15805592

Alloy Design Challenge: Development of Low Density Superalloys for Turbine Blade Applications

NASA Technical Reports Server (NTRS)

MacKay, Rebecca A.; Gabb, Timothy P.; Smialek, James L.; Nathal, Michael V.

2009-01-01

New low density single crystal (LDS) alloys have been developed for turbine blade applications, which have the potential for significant improvements in the thrust to weight ratio over current production alloys. An innovative alloying strategy was identified to achieve high temperature creep resistance, alloy density reductions, microstructural stability, and cyclic oxidation resistance. The approach relies on the use of molybdenum (Mo) as a potent solid solution strengthener for the nickel (Ni)-base superalloy; Mo has a density much closer to Ni than other refractory elements, such as rhenium (Re) or tungsten (W). A host of testing and microstructural examinations was conducted on the superalloy single crystals, including creep rupture testing, microstructural stability, cyclic oxidation, and hot corrosion. The paper will provide an overview of the single crystal properties that were generated in this new superalloy design space. The paper will also demonstrate the feasibility of this innovative approach of low density single crystal superalloy design. It will be shown that the best LDS alloy possesses the best attributes of three generations of single crystal alloys: the low density of first-generation single crystal alloys, the excellent oxidation resistance of second-generation single crystal alloys, and a creep strength which exceeds that of second and third generation alloys.

Thermal Mechanical Stability of Single-Crystal-Oxide Refractive Concentrators Evaluated for High-Temperature Solar-Thermal Propulsion

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Recently, refractive secondary solar concentrator systems were developed for solar thermal power and propulsion (ref. 1). Single-crystal oxides-such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO), and sapphire (Al2O3)-are candidate refractive secondary concentrator materials. However, the refractive concentrator system will experience high-temperature thermal cycling in the solar thermal engine during the sun/shade transition of a space mission. The thermal mechanical reliability of these components in severe thermal environments is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions. In this research at the NASA Lewis Research Center, a controlled heat flux test approach was developed for investigating the thermal mechanical stability of the candidate oxide. This approach used a 3.0-kW continuous-wave (wavelength, 10.6 mm) carbon dioxide (CO2) laser (ref. 2). The CO2 laser is especially well-suited for single-crystal thermal shock tests because it can directly deliver well-characterized heat energy to the oxide surfaces. Since the oxides are opaque at the 10.6-mm wavelength of the laser beam, the light energy is absorbed at the surfaces rather than transmitting into the crystals, and thus generates the required temperature gradients within the specimens. The following figure is a schematic diagram of the test rig.

Applying the X-ray diffraction analysis for estimating the height and width of nanorods in low symmetry crystal multiphase materials

NASA Astrophysics Data System (ADS)

Mokhtari, Ali; Soleimanian, Vishtasb; Dehkordi, Hamed Aleebrahim; Dastafkan, Kamran

2017-11-01

In this work the potential of Rietveld refinement procedure is used to study the shape and size of non-spherical nanocrystallites. The main advantages of this approach are that not only it can successfully extend to all nanomaterials with different crystal symmetries but also it can evaluate the various phases of multiple materials comparing to electron microscopy methods. Therefore, between seven crystal systems, the formulation of monoclinic and hexagonal crystals is developed. This procedure is applied for the mixture of sodium carbonate and zinc oxide nanocrystallites at different fractions of doped gadolinium oxide. It is found that the crystallites of sodium carbonate and zinc oxide have the rod and ellipsoidal shapes, respectively. The microstructure results are compared with the results of scanning electron microscopy imaging. Good agreement is achieved between the results of scanning electron microscopy and Rietveld methods.

Growth of tungsten oxide nanostructures by chemical solution deposition

NASA Astrophysics Data System (ADS)

Jin, L. H.; Bai, Y.; Li, C. S.; Wang, Y.; Feng, J. Q.; Lei, L.; Zhao, G. Y.; Zhang, P. X.

2018-05-01

Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates by a simple chemical solution deposition. The decomposition behavior and phase formation of ammonium tungstate precursor were characterized by thermal analysis and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures were analyzed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectra. The effects of crystallization temperature on the formation of nanodots and nanowires were investigated. The results indicated that the change of nanostructures had close relationship with the crystallization temperature during the chemical solution deposition process. Under higher crystallization temperature, the square-like dots transformed into the dome-like nanodots and nanowires. Moreover high density well-ordered nanodots could be obtained on the substrate with the further increase of crystallization temperature. It also suggested that this simple chemical solution process could be used to adjust the nanostructures of tungsten oxide compounds on substrate.

Crystallization of copper metaphosphate glass

NASA Technical Reports Server (NTRS)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

Reductive Activation of O2 by Non-Heme Iron(II) Benzilate Complexes of N4 Ligands: Effect of Ligand Topology on the Reactivity of O2-Derived Oxidant.

PubMed

Chakraborty, Biswarup; Jana, Rahul Dev; Singh, Reena; Paria, Sayantan; Paine, Tapan Kanti

2017-01-03

A series of iron(II) benzilate complexes (1-7) with general formula [(L)Fe II (benzilate)] + have been isolated and characterized to study the effect of supporting ligand (L) on the reactivity of metal-based oxidant generated in the reaction with dioxygen. Five tripodal N 4 ligands (tris(2-pyridylmethyl)amine (TPA in 1), tris(6-methyl-2-pyridylmethyl)amine (6-Me 3 -TPA in 2), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (iso-BPMEN in 3), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -iso-BPMEN in 4), and tris(2-benzimidazolylmethyl)amine (TBimA in 7)) along with two linear tetradentate amine ligands (N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (BPMEN in 5) and N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -BPMEN in 6)) were employed in the study. Single-crystal X-ray structural studies reveal that each of the complex cations of 1-3 and 5 contains a mononuclear six-coordinate iron(II) center coordinated by a monoanionic benzilate, whereas complex 7 contains a mononuclear five-coordinate iron(II) center. Benzilate binds to the iron center in a monodentate fashion via one of the carboxylate oxygens in 1 and 7, but it coordinates in a bidentate chelating mode through carboxylate oxygen and neutral hydroxy oxygen in 2, 3, and 5. All of the iron(II) complexes react with dioxygen to exhibit quantitative decarboxylation of benzilic acid to benzophenone. In the decarboxylation pathway, dioxygen becomes reduced on the iron center and the resulting iron-oxygen oxidant shows versatile reactivity. The oxidants are nucleophilic in nature and oxidize sulfide to sulfoxide and sulfone. Furthermore, complexes 2 and 4-6 react with alkenes to produce cis-diols in moderate yields with the incorporation of both the oxygen atoms of dioxygen. The oxygen atoms of the nucleophilic oxidants do not exchange with water. On the basis of interception studies, nucleophilic iron(II) hydroperoxides are proposed to generate in situ in the reaction pathways. The difference in reactivity of the complexes toward external substrates could be attributed to the geometry of the O 2 -derived iron-oxygen oxidant. DFT calculations suggest that, among all possible geometries and spin states, high-spin side-on iron(II) hydroperoxides are energetically favorable for the complexes of 6-Me 3 -TPA, 6-Me 2 -iso-BPMEN, BPMEN, and 6-Me 2 -BPMEN ligands, while high spin end-on iron(II) hydroperoxides are favorable for the complexes of TPA, iso-BPMEN, and TBimA ligands.

Production of crystalline refractory metal oxides containing colloidal metal precipitates and useful as solar-effective absorbers

DOEpatents

Narayan, Jagdish; Chen, Yok

1983-01-01

This invention is a new process for producing refractory crystalline oxides having improved or unusual properties. The process comprises the steps of forming a doped-metal crystal of the oxide; exposing the doped crystal in a bomb to a reducing atmosphere at superatmospheric pressure and a temperature effecting precipitation of the dopant metal in the crystal lattice of the oxide but insufficient to effect net diffusion of the metal out of the lattice; and then cooling the crystal. Preferably, the cooling step is effected by quenching. The process forms colloidal precipitates of the metal in the oxide lattice. The process may be used, for example, to produce thermally stable black MgO crystalline bodies containing magnetic colloidal precipitates consisting of about 99% Ni. The Ni-containing bodies are solar-selective absorbers, having a room-temperature absorptivity of about 0.96 over virtually all of the solar-energy spectrum and exhibiting an absorption edge in the region of 2 .mu.m. The process parameters can be varied to control the average size of the precipitates. The process can produce a black MgO crystalline body containing colloidal Ni precipitates, some of which have the face-centered-cubic structure and others of which have the body-centered cubic structure. The products of the process are metal-precipitate-containing refractory crystalline oxides which have improved or unique optical, mechanical, magnetic, and/or electronic properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moddeman, W.E.; Foose, D.S.; Bowling, W.C.

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface chemistry of three BORAZON* materials: Type I, 510, and 550. Samples were examined in the ``as-received`` condition and following heat treatments in air. Boron oxides were found on the Type I and 550 BORAZON crystals; oxide thicknesses were estimated to be 15A. The titanium-coated product, 510, was found to have a discontinuous titanium coating with a TiO{sub 2} layer that was approximately 20A thick. Following heat treatment at 800{degrees}C for 1 hr in air, the boron oxide layer on the Type I crystals was foundmore » to increase in thickness to approximately 30A. The same heat treatment on the 510 crystals yielded a multi-layered structure consisting of an enriched outer layer of B{sub 2}O{sub 3} over a predominantly TiO{sub 2} one. The entire initial titanium coating was oxidized, and segregated patches of B{sub 2}O{sub 3} (``islands``) were observed. The segregated patches can be explained in terms of the coalescence of liquid B{sub 2}O{sub 3} (melting point = 450{degrees}C). The 550 crystals were oxidized at 500{degrees}C. The oxide formed at this temperature was B{sub x}O (x > 0.67). These results were interpreted in terms of their potential use in sealing BORAZON to glass in vitreous bonding.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moddeman, W.E.; Foose, D.S.; Bowling, W.C.

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface chemistry of three BORAZON* materials: Type I, 510, and 550. Samples were examined in the as-received'' condition and following heat treatments in air. Boron oxides were found on the Type I and 550 BORAZON crystals; oxide thicknesses were estimated to be 15A. The titanium-coated product, 510, was found to have a discontinuous titanium coating with a TiO{sub 2} layer that was approximately 20A thick. Following heat treatment at 800{degrees}C for 1 hr in air, the boron oxide layer on the Type I crystals was foundmore » to increase in thickness to approximately 30A. The same heat treatment on the 510 crystals yielded a multi-layered structure consisting of an enriched outer layer of B{sub 2}O{sub 3} over a predominantly TiO{sub 2} one. The entire initial titanium coating was oxidized, and segregated patches of B{sub 2}O{sub 3} ( islands'') were observed. The segregated patches can be explained in terms of the coalescence of liquid B{sub 2}O{sub 3} (melting point = 450{degrees}C). The 550 crystals were oxidized at 500{degrees}C. The oxide formed at this temperature was B{sub x}O (x > 0.67). These results were interpreted in terms of their potential use in sealing BORAZON to glass in vitreous bonding.« less

Liquid Crystalline Behavior and Related Properties of Colloidal Systems of Inorganic Oxide Nanosheets

PubMed Central

Nakato, Teruyuki; Miyamoto, Nobuyoshi

2009-01-01

Inorganic layered crystals exemplified by clay minerals can be exfoliated in solvents to form colloidal dispersions of extremely thin inorganic layers that are called nanosheets. The obtained “nanosheet colloids” form lyotropic liquid crystals because of the highly anisotropic shape of the nanosheets. This system is a rare example of liquid crystals consisting of inorganic crystalline mesogens. Nanosheet colloids of photocatalytically active semiconducting oxides can exhibit unusual photoresponses that are not observed for organic liquid crystals. This review summarizes experimental work on the phase behavior of the nanosheet colloids as well as photochemical reactions observed in the clay and semiconducting nanosheets system.

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide

NASA Astrophysics Data System (ADS)

Mao, Dongsen; Lu, Guanzhong

2007-02-01

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO 2-ZrO 2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO 2-ZrO 2 into a crystalline ZrTiO 4 compound, while a larger amount of boria (⩾8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO 4 units delay, while a build-up of trigonal BO 3 promote, the crystallization of amorphous TiO 2-ZrO 2 to form ZrTiO 4 crystals.

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.; ...

2017-11-14

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bharadwaja, S. S. N., E-mail: s.s.n.bharadwaja@gmail.com; Ko, S. W.; Qu, W.

Excimer laser assisted re-oxidation for reduced, crystallized BaTiO{sub 3} thin films on Ni-foils was investigated. It was found that the BaTiO{sub 3} can be re-oxidized at an oxygen partial pressure of ∼50 mTorr and substrate temperature of 350 °C without forming a NiO{sub x} interface layer between the film and base metal foil. The dielectric permittivity of re-oxidized films was >1000 with loss tangent values <2% at 100 Hz, 30 mV{sub rms} excitation signal. Electron Energy Loss Spectroscopy indicated that BaTiO{sub 3} thin films can be re-oxidized to an oxygen stoichiometry close to ∼3 (e.g., stoichiometric). High resolution cross sectional transmission electronmore » microscopy showed no evidence of NiO{sub x} formation between the BaTiO{sub 3} and the Ni foil upon excimer laser re-oxidation. Spectroscopic ellipsometry studies on laser re-oxidized [001]{sub C} and [111]{sub C} BaTiO{sub 3} single crystals indicate that the re-oxidation of BaTiO{sub 3} single crystals is augmented by photo-excitation of the ozone, as well as laser pulse induced temperature and local stress gradients.« less

Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Jie; Morrow, Darien J.; Fu, Yongping

High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

DOE PAGES

Chen, Jie; Morrow, Darien J.; Fu, Yongping; ...

2017-09-05

High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

Spectral singularities and Bragg scattering in complex crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longhi, S.

2010-02-15

Spectral singularities that spoil the completeness of Bloch-Floquet states may occur in non-Hermitian Hamiltonians with complex periodic potentials. Here an equivalence is established between spectral singularities in complex crystals and secularities that arise in Bragg diffraction patterns. Signatures of spectral singularities in a scattering process with wave packets are elucidated for a PT-symmetric complex crystal.

Coordination polyhedron and chemical vapor deposition of Cu(hfacac)2(t-BuNH2).

PubMed

Woo, Kyoungja; Paek, Hojeong; Lee, Wan In

2003-10-06

A new pentacoordinate Cu(II) complex, Cu(hfacac)(2)(t-BuNH(2)) [hfacac = CF(3)C(O)CHC(O)CF(3)(-), t-BuNH(2) = tert-butylamine], has been synthesized and structurally characterized. Interestingly, the structure of a single crystal occurred as square pyramidal with one O atom at the apical position and one N and three O atoms at the basal positions, showing a serious degree of distortion. This contrasts with the square-pyramidal structure of Cu(hfacac)(2)L (L = H(2)O and pyrazine), which has the L ligand at the axial position. In the Cu(hfacac)(2)(t-BuNH(2)) complex, the t-BuNH(2) ligand is placed at an equatorial position with a lowered angle by 19.9(2) degrees from the basal plane. This distortion seems to reduce sigma influence and steric hindrance and so stabilizes the square-pyramidal geometry. This precursor has a lower melting point and superior stability to air, moisture, and heat than the Cu(hfacac)(2)(xH(2)O) precursor. The deposition rate of copper oxide film on a Pt layer above 450 degrees C was nearly constant with increasing temperature, indicating a mass transport limited reaction. Therefore it would be a useful metal organic chemical vapor deposition precursor for the fabrication of copper oxide film or superconducting materials. Crystal data for Cu(hfacac)(2)(t-BuNH(2)): 293(2) K, a = 9.6699(4) A, b = 18.0831(10) A, c = 12.8864(11) A, beta = 111.839(5) degrees, monoclinic, space group P2(1)/c, Z = 4.

Molecular Dynamics in the Crystalline Regions of Poly(ethylene oxide) Containing a Well-Defined Point Defect in the Middle of the Polymer Chain.

PubMed

Golitsyn, Yury; Pulst, Martin; Kressler, Jörg; Reichert, Detlef

2017-05-04

The chain mobility in crystals of a homopolymer of poly(ethylene oxide) (PEO) with 22 monomer units (PEO 22 ) is compared with that of a PEO having the identical number of monomer units but additionally a 1,4-disubstituted 1,2,3-triazole (TR) point defect in the middle of the chain (PEO 11 -TR-PEO 11 ). In crystals of PEO 22 , the characteristic α c -relaxation (helix jumps) is detected and the activation energy of this process is calculated from the pure crystalline 1 H FIDs to 67 kJ/mol. PEO 11 -TR-PEO 11 exhibits a more complex behavior, i.e. a transition into the high temperature phase HTPh is noticed during heating in the temperature range between -5 and 10 °C which is attributed to the incorporation of the TR ring into the crystalline lamellae. The crystal mobility of the low temperature phase LTPh of PEO 11 -TR-PEO 11 is in good agreement with PEO 22 since helical jump motions could also be detected by analysis of the 1 H FIDs and the corresponding values of their second moments M 2 . In contrast, the high temperature phase of PEO 11 -TR-PEO 11 shows a completely different behavior of the crystal mobility. The crystalline PEO chains are rigid in this HTPh on the time scale of both, the 1 H time-domain technique and in 13 C MAS CODEX NMR spectroscopy, i.e. the α c -mobility of PEO in the HTPh of PEO 11 -TR-PEO 11 is completely suppressed and the PEO 11 chains are converted into a crystal-fixed polymer due to the incorporation of the TR rings into the crystal structure. However, the TR defect of PEO 11 -TR-PEO 11 shows in the HTPh characteristic π-flip motions with an Arrhenius type activation energy of 223 kJ/mol measured by dielectric relaxation spectroscopy. This motion cannot be observed by corresponding 13 C MAS CODEX NMR measurements due to an interfering spin-dynamic effect.

Positron annihilation on the surfaces of SiO 2 films thermally grown on single crystal of Cz-Si

NASA Astrophysics Data System (ADS)

Deng, Wen; Yue, Li; Zhang, Wei; Cheng, Xu-xin; Zhu, Yan-yan; Huang, Yu-yang

2009-09-01

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO2, SiO2 films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10-3m0c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO2 and Si without oxide film. However, for the thermally grown SiO2-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO2-Si system consist of a surface layer, a SiO2 layer, a SiO2-Si interface layer and a semi-infinite Si substrate.

