The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

PubMed

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-12-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Ultra-diffuse hydrothermal venting supports Fe-oxidizing bacteria and massive umber deposition at 5000 m off Hawaii

PubMed Central

Edwards, Katrina J; Glazer, B T; Rouxel, O J; Bach, W; Emerson, D; Davis, R E; Toner, B M; Chan, C S; Tebo, B M; Staudigel, H; Moyer, C L

2011-01-01

A novel hydrothermal field has been discovered at the base of Lōihi Seamount, Hawaii, at 5000 mbsl. Geochemical analyses demonstrate that ‘FeMO Deep', while only 0.2 °C above ambient seawater temperature, derives from a distal, ultra-diffuse hydrothermal source. FeMO Deep is expressed as regional seafloor seepage of gelatinous iron- and silica-rich deposits, pooling between and over basalt pillows, in places over a meter thick. The system is capped by mm to cm thick hydrothermally derived iron-oxyhydroxide- and manganese-oxide-layered crusts. We use molecular analyses (16S rDNA-based) of extant communities combined with fluorescent in situ hybridizations to demonstrate that FeMO Deep deposits contain living iron-oxidizing Zetaproteobacteria related to the recently isolated strain Mariprofundus ferroxydans. Bioenergetic calculations, based on in-situ electrochemical measurements and cell counts, indicate that reactions between iron and oxygen are important in supporting chemosynthesis in the mats, which we infer forms a trophic base of the mat ecosystem. We suggest that the biogenic FeMO Deep hydrothermal deposit represents a modern analog for one class of geological iron deposits known as ‘umbers' (for example, Troodos ophilolites, Cyprus) because of striking similarities in size, setting and internal structures. PMID:21544100

Aspects of remote maintenance in an FRG reprocessing plant from the manufacturer's viewpoint

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

Zeitzchel, G.; Tennie, M.; Saal, G.

In April 1986 a consortium led by Kraftwerk Union AG was commissioned by the German society for nuclear fuel reprocessing (DWK) to build the first West German commercial reprocessing plant for spent fuel assemblies. The main result of the planning efforts regarding remote maintenance operations inside the main process building was the introduction of FEMO technology (FEMO is an acronym based on German for remote handling modular technique). According to this technology the two cells in which the actual reprocessing (which is based on the PUREX technique) takes place are provided with frames to accommodate the process components (tanks, pumps,more » agitators, etc.), each frame together with the components which it supports forming one module. The two cells are inaccessible and windowless. For handling operations each cell is equipped with an overhead crane and a crane-like manipulator carrier system (MTS) with power manipulator. Viewing of the operations from outside the cells is made possible by television (TV) cameras installed at the crane, the MTS, and the manipulator. This paper addresses some examples of problems that still need to be solved in connection with FEMO handling. In particular, the need for close cooperation between the equipment operator, the component designer, the process engineer, the planning engineer, and the licensing authorities will be demonstrated.« less

VTVH-MCD study of the Delta nifB Delta nifZ MoFe protein from Azotobacter vinelandii.

PubMed

Cotton, Marcia S; Rupnik, Kresimir; Broach, Robyn B; Hu, Yilin; Fay, Aaron W; Ribbe, Markus W; Hales, Brian J

2009-04-08

NifZ is a member of a series of proteins associated with the maturation of the nitrogenase MoFe protein. An MCD spectroscopic study was undertaken on the Delta nifB Delta nifZ MoFe protein generated in the absence of both NifZ and NifB (deletion of NifB generates an apo-MoFe protein lacking the FeMo cofactor). Results presented here show that, in the absence of NifZ, only one of the two P-clusters of the MoFe protein is matured to the ultimate [8Fe-7S] structure. The other P-cluster site in the protein contains a [4Fe-4S] cluster pair, representing a P-cluster precursor that is electronically identical to the analogous clusters observed in the Delta nifH MoFe protein. These results suggest that the MoFe protein is synthesized in a stepwise fashion where NifZ is specifically required for the formation of the second P-cluster.

Autonomous Filling of Grain-Boundary Cavities during Creep Loading in Fe-Mo Alloys

NASA Astrophysics Data System (ADS)

Zhang, S.; Fang, H.; Gramsma, M. E.; Kwakernaak, C.; Sloof, W. G.; Tichelaar, F. D.; Kuzmina, M.; Herbig, M.; Raabe, D.; Brück, E.; van der Zwaag, S.; van Dijk, N. H.

2016-10-01

We have investigated the autonomous repair of creep damage by site-selective precipitation in a binary Fe-Mo alloy (6.2 wt pct Mo) during constant-stress creep tests at temperatures of 813 K, 823 K, and 838 K (540 °C, 550 °C, and 565 °C). Scanning electron microscopy studies on the morphology of the creep-failed samples reveal irregularly formed deposits that show a close spatial correlation with the creep cavities, indicating the filling of creep cavities at grain boundaries by precipitation of the Fe2Mo Laves phase. Complementary transmission electron microscopy and atom probe tomography have been used to characterize the precipitation mechanism and the segregation at grain boundaries in detail.

Light-driven carbon dioxide reduction to methane by nitrogenase in a photosynthetic bacterium

DOE PAGES

Fixen, Kathryn R.; Zheng, Yanning; Harris, Derek F.; ...

2016-08-22

Nitrogenase is an ATP-requiring enzyme capable of carrying out multielectron reductions of inert molecules. A purified remodeled nitrogenase containing two amino acid substitutions near the site of its FeMo cofactor was recently described as having the capacity to reduce carbon dioxide (CO 2) to methane (CH 4). Here, we developed the anoxygenic phototroph, Rhodopseudomonas palustris, as a biocatalyst capable of light-driven CO 2 reduction to CH 4 in vivo using this remodeled nitrogenase. Conversion of CO 2 to CH 4 by R. palustris required constitutive expression of nitrogenase, which was achieved by using a variant of the transcription factor NifAmore » that is able to activate expression of nitrogenase under all growth conditions. Also, light was required for generation of ATP by cyclic photophosphorylation. CH 4 production by R. palustris could be controlled by manipulating the distribution of electrons and energy available to nitrogenase. Furthermore, this work shows the feasibility of using microbes to generate hydrocarbons from CO 2 in one enzymatic step using light energy.« less

Photoinduced crystallization of calcium carbonate from a homogeneous precursor solution in the presence of partially hydrolyzed poly(vinyl alcohol)

NASA Astrophysics Data System (ADS)

Nishio, Takashi; Naka, Kensuke

2015-04-01

Photoinduced crystallization of calcium carbonate (CaCO3) was demonstrated by the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphenyl)propionic acid) under alkaline conditions (pH 10). In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol %) was used as the precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. Thermogravimetric analysis of the obtained xerogels showed that increasing the UV irradiation time increased the amount of CaCO3 formed and the complete conversion of calcium ions to calcite was achieved after 50 min of UV irradiation. Furthermore, solid phase analyses suggested that nanometer-to-micron-sized calcite crystals were formed and dispersed in the obtained PVAPS matrix.

A Concise Synthesis of Presilphiperfolane Core through a Tandem TMTU-Co-Catalyzed Pauson-Khand Reaction and a 6π Electrocyclization Reaction (TMTU=Tetramethyl Thiourea).

PubMed

Zhang, Zichun; Li, Yuanhe; Zhao, Dandan; He, Yingdong; Gong, Jianxian; Yang, Zhen

2017-01-26

The synthesis of strained polycyclic systems from readily available precursors with a minimum number of steps and with regio- and stereochemical control constitutes an important synthetic challenge. Herein, we report a tandem reaction comprising Co-TMTU (tetramethyl thiourea)-catalyzed Pauson-Khand (PK) and 6π-electrocyclization reactions for the formation of the highly strained core of presilphiperfolanols. The developed chemistry has been applied to the total syntheses of 4-epi-presilphiperfolan-8-ol and 7-epi-presilphiperfolan-1-ol. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic layer deposition of metal sulfide thin films using non-halogenated precursors

DOEpatents

Martinson, Alex B. F.; Elam, Jeffrey W.; Pellin, Michael J.

2015-05-26

A method for preparing a metal sulfide thin film using ALD and structures incorporating the metal sulfide thin film. The method includes providing an ALD reactor, a substrate, a first precursor comprising a metal and a second precursor comprising a sulfur compound. The first and the second precursors are reacted in the ALD precursor to form a metal sulfide thin film on the substrate. In a particular embodiment, the metal compound comprises Bis(N,N'-di-sec-butylacetamidinato)dicopper(I) and the sulfur compound comprises hydrogen sulfide (H.sub.2S) to prepare a Cu.sub.2S film. The resulting metal sulfide thin film may be used in among other devices, photovoltaic devices, including interdigitated photovoltaic devices that may use relatively abundant materials for electrical energy production.

Carbon composition with hierarchical porosity, and methods of preparation

DOEpatents

Mayes, Richard T; Dai, Sheng

2014-10-21

A method for fabricating a porous carbon material possessing a hierarchical porosity, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic component, (iii) a dione component in which carbonyl groups are adjacent, and (iv) an acidic component, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a carbon material possessing a hierarchical porosity comprised of mesopores and macropores. Also described are the resulting hierarchical porous carbon material, a capacitive deionization device in which the porous carbon material is incorporated, as well as methods for desalinating water by use of said capacitive deionization device.

Mesoporous carbon materials

DOEpatents

Dai, Sheng [Knoxville, TN; Wang, Xiqing [Oak Ridge, TN

2012-02-14

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Mesoporous carbon materials

DOEpatents

Dai, Sheng; Wang, Xiqing

2013-08-20

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Co3O4 nanowires as efficient catalyst precursor for hydrogen generation from sodium borohydride hydrolysis

NASA Astrophysics Data System (ADS)

Wei, Lei; Cao, Xurong; Ma, Maixia; Lu, Yanhong; Wang, Dongsheng; Zhang, Suling; Wang, Qian

Hydrogen generation from the catalytic hydrolysis of sodium borohydride has many advantages, and therefore, significant research has been undertaken on the development of highly efficient catalysts for this purpose. In our present work, Co3O4 nanowires were successfully synthesized as catalyst precursor by employing SBA-15 as a hard template. For material characterization, high-resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and N2 adsorption isotherms were employed, respectively. To measure the catalyst activity, typical water-displacement method was carried out. Using a reaction solution comprising 10wt.% NaBH4 and 2wt.% NaOH, the hydrogen generation rate (HGR) was observed to be as high as 7.74L min-1 g-1 at 25∘C in the presence of Co3O4 nanowires, which is significantly higher than that of CoB nanoparticles and commercial Co3O4 powder. Apparent activation energy was calculated to be 50.9kJ mol-1. After recycling the Co3O4 nanowires six times, HGR was decreased to be 72.6% of the initial level.

Generation of amyloid-β is reduced by the interaction of calreticulin with amyloid precursor protein, presenilin and nicastrin.

PubMed

Stemmer, Nina; Strekalova, Elena; Djogo, Nevena; Plöger, Frank; Loers, Gabriele; Lutz, David; Buck, Friedrich; Michalak, Marek; Schachner, Melitta; Kleene, Ralf

2013-01-01

Dysregulation of the proteolytic processing of amyloid precursor protein by γ-secretase and the ensuing generation of amyloid-β is associated with the pathogenesis of Alzheimer's disease. Thus, the identification of amyloid precursor protein binding proteins involved in regulating processing of amyloid precursor protein by the γ-secretase complex is essential for understanding the mechanisms underlying the molecular pathology of the disease. We identified calreticulin as novel amyloid precursor protein interaction partner that binds to the γ-secretase cleavage site within amyloid precursor protein and showed that this Ca(2+)- and N-glycan-independent interaction is mediated by amino acids 330-344 in the C-terminal C-domain of calreticulin. Co-immunoprecipitation confirmed that calreticulin is not only associated with amyloid precursor protein but also with the γ-secretase complex members presenilin and nicastrin. Calreticulin was detected at the cell surface by surface biotinylation of cells overexpressing amyloid precursor protein and was co-localized by immunostaining with amyloid precursor protein and presenilin at the cell surface of hippocampal neurons. The P-domain of calreticulin located between the N-terminal N-domain and the C-domain interacts with presenilin, the catalytic subunit of the γ-secretase complex. The P- and C-domains also interact with nicastrin, another functionally important subunit of this complex. Transfection of amyloid precursor protein overexpressing cells with full-length calreticulin leads to a decrease in amyloid-β42 levels in culture supernatants, while transfection with the P-domain increases amyloid-β40 levels. Similarly, application of the recombinant P- or C-domains and of a synthetic calreticulin peptide comprising amino acid 330-344 to amyloid precursor protein overexpressing cells result in elevated amyloid-β40 and amyloid-β42 levels, respectively. These findings indicate that the interaction of calreticulin with amyloid precursor protein and the γ-secretase complex regulates the proteolytic processing of amyloid precursor protein by the γ-secretase complex, pointing to calreticulin as a potential target for therapy in Alzheimer's disease.

Method of making metal oxide ceramic powders by using a combustible amino acid compound

DOEpatents

Pederson, L.R.; Chick, L.A.; Exarhos, G.J.

1992-05-19

This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

Method of making metal oxide ceramic powders by using a combustible amino acid compound

DOEpatents

Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

1992-01-01

This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

Precursor polymer compositions comprising polybenzimidazole

DOEpatents

Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

2015-07-14

Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

Galvanic displacement assembly of ultrathin Co3O4 nanosheet arrays on nickel foam for a high-performance supercapacitor

NASA Astrophysics Data System (ADS)

You, Yuxiu; Zheng, Maojun; Ma, Liguo; Yuan, Xiaoliang; Zhang, Bin; Li, Qiang; Wang, Faze; Song, Jingnan; Jiang, Dongkai; Liu, Pengjie; Ma, Li; Shen, Wenzhong

2017-03-01

High-performance supercapacitors are very desirable for many portable electronic devices, electric vehicles and high-power electronic devices. Herein, a facile and binder-free synthesis method, galvanic displacement of the precursor followed by heat treatment, is used to fabricate ultrathin Co3O4 nanosheet arrays on nickel foam substrate. When used as a supercapacitor electrode the prepared Co3O4 on nickel foam exhibits a maximum specific capacitance of 1095 F g-1 at a current density of 1 A g-1 and good cycling stability of 71% retention after 2000 cycling tests. This excellent electrochemical performance can be ascribed to the high specific surface area of each Co3O4 nanosheet that comprises numerous nanoparticles.

Enhancement of Naringenin Biosynthesis from Tyrosine by Metabolic Engineering of Saccharomyces cerevisiae.

PubMed

Lyu, Xiaomei; Ng, Kuan Rei; Lee, Jie Lin; Mark, Rita; Chen, Wei Ning

2017-08-09

Flavonoids are an important class of plant polyphenols that possess a variety of health benefits. In this work, S. cerevisiae was metabolically engineered to produce the flavonoid naringenin, using tyrosine as the precursor. Our strategy to improve naringenin production comprised three modules. In module 1, we employed a modified GAL system to overexpress the genes of the naringenin biosynthesis pathway and investigated their synergistic action. In module 2, we simultaneously up-regulated acetyl-CoA production and down-regulated fatty acid biosynthesis in order to increase the precursor supply, malonyl-CoA. In module 3, we engineered the tyrosine biosynthetic pathway to eliminate the feedback inhibition of tyrosine and also down-regulated competing pathways. It was found that modules 1 and 3 played important roles in improving naringenin production. We succeeded in producing up to ∼90 mg/L of naringenin in our final strain, which is a 20-fold increase as compared to the parental strain.

Mesoporous metal oxides and processes for preparation thereof

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

Suib, Steven L.; Poyraz, Altug Suleyman

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

Chemical modification of nanocrystal surfaces

DOEpatents

Alivisatos, A. Paul; Owen, Jonathan

2013-05-07

A method is disclosed. The method includes obtaining a precursor nanoparticle comprising a base material and a first ligand attached to the base material, and reacting the precursor nanoparticle with a reactant comprising a silicon bond, thereby removing the first ligand.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold; Solovyov, Vyacheslav

2014-02-18

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2008-04-22

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

Fluorinated precursors of superconducting ceramics, and methods of making the same

DOEpatents

Wiesmann, Harold [Stony Brook, NY; Solovyov, Vyacheslav [Rocky Point, NY

2012-07-10

This invention provides a method of making a fluorinated precursor of a superconducting ceramic. The method comprises providing a solution comprising a rare earth salt, an alkaline earth metal salt and a copper salt; spraying the solution onto a substrate to provide a film-covered substrate; and heating the film-covered substrate in an atmosphere containing fluorinated gas to provide the fluorinated precursor.

RuBisCO in Non-Photosynthetic Alga Euglena longa: Divergent Features, Transcriptomic Analysis and Regulation of Complex Formation.

PubMed

Záhonová, Kristína; Füssy, Zoltán; Oborník, Miroslav; Eliáš, Marek; Yurchenko, Vyacheslav

2016-01-01

Euglena longa, a close relative of the photosynthetic model alga Euglena gracilis, possesses an enigmatic non-photosynthetic plastid. Its genome has retained a gene for the large subunit of the enzyme RuBisCO (rbcL). Here we provide new data illuminating the putative role of RuBisCO in E. longa. We demonstrated that the E. longa RBCL protein sequence is extremely divergent compared to its homologs from the photosynthetic relatives, suggesting a possible functional shift upon the loss of photosynthesis. Similarly to E. gracilis, E. longa harbors a nuclear gene encoding the small subunit of RuBisCO (RBCS) as a precursor polyprotein comprising multiple RBCS repeats, but one of them is highly divergent. Both RBCL and the RBCS proteins are synthesized in E. longa, but their abundance is very low compared to E. gracilis. No RBCS monomers could be detected in E. longa, suggesting that processing of the precursor polyprotein is inefficient in this species. The abundance of RBCS is regulated post-transcriptionally. Indeed, blocking the cytoplasmic translation by cycloheximide has no immediate effect on the RBCS stability in photosynthetically grown E. gracilis, but in E. longa, the protein is rapidly degraded. Altogether, our results revealed signatures of evolutionary degradation (becoming defunct) of RuBisCO in E. longa and suggest that its biological role in this species may be rather unorthodox, if any.

Methods for producing thin film charge selective transport layers

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

Hammond, Scott Ryan; Olson, Dana C.; van Hest, Marinus Franciscus Antonius Maria

Methods for producing thin film charge selective transport layers are provided. In one embodiment, a method for forming a thin film charge selective transport layer comprises: providing a precursor solution comprising a metal containing reactive precursor material dissolved into a complexing solvent; depositing the precursor solution onto a surface of a substrate to form a film; and forming a charge selective transport layer on the substrate by annealing the film.

Continuous structural evolution of calcium carbonate particles: a unifying model of copolymer-mediated crystallization.

PubMed

Kulak, Alex N; Iddon, Peter; Li, Yuting; Armes, Steven P; Cölfen, Helmut; Paris, Oskar; Wilson, Rory M; Meldrum, Fiona C

2007-03-28

Two double-hydrophilic block copolymers, each comprising a nonionic block and an anionic block comprising pendent aromatic sulfonate groups, were used as additives to modify the crystallization of CaCO3. Marked morphological changes in the CaCO3 particles were observed depending on the reaction conditions used. A poly(ethylene oxide)-b-poly(sodium 4-styrenesulfonate) diblock copolymer was particularly versatile in effecting a morphological change in calcite particles, and a continuous structural transition in the product particles from polycrystalline to mesocrystal to single crystal was observed with variation in the calcium concentration. The existence of this structural sequence provides unique insight into the mechanism of polymer-mediated crystallization. We propose that it reflects continuity in the crystallization mechanism itself, spanning the limits from nonoriented aggregation of nanoparticles to classical ion-by-ion growth. The various pathways to polycrystalline, mesocrystal, and single-crystal particles, which had previously been considered to be distinct, therefore all form part of a unifying crystallization framework based on the aggregation of precursor subunits.

New triethoxysilylated 10-vertex closo-decaborate clusters. Synthesis and controlled immobilization into mesoporous silica.

PubMed

Abi-Ghaida, Fatima; Laila, Zahra; Ibrahim, Ghassan; Naoufal, Daoud; Mehdi, Ahmad

2014-09-14

Novel silylated hydroborate clusters comprising the closo-decaborate cage were prepared and characterized by (1)H, (13)C, (11)B, (29)Si NMR and mass spectroscopy ESI. The synthesis of such silylated clusters was achieved using reactive derivatives of [B10H10](2-), [1-B10H9N2](-) and [2-B10H9CO](-). These silylated decaborate clusters constitute a new class of precursors that can be covalently anchored onto various silica supports without any prior surface modification. As a proof of concept, the synthesized precursors were successfully anchored on mesoporous silica, SBA-15 type, in different percentages, where the mesoporous material retained its structure. All materials modified with closo-decaborate were characterized by (11)B and (29)Si solid state NMR, XRD, TEM and nitrogen sorption.

The general mitochondrial processing peptidase from potato is an integral part of cytochrome c reductase of the respiratory chain.

PubMed Central

Braun, H P; Emmermann, M; Kruft, V; Schmitz, U K

1992-01-01

The major mitochondrial processing activity removing presequences from nuclear encoded precursor proteins is present in the soluble fraction of fungal and mammalian mitochondria. We found that in potato, this activity resides in the inner mitochondrial membrane. Surprisingly, the proteolytic activity co-purifies with cytochrome c reductase, a protein complex of the respiratory chain. The purified complex is bifunctional, as it has the ability to transfer electrons from ubiquinol to cytochrome c and to cleave off the presequences of mitochondrial precursor proteins. In contrast to the nine subunit fungal complex, cytochrome c reductase from potato comprises 10 polypeptides. Protein sequencing of peptides from individual subunits and analysis of corresponding cDNA clones reveals that subunit III of cytochrome c reductase (51 kDa) represents the general mitochondrial processing peptidase. Images PMID:1324169

Sol-gel derived C-SiC composites and protective coatings for sustained durability in the space environment

NASA Astrophysics Data System (ADS)

Haruvy, Yair; Liedtke, Volker

2003-09-01

Composites and coatings were produced via the fast sol-gel process of a mixture of alkoxysilane precursors. The composites were comprised of carbon fibers, fabrics, or their precursors as reinforcement, and sol-gel-derived silicon carbide as matrix, aiming at high-temperature stable ceramics that can be utilized for re-entry structures. The protective coatings were comprised of fluorine-rich sol-gel derived resins, which exhibit high flexibility and coherence to provide sustained ATOX protection necessary for LEO space-exposed elements. For producing the composites, the sol-gel-derived resin is cast onto the reinforcement fibers/fabrics mat (carbon or its precursors) to produce a 'green' composite that is being cured. The 'green' composite is converted into a C-SiC composite via a gradual heat-pressure process under inert atmosphere, during which the organic substituents on the silicon atoms undergo internal oxidative pyrolysis via the schematic reaction: (SiRO3/2)n -> SiC + CO2 + H2O. The composition of the resultant silicon-oxi-carbide is tailorable via modifying the composition of the sol-gel reactants. The reinforcement, when made of carbon precursors, is converted into carbon during the heat-and-pressure processing as well. The C-SiC composites thus derived exhibit superior thermal stability and comparable thermal conductivity, combined with good mechanical strength features and failure resistance, which render them greatly applicable for re-entry shielding, heat-exchange pipes, and the like. Fluorine rich sol-gel derived coatings were developed as well, via the use of HF rich sol-gel process. These coatings provide oxidation-protection via the silica formation process, together with flexibility that allows 18,000 repetitive folding of the coating without cracking.

Method of fabricating a catalytic structure

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2009-09-22

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Attrition resistant fluidizable reforming catalyst

DOEpatents

Parent, Yves O [Golden, CO; Magrini, Kim [Golden, CO; Landin, Steven M [Conifer, CO; Ritland, Marcus A [Palm Beach Shores, FL

2011-03-29

A method of preparing a steam reforming catalyst characterized by improved resistance to attrition loss when used for cracking, reforming, water gas shift and gasification reactions on feedstock in a fluidized bed reactor, comprising: fabricating the ceramic support particle, coating a ceramic support by adding an aqueous solution of a precursor salt of a metal selected from the group consisting of Ni, Pt, Pd, Ru, Rh, Cr, Co, Mn, Mg, K, La and Fe and mixtures thereof to the ceramic support and calcining the coated ceramic in air to convert the metal salts to metal oxides.

Synthesis, characterization, microstructure, optical and magnetic properties of strontium cobalt carbonate precursor and Sr2Co2O5 oxide material

NASA Astrophysics Data System (ADS)

Agilandeswari, K.; Ruban Kumar, A.

2014-04-01

Sr2Co2O5 ceramic synthesized by the coprecipitation of strontium cobalt carbonate method. XRD analysis shows the single phase strontianite precursor and decomposed oxide product as orthorhombic structure of Sr2Co2O5. Thermal analysis proves the Sr2Co2O5 phase formation temperature of 800 °C. SEM image indicates crystalline rod shaped carbonate precursor transformed to oxide as porous diffused sphere shape particles. Optical band gap it reveals the strontium cobalt carbonate precursor as insulating material and the Sr2Co2O5 as semiconducting nature. The room temperature magnetic study indicates the carbonate precursor as paramagnetic but its oxide Sr2Co2O5 as superparamagnetic behavior.

Highly efficient up-conversion and bright white light in RE co-doped KYF4 nanocrystals in sol-gel silica matrix

NASA Astrophysics Data System (ADS)

Méndez-Ramos, J.; Yanes, A. C.; Santana-Alonso, A.; del-Castillo, J.

2013-01-01

Transparent nano-glass-ceramics comprising Yb3+, Er3+ and Tm3+ co-doped KYF4 nanocrystals have been developed from sol-gel method. A structural analysis by means of X-ray diffraction confirmed the precipitation of cubic KYF4 nanocrystals into a silica matrix. Visible luminescence has been analyzed as function of treatment temperature of precursor sol-gel glasses. Highly efficient up-conversion emissions have been obtained under 980 nm excitation and studied by varying the doping level, processing temperature and pump power. Color tuneability has been quantified in terms of CIE diagram and in particular, a white-balanced overall emission has been achieved for a certain doping level and thermal treatment.

Unzipping of multi-wall carbon nanotubes with different diameter distributions: Effect on few-layer graphene oxide obtention

NASA Astrophysics Data System (ADS)

Torres, D.; Pinilla, J. L.; Suelves, I.

2017-12-01

Few-layer graphene oxide (FLGO) was obtained by chemical unzipping of multi-wall carbon nanotubes (MWCNT) of different diameter distributions. MWCNT were synthesized by catalytic decomposition of methane using Fe-Mo/MgO catalysts. The variation in the Fe/Mo ratio (1, 2 and 5) was very influential in MWCNT diameter distribution and type of MWCNT obtained, including textural, chemical, structural and morphological characteristics. MWCNT diameter distribution and surface defects content had a profound impact on the characteristics of the resulting FLGO. Thus, MWCNT obtained with the catalyst with a Fe/Mo: 5 and presenting a narrow diameter distribution centered at 8.6 ± 3.3 nm led to FLGO maintaining non-oxidized graphite stacking (according to XRD analysis), lower specific surface area and higher thermostability as compared to FLGO obtained from MWCNT showing wider diameter distributions. The presence of more oxygen-containing functionalities and structural defects in large diameter nanotubes promotes the intercalation of species towards the inner layers of the nanotube, resulting in an enhanced MWCNT oxidation and opening into FLGO, what improves both micro- and mesoporosity.

Electro-deposition of superconductor oxide films

DOEpatents

Bhattacharya, Raghu N.

2001-01-01

Methods for preparing high quality superconducting oxide precursors which are well suited for further oxidation and annealing to form superconducting oxide films. The method comprises forming a multilayered superconducting precursor on a substrate by providing an electrodeposition bath comprising an electrolyte medium and a substrate electrode, and providing to the bath a plurality of precursor metal salts which are capable of exhibiting superconducting properties upon subsequent treatment. The superconducting precursor is then formed by electrodepositing a first electrodeposited (ED) layer onto the substrate electrode, followed by depositing a layer of silver onto the first electrodeposited (ED) layer, and then electrodepositing a second electrodeposited (ED) layer onto the Ag layer. The multilayered superconducting precursor is suitable for oxidation at a sufficient annealing temperature in air or an oxygen-containing atmosphere to form a crystalline superconducting oxide film.

Hard metal composition

DOEpatents

Sheinberg, H.

1983-07-26

A composition of matter having a Rockwell A hardness of at least 85 is formed from a precursor mixture comprising between 3 and 10 wt % boron carbide and the remainder a metal mixture comprising from 70 to 90% tungsten or molybdenum, with the remainder of the metal mixture comprising nickel and iron or a mixture thereof. The composition has a relatively low density of between 7 and 14 g/cc. The precursor is preferably hot pressed to yield a composition having greater than 100% of theoretical density.

Hard metal composition

DOEpatents

Sheinberg, Haskell

1986-01-01

A composition of matter having a Rockwell A hardness of at least 85 is formed from a precursor mixture comprising between 3 and 10 weight percent boron carbide and the remainder a metal mixture comprising from 70 to 90 percent tungsten or molybdenum, with the remainder of the metal mixture comprising nickel and iron or a mixture thereof. The composition has a relatively low density of between 7 to 14 g/cc. The precursor is preferably hot pressed to yield a composition having greater than 100% of theoretical density.

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2 O3 for Enhanced CO2 Capture Performance.

PubMed

Armutlulu, Andac; Naeem, Muhammad Awais; Liu, Hsueh-Ju; Kim, Sung Min; Kierzkowska, Agnieszka; Fedorov, Alexey; Müller, Christoph R

2017-11-01

CO 2 capture and storage is a promising concept to reduce anthropogenic CO 2 emissions. The most established technology for capturing CO 2 relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high-temperature CO 2 sorbent can significantly reduce the costs of CO 2 capture. A serious disadvantage of CaO derived from earth-abundant precursors, e.g., limestone, is the rapid, sintering-induced decay of its cyclic CO 2 uptake. Here, a template-assisted hydrothermal approach to develop CaO-based sorbents exhibiting a very high and cyclically stable CO 2 uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al 2 O 3 (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO 2 capture and release, and (iii) a minimal quantity of Al 2 O 3 for structural stabilization, thus maximizing the fraction of CO 2 -capture-active CaO. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Residual Lithium in the precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance

NASA Astrophysics Data System (ADS)

Jo, Minsang; Ku, Heesuk; Park, Sanghyuk; Song, Junho; Kwon, Kyungjung

2018-07-01

Li[Ni1/3Co1/3Mn1/3]O2 cathode active materials are synthesized from co-precipitated hydroxide precursors Lix[Ni1/3Co1/3Mn1/3]1-x(OH)2, and the effect of residual Li in the precursors on the lithium-ion battery (LIB) performance of their corresponding cathode active materials is investigated. Three kinds of precursors that contain different amounts of Li are selected depending on different conditions of the solution composition for the co-precipitation and washing process. It is confirmed that the introduction of Li to the precursors reduces the degree of structural perfection by X-ray diffraction analysis. Undesirable cation mixing occurs with the increasing Li content of the precursors, which is inferred from a decline in lattice parameters and the calculated intensity ratio of (003) and (104) peaks. In the voltage range of 3.0-4.3 V, the initial charge/discharge capacities and the rate capability of the cathode active materials are aggravated when Li exists in the precursors. Therefore, it could be concluded that the strict control of Li in a solution for co-precipitation of precursors is necessary in the resynthesis of cathode active materials from spent LIBs.

The Synthesis and Characterization of Aromatic Hybrid Anderson–Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions

PubMed Central

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-01-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe3+ or Mn3+ as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, 1H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3[FeMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-FeMo6-bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRIS–R=(HOCH2)3C–R)), (TBA)3[FeMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-FeMo6-cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3[MnMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-MnMo6-bzn), and (TBA)3[MnMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-MnMo6-cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mm) sodium salts Na3[FeMo6O18{(OCH2)3CNHCOC6H5}2] (Na-FeMo6-bzn), Na3[FeMo6O18{(OCH2)3CNHCOC8H7}2] (Na-FeMo6-cin), Na3[MnMo6O18{(OCH2)3CNHCOC6H5}2] (Na-MnMo6-bzn), and Na3[MnMo6O18{(OCH2)3CNHCOC8H7}2] (Na-MnMo6-cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate–polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern–Volmer analysis, which suggested the formation of a 1:1 POM–protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. PMID:26527418

Toughened and corrosion- and wear-resistant composite structures and fabrication methods thereof

DOEpatents

Seals, Roland D; Ripley, Edward B; Hallman, Russell L

2014-04-08

Composite structures having a reinforced material interjoined with a substrate and methods of creating a composite material interjoined with a substrate. In some embodiments the composite structure may be a line or a spot or formed by reinforced material interjoined with the substrate. The methods typically include disposing a precursor material comprising titanium diboride and/or titanium monoboride on at least a portion of the substrate and heating the precursor material and the at least a portion of the substrate in the presence of an oxidation preventative until at least a portion of the precursor material forms reinforced material interjoined with the substrate. The precursor material may be disposed on the substrate as a sheet or a tape or a slurry or a paste. Localized surface heating may be used to heat the precursor material. The reinforced material typically comprises a titanium boron compound, such as titanium monoboride, and preferably comprises .beta.-titanium. The substrate is typically titanium-bearing, iron-bearing, or aluminum-bearing. A welding rod is provided as an embodiment. The welding rod includes a metal electrode and a precursor material is disposed adjacent at least a portion of the metal electrode. A material for use in forming a composite structure is provided. The material typically includes a precursor material that includes one or more materials selected from the following group: titanium diboride and titanium monoboride. The material also typically includes a flux.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-04-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, and SnR".sub.3 containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-12-30

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

Evaluating Oil and Gas Speciation Profiles with Factor Analysis of Ambient Volatile Organic Compound Concentrations in the Colorado Front Range

NASA Astrophysics Data System (ADS)

Capps, S.; Paranjothi, G.; Pierce, G. E.; Milford, J. B.

2016-12-01

Increased oil and gas (O&G) development, particularly through the use of hydraulic fracturing, in the Denver-Julesburg Basin (DJB) in Colorado over the last decade has been identified as a source of emissions of air pollutants, which are now included in chemical transport modeling. As one effort to evaluate its impact, ambient concentrations of volatile organic compounds (VOCs) that serve as precursors to ozone formation were measured in an Ozone Precursor Study conducted by the Colorado Department of Public Health and Environment during 2013 and 2014. The study included 6 - 9 a.m. measurements of an extensive suite of ozone-precursor VOCs from a site in an area of intensive O&G development in Platteville, CO, and another site in downtown Denver, CO. To evaluate the influences of urban activity or O&G development on these ambient concentrations, we used the U.S. EPA's Positive Matrix Factorization (PMF) tool. A five-factor PMF solution was selected as providing the best fit to the dataset comprised of VOC measurements for both years and both sites. One PMF factor matches the VOC emissions speciation profile for the flashing gas composition for condensate tanks in the DJB that was developed by the Western Regional Air Partnership for use in chemical transport modeling in the region. The contribution of this factor to individual and total VOC concentrations and ozone production reactivity is evaluated for Platteville and Denver.

Solidus of carbonated fertile peridotite under fluid-saturated conditions

NASA Astrophysics Data System (ADS)

Falloon, Trevor J.; Green, David H.

1990-03-01

The solidus for a fertile peridotite composition ("Hawaiian pyrolite") in the presence of a CO2-H2O fluid phase has been determined from 10 to 35 kbar. The intersection of the decarbonation reaction (olivine + diopside + CO2 ←→ orthopyroxene + dolomite) with the pyrolite solidus defines the point Q‧, located at 22 kbar and 940 °C. At pressures less than Q‧, the solidus passes through a temperature maximum at 14 kbar, 1060 °C. The solidus is coincident with amphibole breakdown at pressures less than 16 kbar. At pressures above Q‧, the solidus is defined by the dissolution of crystalline carbonate into a sodic, dolomitic carbonatite melt. The solidus is at a temperature of 925 °C at ˜28 kbar. The solidus temperature above the point Q‧ is similar to the solidus determined for Hawaiian pyrolite-H2O-CO2 for small contents of H2O (<0.3 wt%) and CO2 (<5 wt%), thus indicating that the primary sodic dolomitic carbonatite melt at both solidi has a very low and limited H2O solubility. The new data clarify the roles of carbonatite melt, carbonated silicate melt, and H2O-rich fluid in mantle conditions that are relatively oxidized (fO2 ˜ MW to FMQ). In particular, a carbonatite melt + garnet lherzolite region is intersected by continental shield geothermal gradients, but such geotherms only intersect regions with carbonated silicate melt if perturbed to higher temperatures ("kinked geotherm").

Aerosol chemical vapor deposition of metal oxide films

DOEpatents

Ott, K.C.; Kodas, T.T.

1994-01-11

A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said substrate.

Preparation of superconductor precursor powders

DOEpatents

Bhattacharya, R.

1998-08-04

A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products. 7 figs.

Preparation of superconductor precursor powders

DOEpatents

Bhattacharya, Raghunath

1998-01-01

A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

Method of fabricating metal- and ceramic- matrix composites and functionalized textiles

DOEpatents

Maxwell, James L [Jemez Springs, NM; Chavez, Craig A [Los Alamos, NM; Black, Marcie R [Lincoln, MA

2012-04-17

A method of manufacturing an article comprises providing a first sheet, wetting the first sheet with a liquid precursor to provide a first wet sheet, and irradiating the first wet sheet in a pattern corresponding to a first cross section of the article such that the liquid precursor is at least partially converted to a solid in the first cross section. A second sheet is disposed adjacent to the first sheet. The method further comprises wetting the second sheet with the liquid precursor to provide a second wet sheet, and irradiating the second wet sheet in a pattern corresponding to a second cross section of the article such that the liquid precursor is at least partially converted to a solid in the second cross section. In particular the liquid precursor may be converted to a metal, ceramic, semiconductor, semimetal, or a combination of these materials.

The Fe-V Cofactor of Vanadium Nitrogenase Contains an Interstitial Carbon Atom.

PubMed

Rees, Julian A; Bjornsson, Ragnar; Schlesier, Julia; Sippel, Daniel; Einsle, Oliver; DeBeer, Serena

2015-11-02

The first direct evidence is provided for the presence of an interstitial carbide in the Fe-V cofactor of Azotobacter vinelandii vanadium nitrogenase. As for our identification of the central carbide in the Fe-Mo cofactor, we employed Fe Kβ valence-to-core X-ray emission spectroscopy and density functional theory calculations, and herein report the highly similar spectra of both variants of the cofactor-containing protein. The identification of an analogous carbide, and thus an atomically homologous active site in vanadium nitrogenase, highlights the importance and influence of both the interstitial carbide and the identity of the heteroatom on the electronic structure and catalytic activity of the enzyme. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Insulating Materials Comprising Polysilazane, Methods of Forming Such Insulating Materials, and Precursor Formulations Comprising Polysilazane

NASA Technical Reports Server (NTRS)

Larson, Robert S. (Inventor); Fuller, Michael E. (Inventor)

2013-01-01

Methods of forming an insulating material comprising combining a polysilazane, a cross-linking compound, and a gas-generating compound to form a reaction mixture, and curing the reaction mixture to form a modified polysilazane. The gas-generating compound may be water, an alcohol, an amine, or combinations thereof. The cross-linking compound may be an isocyanate, an epoxy resin, or combinations thereof. The insulating material may include a matrix comprising one of a reaction product of a polysilazane and an isocyanate and a reaction product of a polysilazane and an epoxy resin. The matrix also comprises a plurality of interconnected pores produced from one of reaction of the polysilazane and the isocyanate and from reaction of the polysilazane and the epoxy resin. A precursor formulation that comprises a polysilazane, a cross-linking compound, and a gas-generating compound is also disclosed.

Autogenic reaction synthesis of photocatalysts for solar fuel generation

DOEpatents

Ingram, Brian J.; Pol, Vilas G.; Cronauer, Donald C.; Ramanathan, Muruganathan

2016-04-19

In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen comprises at least one nanoparticulate metal or metal oxide material that is substantially free of a carbon coating, prepared by heating a metal-containing precursor compound in a sealed reactor under a pressure autogenically generated by dissociation of the precursor material in the sealed reactor at a temperature of at least about 600.degree. C. to form a nanoparticulate carbon-coated metal or metal oxide material, and subsequently substantially removing the carbon coating. The precursor material comprises a solid, solvent-free salt comprising a metal ion and at least one thermally decomposable carbon- and oxygen-containing counter-ion, and the metal of the salt is selected from the group consisting of Mn, Ti, Sn, V, Fe, Zn, Zr, Mo, Nb, W, Eu, La, Ce, In, and Si.

Surface modified aerogel monoliths

NASA Technical Reports Server (NTRS)

Leventis, Nicholas (Inventor); Johnston, James C. (Inventor); Kuczmarski, Maria A. (Inventor); Meador, Mary Ann B. (Inventor)

2013-01-01

This invention comprises reinforced aerogel monoliths such as silica aerogels having a polymer coating on its outer geometric surface boundary, and to the method of preparing said aerogel monoliths. The polymer coatings on the aerogel monoliths are derived from polymer precursors selected from the group consisting of isocyanates as a precursor, precursors of epoxies, and precursors of polyimides. The coated aerogel monoliths can be modified further by encapsulating the aerogel with the polymer precursor reinforced with fibers such as carbon or glass fibers to obtain mechanically reinforced composite encapsulated aerogel monoliths.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2006-10-10

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2007-01-09

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-Containing Low-Valent Early Transition Metal Olefin Polymerization Catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2004-06-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C-containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Preparation of superconductor precursor powders

DOEpatents

Bhattacharya, Raghunath; Blaugher, Richard D.

1995-01-01

A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals, such as nitrate salts of thallium, barium, calcium, and copper, which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of thallium in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

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

Ying, Minju, E-mail: mjying@bnu.edu.cn, E-mail: g.gehring@sheffield.ac.uk; Key Laboratory of Beam Technology and Material Modification of Ministry of Education, College of Nuclear Science and Technology, Beijing Normal University, Beijing 100875; Blythe, Harry J.

We investigate the magnetic properties of ZnCoO thin films grown by pulsed laser deposition (PLD) from targets made containing metallic Co or CoO precursors instead of the usual Co{sub 3}O{sub 4}. We find that the films grown from metallic Co precursors in an oxygen rich environment contain negligible amounts of Co metal and have a large magnetization at room temperature. Structural analysis by X-ray diffraction and magneto-optical measurements indicate that the enhanced magnetism is due, in part, from Zn vacancies that partially compensate the naturally occurring n-type defects. We conclude that strongly magnetic films of Zn{sub 0.95}Co{sub 0.05}O that domore » not contain metallic cobalt can be grown by PLD from Co-metal-precursor targets if the films are grown in an oxygen atmosphere.« less

Mild Hydroprocessing with Dispersed Catalyst of Highly Asphaltenic Pitch

NASA Astrophysics Data System (ADS)

Isquierdo, Fernanda

Asphaltene are known to have diverse negative impacts on heavy oil extraction and hydroprocessing. This research then, explores the optimal conditions to convert asphaltenes into lighter material using mild conditions of pressure and temperature, and investigates changes in asphaltene structure during hydroprocessing. Feedstock and products were characterized by Simulated Distillation, Microdeasphalting, Sulfur content, X-ray diffraction, X-ray photoelectron spectroscopy, and Nuclear magnetic resonance spectroscopy. Solid catalysts were analyzed by Themogravimetric analysis, X-ray diffraction, and Dynamic light scattering. Based on the results obtained from X-ray diffraction and Nuclear magnetic resonance spectroscopy analysis a mechanism for the asphaltene hydroprocessing at mild conditions is proposed in which the alky peripheric portion from the original asphaltenes is partially removed during the reaction. The consequence of that process being an increase in the stacking of the aromatics sheets in the remaining asphaltenes. Also, this study investigates different for ultradispersed catalyst compositions, where CoWS, CoMoS, NiWS, FeWS, NiMo/NaHFeSi 2O6 and NaHFeSi2O6 showed a high asphaltene conversion as determined by asphaltene microdeasphalting, FeMoS and NaHFeSi 2O6 presented a high Vacuum Residue as determined by distillation (SIMDIST) analysis conversion, and in terms of sulfur removal CoMoS gave the higher conversion. In addition, all the catalyst tested showed a coke production lower than 1%. Finally, a kinetic study for the pitch hydroprocessing using CoMoS as catalysts gave a global activation energy of 97.3 kJ/mol.

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

Purification of carbon nanotubes via selective heating

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

Rogers, John A.; Wilson, William L.; Jin, Sung Hun

The present invention provides methods for purifying a layer of carbon nanotubes comprising providing a precursor layer of substantially aligned carbon nanotubes supported by a substrate, wherein the precursor layer comprises a mixture of first carbon nanotubes and second carbon nanotubes; selectively heating the first carbon nanotubes; and separating the first carbon nanotubes from the second carbon nanotubes, thereby generating a purified layer of carbon nanotubes. Devices benefiting from enhanced electrical properties enabled by the purified layer of carbon nanotubes are also described.

NifX and NifEN exchange NifB cofactor and the VK-cluster, a newly isolated intermediate of the iron-molybdenum cofactor biosynthetic pathway.

PubMed

Hernandez, Jose A; Igarashi, Robert Y; Soboh, Basem; Curatti, Leonardo; Dean, Dennis R; Ludden, Paul W; Rubio, Luis M

2007-01-01

The iron-molybdenum cofactor of nitrogenase (FeMo-co) is synthesized in a multistep process catalysed by several Nif proteins and is finally inserted into a pre-synthesized apo-dinitrogenase to generate mature dinitrogenase protein. The NifEN complex serves as scaffold for some steps of this synthesis, while NifX belongs to a family of small proteins that bind either FeMo-co precursors or FeMo-co during cofactor synthesis. In this work, the binding of FeMo-co precursors and their transfer between purified Azotobacter vinelandii NifX and NifEN proteins was studied to shed light on the role of NifX on FeMo-co synthesis. Purified NifX binds NifB cofactor (NifB-co), a precursor to FeMo-co, with high affinity and is able to transfer it to the NifEN complex. In addition, NifEN and NifX exchange another [Fe-S] cluster that serves as a FeMo-co precursor, and we have designated it as the VK-cluster. In contrast to NifB-co, the VK-cluster is electronic paramagnetic resonance (EPR)-active in the reduced and the oxidized states. The NifX/VK-cluster complex is unable to support in vitro FeMo-co synthesis in the absence of NifEN because further processing of the VK-cluster into FeMo-co requires the simultaneous activities of NifEN and NifH. Our in vitro studies suggest that the role of NifX in vivo is to serve as transient reservoir of FeMo-co precursors and thus help control their flux during FeMo-co synthesis.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1986-09-30

A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1--6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1986-10-28

A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is NiC (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Selective growth of chirality-enriched semiconducting carbon nanotubes by using bimetallic catalysts from salt precursors.

PubMed

Zhao, Xiulan; Yang, Feng; Chen, Junhan; Ding, Li; Liu, Xiyan; Yao, Fengrui; Li, Meihui; Zhang, Daqi; Zhang, Zeyao; Liu, Xu; Yang, Juan; Liu, Kaihui; Li, Yan

2018-04-19

Bimetallic catalysts play important roles in the selective growth of single-walled carbon nanotubes (SWNTs). Using the simple salts (NH4)6W7O24·6H2O and Co(CH3COO)2·4H2O as precursors, tungsten-cobalt catalysts were prepared. The catalysts were composed of W6Co7 intermetallic compounds and tungsten-dispersed cobalt. With the increase of the W/Co ratio in the precursors, the content of W6Co7 was increased. Because the W6Co7 intermetallic compound can enable the chirality specified growth of SWNTs, the selectivity of the resulting SWNTs is improved at a higher W/Co ratio. At a W/Co ratio of 6 : 4 and under optimized chemical vapor deposition conditions, we realized the direct growth of semiconducting SWNTs with the purity of ∼96%, in which ∼62% are (14, 4) tubes. Using salts as precursors to prepare tungsten-cobalt bimetallic catalysts is flexible and convenient. This offers an efficient pathway for the large-scale preparation of chirality enriched semiconducting SWNTs.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

NASA Astrophysics Data System (ADS)

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

PubMed Central

2013-01-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail. PMID:24369051

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors.

PubMed

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-26

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Patterning by area selective oxidation

DOEpatents

Nam, Chang-Yong; Kamcev, Jovan; Black, Charles T.; Grubbs, Robert

2015-12-29

Technologies are described for methods for producing a pattern of a material on a substrate. The methods may comprise receiving a patterned block copolymer on a substrate. The patterned block copolymer may include a first polymer block domain and a second polymer block domain. The method may comprise exposing the patterned block copolymer to a light effective to oxidize the first polymer block domain in the patterned block copolymer. The method may comprise applying a precursor to the block copolymer. The precursor may infuse into the oxidized first polymer block domain and generate the material. The method may comprise applying a removal agent to the block copolymer. The removal agent may be effective to remove the first polymer block domain and the second polymer block domain from the substrate, and may not be effective to remove the material in the oxidized first polymer block domain.

Deposition of Ni nanoparticles onto porous supports using supercritical CO2: effect of the precursor and reduction methodology.

PubMed

Morère, Jacobo; Royuela, Sergio; Asensio, Guillermo; Palomino, Pablo; Enciso, Eduardo; Pando, Concepción; Cabañas, Albertina

2015-12-28

The deposition of Ni nanoparticles into porous supports is very important in catalysis. In this paper, we explore the use of supercritical CO(2) (scCO(2)) as a green solvent to deposit Ni nanoparticles on mesoporous SiO2 SBA-15 and a carbon xerogel. The good transport properties of scCO(2) allowed the efficient penetration of metal precursors dissolved in scCO(2) within the pores of the support without damaging its structure. Nickel hexafluoroacetylacetonate hydrate, nickel acetylacetonate, bis(cyclopentadienyl)nickel, Ni(NO(3))2⋅6H(2)O and NiCl(2)⋅6H(2)O were tried as precursors. Different methodologies were used: impregnation in scCO(2) and reduction in H(2)/N(2) at 400°C and low pressure, reactive deposition using H(2) at 200-250°C in scCO(2) and reactive deposition using ethanol at 150-200°C in scCO(2). The effect of precursor and methodology on the nickel particle size and the material homogeneity (on the different substrates) was analysed. This technology offers many opportunities in the preparation of metal-nanostructured materials. © 2015 The Author(s).

Methods of controlling hydrogen fluoride pressure during chemical fabrication processes

DOEpatents

Solovyov, Vyacheslav [Rocky Point, NY; Wiesmann, Harold [Stony Brook, NY

2009-11-24

The present invention is a method for producing a crystalline end-product. The method comprising exposing a fluoride-containing precursor to a hydrogen fluoride absorber under conditions suitable for the conversion of the precursor into the crystalline end-product.

Synthesis of transparent conducting oxide coatings

DOEpatents

Elam, Jeffrey W.; Martinson, Alex B. F.; Pellin, Michael J.; Hupp, Joseph T.

2010-05-04

A method and system for preparing a light transmitting and electrically conductive oxide film. The method and system includes providing an atomic layer deposition system, providing a first precursor selected from the group of cyclopentadienyl indium, tetrakis (dimethylamino) tin and mixtures thereof, inputting to the deposition system the first precursor for reaction for a first selected time, providing a purge gas for a selected time, providing a second precursor comprised of an oxidizer, and optionally inputting a second precursor into the deposition system for reaction and alternating for a predetermined number of cycles each of the first precursor, the purge gas and the second precursor to produce the oxide film.

SiCO-doped carbon fibers with unique dual superhydrophilicity/superoleophilicity and ductile and capacitance properties.

PubMed

Lu, Ping; Huang, Qing; Mukherjee, Amiya; Hsieh, You-Lo

2010-12-01

Silicon oxycarbide (SiCO) glass-doped carbon fibers with an average diameter of 163 nm were successfully synthesized by electrospinning polymer mixtures of preceramic precursor polyureasilazane (PUS) and carbon precursor polyacrylonitrile (PAN) into fibers then converting to ceramic/carbon hybrid via cross-linking, stabilization, and pyrolysis at temperatures up to 1000 °C. The transformation of PUS/PAN polymer precursors to SiCO/carbon structures was confirmed by EDS and FTIR. Both carbon and SiCO/carbon fibers were amorphous and slightly oxidized. Doping with SiCO enhanced the thermal stability of carbon fibers and acquired new ductile behavior in the SiCO/carbon fibers with significantly improved flexibility and breaking elongation. Furthermore, the SiCO/carbon fibers exhibited dual superhydrophilicity and superoleophilicity with water and decane absorbing capacities of 873 and 608%, respectively. The cyclic voltammetry also showed that SiCO/carbon composite fibers possess better capacitor properties than carbon fibers.

Electron doping effect on structural and magnetic phase transitions in Sr{sub 2-x}Nd{sub x}FeMoO{sub 6} double perovskites

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

Azad, A.K.; Eriksson, S.-G.; Khan, Abdullah

2006-05-15

Polycrystalline Sr{sub 2-x}Nd{sub x}FeMoO{sub 6} (x=0.0, 0.1, 0.2, 0.4) materials have been synthesized by a citrate co-precipitation method and studied by neutron powder diffraction (NPD) and magnetization measurements. Rietveld analysis of the temperature-dependent NPD data shows that the compounds (x=0.0, 0.1, 0.2) crystallize in the tetragonal symmetry in the range 10-400K and converts to cubic symmetry above 450K. The unit cell volume increases with increasing Nd{sup 3+} concentration, which is an electronic effect in order to change the valence state of the B-site cations. Antisite defects at the Fe-Mo sublattice increases with the Nd{sup 3+} doping. The Curie temperature wasmore » increased from 430K for x=0 to 443K for x=0.4. The magnetic moment of the Fe-site decreases while the Mo-site moment increases with electron doping. The antiferromagnetic arrangement causes the system to show a net ferrimagnetic moment.« less

Hydrodeoxygenation of coal using organometallic catalyst precursors

NASA Astrophysics Data System (ADS)

Kirby, Stephen R.

2002-04-01

The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these coals. Trends within the data were similar to those reported by other authors. Based on the conclusions from both the model compound studies and the coal analysis, predictions were made of the catalyst precursors' performance in the HDO of the three selected coals. It was concluded that CoMo-T2 is a desirable catalyst precursor for the HDO of coals (particularly low-rank coals), but that an optimum set of conditions must be determined to take full advantage of its HDO ability. (Abstract shortened by UMI.)

A Dual-Intein Autoprocessing Domain that Directs Synchronized Protein Co-Expression in Both Prokaryotes and Eukaryotes

PubMed Central

Zhang, Bei; Rapolu, Madhusudhan; Liang, Zhibin; Han, Zhenlin; Williams, Philip G.; Su, Wei Wen

2015-01-01

Being able to coordinate co-expression of multiple proteins is necessary for a variety of important applications such as assembly of protein complexes, trait stacking, and metabolic engineering. Currently only few options are available for multiple recombinant protein co-expression, and most of them are not applicable to both prokaryotic and eukaryotic hosts. Here, we report a new polyprotein vector system that is based on a pair of self-excising mini-inteins fused in tandem, termed the dual-intein (DI) domain, to achieve synchronized co-expression of multiple proteins. The DI domain comprises an Ssp DnaE mini-intein N159A mutant and an Ssp DnaB mini-intein C1A mutant connected in tandem by a peptide linker to mediate efficient release of the flanking proteins via autocatalytic cleavage. Essentially complete release of constituent proteins, GFP and RFP (mCherry), from a polyprotein precursor, in bacterial, mammalian, and plant hosts was demonstrated. In addition, successful co-expression of GFP with chloramphenicol acetyltransferase, and thioredoxin with RFP, respectively, further substantiates the general applicability of the DI polyprotein system. Collectively, our results demonstrate the DI-based polyprotein technology as a highly valuable addition to the molecular toolbox for multi-protein co-expression which finds vast applications in biotechnology, biosciences, and biomedicine. PMID:25712612

Process for preparing zinc oxide-based sorbents

DOEpatents

Gangwal, Santosh Kumar [Cary, NC; Turk, Brian Scott [Durham, NC; Gupta, Raghubir Prasad [Durham, NC

2011-06-07

The disclosure relates to zinc oxide-based sorbents, and processes for preparing and using them. The sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents comprise an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, comprising a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

Electrode materials for rechargeable battery

DOEpatents

Johnson, Christopher; Kang, Sun-Ho

2015-09-08

A positive electrode is disclosed for a non-aqueous electrolyte lithium rechargeable cell or battery. The electrode comprises a lithium containing material of the formula Na.sub.yLi.sub.xNi.sub.zMn.sub.1-z-z'M.sub.z'O.sub.d, wherein M is a metal cation, x+y>1, 0

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

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

Choi, Daiwon; Li, Xiaolin; Henderson, Wesley A.

2016-02-01

Highly crystalline LiCoPO4/C cathode has been synthesized without any impurities via single step solid-state reaction using CoHPO4xH2O nanoplates as a precursor obtained by simple precipitation route. The electrochemical test shows specific capacity as high as 125mAh/g at charge/discharge rate of C/10. Synthesis approach for obtaining CoHPO4xH2O nanoplate precursor and final LiCoPO4/C cathode using single step solid-state reaction have been characterized using X-ray diffraction, thermos gravimetric analyses (TGA) – differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The electrochemical test and cycling stability using different electrolytes, additive and separator have been investigated.

Aerogel and xerogel composites for use as carbon anodes

DOEpatents

Cooper, John F.; Tillotson, Thomas M.; Hrubesh, Lawrence W.

