High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

PubMed

Wang, Yuesheng; Yang, Shi-Ze; You, Ya; Feng, Zimin; Zhu, Wen; Gariépy, Vincent; Xia, Jiexiang; Commarieu, Basile; Darwiche, Ali; Guerfi, Abdelbast; Zaghib, Karim

2018-02-28

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO 4 and amorphous FePO 4 ·2H 2 O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO 4 ·2H 2 O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO 4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO 4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO 4 ·2H 2 O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO 4 anodes commercially viable configurations for aqueous lithium-ion batteries.

High-performance Ti/Sb-SnO(2)/Pb(3)O(4) electrodes for chlorine evolution: preparation and characteristics.

PubMed

Shao, Dan; Yan, Wei; Cao, Lu; Li, Xiaoliang; Xu, Hao

2014-02-28

Chlorine evolution via electrochemical approach has wide application prospects in drinking water disinfection and wastewater treatment fields. Dimensional stable anodes used for chlorine evolution should have high stability and adequate chlorine evolution efficiency. Thus a novel and cost-effective Ti/Sb-SnO(2)/Pb(3)O(4)electrode was developed. The physicochemical and electrochemical properties as well as the chlorine evolution performances of the electrodes were investigated. The electrocatalytic activity and deactivation course of the electrodes were also explored. Results showed that this novel electrode had strong chlorine evolution ability with high current efficiency ranging from 87.3% to 93.4% depending on the operational conditions. The accelerated service life of Ti/Sb-SnO(2)/Pb(3)O(4) electrode could reach 180 h at a current density of 10,000 A m(-2) in 0.5 molL(-1) H(2)SO(4). During the electrolysis process, it was found that the conversion of Pb(3)O(4) into β-PbO(2) happened gradually on the electrode surface, which not only inhibited the leakage of hazardous Pb(2+) ion but also increased the anti-corrosion capacity of the electrode effectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Optimization of macropore evolution towards high photocatalytic activity enhancement in meso/macro porous Anatase TiO2

NASA Astrophysics Data System (ADS)

Nair, Radhika V.; Gayathri, P. K.; Siva Gummaluri, Venkata; Vijayan, C.

2017-01-01

We report on an optimization strategy for macro pore evolution leading to the design of highly photocatalytic 3D hierarchical meso/macroporous TiO2 via much simpler, faster and cost effective synthesis scheme. Meso/macro porous TiO2 is an excellent candidate material for photocatalytic applications owing to the availability of internal surfaces as active sites for redox reactions. The current research scenario focuses on the design of highly efficient photocatalytic systems as well as rapid, facile and cost effective methods of synthesis and optimization of parameters. The present report is on the gradual evolution of macropores in anatase TiO2 by the effective control of pH of the solvent, reaction time, temperature, solvent ratio and reactant concentration via a facile hydrothermal method in this regard. 3D hierarchical macroporous structures are obtained at pH 7 within a comparatively short reaction time of 5 h and demonstrated to be highly photocatalytic (with rate constant four times that of P25 nanoparticles) through photodegradation of Rhodamine B dye.

Particle Generation And Evolution In Silane (SiH4)/Acetylene (C2H2) Flames In Microgravity

NASA Technical Reports Server (NTRS)

Keil, D. G.

2003-01-01

The objective of this experimental program is to advance the understanding of the coupling of particle formation with gas phase combustion processes. The work utilizes the unique SiH4/C2H2 combustion system which generates particulate products ranging from high purity, white SiC to carbonaceous soot depending on equivalence ratio (Ref. 1). A goal of this work is to identify gas phase or particle formation processes that provide the enthalpy release needed to drive the combustion wave, and to locate the steps of the particle formation process that determine SiC stoichiometry and crystallinity. In a real sense, these SiH4/C2H2 flames act like highly sooty hydrocarbon flames, but with simpler chemistry. This simplification is expected to allow them to be used as surrogates to advance understanding of soot formation in such rich hydrocarbon flames. It is also expected that this improved understanding of SiC particle generation and evolution in these self-sustaining flames will advance the commercial potential of the flame process for the generation of high purity SiC powders.

Impact of fermentation rate changes on potential hydrogen sulfide concentrations in wine.

PubMed

Butzke, Christian E; Park, Seung Kook

2011-05-01

The correlation between alcoholic fermentation rate, measured as carbon dioxide (CO2) evolution, and the rate of hydrogen sulfide (H2S) formation during wine production was investigated. Both rates and the resulting concentration peaks in fermentor headspace H2S were directly impacted by yeast assimilable nitrogenous compounds in the grape juice. A series of model fermentations was conducted in temperature-controlled and stirred fermentors using a complex model juice with defined concentrations of ammonium ions and/or amino acids. The fermentation rate was measured indirectly by noting the weight loss of the fermentor; H2S was quantitatively trapped in realtime using a pre-calibrated H2S detection tube which was inserted into a fermentor gas relief port. Evolution rates for CO2 and H2S as well as the relative ratios between them were calculated. These fermentations confirmed that total sulfide formation was strongly yeast strain-dependent, and high concentrations of yeast assimilable nitrogen did not necessarily protect against elevated H2S formation. High initial concentrations of ammonium ions via addition of diammonium phosphate (DAP) caused a higher evolution of H2S when compared with a non-supplemented but nondeficient juice. It was observed that the excess availability of a certain yeast assimilable amino acid, arginine, could result in a more sustained CO2 production rate throughout the wine fermentation. The contribution of yeast assimilable amino acids from conventional commercial yeast foods to lowering of the H2S formation was marginal.

Photoelectrolysis of water at high current density - Use of laser light excitation of semiconductor-based photoelectrochemical cells

NASA Technical Reports Server (NTRS)

Wrighton, M. S.; Bocarsley, A. B.; Bolts, J. M.

1978-01-01

In the present paper, some results are given for UV laser light irradiation of the photoanode (SnO2, SrTiO3, or TiO2) in a cell for the light-driven electrolysis of H2O, at radiation intensities of up to 380 W/sq cm. The properties of the anode material are found to be independent of light intensity. Conversion of UV light to stored chemical energy in the form of 2H2/O2 from H2O was driven at a rate of up to 30 W/sq cm. High O2 evolution rates at the irradiated anodes without changes in the current-voltage curves are attributed to the excess oxidizing power associated with photogenerated holes. A test for this sort of hypothesis for H2 evolution at p-type materials is proposed.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the (Non)Evolution of H I Gas in Galaxies Over Cosmic Time

NASA Astrophysics Data System (ADS)

Prochaska, J. Xavier; Wolfe, Arthur M.

2009-05-01

We present new results on the frequency distribution of projected H I column densities f(N H I , X), total comoving covering fraction, and integrated mass densities ρH I of high-redshift, H I galactic gas from a survey of damped Lyα systems (DLAs) in the Sloan Digital Sky Survey, Data Release 5. For the full sample spanning z = 2.2-5 (738 DLAs), f(N H I , X) is well fitted by a double power law with a break column density Nd = 1021.55±0.04 cm-2 and low/high-end exponents α = -2.00 ± 0.05, - 6.4+1.1 -1.6. The shape of f(N H I , X) is invariant during this redshift interval and also follows the projected surface density distribution of present-day H I disks as inferred from 21 cm observations. We conclude that H I gas has been distributed in a self-similar fashion for the past 12 Gyr. The normalization of f(N H I , X), in contrast, decreases by a factor of 2 during the ≈2 Gyr interval from z = 4-2.2 with coincident decreases in both the total covering fraction and ρH I . At z ≈ 2, these quantities match the present-day values suggesting no evolution during the past ≈10 Gyr. We argue that the evolution at early times is driven by "violent" processes that removes gas from nearly half the galaxies at z ≈ 3 establishing the antecedents of current early-type galaxies. The perceived constancy of ρH I , meanwhile, implies that H I gas is a necessary but insufficient precondition for star formation and that the global star formation rate is driven by the accretion and condensation of fresh gas from the intergalactic medium.

Characteristics of supercritical turbulence from Direct Numerical Simulations of C(sub 7)H(sub 16)/N(sub 2) and O(sub 2)/H(sub 2)

NASA Technical Reports Server (NTRS)

Okong'o, N. A.; Bellan, J.

2003-01-01

Analysis of Direct Numerical Simulations (DNS) transitional states of temporal, supercritical mixing layers for C7H16/N2 and O2/H2 shows that the evolution of all layers is characterized by the formation of high-density-gradient magnitude (HDGM) regions.

Inelastic Collisions of N2, H2, and H2+He Mixtures in Supersonic Jets by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Fernández, J. M.; Fonfría, J. P.; Ramos, A.; Tejeda, G.; Montero, S.; Thibault, F.

2008-12-01

We present a detailed study of inelastic collisions at low temperature in several supersonic jets of N2, H2, and H2+He mixtures using different nozzles and stagnation conditions. Absolute number density and rotational population data of unprecedented accuracy are measured along the jet axis by Raman spectroscopy with high spatial resolution (<5 μm) and high-sensitivity (<1 photon/sec). The experimental data are interpreted by means of a master equation describing the time evolution of the rotational populations in terms of the state-to-state rate coefficients derived from high-level quantum calculations. This combination of experimental and calculated data leads to a detailed understanding of the underlying physics, consistent with the assumed isentropic behaviour. The breakdown of rotational-translational thermal equilibrium, and its space-time evolution along the jet axis are accounted for by the microscopic (state-to-state rate coefficients) and macroscopic (flow velocity, number density, temperatures) physical quantities. A highly consistent picture, free from any additional parameters, bridges this way the microsopic and macroscopic approaches to fluid dynamics along the jet axis.

Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H2 Evolution.

PubMed

Li, Xiaogang; Bi, Wentuan; Zhang, Lei; Tao, Shi; Chu, Wangsheng; Zhang, Qun; Luo, Yi; Wu, Changzheng; Xie, Yi

2016-03-23

Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reassortant Avian Influenza A(H5N1) Viruses with H9N2-PB1 Gene in Poultry, Bangladesh

PubMed Central

Yamage, Mat; Dauphin, Gwenaëlle; Claes, Filip; Ahmed, Garba; Giasuddin, Mohammed; Salviato, Annalisa; Ormelli, Silvia; Bonfante, Francesco; Schivo, Alessia; Cattoli, Giovanni

2013-01-01

Bangladesh has reported a high number of outbreaks of highly pathogenic avian influenza (HPAI) (H5N1) in poultry. We identified a natural reassortant HPAI (H5N1) virus containing a H9N2-PB1 gene in poultry in Bangladesh. Our findings highlight the risks for prolonged co-circulation of avian influenza viruses and the need to monitor their evolution. PMID:24047513

MSL SAM-Like Evolved Gas Analyses of Si-rich Amorphous Materials

NASA Technical Reports Server (NTRS)

McAdam, Amy; Knudson, Christine; Sutter, Brad; Andrejkovicova, Slavka; Archer, P. Douglas; Franz, Heather; Eigenbrode, Jennifer; Morris, Richard; Ming, Douglas; Sun, Vivian;

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

PubMed

Pan, Zhong-Hua; Tao, Yun-Wen; He, Quan-Feng; Wu, Qiao-Yu; Cheng, Li-Ping; Wei, Zhan-Hua; Wu, Ji-Huai; Lin, Jin-Qing; Sun, Di; Zhang, Qi-Chun; Tian, Dan; Luo, Geng-Geng

2018-06-12

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H 2 evolution turnover frequency (TOF) of 7838 s -1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s -1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H 2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O 2 and H 2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas-phase evolution of Ar/H2O and Ar/CH4 dielectric barrier discharge plasmas

NASA Astrophysics Data System (ADS)

Barni, Ruggero; Riccardi, Claudia

2018-04-01

We present some experimental results of an investigation aimed to hydrogen production with atmospheric pressure plasmas, based on the use of dielectric barrier discharges, fed with a high-voltage alternating signal at frequency 30-50 kHz, in mixtures of methane or water vapor diluted in argon. The plasma gas-phase of the discharge was investigated by means of optical and electrical diagnostics. The emission spectra of the discharges was measured with a wide band spectrometer and a photosensor module, based on a photomultiplier tube. A Rogowski coil allowed to measure the electric current flowing into the circuit and a high voltage probe was employed for evaluating the voltage at the electrodes. The analysis of the signals of voltage and current shows the presence of microdischarges between the electrodes in two alternating phases during the period of oscillation of the applied voltage. The hydrogen concentration in the gaseous mixture was measured too. Besides this experimental campaign, we present also results from a numerical modeling of chemical kinetics in the gas-phase of Ar/H2O and Ar/CH4 plasmas. The simulations were conducted under conditions of single discharge to study the evolution of the system and of fixed frequency repeated discharging. In particular in Ar/H2O mixtures we could study the evolution from early atomic dissociation in the discharge, to longer time scales, when chemical reactions take place producing an increase of the density of species such as OH, H2O2 and subsequently of H and H2. The results of numerical simulations provide some insights into the evolution happening in the plasma gas-phase during the hydrogen reforming process.

Reassortant clade 2.3.4.4 of highly pathogenic avian influenza A (H5N6) virus, Taiwan, 2017

USDA-ARS?s Scientific Manuscript database

A highly pathogenic avian influenza A(H5N6) virus of clade 2.3.4.4 was detected in a domestic duck found dead in Taiwan during February 2017. The endemic situation and continued evolution of various reassortant highly pathogenic avian influenza viruses in Taiwan warrant concern about further reassor...

MoS 2/TiO 2 heterostructures as nonmetal plasmonic photocatalysts for highly efficient hydrogen evolution

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

Guo, L.; Yang, Z.; Marcus, K.

In this study, we report a nonmetal plasmonic MoS2@TiO2 heterostructure for highly efficient photocatalytic H2 generation. Large area laminated Z-scheme MoS2 in conjunction with TiO2 nanocavity arrays are achieved via carefully controlled anodization, physical vapor deposition, and chemical vapor deposition processes. Broad spectral response ranging from ultraviolet (UV)-visible (vis) to near-infrared (NIR) wavelengths and finite element frequency-domain simulation suggest that this MoS2@TiO2 heterostructured photocatalyst possesses an enhanced activity for H+ reduction. A high H2 yield rate of 580 mmol h-1 g-1 is achieved using a low catalyst loading mass of 10.2 μg. The spatially uniform heterostructure, correlated to plasmon-resonance throughmore » conformal coating MoS2 that effectively regulated charge transfer pathways, is proven to be vitally important for the unique solar energy harvesting and photocatalytic H2 production. As an innovative exploration, our study demonstrates that the photocatalytic activities of nonmetal, earth-abundant materials can be enhanced with plasmonic effects, which may serve as an excellent catalytic agent for solar energy conversion to chemical fuel. Periodically patterned MoS 2/TiO 2heterostructures were rationally designed as nonmetal plasmonic photocatalysts for highly efficient hydrogen evolution.« less

In situ one-step hydrothermal synthesis of oxygen-containing groups-modified g-C3N4 for the improved photocatalytic H2-evolution performance

NASA Astrophysics Data System (ADS)

Wu, Xinhe; Chen, Fengyun; Wang, Xuefei; Yu, Huogen

2018-01-01

Surface modification of g-C3N4 is one of the most effective strategies to boost its photocatalytic H2-evolution performance via promoting the interfacial catalytic reactions. In this study, an in situ one-step hydrothermal method was developed to prepare the oxygen-containing groups-modified g-C3N4 (OG/g-C3N4) by a facile and green hydrothermal treatment of bulk g-C3N4 in pure water without any additives. It was found that the hydrothermal treatment (180 °C) not only could greatly increase the specific surface area (from 2.3 to 69.8 m2 g-1), but also caused the formation of oxygen-containing groups (sbnd OH and Cdbnd O) on the OG/g-C3N4 surface, via the interlayer delamination and intralayer depolymerization of bulk g-C3N4. Photocatalytic experimental results indicated that after hydrothermal treatment, the resultant OG/g-C3N4 samples showed an obviously improved H2-evolution performance. Especially, when the hydrothermal time was 6 h, the resultant OG/g-C3N4(6 h) exhibited the highest photocatalytic activity, which was clearly higher than that of the bulk g-C3N4 by a factor of ca. 7. In addition to the higher specific surface area, the enhanced H2-evolution rate of OG/g-C3N4 photocatalysts can be mainly attributed to the formation of oxygen-containing groups, which possibly works as the effective H2-evolution active sites. Considering the facie and green synthesis method, the present work may provide a new insight for the development of highly efficient photocatalytic materials.

Nanocomposites of AgInZnS and graphene nanosheets as efficient photocatalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Tang, Xiaosheng; Chen, Weiwei; Zu, Zhiqiang; Zang, Zhigang; Deng, Ming; Zhu, Tao; Sun, Kuan; Sun, Lidong; Xue, Junmin

2015-11-01

In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field.In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05145b

SlyD-dependent nickel delivery limits maturation of [NiFe]-hydrogenases in late-stationary phase Escherichia coli cells.

PubMed

Pinske, Constanze; Sargent, Frank; Sawers, R Gary

2015-04-01

Fermentatively growing Escherichia coli cells have three active [NiFe]-hydrogenases (Hyd), two of which, Hyd-1 and Hyd-2, contribute to H2 oxidation while Hyd-3 couples formate oxidation to H2 evolution. Biosynthesis of all Hyd involves the insertion of a Fe(CN)2CO group and a subsequent insertion of nickel ions through the HypA/HybF, HypB and SlyD proteins. With high nickel concentrations the presence of none of these proteins is required, but under normal growth conditions and during late stationary growth SlyD is important for hydrogenase activities. The slyD mutation reduced H2 production during exponential phase growth by about 50%. Assaying stationary phase grown cells for the coupling of Hyd activity to the respiratory chain or formate-dependent H2 evolution showed that SlyD is essential for both H2 evolution and H2 oxidation. Although introduction of plasmid-coded slyD resulted in an overall decrease of Hyd-2 polypeptides in slyD and hypA slyD mutants, processing and dye-reducing activity of the Hyd-2 enzyme was nevertheless restored. Similarly, introduction of the slyD plasmid restored only some H2 evolution in the slyD mutant while Hyd-3 polypeptides and dye-reducing activity were fully restored. Taken together, these results indicate an essential role for SlyD in the generation of the fully cofactor-equipped hydrogenase large subunits in the stationary phase where the level of each Hyd enzyme is finely tuned by SlyD for optimal enzyme activity.

In Situ Fabrication of Hierarchically Branched TiO2 Nanostructures: Enhanced Performance in Photocatalytic H2 Evolution and Li-Ion Batteries.

PubMed

Yang, Guorui; Wang, Ling; Peng, Shengjie; Wang, Jianan; Ji, Dongxiao; Yan, Wei; Ramakrishna, Seeram

2017-12-01

1D branched TiO 2 nanomaterials play a significant role in efficient photocatalysis and high-performance lithium ion batteries. In contrast to the typical methods which generally have to employ epitaxial growth, the direct in situ growth of hierarchically branched TiO 2 nanofibers by a combination of the electrospinning technique and the alkali-hydrothermal process is presented in this work. Such the branched nanofibers exhibit improvement in terms of photocatalytic hydrogen evolution (0.41 mmol g -1 h -1 ), in comparison to the conventional TiO 2 nanofibers (0.11 mmol g -1 h -1 ) and P25 (0.082 mmol g -1 h -1 ). Furthermore, these nanofibers also deliver higher lithium specific capacity at different current densities, and the specific capacity at the rate of 2 C is as high as 201. 0 mAh g -1 , roughly two times higher than that of the pristine TiO 2 nanofibers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ one-pot fabrication of g-C3N4 nanosheets/NiS cocatalyst heterojunction with intimate interfaces for efficient visible light photocatalytic H2 generation

NASA Astrophysics Data System (ADS)

He, Kelin; Xie, Jun; Li, Mingli; Li, Xin

2018-02-01

Constructing high-quality earth-abundant semionconductor/cocatalyst heterojunction remains a grand challenge in the promising fields of photocatalytic solar fuel H2 production. Herein, an intimate g-C3N4 nanosheet/NiS cocatalyst heterojunction is fabricated by in situ one-step calcination of urea, thiourea and nickel acetate. Interestingly, thiourea could act as both the precursor of g-C3N4 and the sulfur source of NiS. The H2-evolution activity of as-obtained photocatalysts was tested in a triethanolamine (TEOA) scavenger solution under visible light irradiation. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) mapping analysis clearly demonstrated that the NiS catalyst nanoparticles could be in situ fabricated and homogeneously distributed on the surface of g-C3N4 nanosheets without an obvious aggregation. The maximum H2-production rate of 29.68 μmol h-1 could be achieved, which is nearly comparable to that of 0.5 wt% Pt loaded sample. It is believed that the intimate heterojunction interfaces between NiS nanoparticles and g-C3N4 nanosheets could be in situ constructed by high temperature calcination, which achieved the improved charge separation, the enhanced oxidation ability of TEOA and the accelerated the sluggish H2-evolution kinetics, thus resulting in the remarkably enhanced hydrogen evolution. Therefore, our study provides insights into constructing high-quality robust g-C3N4-based heterojunction material for photocatalytic applications by using a simple one-step in-situ calcination technique.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

Genetic evolution of H5 highly pathogenic avian influenza virus in domestic poultry in Vietnam between 2011 and 2013.

PubMed

Lee, Eun-Kyoung; Kang, Hyun-Mi; Kim, Kwang-Il; Choi, Jun-Gu; To, Thanh Long; Nguyen, Tho Dang; Song, Byung-Min; Jeong, Jipseol; Choi, Kang-Seuk; Kim, Ji-Ye; Lee, Hee-Soo; Lee, Youn-Jeong; Kim, Jae-Hong

2015-04-01

In spite of highly pathogenic avian influenza H5N1 vaccination campaigns for domestic poultry, H5N1 viruses continue to circulate in Vietnam. To estimate the prevalence of avian influenza virus in Vietnam, surveillance was conducted between November 2011 and February 2013. Genetic analysis of 312 highly pathogenic avian influenza H5 viruses isolated from poultry in Vietnam was conducted and possible genetic relationships with strains from neighboring countries were investigated. As previously reported, phylogenetic analysis of the avian influenza virus revealed two H5N1 HPAI clades that were circulating in Vietnam. Clade 1.1, related to Cambodian strains, was predominant in the southern provinces, while clade 2.3.2.1 viruses were predominant in the northern and central provinces. Sequence analysis revealed evidence of active genetic evolution. In the gene constellation of clade 2.3.2.1, genotypes A, B, and B(II) existed during the 2011/2012 winter season. In June 2012, new genotype C emerged by reassortment between genotype A and genotype B(II), and this genotype was predominant in 2013 in the northern and central provinces. Interestingly, enzootic Vietnamese clade 2.3.2.1C H5 virus subsequently reassorted with N2, which originated from wild birds, to generate H5N2 highly pathogenic avian influenza, which was isolated from duck in the northeast region. This investigation indicated that H5N1 outbreaks persist in Vietnam and cause genetic reassortment with circulating viruses. It is necessary to strengthen active influenza surveillance to eradicate highly pathogenic avian influenza viruses and sever the link between highly pathogenic avian influenza and other circulating influenza viruses. © 2015 Poultry Science Association Inc.

Divergent genetic evolution of hemagglutinin in influenza A H1N1 and A H1N2 subtypes isolated in the south-France since the winter of 2001-2002.

PubMed

Al Faress, Shaker; Cartet, Gaëlle; Ferraris, Olivier; Norder, Helene; Valette, Martine; Lina, Bruno

2005-07-01

Influenza A viruses are divided into subtypes based on their hemagglutinin (H1 to H15) and neuraminidase (N1 to N9) glycoproteins. Of these, three A subtypes H1N1, H3N2 and H1N2 circulate in the human population. Influenza A viruses display a high antigenic variability called "antigenic drift" which allows the virus to escape antibody neutralization. Evaluate the mutations apparition that might predict a divergent antigenic evolution of hemagglutinin in influenza A H1N1 and A H1N2 viruses. During the three winters of 2001-2002 to 2003-2004, 58 A H1N1 and 23 A H1N2 subtypes have been isolated from patients with influenza-like illness in the south of France. The HA1 region was analyzed by RT-PCR and subsequently sequenced to compare the HA1 genetic evolution of influenza A H1N1 and A H1N2 subtypes. Our results showed that 28 amino acid substitutions have accumulated in the HA1 region since the circulation of A/New Caledonia/20/99-like viruses in France. Of these, fifteen were located in four antigenic sites (B, C, D and E). Six of them were observed only in the A H1N2 isolates, six only in the A H1N1 isolates and three in both subtypes. Furthermore, nine of twenty two A H1N2 isolates from the winter of 2002-2003 shared a T90A amino acid change which has not been observed in any A H1N1 isolate; resulting in the introduction of a new glycosylation site close to the antigenic site E. This might mask some antigenic E determinants and therefore, modify the A H1N2 antigenicity. The divergent genetic evolution of hemagglutinin may ultimately lead to a significant different antigenicity between A H1N1 and A H1N2 subtypes that would require the introduction of a new subtype in the vaccine batches.

CoMoS2/rGO/C3N4 ternary heterojunctions catalysts with high photocatalytic activity and stability for hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Xu, Xuejun; Si, Zhichun; Liu, Liping; Wang, Zehao; Chen, Ze; Ran, Rui; He, Yonghong; Weng, Duan

2018-03-01

Noble metal free MoS2/g-C3N4 catalyst has attracted intense attentions for visible light photocatalytic hydrogen evolution as a result of its earth abundance, low cost and unique heterojunctions stacked with two dimensional sheets. However, the low charge separation efficiency resulted from the poor conductivity of g-C3N4 and MoS2, and lack of abundant active sites from coordinative unsaturated atoms in MoS2, restricts the photocatalytic hydrogen evolution activity and stability enhancement of MoS2/C3N4 composite catalysts. Herein, CoMoS2/rGO/g-C3N4 catalysts with ternary heterojunctions are prepared by facile solvothermal method, which exhibit high visible light photocatalytic activity and stability for hydrogen evolution. The optimal hydrogen evolution rate of CoMoS2/rGO/g-C3N4 catalysts is 684 μmol g-1 h-1 when the content of CoMoS2 is 2% and the content of rGO is 0.5%. The stability of CoMoS2/rGO/C3N4 catalysts just decrease about 3% after 4 cycling runs for 16 h. The good catalytic performances of catalysts are attributed to the synergistic effect among the g-C3N4 nanosheets, rGO nanosheets and CoMoS2 nanosheets. The high conductivity of rGO nanosheets enhances the electron-hole separation and charge transfer, and Co doping increases the active sites for hydrogen evolution due to the increase of unsaturated atoms in CoMoS2 nanosheets.

Preparation of NiS/ZnIn2S4 as a superior photocatalyst for hydrogen evolution under visible light irradiation

PubMed Central

Wei, Liang; Chen, Yongjuan; Zhao, Jialin

2013-01-01

Summary In this study, NiS/ZnIn2S4 nanocomposites were successfully prepared via a facile two-step hydrothermal process. The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). Their photocatalytic performance for hydrogen evolution under visible light irradiation was also investigated. It was found that the photocatalytic hydrogen evolution activity over hexagonal ZnIn2S4 can be significantly increased by loading NiS as a co-catalyst. The formation of a good junction between ZnIn2S4 and NiS via the two step hydrothermal processes is beneficial for the directional migration of the photo-excited electrons from ZnIn2S4 to NiS. The highest photocatalytic hydrogen evolution rate (104.7 μmol/h), which is even higher than that over Pt/ZnIn2S4 nanocomposite (77.8 μmol/h), was observed over an optimum NiS loading amount of 0.5 wt %. This work demonstrates a high potential of the developing of environmental friendly, cheap noble-metal-free co-catalyst for semiconductor-based photocatalytic hydrogen evolution. PMID:24455453

Photocatalytic hydrogen evolution over β-iron silicide under infrared-light irradiation.

PubMed

Yoshimizu, Masaharu; Kobayashi, Ryoya; Saegusa, Makoto; Takashima, Toshihiro; Funakubo, Hiroshi; Akiyama, Kensuke; Matsumoto, Yoshihisa; Irie, Hiroshi

2015-02-18

We investigated the ability of β-iron silicide (β-FeSi2) to serve as a hydrogen (H2)-evolution photocatalyst due to the potential of its conduction band bottom, which may allow thermodynamically favorable H2 evolution in spite of its small band-gap of 0.80 eV. β-FeSi2 had an apparent quantum efficiency for H2 evolution of ∼24% up to 950 nm (near infrared light), in the presence of the dithionic acid ion (S2O6(2-)) as a sacrificial agent. It was also sensitive to infrared light (>1300 nm) for H2 evolution.

Particle Generation and Evolution in Silane/Acetylene Flames in Microgravity

NASA Technical Reports Server (NTRS)

Keil, D. G.

2001-01-01

The objective of this new experimental program is to advance the understanding of the formation of particles from gas phase combustion processes. The work will utilize the unique SiH4/C2H2 combustion system which generates particulate products ranging from high purity, white SiC to carbonaceous soot depending on equivalence ratio. A key goal of this work is to identify gas phase or particle formation processes that provide the enthalpy release necessary to drive the combustion wave, and to locate the parts of the particle formation process that determine SiC stoichiometry and crystallinity. In a real sense, these SiH4/C2H2 flames act like "highly sooty" hydrocarbon flames, but with simpler chemistry. This simplification is expected to allow them to be used as surrogates to advance understanding of soot formation in such rich hydrocarbon flames. It is also expected that this improved understanding of SiC particle generation and evolution in these self-sustaining flames will advance the commercial potential of the flame process for the generation of high purity SiC powders.

A spongy nickel-organic CO2 reduction photocatalyst for nearly 100% selective CO production

PubMed Central

Niu, Kaiyang; Xu, You; Wang, Haicheng; Ye, Rong; Xin, Huolin L.; Lin, Feng; Tian, Chixia; Lum, Yanwei; Bustillo, Karen C.; Doeff, Marca M.; Koper, Marc T. M.; Ager, Joel; Xu, Rong; Zheng, Haimei

2017-01-01

Solar-driven photocatalytic conversion of CO2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H2 evolution during photocatalytic CO2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO2 to CO, with a production rate of ~1.6 × 104 μmol hour−1 g−1. No measurable H2 is generated during the reaction, leading to nearly 100% selective CO production over H2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO2 reduction reactions generate formic acid and acetic acid. Achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy. PMID:28782031

Robustly photogenerating H2 in water using FeP/CdS catalyst under solar irradiation

NASA Astrophysics Data System (ADS)

Cheng, Huanqing; Lv, Xiao-Jun; Cao, Shuang; Zhao, Zong-Yan; Chen, Yong; Fu, Wen-Fu

2016-01-01

Photosplitting water for H2 production is a promising, sustainable approach for solar-to-chemical energy conversion. However, developing low-cost, high efficient and stable photocatalysts remains the major challenge. Here we report a composite photocatalyst consisting of FeP nanoparticles and CdS nanocrystals (FeP/CdS) for photogenerating H2 in aqueous lactic acid solution under visible light irradiation. Experimental results demonstrate that the photocatalyst is highly active with a H2-evolution rate of 202000 μmol h-1 g-1 for the first 5 h (106000 μmol h-1 g-1 under natural solar irradiation), which is the best H2 evolution activity, even 3-fold higher than the control in situ photo-deposited Pt/CdS system, and the corresponding to an apparent quantum efficiency of over 35% at 520 nm. More important, we found that the system exhibited excellent stability and remained effective after more than 100 h in optimal conditions under visible light irradiation. A wide-ranging analysis verified that FeP effectively separates the photoexcited charge from CdS and showed that the dual active sites in FeP enhance the activity of FeP/CdS photocatalysts.

Electrocatalytic and photocatalytic hydrogen evolution integrated with organic oxidation.

PubMed

You, Bo; Han, Guanqun; Sun, Yujie

2018-06-08

Renewable energy-driven hydrogen production from electrocatalytic and photocatalytic water splitting has been widely recognized as a promising approach to utilize green energy resources and hence reduces our dependence on legacy fossil fuels as well as alleviates net carbon dioxide emissions. The realization of large-scale water splitting, however, is mainly impeded by its slow kinetics, particularly because of its sluggish anodic half reaction, the oxygen evolution reaction (OER), whose product O2 is ironically not of high value. In fact, the co-production of H2 and O2 in conventional water electrolysis may result in the formation of explosive H2/O2 gas mixtures due to gas crossover and reactive oxygen species (ROS); both pose safety concerns and shorten the lifetimes of water splitting cells. With these considerations in mind, replacing the OER with thermodynamically more favorable organic oxidation reactions is much more preferred, which will not only substantially reduce the voltage input for H2 evolution from water and avoid the generation of H2/O2 gas mixtures and ROS, but also possibly lead to the co-production of value-added organic products on the anode. Indeed, such an innovative strategy for H2 production integrated with valuable organic oxidation has attracted increasing attention in both electrocatalysis and photocatalysis. This feature article showcases the most recent examples along this endeavor. As exemplified in the main text, the oxidative transformation of a variety of organic substrates, including alcohols, ammonia, urea, hydrazine, and biomass-derived intermediate chemicals, can be integrated with energy-efficient H2 evolution. We specifically highlight the importance of oxidative biomass valorization coupled with H2 production, as biomass is the only green carbon source whose scale is comparable to fossil fuels. Finally, the remaining challenges and future opportunities are also discussed.

Boosting the catalytic performance of MoSx cocatalysts over CdS nanoparticles for photocatalytic H2 evolution by Co doping via a facile photochemical route

NASA Astrophysics Data System (ADS)

Lei, Yonggang; Hou, Jianhua; Wang, Fang; Ma, Xiaohua; Jin, Zhiliang; Xu, Jing; Min, Shixiong

2017-10-01

Low-crystalline or amorphous molybdenum sulfides (MoSx), bearing abundant unsaturated active sites, have been identified as efficient catalysts for electrocatalytic and photocatalytic H2 evolution reactions, however, their intrinsic activity is still low and need to be further improved for large-scale applications. In this paper, we report that low-crystalline MoSx doped with Co (Co-MoSx) as efficient cocatalysts could be loaded on CdS nanoparticles through a facile and controllable photochemical reduction method and showed high performances in catalyzing H2 evolution under visible light irradiation (≥420 nm). The photochemical loading of Co-MoSx was accomplished by using an in-situ formed molecular complex precursor and photogenerated electrons on CdS as reductants under mild conditions. The optimized CdS/Co-MoSx (Co:Mo = 1:4, 2 mol% loading) photocatalyst exhibited a catalytic H2 evolution rate of 535 μmol h-1, which is 1.8 times higher than that of CdS/MoSx, and an apparent quantum efficiency (AQE) of 23.5% was achieved over CdS/Co-MoSx photocatalyst at 420 nm. Co-MoSx catalyst also shows a long-term stability without noticeable activity degradation. Notably, Co-MoSx cocatalyst was found more efficient than that of noble metals in catalyzing photocatalytic H2 evolution on CdS. The formation of CoMoS phase, the enhanced electrocatalytic activity as well as reduced electron transfer resistance due to the doping effects of Co ions, account for the enhanced catalytic activity of this Co-MoSx cocatalyst.

Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

PubMed

Zhang, Yun-Xiao; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

2018-09-15

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS 2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS 2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS 2 /CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS 2 /CNTs/CN catalyst exhibits high performance for H 2 evolution and the optimized rate is 309.9 μmol·h -1 ·g -1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost. Copyright © 2018 Elsevier Inc. All rights reserved.

An enzyme kinetics study of the pH dependence of chloride activation of oxygen evolution in photosystem II.

PubMed

Baranov, Sergei; Haddy, Alice

2017-03-01

Oxygen evolution by photosystem II (PSII) involves activation by Cl - ion, which is regulated by extrinsic subunits PsbQ and PsbP. In this study, the kinetics of chloride activation of oxygen evolution was studied in preparations of PSII depleted of the PsbQ and PsbP subunits (NaCl-washed and Na 2 SO 4 /pH 7.5-treated) over a pH range from 5.3 to 8.0. At low pH, activation by chloride was followed by inhibition at chloride concentrations >100 mM, whereas at high pH activation continued as the chloride concentration increased above 100 mM. Both activation and inhibition were more pronounced at lower pH, indicating that Cl - binding depended on protonation events in each case. The simplest kinetic model that could account for the complete data set included binding of Cl - at two sites, one for activation and one for inhibition, and four protonation steps. The intrinsic (pH-independent) dissociation constant for Cl - activation, K S , was found to be 0.9 ± 0.2 mM for both preparations, and three of the four pK a s were determined, with the fourth falling below the pH range studied. The intrinsic inhibition constant, K I , was found to be 64 ± 2 and 103 ± 7 mM for the NaCl-washed and Na 2 SO 4 /pH7.5-treated preparations, respectively, and is considered in terms of the conditions likely to be present in the thylakoid lumen. This enzyme kinetics analysis provides a more complete characterization of chloride and pH dependence of O 2 evolution activity than has been previously presented.

Reassortant Clade 2.3.4.4 of Highly Pathogenic Avian Influenza A(H5N6) Virus, Taiwan, 2017.