Anion-free bambus[6]uril and its supramolecular properties.

PubMed

Svec, Jan; Dusek, Michal; Fejfarova, Karla; Stacko, Peter; Klán, Petr; Kaifer, Angel E; Li, Wei; Hudeckova, Edita; Sindelar, Vladimir

2011-05-09

Methods for the preparation of anion-free bambus[6]uril (BU6) are presented. They are based on the oxidation of iodide anion, which is bound inside the macrocycle, utilizing dark oxidation by hydrogen peroxide or photooxidation in the presence of titanium dioxide. Anion-free BU6 was found to be insoluble in any of the investigated solvents; however, it dissolves in methanol/chloroform (1:1) or acetonitrile/water (1:1) mixtures in the presence of the tetrabutylammonium salt of a suitable anion. The association constants with halide ions, BF(4)(-), NO(3)(-), and CN(-), were measured by (1)H NMR spectroscopy. The highest association constant (8.9×10(5) M(-1)) was found for the 1:1 complex of BU6 with I(-) in acetonitrile/water mixture. A number of crystal structures of BU6 complexes with various anions were obtained. The influence of the anion size on the macrocycle diameter is discussed together with an unusual arrangement of the macrocycles into separate layers. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective sensing of two novel coordination polymers based on tris(4-carboxylphenyl)phosphine oxide for organic molecules and Fe3+ and Hg2+ ions

NASA Astrophysics Data System (ADS)

Huo, Liangqin; Zhang, Jie; Gao, Lingling; Wang, Xiaoqing; Fan, Liming; Fang, Kegong; Hu, Tuoping

2017-12-01

Two novel coordination polymers, formulated as {[Zn(HTPO)(bib)]·4H2O}n (1), {[Cu3(TPO)2 (bib)3]·2DMF·0.5EtOH·0.5H2O}n (2) (H3TPO = tris(4-carboxylphenyl)phosphine oxide; bib = 1,4-bis(1H-imidazol-4-yl) benzene), have been synthesized under solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis (EA), IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD). Structural analysis reveals that complex 1 is a 2D 4-connected sheet with an intriguing 2D + 2D→2D network. Complex 2 displays a 3D 3,4-connected net with the point symbol of {103}2{106}3. Furthermore, the photoluminescence properties of 1 and 2 were investigated in the solid state and various solvent emulsions, the results show that 1 and 2 have better fluorescent recognition for organic molecules, Fe3+ and Hg2+ ions.

Molecular and electronic structure of octahedral o-aminophenolato and o-iminobenzosemiquinonato complexes of V(V), Cr(III), Fe(III), and Co(III). Experimental determination of oxidation levels of ligands and metal ions.

PubMed

Chun, H; Verani, C N; Chaudhuri, P; Bothe, E; Bill, E; Weyhermüller, T; Wieghardt, K

2001-08-13

The coordination chemistry of the ligands 2-anilino-4,6-di-tert-butylphenol, H[L(AP)], and N,N"'-bis[2-(4,6-di-tert-butylphenol]diethylenetriamine, H(2)[(L(AP))N(L(AP))], has been studied with the first-row transition metal ions V, Cr, Fe, and Co. The ligands are noninnocent in the sense that the aminophenolato parts, [L(AP)](-) and [L(AP)-H](2)(-), can be readily oxidized to their o-iminobenzosemiquinonato, [L(ISQ)](-), and o-iminobenzoquinone, [L(ISB)], forms. The following neutral octahedral complexes have been isolated as crystalline materials, and their crystal structures have been determined by X-ray crystallography at 100 K: [Cr(III)(L(ISQ))(3)] (1), [Fe(III)(L(ISQ))(3)] (2), [Co(III)(L(ISQ))(3)] (3), [V(V)(L(ISQ))(L(AP)-H)(2)] (4), [V(V)(L(AP)-H)(2)(L(AP))] (5), and [V(V)O[(L(AP))N(L(AP)-H)

Synthesis and Applications of (ONO Pincer)Ruthenium‐Complex‐Bound Norvalines

PubMed Central

Yokoi, Tomoya; Yoshida, Ryota; Ogata, Kazuki; Hashizume, Daisuke; Yasuda, Nobuhiro; Sadakane, Koichiro

2016-01-01

Abstract Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc−[Ru(pydc)(terpy)]Nva−OMe (1; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc−[Ru(pydc)(tBu‐terpy)]Nva−OMe (5), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C−OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C11H23CO−l‐[Ru(pydc)(terpy)]Nva−NH‐n‐C11H23 (l‐4) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l‐1 exhibited a higher catalytic activity for the oxidation of alcohols by H2O2 than parent complex [Ru(pydc)(terpy)] (11 a). PMID:26879368

Structural Characterization of Ferric Hemoglobins from Three Antarctic Fish Species of the Suborder Notothenioidei

PubMed Central

Vergara, Alessandro; Franzese, Marisa; Merlino, Antonello; Vitagliano, Luigi; Verde, Cinzia; di Prisco, Guido; Lee, H. Caroline; Peisach, Jack; Mazzarella, Lelio

2007-01-01

Spontaneous autoxidation of tetrameric Hbs leads to the formation of Fe (III) forms, whose physiological role is not fully understood. Here we report structural characterization by EPR of the oxidized states of tetrameric Hbs isolated from the Antarctic fish species Trematomus bernacchii, Trematomus newnesi, and Gymnodraco acuticeps, as well as the x-ray crystal structure of oxidized Trematomus bernacchii Hb, redetermined at high resolution. The oxidation of these Hbs leads to formation of states that were not usually detected in previous analyses of tetrameric Hbs. In addition to the commonly found aquo-met and hydroxy-met species, EPR analyses show that two distinct hemichromes coexist at physiological pH, referred to as hemichromes I and II, respectively. Together with the high-resolution crystal structure (1.5 Å) of T. bernacchii and a survey of data available for other heme proteins, hemichrome I was assigned by x-ray crystallography and by EPR as a bis-His complex with a distorted geometry, whereas hemichrome II is a less constrained (cytochrome b5-like) bis-His complex. In four of the five Antartic fish Hbs examined, hemichrome I is the major form. EPR shows that for HbCTn, the amount of hemichrome I is substantially reduced. In addition, the concomitant presence of a penta-coordinated high-spin Fe (III) species, to our knowledge never reported before for a wild-type tetrameric Hb, was detected. A molecular modeling investigation demonstrates that the presence of the bulkier Ile in position 67β in HbCTn in place of Val as in the other four Hbs impairs the formation of hemichrome I, thus favoring the formation of the ferric penta-coordinated species. Altogether the data show that ferric states commonly associated with monomeric and dimeric Hbs are also found in tetrameric Hbs. PMID:17545238

A More Reduced Mantle Source for Enriched Shergottites; Insights from the Olivine-Phyric Shergottite Lar 06319

NASA Technical Reports Server (NTRS)

Peslier, A. H.; Hnatyshin, D.; Herd, C. D. K.; Walton, E. L.; Brandon, A. D.; Lapen, T. J.; Shafer, J.

2010-01-01

A detailed petrographic study of melt inclusions and Cr-Fe-Ti oxides of LAR 06319 leads to two main conclusions: 1) this enriched oxidized olivine- phyric shergottite represents nearly continuous crystallization of a basaltic shergottite melt, 2) the melt became more oxidized during differentiation. The first crystallized mineral assemblages record the oxygen fugacity which is closest to that of the melt s mantle source, and which is lower than generally attributed to the enriched shergottite group.

Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts

DOE PAGES

Matheu, Roc; Ertem, Mehmed Z.; Gimbert-Surinach, Carolina; ...

2017-08-15

In this paper, we describe the synthesis, structural characterization, and redox properties of two new Ru complexes containing the dianionic potentially pentadentate [2,2':6',2"-terpyridine]-6,6"-dicarboxylate (tda 2–) ligand that coordinates Ru at the equatorial plane and with additional pyridine or dmso acting as monondentate ligand in the axial positions: [Ru II(tda-κ-N 3O)(py)(dmso)], 1 II and [Ru III(tda-κ-N 3O 2)(py)(H 2O) ax] +, 2 III(H 2O) +. Complex 1 II has been characterized by single-crystal XRD in the solid state and in solution by NMR spectroscopy. The redox properties of 1 II and 2 III(H 2O) + have been thoroughly investigated by meansmore » of cyclic voltammetry and differential pulse voltammetry. Complex 2 II(H 2O) displays poor catalytic activity with regard to the oxidation of water to dioxygen, and its properties have been analyzed on the basis of foot of the wave analysis and catalytic Tafel plots. The activity of 2 II(H 2O) has been compared with related water oxidation catalysts (WOCs) previously described in the literature. Despite its moderate activity, 2 II(H 2O) constitutes the cornerstone that has triggered the rationalization of the different factors that govern overpotentials as well as efficiencies in molecular WOCs. The present work uncovers the interplay between different parameters, namely, coordination number, number of anionic groups bonded to the first-coordination sphere of the metal center, water oxidation catalysis overpotential, p K a and hydrogen bonding, and the performance of a given WOC. It thus establishes the basic principles for the design of efficient WOCs operating at low overpotentials.« less

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

DOEpatents

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

Spectroscopic and structural study of novel interaction product of pyrrolidine-2-thione with molecular iodine. Presumable mechanisms of oxidation

NASA Astrophysics Data System (ADS)

Chernov'yants, Margarita S.; Burykin, Igor V.; Starikova, Zoya A.; Tereznikov, Alexander Yu.; Kolesnikova, Tatiana S.

2013-09-01

Synthesis, spectroscopic and structural characterization of novel interaction product of pyrrolidine-2-thione with molecular iodine is reported. The ability of pyrrolidine-2-thione to form the outer-sphere charge-transfer complex C4H7NS·I2 with iodine molecule in dilute chloroform solution has been studied by UV/vis spectroscopy. Oxidative desulfurization promotes ring fusion of two pyrrolidine-2-thione molecules. The product of iodine induced oxidative desulfurization has been studied by X-ray diffraction method. The crystal structure of the reaction product is formed by 5-(2-thioxopyrrolidine-1-yl)-3,4-dihydro-2H-pyrrolium (C8H13N2S+) cations and pentaiodide anions I5-, which are linked by the intermolecular I⋯Hsbnd C and I⋯C close contacts. The angular pentaiodide anions can be considered as structures formed by coordination of two iodine molecules to the iodide ion (type 1) or by the coordination of iodine molecule to the triiodide ion (type 2).

Mono- and di-bromo platinum(IV) prodrugs via oxidative bromination: synthesis, characterization, and cytotoxicity.

PubMed

Xu, Zoufeng; Wang, Zhigang; Yiu, Shek-Man; Zhu, Guangyu

2015-12-14

Platinum(IV)-based anticancer prodrugs have attracted much attention due to their relative inertness under physiological conditions, being activated inside cells, and their capacity for functionalization with a variety of small-molecule or macromolecule moieties. Novel asymmetric platinum(IV) compounds synthesized through expedient and unique methods are desired. Here we utilize N-bromosuccinimide (NBS) and carry out oxidative bromination on platinum(II) drugs, namely cisplatin, carboplatin, and oxaliplatin, to obtain asymmetric and mono-bromo platinum(IV) prodrugs. Different solvents are used to obtain various compounds, and the compounds are further functionalized. Di-bromo compounds are also obtained through NBS-directed oxidative bromination in ethanol. The crystal structures of representative compounds are discussed, and the reduction potentials of some compounds are examined. A cytotoxicity test shows that the mono- and di-bromo platinum(IV) compounds are active against human ovarian cancer cells. Our study enriches the family of asymmetric platinum(IV) prodrugs and provides with a convenient strategy to obtain brominated platinum(IV) complexes.

Fullerol ionic fluids.

PubMed

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B; Georgakilas, Vasilios; Giannelis, Emmanuel P

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine (liquid-like) and the control (solid-like).

Fullerol ionic fluids

NASA Astrophysics Data System (ADS)

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B.; Georgakilas, Vasilios; Giannelis, Emmanuel P.

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine® (liquid-like) and the control (solid-like).

Quantum chaos and breaking of all anti-unitary symmetries in Rydberg excitons.

PubMed

Aßmann, Marc; Thewes, Johannes; Fröhlich, Dietmar; Bayer, Manfred

2016-07-01

Symmetries are the underlying principles of fundamental interactions in nature. Chaos in a quantum system may emerge from breaking these symmetries. Compared to vacuum, crystals are attractive for studying quantum chaos, as they not only break spatial isotropy, but also lead to novel quasiparticles with modified interactions. Here we study yellow Rydberg excitons in cuprous oxide which couple strongly to the vacuum light field and interact significantly with crystal phonons, leading to inversion symmetry breaking. In a magnetic field, time-reversal symmetry is also broken and the exciton states show a complex splitting pattern, resulting in quadratic level repulsion for small splittings. In contrast to atomic chaotic systems in a magnetic field, which show only a linear level repulsion, this is a signature of a system where all anti-unitary symmetries are broken simultaneously. This behaviour can otherwise be found only for the electro-weak interaction or engineered billiards.

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumah, D. P.; Dogan, M.; Ngai, J. H.

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered Unique Elastic Modes at a BaTiO 3 / ( 2 × 1 ) - Ge ( 001 ) Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumah, D. P.; Dogan, M.; Ngai, J. H.

The strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO3. While the complex crystal structure is predicted using first-principles theory, it is further shown that the details of themore » structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

DOE PAGES

Kumah, D. P.; Dogan, M.; Ngai, J. H.; ...

2016-03-07

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Effect of Sequential Exposition to Short- and Long-Wavelength Radiation on the Optical Absorption in the Bismuth Titanium Oxide Crystal Doped by Aluminum

NASA Astrophysics Data System (ADS)

Dyu, V. G.; Kisteneva, M. G.; Shandarov, S. M.; Khudyakova, E. S.; Smirnov, S. V.; Kargin, Yu. F.

Changes in the spectral dependences of the optical absorption induced in the bismuth titanium oxide crystal doped by aluminum as a result of sequential exposition to cw laser radiation first with the wavelength λi = 532 nm and then with the longer wavelength λn = 633, 655, 663, 780, 871, or 1064 nm are investigated. Our experiments show that after the short-wavelength exposition to radiation with λi = 532 nm, the optical absorption in the crystal increases, and in the range 470-1000 nm, yields the spectrum whose form is independent of the initial crystal state. The subsequent exposition to longer-wavelength radiation leads to enhanced transmittance of the crystal in the examined spectral range. A maximum decrease of the optical absorption in the crystal is observed upon exposure to radiation with the wavelength λn = 663 nm.

Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

DOEpatents

Todt, V.; Miller, D.J.; Shi, D.; Sengupta, S.

1998-07-07

A method of fabricating bulk YBa{sub 2}Cu{sub 3}O{sub x} where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa{sub 2}Cu{sub 3}O{sub x} are heated in the presence of a Nd{sub 1+x}Ba{sub 2{minus}x}Cu{sub 3}O{sub y} seed crystal to a temperature sufficient to form a liquid phase in the YBa{sub 2}Cu{sub 3}O{sub x} while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa{sub 2}Cu{sub 3}O{sub x} material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material. 7 figs.

Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

DOEpatents

Todt, Volker; Miller, Dean J.; Shi, Donglu; Sengupta, Suvankar

1998-01-01

A method of fabricating bulk YBa.sub.2 Cu.sub.3 O.sub.x where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa.sub.2 Cu.sub.3 O.sub.x are heated in the presence of a Nd.sub.1+x Ba.sub.2-x Cu.sub.3 O.sub.y seed crystal to a temperature sufficient to form a liquid phase in the YBa.sub.2 Cu.sub.3 O.sub.x while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa.sub.2 Cu.sub.3 O.sub.x material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material.

Modelling sodium cobaltate by mapping onto magnetic Ising model

NASA Astrophysics Data System (ADS)

Gemperline, Patrick; Morris, David Jonathan Pryce

Fast Ion conductors are a class of crystals that are frequently used as battery materials, especially in smart phones, laptops, and other portable devices. Sodium Cobalt Oxide, NaxCoO2, falls into this class of crystals, but is unique because it possesses the ability to act as a thermoelectric material and a superconductor at different concentrations of Na+. The crystal lattice is mapped onto an Ising Magnetic Spin model and a Monte-Carol Simulation is used to find the most energetically favorable configuration of spins. This spin configuration is mapped back to the crystal lattice resulting in the most stable crystal structure of Sodium Cobalt Oxide at various concentrations. Knowing the atomic structures of the crystals will aid in the research of the materials capabilities and the possible uses of the material commercially. Ohio Supercomputer Center. 1987. Ohio Supercomputer Center. Columbus OH: Ohio Supercomputer Center. and the John Hauck Foundation.

Human 17β-hydroxysteroid dehydrogenase-ligand complexes: crystals of different space groups with various cations and combined seeding and co-crystallization

NASA Astrophysics Data System (ADS)

Zhu, D.-W.; Han, Q.; Qiu, W.; Campbell, R. L.; Xie, B.-X.; Azzi, A.; Lin, S.-X.

1999-01-01

Human estrogenic 17β-hydroxysteroid dehydrogenase (17β-HSD1) is responsible for the synthesis of active estrogens that stimulate the proliferation of breast cancer cells. The enzyme has been crystallized using a Mg 2+/PEG (3500)/β-octyl glucoside system [Zhu et al., J. Mol. Biol. 234 (1993) 242]. The space group of these crystals is C2. Here we report that cations can affect 17β-HSD1 crystallization significantly. In the presence of Mn 2+ instead of Mg 2+, crystals have been obtained in the same space group with similar unit cell dimensions. In the presence of Li + and Na + instead of Mg 2+, the space group has been changed to P2 12 12 1. A whole data set for a crystal of 17ß-HSD1 complex with progesterone grown in the presence of Li + has been collected to 1.95 Å resolution with a synchrotron source. The cell dimensions are a=41.91 Å, b=108.21 Å, c=117.00 Å. The structure has been preliminarily determined by molecular replacement, yielding important information on crystal packing in the presence of different cations. In order to further understand the structure-function relationship of 17β-HSD1, enzyme complexes with several ligands have been crystallized. As the steroids have very low aqueous solubility, we used a combined method of seeding and co-crystallization to obtain crystals of 17β-HSD1 complexed with various ligands. This method provides ideal conditions for growing complex crystals, with ligands such as 20α-hydroxysteroid progesterone, testosterone and 17β-methyl-estradiol-NADP +. Several complex structures have been determined with reliable electronic density of the bound ligands.