2010-10-12

A method for forming a reinforced rigid anode monolith and fuel and product of such method. The method includes providing a solution of organic aerogel or xerogel precursors including at least one of a phenolic resin, phenol (hydroxybenzene), resorcinol(1,3-dihydroxybenzene), or catechol(1,2-dihydroxybenzene); at least one aldehyde compound selected from the group consisting of formaldehyde, acetaldehyde, and furfuraldehyde; and an alkali carbonate or phosphoric acid catalyst; adding internal reinforcement materials comprising carbon to said precursor solution to form a precursor mixture; gelling said precursor mixture to form a composite gel; drying said composite gel; and pyrolyzing said composite gel to form a wettable aerogel/carbon composite or a wettable xerogel/carbon composite, wherein said composites comprise chars and said internal reinforcement materials, and wherein said composite is suitable for use as an anode with the chars being fuel capable of being combusted in a molten salt electrochemical fuel cell in the range from 500 C to 800 C to produce electrical energy. Additional methods and systems/compositions are also provided.

Aerosol chemical vapor deposition of metal oxide films

DOEpatents

Ott, Kevin C.; Kodas, Toivo T.

1994-01-01

A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

Identification of bottlenecks in Escherichia coli engineered for the production of CoQ(10).

PubMed

Cluis, Corinne P; Ekins, Andrew; Narcross, Lauren; Jiang, Heng; Gold, Nicholas D; Burja, Adam M; Martin, Vincent J J

2011-11-01

In this work, Escherichia coli was engineered to produce a medically valuable cofactor, coenzyme Q(10) (CoQ(10)), by removing the endogenous octaprenyl diphosphate synthase gene and functionally replacing it with a decaprenyl diphosphate synthase gene from Sphingomonas baekryungensis. In addition, by over-expressing genes coding for rate-limiting enzymes of the aromatic pathway, biosynthesis of the CoQ(10) precursor para-hydroxybenzoate (PHB) was increased. The production of isoprenoid precursors of CoQ(10) was also improved by the heterologous expression of a synthetic mevalonate operon, which permits the conversion of exogenously supplied mevalonate to farnesyl diphosphate. The over-expression of these precursors in the CoQ(10)-producing E. coli strain resulted in an increase in CoQ(10) content, as well as in the accumulation of an intermediate of the ubiquinone pathway, decaprenylphenol (10P-Ph). In addition, the over-expression of a PHB decaprenyl transferase (UbiA) encoded by a gene from Erythrobacter sp. NAP1 was introduced to direct the flux of DPP and PHB towards the ubiquinone pathway. This further increased CoQ(10) content in engineered E. coli, but decreased the accumulation of 10P-Ph. Finally, we report that the combined over-production of isoprenoid precursors and over-expression of UbiA results in the decaprenylation of para-aminobenzoate, a biosynthetic precursor of folate, which is structurally similar to PHB. Copyright © 2011 Elsevier Inc. All rights reserved.

The origin of free brain malonate

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

Riley, K.M.; Dickson, A.C.; Koeppen, A.H.

Rat brain contains substantial concentrations of free malonate (192 nmol/g wet weight) but origin and biological importance of the dicarboxylic acid are poorly understood. A dietary source has been excluded. A recently described malonyl-CoA decarboxylase deficiency is associated with malonic aciduria and clinical manifestations, including mental retardation. In an effort to study the metabolic origin of free malonate, several labeled acetyl-CoA precursors were administered by intracerebral injection. (2-14C)pyruvate or (1,5-14C)citrate produced radioactive glutamate but failed to label malonate. In contrast, (1-14C)acetate, (2-14C)acetate, and (1-14C)butyrate were converted to labeled glutamate and malonate after the same route of administration. The intracerebral injectionmore » of (1-14C)-beta-alanine as a precursor of malonic semialdehyde and possibly free malonate did not give rise to radioactivity in the dicarboxylate. The labeling pattern of malonic acid is compatible with the reaction sequence: acetyl-CoA----malonyl-CoA----malonate. The final step is thought to occur by transfer of the CoA-group from malonyl-CoA to succinate and/or acetoacetate. Labeling of malonate from acetate is most effective at the age of 7 days when the net concentration of the dicarboxylic acid in rat brain is still very low. At this age, butyrate was a better precursor of malonate than acetate. It is proposed that fatty acid oxidation provides the acetyl-CoA which functions as the precursor of free brain malonate. Compartmentation of malonate biosynthesis is likely because the acetyl-CoA precursors citrate and pyruvate are ineffective.« less

Influence of Water on Chemical Vapor Deposition of Ni and Co thin films from ethanol solutions of acetylacetonate precursors

PubMed Central

Weiss, Theodor; Zielasek, Volkmar; Bäumer, Marcus

2015-01-01

In chemical vapor deposition experiments with pulsed spray evaporation (PSE-CVD) of liquid solutions of Ni and Co acetylacetonate in ethanol as precursors, the influence of water in the feedstock on the composition and growth kinetics of deposited Ni and Co metal films was systematically studied. Varying the water concentration in the precursor solutions, beneficial as well as detrimental effects of water on the metal film growth, strongly depending on the concentration of water and the β-diketonate in the precursor, were identified. For 2.5 mM Ni(acac)2 precursor solutions, addition of 0.5 vol% water improves growth of a metallic Ni film and reduces carbon contamination, while addition of 1.0 vol% water and more leads to significant oxidation of deposited Ni. By tuning the concentration of both, Ni(acac)2 and water in the precursor solution, the fraction of Ni metal and Ni oxide in the film or the film morphology can be adjusted. In the case of Co(acac)2, even smallest amounts of water promote complete oxidation of the deposited film. All deposited films were analyzed with respect to chemical composition quasi in situ by XPS, their morphology was evaluated after deposition by SEM. PMID:26658547

Synthesis of high-performance Li4Ti5O12 and its application to the asymmetric hybrid capacitor

NASA Astrophysics Data System (ADS)

Lee, Byunggwan; Yoon, Jung Rag

2013-11-01

In this work, granule Li4Ti5O12 was successfully synthesized by spray drying a precursor slurry, followed by the solid-state reaction method. The precursor slurry was prepared from a solution of lithium carbonate (Li2CO3) and titanium dioxide (TiO2) in deionized water. A hybrid capacitor was fabricated which comprised a granule Li4Ti5O12 anode and activated carbon cathode. For comparison, an electrical double-layer capacitor (EDLC) cell was fabricated by using activated carbon electrodes in the same way. The electrochemical performance of the hybrid capacitor and the EDLC was characterized by constant current charge/discharge curves and cycle performance testing. The electrochemical testing results showed that the capacitance of the hybrid capacitor is approximately 2.5 times higher than that of the EDLC. Furthermore, the capacitance of the EDLC and the hybrid capacitor barely decreased after 1,000 cycles. The results of this study demonstrate that the hybrid capacitor has the advantages of the high rate capability of a supercapacitor (EDLC) and high battery capacity.

Sentinel-5 Precursor: Preparing the first Copernicus Atmospheric Mission

NASA Astrophysics Data System (ADS)

Nett, Herbert; McMullan, Kevin; Ingmann, Paul; Fehr, Thorsten

2015-11-01

Sentinel-5 Precursor (S-5P) will be the first of a series of atmospheric missions to be launched within the European Commission's Copernicus (former GMES) Programme. With a planned launch in 2016 and a nominal lifetime of 7 years S-5P is expected to provide continuity in the availability of global atmospheric data products between its predecessor missions SCIAMACHY (Envisat) and OMI (AURA) and the future Sentinel-4 and -5 series. The latter will comprise payload instruments on board the operational satellites MTG-S (S-4, geostationary component) and MetOp Second Generation (S-5, polar orbiting component), the first units of which will be launched in the 2020-2021 timeframe.The S-5P satellite will carry a single payload, TROPOMI (TROPOspheric Monitoring Instrument) which is jointly developed by The Netherlands and ESA. Covering spectral channels in the UV, visible, near- and short-wave infrared it will measure various key species including tropospheric/stratospheric ozone, NO2, SO2, CO, CH4, CH2O as well as cloud and aerosol parameters.

Bioaccessibility of micron-sized powder particles of molybdenum metal, iron metal, molybdenum oxides and ferromolybdenum--Importance of surface oxides.

PubMed

Mörsdorf, Alexander; Odnevall Wallinder, Inger; Hedberg, Yolanda

2015-08-01

The European chemical framework REACH requires that hazards and risks posed by chemicals, including alloys and metals, that are manufactured, imported or used in different products (substances or articles) are identified and proven safe for humans and the environment. Metals and alloys need hence to be investigated on their extent of released metals (bioaccessibility) in biologically relevant environments. Read-across from available studies may be used for similar materials. This study investigates the release of molybdenum and iron from powder particles of molybdenum metal (Mo), a ferromolybdenum alloy (FeMo), an iron metal powder (Fe), MoO2, and MoO3 in different synthetic body fluids of pH ranging from 1.5 to 7.4 and of different composition. Spectroscopic tools and cyclic voltammetry have been employed to characterize surface oxides, microscopy, light scattering and nitrogen absorption for particle characterization, and atomic absorption spectroscopy to quantify released amounts of metals. The release of molybdenum from the Mo powder generally increased with pH and was influenced by the fluid composition. The mixed iron and molybdenum surface oxide of the FeMo powder acted as a barrier both at acidic and weakly alkaline conditions. These findings underline the importance of the surface oxide characteristics for the bioaccessibility of metal alloys. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Kinetics of nif Gene Expression in a Nitrogen-Fixing Bacterium

PubMed Central

Poza-Carrión, César; Jiménez-Vicente, Emilio; Navarro-Rodríguez, Mónica; Echavarri-Erasun, Carlos

2014-01-01

Nitrogen fixation is a tightly regulated trait. Switching from N2 fixation-repressing conditions to the N2-fixing state is carefully controlled in diazotrophic bacteria mainly because of the high energy demand that it imposes. By using quantitative real-time PCR and quantitative immunoblotting, we show here how nitrogen fixation (nif) gene expression develops in Azotobacter vinelandii upon derepression. Transient expression of the transcriptional activator-encoding gene, nifA, was followed by subsequent, longer-duration waves of expression of the nitrogenase biosynthetic and structural genes. Importantly, expression timing, expression levels, and NifA dependence varied greatly among the nif operons. Moreover, the exact concentrations of Nif proteins and their changes over time were determined for the first time. Nif protein concentrations were exquisitely balanced, with FeMo cofactor biosynthetic proteins accumulating at levels 50- to 100-fold lower than those of the structural proteins. Mutants lacking nitrogenase structural genes or impaired in FeMo cofactor biosynthesis showed overenhanced responses to derepression that were proportional to the degree of nitrogenase activity impairment, consistent with the existence of at least two negative-feedback regulatory mechanisms. The first such mechanism responded to the levels of fixed nitrogen, whereas the second mechanism appeared to respond to the levels of the mature NifDK component. Altogether, these findings provide a framework to engineer N2 fixation in nondiazotrophs. PMID:24244007

Kinetics of Nif gene expression in a nitrogen-fixing bacterium.

PubMed

Poza-Carrión, César; Jiménez-Vicente, Emilio; Navarro-Rodríguez, Mónica; Echavarri-Erasun, Carlos; Rubio, Luis M

2014-02-01

Nitrogen fixation is a tightly regulated trait. Switching from N2 fixation-repressing conditions to the N2-fixing state is carefully controlled in diazotrophic bacteria mainly because of the high energy demand that it imposes. By using quantitative real-time PCR and quantitative immunoblotting, we show here how nitrogen fixation (nif) gene expression develops in Azotobacter vinelandii upon derepression. Transient expression of the transcriptional activator-encoding gene, nifA, was followed by subsequent, longer-duration waves of expression of the nitrogenase biosynthetic and structural genes. Importantly, expression timing, expression levels, and NifA dependence varied greatly among the nif operons. Moreover, the exact concentrations of Nif proteins and their changes over time were determined for the first time. Nif protein concentrations were exquisitely balanced, with FeMo cofactor biosynthetic proteins accumulating at levels 50- to 100-fold lower than those of the structural proteins. Mutants lacking nitrogenase structural genes or impaired in FeMo cofactor biosynthesis showed overenhanced responses to derepression that were proportional to the degree of nitrogenase activity impairment, consistent with the existence of at least two negative-feedback regulatory mechanisms. The first such mechanism responded to the levels of fixed nitrogen, whereas the second mechanism appeared to respond to the levels of the mature NifDK component. Altogether, these findings provide a framework to engineer N2 fixation in nondiazotrophs.

Effect of different promoter precursors in a model Ru-Cs/graphite system on the catalytic selectivity for Fischer-Tropsch reaction

NASA Astrophysics Data System (ADS)

Eslava, José L.; Iglesias-Juez, Ana; Fernández-García, Marcos; Guerrero-Ruiz, Antonio; Rodríguez-Ramos, Inmaculada

2018-07-01

The effect of using two different promoter precursors on the Fischer-Tropsch synthesis was studied over cesium promoted ruthenium catalysts supported on a high surface area graphite support. In this work we reveal significant modifications in the selectivity values for Fischer-Tropsch reaction depending on the Cs promoter precursor (CsCl vs CsNO3). Specifically the bimetallic catalyst (4Ru-4Cs), prepared from nitrates both for metal and promoter precursors, showed a high selectivity to CO2 during reaction. By modifying the cesium precursor, it was possible to inhibit the water gas shift reaction, decreasing significantly the selectivity to CO2. In order to understand the chemical origin of these modifications a careful characterization of the materials was performed including: X-ray absorption near edge spectroscopy, transmission electron microscopy measurements, temperature programmed reduction studies, determination of the CO uptakes on the catalysts and the evolution of the CO adsorption heats as a function of surface coverages. It was found that upon reduction and under reaction atmosphere the promoter in the ex-nitrate catalyst appears as Cs2O which is considered responsible of the CO2 production, while in the catalysts prepared with Cs chloride the promoter remains as CsCl suffering a slight partial reduction.

Controlled synthesis of Co2C nanochains using cobalt laurate as precursor: Structure, growth mechanism and magnetic properties

NASA Astrophysics Data System (ADS)

Zhang, Yajing; Zhu, Yuan; Wang, Kangjun; Li, Da; Wang, Dongping; Ding, Fu; Meng, Dan; Wang, Xiaolei; Choi, Chuljin; Zhang, Zhidong

2018-06-01

Cobalt carbides (Co2C and Co3C) nanocomposites exhibit interesting hard magnetic property, controlled synthesis of individual phase facilitates to clarify the magnetism of each, but it is difficult to obtain the single phase. We present a new approach to address this issue via a polyol refluxing process, using cobalt laurate as the precursor. The single phase Co2C magnetic nanochains self-assembled by nanoparticles are synthesized. The precursor is the key factor for controlling the growth kinetics of the Co2C nanochains. Cobalt, instead of cobalt carbides, is produced if cobalt chloride, acetate and acetylacetonate replace cobalt laurate as the precursor, respectively. The evolution of the growth process has been studied. In the formation of Co2C, first fcc-Co produces, then it transforms into Co2C by carbon diffusion process, and the produced carbon first exists in disordered state and then a small amount of them transforms into graphite. Saturation magnetization (Ms) of Co2C nanochains obtained at 300 °C for 20, 60, and 180 min are 27.1, 18.9, and 10.9 emu g-1, respectively. The decrease of Ms caused by increasing carbon content, and the carbon content are much larger than the stoichiometric ratio value of Co2C (9.2 wt%). The Co2C nanochains have mesoporous pore of 3.8 nm and the specific surface area of 48.6 m2 g-1.

Zinc-oxide-based sorbents and processes for preparing and using same

DOEpatents

Gangwal, Santosh Kumar; Turk, Brian Scott; Gupta, Raghubir Prasael

2010-03-23

Zinc oxide-based sorbents, and processes for preparing and using them are provided. The sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents comprise an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, comprising a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

Method of fabricating a homogeneous wire of inter-metallic alloy

DOEpatents

Ohriner, Evan Keith; Blue, Craig Alan

2001-01-01

A method for fabricating a homogeneous wire of inter-metallic alloy comprising the steps of providing a base-metal wire bundle comprising a metal, an alloy or a combination thereof; working the wire bundle through at least one die to obtain a desired dimension and to form a precursor wire; and, controllably heating the precursor wire such that a portion of the wire will become liquid while simultaneously maintaining its desired shape, whereby substantial homogenization of the wire occurs in the liquid state and additional homogenization occurs in the solid state resulting in a homogenous alloy product.

Surface-functionalized mesoporous carbon materials

DOEpatents

Dai, Sheng; Gorka, Joanna; Mayes, Richard T.

2016-02-02

A functionalized mesoporous carbon composition comprising a mesoporous carbon scaffold having mesopores in which polyvinyl polymer grafts are covalently attached, wherein said mesopores have a size of at least 2 nm and up to 50 nm. Also described is a method for producing the functionalized mesoporous composition, wherein a reaction medium comprising a precursor mesoporous carbon, vinyl monomer, initiator, and solvent is subjected to sonication of sufficient power to result in grafting and polymerization of the vinyl monomer into mesopores of the precursor mesoporous carbon. Also described are methods for using the functionalized mesoporous carbon, particularly in extracting metal ions from metal-containing solutions.

Chiral and achiral phosphine derivatives of alkylidyne tricobalt carbonyl clusters as catalyst precursors for (asymmetric) inter- and intramolecular Pauson-Khand reactions.

PubMed

Moberg, Viktor; Mottalib, M Abdul; Sauer, Désirée; Poplavskaya, Yulia; Craig, Donald C; Colbran, Stephen B; Deeming, Antony J; Nordlander, Ebbe

2008-05-14

Phosphine derivatives of alkylidyne tricobalt carbonyl clusters have been tested as catalysts/catalyst precursors in intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. A number of new phosphine derivatives of the tricobalt alkylidyne clusters [Co3(micro3-CR)(CO)9] (R = H, CO2Et) were prepared and characterised. The clusters [Co3(micro3-CR)(CO)9-x(PR'3)x] (PR'3 = achiral or chiral monodentate phosphine, x = 1-3) and [Co3(micro3-CR)(CO)7)(P-P)] (P-P = chiral diphosphine; 1,1'- and 1,2-structural isomers) were assayed as catalysts for intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. The phosphine-substituted tricobalt clusters proved to be viable catalysts/catalyst precursors that gave moderate to very good product yields (up to approximately 90%), but the enantiomeric excesses were too low for the clusters to be of practical use in the asymmetric reactions.

Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells

DOEpatents

Jenekhe, Samson A; Subramaniyan, Selvam; Ahmed, Eilaf; Xin, Hao; Kim, Felix Sunjoo

2014-10-28

The inventions disclosed, described, and/or claimed herein relate to copolymers comprising copolymers comprising electron accepting A subunits that comprise thiazolothiazole, benzobisthiazole, or benzobisoxazoles rings, and electron donating subunits that comprise certain heterocyclic groups. The copolymers are useful for manufacturing organic electronic devices, including transistors and solar cells. The invention also relates to certain synthetic precursors of the copolymers. Methods for making the copolymers and the derivative electronic devices are also described.

In Vivo Assessment of the Combat Ready Clamp to Control Junctional Hemorrhage in Swine

DTIC Science & Technology

2013-01-01

JF, Walters TJ, Baer DG, Fox CJ, Wade CE, Salinas J, Holcomb JB. Survival with emergency tourniquets to stop bleeding in major limb trauma. Ann Surg...suppl 4):S65YS69. 8. Walker SB, Cleary S, Higgins M. Comparison of the FemoStop device and manual pressure in reducing groin puncture site...M. Penetrating missile injuries during the Iraqi Insurgency. Ann R Coll Surg Engl. 2009;91 (7):551Y558. 16. Zouris JM, Walker GL, Dye J, Galreau M

Precursor soot synthesis of fullerenes and nanotubes without formation of carbonaceous soot

DOEpatents

Reilly, Peter T. A.

2007-03-20

The present invention is a method for the synthesis of fullerenes and/or nanotubes from precursor soot without the formation of carbonaceous soot. The method comprises the pyrolysis of a hydrocarbon fuel source by heating the fuel source at a sufficient temperature to transform the fuel source to a condensed hydrocarbon. The condensed hydrocarbon is a reaction medium comprising precursor soot wherein hydrogen exchange occurs within the reaction medium to form reactive radicals which cause continuous rearrangement of the carbon skeletal structure of the condensed hydrocarbon. Then, inducing dehydrogenation of the precursor soot to form fullerenes and/or nanotubes free from the formation of carbonaceous soot by continued heating at the sufficient temperature and by regulating the carbon to hydrogen ratio within the reaction medium. The dehydrogenation process produces hydrogen gas as a by-product. The method of the present invention in another embodiment is also a continuous synthesis process having a continuous supply of the fuel source. The method of the present invention can also be a continuous cyclic synthesis process wherein the reaction medium is fed back into the system as a fuel source after extraction of the fullerenes and/or nanotube products. The method of the present invention is also a method for producing precursor soot in bulk quantity, then forming fullerenes and/or nanotubes from the precursor bulk.

Synthesis of porous sheet-like Co{sub 3}O{sub 4} microstructure by precipitation method and its potential applications in the thermal decomposition of ammonium perchlorate

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

Lu Shanshan; Jing Xiaoyan; Liu Jingyuan

2013-01-15

Porous sheet-like cobalt oxide (Co{sub 3}O{sub 4}) were successfully synthesized by precipitation method combined with calcination of cobalt hydroxide precursors. The structure, morphology and porosity properties of the products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption-desorption measurement. The as-prepared sheet-like microstructures were approximately 2-3 {mu}m in average diameter, and the morphology of the cobalt hydroxide precursors was retained after the calcination process. However, it appeared a large number of uniform pores in the sheets after calcination. In order to calculate the potential catalytic activity, the thermal decomposition of ammoniummore » perchlorate (AP) has been analyzed, in which cobalt oxide played a role of an additive and the porous sheet-like Co{sub 3}O{sub 4} microstructures exhibited high catalytic performance and considerable decrease in the thermal decomposition temperature of AP. Moreover, a formation mechanism for the sheet-like microstructures has been discussed. - Graphical abstract: Porous sheet-like Co{sub 3}O{sub 4} were synthesized by facile precipitation method combined with calcination of {beta}-Co(OH){sub 2} precursors. Thermogravimetric-differential scanning calorimetric analysis indicates potential catalytic activity in the thermal decomposition of ammonium perchlorate. Highlights: Black-Right-Pointing-Pointer Synthesis of sheet-like {beta}-Co(OH){sub 2} precursors by precipitation method. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} were obtained by calcining {beta}-Co(OH){sub 2} precursors. Black-Right-Pointing-Pointer The possible formation mechanism of porous sheet-like Co{sub 3}O{sub 4} has been discussed. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} decrease the thermal decomposition temperature of ammonium perchlorate.« less

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1985-03-12

A catalyst and process useful at low temperatures (below about 160/sup 0/C) and preferably in the range 80 to 120/sup 0/C used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH-RONa-M(OAc)/sub 2/ where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1 to 6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)/sub 6/ is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.; Mahajan, Devinder

1986-01-01

A catalyst and process useful at low temperatures (below about 160.degree. C.) and preferably in the range 80.degree.-120.degree. C. used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa--M(OAc).sub.2 where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M=Ni and R=tertiary amyl). Mo(CO).sub.6 is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Thermal shock resistance ceramic insulator

DOEpatents

Morgan, Chester S.; Johnson, William R.

1980-01-01

Thermal shock resistant cermet insulators containing 0.1-20 volume % metal present as a dispersed phase. The insulators are prepared by a process comprising the steps of (a) providing a first solid phase mixture of a ceramic powder and a metal precursor; (b) heating the first solid phase mixture above the minimum decomposition temperature of the metal precursor for no longer than 30 minutes and to a temperature sufficiently above the decomposition temperature to cause the selective decomposition of the metal precursor to the metal to provide a second solid phase mixture comprising particles of ceramic having discrete metal particles adhering to their surfaces, said metal particles having a mean diameter no more than 1/2 the mean diameter of the ceramic particles, and (c) densifying the second solid phase mixture to provide a cermet insulator having 0.1-20 volume % metal present as a dispersed phase.

Highly conductive, multi-layer composite precursor composition to fuel cell flow field plate or bipolar plate

DOEpatents

Jang, Bor Z [Centerville, OH; Zhamu, Aruna [Centerville, OH; Guo, Jiusheng [Centerville, OH

2011-02-15

This invention provides a moldable, multiple-layer composite composition, which is a precursor to an electrically conductive composite flow field plate or bipolar plate. In one preferred embodiment, the composition comprises a plurality of conductive sheets and a plurality of mixture layers of a curable resin and conductive fillers, wherein (A) each conductive sheet is attached to at least one resin-filler mixture layer; (B) at least one of the conductive sheets comprises flexible graphite; and (C) at least one resin-filler mixture layer comprises a thermosetting resin and conductive fillers with the fillers being present in a sufficient quantity to render the resulting flow field plate or bipolar plate electrically conductive with a conductivity no less than 100 S/cm and thickness-direction areal conductivity no less than 200 S/cm.sup.2.

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

Wertsching, Alan Kevin; Trantor, Troy Joseph; Ebner, Matthias Anthony

A method and device for producing secure, high-density tritium bonded with carbon. A substrate comprising carbon is provided. A precursor is intercalated between carbon in the substrate. The precursor intercalated in the substrate is irradiated until at least a portion of the precursor, preferably a majority of the precursor, is transmutated into tritium and bonds with carbon of the substrate forming bonded tritium. The resulting bonded tritium, tritium bonded with carbon, produces electrons via beta decay. The substrate is preferably a substrate from the list of substrates consisting of highly-ordered pyrolytic graphite, carbon fibers, carbon nanotunes, buckministerfullerenes, and combinations thereof.more » The precursor is preferably boron-10, more preferably lithium-6. Preferably, thermal neutrons are used to irradiate the precursor. The resulting bonded tritium is preferably used to generate electricity either directly or indirectly.« less

High Refractive Organic–Inorganic Hybrid Films Prepared by Low Water Sol-Gel and UV-Irradiation Processes

PubMed Central

Ma, Hsiao-Yuan; Wang, Tzong-Liu; Chang, Pei-Yu; Yang, Chien-Hsin

2016-01-01

Organic-inorganic hybrid sols (Ti–O–Si precursor) were first synthesized by the sol-gel method at low addition of water, and were then employed to prepare a highly refractive hybrid optical film. This film was obtained by blending the Ti–O–Si precursor with 2-phenylphenoxyethyl acrylate (OPPEA) to perform photo-polymerization by ultraviolet (UV) irradiation. Results show that the film transparency of poly(Ti–O–Si precursor-co-OPPEA) film is higher than that of a pure poly(Ti–O–Si precursor) film, and that this poly(Ti–O–Si precursor-co-OPPEA) hybrid film exhibits a high transparency of ~93.7% coupled with a high refractive index (n) of 1.83 corresponding to a thickness of 2.59 μm. PMID:28344303

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

NASA Technical Reports Server (NTRS)

Rodriguez, Marc (Inventor); Kaner, Richard B. (Inventor); Bux, Sabah K. (Inventor); Fleurial, Jean-Pierre (Inventor)

2014-01-01

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

Radionuclide-binding compound, a radionuclide delivery system, a method of making a radium complexing compound, a method of extracting a radionuclide, and a method of delivering a radionuclide

DOEpatents

Fisher, Darrell R.; Wai, Chien M.; Chen, Xiaoyuan

2000-01-01

The invention pertains to compounds which specifically bind radionuclides, and to methods of making radionuclide complexing compounds. In one aspect, the invention includes a radionuclide delivery system comprising: a) a calix[n]arene-crown-[m]-ether compound, wherein n is an integer greater than 3, and wherein m is an integer greater than 3, the calix[n]arene-crown-[m]-ether compound comprising at least two ionizable groups; and b) an antibody attached to the calix[n]arene-crown-[m]-ether compound. In another aspect, the invention includes a method of making a radium complexing compound, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising n phenolic hydroxyl groups; b) providing a crown ether precursor, the crown ether precursor comprising a pair of tosylated ends; c) reacting the pair of tosylated ends with a pair of the phenolic hydroxyl groups to convert said pair of phenolic hydroxyl groups to ether linkages, the ether linkages connecting the crown ether precursor to the calix[n]arene to form a calix[n]arene-crown-[m]-ether compound, wherein m is an integer greater than 3; d) converting remaining phenolic hydroxyl groups to esters; e) converting the esters to acids, the acids being proximate a crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound; and f) providing a Ra.sup.2+ ion within the crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound.

Apparatus for fabricating continuous lengths of superconductor

DOEpatents

Kroeger, Donald M.; List, III, Frederick A.

2002-01-01

A process and apparatus for manufacturing a superconductor. The process is accomplished by depositing a superconductor precursor powder on a continuous length of a first substrate ribbon, overlaying a continuous length of a second substrate ribbon on said first substrate ribbon, and applying sufficient pressure to form a bound layered superconductor comprising a layer of said superconducting precursor powder between said first substrate ribbon and said second substrates ribbon. The layered superconductor is then heat treated to establish the superconducting phase of said superconductor precursor powder.

Apparatus for fabricating continuous lengths of superconductor

DOEpatents

Kroeger, Donald M.; List, III, Frederick A.

2001-01-01

A process and apparatus for manufacturing a superconductor. The process is accomplished by depositing a superconductor precursor powder on a continuous length of a first substrate ribbon, overlaying a continuous length of a second substrate ribbon on said first substrate ribbon, and applying sufficient pressure to form a bound layered superconductor comprising a layer of said superconducting precursor powder between said first substrate ribbon and said second substrates ribbon. The layered superconductor is then heat treated to establish the superconducting phase of said superconductor precursor powder.

Synthesis of nanometer-sized fayalite and magnesium-iron(II) mixture olivines

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

Qafoku, Odeta; Ilton, Eugene S.; Bowden, Mark E.

Olivines are divalent orthosilicates with important geologic, biological, and industrial significance and are typically comprised of mixtures of Mg2+ and Fe2+ ranging from forsterite (Mg2SiO4) to fayalite (Fe2SiO4). Investigating the role of Fe(II) in olivine reactivity requires the ability to synthesize olivines that are nanometer-sized, have different percentages of Mg2+ and Fe2+, and have good bulk and surface purity. This article demonstrates a new method for synthesizing nanosized fayalite and Mg-Fe mixture olivines. First, carbonaceous precursors are generated from sucrose, PVA, colloidal silica, Mg2+, and Fe3+. Second, these precursors are calcined in air to burn carbon and create mixtures ofmore » Fe(III)-oxides, forsterite, and SiO2. Finally, calcination in reducing CO-CO2 gas buffer leads to Fe(II)-rich olivines. XRD, Mössbauer, and IR analyses verify good bulk purity and composition. XPS indicates that surface iron is in its reduced Fe(II) form, and surface Si is consistent with olivine. SEM shows particle sizes predominately between 50 and 450 nm, and BET surface areas are 2.8-4.2 m2/g. STEM HAADF analysis demonstrates even distributions of Mg and Fe among the available M1 and M2 sites of the olivine crystals. These nanosized Fe(II)-rich olivines are suitable for laboratory studies with in situ probes that require mineral samples with high reactivity at short timescales.« less

Effects of Bi doping on structural and magnetic properties of double perovskite oxides Sr2FeMoO6

NASA Astrophysics Data System (ADS)

Lan, Yaohai; Feng, Xiaomei; Zhang, Xin; Shen, Yifu; Wang, Ding

2016-08-01

A new series of double perovskite compounds Sr2 - δBixFeMoO6 have been synthesized by solid-state reaction. δ refers to the nominal doping content of Bi (δ = 0, 0.1, 0.2, 0.3, 0.4, 0.5), while the Bi content obtained by the Rietveld refinement is x = 0, 0.01, 0.05, 0.08, 0.10 and 0.12. Their crystal structure and magnetic properties are investigated. Rietveld analysis of the room temperature XRD data shows all the samples crystallize in the cubic crystal structure with the space group Fm 3 ‾ m and have no phase transition. SEM images show that substituted samples present a denser microstructure and bigger grains than Sr2FeMoO6, which is caused by a liquid sintering process due to the effumability of Bi. The unit cell volume increases with augment of Bi3+ concentration despite the smaller ionic radius Bi3+ compared with the Sr2+, which is attributed to the electronic effect. The degree of Fe/Mo order (η) increases first and then decreases to almost disappearance with augment of Bi doping, which is the result of contribution from electronic effect. Calculated saturation magnetization Ms(3) according to our phase separation likeness model matches well with the experimental ones. The observed variations of magnetoresistance (MR) are consistent with the Fe/Mo order (η) due to the internal connection with anti-site defect (ASD).

Efficient Conversion of CO 2 to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts

DOE PAGES

Medina-Ramos, Jonnathan; Pupillo, Rachel C.; Keane, Thomas P.; ...

2015-02-19

The development of affordable electrocatalysts that can drive the reduction of CO 2 to CO with high selectivity, efficiency, and large current densities is a critical step on the path to production of liquid carbon-based fuels. In this work, we show that inexpensive triflate salts of Sn 2+, Pb 2+, Bi 3+, and Sb 3+ can be used as precursors for the electrodeposition of CO 2 reduction cathode materials from MeCN solutions, providing a general and facile electrodeposition strategy, which streamlines catalyst synthesis. The ability of these four platforms to drive the formation of CO from CO 2 in themore » presence of [BMIM]OTf was probed. The electrochemically prepared Sn and Bi catalysts proved to be highly active, selective, and robust platforms for CO evolution, with partial current densities of j CO = 5-8 mA/cm 2 at applied overpotentials of η < 250 mV. By contrast, the electrodeposited Pb and Sb catalysts do not promote rapid CO generation with the same level of selectivity. The Pb material is only ~10% as active as the Sn and Bi systems at an applied potential of E = -1.95 V and is rapidly passivated during catalysis. The Sb-comprised cathode material shows no activity for conversion of CO 2 to CO under analogous conditions. When taken together, this work demonstrates that 1,3-dialkylimidazoliums can promote CO production, but only when used in combination with an appropriately chosen electrocatalyst material. More broadly, these results suggest that the interactions between CO 2, the imidazolium promoter, and the cathode surface are all critical to the observed catalysis.« less

De-alloyed platinum nanoparticles

DOEpatents

Strasser, Peter [Houston, TX; Koh, Shirlaine [Houston, TX; Mani, Prasanna [Houston, TX; Ratndeep, Srivastava [Houston, TX

2011-08-09

A method of producing de-alloyed nanoparticles. In an embodiment, the method comprises admixing metal precursors, freeze-drying, annealing, and de-alloying the nanoparticles in situ. Further, in an embodiment de-alloyed nanoparticle formed by the method, wherein the nanoparticle further comprises a core-shell arrangement. The nanoparticle is suitable for electrocatalytic processes and devices.

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method.

PubMed

Qiu, Haifa; Du, Tengfei; Wu, Junfeng; Wang, Yonglong; Liu, Jian; Ye, Shihai; Liu, Sheng

2018-05-22

Although intensive studies have been conducted on layered transition metal oxide(TMO)-based cathode materials and metal oxide-based anode materials for Li-ion batteries, their precursors generally follow different or even complex synthesis routes. To share one route for preparing precursors of the cathode and anode materials, herein, we demonstrate a facile co-precipitation method to fabricate Ni-rich hydroxide precursors of Ni0.8Co0.1Mn0.1(OH)2. Ni-rich layered oxide of LiNi0.8Co0.1Mn0.1O2 is obtained by lithiation of the precursor in air. An NiO-based anode material is prepared by calcining the precursor or multi-walled carbon nanotubes (MWCNTs) incorporated precursors. The pre-addition of ammonia solution can simplify the co-precipitation procedures and the use of an air atmosphere can also make the heat treatment facile. LiNi0.8Co0.1Mn0.1O2 as the cathode material delivers a reversible capacity of 194 mA h g-1 at 40 mA g-1 and a notable cycling retention of 88.8% after 100 cycles at 200 mA g-1. This noticeable performance of the cathode arises from a decent particle morphology and high crystallinity of the layered oxides. As the anode material, the MWCNTs-incorporated oxides deliver a much higher reversible capacity of 811.1 mA h g-1 after 200 cycles compared to the pristine oxides without MWCNTs. The improvement on electrochemical performance can be attributed to synergistic effects from MWCNTs incorporation, including reinforced electronic conductivity, rich meso-pores and an alleviated volume effect. This facile and sharing method may offer an integrated and economical approach for commercial production of Ni-rich electrode materials for Li-ion batteries.

On the structural intricacies of a metabolic precursor: Direct spectroscopic detection of water-induced conformational reshaping of mevalonolactone

NASA Astrophysics Data System (ADS)

Domingos, Sérgio R.; Pérez, Cristóbal; Schnell, Melanie

2017-09-01

We use high-resolution rotational spectroscopy to investigate the structural intricacies of the lactone form of mevalonic acid, precursor of the mevalonate pathway. By combining microwave spectroscopy with supersonic expansions and quantum-chemical calculations, we determine the two most stable conformations of the precursor. Complementary micro-solvation studies reveal that aggregation of the first water molecule induces a substantial structural rearrangement comprising a hydroxy rotation and an endocyclic core torsion to create a favourable geometry to accommodate the water molecule. We discuss the conformational aspects of the precursor in isolation and under micro-hydrated conditions.

Non-spherical Lobate Chondrules in CO3.0 Y-81020: General Implications for the Formation of Low-FeO Porphyritic Chondrules in CO Chondrites

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Wasson, John T.

2006-01-01

Non-spherical chondrules (arbitrarily defined as having aspect ratios greater than or equal to 1.20) in CO3.0 chondrites comprise multi-lobate, distended, and highly irregular objects with rounded margins; they constitute approx. 70% of the type-I (low-FeO) porphyritic chondrules in Y-81020, approx. 75% of such chondrules in ALHA77307, and approx. 60% of those in Colony. Although the proportion of non-spherical type-I chondrules in LL3.0 Semarkona is comparable (approx. 60%), multi-lobate OC porphyritic chondrules (with lobe heights equivalent to a significant fraction of the mean chondrule diameter) are rare. If the non-spherical type-I chondrules in CO chondrites had formed from totally molten droplets, calculations indicate that they would have collapsed into spheres within approx. 10(exp -3) s, too little time for their 20-micrometer-size olivine phenocrysts to have grown from the melt. These olivine grains must therefore be relicts from an earlier chondrule generation; the final heating episode experienced by the non-spherical chondrules involved only minor amounts of melting and crystallization. The immediate precursors of the individual non-spherical chondrules may have been irregularly shaped chondrule fragments whose fracture surfaces were rounded during melting. Because non-spherical chondrules and circular chondrules form a continuum in shape and have similar grain sizes, mineral and mesostasis compositions, and modal abundances of non-opaque phases, they must have formed by related processes. We conclude that a large majority of low-FeO chondrules in CO3 chondrites experienced a late, low-degree melting event. Previous studies have shown that essentially all type-II (high-FeO) porphyritic chondrules in Y-81020 formed by repeated episodes of low-degree melting. It thus appears that the type-I and type-II porphyritic chondrules in Y-81020 (and, presumably, all CO3 chondrites) experienced analogous formation histories. Because these two types constitute approx. 95% of all CO chondrules, it is clear that chondrule recycling was the rule in the CO chondrule-formation region and that most melting events produced only low degrees of melting. The rarity of significantly non-spherical, multi-lobate chondrules in Semarkona may reflect more-intense heating of chondrule precursors in the ordinary-chondrite region of the solar nebula.

Catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2012-07-24

A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

Photoinduced synthesis of single-digit micrometer-size spheroidal calcite composites in the presence of partially hydrolyzed poly(vinyl alcohol)

NASA Astrophysics Data System (ADS)

Nishio, Takashi; Naka, Kensuke

2015-06-01

Photoinduced crystallization of calcium carbonate (CaCO3), which was based on the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphyenyl)propionic acid) under alkaline conditions of pH 8.4 and 10 was studied for preparation of CaCO3 composite particles in single-digit micrometer-sizes. In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol%) was used as a precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. After the UV irradiation for 50 min, calcite spheroids in single-digit micrometer-sizes were obtained as major products at pH 8.4. The obtained calcite spheroids contained organic components of about 10 wt%. The comparison of the characteristics of the CaCO3 obtained at pH 8.4 and 10 suggests that the nucleation and crystallization of both vaterite and calcite continuously took place in a moderated supersaturation owing to the CO2 hydration equilibrium as long as the photodecarboxylation of KP continued. Consequently, the aggregation-based crystal growth in the presence of PVAPS seemed to enable the formation of the spheroidal composites of calcite in single-digit micrometer-sizes.

Nitrogen-Functionalized Hydrothermal Carbon Materials by Using Urotropine as the Nitrogen Precursor.

PubMed

Straten, Jan Willem; Schleker, Philipp; Krasowska, Małgorzata; Veroutis, Emmanouil; Granwehr, Josef; Auer, Alexander A; Hetaba, Walid; Becker, Sylvia; Schlögl, Robert; Heumann, Saskia

2018-03-25

Nitrogen-containing hydrothermal carbon (N-HTC) materials of spherical particle morphology were prepared by means of hydrothermal synthesis with glucose and urotropine as precursors. The molar ratio of glucose to urotropine has been varied to achieve a continuous increase in nitrogen content. By raising the ratio of urotropine to glucose, a maximal nitrogen fraction of about 19 wt % could be obtained. Decomposition products of both glucose and urotropine react with each other; this opens up a variety of possible reaction pathways. The pH has a pronounced effect on the reaction pathway of the corresponding reaction steps. For the first time, a comprehensive analytical investigation, comprising a multitude of analytical tools and instruments, of a series of nitrogen-containing HTC materials was applied. Functional groups and structural motifs identified were analyzed by means of FTIR spectroscopy, thermogravimetric MS, and solid-state NMR spectroscopy. Information on reaction mechanisms and structural details were obtained by electronic structure calculations that were compared with vibrational spectra of polyfuran or polypyrrole-like groups, which represent structural motifs occurring in the present samples. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Voronoi-Tessellated Graphite Produced by Low-Temperature Catalytic Graphitization from Renewable Resources.

PubMed

Zhao, Leyi; Zhao, Xiuyun; Burke, Luke T; Bennett, J Craig; Dunlap, Richard A; Obrovac, Mark N

2017-09-11

A highly crystalline graphite powder was prepared from the low temperature (800-1000 °C) graphitization of renewable hard carbon precursors using a magnesium catalyst. The resulting graphite particles are composed of Voronoi-tessellated regions comprising irregular sheets; each Voronoi-tessellated region having a small "seed" particle located near their centroid on the surface. This suggests nucleated outward growth of graphitic carbon, which has not been previously observed. Each seed particle consists of a spheroidal graphite shell on the inside of which hexagonal graphite platelets are perpendicularly affixed. This results in a unique high surface area graphite with a high degree of graphitization that is made with renewable feedstocks at temperatures far below that conventionally used for artificial graphites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-Solution Sulfides Derived from Tunable Layered Double Hydroxide Precursors/Graphene Aerogel for Pseudocapacitors and Sodium-Ion Batteries.

PubMed

Song, Yajie; Li, Hui; Yang, Lan; Bai, Daxun; Zhang, Fazhi; Xu, Sailong

2017-12-13

Transition-metal sulfides (TMSs) are suggested as promising electrode materials for electrochemical pseudocapacitors and lithium- and sodium-ion batteries; however, they typically involve mixed composites or conventionally stoichiometric TMSs (such as NiCo 2 S 4 and Ni 2 CoS 4 ). Herein we demonstrate a preparation of solid-solution sulfide (Ni 0.7 Co 0.3 )S 2 supported on three-dimensional graphene aerogel (3DGA) via a sulfuration of NiCo-layered double hydroxide (NiCo-LDH) precursor/3DGA. The electrochemical tests show that the (Ni 0.7 Co 0.3 )S 2 /3DGA electrode exhibits a capacitance of 2165 F g -1 at 1 A g -1 , 2055 F g -1 at 2 A g -1 , and 1478 F g -1 at 10 A g -1 ; preserves 78.5% capacitance retention upon 1000 cycles for pseudocapacitors; and in particular, possesses a relatively high charge capacity of 388.7 mA h g -1 after 50 cycles at 100 mA g -1 as anode nanomaterials for sodium-ion batteries. Furthermore, the electrochemical performances are readily tuned by varying the cationic type of the tunable LDH precursors to prepare different solid-solution sulfides, such as (Ni 0.7 Fe 0.3 )S 2 /3DGA and (Co 0.7 Fe 0.3 )S 2 /3DGA. Our results show that engineering LDH precursors can offer an alternative for preparing diverse transition-metal sulfides for energy storage.

Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip

DOEpatents

Kittrell, W. Carter; Wang, Yuhuang; Kim, Myung Jong; Hauge, Robert H.; Smalley, Richard E.; Marek leg, Irene Morin

2010-06-01

The present invention is directed to fibers of epitaxially grown single-wall carbon nanotubes (SWNTs) and methods of making same. Such methods generally comprise the steps of: (a) providing a spun SWNT fiber; (b) cutting the fiber substantially perpendicular to the fiber axis to yield a cut fiber; (c) etching the cut fiber at its end with a plasma to yield an etched cut fiber; (d) depositing metal catalyst on the etched cut fiber end to form a continuous SWNT fiber precursor; and (e) introducing feedstock gases under SWNT growth conditions to grow the continuous SWNT fiber precursor into a continuous SWNT fiber.

Process for producing metal compounds from graphite oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Process for Producing Metal Compounds from Graphite Oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Process for preparing polymer reinforced silica aerogels

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor); Capadona, Lynn A. (Inventor)

2011-01-01

Process for preparing polymer-reinforced silica aerogels which comprises a one-pot reaction of at least one alkoxy silane in the presence of effective amounts of a polymer precursor to obtain a silica reaction product, the reaction product is gelled and subsequently subjected to conditions that promotes polymerization of the precursor and then supercritically dried to obtain the polymer-reinforced monolithic silica aerogels.

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

DOE PAGES

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; ...

2016-04-04

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Confined-plume chemical deposition: rapid synthesis of crystalline coatings of known hard or superhard materials on inorganic or organic supports by resonant IR decomposition of molecular precursors.

PubMed

Ivanov, Borislav L; Wellons, Matthew S; Lukehart, Charles M

2009-08-26

A one-step process for preparing microcrystalline coatings of known superhard, very hard, or ultraincompressible ceramic compositions on either inorganic or organic supports is reported. Midinfrared pulsed-laser irradiation of preceramic chemical precursors layered between IR-transmissive hard/soft supports under temporal and spatial confinement at a laser wavelength resonant with a precursor vibrational band gives one-step deposition of crystalline ceramic coatings without incurring noticeable collateral thermal damage to the support material. Reaction plume formation at the precursor/laser beam interface initiates confined-plume, chemical deposition (CPCD) of crystalline ceramic product. Continuous ceramic coatings are produced by rastering the laser beam over a sample specimen. CPCD processing of the Re-B single-source precursor, (B(3)H(8))Re(CO)(4), the dual-source mixtures, Ru(3)(CO)(12)/B(10)H(14) or W(CO)(6)/B(10)H(14), and the boron/carbon single-source precursor, o-B(10)C(2)H(12), confined between Si wafer or NaCl plates gives microcrystalline deposits of ReB(2), RuB(2), WB(4), or B(4)C, respectively. CPCD processing of Kevlar fabric wetted by (B(3)H(8))Re(CO)(4) produces an oriented, microcrystalline coating of ReB(2) on the Kevlar fabric without incurring noticeable thermal damage of the polymer support. Similarly, microcrystalline coatings of ReB(2) can be formed on IR-transmissive IR2, Teflon, or Ultralene polymer films.

Exsolved silicate and oxide phases from clinopyroxenes in a single Hawaiian xenolith: Implications for oxidation state of the Hawaiian upper mantle

NASA Astrophysics Data System (ADS)

Sen, Gautam; Jones, Robert E.

1988-01-01

A single garnet-bearing clinopyroxenite xenolith from the Salt Lake crater on Oahu, Hawaii, contains two distinct types of clinopyroxene; one contains exsolved garnet, ilmenite, and magnetite, and the other contains exsolved hercynite-pleonaste spinel, orthopyroxene, and ilmenite. Application of mineral geothermometers, barometers, and oxygen barometers to this unusual combination of exsolved phases defines the following conditions of last mantle equilibration of this xenolith: P = 19 kbar, T =1153 °C, and log10fO2 = -9.7.

Syngas conversion to a light alkene and related methods

DOEpatents

Ginosar, Daniel M.; Petkovic, Lucia M.

2017-11-14

Methods of producing a light alkene. The method comprises contacting syngas and tungstated zirconia to produce a product stream comprising at least one light alkene. The product stream is recovered. Methods of converting syngas to a light alkene are also disclosed. The method comprises heating a precursor of tungstated zirconia to a temperature of between about 350.degree. C. and about 550.degree. C. to form tungstated zirconia. Syngas is flowed over the tungstated zirconia to produce a product stream comprising at least one light alkene and the product stream comprising the at least one light alkene is recovered.

Combinatorial Characterization of TiO2 Chemical Vapor Deposition Utilizing Titanium Isopropoxide.

PubMed

Reinke, Michael; Ponomarev, Evgeniy; Kuzminykh, Yury; Hoffmann, Patrik

2015-07-13

The combinatorial characterization of the growth kinetics in chemical vapor deposition processes is challenging because precise information about the local precursor flow is usually difficult to access. In consequence, combinatorial chemical vapor deposition techniques are utilized more to study functional properties of thin films as a function of chemical composition, growth rate or crystallinity than to study the growth process itself. We present an experimental procedure which allows the combinatorial study of precursor surface kinetics during the film growth using high vacuum chemical vapor deposition. As consequence of the high vacuum environment, the precursor transport takes place in the molecular flow regime, which allows predicting and modifying precursor impinging rates on the substrate with comparatively little experimental effort. In this contribution, we study the surface kinetics of titanium dioxide formation using titanium tetraisopropoxide as precursor molecule over a large parameter range. We discuss precursor flux and temperature dependent morphology, crystallinity, growth rates, and precursor deposition efficiency. We conclude that the surface reaction of the adsorbed precursor molecules comprises a higher order reaction component with respect to precursor surface coverage.

Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica

DOEpatents

Pham, Hien N.; Datye, Abhaya K.

2003-04-15

The present invention relates to catalysts in mesoporous structures. In a preferred embodiment, the invention comprises a method for encapsulating a dispersed insoluble compound in a mesoporous structure comprising combining a soluble oxide precursor, a solvent, and a surfactant to form a mixture; dispersing an insoluble compound in the mixture; spray-drying the mixture to produce dry powder; and calcining the powder to yield a porous structure comprising the dispersed insoluble compound.

Platinum-free catalysts for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Lastovina, Tatiana; Pimonova, Julia; Budnyk, Andriy

2017-04-01

In this work, we have successfully prepared Zn/Co-N/C and Zn/Co-Fe/N/C composites, both derived from single zeolitic imidazolate framework (ZIF) precursor Zn/Co-ZIF containing equivalent quantities of Zn and Co metal sites. The composites were formed by pyrolysis of the precursor at 700 °C in inert gas atmosphere as such and after mixing it with Fe(II) salt and 1,10-phenontraline in ethanol. Catalytic tests for oxygen reduction reaction (ORR) in electrochemical cell demonstrated promising results allowing us to consider these composites as potential Pt-free catalysts for low temperature fuel cells.

Synthesis and characterization of Co3O4 prepared from atmospheric pressure acid leach liquors of nickel laterite ores

NASA Astrophysics Data System (ADS)

Meng, Long; Guo, Zhan-cheng; Qu, Jing-kui; Qi, Tao; Guo, Qiang; Hou, Gui-hua; Dong, Peng-yu; Xi, Xin-guo

2018-01-01

A chemical precipitation-thermal decomposition method was developed to synthesize Co3O4 nanoparticles using cobalt liquor obtained from the atmospheric pressure acid leaching process of nickel laterite ores. The effects of the precursor reaction temperature, the concentration of Co2+, and the calcination temperature on the specific surface area, morphology, and the electrochemical behavior of the obtained Co3O4 particles were investigated. The precursor basic cobaltous carbonate and cobaltosic oxide products were characterized and analyzed by Fourier transform infrared spectroscopy, thermogravimetric differential thermal analysis, X-ray diffraction, field-emission scanning electron microscopy, specific surface area analysis, and electrochemical analysis. The results indicate that the specific surface area of the Co3O4 particles with a diameter of 30 nm, which were obtained under the optimum conditions of a precursor reaction temperature of 30°C, 0.25 mol/L Co2+, and a calcination temperature of 350°C, was 48.89 m2/g. Electrodes fabricated using Co3O4 nanoparticles exhibited good electrochemical properties, with a specific capacitance of 216.3 F/g at a scan rate of 100 mV/s.

Surface-complexation synthesis of silica-supported high-loading well-dispersed reducible nano-Co3O4 catalysts using CoIII ammine hydroxo complexes

NASA Astrophysics Data System (ADS)

Zhang, Weidong; Pan, Feng; Li, Jinjun; Wang, Zhen; Ding, Wei; Qin, Yi; Wu, Feng

2018-06-01

Silica-supported highly dispersed cobalt oxides prepared by adsorption are likely to be poorly reducible Co-phyllosilicates or CoO species. Here we report the synthesis of silica-supported monodispersed spinel nano-Co3O4 catalysts by inner-sphere complexation using CoIII ammine hydroxo complexes as precursors. The precursors were facilely prepared by stirring ammoniacal CoII solutions exposed to air. The cobalt loadings (up to 188 mg/g) and particle sizes (3-10 nm) were tailored by successive complexation-calcination cycles. Such catalysts showed significantly superior reducibility and catalytic activity in complete propane oxidation in comparison to supported Co-phyllosilicates and CoO. A further development of this synthesis process may provide a variety of cobalt-based catalysts for important catalytic applications.

Co-occurrence of biphenotypic acute leukaemia, glucose 6-phosphate dehydrogenase deficiency and haemoglobin E trait in a single child.

PubMed

Mallick, Debkrishna; Thapa, Rajoo; Biswas, Biswajit

2016-02-01

Acute leukaemias occur as the result of clonal expansion subsequent to transformation and arrest at a normal differentiation stage of haematopoietic precursors, which commit to a single lineage, such as myeloid or B-lymphoid or T-lymphoid cells. Biphenotypic acute leukaemia (BAL) constitutes a biologically different group of leukaemia arising from a precursor stem cell and co-expressing more than one lineage specific marker. The present report describes a child with unusual co-occurrence of biphenotypic (B-precursor cell and Myeloid) acute leukaemia, haemoglobin E trait and glucose 6-phosphate dehydrogenase (G6-PD) deficiency. To the best of our knowledge, this constellation of haematological conditions in a single child has never been described before. 2016 BMJ Publishing Group Ltd.

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

Eilert, André; Roberts, F. Sloan; Friebel, Daniel

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Reverse micelle synthesis of nanoscale metal containing catalysts

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

Process for making a ceramic composition for immobilization of actinides

DOEpatents

Ebbinghaus, Bartley B.; Van Konynenburg, Richard A.; Vance, Eric R.; Stewart, Martin W.; Walls, Philip A.; Brummond, William Allen; Armantrout, Guy A.; Herman, Connie Cicero; Hobson, Beverly F.; Herman, David Thomas; Curtis, Paul G.; Farmer, Joseph

2001-01-01

Disclosed is a process for making a ceramic composition for the immobilization of actinides, particularly uranium and plutonium. The ceramic is a titanate material comprising pyrochlore, brannerite and rutile. The process comprises oxidizing the actinides, milling the oxides to a powder, blending them with ceramic precursors, cold pressing the blend and sintering the pressed material.

Vanadium oxide-carbon nanotube composite electrodes for energy storage by supercritical fluid deposition: experiment design and device performance

NASA Astrophysics Data System (ADS)

Do, Quyet H.; Fielitz, Thomas R.; Zeng, Changchun; Arda Vanli, O.; Zhang, Chuck; Zheng, Jim P.

2013-08-01

Vanadium pentoxide (V2O5) deposited on porous multiwalled carbon nanotube (MWCNT) buckypaper using supercritical fluid CO2(scCO2) deposition shows excellent performance for electrochemical capacitors. However, the low weight loading of V2O5 is one of the main problems. In this paper, design of experiments and response surface methods were employed to explore strategies for improving the active material loading by increasing the organo-vanadium precursor adsorption. A second-order response surface model was fitted to the designed experiments to predict the loading of the vanadium precursors onto carbon nanotube buckypaper as a function of time, temperature and pressure of CO2, buckypaper functionalization, precursor type, initial precursor mass and stir speed. Operation conditions were identified by employing a model that led to a precursor loading of 19.33%, an increase of 72.28% over the initial screening design. CNTs-V2O5 composite electrodes fabricated from deposited samples using the optimized conditions demonstrated outstanding electrochemical performance (947.1 F g-1 of V2O5 at a high scan rate 100 mV s-1). The model also predicted operation conditions under which light precursor aggregation took place. The V2O5 from aggregated precursor still possessed considerable specific capacitance (311 F g-1 of V2O5 at a scan rate 100 mV s-1), and the significantly higher V2O5 loading (˜81%) contributed to an increase in overall electrode capacitance.

Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors

NASA Astrophysics Data System (ADS)

Johnson, Kelsea R.; Arevalo Rodriguez, Paul; Brewer, Christopher R.; Brannaka, Joseph A.; Shi, Zhiwei; Yang, Jing; Salazar, Bryan; McElwee-White, Lisa; Walker, Amy V.