PubMed

Chen, Li-Hsuan; Lee, Dong-Hun; Liu, Yu-Pin; Li, Wan-Chen; Swayne, David E; Chang, Jen-Chieh; Chen, Yen-Ping; Lee, Fan; Tu, Wen-Jane; Lin, Yu-Ju

2018-06-01

A highly pathogenic avian influenza A(H5N6) virus of clade 2.3.4.4 was detected in a domestic duck found dead in Taiwan during February 2017. The endemic situation and continued evolution of various reassortant highly pathogenic avian influenza viruses in Taiwan warrant concern about further reassortment and a fifth wave of intercontinental spread.

Hierarchical Heterostructure of ZnO@TiO2 Hollow Spheres for Highly Efficient Photocatalytic Hydrogen Evolution

NASA Astrophysics Data System (ADS)

Li, Yue; Wang, Longlu; Liang, Jian; Gao, Fengxian; Yin, Kai; Dai, Pei

2017-09-01

The rational design and preparation of hierarchical nanoarchitectures are critical for enhanced photocatalytic hydrogen evolution reaction (HER). Herein, well-integrated hollow ZnO@TiO2 heterojunctions were obtained by a simple hydrothermal method. This unique hierarchical heterostructure not only caused multiple reflections which enhances the light absorption but also improved the lifetime and transfer of photogenerated charge carriers due to the potential difference generated on the ZnO-TiO2 interface. As a result, compared to bare ZnO and TiO2, the ZnO@TiO2 composite photocatalyst exhibited higher hydrogen production rated up to 0.152 mmol h-1 g-1 under simulated solar light. In addition, highly repeated photostability was also observed on the ZnO@TiO2 composite photocatalyst even after a continuous test for 30 h. It is expected that this low-cost, nontoxic, and readily available ZnO@TiO2 catalyst could exhibit promising potential in photocatalytic H2 to meet the future fuel needs.

High light harvesting efficiency CuInS2 quantum dots/TiO2/MoS2 photocatalysts for enhanced visible light photocatalytic H2 production.

PubMed

Yuan, Yong-Jun; Fang, Gaoliang; Chen, Daqin; Huang, Yanwei; Yang, Ling-Xia; Cao, Da-Peng; Wang, Jingjing; Yu, Zhen-Tao; Zou, Zhi-Gang

2018-04-24

Expanding the photoresponse range of TiO2-based photocatalysts is of great interest for photocatalytic H2 production. Herein, noble-metal-free CuInS2 quantum dots were employed as a novel inorganic dye to expand the visible light absorption of TiO2/MoS2 for solar H2 generation. The as-prepared CuInS2/TiO2/MoS2 photocatalysts exhibit broad absorption from the ultraviolet to near-infrared region. Under visible light irradiation (λ > 420 nm), the CuInS2/TiO2/MoS2 photocatalyst with 0.6 mmol g-1 CuInS2 and 0.5 wt% MoS2 showed the highest H2 evolution rate with a value of 1034 μmol h-1 g-1. Moreover, a considerable H2 evolution rate of 141 μmol h-1 g-1 was obtained under the irradiation of the optimized CuInS2/TiO2/MoS2 photocatalyst with >500 nm light. The reaction mechanism of the CuInS2/TiO2/MoS2 photocatalyst for photocatalytic H2 evolution was investigated in detail by photoluminescence decay study, and the results showed that the photoexcited electrons of CuInS2 can be transferred efficiently through TiO2 to MoS2 and then react with the absorbed protons to generate H2. The reported sensitization strategy tremendously improves the visible light absorption capacity and the photocatalytic performance of TiO2-based photocatalysts.

Synergetic effect of MoS{sub 2} and g-C{sub 3}N{sub 4} as cocatalysts for enhanced photocatalytic H{sub 2} production activity of TiO{sub 2}

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

Yang, Xixian; Huang, Hongyu, E-mail: huanghy@ms.giec.ac.cn; Kubota, Mitsuhiro

Highlights: • A hydrogen evolution reaction of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst was synthesized. • g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} presents highly efficient H{sub 2} evolution without noble metals. • The effect of g-C{sub 3}N{sub 4} and MoS{sub 2} co-catalyst content in the composites was studied. • The mechanism of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst under UV–vis light was discussed. - Abstract: In this paper, we report a new g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite material as a high-performance photocatalyst for H{sub 2} evolution. Without a noble-metal cocatalyst, the g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite reaches a highmore » H{sub 2} production rate of 125 μmol h{sup −1} when the content of the g-C{sub 3}N{sub 4}/MoS{sub 2} cocatalyst is 1.0 wt.% and the content of g-C{sub 3}N{sub 4} in this cocatalyst is 10 wt.%. This unusual photocatalytic activity is attributed to the positive synergetic effect between the MoS{sub 2} and g-C{sub 3}N{sub 4} components in this cocatalyst, which serve as an electron collector and a source of active adsorption sites, respectively.« less

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

PubMed

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

The Evolution of Hydrocarbon Compounds in Saturn's Stratosphere During the 2010 Northern Storm

NASA Astrophysics Data System (ADS)

Hesman, B. E.; Bjoraker, G. L.; Achterberg, R. K.; Sada, P. V.; Jennings, D. E.; Lunsford, A. W.; Sinclair, J.; Romani, P. N.; Boyle, R.; Fletcher, L. N.; Irwin, P.

2013-12-01

The massive eruption at 40N (planetographic latitude) in December 2010 has produced significant and long-lived changes in temperature and species abundances in Saturn's northern hemisphere (Hesman et al. 2012a, Fletcher et al. 2012). The northern storm region has been observed on many occasions between January 2011 and June of 2012 by Cassini's Composite Infrared Spectrometer (CIRS). In this time period, temperatures in regions referred to as 'beacons' (warm regions in the stratosphere at certain longitudes in the storm latitude) became significantly warmer than pre-storm values of 140K. In this period hydrocarbon emission greatly increased; however, this increased emission could not be attributed due to the temperature changes alone for many of these species (Hesman et al. 2012b, Bjoraker et al 2012). The unique nature of the stratospheric beacons also resulted in the detection of ethylene (C2H4) using CIRS. These beacon regions have also led to the identification of rare hydrocarbon species such as C4H2 and C3H4 in the stratosphere. These species are all expected from photochemical processes in the stratosphere, however high temperatures, unusual chemistry, or dynamics are enhancing these species. The exact cause of these enhancements is still under investigation. Ground-based observations were performed using the high-resolution spectrometer Celeste in May 2011 to confirm the CIRS detection of C2H4 and to study its spectral signatures at higher spectral resolution. In order to follow the evolution of its emission further observations were performed in July 2011 and March 2012. These observations are being used in conjunction with the CIRS observations to investigate the source of the approximately 100-fold increase of ethylene in the stratospheric beacon. The time evolution of hydrocarbon emission from C2H2, C2H4, C2H6, C3H4, and C4H2 in Saturn's Northern Storm beacon regions will be discussed. References: Bjoraker, G., B.E. Hesman, R.K. Achterberg, P.N. Romani. 2012, 'The Evolution of Hydrocarbons in Saturn's Northern Storm Region,' AAS DPS Conference, Vol. 44, #403.05. Fletcher, L.N. et al. 2012, 'The Origin and Evolution of Saturn's 2011-2012 Stratospheric Vortex,' Icarus, 221, 560-586. Hesman, B.E. et al. 2012a, 'Elusive Ethylene Detected in Saturn's Northern Storm Region,' The Astrophysical Journal, 760, 24-30. Hesman, B.E. et al. 2012b, 'Ethylene Emission in the Aftermath of Saturn's 2010 Northern Storm,' AAS DPS Conference, Vol. 44, #403.06.

Klebsiella pneumoniae nitrogenase. Inhibition of hydrogen evolution by ethylene and the reduction of ethylene to ethane.

PubMed Central

Ashby, G A; Dilworth, M J; Thorneley, R N

1987-01-01

Ethylene (C2H4) inhibited H2 evolution by the Mo-containing nitrogenase of Klebsiella pneumoniae. The extent of inhibition depended on the electron flux determined by the ratio of Fe protein (Kp2) to MoFe protein (Kp1) with KiC2H4 = 409 kPa ([Kp2]/[Kp1] = 22:1) and KC2H4i = 88 kPa ([Kp1]/[Kp2] = 21:1) at 23 degrees C at pH 7.4. At [Kp2]/[Kp1] = 1:1, inhibition was minimal with C2H4 (101 kPa). Extrapolation of data obtained when C2H4 was varied from 60 to 290 kPa indicates that at infinite pressure of C2H4 total inhibition of H2 evolution should occur. C2H4 inhibited concomitant S2O4(2-) oxidation to the same extent that it inhibited H2 evolution. Although other inhibitors of total electron flux such as CN- and CH3NC uncouple MgATP hydrolysis from electron transfer, C2H4 did not affect the ATP/2e ratio. Inhibition of H2 evolution by C2H4 was not relieved by CO. C2H4 was reduced to C2H6 at [Kp2]/[Kp1] ratios greater than or equal to 5:1 in a reaction that accounted for no more than 1% of the total electron flux. These data are discussed in terms of the chemistry of alkyne and alkene reduction on transition-metal centres. PMID:3322266

A high deuterium abundance at redshift z = 0.7.

PubMed

Webb, J K; Carswell, R F; Lanzetta, K M; Ferlet, R; Lemoine, M; Vidal-Madjar, A; Bowen, D V

1997-07-17

Of the light elements, the primordial abundance of deuterium relative to hydrogen, (D/H)p, provides the most sensitive diagnostic for the cosmological mass density parameter, omegaB. Recent high-redshift D/H measurements are highly discrepant, although this may reflect observational uncertainties. The larger primordial D/H values imply a low omegaB (requiring the Universe to be dominated by non-baryonic matter), and cause problems for galactic chemical evolution models, which have difficulty in reproducing the steep decline in D/H to the present-day values. Conversely, the lower D/H values measured at high redshift imply an omegaB greater than that derived from 7Li and 4He abundance measurements, and may require a deuterium-abundance evolution that is too low to easily explain. Here we report the first measurement of D/H at intermediate redshift (z = 0.7010), in a gas cloud selected to minimize observational uncertainties. Our analysis yields a value of D/H ((2.0 +/- 0.5) x 10[-4]) which is at the upper end of the range of values measured at high redshifts. This finding, together with other independent observations, suggests that there may be inhomogeneity in (D/H)p of at least a factor of ten.

Hydrothermal fabrication of few-layer MoS2 nanosheets within nanopores on TiO2 derived from MIL-125(Ti) for efficient photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Ye, Fei; Li, Houfen; Yu, Hongtao; Chen, Shuo; Quan, Xie

2017-12-01

Protons tend to bond strongly with unsaturated-coordinate S element located at the edge of nano-MoS2 and are consequently reduced to H2. Therefore, increasing the active S atoms quantity will be a feasible approach to enhance hydrogen evolution. Herein we developed a porous TiO2 derived from metal organic frameworks (MOFs) as scaffold to restrict the growth and inhibit the aggregation of MoS2 nanosheets. As a result, the thickness of the prepared MoS2 nanosheets was less than 3 nm (1-4 layers), with more edges and active S atoms being exposed. This few-layer MoS2-porous TiO2 exhibits a H2 evolution rate of 897.5 μmol h-1 g-1, which is nearly twice as much as free-stand MoS2 nanosheets and twenty times more than physical mixture of MoS2 with porous TiO2. The high performance is attributed to that more active edge sites in few-layer MoS2-porous TiO2 are exposed than pure MoS2. This work provides a new method to construct MOFs derived porous structures for controlling MoS2 to expose active sites for HER.

Robustly photogenerating H2 in water using FeP/CdS catalyst under solar irradiation

PubMed Central

Cheng, Huanqing; Lv, Xiao-Jun; Cao, Shuang; Zhao, Zong-Yan; Chen, Yong; Fu, Wen-Fu

2016-01-01

Photosplitting water for H2 production is a promising, sustainable approach for solar-to-chemical energy conversion. However, developing low-cost, high efficient and stable photocatalysts remains the major challenge. Here we report a composite photocatalyst consisting of FeP nanoparticles and CdS nanocrystals (FeP/CdS) for photogenerating H2 in aqueous lactic acid solution under visible light irradiation. Experimental results demonstrate that the photocatalyst is highly active with a H2-evolution rate of 202000 μmol h−1 g−1 for the first 5 h (106000 μmol h−1 g−1 under natural solar irradiation), which is the best H2 evolution activity, even 3-fold higher than the control in situ photo-deposited Pt/CdS system, and the corresponding to an apparent quantum efficiency of over 35% at 520 nm. More important, we found that the system exhibited excellent stability and remained effective after more than 100 h in optimal conditions under visible light irradiation. A wide-ranging analysis verified that FeP effectively separates the photoexcited charge from CdS and showed that the dual active sites in FeP enhance the activity of FeP/CdS photocatalysts. PMID:26818001

Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

NASA Astrophysics Data System (ADS)

Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

2014-12-01

The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

Highly efficient direct Z-scheme WO3/CdS-diethylenetriamine photocatalyst and its enhanced photocatalytic H2 evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Hu, Taiping; Li, Pengfei; Zhang, Jinfeng; Liang, Changhao; Dai, Kai

2018-06-01

Cadmium sulfide (CdS) has demonstrated great promise in artificial photocataytic hydrogen (H2) production. However, the serious photocorrosion hinders its effective interaction and real-life application. In this work, a typical direct Z-scheme WO3/CdS-diethylenetriamine (CdS-DETA) composite has been designed via facile in-situ solvothermal method, which exhibits excellent H2 production properties in visible light region. In this system, the inorganic-organic CdS-DETA nanobelts (NBs) possess enough active sites and large surface area for the encouraging nanojunction structure information. Furthermore, we also systematically calculated energy band structure and investigated charge transfer of the WO3/CdS-DETA by PL and photocurrent test, the results demonstrated that the suitable band gap matching between CdS-DETA and WO3 and high redox potential improve the separation of photogenerated holes and electrons, restraining intrinsic photocorrosion of CdS as well as improving the photocatalytic activity. 5%WO3/CdS-DETA presented the most outstanding H2 evolution rate (15522 μmol g-1 h-1), which is twice higher than that of pure CdS-DETA. WO3/CdS-DETA composites also presented high stability after three recycle H2 production experiment. Finally, direct Z-scheme photocatalytic mechanism is calculated.

A spongy nickel-organic CO 2 reduction photocatalyst for nearly 100% selective CO production

DOE PAGES

Niu, Kaiyang; Xu, You; Wang, Haicheng; ...

2017-07-28

Solar-driven photocatalytic conversion of CO 2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO 2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H 2 evolution during photocatalytic CO 2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO 2 to CO, with a production rate of ~1.6 × 10 4 μmolmore » hour –1 g –1. No measurable H 2 is generated during the reaction, leading to nearly 100% selective CO production over H 2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO 2 reduction reactions generate formic acid and acetic acid. As a result, achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy.« less

A spongy nickel-organic CO 2 reduction photocatalyst for nearly 100% selective CO production

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

Niu, Kaiyang; Xu, You; Wang, Haicheng

Solar-driven photocatalytic conversion of CO 2 into fuels has attracted a lot of interest; however, developing active catalysts that can selectively convert CO 2 to fuels with desirable reaction products remains a grand challenge. For instance, complete suppression of the competing H 2 evolution during photocatalytic CO 2-to-CO conversion has not been achieved before. We design and synthesize a spongy nickel-organic heterogeneous photocatalyst via a photochemical route. The catalyst has a crystalline network architecture with a high concentration of defects. It is highly active in converting CO 2 to CO, with a production rate of ~1.6 × 10 4 μmolmore » hour –1 g –1. No measurable H 2 is generated during the reaction, leading to nearly 100% selective CO production over H 2 evolution. When the spongy Ni-organic catalyst is enriched with Rh or Ag nanocrystals, the controlled photocatalytic CO 2 reduction reactions generate formic acid and acetic acid. As a result, achieving such a spongy nickel-organic photocatalyst is a critical step toward practical production of high-value multicarbon fuels using solar energy.« less

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.

PubMed

Yuan, Jiangtan; Wu, Jingjie; Hardy, Will J; Loya, Philip; Lou, Minhan; Yang, Yingchao; Najmaei, Sina; Jiang, Menglei; Qin, Fan; Keyshar, Kunttal; Ji, Heng; Gao, Weilu; Bao, Jiming; Kono, Junichiro; Natelson, Douglas; Ajayan, Pulickel M; Lou, Jun

2015-10-07

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

Fukuzumi, Shunichi; Suenobu, Tomoyoshi

2013-01-07

The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

[NiFeSe]-hydrogenase chemistry.

PubMed

Wombwell, Claire; Caputo, Christine A; Reisner, Erwin

2015-11-17

The development of technology for the inexpensive generation of the renewable energy vector H2 through water splitting is of immediate economic, ecological, and humanitarian interest. Recent interest in hydrogenases has been fueled by their exceptionally high catalytic rates for H2 production at a marginal overpotential, which is presently only matched by the nonscalable noble metal platinum. The mechanistic understanding of hydrogenase function guides the design of synthetic catalysts, and selection of a suitable hydrogenase enables direct applications in electro- and photocatalysis. [FeFe]-hydrogenases display excellent H2 evolution activity, but they are irreversibly damaged upon exposure to O2, which currently prevents their use in full water splitting systems. O2-tolerant [NiFe]-hydrogenases are known, but they are typically strongly biased toward H2 oxidation, while H2 production by [NiFe]-hydrogenases is often product (H2) inhibited. [NiFeSe]-hydrogenases are a subclass of [NiFe]-hydrogenases with a selenocysteine residue coordinated to the active site nickel center in place of a cysteine. They exhibit a combination of unique properties that are highly advantageous for applications in water splitting compared with other hydrogenases. They display a high H2 evolution rate with marginal inhibition by H2 and tolerance to O2. [NiFeSe]-hydrogenases are therefore one of the most active molecular H2 evolution catalysts applicable in water splitting. Herein, we summarize our recent progress in exploring the unique chemistry of [NiFeSe]-hydrogenases through biomimetic model chemistry and the chemistry with [NiFeSe]-hydrogenases in semiartificial photosynthetic systems. We gain perspective from the structural, spectroscopic, and electrochemical properties of the [NiFeSe]-hydrogenases and compare them with the chemistry of synthetic models of this hydrogenase active site. Our synthetic models give insight into the effects on the electronic properties and reactivity of the active site upon the introduction of selenium. We have utilized the exceptional properties of the [NiFeSe]-hydrogenase from Desulfomicrobium baculatum in a number of photocatalytic H2 production schemes, which are benchmark systems in terms of single site activity, tolerance toward O2, and in vitro water splitting with biological molecules. Each system comprises a light-harvesting component, which allows for light-driven electron transfer to the hydrogenase in order for it to catalyze H2 production. A system with [NiFeSe]-hydrogenase on a dye-sensitized TiO2 nanoparticle gives an enzyme-semiconductor hybrid for visible light-driven generation of H2 with an enzyme-based turnover frequency of 50 s(-1). A stable and inexpensive polymeric carbon nitride as a photosensitizer in combination with the [NiFeSe]-hydrogenase shows good activity for more than 2 days. Light-driven H2 evolution with the enzyme and an organic dye under high O2 levels demonstrates the excellent robustness and feasibility of water splitting with a hydrogenase-based scheme. This has led, most recently, to the development of a light-driven full water splitting system with a [NiFeSe]-hydrogenase wired to the water oxidation enzyme photosystem II in a photoelectrochemical cell. In contrast to the other systems, this photoelectrochemical system does not rely on a sacrificial electron donor and allowed us to establish the long sought after light-driven water splitting with an isolated hydrogenase.

The evolution of human influenza A viruses from 1999 to 2006: a complete genome study.

PubMed

Bragstad, Karoline; Nielsen, Lars P; Fomsgaard, Anders

2008-03-07

Knowledge about the complete genome constellation of seasonal influenza A viruses from different countries is valuable for monitoring and understanding of the evolution and migration of strains. Few complete genome sequences of influenza A viruses from Europe are publicly available at the present time and there have been few longitudinal genome studies of human influenza A viruses. We have studied the evolution of circulating human H3N2, H1N1 and H1N2 influenza A viruses from 1999 to 2006, we analysed 234 Danish human influenza A viruses and characterised 24 complete genomes. H3N2 was the prevalent strain in Denmark during the study period, but H1N1 dominated the 2000-2001 season. H1N2 viruses were first observed in Denmark in 2002-2003. After years of little genetic change in the H1N1 viruses the 2005-2006 season presented H1N1 of greater variability than before. This indicates that H1N1 viruses are evolving and that H1N1 soon is likely to be the prevalent strain again. Generally, the influenza A haemagglutinin (HA) of H3N2 viruses formed seasonal phylogenetic clusters. Different lineages co-circulating within the same season were also observed. The evolution has been stochastic, influenced by small "jumps" in genetic distance rather than constant drift, especially with the introduction of the Fujian-like viruses in 2002-2003. Also evolutionary stasis-periods were observed which might indicate well fit viruses. The evolution of H3N2 viruses have also been influenced by gene reassortments between lineages from different seasons. None of the influenza genes were influenced by strong positive selection pressure. The antigenic site B in H3N2 HA was the preferred site for genetic change during the study period probably because the site A has been masked by glycosylations. Substitutions at CTL-epitopes in the genes coding for the neuraminidase (NA), polymerase acidic protein (PA), matrix protein 1 (M1), non-structural protein 1 (NS1) and especially the nucleoprotein (NP) were observed. The N-linked glycosylation pattern varied during the study period and the H3N2 isolates from 2004 to 2006 were highly glycosylated with ten predicted sequons in HA, the highest amount of glycosylations observed in this study period. The present study is the first to our knowledge to characterise the evolution of complete genomes of influenza A H3N2, H1N1 and H1N2 isolates from Europe over a time period of seven years from 1999 to 2006. More precise knowledge about the circulating strains may have implications for predicting the following season strains and thereby better matching the vaccine composition.

The evolution of human influenza A viruses from 1999 to 2006: A complete genome study

PubMed Central

Bragstad, Karoline; Nielsen, Lars P; Fomsgaard, Anders

2008-01-01

Background Knowledge about the complete genome constellation of seasonal influenza A viruses from different countries is valuable for monitoring and understanding of the evolution and migration of strains. Few complete genome sequences of influenza A viruses from Europe are publicly available at the present time and there have been few longitudinal genome studies of human influenza A viruses. We have studied the evolution of circulating human H3N2, H1N1 and H1N2 influenza A viruses from 1999 to 2006, we analysed 234 Danish human influenza A viruses and characterised 24 complete genomes. Results H3N2 was the prevalent strain in Denmark during the study period, but H1N1 dominated the 2000–2001 season. H1N2 viruses were first observed in Denmark in 2002–2003. After years of little genetic change in the H1N1 viruses the 2005–2006 season presented H1N1 of greater variability than before. This indicates that H1N1 viruses are evolving and that H1N1 soon is likely to be the prevalent strain again. Generally, the influenza A haemagglutinin (HA) of H3N2 viruses formed seasonal phylogenetic clusters. Different lineages co-circulating within the same season were also observed. The evolution has been stochastic, influenced by small "jumps" in genetic distance rather than constant drift, especially with the introduction of the Fujian-like viruses in 2002–2003. Also evolutionary stasis-periods were observed which might indicate well fit viruses. The evolution of H3N2 viruses have also been influenced by gene reassortments between lineages from different seasons. None of the influenza genes were influenced by strong positive selection pressure. The antigenic site B in H3N2 HA was the preferred site for genetic change during the study period probably because the site A has been masked by glycosylations. Substitutions at CTL-epitopes in the genes coding for the neuraminidase (NA), polymerase acidic protein (PA), matrix protein 1 (M1), non-structural protein 1 (NS1) and especially the nucleoprotein (NP) were observed. The N-linked glycosylation pattern varied during the study period and the H3N2 isolates from 2004 to 2006 were highly glycosylated with ten predicted sequons in HA, the highest amount of glycosylations observed in this study period. Conclusion The present study is the first to our knowledge to characterise the evolution of complete genomes of influenza A H3N2, H1N1 and H1N2 isolates from Europe over a time period of seven years from 1999 to 2006. More precise knowledge about the circulating strains may have implications for predicting the following season strains and thereby better matching the vaccine composition. PMID:18325125

Evolution, global spread, and pathogenicity of highly pathogenic avian influenza H5Nx clade 2.3.4.4

PubMed Central

Lee, Dong-Hun; Bertran, Kateri; Kwon, Jung-Hoon

2017-01-01

Novel subtypes of Asian-origin (Goose/Guangdong lineage) H5 highly pathogenic avian influenza (HPAI) viruses belonging to clade 2.3.4, such as H5N2, H5N5, H5N6, and H5N8, have been identified in China since 2008 and have since evolved into four genetically distinct clade 2.3.4.4 groups (A–D). Since 2014, HPAI clade 2.3.4.4 viruses have spread rapidly via migratory wild aquatic birds and have evolved through reassortment with prevailing local low pathogenicity avian influenza viruses. Group A H5N8 viruses and its reassortant viruses caused outbreaks in wide geographic regions (Asia, Europe, and North America) during 2014–2015. Novel reassortant Group B H5N8 viruses caused outbreaks in Asia, Europe, and Africa during 2016–2017. Novel reassortant Group C H5N6 viruses caused outbreaks in Korea and Japan during the 2016–2017 winter season. Group D H5N6 viruses caused outbreaks in China and Vietnam. A wide range of avian species, including wild and domestic waterfowl, domestic poultry, and even zoo birds, seem to be permissive for infection by and/or transmission of clade 2.3.4.4 HPAI viruses. Further, compared to previous H5N1 HPAI viruses, these reassortant viruses show altered pathogenicity in birds. In this review, we discuss the evolution, global spread, and pathogenicity of H5 clade 2.3.4.4 HPAI viruses. PMID:28859267

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

PubMed

Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

2017-11-28

Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

Closed Bipolar Electrodes for Spatial Separation of H2 and O2 Evolution during Water Electrolysis and the Development of High-Voltage Fuel Cells.

PubMed

Goodwin, Sean; Walsh, Darren A

2017-07-19

Electrolytic water splitting could potentially provide clean H 2 for a future "hydrogen economy". However, as H 2 and O 2 are produced in close proximity to each other in water electrolyzers, mixing of the gases can occur during electrolysis, with potentially dangerous consequences. Herein, we describe an electrochemical water-splitting cell, in which mixing of the electrogenerated gases is impossible. In our cell, separate H 2 - and O 2 -evolving cells are connected electrically by a bipolar electrode in contact with an inexpensive dissolved redox couple (K 3 Fe(CN) 6 /K 4 Fe(CN) 6 ). Electrolytic water splitting occurs in tandem with oxidation/reduction of the K 3 Fe(CN) 6 /K 4 Fe(CN) redox couples in the separate compartments, affording completely spatially separated H 2 and O 2 evolution. We demonstrate operation of our prototype cell using conventional Pt electrodes for each gas-evolving reaction, as well as using earth-abundant Ni 2 P electrocatalysts for H 2 evolution. Furthermore, we show that our cell can be run in reverse and operate as a H 2 fuel cell, releasing the energy stored in the electrogenerated H 2 and O 2 . We also describe how the absence of an ionically conducting electrolyte bridging the H 2 - and O 2 -electrode compartments makes it possible to develop H 2 fuel cells in which the anode and cathode are at different pH values, thereby increasing the voltage above that of conventional fuel cells. The use of our cell design in electrolyzers could result in dramatically improved safety during operation and the generation of higher-purity H 2 than available from conventional electrolysis systems. Our cell could also be readily modified for the electrosynthesis of other chemicals, where mixing of the electrochemical products is undesirable.

Efficient Photocatalytic H2 Evolution: Controlled Dewetting-Dealloying to Fabricate Site-Selective High-Activity Nanoporous Au Particles on Highly Ordered TiO2 Nanotube Arrays.

PubMed

Nguyen, Nhat Truong; Altomare, Marco; Yoo, JeongEun; Schmuki, Patrik

2015-05-27

Anodic self-organized TiO2 nanostumps are formed and exploited for self-ordering dewetting of Au-Ag sputtered films. This forms ordered particle configurations at the tube top (crown position) or bottom (ground position). By dealloying from a minimal amount of noble metal, porous Au nanoparticles are then formed, which, when in the crown position, allow for a drastically improved photocatalytic H2 production compared with nanoparticles produced by conventional dewetting processes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolution and Activity in the Solar Corona: A Comparison of Coronal and Chromospheric Structures Seen in Soft X-Rays, White Light and H-Alpha Emission

NASA Technical Reports Server (NTRS)

Bagenal, Fran

2001-01-01

The work completed under this project, 'Evolution and Activity in the Solar Corona: A Comparison of Coronal and Chromospheric Structures Seen in Soft X-Rays, White Light and H-Alpha Emission', includes the following presentations: (1) Analysis of H-alpha Observations of High-altitude Coronal Condensations; (2) Multi-spectral Imaging of Coronal Activity; (3) Measurement and Modeling of Soft X-ray Loop Arcades; (4) A Study of the Origin and Dynamics of CMEs; and various poster presentations and thesis dissertations.

Evolution of H2O, CO, and CO2 production in Comet C/2009 P1 Garradd during the 2011-2012 apparition

NASA Astrophysics Data System (ADS)

McKay, Adam J.; Cochran, Anita L.; DiSanti, Michael A.; Villanueva, Geronimo; Russo, Neil Dello; Vervack, Ronald J.; Morgenthaler, Jeffrey P.; Harris, Walter M.; Chanover, Nancy J.

2015-04-01

We present analysis of high spectral resolution NIR spectra of CO and H2O in Comet C/2009 P1 (Garradd) taken during its 2011-2012 apparition with the CSHELL instrument on NASA's Infrared Telescope Facility (IRTF). We also present analysis of observations of atomic oxygen in Comet Garradd obtained with the ARCES echelle spectrometer mounted on the ARC 3.5-m telescope at Apache Point Observatory and the Tull Coude spectrograph on the Harlan J. Smith 2.7-m telescope at McDonald Observatory. The observations of atomic oxygen serve as a proxy for H2O and CO2. We confirm the high CO abundance in Comet Garradd and the asymmetry in the CO/H2O ratio with respect to perihelion reported by previous studies. From the oxygen observations, we infer that the CO2/H2O ratio decreased as the comet moved towards the Sun, which is expected based on current sublimation models. We also infer that the CO2/H2O ratio was higher pre-perihelion than post-perihelion. We observe evidence for the icy grain source of H2O reported by several studies pre-perihelion, and argue that this source is significantly less abundant post-perihelion. Since H2O, CO2, and CO are the primary ices in comets, they drive the activity. We use our measurements of these important volatiles in an attempt to explain the evolution of Garradd's activity over the apparition.

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

DOE PAGES

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...

2017-09-05

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Using TiO2 as a conductive protective layer for photocathodic H2 evolution.

PubMed

Seger, Brian; Pedersen, Thomas; Laursen, Anders B; Vesborg, Peter C K; Hansen, Ole; Chorkendorff, Ib

2013-01-23

Surface passivation is a general issue for Si-based photoelectrodes because it progressively hinders electron conduction at the semiconductor/electrolyte interface. In this work, we show that a sputtered 100 nm TiO(2) layer on top of a thin Ti metal layer may be used to protect an n(+)p Si photocathode during photocatalytic H(2) evolution. Although TiO(2) is a semiconductor, we show that it behaves like a metallic conductor would under photocathodic H(2) evolution conditions. This behavior is due to the fortunate alignment of the TiO(2) conduction band with respect to the hydrogen evolution potential, which allows it to conduct electrons from the Si while simultaneously protecting the Si from surface passivation. By using a Pt catalyst the electrode achieves an H(2) evolution onset of 520 mV vs NHE and a Tafel slope of 30 mV when illuminated by the red part (λ > 635 nm) of the AM 1.5 spectrum. The saturation photocurrent (H(2) evolution) was also significantly enhanced by the antireflective properties of the TiO(2) layer. It was shown that with proper annealing conditions these electrodes could run 72 h without significant degradation. An Fe(2+)/Fe(3+) redox couple was used to help elucidate details of the band diagram.

Photo-catalysis water splitting by platinum-loaded zeolite A

NASA Astrophysics Data System (ADS)

Cheng, Jing; Gao, Changda; Jing, Ming; Lu, Jian; Lin, Hui; Han, Zhaoxia; Ni, Zhengji; Zhang, Dawei

2018-05-01

Under the λ≥420 nm visible light illumination, the Pt4+ ions exchanged LTA zeolite powders without further heat-treatment presented H2 evolution at a rate of 5 μl/(15 mg·h) via photocatalysis water splitting. It was shown that the efficiency of H2 generation by the Pt4+ exchanged LTA zeolite powders without further heat-treatment was higher than the counterpart of the samples with heat treatment. In addition, the samples with lower Pt loading concentration showed higher H2 evolution rate than those of higher Pt loading did. The higher H2 evolution efficiency can be attributed to the effective isolation of water molecules and Pt at the atomic or the few atom ‘cluster’ scale by LTA zeolite’s periodical porous structure, which ensures a more efficient electron transfer efficiency for H2 evolution. However, after extra heat treatment, the Pt atoms reduced from Pt4+ in LTA zeolite’s cavities may tend to migrate to the surface and then form nano-particles, which led to the lower H2 evolution efficiency.

Correlation between pH dependence of O2 evolution and sensitivity of Mn cations in the oxygen-evolving complex to exogenous reductants.

PubMed

Semin, Boris K; Davletshina, Lira N; Rubin, Andrei B

2015-08-01

Effects of pH, Ca(2+), and Cl(-) ions on the extraction of Mn cations from oxygen-evolving complex (OEC) in Ca-depleted photosystem II (PSII(-Ca)) by exogenous reductants hydroquinone (H2Q) and H2O2 were studied. Two of 4 Mn cations are released by H2Q and H2O2 at pHs 5.7, 6.5, and 7.5, and their extraction does not depend on the presence of Ca(2+) and Cl(-) ions. One of Mn cations ("resistant" Mn cation) cannot be extracted by H2Q and H2O2 at any pH. Extraction of 4th Mn ion ("flexible" Mn cation) is sensitive to pH, Ca(2+), and Cl(-). This Mn cation is released by reductants at pH 6.5 but not at pHs 5.7 and 7.5. A pH dependence curve of the oxygen-evolving activity in PSII(-Ca) membranes (in the presence of exogenous Ca(2+)) has a bell-shaped form with the maximum at pH 6.5. Thus, the increase in the resistance of flexible Mn cation in OEC to the action of reductants at acidic and alkaline pHs coincides with the decrease in oxygen evolution activity at these pHs. Exogenous Ca(2+) protects the extraction of flexible Mn cation at pH 6.5. High concentration of Cl(-) anions (100 mM) shifts the pH optimum of oxygen evolution to alkaline region (around pH 7.5), while the pH of flexible Mn extraction is also shifted to alkaline pH. This result suggests that flexible Mn cation plays a key role in the water-splitting reaction. The obtained results also demonstrate that only one Mn cation in Mn4 cluster is under strong control of calcium. The change in the flexible Mn cation resistance to exogenous reductants in the presence of Ca(2+) suggests that Ca(2+) can control the redox potential of this cation.

The Role of Hydrogen Sulfide in Evolution and the Evolution of Hydrogen Sulfide in Metabolism and Signaling.

PubMed

Olson, Kenneth R; Straub, Karl D

2016-01-01

The chemical versatility of sulfur and its abundance in the prebiotic Earth as reduced sulfide (H2S) implicate this molecule in the origin of life 3.8 billion years ago and also as a major source of energy in the first seven-eighths of evolution. The tremendous increase in ambient oxygen ∼ 600 million years ago brought an end to H2S as an energy source, and H2S-dependent animals either became extinct, retreated to isolated sulfide niches, or adapted. The first 3 billion years of molecular tinkering were not lost, however, and much of this biochemical armamentarium easily adapted to an oxic environment where it contributes to metabolism and signaling even in humans. This review examines the role of H2S in evolution and the evolution of H2S metabolism and signaling. ©2016 Int. Union Physiol. Sci./Am. Physiol. Soc.

Laboratory Evolved Gas Analyses of Si-rich Amorphous Materials: Implications for Analyses of Si-rich Amorphous Material in Gale Crater by the Mars Science Laboratory Sample Analysis at Mars Instrument

NASA Astrophysics Data System (ADS)

McAdam, A.; Knudson, C. A.; Sutter, B.; Andrejkovicova, S. C.; Archer, P. D., Jr.; Franz, H. B.; Eigenbrode, J. L.; Morris, R. V.; Ming, D. W.; Sun, V. Z.; Milliken, R.; Wilhelm, M. B.; Mahaffy, P. R.; Navarro-Gonzalez, R.