Characterization of divalent and trivalent species generated in the chemical and electrochemical oxidation of a dimeric pincer complex of nickel.

PubMed

Spasyuk, Denis M; Gorelsky, Serge I; van der Est, Art; Zargarian, Davit

2011-03-21

The electrolytic and chemical oxidation of the dimeric pincer complex [κ(P),κ(C),κ(N),μ(N)-(2,6-(i-Pr(2)POC(6)H(3)CH(2)NBn)Ni](2) (1; Bn = CH(2)Ph) has been investigated by various analytic techniques. Cyclic voltammetry measurements have shown that 1 undergoes a quasi-reversible, one electron, Ni-based redox process (ΔE(0)(1/2) = -0.07 V vs Cp(2)Fe/[Cp(2)Fe](+)), and spectroelectrochemical measurements conducted on the product of the electrolytic oxidation, [1](+•), have shown multiple low-energy electronic transitions in the range of 10,000-15,000 cm(-1). Computational studies using Density Functional Theory (B3LYP) have corroborated the experimentally obtained structure of 1, provided the electronic structure description, and helped interpret the experimentally obtained absorption spectra for 1 and [1](+·). These calculations indicate that the radical cation [1](+·) is a dimeric, mixed-valent species (class III) wherein most of the spin density is delocalized over the two nickel centers (Ni(+2.5)(2)N(2)), but some spin density is also present over the two nitrogen atoms (Ni(2+)(2)N(2)·). Examination of alternative structures for open shell species generated from 1 has shown that the spin density distribution is highly sensitive toward changes in the ligand environment of the Ni ions. NMR, UV-vis, electron paramagnetic resonance (EPR), and single crystal X-ray diffraction analyses have shown that chemical oxidation of 1 with N-Bromosuccinimide (NBS) follows a complex process that gives multiple products, including the monomeric trivalent species κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr(2) (2). These studies also indicate that oxidation of 1 with 1 equiv of NBS gives an unstable, paramagnetic intermediate that decomposes to a number of divalent species, including succinimide and the monomeric divalent complexes κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr (3) and κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH(2)N(H)Bn)}NiBr(2) (4); a second equivalent of NBS then oxidizes 3 and 4 to 2 and other unidentified products. The divalent complex 3 was synthesized independently and shown to react with NBS or bromine to form its trivalent homologue 2. The new complexes 2 and 3 have been characterized fully.

Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

NASA Astrophysics Data System (ADS)

Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

2017-01-01

Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is expected to be the dominant As form in hydrothermal fluids. These results show that incorporation of As in apatite is a complicated process, and sensitive to the local fluid composition during crystallization, and that some of the complexity in As zoning in partially reacted apatite may be due to local fluctuations of As(V)/As(III) ratios in the fluid and to kinetic effects during the mineral replacement reaction. Our study shows for the first time that As(III) can be incorporated into the apatite structure, although not as efficiently as As(V). Uptake of As(III) is probably highly dependent on the reaction mechanism. As(III)O33- moieties replace phosphate groups, but cause a high strain on the lattice; as a result, As(III) is easily exchanged (or oxidized) for As(V) during hydrothermal recrystallization, and the fully reacted grains only record the preferred oxidation state (i.e., As(V)) from mixed-oxidation state solutions. Overall this study shows that the observed oxidation state of As in apatite may not reflect the original As(III)/As(V) ratio of the parent fluid, due to the complex nature of As(III) uptake and possible in situ oxidation during recrystallization.

Fabrication and characterization of poly(L-lactic acid) gels induced by fibrous complex crystallization with solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsuda, Yasuhiro; Fukatsu, Akinobu; Wang, Yangyang

2014-01-01

Complex crystal induced gelation of poly(L-lactic acid) (PLLA) solutions was studied for a series of solvents, including N,N-dimethylformamide (DMF). By cooling the solutions prepared at elevated temperatures, PLLA gels were produced in solvents that induced complex crystals ( -crystals) with PLLA. Fibrous structure of PLLA in the gel with DMF was observed by polarizing optical microscopy, field emission electron microscopy, and atomic force microscopy. Upon heating, the crystal form of PLLA in the DMF gel changed from -crystal to a-crystal, the major crystal form in common untreated PLLA films, but the morphology and high elastic modulus of the gel remainedmore » until the a-crystal dissolved at higher temperature. In addition, a solvent exchanging method was developed, which allowed PLLA gels to be prepared in other useful solvents that do not induce -crystals without losing the morphology and mechanical properties.« less

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

On the optical band gap of zinc oxide

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1998-05-01

Three different values (3.1, 3.2, and 3.3 eV) have been reported for the optical band gap of zinc oxide single crystals at room temperature. By comparing the optical properties of ZnO crystals using a variety of optical techniques it is concluded that the room temperature band gap is 3.3 eV and that the other values are attributable to a valence band-donor transition at ˜3.15 eV that can dominate the optical absorption when the bulk of a single crystal is probed.

Controlling Disulfide Bond Formation and Crystal Growth from 2-Mercaptobenzoic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rowland, Clare E.; Cantos, P. M.; Toby, B. H.

2011-03-02

We report disulfide bond formation from 2-mercaptobenzoic acid (2-MBA) under hydrothermal conditions as a function of pH. Under acidic conditions, 2-MBA remains unchanged. Upon increasing pH, however, we observe 50% oxidation to 2,2'-disulfanediyldibenzoic acid (2,2'-DSBA), which is isolated as a cocrystal of both the thiol and disulfide molecules. At neutral pH, we observe complete oxidation and concurrent crystal growth. The pH sensitivity of this system allows targeting crystals of specific composition from simple building units through a straightforward pH manipulation.

Photonic Crystals: Tunable Design of Structural Colors Produced by Pseudo-1D Photonic Crystals of Graphene Oxide (Small 25/2016).

PubMed

Tong, Liping; Qi, Wei; Wang, Mengfan; Huang, Renliang; Su, Rongxin; He, Zhimin

2016-07-01

The production of structural colors based on graphene oxide (GO) pseudo-one-dimensional photonic crystals (p1D-PhCs) in the visible spectrum is reported on page 3433 by W. Qi and co-workers. The structural colors could be tuned by simply changing either the volume or concentration of the aqueous GO dispersion. Moreover, GO p1D-PhCs exhibit visible and rapid responsiveness to humidity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of local field and inherent strain in reflectance anisotropy spectra of A{sup III}B{sup V} semiconductors with naturally oxidized surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berkovits, V. L.; Kosobukin, V. A.; Gordeeva, A. B.

2015-12-28

Reflectance anisotropy (RA) spectra of naturally oxidized (001) surfaces of GaAs and InAs crystals are measured for photon energies from 1.5 up to 5.5 eV. The differential high-accuracy RA spectra reveal features substantially different from those caused by either a reconstruction of clean surface or a built-in near-surface electric field. Models of atomic structure with anisotropic transition layers of excess arsenic atoms specific for GaAs(001)/oxide and InAs(001)/oxide interfaces are proposed. In conformity with these models, a general theory of reflectance anisotropy is developed for semiconductor/oxide interfaces within the Green's function technique. The theory takes into account the combined effect of localmore » field due to interface dipoles and of intrinsic near-surface strain of the crystal. Measured RA spectra are analyzed in the model of valence-bond dipoles occupying a rectangular lattice in a multilayer medium. Comparing the measured and calculated spectra, we conclude that RA spectra of oxidized GaAs(001) and InAs(001) surfaces are simultaneously influenced by interface and near-surface anisotropies. The former is responsible for the broad-band spectral features which are associated with polarizability of the valence bonds attached to As atoms at the crystal/oxide interface. The near-surface anisotropy is due to inherent uniaxial straining the near-surface region of crystal. The effect of strain on RA spectra is experimentally and theoretically substantiated for GaAs crystal wafers undergone a uniaxial applied stress. Basically, this work results in the following. It establishes the physical nature of different levels of RA spectra observed in a majority of papers, but never analyzed. It demonstrates how the studied features of RA spectra could be applied for optical characterization of strained interfaces and atomic layers.« less

Effects of local field and inherent strain in reflectance anisotropy spectra of AIIIBV semiconductors with naturally oxidized surfaces

NASA Astrophysics Data System (ADS)

Berkovits, V. L.; Kosobukin, V. A.; Gordeeva, A. B.

2015-12-01

Reflectance anisotropy (RA) spectra of naturally oxidized (001) surfaces of GaAs and InAs crystals are measured for photon energies from 1.5 up to 5.5 eV. The differential high-accuracy RA spectra reveal features substantially different from those caused by either a reconstruction of clean surface or a built-in near-surface electric field. Models of atomic structure with anisotropic transition layers of excess arsenic atoms specific for GaAs(001)/oxide and InAs(001)/oxide interfaces are proposed. In conformity with these models, a general theory of reflectance anisotropy is developed for semiconductor/oxide interfaces within the Green's function technique. The theory takes into account the combined effect of local field due to interface dipoles and of intrinsic near-surface strain of the crystal. Measured RA spectra are analyzed in the model of valence-bond dipoles occupying a rectangular lattice in a multilayer medium. Comparing the measured and calculated spectra, we conclude that RA spectra of oxidized GaAs(001) and InAs(001) surfaces are simultaneously influenced by interface and near-surface anisotropies. The former is responsible for the broad-band spectral features which are associated with polarizability of the valence bonds attached to As atoms at the crystal/oxide interface. The near-surface anisotropy is due to inherent uniaxial straining the near-surface region of crystal. The effect of strain on RA spectra is experimentally and theoretically substantiated for GaAs crystal wafers undergone a uniaxial applied stress. Basically, this work results in the following. It establishes the physical nature of different levels of RA spectra observed in a majority of papers, but never analyzed. It demonstrates how the studied features of RA spectra could be applied for optical characterization of strained interfaces and atomic layers.

Solution 1H NMR characterization of the axial bonding of the two His in oxidized human cytoglobin

PubMed Central

Bondarenko, Vasyl; Dewilde, Sylvia; Moens, Luc; La Mar, Gerd N.

2008-01-01

Solution 1H NMR spectroscopy has been used to determine the relative strengths (covalency) of the two axial His-Fe bonds in paramagnetic, S = 1/2, human met-cytoglobin. The sequence specific assignments of crucial portions of the proximal and distal helices, together with the magnitude of hyperfine shifts and paramagnetic relaxation, establish that His81 and His113, at the canonical positions E7 and F8 in the myoglobin fold, respectively, are ligated to the iron. The characterized complex (~90%) in solution has protohemin oriented as in crystals, with the remaining ~10% exhibiting the hemin orientation rotated 180° about the α-, γ-meso axis. No evidence could be obtained for any five-coordinate complex (<1%) in equilibrium with the six-coordinate complexes. Extensive sequence-specific assignments on other dipolar shifted helical fragments and loops, together with available alternate crystal coordinates for the complex, allowed the robust determination of the orientation and anisotropies of the paramagnetic susceptibility tensor. The tilt of the major axis is controlled by the His-Fe-His vector, and the rhombic axes by the mean of the imidazole orientations for the two His. The anisotropy of the paramagnetic susceptibility tensor allowed the quantitative factoring of the hyperfine shifts for the two axial His to reveal indistinguishable pattern and magnitudes of the contact shifts or π spin densities, and hence, indistinguishable Fe-imidazole covalency for both Fe-His bonds. PMID:17002396

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

A new route for the synthesis of titanium silicalite-1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasile, Aurelia, E-mail: aurelia_vasile@yahoo.com; Busuioc-Tomoiaga, Alina Maria; Catalysis Research Department, ChemPerformance SRL, Iasi 700337

2012-01-15

Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides wasmore » controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.« less

Transition metal ferrocenyl dithiocarbamates functionalized dye-sensitized solar cells with hydroxy as an anchoring group

NASA Astrophysics Data System (ADS)

Yadav, Reena; Waghadkar, Yogesh; Kociok-Köhn, Gabriele; Kumar, Abhinav; Rane, Sunit B.; Chauhan, Ratna

2016-12-01

Three new transition-metal dithiocarbamates involving ferrocene (Fc), namely [Co(FcCH2EtOHdtc)3] (Co), [M(FcCH2EtOHdtc)2] M = Ni (Ni), Cu (Cu) (EtOHdtc = N-ethanol dithiocarbamate), have been synthesized and characterized by microanalyses, FTIR, 1H and 13C NMR spectroscopies and single crystal X-ray diffraction technique. The peak broadening in the 1H spectrum of the copper complex indicates the paramagnetic behavior of this compound. The observed single quasi-reversible cyclic voltammograms for the complexes indicate the stabilization of a metal center (except copper) other than Fe in their characteristic oxidation state. These complexes have been used as photo-sensitizer in dye-sensitized solar cells which indicates that Co displays the best photosensitization property with an overall conversion efficiency of 3.25 ± 0.04%. The low cell efficiency of Ni and Cu complexes may be due to slow regeneration of the dye by iodine/iodide redox couple followed by charge injection into TiO2.

Copper(II) hexaaza macrocyclic binuclear complexes obtained from the reaction of their copper(I) derivates and molecular dioxygen.

PubMed

Costas, Miquel; Ribas, Xavi; Poater, Albert; López Valbuena, Josep Maria; Xifra, Raül; Company, Anna; Duran, Miquel; Solà, Miquel; Llobet, Antoni; Corbella, Montserrat; Usón, Miguel Angel; Mahía, José; Solans, Xavier; Shan, Xiaopeng; Benet-Buchholz, Jordi

2006-05-01

Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III). For those complexes, the singlet state has also been shown to be more stable than the triplet state. In the case of 8c, the most favored structure is the trans-1,2-peroxodicopper(II) because of the para substitution and the steric encumbrance produced by the methylation of the N atoms. Cu(II) complexes 4e, 5e, and 8e have been obtained by O2 oxidation of their corresponding Cu(I) complexes and structurally and magnetically characterized. X-ray single-crystal structures for those complexes have been solved, and they show three completely different types of Cu(II)2 structures: (a) For 4e, the Cu(II) centers are bridged by a phenolate group and an external hydroxide ligand. The phenolate group is generated from the evolution of 4c via intramolecular arene hydroxylation. (b) For 5e, the two Cu(II) centers are bridged by two hydroxide ligands. (c) For the 8e case, the Cu(II) centers are ligated to terminally bound hydroxide ligands, rare because of its tendency to bridge. The evolution of complexes 1c-8c toward their oxidized species has also been rationalized by DFT calculations based mainly on their structure and electrophilicity. The structural diversity of the oxidized species is also responsible for a variety of magnetic behavior: (a) strong antiferromagnetic (AF) coupling with J = -482.0 cm(-1) (g = 2.30; rho = 0.032; R = 5.6 x 10(-3)) for 4e; (b) AF coupling with J = -286.3 cm(-1) (g = 2.07; rho = 0.064; R = 2.6 x 10(-3)) for 5e; (c) an uncoupled Cu(II)2 complex for 8e.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatman, Shawn ME; Zarzycki, Piotr P.; Preocanin, Tajana

Time dependent potentiometric pH titrations were used to study the effect of atomic scale surface structure on the protonation behavior of the structurally well defined hematite/aqueous electrolyte interfaces. Our recently proposed thermodynamic model [1,23] was applied to measured acidimetric and alkalimetric titration hysteresis loops, collected from highly organized (001), (012), and (113) crystal face terminations using pH equilibration times ranging from 15 to 30 mins. Hysteresis loop areas indicate that (001) faces equilibrate faster than the (012) and (113) faces, consistent with the different expected ensembles of singly, doubly, and triply coordinated surface sites on each face. Strongly non-linear hystereticmore » pH-potential relationships were found, with slopes exceeding Nernstian, collectively indicating that protonation and deprotonation is much more complex than embodied in present day surface complexation models. The asymmetrical shape of the acidimetric and alkalimetric titration branches were used to illustrate a proposed steric "leaky screen" repulsion/trapping interaction mechanism that stems from high affinity singly-coordinated sites electrostatically and sterically screening lower affinity doubly and triply coordinated sites. Our data indicate that site interaction is the dominant phenomenon defining surface potential accumulation behavior on single crystal faces of metal oxide minerals.« less

Crystal structures of monoamine oxidase B in complex with four inhibitors of the N-propargylaminoindan class.

PubMed

Binda, Claudia; Hubálek, Frantisek; Li, Min; Herzig, Yaacov; Sterling, Jeffrey; Edmondson, Dale E; Mattevi, Andrea

2004-03-25

Monoamine oxidase B (MAO B) is an outer mitochondrial membrane enzyme that catalyzes the oxidation of arylalkylamine neurotransmitters. The crystal structures of MAO B in complex with four of the N-propargylaminoindan class of MAO covalent inhibitors (rasagiline, N-propargyl-1(S)-aminoindan, 6-hydroxy-N-propargyl-1(R)-aminoindan, and N-methyl-N-propargyl-1(R)-aminoindan) have been determined at a resolution of better than 2.1 A. Rasagiline, 6-hydroxy-N-propargyl-1(R)-aminoindan, and N-methyl-N-propargyl-1(R)-aminoindan adopt essentially the same conformation with the extended propargyl chain covalently bound to the flavin and the indan ring located in the rear of the substrate cavity. N-Propargyl-1(S)-aminoindan binds with the indan ring in a flipped conformation with respect to the other inhibitors, which causes a slight movement of the Tyr326 side chain. Four ordered water molecules are an integral part of the active site and establish H-bond interactions to the inhibitor atoms. These structural studies may guide future drug design to improve selectivity and efficacy by introducing appropriate substituents on the rasagiline molecular scaffold.