2017-02-01

Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

XPS study of thermal and electron-induced decomposition of Ni and Co acetylacetonate thin films for metal deposition

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

Weiss, Theodor; Warneke, Jonas; Zielasek, Volkmar, E-mail: zielasek@uni-bremen.de

2016-07-15

Optimizing thin metal film deposition techniques from metal-organic precursors such as atomic layer deposition, chemical vapor deposition (CVD), or electron beam-induced deposition (EBID) with the help of surface science analysis tools in ultrahigh vacuum requires a contamination-free precursor delivery technique, especially in the case of the less volatile precursors. For this purpose, the preparation of layers of undecomposed Ni(acac){sub 2} and Co(acac){sub 2} was tried via pulsed spray evaporation of a liquid solution of the precursors in ethanol into a flow of nitrogen on a CVD reactor. Solvent-free layers of intact precursor molecules were obtained when the substrate was heldmore » at a temperature of 115 °C. A qualitative comparison of thermally initiated and electron-induced precursor decomposition and metal center reduction was carried out. All deposited films were analyzed with respect to chemical composition quasi in situ by x-ray photoelectron spectroscopy. Thermally initiated decomposition yielded higher metal-to-metal oxide ratios in the deposit than the electron-induced process for which ratios of 60:40 and 20:80 were achieved for Ni and Co, resp. Compared to continuous EBID processes, all deposits showed low levels of carbon impurities of ∼10 at. %. Therefore, postdeposition irradiation of metal acetylacetonate layers by a focused electron beam and subsequent removal of intact precursor by dissolution in ethanol or by heating is proposed as electron beam lithography technique on the laboratory scale for the production of the metal nanostructures.« less

One-pot electrodeposition of cobalt flower-decorated silver nanotrees for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Cho, Yun-Bin; Moon, Sinyoung; Lee, Chongmok; Lee, Youngmi

2017-02-01

In this paper, we demonstrate a simple fabrication of bimetallic silver (Ag) and cobalt (Co) nanostructures (AgCo) with various Ag to Co relative contents via electrochemical co-deposition. A series of AgCo catalysts was electrodeposited on glassy carbon (GC) electrodes at -0.57 V vs. SCE in the deposition solutions, containing Ag precursor, Co precursor, Triton X-100, and 0.3 M KNO3 aqueous solution, with various Ag to Co precursor concentration ratios (1:x, x was varied from 3 to 11). The films, deposited with the total deposition charge of 0.042C, were denoted as Ag1Cox. SEM and TEM analyses showed that Ag1Cox formed a structure consisted of flower-like Co grown on tree-like Ag backbones while it had more Co flowers with a greater x. The ORR activities were examined in 0.1 M NaOH solution with rotating disk electrode (RDE) voltammetry and Ag1Co7 showed the best catalytic activity. The co-deposition mechanism was further investigated by varying the deposition time of Ag1Co7. At the early stage of deposition, Ag-tree branches were formed predominantly, followed by the growth of flower-like Co nanostructures on the Ag nanotrees: More Co flowers were produced on Ag backbones with longer deposition time, being attributed to both a less negative reduction potential of Ag+ to Ag than Co2+ to Co and promoted Co2+ reduction on the initially formed Ag surface. Ag1Co7 electrodeposited for 200 s, consisted of ∼14% Co, showed the greatest ORR catalytic activity which was better or comparable to noble metal Pt.

Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

DOEpatents

Podtburg, E.R.

1999-06-22

An oxide superconductor composite having improved texture and durability is disclosed. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor. 1 fig.

Precursor composites for oxygen dispersion hardened silver sheathed superconductor composites

DOEpatents

Podtburg, Eric R.

1999-01-01

An oxide superconductor composite having improved texture and durability. The oxide superconductor composite includes an oxide superconductor phase substantially surrounded with/by a noble metal matrix, the noble metal matrix comprising a metal oxide in an amount effective to form metal oxide domains that increase hardness of the composite. The composite is characterized by a degree of texture at least 10% greater than a comparable oxide superconductor composite lacking metal oxide domains. An oxide superconducting composite may be prepared by oxidizing the precursor composite under conditions effective to form solute metal oxide domains within the silver matrix and to form a precursor oxide in the precursor alloy phase; subjecting the oxidized composite to a softening anneal under conditions effective to relieve stress within the noble metal phase; and converting the oxide precursor into an oxide superconductor.

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

PubMed

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

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

3D carbon/cobalt-nickel mixed-oxide hybrid nanostructured arrays for asymmetric supercapacitors.

PubMed

Zhu, Jianhui; Jiang, Jian; Sun, Zhipeng; Luo, Jingshan; Fan, Zhanxi; Huang, Xintang; Zhang, Hua; Yu, Ting

2014-07-23

The electrochemical performance of supercapacitors relies not only on the exploitation of high-capacity active materials, but also on the rational design of superior electrode architectures. Herein, a novel supercapacitor electrode comprising 3D hierarchical mixed-oxide nanostructured arrays (NAs) of C/CoNi3 O4 is reported. The network-like C/CoNi3 O4 NAs exhibit a relatively high specific surface area; it is fabricated from ultra-robust Co-Ni hydroxide carbonate precursors through glucose-coating and calcination processes. Thanks to their interconnected three-dimensionally arrayed architecture and mesoporous nature, the C/CoNi3 O4 NA electrode exhibits a large specific capacitance of 1299 F/g and a superior rate performance, demonstrating 78% capacity retention even when the discharge current jumps by 100 times. An optimized asymmetric supercapacitor with the C/CoNi3 O4 NAs as the positive electrode is fabricated. This asymmetric supercapacitor can reversibly cycle at a high potential of 1.8 V, showing excellent cycling durability and also enabling a remarkable power density of ∼13 kW/kg with a high energy density of ∼19.2 W·h/kg. Two such supercapacitors linked in series can simultaneously power four distinct light-emitting diode indicators; they can also drive the motor of remote-controlled model planes. This work not only presents the potential of C/CoNi3 O4 NAs in thin-film supercapacitor applications, but it also demonstrates the superiority of electrodes with such a 3D hierarchical architecture. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of carbon monoxide pollution from cities and wildfires on regional and urban scales: the benefit of CO column retrievals from SCIAMACHY 2.3 µm measurements under cloudy conditions

NASA Astrophysics Data System (ADS)

Borsdorff, Tobias; Andrasec, Josip; aan de Brugh, Joost; Hu, Haili; Aben, Ilse; Landgraf, Jochen

2018-05-01

In the perspective of the upcoming TROPOMI Sentinel-5 Precursor carbon monoxide data product, we discuss the benefit of using CO total column retrievals from cloud-contaminated SCIAMACHY 2.3 µm shortwave infrared spectra to detect atmospheric CO enhancements on regional and urban scales due to emissions from cities and wildfires. The study uses the operational Sentinel-5 Precursor algorithm SICOR, which infers the vertically integrated CO column together with effective cloud parameters. We investigate its capability to detect localized CO enhancements distinguishing between clear-sky observations and observations with low (< 1.5 km) and medium-high clouds (1.5-5 km). As an example, we analyse CO enhancements over the cities Paris, Los Angeles and Tehran as well as the wildfire events in Mexico-Guatemala 2005 and Alaska-Canada 2004. The CO average of the SCIAMACHY full-mission data set of clear-sky observations can detect weak CO enhancements of less than 10 ppb due to air pollution in these cities. For low-cloud conditions, the CO data product performs similarly well. For medium-high clouds, the observations show a reduced CO signal both over Tehran and Los Angeles, while for Paris no significant CO enhancement can be detected. This indicates that information about the vertical distribution of CO can be obtained from the SCIAMACHY measurements. Moreover, for the Mexico-Guatemala fires, the low-cloud CO data captures a strong outflow of CO over the Gulf of Mexico and the Pacific Ocean and so provides complementary information to clear-sky retrievals, which can only be obtained over land. For both burning events, enhanced CO values are even detectable with medium-high-cloud retrievals, confirming a distinct vertical extension of the pollution. The larger number of additional measurements, and hence the better spatial coverage, significantly improve the detection of wildfire pollution using both the clear-sky and cloudy CO retrievals. Due to the improved instrument performance of the TROPOMI instrument with respect to its precursor SCIAMACHY, the upcoming Sentinel-5 Precursor CO data product will allow improved detection of CO emissions and their vertical extension over cities and fires, making new research applications possible.

Hydrothermal synthesis and characterization of Si and Sr co-substituted hydroxyapatite nanowires using strontium containing calcium silicate as precursors.

PubMed

Zhang, Na; Zhai, Dong; Chen, Lei; Zou, Zhaoyong; Lin, Kaili; Chang, Jiang

2014-04-01

In the absence of any organic surfactants and solvents, the silicon (Si) and strontium (Sr) co-substituted hydroxyapatite [Ca10(PO4)6(OH)2, Si/Sr-HAp] nanowires were synthesized via hydrothermal treatment of the Sr-containing calcium silicate (Sr-CS) powders as the precursors in trisodium phosphate (Na3PO4) aqueous solution. The morphology, phase, chemical compositions, lattice constants and the degradability of the products were characterized. The Si/Sr-HAp nanowires with diameter of about 60nm and up to 2μm in length were obtained after hydrothermal treatment of the Sr-CS precursors. The Sr and Si substitution amount of the HAp nanowires could be well regulated by facile tailoring the Sr substitution level of the precursors and the reaction ratio of the precursor/solution, respectively. The SiO4 tetrahedra and Sr(2+) ions occupied the crystal sites of the HAp, and the lattice constants increased apparently with the increase of the substitution amount. EDS mapping also suggested the uniform distribution of Si and Sr in the synthetic nanowires. Moreover, the Si/Sr-substitution apparently improved the degradability of the HAp materials. Our study suggested that the precursor transformation method provided a facile approach to synthesize the Si/Sr co-substituted HAp nanowires with controllable substitution amount, and the synthetic Si/Sr-HAp nanowires might be used as bioactive materials for hard tissue regeneration applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Characteristics and properties of nano-LiCoO2 synthesized by pre-organized single source precursors: Li-ion diffusivity, electrochemistry and biological assessment.

PubMed

Brog, Jean-Pierre; Crochet, Aurélien; Seydoux, Joël; Clift, Martin J D; Baichette, Benoît; Maharajan, Sivarajakumar; Barosova, Hana; Brodard, Pierre; Spodaryk, Mariana; Züttel, Andreas; Rothen-Rutishauser, Barbara; Kwon, Nam Hee; Fromm, Katharina M

2017-08-22

LiCoO 2 is one of the most used cathode materials in Li-ion batteries. Its conventional synthesis requires high temperature (>800 °C) and long heating time (>24 h) to obtain the micronscale rhombohedral layered high-temperature phase of LiCoO 2 (HT-LCO). Nanoscale HT-LCO is of interest to improve the battery performance as the lithium (Li + ) ion pathway is expected to be shorter in nanoparticles as compared to micron sized ones. Since batteries typically get recycled, the exposure to nanoparticles during this process needs to be evaluated. Several new single source precursors containing lithium (Li + ) and cobalt (Co 2+ ) ions, based on alkoxides and aryloxides have been structurally characterized and were thermally transformed into nanoscale HT-LCO at 450 °C within few hours. The size of the nanoparticles depends on the precursor, determining the electrochemical performance. The Li-ion diffusion coefficients of our LiCoO 2 nanoparticles improved at least by a factor of 10 compared to commercial one, while showing good reversibility upon charging and discharging. The hazard of occupational exposure to nanoparticles during battery recycling was investigated with an in vitro multicellular lung model. Our heterobimetallic single source precursors allow to dramatically reduce the production temperature and time for HT-LCO. The obtained nanoparticles of LiCoO 2 have faster kinetics for Li + insertion/extraction compared to microparticles. Overall, nano-sized LiCoO 2 particles indicate a lower cytotoxic and (pro-)inflammogenic potential in vitro compared to their micron-sized counterparts. However, nanoparticles aggregate in air and behave partially like microparticles.

A facile thermal decomposition route to synthesise CoFe2O4 nanostructures

NASA Astrophysics Data System (ADS)

Kalpanadevi, K.; Sinduja, C. R.; Manimekalai, R.

2014-01-01

The synthesis of CoFe2O4 nanoparticles has been achieved by a simple thermal decomposition method from an inorganic precursor, cobalt ferrous cinnamate hydrazinate (CoFe2(cin)3(N2H4)3) which was obtained by a novel precipitation method from the corresponding metal salts, cinnamic acid and hydrazine hydrate. The precursor was characterized by hydrazine and metal analyses, infrared spectral analysis and thermo gravimetric analysis. Under appropriate annealing, CoFe2(cin)3(N2H4)3 yielded CoFe2O4 nanoparticles, which were characterized for their size and structure using X-Ray diffraction (XRD), high resolution transmission electron microscopic (HRTEM), selected area electron diffraction (SAED) and scanning electron microscopic (SEM) techniques.

Unmixed fuel processors and methods for using the same

DOEpatents

Kulkarni, Parag Prakash; Cui, Zhe

2010-08-24

Disclosed herein are unmixed fuel processors and methods for using the same. In one embodiment, an unmixed fuel processor comprises: an oxidation reactor comprising an oxidation portion and a gasifier, a CO.sub.2 acceptor reactor, and a regeneration reactor. The oxidation portion comprises an air inlet, effluent outlet, and an oxygen transfer material. The gasifier comprises a solid hydrocarbon fuel inlet, a solids outlet, and a syngas outlet. The CO.sub.2 acceptor reactor comprises a water inlet, a hydrogen outlet, and a CO.sub.2 sorbent, and is configured to receive syngas from the gasifier. The regeneration reactor comprises a water inlet and a CO.sub.2 stream outlet. The regeneration reactor is configured to receive spent CO.sub.2 adsorption material from the gasification reactor and to return regenerated CO.sub.2 adsorption material to the gasification reactor, and configured to receive oxidized oxygen transfer material from the oxidation reactor and to return reduced oxygen transfer material to the oxidation reactor.

Nanoporous titanium niobium oxide and titanium tantalum oxide compositions and their use in anodes of lithium ion batteries

DOEpatents

Dai, Sheng; Guo, Bingkun; Sun, Xiao-Guang; Qiao, Zhenan

2017-10-31

Nanoporous metal oxide framework compositions useful as anodic materials in a lithium ion battery, the composition comprising metal oxide nanocrystals interconnected in a nanoporous framework and having interconnected channels, wherein the metal in said metal oxide comprises titanium and at least one metal selected from niobium and tantalum, e.g., TiNb.sub.2-x Ta.sub.xO.sub.y (wherein x is a value from 0 to 2, and y is a value from 7 to 10) and Ti.sub.2Nb.sub.10-vTa.sub.vO.sub.w (wherein v is a value from 0 to 2, and w is a value from 27 to 29). A novel sol gel method is also described in which sol gel reactive precursors are combined with a templating agent under sol gel reaction conditions to produce a hybrid precursor, and the precursor calcined to form the anodic composition. The invention is also directed to lithium ion batteries in which the nanoporous framework material is incorporated in an anode of the battery.

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

1999-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Method for fabrication of ceramic dielectric films on copper foils

DOEpatents

Ma, Beihai; Narayanan, Manoj; Dorris, Stephen E.; Balachandran, Uthamalingam

2017-06-14

The present invention provides copper substrate coated with a lead-lanthanum-zirconium-titanium (PLZT) ceramic film, which is prepared by a method comprising applying a layer of a sol-gel composition onto a copper foil. The sol-gel composition comprises a precursor of a ceramic material suspended in 2-methoxyethanol. The layer of sol-gel is then dried at a temperature up to about 250.degree. C. The dried layer is then pyrolyzed at a temperature in the range of about 300 to about 450.degree. C. to form a ceramic film from the ceramic precursor. The ceramic film is then crystallized at a temperature in the range of about 600 to about 750.degree. C. The drying, pyrolyzing and crystallizing are performed under a flowing stream of an inert gas.

Colloidal nanocrystals and method of making

DOEpatents

Kahen, Keith

2015-10-06

A tight confinement nanocrystal comprises a homogeneous center region having a first composition and a smoothly varying region having a second composition wherein a confining potential barrier monotonically increases and then monotonically decreases as the smoothly varying region extends from the surface of the homogeneous center region to an outer surface of the nanocrystal. A method of producing the nanocrystal comprises forming a first solution by combining a solvent and at most two nanocrystal precursors; heating the first solution to a nucleation temperature; adding to the first solution, a second solution having a solvent, at least one additional and different precursor to form the homogeneous center region and at most an initial portion of the smoothly varying region; and lowering the solution temperature to a growth temperature to complete growth of the smoothly varying region.

Adaptive Evolution of Synthetic Cooperating Communities Improves Growth Performance

PubMed Central

Zhang, Xiaolin; Reed, Jennifer L.

2014-01-01

Symbiotic interactions between organisms are important for human health and biotechnological applications. Microbial mutualism is a widespread phenomenon and is important in maintaining natural microbial communities. Although cooperative interactions are prevalent in nature, little is known about the processes that allow their initial establishment, govern population dynamics and affect evolutionary processes. To investigate cooperative interactions between bacteria, we constructed, characterized, and adaptively evolved a synthetic community comprised of leucine and lysine Escherichia coli auxotrophs. The co-culture can grow in glucose minimal medium only if the two auxotrophs exchange essential metabolites — lysine and leucine (or its precursors). Our experiments showed that a viable co-culture using these two auxotrophs could be established and adaptively evolved to increase growth rates (by ∼3 fold) and optical densities. While independently evolved co-cultures achieved similar improvements in growth, they took different evolutionary trajectories leading to different community compositions. Experiments with individual isolates from these evolved co-cultures showed that changes in both the leucine and lysine auxotrophs improved growth of the co-culture. Interestingly, while evolved isolates increased growth of co-cultures, they exhibited decreased growth in mono-culture (in the presence of leucine or lysine). A genome-scale metabolic model of the co-culture was also constructed and used to investigate the effects of amino acid (leucine or lysine) release and uptake rates on growth and composition of the co-culture. When the metabolic model was constrained by the estimated leucine and lysine release rates, the model predictions agreed well with experimental growth rates and composition measurements. While this study and others have focused on cooperative interactions amongst community members, the adaptive evolution of communities with other types of interactions (e.g., commensalism, ammensalism or parasitism) would also be of interest. PMID:25299364

Electrochemical energy storage device based on carbon dioxide as electroactive species

DOEpatents

Nemeth, Karoly; van Veenendaal, Michel Antonius; Srajer, George

2013-03-05

An electrochemical energy storage device comprising a primary positive electrode, a negative electrode, and one or more ionic conductors. The ionic conductors ionically connect the primary positive electrode with the negative electrode. The primary positive electrode comprises carbon dioxide (CO.sub.2) and a means for electrochemically reducing the CO.sub.2. This means for electrochemically reducing the CO.sub.2 comprises a conductive primary current collector, contacting the CO.sub.2, whereby the CO.sub.2 is reduced upon the primary current collector during discharge. The primary current collector comprises a material to which CO.sub.2 and the ionic conductors are essentially non-corrosive. The electrochemical energy storage device uses CO.sub.2 as an electroactive species in that the CO.sub.2 is electrochemically reduced during discharge to enable the release of electrical energy from the device.

Metal-doped single-walled carbon nanotubes and production thereof

DOEpatents

Dillon, Anne C.; Heben, Michael J.; Gennett, Thomas; Parilla, Philip A.

2007-01-09

Metal-doped single-walled carbon nanotubes and production thereof. The metal-doped single-walled carbon nanotubes may be produced according to one embodiment of the invention by combining single-walled carbon nanotube precursor material and metal in a solution, and mixing the solution to incorporate at least a portion of the metal with the single-walled carbon nanotube precursor material. Other embodiments may comprise sputter deposition, evaporation, and other mixing techniques.

Solution synthesis of mixed-metal chalcogenide nanoparticles and spray deposition of precursor films

DOEpatents

Schulz, Douglas L.; Curtis, Calvin J.; Ginley, David S.

2000-01-01

A colloidal suspension comprising metal chalcogenide nanoparticles and a volatile capping agent. The colloidal suspension is made by reacting a metal salt with a chalcogenide salt in an organic solvent to precipitate a metal chalcogenide, recovering the metal chalcogenide, and admixing the metal chalcogenide with a volatile capping agent. The colloidal suspension is spray deposited onto a substrate to produce a semiconductor precursor film which is substantially free of impurities.

Metal inks

DOEpatents

Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

2014-02-04

Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

DOEpatents

Chen, Fanglin; Wang, Yao

2017-02-21

Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

Highly transparent cerium doped gadolinium gallium aluminum garnet ceramic prepared with precursors fabricated by ultrasonic enhanced chemical co-precipitation.

PubMed

Zhang, Ji-Yun; Luo, Zhao-Hua; Jiang, Hao-Chuan; Jiang, Jun; Chen, Chun-Hua; Zhang, Jing-Xian; Gui, Zhen-Zhen; Xiao, Na

2017-11-01

Cerium doped gadolinium gallium aluminum garnet (GGAG:Ce) ceramic precursors have been synthesized with an ultrasonic chemical co-precipitation method (UCC) and for comparison with a traditional chemical co-precipitation method (TCC). The effect of ultra-sonication on the morphology of powders and the transmittance of GGAG:Ce ceramics are studied. The results indicate that the UCC method can effectively improve the homogenization and sinterability of GGAG:Ce powders, which contribute to obtain high transparent GGAG ceramic with the highest transmittance of 81%. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of SmCo and SmCoN magnetron sputtering coatings for SOFC interconnect applications

NASA Astrophysics Data System (ADS)

Wu, Junwei; Li, Chengming; Johnson, Christopher; Liu, Xingbo

Cobalt or cobalt containing coatings are promising for SOFC interconnect applications because of their high conductivity. We have investigated SmCo and SmCoN coatings deposited by magnetron sputtering from a SmCo (5% Sm) target on to Crofer 22 APU substrates. The composition, structure, surface morphology, and electrical conductivity of the coated substrates were characterized by SEM/EDX, XRD and ASR measurements. Addition of Sm enhances the oxidation resistance and the Cr retention capability of the coatings. The use of nitride as a precursor stabilizes Sm during oxidation of the films, thus inhibiting diffusion of Fe, resulting in a more compact coating and lowering ASR. The combined advantages of Sm addition to cobalt and the use of a nitride as a precursor, makes SmCoN coatings a promising new interconnect coating material.

Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream

DOEpatents

Chang, Shih-Ger; Li, Yang; Zhao, Xinglei

2014-07-08

The present invention provides a system for capturing CO.sub.2 and/or SO.sub.2, comprising: (a) a CO.sub.2 and/or SO.sub.2 absorber comprising an amine and/or amino acid salt capable of absorbing the CO.sub.2 and/or SO.sub.2 to produce a CO.sub.2- and/or SO.sub.2-containing solution; (b) an amine regenerator to regenerate the amine and/or amino acid salt; and, when the system captures CO.sub.2, (c) an alkali metal carbonate regenerator comprising an ammonium catalyst capable catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO.sub.2 gas. The present invention also provides for a system for capturing SO.sub.2, comprising: (a) a SO.sub.2 absorber comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO.sub.2 to produce an alkali metal sulfite/sulfate precipitate and CO.sub.2.

Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition.

PubMed

P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael; Ingólfsson, Oddur

2018-01-01

In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H 2 FeRu 3 (CO) 13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo 3 (CO) 12 , metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H 2 FeRu 3 (CO) 13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8-9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO) 4 from H 2 FeRu 3 (CO) 13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively poor performance of H 2 FeRu 3 (CO) 13 as compared to the structurally similar HFeCo 3 (CO) 12 .

Electron interactions with the heteronuclear carbonyl precursor H2FeRu3(CO)13 and comparison with HFeCo3(CO)12: from fundamental gas phase and surface science studies to focused electron beam induced deposition

PubMed Central

P, Ragesh Kumar T; Weirich, Paul; Hrachowina, Lukas; Hanefeld, Marc; Bjornsson, Ragnar; Hrodmarsson, Helgi Rafn; Barth, Sven; Fairbrother, D Howard; Huth, Michael

2018-01-01

In the current contribution we present a comprehensive study on the heteronuclear carbonyl complex H2FeRu3(CO)13 covering its low energy electron induced fragmentation in the gas phase through dissociative electron attachment (DEA) and dissociative ionization (DI), its decomposition when adsorbed on a surface under controlled ultrahigh vacuum (UHV) conditions and exposed to irradiation with 500 eV electrons, and its performance in focused electron beam induced deposition (FEBID) at room temperature under HV conditions. The performance of this precursor in FEBID is poor, resulting in maximum metal content of 26 atom % under optimized conditions. Furthermore, the Ru/Fe ratio in the FEBID deposit (≈3.5) is higher than the 3:1 ratio predicted. This is somewhat surprising as in recent FEBID studies on a structurally similar bimetallic precursor, HFeCo3(CO)12, metal contents of about 80 atom % is achievable on a routine basis and the deposits are found to maintain the initial Co/Fe ratio. Low temperature (≈213 K) surface science studies on thin films of H2FeRu3(CO)13 demonstrate that electron stimulated decomposition leads to significant CO desorption (average of 8–9 CO groups per molecule) to form partially decarbonylated intermediates. However, once formed these intermediates are largely unaffected by either further electron irradiation or annealing to room temperature, with a predicted metal content similar to what is observed in FEBID. Furthermore, gas phase experiments indicate formation of Fe(CO)4 from H2FeRu3(CO)13 upon low energy electron interaction. This fragment could desorb at room temperature under high vacuum conditions, which may explain the slight increase in the Ru/Fe ratio of deposits in FEBID. With the combination of gas phase experiments, surface science studies and actual FEBID experiments, we can offer new insights into the low energy electron induced decomposition of this precursor and how this is reflected in the relatively poor performance of H2FeRu3(CO)13 as compared to the structurally similar HFeCo3(CO)12. PMID:29527432

Imaging measurements of atomic iron concentration with laser-induced fluorescence in a nanoparticle synthesis flame reactor

NASA Astrophysics Data System (ADS)

Hecht, C.; Kronemayer, H.; Dreier, T.; Wiggers, H.; Schulz, C.

2009-01-01

The iron-atom concentration distribution as well as the gas-phase temperature was measured via laser-induced fluorescence (LIF) during iron-oxide nanoparticle synthesis in a low-pressure hydrogen/oxygen/argon flame reactor using ironpentacarbonyl (Fe(CO)5) as precursor. Temperature measurements based on multi-line NO-LIF imaging are used to correct for temperature-dependent ground-state populations. The concentration measurement is calibrated based on line-of-sight absorption measurements. The influence of the precursor on the flame is observed at precursor concentrations larger than 70 ppm as the flame front moves closer to the burner surface with increasing Fe(CO)5 concentration.

Nanoscale Transforming Mineral Phases in Fresh Nacre.

PubMed

DeVol, Ross T; Sun, Chang-Yu; Marcus, Matthew A; Coppersmith, Susan N; Myneni, Satish C B; Gilbert, Pupa U P A

2015-10-21

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.

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

DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A.

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO 3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropodmore » shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO 3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.« less

Effect of Fluoride on the Morphology and Electrochemical Property of Co3O4 Nanostructures for Hydrazine Detection

PubMed Central

Gao, Wanlin; Wang, Qiang; Umar, Ahmad

2018-01-01

In this paper, we systematically investigated the influence of fluoride on the morphology and electrochemical property of Co3O4 nanostructures for hydrazine detection. The results showed that with the introduction of NH4F during the synthesis process of Co3O4, both Co(CO3)0.5(OH)·0.11H2O and Co(OH)F precursors would be generated. To understand the influence of F on the morphology and electrochemical property of Co3O4, three Co3O4 nanostructures that were respectively obtained from bare Co(CO3)0.5(OH)·0.11H2O, Co(OH)F and Co(CO3)0.5(OH)·0.11H2O mixtures and bare Co(OH)F were successfully synthesized. The electrochemical tests revealed the sensing performance of prepared Co3O4 nanostructures decreased with the increase in the fluoride contents of precursors. The more that dosages of NH4F were used, the higher crystallinity and smaller specific surface area of Co3O4 was gained. Among these three Co3O4 nanostructures, the Co3O4 that was obtained from bare Co(CO3)0.5(OH)·0.11H2O-based hydrazine sensor displayed the best performances, which exhibited a great sensitivity (32.42 μA·mM−1), a low detection limit (9.7 μΜ), and a wide linear range (0.010–2.380 mM), together with good selectivity, great reproducibility and longtime stability. To the best of our knowledge, it was revealed for the first time that the sensing performance of prepared Co3O4 nanostructures decreased with the increase in fluoride contents of precursors. PMID:29382161

Recent progress in [11 C]carbon dioxide ([11 C]CO2 ) and [11 C]carbon monoxide ([11 C]CO) chemistry.

PubMed

Taddei, Carlotta; Gee, Antony D

2018-03-01

[ 11 C]Carbon dioxide ([ 11 C]CO 2 ) and [ 11 C]carbon monoxide ([ 11 C]CO) are 2 attractive precursors for labelling the carbonyl position (C═O) in a vast range of functionalised molecules (eg, ureas, amides, and carboxylic acids). The development of radiosynthetic methods to produce functionalised 11 C-labelled compounds is required to enhance the radiotracers available for positron emission tomography, molecular, and medical imaging applications. Following a brief summary of secondary 11 C-precursor production and uses, the review focuses on recent progress with direct 11 C-carboxylation routes with [ 11 C]CO 2 and 11 C-carbonylation with [ 11 C]CO. Novel approaches to generate [ 11 C]CO using CO-releasing molecules (CO-RMs), such as silacarboxylic acids and disilanes, applied to radiochemistry are described and compared with standard [ 11 C]CO production methods. These innovative [ 11 C]CO synthesis strategies represent efficient and reliable [ 11 C]CO production processes, enabling the widespread use of [ 11 C]CO chemistry within the wider radiochemistry community. Copyright © 2017 John Wiley & Sons, Ltd.

Preparation and characterization of pitch-based nanoporous carbons for improving CO{sub 2} capture

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

Lee, Seul-Yi; Yoo, Hye-Min; Park, Sang Wook

2014-07-01

Pitch is considered a promising low-cost carbon precursor. However, when pitch is pyrolyzed, it forms polycrystalline graphite, which is non-porous, and therefore, not useful for CO{sub 2} adsorption. In this work, pitch was chemically activated to obtain a large specific surface area and micropore volume. Varying weight ratios of KOH (i.e., 0, 1, 2, and 3) were used as the activating agent. The characteristics of the samples were investigated using scanning electron microscopy (SEM), N{sub 2}/77 K adsorption isotherms, and X-ray diffraction (XRD). The CO{sub 2} adsorption performance was studied by isothermal adsorption/desorption measurements. The results showed that an increasemore » in specific surface areas and total pore volumes of pitch-based nanoporous carbons, resulted in an enhancement of CO{sub 2} adsorption capacity. - Graphical abstract: This is the surface morphologies of pitch precursor and pitch-derived activated carbon (AC-2). - Highlights: • Pitch is considered a promising low-cost carbon precursor. • Specific surface area: 1442 m{sup 2}/g and micropore volume: 0.504 cm{sup 3}/g. • CO{sub 2} adsorption capacity showed 203 mg/g (@ RT/1 bar)« less

Sex pheromone in the moth Heliothis virescens is produced as a mixture of two pools: de novo and via precursor storage in glycerolipids.

PubMed

Foster, Stephen P; Anderson, Karin G; Casas, Jérôme

2017-08-01

Most species of moths use a female-produced volatile sex pheromone, typically produced via de novo fatty acid synthesis in a specialized gland, for communication among mates. While de novo biosynthesis of pheromone (DNP) is rapid, suggesting transient precursor acids, substantial amounts of pheromone precursor (and other) acids are stored, predominantly in triacylglycerols in the pheromone gland. Whether these stored acids are converted to pheromone later or not has been the subject of some debate. Using a tracer/tracee approach, in which we fed female Heliothis virescens U- 13 C-glucose, we were able to distinguish two pools of pheromone, in which precursors were temporally separated (after and before feeding on labeled glucose): DNP synthesized from a mixed tracer/tracee acetyl CoA pool after feeding, and pheromone made from precursor acids primarily synthesized before feeding, which we call recycled precursor fat pheromone (RPP). DNP titer varied from high (during scotophase) to low (photophase) and with presence/absence of pheromone biosynthesis activating neuropeptide (PBAN), in accord with native pheromone titer previously observed. By contrast, RPP was constant throughout the photoperiod and did not change with PBAN presence/absence. The amount of RPP (6.3-10.3 ng/female) was typically much lower than that of DNP, especially during the scotophase (peak DNP, 105 ng/female). We propose an integral role for stored fats in pheromone biosynthesis, in which they are hydrolyzed and re-esterified throughout the photoperiod, with a small proportion of liberated precursor acyl CoAs being converted to pheromone. During the sexually active period, release of PBAN results in increased flux of glucose (from trehalose) and hydrolyzed acids entering the mitochondria, producing acetyl CoA precursor for de novo fat and pheromone biosynthesis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Benchmark Gamma Spectroscopy Measurements of Uranium Hexafluoride in Aluminmum Pipe with a Sodium Iodide Detector

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

March-Leuba, Jose A; Uckan, Taner; Gunning, John E

2010-01-01

The expected increased demand in fuel for nuclear power plants, combined with the fact that a significant portion of the current supply from the blend down of weapons-source material will soon be coming to an end, has led to the need for new sources of enriched uranium for nuclear fuel. As a result, a number of countries have announced plans, or are currently building, gaseous centrifuge enrichment plants (GCEPs) to supply this material. GCEPs have the potential to produce uranium at enrichments above the level necessary for nuclear fuel purposes-enrichments that make the uranium potentially usable for nuclear weapons. Asmore » a result, there is a critical need to monitor these facilities to ensure that nuclear material is not inappropriately enriched or diverted for unintended use. Significant advances have been made in instrument capability since the current International Atomic Energy Agency (IAEA) monitoring methods were developed. In numerous cases, advances have been made in other fields that have the potential, with modest development, to be applied in safeguards applications at enrichment facilities. A particular example of one of these advances is the flow and enrichment monitor (FEMO). (See Gunning, J. E. et al., 'FEMO: A Flow and Enrichment Monitor for Verifying Compliance with International Safeguards Requirements at a Gas Centrifuge Enrichment Facility,' Proceedings of the 8th International Conference on Facility Operations - Safeguards Interface. Portland, Oregon, March 30-April 4th, 2008.) The FEMO is a conceptual instrument capable of continuously measuring, unattended, the enrichment and mass flow of {sup 235}U in pipes at a GCEP, and consequently increase the probability that the potential production of HEU and/or diversion of fissile material will be detected. The FEMO requires no piping penetrations and can be installed on pipes containing the flow of uranium hexafluoride (UF{sub 6}) at a GCEP. This FEMO consists of separate parts, a flow monitor (FM) and an enrichment monitor (EM). Development of the FM is primarily the responsibility of Oak Ridge National Laboratory, and development of the EM is primarily the responsibility of Los Alamos National Laboratory. The FM will measure {sup 235}U mass flow rate by combining information from measuring the UF{sub 6} volumetric flow rate and the {sup 235}U density. The UF{sub 6} flow rate will be measured using characteristics of the process pumps used in product and tail UF{sub 6} header process lines of many GCEPs, and the {sup 235}U density will be measured using commercially available sodium iodide (NaI) gamma ray scintillation detectors. This report describes the calibration of the portion of the FM that measures the {sup 235}U density. Research has been performed to define a methodology and collect data necessary to perform this calibration without the need for plant declarations. The {sup 235}U density detector is a commercially available system (GammaRad made by Amptek, www.amptek.com) that contains the NaI crystal, photomultiplier tube, signal conditioning electronics, and a multichannel analyzer (MCA). Measurements were made with the detector system installed near four {sup 235}U sources. Two of the sources were made of solid uranium, and the other two were in the form of UF{sub 6} gas in aluminum piping. One of the UF{sub 6} gas sources was located at ORNL and the other at LANL. The ORNL source consisted of two pipe sections (schedule 40 aluminum pipe of 4-inch and 8-inch outside diameter) with 5.36% {sup 235}U enrichment, and the LANL source was a 4-inch schedule 40 aluminum pipe with 3.3% {sup 235}U enrichment. The configurations of the detector on these test sources, as well as on long straight pipe configurations expected to exist at GCEPs, were modeled using the computer code MCNP. The results of the MCNP calculations were used to define geometric correction factors between the test source and the GCEP application. Using these geometric correction factors, the experimental 186 keV counts in the test geometry were extrapolated to the expected GCEP geometry, and calibration curves were developed. A unique method to analyze the measurement was also developed that separated the detector spectrum into the five detectable decay gamma rays emitted by {sup 235}U in the 120 to 200 keV energy range. This analysis facilitated the assignment of a consistent value for the detector counts originating from {sup 235}U decays at 186 keV. This value is also more accurate because it includes the counts from gamma energies other than 186 keV, which results in increased counting statistics for the same measurement time. The 186 keV counts expected as a function of pressure and enrichment are presented in the body of this report. The main result of this research is a calibration factor for 4-inch and 8-inch schedule 40 aluminum pipes. For 4-inch pipes, the {sup 235}U density is 0.62 {sup 235}U g/m{sup 3} per each measured 186 keV count.« less

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors

PubMed Central

Thorman, Rachel M; Kumar T. P., Ragesh; Fairbrother, D Howard

2015-01-01

Summary Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe3, Pt(PF3)4, Co(CO)3NO, and W(CO)6. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors. PMID:26665061

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors.

PubMed

Thorman, Rachel M; Kumar T P, Ragesh; Fairbrother, D Howard; Ingólfsson, Oddur

2015-01-01

Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe3, Pt(PF3)4, Co(CO)3NO, and W(CO)6. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors.

The rational design of a Au(I) precursor for focused electron beam induced deposition

PubMed Central

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au–Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au–Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au–Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au. PMID:29354346

The rational design of a Au(I) precursor for focused electron beam induced deposition.

PubMed

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M; van Dorp, Willem F

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe 3 , they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe 3 and MeAuPMe 3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe 3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

Cation non-stoichiometry in pulsed laser deposited Sr{sub 2+y}Fe{sub 1+x}Mo{sub 1-x}O₆ epitaxial films

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

Meyer, T. L.; Woodward, P. M., E-mail: woodward.55@osu.edu; Dixit, M.

2014-07-07

Sr₂FeMoO₆ (SFMO) films were grown on SrTiO₃ (100)- and (111)-oriented substrates via pulsed laser deposition (PLD). In order to study the fundamental characteristics of deposition, films were grown in two different PLD chambers. In chamber I, the best films were grown with a relatively long substrate-to-target distance (89 mm), high substrate temperature (850 °C), and low pressure (50 mTorr) in a 95% Ar/5% H₂ atmosphere. Although X-ray diffraction (XRD) measurements indicate these films are single phase, Rutherford Backscattering (RBS) measurements reveal considerable non-stoichiometry, corresponding to a Sr₂Fe{sub 1–x}Mo{sub 1+x}O₆ composition with x≅0.2–0.3. This level of non-stoichiometry results in inferior magneticmore » properties. In chamber II, the best films were grown with a much shorter substrate-to-target distance (38 mm), lower temperature (680 °C), and higher pressure (225 mTorr). XRD measurements show that the films are single phase, and RBS measurements indicate that they are nearly stoichiometric. The degree of ordering between Fe and Mo was dependent on both the temperature and pressure used during deposition, reaching a maximum order parameter of 85%. The saturation magnetization increases as the Fe/Mo ordering increases, reaching a maximum of 2.4 μ B/f.u. Based on prior studies of bulk samples, one would expect a higher saturation magnetization for this degree of Fe/Mo order. The presence of extra strontium oxide layers in the form of Ruddlesden-Popper intergrowths appears to be responsible for the lower than expected saturation magnetization of these films.« less

Dynamics of tungsten hexacarbonyl, dicobalt octacarbonyl, and their fragments adsorbed on silica surfaces.

PubMed

Muthukumar, Kaliappan; Valentí, Roser; Jeschke, Harald O

2014-05-14

Tungsten and cobalt carbonyls adsorbed on a substrate are typical starting points for the electron beam induced deposition of tungsten or cobalt based metallic nanostructures. We employ first principles molecular dynamics simulations to investigate the dynamics and vibrational spectra of W(CO)6 and W(CO)5 as well as Co2(CO)8 and Co(CO)4 precursor molecules on fully and partially hydroxylated silica surfaces. Such surfaces resemble the initial conditions of electron beam induced growth processes. We find that both W(CO)6 and Co2(CO)8 are stable at room temperature and mobile on a silica surface saturated with hydroxyl groups (OH), moving up to half an Angström per picosecond. In contrast, chemisorbed W(CO)5 or Co(CO)4 ions at room temperature do not change their binding site. These results contribute to gaining fundamental insight into how the molecules behave in the simulated time window of 20 ps and our determined vibrational spectra of all species provide signatures for experimentally distinguishing the form in which precursors cover a substrate.

Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

Simultaneous detection and identification of precursors, degradation and co-products of chemical warfare agents in drinking water by ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry.

PubMed

Tak, Vijay; Purohit, Ajay; Pardasani, Deepak; Goud, D Raghavender; Jain, Rajeev; Dubey, D K

2014-11-28

Environmental markers of chemical warfare agents (CWAs) comprise millions of chemical structures. The simultaneous detection and identification of these environmental markers poses difficulty due to their diverse chemical properties. In this work, by using ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QTOF), a generic analytical method for the detection and identification of wide range of environmental markers of CWAs (including precursors, degradation and co-products of nerve agents and sesqui-mustards) in drinking water, was developed. The chromatographic analysis of 55 environmental markers of CWAs including isomeric and isobaric compounds was accomplished within 20 min, using 1.8 μm particle size column. Subsequent identification of the compounds was achieved by the accurate mass measurement of either protonated molecule [M+H](+) or ammonium adduct [M+NH4](+) and fragment ions. Isomeric and isobaric compounds were distinguished by chromatographic retention time, characteristic fragment ions generated by both in-source collision induced dissociation (CID) and CID in the collision cell by MS/MS experiments. The exact mass measurement errors for all ions were observed less than 3 ppm with internal calibration. The method limits of detection (LODs) and limits of quantification (LOQs) were determined in drinking water and found to be 1-50 ng mL(-1) and 5-125 ng mL(-1), respectively. Applicability of the proposed method was proved by determining the environmental markers of CWAs in aqueous samples provided by Organization for the Prohibition of Chemical Weapons during 34th official proficiency test. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of Precursor Selection on the Photocatalytic Performance of Indium Oxide Nanomaterials for Gas-Phase CO 2 Reduction

DOE PAGES

Hoch, Laura B.; He, Le; Qiao, Qiao; ...

2016-06-01

Nonstoichiometric indium oxide nanoparticles, In 2O 3–x(OH)y, have been shown to function as active photocatalysts for gas-phase CO 2 reduction under simulated solar irradiation. We demonstrate that the choice of starting material has a strong effect on the photocatalytic activity of indium oxide nanoparticles. We also examine three indium oxide materials prepared via the thermal decomposition of either indium(III) hydroxide or indium(III) nitrate and correlate their stability and photocatalytic activity to the number and type of defect present in the material. Furthermore, we use 13CO 2 isotope-tracing experiments to clearly identify the origins of the observed carbon-containing products. Significantly, wemore » find that the oxidizing nature of the precursor anion has a substantial impact on the defect formation within the sample. Our study demonstrates the importance of surface defects in designing an active heterogeneous photocatalyst and provides valuable insight into key parameters for the precursor design, selection, and performance optimization of materials for gas-phase CO 2 reduction.« less

Tic40, a membrane-anchored co-chaperone homolog in the chloroplast protein translocon

PubMed Central

Chou, Ming-Lun; Fitzpatrick, Lynda M.; Tu, Shuh-Long; Budziszewski, Gregory; Potter-Lewis, Sharon; Akita, Mitsuru; Levin, Joshua Z.; Keegstra, Kenneth; Li, Hsou-min

2003-01-01

The function of Tic40 during chloroplast protein import was investigated. Tic40 is an inner envelope membrane protein with a large hydrophilic domain located in the stroma. Arabidopsis null mutants of the atTic40 gene were very pale green and grew slowly but were not seedling lethal. Isolated mutant chloroplasts imported precursor proteins at a lower rate than wild-type chloroplasts. Mutant chloroplasts were normal in allowing binding of precursor proteins. However, during subsequent translocation across the inner membrane, fewer precursors were translocated and more precursors were released from the mutant chloroplasts. Cross-linking experiments demonstrated that Tic40 was part of the translocon complex and functioned at the same stage of import as Tic110 and Hsp93, a member of the Hsp100 family of molecular chaperones. Tertiary structure prediction and immunological studies indicated that the C-terminal portion of Tic40 contains a TPR domain followed by a domain with sequence similarity to co-chaperones Sti1p/Hop and Hip. We propose that Tic40 functions as a co-chaperone in the stromal chaperone complex that facilitates protein translocation across the inner membrane. PMID:12805212

Electron induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5, a potential heterobimetallic precursor for focused electron beam induced deposition (FEBID).

PubMed

Unlu, Ilyas; Spencer, Julie A; Johnson, Kelsea R; Thorman, Rachel M; Ingólfsson, Oddur; McElwee-White, Lisa; Fairbrother, D Howard

2018-03-14

Electron-induced surface reactions of (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 were explored in situ under ultra-high vacuum conditions using X-ray photoelectron spectroscopy and mass spectrometry. The initial step involves electron-stimulated decomposition of adsorbed (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 molecules, accompanied by the desorption of an average of five CO ligands. A comparison with recent gas phase studies suggests that this precursor decomposition step occurs by a dissociative ionization (DI) process. Further electron irradiation decomposes the residual CO groups and (η 5 -C 5 H 5 , Cp) ligand, in the absence of any ligand desorption. The decomposition of CO ligands leads to Mn oxidation, while electron stimulated Cp decomposition causes all of the associated carbon atoms to be retained in the deposit. The lack of any Fe oxidation is ascribed to either the presence of a protective carbonaceous matrix around the Fe atoms created by the decomposition of the Cp ligand, or to desorption of both CO ligands bound to Fe in the initial decomposition step. The selective oxidation of Mn in the absence of any Fe oxidation suggests that the fate of metal atoms in mixed-metal precursors for focused electron beam induced deposition (FEBID) will be sensitive to the nature and number of ligands in the immediate coordination sphere. In related studies, the composition of deposits created from (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 under steady state deposition conditions, representative of those used to create nanostructures in electron microscopes, were measured and found to be qualitatively consistent with predictions from the UHV surface science studies.

Efficient production of hyperpolarized bicarbonate by chemical reaction on a DNP precursor to measure pH.

PubMed

Ghosh, Rajat K; Kadlecek, Stephen J; Pourfathi, Mehrdad; Rizi, Rahim R

2015-11-01

To produce hyperpolarized bicarbonate indirectly via chemical reaction from a hyperpolarized precursor and utilize it for the simultaneous regional measurement of metabolism and pH. Alpha keto carboxylic acids are first hyperpolarized by dissolution dynamic nuclear polarization (DNP). These precursor molecules are rapidly reacted with hydrogen peroxide (H2O2) to decarboxylate the species, resulting in new target molecules. Unreacted H2O2 is removed from the system by reaction with sulfite. Interrogation of the ratio of dissolved carbon dioxide (CO2) to bicarbonate can be used to determine pH. Conversion of hyperpolarized alpha keto acids to bicarbonate and CO2 results in a minimal loss of the spin order. The reaction can be conducted to completion within seconds and preserves the nuclear spin polarization. Through a rapid chemical reaction, we can conserve the nuclear spin order of a DNP precursor to generate multiple hyperpolarized bioprobes otherwise unamenable to polarization. This indirect technique for the production of hyperpolarized agents can be applied to different precursor compounds to generate additional novel probes. © 2014 Wiley Periodicals, Inc.

Spinel type CoFe oxide porous nanosheets as magnetic adsorbents with fast removal ability and facile separation.

PubMed

Ge, X; Gu, C D; Wang, X L; Tu, J P

2015-09-15

Adsorption is often time consuming due to slow diffusion kinetic. Sizing he adsorbent down might help to accelerate adsorption. For CoFe spinel oxide, a magnetically separable adsorbent, the preparation of nanosheets faces many challenges including phase separation, grain growth and difficulty in preparing two-dimensional materials. In this work, we prepared porous CoFe oxide nanosheet with chemical formula of Co2.698Fe0.302O4 through topochemical transformation of a CoFe precursor, which has a layered double hydroxide (LDH) analogue structure and a large interlayer spacing. The LDH precursor was synthesized from a cheap deep eutectic solvent (DES) system. The calcined Co2.698Fe0.302O4 has small grain size (10-20nm), nanosheet morphology, and porous structure, which contribute to a large specific surface area of 79.5m(2)g(-1). The Co2.698Fe0.302O4 nanosheets show fast removal ability and good adsorption capacity for both organic waste (305mgg(-1) in 5min for Congo red) and toxic heavy metal ion (5.27mgg(-1) in 30min for Cr (VI)). Furthermore, the Co2.698Fe0.302O4 can be separated magnetically. Considering the precursor can be prepared through a fast, simple, surfactant-free and high-yield synthetic strategy, this work should have practical significance in fabricating adsorbents. Copyright © 2015 Elsevier Inc. All rights reserved.

A Co₃O₄-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO₂ photoreduction.

PubMed

Wang, Tao; Shi, Li; Tang, Jing; Malgras, Victor; Asahina, Shunsuke; Liu, Guigao; Zhang, Huabin; Meng, Xianguang; Chang, Kun; He, Jianping; Terasaki, Osamu; Yamauchi, Yusuke; Ye, Jinhua

2016-03-28

Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.

Mechanical mixtures of metal oxides and phosphorus pentoxide as novel precursors for the synthesis of transition-metal phosphides.

PubMed

Guo, Lijuan; Zhao, Yu; Yao, Zhiwei

2016-01-21

This study presents a new type of precursor, mechanical mixtures of metal oxides (MOs) and phosphorus pentoxide (P2O5) are used to synthesize Ni2P, Co2P and MoP phosphides by the H2 reduction method. In addition, this is first report of common solid-state P2O5 being used as a P source for the synthesis of metal phosphides. The traditional precursors are usually prepared via a complicated preparation procedure involving dissolution, drying and calcination steps. However, these novel MOs/P2O5 precursors can be obtained only by simple mechanical mixing of the starting materials. Furthermore, unlike the direct transformation from amorphous phases to phosphides, various specific intermediates were involved in the transformation from MOs/P2O5 to phosphides. It is worthy to note that the dispersions of Ni2P, Co2P and MoP obtained from MOs/P2O5 precursors were superior to those of the corresponding phosphides prepared from the abovementioned traditional precursors. It is suggested that the morphology of the as-prepared metal phosphides might be inherited from the corresponding MOs. Based on the results of XRD, XPS, SEM and TEM, the formation pathway of phosphides can be defined as MOs/P2O5 precursors → complex intermediates (metals, metal phosphates and metal oxide-phosphates) → metal phosphides.

Electronic Devices with Strontium Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

structure of the barrier film on an atomic level where the barrier film is comprised of a plurality of contiguous monolayers, while FIG. 7B shows another...another embodiment where the barrier film is comprised of a plurality of contiguous monolayers in which different monolayers thereof are formed of...High Energy Electron 10 Diffraction (RHEED) diagnostic system directed toward the substrate 26. A diffusion barrier precursor compound effusion

Electronic Devices with Composite Atomic Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

structure of the barrier film on an atomic level where the barrier film is comprised of a plurality of contiguous monolayers, while FIG. 7B shows...another embodiment where the barrier film is comprised of a plurality of contiguous monolayers in which different monolayers thereof are formed of...High Energy Electron 10 Diffraction (RHEED) diagnostic system directed toward the substrate 26. A diffusion barrier precursor compound effusion

Nanophosphor composite scintillators comprising a polymer matrix

DOEpatents

Muenchausen, Ross Edward; Mckigney, Edward Allen; Gilbertson, Robert David

2010-11-16

An improved nanophosphor composite comprises surface modified nanophosphor particles in a solid matrix. The nanophosphor particle surface is modified with an organic ligand, or by covalently bonding a polymeric or polymeric precursor material. The surface modified nanophosphor particle is essentially charge neutral, thereby preventing agglomeration of the nanophosphor particles during formation of the composite material. The improved nanophosphor composite may be used in any conventional scintillator application, including in a radiation detector.

Oxygen-free atomic layer deposition of indium sulfide

DOEpatents

Martinson, Alex B.; Hock, Adam S.; McCarthy, Robert; Weimer, Matthew S.

2016-07-05

A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.

Stepwise Splitting Growth and Pseudocapacitive Properties of Hierarchical Three-Dimensional Co3O4 Nanobooks

PubMed Central

Chen, Huilong; Lu, Shuang; Gong, Feilong; Liu, Huanzhen; Li, Feng

2017-01-01

Three-dimensional hierarchical Co3O4 nanobooks have been synthesized successfully on a large scale by calcining orthorhombic Co(CO3)0.5(OH)·0.11H2O precursors with identical morphologies. Based on the influence of reaction time and urea concentration on the nanostructures of the precursors, a stepwise splitting growth mechanism can be proposed to understand the formation of the 3D nanobooks. The 3D Co3O4 nanobooks exhibit excellent pseudocapacitive performances with specific capacitances of 590, 539, 476, 453, and 421 F/g at current densities of 0.5, 1, 2, 4, and 8 A/g, respectively. The devices can retain ca. 97.4% of the original specific capacitances after undergoing charge–discharge cycle tests 1000 times continuously at 4 A/g. PMID:28394297

Stoichiometry for binding and transport by the twin arginine translocation system.

PubMed

Celedon, Jose M; Cline, Kenneth

2012-05-14

Twin arginine translocation (Tat) systems transport large folded proteins across sealed membranes. Tat systems accomplish this feat with three membrane components organized in two complexes. In thylakoid membranes, cpTatC and Hcf106 comprise a large receptor complex containing an estimated eight cpTatC-Hcf106 pairs. Protein transport occurs when Tha4 joins the receptor complex as an oligomer of uncertain size that is thought to form the protein-conducting structure. Here, binding analyses with intact membranes or purified complexes indicate that each receptor complex could bind eight precursor proteins. Kinetic analysis of translocation showed that each precursor-bound site was independently functional for transport, and, with sufficient Tha4, all sites were concurrently active for transport. Tha4 titration determined that ∼26 Tha4 protomers were required for transport of each OE17 (oxygen-evolving complex subunit of 17 kD) precursor protein. Our results suggest that, when fully saturated with precursor proteins and Tha4, the Tat translocase is an ∼2.2-megadalton complex that can individually transport eight precursor proteins or cooperatively transport multimeric precursors.

Biophotolysis systems for hydrogen production

NASA Astrophysics Data System (ADS)

Rao, K. K.; Adams, M. W. W.; Morris, P.; Hall, D. O.; Gisby, P. E.

Model systems containing natural and sythetic catalysts were constructed for the production of H2 from water using visible solar radiation as the energy source. Chloroplast membranes were used for light absorption and photodecomposition of water, ferredoxin, flavodoxin, cytochrome, viologen dyes, 'Jeevanu' particles or synthetic clusters containing Fe-Mo-S centers were used as electron transfer catalysts, and hydrogenase or PtO2 served as the proton activator. We have also investigated the use of aqueous systems with proflavine as the light activator and artificial electron donors for subsequent production of H2 when coupled to electron mediators and hydrogenase (or Pt). The characteristics, relative merits and defects of these systems are discussed.

Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

DOE PAGES

Yen, Hung -Ju; Liang, Po -Wei; Chueh, Chu -Chen; ...

2016-05-25

In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. Here, the resultant large grained perovskite thin film possesses negligible physical (structural) gap between each large grain and are highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different to the thin film prepared from the typical precursor route (MAI + PbI 2).

Supported catalysts using nanoparticles as the support material

DOEpatents

Wong, Michael S.; Wachs, Israel E.; Knowles, William V.

2010-11-02

A process for making a porous catalyst, comprises a) providing an aqueous solution containing a nanoparticle precursor, b) forming a composition containing nanoparticles, c) adding a first catalytic component or precursor thereof and a pore-forming agent to the composition containing nanoparticles and allowing the first catalytic component, the pore-forming agent, and the nanoparticles form an organic-inorganic structure, d) removing water from the organic-inorganic structure; and e) removing the pore-forming agent from the organic-inorganic structure so as to yield a porous catalyst.

Sequence analyses reveal that a TPR-DP module, surrounded by recombinable flanking introns, could be at the origin of eukaryotic Hop and Hip TPR-DP domains and prokaryotic GerD proteins.

PubMed

Hernández Torres, Jorge; Papandreou, Nikolaos; Chomilier, Jacques

2009-05-01

The co-chaperone Hop [heat shock protein (HSP) organising protein] is known to bind both Hsp70 and Hsp90. Hop comprises three repeats of a tetratricopeptide repeat (TPR) domain, each consisting of three TPR motifs. The first and last TPR domains are followed by a domain containing several dipeptide (DP) repeats called the DP domain. These analyses suggest that the hop genes result from successive recombination events of an ancestral TPR-DP module. From a hydrophobic cluster analysis of homologous Hop protein sequences derived from gene families, we can postulate that shifts in the open reading frames are at the origin of the present sequences. Moreover, these shifts can be related to the presence or absence of biological function. We propose to extend the family of Hop co-chaperons into the kingdom of bacteria, as several structurally related genes have been identified by hydrophobic cluster analysis. We also provide evidence of common structural characteristics between hop and hip genes, suggesting a shared precursor of ancestral TPR-DP domains.