2016-12-01

The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Science Laboratory (MSL) rover detected Si-rich amorphous or poorly ordered materials in several samples from Murray Formation mudstones and Stimson Formation sandstones. High-SiO2 amorphous materials such as opal-A or rhyolitic glass are candidate phases, but CheMin data cannot be used to distinguish between these possibilities. In the Buckskin (BS) sample from the upper Murray Formation, and the Big Sky (BY) and Greenhorn (GH) samples from the Stimson Formation, evolved gas analyses by the Sample Analysis at Mars (SAM) instrument showed very broad H2O evolutions during sample heating at temperatures >450-500°C, which had not been observed from previous samples. BS also had a significant broad evolution <450-500°C. We have undertaken a laboratory study targeted at understanding if the data from SAM analyses can be used to place constraints on the nature of the amorphous phases. SAM-like evolved gas analyses have been performed on several opal and rhyolitic glass samples. Opal-A samples exhibited wide <500°C H2O evolutions, with lesser H2O evolved above 500°C. H2O evolution traces from rhyolitic glasses varied, having either two broad H2O peaks, <300°C and >500°C, or a broad peak centered around 400°C. For samples that produced two evolutions, the lower temperature peak was more intense than the higher temperature peak, a trend also exhibited by opal-A. This trend is consistent with data from BS, but does not seem consistent with data from BY and GH which evolved most of their H2O >500°C. It may be that dehydration of opal-A and/or rhyolitic glass can result in some preferential loss of lower temperature H2O, to produce traces that more closely resemble BY and GH. This is currently under investigation and results will be reported.

Genomewide analysis of reassortment and evolution of human influenza A(H3N2) viruses circulating between 1968 and 2011.

PubMed

Westgeest, Kim B; Russell, Colin A; Lin, Xudong; Spronken, Monique I J; Bestebroer, Theo M; Bahl, Justin; van Beek, Ruud; Skepner, Eugene; Halpin, Rebecca A; de Jong, Jan C; Rimmelzwaan, Guus F; Osterhaus, Albert D M E; Smith, Derek J; Wentworth, David E; Fouchier, Ron A M; de Graaf, Miranda

2014-03-01

Influenza A(H3N2) viruses became widespread in humans during the 1968 H3N2 virus pandemic and have been a major cause of influenza epidemics ever since. These viruses evolve continuously by reassortment and genomic evolution. Antigenic drift is the cause for the need to update influenza vaccines frequently. Using two data sets that span the entire period of circulation of human influenza A(H3N2) viruses, it was shown that influenza A(H3N2) virus evolution can be mapped to 13 antigenic clusters. Here we analyzed the full genomes of 286 influenza A(H3N2) viruses from these two data sets to investigate the genomic evolution and reassortment patterns. Numerous reassortment events were found, scattered over the entire period of virus circulation, but most prominently in viruses circulating between 1991 and 1998. Some of these reassortment events persisted over time, and one of these coincided with an antigenic cluster transition. Furthermore, selection pressures and nucleotide and amino acid substitution rates of all proteins were studied, including those of the recently discovered PB1-N40, PA-X, PA-N155, and PA-N182 proteins. Rates of nucleotide and amino acid substitutions were most pronounced for the hemagglutinin, neuraminidase, and PB1-F2 proteins. Selection pressures were highest in hemagglutinin, neuraminidase, matrix 1, and nonstructural protein 1. This study of genotype in relation to antigenic phenotype throughout the period of circulation of human influenza A(H3N2) viruses leads to a better understanding of the evolution of these viruses. Each winter, influenza virus infects approximately 5 to 15% of the world's population, resulting in significant morbidity and mortality. Influenza A(H3N2) viruses evolve continuously by reassortment and genomic evolution. This leads to changes in antigenic recognition (antigenic drift) which make it necessary to update vaccines against influenza A(H3N2) viruses frequently. In this study, the relationship of genetic evolution to antigenic change spanning the entire period of A(H3N2) virus circulation was studied for the first time. The results presented in this study contribute to a better understanding of genetic evolution in correlation with antigenic evolution of influenza A(H3N2) viruses.

A Model Study of the Thermal Evolution of Astrophysical Ices

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Teolis, B. D.; Baragiola, R. A.

2006-01-01

We address the question of the evolution of ices that have been exposed to radiation from stellar sources and cosmic rays. We studied in the laboratory the thermal evolution of a model ice sample: a mixture of water, hydrogen peroxide, dioxygen, and ozone produced by irradiating solid H2O2 with 50 keV H(+) at 17 K. The changes in composition and release of volatiles during warming to 200 K were monitored by infrared spectroscopy, mass spectrometry, and microbalance techniques. We find evidence for voids in the water component from the infrared bands due to dangling H bonds. The absorption from these bands increases during heating and can be observed at temperatures as high as approx. 155 K. More O2 is stored in the radiolyzed film than can be retained by codeposition of O2 and H2O. This O2 remains trapped until approx. 155 K, where it desorbs in an outburst as water ice crystallizes. Warming of the ice also drastically decreases the intrinsic absorbance of O2 by annealing defects in the ice. We also observe loss of O3 in two stages during heating, which correlates with desorption and possibly chemical reactions with radicals stored in the ice, triggered by the temperature increase.

Sloan Great Wall as a complex of superclusters with collapsing cores

NASA Astrophysics Data System (ADS)

Einasto, Maret; Lietzen, Heidi; Gramann, Mirt; Tempel, Elmo; Saar, Enn; Liivamägi, Lauri Juhan; Heinämäki, Pekka; Nurmi, Pasi; Einasto, Jaan

2016-10-01

Context. The formation and evolution of the cosmic web is governed by the gravitational attraction of dark matter and antigravity of dark energy (cosmological constant). In the cosmic web, galaxy superclusters or their high-density cores are the largest objects that may collapse at present or during the future evolution. Aims: We study the dynamical state and possible future evolution of galaxy superclusters from the Sloan Great Wall (SGW), the richest galaxy system in the nearby Universe. Methods: We calculated supercluster masses using dynamical masses of galaxy groups and stellar masses of galaxies. We employed normal mixture modelling to study the structure of rich SGW superclusters and search for components (cores) in superclusters. We analysed the radial mass distribution in the high-density cores of superclusters centred approximately at rich clusters and used the spherical collapse model to study their dynamical state. Results: The lower limit of the total mass of the SGW is approximately M = 2.5 × 1016 h-1 M⊙. Different mass estimators of superclusters agree well, the main uncertainties in masses of superclusters come from missing groups and clusters. We detected three high-density cores in the richest SGW supercluster (SCl 027) and two in the second richest supercluster (SCl 019). They have masses of 1.2 - 5.9 × 1015 h-1 M⊙ and sizes of up to ≈60 h-1 Mpc. The high-density cores of superclusters are very elongated, flattened perpendicularly to the line of sight. The comparison of the radial mass distribution in the high-density cores with the predictions of spherical collapse model suggests that their central regions with radii smaller than 8 h-1 Mpc and masses of up to M = 2 × 1015 h-1 M⊙ may be collapsing. Conclusions: The rich SGW superclusters with their high-density cores represent dynamically evolving environments for studies of the properties of galaxies and galaxy systems.

Highly Efficient Photocatalytic H2 Evolution from Water using Visible Light and Structure-Controlled Graphitic Carbon Nitride**

PubMed Central

Martin, David James; Qiu, Kaipei; Shevlin, Stephen Andrew; Handoko, Albertus Denny; Chen, Xiaowei; Guo, Zhengxiao; Tang, Junwang

2014-01-01

The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low-cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g-C3N4) from a low-cost precursor, urea, is reported. The g-C3N4 exhibits an extraordinary hydrogen-evolution rate (ca. 20 000 μmol h−1 g−1 under full arc), which leads to a high turnover number (TON) of over 641 after 6 h. The reaction proceeds for more than 30 h without activity loss and results in an internal quantum yield of 26.5 % under visible light, which is nearly an order of magnitude higher than that observed for any other existing g-C3N4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen-evolution rate is significantly enhanced. PMID:25045013

Defect Engineering and Phase Junction Architecture of Wide-Bandgap ZnS for Conflicting Visible Light Activity in Photocatalytic H₂ Evolution.

PubMed

Fang, Zhibin; Weng, Sunxian; Ye, Xinxin; Feng, Wenhui; Zheng, Zuyang; Lu, Meiliang; Lin, Sen; Fu, Xianzhi; Liu, Ping

2015-07-01

ZnS is among the superior photocatalysts for H2 evolution, whereas the wide bandgap restricts its performance to only UV region. Herein, defect engineering and phase junction architecture from a controllable phase transformation enable ZnS to achieve the conflicting visible-light-driven activities for H2 evolution. On the basis of first-principle density functional theory calculations, electron spin resonance and photoluminescence results, etc., it is initially proposed that the regulated sulfur vacancies in wurtzite phase of ZnS play the key role of photosensitization units for charge generation in visible light and active sites for effective electron utilization. The symbiotic sphalerite-wurtzite phase junctions that dominate the charge-transfer kinetics for photoexciton separation are the indispensable configuration in the present systems. Neither ZnS samples without phase junction nor those without enough sulfur vacancies conduct visible-light photocatalytic H2 evolution, while the one with optimized phase junctions and maximum sulfur vacancies shows considerable photocatalytic activity. This work will not only contribute to the realization of visible light photocatalysis for wide-bandgap semiconductors but also broaden the vision on the design of highly efficient transition metal sulfide photocatalysts.

Metallic 1T-LixMoS2 Cocatalyst Significantly Enhanced the Photocatalytic H2 Evolution over Cd0.5Zn0.5S Nanocrystals under Visible Light Irradiation.

PubMed

Du, Hong; Guo, Hong-Li; Liu, Ya-Nan; Xie, Xiao; Liang, Kuang; Zhou, Xiao; Wang, Xin; Xu, An-Wu

2016-02-17

In the present work, metallic 1T-LixMoS2 is utilized as a novel cocatalyst for Cd0.5Zn0.5S photocatalyst. The obtained LixMoS2/Cd0.5Zn0.5S hybrids show excellent photocatalytic performance for H2 generation from aqueous solution containing Na2S and Na2SO3 under splitting visible light illumination (λ ≥ 420 nm) without precious metal cocatalysts. It turns out that a certain amount of intercalating Li(+) ions ultimately drives the transition of MoS2 crystal from semiconductor triagonal phase (2H phase) to metallic phase (1T phase). The distinct properties of 1T-LixMoS2 promote the efficient separation of photoexcited electrons and holes when used as cocatalyst for Cd0.5Zn0.5S photocatalyst. As compared to 2H-MoS2 nanosheets only having edge active sites, photoinduced electrons not only transfer to the edge sites of 1T-LixMoS2, but also to the plane active sites of 1T-LixMoS2 nanosheets. The content of LixMoS2 in hybrid photocatalysts influences the photocatalytic activity. The optimal 1T-LixMoS2 (1.0 wt %)/Cd0.5Zn0.5S nanojunctions display the best activity for hydrogen production, achieving a hydrogen evolution rate of 769.9 μmol h(-1), with no use of noble metal loading, which is about 3.5 times higher than that of sole Cd0.5Zn0.5S, and 2 times higher than that of 2H-MoS2 (1.0 wt %)/Cd0.5Zn0.5S samples. Our results demonstrate that Li(+)-intercalated MoS2 nanosheets with high conductivity, high densities of active sites, low cost, and environmental friendliness are a prominent H2 evolution cocatalyst that might substitute for noble metal for potential hydrogen energy applications.

Phylodynamics of avian influenza clade 2.2.1 H5N1 viruses in Egypt.

PubMed

Arafa, Abdelsatar; El-Masry, Ihab; Kholosy, Shereen; Hassan, Mohammed K; Dauphin, Gwenaelle; Lubroth, Juan; Makonnen, Yilma J

2016-03-22

Highly pathogenic avian influenza (HPAI) viruses of the H5N1 subtype are widely distributed within poultry populations in Egypt and have caused multiple human infections. Linking the epidemiological and sequence data is important to understand the transmission, persistence and evolution of the virus. This work describes the phylogenetic dynamics of H5N1 based on molecular characterization of the hemagglutinin (HA) gene of isolates collected from February 2006 to May 2014. Full-length HA sequences of 368 H5N1 viruses were generated and were genetically analysed to study their genetic evolution. They were collected from different poultry species, production sectors, and geographic locations in Egypt. The Bayesian Markov Chain Monte Carlo (BMCMC) method was applied to estimate the evolutionary rates among different virus clusters; additionally, an analysis of selection pressures in the HA gene was performed using the Single Likelihood Ancestor Counting (SLAC) method. The phylogenetic analysis of the H5 gene from 2006-14 indicated the presence of one virus introduction of the classic clade (2.2.1) from which two main subgroups were originated, the variant subgroup which was further subdivided into 2 sub-divisions (2.2.1.1 and 2.2.1.1a) and the endemic subgroup (2.2.1.2). The clade 2.2.1.2 showed a high evolution rate over a period of 6 years (6.9 × 10(-3) sub/site/year) in comparison to the 2.2.1.1a variant cluster (7.2 × 10(-3) over a period of 4 years). Those two clusters are under positive selection as they possess 5 distinct positively selected sites in the HA gene. The mutations at 120, 154, and 162 HA antigenic sites and the other two mutations (129∆, I151T) that occurred from 2009-14 were found to be stable in the 2.2.1.2 clade. Additionally, 13 groups of H5N1 HPAI viruses were identified based on their amino acid sequences at the cleavage site and "EKRRKKR" became the dominant pattern beginning in 2013. Continuous evolution of H5N1 HPAI viruses in Egypt has been observed in all poultry farming and production systems in almost all regions of the country. The wide circulation of the 2.2.1.2 clade carrying triple mutations (120, 129∆, I151T) associated with increased binding affinity to human receptors is an alarming finding of public health importance.

The mechanism of Klebsiella pneumoniae nitrogenase action. Pre-steady-state kinetics of H2 formation.

PubMed Central

Lowe, D J; Thorneley, R N

1984-01-01

A comprehensive model for the mechanism of nitrogenase action is used to simulate pre-steady-state kinetic data for H2 evolution in the presence and in the absence of N2, obtained by using a rapid-quench technique with nitrogenase from Klebsiella pneumoniae. These simulations use independently determined rate constants that define the model in terms of the following partial reactions: component protein association and dissociation, electron transfer from Fe protein to MoFe protein coupled to the hydrolysis of MgATP, reduction of oxidized Fe protein by Na2S2O4, reversible N2 binding by H2 displacement and H2 evolution. Two rate-limiting dissociations of oxidized Fe protein from reduced MoFe protein precede H2 evolution, which occurs from the free MoFe protein. Thus Fe protein suppresses H2 evolution by binding to the MoFe protein. This is a necessary condition for efficient N2 binding to reduced MoFe protein. PMID:6395861

Quantifying selection and diversity in viruses by entropy methods, with application to the haemagglutinin of H3N2 influenza

PubMed Central

Pan, Keyao; Deem, Michael W.

2011-01-01

Many viruses evolve rapidly. For example, haemagglutinin (HA) of the H3N2 influenza A virus evolves to escape antibody binding. This evolution of the H3N2 virus means that people who have previously been exposed to an influenza strain may be infected by a newly emerged virus. In this paper, we use Shannon entropy and relative entropy to measure the diversity and selection pressure by an antibody in each amino acid site of H3 HA between the 1992–1993 season and the 2009–2010 season. Shannon entropy and relative entropy are two independent state variables that we use to characterize H3N2 evolution. The entropy method estimates future H3N2 evolution and migration using currently available H3 HA sequences. First, we show that the rate of evolution increases with the virus diversity in the current season. The Shannon entropy of the sequence in the current season predicts relative entropy between sequences in the current season and those in the next season. Second, a global migration pattern of H3N2 is assembled by comparing the relative entropy flows of sequences sampled in China, Japan, the USA and Europe. We verify this entropy method by describing two aspects of historical H3N2 evolution. First, we identify 54 amino acid sites in HA that have evolved in the past to evade the immune system. Second, the entropy method shows that epitopes A and B on the top of HA evolve most vigorously to escape antibody binding. Our work provides a novel entropy-based method to predict and quantify future H3N2 evolution and to describe the evolutionary history of H3N2. PMID:21543352

Nomenclature updates resulting from the evolution of avian influenza A(H5) virus clades 2.1.3.2a, 2.2.1, and 2.3.4 during 2013-2014.

PubMed

Smith, Gavin J D; Donis, Ruben O

2015-09-01

The A/goose/Guangdong/1/96-like hemagglutinin (HA) genes of highly pathogenic avian influenza (HPAI) A(H5) viruses have continued to rapidly evolve since the most recent update to the H5 clade nomenclature by the WHO/OIE/FAO H5N1 Evolution Working Group. New clades diverging beyond established boundaries need to be identified and designated accordingly. Hemagglutinin sequences deposited in publicly accessible databases up to December 31, 2014, were analyzed by phylogenetic and average pairwise distance methods to identify new clades that merit nomenclature changes. Three new clade designations were recommended based on division of clade 2·1·3·2a (Indonesia), 2·2·1 (Egypt), and 2·3·4 (widespread detection in Asia, Europe, and North America) that includes newly emergent HPAI virus subtypes H5N2, H5N3, H5N5, H5N6, and H5N8. Continued global surveillance for HPAI A(H5) viruses in all host species and timely reporting of sequence data will be critical to quickly identify new clades and assess their potential impact on human and animal health. © 2015 The Authors. Influenza and Other Respiratory Viruses Published by John Wiley & Sons Ltd.

Evolution of basal metabolic rate in bank voles from a multidirectional selection experiment.

PubMed

Sadowska, Edyta T; Stawski, Clare; Rudolf, Agata; Dheyongera, Geoffrey; Chrząścik, Katarzyna M; Baliga-Klimczyk, Katarzyna; Koteja, Paweł

2015-05-07

A major theme in evolutionary and ecological physiology of terrestrial vertebrates encompasses the factors underlying the evolution of endothermy in birds and mammals and interspecific variation of basal metabolic rate (BMR). Here, we applied the experimental evolution approach and compared BMR in lines of a wild rodent, the bank vole (Myodes glareolus), selected for 11 generations for: high swim-induced aerobic metabolism (A), ability to maintain body mass on a low-quality herbivorous diet (H) and intensity of predatory behaviour towards crickets (P). Four replicate lines were maintained for each of the selection directions and an unselected control (C). In comparison to C lines, A lines achieved a 49% higher maximum rate of oxygen consumption during swimming, H lines lost 1.3 g less mass in the test with low-quality diet and P lines attacked crickets five times more frequently. BMR was significantly higher in A lines than in C or H lines (60.8, 56.6 and 54.4 ml O2 h(-1), respectively), and the values were intermediate in P lines (59.0 ml O2 h(-1)). Results of the selection experiment provide support for the hypothesis of a positive association between BMR and aerobic exercise performance, but not for the association of adaptation to herbivorous diet with either a high or low BMR. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Antigenic and genetic evolution of contemporary swine H1 influenza viruses in the United States.

PubMed

Rajao, Daniela S; Anderson, Tavis K; Kitikoon, Pravina; Stratton, Jered; Lewis, Nicola S; Vincent, Amy L

2018-05-01

Several lineages of influenza A viruses (IAV) currently circulate in North American pigs. Genetic diversity is further increased by transmission of IAV between swine and humans and subsequent evolution. Here, we characterized the genetic and antigenic evolution of contemporary swine H1N1 and H1N2 viruses representing clusters H1-α (1A.1), H1-β (1A.2), H1pdm (1A.3.3.2), H1-γ (1A.3.3.3), H1-δ1 (1B.2.2), and H1-δ2 (1B.2.1) currently circulating in pigs in the United States. The δ1-viruses diversified into two new genetic clades, H1-δ1a (1B.2.2.1) and H1-δ1b (1B.2.2.2), which were also antigenically distinct from the earlier H1-δ1-viruses. Further characterization revealed that a few key amino acid changes were associated with antigenic divergence in these groups. The continued genetic and antigenic evolution of contemporary H1 viruses might lead to loss of vaccine cross-protection that could lead to significant economic impact to the swine industry, and represents a challenge to public health initiatives that attempt to minimize swine-to-human IAV transmission. Published by Elsevier Inc.

Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

NASA Astrophysics Data System (ADS)

Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan

2017-04-01

Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H2-production rate of 920 μmol h-1, exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H2-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst.

On the origin of the photocurrent of electrochemically passivated p-InP(100) photoelectrodes.

PubMed

Goryachev, Andrey; Gao, Lu; van Veldhoven, René P J; Haverkort, Jos E M; Hofmann, Jan P; Hensen, Emiel J M

2018-05-15

III-V semiconductors such as InP are highly efficient light absorbers for photoelectrochemical (PEC) water splitting devices. Yet, their cathodic stability is limited due to photocorrosion and the measured photocurrents do not necessarily originate from H2 evolution only. We evaluated the PEC stability and activation of model p-InP(100) photocathodes upon photoelectrochemical passivation (i.e. repeated surface oxidation/reduction). The electrode was subjected to a sequence of linear potential scans with or without intermittent passivation steps (repeated passivation and continuous reduction, respectively). The evolution of H2 and PH3 gases was monitored by online electrochemical mass spectrometry (OLEMS) and the Faradaic efficiencies of these processes were determined. Repeated passivation led to an increase of the photocurrent in 0.5 M H2SO4, while continuous reduction did not affect the photocurrent of p-InP(100). Neither H2 nor PH3 formation increased to the same extent as the photocurrent during the repeated passivation treatment. Surface analysis of the spent electrodes revealed substantial roughening of the electrode surface by repeated passivation, while continuous reduction left the surface unaltered. On the other hand, photocathodic conditioning performed in 0.5 M HCl led to the expected correlation between photocurrent increase and H2 formation. Ultimately, the H2 evolution rates of the photoelectrodes in H2SO4 and HCl are comparable. The much higher photocurrent in H2SO4 is due to competing side-reactions. The results emphasize the need for a detailed evaluation of the Faradaic efficiencies of all the involved processes using a chemical-specific technique like OLEMS. Photo-OLEMS can be beneficial in the study of photoelectrochemical reactions enabling the instantaneous detection of small amounts of reaction by-products.

A physiological perspective on the origin and evolution of photosynthesis

PubMed Central

Martin, William F; Bryant, Donald A; Beatty, J Thomas

2017-01-01

Abstract The origin and early evolution of photosynthesis are reviewed from an ecophysiological perspective. Earth's first ecosystems were chemotrophic, fueled by geological H2 at hydrothermal vents and, required flavin-based electron bifurcation to reduce ferredoxin for CO2 fixation. Chlorophyll-based phototrophy (chlorophototrophy) allowed autotrophs to generate reduced ferredoxin without electron bifurcation, providing them access to reductants other than H2. Because high-intensity, short-wavelength electromagnetic radiation at Earth's surface would have been damaging for the first chlorophyll (Chl)-containing cells, photosynthesis probably arose at hydrothermal vents under low-intensity, long-wavelength geothermal light. The first photochemically active pigments were possibly Zn-tetrapyrroles. We suggest that (i) after the evolution of red-absorbing Chl-like pigments, the first light-driven electron transport chains reduced ferredoxin via a type-1 reaction center (RC) progenitor with electrons from H2S; (ii) photothioautotrophy, first with one RC and then with two, was the bridge between H2-dependent chemolithoautotrophy and water-splitting photosynthesis; (iii) photothiotrophy sustained primary production in the photic zone of Archean oceans; (iv) photosynthesis arose in an anoxygenic cyanobacterial progenitor; (v) Chl a is the ancestral Chl; and (vi), anoxygenic chlorophototrophic lineages characterized so far acquired, by horizontal gene transfer, RCs and Chl biosynthesis with or without autotrophy, from the architects of chlorophototrophy—the cyanobacterial lineage. PMID:29177446

Structural Evolution of Silicon Oxynitride Fiber Reinforced Boron Nitride Matrix Composite at High Temperatures

NASA Astrophysics Data System (ADS)

Zou, Chunrong; Li, Bin; Zhang, Changrui; Wang, Siqing; Xie, Zhengfang; Shao, Changwei

2016-02-01

The structural evolution of a silicon oxynitride fiber reinforced boron nitride matrix (Si-N-Of/BN) wave-transparent composite at high temperatures was investigated. When heat treated at 1600 °C, the composite retained a favorable bending strength of 55.3 MPa while partially crystallizing to Si2N2O and h-BN from the as-received amorphous structure. The Si-N-O fibers still performed as effective reinforcements despite the presence of small pores due to fiber decomposition. Upon heat treatment at 1800 °C, the Si-N-O fibers already lost their reinforcing function and rough hollow microstructure formed within the fibers because of the accelerated decomposition. Further heating to 2000 °C led to the complete decomposition of the reinforcing fibers and only h-BN particles survived. The crystallization and decomposition behaviors of the composite at high temperatures are discussed.

Ternary Pt/SnO(x)/TiO2 photocatalysts for hydrogen production: consequence of Pt sites for synergy of dual co-catalysts.

PubMed

Gu, Quan; Long, Jinlin; Zhuang, Huaqiang; Zhang, Chaoqiang; Zhou, Yangen; Wang, Xuxu

2014-06-28

A variety of ternary nanoheterostructures composed of Pt nanoparticles (NPs), SnOx species, and anatase TiO2 are designed elaborately to explore the effect of interfacial electron transfer on photocatalytic H2 evolution from a biofuel-water solution. Among numerous factors controlling the H2 evolution, the significance of Pt sites for the H2 evolution is highlighted by tuning the loading procedure of Pt NPs and SnOx species over TiO2. A synergistic enhancement of H2 evolution can be achieved over the Pt/SnOx/TiO2 heterostructures formed by anchoring Pt NPs at atomically-isolated Sn-oxo sites, whereas the Pt/TiO2/SnOx counterparts prepared by grafting single-site Sn-oxo species on Pt/TiO2 show a marked decrease in the rate of H2 evolution. The characterization results clearly reveal that the synergy of Pt NPs and SnOx species originates from the vectorial electron transfer of TiO2 → SnOx → Pt occurring on the former, while the latter results from the competitive electron transfer from TiO2 to SnOx and to Pt NPs.

Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

PubMed

Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

2017-11-16

The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolution of H3N2v viruses in North American swine and humans, 2009-2011

USDA-ARS?s Scientific Manuscript database

Novel H3N2 influenza viruses (H3N2v) containing seven genome segments from swine-lineage triple reassortant H3N2 viruses and a 2009 pandemic H1N1 (H1N1pdm09) matrix protein segment (pM) have been isolated from 12 humans in the United States between August – December 2011. To understand the evolution...

Catalytic activity in lithium-treated core–shell MoO x/MoS 2 nanowires

DOE PAGES

Cummins, Dustin R.; Martinez, Ulises; Kappera, Rajesh; ...

2015-09-22

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoO x/MoS 2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H 2 evolution. The 1D nanowires exhibit significant improvement in H 2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS 2 layersmore » in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).« less

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Liu, Yuanyue; Wu, Jingjie; Hackenberg, Ken P.; Zhang, Jing; Wang, Y. Morris; Yang, Yingchao; Keyshar, Kunttal; Gu, Jing; Ogitsu, Tadashi; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M.; Wood, Brandon C.; Yakobson, Boris I.

2017-09-01

Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm-2 current density at an overpotential of ˜50-60 mV with a loading of 10-55 μg cm-2, surpassing other reported MX2 candidates without any performance-enhancing additives.

Evolution of the hemagglutinin expressed by human influenza A(H1N1)pdm09 and A(H3N2) viruses circulating between 2008-2009 and 2013-2014 in Germany.

PubMed

Wedde, Marianne; Biere, Barbara; Wolff, Thorsten; Schweiger, Brunhilde

2015-10-01

This report describes the evolution of the influenza A(H1N1)pdm09 and A(H3N2) viruses circulating in Germany between 2008-2009 and 2013-2014. The phylogenetic analysis of the hemagglutinin (HA) genes of both subtypes revealed similar evolution of the HA variants that were also seen worldwide with minor exceptions. The analysis showed seven distinct HA clades for A(H1N1)pdm09 and six HA clades for A(H3N2) viruses. Herald strains of both subtypes appeared sporadically since 2008-2009. Regarding A(H1N1)pdm09, herald strains of HA clade 3 and 4 were detected late in the 2009-2010 season. With respect to A(H3N2), we found herald strains of HA clade 3, 4 and 7 between 2009 and 2012. Those herald strains were predominantly seen for minor and not for major HA clades. Generally, amino acid substitutions were most frequently found in the globular domain, including substitutions near the antigenic sites or the receptor binding site. Differences between both influenza A subtypes were seen with respect to the position of the indicated substitutions in the HA. For A(H1N1)pdm09 viruses, we found more substitutions in the stem region than in the antigenic sites. In contrast, in A(H3N2) viruses most changes were identified in the major antigenic sites and five changes of potential glycosylation sites were identified in the head of the HA monomer. Interestingly, we found in seasons with less influenza activity a relatively high increase of substitutions in the head of the HA in both subtypes. This might be explained by the fact that mutations under negative selection are subsequently compensated by secondary mutations to restore important functions e.g. receptor binding properties. A better knowledge of basic evolution strategies of influenza viruses will contribute to the refinement of predictive mathematical models for identifying novel antigenic drift variants. Copyright © 2015 Elsevier GmbH. All rights reserved.

[An overview on swine influenza viruses].

PubMed

Yang, Shuai; Zhu, Wen-Fei; Shu, Yue-Long

2013-05-01

Swine influenza viruses (SIVs) are respiratory pathogens of pigs. They cause both economic bur den in livestock-dependent industries and serious global public health concerns in humans. Because of their dual susceptibility to human and avian influenza viruses, pigs are recognized as intermediate hosts for genetic reassortment and interspecies transmission. Subtypes H1N1, H1N2, and H3N2 circulate in swine populations around the world, with varied origin and genetic characteristics among different continents and regions. In this review, the role of pigs in evolution of influenza A viruses, the genetic evolution of SIVs and interspecies transmission of SIVs are described. Considering the possibility that pigs might produce novel influenza viruses causing more outbreaks and pandemics, routine epidemiological surveillance of influenza viruses in pig populations is highly recommended.

Ni-C-N Nanosheets as Catalyst for Hydrogen Evolution Reaction.

PubMed

Yin, Jie; Fan, Qiaohui; Li, Yuxuan; Cheng, Fangyi; Zhou, Panpan; Xi, Pinxian; Sun, Shouheng

2016-11-09

We report a facile nitrogenation/exfoliation process to prepare hybrid Ni-C-N nanosheets. These nanosheets are <2 nm thin, chemically stable, and metallically conductive. They serve as a robust catalyst for the hydrogen evolution reaction in 0.5 M H 2 SO 4 , or 1.0 M KOH or 1.0 M PBS (pH = 7). For example, they catalyze the hydrogen evolution reaction in 0.5 M H 2 SO 4 at an onset potential of 34.7 mV, an overpotential of 60.9 mV (at j = 10 mA cm -2 ) and with remarkable long-term stability (∼10% current drop after 70 h testing period). They are promising as a non-Pt catalyst for practical hydrogen evolution reaction.

Early evolution of the earth - Accretion, atmosphere formation, and thermal history

NASA Technical Reports Server (NTRS)

Abe, Yutaka; Matsui, Takafumi

1986-01-01

The thermal and atmospheric evolution of the earth growing planetesimal impacts are studied. The generation of an H2O protoatmosphere is examined, and the surface temperatures are estimated. The evolution of an impact-induced H2O atmosphere is analyzed. Consideration is given to the formation time of a 'magma ocean'and internal water budgets. The thermal history of an accreting earth is reviewed. The wet convection and greenhouse effects are discussed, and the role of Fe oxidation on the evolution of an impact-induced H2O atmopshere is described. The relationship between differentiation processes and core segregation, the H2O and FeO content of the mantle, and the origin of the hydrosphere is also examined.

Highly Pathogenic Influenza A(H5Nx) Viruses with Altered H5 Receptor-Binding Specificity

PubMed Central

Guo, Hongbo; de Vries, Erik; McBride, Ryan; Dekkers, Jojanneke; Peng, Wenjie; Bouwman, Kim M.; Nycholat, Corwin; Verheije, M. Helene; Paulson, James C.; van Kuppeveld, Frank J.M.

2017-01-01

Emergence and intercontinental spread of highly pathogenic avian influenza A(H5Nx) virus clade 2.3.4.4 is unprecedented. H5N8 and H5N2 viruses have caused major economic losses in the poultry industry in Europe and North America, and lethal human infections with H5N6 virus have occurred in Asia. Knowledge of the evolution of receptor-binding specificity of these viruses, which might affect host range, is urgently needed. We report that emergence of these viruses is accompanied by a change in receptor-binding specificity. In contrast to ancestral clade 2.3.4 H5 proteins, novel clade 2.3.4.4 H5 proteins bind to fucosylated sialosides because of substitutions K222Q and S227R, which are unique for highly pathogenic influenza virus H5 proteins. North American clade 2.3.4.4 virus isolates have retained only the K222Q substitution but still bind fucosylated sialosides. Altered receptor-binding specificity of virus clade 2.3.4.4 H5 proteins might have contributed to emergence and spread of H5Nx viruses. PMID:27869615

Highly-active oxygen evolution electrocatalyzed by an Fe-doped NiCr2O4 nanoparticle film.

PubMed

Zhao, Jinxiu; Li, Xianghong; Cui, Guanwei; Sun, Xuping

2018-05-11

Alkaline water splitting offers a simple method for the mass production of hydrogen but suffers from the sluggish kinetics of the anodic oxygen evolution reaction (OER). Here, we report on the development of an Fe-doped NiCr2O4 nanoparticle film on Ni foam (Fe-NiCr2O4/NF) as a non-noble-metal OER electrocatalyst with superior catalytic activity at alkaline pH. Such Fe-NiCr2O4/NF demands overpotentials as low as 228 and 318 mV to drive current densities of 20 and 500 mA cm-2, respectively, in 1.0 M KOH. Notably, it also shows strong long-term electrochemical durability with its activity being retained for at least 60 h.

The Role of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces

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

Stoerzinger, Kelsey A.; Rao, Reshma R.; Wang, Xiao Renshaw

Rutile RuO 2 is known to exhibit high catalytic activity for the oxygen evolution reaction (OER) and large pseudocapacitance associated with redox of surface Ru, however the mechanistic link between these properties and the role of pH is yet to be understood. Here we report that the OER activities of the (101), (001) and (111) RuO 2 surfaces were found to increase while the potential of a pseudocapacitive feature just prior to OER shifted to lower potentials (“super-Nernstian” shift) with increasing pH on the reversible hydrogen electrode (RHE) scale. This behavior is in contrast to the (100) and (110) surfacesmore » that have pH-independent Ru redox and OER activity. The link in catalytic and pseudocapacitive behavior illustrates the importance of this redox feature in generating active sites, building new mechanistic understanding of the OER.« less

Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis.

PubMed

Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang; Cai, Jinyan; Wu, Shaoyang; Kang, Jian; Zhou, Jianbin; Chen, Zhiyan; Zheng, Xusheng; Xiao, Xiangheng; Wang, Gongming

2018-04-12

Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo 2 S 4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm -2 and a Tafel slope of 37 mV dec -1 , which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo 2 S 4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.

Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production.

PubMed

Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

2013-01-21

Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu(2)O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO(2) catalyst has enhanced the photocatalytic H(2) production. Comparatively, H(2) treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H(2) production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO(2) catalyst systems due to their low cost and high performance in photocatalytic applications.

General Strategy for the Synthesis of Transition-Metal Phosphide/N-Doped Carbon Frameworks for Hydrogen and Oxygen Evolution.

PubMed

Pu, Zonghua; Zhang, Chengtian; Amiinu, Ibrahim Saana; Li, Wenqiang; Wu, Lin; Mu, Shichun

2017-05-17

Transition metal phosphides (TMPs) have been identified as promising nonprecious metal electrocatalyst for hydrogen evolution reaction (HER) and other energy conversion reactions. Herein, we reported a general strategy for synthesis of a series of TMPs (Fe 2 P, FeP, Co 2 P, CoP, Ni 2 P, and Ni 12 P 5 ) nanoparticles (NPs) with different metal phases embedded in a N-doped carbon (NC) matrix using metal salt, ammonium dihydrogen phosphate, and melamine as precursor with varying molar ratios and thermolysis temperatures. The resultant TMPs can serve as highly active and durable bifunctional electrocatalyst toward HER and oxygen evolution reaction (OER). In particular, the Ni 2 P@NC phase only requires an overpotential of ∼138 mV to derive HER in 0.5 M H 2 SO 4, and ∼320 mV for OER in 1.0 M KOH at the current density of 10 mA cm -2 . Because of the encapsulation of NC that can effectively prevent corrosion of embedded TMP NPs, Ni 2 P@NC exhibits almost unfading catalytic performance even after 10 h under both acidic and alkaline solutions. This synthesis strategy provides a new avenue to exploring TMPs as highly active and stable electrocatalyst for the HER, OER, and other electrochemical applications.