Excitons in Cuprous Oxide: Photoionization and Other Multiphoton Processes

NASA Astrophysics Data System (ADS)

Frazer, Nicholas Laszlo

In cuprous oxide (Cu2O), momentum from the absorption of two infrared photons to make an orthoexciton is conserved and detected through the photon component of a resulting mixed exciton/photon (quadrupole exciton polariton) state. I demonstrated that this process, which actually makes the photon momentum more precisely defined, is disrupted by photoionization of excitons. Some processes are known to affect exciton propagation in both the pump and exciton stages, such as phonon emission, exciton-exciton (Auger) scattering, and third harmonic generation. These processes alone were not able to explain all observed losses of excitons or all detected scattering products, which lead me to design an optical pump-probe experiment to measure the exciton photoionization cross section, which is (3.9+/-0.2) x 10-22 m2. This dissertation describes the synthesis of cuprous oxide crystals using oxidation of copper, crystallization from melt with the optical floating zone method, and annealing. The cuprous oxide crystals were characterized using time and space resolved luminescence, leading to the discovery of new defect properties. Selection rules and overall efficiency of third harmonic generation in these crystals were characterized. Exciton photoionization was demonstrated through the depletion of polariton luminescence by an optical probe, the production of phonon linked luminescence as a scattering product, temporal delay of the probe, and time resolved luminescence. The results are integrated with the traditional dynamical model of exciton densities. An additional investigation of copper/cuprous oxide/gold photovoltaic devices is appended.

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

PubMed

Xu, Tao; Dick, Kimberly A; Plissard, Sébastien; Nguyen, Thanh Hai; Makoudi, Younes; Berthe, Maxime; Nys, Jean-Philippe; Wallart, Xavier; Grandidier, Bruno; Caroff, Philippe

2012-03-09

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Faucher, Frédérick; Robey-Bond, Susan M.; Wallace, Susan S.

DNA is subject to a multitude of oxidative damages generated by oxidizing agents from metabolism and exogenous sources and by ionizing radiation. Guanine is particularly vulnerable to oxidation, and the most common oxidative product 8-oxoguanine (8-oxoG) is the most prevalent lesion observed in DNA molecules. 8-OxoG can form a normal Watson-Crick pair with cytosine (8-oxoG:C), but it can also form a stable Hoogsteen pair with adenine (8-oxoG:A), leading to a G:C {yields} T:A transversion after replication. Fortunately, 8-oxoG is recognized and excised by either of two DNA glycosylases of the base excision repair pathway: formamidopyrimidine-DNA glycosylase and 8-oxoguanine DNA glycosylasemore » (Ogg). While Clostridium acetobutylicum Ogg (CacOgg) DNA glycosylase can specifically recognize and remove 8-oxoG, it displays little preference for the base opposite the lesion, which is unusual for a member of the Ogg1 family. This work describes the crystal structures of CacOgg in its apo form and in complex with 8-oxo-2'-deoxyguanosine. A structural comparison between the apo form and the liganded form of the enzyme reveals a structural reorganization of the C-terminal domain upon binding of 8-oxoG, similar to that reported for human OGG1. A structural comparison of CacOgg with human OGG1, in complex with 8-oxoG containing DNA, provides a structural rationale for the lack of opposite base specificity displayed by CacOgg.« less

Low Temperature Flux Growth of 2H-SiC and Beta-Gallium Oxide

NASA Technical Reports Server (NTRS)

Singh, N. B.; Choa, Fow-Sen; Su, Ching-Hua; Arnold, Bradley; Kelly, Lisa

2016-01-01

We present brief overview of our study on the low temperature flux growth of two very important novel wide bandgap materials 2H-SiC and Beta-gallium oxide (Beta-Ga2O3). We have synthesized and grown 5 millimeter to 1 centimeter size single crystals of Beta-gallium oxide (Beta-Ga2O3). We used a flux and semi wet method to grow transparent good quality crystals. In the semi-wet method Ga2O3 was synthesized with starting gallium nitrate solution and urea as a nucleation agent. In the flux method we used tin and other metallic flux. This crystal was placed in an alumina crucible and temperature was raised above 1050 degrees Centigrade. After a time period of thirty hours, we observed prismatic and needle shaped crystals of gallium oxide. Scanning electron microscopic studies showed step growth morphology. Crystal was polished to measure the properties. Bandgap was measured 4.7electronvolts using the optical absorption curve. Another wide bandgap hexagonal 2H-SiC was grown by using Si-Al eutectic flux in the graphite crucible. We used slight AlN also as the impurity in the flux. The temperature was raised up to 1050 degrees Centigrade and slowly cooled to 850 degrees Centigrade. Preliminary characterization results of this material are also reported.

On the Role of Boron in CdTe and CdZnTe Crystals

NASA Astrophysics Data System (ADS)

Pavesi, M.; Marchini, L.; Zha, M.; Zappettini, A.; Zanichelli, M.; Manfredi, M.

2011-10-01

It is well known that group III elements act as donors if they play a substitutional role at the metallic site in II-tellurides; nevertheless, several studies report both on the creation of complexes with vacancies, named A-centers, and on the involvement in self-compensation mechanisms, especially for indium. The boron concentration in II-tellurides is negligible, and its contribution to transport mechanisms has not been studied yet. For the last few years the authors have been developing a new technique to grow CdZnTe by the vertical Bridgman technique, taking advantage of encapsulation by means of boron oxide. In this way, crystals characterized by large single grains, low etch pit density, and high resistivity have been obtained. Recently, x-ray detectors with state-of-the-art performance have been produced from such crystals. Boron contamination, as a consequence of this growth method, is quite low but at least one order of magnitude above values obtained with other growth techniques. Besides being a low-cost technique which is also suitable for large-scale mass production, the encapsulated vertical Bridgman technique is quite useful to prevent dislocations, grain boundaries, and stacking faults; for these reasons, careful characterization was performed to understand the effect of boron both on the electrical properties and on the spectroscopic performance of the final crystals. Our characterization is mainly based on low-temperature photoluminescence in addition to electrical current-voltage measurements, photostimulated current, and x-ray spectroscopy. The results indicate that boron behaves like other group III elements; in fact, boron forms a complex that does not affect the good performance of our x-ray detectors, even if it shows some properties which are typical of A-centers.

Ab-initio calculation for cation vacancy formation energy in anti-fluorite structure

NASA Astrophysics Data System (ADS)

Saleel, V. P. Saleel Ahammad; Chitra, D.; Veluraja, K.; Eithiraj, R. D.

2018-04-01

Lithium oxide (Li2O) has been suggested as a suitable breeder blanket material for fusion reactors. Li+ vacancies are created by neutron irradiation, forming bulk defect complex whose extra character is experimentally unclear. We present a theoretical study of Li2O using density functional theory (DFT) with a plane-wave basis set. The generalized gradient approximation (GGA) and local-density approximation (LDA) were used for exchange and correlation. Here we address the total energy for defect free, cation defect, cation vacancy and vacancy formation energy in Li2O crystal in anti-fluorite structure.

Implications of room temperature oxidation on crystal structure and exchange bias effect in Co/CoO nanoparticles

DOE PAGES

Feygenson, Mikhail; Formo, Eric V.; Freeman, Katherine; ...

2015-11-02

In this study, we describe how the exchange bias effect in Co/CoO nanoparticles depends on the size focusing and temperature treatment of precursor Co nanoparticles before oxidation at ambient conditions. By appealing to magnetization, microscopy, neutron and synchrotron x-ray measurements we found that as-synthesized Co nanoparticles readily oxidize in air only after 20 days. The highest exchange bias field of 814 Oe is observed at T = 2K. When the same nanoparticles are centrifuged and annealed at 70 °C in vacuum prior to oxidation, the exchange bias field is increased to 2570 Oe. Annealing of Co nanoparticles in vacuum improvesmore » their crystallinity and prevents complete oxidation, so that Co-core/CoO-shell structure is preserved even after 120 days. The crystal structure of CoO shell in both samples is different from its bulk counterpart. Implications of such distorted CoO shells on exchange bias are discussed. Coating of Co nanoparticles with amorphous silica shell makes them resistant to oxidation, but ultimately modifies the crystal structure of both Co core and SiO 2 shell.« less

Lateral Variability of the Lower Ocean Crust at Atlantis Bank, SW Indian Ridge, Results of IODP Expedition 360

NASA Astrophysics Data System (ADS)

Dick, H. J.; MacLeod, C. J.; Blum, P.; Scientific Party, E.

2016-12-01

IODP Hole U1473A drilled 809.4 m into a 700-m depth wave-cut platform at Atlantis Bank on the SW Indian Ridge. It is an oceanic core complex where massive gabbro was emplaced into the footwall of a single detachment fault for ≥2.7 Myr, with total slip ≥39 km. It was then uplifted to its present position flanking the 6,100 m deep 199-km Atlantis II Transform. The gabbros are back-tilted 20°S, while a sub-horizontal 15 km long mantle peridotite-gabbro contact lies along the transform wall at 4200 m depth 11.5 km west of Hole U1473A. Hole U1473A is 1.4 km north of 158-m deep Hole 1105A and 2.2 km NNE of 1508-m deep Hole 735B. Thus we examine the lateral continuity of the lower ocean crust at ultraslow rates ( 15-16 mm/yr.), and compare it to 1400-m Hole U1309D in the Atlantis Massif MAR core complex (24 mm/yr.) flanking the 63-km Atlantis Transform. The three Atlantis Bank holes are very similar, consisting of a complex series of oxide-rich gabbros and olivine gabbros. Several dikes crosscutting the gabbro sections show that they passed through the dike-gabbro transition after crystallizing and cooling deeper in the crust. They all show extensive high-temperature crystal-plastic deformation predating dike intrusion. A small amount of troctolite was recovered only in Hole 735B. By contrast, gabbro, rather than olivine gabbro was the dominant lithology in Hole U1309D, with intercalations of troctolite and mantle peridotite, and subordinate oxide gabbro. Oxide gabbro is often associated with crystal-plastic deformation. While these are concentrated in the upper 1/3 of Hole 735B, they are more uniformly distributed in Hole U1309D. While one section cannot be traced directly to the other at Atlantis Bank, it appears that they can be correlated based on chemical and structural similarities, with the 1105A and 1473A sections lying some hundreds of meters deeper structurally than Hole 735B, consistent with erosion on the platform. All these sections represent sequential emplacement of small gabbro bodies, with upward compaction of late melt, often fault controlled. The primary differences in the sections are due to variations in the melt supply, which was significantly lower at Hole U1309D, resulting in incorporation of mantle peridotite screens into the section as additional gabbro intrusions were added to the base of the section.

Crystallization and preliminary crystallographic analysis of calcium-binding protein-2 from Entamoeba histolytica and its complexes with strontium and the IQ1 motif of myosin V

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gourinath, S., E-mail: sgourinath@mail.jnu.ac.in; Padhan, Narendra; Alam, Neelima

2005-04-01

Calcium-binding protein-2 (EhCaBP2) crystals were grown using MPD as a precipitant. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. Calcium plays a pivotal role in the pathogenesis of amoebiasis, a major disease caused by Entamoeba histolytica. Two domains with four canonical EF-hand-containing calcium-binding proteins (CaBPs) have been identified from E. histolytica. Even though they have very high sequence similarity, these bind to different target proteins in a Ca{sup 2+}-dependent manner, leading to different functional pathways. Calcium-binding protein-2 (EhCaBP2) crystals were grown usingmore » MPD as a precipitant. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 111.74, b = 68.83, c = 113.25 Å, β = 116.7°. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 69.18, b = 112.03, c = 93.42 Å, β = 92.8°. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. This complex was crystallized with MPD and ethanol as precipitating agents. These crystals belong to space group P2{sub 1}, with unit-cell parameters a = 60.5, b = 69.86, c = 86.5 Å, β = 97.9°.« less

Fabrication and secondary-phase crystallization of rare-earth disilicate-silicon nitride ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinibulk, M.K.; Thomas, G.; Johnson, S.M.

1992-08-01

In this paper, the fabrication and intergranular-phase devitrification of silicon nitride densified with rare-earth (RE) oxide additives is investigated. The additions of the oxides of Sm, Gd, Dy, Er, and Yb, having high melting points and behaving similarly to Y[sub 2]O[sub 3], were compositionally controlled to tailor a microstructure with a crystalline secondary phase of RE[sub 2]Si[sub 2]O[sub 7]. The lanthanide oxides were found to be ass effective as Y[sub 2]O[sub 3] in densifying Si[sub 3]N[sub 4], resulting in identical microstructures and densities of 98-99% of theoretical density. The crystallization behavior of all six disilicates was similar, characterized by amore » limited nucleation and rapid growth mechanism resulting in large single crystals. Complete crystallization of the intergranular phase was obtained with the exception of a thin residual amorphous film which was observed at interfaces and believed to be rich in impurities, the cause of incomplete devitrification.« less

Passively mode-locked fiber laser based on a hollow-core photonic crystal fiber filled with few-layered graphene oxide solution.

PubMed

Liu, Zhi-Bo; He, Xiaoying; Wang, D N

2011-08-15

We demonstrate a nanosecond-pulse erbium-doped fiber laser that is passively mode locked by a hollow-core photonic crystal fiber filled with few-layered graphene oxide solution. Owing to the good solution processing capability of few-layered graphene oxide, which can be filled into the core of a hollow-core photonic crystal fiber through a selective hole filling process, a graphene saturable absorber can be successfully fabricated. The output pulses obtained have a center wavelength, pulse width, and repetition rate of 1561.2 nm, 4.85 ns, and 7.68 MHz, respectively. This method provides a simple and efficient approach to integrate the graphene into the optical fiber system. © 2011 Optical Society of America

Spectroscopic characterization of zinc oxide nanorods synthesized by solid-state reaction

NASA Astrophysics Data System (ADS)

Prasad, Virendra; D'Souza, Charlene; Yadav, Deepti; Shaikh, A. J.; Vigneshwaran, Nadanathangam

2006-09-01

Well-crystallized zinc oxide nanorods have been fabricated by single step solid-state reaction using zinc acetate and sodium hydroxide, at room temperature. The sodium lauryl sulfate (SLS) stabilized zinc oxide nanorods were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and photoluminescence spectroscopy. The X-ray diffraction revealed the wurtzite structure of zinc oxide. The size estimation by XRD and TEM confirmed that the ZnO nanorods are made of single crystals. The growth of zinc oxide crystals into rod shape was found to be closely related to its hexagonal nature. The mass ratio of SLS:ZnO in the nanorods was found to be 1:10 based on the thermogravimetric analysis. Blue shift of photoluminescence emission was noticed in the ZnO nanorods when compared to that of ZnO bulk. FT-IR analysis confirmed the binding of SLS with ZnO nanorods. Apart from ease of preparation, this method has the advantage of eco-friendliness since the solvent and other harmful chemicals were eliminated in the synthesis protocol.

The effect of Argon pressure dependent V thin film on the phase transition process of (020) VO2 thin film

NASA Astrophysics Data System (ADS)

Meng, Yifan; Huang, Kang; Tang, Zhou; Xu, Xiaofeng; Tan, Zhiyong; Liu, Qian; Wang, Chunrui; Wu, Binhe; Wang, Chang; Cao, Juncheng

2018-01-01

It has been proved challenging to fabricate the single crystal orientation of VO2 thin film by a simple method. Based on chemical reaction thermodynamic and crystallization analysis theory, combined with our experimental results, we find out that when stoichiometric number of metallic V in the chemical equation is the same, the ratio of metallic V thin film surface average roughness Ra to thin film average particle diameter d decreases with the decreasing sputtering Argon pressure. Meanwhile, the oxidation reaction equilibrium constant K also decreases, which will lead to the increases of oxidation time, thereby the crystal orientation of the VO2 thin film will also become more uniform. By sputtering oxidation coupling method, metallic V thin film is deposited on c-sapphire substrate at 1 × 10-1 Pa, and then oxidized in the air with the maximum oxidation time of 65s, high oriented (020) VO2 thin film has been fabricated successfully, which exhibits ∼4.6 orders sheet resistance change across the metal-insulator transition.

Scalable salt-templated synthesis of two-dimensional transition metal oxides

PubMed Central

Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; Jiao, Liying; Zhou, Jun; Tang, Jiang; Gogotsi, Yury

2016-01-01

Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm−3 in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications. PMID:27103200

Organic chemistry on solid surfaces

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zaera, Francisco

2006-07-01

Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed.

One-pot synthesis and optical properties of Eu3+-doped nanocrystalline TiO2 and ZrO2

NASA Astrophysics Data System (ADS)

Julián, Beatriz; Corberán, Rosa; Cordoncillo, Eloisa; Escribano, Purificación; Viana, Bruno; Sanchez, Clément

2005-11-01

A simple and versatile one-pot sol-gel synthesis of Eu3+-doped nanocrystalline TiO2 and ZrO2 nanomaterials is reported in this paper. It consists of the controlled crystallization of Eu3+-doped TiO2 or ZrO2 nanoparticles from an initial solution containing the metal alkoxide, the lanthanide precursor, a complexing agent and a non-complexing acid. The main interest is that it could be extended to different lanthanide ions and inorganic metal oxides to prepare other multifunctional nanomaterials. The characterization by XRD, HRTEM and SAED techniques showed that the TiO2 and ZrO2 crystallization takes place at very low temperatures (60 °C) and that the crystallite size can be tailored by modifying the synthetic conditions. The optical properties of the resulting materials were studied by emission spectra and decay measurements. Both Eu3+:TiO2 and Eu3+:ZrO2 samples exhibited long lifetime values after removing organic components (τ = 0.7 and 1.3 ms, respectively), but the Eu3+:ZrO2 system is specially promising for photonic applications since its τ value is longer than some reported for other inorganic or hybrid matrices in which Eu3+ ions are complexed. This behaviour has been explained through an effective dispersion of the lanthanide ions within the ZrO2 nanocrystals.

Probing the Pathways and Interactions Controlling Crystallization by Particle Attachment

NASA Astrophysics Data System (ADS)

De Yoreo, J. J.; Li, D.; Chun, J.; Schenter, G.; Mundy, C.; Rosso, K. M.