Method of manufacturing tin-doped indium oxide nanofibers

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

Ozcan, Soydan; Naskar, Amit K

2017-06-06

A method of making indium tin oxide nanofibers includes the step of mixing indium and tin precursor compounds with a binder polymer to form a nanofiber precursor composition. The nanofiber precursor composition is co-formed with a supporting polymer to form a composite nanofiber having a precursor composition nanofiber completely surrounded by the supporting polymer composition. The supporting polymer composition is removed from the composite nanofiber to expose the precursor composition nanofiber. The precursor composition nanofiber is then heated in the presence of oxygen such as O.sub.2 to form indium tin oxide and to remove the binder polymer to form anmore » indium tin oxide nanofiber. A method of making metal oxide nanofibers is also disclosed.« less

Mitochondrial COQ9 is a lipid-binding protein that associates with COQ7 to enable coenzyme Q biosynthesis

PubMed Central

Lohman, Danielle C.; Forouhar, Farhad; Beebe, Emily T.; Stefely, Matthew S.; Minogue, Catherine E.; Ulbrich, Arne; Stefely, Jonathan A.; Sukumar, Shravan; Luna-Sánchez, Marta; Jochem, Adam; Lew, Scott; Seetharaman, Jayaraman; Xiao, Rong; Wang, Huang; Westphall, Michael S.; Wrobel, Russell L.; Everett, John K.; Mitchell, Julie C.; López, Luis C.; Coon, Joshua J.; Tong, Liang; Pagliarini, David J.

2014-01-01

Coenzyme Q (CoQ) is an isoprenylated quinone that is essential for cellular respiration and is synthesized in mitochondria by the combined action of at least nine proteins (COQ1–9). Although most COQ proteins are known to catalyze modifications to CoQ precursors, the biochemical role of COQ9 remains unclear. Here, we report that a disease-related COQ9 mutation leads to extensive disruption of the CoQ protein biosynthetic complex in a mouse model, and that COQ9 specifically interacts with COQ7 through a series of conserved residues. Toward understanding how COQ9 can perform these functions, we solved the crystal structure of Homo sapiens COQ9 at 2.4 Å. Unexpectedly, our structure reveals that COQ9 has structural homology to the TFR family of bacterial transcriptional regulators, but that it adopts an atypical TFR dimer orientation and is not predicted to bind DNA. Our structure also reveals a lipid-binding site, and mass spectrometry-based analyses of purified COQ9 demonstrate that it associates with multiple lipid species, including CoQ itself. The conserved COQ9 residues necessary for its interaction with COQ7 comprise a surface patch around the lipid-binding site, suggesting that COQ9 might serve to present its bound lipid to COQ7. Collectively, our data define COQ9 as the first, to our knowledge, mammalian TFR structural homolog and suggest that its lipid-binding capacity and association with COQ7 are key features for enabling CoQ biosynthesis. PMID:25339443

Cinnamate:CoA ligase initiates the biosynthesis of a benzoate-derived xanthone phytoalexin in Hypericum calycinum cell cultures.

PubMed

Gaid, Mariam M; Sircar, Debabrata; Müller, Andreas; Beuerle, Till; Liu, Benye; Ernst, Ludger; Hänsch, Robert; Beerhues, Ludger

2012-11-01

Although a number of plant natural products are derived from benzoic acid, the biosynthesis of this structurally simple precursor is poorly understood. Hypericum calycinum cell cultures accumulate a benzoic acid-derived xanthone phytoalexin, hyperxanthone E, in response to elicitor treatment. Using a subtracted complementary DNA (cDNA) library and sequence information about conserved coenzyme A (CoA) ligase motifs, a cDNA encoding cinnamate:CoA ligase (CNL) was isolated. This enzyme channels metabolic flux from the general phenylpropanoid pathway into benzenoid metabolism. HcCNL preferred cinnamic acid as a substrate but failed to activate benzoic acid. Enzyme activity was strictly dependent on the presence of Mg²⁺ and K⁺ at optimum concentrations of 2.5 and 100 mM, respectively. Coordinated increases in the Phe ammonia-lyase and HcCNL transcript levels preceded the accumulation of hyperxanthone E in cell cultures of H. calycinum after the addition of the elicitor. HcCNL contained a carboxyl-terminal type 1 peroxisomal targeting signal made up by the tripeptide Ser-Arg-Leu, which directed an amino-terminal reporter fusion to the peroxisomes. Masking the targeting signal by carboxyl-terminal reporter fusion led to cytoplasmic localization. A phylogenetic tree consisted of two evolutionarily distinct clusters. One cluster was formed by CoA ligases related to benzenoid metabolism, including HcCNL. The other cluster comprised 4-coumarate:CoA ligases from spermatophytes, ferns, and mosses, indicating divergence of the two clades prior to the divergence of the higher plant lineages.

Low temperature stabilization process for production of carbon fiber having structural order

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

Rios, Orlando; McGuire, Michael Alan; More, Karren Leslie

A method for producing a carbon fiber, the method comprising: (i) subjecting a continuous carbon fiber precursor having a polymeric matrix in which strength-enhancing particles are incorporated to a stabilization process during which the carbon fiber precursor is heated to within a temperature range ranging from the glass transition temperature to no less than 20.degree. C. below the glass transition temperature of the polymeric matrix, wherein the maximum temperature employed in the stabilization process is below 400.degree. C., for a processing time within said temperature range of at least 1 hour in the presence of oxygen and in the presencemore » of a magnetic field of at least 1 Tesla, while said carbon fiber precursor is held under an applied axial tension; and (ii) subjecting the stabilized carbon fiber precursor, following step (i), to a carbonization process. The stabilized carbon fiber precursor, resulting carbon fiber, and articles made thereof are also described.« less

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001).

PubMed

Beye, M; Anniyev, T; Coffee, R; Dell'Angela, M; Föhlisch, A; Gladh, J; Katayama, T; Kaya, S; Krupin, O; Møgelhøj, A; Nilsson, A; Nordlund, D; Nørskov, J K; Öberg, H; Ogasawara, H; Pettersson, L G M; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Wolf, M; Wurth, W; Oström, H

2013-05-03

We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.

Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

PubMed Central

2013-01-01

A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

Recent advances in engineering propionyl-CoA metabolism for microbial production of value-added chemicals and biofuels.

PubMed

Srirangan, Kajan; Bruder, Mark; Akawi, Lamees; Miscevic, Dragan; Kilpatrick, Shane; Moo-Young, Murray; Chou, C Perry

2017-09-01

Diminishing fossil fuel reserves and mounting environmental concerns associated with petrochemical manufacturing practices have generated significant interests in developing whole-cell biocatalytic systems for the production of value-added chemicals and biofuels. Although acetyl-CoA is a common natural biogenic precursor for the biosynthesis of numerous metabolites, propionyl-CoA is unpopular and non-native to most organisms. Nevertheless, with its C3-acyl moiety as a discrete building block, propionyl-CoA can serve as another key biogenic precursor to several biological products of industrial importance. As a result, engineering propionyl-CoA metabolism, particularly in genetically tractable hosts with the use of inexpensive feedstocks, has paved an avenue for novel biomanufacturing. Herein, we present a systematic review on manipulation of propionyl-CoA metabolism as well as relevant genetic and metabolic engineering strategies for microbial production of value-added chemicals and biofuels, including odd-chain alcohols and organic acids, bio(co)polymers and polyketides. [Formula: see text].

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

Engineering cytosolic acetyl-coenzyme A supply in Saccharomyces cerevisiae: Pathway stoichiometry, free-energy conservation and redox-cofactor balancing.

PubMed

van Rossum, Harmen M; Kozak, Barbara U; Pronk, Jack T; van Maris, Antonius J A

2016-07-01

Saccharomyces cerevisiae is an important industrial cell factory and an attractive experimental model for evaluating novel metabolic engineering strategies. Many current and potential products of this yeast require acetyl coenzyme A (acetyl-CoA) as a precursor and pathways towards these products are generally expressed in its cytosol. The native S. cerevisiae pathway for production of cytosolic acetyl-CoA consumes 2 ATP equivalents in the acetyl-CoA synthetase reaction. Catabolism of additional sugar substrate, which may be required to generate this ATP, negatively affects product yields. Here, we review alternative pathways that can be engineered into yeast to optimize supply of cytosolic acetyl-CoA as a precursor for product formation. Particular attention is paid to reaction stoichiometry, free-energy conservation and redox-cofactor balancing of alternative pathways for acetyl-CoA synthesis from glucose. A theoretical analysis of maximally attainable yields on glucose of four compounds (n-butanol, citric acid, palmitic acid and farnesene) showed a strong product dependency of the optimal pathway configuration for acetyl-CoA synthesis. Moreover, this analysis showed that combination of different acetyl-CoA production pathways may be required to achieve optimal product yields. This review underlines that an integral analysis of energy coupling and redox-cofactor balancing in precursor-supply and product-formation pathways is crucial for the design of efficient cell factories. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Creation of Rift Valley Fever Viruses with Four-Segmented Genomes Reveals Flexibility in Bunyavirus Genome Packaging

PubMed Central

Oreshkova, Nadia; Moormann, Rob J. M.; Kortekaas, Jeroen

2014-01-01

ABSTRACT Bunyavirus genomes comprise a small (S), a medium (M), and a large (L) RNA segment of negative polarity. Although the untranslated regions have been shown to comprise signals required for transcription, replication, and encapsidation, the mechanisms that drive the packaging of at least one S, M, and L segment into a single virion to generate infectious virus are largely unknown. One of the most important members of the Bunyaviridae family that causes devastating disease in ruminants and occasionally humans is the Rift Valley fever virus (RVFV). We studied the flexibility of RVFV genome packaging by splitting the glycoprotein precursor gene, encoding the (NSm)GnGc polyprotein, into two individual genes encoding either (NSm)Gn or Gc. Using reverse genetics, six viruses with a segmented glycoprotein precursor gene were rescued, varying from a virus comprising two S-type segments in the absence of an M-type segment to a virus consisting of four segments (RVFV-4s), of which three are M-type. Despite that all virus variants were able to grow in mammalian cell lines, they were unable to spread efficiently in cells of mosquito origin. Moreover, in vivo studies demonstrated that RVFV-4s is unable to cause disseminated infection and disease in mice, even in the presence of the main virulence factor NSs, but induced a protective immune response against a lethal challenge with wild-type virus. In summary, splitting bunyavirus glycoprotein precursor genes provides new opportunities to study bunyavirus genome packaging and offers new methods to develop next-generation live-attenuated bunyavirus vaccines. IMPORTANCE Rift Valley fever virus (RVFV) causes devastating disease in ruminants and occasionally humans. Virions capable of productive infection comprise at least one copy of the small (S), medium (M), and large (L) RNA genome segments. The M segment encodes a glycoprotein precursor (GPC) protein that is cotranslationally cleaved into Gn and Gc, which are required for virus entry and fusion. We studied the flexibility of RVFV genome packaging and developed experimental live-attenuated vaccines by applying a unique strategy based on the splitting of the GnGc open reading frame. Several RVFV variants, varying from viruses comprising two S-type segments to viruses consisting of four segments (RVFV-4s), of which three are M-type, could be rescued and were shown to induce a rapid protective immune response. Altogether, the segmentation of bunyavirus GPCs provides a new method for studying bunyavirus genome packaging and facilitates the development of novel live-attenuated bunyavirus vaccines. PMID:25008937

Creation of Rift Valley fever viruses with four-segmented genomes reveals flexibility in bunyavirus genome packaging.

PubMed

Wichgers Schreur, Paul J; Oreshkova, Nadia; Moormann, Rob J M; Kortekaas, Jeroen

2014-09-01

Bunyavirus genomes comprise a small (S), a medium (M), and a large (L) RNA segment of negative polarity. Although the untranslated regions have been shown to comprise signals required for transcription, replication, and encapsidation, the mechanisms that drive the packaging of at least one S, M, and L segment into a single virion to generate infectious virus are largely unknown. One of the most important members of the Bunyaviridae family that causes devastating disease in ruminants and occasionally humans is the Rift Valley fever virus (RVFV). We studied the flexibility of RVFV genome packaging by splitting the glycoprotein precursor gene, encoding the (NSm)GnGc polyprotein, into two individual genes encoding either (NSm)Gn or Gc. Using reverse genetics, six viruses with a segmented glycoprotein precursor gene were rescued, varying from a virus comprising two S-type segments in the absence of an M-type segment to a virus consisting of four segments (RVFV-4s), of which three are M-type. Despite that all virus variants were able to grow in mammalian cell lines, they were unable to spread efficiently in cells of mosquito origin. Moreover, in vivo studies demonstrated that RVFV-4s is unable to cause disseminated infection and disease in mice, even in the presence of the main virulence factor NSs, but induced a protective immune response against a lethal challenge with wild-type virus. In summary, splitting bunyavirus glycoprotein precursor genes provides new opportunities to study bunyavirus genome packaging and offers new methods to develop next-generation live-attenuated bunyavirus vaccines. Rift Valley fever virus (RVFV) causes devastating disease in ruminants and occasionally humans. Virions capable of productive infection comprise at least one copy of the small (S), medium (M), and large (L) RNA genome segments. The M segment encodes a glycoprotein precursor (GPC) protein that is cotranslationally cleaved into Gn and Gc, which are required for virus entry and fusion. We studied the flexibility of RVFV genome packaging and developed experimental live-attenuated vaccines by applying a unique strategy based on the splitting of the GnGc open reading frame. Several RVFV variants, varying from viruses comprising two S-type segments to viruses consisting of four segments (RVFV-4s), of which three are M-type, could be rescued and were shown to induce a rapid protective immune response. Altogether, the segmentation of bunyavirus GPCs provides a new method for studying bunyavirus genome packaging and facilitates the development of novel live-attenuated bunyavirus vaccines. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

A model for regulation of mammalian ribosomal DNA transcription. Co-ordination of initiation and termination.

PubMed Central

Nashimoto, M; Mishima, Y

1988-01-01

Based on recent experimental data about transcription initiation and termination, a model for regulation of mammalian ribosomal DNA transcription is developed using a simple kinetic scheme. In this model, the existence of the transition pathway from the terminator to the promoter increases the rate of ribosomal RNA precursor synthesis. In addition to this 'non-transcribed spacer' traverse of RNA polymerase I, the co-ordination of initiation and termination allows a rapid on/off switch transition from the minimum to the maximum rate of ribosomal RNA precursor synthesis. Furthermore, taking account of the participation of two factors in the termination event, we propose a plausible molecular mechanism for the co-ordination of initiation and termination. This co-ordination is emphasized by repetition of the terminator unit. PMID:3223915

Nanoscale Transforming Mineral Phases in Fresh Nacre

DOE PAGES

DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A.; ...

2015-09-24

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO 3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropodmore » shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO 3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.« less

The influences of microwave irradiation and polyol precursor pH on Cu/AC catalyst and its CO oxidation performance

NASA Astrophysics Data System (ADS)

Chuang, Kui-Hao; Shih, Kaimin; Wey, Ming-Yen

2012-10-01

This study evaluated the effects of microwave irradiation parameters and the pH of the polyol precursor on the morphological features and catalytic performances of Cu/activated carbon (AC) catalysts. Experimental results of carbon monoxide (CO) oxidation indicated that the highest catalytic activity is achieved when the Cu/AC catalyst is prepared with microwave irradiation at 700 W for 60 s. Scanning electron microscopy revealed the presence of beneficial small copper aciculae on the Cu/AC catalyst under such a microwave irradiation scheme. Further investigation of operational parameters found that the performance of Cu/AC catalysts is enhanced by adopting a pH = 12 polyol precursor solution. With the observation that small cube copper ( 16 nm) aggregates form when a pH = 12 polyol precursor solution is used, this study also demonstrated the importance of controlling the morphology of metal nanoparticles on Cu/AC catalysts when using the microwave-assisted polyol method.

A Co3O4-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO2 photoreduction

NASA Astrophysics Data System (ADS)

Wang, Tao; Shi, Li; Tang, Jing; Malgras, Victor; Asahina, Shunsuke; Liu, Guigao; Zhang, Huabin; Meng, Xianguang; Chang, Kun; He, Jianping; Terasaki, Osamu; Yamauchi, Yusuke; Ye, Jinhua

2016-03-01

Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO. Electronic supplementary information (ESI) available: Additional TG and DTA curves, XRD patterns, SEM images, TEM images, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and GC-MS spectra of the samples. See DOI: 10.1039/c5nr08747c

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Electronic Devices with Barium Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

structure of the barrier film on an atomic level 15 where the barrier .film is comprised of a plurality of contiguous monolayers, while FIG. 7B...yet another embodiment where the barrier film is comprised of a plurality of 20 contiguous monolayers in which different monolayers thereof are...barrier precursor compound effusion cell, for example a barium fluoride, strontium fluoride or the like effusion cell, is provided at 32, and has a

A Co-Precursor Approach Coupled with a Supercritical Modification Method for Constructing Highly Transparent and Superhydrophobic Polymethylsilsesquioxane Aerogels.

PubMed

Lei, Chaoshuai; Li, Junning; Sun, Chencheng; Yang, Hailong; Xia, Tao; Hu, Zijun; Zhang, Yue

2018-03-30

Polymethylsilsesquioxane (PMSQ) aerogels obtained from methyltrimethoxysilane (MTMS) are well-known high-performance porous materials. Highly transparent and hydrophobic PMSQ aerogel would play an important role in transparent vacuum insulation panels. Herein, the co-precursor approach and supercritical modification method were developed to prepare the PMSQ aerogels with high transparency and superhydrophobicity. Firstly, benefiting from the introduction of tetramethoxysilane (TMOS) in the precursor, the pore structure became more uniform and the particle size was decreased. As the TMOS content increased, the light transmittance increased gradually from 54.0% to 81.2%, whereas the contact angle of water droplet decreased from 141° to 99.9°, ascribed to the increase of hydroxyl groups on the skeleton surface. Hence, the supercritical modification method utilizing hexamethyldisilazane was also introduced to enhance the hydrophobic methyl groups on the aerogel's surface. As a result, the obtained aerogels revealed superhydrophobicity with a contact angle of 155°. Meanwhile, the developed surface modification method did not lead to any significant changes in the pore structure resulting in the superhydrophobic aerogel with a high transparency of 77.2%. The proposed co-precursor approach and supercritical modification method provide a new horizon in the fabrication of highly transparent and superhydrophobic PMSQ aerogels.

Directed Synthesis of Nanoporous Carbons from Task-Specific Ionic Liquid Precursors for the Adsorption of CO 2

DOE PAGES

Mahurin, Shannon M.; Fulvio, Pasquale F.; Hillesheim, Patrick C.; ...

2014-07-31

Postcombustion CO 2 capture has become a key component of greenhouse-gas reduction as anthropogenic emissions continue to impact the environment. In this paper, we report a one-step synthesis of porous carbon materials using a series of task-specific ionic liquids for the adsorption of CO 2. By varying the structure of the ionic liquid precursor, we were able to control pore architecture and surface functional groups of the carbon materials in this one-step synthesis process leading to adsorbents with high CO 2 sorption capacities (up to 4.067 mmol g -1) at 0 °C and 1 bar. Finally, added nitrogen functional groupsmore » led to high CO 2/N 2 adsorption-selectivity values ranging from 20 to 37 whereas simultaneously the interaction energy was enhanced relative to carbon materials with no added nitrogen.« less

Preparation, ferromagnetic and photocatalytic performance of NiO and hollow Co{sub 3}O{sub 4} fibers through centrifugal-spinning technique

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

Feng, Cong; Lin, Xuejun; Wang, Xinqiang, E-mail: xqwang@sdu.edu.cn

Highlights: • NiO and hollow Co{sub 3}O{sub 4} fibers with the diameter of about 10 μm were prepared through centrifugal-spinning technique. • The evolution mechanism from precursor to crystalline fibers was explored. • Both NiO and hollow Co{sub 3}O{sub 4} fibers show ferromagnetism. • The NiO fibers exhibit good photocatalytic performance. - Abstract: Both NiO and hollow Co{sub 3}O{sub 4} fibers with the diameter of about 10 μm have been successfully prepared through spinning high viscous sols into precursor fibers and followed calcination process. The evolution process from precursor to crystalline fibers and the microstructures of the obtained fibers weremore » characterized by TG-DSC, FT-IR, XRD, HRTEM, SEM and the like. The method is facile and cost-effective for mass production of fibers and the obtained fibers are pure phase with high crystallinity. Their magnetic properties were investigated, showing that both the fibers are ferromagnetic. Meanwhile, the NiO fibers exhibit good photocatalytic performance for the removal of Congo red from water under UV light irradiation.« less

Preparation and electrochemical properties of NiO-Co3O4 composite as electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Wang, X. W.; Zheng, D. L.; Yang, P. Z.; Wang, X. E.; Zhu, Q. Q.; Ma, P. F.; Sun, L. Y.

2017-01-01

The precursor of NiO-Co3O4 composites was synthesized via a simple hydrothermal process. After that, the precursor was calcined at 300 °C for 3 h to obtain the composite powders. The powders calcined at 300 °C showed amorphous, and the powders calcined at 400 °C and 500 °C for comparison showed the composite phase of NiO and Co3O4. The composite products showed a microstructure of micro-spheres. For the samples calcined at 300 °C for 3 h, the specific capacitance reached 801 F g-1 at a current density of 1 A g-1.

Plasma enhanced chemical vapor deposition (PECVD) method of forming vanadium oxide films and vanadium oxide thin-films prepared thereby

DOEpatents

Zhang, Ji-Guang; Tracy, C. Edwin; Benson, David K.; Turner, John A.; Liu, Ping

2000-01-01

A method is disclosed of forming a vanadium oxide film on a substrate utilizing plasma enhanced chemical vapor deposition. The method includes positioning a substrate within a plasma reaction chamber and then forming a precursor gas comprised of a vanadium-containing chloride gas in an inert carrier gas. This precursor gas is then mixed with selected amounts of hydrogen and oxygen and directed into the reaction chamber. The amounts of precursor gas, oxygen and hydrogen are selected to optimize the final properties of the vanadium oxide film An rf plasma is generated within the reaction chamber to chemically react the precursor gas with the hydrogen and the oxygen to cause deposition of a vanadium oxide film on the substrate while the chamber deposition pressure is maintained at about one torr or less. Finally, the byproduct gases are removed from the plasma reaction chamber.

Carbon Dioxide (CO2) Adsorption by Activated Carbon Functionalized with Deep Eutectic Solvent (DES)

NASA Astrophysics Data System (ADS)

Zulkurnai, N. Z.; Ali, U. F. Md.; Ibrahim, N.; Manan, N. S. Abdul

2017-06-01

In recent years, carbon dioxide (CO2) emission has become a major concern as the amount of the emitted gas significantly increases annually. Consequently, this phenomenon contributes to global warming. Several CO2 capture methods, including chemical adsorption by activated carbon, have been proposed. In this study, activated carbon was prepared from sea mango (Cerbera odollam), which was functionalized with deep eutectic solvent (DES) composed of choline chloride and glycerol to increase the efficiency of CO2 capture. The samples underwent pre-carbonization and carbonization processes at 200 °C and 500 °C, respectively, with nitrogen gas and flowing several gases, namely, CO2 and steam, and then followed by impregnation with 50 phosphoric acid (H3PO4) at 1:2 precursor-to-activant ratio. The prepared activated carbon was impregnated with DES at 1:2 precursor-to-activant ratio. The optimum CO2 adsorption capacity of the activated carbon was obtained by using CO2 gas treatment method (9.851 mgCO2/gsol), followed by the absence of gases (9.685 mgCO2/gsol), steam (9.636 mgCO2/gsol), and N2 (9.536 mgCO2/gsol).

Processing of alkaline phosphatase precursor to the mature enzyme by an Escherichia coli inner membrane preparation.

PubMed Central

Chang, C N; Inouye, H; Model, P; Beckwith, J

1980-01-01

An inner membrane preparation co-translationally cleaved both the alkaline phosphatase and bacteriophage f1 coat protein precursors to the mature proteins. Post-translational outer membrane proteolysis of pre-alkaline phosphatase generated a protein smaller than the authentic monomer. Images PMID:6991486

Glutamine: precursor or nitrogen donor for citrulline synthesis?

USDA-ARS?s Scientific Manuscript database

Glutamine (Gln) is considered the main precursor for citrulline (Cit) synthesis, but no attempts have been made to differentiate the contribution of Gln carbon (Gln-C) skeleton vs. the nonspecific contribution through NH3 and CO2. To study the contribution of dietary Gln-N to the synthesis of Cit, t...

CO.sub.2 laser

DOEpatents

Rink, John P.

1977-01-01

The disclosure relates to a pulsed gas laser comprising an optical resonant cavity, a CO.sub.2 lasing medium, structure for containing the CO.sub.2 lasing medium within the optical cavity and a device for causing a population inversion in the lasing medium, with a novel improvement comprising structure for causing a laser pulse comprising a wavelength in the near 14 .mu.m and near 16 .mu.m range. The structure for cooling the CO.sub.2 lasing medium to less than about -40.degree. C as well is a structure for pumping the maximum inversion of CO.sub.2 molecules within the lasing medium by minimizing the population in the 010 level.

De novo biosynthesis of sterols and fatty acids in the Trypanosoma brucei procyclic form: Carbon source preferences and metabolic flux redistributions

PubMed Central

Bouyssou, Guillaume; Allmann, Stefan; Kiema, Tiila-Riikka; Biran, Marc; Plazolles, Nicolas; Dittrich-Domergue, Franziska; Crouzols, Aline; Wierenga, Rik K.; Rotureau, Brice; Moreau, Patrick

2018-01-01

De novo biosynthesis of lipids is essential for Trypanosoma brucei, a protist responsible for the sleeping sickness. Here, we demonstrate that the ketogenic carbon sources, threonine, acetate and glucose, are precursors for both fatty acid and sterol synthesis, while leucine only contributes to sterol production in the tsetse fly midgut stage of the parasite. Degradation of these carbon sources into lipids was investigated using a combination of reverse genetics and analysis of radio-labelled precursors incorporation into lipids. For instance, (i) deletion of the gene encoding isovaleryl-CoA dehydrogenase, involved in the leucine degradation pathway, abolished leucine incorporation into sterols, and (ii) RNAi-mediated down-regulation of the SCP2-thiolase gene expression abolished incorporation of the three ketogenic carbon sources into sterols. The SCP2-thiolase is part of a unidirectional two-step bridge between the fatty acid precursor, acetyl-CoA, and the precursor of the mevalonate pathway leading to sterol biosynthesis, 3-hydroxy-3-methylglutaryl-CoA. Metabolic flux through this bridge is increased either in the isovaleryl-CoA dehydrogenase null mutant or when the degradation of the ketogenic carbon sources is affected. We also observed a preference for fatty acids synthesis from ketogenic carbon sources, since blocking acetyl-CoA production from both glucose and threonine abolished acetate incorporation into sterols, while incorporation of acetate into fatty acids was increased. Interestingly, the growth of the isovaleryl-CoA dehydrogenase null mutant, but not that of the parental cells, is interrupted in the absence of ketogenic carbon sources, including lipids, which demonstrates the essential role of the mevalonate pathway. We concluded that procyclic trypanosomes have a strong preference for fatty acid versus sterol biosynthesis from ketogenic carbon sources, and as a consequence, that leucine is likely to be the main source, if not the only one, used by trypanosomes in the infected insect vector digestive tract to feed the mevalonate pathway. PMID:29813135

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Method for production of carbon nanofiber mat or carbon paper

DOEpatents

Naskar, Amit K.

2015-08-04

Method for the preparation of a non-woven mat or paper made of carbon fibers, the method comprising carbonizing a non-woven mat or paper preform (precursor) comprised of a plurality of bonded sulfonated polyolefin fibers to produce said non-woven mat or paper made of carbon fibers. The preforms and resulting non-woven mat or paper made of carbon fiber, as well as articles and devices containing them, and methods for their use, are also described.

Process for forming shaped group III-V semiconductor nanocrystals, and product formed using process

DOEpatents

Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

2001-01-01

A process for the formation of shaped Group III-V semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process

DOEpatents

Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

2001-01-01

A process for the formation of shaped Group II-VI semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

Formation of CuAlO2 Film by Ultrasonic Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Iping, S.; Lockman, Zainovia; Hutagalung, S. D.; Kamsul, A.; Matsuda, Atsunori

2011-10-01

Smooth, crack free and homogenous CuAlO2 film was produced by chemical solution deposition process via spray pyrolysis technique on a cleaned Si substrate. The precursor solution used was comprised of a mixture of 45.87 mmol Cu(NO3)2.3H2O and 90 mmol Al(NO3)3.9H2O at ratio of Cu:Al = 1.2:1. The precursor solution was placed in a mist chamber and was atomized by a nebulizer to produce precursor mist. The precursor mist was then carried out by Ar gas and was sprayed onto a heated Si. Two main parameters were studied: the distance between the nozzle of the precursor mist chamber and the Si and the temperature of the Si substrate. It appears that from the XRD data, CuAlO2 can be detected for samples prepared by spraying the precursor mist at temperature of > 550 °C with distance between the nozzle and the substrate of 3cm. Reaction of the Cu and Al ions in the mist near the substrate may have promoted the crystallisation of CuAlO2.

Hydrothermal synthesis of bismuth germanium oxide

DOEpatents

Boyle, Timothy J.

2016-12-13

A method for the hydrothermal synthesis of bismuth germanium oxide comprises dissolving a bismuth precursor (e.g., bismuth nitrate pentahydrate) and a germanium precursor (e.g., germanium dioxide) in water and heating the aqueous solution to an elevated reaction temperature for a length of time sufficient to produce the eulytite phase of bismuth germanium oxide (E-BGO) with high yield. The E-BGO produced can be used as a scintillator material. For example, the air stability and radioluminescence response suggest that the E-BGO can be employed for medical applications.

Preparation, Structural Characterization and Magnetic Properties of La-SUBSTITUTED co Ferrites via a Modified Citrate Precursor Route

NASA Astrophysics Data System (ADS)

Ai, Lunhong; Jiang, Jing

CoLaxFe2-xO4 (x = 0.00, 0.05 and 0.1) nanoparticles were prepared simply by a modified citrate precursor route. Effects of La-substituting level on the their magnetic properties were investigated on the basis of the structural analysis. The thermal evolution of the precursor, as well as the microstructure of as-prepared products were studied by means of a thermogravimetric analyzer (TGA), X-ray diffractometer (XRD) and Fourier transform infrared (FTIR) spectrometer. The magnetic properties of the as-prepared samples were measured using a vibrating sample magnetometer (VSM). It was found that the magnetic properties were dependent on many factors such as La-substituting level, particle size and microstructure. The observed saturation magnetization decreased with increasing La content, whereas coercivity exhibited reverse behavior.

Production of MHD fluid

DOEpatents

Lacey, James J.; Kurtzrock, Roy C.; Bienstock, Daniel

1976-08-24

A hot gaseous fluid of low ash content, suitable for use in open-cycle MHD (magnetohydrodynamic) power generation, is produced by means of a three-stage process comprising (1) partial combustion of a fossil fuel to produce a hot gaseous product comprising CO.sub.2 CO, and H.sub.2 O, (2) reformation of the gaseous product from stage (1) by means of a fluidized char bed, whereby CO.sub.2 and H.sub.2 O are converted to CO and H.sub.2, and (3) combustion of CO and H.sub.2 from stage (2) to produce a low ash-content fluid (flue gas) comprising CO.sub.2 and H.sub.2 O and having a temperature of about 4000.degree. to 5000.degree.F.

Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals.

PubMed

Phillips, Katherine R; Shirman, Tanya; Shirman, Elijah; Shneidman, Anna V; Kay, Theresa M; Aizenberg, Joanna

2018-05-01

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self-assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine-tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self-assembly and minimize crack formation. Co-assembly of templating colloidal particles together with a sol-gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high-quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large-area (mm 2 ) crack-free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of making organic light emitting devices

DOEpatents

Shiang, Joseph John [Niskayuna, NY; Janora, Kevin Henry [Schenectady, NY; Parthasarathy, Gautam [Saratoga Springs, NY; Cella, James Anthony [Clifton Park, NY; Chichak, Kelly Scott [Clifton Park, NY

2011-03-22

The present invention provides a method for the preparation of organic light-emitting devices comprising a bilayer structure made by forming a first film layer comprising an electroactive material and an INP precursor material, and exposing the first film layer to a radiation source under an inert atmosphere to generate an interpenetrating network polymer composition comprising the electroactive material. At least one additional layer is disposed on the reacted first film layer to complete the bilayer structure. The bilayer structure is comprised within an organic light-emitting device comprising standard features such as electrodes and optionally one or more additional layers serving as a bipolar emission layer, a hole injection layer, an electron injection layer, an electron transport layer, a hole transport layer, exciton-hole transporting layer, exciton-electron transporting layer, a hole transporting emission layer, or an electron transporting emission layer.

Unusual CoS2 ellipsoids with anisotropic tube-like cavities and their application in supercapacitors.

PubMed

Zhang, Lei; Wu, Hao Bin; Lou, Xiong Wen

2012-07-14

Unusual CoS(2) ellipsoids with anisotropic tube-like cavities have been synthesized from the simultaneous thermal decomposition and sulfidation of a preformed cobalt carbonate precursor. The as-prepared CoS(2) ellipsoids show interesting supercapacitive properties with high capacitance and good cycling performance.

The effects of preparation conditions for a BaNbO2 N photocatalyst on its physical properties.

PubMed

Hisatomi, Takashi; Katayama, Chisato; Teramura, Kentaro; Takata, Tsuyoshi; Moriya, Yosuke; Minegishi, Tsutomu; Katayama, Masao; Nishiyama, Hiroshi; Yamada, Taro; Domen, Kazunari

2014-07-01

BaNbO2 N is a semiconductor photocatalyst active for water oxidation under visible-light irradiation up to λ=740 nm. It is important to understand the nitridation processes of precursor materials to form BaNbO2 N to tune the physical properties and improve the photocatalytic activity. Comprehensive experiments and analyses of temperatures, durations, ammonia flow rates, and barium/niobium ratios in the precursor during the nitridation process reveals that faster ammonia flow rates and higher barium/niobium ratios in the precursors help to suppress reduction of pentavalent niobium ions in the nitridation products and that the use of a precursor prepared by a soft-chemistry route allows the production of BaNbO2 N at lower temperatures in shorter times than the use of physical mixtures of BaCO3 and Nb2 O5 because the niobium species is dispersed among the barium species. BaNbO2 N prepared by the soft-chemistry route exhibits comparatively higher activity than that prepared from physical mixtures of BaCO3 and Nb2 O5 , probably because of lower nitridation temperatures, which suppress excessive dissociation of ammonia, and thereby reduce pentavalent niobium ions, and intimate interaction of niobium and barium sources, which lowers the densities of mid-gap states associated with defects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and optical properties of Mg-Al layered double hydroxides precursor powders

NASA Astrophysics Data System (ADS)

Lin, Chia-Hsuan; Chu, Hsueh-Liang; Hwang, Weng-Sing; Wang, Moo-Chin; Ko, Horng-Huey

2017-12-01

The synthesis and optical properties of Mg-Al layered double hydroxide (LDH) precursor powders were investigated using X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution TEM (HRTEM), UV-transmission spectrometer, and fluorescence spectrophotometer. The FT-IR results show that the intense absorption at around 1363-1377 cm-1 can be assigned to the antisymmetric ν3 mode of interlayer carbonate anions because the LDH phase contains some CO32-. The XRD results show that all of the Mg-Al LDH precursor powders contain only a single phase of [Mg0.833Al0.167(OH)2](CO3)0.083.(H2O)0.75 but have broad and weak intensities of peaks. All of Mg-Al LDHs precursor powders before calcination have the same photoluminescence (PL) spectra. Moreover, these spectra were excited at λex = 235 nm, and the broad emission band was in the range 325-650 nm. In the range, there were relatively strong intensity at around 360, 407 and 510 nm, respectively.

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE PAGES

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia; ...

2017-10-31

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

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

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

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

Whittaker, Michael L.; Joester, Derk

2017-04-28

Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca0.5Ba0.5CO3) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca1- x Ba x CO3·1.2H2O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sitesmore » that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.« less

Engineering of living cells for the expression of holo-phycobiliprotein-based constructs

DOEpatents

Glazer, Alexander N.; Tooley, Aaron J.; Cai, Yuping

2004-05-25

Recombinant cells which express a fluorescent holo-phycobiliprotein fusion protein and methods of use are described. The cells comprises a bilin, a recombinant bilin reductase, an apo-phycobiliprotein fusion protein precursor of the fusion protein comprising a corresponding apo-phycobiliprotein domain, and a recombinant phycobiliprotein domain-bilin lyase, which components react to form the holo-phycobiliprotein fusion protein. Also described are holo-phycobiliprotein based transcription reporter cells and assays, which cells conditionally express a heterologous-to-the-cell, fluorescent, first holo-phycobiliprotein domain.

Preparation of metallic Pd nanoparticles using supercritical CO2 deposition: An efficient catalyst for Suzuki cross-coupling reaction

NASA Astrophysics Data System (ADS)

Tezcan, Burcu; Ulusal, Fatma; Egitmen, Asım; Guzel, Bilgehan

2018-05-01

Ligand-free palladium nanoparticles supported on multi-walled carbon nanotubes (Pd/MWCNT) were prepared by the supercritical carbon dioxide (scCO2) deposition method using a novel scCO2-soluble Pd organometallic complex as a precursor. The precursor with the perfluoroalkyl chain group was synthesized and identified by microanalytic methods. The deposition was carried out at the temperature of 363.15 K and pressure of 27.6 MPa CO2. The prepared metallic nanoparticles were obtained with an average size of 2 nm. Pd/MWCNT was utilized as a heterogeneous catalyst in Suzuki cross-coupling reaction. The nanocatalyst was found very effective in Suzuki reaction and it could also be recovered easily from the reaction media and reused over several cycles without significant loss of catalytic activity under mild conditions. [Figure not available: see fulltext.

Chemical vapor deposition of Mo thin films from Mo(CO){sub 6}

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

Sharma, P.; Bond, J.; Westmore, T.

1995-12-01

Low levels of carbon and/or oxygen contamination in metallic thin films significantly alter the physical and chemical properties of these films often rendering them useless for any commercial applications. These impurities are often observed in films grown by a technique called metallorganic chemical vapor deposition (MOCVD). MOCVD films are grown by heating a substrate in the presence of a metallorganic precursor. We wish to identify the source(s) of contamination in films produced from the Group VIB metal hexacarbonyls, M(CO){sub 6}. Towards attaining this goal we have initiated studies on the elemental composition of thin films deposited by MOCVD using Mo(CO){submore » 6} as the precursor. The results obtained so far indicate that the level of contamination of the films partially depends on the deposition temperature. Our results will be compared to published work on films deposited by laser assisted CVD from Mo(CO){sub 6}.« less

SOA YIELDS AND ORGANIC PRODUCT DISTRIBUTION FROM NATURAL HYDROCARBON/NOX IRRADIATIONS

EPA Science Inventory

Secondary organic aerosol (SOA) typically comprises one-quarter to one-third of the ambient aerosol mass in summertime urban atmospheres. In tropospheric environments, the main precursors of SOA come from aromatic and natural hydrocarbons. Recent work by various investigators...

ZnO-based regenerable sulfur sorbents for fluid-bed/transport reactor applications

DOEpatents

Slimane, Rachid B.; Abbasian, Javad; Williams, Brett E.

2004-09-21

A method for producing regenerable sulfur sorbents in which a support material precursor is mixed with isopropanol and a first portion of deionized water at an elevated temperature to form a sol mixture. A metal oxide precursor comprising a metal suitable for use as a sulfur sorbent is dissolved in a second portion of deionized water, forming a metal salt solution. The metal salt solution and the sol mixture are mixed with a sol peptizing agent while heating and stirring, resulting in formation of a peptized sol mixture. The metal oxide precursor is dispersed substantially throughout the peptized sol mixture, which is then dried, forming a dry peptized sol mixture. The dry peptized sol mixture is then calcined and the resulting calcined material is then converted to particles.

Amphiphilic polypeptides as a bifunctional template in the mineralization of calcium carbonate at the air/water interface.

PubMed

Cao, Heng; Lin, Guoqiang; Yao, Jinrong; Shao, Zhengzhong

2013-05-01

A well-defined amphiphilic polypeptide, poly(glutamic acid)22 -block-poly(alanine)8 (PGlu22 -b-PAla8 ), which plays the roles of both soluble (functional) additive and insoluble (structural) matrix, is employed to mediate the mineralization of CaCO3 at the air/water interface. X-ray diffraction (XRD) and Raman spectroscopy, for example, show that the polymorph of CaCO3 particles obtained is calcite. The observations from SEM and TEM suggest that PGlu22 -b-PAla8 initiates the amorphous precursor phase and heterogeneous nucleation of CaCO3 at the air/water interface, while temporarily stabilizes the gelatinous precursors as a process-directing agent; nevertheless, the initial concentration of Ca(2+) controls the procedure of crystallization and the final morphology of CaCO3 particles. Such "bifunctional" amphiphilic-polypeptide-regulated mineralization at the air/water interface may be applied to the synthesis of many kinds of symmetrical inorganic/organic hybrids. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequence Effects in Conjugated Donor-Acceptor Trimers and Polymers.

PubMed

Zhang, Shaopeng; Hutchison, Geoffrey R; Meyer, Tara Y

2016-06-01

To investigate the sequence effect on donor-acceptor conjugated oligomers and polymers, the trimeric isomers PBP and BPP, comprising dialkoxy phenylene vinylene (P), benzothiadiazole vinylene (B), and alkyl endgroups with terminal olefins, are synthesized. Sequence effects are evident in the optical/electrochemical properties and thermal properties. Absorption maxima for PBP and BPP differ by 41 nm and the electrochemical band gaps by 0.1 V. The molar emission intensity is five times greater in PBP than BPP. Both trimers are crystalline and the melting points differ by 17 °C. The PBP and BPP trimers are used as macromonomers in an acyclic diene metathesis polymerization to give PolyPBP and PolyBPP. The optical and electrochemical properties are similar to those of their trimer precursors-sequence effects are still evident. These results suggest that sequence is a tunable variable for electronic materials and that the polymerization of oligomeric sequences is a useful approach to introducing sequence into polymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Portable thin layer chromatography for field detection of explosives and propellants

NASA Astrophysics Data System (ADS)

Satcher, Joe H.; Maienschein, Jon L.; Pagoria, Philip F.; Racoveanu, Ana; Carman, M. Leslie; Whipple, Richard E.; Reynolds, John G.

2012-06-01

A field deployable detection kit for explosives and propellants using thin layer chromatography (TLC) has been developed at Lawrence Livermore National Laboratory (LLNL). The chemistry of the kit has been modified to allow for field detection of propellants (through propellant stabilizers), military explosives, peroxide explosives, nitrates and inorganic oxidizer precursors. For many of these target analytes, the detection limit is in the μg to pg range. A new miniaturized, bench prototype, field portable TLC (Micro TLC) kit has also been developed for the detection and identification of common military explosives. It has been demonstrated in a laboratory environment and is ready for field-testing. The kit is comprised of a low cost set of commercially available components specifically assembled for rapid identification needed in the field and identifies the common military explosives: HMX, RDX, Tetryl, Explosive D or picric acid, and TNT all on one plate. Additional modifications of the Micro TLC system have been made with fluorescent organosilicon co-polymer coatings to detect a large suite of explosives.

Organic solvent soluble oxide supported hydrogenation catalyst precursors

DOEpatents

Edlund, David J.; Finke, Richard G.; Saxton, Robert J.

1992-01-01

The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise A.sub.x [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.15 M'.sub.3 O.sub.62 ].sup.x- and A.sub.y [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.9 M'.sub.3 O.sub.40 ].sup.y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, Hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.

Strategies to mitigate N2O emissions from biological nitrogen removal systems.

PubMed

Desloover, Joachim; Vlaeminck, Siegfried E; Clauwaert, Peter; Verstraete, Willy; Boon, Nico

2012-06-01

N2O emissions from the biological treatment of sewage, manure, landfill leachates and industrial effluents have gained considerable interest among policy makers and environmental scientists. Estimated global emission rates from these sources can contribute up to 10% of the anthropogenic N2O emissions. Particularly at the level of a treatment plant, the N2O impact can be very significant and reach up to 80% of the operational CO2 footprint. Imperfect nitritation by an imbalance in the two-step nitritation metabolism of ammonia-oxidizing bacteria is considered as the main contributor to N2O production with hydroxylamine and particularly nitrite as key precursors. Monitoring of these compounds is warranted to understand and abate N2O emissions. Mitigation strategies should also comprise optimizations of the process parameters as well as bio-augmentative approaches empowered to restore the functional capacity and to deal with unwanted accumulation of intermediates. These strategies require validation for their effectiveness and costs at full-scale. Copyright © 2012 Elsevier Ltd. All rights reserved.

Method of CO and/or CO.sub.2 hydrogenation to higher hydrocarbons using doped mixed-metal oxides

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

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.

2017-03-21

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a pyrochlore, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate amore » hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises olefins, paraffins, or mixtures thereof.« less

A Novel and Facile Route to Synthesize Atomic-Layered MoS2 Film for Large-Area Electronics.

PubMed

Boandoh, Stephen; Choi, Soo Ho; Park, Ji-Hoon; Park, So Young; Bang, Seungho; Jeong, Mun Seok; Lee, Joo Song; Kim, Hyeong Jin; Yang, Woochul; Choi, Jae-Young; Kim, Soo Min; Kim, Ki Kang

2017-10-01

High-quality and large-area molybdenum disulfide (MoS 2 ) thin film is highly desirable for applications in large-area electronics. However, there remains a challenge in attaining MoS 2 film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few-layered MoS 2 film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO) 6 ) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS 2 film is readily achievable in 20 min. Large-area MoS 2 field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm 2 V -1 s -1 , which is the highest reported for bottom-gated MoS 2 -FETs fabricated via photolithography with an on/off ratio of ≈10 5 at room temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cellular compartmentalization of secondary metabolism

PubMed Central

Kistler, H. Corby; Broz, Karen

2015-01-01

Fungal secondary metabolism is often considered apart from the essential housekeeping functions of the cell. However, there are clear links between fundamental cellular metabolism and the biochemical pathways leading to secondary metabolite synthesis. Besides utilizing key biochemical precursors shared with the most essential processes of the cell (e.g., amino acids, acetyl CoA, NADPH), enzymes for secondary metabolite synthesis are compartmentalized at conserved subcellular sites that position pathway enzymes to use these common biochemical precursors. Co-compartmentalization of secondary metabolism pathway enzymes also may function to channel precursors, promote pathway efficiency and sequester pathway intermediates and products from the rest of the cell. In this review we discuss the compartmentalization of three well-studied fungal secondary metabolite biosynthetic pathways for penicillin G, aflatoxin and deoxynivalenol, and summarize evidence used to infer subcellular localization. We also discuss how these metabolites potentially are trafficked within the cell and may be exported. PMID:25709603

Morphological control of heterostructured nanowires synthesized by sol-flame method

PubMed Central

2013-01-01

Heterostructured nanowires, such as core/shell nanowires and nanoparticle-decorated nanowires, are versatile building blocks for a wide range of applications because they integrate dissimilar materials at the nanometer scale to achieve unique functionalities. The sol-flame method is a new, rapid, low-cost, versatile, and scalable method for the synthesis of heterostructured nanowires, in which arrays of nanowires are decorated with other materials in the form of shells or chains of nanoparticles. In a typical sol-flame synthesis, nanowires are dip-coated with a solution containing precursors of the materials to be decorated, then dried in air, and subsequently heated in the post-flame region of a flame at high temperature (over 900°C) for only a few seconds. Here, we report the effects of the precursor solution on the final morphology of the heterostructured nanowire using Co3O4 decorated CuO nanowires as a model system. When a volatile cobalt salt precursor is used with sufficient residual solvent, both solvent and cobalt precursor evaporate during the flame annealing step, leading to the formation of Co3O4 nanoparticle chains by a gas-solid transition. The length of the nanoparticle chains is mainly controlled by the temperature of combustion of the solvent. On the other hand, when a non-volatile cobalt salt precursor is used, only the solvent evaporates and the cobalt salt is converted to nanoparticles by a liquid–solid transition, forming a conformal Co3O4 shell. This study facilitates the use of the sol-flame method for synthesizing heterostructured nanowires with controlled morphologies to satisfy the needs of diverse applications. PMID:23924299

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents.

PubMed

Olivares-Marín, M; García, S; Pevida, C; Wong, M S; Maroto-Valer, M

2011-10-01

Adsorption is one of the most promising technologies for reducing CO(2) emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600-900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N(2), -196 °C; CO(2), 0 °C), and tested for CO(2) adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO(2) capture capacities. The carbon-based adsorbent that presented the maximum CO(2) capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm(3) g(-1)), thus confirming that only pores of less than 1 nm are effective for CO(2) adsorption at atmospheric pressure. Copyright © 2011 Elsevier Ltd. All rights reserved.

Co3O4 nanorod-supported Pt with enhanced performance for catalytic HCHO oxidation at room temperature

NASA Astrophysics Data System (ADS)

Yan, Zhaoxiong; Xu, Zhihua; Cheng, Bei; Jiang, Chuanjia

2017-05-01

Formaldehyde (HCHO) removal from air at room (ambient) temperature by effective catalysts is of significance for improving indoor air quality, and catalysts with high efficiency and good recyclability are highly desirable. In this study, platinum (Pt) supported on nanorod-shaped Co3O4 (Pt/Co3O4) was prepared by calcination of microwave-assisted synthesized Co3O4 precursor followed by NaBH4-reduction of Pt precursor. The as-prepared Co3O4 exhibited a morphology of nanorods with lengths of 400-700 nm and diameters of approximately 40-50 nm, which were self-assembled by nanoparticles. The Pt/Co3O4 catalyst exhibited a superior catalytic performance for HCHO oxidation at room temperature compared to Pt supported on commercial Co3O4 (Pt/Co3O4-c) and Pt supported on commercial TiO2 (Pt/TiO2), which is mainly due to the high oxygen mobility resulting from its distinct nanorod morphology, strong metal-support interaction between Pt and Co3O4, and the intrinsic redox nature of the Co3O4 support. This study provides new insights into the fabrication of high-performance catalysts for indoor air purification.

Formation, expansion, and interconversion of metallarings in a sulfur-bridged Au(I) Co(III) coordination system.

PubMed

Oji, Katsuya; Igashira-Kamiyama, Asako; Yoshinari, Nobuto; Konno, Takumi

2014-02-10

A novel Au(I) Co(III) coordination system that is derived from the newly prepared [Co(D-nmp)2 ](-) (1(-) ; D-nmp=N-methyl-D-penicillaminate) and a gold(I) precursor Au(I) is reported. Complex 1(-) acts as a sulfur-donating metallaligand and reacts with the gold(I) precursor to give [Au2 Co2 (D-nmp)4 ] (2), which has an eight-membered Au(I) 2 Co(III) 2 metallaring. Treatment of 2 with [Au2 (dppe)2 ](2+) (dppe=1,2-bis(diphenylphosphino)ethane) leads to the formation of [Au4 Co2 (dppe)2 (D-nmp)4 ](2+) (3(2+) ), which consists of an 18-membered Au(I) 4 Co(III) 2 metallaring that accommodates a tetrahedral anion (BF4 (-) , ClO4 (-) , ReO4 (-) ). In solution, the metallaring structure of 3(2+) is readily interconvertible with the nine-membered Au(I) 2 Co(III) metallaring structure of [Au2 Co(dppe)(D-nmp)2 ](+) (4(+) ); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the AuS and AuP bonds, which is essential for metallaring expansion and contraction. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel approach in LC-MS/MS using MRM to generate a full profile of acyl-CoAs: discovery of acyl-dephospho-CoAs.

PubMed

Li, Qingling; Zhang, Shenghui; Berthiaume, Jessica M; Simons, Brigitte; Zhang, Guo-Fang

2014-03-01

A metabolomic approach to selectively profile all acyl-CoAs was developed using a programmed multiple reaction monitoring (MRM) method in LC-MS/MS and was employed in the analysis of various rat organs. The programmed MRM method possessed 300 mass ion transitions with the mass difference of 507 between precursor ion (Q1) and product ion (Q3), and the precursor ion started from m/z 768 and progressively increased one mass unit at each step. Acyl-dephospho-CoAs resulting from the dephosphorylation of acyl-CoAs were identified by accurate MS and fragmentation. Acyl-dephospho-CoAs were also quantitatively scanned by the MRM method with the mass difference of 427 between Q1 and Q3 mass ions. Acyl-CoAs and dephospho-CoAs were assayed with limits of detection ranging from 2 to 133 nM. The accuracy of the method was demonstrated by assaying a range of concentrations of spiked acyl-CoAs with the results of 80-114%. The distribution of acyl-CoAs reflects the metabolic status of each organ. The physiological role of dephosphorylation of acyl-CoAs remains to be further characterized. The methodology described herein provides a novel strategy in metabolomic studies to quantitatively and qualitatively profile all potential acyl-CoAs and acyl-dephospho-CoAs.

Improving coenzyme Q8 production in Escherichia coli employing multiple strategies.

PubMed

Xu, Wen; Yang, Shuiyun; Zhao, Junchao; Su, Tingting; Zhao, Liangrui; Liu, Jiankang

2014-08-01

Coenzyme Q (CoQ) is a medically valuable compound and a high yielding strain for CoQ will have several benefits for the industrial production of CoQ. To increase the CoQ(8) content of E. coli, we blocked the pathway for the synthesis of menaquinone by deleting the menA gene. The blocking of menaquinone pathway increased the CoQ(8) content by 81 % in E. coli (ΔmenA). To study the CoQ producing potential of E. coli, we employed previous known increasing strategies for systematic metabolic engineering. These include the supplementation with substrate precursors and the co-expression of rate-limiting genes. The co-expression of dxs-ubiA and the supplementation with substrate precursors such as pyruvate (PYR) and parahydroxybenzoic acid (pHBA) increased the content of CoQ(8) in E. coli (ΔmenA) by 125 and 59 %, respectively. Moreover, a 180 % increase in the CoQ(8) content in E. coli (ΔmenA) was realized by the combination of the co-expression of dxs-ubiA and the supplementation with PYR and pHBA. All in all, CoQ(8) content in E. coli increased 4.06 times by blocking the menaquinone pathway, dxs-ubiA co-expression and the addition of sodium pyruvate and parahydroxybenzoic acid to the medium. Results suggested a synergistic effect among different metabolic engineering strategies.

CuInSe₂ thin-film solar cells with 7.72 % efficiency prepared via direct coating of a metal salts/alcohol-based precursor solution.

PubMed

Ahn, Sejin; Son, Tae Hwa; Cho, Ara; Gwak, Jihye; Yun, Jae Ho; Shin, Keeshik; Ahn, Seoung Kyu; Park, Sang Hyun; Yoon, Kyunghoon

2012-09-01

A simple direct solution coating process for forming CuInSe₂ (CIS) thin films was described, employing a low-cost and environmentally friendly precursor solution. The precursor solution was prepared by mixing metal acetates, ethanol, and ethanolamine. The facile formation of a precursor solution without the need to prefabricate nanoparticles enables a rapid and easy processing, and the high stability of the solution in air further ensures the precursor preparation and the film deposition in ambient conditions without a glove box. The thin film solar cell fabricated with the absorber film prepared by this route showed an initial conversion efficiency of as high as 7.72 %. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetostructural coupling behavior at the ferromagnetic transition in double-perovskite S r2FeMo O6

NASA Astrophysics Data System (ADS)

Yang, Dexin; Harrison, Richard J.; Schiemer, Jason A.; Lampronti, Giulio I.; Liu, Xueyin; Zhang, Fenghua; Ding, Hao; Liu, Yan'gai; Carpenter, Michael A.

2016-01-01

The ordered double-perovskite S r2FeMo O6 (SFMO) possesses remarkable room-temperature low-field colossal magnetoresistivity and transport properties which are related, at least in part, to combined structural and magnetic instabilities that are responsible for a cubic-tetragonal phase transition near 420 K. A formal strain analysis combined with measurements of elastic properties from resonant ultrasound spectroscopy reveal a system with weak biquadratic coupling between two order parameters belonging to Γ4+ and m Γ4+ of parent space group F m 3 ¯m . The observed softening of the shear modulus by ˜50% is due to the classical effects of strain/order parameter coupling at an improper ferroelastic (Γ4+) transition which is second order in character, while the ferromagnetic order parameter (m Γ4+ ) couples only with volume strain. The influence of a third order parameter, for ordering of Fe and Mo on crystallographic B sites, is to change the strength of coupling between the Γ4+ order parameter and the tetragonal shear strain due to the influence of changes in local strain heterogeneity at a unit cell scale. High anelastic loss below the transition point reveals the presence of mobile ferroelastic twin walls which become pinned by oxygen vacancies in a temperature interval near 340 K. The twin walls must be both ferroelastic and ferromagnetic, but due to the weak coupling between the magnetic and structural order parameters it should be possible to pull them apart with a weak magnetic field. These insights into the role of strain coupling and relaxational effects in a system with only weak coupling between three order parameters allow rationalization and prediction of how static and dynamic properties of the material might be tuned in thin film form by choice of strain contrast with a substrate.

Fabrication of low-crystalline carbonate apatite foam bone replacement based on phase transformation of calcite foam.

PubMed

Maruta, Michito; Matsuya, Shigeki; Nakamura, Seiji; Ishikawa, Kunio

2011-01-01

Carbonate apatite (CO(3)Ap) foam may be an ideal bone substitute as it is sidelined to cancellous bone with respect to its chemical composition and structure. However, CO(3)Ap foam fabricated using α-tricalcium phosphate foam showed limited mechanical strength. In the present study, feasibility of the fabrication of calcite which could be a precursor of CO(3)Ap was studied. Calcite foam was successfully fabricated by the so-called "ceramic foam" method using calcium hydroxide coated polyurethane foam under CO(2)+O(2) atmosphere. Then the calcite foam was immersed in Na(2)HPO(4) aqueous solution for phase transformation based on dissolution-precipitation reaction. When CaO-free calcite foam was immersed in Na(2)HPO(4) solution, low-crystalline CO(3)Ap foam with 93-96% porosity and fully interconnected porous structure was fabricated. The compressive strength of the foam was 25.6 ± 6 kPa. In light of these results, we concluded that the properties of the precursor foam were key factors for the fabrication of CO(3)Ap foams.