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

Maas, Z. G.; Pilachowski, C. A.; Hinkle, K., E-mail: zmaas@indiana.edu, E-mail: cpilacho@indiana.edu, E-mail: hinkle@noao.edu

Chlorine abundances are reported in 15 evolved giants and 1 M dwarf in the solar neighborhood. The Cl abundance was measured using the vibration-rotation 1-0 P8 line of H{sup 35}Cl at 3.69851 μ m. The high-resolution L -band spectra were observed using the Phoenix infrared spectrometer on the Kitt Peak Mayall 4 m telescope. The average [{sup 35}Cl/Fe] abundance in stars with −0.72 < [Fe/H] < 0.20 is [{sup 35}Cl/Fe] = (−0.10 ± 0.15) dex. The mean difference between the [{sup 35}Cl/Fe] ratios measured in our stars and chemical evolution model values is (0.16 ± 0.15) dex. The [{sup 35}Cl/Ca] ratio has an offset of ∼0.35more » dex above model predictions, suggesting that chemical evolution models are underproducing Cl at the high metallicity range. Abundances of C, N, O, Si, and Ca were also measured in our spectral region and are consistent with F and G dwarfs. The Cl versus O abundances from our sample match Cl abundances measured in planetary nebula and H ii regions. In one star where both H{sup 35}Cl and H{sup 37}Cl could be measured, a {sup 35}Cl/{sup 37}Cl isotope ratio of 2.2 ± 0.4 was found, consistent with values found in the Galactic ISM and predicted chemical evolution models.« less

Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

PubMed

Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

2016-05-04

To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

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

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE PAGES

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

2016-12-09

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Vibrational and rotational sequences in 101Mo and 103,4Ru studied via multinucleon transfer reactions

DOE PAGES

Regan, P. H.; Wheldon, C.; Yamamoto, A. D.; ...

2005-04-01

The near-yrast states of 42 101Mo 59 and 44 103,4Ru 59,60 have been studied following their population via heavy-ion multinucleon transfer reactions between a 136 Xe beam and a thin, self-supporting 100Mo target. The ground state sequence in 104Ru can be understood as demonstrating a simple evolution from a quasi-vibrational structure at lower spins to statically deformed, quasi-rotational excitation involving the population of a pair of low-Ω h 11/2 neutron orbitals. The effect of the decoupled h 11/2 orbital on this vibration-to-rotational evolution is demonstrated by an extension of the "E-GOS" prescription to include odd-A nuclei. The experimental results aremore » also compared with self-consistent Total Routhian Surface calculations which also highlight the polarising role of the highly aligned neutron h 11/2 orbital in these nuclei.« less

Photorespiration and carbon limitation determine productivity in temperate seagrasses.

PubMed

Buapet, Pimchanok; Rasmusson, Lina M; Gullström, Martin; Björk, Mats

2013-01-01

The gross primary productivity of two seagrasses, Zostera marina and Ruppia maritima, and one green macroalga, Ulva intestinalis, was assessed in laboratory and field experiments to determine whether the photorespiratory pathway operates at a substantial level in these macrophytes and to what extent it is enhanced by naturally occurring shifts in dissolved inorganic carbon (DIC) and O2 in dense vegetation. To achieve these conditions in laboratory experiments, seawater was incubated with U. intestinalis in light to obtain a range of higher pH and O2 levels and lower DIC levels. Gross photosynthetic O2 evolution was then measured in this pretreated seawater (pH, 7.8-9.8; high to low DIC:O2 ratio) at both natural and low O2 concentrations (adjusted by N2 bubbling). The presence of photorespiration was indicated by a lower gross O2 evolution rate under natural O2 conditions than when O2 was reduced. In all three macrophytes, gross photosynthetic rates were negatively affected by higher pH and lower DIC. However, while both seagrasses exhibited significant photorespiratory activity at increasing pH values, the macroalga U. intestinalis exhibited no such activity. Rates of seagrass photosynthesis were then assessed in seawater collected from the natural habitats (i.e., shallow bays characterized by high macrophyte cover and by low DIC and high pH during daytime) and compared with open baymouth water conditions (where seawater DIC is in equilibrium with air, normal DIC, and pH). The gross photosynthetic rates of both seagrasses were significantly higher when incubated in the baymouth water, indicating that these grasses can be significantly carbon limited in shallow bays. Photorespiration was also detected in both seagrasses under shallow bay water conditions. Our findings indicate that natural carbon limitations caused by high community photosynthesis can enhance photorespiration and cause a significant decline in seagrass primary production in shallow waters.

Development of a Long-Range Underwater Vehicle

DTIC Science & Technology

2015-09-30

contained lithium primary batteries . Based on reaction energy and reactant mass, oxidation of lithium is a particularly high energy density option. Each...LiOH E ~ 3.45 V Hydrogen evolution in seawater 2Li + 2H2O = 2 LiOH + H2 E ~ 2.60 V PolyPlus Battery Company has developed a lithium -seawater...PolyPlus achieves energy densities near 4.7 MJ/kg, four times that available from the primary lithium batteries used in gliders today. The seawater cells

ZnO-dotted porous ZnS cluster microspheres for high efficient, Pt-free photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Wu, Aiping; Jing, Liqiang; Wang, Jianqiang; Qu, Yang; Xie, Ying; Jiang, Baojiang; Tian, Chungui; Fu, Honggang

2015-03-01

The Pt-free photocatalytic hydrogen evolution (PHE) has been the focus in the photocatalysis field. Here, the ZnO-dotted porous ZnS cluster microsphere (PCMS) is designed for high efficient, Pt-free PHE. The PCMS is designed through an easy ``controlling competitive reaction'' strategy by selecting the thiourea as S2- source and Zn(Ac)2.2H2O as Zn source in ethylene glycol medium. Under suitable conditions, one of the PCMS, named PCMS-1, with high SBET specific area of 194 m2g-1, microsphere size of 100 nm and grain size of 3 nm can be obtained. The formation of PCMS is verified by TEM, XAES, XPS, Raman and IR methods. Importantly, a series of the experiments and theoretical calculation demonstrate that the dotting of ZnO not only makes the photo-generated electrons/hole separate efficiently, but also results in the formation of the active catalytic sites for PHE. As a result, the PCMS-1 shows the promising activity up to 367 μmol h-1 under Pt-free condition. The PHE activity has no obvious change after addition 1 wt.% Pt, implying the presence of active catalytic sites for hydrogen evolution in the PCMS-1. The easy synthesis process, low preparation cost of the PCMS makes their large potential for Pt-free PHE.

[Genetic Diversity and Evolution of the M Gene of Human Influenza A Viruses from 2009 to 2013 in Hangzhou, China].

PubMed

Shao, Tiejuan; Li, Jun; Pu, Xiaoying; Yu, Xinfen; Kou, Yu; Zhou, Yinyan; Qian, Xin

2015-03-01

We investigated the genetic diversity and evolution of the M gene of human influenza A viruses in Hangzhou (Zhejiang province, China) from 2009 to 2013, including subtypes of A(H1N1) pdm09 strains and seasonal A(H3N2) strains. Subtypes of analyzed viruses were identified by cell culture and real-time reverse transcription-polymerase chain reaction, followed by cloning, sequencing and phylogenetic analyses of the M gene. Assessment of 5675 throat swabs revealed a positive rate for the influenza virus of 20.46%, and 827 cases were diagnosed as. infections due to influenza A viruses. Seventy-six influenza-A strains were selected randomly from nine stages during six phases of a virus epidemic. Sequences of the M gene showed high homology among six epidemics with identities of amino-acid sequences of 98.98-100%. All strains contained the adamantine-resistant mutation S31N in its M2 protein. Two of the A(H1N1)pdm09 strains had double mutants of V27A/S31N or V271/S31N. One of the seasonal A(H3N2) viruses had another form of double-mutant R45H/S31N. Evolutionary rate of the M gene was much lower than that of the HA gene and NA gene. Compared with A(H3N2) strains, higher positive pressure on the M1 and M2 proteins of A(H1N1) pdm09 viruses was observed. Separate analyses of M1 and M2 proteins revealed very different selection pressures. Knowledge of the genetic diversity and evolution of the M gene of human influenza-A viruses will be valuable for the control and prevention of diseases.

Sustained Photobiological Hydrogen Gas Production upon Reversible Inactivation of Oxygen Evolution in the Green Alga Chlamydomonas reinhardtii1

PubMed Central

Melis, Anastasios; Zhang, Liping; Forestier, Marc; Ghirardi, Maria L.; Seibert, Michael

2000-01-01

The work describes a novel approach for sustained photobiological production of H2 gas via the reversible hydrogenase pathway in the green alga Chlamydomonas reinhardtii. This single-organism, two-stage H2 production method circumvents the severe O2 sensitivity of the reversible hydrogenase by temporally separating photosynthetic O2 evolution and carbon accumulation (stage 1) from the consumption of cellular metabolites and concomitant H2 production (stage 2). A transition from stage 1 to stage 2 was effected upon S deprivation of the culture, which reversibly inactivated photosystem II (PSII) and O2 evolution. Under these conditions, oxidative respiration by the cells in the light depleted O2 and caused anaerobiosis in the culture, which was necessary and sufficient for the induction of the reversible hydrogenase. Subsequently, sustained cellular H2 gas production was observed in the light but not in the dark. The mechanism of H2 production entailed protein consumption and electron transport from endogenous substrate to the cytochrome b6-f and PSI complexes in the chloroplast thylakoids. Light absorption by PSI was required for H2 evolution, suggesting that photoreduction of ferredoxin is followed by electron donation to the reversible hydrogenase. The latter catalyzes the reduction of protons to molecular H2 in the chloroplast stroma. PMID:10631256

Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

2014-11-01

We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

Ratiometric photoluminescence sensing based on Ti3C2 MXene quantum dots as an intracellular pH sensor.

PubMed

Chen, Xu; Sun, Xueke; Xu, Wen; Pan, Gencai; Zhou, Donglei; Zhu, Jinyang; Wang, He; Bai, Xue; Dong, Biao; Song, Hongwei

2018-01-18

Intracellular pH sensing is of importance and can be used as an indicator for monitoring the evolution of various diseases and the health of cells. Here, we developed a new class of surface-functionalized MXene quantum dots (QDs), Ti 3 C 2 , by the sonication cutting and hydrothermal approach and further explored their intracellular pH sensing. The functionalized Ti 3 C 2 QDs exhibit bright excitation-dependent blue photoluminescence (PL) originating from the size effect and surface defects. Meanwhile, Ti 3 C 2 QDs demonstrate a high PL response induced by the deprotonation of the surface defects. Furthermore, combining the highly pH sensitive Ti 3 C 2 QDs with the pH insensitive [Ru(dpp) 3 ]Cl 2 , we developed a ratiometric pH sensor to quantitatively monitor the intracellular pH values. These novel MXene quantum dots can serve as a promising platform for developing practical fluorescent nanosensors.

Strongly Coupled Molybdenum Carbide on Carbon Sheets as a Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Wang, Hao; Cao, Yingjie; Sun, Cheng; Zou, Guifu; Huang, Jianwen; Kuai, Xiaoxiao; Zhao, Jianqing; Gao, Lijun

2017-09-22

High-performance and affordable electrocatalysts from earth-abundant elements are desirably pursued for water splitting involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, a bifunctional electrocatalyst of highly crystalline Mo 2 C nanoparticles supported on carbon sheets (Mo 2 C/CS) was designed toward overall water splitting. Owing to the highly active catalytic nature of Mo 2 C nanoparticles, the high surface area of carbon sheets and efficient charge transfer in the strongly coupled composite, the designed catalysts show excellent bifunctional behavior with an onset potential of -60 mV for HER and an overpotential of 320 mV to achieve a current density of 10 mA cm -2 for OER in 1 m KOH while maintaining robust stability. Moreover, the electrolysis cell using the catalyst only requires a low cell voltage of 1.73 V to achieve a current density of 10 mA cm -2 and maintains the activity for more than 100 h when employing the Mo 2 C/CS catalyst as both anode and cathode electrodes. Such high performance makes Mo 2 C/CS a promising electrocatalyst for practical hydrogen production from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synergistically enhanced photocatalytic hydrogen evolution performance of ZnCdS by co-loading graphene quantum dots and PdS dual cocatalysts under visible light

NASA Astrophysics Data System (ADS)

Wang, Fang; Su, Yanhong; Min, Shixiong; Li, Yanan; Lei, Yonggang; Hou, Jianhua

2018-04-01

Here, we report that the co-loading of graphene quantum dots (GQDs) and PdS dual cocatalysts on ZnCdS surface achieves a high efficiency photocatalytic H2 evolution under visible light (≥420 nm). The GQDs/ZnCdS/PdS photocatalyst was prepared by a facile two steps: hydrothermal coupling of GQDs on ZnCdS surface followed by an in-situ chemical deposition of PdS. The resulted GQDs/ZnCdS/PdS exhibits a H2 evolution rate of 517 μmol h-1, which is 15, 7, and 1.7 times higher than that of pure ZnCdS, GQDs/ZnCdS, and ZnCdS/PdS, respectively, demonstrating the synergistic effects of GQDs and PdS dual cocatalysts. A high apparent quantum efficiency (AQE) up to 22.4% can be achieved over GQDs/ZnCdS/PdS at 420 nm. GQDs/ZnCdS/PdS also has a relatively good stability. Such a considerable enhancement of photocatalytic activity was attributable to the co-loading of the GQDs and PdS as respective reduction and oxidation cocatalysts, leading to an efficient charge separation and surface reactions.

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimentally infected domestic ducks show efficient transmission of Indonesian H5N1 highly pathogenic avian influenza virus, but lack persistent viral shedding.

PubMed

Wibawa, Hendra; Bingham, John; Nuradji, Harimurti; Lowther, Sue; Payne, Jean; Harper, Jenni; Junaidi, Akhmad; Middleton, Deborah; Meers, Joanne

2014-01-01

Ducks are important maintenance hosts for avian influenza, including H5N1 highly pathogenic avian influenza viruses. A previous study indicated that persistence of H5N1 viruses in ducks after the development of humoral immunity may drive viral evolution following immune selection. As H5N1 HPAI is endemic in Indonesia, this mechanism may be important in understanding H5N1 evolution in that region. To determine the capability of domestic ducks to maintain prolonged shedding of Indonesian clade 2.1 H5N1 virus, two groups of Pekin ducks were inoculated through the eyes, nostrils and oropharynx and viral shedding and transmission investigated. Inoculated ducks (n = 15), which were mostly asymptomatic, shed infectious virus from the oral route from 1 to 8 days post inoculation, and from the cloacal route from 2-8 dpi. Viral ribonucleic acid was detected from 1-15 days post inoculation from the oral route and 1-24 days post inoculation from the cloacal route (cycle threshold <40). Most ducks seroconverted in a range of serological tests by 15 days post inoculation. Virus was efficiently transmitted during acute infection (5 inoculation-infected to all 5 contact ducks). However, no evidence for transmission, as determined by seroconversion and viral shedding, was found between an inoculation-infected group (n = 10) and contact ducks (n = 9) when the two groups only had contact after 10 days post inoculation. Clinical disease was more frequent and more severe in contact-infected (2 of 5) than inoculation-infected ducks (1 of 15). We conclude that Indonesian clade 2.1 H5N1 highly pathogenic avian influenza virus does not persist in individual ducks after acute infection.

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide.

DOE PAGES

Chou, Stanley Shihyao; Sai, Na; Lu, Ping; ...

2015-10-07

Establishing processing–structure–property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T' (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T'more » transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Furthermore, we show basal plane activation of 1T' molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T', comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.« less

Enhancement of photoelectrochemical activity of SnS thin-film photoelectrodes using TiO2, Nb2O5, and Ta2O5 metal oxide layers

NASA Astrophysics Data System (ADS)

Vequizo, Junie Jhon M.; Yokoyama, Masanori; Ichimura, Masaya; Yamakata, Akira

2016-06-01

Tin sulfide (SnS) fine photoelectrodes fabricated by three-step pulsed electrodeposition were active for H2 evolution. The incident-photon-conversion-efficiency increases from 900 nm and offers a good fit with the absorption spectrum. The activity was enhanced by 3.4, 3.0, and 1.8 times compared to bare SnS by loading Nb2O5, TiO2, and Ta2O5, respectively. Nb2O5 was most efficient because its conduction band is low enough to facilitate effective electron transfer from SnS; it also has sufficiently high potential for H2 evolution. The overall activity is determined by the competitive interfacial electron transfer between SnS/metal-oxide and metal-oxide/water. Therefore, constructing appropriate heterojunctions is necessary for further improving photoelectrochemical systems.

Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

PubMed

Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G

2016-11-23

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP 4+ ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P 2 Mo 18 O 62 6- and P 2 W 18 O 62 6- anions, and one Keplerate {Mo 132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP 4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P 2 Mo 18 O 62 6- anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P 2 W 18 O 62 6- anion; and (c) the high nuclearity Keplerate {Mo 132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A very deep IRAS survey - Constraints on the evolution of starburst galaxies

NASA Astrophysics Data System (ADS)

Hacking, Perry; Condon, J. J.; Houck, J. R.

1987-05-01

Counts of sources (primarily starburst galaxies) from a deep 60 microns IRAS survey published by Hacking and Houck (1987) are compared with four evolutionary models. The counts below 100 mJy are higher than expected if no evolution has taken place out to a redshift of approximately 0.2. Redshift measurements of the survey sources should be able to distinguish between luminosity-evolution and density-evolution models and detect as little as a 20 percent brightening or increase in density of infrared sources per billion years ago (H/0/ = 100 km/s per Mpc). Starburst galaxies cannot account for the reported 100 microns background without extreme evolution at high redshifts.

Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

NASA Technical Reports Server (NTRS)

Freund, Friedemann

2001-01-01

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

In situ photodeposition of amorphous CoSx on the TiO2 towards hydrogen evolution

NASA Astrophysics Data System (ADS)

Chen, Feng; Luo, Wei; Mo, Yanping; Yu, Huogen; Cheng, Bei

2018-02-01

Cocatalyst modification of photocatalysts is an important strategy to enhance the photocatalytic performance by promoting effective separation of photoinduced electron-hole pairs and providing abundant active sites. In this study, a facile in situ photodeposition method was developed to prepare amorphous CoSx-modified TiO2 photocatalysts. It was found that amorphous CoSx nanoparticles were solidly loaded on the TiO2 surface, resulting in a greatly improved photocatalytic H2-evolution performance. When the amount of amorphous CoSx was 10 wt%, the hydrogen evolution rate of the CoSx/TiO2 reached 119.7 μmol h-1, which was almost 16.7 times that of the pure TiO2. According to the above experimental results, a reasonable mechanism of improved photocatalytic performance is proposed for the CoSx/TiO2 photocatalysts, namely, the photogenerated electrons of TiO2 can rapidly transfer to amorphous CoSx nanoparticles due to the solid contact between them, and then amorphous CoSx can provide plenty of sulfur active sites to rapidly adsorb protons from solution to produce hydrogen by the photogenerated electrons. Considering the facile synthesis method, the present cheap and highly efficient amorphous CoSx-modified TiO2 photocatalysts would have great potential for practical use in photocatalytic H2 production.

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

Yan Changshuo; Wang Jianmin, E-mail: wangjm@ihep.ac.c

High spatial resolution observations show that high-redshift galaxies are undergoing intensive evolution of dynamical structure and morphologies displayed by the H{alpha}, H{beta}, [O III], and [N II] images. It has been shown that supernova explosion (SNexp) of young massive stars during the star formation epoch, as kinetic feedback to host galaxies, can efficiently excite the turbulent viscosity. We incorporate the feedback into the dynamical equations through mass dropout and angular momentum transportation driven by the SNexp-excited turbulent viscosity. The empirical Kennicutt-Schmidt law is used for star formation rates (SFRs). We numerically solve the equations and show that there can bemore » intensive evolution of structure of the gaseous disk. Secular evolution of the disk shows interesting characteristics: (1) high viscosity excited by SNexp can efficiently transport the gas from 10 kpc to {approx}1 kpc forming a stellar disk whereas a stellar ring forms for the case with low viscosity; (2) starbursts trigger SMBH activity with a lag of {approx}10{sup 8} yr depending on SFRs, prompting the joint evolution of SMBHs and bulges; and (3) the velocity dispersion is as high as {approx}100 km s{sup -1} in the gaseous disk. These results are likely to vary with the initial mass function (IMF) that the SNexp rates rely on. Given the IMF, we use the GALAXEV code to compute the spectral evolution of stellar populations based on the dynamical structure. In order to compare the present models with the observed dynamical structure and images, we use the incident continuum from the simple stellar synthesis and CLOUDY to calculate emission line ratios of H{alpha}, H{beta}, [O III], and [N II], and H{alpha} brightness of gas photoionized by young massive stars formed on the disks. The models can produce the main features of emission from star-forming galaxies. We apply the present model to two galaxies, BX 389 and BX 482 observed in the SINS high-z sample, which are bulge and disk-dominated, respectively. Two successive rings independently evolving are able to reproduce the main dynamical and emission properties of the two galaxies, such as the Baldwin-Phillips-Terlevich diagram, the relation between line ratios, and H{alpha} brightness. The observed relation between turbulent velocity and the H{alpha} brightness can be explained by the present model. High viscosity excited by SNexp is able to efficiently transport the gas into a bulge to maintain high SFRs or to form a stellar ring close enough to the bulge so that it immigrates into the bulge of its host galaxy. This leads to a fast growing bulge. Implications and future work of the present models have been extensively discussed for galaxy formation in high-z universe.« less

Multiple incursions and recurrent epidemic fade-out of H3N2 canine influenza A virus in the United States.

PubMed

Voorhees, Ian E H; Dalziel, Benjamin D; Glaser, Amy; Dubovi, Edward J; Murcia, Pablo R; Newbury, Sandra; Toohey-Kurth, Kathy; Su, Shuo; Kriti, Divya; Van Bakel, Harm; Goodman, Laura B; Leutenegger, Christian; Holmes, Edward C; Parrish, Colin R

2018-06-06

Avian-origin H3N2 canine influenza virus (CIV) transferred to dogs in Asia around 2005, becoming enzootic throughout China and Korea before reaching the USA in early 2015. To understand the post-transfer evolution and epidemiology of this virus, particularly the cause of recent and ongoing increases in incidence in the USA, we performed an integrated analysis of whole-genome sequence data from 64 newly sequenced viruses and comprehensive surveillance data. This reveals that the circulation of H3N2 CIV within the USA is typified by recurrent epidemic burst-fadeout dynamics driven by multiple introductions of virus from Asia. Although all major viral lineages displayed similar rates of genomic sequence evolution, H3N2 CIV consistently exhibited proportionally more non-synonymous substitutions per site compared to avian reservoir viruses, indicative of a large-scale change in selection pressures. Despite these genotypic differences, we found no evidence of adaptive evolution or increased viral transmission, with epidemiological models indicating a basic reproductive number, R 0 , of between 1 and 1.5 across nearly all USA outbreaks, consistent with maintained, but heterogeneous circulation. We propose that CIV's mode of viral circulation may have resulted in evolutionary cul-de-sacs, in which there is little opportunity for the selection of the more transmissible H3N2 CIV phenotypes necessary to enable circulation through a general dog population characterized by widespread contact heterogeneity. CIV must therefore rely on metapopulations of high host density (notably animal shelters) within the greater dog population and reintroduction from other populations or face complete epidemic extinction. IMPORTANCE The relatively recent appearance of influenza A virus (IAV) epidemics in dogs expands our understanding of IAV host-range and ecology, providing useful and relevant models for understanding critical factors involved in viral emergence. Here, we integrate viral whole-genome sequence analysis and comprehensive surveillance data to examine the evolution of the emerging avian-origin H3N2 canine influenza virus (CIV), particularly the factors driving ongoing circulation and recent increase in incidence of the virus within the USA. Our results provide a detailed understanding of how H3N2 CIV achieves sustained circulation within the USA, despite widespread host contact heterogeneity and recurrent epidemic fade-out. Moreover, our findings suggest that the types and intensity of selection pressures an emerging virus experiences are highly dependent on host population structure and ecology, and may inhibit an emerging virus from acquiring sustained epidemic or pandemic circulation. Copyright © 2018 American Society for Microbiology.

Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

PubMed

Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

2015-01-07

Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Kargel, J.S.

2003-01-01

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Krivovichev, Sergey V.; Tananaev, Ivan G.

Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals ofmore » four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.« less

Angular correlation function of 1.5 million luminous red galaxies: clustering evolution and a search for baryon acoustic oscillations

NASA Astrophysics Data System (ADS)

Sawangwit, U.; Shanks, T.; Abdalla, F. B.; Cannon, R. D.; Croom, S. M.; Edge, A. C.; Ross, Nicholas P.; Wake, D. A.

2011-10-01

We present the angular correlation function measured from photometric samples comprising 1562 800 luminous red galaxies (LRGs). Three LRG samples were extracted from the Sloan Digital Sky Survey (SDSS) imaging data, based on colour-cut selections at redshifts, z≈ 0.35, 0.55 and 0.7 as calibrated by the spectroscopic surveys, SDSS-LRG, 2dF-SDSS LRG and QSO (quasi-stellar object) (2SLAQ) and the AAΩ-LRG survey. The galaxy samples cover ≈7600 deg2 of sky, probing a total cosmic volume of ≈5.5 h-3 Gpc3. The small- and intermediate-scale correlation functions generally show significant deviations from a single power-law fit with a well-detected break at ≈1 h-1 Mpc, consistent with the transition scale between the one- and two-halo terms in halo occupation models. For galaxy separations 1-20 h-1 Mpc and at fixed luminosity, we see virtually no evolution of the clustering with redshift and the data are consistent with a simple high peaks biasing model where the comoving LRG space density is constant with z. At fixed z, the LRG clustering amplitude increases with luminosity in accordance with the simple high peaks model, with a typical LRG dark matter halo mass 1013-1014 h-1 M⊙. For r < 1 h-1 Mpc, the evolution is slightly faster and the clustering decreases towards high redshift consistent with a virialized clustering model. However, assuming the halo occupation distribution (HOD) and Λ cold dark matter (ΛCDM) halo merger frameworks, ˜2-3 per cent/Gyr of the LRGs are required to merge in order to explain the small scales clustering evolution, consistent with previous results. At large scales, our result shows good agreement with the SDSS-LRG result of Eisenstein et al. but we find an apparent excess clustering signal beyond the baryon acoustic oscillations (BAO) scale. Angular power spectrum analyses of similar LRG samples also detect a similar apparent large-scale clustering excess but more data are required to check for this feature in independent galaxy data sets. Certainly, if the ΛCDM model were correct then we would have to conclude that this excess was caused by systematics at the level of Δw≈ 0.001-0.0015 in the photometric AAΩ-LRG sample.

Decoupling the NLO-coupled QED⊗QCD, DGLAP evolution equations, using Laplace transform method

NASA Astrophysics Data System (ADS)

Mottaghizadeh, Marzieh; Eslami, Parvin; Taghavi-Shahri, Fatemeh

2017-05-01

We analytically solved the QED⊗QCD-coupled DGLAP evolution equations at leading order (LO) quantum electrodynamics (QED) and next-to-leading order (NLO) quantum chromodynamics (QCD) approximations, using the Laplace transform method and then computed the proton structure function in terms of the unpolarized parton distribution functions. Our analytical solutions for parton densities are in good agreement with those from CT14QED (1.2952 < Q2 < 1010) (Ref. 6) global parametrizations and APFEL (A PDF Evolution Library) (2 < Q2 < 108) (Ref. 4). We also compared the proton structure function, F2p(x,Q2), with the experimental data released by the ZEUS and H1 collaborations at HERA. There is a nice agreement between them in the range of low and high x and Q2.

2.1 Natural History of Highly Pathogenic Avian Influenza H5N1

PubMed Central

Sonnberg, Stephanie; Webby, Richard J.; Webster, Robert G.

2013-01-01

The ecology of highly pathogenic avian influenza (HPAI) H5N1 has significantly changed from sporadic outbreaks in terrestrial poultry to persistent circulation in terrestrial and aquatic poultry and potentially in wild waterfowl. A novel genotype of HPAI H5N1 arose in 1996 in southern China and through ongoing mutation, reassortment, and natural selection, has diverged into distinct lineages and expanded into multiple reservoir hosts. The evolution of Goose/Guangdong-lineage highly pathogenic H5N1 viruses is ongoing: while stable interactions exist with some reservoir hosts, these viruses are continuing to evolve and adapt to others, and pose an un-calculable risk to sporadic hosts, including humans. PMID:23735535

Photochemical Water Splitting by Bismuth Chalcogenide Topological Insulators.

PubMed

Rajamathi, Catherine R; Gupta, Uttam; Pal, Koushik; Kumar, Nitesh; Yang, Hao; Sun, Yan; Shekhar, Chandra; Yan, Binghai; Parkin, Stuart; Waghmare, Umesh V; Felser, Claudia; Rao, C N R

2017-09-06

As one of the major areas of interest in catalysis revolves around 2D materials based on molybdenum sulfide, we have examined the catalytic properties of bismuth selenides and tellurides, which are among the first chalcogenides to be proven as topological insulators (TIs). We find significant photochemical H 2 evolution activity with these TIs as catalysts. H 2 evolution increases drastically in nanosheets of Bi 2 Te 3 compared to single crystals. First-principles calculations show that due to the topology, surface states participate and promote the hydrogen evolution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

DOE PAGES

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan; ...

2016-11-10

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

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

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

Ta2O5 nanowires: a novel synthetic method and their solar energy utilization.

PubMed

Lü, Xujie; Ding, Shangjun; Lin, Tianquan; Mou, Xinliang; Hong, Zhanglian; Huang, Fuqiang

2012-01-14

Single-crystalline uniform Ta(2)O(5) nanowires are prepared by a novel synthetic route. The formation of the nanowires involves an oriented attachment process caused by the reduction of surface energy. The nanowires are successfully applied to photocatalytic H(2) evolution, contaminant degradation, and dye-sensitized solar cells (DSCs). The Ta(2)O(5)-based DSCs reveal a significant photovoltaic response, which has not been reported. As a photocatalyst, the Ta(2)O(5) nanowires possess high H(2) evolution efficiency under Xe lamp irradiation, nearly 27-fold higher than the commercial powders. A better performance of photocatalytic contaminant degradation is also observed. Such improvements are ascribed to better charge transport ability for the single-crystalline wire and a higher potential energy of the conduction band. This new synthetic approach using a water-soluble precursor provides a versatile way to prepare nanostructured metal oxides.

The effects of a deleterious mutation load on patterns of influenza A/H3N2's antigenic evolution in humans

PubMed Central

Koelle, Katia; Rasmussen, David A

2015-01-01

Recent phylogenetic analyses indicate that RNA virus populations carry a significant deleterious mutation load. This mutation load has the potential to shape patterns of adaptive evolution via genetic linkage to beneficial mutations. Here, we examine the effect of deleterious mutations on patterns of influenza A subtype H3N2's antigenic evolution in humans. By first analyzing simple models of influenza that incorporate a mutation load, we show that deleterious mutations, as expected, act to slow the virus's rate of antigenic evolution, while making it more punctuated in nature. These models further predict three distinct molecular pathways by which antigenic cluster transitions occur, and we find phylogenetic patterns consistent with each of these pathways in influenza virus sequences. Simulations of a more complex phylodynamic model further indicate that antigenic mutations act in concert with deleterious mutations to reproduce influenza's spindly hemagglutinin phylogeny, co-circulation of antigenic variants, and high annual attack rates. DOI: http://dx.doi.org/10.7554/eLife.07361.001 PMID:26371556

Vectorial electron transfer for improved hydrogen evolution by mercaptopropionic-acid-regulated CdSe quantum-dots-TiO2 -Ni(OH)2 assembly.

PubMed

Yu, Shan; Li, Zhi-Jun; Fan, Xiang-Bing; Li, Jia-Xin; Zhan, Fei; Li, Xu-Bing; Tao, Ye; Tung, Chen-Ho; Wu, Li-Zhu

2015-02-01

A visible-light-induced hydrogen evolution system based on a CdSe quantum dots (QDs)-TiO2 -Ni(OH)2 ternary assembly has been constructed under an ambient environment, and a bifunctional molecular linker, mercaptopropionic acid, is used to facilitate the interaction between CdSe QDs and TiO2 . This hydrogen evolution system works effectively in a basic aqueous solution (pH 11.0) to achieve a hydrogen evolution rate of 10.1 mmol g(-1)  h(-1) for the assembly and a turnover frequency of 5140 h(-1) with respect to CdSe QDs (10 h); the latter is comparable with the highest value reported for QD systems in an acidic environment. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and control experiments demonstrate that Ni(OH)2 is an efficient hydrogen evolution catalyst. In addition, inductively coupled plasma optical emission spectroscopy and the emission decay of the assembly combined with the hydrogen evolution experiments show that TiO2 functions mainly as the electron mediator; the vectorial electron transfer from CdSe QDs to TiO2 and then from TiO2 to Ni(OH)2 enhances the efficiency for hydrogen evolution. The assembly comprises light antenna CdSe QDs, electron mediator TiO2 , and catalytic Ni(OH)2 , which mimics the strategy of photosynthesis exploited in nature and takes us a step further towards artificial photosynthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrite-Induced Hydrogen Peroxide Formation as a Driving Force in the Evolution of Photosynthetic Organisms on an Early Earth

NASA Astrophysics Data System (ADS)

Borda, Michael J.; Elsetinow, Alicia R.; Schoonen, Martin A.; Strongin, Daniel R.

2001-09-01

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2018-03-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (Δ F/ F' m ), photosynthetic efficiency ( α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCOˉ 3 via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae)

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2017-06-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (ΔF/F' m ), photosynthetic efficiency (α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCO3 - via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P(001) surface: the importance of ensemble effect.

PubMed

Liu, Ping; Rodriguez, José A

2005-10-26

Density functional theory (DFT) was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H(+) + 2e(-) --> H(2)). The kinetics of the HER was studied on the [NiFe] hydrogenase, the [Ni(PS3*)(CO)](1)(-) and [Ni(PNP)(2)](2+) complexes, and surfaces such as Ni(111), Pt(111), or Ni(2)P(001). Our results show that the [NiFe] hydrogenase exhibits the highest activity toward the HER, followed by [Ni(PNP)(2)](2+) > Ni(2)P > [Ni(PS3*)(CO)](1)(-) > Pt > Ni in a decreasing sequence. The slow kinetics of the HER on the surfaces is due to the fact that the metal hollow sites bond hydrogen too strongly to allow the facile removal of H(2). In fact, the strong H-Ni interaction on Ni(2)P(001) can lead to poisoning of the highly active sites of the surface, which enhances the rate of the HER and makes it comparable to that of the [NiFe] hydrogenase. In contrast, the promotional effect of H-poisoning on the HER on Pt and Ni surfaces is relatively small. Our calculations suggest that among all of the systems investigated, Ni(2)P should be the best practical catalyst for the HER, combining the high thermostability of the surfaces and high catalytic activity of the [NiFe] hydrogenase. The good behavior of Ni(2)P(001) toward the HER is found to be associated with an ensemble effect, where the number of active Ni sites is decreased due to presence of P, which leads to moderate bonding of the intermediates and products with the surface. In addition, the P sites are not simple spectators and directly participate in the HER.

H2 evolution at Si-based metal-insulator-semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover.

PubMed

Esposito, Daniel V; Levin, Igor; Moffat, Thomas P; Talin, A Alec

2013-06-01

Photoelectrochemical (PEC) water splitting represents a promising route for renewable production of hydrogen, but trade-offs between photoelectrode stability and efficiency have greatly limited the performance of PEC devices. In this work, we employ a metal-insulator-semiconductor (MIS) photoelectrode architecture that allows for stable and efficient water splitting using narrow bandgap semiconductors. Substantial improvement in the performance of Si-based MIS photocathodes is demonstrated through a combination of a high-quality thermal SiO2 layer and the use of bilayer metal catalysts. Scanning probe techniques were used to simultaneously map the photovoltaic and catalytic properties of the MIS surface and reveal the spillover-assisted evolution of hydrogen off the SiO2 surface and lateral photovoltage driven minority carrier transport over distances that can exceed 2 cm. The latter finding is explained by the photo- and electrolyte-induced formation of an inversion channel immediately beneath the SiO2/Si interface. These findings have important implications for further development of MIS photoelectrodes and offer the possibility of highly efficient PEC water splitting.

Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

NASA Astrophysics Data System (ADS)

Wu, Tianli; Pi, Mingyu; Wang, Xiaodeng; Guo, Weimeng; Zhang, Dingke; Chen, Shijian

2018-01-01

Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of -69 mV and -118 mV with a small Tafel slope of 51 mV dec-1 to obtain current densities of 10 mA cm-2 and 50 mA cm-2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.

Very deep IRAS survey - constraints on the evolution of starburst galaxies

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

Hacking, P.; Houck, J.R.; Condon, J.J.