2016-12-01

Crystallization by particle attachment appears to be a widespread mechanism of mineralization. Yet many long-standing questions surrounding nucleation and assembly of precursor particles remain unanswered, due in part to a lack of tools to probe mineralization dynamics with adequate spatial and temporal resolution. Here we report results of liquid phase TEM studies of nucleation and particle assembly in a number of mineral systems. We interpret the results within a framework that considers the impact of both the complexity of free energy landscapes and kinetic factors associated with high supersaturation or slow dynamics. In the calcium carbonate system, the need for high supersturations to overcome the high barrier to nucleation of calcite leads to simultaneous occurrence of multiple pathways, including direct formation of all the common ploymorphs, as well as two-step pathways through which initial precursors, particularly ACC, undergo a direct transformation to a more stable phase. Introduction of highly charged polymers that bind calcium inhibits nucleation, but directs the pathway to a metastable amorphous phase that no longer transforms to more stable polymorphs. Experiments in the iron oxide and oxyhydroxide systems show that, when high supersaturations lead to nucleation of many nanoprticles, further growth occurs through a combination of particle aggregation events and Ostwald ripening. In some cases, aggregation occurs only through oriented attachment on lattice matched faces, leading to single crystals with complex topologies and internal twin boundaries, while in others aggregation results initially in poor co-alignment, but over time the particles undergo atomic rearrangements to achieve a single crystal structure. AFM-based measurements of forces between phyllosilicate surfaces reveal the importance of long-range dispersion interactions in driving alignment, as well as the impact of electrolyte concentration and temperature on the competition of those attractive forces with repulsive electrostatic interactions. Taken together, the results help to define an emerging framework for understanding crystallization by particle attachment.

Crystallization and preliminary X-ray diffraction analysis of the wild-type haloalkane dehalogenase DhaA and its variant DhaA13 complexed with different ligands.

PubMed

Stsiapanava, Alena; Chaloupkova, Radka; Fortova, Andrea; Brynda, Jiri; Weiss, Manfred S; Damborsky, Jiri; Smatanova, Ivana Kuta

2011-02-01

Haloalkane dehalogenases make up an important class of hydrolytic enzymes which catalyse the cleavage of carbon-halogen bonds in halogenated aliphatic compounds. There is growing interest in these enzymes owing to their potential use in environmental and industrial applications. The haloalkane dehalogenase DhaA from Rhodococcus rhodochrous NCIMB 13064 can slowly detoxify the industrial pollutant 1,2,3-trichloropropane (TCP). Structural analysis of this enzyme complexed with target ligands was conducted in order to obtain detailed information about the structural limitations of its catalytic properties. In this study, the crystallization and preliminary X-ray analysis of complexes of wild-type DhaA with 2-propanol and with TCP and of complexes of the catalytically inactive variant DhaA13 with the dye coumarin and with TCP are described. The crystals of wild-type DhaA were plate-shaped and belonged to the triclinic space group P1, while the variant DhaA13 can form prism-shaped crystals belonging to the orthorhombic space group P2(1)2(1)2(1) as well as plate-shaped crystals belonging to the triclinic space group P1. Diffraction data for crystals of wild-type DhaA grown from crystallization solutions with different concentrations of 2-propanol were collected to 1.70 and 1.26 Å resolution, respectively. A prism-shaped crystal of DhaA13 complexed with TCP and a plate-shaped crystal of the same variant complexed with the dye coumarin diffracted X-rays to 1.60 and 1.33 Å resolution, respectively. A crystal of wild-type DhaA and a plate-shaped crystal of DhaA13, both complexed with TCP, diffracted to atomic resolutions of 1.04 and 0.97 Å, respectively.

Heme-Coordinating Inhibitors of Neuronal Nitric Oxide Synthase. Iron-Thioether Coordination is Stabilized by Hydrophobic Contacts Without Increased Inhibitor Potency

PubMed Central

Martell, Jeffrey D.; Li, Huiying; Doukov, Tzanko; Martásek, Pavel; Roman, Linda J.; Soltis, Michael; Poulos, Thomas L.; Silverman, Richard B.

2010-01-01

The heme-thioether ligand interaction often occurs between heme iron and native methionine ligands, but thioether-based heme-coordinating (type II) inhibitors are uncommon due to the difficulty in stabilizing the Fe-S bond. Here, a thioether-based inhibitor (3) of neuronal nitric oxide synthase (nNOS) was designed, and its binding was characterized by spectrophotometry and crystallography. A crystal structure of inhibitor 3 coordinated to heme iron was obtained, representing, to our knowledge, the first crystal structure of a thioether inhibitor complexed to any heme enzyme. A series of related potential inhibitors (4-8) also were evaluated. Compounds 4-8 were all found to be type I (non-heme-coordinating) inhibitors of ferric nNOS, but 4 and 6-8 were found to switch to type II upon heme reduction to the ferrous state, reflecting the higher affinity of thioethers for ferrous heme than for ferric heme. Contrary to what has been widely thought, thioether-heme ligation was found not to increase inhibitor potency, illustrating the intrinsic weakness of the thioether-ferric heme linkage. Subtle changes in the alkyl groups attached to the thioether sulfur caused drastic changes in binding conformation, indicating that hydrophobic contacts play a crucial role in stabilizing the thioether-heme coordination. PMID:20014790

Resolving the structure and properties of τ1-Cr-Ni-Al for high temperature protective applications

NASA Astrophysics Data System (ADS)

Simonson, J. W.; Nicasio, J. E.; Ilyas, H.; Pabla, J.; Horvat, K.; Misuraca, J. C.

Increasing the temperature of the steam in turbine power plants enhances thermal efficiency while reducing CO2 emissions. Exposed steel components, however, must be coated to withstand the harsh environments present in next-generation advanced ultra-supercritical plants. Proposed coating materials must exhibit low density, high hardness, high toughness, excellent oxidation resistance, and low thermal conductivity. With an eye towards satisfying this diverse array of requirements, we report the properties of the so-called τ1 phase of Cr-Ni-Al. We resolve the previously controversial composition and crystal structure of this material. The complex structure is composed of distorted icosahedra and octahedra of Al, with nearest-neighbor transition metal-Al bond lengths as short as 2.4 Å, far shorter than typical distances in Ni-Al and Cr-Al binaries. Accordingly, Vickers hardness is 6 . 88 +/- 0 . 13 GPa, as hard as extra-high-hardness armor plating at only 45% the density. We discuss these properties in light of the result of transport and oxidation resistance measurements. The apparent dependencies of these properties on crystal structure suggests new criteria for materials research. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund, for support of this research under contract 56764-UNI10.

pH-Dependent Assembly and Conversions of Six Cadmium(II)-Based Coordination Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Hua-Cai; Zhu, Ji-Qin; Zhou, Li-Jiang

2010-07-07

Six cadmium(II) complexes containing N2O2 donor tetradentate asymmetrical Schiff base ligand 2-{[2-(dimethylamino)ethylimino]methyl}-6-methoxyphenol (HL5), namely, [(Cd3L52Cl4)2]•CH3OH•H2O (1), [Cd(L5)Cl]2•CH3OH (2), [Cd2(HL5)Cl4]n (3), {[Cd3(H2L5)2Cl8]•2H2O}n (4), [(H2L5)2]2+•[CdCl4]2-•H2O (5), and [(H2L5)2]2+•[CdCl4]2- (6), have been synthesized using cadmium(II) chloride and asymmetrical Schiff base ligand HL5 under different pH conditions at room temperature. The diverse structures show the marked sensitivity of the structural chemistry of the tetradentate asymmetrical Schiff base ligand HL5. Complex 1 formed at pH = 10 exhibits a rare zero- dimensional structure of trinuclear cadmium (II). At pH = 8-9, a dinuclear cadmium (II) complex 2 is formed. The reaction at pH = 5-7more » leads to two one-dimensional structures of 3 and 4. A further decrease of the pH to 3-5 results in a zero-dimensional structure 5. Owing to the departure of lattice water molecules in the crystal, complex 5 at room temperature can gradually undergo single-crystal-to-single-crystal transformation to result complex 6. The results further show that conversions of complex 1 to 5 can also be achieved by adjusting the pH value of the reaction solution, 1→2pH=8→5pH=3 and 3→4pH=5. Comparing these experimental results, it is clear that the pH plays a crucial role in the formation of the resulting structures, which simultaneously provide very effective strategies for constructing the CdII compounds with N2O2 donor tetradentate asymmetrical Schiff base ligand. The strong fluorescent emissions of the six compounds (1-6) make them potentially useful photoactive materials. Furthermore, six Schiff base cadmium complexes (1–6), with DPPH (2,2-dipheny1-1-picrylhydrazy1) as a co-oxidant exhibited the stronger scavenging activity.« less

Synthesis, crystal growth and characterization of bioactive material: 2-amino-1H-benzo[d]imidazol-3-ium salicylate single crystal-a proton transfer molecular complex

NASA Astrophysics Data System (ADS)

Fathima, K. Saiadali; Anitha, K.

2017-05-01

The 1:1 molecular adducts 2-aminobenzimidazolium salicylate (ABIS) single crystal was synthesized and grown from 2-aminobenzimidazole (ABI) as a donor and salicylic acid (SA) as an acceptor. The cell parameter was determined using single crystal X-Ray diffraction method and the complex ABIS belongs to monoclinic system. The spectroscopic studies showed that ABIS crystal was an ion pair complex. The FTIR and Raman spectra showed that the presence of O-H, C=N, C=O vibration which confirms the proton transfer from SA to ABI. The UV-Vis spectrum exhibited a visible band at 359nm for ABIS due to the salicylate anion of the molecule. Further the antimicrobial activity of ABIS complex against Staphylococcus aureus, klebsiella pneumonia, Pseudomonas eruginos and E.coli pathogens was investigated. So the complex molecule inhibits both Gram positive and Gram negative bacterial. It is found that benzimidazole with aminogroup at position 2 increases the general antimicrobial activities of ABIS crystal.

Effect of negative bias on the composition and structure of the tungsten oxide thin films deposited by magnetron sputtering

NASA Astrophysics Data System (ADS)

Wang, Meihan; Lei, Hao; Wen, Jiaxing; Long, Haibo; Sawada, Yutaka; Hoshi, Yoichi; Uchida, Takayuki; Hou, Zhaoxia

2015-12-01

Tungsten oxide thin films were deposited at room temperature under different negative bias voltages (Vb, 0 to -500 V) by DC reactive magnetron sputtering, and then the as-deposited films were annealed at 500 °C in air atmosphere. The crystal structure, surface morphology, chemical composition and transmittance of the tungsten oxide thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis spectrophotometer. The XRD analysis reveals that the tungsten oxide films deposited at different negative bias voltages present a partly crystallized amorphous structure. All the films transfer from amorphous to crystalline (monoclinic + hexagonal) after annealing 3 h at 500 °C. Furthermore, the crystallized tungsten oxide films show different preferred orientation. The morphology of the tungsten oxide films deposited at different negative bias voltages is consisted of fine nanoscale grains. The grains grow up and conjunct with each other after annealing. The tungsten oxide films deposited at higher negative bias voltages after annealing show non-uniform special morphology. Substoichiometric tungsten oxide films were formed as evidenced by XPS spectra of W4f and O1s. As a result, semi-transparent films were obtained in the visible range for all films deposited at different negative bias voltages.

Synthesis and (spectro)electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives.

PubMed

Kowalski, Konrad; Karpowicz, Rafał; Mlostoń, Grzegorz; Miesel, Dominique; Hildebrandt, Alexander; Lang, Heinrich; Czerwieniec, Rafał; Therrien, Bruno

2015-04-07

Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (1, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of 1 gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1-oxide (2, sulfoxide) and 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1,1-dioxide (3, sulfone), respectively. The molecular structures of 1 and 3 in the solid state were determined by single crystal X-ray crystallography. The oxidation of sulphide 1 to sulfone 3, plays only a minor role on the overall structure of the two compounds. Electrochemical (cyclic voltammetry (= CV), square wave voltammetry (= SWV)) and spectroelectrochemical (in situ UV-Vis/NIR spectroscopy) studies were carried out. The CV and SWV measurements showed that an increase of the sulphur atom oxidation from -2 in 1 to +2 in 3 causes an anodic shift of the ferrocenyl-based oxidation potentials of about 100 mV. The electrochemical oxidation of 1-3 generates mixed-valent cations 1(+)-3(+). These monooxidised species display low-energy electronic absorption bands between 1000 and 3000 nm assigned to IVCT (= Inter-Valence Charge Transfer) electronic transitions. Accordingly, the mixed-valent cations 1(+)-3(+) are classified as weakly coupled class II systems according to Robin and Day.

Growing Oxide Nanowires and Nanowire Networks by Solid State Contact Diffusion into Solution-Processed Thin Films.

PubMed

Glynn, Colm; McNulty, David; Geaney, Hugh; O'Dwyer, Colm

2016-11-01

New techniques to directly grow metal oxide nanowire networks without the need for initial nanoparticle seed deposition or postsynthesis nanowire casting will bridge the gap between bottom-up formation and top-down processing for many electronic, photonic, energy storage, and conversion technologies. Whether etched top-down, or grown from catalyst nanoparticles bottom-up, nanowire growth relies on heterogeneous material seeds. Converting surface oxide films, ubiquitous in the microelectronics industry, to nanowires and nanowire networks by the incorporation of extra species through interdiffusion can provide an alternative deposition method. It is shown that solution-processed thin films of oxides can be converted and recrystallized into nanowires and networks of nanowires by solid-state interdiffusion of ionic species from a mechanically contacted donor substrate. NaVO 3 nanowire networks on smooth Si/SiO 2 and granular fluorine-doped tin oxide surfaces can be formed by low-temperature annealing of a Na diffusion species-containing donor glass to a solution-processed V 2 O 5 thin film, where recrystallization drives nanowire growth according to the crystal habit of the new oxide phase. This technique illustrates a new method for the direct formation of complex metal oxide nanowires on technologically relevant substrates, from smooth semiconductors, to transparent conducting materials and interdigitated device structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and spectroscopy of micro-oxo (O(2)(-))-bridged heme/non-heme diiron complexes: models for the active site of nitric oxide reductase.

PubMed

Wasser, Ian M; Martens, Constantinus F; Verani, Claudio N; Rentschler, Eva; Huang, Hong-Wei; Moënne-Loccoz, Pierre; Zakharov, Lev N; Rheingold, Arnold L; Karlin, Kenneth D

2004-01-26

In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe' complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [((6)L)Fe-O-Fe(X)](+) (1) (X = OMe(-) or Cl(-), 69:31 ratio), where (6)L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10,15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1.PF(6) reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe' moiety; 90 degree angle (Fe-O-Fe') = 166.7(3) degrees, and d(Fe.Fe') = 3.556 A. Crystal data for C(70)H(57)ClF(12)Fe(2)N(8)O(3)P (1.PF(6)): triclinic, Ponemacr;, a = 13.185(3) A, b = 14.590 (3) A, c = 16.885(4) A, alpha = 104.219(4) degrees, beta = 91.572(4) degrees, gamma = 107.907(4) degrees, V = 2977.3(11) A(3), Z = 2, T = 150(2) K. Complex 1 (where X = Cl(-)) is further characterized by UV-vis (lambda(max) = 328, 416 (Soret), 569 nm), (1)H NMR (delta 27-24 [TMPA -CH(2)-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (nu(as)(Fe-O-Fe') 844 cm(-)(1)), and Mössbauer (delta(Fe) = 0.47, 0.41 mm/s; deltaE(A) = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114.82 cm(-)(1), S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe') complexes and condensed these with the hydroxo complex (F(8))FeOH or (F(8)-d(8))FeOH to yield "untethered" Fe-O-Fe' analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete (1)H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.

Crystallization and crystal manipulation of a steric chaperone in complex with its lipase substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pauwels, Kris, E-mail: krpauwel@vub.ac.be; Loris, Remy; Vandenbussche, Guy

2005-08-01

Crystals of the lipase of B. glumae in complex with its specific foldase were obtained in two forms. Crystallization, crystal manipulation and preliminary X-ray diffraction analysis are described. Bacterial lipases that are secreted via the type II secretion pathway require a lipase-specific foldase in order to obtain their native and biologically active conformation in the periplasmic space. The lipase–foldase complex from Burkholderia glumae (319 and 333 residues, respectively) was crystallized in two crystal forms. One crystal form belongs to space group P3{sub 1}21 (P3{sub 2}21), with unit-cell parameters a = b = 122.3, c = 98.2 Å. A procedure ismore » presented which improved the diffraction of these crystals from ∼5 to 2.95 Å. For the second crystal form, which belonged to space group C2 with unit-cell parameters a = 183.0, b = 75.7, c = 116.6 Å, X-ray data were collected to 1.85 Å.« less

METHOD FOR REMOVING SODIUM OXIDE FROM LIQUID SODIUM

DOEpatents

Bruggeman, W.H.; Voorhees, B.G.

1957-12-01

A method is described for removing sodium oxide from a fluent stream of liquid sodium by coldtrapping the sodium oxide. Apparatus utilizing this method is disclosed in United States Patent No. 2,745,552. Sodium will remain in a molten state at temperatures below that at which sodium oxide will crystallize out and form solid deposits, therefore, the contaminated stream of sodium is cooled to a temperature at which the solubility of sodium oxide in sodium is substantially decreased. Thereafter the stream of sodium is passed through a bed of stainless steel wool maintained at a temperature below that of the stream. The stream is kept in contact with the wool until the sodium oxide is removed by crystal growth on the wool, then the stream is reheated and returned to the system. This method is useful in purifying reactor coolants where the sodium oxide would otherwise deposit out on the walls and eventually plug the coolant tubes.

Structural characterization of nano-oxide layers in PtMn based specular spin valves

NASA Astrophysics Data System (ADS)

Zhou, Min; Chen, Lifan; Diao, Zhitao; Park, Chang-Man; Huai, Yiming

2005-05-01

A systematic structure characterization of nano-oxide layers (NOLs) and specular spin valves using x-ray diffraction and high-resolution transmission electron microscopy (HRTEM) has been studied. High-angle x-ray diffraction data show almost identical fcc textures for both natural and plasma NOL spin-valves. Low-angle x-ray reflectivity spectrum shows more deteriorated Kiessig fringes at high incident angles for natural oxide sample, indicating rougher interfaces in natural oxidation than in plasma oxidation. Oxygen exposure plays an important role in NOLs process. Fabricating NOLs without any crystal structure degradation is critical to obtain high MR ratio. HRTEM reveals that oxide clusters mixing with insufficiently oxidized CoFe layers prevailed in natural NOL, and the natural oxidation was inhomogeneous. In contrast, plasma NOL has a thinner, more homogeneously oxidized CoFe layers with sharp interfaces. In plasma NOLs, the structures still maintain CoFe crystal structure. The structures and magnetic correlation of the NOL specular spin valves are discussed.