Fabrication of hierarchical CoP nanosheet@microwire arrays via space-confined phosphidation toward high-efficiency water oxidation electrocatalysis under alkaline conditions.

PubMed

Ji, Xuqiang; Zhang, Rong; Shi, Xifeng; Asiri, Abdullah M; Zheng, Baozhan; Sun, Xuping

2018-05-03

In spite of recent advances in the synthesis of transition metal phosphide nanostructures, the simple fabrication of hierarchical arrays with more accessible active sites still remains a great challenge. In this Communication, we report a space-confined phosphidation strategy toward developing hierarchical CoP nanosheet@microwire arrays on nickel foam (CoP NS@MW/NF) using a Co(H2PO4)2·2H3PO4 microwire array as the precursor. The thermally stable nature of the anion in the precursor is key to hierarchical nanostructure formation. When used as a 3D electrode for water oxidation electrocatalysis, such CoP NS@MW/NF needs an overpotential as low as 296 mV to drive a geometrical catalytic current density of 100 mA cm-2 in 1.0 M KOH, outperforming all reported Co phosphide catalysts in alkaline media. This catalyst also shows superior long-term electrochemical durability, maintaining its activity for at least 65 h. This study offers us a general method for facile preparation of hierarchical arrays for applications.

Ductile long range ordered alloys with high critical ordering temperature and wrought articles fabricated therefrom

DOEpatents

Liu, Chain T.; Inouye, Henry

1979-01-01

Malleable long range ordered alloys having high critical ordering temperatures exist in the V(Fe, Co).sub.3 and V(Fe, Co, Ni).sub.3 systems. These alloys have the following compositions comprising by weight: 22-23% V, 14-30% Fe, and the remainder Co or Co and Ni with an electron density no more than 7.85. The maximum combination of high temperature strength, ductility and creep resistance are manifested in the alloy comprising by weight 22-23% V, 14-20% Fe and the remainder Co and having an atomic composition of V(Fe .sub.0.20-0.26 C Co.sub.0.74-0.80).sub.3. The alloy comprising by weight 22-23% V, 16-17% Fe and 60-62% Co has excellent high temperature properties. The alloys are fabricable into wrought articles by casting, deforming, and annealing for sufficient time to provide ordered structure.

Sequence analyses reveal that a TPR–DP module, surrounded by recombinable flanking introns, could be at the origin of eukaryotic Hop and Hip TPR–DP domains and prokaryotic GerD proteins

PubMed Central

Papandreou, Nikolaos; Chomilier, Jacques

2008-01-01

The co-chaperone Hop [heat shock protein (HSP) organising protein] is known to bind both Hsp70 and Hsp90. Hop comprises three repeats of a tetratricopeptide repeat (TPR) domain, each consisting of three TPR motifs. The first and last TPR domains are followed by a domain containing several dipeptide (DP) repeats called the DP domain. These analyses suggest that the hop genes result from successive recombination events of an ancestral TPR–DP module. From a hydrophobic cluster analysis of homologous Hop protein sequences derived from gene families, we can postulate that shifts in the open reading frames are at the origin of the present sequences. Moreover, these shifts can be related to the presence or absence of biological function. We propose to extend the family of Hop co-chaperons into the kingdom of bacteria, as several structurally related genes have been identified by hydrophobic cluster analysis. We also provide evidence of common structural characteristics between hop and hip genes, suggesting a shared precursor of ancestral TPR–DP domains. Electronic supplementary material The online version of this article (doi:10.1007/s12192-008-0083-8) contains supplementary material, which is available to authorized users. PMID:18987995

Mixed ion/electron-conductive protective soft nanomatter-based conformal surface modification of lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Park, Jang-Hoon; Kim, Ju-Myung; Lee, Chang Kee; Lee, Sang-Young

2014-10-01

Understanding and control of interfacial phenomena between electrode material and liquid electrolytes are of major scientific importance for boosting development of high-performance lithium ion batteries with reliable electrochemical/safety attributes. Here, as an innovative surface engineering approach to address the interfacial issues, a new concept of mixed ion/electron-conductive soft nanomatter-based conformal surface modification of the cathode material is presented. The soft nanomatter is comprised of an electron conductive carbonaceous (C) substance embedded in an ion conductive polyimide (PI) nanothin compliant film. In addition to its structural uniqueness, the newly proposed surface modification benefits from a simple fabrication process. The PI/carbon soft nanomatter is directly synthesized on LiCoO2 surface via one-pot thermal treatment of polyamic acid (=PI precursor) and sucrose (=carbon source) mixture, where the LiCoO2 powders are chosen as a model system to explore the feasibility of this surface engineering strategy. The resulting PI/carbon coating layer facilitates electronic conduction and also suppresses unwanted side reactions arising from the cathode material-liquid electrolyte interface. These synergistic coating effects of the multifunctional PI/carbon soft nanomatter significantly improve high-voltage cell performance and also mitigate interfacial exothermic reaction between cathode material and liquid electrolyte.

Processing approach towards the formation of thin-film Cu(In,Ga)Se2

DOEpatents

Beck, Markus E.; Noufi, Rommel

2003-01-01

A two-stage method of producing thin-films of group IB-IIIA-VIA on a substrate for semiconductor device applications includes a first stage of depositing an amorphous group IB-IIIA-VIA precursor onto an unheated substrate, wherein the precursor contains all of the group IB and group IIIA constituents of the semiconductor thin-film to be produced in the stoichiometric amounts desired for the final product, and a second stage which involves subjecting the precursor to a short thermal treatment at 420.degree. C.-550.degree. C. in a vacuum or under an inert atmosphere to produce a single-phase, group IB-III-VIA film. Preferably the precursor also comprises the group VIA element in the stoichiometric amount desired for the final semiconductor thin-film. The group IB-IIIA-VIA semiconductor films may be, for example, Cu(In,Ga)(Se,S).sub.2 mixed-metal chalcogenides. The resultant supported group IB-IIIA-VIA semiconductor film is suitable for use in photovoltaic applications.

Controlled chemical stabilization of polyvinyl precursor fiber, and high strength carbon fiber produced therefrom

DOEpatents

Naskar, Amit K.

2016-12-27

Method for the preparation of carbon fiber, which comprises: (i) immersing functionalized polyvinyl precursor fiber into a liquid solution having a boiling point of at least 60.degree. C.; (ii) heating the liquid solution to a first temperature of at least 25.degree. C. at which the functionalized precursor fiber engages in an elimination-addition equilibrium while a tension of at least 0.1 MPa is applied to the fiber; (iii) gradually raising the first temperature to a final temperature that is at least 20.degree. C. above the first temperature and up to the boiling point of the liquid solution for sufficient time to convert the functionalized precursor fiber to a pre-carbonized fiber; and (iv) subjecting the pre-carbonized fiber produced according to step (iii) to high temperature carbonization conditions to produce the final carbon fiber. Articles and devices containing the fibers, including woven and non-woven mats or paper forms of the fibers, are also described.

Co@Carbon and Co 3 O4@Carbon nanocomposites derived from a single MOF for supercapacitors.

PubMed

Dai, Engao; Xu, Jiao; Qiu, Junjie; Liu, Shucheng; Chen, Ping; Liu, Yi

2017-10-03

Developing a composite electrode containing both carbon and transition metal/metal oxide as the supercapacitor electrode can combine the merits and mitigate the shortcomings of both the components. Herein, we report a simple strategy to prepare the hybrid nanostructure of Co@Carbon and Co 3 O 4 @Carbon by pyrolysis a single MOFs precursor. Co-based MOFs (Co-BDC) nanosheets with morphology of regular parallelogram slice have been prepared by a bottom-up synthesis strategy. One-step pyrolysis of Co-BDC, produces a porous carbon layer incorporating well-dispersed Co and Co 3 O 4 nanoparticles. The as-prepared cobalt-carbon composites exhibit the thin layer morphology and large specific surface area with hierarchical porosity. These features significantly improve the ion-accessible surface area for charge storage and shorten the ion transport length in thin dimension, thus contributing to a high specific capacitance. Improved capacitance performance was successfully realized for the asymmetric supercapacitors (ASCs) (Co@Carbon//Co 3 O 4 @Carbon), better than those of the symmetric supercapacitors (SSCs) based on Co@Carbon and Co 3 O 4 @Carbon materials (i.e., Co@Carbon//Co@Carbon and Co 3 O 4 @Carbon//Co 3 O 4 @Carbon). The working voltage of the ASCs can be extended to 1.5 V and show a remarkable high power capability in aqueous electrolyte. This work provides a controllable strategy for nanostructured carbon-metal and carbon-metal oxide composite electrodes from a single precursor.

fac-[Re(CO)3(dmso-O)3](CF3SO3): a new versatile and efficient Re(I) precursor for the preparation of mono and polynuclear compounds containing fac-[Re(CO)3]+ fragments.

PubMed

Casanova, Massimo; Zangrando, Ennio; Munini, Fabio; Iengo, Elisabetta; Alessio, Enzo

2006-11-14

We show here that the new complex fac-[Re(CO)3(dmso-O)3](CF3SO3) (1), efficiently prepared in one step from [ReBr(CO)5] and featuring a broad range of solubility, is, in general, a better precursor for the one-step synthesis of mono- and polynuclear inorganic compounds containing fac-[Re(CO)3]+ fragments compared to the commonly used (NEt4)2fac-[ReBr3(CO)3] and fac-[Re(CO)3(CH3CN)3](Y) (Y = PF6, BF4, ClO4) species. Compound 1 is the first example of a Re(I)-dmso complex structurally characterized and confirms the rule that dmso is always O-bonded when trans to CO. The reactivity of 1 was tested in the one-step preparation of several new and known complexes. The O-bonded sulfoxides of 1 are replaced under mild conditions by tri- (L3) and bidentate ligands (L2) to produce fac-[Re(CO)3(L3)]+ and fac-[Re(CO)3(L2)(dmso-O)]+ compounds, respectively. An excess of monodentate ligands (L) and more forcing conditions are needed to prepare fac-[Re(CO)3(L)3]+ compounds. The new compounds include fac-[Re(CO)3(bipy)(dmso-O)](CF3SO3) (4), that turned out to be an excellent precursor for binding the luminescent fac-[Re(CO)3(bipy)]+ fragment to polytopic ligands for the construction of more elaborate assemblies. One example reported here is the two-step preparation of fac-[{Re(CO)3(bipy)}(mu-4,4'-bipy){Ru(TPP)(CO)}](CF3SO3) (8) (TPP = tetraphenylporphyrin). The X-ray structures of the new compounds 1, 4, of the bis-porphyrin complex fac-[Re(CO)3Cl(4'MPyP)2] (13) (4'MPyP = 5-(4'pyridyl)-10,15,20-triphenylporphyrin), and of the rhenium-cyclophane [{(CO)3Re(mu-OH)2Re(CO)3}2(micro-4,4'-bipy)2] (15), among others, are described. Compound 1 might find useful applications in supramolecular chemistry (metal-mediated assembly of large architectures), in the in situ preparation of stable Re compounds to be used in nuclear medicine, and for the labeling of biomolecules.

Solar Powered CO.Sub.2 Conversion

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor)

2016-01-01

Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.

Monolithic microfluidic concentrators and mixers

DOEpatents

Frechet, Jean M.; Svec, Frantisek; Yu, Cong; Rohr, Thomas

2005-05-03

Microfluidic devices comprising porous monolithic polymer for concentration, extraction or mixing of fluids. A method for in situ preparation of monolithic polymers by in situ initiated polymerization of polymer precursors within microchannels of a microfluidic device and their use for solid phase extraction (SPE), preconcentration, concentration and mixing.

Method for forming solar cell materials from particulars

DOEpatents

Eberspacher, Chris; Pauls, Karen Lea

2001-01-01

Materials in bulk and film forms are prepared from fine particulate precursors such as single-phase, mixed-metal oxides; multi-phase, mixed-metal particles comprising a metal oxide; multinary metal particles; mixtures of such particles with other particles; and particulate materials intercalated with other materials.

Spore coat protein of Bacillus subtilis. Structure and precursor synthesis.

PubMed

Munoz, L; Sadaie, Y; Doi, R H

1978-10-10

The coat protein of Bacillus subtilis spores comprises about 10% of the total dry weight of spores and 25% of the total spore protein. One protein with a molecular weight of 13,000 to 15,000 comprises a major portion of the spore coat. This mature spore coat protein has histidine at its NH2 terminus and is relatively rich in hydrophobic amino acids. Netropsin, and antibiotic which binds to A-T-rich regions of DNA and inhibits sporulation, but not growth, decreased the synthesis of this spore coat protein by 75%. A precursor spore coat protein with a molecular weight of 25,000 is made initially at t1 of sporulation and is converted to the mature spore coat protein with a molecular weight of 13,500 at t2 - t3. These data indicate that the spore coat protein gene is expressed very early in sporulation prior to the modifications of RNA polymerase which have been noted.

Ultrasound assisted co-precipitation of nanostructured CuO-ZnO-Al2O3 over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME.

PubMed

Allahyari, Somaiyeh; Haghighi, Mohammad; Ebadi, Amanollah; Hosseinzadeh, Shahin

2014-03-01

Nanostructured CuO-ZnO-Al2O3/HZSM-5 was synthesized from nitrate and acetate precursors using ultrasound assisted co-precipitation method under different irradiation powers. The CuO-ZnO-Al2O3/HZSM-5 nanocatalysts were characterized using XRD, FESEM, BET, FTIR and EDX Dot-mapping analyses. The results indicated precursor type and irradiation power have significant influences on phase structure, morphology, surface area and functional groups. It was observed that the acetate formulated CuO-ZnO-Al2O3/HZSM-5 nanocatalyst have smaller CuO crystals with better dispersion and stronger interaction between components in comparison to nitrate based nanocatalysts. Ultrasound assisted co-precipitation synthesis method resulted in nanocatalyst with more uniform morphology compared to conventional method and increasing irradiation power yields smaller particles with better dispersion and higher surface area. Additionally the crystallinity of CuO is lower at high irradiation powers leading to stronger interaction between metal oxides. The nanocatalysts performance were tested at 200-300 °C, 10-40 bar and space velocity of 18,000-36,000 cm(3)/g h with the inlet gas composition of H2/CO = 2/1 in a stainless steel autoclave reactor. The acetate based nanocatalysts irradiated with higher levels of power exhibited better reactivity in terms of CO conversion and DME yield. While there is an optimal temperature for CO conversion and DME yield in direct synthesis of DME, CO conversion and DME yield both increase with the pressure increase. Furthermore ultrasound assisted co-precipitation method yields more stable CuO-ZnO-Al2O3/HZSM-5 nanocatalyst while conventional precipitated nanocatalyst lost their activity ca. 18% and 58% in terms of CO conversion and DME yield respectively in 24 h time on stream test.

Efficiently Communicating Rich Heterogeneous Geospatial Data from the FeMO2008 Dive Cruise with FlashMap on EarthRef.org

NASA Astrophysics Data System (ADS)

Minnett, R. C.; Koppers, A. A.; Staudigel, D.; Staudigel, H.

2008-12-01

EarthRef.org is comprehensive and convenient resource for Earth Science reference data and models. It encompasses four main portals: the Geochemical Earth Reference Model (GERM), the Magnetics Information Consortium (MagIC), the Seamount Biogeosciences Network (SBN), and the Enduring Resources for Earth Science Education (ERESE). Their underlying databases are publically available and the scientific community has contributed widely and is urged to continue to do so. However, the net result is a vast and largely heterogeneous warehouse of geospatial data ranging from carefully prepared maps of seamounts to geochemical data/metadata, daily reports from seagoing expeditions, large volumes of raw and processed multibeam data, images of paleomagnetic sampling sites, etc. This presents a considerable obstacle for integrating other rich media content, such as videos, images, data files, cruise tracks, and interoperable database results, without overwhelming the web user. The four EarthRef.org portals clearly lend themselves to a more intuitive user interface and has, therefore, been an invaluable test bed for the design and implementation of FlashMap, a versatile KML-driven geospatial browser written for reliability and speed in Adobe Flash. FlashMap allows layers of content to be loaded and displayed over a streaming high-resolution map which can be zoomed and panned similarly to Google Maps and Google Earth. Many organizations, from National Geographic to the USGS, have begun using Google Earth software to display geospatial content. However, Google Earth, as a desktop application, does not integrate cleanly with existing websites requiring the user to navigate away from the browser and focus on a separate application and Google Maps, written in Java Script, does not scale up reliably to large datasets. FlashMap remedies these problems as a web-based application that allows for seamless integration of the real-time display power of Google Earth and the flexibility of the web without losing scalability and control of the base maps. Our Flash-based application is fully compatible with KML (Keyhole Markup Language) 2.2, the most recent iteration of KML, allowing users with existing Google Earth KML files to effortlessly display their geospatial content embedded in a web page. As a test case for FlashMap, the annual Iron-Oxidizing Microbial Observatory (FeMO) dive cruise to the Loihi Seamount, in conjunction with data available from ongoing and published FeMO laboratory studies, showcases the flexibility of this single web-based application. With a KML 2.2 compatible web-service providing the content, any database can display results in FlashMap. The user can then hide and show multiple layers of content, potentially from several data sources, and rapidly digest a vast quantity of information to narrow the search results. This flexibility gives experienced users the ability to drill down to exactly the record they are looking for (SERC at Carleton College's educational application of FlashMap at http://serc.carleton.edu/sp/erese/activities/22223.html) and allows users familiar with Google Earth the ability to load and view geospatial data content within a browser from any computer with an internet connection.

Preparation of hydrophobic coatings

DOEpatents

Branson, Eric D [Albuquerque, NM; Shah, Pratik B [Albuquerque, NM; Singh, Seema [Rio Rancho, NM; Brinker, C Jeffrey [Albuquerque, NM

2009-02-03

A method for preparing a hydrophobic coating by preparing a precursor sol comprising a metal alkoxide, a solvent, a basic catalyst, a fluoroalkyl compound and water, depositing the precursor sol as a film onto a surface, such as a substrate or a pipe, heating, the film and exposing the film to a hydrophobic silane compound to form a hydrophobic coating with a contact angle greater than approximately 150.degree.. The contact angle of the film can be controlled by exposure to ultraviolet radiation to reduce the contact angle and subsequent exposure to a hydrophobic silane compound to increase the contact angle.

Gelcasting polymeric precursors for producing net-shaped graphites

DOEpatents

Klett, James W.; Janney, Mark A.

2002-01-01

The present invention discloses a method for molding complex and intricately shaped high density monolithic carbon, carbon-carbon, graphite, and thermoplastic composites using gelcasting technology. The method comprising a polymeric carbon precursor, a solvent, a dispersant, an anti-foaming agent, a monomer system, and an initiator system. The components are combined to form a suspension which is poured into a mold and heat-treated to form a thermoplastic part. The thermoplastic part can then be further densified and heat-treated to produce a high density carbon or graphite composite. The present invention also discloses the products derived from this method.

Total N-nitrosamine Precursor Adsorption with Carbon Nanotubes: Elucidating Controlling Physiochemical Properties and Developing a Size-Resolved Precursor Surrogate

NASA Astrophysics Data System (ADS)

Needham, Erin Michelle

As drinking water sources become increasingly impaired with nutrients and wastewater treatment plant (WWTP) effluent, formation of disinfection byproducts (DBPs)--such as trihalomethanes (THMs), dihaloacetonitriles (DHANs), and N-nitrosamines--during water treatment may also increase. N-nitrosamines may comprise the bulk of the chronic toxicity in treated drinking waters despite forming at low ng/L levels. This research seeks to elucidate physicochemical properties of carbon nanotubes (CNTs) for removal of DBP precursors, with an emphasis on total N-nitrosamines (TONO). Batch experiments with CNTs were completed to assess adsorption of THM, DHAN, and TONO precursors; physiochemical properties of CNTs were quantified through gas adsorption isotherms and x-ray photoelectron spectroscopy. Numerical modeling was used to elucidate characteristics of CNTs controlling DBP precursor adsorption. Multivariate models developed with unmodified CNTs revealed that surface carboxyl groups and, for TONO precursors, cumulative pore volume (CPV), controlled DBP precursor adsorption. Models developed with modified CNTs revealed that specific surface area controlled adsorption of THM and DHAN precursors while CPV and surface oxygen content were significant for adsorption of TONO precursors. While surrogates of THM and DHAN precursors leverage metrics from UV absorbance and fluorescence spectroscopy, a TONO precursor surrogate has proved elusive. This is important as measurements of TONO formation potential (TONOFP) require large sample volumes and long processing times, which impairs development of treatment processes. TONO precursor surrogates were developed using samples that had undergone oxidative or sorption treatments. Precursors were analyzed with asymmetric flow field-flow fractionation (AF4) with inline fluorescence detection (FLD) and whole water fluorescence excitation-emission matrices (EEMs). TONO precursor surrogates were discovered, capable of predicting changes in TONOFP in WWTP samples that have undergone oxidation (R2 = 0.996) and sorption (R2 = 0.576). Importantly, both surrogates only require just 2 mL of sample volume to measure and take only 1 hour. Application of the sorption precursor surrogate revealed that DBP precursor adsorption was feasible with freeform CNT microstructures with various dimensions and surface chemistries, establishing a framework for development of this novel CNT application for drinking water treatment.

Discovery of novel representatives of bilaterian neuropeptide families and reconstruction of neuropeptide precursor evolution in ophiuroid echinoderms

PubMed Central

Abylkassimova, Nikara; Hugall, Andrew F.; O'Hara, Timothy D.; Elphick, Maurice R.

2017-01-01

Neuropeptides are a diverse class of intercellular signalling molecules that mediate neuronal regulation of many physiological and behavioural processes. Recent advances in genome/transcriptome sequencing are enabling identification of neuropeptide precursor proteins in species from a growing variety of animal taxa, providing new insights into the evolution of neuropeptide signalling. Here, detailed analysis of transcriptome sequence data from three brittle star species, Ophionotus victoriae, Amphiura filiformis and Ophiopsila aranea, has enabled the first comprehensive identification of neuropeptide precursors in the class Ophiuroidea of the phylum Echinodermata. Representatives of over 30 bilaterian neuropeptide precursor families were identified, some of which occur as paralogues. Furthermore, homologues of endothelin/CCHamide, eclosion hormone, neuropeptide-F/Y and nucleobinin/nesfatin were discovered here in a deuterostome/echinoderm for the first time. The majority of ophiuroid neuropeptide precursors contain a single copy of a neuropeptide, but several precursors comprise multiple copies of identical or non-identical, but structurally related, neuropeptides. Here, we performed an unprecedented investigation of the evolution of neuropeptide copy number over a period of approximately 270 Myr by analysing sequence data from over 50 ophiuroid species, with reference to a robust phylogeny. Our analysis indicates that the composition of neuropeptide ‘cocktails’ is functionally important, but with plasticity over long evolutionary time scales. PMID:28878039

Metallopolymer precursors to L10-CoPt nanoparticles: synthesis, characterization, nanopatterning and potential application

NASA Astrophysics Data System (ADS)

Dong, Qingchen; Qu, Wenshan; Liang, Wenqing; Guo, Kunpeng; Xue, Haibin; Guo, Yuanyuan; Meng, Zhengong; Ho, Cheuk-Lam; Leung, Chi-Wah; Wong, Wai-Yeung

2016-03-01

Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium.Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium. Electronic supplementary information (ESI) available: PXRD, EDX and SEM original data. See DOI: 10.1039/c6nr00034g

Nano-composite materials

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Pitts, J. Roland

2010-05-25

Nano-composite materials are disclosed. An exemplary method of producing a nano-composite material may comprise co-sputtering a transition metal and a refractory metal in a reactive atmosphere. The method may also comprise co-depositing a transition metal and a refractory metal composite structure on a substrate. The method may further comprise thermally annealing the deposited transition metal and refractory metal composite structure in a reactive atmosphere.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

Dual, differential isotope labeling shows the preferential movement of labile plant constituents into mineral-bonded soil organic matter.

PubMed

Haddix, Michelle L; Paul, Eldor A; Cotrufo, M Francesca

2016-06-01

The formation and stabilization of soil organic matter (SOM) are major concerns in the context of global change for carbon sequestration and soil health. It is presently believed that lignin is not selectively preserved in soil and that chemically labile compounds bonding to minerals comprise a large fraction of the SOM. Labile plant inputs have been suggested to be the main precursor of the mineral-bonded SOM. Litter decomposition and SOM formation are expected to have temperature sensitivity varying with the lability of plant inputs. We tested this framework using dual (13) C and (15) N differentially labeled plant material to distinguish the metabolic and structural components within a single plant material. Big Bluestem (Andropogon gerardii) seedlings were grown in an enriched (13) C and (15) N environment and then prior to harvest, removed from the enriched environment and allowed to incorporate natural abundance (13) C-CO2 and (15) N fertilizer into the metabolic plant components. This enabled us to achieve a greater than one atom % difference in (13) C between the metabolic and structural components within the plant litter. This differentially labeled litter was incubated in soil at 15 and 35 °C, for 386 days with CO2 measured throughout the incubation. After 14, 28, 147, and 386 days of incubation, the soil was subsequently fractionated. There was no difference in temperature sensitivity of the metabolic and structural components with regard to how much was respired or in the amount of litter biomass stabilized. Only the metabolic litter component was found in the sand, silt, or clay fraction while the structural component was exclusively found in the light fraction. These results support the stabilization framework that labile plant components are the main precursor of mineral-associated organic matter. © 2016 John Wiley & Sons Ltd.

Synchronicity of mononuclear and dinuclear events in homogeneous catalysis. Hydroformylation of cyclopentene using Rh4(CO)12 and HRe(CO)5 as precursors.

PubMed

Li, Chuanzhao; Chen, Li; Garland, Marc

2007-10-31

The combined application of two or more metals in homogeneous catalysis can lead to synergistic effects; however, the phenomenological basis for these observations often goes undetermined. The hetero-bimetallic catalytic binuclear elimination reaction, a system involving both mononuclear and dinuclear intermediates, has been repeatedly suggested as a possible mechanism. In the present contribution, the simultaneous application of Rh4(CO)12 and HRe(CO)5 as precursors in the hydroformylation reaction leads to a very strong synergistic rate effect. In situ spectroscopic measurements confirm the presence of both mononuclear and dinuclear intermediates such as RCORh(CO)4 and RhRe(CO)9 in the active system. Moreover, kinetic analysis confirms interconversion of these intermediates as well as their statistical correlation with organic product formation. Specifically, the rate of hydrogen activation by RhRe(CO)9 is exactly equal to the rate of aldehyde formation from binuclear elimination between HRe(CO)5 and RCORh(CO)4 at all reaction conditions studied. Thus the catalytic events involving mononuclear species and those involving dinuclear species are synchronized. In the present experiments, the new topology is orders of magnitude more efficient than the corresponding unicyclic rhodium system.

Synthesis and photocatalytic activity of p–n junction CeO2/Co3O4 photocatalyst for the removal of various dyes from wastewater

NASA Astrophysics Data System (ADS)

Tang, Yuanzheng; Zhang, Meng; Wu, Zhengying; Chen, Zhigang; Liu, Chengbao; Lin, Yun; Chen, Feng

2018-04-01

CeO2, Co3O4, and Co3O4/CeO2 composites are successfully synthesized by a simple coprecipitation method. X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) results indicate that the CeO2, Co3O4, and Co3O4/CeO2 precursors sintered at 500 °C has good crystallization. The cerium nitrate introduced into cobalt nitrate precursor solution improved the surface morphology and photocatalytic activity of Co3O4 significantly. The photo-degradation of methylene blue (MB), xylenol orange (XO), methyl orange (MO), and methyl red (MR) catalyzed by prepared nanocomposites were studied under visible light irradiation. Photocatalytic experiment results indicate that the photocatalytic activity of Co3O4/CeO2 composites for degradation of various dyes highly depend on pH value. The optimum conditions for the photocatalytic experiments of Co3O4/CeO2 composites were determined to be as follows: dye concentration, 50 mg L‑1, and catalyst concentration, 50 mg L‑1. The excellent photocatalytic activity of the p–n junction Co3O4/CeO2 composites can be ascribed to the ·O2‑ radicals and h+.

3-D dumbbell-like LiNi1/3Mn1/3Co1/3O2 cathode materials assembled with nano-building blocks for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ryu, Won-Hee; Lim, Sung-Jin; Kim, Won-Keun; Kwon, HyukSang

2014-07-01

Dumbbell-like microsphere carbonate precursors including multi-transition metal components (Ni1/3Mn1/3Co1/3CO3) assembled with nano-building blocks were synthesized by urea-assisted solvo/hydrothermal method, and layered cathode materials (LiNi1/3Mn1/3Co1/3O2) were subsequently prepared using the similarly shaped carbonate precursors for Li-ion batteries. For the synthesis of hierarchical microsphere structures, the partial addition of viscous organic solvent (e.g. ethylene glycol) in aqueous solution played a crucial role, not only in suppressing the sudden particle growth but also in regulating the directional crystallization of carbonate particles on the surface. The dumbbell-like LiNi1/3Mn1/3Co1/3O2 assembled with nanocubes prepared via the urea-assisted solvo/hydrothermal method exhibited better electrochemical characteristics, such as initial discharge capacity, cyclic performance, and rate-capability as a cathode material of Li-ion batteries, compared with the LiNi1/3Mn1/3Co1/3O2 materials prepared via the conventional co-precipitation method.

Non-precious metal catalysts prepared from precursor comprising cyanamide

DOEpatents

Chung, Hoon Taek; Zelenay, Piotr

2015-10-27

Catalyst comprising graphitic carbon and methods of making thereof; said graphitic carbon comprising a metal species, a nitrogen-containing species and a sulfur containing species. A catalyst for oxygen reduction reaction for an alkaline fuel cell was prepared by heating a mixture of cyanamide, carbon black, and a salt selected from an iron sulfate salt and an iron acetate salt at a temperature of from about 700.degree. C. to about 1100.degree. C. under an inert atmosphere. Afterward, the mixture was treated with sulfuric acid at elevated temperature to remove acid soluble components, and the resultant mixture was heated again under an inert atmosphere at the same temperature as the first heat treatment step.

Proliferative and transcriptional identity of distinct classes of neural precursors in the mammalian olfactory epithelium.

PubMed

Tucker, Eric S; Lehtinen, Maria K; Maynard, Tom; Zirlinger, Mariela; Dulac, Catherine; Rawson, Nancy; Pevny, Larysa; Lamantia, Anthony-Samuel

2010-08-01

Neural precursors in the developing olfactory epithelium (OE) give rise to three major neuronal classes - olfactory receptor (ORNs), vomeronasal (VRNs) and gonadotropin releasing hormone (GnRH) neurons. Nevertheless, the molecular and proliferative identities of these precursors are largely unknown. We characterized two precursor classes in the olfactory epithelium (OE) shortly after it becomes a distinct tissue at midgestation in the mouse: slowly dividing self-renewing precursors that express Meis1/2 at high levels, and rapidly dividing neurogenic precursors that express high levels of Sox2 and Ascl1. Precursors expressing high levels of Meis genes primarily reside in the lateral OE, whereas precursors expressing high levels of Sox2 and Ascl1 primarily reside in the medial OE. Fgf8 maintains these expression signatures and proliferative identities. Using electroporation in the wild-type embryonic OE in vitro as well as Fgf8, Sox2 and Ascl1 mutant mice in vivo, we found that Sox2 dose and Meis1 - independent of Pbx co-factors - regulate Ascl1 expression and the transition from lateral to medial precursor state. Thus, we have identified proliferative characteristics and a dose-dependent transcriptional network that define distinct OE precursors: medial precursors that are most probably transit amplifying neurogenic progenitors for ORNs, VRNs and GnRH neurons, and lateral precursors that include multi-potent self-renewing OE neural stem cells.

Proliferative and transcriptional identity of distinct classes of neural precursors in the mammalian olfactory epithelium

PubMed Central

Tucker, Eric S.; Lehtinen, Maria K.; Maynard, Tom; Zirlinger, Mariela; Dulac, Catherine; Rawson, Nancy; Pevny, Larysa; LaMantia, Anthony-Samuel

2010-01-01

Neural precursors in the developing olfactory epithelium (OE) give rise to three major neuronal classes – olfactory receptor (ORNs), vomeronasal (VRNs) and gonadotropin releasing hormone (GnRH) neurons. Nevertheless, the molecular and proliferative identities of these precursors are largely unknown. We characterized two precursor classes in the olfactory epithelium (OE) shortly after it becomes a distinct tissue at midgestation in the mouse: slowly dividing self-renewing precursors that express Meis1/2 at high levels, and rapidly dividing neurogenic precursors that express high levels of Sox2 and Ascl1. Precursors expressing high levels of Meis genes primarily reside in the lateral OE, whereas precursors expressing high levels of Sox2 and Ascl1 primarily reside in the medial OE. Fgf8 maintains these expression signatures and proliferative identities. Using electroporation in the wild-type embryonic OE in vitro as well as Fgf8, Sox2 and Ascl1 mutant mice in vivo, we found that Sox2 dose and Meis1 – independent of Pbx co-factors – regulate Ascl1 expression and the transition from lateral to medial precursor state. Thus, we have identified proliferative characteristics and a dose-dependent transcriptional network that define distinct OE precursors: medial precursors that are most probably transit amplifying neurogenic progenitors for ORNs, VRNs and GnRH neurons, and lateral precursors that include multi-potent self-renewing OE neural stem cells. PMID:20573694

In-situ formation of nanoparticles within a silicon-based matrix

DOEpatents

Thoma, Steven G [Albuquerque, NM; Wilcoxon, Jess P [Albuquerque, NM; Abrams, Billie L [Albuquerque, NM

2008-06-10

A method for encapsulating nanoparticles with an encapsulating matrix that minimizes aggregation and maintains favorable properties of the nanoparticles. The matrix comprises silicon-based network-forming compounds such as ormosils and polysiloxanes. The nanoparticles are synthesized from precursors directly within the silicon-based matrix.

Yb3+-Er3+-Tm3+ co-doped nano-glass-ceramics tuneable up-conversion phosphor

NASA Astrophysics Data System (ADS)

Méndez-Ramos, J.; Rodriguez, V. D.; Tikhomirov, V. K.; Del-Castillo, J.; Yanes, A. C.

2008-08-01

Transparent Yb3+-Er3+-Tm3+ co-doped nano-glass-ceramics have been prepared, 32(SiO{2}) 9(AlO{1.5}) 31.5(CdF{2}) 18.5(PbF{2}) 5.5(ZnF{2}): 3.5(Yb-Er-TmF{3}) mol%, where the co-dopants partition mostly to the fluoride PbF{2}-based nano-crystals. A comparative study of the up-conversion luminescence in nano-glass-ceramics and its precursor glass indicates that these materials can be used as blue/green/red tuneable up-conversion phosphor, in particular for white light generation. A ratio between blue, green and red emission bands of the Tm3+ and Er3+ can be widely varied with nano-ceramming of the precursor glass and with changing a pump power of luminescence. The change in the ratio between the blue, green and red emission bands is explained to be due to substantial lowering phonon energy and shortening of inter-dopant distances with nano-ceramming of the precursor glass and due to change in the ratio of 2- and 3-photon up-conversion processes with pump power.

Tentative characterization of precursor compounds and co-factors of pigment formation in production of 'wu mi' from Vaccinium bracteatum Thunb. Leaves.

PubMed

Fan, Mingcong; Fan, Yihui; Huang, Weiping; Wang, Li; Li, Yan; Qian, Haifeng; Zhang, Hui; Qi, Xiguang

2018-10-01

Vaccinium bracteatum leaves (VBTL) are traditionally used in China to dye rice grains, which assume a deep blue color, named 'Wu mi'. Information on the mechanism of pigment formation is limited. In this study, CIELAB color space parameters were used to represent the color of 'Wu mi'. Precursor compounds of pigments formed during the dyeing process were identified by UPLC Q-TOF MS analysis. The changes in co-factors for pigment formation in VBTL were measured at different growth stages. The L ∗ and b ∗ values of dyed rice increased as the leaves aged, whereas a ∗ values showed irregular changes. Six compounds were tentatively identified as pigment precursors by UPLC Q-TOF MS analysis. The pH and β-glucosidase activity at different growth stages of VBTL were indicated to be crucial co-factors for pigment formation. A tentative hypothesis is presented that iridoid glycosides are hydrolyzed by acids and β-glucosidases to form a dialdehyde structure that binds covalently with amino residues of lysine side chains in rice protein molecules. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of cetyl trimethyl ammonium bromide concentration on structure, morphology and carbon dioxide adsorption capacity of calcium hydroxide based sorbents

NASA Astrophysics Data System (ADS)

Hlaing, Nwe Ni; Vignesh, K.; Sreekantan, Srimala; Pung, Swee-Yong; Hinode, Hirofumi; Kurniawan, Winarto; Othman, Radzali; Thant, Aye Aye; Mohamed, Abdul Rahman; Salim, Chris

2016-02-01

Calcium hydroxide (Ca(OH)2) has been proposed as an important material for industrial, architectural, and environmental applications. In this study, calcium acetate was used as a precursor and cetyl trimethyl ammonium bromide (CTAB) was used as a surfactant to synthesize Ca(OH)2 based adsorbents for carbon dioxide (CO2) capture. The effect of CTAB concentration (0.2-0.8 M) on the structure, morphology and CO2 adsorption performance of Ca(OH)2 was studied in detail. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), BET surfaced area and thermogravimetry-differential thermal analysis (TG-DTA) techniques. The phase purity, crystallite size, Brunauer-Emmett-Teller (BET) surface area and CO2 adsorption performance of Ca(OH)2 precursor adsorbents were significantly increased when the concentration of CTAB was increased. XRD results showed that pure Ca(OH)2 phase was obtained at the CTAB concentration of 0.8 M. TGA results exhibited that 0.8 M of CTAB-assisted Ca(OH)2 precursor adsorbent possessed a residual carbonation conversion of ∼56% after 10 cycles.

Molecular cloning of mevalonate pathway genes from Taraxacum brevicorniculatum and functional characterisation of the key enzyme 3-hydroxy-3-methylglutaryl-coenzyme A reductase.

PubMed

van Deenen, Nicole; Bachmann, Anne-Lena; Schmidt, Thomas; Schaller, Hubert; Sand, Jennifer; Prüfer, Dirk; Schulze Gronover, Christian

2012-04-01

Taraxacum brevicorniculatum is known to produce high quality rubber. The biosynthesis of rubber is dependent on isopentenyl pyrophosphate (IPP) precursors derived from the mevalonate (MVA) pathway. The cDNA sequences of seven MVA pathway genes from latex of T. brevicorniculatum were isolated, including three cDNA sequences encoding for 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) reductases (TbHMGR1-3). Expression analyses indicate an important role of TbHMGR1 as well as for the HMG-CoA synthase (TbHMGS), the diphosphomevalonate decarboxylase and the mevalonate kinase in the provision of precursors for rubber biosynthesis. The amino acid sequences of the TbHMGRs show the typical motifs described for plant HMGRs such as two transmembrane domains and a catalytic domain containing two HMG-CoA and two NADP(H) binding sites. The functionality of the HMGRs was demonstrated by complementation assay using an IPP auxotroph mutant of Escherichia coli. Furthermore, the transient expression of the catalytic domains of TbHMGR1 and TbHMGR2 in Nicotiana benthamiana resulted in a strong accumulation of sterol precursors, one of the major groups of pathway end-products.

Method of making nanopatterns and nanostructures and nanopatterned functional oxide materials

DOEpatents

Dravid, Vinayak P; Donthu, Suresh K; Pan, Zixiao

2014-02-11

Method for nanopatterning of inorganic materials, such as ceramic (e.g. metal oxide) materials, and organic materials, such as polymer materials, on a variety of substrates to form nanopatterns and/or nanostructures with control of dimensions and location, all without the need for etching the materials and without the need for re-alignment between multiple patterning steps in forming nanostructures, such as heterostructures comprising multiple materials. The method involves patterning a resist-coated substrate using electron beam lithography, removing a portion of the resist to provide a patterned resist-coated substrate, and spin coating the patterned resist-coated substrate with a liquid precursor, such as a sol precursor, of the inorganic or organic material. The remaining resist is removed and the spin coated substrate is heated at an elevated temperature to crystallize the deposited precursor material.

Method of preparation of carbon materials for use as electrodes in rechargeable batteries

DOEpatents

Doddapaneni, Narayan; Wang, James C. F.; Crocker, Robert W.; Ingersoll, David; Firsich, David W.

1999-01-01

A method of producing carbon materials for use as electrodes in rechargeable batteries. Electrodes prepared from these carbon materials exhibit intercalation efficiencies of .apprxeq.80% for lithium, low irreversible loss of lithium, long cycle life, are capable of sustaining a high rates of discharge and are cheap and easy to manufacture. The method comprises a novel two-step stabilization process in which polymeric precursor materials are stabilized by first heating in an inert atmosphere and subsequently heating in air. During the stabilization process, the polymeric precursor material can be agitated to reduce particle fusion and promote mass transfer of oxygen and water vapor. The stabilized, polymeric precursor materials can then be converted to a synthetic carbon, suitable for fabricating electrodes for use in rechargeable batteries, by heating to a high temperature in a flowing inert atmosphere.

Synthesis of quantum dots

DOEpatents

McDaniel, Hunter

2017-10-17

Common approaches to synthesizing alloyed quantum dots employ high-cost, air-sensitive phosphine complexes as the selenium precursor. Disclosed quantum dot synthesis embodiments avoid these hazardous and air-sensitive selenium precursors. Certain embodiments utilize a combination comprising a thiol and an amine that together reduce and complex the elemental selenium to form a highly reactive selenium precursor at room temperature. The same combination of thiol and amine acts as the reaction solvent, stabilizing ligand, and sulfur source in the synthesis of quantum dot cores. A non-injection approach may also be used. The optical properties of the quantum dots synthesized by this new approach can be finely tuned for a variety of applications by controlling size and/or composition of size and composition. Further, using the same approach, a shell can be grown around a quantum dot core that improves stability, luminescence efficiency, and may reduce toxicity.

Extreme and superextreme events in a loss-modulated CO2 laser: Nonlinear resonance route and precursors

NASA Astrophysics Data System (ADS)

Bonatto, Cristian; Endler, Antonio

2017-07-01

We investigate the occurrence of extreme and rare events, i.e., giant and rare light pulses, in a periodically modulated CO2 laser model. Due to nonlinear resonant processes, we show a scenario of interaction between chaotic bands of different orders, which may lead to the formation of extreme and rare events. We identify a crisis line in the modulation parameter space, and we show that, when the modulation amplitude increases, remaining in the vicinity of the crisis, some statistical properties of the laser pulses, such as the average and dispersion of amplitudes, do not change much, whereas the amplitude of extreme events grows enormously, giving rise to extreme events with much larger deviations than usually reported, with a significant probability of occurrence, i.e., with a long-tailed non-Gaussian distribution. We identify recurrent regular patterns, i.e., precursors, that anticipate the emergence of extreme and rare events, and we associate these regular patterns with unstable periodic orbits embedded in a chaotic attractor. We show that the precursors may or may not lead to the emergence of extreme events. Thus, we compute the probability of success or failure (false alarm) in the prediction of the extreme events, once a precursor is identified in the deterministic time series. We show that this probability depends on the accuracy with which the precursor is identified in the laser intensity time series.

Predicting the stability of ternary intermetallics with density functional theory and machine learning

NASA Astrophysics Data System (ADS)

Schmidt, Jonathan; Chen, Liming; Botti, Silvana; Marques, Miguel A. L.

2018-06-01

We use a combination of machine learning techniques and high-throughput density-functional theory calculations to explore ternary compounds with the AB2C2 composition. We chose the two most common intermetallic prototypes for this composition, namely, the tI10-CeAl2Ga2 and the tP10-FeMo2B2 structures. Our results suggest that there may be ˜10 times more stable compounds in these phases than previously known. These are mostly metallic and non-magnetic. While the use of machine learning reduces the overall calculation cost by around 75%, some limitations of its predictive power still exist, in particular, for compounds involving the second-row of the periodic table or magnetic elements.

Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

PubMed Central

Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

2016-01-01

Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

Methyltrimethoxysilane (MTMS)-based silica-iron oxide superhydrophobic nanocomposites.

PubMed

Nadargi, Digambar; Gurav, Jyoti; Marioni, Miguel A; Romer, Sara; Matam, Santhosh; Koebel, Matthias M

2015-12-01

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Pulsed infrared difference frequency generation in CdGeAs.sub.2

DOEpatents

Piltch, Martin S.; Rink, John P.; Tallman, Charles R.

1977-03-08

The disclosure relates to a laser apparatus for generating a line-tunable pulsed infrared difference frequency output. The apparatus comprises a CO.sub.2 laser which produces a first frequency, a CO laser which produces a second frequency and a mixer for combining the output of the CO.sub.2 and CO lasers so as to produce a final output comprising a difference frequency from the first and second frequency outputs.

Pulsed infrared difference frequency generation in CdGeAs/sub 2/

DOEpatents

Piltch, M.S.; Rink, J.P.; Tallman, C.R.

1975-11-26

A laser apparatus for generating a line-tunable pulsed infrared difference frequency output is described. The apparatus comprises a CO/sub 2/ laser which produces a first frequency, a CO laser which produces a second frequency, and a mixer for combining the output of the CO/sub 2/ and CO lasers so as to produce a final output comprising a difference frequency from the first and second frequency outputs.

Structural and biochemical characterization of cinnamoyl-coa reductases

USDA-ARS?s Scientific Manuscript database

Cinnamoyl-coenzyme A reductase (CCR) catalyzes the reduction of hydroxycinnamoyl-coenzyme A (CoA) esters using NADPH to produce hydroxycinnamyl aldehyde precursors in lignin synthesis. The catalytic mechanism and substrate specificity of cinnamoyl-CoA reductases from sorghum (Sorghum bicolor), a str...

Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

F-T process using an iron on mixed zirconia-titania supported catalyst

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1987-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

Method of CO and/or CO.sub.2 hydrogenation using doped mixed-metal oxides

DOEpatents

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.; Abdelsayed, Victor; Smith, Mark W.; Spivey, James J.

2015-10-06

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

Double perovskite Sr2FeMoO6-xNx (x=0.3, 1.0) oxynitrides with anionic ordering

NASA Astrophysics Data System (ADS)

Retuerto, M.; de la Calle, C.; Martínez-Lope, M. J.; Porcher, F.; Krezhov, K.; Menéndez, N.; Alonso, J. A.

2012-01-01

Two new oxynitride double perovskites of composition Sr2FeMoO6-xNx (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 °C and 650 °C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Mössbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) Å, c=7.9024(2) Å, V=247.46(2) Å3 for Sr2FeMoO5.7N0.3; and a=5.6202(2) Å, c=7.9102(4) Å, V=249.85(2) Å3 for Sr2FeMoO5N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 °C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the and distances suggests a shift towards a configuration close to Fe4+(3d4, S=2):Mo5+(4d1, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr2FeMoO6, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization.

Out-of-equilibrium Sm Fe based phases

NASA Astrophysics Data System (ADS)

Djéga-Mariadassou, C.; Bessais, L.

2008-02-01

Structure and magnetic properties of nanocrystalline P6/mmm out-of-equilibrium precursors of hard magnetic R-3m Sm2(Fe,M)17C (M=Ga,Si,) and I4/mmm Sm(Fe,Co,Ti)11 equilibrium phases, are presented. Their structure is explained with a model ground on the R1 - s T5 + 2 s formula (R=rare-earth, s=vacancy rate, T=transition metal) where s Sm atoms are statistically substituted by s transition metal pairs. The Rietveld analysis (RA) provides the stoichiometry of the precursors, 1:9 and 1:10, respectively precursor of 2:17 and 1:12 phases. The interpretation of the Mössbauer spectra of the 1:9 and 1:10 phases, is based on the correlation between δ and the Wigner Seitz Cell volumes, calculated from the structural parameters. The δ behaviour of each crystallographic site versus Co content, defines the Co location while it confirms that of Si and Ga obtained by RA. Substitution occurs in 3 g site, whatever Co or M. The Sm(Fe,Co,Ti)10 and Sm(Fe,M)9C Curie temperature (Tc) are compared to those of the equilibrium phases, the effects of Fe substitution and C addition are discussed. The maximum μ 0Hc is obtained for low M or Co content, for auto-coherent diffraction domain size ˜30 nm. SmFe8.75Ga0.25C and SmFe8.75Si0.25C with Tc of 680 and 690 K, show respectively Mr and μ 0Hc of 58 emu/g, 27 kOe and 95 emu/g, 15 kOe, values higher than those obtained for Sm2(Fe,M)17 carbides.

Mechanism of calcite co-orientation in the sea urchin tooth.

PubMed

Killian, Christopher E; Metzler, Rebecca A; Gong, Y U T; Olson, Ian C; Aizenberg, Joanna; Politi, Yael; Wilt, Fred H; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N; Gilbert, P U P A

2009-12-30

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO(3)) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin ( Strongylocentrotus purpuratus ), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction (muXRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO(3) is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

A three body problem: a genuine heterotrimetallic molecule vs. a mixture of two parent heterobimetallic molecules.

PubMed

Han, Haixiang; Wei, Zheng; Barry, Matthew C; Carozza, Jesse C; Alkan, Melisa; Rogachev, Andrey Yu; Filatov, Alexander S; Abakumov, Artem M; Dikarev, Evgeny V

2018-06-07

This work raises a fundamental question about the "real" structure of molecular compounds containing three different metals: whether they consist of genuine hetero tri metallic species or of a mixture of parent hetero bi metallic species. Heterotrimetallic complex Li 2 CoNi(tbaoac) 6 ( 1 , tbaoac = tert -butyl acetoacetate) has been designed based on the model tetranuclear structure featuring two transition metal sites in order to be utilized as a molecular precursor for the low-temperature preparation of the LiCo 0.5 Ni 0.5 O 2 battery cathode material. An investigation of the structure of 1 appeared to be very challenging, since the Co and Ni atoms have very similar atomic numbers, monoisotopic masses, and radii as well as the same oxidation state and coordination number/environment. Using a statistical analysis of heavily overlaid isotope distribution patterns of the [Li 2 MM'L 5 ] + (M/M' = Co 2 , Ni 2 , and CoNi) ions in DART mass spectra, it was concluded that the reaction product 1 contains both heterotrimetallic and bimetallic species. A structural analogue approach has been applied to obtain Li 2 MMg(tbaoac) 6 (M = Co ( 2 ) and Ni ( 3 )) complexes that contain lighter, diamagnetic magnesium in the place of one of the 3d transition metals. X-ray crystallography, mass spectrometry, and NMR spectroscopy unambiguously confirmed the presence of three types of molecules in the reaction mixture that reaches an equilibrium, Li 2 M 2 L 6 + Li 2 Mg 2 L 6 ↔ 2Li 2 MMgL 6 , upon prolonged reflux in solution. The equilibrium mixture was shown to have a nearly statistical distribution of the three molecules, and this is fully supported by the results of theoretical calculations revealing that the stabilization energies of hetero tri metallic assemblies fall exactly in between those for the parent hetero bi metallic species. The LiCo 0.5 Ni 0.5 O 2 quaternary oxide has been obtained in its phase-pure form by thermal decomposition of heterometallic precursor 1 at temperatures as low as 450 °C. Its chemical composition, structure, morphology, and transition metal distribution have been studied by X-ray and electron diffraction techniques and compositional energy-dispersive X-ray mapping with nanometer resolution. The work clearly illustrates the advantages of heterometallic single-source precursors over the corresponding multi-source precursors.

Fabrication of carbonate apatite blocks from set gypsum based on dissolution-precipitation reaction in phosphate-carbonate mixed solution.

PubMed

Nomura, Shunsuke; Tsuru, Kanji; Maruta, Michito; Matsuya, Shigeki; Takahashi, Ichiro; Ishikawa, Kunio

2014-01-01

Carbonate apatite (CO3Ap), fabricated by dissolution-precipitation reaction based on an appropriate precursor, is expected to be replaced by bone according to bone remodeling cycle. One of the precursor candidates is gypsum because it shows self-setting ability, which then enables it to be shaped and molded. The aim of this study, therefore, was to fabricate CO3Ap blocks from set gypsum. Set gypsum was immersed in a mixed solution of 0.4 mol/L disodium hydrogen phosphate (Na2HPO4) and 0.4 mol/L sodium hydrogen carbonate (NaHCO3) at 80-200°C for 6-48 h. Powder X-ray diffraction patterns and Fourier transform infrared spectra showed that CO3Ap block was fabricated by dissolution-precipitation reaction in Na2HPO4-NaHCO3 solution using set gypsum in 48 h when the temperature was 100°C or higher. Conversion rate to CO3Ap increased with treatment temperature. CO3Ap block containing a larger amount of carbonate was obtained when treated at lower temperature.

NGFFFamide and echinotocin: structurally unrelated myoactive neuropeptides derived from neurophysin-containing precursors in sea urchins.

PubMed

Elphick, Maurice R; Rowe, Matthew L

2009-04-01

The myoactive neuropeptide NGIWYamide was originally isolated from the holothurian (sea cucumber) Apostichopus japonicus but there is evidence that NGIWYamide-like peptides also occur in other echinoderms. Here we report the discovery of a gene in the sea urchin Strongylocentrotus purpuratus that encodes two copies of an NGIWYamide-like peptide: Asn-Gly-Phe-Phe-Phe-(NH(2)) or NGFFFamide. Interestingly, the C-terminal region of the NGFFFamide precursor shares sequence similarity with neurophysins, carrier proteins hitherto uniquely associated with precursors of vasopressin/oxytocin-like neuropeptides. Thus, the NGFFFamide precursor is the first neurophysin-containing neuropeptide precursor to be discovered that does not contain a vasopressin/oxytocin-like peptide. However, it remains to be determined whether neurophysin acts as a carrier protein for NGFFFamide. The S. purpuratus genome also contains a gene encoding a precursor comprising a neurophysin polypeptide and 'echinotocin' (CFISNCPKGamide) - the first vasopressin/oxytocin-like peptide to be identified in an echinoderm. Therefore, in S. purpuratus there are two genes encoding precursors that have a neurophysin domain but which encode neuropeptides that are structurally unrelated. Furthermore, both NGFFFamide and echinotocin cause contraction of tube foot and oesophagus preparations from the sea urchin Echinus esculentus, consistent with the myoactivity of NGIWYamide in sea cucumbers and the myoactivity of vasopressin/oxytocin-like peptides in other animal phyla. Presumably the NGFFFamide precursor acquired its neurophysin domain following partial or complete duplication of a gene encoding a vasopressin/oxytocin-like peptide, but it remains to be determined when in evolutionary history this occurred.

The hybrid nanostructure of MnCo2O4.5 nanoneedle/carbon aerogel for symmetric supercapacitors with high energy density

NASA Astrophysics Data System (ADS)

Hao, Pin; Zhao, Zhenhuan; Li, Liyi; Tuan, Chia-Chi; Li, Haidong; Sang, Yuanhua; Jiang, Huaidong; Wong, C. P.; Liu, Hong

2015-08-01

Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg-1 at a power density of 600 W kg-1. The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles.Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg-1 at a power density of 600 W kg-1. The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04421a

A [4Fe-4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly

NASA Astrophysics Data System (ADS)

Rao, Guodong; Tao, Lizhi; Suess, Daniel L. M.; Britt, R. David

2018-05-01

Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate—the first organometallic precursor to the H-cluster—validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster.

Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

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

Tang, Lulu; Nguyen, Van Hoa; Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang

2015-11-15

Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electronmore » microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.« less

Conversion of the high-yield salinomycin producer Streptomyces albus BK3-25 into a surrogate host for polyketide production.

PubMed

Zhang, Xiaojie; Lu, Chenyang; Bai, Linquan

2017-09-01

An ideal surrogate host for heterologous production of various natural products is expected to have efficient nutrient utilization, fast growth, abundant precursors and energy supply, and a pronounced gene expression. Streptomyces albus BK3-25 is a high-yield industrial strain producing type-I polyketide salinomycin, with a unique ability of bean oil utilization. Its potential of being a surrogate host for heterologous production of PKS was engineered and evaluated herein. Firstly, introduction of a three-gene cassette for the biosynthesis of ethylmalonyl-CoA resulted in accumulation of ethylmalonyl-CoA precursor and salinomycin, and subsequent deletion of the salinomycin biosynthetic gene cluster resulted in a host with rich supplies of common polyketide precursors, including malonyl-CoA, methylmalonyl-CoA, and ethylmalonyl-CoA. Secondly, the energy and reducing force were measured, and the improved accumulation of ATP and NADPH was observed in the mutant. Furthermore, the strength of a series of selected endogenous promoters based on microarray data was assessed at different growth phases, and a strong constitutive promoter was identified, providing a useful tool for further engineered gene expression. Finally, the potential of the BK3-25 derived host ZXJ-6 was evaluated with the introduction of the actinorhodin biosynthetic gene cluster from Streptomyces coelicolor, and the heterologous production of actinorhodin was obtained. This work clearly indicated the potential of the high-yield salinomycin producer as a surrogate host for heterologous production of polyketides, although more genetic manipulation should be conducted to streamline its performance.

Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Hsu, Chun-Tsung; Hu, Chi-Chang

2013-11-01

A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

Modeling of the HiPco process for carbon nanotube production. I. Chemical kinetics

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Gokcen, Tahir; Meyyappan, M.