1987-05-01

Counts of sources (primarily starburst galaxies) from a deep 60 microns IRAS survey published by Hacking and Houck (1987) are compared with four evolutionary models. The counts below 100 mJy are higher than expected if no evolution has taken place out to a redshift of approximately 0.2. Redshift measurements of the survey sources should be able to distinguish between luminosity-evolution and density-evolution models and detect as little as a 20 percent brightening or increase in density of infrared sources per billion years ago (H/0/ = 100 km/s per Mpc). Starburst galaxies cannot account for the reported 100 microns background withoutmore » extreme evolution at high redshifts. 21 references.« less

Low Masses and High Redshifts: The Evolution of the Mass-Metallicity Relation

NASA Technical Reports Server (NTRS)

Henry, Alaina; Scarlata, Claudia; Dominguez, Alberto; Malkan, Matthew; Martin, Crystal L.; Siana, Brian; Atek, Hakim; Bedregal, Alejandro G.; Colbert, James W.; Rafelski, Marc;

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand.

PubMed

Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D; Lowry, Gregory V

2017-01-15

The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW=12K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7×10 -4 Lhr -1 m -2 ) and hydrogen evolution rate constant (1.4 nanomolLhr -1 m -2 ) were independent of nZVI concentration above 10g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H 2 evolution was explained by differences in pH and E h at each nZVI mass loading; PCE reactivity increased when solution E h decreased, and the H 2 evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime. Copyright © 2016 Elsevier B.V. All rights reserved.

Isolation Of PS II Nanoparticles And Oxygen Evolution Studies In Synechococcus Spp. PCC 7942 Under Heavy Metal Stress

NASA Astrophysics Data System (ADS)

Ahmad, Iffat Zareen; Sundaram, Shanthy; Tripathi, Ashutosh; Soumya, K. K.

2009-06-01

The effect of heavy metals was seen on the oxygen evolution pattern of a unicellular, non-heterocystous cyanobacterial strain of Synechococcus spp. PCC 7942. It was grown in a BG-11 medium supplemented with heavy metals, namely, nickel, copper, cadmium and mercury. Final concentrations of the heavy metal solution used in the culture were 0.1, 0.4 and 1 μM. All the experiments were performed in the exponential phase of the culture. Oxygen-evolving photosystem II (PS II) particles were purified from Synechococcus spp. PCC 7942 by a single-step Ni2+-affinity column chromatography after solubilization of thylakoid membranes with sucrose monolaurate. Oxygen evolution was measured with Clark type oxygen electrode fitted with a circulating water jacket. The light on the surface of the vessel was 10 w/m2. The cultures were incubated in light for 15 minutes prior to the measurement of oxygen evolution. Oxygen evolution was measured in assay mixture containing phosphate buffer (pH-7.5, 0.1 M) in the presence of potassium ferricyanide as the electron acceptor. The preparation from the control showed a high oxygen-evolving activity of 2, 300-2, 500 pmol O2 (mg Chl)-1 h-1 while the activity was decreased in the cultures grown with heavy metals. The inhibition of oxygen evolution shown by the organism in the presence of different metals was in the order Hg>Ni>Cd>Cu. Such heavy metal resistant strains will find application in the construction of PS II- based biosensors for the monitoring of pollutants.

A close-up view on ITS2 evolution and speciation - a case study in the Ulvophyceae (Chlorophyta, Viridiplantae)

PubMed Central

2011-01-01

Background The second Internal Transcriber Spacer (ITS2) is a fast evolving part of the nuclear-encoded rRNA operon located between the 5.8S and 28S rRNA genes. Based on crossing experiments it has been proposed that even a single Compensatory Base Change (CBC) in helices 2 and 3 of the ITS2 indicates sexual incompatibility and thus separates biological species. Taxa without any CBC in these ITS2 regions were designated as a 'CBC clade'. However, in depth comparative analyses of ITS2 secondary structures, ITS2 phylogeny, the origin of CBCs, and their relationship to biological species have rarely been performed. To gain 'close-up' insights into ITS2 evolution, (1) 86 sequences of ITS2 including secondary structures have been investigated in the green algal order Ulvales (Chlorophyta, Viridiplantae), (2) after recording all existing substitutions, CBCs and hemi-CBCs (hCBCs) were mapped upon the ITS2 phylogeny, rather than merely comparing ITS2 characters among pairs of taxa, and (3) the relation between CBCs, hCBCs, CBC clades, and the taxonomic level of organisms was investigated in detail. Results High sequence and length conservation allowed the generation of an ITS2 consensus secondary structure, and introduction of a novel numbering system of ITS2 nucleotides and base pairs. Alignments and analyses were based on this structural information, leading to the following results: (1) in the Ulvales, the presence of a CBC is not linked to any particular taxonomic level, (2) most CBC 'clades' sensu Coleman are paraphyletic, and should rather be termed CBC grades. (3) the phenetic approach of pairwise comparison of sequences can be misleading, and thus, CBCs/hCBCs must be investigated in their evolutionary context, including homoplasy events (4) CBCs and hCBCs in ITS2 helices evolved independently, and we found no evidence for a CBC that originated via a two-fold hCBC substitution. Conclusions Our case study revealed several discrepancies between ITS2 evolution in the Ulvales and generally accepted assumptions underlying ITS2 evolution as e.g. the CBC clade concept. Therefore, we developed a suite of methods providing a critical 'close-up' view into ITS2 evolution by directly tracing the evolutionary history of individual positions, and we caution against a non-critical use of the ITS2 CBC clade concept for species delimitation. PMID:21933414

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE PAGES

Alfonso, Dominic R.; Kauffman, Douglas R.

2017-08-14

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

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

Alfonso, Dominic R.; Kauffman, Douglas R.

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Is a Higgs vacuum instability fatal for high-scale inflation?

DOE PAGES

Kearney, John; Yoo, Hojin; Zurek, Kathryn M.

2015-06-25

We study the inflationary evolution of a scalar field h with an unstable potential for the case where the Hubble parameter H during inflation is larger than the instability scale Λ I of the potential. Quantum fluctuations in the field of size δh ~ H/2π imply that the unstable part of the potential is sampled during inflation. We investigate the evolution of these fluctuations to the unstable regime and in particular whether they generate cosmological defects or even terminate inflation. We apply the results of a toy scalar model to the case of the Standard Model (SM) Higgs boson, themore » quartic of which evolves to negative values at high scales, and extend previous analyses of Higgs dynamics during inflation utilizing statistical methods to a perturbative and fully gauge-invariant formulation. We show that the dynamics are controlled by the renormalization group-improved quartic coupling λ(μ) evaluated at a scale μ = H, such that Higgs fluctuations are enhanced by the instability if H > Λ I. Even if H > Λ I, the instability in the Standard Model Higgs potential does not end inflation; instead the universe slowly sloughs off crunching patches of space that never come to dominate the evolution. As inflation proceeds past 50 e-folds, a significant proportion of patches exits inflation in the unstable vacuum, and as much as 1% of the spacetime can rapidly evolve to a defect. Depending on the nature of these defects, however, the resulting universe could still be compatible with ours.« less

Constraining the evolution of the Hubble Parameter using cosmic chronometers

NASA Astrophysics Data System (ADS)

Dickinson, Hugh

2017-08-01

Substantial investment is being made in space- and ground-based missions with the goal of revealing the nature of the observed cosmic acceleration. This is one of the most important unsolved problems in cosmology today.We propose here to constrain the evolution of the Hubble parameter [H(z)] between 1.3 < z < 2, using the cosmic chronometer method, based on differential age measurements for passively evolving galaxies. Existing WFC3-IR G102 and G141 grisms data obtained by the WISP, 3D-HST+AGHAST, FIGS, and CLEAR surveys will yield a sample of 140 suitable standard clocks, expanding existing samples by a factor of five. These additional data will enable us to improve existing constraints on the evolution of H at high redshift, and insodoing to better understand the fundamental nature of dark energy.

Characterization of H2 photoproduction by marine green alga Tetraselmis subcordiformis integrated with an alkaline fuel cell.

PubMed

Guo, Zhen; Li, Ying; Guo, Haiyan

2016-03-01

To investigate the feasibility of coupling carbonyl cyanide m-chlorophenylhydrazone-regulated photohydrogen production by Tetraselmis subcordiformis in a photobioreactor to an alkaline fuel cell (AFC). H2 evolution kinetics in the AFC integrated process was characterized. The duration of H2 evolution was prolonged and its yield was improved about 1.5-fold (to 78 ± 5 ml l(-1)) compared with that of the process without AFC. Improved H2 yield was possibly caused by removal of H2 feedback inhibition by H2 consumption in situ. Decreases in the H2 production rate correlated with the gradual deactivation of PSII and hydrogenase activities. The H2 yield was closely associated with catabolism of starch and protein. A marine green algal CO2-supplemented culture integrated with in situ H2-consumption by an AFC system was developed as a viable protocol for the H2 production.

High-performance for hydrogen evolution and pollutant degradation of reduced graphene oxide/two-phase g-C3N4 heterojunction photocatalysts.

PubMed

Song, Chengjie; Fan, Mingshan; Shi, Weidong; Wang, Wei

2018-05-01

We have successfully synthesized the composites of two-phase g-C 3 N 4 heterojunction photocatalysts by one-step method. And the reduced graphene oxide/two-phase g-C 3 N 4 heterojunction photocatalyst was fabricated via a facile hydrothermal reduction method. The characterization results indicated that the two-phase g-C 3 N 4 was integrated closely, and the common phenomenon of agglomeration for g-C 3 N 4 was significantly reduced. Moreover, the oxidized graphene was reduced successfully in the composites and the graphene was overlaid on the surface or the interlayers of g-C 3 N 4 heterojunction composite uniformly. In addition, we have carried out the photocatalytic activity experiments by H 2 evolution and rhodamine B removal, tetracycline removal under the visible light irradiation. The results revealed that the composite has improved the separation efficiency a lot than the pure photocatalyst. The photocurrent test demonstrated that the recombination of electrons and holes were efficiently inhibited as well as enhanced the photocatalytic activity. The 0.4% rGO loaded samples, 0.4% rGOCN2, own the best performance. Its rate of H 2 evolution was 15 times as high as that of the pure g-C 3 N 4 .

Hydrogen production by a thermophilic blue-green alga Mastigocladus laminosus

NASA Astrophysics Data System (ADS)

Miura, Y.; Yokoyama, H.; Miyamoto, K.; Okazaki, M.; Komemushi, S.

Light-driven hydrogen evolution by a thermophilic blue-green alga, Mastigocladus laminosus, was demonstrated and characterized under nitrogen-starved conditions. Air-grown cultures of this alga evolved hydrogen under Ar/CO2 at rates up to 2.2 ml/mg chl/hr. The optimum temperature and pH for the hydrogen evolution were 44-49 C and pH 7.0-7.5, respectively. Evolution in light was depressed by N2 gas and inhibited by salicylaldoxime or 2,4-dinitrophenol, indicating that nitrogenase was mainly responsible for the hydrogen evolution. The evolution rate was improved by adding carbon monoxide and acetylene to the gas phase of Ar/CO2. In addition, photobiological production of hydrogen (biophotolysis) by various blue-green algae is briefly reviewed and discussed.

Evolution of the Active Phase of CoMo/Al2O3 Catalysts under Industrial Conditions: a High-Pressure MES Study

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

Dugulan, A.I.; Overweg, A.R.; Craje, M.W.J.

2005-04-26

The behavior of CoMo/Al2O3 catalysts sulfided in H2S/H2 gas mixture, under industrial conditions, was investigated using Moessbauer emission spectroscopy (MES). An intermediate Co-Mo phase is formed after increasing the sulfidation pressure to 4 MPa, favoring the Co-Mo-S phase formation. An increase in the quadrupole splitting value of the Co-sulfide species after treatment at 573 K is proposed as a prerequisite for the formation of ideal Co-Mo-S structures.

Microstructural Evolution of Ni-Sn Transient Liquid Phase Sintering Bond during High-Temperature Aging

NASA Astrophysics Data System (ADS)

Feng, Hongliang; Huang, Jihua; Peng, Xianwen; Lv, Zhiwei; Wang, Yue; Yang, Jian; Chen, Shuhai; Zhao, Xingke

2018-05-01

For high-temperature-resistant packaging of new generation power chip, a chip packaging simulation structure of Ni/Ni-Sn/Ni was bonded by a transient liquid-phase sintering process. High-temperature aging experiments were carried out to investigate joint heat stability. The microstructural evolution and mechanism during aging, and mechanical properties after aging were analyzed. The results show that the 30Ni-70Sn bonding layer as-bonded at 340°C for 240 min is mainly composed of Ni3Sn4 and residual Ni particles. When aged at 350°C, because of the difficulty of nucleation for Ni3Sn and quite slow growth of Ni3Sn2, the bonding layer is stable and the strength of that doesn't change obviously with aging time. When aging temperature increased to 500°C, however, the residual Ni particles were gradually dissolved and the bonding layer formed a stable structure with dominated Ni3Sn2 after 36 h. Meanwhile, due to the volume shrinkage (4.43%) from Ni3Sn2 formation, a number of voids were formed. The shear strength shows an increase, resulting from Ni3Sn2 formation, but then it decreases slightly caused by voids. After aging at 500°C for 100 h, shear strength is still maintained at 29.6 MPa. In addition, the mechanism of void formation was analyzed and microstructural evolution model was also established.

The SILCC (SImulating the LifeCycle of molecular Clouds) project - I. Chemical evolution of the supernova-driven ISM

NASA Astrophysics Data System (ADS)

Walch, S.; Girichidis, P.; Naab, T.; Gatto, A.; Glover, S. C. O.; Wünsch, R.; Klessen, R. S.; Clark, P. C.; Peters, T.; Derigs, D.; Baczynski, C.

2015-11-01

The SILCC (SImulating the Life-Cycle of molecular Clouds) project aims to self-consistently understand the small-scale structure of the interstellar medium (ISM) and its link to galaxy evolution. We simulate the evolution of the multiphase ISM in a (500 pc)2 × ±5 kpc region of a galactic disc, with a gas surface density of Σ _{_GAS} = 10 M_{⊙} pc^{-2}. The FLASH 4 simulations include an external potential, self-gravity, magnetic fields, heating and radiative cooling, time-dependent chemistry of H2 and CO considering (self-) shielding, and supernova (SN) feedback but omit shear due to galactic rotation. We explore SN explosions at different rates in high-density regions (peak), in random locations with a Gaussian distribution in the vertical direction (random), in a combination of both (mixed), or clustered in space and time (clus/clus2). Only models with self-gravity and a significant fraction of SNe that explode in low-density gas are in agreement with observations. Without self-gravity and in models with peak driving the formation of H2 is strongly suppressed. For decreasing SN rates, the H2 mass fraction increases significantly from <10 per cent for high SN rates, i.e. 0.5 dex above Kennicutt-Schmidt, to 70-85 per cent for low SN rates, i.e. 0.5 dex below KS. For an intermediate SN rate, clustered driving results in slightly more H2 than random driving due to the more coherent compression of the gas in larger bubbles. Magnetic fields have little impact on the final disc structure but affect the dense gas (n ≳ 10 cm-3) and delay H2 formation. Most of the volume is filled with hot gas (˜80 per cent within ±150 pc). For all but peak driving a vertically expanding warm component of atomic hydrogen indicates a fountain flow. We highlight that individual chemical species populate different ISM phases and cannot be accurately modelled with temperature-/density-based phase cut-offs.

Evolution of highly pathogenic avian H5N1 influenza viruses

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

Macken, Catherine A; Green, Margaret A

2009-01-01

Highly pathogenic avian H5N1 viruses have circulated in Southeast Asia for more than a decade, are now endemic in parts of this region, and have also spread to more than 60 countries on three continents. The evolution of these viruses is characterized by frequent reassortment events that have created a significant number of different genotypes, both transient and longer lasting. However, fundamental questions remain about the generation and perpetuation of this substantial genetic diversity. These gaps in understanding may, in part, be due to the difficulties of genotyping closely related viruses, and limitations in the size of the data setsmore » used in analysis. Using our recently published novel genotyping procedure ('two-time test'), which is amenable to high throughput analysis and provides an increased level of resolution relative to previous analyses, we propose a detailed model for the evolution and diversification of avian H5N1 viruses. Our analysis suggests that (i) all current H5N1 genotypes are derived from a single, clearly defined sequence of initial reassortment events; (ii) reassortment of the polymerase and NP genes may have played an important role in avian H5N1 virus evolution; (iii) the current genotype Z viruses have diverged into three distinguishable sub-genotypes in the absence of reassortment; (iv) some potentially significant molecular changes appear to be correlated with particular genotypes (for example, reassortment of the internal genes is often paralleled by a change in the HA clade); and (v) as noted in earlier studies of avian influenza A virus evolution, novel segments are typically derived from different donors (i.e., there is no obvious pattern of gene linkage in reassortment). The model of avian H5N1 viral evolution by reassortment and mutation that emerges from our study provides a context within which significant amino acid changes may be revealed; it also may help in predicting the 'success' of newly emerging avian H5N1 viruses.« less

Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

NASA Astrophysics Data System (ADS)

Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

2018-05-01

Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

Simutaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO2, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere - Part 2: Stratospheric ozone

NASA Astrophysics Data System (ADS)

Wang, D.; Jia, W.; Olsen, S. C.; Wuebbles, D. J.; Dubey, M. K.; Rockett, A. A.

2013-07-01

The prospective future adoption of molecular hydrogen (H2) to power the road transportation sector could greatly improve tropospheric air quality but also raises the question of whether the adoption would have adverse effects on the stratospheric ozone. The possibility of undesirable impacts must be fully evaluated to guide future policy decisions. Here we evaluate the possible impact of a future (2050) H2-based road transportation sector on stratospheric composition and chemistry, especially on the stratospheric ozone, with the MOZART (Model for OZone And Related chemical Tracers) model. Since future growth is highly uncertain, we evaluate the impact of two world evolution scenarios, one based on an IPCC (Intergovernmental Panel on Climate Change) high-emitting scenario (A1FI) and the other on an IPCC low-emitting scenario (B1), as well as two technological options: H2 fuel cells and H2 internal combustion engines. We assume a H2 leakage rate of 2.5% and a complete market penetration of H2 vehicles in 2050. The model simulations show that a H2-based road transportation sector would reduce stratospheric ozone concentrations as a result of perturbed catalytic ozone destruction cycles. The magnitude of the impact depends on which growth scenario evolves and which H2 technology option is applied. For the evolution growth scenario, stratospheric ozone decreases more in the H2 fuel cell scenarios than in the H2 internal combustion engine scenarios because of the NOx emissions in the latter case. If the same technological option is applied, the impact is larger in the A1FI emission scenario. The largest impact, a 0.54% decrease in annual average global mean stratospheric column ozone, is found with a H2 fuel cell type road transportation sector in the A1FI scenario; whereas the smallest impact, a 0.04% increase in stratospheric ozone, is found with applications of H2 internal combustion engine vehicles in the B1 scenario. The impacts of the other two scenarios fall between the above two boundary scenarios. However, the magnitude of these changes is much smaller than the increases in 2050 stratospheric ozone projected, as stratospheric ozone is expected to recover due to the limits in ozone depleting substance emissions imposed in the Montreal Protocol.

Enhanced electrocatalytic activity of MoS(x) on TCNQ-treated electrode for hydrogen evolution reaction.

PubMed

Chang, Yung-Huang; Nikam, Revannath D; Lin, Cheng-Te; Huang, Jing-Kai; Tseng, Chien-Chih; Hsu, Chang-Lung; Cheng, Chia-Chin; Su, Ching-Yuan; Li, Lain-Jong; Chua, Daniel H C

2014-10-22

Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo(5+) and S2(2-) species in the MoSx, especially with S2(2-) serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g(-1) cm(-2) h(-1) (286 mmol g(-1) cm(-2) h(-1)) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

Potassium ions intercalated into g-C3N4-modified TiO2 nanobelts for the enhancement of photocatalytic hydrogen evolution activity under visible-light irradiation

NASA Astrophysics Data System (ADS)

Ma, Jian; Zhou, Wei; Tan, Xin; Yu, Tao

2018-05-01

Solar-to-chemical energy conversion is a challenging photochemical reaction for renewable energy storage. In recent decades, photocatalytic H2 evolution has been studied extensively. TiO2 is a well-established semiconductor in the field of photocatalytic H2 production; however, its low efficiency for solar energy utilization, and high photocarrier recombination rate, restrict its photocatalytic efficiency. Here, a series of K-intercalated g-C3N4-modified TiO2 nanobelts (TCN–Kx) with different dosages of K atoms were fabricated using a hydrothermal method followed by a calcination process. XRD, TEM and XPS tests indicate that a tight interfacial connection is formed between K–g-C3N4 and the TiO2 nanobelts. DFT calculations indicated that K dopants prefer to be at the interlayer sites of g-C3N4, suggesting increased charge transfer efficiency. The H2 production efficiency of the TCN–Kx composite materials from water splitting under visible-light irradiation was clearly improved. Steady fluorescence spectroscopy and photocurrent measurements confirmed that the improvement in photocatalytic H2 production activity was due to the superior charge separation and electron transfer efficiency of TCN–Kx composite materials.

Potassium ions intercalated into g-C3N4-modified TiO2 nanobelts for the enhancement of photocatalytic hydrogen evolution activity under visible-light irradiation.

PubMed

Ma, Jian; Zhou, Wei; Tan, Xin; Yu, Tao

2018-05-25

Solar-to-chemical energy conversion is a challenging photochemical reaction for renewable energy storage. In recent decades, photocatalytic H 2 evolution has been studied extensively. TiO 2 is a well-established semiconductor in the field of photocatalytic H 2 production; however, its low efficiency for solar energy utilization, and high photocarrier recombination rate, restrict its photocatalytic efficiency. Here, a series of K-intercalated g-C 3 N 4 -modified TiO 2 nanobelts (TCN-Kx) with different dosages of K atoms were fabricated using a hydrothermal method followed by a calcination process. XRD, TEM and XPS tests indicate that a tight interfacial connection is formed between K-g-C 3 N 4 and the TiO 2 nanobelts. DFT calculations indicated that K dopants prefer to be at the interlayer sites of g-C 3 N 4 , suggesting increased charge transfer efficiency. The H 2 production efficiency of the TCN-Kx composite materials from water splitting under visible-light irradiation was clearly improved. Steady fluorescence spectroscopy and photocurrent measurements confirmed that the improvement in photocatalytic H 2 production activity was due to the superior charge separation and electron transfer efficiency of TCN-Kx composite materials.

High resolution spectroscopy of the disk chromosphere. II - Time sequence observations of Ca II H and K emissions.

NASA Technical Reports Server (NTRS)

Wilson, P. R.; Rees, D. E.; Beckers, J. M.; Brown, D. R.

1972-01-01

Two independent sets of high resolution time series spectra of the Ca II H and K emission obtained at the Solar Tower and at the Big Dome of the Sacramento Peak Observatory on September 11th, 1971 are reported. The evolutionary behavior of the emission first reported by Wilson and Evans is confirmed, but the detail of the evolution is found to be more complex. In one case, a doubly peaked feature showing some K3 emission evolves into a single K2 (red) peak with no K3 emission. Coincidentally, a neighboring doubly peaked feature evolves to a very strong blue peak. In an entirely independent sequence a doubly peaked feature evolves into a single red peak. The K2 emission then fades completely although the continuum threads are still strong. Finally a strong K2 blue peak appears. It is concluded that the observed evolution of the K2 emission is due to temporal variations in the physical conditions which give rise to them.

A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

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

Masud, J; Nguyen, TV; Singh, N

Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600 degrees C to 850 degrees C) in presence of argon resulted in the transformation of Rh2S3 into Rh3S4, Rh17S15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H2SO4 and HBr solutions. The thermally treated catalysts show high activity for themore » hydrogen reactions. The exchange current densities (i(o)) of the synthesized RhxSy catalysts in H-2-saturated 1M H2SO4 and 1M HBr for HER and HOR were 0.9 mA/cm(2) to 1.0 mA/cm(2) and 0.8 to 0.9 mA/cm(2), respectively. The lower i(o) values obtained in 1M HBr solution compared to in H2SO4 might be due to the adsorption of Br- on the active surface. Stable electrochemical active surface area (ECSA) of RhxSy catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements. (C) The Author(s) 2015. Published by ECS. All rights reserved.« less

A Rh xS y/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

DOE PAGES

Masud, Jahangir; Nguyena, Trung V.; Singh, Nirala; ...

2015-02-01

Rhodium sulfide (Rh 2S 3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh 2S 3 at high temperatures (600°C to 850°C) in presence of argon resulted in the transformation of Rh 2S 3 into Rh 3S 4, Rh 17S 15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H 2SO 4 and HBr solutions. Themore » thermally treated catalysts show high activity for the hydrogen reactions. The exchange current densities (i o) of the synthesized Rh xS y catalysts in H 2-saturated 1M H 2SO 4 and 1M HBr for HER and HOR were 0.9 mA/cm 2 to 1.0 mA/cm 2 and 0.8 to 0.9 mA/cm 2, respectively. The lower i o values obtained in 1M HBr solution compared to in H 2SO 4 might be due to the adsorption of Br - on the active surface. Stable electrochemical active surface area (ECSA) of Rh xS y catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements.« less

Simultaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron, P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production.

PubMed

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-06

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g(-1) at 1.25 A g(-1)) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h(-1).

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production

NASA Astrophysics Data System (ADS)

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-01

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g-1 at 1.25 A g-1) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h-1.

FeS2 /CoS2 Interface Nanosheets as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Li, Yuxuan; Yin, Jie; An, Li; Lu, Min; Sun, Ke; Zhao, Yong-Qin; Gao, Daqiang; Cheng, Fangyi; Xi, Pinxian

2018-05-28

Electrochemical water splitting to produce hydrogen and oxygen, as an important reaction for renewable energy storage, needs highly efficient and stable catalysts. Herein, FeS 2 /CoS 2 interface nanosheets (NSs) as efficient bifunctional electrocatalysts for overall water splitting are reported. The thickness and interface disordered structure with rich defects of FeS 2 /CoS 2 NSs are confirmed by atomic force microscopy and high-resolution transmission electron microscopy. Furthermore, extended X-ray absorption fine structure spectroscopy clarifies that FeS 2 /CoS 2 NSs with sulfur vacancies, which can further increase electrocatalytic performance. Benefiting from the interface nanosheets' structure with abundant defects, the FeS 2 /CoS 2 NSs show remarkable hydrogen evolution reaction (HER) performance with a low overpotential of 78.2 mV at 10 mA cm -2 and a superior stability for 80 h in 1.0 m KOH, and an overpotential of 302 mV at 100 mA cm -2 for the oxygen evolution reaction (OER). More importantly, the FeS 2 /CoS 2 NSs display excellent performance for overall water splitting with a voltage of 1.47 V to achieve current density of 10 mA cm -2 and maintain the activity for at least 21 h. The present work highlights the importance of engineering interface nanosheets with rich defects based on transition metal dichalcogenides for boosting the HER and OER performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The photochemical fractionation of nitrogen isotopologues in Titan's atmosphere

NASA Astrophysics Data System (ADS)

Dobrijevic, M.; Loison, J. C.

2018-06-01

Nitrogen isotopologues could give in principle valuable constraints on the formation and evolution of Titan's atmosphere and its interior over geological time. For this purpose, we developed the first photochemical model dedicated to the study of the fractionation of several nitrogen isotopologues. Emphasis has been placed on several nitriles: HCN, CH3CN, HC3N, C2H3CN, C2H5CN. We show that the HCN/HC15N and HC3N/HC315N ratios are very sensitive to the production of magnetospheric electrons. So, these compounds can serve as probes to study the putative evolution with time of the production of magnetospheric electrons throughout the atmosphere. We also show that the CH3CN/CH3C15N and C2H5CN/C2H5C15N ratios are highly sensitive to cosmic rays. So, they can serve as probes to estimate their effect in the lower atmosphere of Titan (100-300 km). Detection of new isotopologues (particularly CH3C15N) could give strong constraints to photochemical models and could improve our understanding of the main physical and chemical processes at work in Titan's atmosphere.

The RAVE Survey: Rich in Very Metal-poor Stars

NASA Astrophysics Data System (ADS)

Fulbright, Jon P.; Wyse, Rosemary F. G.; Ruchti, Gregory R.; Gilmore, G. F.; Grebel, Eva; Bienaymé, O.; Binney, J.; Bland-Hawthorn, J.; Campbell, R.; Freeman, K. C.; Gibson, B. K.; Helmi, A.; Munari, U.; Navarro, J. F.; Parker, Q. A.; Reid, W.; Seabroke, G. M.; Siebert, A.; Siviero, A.; Steinmetz, M.; Watson, F. G.; Williams, M.; Zwitter, T.

2010-11-01

Very metal-poor stars are of obvious importance for many problems in chemical evolution, star formation, and galaxy evolution. Finding complete samples of such stars which are also bright enough to allow high-precision individual analyses is of considerable interest. We demonstrate here that stars with iron abundances [Fe/H] <-2 dex, and down to below -4 dex, can be efficiently identified within the Radial Velocity Experiment (RAVE) survey of bright stars, without requiring additional confirmatory observations. We determine a calibration of the equivalent width of the calcium triplet lines measured from the RAVE spectra onto true [Fe/H], using high spectral resolution data for a subset of the stars. These RAVE iron abundances are accurate enough to obviate the need for confirmatory higher-resolution spectroscopy. Our initial study has identified 631 stars with [Fe/H] <=-2, from a RAVE database containing approximately 200,000 stars. This RAVE-based sample is complete for stars with [Fe/H] lsim-2.5, allowing statistical sample analysis. We identify three stars with [Fe/H] lsim-4. Of these, one was already known to be "ultra metal-poor," one is a known carbon-enhanced metal-poor star, but we obtain [Fe/H] = -4.0, rather than the published [Fe/H] = -3.3, and derive [C/Fe] = +0.9, and [N/Fe] = +3.2, and the third is at the limit of our signal-to-noise ratio. RAVE observations are ongoing and should prove to be a rich source of bright, easily studied, very metal-poor stars. Based in part on observations collected at the European Organization for Astronomical Research in the Southern Hemisphere, Chile, in the framework of proposals 081.B-0900 and 080.B-0927.

Spatiotemporal Structure of Molecular Evolution of H5N1 Highly Pathogenic Avian Influenza Viruses in Vietnam

PubMed Central

Emch, Michael; Jobe, R. Todd; Moody, Aaron

2010-01-01

Background Vietnam is one of the countries most affected by outbreaks of H5N1 highly pathogenic avian influenza viruses. First identified in Vietnam in poultry in 2001 and in humans in 2004, the virus has since caused 111 cases and 56 deaths in humans. In 2003/2004 H5N1 outbreaks, nearly the entire poultry population of Vietnam was culled. Our earlier study (Wan et al., 2008, PLoS ONE, 3(10): e3462) demonstrated that there have been at least six independent H5N1 introductions into Vietnam and there were nine newly emerged reassortants from 2001 to 2007 in Vietnam. H5N1 viruses in Vietnam cluster distinctly around Hanoi and Ho Chi Minh City. However, the nature of the relationship between genetic divergence and geographic patterns is still unclear. Methodology/Principal Findings In this study, we hypothesized that genetic distances between H5N1 viruses in Vietnam are correlated with geographic distances, as the result of distinct population and environment patterns along Vietnam's long north to south longitudinal extent. Based on this hypothesis, we combined spatial statistical methods with genetic analytic techniques and explicitly used geographic space to explore genetic evolution of H5N1 highly pathogenic avian influenza viruses at the sub-national scale in Vietnam. Our dataset consisted of 125 influenza viruses (with whole genome sets) isolated in Vietnam from 2003 to 2007. Our results document the significant effect of space and time on genetic evolution and the rise of two regional centers of genetic mixing by 2007. These findings give insight into processes underlying viral evolution and suggest that genetic differentiation is associated with the distance between concentrations of human and poultry populations around Hanoi and Ho Chi Minh City. Conclusions/Significance The results show that genetic evolution of H5N1 viruses in Vietnamese domestic poultry is highly correlated with the location and spread of those viruses in geographic space. This correlation varies by scale, time, and gene, though a classic isolation by distance pattern is observed. This study is the first to characterize the geographic structure of influenza viral evolution at the sub-national scale in Vietnam and can shed light on how H5N1 HPAIVs evolve in certain geographic settings. PMID:20072619

Spatiotemporal structure of molecular evolution of H5N1 highly pathogenic avian influenza viruses in Vietnam.

PubMed

Carrel, Margaret A; Emch, Michael; Jobe, R Todd; Moody, Aaron; Wan, Xiu-Feng

2010-01-08

Vietnam is one of the countries most affected by outbreaks of H5N1 highly pathogenic avian influenza viruses. First identified in Vietnam in poultry in 2001 and in humans in 2004, the virus has since caused 111 cases and 56 deaths in humans. In 2003/2004 H5N1 outbreaks, nearly the entire poultry population of Vietnam was culled. Our earlier study (Wan et al., 2008, PLoS ONE, 3(10): e3462) demonstrated that there have been at least six independent H5N1 introductions into Vietnam and there were nine newly emerged reassortants from 2001 to 2007 in Vietnam. H5N1 viruses in Vietnam cluster distinctly around Hanoi and Ho Chi Minh City. However, the nature of the relationship between genetic divergence and geographic patterns is still unclear. In this study, we hypothesized that genetic distances between H5N1 viruses in Vietnam are correlated with geographic distances, as the result of distinct population and environment patterns along Vietnam's long north to south longitudinal extent. Based on this hypothesis, we combined spatial statistical methods with genetic analytic techniques and explicitly used geographic space to explore genetic evolution of H5N1 highly pathogenic avian influenza viruses at the sub-national scale in Vietnam. Our dataset consisted of 125 influenza viruses (with whole genome sets) isolated in Vietnam from 2003 to 2007. Our results document the significant effect of space and time on genetic evolution and the rise of two regional centers of genetic mixing by 2007. These findings give insight into processes underlying viral evolution and suggest that genetic differentiation is associated with the distance between concentrations of human and poultry populations around Hanoi and Ho Chi Minh City. The results show that genetic evolution of H5N1 viruses in Vietnamese domestic poultry is highly correlated with the location and spread of those viruses in geographic space. This correlation varies by scale, time, and gene, though a classic isolation by distance pattern is observed. This study is the first to characterize the geographic structure of influenza viral evolution at the sub-national scale in Vietnam and can shed light on how H5N1 HPAIVs evolve in certain geographic settings.

Coherent evolution of parahydrogen induced polarisation using laser pump, NMR probe spectroscopy: Theoretical framework and experimental observation.

PubMed

Halse, Meghan E; Procacci, Barbara; Henshaw, Sarah-Louise; Perutz, Robin N; Duckett, Simon B

2017-05-01

We recently reported a pump-probe method that uses a single laser pulse to introduce parahydrogen (p-H 2 ) into a metal dihydride complex and then follows the time-evolution of the p-H 2 -derived nuclear spin states by NMR. We present here a theoretical framework to describe the oscillatory behaviour of the resultant hyperpolarised NMR signals using a product operator formalism. We consider the cases where the p-H 2 -derived protons form part of an AX, AXY, AXYZ or AA'XX' spin system in the product molecule. We use this framework to predict the patterns for 2D pump-probe NMR spectra, where the indirect dimension represents the evolution during the pump-probe delay and the positions of the cross-peaks depend on the difference in chemical shift of the p-H 2 -derived protons and the difference in their couplings to other nuclei. The evolution of the NMR signals of the p-H 2 -derived protons, as well as the transfer of hyperpolarisation to other NMR-active nuclei in the product, is described. The theoretical framework is tested experimentally for a set of ruthenium dihydride complexes representing the different spin systems. Theoretical predictions and experimental results agree to within experimental error for all features of the hyperpolarised 1 H and 31 P pump-probe NMR spectra. Thus we establish the laser pump, NMR probe approach as a robust way to directly observe and quantitatively analyse the coherent evolution of p-H 2 -derived spin order over micro-to-millisecond timescales. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Dual-Native Vacancy Activated Basal Plane and Conductivity of MoSe2 with High-Efficiency Hydrogen Evolution Reaction.

PubMed

Gao, Daqiang; Xia, Baorui; Wang, Yanyan; Xiao, Wen; Xi, Pinxian; Xue, Desheng; Ding, Jun

2018-04-01

Although transition metal dichalcogenide MoSe 2 is recognized as one of the low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER), its thermodynamically stable basal plane and semiconducting property still hamper the electrocatalytic activity. Here, it is demonstrated that the basal plane and edges of 2H-MoSe 2 toward HER can be activated by introducing dual-native vacancy. The first-principle calculations indicate that both the Se and Mo vacancies together activate the electrocatalytic sites in the basal plane and edges of MoSe 2 with the optimal hydrogen adsorption free energy (ΔG H* ) of 0 eV. Experimentally, 2D MoSe 2 nanosheet arrays with a large amount of dual-native vacancies are fabricated as a catalytic working electrode, which possesses an overpotential of 126 mV at a current density of 100 mV cm -2 , a Tafel slope of 38 mV dec -1 , and an excellent long-term durability. The findings pave a rational pathway to trigger the activity of inert MoSe 2 toward HER and also can be extended to other layered dichalcogenide. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Brown Mesoporous TiO2-x /MCF Composite with an Extremely High Quantum Yield of Solar Energy Photocatalysis for H2 Evolution.