Synthesis, structure, and electrochemistry of di- and zerovalent nickel, palladium, and platinum monomers and dimers derived from an enantiopure (S,S)-tetra(tertiary phosphine).

PubMed

Kitto, Heather J; Rae, A David; Webster, Richard D; Willis, Anthony C; Wild, S Bruce

2007-09-17

The ligand (S,S)-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane, (S,S)-tetraphos, reacts with hexa(aqua)nickel(II) chloride in the presence of trimethylsilyl triflate (TMSOTf) in dichloromethane to give the yellow square-planar complex [Ni{(R,R)-tetraphos}](OTf)2, which has been crystallographically characterized as the square-pyramidal, acetonitrile adduct [Ni(NCMe){(R,R)-tetraphos}]OTf. Cyclic voltammograms of the nickel(II) complex in dichloromethane and acetonitrile at 20 degrees C showed two reduction processes at negative potentials with oxidative (E(p)(ox)) and reductive (E(p)(red)) peak separations similar to those observed for ferrocene/ferrocenium under identical conditions, suggesting two one-electron steps. The cyclic voltammetric data for the divalent nickel complex in acetonitrile at temperatures below -20 degrees C were interpreted according to reversible coordination of acetonitrile to the nickel(I) and nickel(0) complexes. The divalent palladium and platinum complexes [M{(R,R)-tetraphos}](PF6)2 and [M2{(R,R)-tetraphos}2](OTf)4 have been prepared. The reduction potentials for the complexes [M{(R,R)-tetraphos}](PF6)2 increase in the order nickel(II) < palladium(II) < platinum(II). The reaction of (S,S)-tetraphos with bis(cycloocta-1,5-diene)nickel(0) in benzene affords orange [Ni{(R,R)-tetraphos}], which slowly rearranges into the thermodynamically more stable, yellow, double-stranded helicate [Ni2{(R,R)-tetraphos}2]; the crystal structures of both complexes have been determined. The reactions of (S,S)-tetraphos with [M(PPh3)4] in toluene (M = Pd) or benzene (M = Pt) furnish the double-stranded helicates [M2{(R,R)-tetraphos}2]; the palladium complex crystallizes from hot benzene as the 2-benzene solvate and was structurally characterized by X-ray crystallography. In each of the three zerovalent complexes, the coordinated (R,R)-tetraphos stereospecifically generates tetrahedral M(PP)2 stereocenters of M configuration.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

PubMed

Venkatasubramanian, Rajesh; He, Jibao; Johnson, Michael W; Stern, Ilan; Kim, Dae Ho; Pesika, Noshir S

2013-10-29

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Preliminary neutron diffraction analysis of challenging human manganese superoxide dismutase crystals

DOE PAGES

Azadmanesh, Jahaun; Trickel, Scott R.; Weiss, Kevin L.; ...

2017-03-29

Superoxide dismutases (SODs) are enzymes that protect against oxidative stress by dismutation of superoxide into oxygen and hydrogen peroxide through cyclic reduction and oxidation of the active-site metal. The complete enzymatic mechanisms of SODs are unknown since data on the positions of hydrogen are limited. Here, we present, methods for large crystal growth and neutron data collection of human manganese SOD (MnSOD) using perdeuteration and the MaNDi beamline at Oak Ridge National Laboratory. Furthermore, The crystal from which the human MnSOD data set was obtained is the crystal with the largest unit-cell edge (240 Å) from which data have beenmore » collectedvianeutron diffraction to sufficient resolution (2.30 Å) where hydrogen positions can be observed.« less

Dynamic global model of oxide Czochralski process with weighing control

NASA Astrophysics Data System (ADS)

Mamedov, V. M.; Vasiliev, M. G.; Yuferev, V. S.

2011-03-01

A dynamic model of oxide Czochralski growth with weighing control has been developed for the first time. A time-dependent approach is used for the calculation of temperature fields in different parts of a crystallization set-up and convection patterns in a melt, while internal radiation in crystal is considered in a quasi-steady approximation. A special algorithm is developed for the calculation of displacement of a triple point and simulation of a crystal surface formation. To calculate variations in the heat generation, a model of weighing control with a commonly used PID regulator is applied. As an example, simulation of the growth process of gallium-gadolinium garnet (GGG) crystals starting from the stage of seeding is performed.

Preliminary neutron diffraction analysis of challenging human manganese superoxide dismutase crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Azadmanesh, Jahaun; Trickel, Scott R.; Weiss, Kevin L.

Superoxide dismutases (SODs) are enzymes that protect against oxidative stress by dismutation of superoxide into oxygen and hydrogen peroxide through cyclic reduction and oxidation of the active-site metal. The complete enzymatic mechanisms of SODs are unknown since data on the positions of hydrogen are limited. Here, we present, methods for large crystal growth and neutron data collection of human manganese SOD (MnSOD) using perdeuteration and the MaNDi beamline at Oak Ridge National Laboratory. Furthermore, The crystal from which the human MnSOD data set was obtained is the crystal with the largest unit-cell edge (240 Å) from which data have beenmore » collectedvianeutron diffraction to sufficient resolution (2.30 Å) where hydrogen positions can be observed.« less

Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

PubMed

Ma, Xiao; Lin, Chen-Sheng; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Sheng, Tian-Lu; Wu, Xin-Tao

2014-06-02

To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Materials by Raman Scattering

NASA Astrophysics Data System (ADS)

Kozielski, M.

2007-03-01

The paper reports on the use of phonon spectra obtained with the Raman spectroscopy for characterization of different materials. The Raman scattering spectra obtained for zinc selenide crystals, mixed crystals zinc selenide admixtured with magnesium or beryllium, oxide crystals including strontium lanthanum gallate, molecular crystals of triammonium hydrogen diseleniate and a homologous series of polyoxyethylene glycols are analysed.

Economic analysis of crystal growth in space

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Chung, A. M.; Yan, C. S.; Mccreight, L. R.

1972-01-01

Many advanced electronic technologies and devices for the 1980's are based on sophisticated compound single crystals, i.e. ceramic oxides and compound semiconductors. Space processing of these electronic crystals with maximum perfection, purity, and size is suggested. No ecomonic or technical justification was found for the growth of silicon single crystals for solid state electronic devices in space.

Crystal engineering in 3D: Converting nanoscale lamellar manganese oxide to cubic spinel while affixed to a carbon architecture

DOE PAGES

Donakowski, Martin D.; Wallace, Jean M.; Sassin, Megan B.; ...

2016-06-17

Here, by applying differential pair distribution function (DPDF) analyses to the energy–storage relevant MnOx/carbon system— but in a 3D architectural rather than powder–composite configuration—we can remove contributions of the carbon nanofoam paper scaffold and quantify the multiphasic oxide speciation as the nanoscale, disordered MnOx grafted to the carbon walls (MnOx@CNF) structurally rearranges in situ from birnessite AMnOx (A = Na +; Li +) to tetragonal Mn 3O 4 to spinel LiMn 2O 4. The first reaction step involves topotactic exchange of interlayer Na + by Li + in solution followed by thermal treatments to crystal engineer the –10–nm–thick 2D layeredmore » oxide throughout the macroscale nanofoam paper into a spinel phase. The oxide remains affixed to the walls of the nanofoam throughout the phase transformations. The DPDF fits are improved by retention of one plane of birnessite–like oxide after conversion to spinel. We support the DPDF–derived assignments by X–ray photoelectron spectroscopy and Raman spectroscopy, the latter of which tracks how crystal engineering the oxide affects the disorder of the carbon substrate. We further benchmark MnOx@CNF with nonaqueous electrochemical measurements versus lithium as the oxide converts from X–ray–amorphous birnessite to interlayer-registered LiMnOx to spinel. The lamellar AMnOx displays pseudocapacitive electrochemical behavior, with a doubling of specific capacitance for the interlayer–registered LiMnOx, while the spinel LiMn 2O 4@CNF displays a faradaic electrochemical response characteristic of Li–ion insertion. Our results highlight the need for holistic understanding when crystal engineering an (atomistic) charge–storing phase within the (architectural) structure of practical electrodes.« less

The mechanism of deceleration of nucleation and crystal growth by the small addition of transition metals to lithium disilicate glasses

PubMed Central

Thieme, Katrin; Avramov, Isak; Rüssel, Christian

2016-01-01

The addition of small amounts of niobium or tantalum oxide to lithium disilicate glass provokes a drastic decrease of the steady-state nucleation rates and the crystal growth velocities. The viscosity of the residual glassy matrix is considered as a function of the crystallization degree in the course of a non-isothermal crystallization. For simplification, a homogeneous distribution of the added oxides in the glass matrix is assumed. While the viscosity initially decreases, it significantly increases again for higher crystallization degrees hindering crystal growth. However, it was shown that the additives are enriched at the crystal interface. Several possible reasons for the inhibition of nucleation and growth kinetics such as viscosity, interfacial energy crystal/glassy phase, thermodynamic driving force or impingement rate are discussed. Since the crystallization front is blocked by the additives the impingement rate is decreased with increasing additive concentration. Since small concentrations of Nb2O5 and Ta2O5 have a drastic effect on the nucleation, these components should be enriched at the interface crystal/glass. This will only take place, if it leads to a decrease in the interfacial energy. Since this effect alone should result in an increase of the nucleation rate, it must be overcompensated by kinetic effects. PMID:27150844

Sent packing: protein engineering generates a new crystal form of Pseudomonas aeruginosa DsbA1 with increased catalytic surface accessibility

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMahon, Roisin M., E-mail: r.mcmahon1@uq.edu.au; Coinçon, Mathieu; Tay, Stephanie

The crystal structure of a P. aeruginosa DsbA1 variant is more suitable for fragment-based lead discovery efforts to identify inhibitors of this antimicrobial drug target. In the reported structures the active site of the protein can simultaneously bind multiple ligands introduced in the crystallization solution or via soaking. Pseudomonas aeruginosa is an opportunistic human pathogen for which new antimicrobial drug options are urgently sought. P. aeruginosa disulfide-bond protein A1 (PaDsbA1) plays a pivotal role in catalyzing the oxidative folding of multiple virulence proteins and as such holds great promise as a drug target. As part of a fragment-based lead discoverymore » approach to PaDsbA1 inhibitor development, the identification of a crystal form of PaDsbA1 that was more suitable for fragment-soaking experiments was sought. A previously identified crystallization condition for this protein was unsuitable, as in this crystal form of PaDsbA1 the active-site surface loops are engaged in the crystal packing, occluding access to the target site. A single residue involved in crystal-packing interactions was substituted with an amino acid commonly found at this position in closely related enzymes, and this variant was successfully used to generate a new crystal form of PaDsbA1 in which the active-site surface is more accessible for soaking experiments. The PaDsbA1 variant displays identical redox character and in vitro activity to wild-type PaDsbA1 and is structurally highly similar. Two crystal structures of the PaDsbA1 variant were determined in complex with small molecules bound to the protein active site. These small molecules (MES, glycerol and ethylene glycol) were derived from the crystallization or cryoprotectant solutions and provide a proof of principle that the reported crystal form will be amenable to co-crystallization and soaking with small molecules designed to target the protein active-site surface.« less

Structure of bovine cytochrome c oxidase crystallized at a neutral pH using a fluorinated detergent.

PubMed

Luo, Fangjia; Shinzawa-Itoh, Kyoko; Hagimoto, Kaede; Shimada, Atsuhiro; Shimada, Satoru; Yamashita, Eiki; Yoshikawa, Shinya; Tsukihara, Tomitake

2017-07-01

Cytochrome c oxidase (CcO) couples proton pumping to O 2 reduction. Its enzymatic activity depends sensitively on pH over a wide range. However, owing to difficulty in crystallizing this protein, X-ray structure analyses of bovine CcO aimed at understanding its reaction mechanism have been conducted using crystals prepared at pH 5.7, which is significantly lower than that in the cell. Here, oxidized CcO at pH 7.3 was crystallized using a fluorinated octyl-maltoside derivative, and the structure was determined at 1.77 Å resolution. No structural differences between crystals obtained at the neutral pH and the acidic pH were detected within the molecules. On the other hand, some differences in intermolecular interactions were detected between the two types of crystal. The influence of pH on the molecular surface is likely to contribute to the pH dependency of the aerobic oxidation of ferrocytochrome c.

Six new complexes constructed from silver(I) and 2-(dinitromethylene)-1,3-diazacyclopentane (DNDZ): Synthesis, crystal structure and properties

NASA Astrophysics Data System (ADS)

Feng, Zhicun; Zhang, Hang; Xu, Kangzhen; Song, Jirong; Zhao, Fengqi

2018-04-01

Six different energetic silver complexes of 2-(dinitromethylene)-1,3-diazacyclopentane (DNDZ), Ag(DNDZ) (1), [Ag2(H2O)(DNDZ)]n (2), Ag(NH3)DNDZ (3), Ag(CH3NH2)(DNDZ) (4), Ag(C2H5NH2)(DNDZ) (5) and Ag(C3H7NH2)(DNDZ) (6), were first synthesized and structurally characterized. Complexes 2, 3, 5 and 6 were characterized by the single crystal X-ray diffraction analysis. Complexes 2, 5 and 6 crystallize in the monoclinic crystal system with space group P21/n containing four molecules per unit cell, but the crystal of complex 3 is triclinic with space group P-1 containing two molecules in each unit cell. Complexes 2 and 3 possess Ag⋯Ag interaction and corresponding central symmetric structure, but complexes 5 and 6 do not. Thermal behaviors of complexes 1-6 were determined and analyzed. The order of thermal stability for the six complexes is 4 > 3 >1 > 2 >5 > 6. Impact sensitivities for complexes 1-6 are >12 J, > 4 J, > 13 J, > 16 J, > 8 J and >7 J respectively, which corresponds well to the results of thermal stability for the six complexes except for complex 2. Moreover, natural bond orbital (NBO) analysis was used to investigate the bonding and hybridization of complex 3.

Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

PubMed

Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

2016-09-28

A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength.

Nature of the magma storage system beneath the Damavand volcano (N. Iran): An integrated study

NASA Astrophysics Data System (ADS)

Eskandari, Amir; Amini, Sadraddin; De Rosa, Rosanna; Donato, Paola

2018-02-01

Damavand intraplate stratovolcano constructed upon a moderately thick crust (58-67 km) over the last 2 Ma. The erupted products are dominantly trachyandesite-trachyte (TT) lavas and pyroclasts, with minor mafic magmas including tephrite-basanite-trachybasalt and alkali olivine basalts emplaced as cinder cones at the base of the stratovolcano. The TT products are characterized by a mineral assemblage of clinopyroxene (diopside-augite), orthopyroxene (clinoenstatite), feldspar (An2-58, Ab6-69, Or2-56), high Ti phlogopite, F-apatite, Fesbnd Ti oxides, and minor amounts of olivine (Fo73-80), amphibole and zircon, whereas olivine (Fo78-88), high Mg# (80-89) diopside, feldspar, apatite and Fesbnd Ti oxide occur in the mafic magmas. The presence of hydrous and anhydrous minerals, normal zonings, mafic cumulates, and the composition of magmatic inclusions in the TT products suggest evolutionary processes in polybaric conditions. In the same way, disequilibrium textures - including orthopyroxene mantled with clinopyroxene, reaction rim of phlogopite and amphibole, the coexistence of olivine and orthopyroxene, reverse, oscillatory and complex zonings of pyroxene and feldspar crystals - suggest magmatic evolutions in open systems with a varying temperature, oxygen fugacity, water as well as pressure and, to a lesser extent, melt chemistry. Mineral assemblages are used to model the physicochemical conditions and assess default parameters for the thermodynamic simulation of crystallization using MELTS software to track the P-T-H2O-ƒO2 evolution of the magma plumbing system. Thermobarometry and MELTS models estimated the initial nucleation depth at 16-17 kb (56-60 km) for olivine (Fo89) and high Al diopside crystals occurring in the mafic primary magma; it then stopped and underwent fractionation between 8 and 10 kb (28-35 km), corresponding with Moho depth, and continued to differentiate in the lower crust, in agreement with the geophysical models. The mafic rocks were formed by crystal fractionation from the reconstructed primary magma (13 wt% MgO) with the minor role of recharge and crustal assimilation. Phenocrysts in TT lavas recorded a wide range of temperature and pressure of crystallization; at least three main levels of magma storage can be recognized according to the statistical analysis of the models, at 6-8 kb (22-28 km), 4-6 kb (15-22 km), and 0.6-3 kb (2-11 km), respectively. The temperature of crystallization ranged from 1430 to 1180 °C for primary mafic magma to alkali olivine basalts and 1180-800 °C for TT suite. According to the current geophysical models, the present structure of the magma storage system in the crust beneath the Damavand volcano consists of three major accumulation zones located at 20 km, 6-8 km and 3-4.5 km depth. Our data enlarge this scenario, suggesting a more complex magma storage system strongly controlled by the transpressional tectonic regime. Multi-depth magma reservoirs may account for the local thickening of crust below the volcano. The polybaric fractionation model, using the MELTS algorithm, reproduces mineralogy and chemical variations of minerals and whole rock of the Damavand TT lavas. However, some discrepancies between major elements of models and trends of data can be ascribed to the recharge of more mafic magma, minor crustal assimilation, disaggregation of crystal-rich mushes and uptake of magmatic inclusions, as well as crystals from different crustal levels. The polybaric differentiation as the fractionation and/or accumulation of crystals was the probable mechanism for explaining the scarcity of mafic volcanic rocks at the Damavand volcano.

The Mobility Enhancement of Indium Gallium Zinc Oxide Transistors via Low-temperature Crystallization using a Tantalum Catalytic Layer.

PubMed

Shin, Yeonwoo; Kim, Sang Tae; Kim, Kuntae; Kim, Mi Young; Oh, Saeroonter; Jeong, Jae Kyeong

2017-09-07

High-mobility indium gallium zinc oxide (IGZO) thin-film transistors (TFTs) are achieved through low-temperature crystallization enabled via a reaction with a transition metal catalytic layer. For conventional amorphous IGZO TFTs, the active layer crystallizes at thermal annealing temperatures of 600 °C or higher, which is not suitable for displays using a glass substrate. The crystallization temperature is reduced when in contact with a Ta layer, where partial crystallization at the IGZO back-channel occurs with annealing at 300 °C, while complete crystallization of the active layer occurs at 400 °C. The field-effect mobility is significantly boosted to 54.0 cm 2 /V·s for the IGZO device with a metal-induced polycrystalline channel formed at 300 °C compared to 18.1 cm 2 /V·s for an amorphous IGZO TFT without a catalytic layer. This work proposes a facile and effective route to enhance device performance by crystallizing the IGZO layer with standard annealing temperatures, without the introduction of expensive laser irradiation processes.