2002-01-01

A chemical kinetic model is developed to help understand and optimize the production of single-walled carbon nanotubes via the high-pressure carbon monoxide (HiPco) process, which employs iron pentacarbonyl as the catalyst precursor and carbon monoxide as the carbon feedstock. The model separates the HiPco process into three steps, precursor decomposition, catalyst growth and evaporation, and carbon nanotube production resulting from the catalyst-enhanced disproportionation of carbon monoxide, known as the Boudouard reaction: 2 CO(g)-->C(s) + CO2(g). The resulting detailed model contains 971 species and 1948 chemical reactions. A second model with a reduced reaction set containing 14 species and 22 chemical reactions is developed on the basis of the detailed model and reproduces the chemistry of the major species. Results showing the parametric dependence of temperature, total pressure, and initial precursor partial pressures are presented, with comparison between the two models. The reduced model is more amenable to coupled reacting flow-field simulations, presented in the following article.

Identification of two structurally related proteins involved in proteolytic processing of precursors targeted to the chloroplast.

PubMed Central

Oblong, J E; Lamppa, G K

1992-01-01

Two proteins of 145 and 143 kDa were identified in pea which co-purify with a chloroplast processing activity that cleaves the precursor for the major light-harvesting chlorophyll binding protein (preLHCP). Antiserum generated against the 145/143 kDa doublet recognizes only these two polypeptides in a chloroplast soluble extract. In immunodepletion experiments the antiserum removed the doublet, and there was a concomitant loss of cleavage of preLHCP as well as of precursors for the small subunit of Rubisco and the acyl carrier protein. The 145 and 143 kDa proteins co-eluted in parallel with the peak of processing activity during all fractionation procedures, but they were not detectable as a homo- or heterodimeric complex. The 145 and 143 kDa proteins were used separately to affinity purify immunoglobulins; each preparation recognized both polypeptides, indicating that they are antigenically related. Wheat chloroplasts contain a soluble species similar in size to the 145/143 kDa doublet. Images PMID:1385116

Microporous Co@C Nanoparticles Prepared by Dealloying CoAl@C Precursors: Achieving Strong Wideband Microwave Absorption via Controlling Carbon Shell Thickness.

PubMed

Li, Da; Liao, Haoyan; Kikuchi, Hiroaki; Liu, Tong

2017-12-27

Excellent magnetic features make Co-based materials promising candidates as high-performance microwave absorbers. However, it is still a significant challenge for Co-based absorbers to possess high-intensity and broadband absorption simultaneously, owing to the lack of dielectric loss and impedance matching. Herein, microporous Co@C nanoparticles (NPs) with carbon shell thicknesses ranging from 1.8-4.9 nm have been successfully synthesized by dealloying CoAl@C precursors. All of the samples exhibit high microwave absorption performance. The microporous Co@C sample possessing a carbon shell of 1.8 nm exhibits the highest absorption intensity among these samples with a minimum reflection loss (RL) of -141.1 dB, whose absorption bandwidth for RL ≤ -10 dB is 7.3 GHz. As the thickness of the carbon shell increases, the absorption bandwidth of the NPs becomes wider. For the sample with the carbon shell thickness of 4.9 nm, the absorption bandwidth for RL ≤ -10 dB reaches a record high of 13.2 GHz. The outstanding microwave attenuation properties are attributed to the dielectric loss of the carbon shell, the magnetic loss of the Co core, and the cooperation of the core-shell structure and microporous morphology. The strong wideband microwave absorption of the carbon-coated microporous Co NPs highlights their potential applications in microwave absorbing systems.

Geoelectric precursors to strong earthquakes in China

NASA Astrophysics Data System (ADS)

Yulin, Zhao; Fuye, Qian

1994-05-01

The main results of searching for electrical precursors to strong earthquakes in China for the last 25 yr are presented. This comprises: the continuous twenty-year resistivity record before and after the great Tangshan earthquake of 1976; spatial and temporal variations in resistivity anomalies observed at more than 6 stations within 150 km of the Tangshan earthquake epicenter; the travel-time curve for the front of the resistivity precursor; and a method of intersection for predicting the epicenter location. These results reveal a number of interesting facts: (1) Resistivity measurements with accuracies of 0.5% or better for over 20 yr show that resistivity decreases of several percent, which began approximately 3 yr prior to the Tangshan earthquake, were larger than the background fluctuations and hence statistically significant. An outstanding example of an intermediate-term resistivity precursor is given. (2) The intermediate-term resistivity precursor decrease before Tangshan earthquake is such a pervasive phenomenon that the mean decrease, in percent, can be contoured on a map of the Beijing-Tianjin-Tangshan region. This shows the maximum decrease centered over the epicenter. (3) The anomalies in resistivity and self-potential, which began 2-0.5 months before the Tangshan main shock, had periods equal to that of the tidal waves M 2 and MS f, respectively, so that the associated anomalies can be identified as impending-earthquake precursors and a modal related to stress-displacement weakening is proposed.

Method of fabricating free-form, high-aspect ratio components for high-current, high-speed microelectrics

DOEpatents

Maxwell, James L; Rose, Chris R; Black, Marcie R; Springer, Robert W

2014-03-11

Microelectronic structures and devices, and method of fabricating a three-dimensional microelectronic structure is provided, comprising passing a first precursor material for a selected three-dimensional microelectronic structure into a reaction chamber at temperatures sufficient to maintain said precursor material in a predominantly gaseous state; maintaining said reaction chamber under sufficient pressures to enhance formation of a first portion of said three-dimensional microelectronic structure; applying an electric field between an electrode and said microelectronic structure at a desired point under conditions whereat said first portion of a selected three-dimensional microelectronic structure is formed from said first precursor material; positionally adjusting either said formed three-dimensional microelectronic structure or said electrode whereby further controlled growth of said three-dimensional microelectronic structure occurs; passing a second precursor material for a selected three-dimensional microelectronic structure into a reaction chamber at temperatures sufficient to maintain said precursor material in a predominantly gaseous state; maintaining said reaction chamber under sufficient pressures whereby a second portion of said three-dimensional microelectronic structure formation is enhanced; applying an electric field between an electrode and said microelectronic structure at a desired point under conditions whereat said second portion of a selected three-dimensional microelectronic structure is formed from said second precursor material; and, positionally adjusting either said formed three-dimensional microelectronic structure or said electrode whereby further controlled growth of said three-dimensional microelectronic structure occurs.

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

NASA Astrophysics Data System (ADS)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Method of preparation of carbon materials for use as electrodes in rechargeable batteries

DOEpatents

Doddapaneni, N.; Wang, J.C.F.; Crocker, R.W.; Ingersoll, D.; Firsich, D.W.

1999-03-16

A method is described for producing carbon materials for use as electrodes in rechargeable batteries. Electrodes prepared from these carbon materials exhibit intercalation efficiencies of {approx_equal} 80% for lithium, low irreversible loss of lithium, long cycle life, are capable of sustaining a high rates of discharge and are cheap and easy to manufacture. The method comprises a novel two-step stabilization process in which polymeric precursor materials are stabilized by first heating in an inert atmosphere and subsequently heating in air. During the stabilization process, the polymeric precursor material can be agitated to reduce particle fusion and promote mass transfer of oxygen and water vapor. The stabilized, polymeric precursor materials can then be converted to a synthetic carbon, suitable for fabricating electrodes for use in rechargeable batteries, by heating to a high temperature in a flowing inert atmosphere. 4 figs.

Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

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

Oyola, Yatsandra; Tian, Chengcheng; Bauer, John Christopher

An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted inmore » liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphoric acid groups appended thereto.« less

Lightning NOx and Impacts on Air Quality

NASA Technical Reports Server (NTRS)

Murray, Lee T.

2016-01-01

Lightning generates relatively large but uncertain quantities of nitrogen oxides, critical precursors for ozone and hydroxyl radical (OH), the primary tropospheric oxidants. Lightning nitrogen oxide strongly influences background ozone and OH due to high ozone production efficiencies in the free troposphere, effecting small but non-negligible contributions to surface pollutant concentrations. Lightning globally contributes 3-4 ppbv of simulated annual-mean policy-relevant background (PRB) surface ozone, comprised of local, regional, and hemispheric components, and up to 18 ppbv during individual events. Feedbacks via methane may counter some of these effects on decadal time scales. Lightning contributes approximately 1 percent to annual-mean surface particulate matter, as a direct precursor and by promoting faster oxidation of other precursors. Lightning also ignites wildfires and contributes to nitrogen deposition. Urban pollution influences lightning itself, with implications for regional lightning-nitrogen oxide production and feedbacks on downwind surface pollution. How lightning emissions will change in a warming world remains uncertain.

Multiscale multifractal properties between ground-level ozone and its precursors in rural area in Hong Kong.

PubMed

He, Hong-di; Qiao, Zhong-Xia; Pan, Wei; Lu, Wei-Zhen

2017-07-01

In rural area, due to the reduction of NOx and CO emitted from vehicle exhausts, the ozone photochemical reaction exhibits relatively weak effect and ozone formation presents different pattern with its precursors in contrast to urban situation. Hence, in this study, we apply detrended cross-correlation analysis to investigate the multifractal properties between ozone and its precursors in a rural area in Hong Kong. The observed databases of ozone, NO 2 , NOx and CO levels during 2005-2014 are obtained from a rural monitoring station in Hong Kong. Based on the collected database, the cross-correlation analysis is carried out firstly to examine the cross-correlation patterns and the results indicate that close interactive relations exist between them. Then the detrended cross-correlation analysis is performed for further analysis. The multifractal characters occur between ozone and its precursors. The long-term cross-correlations behaviors in winter are verified to be stronger than that in other seasons. Additionally, the method is extended on daily averaged data to explore the multifractal property on various time scales. The long-term cross-correlation behavior of ozone vs NO 2 and NOx on daily basis becomes weaker while that of ozone vs CO becomes stronger. The multifractal properties for all pairs in summer are found to be the strongest among the whole year. These findings successfully illustrate that the multifractal analysis is a useful tool for describing the temporal scaling behaviors of ozone trends in different time series in rural areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD).more » All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.« less

Co-ultramicronized Palmitoylethanolamide/Luteolin Promotes the Maturation of Oligodendrocyte Precursor Cells.

PubMed

Barbierato, Massimo; Facci, Laura; Marinelli, Carla; Zusso, Morena; Argentini, Carla; Skaper, Stephen D; Giusti, Pietro

2015-11-18

Oligodendrocytes have limited ability to repair the damage to themselves or to other nerve cells, as seen in demyelinating diseases like multiple sclerosis. An important strategy may be to replace the lost oligodendrocytes and/or promote the maturation of undifferentiated oligodendrocyte precursor cells (OPCs). Recent studies show that a composite of co-ultramicronized N-palmitoylethanolamine (PEA) and luteolin (co-ultramicronized PEA/luteolin, 10:1 by mass) is efficacious in improving outcome in experimental models of spinal cord and traumatic brain injuries. Here, we examined the ability of co-ultramicronized PEA/luteolin to promote progression of OPCs into a more differentiated phenotype. OPCs derived from newborn rat cortex were placed in culture and treated the following day with 10 μM co-ultramicronized PEA/luteolin. Cells were collected 1, 4 and 8 days later and analyzed for expression of myelin basic protein (MBP). qPCR and Western blot analyses revealed a time-dependent increase in expression of both mRNA for MBP and MBP content, along with an increased expression of genes involved in lipid biogenesis. Ultramicronized PEA or luteolin, either singly or in simple combination, were ineffective. Further, co-ultramicronized PEA/luteolin promoted morphological development of OPCs and total protein content without affecting proliferation. Co-ultramicronized PEA/luteolin may represent a novel pharmacological strategy to promote OPC maturation.

A study on the electrical, optical, and physicochemical properties of poly(MMA-co-MAA)/ poly(3,4-ethylenedioxythiophene) hybrid thin films.

PubMed

Han, Yong-Hyeon; Kim, Hyeong Eun; Hwangbo, Kyung-Hee; Yim, Jin-Heong; Cho, Kuk Young

2013-08-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) has good properties as a conductive polymer such as high conductivity, optical transmittance, and chemical stability, while offering relatively weak physicochemical properties. The main purpose of this paper is to improve physicochemical properties such as solvent resistance and pencil hardness of PEDOT. Carboxyl groups in the poly(MMA-co-MAA) polymer chains can effectively crosslink each other in the presence of aziridine, resulting in physicochemically robust PEDOT/poly(MMA-co-MAA) hybrid conductive films. The electrical conductivity, optical properties, and physicochemical properties of the hybrid conductive film were compared by varying the solid content and poly(MMA-co-MAA) portion in the coating precursor solution. From the results, the transparency and surface resistance of the hybrid film show a tendency to decrease with increasing solid content in the coating precursor. Moreover, solvent resistance and hardness were dramatically enhanced by hybridization of PEDOT and crosslinked poly(MMA-co-MAA) due to curing reactions between carboxyl groups. The chemical composition of 30 wt-% of poly(MMA-co-MAA) (MMA:MAA mole ratio 9:1) and 3 wt-% - 5 wt-% of aziridine yields the best physicochemical properties of poly(MMA-co-MAA)/PEDOT hybrid thin films.

Characterization of Nanoporous Materials with Atom Probe Tomography.

PubMed

Pfeiffer, Björn; Erichsen, Torben; Epler, Eike; Volkert, Cynthia A; Trompenaars, Piet; Nowak, Carsten

2015-06-01

A method to characterize open-cell nanoporous materials with atom probe tomography (APT) has been developed. For this, open-cell nanoporous gold with pore diameters of around 50 nm was used as a model system, and filled by electron beam-induced deposition (EBID) to obtain a compact material. Two different EBID precursors were successfully tested-dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9]. Penetration and filling depth are sufficient for focused ion beam-based APT sample preparation. With this approach, stable APT analysis of the nanoporous material can be performed. Reconstruction reveals the composition of the deposited precursor and the nanoporous material, as well as chemical information of the interfaces between them. Thus, it is shown that, using an appropriate EBID process, local chemical information in three dimensions with sub-nanometer resolution can be obtained from nanoporous materials using APT.

Source attribution of tropospheric ozone

NASA Astrophysics Data System (ADS)

Butler, T. M.

2015-12-01

Tropospheric ozone is a harmful pollutant with adverse effects on human health and ecosystems. As well as these effects, tropospheric ozone is also a powerful greenhouse gas, with an anthropogenic radiative forcing one quarter of that of CO2. Along with methane and atmospheric aerosol, tropospheric ozone belongs to the so-called Short Lived Climate forcing Pollutants, or SLCP. Recent work has shown that efforts to reduce concentrations of SLCP in the atmosphere have the potential to slow the rate of near-term climate change, while simultaneously improving public health and reducing crop losses. Unlike many other SLCP, tropospehric ozone is not directly emitted, but is instead influenced by two distinct sources: transport of air from the ozone-rich stratosphere; and photochemical production in the troposphere from the emitted precursors NOx (oxides of nitrogen), CO (Carbon Monoxide), and VOC (volatile organic compounds, including methane). Better understanding of the relationship between ozone production and the emissions of its precursors is essential for the development of targeted emission reduction strategies. Several modeling methods have been employed to relate the production of tropospheric ozone to emissions of its precursors; emissions perturbation, tagging, and adjoint sensitivity methods all deliver complementary information about modelled ozone production. Most studies using tagging methods have focused on attribution of tropospheric ozone production to emissions of NOx, even though perturbation methods have suggested that tropospheric ozone is also sensitive to VOC, particularly methane. In this study we describe the implementation into a global chemistry-climate model of a scheme for tagging emissions of NOx and VOC with an arbitrary number of labels, which are followed through the chemical reactions of tropospheric ozone production in order to perform attribution of tropospehric ozone to its emitted precursors. Attribution is performed to both geographical regions and to emission sectors. Source-receptor relationships are defined for intercontinental transport of ozone and its precursors, and the relative contributions of NOx, methane, CO, NMVOC, and stratosphere-troposphere exchange to tropospheric background ozone are determined.

Detection and Phylogenetic Analysis of Group 1 Coronaviruses in South American Bats

PubMed Central

Foster, Jerome E.; Zhu, Hua Chen; Zhang, Jin Xia; Smith, Gavin J.D.; Thompson, Nadin; Auguste, Albert J.; Ramkissoon, Vernie; Adesiyun, Abiodun A.; Guan, Yi

2008-01-01

Bat coronaviruses (Bt-CoVs) are thought to be the precursors of severe acute respiratory syndrome coronavirus. We detected Bt-CoVs in 2 bat species from Trinidad. Phylogenetic analysis of the RNA-dependent RNA polymerase gene and helicase confirmed them as group 1 coronaviruses. PMID:19046513

Polymide gas separation membranes

DOEpatents

Ding, Yong; Bikson, Benjamin; Nelson, Joyce Katz

2004-09-14

Soluble polyamic acid salt (PAAS) precursors comprised of tertiary and quaternary amines, ammonium cations, sulfonium cations, or phosphonium cations, are prepared and fabricated into membranes that are subsequently imidized and converted into rigid-rod polyimide articles, such as membranes with desirable gas separation properties. A method of enhancing solubility of PAAS polymers in alcohols is also disclosed.

Chemical vapor deposition of W-Si-N and W-B-N

DOEpatents

Fleming, James G.; Roherty-Osmun, Elizabeth Lynn; Smith, Paul M.; Custer, Jonathan S.; Jones, Ronald V.; Nicolet, Marc-A.; Madar, Roland; Bernard, Claude

1999-01-01

A method of depositing a ternary, refractory based thin film on a substrate by chemical vapor deposition employing precursor sources of tungsten comprising WF.sub.6, either silicon or boron, and nitrogen. The result is a W--Si--N or W--B--N thin film useful for diffusion barrier and micromachining applications.

Novel amine-based presursor compounds and composite membranes thereof

DOEpatents

Lee, Eric K. L.; Tuttle, Mark E.

1989-01-01

Novel amine-based precursor compounds comprising the condensation products of dialkylenetriamine and alpha, beta-unsaturated acid halides are disclosed, as well as composite membranes containing such compounds, the membranes being useful in RO-type processes for desalination and the removal of low molecular weight organic compounds such as phenols and carboxylic acids.

Chemical vapor deposition of fluorine-doped zinc oxide

DOEpatents

Gordon, Roy G.; Kramer, Keith; Liang, Haifan

2000-06-06

Fims of fluorine-doped zinc oxide are deposited from vaporized precursor compounds comprising a chelate of a dialkylzinc, such as an amine chelate, an oxygen source, and a fluorine source. The coatings are highly electrically conductive, transparent to visible light, reflective to infrared radiation, absorbing to ultraviolet light, and free of carbon impurity.

Method for fabrication of ceramic dielectric films on copper foils

DOEpatents

Ma, Beihai; Narayanan, Manoj; Dorris, Stephen E.; Balachandran, Uthamalingam

2015-03-10

The present invention provides a method for fabricating a ceramic film on a copper foil. The method comprises applying a layer of a sol-gel composition onto a copper foil. The sol-gel composition comprises a precursor of a ceramic material suspended in 2-methoxyethanol. The layer of sol-gel is then dried at a temperature up to about 250.degree. C. The dried layer is then pyrolyzed at a temperature in the range of about 300 to about 450.degree. C. to form a ceramic film from the ceramic precursor. The ceramic film is then crystallized at a temperature in the range of about 600 to about 750.degree. C. The drying, pyrolyzing and crystallizing are performed under a flowing stream of an inert gas. In some embodiments an additional layer of the sol-gel composition is applied onto the ceramic film and the drying, pyrolyzing and crystallizing steps are repeated for the additional layer to build up a thicker ceramic layer on the copper foil. The process can be repeated one or more times if desired.

Trends in multi-pollutant emissions from a technology-linked inventory for India: I. Industry and transport sectors

NASA Astrophysics Data System (ADS)

Sadavarte, Pankaj; Venkataraman, Chandra

2014-12-01

Emissions estimation, for research and regulatory applications including reporting to international conventions, needs treatment of detailed technology divisions and high-emitting technologies. Here we estimate Indian emissions, for 1996-2015, of aerosol constituents (PM2.5, BC and OC) and precursor gas SO2, ozone precursors (CO, NOx, NMVOC and CH4) and greenhouse gases (CO2 and N2O), using a common fuel consumption database and consistent assumptions. Six source categories and 45 technologies/activities in the industry and transport sectors were used for estimating emissions for 2010. Mean emission factors, developed at the source-category level, were used with corresponding fuel consumption data, available for 1996-2011, projected to 2015. New activities were included to account for fugitive emissions of NMVOC from chemical and petrochemical industries. Dynamic emission factors, reflecting changes in technology-mix and emission regulations, were developed for thermal power plants and on-road transport vehicles. Modeled emission factors were used for gaseous pollutants for on-road vehicles. Emissions of 2.4 (0.6-7.5) Tg y-1 PM2.5, 0.23 (0.1-0.7) Tg y-1 BC, 0.15 (0.04-0.5) Tg y-1 OC, 7.3 (6-10) Tg y-1 SO2, 19 (7.5-33) Tg y-1 CO, 1.5 (0.1-9) Tg y-1 CH4, 4.3 (2-9) Tg y-1 NMVOC, 5.6 (1.7-15.9) Tg y-1 NOx, 1750 (1397-2231) Tg y-1 CO2 and 0.13 (0.05-0.3) Tg y-1 N2O were estimated for 2015. Significant emissions of aerosols and their precursors were from coal use in thermal power and industry (PM2.5 and SO2), and on-road diesel vehicles (BC), especially superemitters. Emissions of ozone precursors were largely from thermal power plants (NOx), on-road gasoline vehicles (CO and NMVOC) and fugitive emissions from mining (CH4). Highly uncertain default emission factors were the principal contributors to uncertainties in emission estimates, indicating the need for region specific measurements.

Application of multi-constituent satellite data assimilation for KORUS-AQ

NASA Astrophysics Data System (ADS)

Miyazaki, K.; Sekiya, T.; Fu, D.; Bowman, K. W.; Kulawik, S. S.; Walker, T.; Takigawa, M.; Ogochi, K.; Gaubert, B.; Barré, J.; Emmons, L. K.

2017-12-01

Comprehensive tropospheric maps of multi-constituent fields at 1.1 degree resolution, provided by an assimilation of multiple satellite measurements of O3, CO, NO2, and HNO3 from multiple satellite (OMI, GOME-2, MOPITT, MLS, and AIRS) using an ensemble Kalman filter, are used to study variations in tropospheric composition over east Asia during KORUS-AQ. Assimilated model results for both direct ozone assimilations and assimilations of ozone precursors (NOx and CO) were compared to DC-8 aircraft observations, with significant improvements in model/aircraft comparisons for ozone (the negative model bias was reduced by up to 80 %), CO (by up to 90 %), OH (by up to 40 %), and NOx seen in both approaches. Corrections made to the precursor emissions (i.e., surface NOx and CO emissions), especially over eastern and central China and over South Korea, were important in reducing the negative bias of O3 and CO over South Korea. We obtained additional bias reductions from assimilation of multispectral retrievals of tropospheric ozone profiles from AIRS and OMI, especially for the middle troposphere ozone. Improved agreements with the ground-based measurements at remote sites over South Korea and western Japan suggest that the representation of long-range transport of polluted air is improved by data assimilation, as a result of the optimization of precursor emissions, mainly over China. The higher estimated NOx, by 60-90 % over South Korea and by 20-40 % over eastern China compared to bottom-up inventories, suggests an important underestimation of anthropogenic sources in the emission inventories in these areas. Additional bias reductions were obtained by assimilating the multispectral retrievals, especially for the middle troposphere O3. In the future, assimilating datasets from a new constellation of low Earth orbiting sounders (e.g., IASI, AIRS, CrIS, Sentinel-5p (TROPOMI), and Sentinel-5) and geostationary satellites (Sentinel-4, GEMS, and TEMPO) will provide more detailed knowledge of ozone and its precursors for east Asia and the entire globe. The data assimilation framework will also be used for chemical OSSE studies to evaluate and optimize the current and future observing systems.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

Global combined precursor isotopic labeling and isobaric tagging (cPILOT) approach with selective MS(3) acquisition.

PubMed

Evans, Adam R; Robinson, Renã A S

2013-11-01

Recently, we reported a novel proteomics quantitation scheme termed "combined precursor isotopic labeling and isobaric tagging (cPILOT)" that allows for the identification and quantitation of nitrated peptides in as many as 12-16 samples in a single experiment. cPILOT offers enhanced multiplexing and posttranslational modification specificity, however excludes global quantitation for all peptides present in a mixture and underestimates reporter ion ratios similar to other isobaric tagging methods due to precursor co-isolation. Here, we present a novel chemical workflow for cPILOT that can be used for global tagging of all peptides in a mixture. Specifically, through low pH precursor dimethylation of tryptic or LysC peptides followed by high pH tandem mass tags, the same reporter ion can be used twice in a single experiment. Also, to improve triple-stage mass spectrometry (MS(3) ) data acquisition, a selective MS(3) method that focuses on product selection of the y1 fragment of lysine-terminated peptides is incorporated into the workflow. This novel cPILOT workflow has potential for global peptide quantitation that could lead to enhanced sample multiplexing and increase the number of quantifiable spectra obtained from MS(3) acquisition methods. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of the processing conditions for the synthesis of rod-shaped LiCoO2

NASA Astrophysics Data System (ADS)

Kim, Taejoong; Kim, Yongseon

2018-07-01

We investigate the processing conditions for the synthesis of rod-shaped LiCoO2 (LCO) by a solid-state calcination of a precursor material which was prepared by a hydrothermal method. The rod-like morphology appeared to be easily broken due to the growth of primary crystals recrystallized during the calcination process. Therefore, it is crucial to maintain the temperature under a certain limit. However, the temperature must be high enough to obtain proper crystallinity of the LCO, ideally above 800 °C. Thus, we determined the optimal calcination temperature condition from the common range of temperatures that satisfies both these limiting conditions. The precursor with average diameter of 1 µm sustained the rod shape at calcination temperatures of up to 900 °C; therefore, the optimum calcination temperature could be determined between 800 and 900 °C. Whereas, a proper calcination temperature could not be found for the precursor with 500 nm of diameter because the rod shape did not maintain even at 700 °C. Thus, the maximum temperature at which the rod shape is retained decreases with smaller diameter of the precursor rods, indicating adjusting the diameter above a limiting value is necessary to prepare LCO rod by conventional solid state calcination.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Gas-Flow Tailoring Fabrication of Graphene-like Co-Nx-C Nanosheet Supported Sub-10 nm PtCo Nanoalloys as Synergistic Catalyst for Air-Cathode Microbial Fuel Cells.

PubMed

Cao, Chun; Wei, Liling; Zhai, Qiran; Ci, Jiliang; Li, Weiwei; Wang, Gang; Shen, Jianquan

2017-07-12

In this work, we presented a novel, facile, and template-free strategy for fabricating graphene-like N-doped carbon as oxygen reduction catalyst in sustainable microbial fuel cells (MFCs) by using an ion-inducing and spontaneous gas-flow tailoring effect from a unique nitrogen-rich polymer gel precursor which has not been reported in materials science. Remarkably, by introduction of trace platinum- and cobalt- precursor in polymer gel, highly dispersed sub-10 nm PtCo nanoalloys can be in situ grown and anchored on graphene-like carbon. The as-prepared catalysts were investigated by a series of physical characterizations, electrochemical measurements, and microbial fuel cell tests. Interestingly, even with a low Pt content (5.13 wt %), the most active Co/N codoped carbon supported PtCo nanoalloys (Co-N-C/Pt) exhibited dramatically improved catalytic activity toward oxygen reduction reaction coupled with superior output power density (1008 ± 43 mW m -2 ) in MFCs, which was 29.40% higher than the state of the art Pt/C (20 wt %). Notability, the distinct catalytic activity of Co-N-C/Pt was attributed to the highly efficient synergistic catalytic effect of Co-Nx-C and PtCo nanoalloys. Therefore, Co-N-C/Pt should be a promising oxygen reduction catalyst for application in MFCs. Further, the novel strategy for graphene-like carbon also can be widely used in many other energy conversion and storage devices.

ALH85085: a unique volatile-poor carbonaceous chondrite with possible implications for nebular fractionation processes

USGS Publications Warehouse

Grossman, J.N.; Rubin, A.E.; MacPherson, G.J.

1988-01-01

Allan Hills 85085 is a unique chondrite with affinities to the Al Rais-Renazzo clan of carbonaceous chondrites. Its constituents are less than 50 ??m in mean size. Chondrules and microchondrules of all textures are present; nonporphyritic chondrules are unusually abundant. The mean compositions of porphyritic, nonporphyritic and barred olivine chondrules resemble those in ordinary chondrites except that they are depleted in volatile elements. Ca-, Al-rich inclusions are abundant and largely free of nebular alteration; they comprise types similar to those in CM and CO chondrites, as well as unique types. Calcium dialuminate occurs in several inclusions. Metal, silicate and sulfide compositions are close to those in CM-CO chondrites and Al Rais and Renazzo. C1-chondrite clasts and metal-rich "reduced" clasts are present, but opaque matrix is absent. Siderophile abundances in ALH85085 are extremely high (e.g., Fe Si = 1.7 ?? solar), and volatiles are depleted (e.g., Na Si = 0.25 ?? solar, S Si = 0.03 ?? solar). Nonvolatile lithophile abundances are similar to those in Al Rais, Renazzo, and CM and CO chondrites. ALH85085 agglomerated when temperatures in the nebula were near 1000 K, in the same region where Renazzo, Al Rais and the CI chondrites formed. Agglomeration of high-temperature material may thus be a mechanism by which the fractionation of refractory lithophiles occurred in the nebula. Chondrule formation must have occurred at high temperatures when clumps of precursors were small. After agglomeration, ALH85085 was annealed and lightly shocked. C1 and other clasts were subsequently incorporated during late-stage brecciation. ?? 1988.

Electrodeposition of biaxially textured layers on a substrate

DOEpatents

Bhattacharya, Raghu N; Phok, Sovannary; Spagnol, Priscila; Chaudhuri, Tapas

2013-11-19

Methods of producing one or more biaxially textured layer on a substrate, and articles produced by the methods, are disclosed. An exemplary method may comprise electrodepositing on the substrate a precursor material selected from the group consisting of rare earths, transition metals, actinide, lanthanides, and oxides thereof. An exemplary article (150) may comprise a biaxially textured base material (130), and at least one biaxially textured layer (110) selected from the group consisting of rare earths, transition metals, actinides, lanthanides, and oxides thereof. The at least one biaxially textured layer (110) is formed by electrodeposition on the biaxially textured base material (130).

Molecular design of cage iron(II) and cobalt(II,III) complexes with a second fluorine-enriched superhydrophobic shell.

PubMed

Belov, Alexander S; Zelinskii, Genrikh E; Varzatskii, Oleg A; Belaya, Irina G; Vologzhanina, Anna V; Dolganov, Alexander V; Novikov, Valentin V; Voloshin, Yan Z

2015-02-28

Pentafluorophenylboron-capped iron and cobalt(II) hexachloroclathrochelate precursors were obtained by the one-pot template condensation of dichloroglyoxime with pentafluorophenylboronic acid on iron and cobalt(II) ions under vigorous reaction conditions in trifluoroacetic acid media. These reactive precursors easily undergo nucleophilic substitution with (per)fluoroarylthiolate anions, giving (per)fluoroarylsulfide macrobicyclic complexes with encapsulated iron and cobalt(II) ions; nucleophilic substitution of the cobalt(II) hexachloroclathrochelate precursor with a pentafluorophenylsulfide anion gave the target hexasulfide monoclathrochelate and the mixed-valence Co(III)Co(II)Co(III) bis-clathrochelate as a side product. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (57)Fe Mössbauer (for the X-rayed iron complexes), (1)H, (11)B, (13)C and (19)F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry and gas chromatography. As can be seen from the single-crystal X-ray diffraction data, the second superhydrophobic shell of such caged metal ions is formed by fluorine atoms of both the apical and ribbed (per)fluoroaryl peripheral groups. The main bond distances and chelate N=C-C=N angles in their molecules are similar, but rotational elongation (contraction) along the molecular C3-pseudoaxes, accompanied by changes in the geometry of the corresponding MN6-coordination polyhedra from a trigonal prism to a trigonal antiprism, allowed encapsulating Fe(2+), Co(2+) and Co(3+) ions. The nature of an encapsulated metal ion and its oxidation state affect the M-N bond lengths, and, for cobalt(ii) clathrochelate with an electronic configuration d(7) the Jahn-Teller structural effect is observed as an alternation of the Co-N distances. Pentafluorophenylboron-capped hexachloroclathrochelate precursors, giving stable catalytically active metal(I)-containing intermediates due to the electron-withdrawing effect of their six ribbed chlorine substituents, were found to show moderate electrocatalytic activity in a 2H(+)/H2 hydrogen-forming reaction. In the case of their ribbed-functionalized sulfide derivatives, the strong electron-withdrawing (per)fluoroaryl groups do not stabilize the reduced electrocatalytically active metal(i)-containing species as their mesomeric effect is absent or substantially decreased by steric hindrances between them.

Identification of secondary aerosol precursors emitted by an aircraft turbofan

NASA Astrophysics Data System (ADS)

Kılıç, Doğuşhan; El Haddad, Imad; Brem, Benjamin T.; Bruns, Emily; Bozetti, Carlo; Corbin, Joel; Durdina, Lukas; Huang, Ru-Jin; Jiang, Jianhui; Klein, Felix; Lavi, Avi; Pieber, Simone M.; Rindlisbacher, Theo; Rudich, Yinon; Slowik, Jay G.; Wang, Jing; Baltensperger, Urs; Prévôt, Andre S. H.

2018-05-01

Oxidative processing of aircraft turbine-engine exhausts was studied using a potential aerosol mass (PAM) chamber at different engine loads corresponding to typical flight operations. Measurements were conducted at an engine test cell. Organic gases (OGs) and particle emissions pre- and post-PAM were measured. A suite of instruments, including a proton-transfer-reaction mass spectrometer (PTR-MS) for OGs, a multigas analyzer for CO, CO2, NOx, and an aerosol mass spectrometer (AMS) for nonrefractory particulate matter (NR-PM1) were used. Total aerosol mass was dominated by secondary aerosol formation, which was approximately 2 orders of magnitude higher than the primary aerosol. The chemical composition of both gaseous and particle emissions were also monitored at different engine loads and were thrust-dependent. At idling load (thrust 2.5-7 %), more than 90 % of the secondary particle mass was organic and could mostly be explained by the oxidation of gaseous aromatic species, e.g., benzene; toluene; xylenes; tri-, tetra-, and pentamethyl-benzene; and naphthalene. The oxygenated-aromatics, e.g., phenol, furans, were also included in this aromatic fraction and their oxidation could alone explain up to 25 % of the secondary organic particle mass at idling loads. The organic fraction decreased with thrust level, while the inorganic fraction increased. At an approximated cruise load sulfates comprised 85 % of the total secondary particle mass.

Supported mesoporous carbon ultrafiltration membrane and process for making the same

DOEpatents

Strano, Michael; Foley, Henry C.; Agarwal, Hans

2004-04-13

A novel supported mesoporous carbon ultrafiltration membrane and process for producing the same. The membranes comprise a mesoporous carbon layer that exists both within and external to the porous support. A liquid polymer precursor composition comprising both carbonizing and noncarbonizing templating polymers is deposited on the porous metal support. The coated support is then heated in an inert-gas atmosphere to pyrolyze the polymeric precursor and form a mesoporous carbon layer on and within the support. The pore-size of the membranes is dependent on the molecular weight of the noncarbonizing templating polymer precursor. The mesoporous carbon layer is stable and can withstand high temperatures and exposure to organic chemicals. Additionally, the porous metal support provides excellent strength properties. The composite structure of the membrane provides novel structural properties and allows for increased operating pressures allowing for greater membrane flow rates. The invention also relates to the use of the novel ultrafiltration membrane to separate macromolecules from solution. An example is shown separating bovine serum albumin from water. The membrane functions by separating and by selective adsorption. Because of the membrane's porous metal support, it is well suited to industrial applications. The unique properties of the supported mesoporous carbon membrane also allow the membrane to be used in transient pressure or temperature swing separations processes. Such processes were not previously possible with existing mesoporous membranes. The present invention, however, possesses the requisite physical properties to perform such novel ultrafiltration processes.

General Synthetic Strategy for Libraries of Supported Multicomponent Metal Nanoparticles.

PubMed

Yang, Hui; Bradley, Siobhan J; Wu, Xin; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Zhang, Jian; Kruger, Paul E; Ma, Shengqian; Telfer, Shane G

2018-04-18

Nanoparticles comprising three or more different metals are challenging to prepare. General methods that tackle this challenge are highly sought after as multicomponent metal nanoparticles display favorable properties in applications such as catalysis, biomedicine, and imaging. Herein, we report a practical and versatile approach for the synthesis of nanoparticles composed of up to four different metals. This method relies on the thermal decomposition of nanostructured composite materials assembled from platinum nanoparticles, a metal-organic framework (ZIF-8), and a tannic acid coordination polymer. The controlled integration of multiple metal cations (Ni, Co, Cu, Mn, Fe, and/or Tb) into the tannic acid shell of the precursor material dictates the composition of the final multicomponent metal nanoparticles. Upon thermolysis, the platinum nanoparticles seed the growth of the multicomponent metal nanoparticles via coalescence with the metallic constituents of the tannic acid coordination polymer. The nanoparticles are supported in the walls of hollow nitrogen-doped porous carbon capsules created by the decomposition of the organic components of the precursor. The capsules prevent sintering and detachment of the nanoparticles, and their porosity allows for efficient mass transport. To demonstrate the utility of producing a broad library of supported multicomponent metal nanoparticles, we tested their electrocatalytic performance toward the hydrogen evolution reaction and oxygen evolution reaction. We discovered functional relationships between the composition of the nanoparticles and their electrochemical activity and identified the PtNiCu and PtNiCuFe nanoparticles as particularly efficient catalysts. This highlights how to generate diverse libraries of multicomponent metal nanoparticles that can be synthesized and subsequently screened to identify high-performance materials for target applications.

A novel prosthetic group for site-selective labeling of peptides for positron emission tomography.

PubMed

Olberg, Dag Erlend; Hjelstuen, Ole Kristian; Solbakken, Magne; Arukwe, Joseph; Karlsen, Hege; Cuthbertson, Alan

2008-06-01

Efficient methodologies for the radiolabeling of peptides with [(18)F]fluoride are a prerequisite to enabling commercialization of peptide-containing radiotracers for positron emission tomography (PET) imaging. It was the purpose of this study to investigate a novel chemoselective ligation reaction comprising conjugation of an [(18)F]-N-methylaminooxy-containing prosthetic group to a functionalized peptide. Twelve derivatives of general formula R1-CO-NH-Lys-Gly-Phe-Gly-Lys-OH were synthesized where R1 was selected from a short list of moieties anticipated to be reactive toward the N-methylaminooxy group. Conjugation reactions were initially carried out with nonradioactive precursors to assess, in a qualitative manner, their general suitability for PET chemistry with only the most promising pairings progressing to full radiochemical assessment. Best results were obtained for the ligation of O-[2-(2-[(18)F]fluoroethoxy)ethyl]-N-methyl-N-hydroxylamine 18 to the maleimidopropionyl-Lys-Gly-Phe-Gly-Lys-OH precursor 10 in acetate buffer (pH 5) after 1 h at 70 degrees C. The non-decay-corrected isolated yield was calculated to be 8.5%. The most encouraging result was observed with the combination 18 and 4-(2-nitrovinyl)benzoyl-Lys-Gly-Phe-Gly-Lys-OH, 9, where the conjugation reaction proceeded rapidly to completion at 30 degrees C after only 5 min. The corresponding non-decay-corrected radiochemical yield for the isolated (18)F-labeled product 27 was 12%. The preliminary results from this study demonstrate the considerable potential of this novel strategy for the radiolabeling of peptides.

MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery

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

Chen, Biaohua; He, Xiaobo; Yin, Fengxiang

A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-xmore » and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO2.« less

Vitamin B5 and N-acetylcysteine in nonalcoholic steatohepatitis: a pre-clinical study in a dietary mouse model

PubMed Central

Machado, Mariana Verdelho; Kruger, Leandi; Jewell, Mark L.; Michelotti, Gregory Alexander; de Almeida Pereira, Thiago; Xie, Guanhua; Moylan, Cynthia A.; Diehl, Anna Mae

2015-01-01

Background Nonalcoholic fatty liver disease (NAFLD) is the number one cause of chronic liver disease and second indication for liver transplantation in the Western world. Effective therapy is still not available. Previously we showed a critical role for caspase-2 in the pathogenesis of nonalcoholic steatohepatitis (NASH), the potentially progressive form of NAFLD. An imbalance between free Coenzyme A (CoA) and acyl-CoA ratio is known to induce caspase-2 activation. Objectives We aimed to evaluate CoA metabolism and the effects of supplementation with CoA precursors, pantothenate and cysteine, in mouse models of NASH. Methods CoA metabolism was evaluated in methionine-choline deficient (MCD) and Western diet mouse models of NASH. MCD-diet fed mice were treated with pantothenate and N-acetylcysteine or placebo to determine effects on NASH. Results Liver free CoA content was reduced, pantothenate kinase (PANK), the rate-limiting enzyme in the CoA biosynthesis pathway, was down-regulated, and CoA degrading enzymes were increased in mice with NASH. Decreased hepatic free CoA content was associated with increased caspase-2 activity, and correlated with worse liver cell apoptosis, inflammation and fibrosis. Treatment with pantothenate and N-acetylcysteine did not inhibit caspase-2 activation, improve NASH, normalize PANK expression, or restore free CoA levels in MCD diet-fed mice. Conclusion In mice with NASH, hepatic CoA metabolism is impaired, leading to decreased free CoA content, activation of caspase-2, and increased liver cell apoptosis. Dietary supplementation with CoA precursors did not restore CoA levels or improve NASH, suggesting that alternative approaches are necessary to normalize free CoA during NASH. PMID:26403427

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

PubMed

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0

Simple, Green, and High-Yield Production of Boron-Based Nanostructures with Diverse Morphologies by Dissolution and Recrystallization of Layered Magnesium Diboride Crystals in Water.

PubMed

Gunda, Harini; Das, Saroj Kumar; Jasuja, Kabeer

2018-04-05

Layered metal diborides that contain metal atoms sandwiched between boron honeycomb planes offer a rich opportunity to access graphenic forms of boron. We recently demonstrated that magnesium diboride (MgB 2 ) could be exfoliated by ultrasonication in water to yield boron-based nanosheets. However, knowledge of the fate of metal boride crystals in aqueous phases is still in its incipient stages. This work presents our preliminary findings on the discovery that MgB 2 crystals can undergo dissolution in water under ambient conditions to result in precursors (prenucleation clusters) that, upon aging, undergo nonclassical crystallization preferentially growing in lateral directions by two-dimensional (2D) oriented attachment. We show that this recrystallization can be utilized as an avenue to obtain a high yield (≈92 %) of boron-based nanostructures, including nanodots, nanograins, nanoflakes, and nanosheets. These nanostructures comprise boron honeycomb planes chemically modified with hydride and oxy functional groups, which results in an overall negative charge on their surfaces. This ability of MgB 2 crystals to yield prenucleation clusters that can self-seed to form nanostructures comprising chemically modified boron honeycomb planes presents a new facet to the physicochemical interaction of MgB 2 with water. These findings also open newer avenues to obtain boron-based nanostructures with tunable morphologies by varying the chemical milieu during recrystallization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospinning of calcium carbonate fibers and their conversion to nanocrystalline hydroxyapatite.

PubMed

Holopainen, Jani; Santala, Eero; Heikkilä, Mikko; Ritala, Mikko

2014-12-01

Calcium carbonate (CaCO3) fibers were prepared by electrospinning followed by annealing. Solutions consisting of calcium nitrate tetrahydrate (Ca(NO3)2·4H2O) and polyvinylpyrrolidone (PVP) dissolved in ethanol or 2-methoxyethanol were used for the fiber preparation. By varying the precursor concentrations in the electrospinning solutions CaCO3 fibers with average diameters from 140 to 290 nm were obtained. After calcination the fibers were identified as calcite by X-ray diffraction (XRD). The calcination process was studied in detail with high temperature X-ray diffraction (HTXRD) and thermogravimetric analysis (TGA). The initially weak fiber-to-substrate adhesion was improved by adding a strengthening CaCO3 layer by spin or dip coating Ca(NO3)2/PVP precursor solution on the CaCO3 fibers followed by annealing of the gel formed inside the fiber layer. The CaCO3 fibers were converted to nanocrystalline hydroxyapatite (HA) fibers by treatment in a dilute phosphate solution. The resulting hydroxyapatite had a plate-like crystal structure with resemblance to bone mineral. The calcium carbonate and hydroxyapatite fibers are interesting materials for bone scaffolds and bioactive coatings. Copyright © 2014 Elsevier B.V. All rights reserved.

Cation ordering/disordering kinetics in Ba3CoNb2O9: An in situ study using synchrotron x-ray powder diffraction

NASA Astrophysics Data System (ADS)

Mallinson, P. M.; Claridge, J. B.; Rosseinsky, M. J.; Ibberson, R. M.; Wright, J. P.; Fitch, A. N.; Price, T.; Iddles, D. M.

2007-11-01

In situ synchrotron x-ray powder diffraction has been used to study the kinetics of cation ordering and disordering in the microwave dielectric electroceramic Ba3CoNb2O9 with a time resolution of 15s. The method enables the order/disorder temperature (To /d) in this material of 1430°C to be directly observed. The changes in the rate and degree of cation ordering and in the growth of ordered domains between samples ordered from standard precursor material and then subsequently reordered following an annealing period above To /d show that small changes in precursor order state and phase assemblage strongly influence the final domain size.

Syntheses of near-net-shaped monolithic hydroxyapatite and hydroxyapatite-ASTM F75 composites by the oxidation of solid metal-bearing precursors

NASA Astrophysics Data System (ADS)

Saw, Eaden

A novel powder-metallurgical route was used to fabricate near net-shaped hydroxyapatite, Ca10(PO4)6(OH)2 (HA) and HA+Co-C-Mo composite bodies. Ca and beta-Ca2P 2O7 with Ca/P ˜ 1.67 was intimately mixed by high-energy mechanical alloying, formed into desired shapes by pressing and machining, and then converted into HA with a series of heat treatments: a 600°C annealing in dry O2 completely oxidized calcium within 3 h, and a subsequent annealing at ≤1150°C in moist O2 yielded phase-pure HA. The reduction in solid volume associated with the oxidation of calcium (Vm[CaO] < Vm[Ca]) was offset by the increase in solid volume associated with the conversion of CaO and Ca2P2O7 into HA. Thus, the overall dimensional changes upon transformation of Ca+beta-Ca2P 2O7 precursors into HA can be relatively small. A mixture of Co-Cr-Mo powder with the precursor prepared from Ca and beta-Ca 2P2O7, targeted to yield a 75 to 25 volume ratio of Co-Cr-Mo to stoichiometric HA were prepared with the same method but different annealing cycles: annealing at 1150°C in de-oxygenized, flowing Ar resulted in partial densification of the composite bodies, and subsequent annealing at 850°C in a moist O2 atmosphere yielded a composite of Co-Cr-Mo alloy with phase-pure HA. The overall dimensional changes upon transformation of Ca+beta-Ca2P2O7+CO-Cr-Mo precursors into HA/Co-Cr-Mo composite were relatively small. In this thesis, the phase and microstructural evolution at various stages of transformation to monolithic HA and to HA/Co-Cr-Mo alloy composites are discussed. Planar reaction couples and powder compacts of CaO-TCP were prepared to study the kinetics for HA formation from CaO+TCP. Pt strips were used in the planar reaction couples as inert markers. These reaction couples were heated at 1150°C for various times in moist O2. The results of powder compact analyses fits Carter's model, which indicated that the rate of HA conversion from CaO and TCP is limited by solid state diffusion of Ca 2+ and/or OH- through the HA layer.

Organic materials as templates for the formation of mesoporous inorganic materials and ordered inorganic nanocomposites

NASA Astrophysics Data System (ADS)

Ziegler, Christopher R.

Hierarchically structured inorganic materials are everywhere in nature. From unicellular aquatic algae such as diatoms to the bones and/or cartilage that comprise the skeletal systems of vertebrates. Complex mechanisms involving site-specific chemistries and precision kinetics are responsible for the formation of such structures. In the synthetic realm, reproduction of even the most basic hierarchical structure effortlessly produced in nature is difficult. However, through the utilization of self-assembling structures or "templates", such as polymers or amphiphilic surfactants, combined with some favorable interaction between a chosen inorganic, the potential exists to imprint an inorganic material with a morphology dictated via synthetic molecular self-assembly. In doing so, a very basic hierarchical structure is formed on the angstrom and nanometer scales. The work presented herein utilizes the self-assembly of either surfactants or block copolymers with the desired inorganic or inorganic precursor to form templated inorganic structures. Specifically, mesoporous silica spheres and copolymer directed calcium phosphate-polymer composites were formed through the co-assembly of an organic template and a precursor to form the desired mesostructured inorganic. For the case of the mesoporous silica spheres, a silica precursor was mixed with cetyltrimethylammonium bromide and cysteamine, a highly effective biomimetic catalyst for the conversion of alkoxysilanes to silica. Through charge-based interactions between anionic silica species and the micelle-forming cationic surfactant, ordered silica structures resulted. The incorporation of a novel, effective catalyst was found to form highly condensed silica spheres for potential application as catalyst supports or an encapsulation media. Ordered calcium phosphate-polymer composites were formed using two routes. Both routes take advantage of hydrogen bonding and ionic interactions between the calcium and phosphate precursors and the self-assembling copolymer template. Some evidence suggests that the copolymer morphology remained in the composite despite the known tendency for calcium phosphates to form highly elongated crystalline structures with time, as is commonly the case for synthetic hydroxyapatites. Such materials have obvious application as bone grafts and bone coatings due, in part, to the osteoconductive nature of calcium phosphate as well as to the mesoporosity generated through the cooperative assembly of the block copolymer and the inorganic. Future work, including potential experiments to determine osteoconductivity of as-prepared composites, is also presented herein.

40 CFR 141.135 - Treatment technique for control of disinfection byproduct (DBP) precursors.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., measured according to § 141.131(d)(1), is greater than 60 mg/L (as CaCO3), calculated quarterly as a... treated water alkalinity to less than 60 mg/L (as CaCO3), measured monthly according to § 141.131(d)(1... 10 mg/L of magnesium hardness (as CaCO3), measured monthly according to § 141.131(d)(6) and...

40 CFR 141.135 - Treatment technique for control of disinfection byproduct (DBP) precursors.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., measured according to § 141.131(d)(1), is greater than 60 mg/L (as CaCO3), calculated quarterly as a... treated water alkalinity to less than 60 mg/L (as CaCO3), measured monthly according to § 141.131(d)(1... 10 mg/L of magnesium hardness (as CaCO3), measured monthly according to § 141.131(d)(6) and...

40 CFR 141.135 - Treatment technique for control of disinfection byproduct (DBP) precursors.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., measured according to § 141.131(d)(1), is greater than 60 mg/L (as CaCO3), calculated quarterly as a... treated water alkalinity to less than 60 mg/L (as CaCO3), measured monthly according to § 141.131(d)(1... 10 mg/L of magnesium hardness (as CaCO3), measured monthly according to § 141.131(d)(6) and...

40 CFR 141.135 - Treatment technique for control of disinfection byproduct (DBP) precursors.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., measured according to § 141.131(d)(1), is greater than 60 mg/L (as CaCO3), calculated quarterly as a... treated water alkalinity to less than 60 mg/L (as CaCO3), measured monthly according to § 141.131(d)(1... 10 mg/L of magnesium hardness (as CaCO3), measured monthly according to § 141.131(d)(6) and...

Synthesis of LiCoO 2 thin films by sol/gel process

NASA Astrophysics Data System (ADS)

Porthault, H.; Le Cras, F.; Franger, S.

LiCoO 2 thin films were synthesized by sol/gel process using acrylic acid (AA) as chelating agent. The gel formulation was optimized by varying solvent (ethylene glycol or water) and precursors molar ratios (Li, Co, AA) in order to obtain a dense film for positive electrode of lithium batteries. The gel was deposited by spin-coating technique on an Au/TiO 2/SiN/SiO 2/Si substrate. Thin films were deposited by either single or multistep process to enhance the density of the thin film and then calcined during 5 h at 800 °C to obtain the R-3m phase (HT-LiCoO 2). A chemical characterization of the solution was realized by Fourier Transform Infrared (FTIR) spectroscopy. Thermal decomposition of precursors and gel was studied by Thermo Gravimetric Analyses (TGA). Further investigations were done to characterize rheologic behaviour of the gel and solvents affinity with the substrate. Crystallinity and morphology were analyzed respectively by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The formation of R-3m phase was confirmed by the electrochemical behaviour of the gel derived LiCoO 2. Cyclic voltammograms and galvanostatic cycling show typical curve shape of the HT-LiCoO 2.

The acyl-activating enzyme PhAAE13 is an alternative enzymatic source of precursors for anthocyanin biosynthesis in petunia flowers

PubMed Central

Chen, Guoju; Liu, Heping; Wei, Qian; Zhao, Huina

2017-01-01

Abstract Anthocyanins, a class of flavonoids, are responsible for the orange to blue coloration of flowers and act as visual attractors to aid pollination and seed dispersal. Malonyl-CoA is the precursor for the formation of flavonoids and anthocyanins. Previous studies have suggested that malonyl-CoA is formed almost exclusively by acetyl-CoA carboxylase, which catalyzes the ATP-dependent formation of malonyl-CoA from acetyl-CoA and bicarbonate. In the present study, the full-length cDNA of Petunia hybrida acyl-activating enzyme 13 (PhAAE13), a member of clade VII of the AAE superfamily that encodes malonyl-CoA synthetase, was isolated. The expression of PhAAE13 was highest in corollas and was down-regulated by ethylene. Virus-induced gene silencing of petunia PhAAE13 significantly reduced anthocyanin accumulation, fatty acid content, and cuticular wax components content, and increased malonic acid content in flowers. The silencing of PhAAE3 and PhAAE14, the other two genes in clade VII of the AAE superfamily, did not change the anthocyanin content in petunia flowers. This study provides strong evidence indicating that PhAAE13, among clade VII of the AAE superfamily, is specifically involved in anthocyanin biosynthesis in petunia flowers. PMID:28204578

Microemulsion flame pyrolysis for hopcalite nanoparticle synthesis: a new concept for catalyst preparation.

PubMed

Biemelt, T; Wegner, K; Teichert, J; Kaskel, S

2015-04-07

A new route to highly active hopcalite catalysts via flame spray pyrolysis of an inverse microemulsion precursor is reported. The nitrate derived nanoparticles are around 15 nm in diameter and show excellent conversion of CO under ambient conditions, outperforming commercial reference hopcalite materials produced by co-precipitation.

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

Xu, Wu; Canfield, Nathan L.; Zhang, Ji-Guang

Methods for making composite anodes, such as macroporous composite anodes, are disclosed. Embodiments of the methods may include forming a tape from a slurry including a substrate metal precursor, an anode active material, a pore-forming agent, a binder, and a solvent. A laminated structure may be prepared from the tape and sintered to produce a porous structure, such as a macroporous structure. The macroporous structure may be heated to reduce a substrate metal precursor and/or anode active material. Macroporous composite anodes formed by some embodiments of the disclosed methods comprise a porous metal and an anode active material, wherein themore » anode active material is both externally and internally incorporated throughout and on the surface of the macroporous structure.« less

Nanostructures produced by phase-separation during growth of (III-V).sub.1-x(IV.sub.2).sub.x alloys

DOEpatents

Norman, Andrew G [Evergreen, CO; Olson, Jerry M [Lakewood, CO

2007-06-12

Nanostructures (18) and methods for production thereof by phase separation during metal organic vapor-phase epitaxy (MOVPE). An embodiment of one of the methods may comprise providing a growth surface in a reaction chamber and introducing a first mixture of precursor materials into the reaction chamber to form a buffer layer (12) thereon. A second mixture of precursor materials may be provided into the reaction chamber to form an active region (14) on the buffer layer (12), wherein the nanostructure (18) is embedded in a matrix (16) in the active region (14). Additional steps are also disclosed for preparing the nanostructure (18) product for various applications.

Photochemical production of ozone in the upper troposphere in association with cumulus convection over Indonesia

NASA Astrophysics Data System (ADS)

Kita, K.; Kawakami, S.; Miyazaki, Y.; Higashi, Y.; Kondo, Y.; Nishi, N.; Koike, M.; Blake, D. R.; Machida, T.; Sano, T.; Hu, W.; Ko, M.; Ogawa, T.