PubMed

Xing, Mingyang; Zhang, Jinlong; Qiu, Bocheng; Tian, Baozhu; Anpo, Masakazu; Che, Michel

2015-04-24

A brown mesoporous TiO2-x /MCF composite with a high fluorine dopant concentration (8.01 at%) is synthesized by a vacuum activation method. It exhibits an excellent solar absorption and a record-breaking quantum yield (Φ = 46%) and a high photon-hydrogen energy conversion efficiency (η = 34%,) for solar photocatalytic H2 production, which are all higher than that of the black hydrogen-doped TiO2 (Φ = 35%, η = 24%). The MCFs serve to improve the adsorption of F atoms onto the TiO2 /MCF composite surface, which after the formation of oxygen vacancies by vacuum activation, facilitate the abundant substitution of these vacancies with F atoms. The decrease of recombination sites induced by high-concentration F doping and the synergistic effect between lattice Ti(3+)-F and surface Ti(3+)-F are responsible for the enhanced lifetime of electrons, the observed excellent absorption of solar light, and the photocatalytic production of H2 for these catalysts. The as-prepared F-doped composite is an ideal solar light-driven photocatalyst with great potential for applications ranging from the remediation of environmental pollution to the harnessing of solar energy for H2 production. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR.

PubMed

Bordiga, S; Regli, L; Bonino, F; Groppo, E; Lamberti, C; Xiao, B; Wheatley, P S; Morris, R E; Zecchina, A

2007-06-07

Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N2 and H2). From a temperature dependent IR study, it has been estimated that the H2 adsorption energy is as high as 10 kJ mol(-1). A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho-para conversion of the adsorbed H2 species.

High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

PubMed

Feng, Liang-Liang; Yu, Guangtao; Wu, Yuanyuan; Li, Guo-Dong; Li, Hui; Sun, Yuanhui; Asefa, Tewodros; Chen, Wei; Zou, Xiaoxin

2015-11-11

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.

Carbon-armored Co9S8 nanoparticles as all-pH efficient and durable H2-evolving electrocatalysts.

PubMed

Feng, Liang-Liang; Li, Guo-Dong; Liu, Yipu; Wu, Yuanyuan; Chen, Hui; Wang, Yun; Zou, Yong-Cun; Wang, Dejun; Zou, Xiaoxin

2015-01-14

Splitting water to produce hydrogen requires the development of non-noble-metal catalysts that are able to make this reaction feasible and energy efficient. Herein, we show that cobalt pentlandite (Co9S8) nanoparticles can serve as an electrochemically active, noble-metal-free material toward hydrogen evolution reaction, and they work stably in neutral solution (pH 7) but not in acidic (pH 0) and basic (pH 14) media. We, therefore, further present a carbon-armoring strategy to increase the durability and activity of Co9S8 over a wider pH range. In particular, carbon-armored Co9S8 nanoparticles (Co9S8@C) are prepared by direct thermal treatment of a mixture of cobalt nitrate and trithiocyanuric acid at 700 °C in N2 atmosphere. Trithiocyanuric acid functions as both sulfur and carbon sources in the reaction system. The resulting Co9S8@C material operates well with high activity over a broad pH range, from pH 0 to 14, and gives nearly 100% Faradaic yield during hydrogen evolution reaction under acidic (pH 0), neutral (pH 7), and basic (pH 14) media. To the best of our knowledge, this is the first time that a transition-metal chalcogenide material is shown to have all-pH efficient and durable electrocatalytic activity. Identifying Co9S8 as the catalytically active phase and developing carbon-armoring as the improvement strategy are anticipated to give a fresh impetus to rational design of high-performance noble-metal-free water splitting catalysts.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Experimentally Infected Domestic Ducks Show Efficient Transmission of Indonesian H5N1 Highly Pathogenic Avian Influenza Virus, but Lack Persistent Viral Shedding

PubMed Central

Wibawa, Hendra; Bingham, John; Nuradji, Harimurti; Lowther, Sue; Payne, Jean; Harper, Jenni; Junaidi, Akhmad; Middleton, Deborah; Meers, Joanne

2014-01-01

Ducks are important maintenance hosts for avian influenza, including H5N1 highly pathogenic avian influenza viruses. A previous study indicated that persistence of H5N1 viruses in ducks after the development of humoral immunity may drive viral evolution following immune selection. As H5N1 HPAI is endemic in Indonesia, this mechanism may be important in understanding H5N1 evolution in that region. To determine the capability of domestic ducks to maintain prolonged shedding of Indonesian clade 2.1 H5N1 virus, two groups of Pekin ducks were inoculated through the eyes, nostrils and oropharynx and viral shedding and transmission investigated. Inoculated ducks (n = 15), which were mostly asymptomatic, shed infectious virus from the oral route from 1 to 8 days post inoculation, and from the cloacal route from 2–8 dpi. Viral ribonucleic acid was detected from 1–15 days post inoculation from the oral route and 1–24 days post inoculation from the cloacal route (cycle threshold <40). Most ducks seroconverted in a range of serological tests by 15 days post inoculation. Virus was efficiently transmitted during acute infection (5 inoculation-infected to all 5 contact ducks). However, no evidence for transmission, as determined by seroconversion and viral shedding, was found between an inoculation-infected group (n = 10) and contact ducks (n = 9) when the two groups only had contact after 10 days post inoculation. Clinical disease was more frequent and more severe in contact-infected (2 of 5) than inoculation-infected ducks (1 of 15). We conclude that Indonesian clade 2.1 H5N1 highly pathogenic avian influenza virus does not persist in individual ducks after acute infection. PMID:24392085

The impact of a future H2-based road transportation sector on the composition and chemistry of the atmosphere - Part 2: Stratospheric ozone

NASA Astrophysics Data System (ADS)

Wang, D.; Jia, W.; Olsen, S. C.; Wuebbles, D. J.; Dubey, M. K.; Rockett, A. A.

2012-08-01

The prospective future adoption of hydrogen to power the road transportation sector could greatly improve tropospheric air quality but also raises the question whether the adoption would have adverse effects on stratospheric ozone. The possibility of these undesirable impacts must be fully evaluated to guide future policy decisions. Here we evaluate the possible impact of a future (2050) H2-based road transportation sector on stratospheric composition and chemistry, especially on stratospheric ozone, with the MOZART chemical transport model. Since future growth is highly uncertain we evaluate the impact for two world evolution scenarios, one based on a high emitting scenario (IPCC A1FI) and the other on a low emitting scenario (IPCC B1), as well as two technological options: H2 fuel cells and H2 internal combustion engines. We assume a H2 leakage rate of 2.5% and a complete market penetration of H2 vehicles in 2050. The model simulations show that a H2-based road transportation sector would reduce stratospheric ozone concentrations as a result of perturbed catalytic ozone destruction cycles. The magnitude of the impact depends on which growth scenario the world evolves and which H2 technology option is applied. For the same world evolution scenario, stratospheric ozone decreases more in the H2 fuel cell scenarios than in the H2 internal combustion engine scenarios because of the NOx emissions in the latter case. If the same technological option is applied, the impact is larger in the A1FI emission scenario. The largest impact, a 0.54% decrease in annual average global mean stratospheric column ozone, is found with a H2 fuel cell type road transportation sector in the A1FI scenario; whereas the smallest impact, a 0.04% increase in stratospheric ozone, is found with applications of H2 internal combustion engine vehicles in the B1 scenario. The impacts of the other two scenarios fall between the above two bounding scenarios. However, the magnitude of these changes is much smaller than the increases in 2050 stratospheric ozone expected as stratospheric ozone recovers due to the limits in ozone depleting substance emissions imposed in the Montreal Protocol.

rGO-ZnO nanocomposites for high electrocatalytic effect on water oxidation obtained by microwave-hydrothermal method

NASA Astrophysics Data System (ADS)

Romeiro, Fernanda C.; Rodrigues, Mônica A.; Silva, Luiz A. J.; Catto, Ariadne C.; da Silva, Luis F.; Longo, Elson; Nossol, Edson; Lima, Renata C.

2017-11-01

Reduced graphene oxide-zinc oxide (rGO-ZnO) nanocomposites were successfully synthesized using a facile microwave-hydrothermal method under mild conditions, and their electrocatalytic properties towards O2 evolution were investigated. The microwave radiation played an important role in obtainment of well dispersed ZnO nanoparticles directly on reduced graphene oxide sheets without any additional reducing reagents or passivation agent. X-ray diffraction (XRD), Raman and infrared spectroscopies indicated the reduction of GO as well as the successful synthesis of rGO-ZnO nanocomposites. The chemical states of the samples were shown by XPS analyses. Due to the synergic effect, the resulting nanocomposites exhibited high electronic interaction between ZnO and rGO sheets, which improved the electrocatalytic oxidation of water with low onset potential of 0.48 V (vs. Ag/AgCl) in neutral pH and long-term stability, with high current density during electrolysis. The overpotential for water oxidation decreased in alkaline pH, suggesting useful insight on the catalytic mechanism for O2 evolution.

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Avian influenza viruses in wild birds: virus evolution in a multi-host ecosystem.

PubMed

Venkatesh, Divya; Poen, Marjolein J; Bestebroer, Theo M; Scheuer, Rachel D; Vuong, Oanh; Chkhaidze, Mzia; Machablishvili, Anna; Mamuchadze, Jimsher; Ninua, Levan; Fedorova, Nadia B; Halpin, Rebecca A; Lin, Xudong; Ransier, Amy; Stockwell, Timothy B; Wentworth, David E; Kriti, Divya; Dutta, Jayeeta; van Bakel, Harm; Puranik, Anita; Slomka, Marek J; Essen, Steve; Brown, Ian H; Fouchier, Ron A M; Lewis, Nicola S

2018-05-16

Wild ducks and gulls are the major reservoirs for avian influenza A viruses (AIVs). The mechanisms that drive AIV evolution are complex at sites where various duck and gull species from multiple flyways breed, winter or stage. The Republic of Georgia is located at the intersection of three migratory flyways: Central Asian Flyway, East Asian/East African Flyway and Black Sea/Mediterranean Flyway. For six consecutive years (2010-2016), we collected AIV samples from various duck and gull species that breed, migrate and overwinter in Georgia. We found substantial subtype diversity of viruses that varied in prevalence from year to year. Low pathogenic (LP)AIV subtypes included H1N1, H2N3, H2N5, H2N7, H3N8, H4N2, H6N2, H7N3, H7N7, H9N1, H9N3, H10N4, H10N7, H11N1, H13N2, H13N6, H13N8, H16N3, plus two H5N5 and H5N8 highly pathogenic (HP)AIVs belonging to clade 2.3.4.4. Whole genome phylogenetic trees showed significant host species lineage restriction for nearly all gene segments and significant differences for LPAIVs among different host species in observed reassortment rates, as defined by quantification of phylogenetic incongruence, and in nucleotide diversity. Hemagglutinin clade 2.3.4.4 H5N8 viruses, circulated in Eurasia during 2014-2015 did not reassort, but analysis after its subsequent dissemination during 2016-2017 revealed reassortment in all gene segments except NP and NS. Some virus lineages appeared to be unrelated to AIVs in wild bird populations in other regions with maintenance of local AIV viruses in Georgia, whereas other lineages showed considerable genetic inter-relationship with viruses circulating in other parts of Eurasia and Africa, despite relative under-sampling in the area. Importance Waterbirds (e.g., gulls/ducks) are natural reservoirs of avian influenza viruses (AIVs) and have been shown to mediate dispersal of AIV at inter-continental scales during seasonal migration. The segmented genome of influenza viruses enables viral RNA from different lineages to mix or re-assort when two viruses infect the same host. Such reassortant viruses have been identified in most major human influenza pandemics and several poultry outbreaks. Despite their importance, we have only recently begun to understand AIV evolution and reassortment in their natural host reservoirs. This comprehensive study illustrates of AIV evolutionary dynamics within a multi-host ecosystem at a stop-over site where three major migratory flyways intersect. Our analysis of this ecosystem over a six-year period provides a snapshot of how these viruses are linked to global AIV populations. Understanding the evolution of AIVs in the natural host is imperative to both mitigating the risk of incursion into domestic poultry and potential risk to mammalian hosts including humans. © Crown copyright 2018.

Modification of Ga2O3 by an Ag-Cr core-shell cocatalyst enhances photocatalytic CO evolution for the conversion of CO2 by H2O.

PubMed

Pang, Rui; Teramura, Kentaro; Tatsumi, Hiroyuki; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2018-01-25

A core-shell structure of Ag-Cr dual cocatalyst loaded-Ga 2 O 3 was found to significantly enhance the formation rate of CO and selectivity toward CO evolution for the photocatalytic conversion of CO 2 where H 2 O is used as an electron donor.

Diffusive smoothing of surfzone bathymetry by gravity-driven sediment transport

NASA Astrophysics Data System (ADS)

Moulton, M. R.; Elgar, S.; Raubenheimer, B.

2012-12-01

Gravity-driven sediment transport often is assumed to have a small effect on the evolution of nearshore morphology. Here, it is shown that down-slope gravity-driven sediment transport is an important process acting to smooth steep bathymetric features in the surfzone. Gravity-driven transport can be modeled as a diffusive term in the sediment continuity equation governing temporal (t) changes in bed level (h): ∂h/∂t ≈ κ ▽2h, where κ is a sediment diffusion coefficient that is a function of the bed shear stress (τb) and sediment properties, such as the grain size and the angle of repose. Field observations of waves, currents, and the evolution of large excavated holes (initially 10-m wide and 2-m deep, with sides as steep as 35°) in an energetic surfzone are consistent with diffusive smoothing by gravity. Specifically, comparisons of κ estimated from the measured bed evolution with those estimated with numerical model results for several transport theories suggest that gravity-driven sediment transport dominates the bed evolution, with κ proportional to a power of τb. The models are initiated with observed bathymetry and forced with observed waves and currents. The diffusion coefficients from the measurements and from the model simulations were on average of order 10-5 m2/s, implying evolution time scales of days for features with length scales of 10 m. The dependence of κ on τb varies for different transport theories and for high and low shear stress regimes. The US Army Corps of Engineers Field Research Facility, Duck, NC provided excellent logistical support. Funded by a National Security Science and Engineering Faculty Fellowship, a National Defense Science and Engineering Graduate Fellowship, and the Office of Naval Research.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

PubMed Central

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-01-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions. PMID:26355955

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co(2+) Solution: Interactional Performance and Mechanism.

PubMed

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-10

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co(2+) solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co(2+) reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the "structural influence" crucial for the full and dynamical understanding of nZVI reactions.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions.

Ni nanoparticles and the Kirkendall effect in dry reforming of methane

NASA Astrophysics Data System (ADS)

Pegios, N.; Bliznuk, V.; Theofanidis, S. A.; Galvita, V. V.; Marin, G. B.; Palkovits, R.; Simeonov, K.

2018-09-01

In this study we report a simple preparation technique for Ni/γ-Al2O3 catalysts for the dry reforming of methane (DRM) at 800 °C to produce CO and H2 (synthesis gas). Hard-templating with low and high surface area activated carbon was applied. The produced synthesis gas exhibited a low product ratio of H2:CO [0.04-0.12], due to reverse water-gas shift. After 75 h time on stream (TOS) minimal deactivation of the catalyst could be observed. A rather unusual activity evolution was found involving a sequence of minimum-maximum-plateau. A scheme was suggested, explaining the activity evolution based on the Ni-nanoparticle positioning from being bare or encapsulated by Al2O3. The Al2O3 shell cracks and undergoes restructuring during reaction making more active sites available for the reaction. Superior metal dispersion was achieved with average nickel nanoparticle size at 4.9 ± 1.3 nm. The sintering mechanism was also investigated. Surprisingly, hollow nickel nanoparticles were observed at 25 h TOS due to the nanoscale Kirkendall effect. This diffusion phenomenon between the core, Ni0, and the outer shell, NiO, (Ni2+) lead to pronounced structural and morphological changes of the catalyst.

Bioelectrochemical sulphate reduction on batch reactors: Effect of inoculum-type and applied potential on sulphate consumption and pH.

PubMed

Gacitúa, Manuel A; Muñoz, Enyelbert; González, Bernardo

2018-02-01

Microbial electrolysis batch reactor systems were studied employing different conditions, paying attention on the effect that biocathode potential has on pH and system performance, with the overall aim to distinguish sulphate reduction from H 2 evolution. Inocula from pure strains (Desulfovibrio paquesii and Desulfobacter halotolerans) were compared to a natural source conditioned inoculum. The natural inoculum possess the potential for sulphate reduction on serum bottles experiments due to the activity of mutualistic bacteria (Sedimentibacter sp. and Bacteroides sp.) that assist sulphate-reducing bacterial cells (Desulfovibrio sp.) present in the consortium. Electrochemical batch reactors were monitored at two different potentials (graphite-bar cathodes poised at -900 and -400mV versus standard hydrogen electrode) in an attempt to isolate bioelectrochemical sulphate reduction from hydrogen evolution. At -900mV all inocula were able to reduce sulphate with the consortium demonstrating superior performance (SO 4 2- consumption: 25.71gm -2 day -1 ), despite the high alkalinisation of the media. At -400mV only the pure Desulfobacter halotolerans inoculated system was able to reduce sulphate (SO 4 2- consumption: 17.47gm -2 day -1 ) and, in this potential condition, pH elevation was less for all systems, confirming direct (or at least preferential) bioelectrochemical reduction of sulphate over H 2 production. Copyright © 2017 Elsevier B.V. All rights reserved.

In vivo kinetics of lipids and astaxanthin evolution in Haematococcus pluvialis mutant under 15% CO2 using Raman microspectroscopy.

PubMed

Li, Ke; Cheng, Jun; Ye, Qing; He, Yong; Zhou, Junhu; Cen, Kefa

2017-11-01

In vivo spatiotemporal dynamics of lipids and astaxanthin evolution in Haematococcus pluvialis mutant induced with 15% CO 2 and high light intensity were monitored with high spatial resolution in a non-destructive and label-free manner using single-cell Raman imaging. Astaxanthin intensity increased by 3.5 times within 12h under 15% CO 2 , and the accumulation rate was 5.8 times higher than that under air. Lipids intensity under 15% CO 2 was 27% higher than that under air. The lipids initially concentrated in chloroplast under 15% CO 2 due to an increase of directly photosynthetic fatty acid, which was different from the whole-cell dispersed lipids under air. Astaxanthin produced in chloroplast first accumulated around nucleus and then spread in cytoplasmic lipids under both air and 15% CO 2 . The calculation results of kinetic models for lipids and astaxanthin evolutions showed that accumulation rate of lipids was much higher than that of astaxanthin in cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

The glycogen synthase 2 gene (Gys2) displays parallel evolution between Old World and New World fruit bats.

PubMed

Qian, Yamin; Fang, Tao; Shen, Bin; Zhang, Shuyi

2014-01-01

Frugivorous and nectarivorous bats rely largely on hepatic glycogenesis and glycogenolysis for postprandial blood glucose disposal and maintenance of glucose homeostasis during short time starvation, respectively. The glycogen synthase 2 encoded by the Gys2 gene plays a critical role in liver glycogen synthesis. To test whether the Gys2 gene has undergone adaptive evolution in bats with carbohydrate-rich diets in relation to their insect-eating sister taxa, we sequenced the coding region of the Gys2 gene in a number of bat species, including three Old World fruit bats (OWFBs) (Pteropodidae) and two New World fruit bats (NWFBs) (Phyllostomidae). Our results showed that the Gys2 coding sequences are highly conserved across all bat species we examined, and no evidence of positive selection was detected in the ancestral branches leading to OWFBs and NWFBs. Our explicit convergence test showed that posterior probabilities of convergence between several branches of OWFBs, and the NWFBs were markedly higher than that of divergence. Three parallel amino acid substitutions (Q72H, K371Q, and E666D) were detected among branches of OWFBs and NWFBs. Tests for parallel evolution showed that two parallel substitutions (Q72H and E666D) were driven by natural selection, while the K371Q was more likely to be fixed randomly. Thus, our results suggested that the Gys2 gene has undergone parallel evolution on amino acid level between OWFBs and NWFBs in relation to their carbohydrate metabolism.

Constructing 2D layered MoS2 nanosheets-modified Z-scheme TiO2/WO3 nanofibers ternary nanojunction with enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Zhao, Jiangtao; Zhang, Peng; Fan, Jiajie; Hu, Junhua; Shao, Guosheng

2018-02-01

Advanced materials for photoelectrochemical H2 production are important to the field of renewable energy. Despite great efforts have been made, the present challenge in materials science is to explore highly active photocatalysts for splitting of water at low cost. In this work, we report a new composite material consisting of 2D layered MoS2 nanosheets grown on the presence of TiO2/WO3 nanofibers (TW) as a high-performance photocatalyst for H2 evolution. This composite material was prepared by a two-step simple process of electrospinning and hydrothermal. We found that the as-prepared TiO2/WO3@MoS2 (TWM) hybrid exhibited superior photocatalytic activity in the hydrogen evolution reaction (HER) even without the noble metal-cocatalyst. Importantly, the TiO2/WO3@MoS2 heterostructure with 60 wt% of MoS2 exhibits the highest hydrogen production rate. This great improvement is attributed to the positive synergetic effect between the WO3 and MoS2 components in this hybrid cocatalyst, which serve as hole collector and electron collector, respectively. Moreover, the effective charge separation was directly proved by ultraviolet photoelectron spectroscopy, electrochemical impedance spectroscopy, and photocurrent analysis.

Cationic Surface Charge Combined with Either Vitronectin or Laminin Dictates the Evolution of Human Embryonic Stem Cells/Microcarrier Aggregates and Cell Growth in Agitated Cultures

PubMed Central

Lam, Alan Tin-Lun; Li, Jian; Chen, Allen Kuan-Liang; Reuveny, Shaul

2014-01-01

The expansion of human pluripotent stem cells (hPSC) for biomedical applications generally compels a defined, reliable, and scalable platform. Bioreactors offer a three-dimensional culture environment that relies on the implementation of microcarriers (MC), as supports for cell anchorage and their subsequent growth. Polystyrene microspheres/MC coated with adhesion-promoting extracellular matrix (ECM) protein, vitronectin (VN), or laminin (LN) have been shown to support hPSC expansion in a static environment. However, they are insufficient to promote human embryonic stem cells (hESC) seeding and their expansion in an agitated environment. The present study describes an innovative technology, consisting of a cationic charge that underlies the ECM coatings. By combining poly-L-lysine (PLL) with a coating of ECM protein, cell attachment efficiency and cell spreading are improved, thus enabling seeding under agitation in a serum-free medium. This coating combination also critically enables the subsequent formation and evolution of hPSC/MC aggregates, which ensure cell viability and generate high yields. Aggregate dimensions of at least 300 μm during early cell growth give rise to ≈15-fold expansion at 7 days' culture. Increasing aggregate numbers at a quasi-constant size of ≈300 μm indicates hESC growth within a self-regulating microenvironment. PLL+LN enables cell seeding and aggregate evolution under constant agitation, whereas PLL+VN requires an intermediate 2-day static pause to attain comparable aggregate sizes and correspondingly high expansion yields. The cells' highly reproducible bioresponse to these defined and characterized MC surface properties is universal across multiple cell lines, thus confirming the robustness of this scalable expansion process in a defined environment. PMID:24641164

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production

PubMed Central

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-01

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g−1 at 1.25 A g−1) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h−1. PMID:24389929

Enhancement of solar hydrogen evolution from water by surface modification with CdS and TiO2 on porous CuInS2 photocathodes prepared by an electrodeposition-sulfurization method.

PubMed

Zhao, Jiao; Minegishi, Tsutomu; Zhang, Li; Zhong, Miao; Gunawan; Nakabayashi, Mamiko; Ma, Guijun; Hisatomi, Takashi; Katayama, Masao; Ikeda, Shigeru; Shibata, Naoya; Yamada, Taro; Domen, Kazunari

2014-10-27

Porous films of p-type CuInS2, prepared by sulfurization of electrodeposited metals, are surface-modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n-type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p-n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metallic Ni3S2 Films Grown by Atomic Layer Deposition as an Efficient and Stable Electrocatalyst for Overall Water Splitting.

PubMed

Ho, Thi Anh; Bae, Changdeuck; Nam, Hochul; Kim, Eunsoo; Lee, Seung Yong; Park, Jong Hyeok; Shin, Hyunjung

2018-04-18

We describe the direct preparation of crystalline Ni 3 S 2 thin films via atomic layer deposition (ALD) techniques at temperatures as low as 250 °C without postthermal treatments. A new ALD chemistry is proposed using bis(1-dimethylamino-2-methyl-2-butoxy) nickel(II) [Ni(dmamb) 2 ] and H 2 S as precursors. Homogeneous and conformal depositions of Ni 3 S 2 films were achieved on 4 in. wafers (both metal and oxide substrates, including Au and SiO 2 ). The resulting crystalline Ni 3 S 2 layers exhibited highly efficient and stable performance as electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solutions, with a low overpotential of 300 mV and a high turnover frequency for HER and an overpotential of 400 mV for OER (at a current density of 10 mA/cm 2 ). Using our Ni 3 S 2 films as both the cathode and the anode, two-electrode full-cell electrolyzers were constructed, which showed stable operation for 100 h at a current density of 10 mA/cm 2 . The proposed ALD electrocatalysts on planar surfaces exhibited the best performance among Ni 3 S 2 materials for overall water splitting recorded to date.

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

NASA Technical Reports Server (NTRS)

McAdam, A. C.; Knudson, C. A.; Sutter, B.; Franz, H. B.; Archer, P. D., Jr.; Eigenbrode, J. L.; Ming, D. W.; Morris, R. V.; Hurowitz, J. A.; Mahaffy, P. R.;

Nickel centred H+ reduction catalysis in a model of [NiFe] Hydrogenase

PubMed Central

Brazzolotto, Deborah; Gennari, Marcello; Queyriaux, Nicolas; Simmons, Trevor R.; Pécaut, Jacques; Demeshko, Serhiy; Meyer, Franc; Orio, Maylis; Artero, Vincent; Duboc, Carole

2017-01-01

Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centers that catalyze hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centered reactivity found at the active site of [NiFe] hydrogenases. Here we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second order rate constant of 2.5 104 M-1s-1; turnover frequency of 225 s-1 at 10 mM H+ concentration) from mildly acidic solutions. PMID:27768098

A mix-and-read drop-based in vitro two-hybrid method for screening high-affinity peptide binders

PubMed Central

Cui, Naiwen; Zhang, Huidan; Schneider, Nils; Tao, Ye; Asahara, Haruichi; Sun, Zhiyi; Cai, Yamei; Koehler, Stephan A.; de Greef, Tom F. A.; Abbaspourrad, Alireza; Weitz, David A.; Chong, Shaorong

2016-01-01

Drop-based microfluidics have recently become a novel tool by providing a stable linkage between phenotype and genotype for high throughput screening. However, use of drop-based microfluidics for screening high-affinity peptide binders has not been demonstrated due to the lack of a sensitive functional assay that can detect single DNA molecules in drops. To address this sensitivity issue, we introduced in vitro two-hybrid system (IVT2H) into microfluidic drops and developed a streamlined mix-and-read drop-IVT2H method to screen a random DNA library. Drop-IVT2H was based on the correlation between the binding affinity of two interacting protein domains and transcriptional activation of a fluorescent reporter. A DNA library encoding potential peptide binders was encapsulated with IVT2H such that single DNA molecules were distributed in individual drops. We validated drop-IVT2H by screening a three-random-residue library derived from a high-affinity MDM2 inhibitor PMI. The current drop-IVT2H platform is ideally suited for affinity screening of small-to-medium-sized libraries (103–106). It can obtain hits within a single day while consuming minimal amounts of reagents. Drop-IVT2H simplifies and accelerates the drop-based microfluidics workflow for screening random DNA libraries, and represents a novel alternative method for protein engineering and in vitro directed protein evolution. PMID:26940078

MoS2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions.

PubMed

Wang, Chengli; Su, Yingchun; Zhao, Xiaole; Tong, Shanshan; Han, Xiaojun

2018-01-24

A novel MoS 2 -based flower-like nanohybrid for hydrogen evolution was fabricated through coating the Cu-containing metal-organic framework (HKUST-1) onto MoS 2 nanosheets. It is the first time that MoS 2 @HKUST-1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS 2 @HKUST-1 flower-like nanohybrids were characterized by scanning electron microscopy, X-ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS 2 , the MoS 2 @HKUST-1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of -99 mV, a smaller Tafel slope of 69 mV dec -1 , and a Faradaic efficiency of nearly 100 %. The MoS 2 @HKUST-1 flower-like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non-noble metal catalysts with high performance for the hydrogen evolution reaction (HER). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

PubMed

Chen, Ziliang; Wu, Renbing; Liu, Yang; Ha, Yuan; Guo, Yanhui; Sun, Dalin; Liu, Miao; Fang, Fang

2018-06-10

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm -2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H 2 SO 4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protein consensus-based surface engineering (ProCoS): a computer-assisted method for directed protein evolution.

PubMed

Shivange, Amol V; Hoeffken, Hans Wolfgang; Haefner, Stefan; Schwaneberg, Ulrich

2016-12-01

Protein consensus-based surface engineering (ProCoS) is a simple and efficient method for directed protein evolution combining computational analysis and molecular biology tools to engineer protein surfaces. ProCoS is based on the hypothesis that conserved residues originated from a common ancestor and that these residues are crucial for the function of a protein, whereas highly variable regions (situated on the surface of a protein) can be targeted for surface engineering to maximize performance. ProCoS comprises four main steps: ( i ) identification of conserved and highly variable regions; ( ii ) protein sequence design by substituting residues in the highly variable regions, and gene synthesis; ( iii ) in vitro DNA recombination of synthetic genes; and ( iv ) screening for active variants. ProCoS is a simple method for surface mutagenesis in which multiple sequence alignment is used for selection of surface residues based on a structural model. To demonstrate the technique's utility for directed evolution, the surface of a phytase enzyme from Yersinia mollaretii (Ymphytase) was subjected to ProCoS. Screening just 1050 clones from ProCoS engineering-guided mutant libraries yielded an enzyme with 34 amino acid substitutions. The surface-engineered Ymphytase exhibited 3.8-fold higher pH stability (at pH 2.8 for 3 h) and retained 40% of the enzyme's specific activity (400 U/mg) compared with the wild-type Ymphytase. The pH stability might be attributed to a significantly increased (20 percentage points; from 9% to 29%) number of negatively charged amino acids on the surface of the engineered phytase.

Hydrogen-bond symmetrization breakdown and dehydrogenation mechanism in FeO2H at high pressure

NASA Astrophysics Data System (ADS)

Hu, Q.; Zhu, S.; Mao, H. K.; Mao, W. L.; Sheng, H.

2017-12-01

The cycling of hydrogen plays an important role in the geochemical evolution of our planet. In Earth's interiors, hydrogen cycling is mainly carried out by hydrous minerals. Under high-pressure conditions, asymmetric hydroxyl bonds in hydrous minerals tend to form a symmetric O-H-O configuration that improves their thermal stability. Therefore it is possible to transport water into the deeper part of the Earth's lower mantle. Here, we employ first-principles free-energy landscape sampling methods based on a recently developed stochastic surface walking algorithm to reveal the transition mechanism of a water-bearing mineral, FeO2H, at deep mantle conditions. By resolving the lowest-energy transition pathway from ɛ-FeO2H to the high-pressure Py-phase, we demonstrate that half of the O-H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. Our study sheds new light on the stability of symmetric hydrogen bonds in hydrous minerals during structural transitions and suggests a dehydrogenation mechanism from water in the deep mantle.

The set of triple-resonance sequences with a multiple quantum coherence evolution period

NASA Astrophysics Data System (ADS)

Koźmiński, Wiktor; Zhukov, Igor

2004-12-01

The new pulse sequence building block that relies on evolution of heteronuclear multiple quantum coherences is proposed. The particular chemical shifts are obtained in multiple quadrature, using linear combinations of frequencies taken from spectra measured at different quantum levels. The pulse sequences designed in this way consist of small number of RF-pulses, are as short as possible, and could be applied for determination of coupling constants. The examples presented involve 2D correlations H NCO, H NCA, H N(CO) CA, and H(N) COCA via heteronuclear zero and double coherences, as well as 2D H NCOCA technique with simultaneous evolution of triple and three distinct single quantum coherences. Applications of the new sequences are presented for 13C, 15N-labeled ubiquitin.

Photosensitization of different ruthenium(II) complex dyes on TiO 2 for photocatalytic H 2 evolution under visible-light

NASA Astrophysics Data System (ADS)

Peng, Tianyou; Dai, Ke; Yi, Huabing; Ke, Dingning; Cai, Ping; Zan, Ling

2008-07-01

Hydrogen production over dye-sensitized Pt/P25 under visible-light irradiation was investigated by using methanol or TEOA as an electron donor. Ru 2(bpy) 4L 1-PF 6 shows the best photosensitization due to its largest conjugation system, widest range of visible-light and 'antenna effect' among the used three Ru(II)-bipyridyl dyes. Ru 2(bpy) 4L 1-PF 6 loosely linked with TiO 2 also exhibit more steady and higher increases in H 2 evolution upon prolonging the irradiation time than the tightly linked N719. The dynamic equilibrium between the linkage of ground dye and divorce of oxidized dye from TiO 2 can enhance the electron-injection and hinder the backward transfer, and then improve the H 2 evolution efficiency.

Evolution of long-period stacking order (LPSO) in Mg97Zn1Gd2 cast alloys viewed by HAADF-STEM multi-scale electron tomography

NASA Astrophysics Data System (ADS)

Sato, Kazuhisa; Tashiro, Shunya; Matsunaga, Shuhei; Yamaguchi, Yohei; Kiguchi, Takanori; Konno, Toyohiko J.

2018-07-01

We have studied three-dimensional (3D) structures and growth processes of 14H-type long-period stacking order (LPSO) formed in Mg97Zn1Gd2 cast alloys by single tilt-axis electron tomography (ET) using high-angle annular dark-field scanning transmission electron microscopy. Evolution of the solute-enriched stacking faults (SFs) and the 14H LPSO by ageing were visualised in 3D with a high spatial resolution in multi-scale fields of views from a few nanometres to 10 μm. Lateral growth of the solute-enriched SFs and the LPSO in the (0 0 0 1)Mg plane is notable compared to the out-of-plane growth in the [0 0 0 1]Mg direction. The 14H LPSO grows at the cost of decomposition of the (Mg, Zn)3Gd-type precipitates, and accompany a change of in-plane edge angles from 30 to 60°. We have updated the Time-Temperature-Transformation diagram for precipitation in Mg97Zn1Gd2 alloys: starting temperatures of both solute-enriched SFs and LPSO formation shifted to a shorter time side than those in the previous diagram.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

NASA Astrophysics Data System (ADS)

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-05-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm-2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec-1. Moreover, we achieve 10 mA cm-2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2.

Post-activation of in situ Bsbnd F codoped g-C3N4 for enhanced photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Cui, Yanjuan; Wang, Hao; Yang, Chuanfeng; Li, Ming; Zhao, Yimeng; Chen, Fangyan

2018-05-01

Porous graphitic carbon nitride polymer (p-CN-BF) with enhanced photoproduction of H2 from water was prepared by a two-step treatment process including in-situ Boron and fluorine codoping using [Emim]BF4 as dopants followed by post-calcination in air. Several techniques were employed to characterize the modified structure and elucidate the doping state of B and F. It was shown that in-situ doping method is necessary for efficient doping of heteroatoms into the molecular composition of CN. The difference of doping state of B and F was that B doping primary existing in the inside skeleton of CN, but F doping merely presents in the surface layer. The inside doped B made for the enhanced visible light absorption and the production of uniform porous structure during post-sintering process. By the synergistic effect of Bsbnd F codoping and post-activation, p-CN-BF showed much enhanced photoelectron generation, transmission and separation, therefore, it performs high photocatalytic activity for H2 evolution (351 μmol h-1), which was 13 and 5 times higher than samples only modified by Bsbnd F codoping (CN-BF) or post-annealing (P-CN).

Disorder engineering of undoped TiO2 nanotube arrays for highly efficient solar-driven oxygen evolution.

PubMed

Salari, M; Aboutalebi, S H; Aghassi, A; Wagner, P; Mozer, A J; Wallace, G G

2015-02-28

The trade-off between performance and complexity of the device manufacturing process should be balanced to enable the economic harvest of solar energy. Here, we demonstrate a conceptual, yet practical and well-regulated strategy to achieve efficient solar photocatalytic activity in TiO2 through controlled phase transformation and disorder engineering in the surface layers of TiO2 nanotubes. This approach enabled us to fine-tune the bandgap structure of undoped TiO2 according to our needs while simultaneously obtaining robust separation of photo-excited charge carriers. Introduction of specific surface defects also assisted in utilization of the visible part of sunlight to split water molecules for the production of oxygen. The strategy proposed here can serve as a guideline to overcome the practical limitation in the realization of efficient, non-toxic, chemically stable photoelectrochemical systems with high catalytic activity at neutral pH under visible illumination conditions. We also successfully incorporated TiO2 nanotube arrays (TNTAs) with free-based porphyrin affording a pathway with an overall 140% enhanced efficiency, an oxygen evolution rate of 436 μL h(-1) and faradic efficiencies over 100%.