Cognitive Complexity and Interest Crystallization.

ERIC Educational Resources Information Center

Winer, Dov; Gati, Itamar

1986-01-01

Investigated the relationship between cognitive differentiation and vocational interest crystallization. Results indicated the relationships between measures of cognitive differentiation were generally low, and that interest crystallization was related to between-construct differentiation, but not to the other measures of cognitive complexity.…

Clear microstructure-performance relationships in Mn-containing perovskite and hexaaluminate compounds prepared by activated reactive synthesis.

PubMed

Laassiri, Said; Bion, Nicolas; Duprez, Daniel; Royer, Sébastien; Alamdari, Houshang

2014-03-07

Microstructural properties of mixed oxides play essential roles in their oxygen mobility and consequently in their catalytic performances. Two families of mixed oxides (perovskite and hexaaluminate) with different microstructural features, such as crystal size and specific surface area, were prepared using the activated reactive synthesis (ARS) method. It was shown that ARS is a flexible route to synthesize both mixed oxides with nano-scale crystal size and high specific surface area. Redox properties and oxygen mobility were found to be strongly affected by the material microstructure. Catalytic activities of hexaaluminate and perovskite materials for methane oxidation were discussed in the light of structural, redox and oxygen mobility properties.

Single crystal X- and Q-band EPR spectroscopy of a binuclear Mn(2)(III,IV) complex relevant to the oxygen-evolving complex of photosystem II.

PubMed

Yano, Junko; Sauer, Kenneth; Girerd, Jean-Jacques; Yachandra, Vittal K

2004-06-23

The anisotropic g and hyperfine tensors of the Mn di-micro-oxo complex, [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN, were derived by single-crystal EPR measurements at X- and Q-band frequencies. This is the first simulation of EPR parameters from single-crystal EPR spectra for multinuclear Mn complexes, which are of importance in several metalloenzymes; one of them is the oxygen-evolving complex in photosystem II (PS II). Single-crystal [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN EPR spectra showed distinct resolved (55)Mn hyperfine lines in all crystal orientations, unlike single-crystal EPR spectra of other Mn(2)(III,IV) di-micro-oxo bridged complexes. We measured the EPR spectra in the crystal ab- and bc-planes, and from these spectra we obtained the EPR spectra of the complex along the unique a-, b-, and c-axes of the crystal. The crystal orientation was determined by X-ray diffraction and single-crystal EXAFS (Extended X-ray Absorption Fine Structure) measurements. In this complex, the three crystallographic axes, a, b, and c, are parallel or nearly parallel to the principal molecular axes of Mn(2)(III,IV)O(2)(phen)(4) as shown in the crystallographic data by Stebler et al. (Inorg. Chem. 1986, 25, 4743). This direct relation together with the resolved hyperfine lines significantly simplified the simulation of single-crystal spectra in the three principal directions due to the reduction of free parameters and, thus, allowed us to define the magnetic g and A tensors of the molecule with a high degree of reliability. These parameters were subsequently used to generate the solution EPR spectra at both X- and Q-bands with excellent agreement. The anisotropic g and hyperfine tensors determined by the simulation of the X- and Q-band single-crystal and solution EPR spectra are as follows: g(x) = 1.9887, g(y) = 1.9957, g(z) = 1.9775, and hyperfine coupling constants are A(III)(x) = |171| G, A(III)(y) = |176| G, A(III)(z) = |129| G, A(IV)(x) = |77| G, A(IV)(y) = |74| G, A(IV)(z) = |80| G.

Britanin Ameliorates Cerebral Ischemia-Reperfusion Injury by Inducing the Nrf2 Protective Pathway.

PubMed

Wu, Guozhen; Zhu, Lili; Yuan, Xing; Chen, Hao; Xiong, Rui; Zhang, Shoude; Cheng, Hao; Shen, Yunheng; An, Huazhang; Li, Tiejun; Li, Honglin; Zhang, Weidong

2017-10-10

Oxidative stress is considered the major cause of tissue injury after cerebral ischemia. The nuclear factor erythroid 2-related factor 2 (Nrf2) pathway is one of the most important defensive mechanisms against oxidative stresses and has been confirmed as a target for stroke treatment. Thus, we desired to find new Nrf2 activators and test their neuronal protective activity both in vivo and in vitro. The herb-derived compound, Britanin, is a potent inducer of the Nrf2 system. Britanin can induce the expression of protective enzymes and reverse oxygen-glucose deprivation, followed by reperfusion (OGD-R)-induced neuronal injury in primary cortical neurons in vitro. Furthermore, the administration of Britanin significantly ameliorated middle cerebral artery occlusion-reperfusion (MCAO-R) insult in vivo. We report here the crystal structure of the complex of Britanin and the BTB domain of Keap1. Britanin selectively binds to a conserved cysteine residue, cysteine 151, of Keap1 and inhibits Keap1-mediated ubiquitination of Nrf2, leading to induction of the Nrf2 pathway. Britanin is a potent inducer of Nrf2. The complex crystal structure of Britanin and the BTB domain of Keap1 help clarify the mechanism of Nrf2 induction. Britanin was proven to protect primary cortical neurons against OGD-R-induced injury in an Nrf2-dependant way. Additionally, Britanin had excellent cerebroprotective effect in an MCAO-R model. Our results demonstrate that the natural product Britanin with potent Nrf2-activating and neural protective activities both in vitro and in vivo could be developed into a cerebroprotective therapeutic agent. Antioxid. Redox Signal. 27, 754-768.

Pseudoracemic amino acid complexes: blind predictions for flexible two-component crystals.

PubMed

Görbitz, Carl Henrik; Dalhus, Bjørn; Day, Graeme M

2010-08-14

Ab initio prediction of the crystal packing in complexes between two flexible molecules is a particularly challenging computational chemistry problem. In this work we present results of single crystal structure determinations as well as theoretical predictions for three 1 ratio 1 complexes between hydrophobic l- and d-amino acids (pseudoracemates), known from previous crystallographic work to form structures with one of two alternative hydrogen bonding arrangements. These are accurately reproduced in the theoretical predictions together with a series of patterns that have never been observed experimentally. In this bewildering forest of potential polymorphs, hydrogen bonding arrangements and molecular conformations, the theoretical predictions succeeded, for all three complexes, in finding the correct hydrogen bonding pattern. For two of the complexes, the calculations also reproduce the exact space group and side chain orientations in the best ranked predicted structure. This includes one complex for which the observed crystal packing clearly contradicted previous experience based on experimental data for a substantial number of related amino acid complexes. The results highlight the significant recent advances that have been made in computational methods for crystal structure prediction.

Manganese oxide nanowires, films, and membranes and methods of making

DOEpatents

Suib, Steven Lawrence [Storrs, CT; Yuan, Jikang [Storrs, CT

2008-10-21

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

Complex assembly, crystallization and preliminary X-ray crystallographic studies of rhesus macaque MHC Mamu-A*01 complexed with an immunodominant SIV-Gag nonapeptide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, Fuliang; Graduate School, Chinese Academy of Sciences, Beijing; Lou, Zhiyong

2005-06-01

Crystallization of the first rhesus macaque MHC class I complex. Simian immunodeficiency virus (SIV) infection in rhesus macaques has been used as the best model for the study of human immunodeficiency virus (HIV) infection in humans, especially in the cytotoxic T-lymphocyte (CTL) response. However, the structure of rhesus macaque (or any other monkey model) major histocompatibility complex class I (MHC I) presenting a specific peptide (the ligand for CTL) has not yet been elucidated. Here, using in vitro refolding, the preparation of the complex of the rhesus macaque MHC I allele (Mamu-A*01) with human β{sub 2}m and an immunodominant peptide,more » CTPYDINQM (Gag-CM9), derived from SIV Gag protein is reported. The complex (45 kDa) was crystallized; the crystal belongs to space group I422, with unit-cell parameters a = b = 183.8, c = 155.2 Å. The crystal contains two molecules in the asymmetric unit and diffracts X-rays to 2.8 Å resolution. The structure is being solved by molecular replacement and this is the first attempt to determined the crystal structure of a peptide–nonhuman primate MHC complex.« less

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lieberman, Craig M.; Barry, Matthew C.; Wei, Zheng

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M xM' 3–xO 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III(acac) 3][Co II(hfac) 2] (1), [Co II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2] (2), and [Fe II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2]more » (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe III- and Co II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III, Fe II, and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe III(acac) 3][Co II(hfac) 2] (1) and [Co III(acac) 3][Fe II(hfac) 2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1–3 were found to act as effective single-source precursors for the low-temperature preparation of iron–cobalt spinel oxides Fe xCo 3–xO 4 known as important materials for diverse energy-related applications.« less

Controllable cyanation of carbon-hydrogen bonds by zeolite crystals over manganese oxide catalyst

PubMed Central

Wang, Liang; Wang, Guoxiong; Zhang, Jian; Bian, Chaoqun; Meng, Xiangju; Xiao, Feng-Shou

2017-01-01

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds. PMID:28504259

Quantitative determination of oxygen defects, surface lewis acidity, and catalytic properties of mesoporous MoO3/SBA-15 catalysts

NASA Astrophysics Data System (ADS)

González, Julio; Wang, Jin An; Chen, Lifang; Manríquez, Maria; Salmones, José; Limas, Roberto; Arellano, Ulises

2018-07-01

A set of MoO3/SBA-15 mesoporous catalysts were characterized with a variety of spectroscopic techniques and their crystalline structures were refined with Rietveld method. Oxygen defect concentration, crystallite size, phase composition, surface acidity, mesoporous regularity, and textural properties were reported. Both α-MoO3 and β-MoO3 phases coexisted but α-MoO3 was predominated. Oxygen defects were created in the orthorhombic structure and its concentration decreased from 3.08% for the 20 wt%MoO3/SBA-15 to 0.55% for the 25 wt%MoO3/SBA-15. All the MoO3/SBA-15 catalysts chiefly contained a big number of Lewis acid sites originating from oxygen defects in MoO3 crystals. In the absence of formic acid, the oxidation of 4,6-dibenzothiophene (4,6-DMDBT) in a model diesel was almost proportional to the number of Lewis acid sites. In the presence of formic acid, 4,6-DMDBT oxidation was significantly affected by the formation of surface peroxometallic complex and Lewis acidity. Formic acid addition could improve the ODS efficiency by promoting peroxometallic complex formation and enhancing oxidant stability. Under the optimal reaction condition using the best 15 and 20 wt%MoO3/SBA-15 catalysts, more than 99% 4,6-DMDBT could be removed at 70 °C within 30 min. This work confirmed that 4,6-DMDBT oxidation is a texture and particle size sensitive and Lewis acidity dependent reaction. This work also shows that crystalline structure refinement combination with experiments can gain new insights in the design of heterogeneous nanocatalysts and help to better understand the catalytic behavior in the oxidative desulfurization reactions.

Synthesis, X-ray crystallography, spectroscopic characterization and spectroscopic/electrochemical evidence of formation of phenoxy free radical in active center analogs of galactose oxidase - [Cu(Salgly)H₂O] and [Cu(Salphenylalanine)H₂O].

PubMed

Das, Biva; Medhi, Okhil K

2013-03-01

The formation of phenolate free radical is the factor of high turnover for catalytic activity of galactose oxidase (GO) compared to that by inorganic complexes. A new active center analog of GO, [Cu(II)(Salphenylalanine)H(2)O] have been synthesized and its single crystal X-ray analysis was done. In aqueous surfactant micellar solution chemical oxidation as well as electrochemical oxidation of structural models of galactose oxidase - [Cu(II)Salgly·H(2)O] and [Cu(II)(Salphenylalanine)·H(2)O], have been found to generate free radical originating at the phenolate group. Formation of the free radical have been proved by electron paramagnetic resonance spectroscopy, electronic spectroscopy and electrochemistry. Copyright © 2012 Elsevier B.V. All rights reserved.

Binuclear cyclometalated organoplatinum complexes containing 1,1'-bis(diphenylphosphino)ferrocene as spacer ligand: kinetics and mechanism of MeI oxidative addition.

PubMed

Jamali, Sirous; Nabavizadeh, S Masoud; Rashidi, Mehdi

2008-06-16

The binuclear complex [Pt2Me2(ppy)2(mu-dppf)], 1, in which ppy = deprotonated 2-phenylpyridyl and dppf = 1,1'-bis(diphenylphosphino)ferrocene, was synthesized by the reaction of [PtMe(SMe2)(ppy)] with 0.5 equiv of dppf at room temperature. In this reaction when 1 equiv of dppf was used, the dppf chelating complex 2, [PtMe(dppf)(ppy-kappa1C)], was obtained. The reaction of Pt(II)-Pt(II) complex 1 with excess MeI gave the Pt(IV)-Pt(IV) complex [Pt2I2Me4(ppy)2(mu-dppf)], 3. When the reaction was performed with 1 equiv of MeI, a mixture containing unreacted complex 1, a mixed-valence Pt(II)-Pt(IV) complex [PtMe(ppy)(mu-dppf)PtIMe2(ppy)], 4, and complex 3 was obtained. In a comparative study, the reaction of [PtMe(SMe2)(ppy)] with 1 equiv of monodentate phosphine PPh3 gave [PtMe(ppy)(PPh3)], A. MeI was reacted with A to give the platinum(IV) complex [PtMe2I(ppy)(PPh3)], C. All the complexes were fully characterized using multinuclear (1H, 31P, 13C, and 195Pt) NMR spectroscopy, and complex 2 was further identified by single crystal X-ray structure determination. The reaction of binuclear Pt(II)-Pt(II) complex 1 with excess MeI was monitored by low temperature 31P NMR spectroscopy and further by 1H NMR spectroscopy, and the kinetics of the reaction was studied by UV-vis spectroscopy. On the basis of the data, a mechanism has been suggested for the reaction which overall involved stepwise oxidative addition of MeI to the two Pt(II) centers. In this suggested mechanism, the reaction proceeded through a number of Pt(II)-Pt(IV) and Pt(IV)-Pt(IV) intermediates. Although MeI in each step was trans oxidatively added to one of the Pt(II) centers, further trans to cis isomerizations of Me and I groups were also identified. A comparative kinetic study of the reaction of monomeric platinum(II) complex A with MeI was also performed. The rate of reaction of MeI with complex 1 was some 3.5 times faster than that with complex A, indicating that dppf in the complex 1, as compared with PPh 3 in the complex A, has significantly enhanced the electron richness of the platinum centers.

X-ray analyses of thermally grown and reactively sputtered tantalum oxide films on NiTi alloy

NASA Astrophysics Data System (ADS)

McNamara, Karrina; Tofail, Syed A. M.; Conroy, Derek; Butler, James; Gandhi, Abbasi A.; Redington, Wynette

2012-08-01

Sputter deposition of tantalum (Ta) on the surface of NiTi alloy is expected to improve the alloy's corrosion resistance and biocompatibility. Tantalum is a well-known biomaterial which is not affected by body fluids and is not irritating to human tissue. Here we compare the oxidation chemistry crystal structure evolution of tantalum oxide films grown on NiTi by reactive O2 sputtering and by thermal oxidation of sputter deposited Ta films. The effect of sputtering parameters and post-sputtering treatments on the morphology, oxidation state and crystal structure of the tantalum oxide layer have been investigated by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The study has found that it may be better to avoid oxidation at and above 600 °C. The study establishes that reactive sputtering in presence of low oxygen mixture yields thicker film with better control of the film quality except that the surface oxidation state of Ta is slightly lower.

Structural insight into the substrate- and dioxygen-binding manner in the catalytic cycle of rieske nonheme iron oxygenase system, carbazole 1,9a-dioxygenase.

PubMed

Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki

2012-06-24

Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.

Bio-inspired band gap engineering of zinc oxide by intracrystalline incorporation of amino acids.

PubMed

Brif, Anastasia; Ankonina, Guy; Drathen, Christina; Pokroy, Boaz

2014-01-22

Bandgap engineering of zinc oxide semiconductors can be achieved using a bio-inspired method. During a bioInspired crystallization process, incorporation of amino acids into the crystal structure of ZnO induces lattice strain that leads to linear bandgap shifts. This allows for fine tuning of the bandgap in a bio-inspired route. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixed valence transition metal 2D-oxides: Comparison between delafossite and crednerite compounds

NASA Astrophysics Data System (ADS)

Martin, Christine; Poienar, Maria

2017-08-01

Transition metal oxides offer large opportunities to study relationships between structures and properties. Indeed these compounds crystallize in numerous frameworks corresponding to different dimensionalities and, accordingly, show a huge variety of properties (as high Tc superconductivity, colossal magnetoresistivity, multiferroicity..). The control of the oxidation state of the transition metal, via the monitoring of the oxygen content, is of prime importance to understand and optimize the properties, due to the strong coupling that exists between the lattice and the charges and spins of the transition metals. In this large playground for chemists, we reinvestigated several 2D-compounds derived from delafossite structure. Considering this paper as a very short review, we report here the results obtained on CuMO2 compounds (with M = Cr, Mn or Mn+Cu) by using a combination of techniques, as X-ray, neutrons and/or electrons diffraction on poly-crystals for structural characterisations that are correlated with electrical and/or magnetic properties. The complementarity of studies is also addressed by the synthesis and characterization of single crystals in addition to poly-crystals. Moreover the comparison of the structures of similar Cr and Mn based oxides highlights the crucial role of the Jahn-Teller effect of trivalent manganese to lift the degeneracy, which is responsible of the magnetic frustration in CuCrO2.

Dislocation, crystallite size distribution and lattice strain of magnesium oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sutapa, I. W.; Wahid Wahab, Abdul; Taba, P.; Nafie, N. L.