2002-02-01

The Biomass Burning and Lightning Experiment phase A (BIBLE-A) aircraft observation campaign was conducted from 24 September to 10 October 1998, during a La Niña period. During this campaign, distributions of ozone and its precursors (NO, CO, and nonmethane hydrocarbons (NMHCs)) were observed over the tropical Pacific Ocean, Indonesia, and northern Australia. Mixing ratios of ozone and its precursors were very low at altitudes between 0 and 13.5 km over the tropical Pacific Ocean. The mixing ratios of ozone precursors above 8 km over Indonesia were often significantly higher than those over the tropical Pacific Ocean, even though the prevailing easterlies carried the air from the tropical Pacific Ocean to over Indonesia within several days. For example, median NO and CO mixing ratios in the upper troposphere were 12 parts per trillion (pptv) and 72 parts per billion (ppbv) over the tropical Pacific Ocean and were 83 pptv and 85 ppbv over western Indonesia, respectively. Meteorological analyses and high ethene (C2H4) mixing ratios indicate that the increase of the ozone precursors was caused by active convection over Indonesia through upward transport of polluted air, mixing, and lightning all within the few days prior to observation. Sources of ozone precursors are discussed by comparing correlations of some NMHCs and CH3Cl concentrations with CO between the lower and upper troposphere. Biomass burning in Indonesia was nearly inactive during BIBLE-A and was not a dominant source of the ozone precursors, but urban pollution and lightning contributed importantly to their increases. The increase in ozone precursors raised net ozone production rates over western Indonesia in the upper troposphere, as shown by a photochemical model calculation. However, the ozone mixing ratio (˜20 ppbv) did not increase significantly over Indonesia because photochemical production of ozone did not have sufficient time since the augmentation of ozone precursors. Backward trajectories show that many air masses sampled over the ocean south of Indonesia and over northern Australia passed over western Indonesia 4-9 days prior to being measured. In these air masses the mixing ratios of ozone precursors, except for short-lived species, were similar to those over western Indonesia. In contrast, the ozone mixing ratio was higher by about 10 ppbv than that over Indonesia, indicating that photochemical production of ozone occurred during transport from Indonesia. The average rate of ozone increase (1.8 ppbv/d) during this transport is similar to the net ozone formation rate calculated by the photochemical model. This study shows that active convection over Indonesia carried polluted air upward from the surface and had a discernable influence on the distribution of ozone in the upper troposphere over the Indian Ocean, northern Australia, and the south subtropical Pacific Ocean, combined with NO production by lightning.

Photochemical production of ozone in the upper troposphere in association with cumulus convection over Indonesia

NASA Astrophysics Data System (ADS)

Kita, K.; Kawakami, S.; Miyazaki, Y.; Higashi, Y.; Kondo, Y.; Nishi, N.; Koike, M.; Blake, D. R.; Machida, T.; Sano, T.; Hu, W.; Ko, M.; Ogawa, T.

2003-02-01

The Biomass Burning and Lightning Experiment phase A (BIBLE-A) aircraft observation campaign was conducted from 24 September to 10 October 1998, during a La Niña period. During this campaign, distributions of ozone and its precursors (NO, CO, and nonmethane hydrocarbons (NMHCs)) were observed over the tropical Pacific Ocean, Indonesia, and northern Australia. Mixing ratios of ozone and its precursors were very low at altitudes between 0 and 13.5 km over the tropical Pacific Ocean. The mixing ratios of ozone precursors above 8 km over Indonesia were often significantly higher than those over the tropical Pacific Ocean, even though the prevailing easterlies carried the air from the tropical Pacific Ocean to over Indonesia within several days. For example, median NO and CO mixing ratios in the upper troposphere were 12 parts per trillion (pptv) and 72 parts per billion (ppbv) over the tropical Pacific Ocean and were 83 pptv and 85 ppbv over western Indonesia, respectively. Meteorological analyses and high ethene (C2H4) mixing ratios indicate that the increase of the ozone precursors was caused by active convection over Indonesia through upward transport of polluted air, mixing, and lightning all within the few days prior to observation. Sources of ozone precursors are discussed by comparing correlations of some NMHCs and CH3Cl concentrations with CO between the lower and upper troposphere. Biomass burning in Indonesia was nearly inactive during BIBLE-A and was not a dominant source of the ozone precursors, but urban pollution and lightning contributed importantly to their increases. The increase in ozone precursors raised net ozone production rates over western Indonesia in the upper troposphere, as shown by a photochemical model calculation. However, the ozone mixing ratio (~20 ppbv) did not increase significantly over Indonesia because photochemical production of ozone did not have sufficient time since the augmentation of ozone precursors. Backward trajectories show that many air masses sampled over the ocean south of Indonesia and over northern Australia passed over western Indonesia 4-9 days prior to being measured. In these air masses the mixing ratios of ozone precursors, except for short-lived species, were similar to those over western Indonesia. In contrast, the ozone mixing ratio was higher by about 10 ppbv than that over Indonesia, indicating that photochemical production of ozone occurred during transport from Indonesia. The average rate of ozone increase (1.8 ppbv/d) during this transport is similar to the net ozone formation rate calculated by the photochemical model. This study shows that active convection over Indonesia carried polluted air upward from the surface and had a discernable influence on the distribution of ozone in the upper troposphere over the Indian Ocean, northern Australia, and the south subtropical Pacific Ocean, combined with NO production by lightning.

Distinct cortical and sub-cortical neurogenic domains for GABAergic interneuron precursor transcription factors NKX2.1, OLIG2 and COUP-TFII in early fetal human telencephalon.

PubMed

Alzu'bi, Ayman; Lindsay, Susan; Kerwin, Janet; Looi, Shi Jie; Khalil, Fareha; Clowry, Gavin J

2017-07-01

The extent of similarities and differences between cortical GABAergic interneuron generation in rodent and primate telencephalon remains contentious. We examined expression of three interneuron precursor transcription factors, alongside other markers, using immunohistochemistry on 8-12 post-conceptional weeks (PCW) human telencephalon sections. NKX2.1, OLIG2, and COUP-TFII expression occupied distinct (although overlapping) neurogenic domains which extended into the cortex and revealed three CGE compartments: lateral, medial, and ventral. NKX2.1 expression was very largely confined to the MGE, medial CGE, and ventral septum confirming that, at this developmental stage, interneuron generation from NKX2.1+ precursors closely resembles the process observed in rodents. OLIG2 immunoreactivity was observed in GABAergic cells of the proliferative zones of the MGE and septum, but not necessarily co-expressed with NKX2.1, and OLIG2 expression was also extensively seen in the LGE, CGE, and cortex. At 8 PCW, OLIG2+ cells were only present in the medial and anterior cortical wall suggesting a migratory pathway for interneuron precursors via the septum into the medial cortex. By 12 PCW, OLIG2+ cells were present throughout the cortex and many were actively dividing but without co-expressing cortical progenitor markers. Dividing COUP-TFII+ progenitor cells were localized to ventral CGE as previously described but were also numerous in adjacent ventral cortex; in both the cases, COUP-TFII was co-expressed with PAX6 in proliferative zones and TBR1 or calretinin in post-mitotic cortical neurons. Thus COUP-TFII+ progenitors gave rise to pyramidal cells, but also interneurons which not only migrated posteriorly into the cortex from ventral CGE but also anteriorly via the LGE.

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass-ceramics

NASA Astrophysics Data System (ADS)

Narro-García, R.; Desirena, H.; López-Luke, T.; Guerrero-Contreras, J.; Jayasankar, C. K.; Quintero-Torres, R.; De la Rosa, E.

2015-08-01

This paper reports the fabrication and characterization of Eu3+/Nd3+ co-doped phosphate (PNE) glasses and glass-ceramics as a function of Eu3+ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass-ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass-ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV-VIS-IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass-ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm-1 to 1277 cm-1 with the thermal treatment. The luminescence spectra of the glass and glass-ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass-ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu3+ ion concentration in the Nd3+ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the 4F3/2 state of Nd3+ ion in Eu3+/Nd3+ co-doped phosphate glasses and glass-ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the 4F3/2 level of Nd3+ of both glasses and glass-ceramics decrease with the increasing Eu3+ concentration. However in the case of opaque glass-ceramics the lifetimes decrease only 16%.

Thermal neutron shield and method of manufacture

DOEpatents

Metzger, Bert Clayton; Brindza, Paul Daniel

2014-03-04

A thermal neutron shield comprising boron shielding panels with a high percentage of the element Boron. The panel is least 46% Boron by weight which maximizes the effectiveness of the shielding against thermal neutrons. The accompanying method discloses the manufacture of boron shielding panels which includes enriching the pre-cursor mixture with varying grit sizes of Boron Carbide.

Chemical vapor deposition of W-Si-N and W-B-N

DOEpatents

Fleming, J.G.; Roherty-Osmun, E.L.; Smith, P.M.; Custer, J.S.; Jones, R.V.; Nicolet, M.; Madar, R.; Bernard, C.

1999-06-29

A method of depositing a ternary, refractory based thin film on a substrate by chemical vapor deposition employing precursor sources of tungsten comprising WF[sub 6], either silicon or boron, and nitrogen. The result is a W-Si-N or W-B-N thin film useful for diffusion barrier and micromachining applications. 10 figs.

Comparative study of post-growth annealing of Cu(hfac)2, Co2(CO)8 and Me2Au(acac) metal precursors deposited by FEBID.

PubMed

Puydinger Dos Santos, Marcos Vinicius; Szkudlarek, Aleksandra; Rydosz, Artur; Guerra-Nuñez, Carlos; Béron, Fanny; Pirota, Kleber Roberto; Moshkalev, Stanislav; Diniz, José Alexandre; Utke, Ivo

2018-01-01

Non-noble metals, such as Cu and Co, as well as noble metals, such as Au, can be used in a number modern technological applications, which include advanced scanning-probe systems, magnetic memory and storage, ferroelectric tunnel junction memristors, metal interconnects for high performance integrated circuits in microelectronics and nano-optics applications, especially in the areas of plasmonics and metamaterials. Focused-electron-beam-induced deposition (FEBID) is a maskless direct-write tool capable of defining 3-dimensional metal deposits at nanometre scale for above applications. However, codeposition of organic ligands when using organometallic precursors is a typical problem that limits FEBID of pure metal nanostructures. In this work, we present a comparative study using a post-growth annealing protocol at 100, 200, and 300 °C under high vacuum on deposits obtained from Co 2 (CO) 8 , Cu(II)(hfac) 2 , and Me 2 Au(acac) to study improvements on composition and electrical conductivity. Although the as-deposited material was similar for all precursors, metal grains embedded in a carbonaceous matrix, the post-growth annealing results differed. Cu-containing deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit for temperatures above 100 °C, due to the migration of Cu atoms from the carbonaceous matrix containing carbon, oxygen, and fluorine atoms. The average size of the Cu crystals doubles between 100 and 300 °C of annealing temperature, while the composition remains constant. In contrast, for Co-containing deposits oxygen release was observed upon annealing, while the carbon content remained approximately constant; the cobalt atoms coalesced to form a metallic film. The as-deposited Au-containing material shows subnanometric grains that coalesce at 100 °C, maintaining the same average size at annealing temperatures up to 300 °C. Raman analysis suggests that the amorphous carbonaceous matrix of the as-written Co, Cu and Au deposits turned into nanocrystalline graphite with comparable crystal sizes of 12-14 nm at 300 °C annealing temperature. However, we observed a more effective formation of graphite clusters in Co- than in Cu- and Au-containing deposits. The graphitisation has a minor influence on the electrical conductivity improvements of Co-C deposits, which is attributed to the high as-deposited Co content and the related metal grain percolation. On the contrary, electrical conductivity improvements by factors of 30 and 12 for, respectively, Cu-C and Au-C deposits with low metal content are mainly attributed to the graphitisation. This relatively simple vacuum-based post-growth annealing protocol may be useful for other precursors as it proved to be efficient in reliably tuning the electrical properties of as-deposited FEBID materials. Finally, a H 2 -assisted gold purification protocol is demonstrated at temperatures around 300 °C by fully removing the carbon matrix and drastically reducing the electrical resistance of the deposit.

Emission properties of Ce3+ centers in barium borate glasses prepared from different precursor materials

NASA Astrophysics Data System (ADS)

Torimoto, Aya; Masai, Hirokazu; Okada, Go; Kawaguchi, Noriaki; Yanagida, Takayuki; Ohkubo, Takahiro

2017-10-01

The photoluminescence (PL) and X-ray induced luminescence properties of Ce-doped barium borate glasses prepared from different precursor materials have been investigated. Oxidation of Ce3+ takes place during the melting process performed using a pre-vitrified non-doped glass. Residual groups originated from the precursor materials, such as fluorine atoms and OH groups, are found to affect the optical and emission properties of the glasses. Moreover, both the PL and the X-ray induced luminescence properties of the glasses depend on the precursor materials used for their synthesis. Based on a thorough analysis of the emission properties, we conclude that the best synthesis conditions involve melting a batch containing Ce(CH3COO)3·H2O, BaCO3, and B2O3 in Ar atmosphere.

The hybrid nanostructure of MnCo2O4.5 nanoneedle/carbon aerogel for symmetric supercapacitors with high energy density.

PubMed

Hao, Pin; Zhao, Zhenhuan; Li, Liyi; Tuan, Chia-Chi; Li, Haidong; Sang, Yuanhua; Jiang, Huaidong; Wong, C P; Liu, Hong

2015-09-14

Current applications of carbon-based supercapacitors are limited by their low energy density. One promising strategy to enhance the energy density is to couple metal oxides with carbon materials. In this study, a porous MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure was synthesized by assembling MnCo2O4.5 nanoneedle arrays on the surface of channel walls of hierarchical porous carbon aerogels derived from chitosan for the supercapacitor application. The synthetic process of the hybrid nanostructure involves two steps, i.e. the growth of Mn-Co precursors on carbon aerogel by a hydrothermal process and the conversion of the precursor into MnCo2O4.5 nanoneedles by calcination. The carbon aerogel exhibits a high electrical conductivity, high specific surface area and porous structure, ensuring high electrochemical performance of the hybrid nanostructure when coupled with the porous MnCo2O4.5 nanoneedles. The symmetric supercapacitor using the MnCo2O4.5 nanoneedle/carbon aerogel hybrid nanostructure as the active electrode material exhibits a high energy density of about 84.3 Wh kg(-1) at a power density of 600 W kg(-1). The voltage window is as high as 1.5 V in neutral aqueous electrolytes. Due to the unique nanostructure of the electrodes, the capacitance retention reaches 86% over 5000 cycles.

Co-ultramicronized Palmitoylethanolamide/Luteolin Promotes the Maturation of Oligodendrocyte Precursor Cells

PubMed Central

Barbierato, Massimo; Facci, Laura; Marinelli, Carla; Zusso, Morena; Argentini, Carla; Skaper, Stephen D.; Giusti, Pietro

2015-01-01

Oligodendrocytes have limited ability to repair the damage to themselves or to other nerve cells, as seen in demyelinating diseases like multiple sclerosis. An important strategy may be to replace the lost oligodendrocytes and/or promote the maturation of undifferentiated oligodendrocyte precursor cells (OPCs). Recent studies show that a composite of co-ultramicronized N-palmitoylethanolamine (PEA) and luteolin (co-ultramicronized PEA/luteolin, 10:1 by mass) is efficacious in improving outcome in experimental models of spinal cord and traumatic brain injuries. Here, we examined the ability of co-ultramicronized PEA/luteolin to promote progression of OPCs into a more differentiated phenotype. OPCs derived from newborn rat cortex were placed in culture and treated the following day with 10 μM co-ultramicronized PEA/luteolin. Cells were collected 1, 4 and 8 days later and analyzed for expression of myelin basic protein (MBP). qPCR and Western blot analyses revealed a time-dependent increase in expression of both mRNA for MBP and MBP content, along with an increased expression of genes involved in lipid biogenesis. Ultramicronized PEA or luteolin, either singly or in simple combination, were ineffective. Further, co-ultramicronized PEA/luteolin promoted morphological development of OPCs and total protein content without affecting proliferation. Co-ultramicronized PEA/luteolin may represent a novel pharmacological strategy to promote OPC maturation. PMID:26578323

A classical view on nonclassical nucleation.

PubMed

Smeets, Paul J M; Finney, Aaron R; Habraken, Wouter J E M; Nudelman, Fabio; Friedrich, Heiner; Laven, Jozua; De Yoreo, James J; Rodger, P Mark; Sommerdijk, Nico A J M

2017-09-19

Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid-liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4-7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2- → z CaCO 3 The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.

Mesenchymal precursor cells maintain the differentiation and proliferation potentials of breast epithelial cells

PubMed Central

2014-01-01

Introduction Stromal-epithelial interactions play a fundamental role in tissue homeostasis, controlling cell proliferation and differentiation. Not surprisingly, aberrant stromal-epithelial interactions contribute to malignancies. Studies of the cellular and molecular mechanisms underlying these interactions require ex vivo experimental model systems that recapitulate the complexity of human tissue without compromising the differentiation and proliferation potentials of human primary cells. Methods We isolated and characterized human breast epithelial and mesenchymal precursors from reduction mammoplasty tissue and tagged them with lentiviral vectors. We assembled heterotypic co-cultures and compared mesenchymal and epithelial cells to cells in corresponding monocultures by analyzing growth, differentiation potentials, and gene expression profiles. Results We show that heterotypic culture of non-immortalized human primary breast epithelial and mesenchymal precursors maintains their proliferation and differentiation potentials and constrains their growth. We further describe the gene expression profiles of stromal and epithelial cells in co-cultures and monocultures and show increased expression of the tumor growth factor beta (TGFβ) family member inhibin beta A (INHBA) in mesenchymal cells grown as co-cultures compared with monocultures. Notably, overexpression of INHBA in mesenchymal cells increases colony formation potential of epithelial cells, suggesting that it contributes to the dynamic reciprocity between breast mesenchymal and epithelial cells. Conclusions The described heterotypic co-culture system will prove useful for further characterization of the molecular mechanisms mediating interactions between human normal or neoplastic breast epithelial cells and the stroma, and will provide a framework to test the relevance of the ever-increasing number of oncogenomic alterations identified in human breast cancer. PMID:24916766

Chemistry of Volatile Organic Compounds in the Los Angeles Basin: Formation of Oxygenated Compounds and Determination of Emission Ratios

NASA Astrophysics Data System (ADS)

de Gouw, J. A.; Gilman, J. B.; Kim, S.-W.; Alvarez, S. L.; Dusanter, S.; Graus, M.; Griffith, S. M.; Isaacman-VanWertz, G.; Kuster, W. C.; Lefer, B. L.; Lerner, B. M.; McDonald, B. C.; Rappenglück, B.; Roberts, J. M.; Stevens, P. S.; Stutz, J.; Thalman, R.; Veres, P. R.; Volkamer, R.; Warneke, C.; Washenfelder, R. A.; Young, C. J.

2018-02-01

We analyze an expanded data set of oxygenated volatile organic compounds (OVOCs) in air measured by several instruments at a surface site in Pasadena near Los Angeles during the National Oceanic and Atmospheric Administration California Nexus study in 2010. The contributions of emissions, chemical formation, and removal are quantified for each OVOC using CO as a tracer of emissions and the OH exposure of the sampled air masses calculated from hydrocarbon ratios. The method for separating emissions from chemical formation is evaluated using output for Pasadena from the Weather Research and Forecasting-Chemistry model. The model is analyzed by the same method as the measurement data, and the emission ratios versus CO calculated from the model output agree for ketones with the inventory used in the model but overestimate aldehydes by 70%. In contrast with the measurements, nighttime formation of OVOCs is significant in the model and is attributed to overestimated precursor emissions and overestimated rate coefficients for the reactions of the precursors with ozone and NO3. Most measured aldehydes correlated strongly with CO at night, suggesting a contribution from motor vehicle emissions. However, the emission ratios of most aldehydes versus CO are higher than those reported in motor vehicle emissions and the aldehyde sources remain unclear. Formation of several OVOCs is investigated in terms of the removal of specific precursors. Direct emissions of alcohols and aldehydes contribute significantly to OH reactivity throughout the day, and these emissions should be accurately represented in models describing ozone formation.

COI oxidation on a single Pd atom supported on magnesia.

PubMed

Abbet, S; Heiz, U; Häkkinen, H; Landman, U

2001-06-25

The oxidation of CO on single Pd atoms anchored to MgO(100) surface oxygen vacancies is studied with temperature-programmed-reaction mass spectrometry and infrared spectroscopy. In one-heating-cycle experiments, CO(2), formed from O(2) and CO preadsorbed at 90 K, is detected at 260 and 500 K. Ab-initio simulations suggest two reaction routes, with Pd(CO)(2)O(2) and PdCO(3)CO found as precursors for the low and high temperature channels, respectively. Both reactions result in annealing of the vacancy and induce migration and coalescence of the remaining Pd-CO to form larger clusters.

In Vitro Enzymatic Synthesis of New Penicillins Containing Keto Acids as Side Chains

PubMed Central

Ferrero, Miguel A.; Reglero, Angel; Martínez-Blanco, Honorina; Fernández-Valverde, Martiniano; Luengo, Jose M.

1991-01-01

Seven different penicillins containing α-ketobutyric, β-ketobutyric, γ-ketovaleric, α-ketohexanoic, δ-ketohexanoic, ε-ketoheptanoic, and α-ketooctanoic acids as side chains have been synthesized in vitro by incubating the enzymes phenylacetyl coenzyme A (CoA) ligase from Pseudomonas putida and acyl-CoA:6-aminopenicillanic acid acyltransferase from Penicillium chrysogenum with CoA, ATP, Mg2+, dithiothreitol, 6-aminopenicillanic acid, and the corresponding side chain precursor. PMID:1952871

Split2 Protein-Ligation Generates Active IL-6-Type Hyper-Cytokines from Inactive Precursors.

PubMed

Moll, Jens M; Wehmöller, Melanie; Frank, Nils C; Homey, Lisa; Baran, Paul; Garbers, Christoph; Lamertz, Larissa; Axelrod, Jonathan H; Galun, Eithan; Mootz, Henning D; Scheller, Jürgen

2017-12-15

Trans-signaling of the major pro- and anti-inflammatory cytokines Interleukin (IL)-6 and IL-11 has the unique feature to virtually activate all cells of the body and is critically involved in chronic inflammation and regeneration. Hyper-IL-6 and Hyper-IL-11 are single chain designer trans-signaling cytokines, in which the cytokine and soluble receptor units are trapped in one complex via a flexible peptide linker. Albeit, Hyper-cytokines are essential tools to study trans-signaling in vitro and in vivo, the superior potency of these designer cytokines are accompanied by undesirable stress responses. To enable tailor-made generation of Hyper-cytokines, we developed inactive split-cytokine-precursors adapted for posttranslational reassembly by split-intein mediated protein trans-splicing (PTS). We identified cutting sites within IL-6 (E 134 /S 135 ) and IL-11 (G 116 /S 117 ) and obtained inactive split-Hyper-IL-6 and split-Hyper-IL-11 cytokine precursors. After fusion with split-inteins, PTS resulted in reconstitution of active Hyper-cytokines, which were efficiently secreted from transfected cells. Our strategy comprises the development of a background-free cytokine signaling system from reversibly inactivated precursor cytokines.

Morphological evolution of carbon nanofibers encapsulating SnCo alloys and its effect on growth of the solid electrolyte interphase layer.

PubMed

Shin, Jungwoo; Ryu, Won-Hee; Park, Kyu-Sung; Kim, Il-Doo

2013-08-27

Two distinctive one-dimensional (1-D) carbon nanofibers (CNFs) encapsulating irregularly and homogeneously segregated SnCo nanoparticles were synthesized via electrospinning of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) polymers containing Sn-Co acetate precursors and subsequent calcination in reducing atmosphere. CNFs synthesized with PVP, which undergoes structural degradation of the polymer during carbonization processes, exhibited irregular segregation of heterogeneous alloy particles composed of SnCo, Co3Sn2, and SnO with a size distribution of 30-100 nm. Large and exposed multiphase SnCo particles in PVP-driven amorphous CNFs (SnCo/PVP-CNFs) kept decomposing liquid electrolyte and were partly detached from CNFs during cycling, leading to a capacity fading at the earlier cycles. The closer study of solid electrolyte interphase (SEI) layers formed on the CNFs reveals that the gradual growth of fiber radius due to continuous increment of SEI layer thickness led to capacity fading. In contrast, SnCo particles in PAN-driven CNFs (SnCo/PAN-CNFs) showed dramatically reduced crystallite sizes (<10 nm) of single phase SnCo nanoparticles which were entirely embedded in dense, semicrystalline, and highly conducting 1-D carbon matrix. The growth of SEI layer was limited and saturated during cycling. As a result, SnCo/PAN-CNFs showed much improved cyclability (97.9% capacity retention) and lower SEI layer thickness (86 nm) after 100 cycles compared to SnCo/PVP-CNFs (capacity retention, 71.9%; SEI layer thickness, 593 nm). This work verifies that the thermal behavior of carbon precursor is highly responsible for the growth mechanism of SEI layer accompanied with particles detachment and cyclability of alloy particle embedded CNFs.

Impact of carbon monoxide partial pressures on methanogenesis and medium chain fatty acids production during ethanol fermentation.

PubMed

Esquivel-Elizondo, Sofia; Miceli, Joseph; Torres, Cesar I; Krajmalnik-Brown, Rosa

2018-02-01

Medium-chain fatty acids (MCFA) are important biofuel precursors. Carbon monoxide (CO) is a sustainable electron and carbon donor for fatty acid elongation, since it is metabolized to MCFA precursors, it is toxic to most methanogens, and it is a waste product generated in the gasification of waste biomass. The main objective of this work was to determine if the inhibition of methanogenesis through the continuous addition of CO would lead to increased acetate or MCFA production during fermentation of ethanol. The effects of CO partial pressures (P CO ; 0.08-0.3 atm) on methanogenesis, fatty acids production, and the associated microbial communities were studied in batch cultures fed with CO and ethanol. Methanogenesis was partially inhibited at P CO  ≥ 0.11 atm. This inhibition led to increased acetate production during the first phase of fermentation (0-19 days). However, a second addition of ethanol (day 19) triggered MCFA production only at P CO  ≥ 0.11 atm, which probably occurred through the elongation of acetate with CO-derived ethanol and H 2 :CO 2 . Accordingly, during the second phase of fermentation (days 20-36), the distribution of electrons to acetate decreased at higher P CO , while electrons channeled to MCFA increased. Most probably, Acetobacterium, Clostridium, Pleomorphomonas, Oscillospira, and Blautia metabolized CO to H 2 :CO 2 , ethanol and/or fatty acids, while Peptostreptococcaceae, Lachnospiraceae, and other Clostridiales utilized these metabolites, along with the provided ethanol, for MCFA production. These results are important for biotechnological systems where fatty acids production are preferred over methanogenesis, such as in chain elongation systems and microbial fuel cells. © 2017 Wiley Periodicals, Inc.

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study.

PubMed

Hu, Xiao; Schuster, Jörg; Schulz, Stefan E; Gessner, Thomas

2015-10-28

Atomistic mechanisms for the atomic layer deposition using the Cu(acac)2 (acac = acetylacetonate) precursor are studied using first-principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)2 chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac-ligands. A sequential dissociation and reduction of the Cu precursor [Cu(acac)2 → Cu(acac) → Cu] are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)2 on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)2 on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by-products CO2 and H2O are observed during the reaction between Cu(acac)2 and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)2 follows the order H > O3 > H2O.

General control of transition-metal-doped GaN nanowire growth: toward understanding the mechanism of dopant incorporation.

PubMed

Stamplecoskie, Kevin G; Ju, Ling; Farvid, Shokouh S; Radovanovic, Pavle V

2008-09-01

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.

Co-polymer Films for Sensors

NASA Technical Reports Server (NTRS)

Ryan, Margaret A. (Inventor); Jewell, April D. (Inventor); Taylor, Charles (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Manatt, Kenneth S. (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor); Homer, Margie L. (Inventor); Shevade, Abhijit V. (Inventor)

2012-01-01

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Co-polymer films for sensors

NASA Technical Reports Server (NTRS)

Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

2010-01-01

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Chemical solution-deposited PbZr 0.53 Ti 0.47 O3 on La 0.5 Sr 0.5 Co O3. SIMS investigation of the effect of different precursor additives on the layer structure.

PubMed

Pollak, C; Malic, B; Kosec, M; Javoric, S; Hutter, H

2002-10-01

Chemical solution-deposited thin films of PbZr(0.53)Ti(0.47)O(3)/La(0.5)Sr(0.5)CoO(3) on Pt/TiO(2)/SiO(2)/Si substrates have been investigated by dynamic SIMS. The PbZr(0.53)Ti(0.47)O(3) (PZT) is intended to serve as a ferroelectric layer for microelectronic or microelectromechanical applications; conducting La(0.5)Sr(0.5)CoO(3) (LSCO) is a buffer layer intended to eliminate fatigue effects which usually occur at the Pt/PZT interface. Depth profiles of the main components were obtained and revealed that significant diffusion occurred during the deposition and crystallisation processes. Two types of sample, with different thickness of PZT and different types of poly(vinyl alcohol) (PVA) added to the LSCO precursor, were investigated.

Methane and water spectroscopic database for TROPOMI/Sentinel-5 Precursor in the 2.3 μm region

NASA Astrophysics Data System (ADS)

Birk, Manfred; Wagner, Georg; Loos, Joep; Wilzewski, Jonas; Mondelain, Didier; Campargue, Alain; Hase, Frank; Orphal, Johannes; Perrin, Agnes; Tran, Ha; Daumont, Ludovic; Rotger-Languereau, Maud; Bigazzi, Alberto; Zehner, Claus

2017-04-01

The ESA project „SEOM-Improved Atmospheric Spectroscopy Databases (IAS)" will improve the spectroscopic database for retrieval of the data products CO, CH4, O3 and SO2 column amounts measured by the TROPOMI instrument (TROPOspheric Monitoring Instrument) aboard the Sentinel-5 Precursor. The project was launched in February 2014 with 3 years duration extended to 4 years recently. The spectroscopy of CO, CH4 and O3 in the 2.3 μm region is covered first while UV measurements of SO2 and UV/FIR/IR measurements of ozone will be carried out later. Measurements were mainly taken with a high resolution Fourier Transform spectrometer combined with a coolable multi reflection cell. Cavity ring down measurements served for validation. The analysis has been completed. A clear improvement can be seen when using the new data for CH4, H2O and CO retrieval from ground-based high resolution solar occultation measurements obtained with instrumentation in the TCCON and NDACC network.

Dynamics of Monoterpene Formation in Spike Lavender Plants

PubMed Central

Kutzner, Erika; Huber, Claudia; Segura, Juan; Arrillaga, Isabel

2017-01-01

The metabolic cross-talk between the mevalonate (MVA) and the methylerythritol phosphate (MEP) pathways was analyzed in spike lavender (Lavandula latifolia Med) on the basis of 13CO2-labelling experiments using wildtype and transgenic plants overexpressing the 3-hydroxy-3-methylglutaryl CoA reductase (HMGR), the first and key enzyme of the MVA pathway. The plants were labelled in the presence of 13CO2 in a gas chamber for controlled pulse and chase periods of time. GC/MS and NMR analysis of 1,8-cineole and camphor, the major monoterpenes present in their essential oil, indicated that the C5-precursors, isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP) of both monoterpenes are predominantly biosynthesized via the MEP pathway. Surprisingly, overexpression of HMGR did not have significant impact upon the crosstalk between the MVA and MEP pathways indicating that the MEP route is the preferred pathway for the synthesis of C5 monoterpene precursors in spike lavender. PMID:29257083

Cleavage of precursors by the mitochondrial processing peptidase requires a compatible mature protein or an intermediate octapeptide

PubMed Central

1991-01-01

Many precursors of mitochondrial proteins are processed in two successive steps by independent matrix peptidases (MPP and MIP), whereas others are cleaved in a single step by MPP alone. To explain this dichotomy, we have constructed deletions of all or part of the octapeptide characteristic of a twice cleaved precursor (human ornithine transcarbamylase [pOTC]), have exchanged leader peptide sequences between once-cleaved (human methylmalonyl-CoA mutase [pMUT]; yeast F1ATPase beta-subunit [pF1 beta]) and twice-cleaved (pOTC; rat malate dehydrogenase (pMDH); Neurospora ubiquinol-cytochrome c reductase iron-sulfur subunit [pFe/S]) precursors, and have incubated these proteins with purified MPP and MIP. When the octapeptide of pOTC was deleted, or when the entire leader peptide of a once-cleaved precursor (pMUT or pF1 beta) was joined to the mature amino terminus of a twice-cleaved precursor (pOTC or pFe/S), no cleavage was produced by either protease. Cleavage of these constructs by MPP was restored by re- inserting as few as two amino-terminal residues of the octapeptide or of the mature amino terminus of a once-cleaved precursor. We conclude that the mature amino terminus of a twice-cleaved precursor is structurally incompatible with cleavage by MPP; such proteins have evolved octapeptides cleaved by MIP to overcome this incompatibility. PMID:1672532

Carbon films produced from ionic liquid carbon precursors

DOEpatents

Dai, Sheng; Luo, Huimin; Lee, Je Seung

2013-11-05

The invention is directed to a method for producing a film of porous carbon, the method comprising carbonizing a film of an ionic liquid, wherein the ionic liquid has the general formula (X.sup.+a).sub.x(Y.sup.-b).sub.y, wherein the variables a and b are, independently, non-zero integers, and the subscript variables x and y are, independently, non-zero integers, such that ax=by, and at least one of X.sup.+ and Y.sup.- possesses at least one carbon-nitrogen unsaturated bond. The invention is also directed to a composition comprising a porous carbon film possessing a nitrogen content of at least 10 atom %.

Methods for producing complex films, and films produced thereby

DOEpatents

Duty, Chad E.; Bennett, Charlee J. C.; Moon, Ji -Won; Phelps, Tommy J.; Blue, Craig A.; Dai, Quanqin; Hu, Michael Z.; Ivanov, Ilia N.; Jellison, Jr., Gerald E.; Love, Lonnie J.; Ott, Ronald D.; Parish, Chad M.; Walker, Steven

2015-11-24

A method for producing a film, the method comprising melting a layer of precursor particles on a substrate until at least a portion of the melted particles are planarized and merged to produce the film. The invention is also directed to a method for producing a photovoltaic film, the method comprising depositing particles having a photovoltaic or other property onto a substrate, and affixing the particles to the substrate, wherein the particles may or may not be subsequently melted. Also described herein are films produced by these methods, methods for producing a patterned film on a substrate, and methods for producing a multilayer structure.

Method for Waterproofing Ceramic Materials

NASA Technical Reports Server (NTRS)

Cagliostro, Domenick E. (Inventor); Hsu, Ming-Ta S. (Inventor)

1998-01-01

Hygroscopic ceramic materials which are difficult to waterproof with a silane, substituted silane or silazane waterproofing agent, such as an alumina containing fibrous, flexible and porous, fibrous ceramic insulation used on a reentry space vehicle, are rendered easy to waterproof if the interior porous surface of the ceramic is first coated with a thin coating of silica. The silica coating is achieved by coating the interior surface of the ceramic with a silica precursor converting the precursor to silica either in-situ or by oxidative pyrolysis and then applying the waterproofing agent to the silica coated ceramic. The silica precursor comprises almost any suitable silicon containing material such as a silane, silicone, siloxane, silazane and the like applied by solution, vapor deposition and the like. If the waterproofing is removed by e.g., burning, the silica remains and the ceramic is easily rewaterproofed. An alumina containing TABI insulation which absorbs more that five times its weight of water, absorbs less than 10 wt. % water after being waterproofed according to the method of the invention.

Preparation of powders suitable for conversion to useful .beta.-aluminas

DOEpatents

Morgan, Peter E. D.

1982-01-01

A process for forming a precursor powder which, when suitably pressed and sintered forms highly pure, densified .beta.- or .beta."-alumina, comprising the steps of: (1) forming a suspension (or slurry) of Bayer-derived Al(OH).sub.3 in a water-miscible solvent; (2) adding an aqueous solution of a Mg compound, a Li compound, a Na compound or mixtures thereof to the Bayer-derived Al(OH).sub.3 suspension while agitating the mixture formed thereby, to produce a gel; (3) drying the gel at a temperature above the normal boiling point of water to produce a powder material; (4) lightly ball milling and sieving said powder material; and (5) heating the ball-milled and sieved powder material at a temperature of between 350.degree. to 900.degree. C. to form the .beta.- or .beta."-alumina precursor powder. The precursor powder, thus formed, may be subsequently isopressed at a high pressure and sintered at an elevated temperature to produce .beta.- or .beta."-alumina. BACKGROUND OF THE INVENTION

Enzyme structures of the bacterial peptidoglycan and wall teichoic acid biogenesis pathways.

PubMed

Caveney, Nathanael A; Li, Franco Kk; Strynadka, Natalie Cj

2018-06-06

The bacterial cell wall is a complex polymeric structure with essential roles in defence, survival and pathogenesis. Common to both Gram-positive and Gram-negative bacteria is the mesh-like peptidoglycan sacculus that surrounds the outer leaflet of the cytoplasmic membrane. Recent crystallographic studies of enzymes that comprise the peptidoglycan biosynthetic pathway have led to significant new understanding of all stages. These include initial multi-step cytosolic formation of sugar-pentapeptide precursors, transfer of the precursors to activated polyprenyl lipids at the membrane inner leaflet and flippase mediated relocalization of the resulting lipid II precursors to the outer leaflet where glycopolymerization and subsequent peptide crosslinking are finalized. Additional, species-specific enzymes allow customized peptidoglycan modifications and biosynthetic regulation that are important to bacterial virulence and survival. These studies have reinforced the unique and specific catalytic mechanisms at play in cell wall biogenesis and expanded the atomic foundation to develop novel, structure guided, antibacterial agents. Copyright © 2018 Elsevier Ltd. All rights reserved.

Glycosylphosphatidylinositol membrane anchors in Saccharomyces cerevisiae: absence of ceramides from complete precursor glycolipids.

PubMed Central

Sipos, G; Puoti, A; Conzelmann, A

1994-01-01

Glycosylphosphatidylinositol (GPI) anchoring of membrane proteins occurs through two distinct steps, namely the assembly of a precursor glycolipid and its subsequent transfer onto newly synthesized proteins. To analyze the structure of the yeast precursor glycolipid we made use of the pmi40 mutant that incorporates very high amounts of [3H]mannose. Two very polar [3H]mannose-labeled glycolipids named CP1 and CP2 qualified as GPI precursor lipids since their carbohydrate head group, Man alpha 1,2(X-->PO4-->6)Man alpha 1,2Man alpha 1,6Man alpha-GlcN-inositol (with X most likely being ethanolamine) comprises the core structure which is common to all GPI anchors described so far. CP1 predominates in cells grown at 24 degrees C whereas CP2 is induced by stress conditions. The apparent structural identity of the head groups suggests that CP1 and CP2 contain different lipid moieties. The lipid moieties of both CP1 and CP2 can be removed by mild alkaline hydrolysis although the protein-bound GPI anchors made by the pmi40 cells under identical labeling conditions contain mild base resistant ceramides. These findings imply that the ceramide moiety found on the majority of yeast GPI anchored proteins is added through a lipid remodeling step that occurs after the addition of the GPI precursor glycolipids to proteins. Images PMID:8026463

Self-assembly of water-soluble nanocrystals

DOEpatents

Fan, Hongyou [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM; Lopez, Gabriel P [Albuquerque, NM

2012-01-10

A method for forming an ordered array of nanocrystals where a hydrophobic precursor solution with a hydrophobic core material in an organic solvent is added to a solution of a surfactant in water, followed by removal of a least a portion of the organic solvent to form a micellar solution of nanocrystals. A precursor co-assembling material, generally water-soluble, that can co-assemble with individual micelles formed in the micellar solution of nanocrystals can be added to this micellar solution under specified reaction conditions (for example, pH conditions) to form an ordered-array mesophase material. For example, basic conditions are used to precipitate an ordered nanocrystal/silica array material in bulk form and acidic conditions are used to form an ordered nanocrystal/silica array material as a thin film.

Fe-based long range ordered alloys

DOEpatents

Liu, Chain T; Inouye, Henry; Schaffhauser, Anthony C.

1980-01-01

Malleable long range ordered alloys having high critical ordering temperatures exist in the V(Co,Fe).sub.3 and V(Co,Fe,Ni).sub.3 system having the composition comprising by weight 22-23% V, 35-50% Fe, 0-22% Co and 19-40% Ni with an electron density no greater than 8.00. Excellent high temperature properties occur in alloys having compositions comprising by weight 22-23% V, 35-45% Fe, 0-10% Co, 25-35% Ni; 22-23% V, 28-33% Ni and the remainder Fe; and 22-23% V, 19-22% Ni, 19-22% Co and the remainder Fe. The alloys are fabricable by casting, deforming and annealing for sufficient time to provide ordered structure.

Abiotically-formed, primary dolomite in the mid-Eocene lacustrine succession at Gebel El-Goza El-Hamra, NE Egypt: An approach to the role of smectitic clays

NASA Astrophysics Data System (ADS)

Wanas, H. A.; Sallam, E.

2016-08-01

This study discusses the role of smectitic clays in the formation of an abiotic (physio-chemical) primary dolomite within an evaporative alkaline-saline marginal lake system, in the absence of carbonate precursor and microbes. The present work has been achieved in terms of textural, mineralogical, and geochemical characteristics of dolostones in the Mid-Eocene (Bartonian) lacustrine succession cropping out at Gebel El-Goza El-Hamra (Shabrawet area, NE Egypt). This lacustrine succession is 15-16 m thick, and made up of alternating horizontal beds of dolostone, marlstone and mudrock that show some pedogenic and subaerial exposure features. The dolostones are composed mainly of dolomite (60-90%), smectite (20-30%) and quartz grains (5-10%). The dolomite comprises fine-crystalline rhombs to micro-spherical crystals with no obvious relics of microbial activity and/or carbonate precursor. It is, ordered, nearly stoichiometric (with 46-50% mole of MgCO3) and has δ18O and δ13C values ranging from + 0.44 to + 2.96 VPDB ‰, and 0.93 to - 8.95 VPDB ‰, respectively. The smectite occurs as thin mats that are commonly intergrown and associated with dolomite. Mineralogical, textural and stable isotopic results of the dolomite indicated that the dolomite was formed as an abiotic primary precipitate in alkaline saline lacustrine systems. In this respect, the gel-like highly viscous smectitic medium plus progressive CO2 degassing, elevated evaporation, low sedimentation rate, low sulphates level and alkaline soil solution lowered the kinetic barriers of dolomite precipitation from solution and promoted the incorporation of Mg2 + in the structure of dolomite. Consequently, the presence of smectitic clays in evaporative saline lakes is significant for dolomite formation because they can generate a gel-like highly viscous medium and provide Mg2 + that can facilitate the physcio-chemical precipitation of primary dolomite from solution at ambient temperatures. However, more work is needed to better characterize the role of clays during dolomite formation in alkaline lacustrine environments at ambient temperatures.

Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts

NASA Astrophysics Data System (ADS)

Schütte, Kai; Doddi, Adinarayana; Kroll, Clarissa; Meyer, Hajo; Wiktor, Christian; Gemel, Christian; van Tendeloo, Gustaaf; Fischer, Roland A.; Janiak, Christoph

2014-04-01

Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions. Electronic supplementary information (ESI) available: Ni-Ga phase diagrams, EDX (XPS) of NP1-NP8, table of Ni : Ga ratios, TG of Ni-Ga SSPs, analysis of NP4, dec. of [Ni(GaCp*)3(PCy3)] with characterization, local resolution EDX of NP3-IL, Ni-NP characterization from Ni(COD)2 and details of (semi-)hydrogenation catalysis. See DOI: 10.1039/c4nr00111g

Loss of T cell precursors after spaceflight and exposure to vector-averaged gravity

NASA Technical Reports Server (NTRS)

Woods, Chris C.; Banks, Krista E.; Gruener, Raphael; DeLuca, Dominick

2003-01-01

Using fetal thymus organ culture (FTOC), we examined the effects of spaceflight and vector-averaged gravity on T cell development. Under both conditions, the development of T cells was significantly attenuated. Exposure to spaceflight for 16 days resulted in a loss of precursors for CD4+, CD8+, and CD4+CD8+ T cells in a rat/mouse xenogeneic co-culture. A significant decrease in the same precursor cells, as well as a decrease in CD4-CD8- T cell precursors, was also observed in a murine C57BL/6 FTOC after rotation in a clinostat to produce a vector-averaged microgravity-like environment. The block in T cell development appeared to occur between the pre-T cell and CD4+CD8+ T cell stage. These data indicate that gravity plays a decisive role in the development of T cells.

Chemical deposition methods using supercritical fluid solutions

DOEpatents

Sievers, Robert E.; Hansen, Brian N.

1990-01-01

A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

NASA Astrophysics Data System (ADS)

Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

A combined approach of classical mutagenesis and rational metabolic engineering improves rapamycin biosynthesis and provides insights into methylmalonyl-CoA precursor supply pathway in Streptomyces hygroscopicus ATCC 29253.

PubMed

Jung, Won Seok; Yoo, Young Ji; Park, Je Won; Park, Sung Ryeol; Han, Ah Reum; Ban, Yeon Hee; Kim, Eun Ji; Kim, Eunji; Yoon, Yeo Joon

2011-09-01

Rapamycin is a macrocyclic polyketide with immunosuppressive, antifungal, and anticancer activity produced by Streptomyces hygroscopicus ATCC 29253. Rapamycin production by a mutant strain (UV2-2) induced by ultraviolet mutagenesis was improved by approximately 3.2-fold (23.6 mg/l) compared to that of the wild-type strain. The comparative analyses of gene expression and intracellular acyl-CoA pools between wild-type and the UV2-2 strains revealed that the increased production of rapamycin in UV2-2 was due to the prolonged expression of rapamycin biosynthetic genes, but a depletion of intracellular methylmalonyl-CoA limited the rapamycin biosynthesis of the UV2-2 strain. Therefore, three different metabolic pathways involved in the biosynthesis of methylmalonyl-CoA were evaluated to identify the effective precursor supply pathway that can support the high production of rapamycin: propionyl-CoA carboxylase (PCC), methylmalonyl-CoA mutase, and methylmalonyl-CoA ligase. Among them, only the PCC pathway along with supplementation of propionate was found to be effective for an increase in intracellular pool of methylmalonyl-CoA and rapamycin titers in UV2-2 strain (42.8 mg/l), indicating that the PCC pathway is a major methylmalonyl-CoA supply pathway in the rapamycin producer. These results demonstrated that the combined approach involving traditional mutagenesis and metabolic engineering could be successfully applied to the diagnosis of yield-limiting factors and the enhanced production of industrially and clinically important polyketide compounds.

Reactive oxygen species are required for zoledronic acid-induced apoptosis in osteoclast precursors and mature osteoclast-like cells

PubMed Central

Tai, Ta-Wei; Chen, Ching-Yu; Su, Fong-Chin; Tu, Yuan-Kun; Tsai, Tsung-Ting; Lin, Chiou-Feng; Jou, I.-Ming

2017-01-01

Inhibiting osteoclasts and osteoclast precursors to reduce bone resorption is an important strategy to treat osteoclast-related diseases, such as osteoporosis, inflammatory bone loss, and malignant bone metastasis. However, the mechanism by which apoptosis is induced in the osteoclasts and their precursors are not completely understood. Here, we used nitrogen-containing bisphosphonate zoledronic acid (ZA) to induce cell apoptosis in human and murine osteoclast precursors and mature osteoclast-like cells. Caspase-3-mediated cell apoptosis occurred following the ZA (100 μM) treatment. Reactive oxygen species (ROS) were also generated in a time-dependent manner. Following knock-down of the p47phox expression, which is required for ROS activation, or co-treatment with the ROS inhibitor, N-acetyl-L-cysteine, ZA-induced apoptosis was significantly suppressed in both osteoclast precursors and mature osteoclast-like cells. The ROS-activated mitogen-activated protein kinases pathways did not trigger cell apoptosis. However, a ROS-regulated Mcl-1 decrease simultaneously with glycogen synthase kinase (GSK)-3β promoted cell apoptosis. These findings show that ZA induces apoptosis in osteoclast precursors and mature osteoclast-like cells by triggering ROS- and GSK-3β-mediated Mcl-1 down-regulation. PMID:28281643

Wet-chemical synthesis and properties of CoPt and CoPt3 alloy nanoparticles.

PubMed

Frommen, Christoph; Rösner, Harald; Fenske, Dieter

2002-10-01

Surface-protected, air-stable nanoparticles of CoPt and CoPt3 were prepared by thermal decomposition/reduction of organometallic precursors with a long-chain aliphatic diol, also known as the polyol process. Particles 3 nm in diameter showed ferromagnetic behavior up to 350 K (Hc = 65 Oe at T = 300 K; Hc = 410 Oe at T = 5K) and underwent a disordering-ordering phase transformation after annealing that resulted in an increase in coercivity (Hc = 170 Oe at T = 300 K; Hc = 2000 Oe at T = 5 K).

Deuterated methanol map towards L1544

NASA Astrophysics Data System (ADS)

Chacón-Tanarro, A.; Caselli, P.; Bizzocchi, L.; Pineda, J. E.; Spezzano, S.; Giuliano, B. M.; Lattanzi, V.; Punanova, A.

Pre-stellar cores are self-gravitating starless dense cores with clear signs of contraction and chemical evolution (Crapsi et al. 2005), considered to represent the initial conditions in the process of star formation (Caselli & Ceccarelli 2012). Theoretical studies predict that CO is one of the precursors of complex organic molecules (COMs) during this cold and dense phase (Tielens et al. 1982; Watanabe et al. 2002). Moreover, when CO starts to deplete onto dust grains (at densities of a few 104 cm-3), the formation of deuterated species is enhanced, as CO accelerates the destruction of important precursors of deuterated molecules (Dalgarno & Lepp 1984). Here, we present the CH_2DOH/CH_3OH column density map toward the pre-stellar core L1544 (Chacón-Tanarro et al., in prep.), taken with the IRAM 30 m antenna. The results are compared with the C17O (1-0) distribution across L1544. As methanol is formed on dust grains via hydrogenation of frozen-out CO, this work allows us to measure the deuteration on surfaces and compared it with gas phase deuteration, as well as CO freeze-out and dust properties. This is important to shed light on the basic chemical processes just before the formation of a stellar system.

Electron Beam-Induced Deposition for Atom Probe Tomography Specimen Capping Layers.

PubMed

Diercks, David R; Gorman, Brian P; Mulders, Johannes J L

2017-04-01

Six precursors were evaluated for use as in situ electron beam-induced deposition capping layers in the preparation of atom probe tomography specimens with a focus on near-surface features where some of the deposition is retained at the specimen apex. Specimens were prepared by deposition of each precursor onto silicon posts and shaped into sub-70-nm radii needles using a focused ion beam. The utility of the depositions was assessed using several criteria including composition and uniformity, evaporation behavior and evaporation fields, and depth of Ga+ ion penetration. Atom probe analyses through depositions of methyl cyclopentadienyl platinum trimethyl, palladium hexafluoroacetylacetonate, and dimethyl-gold-acetylacetonate [Me2Au(acac)] were all found to result in tip fracture at voltages exceeding 3 kV. Examination of the deposition using Me2Au(acac) plus flowing O2 was inconclusive due to evaporation of surface silicon from below the deposition under all analysis conditions. Dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9] depositions were found to be effective as in situ capping materials for the silicon specimens. Their very different evaporation fields [36 V/nm for Co2(CO)8 and 21 V/nm for Fe2(CO)9] provide options for achieving reasonably close matching of the evaporation field between the capping material and many materials of interest.

Laser-induced multi-energy processing in diamond growth

NASA Astrophysics Data System (ADS)

Xie, Zhiqiang

Laser-induced multi-energy processing (MEP) introduces resonant vibrational excitations of precursor molecules to conventional chemical vapor deposition methods for material synthesis. In this study, efforts were extended to explore the capability of resonant vibrational excitations for promotion of energy efficiency in chemical reactions, for enhancement of diamond deposition, and for control of chemical reactions. The research project mainly focused on resonant vibrational excitations of precursor molecules using lasers in combustion flame deposition of diamond, which led to: 1) promotion of chemical reactions; 2) enhancement of diamond growth with higher growth rate and better crystallizations; 3) steering of chemical reactions which lead to preferential growth of {100}-oriented diamond films and crystals; and 4) mode-selective excitations of precursor molecules toward bond-selective control of chemical reactions. Diamond films and crystals were deposited in open air by combustion flame deposition through resonant vibrational excitations of precursor molecules, including ethylene (C2H4) and propylene (C3H 6). A kilowatt wavelength-tunable CO2 laser with spectral range from 9.2 to 10.9 microm was tuned to match vibrational modes of the precursor molecules. Resonant vibrational excitations of these molecules were achieved with high energy efficiency as compared with excitations using a common CO2 laser (fixed wavelength at 10.591microm). With resonant vibrational excitations, the diamond growth rate was increased; diamond quality was promoted; diamond crystals with lengths up to 5 mm were deposited in open air; preferential growth of {100}-oriented diamond films and single crystals was achieved; mode-selective excitations of precursor molecules were investigated toward control of chemical reactions. Optical emission spectroscopy (OES), mass spectrometry (MS), and molecular dynamic simulations were conducted to obtain an in-depth understanding of the resonant vibrational excitations. Species concentrations in flames without and with laser excitations under different wavelengths were investigated both experimentally and theoretically. Detection of C2, CH, and OH radicals, as well as CxHy species and their oxides (CxH yO) (x=1, 2; y=0˜5) using OES and MS, together with reaction pathway simulations, were used to explain the effect of vibrational excitations of precursor molecules on chemical reactions and on diamond depositions.

Carbon dioxide sensor

DOEpatents

Dutta, Prabir K [Worthington, OH; Lee, Inhee [Columbus, OH; Akbar, Sheikh A [Hilliard, OH

2011-11-15

The present invention generally relates to carbon dioxide (CO.sub.2) sensors. In one embodiment, the present invention relates to a carbon dioxide (CO.sub.2) sensor that incorporates lithium phosphate (Li.sub.3PO.sub.4) as an electrolyte and sensing electrode comprising a combination of lithium carbonate (Li.sub.2CO.sub.3) and barium carbonate (BaCO.sub.3). In another embodiment, the present invention relates to a carbon dioxide (CO.sub.2) sensor has a reduced sensitivity to humidity due to a sensing electrode with a layered structure of lithium carbonate and barium carbonate. In still another embodiment, the present invention relates to a method of producing carbon dioxide (CO.sub.2) sensors having lithium phosphate (Li.sub.3PO.sub.4) as an electrolyte and sensing electrode comprising a combination of lithium carbonate (Li.sub.2CO.sub.3) and barium carbonate (BaCO.sub.3).

Low-temperature liquid precursors of crystalline metal oxides assisted by heterogeneous photocatalysis.

PubMed

Bretos, Iñigo; Jiménez, Ricardo; Pérez-Mezcua, Dulce; Salazar, Norberto; Ricote, Jesús; Calzada, M Lourdes

2015-04-24

The photocatalytically assisted decomposition of liquid precursors of metal oxides incorporating TiO2 particles enables the preparation of functional layers from the ferroelectric Pb(Zr,Ti)O3 and multiferroic BiFeO3 perovskite systems at temperatures not exceeding 350 ºC. This enables direct deposition on flexible plastic, where the multifunctionality provided by these complex-oxide materials guarantees their potential use in next-generation flexible electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure and property of diamond-like carbon films with Al and Cr co-doping deposited using a hybrid beams system

NASA Astrophysics Data System (ADS)

Dai, Wei; Liu, Jingmao; Geng, Dongsen; Guo, Peng; Zheng, Jun; Wang, Qimin

2016-12-01

DLC films with weak carbide former Al and carbide former Cr co-doping (Al:Cr-DLC) were deposited by a hybrid beams system comprising an anode-layer linear ion beam source (LIS) and high power impulse magnetron sputtering using a gas mixture of C2H2 and Ar as the precursor. The doped Al and Cr contents were controlled via adjusting the C2H2 fraction in the gas mixture. The composition, microstructure, compressive stress, mechanical properties and tribological behaviors of the Al:Cr-DLC films were researched carefully using X-ray photoelectron spectroscopy, transmission electron microscopy, Raman spectroscopy, stress-tester, nanoindentation and ball-on-plate tribometer as function of the C2H2 fraction. The results show that the Al and Cr contents in the films increased continuously as the C2H2 fraction decreased. The doped Cr atoms preferred to bond with the carbon while the Al atoms mainly existed in metallic state. Structure modulation with alternate multilayer consisted of Al-poor DLC layer and Al-rich DLC layer was found in the films. Those periodic Al-rich DLC layers can effectively release the residual stress of the films. On the other hand, the formation of the carbide component due to Cr incorporation can help to increase the film hardness. Accordingly, the residual stress of the DLC films can be reduced without sacrificing the film hardness though co-doping Al and Cr atoms. Furthermore, it was found that the periodic Al-rich layer can greatly improve the elastic resilience of the DLC films and thus decreases the film friction coefficient and wear rate significantly. However, the existence of the carbide component would cause abrasive wear and thus deteriorate the wear performance of the films.