Properties of Starless Clumps through Protoclusters from the Bolocam Galactic Plane Survey

NASA Astrophysics Data System (ADS)

Svoboda, Brian E.; Shirley, Yancy

2014-07-01

High mass stars play a key role in the physical and chemical evolution of the interstellar medium, yet the evolution of physical properties for high-mass star-forming regions remains unclear. We sort a sample of ~4668 molecular cloud clumps from the Bolocam Galactic Plane Survey (BGPS) into different evolutionary stages by combining the BGPS 1.1 mm continuum and observational diagnostics of star-formation activity from a variety of Galactic plane surveys: 70 um compact sources, mid-IR color-selected YSOs, H2O and CH3OH masers, EGOs, and UCHII regions. We apply Monte Carlo techniques to distance probability distribution functions (DPDFs) in order to marginalize over the kinematic distance ambiguity and calculate distributions for derived quantities of clumps in different evolutionary stages. We also present a combined NH3 and H2O maser catalog for ~1590 clumps from the literature and our own GBT 100m observations. We identify a sub-sample of 440 dense clumps with no star-formation indicators, representing the largest and most robust sample of pre-protocluster candidates from a blind survey to date. Distributions of I(HCO+), I(N2H+), dv(HCO+), dv(N2H+), mass surface density, and kinetic temperature show strong progressions when separated by evolutionary stage. No progressions are found in size or dust mass; however, weak progressions are observed in area > 2 pc^2 and dust mass > 3 10^3 Msun. An observed breakdown occurs in the size-linewidth relationship and we find no improvement when sampling by evolutionary stage.

[Swine influenza virus: evolution mechanism and epidemic characterization--a review].

PubMed

Qi, Xian; Lu, Chengping

2009-09-01

Pigs may play an important role in the evolution and ecology of influenza A virus. The tracheal epithelium of pigs contain both SA alpha 2,6 Gal and SA alpha 2,3 Gal receptors and can be infected with swine, human and avian viruses, therefore, pigs have been considered as an intermediate host for the adaptation of avian influenza viruses to humans or as mixing vessels for the generation of genetically reassortant viruses. Evolution patterns among swine influenza viruses including evolution of host adaptation, antigenic drift and genetic reassortment, and the latter is the main one. Unlike human influenza viruses, swine viruses have different epizootiological patterns in different areas of world, which is enzootic and geographic dependence. Currently, three predominant subtypes of influenza virus are prevalent in pig populations worldwide: H1N1, H3N2, and H1N2, and these include classical swine H1N1, avian-like H1N1, human-like H3N2, reassortant H3N2 and various genotype H1N2 viruses. In Europe, North America and China, influenza A viruses circulating in pigs are distinct in the genetic characteristics and genetic sources. Since 1979, three subtypes, avian-like H1N1, reassortant H1N2 and H3N2 viruses, have been co-circulating in European swine. Before 1998, classical H1N1 viruses were the exclusive cause of swine influenza in North America. However, after that, three triple-reassortant H1N2, H3N2 and H1N1 viruses with genes of human, swine and avian virus began to emerge in pigs. Genetically, the pandemic viruses emerging in human, so called influenza A (H1N1) viruses, contain genes from both Europe and North American SIV lineages. SIV is not the same as Europe and the United States in the prevalence and genetic background in China, mainly classical swine H1N1 and human-like H3N2 type virus. However, in recent years, SIV from Europe and North America have been introduced into Chinese pig herds, so more attention should be given on the evolutionary of SIV in China. Worldwide, more than 50 cases of SIV infection in human have been documented since the 1970s, which indicate that SIV is also an important zoonosis, and the potential of SIV as human pandemic virus or genes donator. In view of SIV in the importance of ecology, as well as a potential threat to human public health, it is recommended to start as soon as possible regular surveillance, paying close attention to its prevalence and molecular evolution. At the same time, we should establish the surveillance network of the whole influenza virus (including human and animal influenza virus) in China, ecologically mastering the prevalence and evolution of influenza viruses, which is of great significance for the protection of animal health and the prevention of human pandemic.

A(H5N1) Virus Evolution in South East Asia

PubMed Central

Gutiérrez, Ramona Alikiiteaga; Naughtin, Monica Jane; Horm, Srey Viseth; San, Sorn; Buchy, Philippe

2009-01-01

Highly Pathogenic Avian Influenza (HPAI) H5N1 virus is an ongoing public health and socio-economic challenge, particularly in South East Asia. H5N1 is now endemic in poultry in many countries, and represents a major pandemic threat. Here, we describe the evolution of H5N1 virus in South East Asia, the reassortment events leading to high genetic diversity in the region, and factors responsible for virus spread. The virus has evolved with genetic variations affecting virulence, drug-resistance, and adaptation to new host species. The constant surveillance of these changes is of primary importance in the global efforts of the scientific community. PMID:21994553

Isolation and phylogenetic characterization of haemagglutinin and neuraminidase genes of H9N2 low pathogenicity avian influenza virus isolated from commercial layers in India.

PubMed

Gowthaman, Vasudevan; Singh, Shambu Dayal; Dhama, Kuldeep; Srinivasan, Palani; Saravanan, Sellappan; Murthy, Thippichettypalayam Ramasamy Gopala Krishna; Sukumar, Kuppanan; Mathapati, Basavaraj; Lebarbenchon, Camille; Malik, Yashpal Singh; Ramakrishnan, Muthannan Andavar

2016-12-01

Avian influenza is a highly infectious and dynamically evolving disease of birds causing high morbidity and mortality. It is caused by avian influenza virus (AIV) that belongs to the family Orthomyxoviridae. Two types of AIV have been described based on their pathogenicity viz. highly pathogenic avian influenza virus that causes severe disease with high mortality and low pathogenic avian influenza virus (LPAI) that generally causes asymptomatic infection or a mild disease. The H9N2 subtype is the widely circulated LPAI type in the world. The H9N2 subtype of was first reported from northern India in March 2003. However, systematical surveillance information for the evolution of H9N2 viruses in poultry flocks of Southern India is lacking. The present study reports the isolation and characterization of H9N2 isolates from the southern parts of the country during the period between May 2010 and September 2011. Out of the 30 poultry flocks investigated, six were found to be positive for HA activity. Further, all the six samples conformed as AIV. Partial nucleotide sequencing of the HA and NA genes revealed that all were belonging to the H9N2 subtype. Phylogenetically, the HA and NA genes of the H9N2 viruses from India clustered with those isolated from Bangladesh, Pakistan and the Middle East, although we were not able to conclude on their exact geographic origin.

Modelling landscape evolution at the flume scale

NASA Astrophysics Data System (ADS)

Cheraghi, Mohsen; Rinaldo, Andrea; Sander, Graham C.; Barry, D. Andrew

2017-04-01

The ability of a large-scale Landscape Evolution Model (LEM) to simulate the soil surface morphological evolution as observed in a laboratory flume (1-m × 2-m surface area) was investigated. The soil surface was initially smooth, and was subjected to heterogeneous rainfall in an experiment designed to avoid rill formation. Low-cohesive fine sand was placed in the flume while the slope and relief height were 5 % and 20 cm, respectively. Non-uniform rainfall with an average intensity of 85 mm h-1 and a standard deviation of 26 % was applied to the sediment surface for 16 h. We hypothesized that the complex overland water flow can be represented by a drainage discharge network, which was calculated via the micro-morphology and the rainfall distribution. Measurements included high resolution Digital Elevation Models that were captured at intervals during the experiment. The calibrated LEM captured the migration of the main flow path from the low precipitation area into the high precipitation area. Furthermore, both model and experiment showed a steep transition zone in soil elevation that moved upstream during the experiment. We conclude that the LEM is applicable under non-uniform rainfall and in the absence of surface incisions, thereby extending its applicability beyond that shown in previous applications. Keywords: Numerical simulation, Flume experiment, Particle Swarm Optimization, Sediment transport, River network evolution model.

Photocatalysis using a Wide Range of the Visible Light Spectrum: Hydrogen Evolution from Doped AgGaS2.

PubMed

Yamato, Kohei; Iwase, Akihide; Kudo, Akihiko

2015-09-07

Doping of nickel into AgGaS2 yields a new absorption band, at a wavelength longer than the intrinsic absorption band of the AgGaS2 host. The doped nickel forms an electron donor level in a forbidden band of AgGaS2 . The nickel-doped AgGaS2 with rhodium co-catalyst shows photocatalytic activity for sacrificial H2 evolution under the light of up to 760 nm due to the transition from the electron donor level consisting of Ni(2+) to the conduction band of AgGaS2 . Apparent quantum yields for the sacrificial H2 evolution at 540-620 nm are about 1 %. Moreover, the nickel-doped AgGa0.75 In0.25 S2 also responds to near-IR light, up to 900 nm. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces.

PubMed

Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine A

2016-11-23

A detailed understanding of the electrochemical reduction of CO 2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO 2 (1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO 2 reduction reaction (CO2RR) based on thermodynamic analysis. We aim to specify the requirements for CO2RR catalysts to establish adsorbate scaling relations and use these to derive activity volcanoes. Computational results show that the OH* binding free energy is a good descriptor of the thermodynamic limitations and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits their suitability. We determine the ideal binding free energy for H* and OH* to facilitate selective CO2RR over H 2 /CO evolution to be ΔG B [H]>0.5 eV and -0.5 eV<ΔG B [OH]<0.1 eV. The Re-containing overlayers considered in this work display excellent promise for selectivity, although they are active at a highly reducing potential. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion.

PubMed

Wang, Peng; Chang, Angela Y; Novosad, Valentyn; Chupin, Vladimir V; Schaller, Richard D; Rozhkova, Elena A

2017-07-25

We report on an entirely man-made nano-bio architecture fabricated through noncovalent assembly of a cell-free expressed transmembrane proton pump and TiO 2 semiconductor nanoparticles as an efficient nanophotocatalyst for H 2 evolution. The system produces hydrogen at a turnover of about 240 μmol of H 2 (μmol protein) -1 h -1 and 17.74 mmol of H 2 (μmol protein) -1 h -1 under monochromatic green and white light, respectively, at ambient conditions, in water at neutral pH and room temperature, with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allow for systemic manipulation at the nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Widespread Positive Selection Drives Differentiation of Centromeric Proteins in the Drosophila melanogaster subgroup.

PubMed

Beck, Emily A; Llopart, Ana

2015-11-25

Rapid evolution of centromeric satellite repeats is thought to cause compensatory amino acid evolution in interacting centromere-associated kinetochore proteins. Cid, a protein that mediates kinetochore/centromere interactions, displays particularly high amino acid turnover. Rapid evolution of both Cid and centromeric satellite repeats led us to hypothesize that the apparent compensatory evolution may extend to interacting partners in the Condensin I complex (i.e., SMC2, SMC4, Cap-H, Cap-D2, and Cap-G) and HP1s. Missense mutations in these proteins often result in improper centromere formation and aberrant chromosome segregation, thus selection for maintained function and coevolution among proteins of the complex is likely strong. Here, we report evidence of rapid evolution and recurrent positive selection in seven centromere-associated proteins in species of the Drosophila melanogaster subgroup, and further postulate that positive selection on these proteins could be a result of centromere drive and compensatory changes, with kinetochore proteins competing for optimal spindle attachment.

Infrared Spectral Studies of the Thermally-Driven Chemistry Present on Icy Satellites

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2012-01-01

Remote sensing of Jupiters icy satellites has revealed that even though their surfaces arc composed mostly of water ice, molecules such as SO2, CO2, H2O2. O2, and O3 also are present. On Europa, a high radiation flux is believed to play a role in the formation of many of the minor species detected, and numerous laboratory studies have been devoted to explore this hypothesis. In this presentation we will discuss some of our recent research on another alteration pathway, thermally-driven chemical reactions, which are also important for understanding the chemical evolution of Europa's surface and sub-surface ices. We will focus on the infrared spectra of and reactions between H2O, SO2 and H2O2, at 80 - 130 K.

Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution.

PubMed

Liu, Yueqiang; Phenrat, Tanapon; Lowry, Gregory V

2007-11-15

Nanoscale zero-valent iron (NZVI) is used to remediate contaminated groundwater plumes and contaminant source zones. The target contaminant concentration and groundwater solutes (NO3-, Cl-, HCO3-, SO4(2-), and HPO4(2-)) should affect the NZVI longevity and reactivity with target contaminants, but these effects are not well understood. This study evaluates the effect of trichloroethylene (TCE) concentration and common dissolved groundwater solutes on the rates of NZVI-promoted TCE dechlorination and H2 evolution in batch reactors. Both model systems and real groundwater are evaluated. The TCE reaction rate constant was unaffected by TCE concentration for [TCE] < or = 0.46 mM and decreased by less than a factor of 2 for further increases in TCE concentration up to water saturation (8.4 mM). For [TCE] > or = 0.46 mM, acetylene formation increased, and the total amount of H2 evolved at the end of the particle reactive lifetime decreased with increasing [TCE], indicating a higher Fe0 utilization efficiency for TCE dechlorination. Common groundwater anions (5mN) had a minor effect on H2 evolution but inhibited TCE reduction up to 7-fold in increasing order of Cl- < SO4(2-) < HCO3- < HPO4(2). This order is consistent with their affinity to form complexes with iron oxide. Nitrate, a NZVI-reducible groundwater solute, present at 0.2 and 1 mN did not affect the rate of TCE reduction but increased acetylene production and decreased H2 evolution. NO3- present at > 3 mM slowed TCE dechlorination due to surface passivation. NO3- present at 5 mM stopped TCE dechlorination and H2 evolution after 3 days. Dissolved solutes accounted for the observed decrease of NZVI reactivity for TCE dechlorination in natural groundwater when the total organic content was small (< 1 mg/L).

Pore Formation Process of Porous Ti3SiC2 Fabricated by Reactive Sintering

PubMed Central

Zhang, Huibin; Liu, Xinli; Jiang, Yao

2017-01-01

Porous Ti3SiC2 was fabricated with high purity, 99.4 vol %, through reactive sintering of titanium hydride (TiH2), silicon (Si) and graphite (C) elemental powders. The reaction procedures and the pore structure evolution during the sintering process were systematically studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). Our results show that the formation of Ti3SiC2 from TiH2/Si/C powders experienced the following steps: firstly, TiH2 decomposed into Ti; secondly, TiC and Ti5Si3 intermediate phases were generated; finally, Ti3SiC2 was produced through the reaction of TiC, Ti5Si3 and Si. The pores formed in the synthesis procedure of porous Ti3SiC2 ceramics are derived from the following aspects: interstitial pores left during the pressing procedure; pores formed because of the TiH2 decomposition; pores formed through the reactions between Ti and Si and Ti and C powders; and the pores produced accompanying the final phase synthesized during the high temperature sintering process. PMID:28772515

Large-scale Distribution of CH4 in the Western North Pacific: Sources and Transport from the Asian Continent

NASA Technical Reports Server (NTRS)

Bartlett, Karen B.; Sachse, Glen W.; Slate, Thomas; Harward, Charles; Blake, Donald R.

2003-01-01

Methane (CH4) mixing ratios in the northern Pacific Basin were sampled from two aircraft during the TRACE-P mission (Transport and Chemical Evolution over the Pacific) from late February through early April 2001 using a tunable diode laser system. Described in more detail by Jacob et al., the mission was designed to characterize Asian outflow to the Pacific, determine its chemical evolution, and assess changes to the atmosphere resulting from the rapid industrialization and increased energy usage on the Asian continent. The high-resolution, high-precision data set of roughly 13,800 CH4 measurements ranged between 1602 ppbv in stratospherically influenced air and 2149 ppbv in highly polluted air. Overall, CH4 mixing ratios were highly correlated with a variety of other trace gases characteristic of a mix of anthropogenic industrial and combustion sources and were strikingly correlated with ethane (C2H6) in particular. Averages with latitude in the near-surface (0-2 km) show that CH4 was elevated well above background levels north of 15 deg N close to the Asian continent. In the central and eastern Pacific, levels of CH4 were lower as continental inputs were mixed horizontally and vertically during transport. Overall, the correlation between CH4 and other hydrocarbons such as ethane (C2H6), ethyne (C2H2), and propane (C3H8) as well as the urban/industrial tracer perchloroethene (C2Cl4), suggests that for CH4 colocated sources such as landfills, wastewater treatment, and fossil fuel use associated with urban areas dominate regional inputs at this time. Comparisons between measurements made during TRACE-P and those of PEM-West B, flown during roughly the same time of year and under a similar meteorological setting 7 years earlier, suggest that although the TRACE-P CH4 observations are higher, the changes are not significantly greater than the increases seen in background air over this time interval.

Sex chromosome linked genetic variance and the evolution of sexual dimorphism of quantitative traits.

PubMed

Husby, Arild; Schielzeth, Holger; Forstmeier, Wolfgang; Gustafsson, Lars; Qvarnström, Anna

2013-03-01

Theory predicts that sex chromsome linkage should reduce intersexual genetic correlations thereby allowing the evolution of sexual dimorphism. Empirical evidence for sex linkage has come largely from crosses and few studies have examined how sexual dimorphism and sex linkage are related within outbred populations. Here, we use data on an array of different traits measured on over 10,000 individuals from two pedigreed populations of birds (collared flycatcher and zebra finch) to estimate the amount of sex-linked genetic variance (h(2)z ). Of 17 traits examined, eight showed a nonzero h(2)Z estimate but only four were significantly different from zero (wing patch size and tarsus length in collared flycatchers, wing length and beak color in zebra finches). We further tested how sexual dimorphism and the mode of selection operating on the trait relate to the proportion of sex-linked genetic variance. Sexually selected traits did not show higher h(2)Z than morphological traits and there was only a weak positive relationship between h(2)Z and sexual dimorphism. However, given the relative scarcity of empirical studies, it is premature to make conclusions about the role of sex chromosome linkage in the evolution of sexual dimorphism. © 2012 The Author(s). Evolution© 2012 The Society for the Study of Evolution.

The Interactive Effects of Elevated CO2 and Ammonium Enrichment on the Physiological Performances of Saccharina japonica (Laminariales, Phaeophyta)

NASA Astrophysics Data System (ADS)

Kang, Jin Woo; Chung, Ik Kyo

2018-04-01

Environmental challenges such as ocean acidification and eutrophication influence the physiology of kelp species. We investigated their interactive effects on Saccharina japonica (Laminariales, Phaeophyta) under two pH conditions [Low, 7.50; High (control), 8.10] and three NH4 +concentrations (Low, 4; Medium, 60; High, 120 μM). The degree of variation of pH values in the culture medium and inhibition rate of photosynthetic oxygen evolution by acetazolamide were affected by pH treatments. Relative growth rates, carbon, nitrogen, and the C:N ratio in tissue samples were influenced by higher concentrations of NH4 + . Rates of photosynthetic oxygen evolution were enhanced under elevated CO2 or NH4 +conditions, independently, but these two factors did not show an interactive effect. However, rates of NH4 +uptake were influenced by the interactive effect of increased CO2 under elevated NH4 +treatment. Although ocean acidification and eutrophication states had an impact on physiological performance, chlorophyll fluorescence was not affected by those conditions. Our results indicated that the physiological reactions by this alga were influenced to some extent by a rise in the levels of CO2 and NH4 + . Therefore, we expect that the biomass accumulation of S. japonica may well increase under future scenarios of ocean acidification and eutrophication.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

The electrochemical selective reduction of NO using CoSe2@CNTs hybrid.

PubMed

Liu, Hui; Xiang, Kaisong; Yang, Bentao; Xie, Xiaofeng; Wang, Dongli; Zhang, Cong; Liu, Zhilou; Yang, Shu; Liu, Cao; Zou, Jianping; Chai, Liyuan

2017-06-01

Converting the NO from gaseous pollutant into NH 4 + through electrocatalytical reduction using cost-effective materials holds great promise for pollutant purifying and resources recycling. In this work, we developed a highly selective and stable catalyst CoSe 2 nanoparticle hybridized with carbon nanotubes (CoSe 2 @CNTs). The CoSe 2 @CNTs hybrid catalysts performed an extraordinary high selectivity for NH 4 + formation in NO electroreduction with minimal N 2 O production and H 2 evolution. The specific spatial structure of CoSe 2 is conductive to the predominant formation of N-H bond between the N from adsorbed NO and H and inhibition of N-N formation from adjacent adsorbed NO. It was also the first time to convert the coordinated NO into NH 4 + using non-noble metal catalysis. Moreover, the original concept of employing CoSe 2 as eletrocatalyst for NO hydrogenation presented in this work can broaden horizons and provide new dimensions in the design of new highly efficient catalysts for NH 4 + synthesis in aqueous solution.

THERMAL EVOLUTION AND STRUCTURE MODELS OF THE TRANSITING SUPER-EARTH GJ 1214b

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

Nettelmann, N.; Fortney, J. J.; Kramm, U.

The planet GJ 1214b is the second known super-Earth with a measured mass and radius. Orbiting a quiet M star, it receives considerably less mass-loss driving X-ray and UV radiation than CoRoT-7b, so that the interior may be quite dissimilar in composition, including the possibility of a large fraction of water. We model the interior of GJ 1214b assuming a two-layer (envelope+rock core) structure where the envelope material is either H/He, pure water, or a mixture of H/He and H{sub 2}O. Within this framework, we perform models of the thermal evolution and contraction of the planet. We discuss possible compositionsmore » that are consistent with M{sub p} = 6.55 M{sub +}, R{sub p} = 2.678 R{sub +}, an age {tau} = 3-10 Gyr, and the irradiation level of the atmosphere. These conditions require that if water exists in the interior, it must remain in a fluid state, with important consequences for magnetic field generation. These conditions also require the atmosphere to have a deep isothermal region extending down to 80-800 bar, depending on composition. Our results bolster the suggestion of a metal-enriched H/He atmosphere for the planet, as we find water-world models that lack an H/He atmosphere to require an implausibly large water-to-rock ratio of more than 6:1. We instead favor an H/He/H{sub 2}O envelope with high water mass fraction ({approx}0.5-0.85), similar to recent models of the deep envelope of Uranus and Neptune. Even with these high water mass fractions in the H/He envelope, generally the bulk composition of the planet can have subsolar water:rock ratios. Dry, water-enriched, and pure water envelope models differ to an observationally significant level in their tidal Love numbers k{sub 2} of, respectively, {approx}0.018, {approx}0.15, and {approx}0.7.« less

Photo-induced oxidant-free oxidative C-H/N-H cross-coupling between arenes and azoles

NASA Astrophysics Data System (ADS)

Niu, Linbin; Yi, Hong; Wang, Shengchun; Liu, Tianyi; Liu, Jiamei; Lei, Aiwen

2017-02-01

Direct cross-coupling between simple arenes and heterocyclic amines under mild conditions is undoubtedly important for C-N bonds construction. Selective C(sp2)-H amination is more valuable. Herein we show a selective C(sp2)-H amination of arenes (alkyl-substituted benzenes, biphenyl and anisole derivatives) accompanied by hydrogen evolution by using heterocyclic azoles as nitrogen sources. The reaction is selective for C(sp2)-H bonds, providing a mild route to N-arylazoles. The KIE (kinetic isotope effect) experiment reveals the cleavage of C-H bond is not involved in the rate-determining step. Kinetic studies indicate the first-order behaviour with respect to the arene component. It is interesting that this system works without the need for any sacrificial oxidant and is highly selective for C(sp2)-H activation, whereas C(sp3)-H bonds are unaffected. This study may have significant implications for the functionalization of methylarenes which are sensitive to oxidative conditions.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion

DOE PAGES

Wang, Peng; Chang, Angela Y.; Novosad, Valentyn; ...

2017-06-11

We report on entirely man-made nanobio hybrid fabricated through assembly of cell-free expressed transmembrane proton pump and semiconductor nanoparticles as an efficient nanocatalysis for photocatalytic H 2 evolution. The system produces H 2 at a turnover rate of 239 (μmole protein) -1 h -1 under green and 17742 (μmole protein) -1 h -1 under white light at ambient conditions, in water at neutral pH with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allows for systemic manipulation at nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion

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

Wang, Peng; Chang, Angela Y.; Novosad, Valentyn

We report on entirely man-made nanobio hybrid fabricated through assembly of cell-free expressed transmembrane proton pump and semiconductor nanoparticles as an efficient nanocatalysis for photocatalytic H 2 evolution. The system produces H 2 at a turnover rate of 239 (μmole protein) -1 h -1 under green and 17742 (μmole protein) -1 h -1 under white light at ambient conditions, in water at neutral pH with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allows for systemic manipulation at nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Prebiotic Synthesis of Glycine from Ethanolamine in Simulated Archean Alkaline Hydrothermal Vents

NASA Astrophysics Data System (ADS)

Zhang, Xianlong; Tian, Ge; Gao, Jing; Han, Mei; Su, Rui; Wang, Yanxiang; Feng, Shouhua

2017-12-01

Submarine hydrothermal vents are generally considered as the likely habitats for the origin and evolution of early life on Earth. In recent years, a novel hydrothermal system in Archean subseafloor has been proposed. In this model, highly alkaline and high temperature hydrothermal fluids were generated in basalt-hosted hydrothermal vents, where H2 and CO2 could be abundantly provided. These extreme conditions could have played an irreplaceable role in the early evolution of life. Nevertheless, sufficient information has not yet been obtained for the abiotic synthesis of amino acids, which are indispensable components of life, at high temperature and alkaline condition. This study aims to propose a new method for the synthesis of glycine in simulated Archean submarine alkaline vent systems. We investigated the formation of glycine from ethanolamine under conditions of high temperature (80-160 °C) and highly alkaline solutions (pH = 9.70). Experiments were performed in an anaerobic environment under mild pressure (0.1-8.0 MPa) at the same time. The results suggested that the formation of glycine from ethanolamine occurred rapidly and efficiently in the presence of metal powders, and was favored by high temperatures and high pressures. The experiment provides a new pathway for prebiotic glycine formation and points out the phenomenal influence of high-temperature alkaline hydrothermal vents in origin of life in the early ocean.

Chemistry in Infrared Dark Cloud Clumps: A Molecular Line Survey at 3 mm

NASA Astrophysics Data System (ADS)

Sanhueza, Patricio; Jackson, James M.; Foster, Jonathan B.; Garay, Guido; Silva, Andrea; Finn, Susanna C.

2012-09-01

We have observed 37 Infrared Dark Clouds (IRDCs), containing a total of 159 clumps, in high-density molecular tracers at 3 mm using the 22 m ATNF Mopra Telescope located in Australia. After determining kinematic distances, we eliminated clumps that are not located in IRDCs and clumps with a separation between them of less than one Mopra beam. Our final sample consists of 92 IRDC clumps. The most commonly detected molecular lines are (detection rates higher than 8%) N2H+, HNC, HN13C, HCO+, H13CO+, HCN, C2H, HC3N, HNCO, and SiO. We investigate the behavior of the different molecular tracers and look for chemical variations as a function of an evolutionary sequence based on Spitzer IRAC and MIPS emission. We find that the molecular tracers behave differently through the evolutionary sequence and some of them can be used to yield useful relative age information. The presence of HNC and N2H+ lines does not depend on the star formation activity. On the other hand, HC3N, HNCO, and SiO are predominantly detected in later stages of evolution. Optical depth calculations show that in IRDC clumps the N2H+ line is optically thin, the C2H line is moderately optically thick, and HNC and HCO+ are optically thick. The HCN hyperfine transitions are blended, and, in addition, show self-absorbed line profiles and extended wing emission. These factors combined prevent the use of HCN hyperfine transitions for the calculation of physical parameters. Total column densities of the different molecules, except C2H, increase with the evolutionary stage of the clumps. Molecular abundances increase with the evolutionary stage for N2H+ and HCO+. The N2H+/HCO+ and N2H+/HNC abundance ratios act as chemical clocks, increasing with the evolution of the clumps.

Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage† †Electronic supplementary information (ESI) available: Experimental and computational details, free energy plots for the NH3 evolution and N2 reduction with Co3N/Co, Fe4N/Fe, Mn5N2/Mn4N, Mo2N/Mo, CrN/Cr2N, TaN/Ta2N, NbN/Nb2N, Li3N/LiH, Ba3N2/BaH2, Sr3N2/SrH2, and Ca3N2/CaH2, surface oxidation energetics, ΔGvac[NH*x, yH*] based on gas phase H2 as hydrogen source, NH3 evolution with Fe-doped Mn4N, NH3 evolution with Mn6N2.58, Ca3N2 and Sr2N after correcting for partial nitride hydrolysis, NH3 yield from Ca3N2vs. time and H2 gas flow rate. See DOI: 10.1039/c5sc00789e

PubMed Central

Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A.

2015-01-01

The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH3), a fertilizer and chemical fuel, from N2 and H2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn6N2.58 to Mn4N and hydrogenation of Ca3N2 and Sr2N to Ca2NH and SrH2, respectively. PMID:29218166

Chemical evolution in spiral and irregular galaxies

NASA Technical Reports Server (NTRS)

Torres-Peimbert, S.

1986-01-01

A brief review of models of chemical evolution of the interstellar medium in our galaxy and other galaxies is presented. These models predict the time variation and radial dependence of chemical composition in the gas as function of the input parameters; initial mass function, stellar birth rate, chemical composition of mass lost by stars during their evolution (yields), and the existence of large scale mass flows, like infall from the halo, outflow to the intergalactic medium or radial flows within a galaxy. At present there is a considerable wealth of observational data on the composition of HII regions in spiral and irregular galaxies to constrain the models. Comparisons are made between theory and the observed physical conditions. In particular, studies of helium, carbon, nitrogen and oxygen abundances are reviewed. In many molecular clouds the information we have on the amount of H2 is derived from the observed CO column density, and a standard CO/H2 ratio derived for the solar neighborhood. Chemical evolution models and the observed variations in O/H and N/O values, point out the need to include these results in a CO/H2 relation that should be, at least, a function of the O/H ratio. This aspect is also discussed.

Monopole-driven shell evolution below the doubly magic nucleus 132Sn explored with the long-lived isomer in 126Pd.

PubMed

Watanabe, H; Lorusso, G; Nishimura, S; Otsuka, T; Ogawa, K; Xu, Z Y; Sumikama, T; Söderström, P-A; Doornenbal, P; Li, Z; Browne, F; Gey, G; Jung, H S; Taprogge, J; Vajta, Zs; Wu, J; Yagi, A; Baba, H; Benzoni, G; Chae, K Y; Crespi, F C L; Fukuda, N; Gernhäuser, R; Inabe, N; Isobe, T; Jungclaus, A; Kameda, D; Kim, G D; Kim, Y K; Kojouharov, I; Kondev, F G; Kubo, T; Kurz, N; Kwon, Y K; Lane, G J; Moon, C-B; Montaner-Pizá, A; Moschner, K; Naqvi, F; Niikura, M; Nishibata, H; Nishimura, D; Odahara, A; Orlandi, R; Patel, Z; Podolyák, Zs; Sakurai, H; Schaffner, H; Simpson, G S; Steiger, K; Suzuki, H; Takeda, H; Wendt, A; Yoshinaga, K

2014-07-25

A new isomer with a half-life of 23.0(8) ms has been identified at 2406 keV in (126)Pd and is proposed to have a spin and parity of 10(+) with a maximally aligned configuration comprising two neutron holes in the 1h(11/2) orbit. In addition to an internal-decay branch through a hindered electric octupole transition, β decay from the long-lived isomer was observed to populate excited states at high spins in (126)Ag. The smaller energy difference between the 10(+) and 7(-) isomers in (126)Pd than in the heavier N=80 isotones can be interpreted as being ascribed to the monopole shift of the 1h(11/2) neutron orbit. The effects of the monopole interaction on the evolution of single-neutron energies below (132)Sn are discussed in terms of the central and tensor forces.

Seeing diabetes: visual detection of glucose based on the intrinsic peroxidase-like activity of MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Lin, Tianran; Zhong, Liangshuang; Guo, Liangqia; Fu, Fengfu; Chen, Guonan

2014-09-01

Molybdenum disulfide (MoS2) has attracted increasing research interest recently due to its unique physical, optical and electrical properties, correlated with its 2D ultrathin atomic-layered structure. Until now, however, great efforts have focused on its applications such as lithium ion batteries, transistors, and hydrogen evolution reactions. Herein, for the first time, MoS2 nanosheets are discovered to possess an intrinsic peroxidase-like activity and can catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce a color reaction. The catalytic activity follows the typical Michaelis-Menten kinetics and is dependent on temperature, pH, H2O2 concentration, and reaction time. Based on this finding, a highly sensitive and selective colorimetric method for H2O2 and glucose detection is developed and applied to detect glucose in serum samples. Moreover, a simple, inexpensive, instrument-free and portable test kit for the visual detection of glucose in normal and diabetic serum samples is constructed by utilizing agarose hydrogel as a visual detection platform.Molybdenum disulfide (MoS2) has attracted increasing research interest recently due to its unique physical, optical and electrical properties, correlated with its 2D ultrathin atomic-layered structure. Until now, however, great efforts have focused on its applications such as lithium ion batteries, transistors, and hydrogen evolution reactions. Herein, for the first time, MoS2 nanosheets are discovered to possess an intrinsic peroxidase-like activity and can catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce a color reaction. The catalytic activity follows the typical Michaelis-Menten kinetics and is dependent on temperature, pH, H2O2 concentration, and reaction time. Based on this finding, a highly sensitive and selective colorimetric method for H2O2 and glucose detection is developed and applied to detect glucose in serum samples. Moreover, a simple, inexpensive, instrument-free and portable test kit for the visual detection of glucose in normal and diabetic serum samples is constructed by utilizing agarose hydrogel as a visual detection platform. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03393k

Scalable Low-Band-Gap Sb2Se3 Thin-Film Photocathodes for Efficient Visible-Near-Infrared Solar Hydrogen Evolution.

PubMed

Zhang, Li; Li, Yanbo; Li, Changli; Chen, Qiao; Zhen, Zhen; Jiang, Xin; Zhong, Miao; Zhang, Fuxiang; Zhu, Hongwei

2017-12-26

A highly efficient low-band-gap (1.2-0.8 eV) photoelectrode is critical for accomplishing efficient conversion of visible-near-infrared sunlight into storable hydrogen. Herein, we report an Sb 2 Se 3 polycrystalline thin-film photocathode having a low band gap (1.2-1.1 eV) for efficient hydrogen evolution for wide solar-spectrum utilization. The photocathode was fabricated by a facile thermal evaporation of a single Sb 2 Se 3 powder source onto the Mo-coated soda-lime glass substrate, followed by annealing under Se vapor and surface modification with an antiphotocorrosive CdS/TiO 2 bilayer and Pt catalyst. The fabricated Sb 2 Se 3 (Se-annealed)/CdS/TiO 2 /Pt photocathode achieves a photocurrent density of ca. -8.6 mA cm -2 at 0 V RHE , an onset potential of ca. 0.43 V RHE , a stable photocurrent for over 10 h, and a significant photoresponse up to the near-infrared region (ca. 1040 nm) in near-neutral pH buffered solution (pH 6.5) under AM 1.5G simulated sunlight. The obtained photoelectrochemical performance is attributed to the reliable synthesis of a micrometer-sized Sb 2 Se 3 (Se-annealed) thin film as photoabsorber and the successful construction of an appropriate p-n heterojunction at the electrode-liquid interface for effective charge separation. The demonstration of a low-band-gap and high-performance Sb 2 Se 3 photocathode with facile fabrication might facilitate the development of cost-effective PEC devices for wide solar-spectrum utilization.

Approaches to efficient molecular catalyst systems for photochemical H2 production using [FeFe]-hydrogenase active site mimics.

PubMed

Wang, Mei; Chen, Lin; Li, Xueqiang; Sun, Licheng

2011-12-28

The research on structural and functional biomimics of the active site of [FeFe]-hydrogenases is in an attempt to elucidate the mechanisms of H(2)-evolution and uptake at the [FeFe]-hydrogenase active site, and to learn from Nature how to create highly efficient H(2)-production catalyst systems. Undoubtedly, it is a challenging, arduous, and long-term work. In this perspective, the progresses in approaches to photochemical H(2) production using mimics of the [FeFe]-hydrogenase active site as catalysts in the last three years are reviewed, with emphasis on adjustment of the redox potentials and hydrophilicity of the [FeFe]-hydrogenase active site mimics to make them efficient catalysts for H(2) production. With gradually increasing understanding of the chemistry of the [FeFe]-hydrogenases and their mimics, more bio-inspired proton reduction catalysts with significantly improved efficiency of H(2) production will be realized in the future. This journal is © The Royal Society of Chemistry 2011

High-temperature morphological evolution of lithographically introduced cavities in silicon carbide

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

Narushima, Takayuki; Glaeser, Andreas M.