2018-03-01

The oxide of magnesium nanoparticles synthesized using sol-gel method and analysis of the structural properties was conducted. The functional groups of nanoparticles has been analysed by Fourier Transform Infrared Spectroscopy (FT-IR). Dislocations, average size of crystal, strain, stress, the energy density of crystal, crystallite size distribution and morphologies of the crystals were determined based on X-ray diffraction profile analysis. The morphological of the crystal was analysed based on the image resulted from SEM analysis. The crystallite size distribution was calculated with the contention that the particle size has a normal logarithmic form. The most orientations of crystal were determined based on the textural crystal from diffraction data of X-ray diffraction profile analysis. FT-IR results showed the stretching vibration mode of the Mg-O-Mg in the range of 400.11-525 cm-1 as a broad band. The average size crystal of nanoparticles resulted is 9.21 mm with dislocation value of crystal is 0.012 nm-2. The strains, stress, the energy density of crystal are 1.5 x 10-4 37.31 MPa; 0.72 MPa respectively. The highest texture coefficient value of the crystal is 0.98. This result is supported by morphological analysis using SEM which shows most of the regular cubic-shaped crystals. The synthesis method is suitable for simple and cost-effective synthesis model of MgO nanoparticles.

Engineering p-n junctions and bandgap tuning of InSe nanolayers by controlled oxidation

NASA Astrophysics Data System (ADS)

Balakrishnan, Nilanthy; Kudrynskyi, Zakhar R.; Smith, Emily F.; Fay, Michael W.; Makarovsky, Oleg; Kovalyuk, Zakhar D.; Eaves, Laurence; Beton, Peter H.; Patanè, Amalia

2017-06-01

Exploitation of two-dimensional (2D) van der Waals (vdW) crystals can be hindered by the deterioration of the crystal surface over time due to oxidation. On the other hand, the existence of a stable oxide at room temperature can offer prospects for several applications. Here we report on the chemical reactivity of γ-InSe, a recent addition to the family of 2D vdW crystals. We demonstrate that, unlike other 2D materials, InSe nanolayers can be chemically stable under ambient conditions. However, both thermal- and photo-annealing in air induces the oxidation of the InSe surface, which converts a few surface layers of InSe into In2O3, thus forming an InSe/In2O3 heterostructure with distinct and interesting electronic properties. The oxidation can be activated in selected areas of the flake by laser writing or prevented by capping the InSe surface with an exfoliated flake of hexagonal boron nitride. We exploit the controlled oxidation of p-InSe to fabricate p-InSe/n-In2O3 junction diodes with room temperature electroluminescence and spectral response from the near-infrared to the visible and near-ultraviolet ranges. These findings reveal the limits and potential of thermal- and photo-oxidation of InSe in future technologies.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

NASA Astrophysics Data System (ADS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-05-01

The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

Crystallization and preliminary X-ray diffraction analysis of the peripheral light-harvesting complex LH2 from Marichromatium purpuratum.

PubMed

Cranston, Laura J; Roszak, Aleksander W; Cogdell, Richard J

2014-06-01

LH2 from the purple photosynthetic bacterium Marichromatium (formerly known as Chromatium) purpuratum is an integral membrane pigment-protein complex that is involved in harvesting light energy and transferring it to the LH1-RC `core' complex. The purified LH2 complex was crystallized using the sitting-drop vapour-diffusion method at 294 K. The crystals diffracted to a resolution of 6 Å using synchrotron radiation and belonged to the tetragonal space group I4, with unit-cell parameters a=b=109.36, c=80.45 Å. The data appeared to be twinned, producing apparent diffraction symmetry I422. The tetragonal symmetry of the unit cell and diffraction for the crystals of the LH2 complex from this species reveal that this complex is an octamer.

Crystallization and preliminary X-ray diffraction analysis of the peripheral light-harvesting complex LH2 from Marichromatium purpuratum

PubMed Central

Cranston, Laura J.; Roszak, Aleksander W.; Cogdell, Richard J.

2014-01-01

LH2 from the purple photosynthetic bacterium Marichromatium (formerly known as Chromatium) purpuratum is an integral membrane pigment–protein complex that is involved in harvesting light energy and transferring it to the LH1–RC ‘core’ complex. The purified LH2 complex was crystallized using the sitting-drop vapour-diffusion method at 294 K. The crystals diffracted to a resolution of 6 Å using synchrotron radiation and belonged to the tetragonal space group I4, with unit-cell parameters a = b = 109.36, c = 80.45 Å. The data appeared to be twinned, producing apparent diffraction symmetry I422. The tetragonal symmetry of the unit cell and diffraction for the crystals of the LH2 complex from this species reveal that this complex is an octamer. PMID:24915099

Re-187 Os-187 Isotopic and Highly Siderophile Element Systematics of Group IVB Irons

NASA Technical Reports Server (NTRS)

Honesto, J.; McDonough, W. F.; Walker, R. J.; McCoy, T. J.; Ash, R. D.

2005-01-01

Study of the magmatic iron meteorite groups permits constraints to be placed on the chemical and isotopic composition of parent bodies, and the timing of, and crystal-liquid fractionation processes involved in the crystallization of asteroidal cores. Here we examine Re-Os isotopic and trace elemental systematics of group IVB irons. Compared to most irons, the irons comprising this group are enriched in some of the most refractory siderophile elements, yet highly-depleted in most volatile siderophile elements. These characteristics have been attributed to processes such as high temperature condensation of precursor materials and oxidation in the parent body. Most recently it has been suggested that both processes may be involved in the chemical complexity of the group. Here, high precision isotopic and highly siderophile element (HSE) concentrations are used to further examine these possible origins, and the crystallization history of the group. In addition, we have begun to assess the possibility of relating certain ungrouped irons with major groups via multi-element, trace element modeling. In a companion abstract, the isotopic and trace element systematics of the ungrouped iron Tishomingo are compared with the IVB irons.

Following DNA chain extension and protein conformational changes in crystals of a Y-family DNA polymerase via Raman crystallography.

PubMed

Espinoza-Herrera, Shirly J; Gaur, Vineet; Suo, Zucai; Carey, Paul R

2013-07-23

Y-Family DNA polymerases are known to bypass DNA lesions in vitro and in vivo. Sulfolobus solfataricus DNA polymerase (Dpo4) was chosen as a model Y-family enzyme for investigating the mechanism of DNA synthesis in single crystals. Crystals of Dpo4 in complexes with DNA (the binary complex) in the presence or absence of an incoming nucleotide were analyzed by Raman microscopy. (13)C- and (15)N-labeled d*CTP, or unlabeled dCTP, were soaked into the binary crystals with G as the templating base. In the presence of the catalytic metal ions, Mg(2+) and Mn(2+), nucleotide incorporation was detected by the disappearance of the triphosphate band of dCTP and the retention of *C modes in the crystal following soaking out of noncovalently bound C(or *C)TP. The addition of the second coded base, thymine, was observed by adding cognate dTTP to the crystal following a single d*CTP addition. Adding these two bases caused visible damage to the crystal that was possibly caused by protein and/or DNA conformational change within the crystal. When d*CTP is soaked into the Dpo4 crystal in the absence of Mn(2+) or Mg(2+), the primer extension reaction did not occur; instead, a ternary protein·template·d*CTP complex was formed. In the Raman difference spectra of both binary and ternary complexes, in addition to the modes of d(*C)CTP, features caused by ring modes from the template/primer bases being perturbed and from the DNA backbone appear, as well as features from perturbed peptide and amino acid side chain modes. These effects are more pronounced in the ternary complex than in the binary complex. Using standardized Raman intensities followed as a function of time, the C(*C)TP population in the crystal was maximal at ∼20 min. These remained unchanged in the ternary complex but declined in the binary complexes as chain incorporation occurred.

Parallel computing and first-principles calculations: Applications to complex ceramics and Vitamin B12

NASA Astrophysics Data System (ADS)

Ouyang, Lizhi

A systematic improvement and extension of the orthogonalized linear combinations of atomic orbitals method was carried out using a combined computational and theoretical approach. For high performance parallel computing, a Beowulf class personal computer cluster was constructed. It also served as a parallel program development platform that helped us to port the programs of the method to the national supercomputer facilities. The program, received a language upgrade from Fortran 77 to Fortran 90, and a dynamic memory allocation feature. A preliminary parallel High Performance Fortran version of the program has been developed as well. To be of more benefit though, scalability improvements are needed. In order to circumvent the difficulties of the analytical force calculation in the method, we developed a geometry optimization scheme using the finite difference approximation based on the total energy calculation. The implementation of this scheme was facilitated by the powerful general utility lattice program, which offers many desired features such as multiple optimization schemes and usage of space group symmetry. So far, many ceramic oxides have been tested with the geometry optimization program. Their optimized geometries were in excellent agreement with the experimental data. For nine ceramic oxide crystals, the optimized cell parameters differ from the experimental ones within 0.5%. Moreover, the geometry optimization was recently used to predict a new phase of TiNx. The method has also been used to investigate a complex Vitamin B12-derivative, the OHCbl crystals. In order to overcome the prohibitive disk I/O demand, an on-demand version of the method was developed. Based on the electronic structure calculation of the OHCbl crystal, a partial density of states analysis and a bond order analysis were carried out. The calculated bonding of the corrin ring of OHCbl model was coincident with the big open-ring pi bond. One interesting find of the calculation was that the Co-OH bond was weak. This, together with the ongoing projects studying different Vitamin B12 derivatives, might help us to answer questions about the Co-C cleavage of the B12 coenzyme, which is involved in many important B12 enzymatic reactions.

Superoxide reductase from the syphilis spirochete Treponema pallidum: crystallization and structure determination using soft X-rays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santos-Silva, Teresa; Trincão, José; Carvalho, Ana L.

2005-11-01

Superoxide reductase is a non-haem iron-containing protein involved in resistance to oxidative stress. The oxidized form of the protein has been crystallized and its three-dimensional structure solved. A highly redundant X-ray diffraction data set was collected on a rotating-anode generator using Cu Kα X-ray radiation. Four Fe atoms were located in the asymmetric unit corresponding to four protein molecules arranged as a dimer of homodimers. Superoxide reductase is a 14 kDa metalloprotein containing a catalytic non-haem iron centre [Fe(His){sub 4}Cys]. It is involved in defence mechanisms against oxygen toxicity, scavenging superoxide radicals from the cell. The oxidized form of Treponemamore » pallidum superoxide reductase was crystallized in the presence of polyethylene glycol and magnesium chloride. Two crystal forms were obtained depending on the oxidizing agents used after purification: crystals grown in the presence of K{sub 3}Fe(CN){sub 6} belonged to space group P2{sub 1} (unit-cell parameters a = 60.3, b = 59.9, c = 64.8 Å, β = 106.9°) and diffracted beyond 1.60 Å resolution, while crystals grown in the presence of Na{sub 2}IrCl{sub 6} belonged to space group C2 (a = 119.4, b = 60.1, c = 65.6 Å, β = 104.9°) and diffracted beyond 1.55 Å. A highly redundant X-ray diffraction data set from the C2 crystal form collected on a copper rotating-anode generator (λ = 1.542 Å) clearly defined the positions of the four Fe atoms present in the asymmetric unit by SAD methods. A MAD experiment at the iron absorption edge confirmed the positions of the previously determined iron sites and provided better phases for model building and refinement. Molecular replacement using the P2{sub 1} data set was successful using a preliminary trace as a search model. A similar arrangement of the four protein molecules could be observed.« less

Method of forming a joint

DOEpatents

Butt, Darryl Paul; Cutler, Raymond Ashton; Rynders, Steven Walton; Carolan, Michael Francis

2006-08-22

A method of joining at least two sintered bodies to form a composite structure, including providing a first multicomponent metallic oxide having a perovskitic or fluorite crystal structure; providing a second sintered body including a second multicomponent metallic oxide having a crystal structure of the same type as the first; and providing at an interface a joint material containing at least one metal oxide containing at least one metal identically contained in at least one of the first and second multicomponent metallic oxides. The joint material is free of cations of Si, Ge, Sn, Pb, P and Te and has a melting point below the sintering temperatures of both sintered bodies. The joint material is heated to a temperature above the melting point of the metal oxide(s) and below the sintering temperatures of the sintered bodies to form the joint. Structures containing such joints are also disclosed.

Study of the Anisotropic Elastoplastic Properties of β-Ga2O3 Films Synthesized on SiC/Si Substrates

NASA Astrophysics Data System (ADS)

Grashchenko, A. S.; Kukushkin, S. A.; Nikolaev, V. I.; Osipov, A. V.; Osipova, E. V.; Soshnikov, I. P.

2018-05-01

The structural and mechanical properties of gallium oxide films grown on silicon crystallographic planes (001), (011), and (111) with a buffer layer of silicon carbide are investigated. Nanoindentation was used to study the elastoplastic properties of gallium oxide and also to determine the elastic recovery parameter of the films under study. The tensile strength, hardness, elasticity tensor, compliance tensor, Young's modulus, Poisson's ratio, and other characteristics of gallium oxide were calculated using quantum chemistry methods. It was found that the gallium oxide crystal is auxetic because, for some stretching directions, the Poisson's ratio takes on negative values. The calculated values correspond quantitatively to the experimental data. It is concluded that the elastoplastic properties of gallium oxide films approximately correspond to the properties of bulk crystals and that a change in the orientation of the silicon surface leads to a significant change in the orientation of gallium oxide.

An Atomic-Scale X-ray View of Functional Oxide Films

NASA Astrophysics Data System (ADS)

Tung, I.-Cheng

Complex oxides are a class of materials that exhibit a wide variety of physical functionalities, such as ferroelectricity, colossal magnetoresistance, mulitferroicity and superconductivity, with outstanding potential for meeting many of our technological demands. The primary objective of this dissertation is to understand the structural and electronic behavior of complex oxide ultrathin films subjected to confinement, lattice misfit and broken symmetry at the interface. In complex oxide ultrathin films, heteroepitaxial synthesis has evolved into a reliable strategy to engineer orbital-lattice interactions in correlated materials and led to new and entirely unexpected phenomena at their interfaces. I experimentally demonstrated that the bulk crystal symmetry directs the atomic and orbital responses adopted by coherently strained ultrathin films of RNiO3 (R = La, Nd) with detailed X-ray scattering, polarization-dependent X-ray absorption spectroscopy (XAS) and supported by a mathematical point group symmetry analysis, found that strain-stabilized phases maintain a ``memory'' of their bulk state. This topic, however, touched only upon the properties of such films. A fundamental challenge in this research area occurs before this and centers around the understanding of how to create high-quality films with arbitrary configurations. A longstanding challenge in the oxide thin film community has been the growth of An+1BnO3 n+1 Ruddlesden-Popper (RP) compounds. To understand this problem, we have utilized a newly constructed oxide MBE with in situ synchrotron X-ray scattering capability to study the initial growth of such layered oxides and track the dynamic evolution. X-ray results are supported by theoretical calculations that demonstrated the layered oxide films dynamically rearrange during growth, leading to structures that are highly unexpected, and suggest a general approach that may be essential for the construction of metastable RP phases with performing the first atomically controlled synthesis of single-crystalline La3Ni2O7. By building upon this knowledge, I have completed the first to date study of in situ surface X-ray scattering during homoepitaxial MBE growth of SrTiO3, which demonstrates codeposition is consistent with a 2D island growth mode with SrTiO3 islands, but shuttered deposition proceeds by the growth of SrO islands which then restructure into atomically flat SrTiO3 layer during the deposition of the TiO2. From this point, we have conducted a detailed microscopic study of epitaxial LaNiO3 ultrathin films grown on SrTiO3 (001) by using reactive MBE with in situ surface X-ray diffraction and ex situ soft XAS to explore the influence of polar mismatch on the resulting structural and electronic properties. Overall, this thesis highlights the power of artificial confinement to harness control over competing phases in complex oxides with atomic-scale precision.

Electrochemical liquid-liquid-solid (ec-LLS) crystal growth: a low-temperature strategy for covalent semiconductor crystal growth.

PubMed

Fahrenkrug, Eli; Maldonado, Stephen

2015-07-21

This Account describes a new electrochemical synthetic strategy for direct growth of crystalline covalent group IV and III-V semiconductor materials at or near ambient temperature conditions. This strategy, which we call "electrochemical liquid-liquid-solid" (ec-LLS) crystal growth, marries the semiconductor solvation properties of liquid metal melts with the utility and simplicity of conventional electrodeposition. A low-temperature liquid metal (i.e., Hg, Ga, or alloy thereof) acts simultaneously as the source of electrons for the heterogeneous reduction of oxidized semiconductor precursors dissolved in an electrolyte as well as the solvent for dissolution of the zero-valent semiconductor. Supersaturation of the semiconductor in the liquid metal triggers eventual crystal nucleation and growth. In this way, the liquid electrolyte-liquid metal-solid crystal phase boundary strongly influences crystal growth. As a synthetic strategy, ec-LLS has several intrinsic features that are attractive for preparing covalent semiconductor crystals. First, ec-LLS does not require high temperatures, toxic precursors, or high-energy-density semiconductor reagents. This largely simplifies equipment complexity and expense. In practice, ec-LLS can be performed with only a beaker filled with electrolyte and an electrical circuit capable of supplying a defined current (e.g., a battery in series with a resistor). By this same token, ec-LLS is compatible with thermally and chemically sensitive substrates (e.g., plastics) that cannot be used as deposition substrates in conventional syntheses of covalent semiconductors. Second, ec-LLS affords control over a host of crystal shapes and sizes through simple changes in common experimental parameters. As described in detail herein, large and small semiconductor crystals can be grown both homogeneously within a liquid metal electrode and heterogeneously at the interface of a liquid metal electrode and a seed substrate, depending on the particular details chosen for ec-LLS. Third, the rate of introduction of zero-valent materials into the liquid metal is precisely gated with a high degree of resolution by the applied potential/current. The intent of this Account is to summarize the key elements of ec-LLS identified to date, first contextualizing this method with respect to other semiconductor crystal growth methods and then highlighting some unique capabilities of ec-LLS. Specifically, we detail ec-LLS as a platform to prepare Ge and Si crystals from bulk- (∼1 cm(3)), micro- (∼10(-10) cm(3)), and nano-sized (∼10(-16) cm(3)) liquid metal electrodes in common solvents at low temperature. In addition, we describe our successes in the preparation of more compositionally complex binary covalent III-V semiconductors.