Physiological and Molecular Biological Characterization of Intracellular Carbonic Anhydrase from the Marine Diatom Phaeodactylum tricornutum1

PubMed Central

Satoh, Dan; Hiraoka, Yasutaka; Colman, Brian; Matsuda, Yusuke

2001-01-01

A single intracellular carbonic anhydrase (CA) was detected in air-grown and, at reduced levels, in high CO2-grown cells of the marine diatom Phaeodactylum tricornutum (UTEX 642). No external CA activity was detected irrespective of growth CO2 conditions. Ethoxyzolamide (0.4 mm), a CA-specific inhibitor, severely inhibited high-affinity photosynthesis at low concentrations of dissolved inorganic carbon, whereas 2 mm acetazolamide had little effect on the affinity for dissolved inorganic carbon, suggesting that internal CA is crucial for the operation of a carbon concentrating mechanism in P. tricornutum. Internal CA was purified 36.7-fold of that of cell homogenates by ammonium sulfate precipitation, and two-step column chromatography on diethylaminoethyl-sephacel and p-aminomethylbenzene sulfone amide agarose. The purified CA was shown, by SDS-PAGE, to comprise an electrophoretically single polypeptide of 28 kD under both reduced and nonreduced conditions. The entire sequence of the cDNA of this CA was obtained by the rapid amplification of cDNA ends method and indicated that the cDNA encodes 282 amino acids. Comparison of this putative precursor sequence with the N-terminal amino acid sequence of the purified CA indicated that it included a possible signal sequence of up to 46 amino acids at the N terminus. The mature CA was found to consist of 236 amino acids and the sequence was homologous to β-type CAs. Even though the zinc-ligand amino acid residues were shown to be completely conserved, the amino acid residues that may constitute a CO2-binding site appeared to be unique among the β-CAs so far reported. PMID:11500545

Fabrication of nanostructured metal oxide films with supercritical carbon dioxide: Processing and applications

NASA Astrophysics Data System (ADS)

You, Eunyoung

Nanostructured metal oxide films have many applications in catalysis, microelectronics, microfluidics, photovoltaics and other fields. Since the performance of a device depends greatly on the structure of the material, the development of methodologies that enable prescriptive control of morphology are of great interest. The focus of this work is to control the structure and properties of the nanostructured metal oxide films using novel synthetic schemes in supercritical fluids and to use those films as key building components in alternative energy applications. A supercritical fluid is a substance at a temperature and pressure above its critical point. It typically exhibits gas-like transport properties and liquid-like densities. Supercritical fluid deposition (SFD) utilizes these properties of supercritical CO2 (scCO2) to deposit chemically pure metal, oxides and alloys of metal films. SFD is a chemical vapor deposition (CVD)-like process in the sense that it uses similar metal organic precursors and deposits films at elevated temperatures. Instead of vaporizing or subliming the precursors, they are dissolved in supercritical fluids. SFD has typically shown to exhibit higher precursor concentrations, lower deposition temperatures, conformal deposition of films on high aspect ratio features as compared to CVD. In2 O3, ZnO and SnO2 are attractive materials because they are used in transparent conductors. SFD of these materials were studied and In2 O3 deposition kinetics using tris(2,2,6,6-tetramethyl-3,5-heptanedionato) In (III) as precursor were determined. Growth rate dependence on the deposition temperature and the precursor concentrations were studied and the physicochemical and optical properties of In2 O3 films were characterized. Metal oxide nanochannels that can potentially be used for microfluidics have been fabricated by sequentially performing nanoimprint lithography (NIL) and SFD. NIL was used to pattern photoresist grating on substrates and SFD of TiO2 was performed thereafter. Subsequent calcination of the samples at high temperature of 400 °C revealed TiO2 nanochannels. H2-assisted-codeposition of Pt and cerium oxide using SFD was performed on porous carbon substrates for their use as anodes for direct methanol fuel cells. X-ray photoelectron analysis revealed that Pt was deposited as a pure metal and Ce was deposited as an oxide. Electrochemical analysis of a full cell revealed that an anode prepared with SFD exhibited better performance than that prepared with conventional brush-painting method. The second process that was developed is a direct spray-on technique to rapidly deposit crystalline nanoscale dendritic TiO2 onto a solid surface. This technique employs atomization of precursor solutions in supercritical fluids combined with the plasma thermal spraying. A solution of metal oxide precursor in scCO2 was expanded across a nozzle into the plasma jet where it is converted to metal oxide. We have investigated TiO2 as our model system using titanium tetra isopropoxide (Ttip) as a precursor. The film structure depends on key process variables including precursor concentration, precursor solution flow rate and plasma gun to substrate distance. The high surface area of the deposited films is attractive for applications in photovoltaics and we have fabricated dye-sensitized solar cells using these films.

Monodisperse cobalt ferrite nanoparticles assembled on mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4): A magnetically recoverable nanocomposite for the photocatalytic degradation of organic dyes

NASA Astrophysics Data System (ADS)

Hassani, Aydin; Eghbali, Paria; Ekicibil, Ahmet; Metin, Önder

2018-06-01

Monodisperse cobalt ferrite (CoFe2O4) nanoparticles (NPs) were synthesized by thermal decomposition of metal precursors in the presence of surfactants and then assembled on mesoporous graphitic carbon nitride (mpg-C3N4) via sonication of two components in ethanol solution. The yielded nanocomposite, namely CoFe2O4/mpg-C3N4, were characterized by using many advanced analytical techniques (TEM, HR-SEM, EDX, XRD, BET, PPMS-VSM, UV-vis DRS and ICP-MS). The magnetic properties of the CoFe2O4/mpg-C3N4 nanocomposite were studied by using M-H and M-T loops and the magnetic saturation and blocking temperature of the nanocomposite were found to be 6.1 emu/g and 269 K, respectively. The nanocomposite were then tested in the photocatalytic degradation of Malachite Green (MG) and showed considerably high photocatalytic activity under UV-light irradiation. The effects of various key operating parameters comprising catalyst amount, initial dye concentration, pH and reaction time span for the degradation of MG dye were studied to optimize the reaction conditions. The maximum degradation efficiency (DE %) of 93.41% was obtained by using 0.08 g L-1 catalyst and 10 mg L-1 MG dye at pH 5 within 120 min reaction time. Besides MG, the photocatalytic degradation of several other organic dyes (methylene blue, acid orange 7 and rhodamine B) was also studied to exhibit the performance of CoFe2O4/mpg-C3N4 nanocomposite under the optimized conditions. The results revealed that the kinetic of dye removal process could be designated through the application of pseudo-first-order kinetic model. In addition to high photocatalytic activity, CoFe2O4/mpg-C3N4 nanocomposite could be magnetically recovered after the dye degradation and reused for consecutive five runs without a significant loss (nearly 17%) in their initial performance.

Chlorogenic Acid Biosynthesis Appears Linked with Suberin Production in Potato Tuber (Solanum tuberosum).

PubMed

Valiñas, Matías Ariel; Lanteri, María Luciana; ten Have, Arjen; Andreu, Adriana Balbina

2015-05-20

Potato (Solanum tuberosum L.) is a good source of dietary antioxidants. Chlorogenic acid (CGA) and caffeic acid (CA) are the most abundant phenolic acid antioxidants in potato and are formed by the phenylpropanoid pathway. A number of CGA biosynthetic routes that involve hydroxycinnamoyl-CoA quinate hydroxycinnamoyl transferase (HQT) and/or hydroxycinnamoyl-CoA shikimate/quinate hydroxycinnamoyl transferase (HCT) have been proposed, but little is known about their path in potato. CA production requires a caffeoyl shikimate esterase (CSE), and CA serves as a substrate of lignin precursor ferulic acid via the action of caffeic/5-hydroxyferulic acid O-methyltransferase (COMT I). CGA is precursor of caffeoyl-CoA and, via caffeoyl-CoA O-methyltransferase (CCoAOMT), of feruloyl-CoA. Feruloyl-CoA is required for lignin and suberin biosynthesis, crucial for tuber development. Here, metabolite and transcript levels of the mentioned and related enzymes, such as cinnamate 4-hydroxylase (C4H), were determined in the flesh and skin of fresh and stored tubers. Metabolite and transcript levels were higher in skin than in flesh, irrespective of storage. CGA and CA production appear to occur via p-coumaroyl-CoA, using HQT and CSE, respectively. HCT is likely involved in CGA remobilization toward suberin. The strong correlation between CGA and CA, the correspondence with C4H, HQT, CCoAOMT2, and CSE, and the negative correlation of HCT and COMT I in potato tubers suggest a major flux toward suberin.

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

Wang, Kuaibing, E-mail: wangkb@njau.edu.cn; State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, Nanjing 210093; Lv, Bo

Hollow CuO/Co{sub 3}O{sub 4} hybrids, which inherited from its coordination polymer precursor consisting of sheets layer and nanoparticles layer composites, were synthesized and characterized by SEM, EDX, XRD and XPS. To assess its electrochemical capacitive performances, cyclic voltammetry, galvanostatic charging-discharging measurements and A.C. impedance tests were performed successively. The CuO/Co{sub 3}O{sub 4} hybrids had higher capacitance and lower charge transfer resistance than bare Co{sub 3}O{sub 4} nanostructures, revealing that it provided a protection layer and produced a synergistic effect due to the existence of CuO layer. The distinct synergistic effect could be further confirmed by endurance cycling tests. The capacitancemore » of the CuO/Co{sub 3}O{sub 4} hybrids was 111% retained after 500 cycles at a charging rate of 1.0 A g{sup −1} and remained an intense growth trend after 2000 cycles at scan rate of 200 mV s{sup −1}. - Graphical abstract: Hollow CuO/Co{sub 3}O{sub 4} hybrids are synthesized and display a peculiar synergetic effect on the resulting performances, which can further be evaluated and confirmed by series of electrochemical measurements. - Highlights: • Hollow CuO/Co{sub 3}O{sub 4} hybrids are synthesized from bimetallic-Schiff base polymer precursors. • The capacitance of the CuO/Co{sub 3}O{sub 4} hybrids keeps a growth tendency after 2000 cycles. • A synergetic effect is found for the hybrids in electrochemical energy storage process.« less

Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

USDA-ARS?s Scientific Manuscript database

A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

In Vivo Roles of Fatty Acid Biosynthesis Enzymes in Biosynthesis of Biotin and α-Lipoic Acid in Corynebacterium glutamicum.

PubMed

Ikeda, Masato; Nagashima, Takashi; Nakamura, Eri; Kato, Ryosuke; Ohshita, Masakazu; Hayashi, Mikiro; Takeno, Seiki

2017-10-01

For fatty acid biosynthesis, Corynebacterium glutamicum uses two type I fatty acid synthases (FAS-I), FasA and FasB, in addition to acetyl-coenzyme A (CoA) carboxylase (ACC) consisting of AccBC, AccD1, and AccE. The in vivo roles of the enzymes in supplying precursors for biotin and α-lipoic acid remain unclear. Here, we report genetic evidence demonstrating that the biosynthesis of these cofactors is linked to fatty acid biosynthesis through the FAS-I pathway. For this study, we used wild-type C. glutamicum and its derived biotin vitamer producer BFI-5, which was engineered to express Escherichia coli bioBF and Bacillus subtilis bioI Disruption of either fasA or fasB in strain BFI-5 led to decreased production of biotin vitamers, whereas its amplification contributed to increased production, with a larger impact of fasA in both cases. Double disruptions of fasA and fasB resulted in no biotin vitamer production. The acc genes showed a positive effect on production when amplified simultaneously. Augmented fatty acid biosynthesis was also reflected in pimelic acid production when carbon flow was blocked at the BioF reaction. These results indicate that carbon flow down the FAS-I pathway is destined for channeling into the biotin biosynthesis pathway, and that FasA in particular has a significant impact on precursor supply. In contrast, fasB disruption resulted in auxotrophy for lipoic acid or its precursor octanoic acid in both wild-type and BFI-5 strains. The phenotypes were fully complemented by plasmid-mediated expression of fasB but not fasA These results reveal that FasB plays a specific physiological role in lipoic acid biosynthesis in C. glutamicum IMPORTANCE For the de novo biosynthesis of fatty acids, C. glutamicum exceptionally uses a eukaryotic multifunctional type I fatty acid synthase (FAS-I) system comprising FasA and FasB, in contrast to most bacteria, such as E. coli and B. subtilis , which use an individual nonaggregating type II fatty acid synthase (FAS-II) system. In this study, we reported genetic evidence demonstrating that the FAS-I system is the source of the biotin precursor in vivo in the engineered biotin-prototrophic C. glutamicum strain. This study also uncovered the important physiological role of FasB in lipoic acid biosynthesis. Here, we present an FAS-I enzyme that functions in supplying the lipoic acid precursor, although its biosynthesis has been believed to exclusively depend on FAS-II in organisms. The findings obtained here provide new insights into the metabolic engineering of this industrially important microorganism to produce these compounds effectively. Copyright © 2017 American Society for Microbiology.

In Vivo Roles of Fatty Acid Biosynthesis Enzymes in Biosynthesis of Biotin and α-Lipoic Acid in Corynebacterium glutamicum

PubMed Central

Nagashima, Takashi; Nakamura, Eri; Kato, Ryosuke; Ohshita, Masakazu; Hayashi, Mikiro; Takeno, Seiki

2017-01-01

ABSTRACT For fatty acid biosynthesis, Corynebacterium glutamicum uses two type I fatty acid synthases (FAS-I), FasA and FasB, in addition to acetyl-coenzyme A (CoA) carboxylase (ACC) consisting of AccBC, AccD1, and AccE. The in vivo roles of the enzymes in supplying precursors for biotin and α-lipoic acid remain unclear. Here, we report genetic evidence demonstrating that the biosynthesis of these cofactors is linked to fatty acid biosynthesis through the FAS-I pathway. For this study, we used wild-type C. glutamicum and its derived biotin vitamer producer BFI-5, which was engineered to express Escherichia coli bioBF and Bacillus subtilis bioI. Disruption of either fasA or fasB in strain BFI-5 led to decreased production of biotin vitamers, whereas its amplification contributed to increased production, with a larger impact of fasA in both cases. Double disruptions of fasA and fasB resulted in no biotin vitamer production. The acc genes showed a positive effect on production when amplified simultaneously. Augmented fatty acid biosynthesis was also reflected in pimelic acid production when carbon flow was blocked at the BioF reaction. These results indicate that carbon flow down the FAS-I pathway is destined for channeling into the biotin biosynthesis pathway, and that FasA in particular has a significant impact on precursor supply. In contrast, fasB disruption resulted in auxotrophy for lipoic acid or its precursor octanoic acid in both wild-type and BFI-5 strains. The phenotypes were fully complemented by plasmid-mediated expression of fasB but not fasA. These results reveal that FasB plays a specific physiological role in lipoic acid biosynthesis in C. glutamicum. IMPORTANCE For the de novo biosynthesis of fatty acids, C. glutamicum exceptionally uses a eukaryotic multifunctional type I fatty acid synthase (FAS-I) system comprising FasA and FasB, in contrast to most bacteria, such as E. coli and B. subtilis, which use an individual nonaggregating type II fatty acid synthase (FAS-II) system. In this study, we reported genetic evidence demonstrating that the FAS-I system is the source of the biotin precursor in vivo in the engineered biotin-prototrophic C. glutamicum strain. This study also uncovered the important physiological role of FasB in lipoic acid biosynthesis. Here, we present an FAS-I enzyme that functions in supplying the lipoic acid precursor, although its biosynthesis has been believed to exclusively depend on FAS-II in organisms. The findings obtained here provide new insights into the metabolic engineering of this industrially important microorganism to produce these compounds effectively. PMID:28754705

The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

NASA Astrophysics Data System (ADS)

Farjamnia, Azar; Jackson, Bret

2017-02-01

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

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

Farjamnia, Azar; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

DOE PAGES

Farjamnia, Azar; Jackson, Bret

2017-02-21

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

Reaction pathways towards the formation of dolomite-analogues at ambient conditions

NASA Astrophysics Data System (ADS)

Pimentel, Carlos; Pina, Carlos M.

2016-04-01

In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

A phase coherence approach to identifying co-located earthquakes and tremor

NASA Astrophysics Data System (ADS)

Hawthorne, J. C.; Ampuero, J.-P.

2018-05-01

We present and use a phase coherence approach to identify seismic signals that have similar path effects but different source time functions: co-located earthquakes and tremor. The method used is a phase coherence-based implementation of empirical matched field processing, modified to suit tremor analysis. It works by comparing the frequency-domain phases of waveforms generated by two sources recorded at multiple stations. We first cross-correlate the records of the two sources at a single station. If the sources are co-located, this cross-correlation eliminates the phases of the Green's function. It leaves the relative phases of the source time functions, which should be the same across all stations so long as the spatial extent of the sources are small compared with the seismic wavelength. We therefore search for cross-correlation phases that are consistent across stations as an indication of co-located sources. We also introduce a method to obtain relative locations between the two sources, based on back-projection of interstation phase coherence. We apply this technique to analyse two tremor-like signals that are thought to be composed of a number of earthquakes. First, we analyse a 20 s long seismic precursor to a M 3.9 earthquake in central Alaska. The analysis locates the precursor to within 2 km of the mainshock, and it identifies several bursts of energy—potentially foreshocks or groups of foreshocks—within the precursor. Second, we examine several minutes of volcanic tremor prior to an eruption at Redoubt Volcano. We confirm that the tremor source is located close to repeating earthquakes identified earlier in the tremor sequence. The amplitude of the tremor diminishes about 30 s before the eruption, but the phase coherence results suggest that the tremor may persist at some level through this final interval.

Recent advances in understanding atmospheric CO based on stable isotope measurements

NASA Astrophysics Data System (ADS)

Popa, Maria Elena; Naus, Stijn; Ferrero Lopez, Noelia; Vijverberg, Sem; de Leeuw, Selma; Röckmann, Thomas

2017-04-01

Carbon monoxide (CO) plays an important role for atmospheric chemistry and for carbon cycling in the atmosphere. Via its reaction with the OH radical it influences concentrations of many other trace gases, it is an important precursor for O3 formation, and its oxidation leads to the formation of about 1 Pg C per year of CO2. The natural and anthropogenic sources of CO are subject to relatively large temporal changes due to natural variability (e.g. biomass burning), industrial activity and mitigation measures (e.g. fossil fuel burning), variations in precursor compounds (e.g. CH4 and VOC) and variations in the abundance of the OH radical in the atmosphere, which are difficult to quantify. Isotope measurements can be used to distinguish between the effects of individual sources and sinks to put tighter constrains on its budget, but the isotopic characterization of the CO sources is in many cases still based on a few relatively old measurements that did not allow to account for dependence on parameters. We will present an update of the isotopic composition of several sources and removal processes of CO that have been carried out in the past years with the automated continuous-flow IRMS system at Utrecht University. This includes: - the previously unknown isotopic composition of direct biogenic CO emissions - a surprisingly large variability in the isotopic composition of CO emitted by different vehicles and single vehicles under various driving conditions - previously very poorly investigated signatures, like the fractionation in the removal of CO by soils, and its interaction with CO that is simultaneously emitted from soil. These results from process specific investigations will be linked to recent atmospheric measurements at various locations.

Fe-based long range ordered alloys

DOEpatents

Liu, C.T.

Malleable long range ordered alloys with high critical ordering temperatures exist in the V(Co,Fe)/sub 3/ and V(Co,Fe,Ni)/sub 3/ system. The composition comprising by weight 22 to 23% V, 35 to 50% Fe, 0 to 22% Co and 19 to 40% Ni with an electron density no greater than 8.00. Excellent high temperature properties occur in alloys having compositions comprising by weight 22 to 23% V, 35 to 45% Fe, 0 to 10% Co, 25 to 35% Ni; 22 to 23% V, 28 to 33% Ni and the remainder Fe; and 22 to 23% V, 19 to 22% Co and the remainder Fe. The alloys are fabricable by casting, deforming and annealing for sufficient time to provide ordered structure.

Vapour-phase method in the synthesis of polymer-ibuprofen sodium-silica gel composites.

PubMed

Kierys, Agnieszka; Krasucka, Patrycja; Grochowicz, Marta

2017-11-01

The study discusses the synthesis of polymer-silica composites comprising water soluble drug (ibuprofen sodium, IBS). The polymers selected for this study were poly(TRIM) and poly(HEMA- co -TRIM) produced in the form of permanently porous beads via the suspension-emulsion polymerization method. The acid and base set ternary composites were prepared by the saturation of the solid dispersions of drug (poly(TRIM)-IBS and/or poly(HEMA- co -TRIM)-IBS) with TEOS, and followed by their exposition to the vapour mixture of water and ammonia, or water and hydrochloric acid, at autogenous pressure. The conducted analyses reveal that the internal structure and total porosity of the resulting composites strongly depend on the catalyst which was used for silica precursor gelation. The parameters characterizing the porosity of both of the acid set composites are much lower than the parameters of the base set composites. Moreover, the basic catalyst supplied in the vapour phase does not affect the ibuprofen sodium molecules, whereas the acid one causes transformation of the ibuprofen sodium into the sodium chloride and a derivative of propanoic acid, which is poorly water soluble. The release profiles of ibuprofen sodium from composites demonstrate that there are differences in the rate and efficiency of drug desorption from them. They are mainly affected by the chemical character of the polymeric carrier but are also associated with the restricted swelling of the composites in the buffer solution after precipitation of silica gel.

A Splash to Nano-Sized Inorganic Energy-Materials by the Low-Temperature Molecular Precursor Approach.

PubMed

Driess, Matthias; Panda, Chakadola; Menezes, Prashanth Wilfried

2018-05-07

The low-temperature synthesis of inorganic materials and their interfaces at the atomic and molecular level provides numerous opportunities for the design and improvement of inorganic materials in heterogeneous catalysis for sustainable chemical energy conversion or other energy-saving areas. Using suitable molecular precursors for functional inorganic nanomaterial synthesis allows for facile control over uniform particle size distribution, stoichiometry, and leads to desired chemical and physical properties. This minireview outlines some advantages of the molecular precursor approach in light of selected recent developments of molecule-to-nanomaterials synthesis for renewable energy applications, relevant for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and overall water-splitting. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of synthesis methods on the Ca{sub 3}Co{sub 4}O{sub 9} thermoelectric ceramic performances

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

Sotelo, A.; Rasekh, Sh.; Torres, M.A.

2015-01-15

Three different synthesis methods producing nanometric grain sizes, coprecipitation with ammonium carbonate, oxalic acid, and by attrition milling have been studied to produce Ca{sub 3}Co{sub 4}O{sub 9} ceramics and compared with the classical solid state route. These three processes have produced high reactive precursors and all the organic material and CaCO{sub 3}·have been decomposed in a single thermal treatment. Coprecipitation leads to pure Ca{sub 3}Co{sub 4}O{sub 9} phase, while attrition milling and classical solid state produce small amounts of Ca{sub 3}Co{sub 2}O{sub 6} secondary phase. Power factor values are similar for all three samples, being slightly lower for the onesmore » produced by attrition milling. These values are much higher than the obtained in samples prepared by the classical solid state method, used as reference. The maximum power factor values determined at 800 °C (∼0.43 mW/K{sup 2} m) are slightly higher than the best reported values obtained in textured ones which also show much higher density values. - Graphical abstract: Impressive raise of PF in Ca{sub 3}Co{sub 4}O{sub 9} thermoelectric materials obtained from nanometric grains. - Highlights: • Ca{sub 3}Co{sub 4}O{sub 9} has been produced by four different methods. • Precursors particle sizes influences on the final performances. • Coprecipitation methods produce single Ca{sub 3}Co{sub 4}O{sub 9} phase. • Power factor reaches values comparable to high density textured materials.« less

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.

PubMed Central

Smith, Paul J.; Kondrat, Simon A.; Chater, Philip A.; Yeo, Benjamin R.; Shaw, Greg M.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.

2017-01-01

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate. PMID:28451351

Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

NASA Astrophysics Data System (ADS)

Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

2016-04-01

It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D., Shaw S., Bots P., Roncal-Herrero T. and Benning L. G (2014) Geochimica et Cosmochimica Acta 127, 204-220

Catalytically-etched hexagonal boron nitride flakes and their surface activity

NASA Astrophysics Data System (ADS)

Kim, Do-Hyun; Lee, Minwoo; Ye, Bora; Jang, Ho-Kyun; Kim, Gyu Tae; Lee, Dong-Jin; Kim, Eok-Soo; Kim, Hong Dae

2017-04-01

Hexagonal boron nitride (h-BN) is a ceramic compound which is thermally stable up to 1000 °C in air. Due to this, it is a very challenging task to etch h-BN under air atmosphere at low temperature. In this study, we report that h-BN flakes can be easily etched by oxidation at 350 °C under air atmosphere in the presence of transition metal (TM) oxide. After selecting Co, Cu, and Zn elements as TM precursors, we simply oxidized h-BN sheets impregnated with the TM precursors at 350 °C in air. As a result, microscopic analysis revealed that an etched structure was created on the surface of h-BN flakes regardless of catalyst type. And, X-ray diffraction patterns indicated that the air oxidation led to the formation of Co3O4, CuO, and ZnO from each precursor. Thermogravimetric analysis showed a gradual weight loss in the temperature range where the weight of h-BN flakes increased by air oxidation. As a result of etching, pore volume and pore area of h-BN flakes were increased after catalytic oxidation in all cases. In addition, the surface of h-BN flakes became highly active when the h-BN samples were etched by Co3O4 and CuO catalysts. Based on these results, we report that h-BN flakes can be easily oxidized in the presence of a catalyst, resulting in an etched structure in the layered structure.

Efficient electrocatalytic conversion of CO.sub.2 to CO using ligand-protected Au.sub.25 clusters

DOEpatents

Kauffman, Douglas; Matranga, Christopher; Qian, Huifeng; Jin, Rongchao; Alfonso, Dominic R.

2015-09-22

An apparatus and method for CO.sub.2 reduction using an Au.sub.25 electrode. The Au.sub.25 electrode is comprised of ligand-protected Au.sub.25 having a structure comprising an icosahedral core of 13 atoms surrounded by a shell of six semi-ring structures bonded to the core of 13 atoms, where each semi-ring structure is typically --SR--Au--SR--Au--SR or --SeR--Au--SeR--Au--SeR. The 12 semi-ring gold atoms within the six semi-ring structures are stellated on 12 of the 20 faces of the icosahedron of the Au.sub.13 core, and organic ligand --SR or --SeR groups are bonded to the Au.sub.13 core with sulfur or selenium atoms. The Au.sub.25 electrode and a counter-electrode are in contact with an electrolyte comprising CO.sub.2 and H+, and a potential of at least -0.1 volts is applied from the Au.sub.25 electrode to the counter-electrode.

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

Ramkumar, Shwetha; Fan, Liang-Shih

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO bymore » calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.« less

Externally triggered microcapsules

NASA Technical Reports Server (NTRS)

Mosier, Benjamin (Inventor); Morrison, Dennis R. (Inventor)

2011-01-01

Disclosed are microcapsules comprising a polymer shell enclosing one or more immiscible liquid phases in which a drug or drug precursor are contained in a liquid phase. The microparticles also contain magnetic particles that can be heated by application of an external magnetic field and thus heated to a predetermined Curie temperature. Heating of the particles melts the polymer shell and releases the drug without causing heating of surrounding tissues.

Method of improving superconducting qualities of fabricated constructs by shock preprocessing of precursor materials

DOEpatents

Nellis, William J.; Maple, M. Brian

1992-01-01

Disclosed is a method of improving the physical properties of superconducting materials which comprises: a. applying a high strain rate deformation to said materi The United States Government has rights in this invention pursuant to Contract No. W-7405-ENG-48 between the U.S. Department of Energy and the University of California, for the operation of Lawrence Livermore National Laboratory.

Microwave assisted combustion synthesis of nanocrystalline CoFe2O4 for LPG sensing

NASA Astrophysics Data System (ADS)

Chaudhari, Prashant; Acharya, S. A.; Darunkar, S. S.; Gaikwad, V. M.

2015-08-01

A microwave-assisted citrate precursor method has been utilized for synthesis of nanocrystalline powders of CoFe2O4. The process takes only a few minutes to obtain as-synthesized CoFe2O4. Structural properties of the synthesized material were investigated by X-ray diffraction; scanning electron microscopy, Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy. The gas sensing properties of thick film of CoFe2O4 prepared by screen printing towards Liquid Petroleum Gas (LPG) revealed that CoFe2O4 thick films are sensitive and shows maximum sensitivity at 350°C for 2500 ppm of LPG.

Process of making titanium carbide (TiC) nano-fibrous felts

DOEpatents

Fong, Hao; Zhang, Lifeng; Zhao, Yong; Zhu, Zhengtao

2015-01-13

A method of synthesizing mechanically resilient titanium carbide (TiC) nanofibrous felts comprising continuous nanofibers or nano-ribbons with TiC crystallites embedded in carbon matrix, comprising: (a) electrospinning a spin dope for making precursor nanofibers with diameters less than 0.5 J.Lm; (b) overlaying the nanofibers to produce a nanofibrous mat (felt); and then (c) heating the nano-felts first at a low temperature, and then at a high temperature for making electrospun continuous nanofibers or nano-ribbons with TiC crystallites embedded in carbon matrix; and (d) chlorinating the above electrospun nano-felts at an elevated temperature to remove titanium for producing carbide derived carbon (CDC) nano-fibrous felt with high specific surface areas.

Production of aligned microfibers and nanofibers and derived functional monoliths

DOEpatents

Hu, Michael Z [Knoxville, TN; DePaoli, David W [Knoxville, TN; Kuritz, Tanya [Kingston, TN; Omatete, Ogbemi [New Port Richey, FL

2007-08-14

The present invention comprises a method for producing microfibers and nanofibers and further fabricating derived solid monolithic materials having aligned uniform micro- or nanofibrils. A method for producing fibers ranging in diameter from micrometer-sized to nanometer-sized comprises the steps of producing an electric field and preparing a solid precipitative reaction media wherein the media comprises at least one chemical reactive precursor and a solvent having low electrical conductivity and wherein a solid precipitation reaction process for nucleation and growth of a solid phase occurs within the media. Then, subjecting the media to the electric field to induce in-situ growth of microfibers or nanofibers during the reaction process within the media causing precipitative growth of solid phase particles wherein the reaction conditions and reaction kinetics control the size, morphology and composition of the fibers. The fibers can then be wet pressed while under electric field into a solid monolith slab, dried and consolidated.

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos Ph Complexes.

PubMed

Phanopoulos, Andreas; Long, Nicholas; Miller, Philip

2015-04-10

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphos(Ph)) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphos(Ph) ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphos(Ph) ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-κ(3)P] (2) were isolated on cooling to RT. The (31)P{(1)H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-κ(3)P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-κ(3)P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-κ(3)P{CH3CO(CH2)2CO2H}-κ(2)O](PF6) (6).

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

PubMed Central

Phanopoulos, Andreas; Long, Nicholas; Miller, Philip

2015-01-01

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-κ3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-κ3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-κ3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-κ3P{CH3CO(CH2)2CO2H}-κ2O](PF6) (6). PMID:25938678

Synthesis and magnetic properties of superparamagnetic CoAs nanostructures

NASA Astrophysics Data System (ADS)

Desai, P.; Ashokaan, N.; Masud, J.; Pariti, A.; Nath, M.

2015-03-01

This article provides a comprehensive guide on the synthesis and characterization of superparamagnetic CoAs nanoparticles and elongated nanostructures with high blocking temperature, (TB), via hot-injection precipitation and solvothermal methods. Cobalt arsenides constitute an important family of magnetically active solids that find a variety of applications ranging from magnetic semiconductors to biomedical imaging. While the higher temperature hot-injection precipitation technique (300 °C) yields pure CoAs nanostructures, the lower temperature solvothermal method (200 °C) yields a mixture of CoAs nanoparticles along with other Co-based impurity phases. The synthesis in all these cases involved usage of triphenylarsine ((C6H5)3As) as the As precursor which reacts with solid Co2(CO)8 by ligand displacement to yield a single source precursor. The surfactant, hexadecylamine (HDA) further assists in controlling the morphology of the nanostructures. HDA also provides a basic medium and molten flux-like conditions for the redox chemistry to occur between Co and As at elevated temperatures. The influence of the length of reaction time was investigated by studying the evolution of product morphology over time. It was observed that while spontaneous nucleation at higher temperature followed by controlled growth led to the predominant formation of short nanorods, with longer reaction time, the nanorods were further converted to nanoparticles. The size of the nanoparticles obtained, was mostly in the range of 10-15 nm. The key finding of this work is exceptionally high coercivity in CoAs nanostructures for the first time. Coercivity observed was as high as 0.1 T (1000 Oe) at 2 K. These kinds of magnetic nanostructures find multiple applications in spintronics, whereas the superparamagnetic nanoparticles are viable for use in magnetic storage, ferrofluids and as contrast enhancing agents in MRI.

Wetlands receiving water treated with coagulants improve water quality by removing dissolved organic carbon and disinfection byproduct precursors.

PubMed

Hansen, Angela M; Kraus, Tamara E C; Bachand, Sandra M; Horwath, William R; Bachand, Philip A M

2018-05-01

Constructed wetlands are used worldwide to improve water quality while also providing critical wetland habitat. However, wetlands have the potential to negatively impact drinking water quality by exporting dissolved organic carbon (DOC) that upon disinfection can form disinfection byproducts (DBPs) like trihalomethanes (THMs) and haloacetic acids (HAAs). We used a replicated field-scale study located on organic rich soils in California's Sacramento-San Joaquin Delta to test whether constructed flow-through wetlands which receive water high in DOC that is treated with either iron- or aluminum-based coagulants can improve water quality with respect to DBP formation. Coagulation alone removed DOC (66-77%) and THM (67-70%) precursors, and was even more effective at removing HAA precursors (77-90%). Passage of water through the wetlands increased DOC concentrations (1.5-7.5mgL -1 ), particularly during the warmer summer months, thereby reversing some of the benefits from coagulant addition. Despite this addition, water exiting the wetlands treated with coagulants had lower DOC and DBP precursor concentrations relative to untreated source water. Benefits of the coagulation-wetland systems were greatest during the winter months (approx. 50-70% reduction in DOC and DBP precursor concentrations) when inflow water DOC concentrations were higher and wetland DOC production was lower. Optical properties suggest DOC in this system is predominantly comprised of high molecular weight, aromatic compounds, likely derived from degraded peat soils. Published by Elsevier B.V.

Strains for the production of flavonoids from glucose

DOEpatents

Stephanopoulos, Gregory; Santos, Christine; Koffas, Mattheos

2015-11-13

The invention relates to the production of flavonoids and flavonoid precursors in cells through recombinant expression of tyrosine ammonia lyase (TAL), 4-coumarate:CoA ligase (4CL), chalcone synthase (CHS), and chalcone isomerase (CHI).

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

Parental punishment and peer victimization as developmental precursors to physical dating violence involvement among girls

PubMed Central

Hipwell, Alison E.; Stepp, Stephanie D.; Xiong, Shuangyan; Keenan, Kate; Blokland, Arjan; Loeber, Rolf

2012-01-01

The current study examined harsh punishment and peer victimization as developmental precursors to girls’ involvement in physical dating violence (PDV), and the putative mediating effect of rejection sensitivity. The sample comprised 475 African American and European American participants of the longitudinal Pittsburgh Girls Study who were dating at age 17. About 10% of girls reported significant perpetration and/or victimization of physical aggression in the relationship. Results showed that initial level and escalation in harsh punishment (between 10–13 years) and escalation in peer victimization (10–15 years) predicted PDV involvement, but this relationship was not mediated by rejection sensitivity. The results highlight the need to consider the impact of early experience of different forms of aggression on girls’ risk for PDV involvement. PMID:24591807

Pluripotency and lineages in the mammalian blastocyst: an evolutionary view.

PubMed

Cañon, Susana; Fernandez-Tresguerres, Beatriz; Manzanares, Miguel

2011-06-01

Early mammalian development is characterized by a highly specific stage, the blastocyst, by which embryonic and extraembryonic lineages have been determined, but pattern formation has not yet begun. The blastocyst is also of interest because cell precursors of the embryo proper retain for a certain time the capability to generate all the cell types of the adult animal. This embryonic pluripotency is established and maintained by a regulatory network under the control of a small set of transcription factors, comprising Oct4, Sox2 and Nanog. This network is largely conserved in eutherian mammals, but there is scarce information about how it arose in vertebrates. We have analysed the conservation of gene regulatory networks controlling blastocyst lineages and pluripotency in the mouse by comparison with the chick. We found that few of elements of the network are novel to mammals; rather, most of them were present before the separation of the mammalian lineage from other amniotes, but acquired novel expression domains during early mammalian development. Our results strongly support the hypothesis that mammalian blastocyst regulatory networks evolved through rewiring of pre-existing components, involving the co-option and duplication of existing genes and the establishment of new regulatory interactions among them.

A novel type of pathogen defense-related cinnamyl alcohol dehydrogenase.

PubMed

Logemann, E; Reinold, S; Somssich, I E; Hahlbrock, K

1997-08-01

We describe an aromatic alcohol dehydrogenase with properties indicating a novel type of function in the defense response of plants to pathogens. To obtain the enzyme free of contamination with possible isoforms, a parsley (Petroselinum crispum) cDNA comprising the entire coding region of the elicitor-responsive gene, ELI3, was expressed in Escherichia coli. In accord with large amino acid sequence similarities with established cinnamyl and benzyl alcohol dehydrogenases from other plants, the enzyme efficiently reduced various cinnamyl and benzyl aldehydes using NADPH as a co-substrate. Highest substrate affinities were observed for cinnamaldehyde, 4-coumaraldehyde and coniferaldehyde, whereas sinapaldehyde, one of the most efficient substrates of several previously analyzed cinnamyl alcohol dehydrogenases and a characteristic precursor molecule of angiosperm lignin, was not converted. A single form of ELI3 mRNA was strongly and rapidly induced in fungal elicitor-treated parsley cells. These results, together with earlier findings that the ELI3 gene is strongly activated both in elicitor-treated parsley cells and at fungal infection sites in parsley leaves, but not in lignifying tissue, suggest a specific role of this enzyme in pathogen defense-related phenylpropanoid metabolism.

High strength nanostructured Al-based alloys through optimized processing of rapidly quenched amorphous precursors.

PubMed

Kim, Song-Yi; Lee, Gwang-Yeob; Park, Gyu-Hyeon; Kim, Hyeon-Ah; Lee, A-Young; Scudino, Sergio; Prashanth, Konda Gokuldoss; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

2018-01-18

We report the methods increasing both strength and ductility of aluminum alloys transformed from amorphous precursor. The mechanical properties of bulk samples produced by spark-plasma sintering (SPS) of amorphous Al-Ni-Co-Dy powders at temperatures above 673 K are significantly enhanced by in-situ crystallization of nano-scale intermetallic compounds during the SPS process. The spark plasma sintered Al 84 Ni 7 Co 3 Dy 6 bulk specimens exhibit 1433 MPa compressive yield strength and 1773 MPa maximum strength together with 5.6% plastic strain, respectively. The addition of Dy enhances the thermal stability of primary fcc Al in the amorphous Al-TM -RE alloy. The precipitation of intermetallic phases by crystallization of the remaining amorphous matrix plays important role to restrict the growth of the fcc Al phase and contributes to the improvement of the mechanical properties. Such fully crystalline nano- or ultrafine-scale Al-Ni-Co-Dy systems are considered promising for industrial application because their superior mechanical properties in terms of a combination of very high room temperature strength combined with good ductility.

Amyloid precursor protein controls cholesterol turnover needed for neuronal activity

PubMed Central

Pierrot, Nathalie; Tyteca, Donatienne; D'auria, Ludovic; Dewachter, Ilse; Gailly, Philippe; Hendrickx, Aurélie; Tasiaux, Bernadette; Haylani, Laetitia El; Muls, Nathalie; N'Kuli, Francisca; Laquerrière, Annie; Demoulin, Jean-Baptiste; Campion, Dominique; Brion, Jean-Pierre; Courtoy, Pierre J; Kienlen-Campard, Pascal; Octave, Jean-Noël

2013-01-01

Perturbation of lipid metabolism favours progression of Alzheimer disease, in which processing of Amyloid Precursor Protein (APP) has important implications. APP cleavage is tightly regulated by cholesterol and APP fragments regulate lipid homeostasis. Here, we investigated whether up or down regulation of full-length APP expression affected neuronal lipid metabolism. Expression of APP decreased HMG-CoA reductase (HMGCR)-mediated cholesterol biosynthesis and SREBP mRNA levels, while its down regulation had opposite effects. APP and SREBP1 co-immunoprecipitated and co-localized in the Golgi. This interaction prevented Site-2 protease-mediated processing of SREBP1, leading to inhibition of transcription of its target genes. A GXXXG motif in APP sequence was critical for regulation of HMGCR expression. In astrocytes, APP and SREBP1 did not interact nor did APP affect cholesterol biosynthesis. Neuronal expression of APP decreased both HMGCR and cholesterol 24-hydroxylase mRNA levels and consequently cholesterol turnover, leading to inhibition of neuronal activity, which was rescued by geranylgeraniol, generated in the mevalonate pathway, in both APP expressing and mevastatin treated neurons. We conclude that APP controls cholesterol turnover needed for neuronal activity. PMID:23554170

Ferromagnetism in spin-coated cobalt-doped TiO2 thin films and the role of crystalline phases

NASA Astrophysics Data System (ADS)

Salazar Cuaila, J. L.; Alayo, W.; Avellaneda, César O.

2017-11-01

Two sets of Cobalt-doped (1-10% at) TiO2 thin films, for different molar concentrations of the Ti precursor (0.3 and 0.5 mol/L), have been deposited onto Si substrates by combining the Sol Gel process and the Spin Coating technique. The structure of the samples was studied by X-ray reflectivity (XRR) and X-ray diffraction (XRD) and their magnetic properties were analyzed by magnetization measurements as a function of the applied magnetic field. The XRR results provided the thickness and interfacial roughness of the films, while XRD patterns revealed the crystalline phases and lattice parameters. Room temperature ferromagnetic behaviour was observed for some of the atomic Co concentrations by the magnetization measurements. This behaviour has been correlated to the crystalline phases, which were found to be modified by both the molar ratio of Ti precursor and the concentration of the Co dopant. A suppression of ferromagnetism is observed for some atomic Co fractions and it was attributed to the presence of secondary crystalline phases.

Imaging prostate cancer (PCa) with [99m Tc(CO)3 ]finasteride dithiocarbamate.

PubMed

Shah, Syed Qaiser; Gul-E-Raana; Uddin, Ghias

2018-06-15

This investigation aimed to modify finasteride (1) to finasteride dithiocarbamate (2) for subsequent synthesis of the rhenium analogue (3) and [ 99m Tc]tricarbonyl complexes (4), to assess its prostate cancer (PCa) targeting potential in a rat model. To validate the identity of (4), reference (3) has been synthesized by using fac-[Net 4 ] 2 [ReBr 3 (CO) 3 ] precursor and characterized by 1 H-NMR, 13 C-NMR, ESI-MS, and elemental analysis. The analogue (4) was synthesized by using fac-[ 99m Tc(H 2 O) 3 (CO) 3 ] + precursor, and its structure was confirmed by comparative HPLC by using (3) as a reference. Further, the suitability of (4) as a PCa imaging agent was investigated in vitro and in vivo. At room temperature, (4) had ≥99% radiochemical purity and remained ≥84% stable in serum. In preclinical studies, biodistribution of (4) in histopathologically established rat model showed adequately high in vivo uptake in the prostate attracting the possibility of using it for noninvasive imaging of PCa. Copyright © 2018 John Wiley & Sons, Ltd.

Evaluation of co-cokes from bituminous coal with vacuum resid or decant oil, and evaluation of anthracites, as precursors to graphite

NASA Astrophysics Data System (ADS)

Nyathi, Mhlwazi S.

2011-12-01

Graphite is utilized as a neutron moderator and structural component in some nuclear reactor designs. During the reactor operaction the structure of graphite is damaged by collision with fast neutrons. Graphite's resistance to this damage determines its lifetime in the reactor. On neutron irradiation, isotropic or near-isotropic graphite experiences less structural damage than anisotropic graphite. The degree of anisotropy in a graphite artifact is dependent on the structure of its precursor coke. Currently, there exist concerns over a short supply of traditional precursor coke, primarily due to a steadily increasing price of petroleum. The main goal of this study was to study the anisotropic and isotropic properties of graphitized co-cokes and anthracites as a way of investigating the possibility of synthesizing isotropic or near-isotropic graphite from co-cokes and anthracites. Demonstrating the ability to form isotropic or near-isotropic graphite would mean that co-cokes and anthracites have a potential use as filler material in the synthesis of nuclear graphite. The approach used to control the co-coke structure was to vary the reaction conditions. Co-cokes were produced by coking 4:1 blends of vacuum resid/coal and decant oil/coal at temperatures of 465 and 500 °C for reaction times of 12 and 18 hours under autogenous pressure. Co-cokes obtained were calcined at 1420 °C and graphitized at 3000 °C for 24 hours. Optical microscopy, X-ray diffraction, temperature-programmed oxidation and Raman spectroscopy were used to characterize the products. It was found that higher reaction temperature (500 °C) or shorter reaction time (12 hours) leads to an increase in co-coke structural disorder and an increase in the amount of mosaic carbon at the expense of textural components that are necessary for the formation of anisotropic structure, namely, domains and flow domains. Characterization of graphitized co-cokes showed that the quality, as expressed by the degree of graphitization and crystallite dimensions, of the final product is dependent on the nature of the precursor co-coke. The methodology for studying anthracites was to select two anthracites on basis of rank, PSOC1515 being semi-anthracite and DECS21 anthracite. The selected anthracites were graphitized, in both native and demineralized states, under the same conditions as co-cokes. Products obtained from DECS21 showed higher degrees of graphitization and larger crystallite dimensions than products obtained from PSOC1515. Demineralization of anthracites served to increase the degree of graphitization, indicating that the minerals contained in these anthracites have no graphitization-enhancing ability. A larger crystallite length for products obtained from native versions, compared to demineralized versions, was attributed to a formation and decomposition of a silicon carbide during graphitization of native versions. In order to examine the anisotropic and isotropic properties, nuclear-grade graphite samples obtained from Oak Ridge National Laboratory (ORNL) and commercial graphite purchased from Fluka were characterized under similar conditions as graphitized co-cokes and anthracites. These samples served as representatives of "two extremes", with ORNL samples being the isotropic end and commercial graphite being the anisotropic end. Through evaluating relationships between structural parameters, it was observed that graphitized co-cokes are situated, structurally, somewhere between the "two extremes", whereas graphitized anthracites are closer to the anisotropic end. Basically, co-cokes have a better potential than anthracites to transform to isotropic or near-isotropic graphite upon graphitization. By co-coking vacuum resid/coal instead of decant oil/coal or using 500 °C instead of 465 °C, a shift away from commercial graphite towards ORNL samples was attained. Graphitizing a semi-anthracite or demineralizing anthracites before graphitization also caused a shift towards ORNL samples.

User's Manual for FEMOM3DR. Version 1.0

NASA Technical Reports Server (NTRS)

Reddy, C. J.

1998-01-01

FEMoM3DR is a computer code written in FORTRAN 77 to compute radiation characteristics of antennas on 3D body using combined Finite Element Method (FEM)/Method of Moments (MoM) technique. The code is written to handle different feeding structures like coaxial line, rectangular waveguide, and circular waveguide. This code uses the tetrahedral elements, with vector edge basis functions for FEM and triangular elements with roof-top basis functions for MoM. By virtue of FEM, this code can handle any arbitrary shaped three dimensional bodies with inhomogeneous lossy materials; and due to MoM the computational domain can be terminated in any arbitrary shape. The User's Manual is written to make the user acquainted with the operation of the code. The user is assumed to be familiar with the FORTRAN 77 language and the operating environment of the computers on which the code is intended to run.

Muon spin rotation research program

NASA Technical Reports Server (NTRS)

Stronach, C. E.

1980-01-01

Data from cyclotron experiments and room temperature studies of dilute iron alloys and iron crystals under strain were analyzed. The Fe(Mo) data indicate that the effect upon the contact hyperfine field in Fe due to the introduction of Mo is considerably less than that expected from pure dilution, and the muon (+) are attracted to the Mo impurity sites. There is a significant change in the interstitial magnetic field with Nb concentration. The Fe(Ti) data, for which precession could clearly be observed early only at 468K and above, show that the Ti impurities are attractive to muon (+), and the magnitude of B(hf) is reduced far beyond the amount expected from pure dilution. Changes in the intersitital magnetic field with the introduction of Cr, W, Ge, and Si are also discussed. When strained to the elastic limit, the interstitial magnetic field in Fe crystals is reduced by 33 gauss, and the relaxation rate of the precession signal increases by 47%.

Fabrication of ultralong and electrically uniform single-walled carbon nanotubes on clean substrates.

PubMed

Wang, Xueshen; Li, Qunqing; Xie, Jing; Jin, Zhong; Wang, Jinyong; Li, Yan; Jiang, Kaili; Fan, Shoushan

2009-09-01

We report the controlled growth of ultralong single-wall carbon nanotube (SWNT) arrays using an improved chemical vapor deposition strategy. Using ethanol or methane as the feed gas, monodispersed Fe-Mo as the catalyst, and a superaligned carbon nanotube (CNT) film as the catalyst supporting frame, ultralong CNTs over 18.5 cm long were grown on Si substrates. The growth rate of the CNTs was more than 40 mum/s. No catalyst-related residual material was found on the substrates due to the use of a CNT film as the catalyst supporting frame, facilitating any subsequent fabrication of SWNT-based devices. Electrical transport measurements indicated that the electrical characteristics along a single ultralong SWNT were uniform. We also found that maintaining a spatially homogeneous temperature during the growth process was a critical factor for obtaining constant electrical characteristics along the length of the ultralong SWNTs.

β-K3Fe(MoO4)2Mo2O7

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2014-01-01

The title compound, tripotassium iron(III) bis­(ortho­molyb­date) dimolybdate, was obtained by a solid-state reaction. The main structural building units are one FeO6 octa­hedron, two MoO4 tetra­hedra and one Mo2O7 dimolybdate group, all with point group symmetries m. These units are linked via corner-sharing to form ribbons parallel to [010]. The three K+ cations are located between the ribbons on mirror planes and have coordination numbers of 10 and 12. Two O atoms of one of the MoO4 tetra­hedra of the dimolybdate group are disordered over two positions in a 0.524 (11):0.476 (11) ratio. The structure of the title compound is compared briefly with that of Rb3FeMo4O15. PMID:25161509

An Effective Way to Optimize the Functionality of Graphene-Based Nanocomposite: Use of the Colloidal Mixture of Graphene and Inorganic Nanosheets

NASA Astrophysics Data System (ADS)

Jin, Xiaoyan; Adpakpang, Kanyaporn; Young Kim, In; Mi Oh, Seung; Lee, Nam-Suk; Hwang, Seong-Ju

2015-06-01

The best electrode performance of metal oxide-graphene nanocomposite material for lithium secondary batteries can be achieved by using the colloidal mixture of layered CoO2 and graphene nanosheets as a precursor. The intervention of layered CoO2 nanosheets in-between graphene nanosheets is fairly effective in optimizing the pore and composite structures of the Co3O4-graphene nanocomposite and also in enhancing its electrochemical activity via the depression of interaction between graphene nanosheets. The resulting CoO2 nanosheet-incorporated nanocomposites show much greater discharge capacity of ~1750 mAhg-1 with better cyclability and rate characteristics than does CoO2-free Co3O4-graphene nanocomposite (~1100 mAhg-1). The huge discharge capacity of the present nanocomposite is the largest one among the reported data of cobalt oxide-graphene nanocomposite. Such a remarkable enhancement of electrode performance upon the addition of inorganic nanosheet is also observed for Mn3O4-graphene nanocomposite. The improvement of electrode performance upon the incorporation of inorganic nanosheet is attributable to an improved Li+ ion diffusion, an enhanced mixing between metal oxide and graphene, and the prevention of electrode agglomeration. The present experimental findings underscore an efficient and universal role of the colloidal mixture of graphene and redoxable metal oxide nanosheets as a precursor for improving the electrode functionality of graphene-based nanocomposites.

DDR-type zeolite membrane synthesis, modification and gas permeation studies

DOE PAGES

Yang, Shaowei; Cao, Zishu; Arvanitis, Antonios; ...

2016-01-22

DDR-type zeolite membrane was synthesized on porous α-alumina substrate by hydrothermal treatment of a ball-milled Sigmal-1 crystal seed layer in an aluminum-free precursor solution containing 1-Adamantylamine as the structure directing agent (SDA). The as-synthesized DDR zeolite membranes were defect-free but the supported zeolite layers were susceptible to crack development during the subsequent high-temperature SDA removal process. The cracks were effectively eliminated by the liquid phase chemical deposition method using tetramethoxysilane as the precursor for silica deposits. The modified membrane was extensively studied for H 2, He, O 2, N 2, CO 2, CH 4, and i-C 4H 10 pure gasmore » permeation and CO 2/CH 4 mixture separation. At 297 K and 2-bar feed gas pressure, the membrane achieved a CO 2/CH 4 separation factor of ~92 for a feed containing 90% CO 2, which decreased to 62 for a feed containing 10% CO 2 with the CO 2 permeance virtually unchanged at ~1.8×10 –7 mol/m• sup>2 s • Pa regardless of the feed composition. It also exhibited an O 2/N 2 permselectivity of 1.8 at 297 K. Furthermore, the gas permeation behaviors of the current aluminum-containing DDR type zeolite membrane are generally in good agreement with the findings in both experimental and theoretical studies on the pure-silica DDR membranes in recent literature.« less

Determining sources of dissolved organic carbon and disinfection byproduct precursors to the McKenzie River, Oregon

USGS Publications Warehouse

Kraus, Tamara E.C.; Anderson, Chauncey W.; Morgenstern, Karl; Downing, Bryan D.; Pellerin, Brian A.; Bergamaschi, Brian A.

2010-01-01

This study was conducted to determine the main sources of dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors to the McKenzie River, Oregon (USA). Water samples collected from the mainstem, tributaries, and reservoir outflows were analyzed for DOC concentration and DBP formation potentials (trihalomethanes [THMFPs] and haloacetic acids [HAAFPs]). In addition, optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) were measured to provide insight into DOM composition and assess whether optical properties are useful proxies for DOC and DBP precursor concentrations. Optical properties indicative of composition suggest that DOM in the McKenzie River mainstem was primarily allochthonous - derived from soils and plant material in the upstream watershed. Downstream tributaries had higher DOC concentrations than mainstem sites (1.6 ?? 0.4 vs. 0.7 ?? 0.3 mg L-1) but comprised <5% of mainstem flows and had minimal effect on overall DBP precursor loads. Water exiting two large upstream reservoirs also had higher DOC concentrations than the mainstem site upstream of the reservoirs, but optical data did not support in situ algal production as a source of the added DOC during the study. Results suggest that the first major rain event in the fall contributes DOM with high DBP precursor content. Although there was interference in the absorbance spectra in downstream tributary samples, fluorescence data were strongly correlated to DOC concentration (R 2 = 0.98), THMFP (R2 = 0.98), and HAAFP (R2 = 0.96). These results highlight the value of using optical measurements for identifying the concentration and sources of DBP precursors in watersheds, which will help drinking water utilities improve source water monitoring and management programs. Copyright ?? 2010 by the American Society of Agronomy.

Polymers containing borane or carborane cage compounds and related applications

DOEpatents

Bowen, III, Daniel E; Eastwood, Eric A

2013-04-23

Polymers comprising residues of cage compound monomers having at least one polyalkoxy silyl substituent are provided. The cage compound monomers are selected from borane cage compound monomers comprising at least 7 cage atoms and/or carborane cage compound monomers comprising 7 to 11 cage compound monomers. Such polymers can further comprise one or more reactive matrices and/or co-monomers covalently bound with the cage compound monomer residues. Articles of manufacture comprising such polymers are also disclosed.

Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme

NASA Technical Reports Server (NTRS)

Meador, Ann B.; Capadona, Lynn A.

2008-01-01

A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.

The formation mechanism of binary semiconductor nanomaterials: shared by single-source and dual-source precursor approaches.

PubMed

Yu, Kui; Liu, Xiangyang; Zeng, Qun; Yang, Mingli; Ouyang, Jianying; Wang, Xinqin; Tao, Ye

2013-10-11

One thing in common: The formation of binary colloidal semiconductor nanocrystals from single- (M(EEPPh2 )n ) and dual-source precursors (metal carboxylates M(OOCR)n and phosphine chalcogenides such as E=PHPh2 ) is found to proceed through a common mechanism. For CdSe as a model system (31) P NMR spectroscopy and DFT calculations support a reaction mechanism which includes numerous metathesis equilibriums and Se exchange reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of 6-demethoxyubiquinone in CoQ10 deficiency disorders: Insights into enzyme interactions and identification of potential therapeutics.

PubMed

Herebian, Diran; Seibt, Annette; Smits, Sander H J; Bünning, Gisela; Freyer, Christoph; Prokisch, Holger; Karall, Daniela; Wredenberg, Anna; Wedell, Anna; López, Luis C; Mayatepek, Ertan; Distelmaier, Felix

2017-07-01

Coenzyme Q 10 (CoQ 10 ) is an essential cofactor of the mitochondrial oxidative phosphorylation (OXPHOS) system and its deficiency has important implications for several inherited metabolic disorders of childhood. The biosynthesis of CoQ 10 is a complicated process, which involves at least 12 different enzymes. One of the metabolic intermediates that are formed during CoQ 10 biosynthesis is the molecule 6-demethoxyubiquinone (6-DMQ). This CoQ precursor is processed at the level of COQ7 and COQ9. We selected this metabolite as a marker substance for metabolic analysis of cell lines with inherited genetic defects (COQ2, COQ4, COQ7 and COQ9) or siRNA knockdown in CoQ biosynthesis enzymes using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). In COQ4, COQ7 and COQ9 deficient cell lines, we detected significantly elevated levels of 6-DMQ. This suggests a functional interplay of these proteins. However, additional siRNA studies demonstrated that elevated 6-DMQ levels are not an exclusive marker of the COQ7/COQ9 enzymatic step of CoQ 10 biosynthesis but constitute a more general phenomenon that occurs in disorders impairing the function or stability of the CoQ-synthome. To further investigate the interdependence of CoQ 10 biosynthesis enzyme expression, we performed immunoblotting in various cell lines with CoQ 10 deficiency, indicating that COQ4, COQ7 and COQ9 protein expression levels are highly regulated depending on the underlying defect. Supplementation of cell lines with synthetic CoQ precursor compounds demonstrated beneficial effects of 2,4-dihydroxybenzoic acid in COQ7 and COQ9 deficiency. Moreover, vanillic acid selectively stimulated CoQ 10 biosynthesis and improved cell viability in COQ9 deficiency. However, compounds tested in this study failed to rescue COQ4 deficiency. Copyright © 2017 Elsevier Inc. All rights reserved.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

PubMed

Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

2018-04-02

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.