2000-12-01

Internal cavities of controlled geometry and crystallography were introduced in 6H silicon carbide single crystals by combining lithographic methods, ion beam etching, and solid-state diffusion bonding. The morphological evolution of these internal cavities (negative crystals) in response to anneals of up to 128 h duration at 1900 degrees C was examined using optical microscopy. Surface energy anisotropy and faceting have a strong influence on both the geometric and kinetic characteristics of evolution. Decomposition of 12{bar 1}0 cavity edges into 101{bar 0} facets was observed after 16 h anneals, indicating that 12{bar 1}0 faces are not components of the Wulff shape.more » The shape evolution kinetics of penny-shaped cavities were also investigated. Experimentally observed evolution rates decreased much more rapidly with those predicted by a model in which surface diffusion is assumed to be rate-limiting. This suggests that the development of facets, and the associated loss of ledges and terraces during the initial stages of evolution results in an evolution process limited by the nucleation rate of attachment/detachment sites (ledges) on the facets.« less

Boron-capped tris(glyoximato) cobalt clathrochelate as a precursor for the electrodeposition of nanoparticles catalyzing H2 evolution in water.

PubMed

Anxolabéhère-Mallart, Elodie; Costentin, Cyrille; Fournier, Maxime; Nowak, Sophie; Robert, Marc; Savéant, Jean-Michel

2012-04-11

Electrochemical investigation of a boron-capped tris(glyoximato)cobalt clathrochelate complex in the presence of acid reveals that the catalytic activity toward hydrogen evolution results from an electrodeposition of cobalt-containing nanoparticles on the electrode surface at a modest cathodic potential. The deposited particles act as remarkably active catalysts for H(2) production in water at pH 7. © 2012 American Chemical Society

One- or two-electron water oxidation, hydroxyl radical, or H 2O 2 evolution

DOE PAGES

Siahrostami, Samira; Li, Guo -Ling; Viswanathan, Venkatasubramanian; ...

2017-02-23

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H 2O 2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O 2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H 2O 2, and O 2.

An Earth-Abundant Catalyst-Based Seawater Photoelectrolysis System with 17.9% Solar-to-Hydrogen Efficiency.

PubMed

Hsu, Shao-Hui; Miao, Jianwei; Zhang, Liping; Gao, Jiajian; Wang, Hongming; Tao, Huabing; Hung, Sung-Fu; Vasileff, Anthony; Qiao, Shi Zhang; Liu, Bin

2018-05-01

The implementation of water splitting systems, powered by sustainable energy resources, appears to be an attractive strategy for producing high-purity H 2 in the absence of the release of carbon dioxide (CO 2 ). However, the high cost, impractical operating conditions, and unsatisfactory efficiency and stability of conventional methods restrain their large-scale development. Seawater covers 70% of the Earth's surface and is one of the most abundant natural resources on the planet. New research is looking into the possibility of using seawater to produce hydrogen through electrolysis and will provide remarkable insight into sustainable H 2 production, if successful. Here, guided by density functional theory (DFT) calculations to predict the selectivity of gas-evolving catalysts, a seawater-splitting device equipped with affordable state-of-the-art electrocatalysts composed of earth-abundant elements (Fe, Co, Ni, and Mo) is demonstrated. This device shows excellent durability and specific selectivity toward the oxygen evolution reaction in seawater with near 100% Faradaic efficiency for the production of H 2 and O 2 . Powered by a single commercial III-V triple-junction photovoltaic cell, the integrated system achieves spontaneous and efficient generation of high-purity H 2 and O 2 from seawater at neutral pH with a remarkable 17.9% solar-to-hydrogen efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental infection of highly pathogenic avian influenza viruses, Clade 2.3.4.4 H5N6 and H5N8, in Mandarin ducks from South Korea.

PubMed

Son, K; Kim, Y-K; Oem, J-K; Jheong, W-H; Sleeman, J M; Jeong, J

2018-06-01

Outbreaks of highly pathogenic avian influenza (HPAI) have been reported worldwide. Wild waterfowl play a major role in the maintenance and transmission of HPAI. Highly pathogenic avian influenza subtype H5N6 and H5N8 viruses simultaneously emerged in South Korea. In this study, the comparative pathogenicity and infectivity of Clade 2.3.4.4 Group B H5N8 and Group C H5N6 viruses were evaluated in Mandarin duck (Aix galericulata). None of the ducks infected with H5N6 or H5N8 viruses showed clinical signs or mortality. Serological assays revealed that the HA antigenicity of H5N8 and H5N6 viruses was similar to each other. Moreover, both the viruses did not replicate after cross-challenging with H5N8 and H5N6 viruses, respectively, as the second infection. Although both the viruses replicated in most of the internal organs of the ducks, viral replication and shedding through cloaca were higher in H5N8-infected ducks than in H5N6-infected ducks. The findings of this study provide preliminary information to help estimate the risks involved in further evolution and dissemination of Clade 2.3.4.4 HPAI viruses among wild birds. © 2017 The Authors. Transboundary and Emerging Diseases Published by Blackwell Verlag GmbH.

Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

PubMed

Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

2015-09-01

The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terrestrial soil pH and MAAT records based on the MBT/CBT in the southern South China Sea: implications for the atmospheric CO2 evolution in Southeast Asia

NASA Astrophysics Data System (ADS)

Dong, L.; Li, L.; Li, Q.; Zhang, C.

2013-12-01

Liang Dong1, Li Li1, Qianyu Li1,2, Chuanlun L. Zhang1,3 1State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092, China 2School of Earth and Environment Sciences, University of Adelaide, SA 5005, Australia 3Department of Marine Sciences, University of Georgia, Athens, GA 30602, USA The methylation index of branched tetraethers (MBT) and/or the cyclization ratio of branched tetraethers (CBT) are derived from the branched glycerol dialkyl Glycerol tetraethers (GDGTs) of bacterial origin and are widely used to reconstruct the terrestrial soil pH and mean annual air temperature (MAAT); however, these proxies are less frequently used in the oceanic settings. Here we provide the first high resolution records of soil pH and MAAT since the last glacial maximum based on the sedimentary core of MD05-2896 in the southern South China Sea. The MAAT record exhibited typical glacial and interglacial cycles and was consistent with the winter insolation variation. The pH values were lower (6.4-7) in the glacial time and higher (7-8.4) in the interglacial time. Changes in soil pH allowed the evaluation of changes in soil CO2 based on the atmosphere-soil CO2 balance. The results imply that the lower winter MAAT variation with a lower winter atmospheric CO2 concentration might have resulted in a higher pH in the interglacial period. Our records provide a new insight into the evolution of atmospheric CO2 between glacial and interglacial cycles in East Asia. Key words: South China Sea, MBT/CBT, b-GDGTs, MAAT, pH

High H2O/Ce of K-rich MORB from Lena Trough and Gakkel Ridge, Arctic Ocean

NASA Astrophysics Data System (ADS)

Snow, J. E.; Feig, S. T.

2014-12-01

Lena Trough in the Arctic ocean is the oblique spreading continuation of Gakkel Ridge through the Fram Strait (eg Snow et al. 2011). Extreme trace element and isotopic compositions seen in Lena Trough basalt appear to be the enriched end member dominating the geochemistry of the Western Volcanic Zone of the Western Gakkel Ridge as traced by Pb isotopes, K2O/TiO2, Ba/Nb and other isotopic, major and trace element indicators of mixing (Nauret et al., 2011). This is in contrast to neighboring Gakkel Ridge which has been spreading for 50-60 million years. Basalts from Lena Trough also show a pure MORB noble gas signature (Nauret et al., 2010) and peridotites show no evidence of ancient components in their Os isotopes (Lassiter, et al., in press). The major and trace element compositions of the basalts, however are very distinct from MORB, being far more potassic than all but a single locality on the SW Indian Ridge. We determined H2O and trace element composiitions of a suite of 17 basalt glasses from the Central Lena Trough (CLT) and the Gakkel Western Volcanic Zone, including many of those previously analyzed by Nauret et al. (2012). The Western Gakkel glasses have high H2O/Ce for MORB (>300) suggesting a water rich source consistent with the idea that the northernmost Atlantic mantle is enriched in water (Michael et al., 1995). They are within the range of Eastern Gakkel host glasses determined by Wanless et al, 2013. The Lena Trough (CLT) glasses are very rich in water for MORB (>1% H2O) and are among the highest H2O/Ce (>400) ever measured in MORB aside from melt inclusions in olivine. Mantle melting dynamics and melt evolution cannot account for the H2O/Ce variations in MORB, as these elements have similar behavior during melting and crustal evolution. Interestingly, the H2O/K2O ratios in the basalts are only around 1. This is because the K2O levels in the CLT glasses are very high as well relative to REE. The absolutely linear relationship between H2O and K2O/TiO2 in Lena and Gakkel basalts shows that water systematics in these rocks are completely governed by source composition, with little or no modification by mantle melting dynamics or crystal fractionation. The geochemical influence of the WVZ enriched mantle source declines with distance from Lena Trough along Gakkel Ridge.

Protective efficacy of an inactivated vaccine against H9N2 avian influenza virus in ducks.

PubMed

Teng, Qiaoyang; Shen, Weixia; Liu, Qinfang; Rong, Guangyu; Chen, Lin; Li, Xuesong; Chen, Hongjun; Yang, Jianmei; Li, Zejun

2015-09-17

Wild ducks play an important role in the evolution of avian influenza viruses (AIVs). Domestic ducks in China are known to carry and spread H9N2 AIVs that are thought to have contributed internal genes for the recent outbreak of zoonotic H7N9 virus. In order to protect animal and public health, an effective vaccine is urgently needed to block and prevent the spread of H9N2 virus in ducks. We developed an inactivated H9N2 vaccine (with adjuvant Montanide ISA 70VG) based on an endemic H9N2 AIV and evaluated this vaccine in ducks. The results showed that the inactivated H9N2 vaccine was able to induce a strong and fast humoral immune response in vaccinated ducks. The hemagglutination inhibition titer in the sera increased fast, and reached its peak of 12.3 log2 at 5 weeks post-vaccination in immunized birds and remained at a high level for at least 37 weeks post-vaccination. Moreover, viral shedding was completely blocked in vaccinated ducks after challenge with a homologous H9N2 AIV at both 3 and 37 weeks post-vaccination. The results of this study indicate that the inactivated H9N2 vaccine induces high and prolonged immune response in vaccinated ducks and are efficacious in protecting ducks from H9N2 infection.

Highly Rechargeable Lithium-CO2 Batteries with a Boron- and Nitrogen-Codoped Holey-Graphene Cathode.

PubMed

Qie, Long; Lin, Yi; Connell, John W; Xu, Jiantie; Dai, Liming

2017-06-06

Metal-air batteries, especially Li-air batteries, have attracted significant research attention in the past decade. However, the electrochemical reactions between CO 2 (0.04 % in ambient air) with Li anode may lead to the irreversible formation of insulating Li 2 CO 3 , making the battery less rechargeable. To make the Li-CO 2 batteries usable under ambient conditions, it is critical to develop highly efficient catalysts for the CO 2 reduction and evolution reactions and investigate the electrochemical behavior of Li-CO 2 batteries. Here, we demonstrate a rechargeable Li-CO 2 battery with a high reversibility by using B,N-codoped holey graphene as a highly efficient catalyst for CO 2 reduction and evolution reactions. Benefiting from the unique porous holey nanostructure and high catalytic activity of the cathode, the as-prepared Li-CO 2 batteries exhibit high reversibility, low polarization, excellent rate performance, and superior long-term cycling stability over 200 cycles at a high current density of 1.0 A g -1 . Our results open up new possibilities for the development of long-term Li-air batteries reusable under ambient conditions, and the utilization and storage of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron vs. cobalt clathrochelate electrocatalysts of HER: the first example on a cage iron complex.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Mokhir, Andriy; Bubnov, Yurii N; Voloshin, Yan Z

2013-04-07

New macrobicyclic 2-thiopheneboron-capped iron and cobalt(II) tris-dioximates showed high electrocatalytic activity for hydrogen production from H(+) ions. This is the first example of the hydrogen evolution reaction electrocatalyzed by a clathrochelate iron complex, which catalyzes the hydrogen production at low overpotential.

Evolution Of The Galaxy Major Merger Rate Since Z 6 In The Muse Hubble Ultra Deep Field Survey.

NASA Astrophysics Data System (ADS)

Ventou, E.; Contini, T.; MUSE-GTO Collaboration

2017-06-01

Over the past two decades, strong evidence that galaxies have undergone a significant evolution over cosmic time were found. Do galaxy mergers, one of the main driving mechanisms behind the growth of galaxies, played a key role in their evolution at significant look-back time? Due to the difficulty to identify these violent interactions between galaxies at high redshifts, the major merger rate, involving two galaxies of similar masses, was constrained so far up to redshift z 3, from previous studies of spectrocopic pair counts. Thanks to MUSE, which is perfectly suited to identify close pairs of galaxies with secure spectroscopic redshifts, we are now able to extend such studies up to z 6. I will present the results obtained from deep (10-30h) MUSE observations in the Hubble Ultra Deep Field. We provide the first constraints on the galaxy major merger evolution over 12 Gyrs (0.2 < z < 6) and over a broad range of stellar masses, showing that there is a flattening of the major merger rate evolution at very high redshift.

A Molecular Ni-complex Containing Tetrahedral Nickel Selenide Core as Highly Efficient Electrocatalyst for Water Oxidation.

PubMed

Masud, Jahangir; Ioannou, Polydoros-Chrysovalantis; Levesanos, Nikolaos; Kyritsis, Panayotis; Nath, Manashi

2016-11-23

We report the highly efficient catalytic activity of a transition metal selenide-based coordination complex, [Ni{(SeP i Pr 2 ) 2 N} 2 ], (1) for oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solution. Very low overpotentials of 200 mV and 310 mV were required to achieve 10 mA cm -2 for OER and HER, respectively. The overpotential for OER is one of the lowest that has been reported up to now, making this one of the best OER electrocatalysts. In addition, this molecular complex exhibits an exceptionally high mass activity (111.02 A g -1 ) and a much higher TOF value (0.26 s -1 ) at a overpotential of 300 mV. This bifunctional electrocatalyst enables water electrolysis in alkaline solutions at a cell voltage of 1.54 V. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

MnFe2 O4 Nanocrystals Wrapped in a Porous Organic Polymer: A Designed Architecture for Water-Splitting Photocatalysis.

PubMed

Dhanalaxmi, Karnekanti; Yadav, Rajkumar; Kundu, Sudipta K; Reddy, Benjaram Mahipal; Amoli, Vipin; Sinha, Anil Kumar; Mondal, John

2016-10-24

A novel MnFe 2 O 4 -porous organic polymer (POP) nanocomposite was synthesized by a facile hydrothermal method and using the highly cross-linked N-rich benzene-benzylamine POP. The nanocomposite presented highly efficient photocatalytic performance in the hydrogen evolution reaction (HER) from pure water without addition of any sacrificial agent under one AM 1.5 G sunlight illumination. A photocatalytic activity of 6.12 mmol h -1  g -1 was achieved in the absence of any noble metal cocatalyst, which is the highest H 2 production rate reported for nonprecious metal catalysts. The photocatalytic performance of MnFe 2 O 4 -POP could be attributed to the intrinsic synergistic effects of manganese ferrite (MnFe 2 O 4 ) nanoclusters interacting with the nitrogen dopant POP with a unique mesoporous nanoarchitecture and spatially confined growth of MnFe 2 O 4 in the interconnected POP network, leading to high visible-light absorption with fast electron transport. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water Emission from Early Universe

NASA Astrophysics Data System (ADS)

Jarugula, Sreevani; Vieira, Joaquin

2017-06-01

The study of dusty star forming galaxies (DSFGs) is important to understand galaxy assembly in early universe. A bulk of star formation at z ˜ 2-3 takes place in DSFGs but are obscured by dust in optical/UV. However, they are extremely bright in far infrared (FIR) and submillimeter with infrared luminosities of 10^{11} - 10^{13} L_{⊙}. ALMA, with its high spatial and spectral resolution, has opened up a new window to study molecular lines, which are vital to our understanding of the excitation and physical processes in the galaxy. Carbon monoxide (CO) being the second most abundant and bright molecule after hydrogen (H_{2}), is an important tracer of star forming potential. Besides CO, water (H_{2}O) is also abundant and it's line strength is comparable to high-J CO lines in high redshift Ultra Luminous Infrared Galaxies (ULIRGs). Studies have shown H_{2}O to directly trace the FIR field and hence the star forming regions. Moreover, L_{H_{2}O}/L_{IR} ratio is nearly constant for five of the most important water lines and does not depend on the presence of AGN implying that H_{2}O is one of the best tracers of star forming regions (SFRs). This incredible correlation holds for nearly five orders of magnitude in luminosity and observed in both local and high redshift luminous infrared galaxies. In this talk, I will discuss the importance of H_{2}O in tracing FIR field and show the preliminary results of resolved water emission from three high-redshift gravitationally lensed South Pole Telescope (SPT) sources obtained from ALMA cycle 3 and cycle 4. These sources are among the first H_{2}O observations with resolved spatial scales ˜ 1 kpc and will prove to be important for ALMA and galaxy evolution studies.

Phylogenetic study-based hemagglutinin (HA) gene of highly pathogenic avian influenza virus (H5N1) detected from backyard chickens in Iran, 2015.

PubMed

Ghafouri, Syed Ali; Langeroudi, Arash Ghalyanchi; Maghsoudloo, Hossein; Tehrani, Farshad; Khaltabadifarahani, Reza; Abdollahi, Hamed; Fallah, Mohammad Hossein

2017-02-01

Highly pathogenic avian influenza (HPAI) viruses of the H5N1 subtype have been diversified into multiple phylogenetic clades over the past decade and are highly genetically variable. In June 2015, one outbreak of HPAI H5N1 in backyard chickens was reported in the Nogardan village of the Mazandaran Province. Tracheal tissues were taken from the dead domestic chickens (n = 10) and processed for RT-PCR. The positive samples (n = 10) were characterized as HPAI H5N1 by sequencing analysis for the hemagglutinin and neuraminidase genes. Phylogenetic analysis of the samples revealed that the viruses belonged to clade 2.3.2.1c, and cluster with the HPAI H5N1 viruses isolated from different avian species in Bulgaria, Romania, and Nigeria in 2015. They were not closely related to other H5N1 isolates detected in previous years in Iran. Our study provides new insights into the evolution and genesis of H5N1 influenza in Iran and has important implications for targeting surveillance efforts to rapidly identify the spread of the virus into and within Iran.

Reconstructing the history of water ice formation from HDO/H2O and D2O/HDO ratios in protostellar cores

NASA Astrophysics Data System (ADS)

Furuya, K.; van Dishoeck, E. F.; Aikawa, Y.

2016-02-01

Recent interferometer observations have found that the D2O/HDO abundance ratio is higher than that of HDO/H2O by about one order of magnitude in the vicinity of low-mass protostar NGC 1333-IRAS 2A, where water ice has sublimated. Previous laboratory and theoretical studies show that the D2O/HDO ice ratio should be lower than the HDO/H2O ice ratio, if HDO and D2O ices are formed simultaneously with H2O ice. In this work, we propose that the observed feature, D2O/HDO > HDO/H2O, is a natural consequence of chemical evolution in the early cold stages of low-mass star formation as follows: 1) majority of oxygen is locked up in water ice and other molecules in molecular clouds, where water deuteration is not efficient; and 2) water ice formation continues with much reduced efficiency in cold prestellar/protostellar cores, where deuteration processes are highly enhanced as a result of the drop of the ortho-para ratio of H2, the weaker UV radiation field, etc. Using a simple analytical model and gas-ice astrochemical simulations, which traces the evolution from the formation of molecular clouds to protostellar cores, we show that the proposed scenario can quantitatively explain the observed HDO/H2O and D2O/HDO ratios. We also find that the majority of HDO and D2O ices are likely formed in cold prestellar/protostellar cores rather than in molecular clouds, where the majority of H2O ice is formed. This work demonstrates the power of the combination of the HDO/H2O and D2O/HDO ratios as a tool to reveal the past history of water ice formation in the early cold stages of star formation, and when the enrichment of deuterium in the bulk of water occurred. Further observations are needed to explore if the relation, D2O/HDO > HDO/H2O, is common in low-mass protostellar sources.

Finite-element time evolution operator for the anharmonic oscillator

NASA Technical Reports Server (NTRS)

Milton, Kimball A.

1995-01-01

The finite-element approach to lattice field theory is both highly accurate (relative errors approximately 1/N(exp 2), where N is the number of lattice points) and exactly unitary (in the sense that canonical commutation relations are exactly preserved at the lattice sites). In this talk I construct matrix elements for dynamical variables and for the time evolution operator for the anharmonic oscillator, for which the continuum Hamiltonian is H = p(exp 2)/2 + lambda q(exp 4)/4. Construction of such matrix elements does not require solving the implicit equations of motion. Low order approximations turn out to be extremely accurate. For example, the matrix element of the time evolution operator in the harmonic oscillator ground state gives a results for the anharmonic oscillator ground state energy accurate to better than 1 percent, while a two-state approximation reduces the error to less than 0.1 percent.

Promotion effect of nickel loaded on CdS for photocatalytic H2 production in lactic acid solution

NASA Astrophysics Data System (ADS)

Chen, Shu; Chen, Xiaoping; Jiang, Qizhong; Yuan, Jian; Lin, Caifang; Shangguan, Wenfeng

2014-10-01

Low-cost Ni modified CdS was prepared via a hydrothermal reduction method. The hydrogen production activity of CdS loaded with 5 wt% Ni under visible light was even higher than that of the one loaded with 0.5 wt% Pt. The highest H2 evolution rate (3004.8 μmol h-1) occurred when the concentration of sacrificial agent (lactic acid) was 50 vol%. The nickel can quickly transfer excited electrons and enhance the photocatalytic H2 production activity. It was also found that the hydrogen evolution in this system was generated steadily from both water and lactic acid.

Rules of co-occurring mutations characterize the antigenic evolution of human influenza A/H3N2, A/H1N1 and B viruses.

PubMed

Chen, Haifen; Zhou, Xinrui; Zheng, Jie; Kwoh, Chee-Keong

2016-12-05

The human influenza viruses undergo rapid evolution (especially in hemagglutinin (HA), a glycoprotein on the surface of the virus), which enables the virus population to constantly evade the human immune system. Therefore, the vaccine has to be updated every year to stay effective. There is a need to characterize the evolution of influenza viruses for better selection of vaccine candidates and the prediction of pandemic strains. Studies have shown that the influenza hemagglutinin evolution is driven by the simultaneous mutations at antigenic sites. Here, we analyze simultaneous or co-occurring mutations in the HA protein of human influenza A/H3N2, A/H1N1 and B viruses to predict potential mutations, characterizing the antigenic evolution. We obtain the rules of mutation co-occurrence using association rule mining after extracting HA1 sequences and detect co-mutation sites under strong selective pressure. Then we predict the potential drifts with specific mutations of the viruses based on the rules and compare the results with the "observed" mutations in different years. The sites under frequent mutations are in antigenic regions (epitopes) or receptor binding sites. Our study demonstrates the co-occurring site mutations obtained by rule mining can capture the evolution of influenza viruses, and confirms that cooperative interactions among sites of HA1 protein drive the influenza antigenic evolution.

Highly Efficient Catalytic Hydrogen Evolution from Ammonia Borane Using the Synergistic Effect of Crystallinity and Size of Noble-Metal-Free Nanoparticles Supported by Porous Metal-Organic Frameworks.

PubMed

Liu, Penglong; Gu, Xiaojun; Kang, Kai; Zhang, Hao; Cheng, Jia; Su, Haiquan

2017-03-29

A series of nonprecious metal nanoparticles (NPs) supported by metal-organic framework MIL-101 were synthesized using four methods and their catalytic performance on hydrogen evolution from ammonia borane (NH 3 BH 3 ) was studied. The results showed that the crystalline Co NPs with size of 4.5-8.5 and 14.5-24.5 nm had low activities featuring the total turnover frequency (TOF) values of 9.9 and 4.5 mol H2 mol cat -1 min -1 , respectively. In contrast, the amorphous Co NPs with size of 1.6-2.6 and 13.5-24.5 nm exhibited high activities featuring the total TOF values of 51.4 and 22.3 mol H2 mol cat -1 min -1 , respectively. The remarkably different activities could be ascribed to the different crystallinity and size of Co NPs in the catalysts. Moreover, the ultrasound-assisted in situ method was also successfully applied to bimetallic systems, and MIL-101-supported amorphous CuCo, FeCo and NiCo NPs had the catalytic activities with total TOF values of 51.7, 50.8, and 44.3 mol H2 mol cat -1 min -1 , respectively, which were the highest in the values of the reported non-noble metal Co-based catalysts. The present approach, namely, using the synergistic effect of crystallinity and size of metal NPs, may offer a new prospect for high-performance and low-cost nanocatalysts.

ENHANCED WARM H{sub 2} EMISSION IN THE COMPACT GROUP MID-INFRARED ''GREEN VALLEY''

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

Cluver, M. E.; Ogle, P.; Guillard, P.

2013-03-10

We present results from a Spitzer mid-infrared spectroscopy study of a sample of 74 galaxies located in 23 Hickson Compact Groups (HCGs), chosen to be at a dynamically active stage of H I depletion. We find evidence for enhanced warm H{sub 2} emission (i.e., above that associated with UV excitation in star-forming regions) in 14 galaxies ({approx}20%), with 8 galaxies having extreme values of L(H{sub 2} S(0)-S(3))/L(7.7 {mu}m polycyclic aromatic hydrocarbon), in excess of 0.07. Such emission has been seen previously in the compact group HCG 92 (Stephan's Quintet), and was shown to be associated with the dissipation of mechanicalmore » energy associated with a large-scale shock caused when one group member collided, at high velocity, with tidal debris in the intragroup medium. Similarly, shock excitation or turbulent heating is likely responsible for the enhanced H{sub 2} emission in the compact group galaxies, since other sources of heating (UV or X-ray excitation from star formation or active galactic nuclei) are insufficient to account for the observed emission. The group galaxies fall predominantly in a region of mid-infrared color-color space identified by previous studies as being connected to rapid transformations in HCG galaxy evolution. Furthermore, the majority of H{sub 2}-enhanced galaxies lie in the optical ''green valley'' between the blue cloud and red sequence, and are primarily early-type disk systems. We suggest that H{sub 2}-enhanced systems may represent a specific phase in the evolution of galaxies in dense environments and provide new insight into mechanisms which transform galaxies onto the optical red sequence.« less

Phase diagram of URu 2–xFe xSi 2 in high magnetic fields

DOE PAGES

Ran, Sheng; Jeon, Inho; Pouse, Naveen; ...

2017-08-28

Here, electrical transport measurements were performed on URu 2-xFe xSi 2 single-crystal specimens in high magnetic fields up to 45 T (DC fields) and 60 T (pulsed fields). We observed a systematic evolution of the critical fields for both the hidden-order (HO) and large-moment antiferromagnetic (LMAFM) phases and established the 3D phase diagram of T–H–x. In the HO phase, H/H 0 scales with T/T 0 and collapses onto a single curve. However, in the LMAFM phase, this single scaling relation is not satisfied. Within a certain range of x values, the HO phase reenters after the LMAFM phase is suppressedmore » by the magnetic field, similar to the behavior observed for URu 2Si 2 within a certain range of pressures.« less

Phase diagram of URu 2–xFe xSi 2 in high magnetic fields

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

Ran, Sheng; Jeon, Inho; Pouse, Naveen

Here, electrical transport measurements were performed on URu 2-xFe xSi 2 single-crystal specimens in high magnetic fields up to 45 T (DC fields) and 60 T (pulsed fields). We observed a systematic evolution of the critical fields for both the hidden-order (HO) and large-moment antiferromagnetic (LMAFM) phases and established the 3D phase diagram of T–H–x. In the HO phase, H/H 0 scales with T/T 0 and collapses onto a single curve. However, in the LMAFM phase, this single scaling relation is not satisfied. Within a certain range of x values, the HO phase reenters after the LMAFM phase is suppressedmore » by the magnetic field, similar to the behavior observed for URu 2Si 2 within a certain range of pressures.« less

Fluids of the Lower Crust: Deep Is Different

NASA Astrophysics Data System (ADS)

Manning, Craig E.

2018-05-01

Deep fluids are important for the evolution and properties of the lower continental and arc crust in tectonically active settings. They comprise four components: H2O, nonpolar gases, salts, and rock-derived solutes. Contrasting behavior of H2O-gas and H2O-salt mixtures yields immiscibility and potential separation of phases with different chemical properties. Equilibrium thermodynamic modeling of fluid-rock interaction using simple ionic species known from shallow-crustal systems yields solutions too dilute to be consistent with experiments and resistivity surveys, especially if CO2 is added. Therefore, additional species must be present, and H2O-salt solutions likely explain much of the evidence for fluid action in high-pressure settings. At low salinity, H2O-rich fluids are powerful solvents for aluminosilicate rock components that are dissolved as polymerized clusters. Addition of salts changes solubility patterns, but aluminosilicate contents may remain high. Fluids with Xsalt = 0.05 to 0.4 in equilibrium with model crustal rocks have bulk conductivities of 10‑1.5 to 100 S/m at porosity of 0.001. Such fluids are consistent with observed conductivity anomalies and are capable of the mass transfer seen in metamorphic rocks exhumed from the lower crust.

Genetic analysis and biological characteristics of different internal gene origin H5N6 reassortment avian influenza virus in China in 2016.

PubMed

Sun, Wenqiang; Li, Jiaxin; Hu, Jiao; Jiang, Daxiu; Xing, Chaonan; Zhan, Tiansong; Liu, Xiufan

2018-06-01

Clade 2.3.4.4 of H5N6 subtype Avian Influenza Viruses (AIVs) has become dominant clade in South-East Asia. So far, a total of 16 cases of human infection, including 6 deaths, have been confirmed since 2014. In this study, we systematically investigated the genetic evolution and biological characteristics of these viruses. We first carried out phylogenetic and statistical analysis of all H5N6 viruses that were downloaded from Influenza Research Database, GISAID and isolates from our lab. We found that H5N6 AIVs continued to reassort with other AIVs subtypes since 2014. Among these H5N6 reassortments, four main gene types were identified: A (internal genes of H5N1-origin), B (PB2 of H6-origin, and others of H5N1-origin), C (internal genes of H9-origin) and D (PB2 of H6-origin and PB1of H3-origin, and others of H5N1). In addition, after several years of evolution, gene type D is currently the dominant gene type. To systematically compare the genetic and evolutionary characteristics and pathogenicity of these viruses, four H5N6 AIVs of different gene types were selected for further analysis. S4, XZ6, GD1602 and YZ587 virus represented gene type A, B, C and D, respectively. Their NA genes were all originated from H6 and their whole genome showed a high similarity with human isolates. All these isolates could both bind with SA-α2,3 Gal and SA-α2,6 Gal receptors. Pathogenicity test showed that these viruses were highly pathogenic in chickens, while YZ587 showed the lowest virulence. Moreover, XZ6 and S4 viruses were highly pathogenic in ducks and moderately pathogenic in mice, while GD1602 and YZ587 viruses were no-pathogenic in these animals. Interestingly, GD1602 and YZ587-like viruses were responsible for 4 and 2 human infection cases in 2016, respectively. Therefore, our study showed that the YZ587 virus which has mixed internal genes, showed lower virulence in avian species and mammals compared to other genotype viruses. Overall, our findings suggest that the H5N6 avian influenza virus is undergoing constantly evolving and reassortment. Thus, our study highlights the necessary of continued surveillance of the H5N6 AIVs in birds and paying close attention to the spread of these novel reassortment viruses. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution.

PubMed

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy-carbon core-shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10-30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2-6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

DOE PAGES

Saadi, Fadl H.; Carim, Azhar I.; Drisdell, Walter S.; ...

2017-08-28

Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η of -η < 100 mV at a current density of -10 mA cm -2 in 0.500 M H 2SO 4 (aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H 2SO 4 (aq).more » Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Lastly, operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.« less

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

An ultrafine platinum-cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution.

PubMed

Wang, Ziqiang; Ren, Xiang; Luo, Yonglan; Wang, Liang; Cui, Guanwei; Xie, Fengyu; Wang, Hongjing; Xie, Ying; Sun, Xuping

2018-06-22

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

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

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

DOE PAGES

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.; ...

2017-01-06

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

2 years with comet 67P/Churyumov-Gerasimenko: H2O, CO2, CO as seen by ROSINA RTOF

NASA Astrophysics Data System (ADS)

Hoang, M.; Garnier, P.; Lasue, J.; Reme, H.; Altwegg, K.; Balsiger, H. R.; Bieler, A. M.; Calmonte, U.; Capria, M. T.; Combi, M. R.; De Keyser, J. M.; Fiethe, B.; Fougere, N.; Fuselier, S. A.; Galli, A.; Gasc, S.; Gombosi, T. I.; Hansen, K. C.; Jäckel, A.; Korth, A.; Mall, U.; Migliorini, A.; Rubin, M.; Sémon, T.; Tzou, C. Y.; Waite, J. H., Jr.; Wurz, P.

2017-12-01

The Rosetta space mission investigated comet 67P/Churyumov-Gerasimenko (67P) over two years from August 2014 to September 2016. Onboard the spacecraft, the ROSINA experiment included two mass spectrometers to derive the composition of neutrals and ions, and a COmet Pressure Sensor (COPS) to monitor the density and velocity of the neutrals in the coma. We will here analyse and discuss data from the Reflectron-type Time-Of-Flight instrument during the comet escort phase. The RTOF mass spectrometer possessed a wide mass range and a high temporal resolution (Balsiger et al., 2007). The analysis of 67P/C-G's coma major molecules over the mission showed strong variability of the comet coma's main volatiles concentrations (H2O, CO2, CO) and their relative abundances. The 2 years long Rosetta mission allowed us to observe the seasonal evolution in the atmosphere of 67P, in particular the change occurring during the equinoxes and at perihelion. In this work, we analyze the asymmetry in the outgassing rate before and after the perihelion (13/08/2015), the evolution of abundance ratios through the whole mission, and in particular the behavior of the very volatile CO molecules. Density maps projected on the surface of 67P demonstrate the evolution of the three main coma species after the outbound equinox. We will present first results of our comet nucleus thermal modelling used to simulate the internal structure and temperature evolution of 67P at characteristic surface areas. These results will be compared with the coma composition measurements obtained by ROSINA.

Directed evolution of an ultrastable carbonic anhydrase for highly efficient carbon capture from flue gas

DOE PAGES

Alvizo, Oscar; Nguyen, Luan J.; Savile, Christopher K.; ...

2014-11-03

Carbonic anhydrase (CA) is one of nature’s fastest enzymes and can dramatically improve the economics of carbon capture under demanding environments such as coal-fired power plants. The use of CA to accelerate carbon capture is limited by the enzyme’s sensitivity to the harsh process conditions. Using directed evolution, the properties of a β-class CA from Desulfovibrio vulgaris were dramatically enhanced. Iterative rounds of library design, library generation, and high-throughput screening identified highly stable CA variants that tolerate temperatures of up to 107 °C in the presence of 4.2 M alkaline amine solvent at pH >10.0. This increase in thermostability andmore » alkali tolerance translates to a 4,000,000-fold improvement over the natural enzyme. In conclusion, at pilot scale, the evolved catalyst enhanced the rate of CO2 absorption 25-fold compared with the noncatalyzed reaction.« less

Directed evolution of an ultrastable carbonic anhydrase for highly efficient carbon capture from flue gas

PubMed Central

Alvizo, Oscar; Nguyen, Luan J.; Savile, Christopher K.; Bresson, Jamie A.; Lakhapatri, Satish L.; Solis, Earl O. P.; Fox, Richard J.; Broering, James M.; Benoit, Michael R.; Zimmerman, Sabrina A.; Novick, Scott J.; Liang, Jack; Lalonde, James J.

2014-01-01

Carbonic anhydrase (CA) is one of nature’s fastest enzymes and can dramatically improve the economics of carbon capture under demanding environments such as coal-fired power plants. The use of CA to accelerate carbon capture is limited by the enzyme’s sensitivity to the harsh process conditions. Using directed evolution, the properties of a β-class CA from Desulfovibrio vulgaris were dramatically enhanced. Iterative rounds of library design, library generation, and high-throughput screening identified highly stable CA variants that tolerate temperatures of up to 107 °C in the presence of 4.2 M alkaline amine solvent at pH >10.0. This increase in thermostability and alkali tolerance translates to a 4,000,000-fold improvement over the natural enzyme. At pilot scale, the evolved catalyst enhanced the rate of CO2 absorption 25-fold compared with the noncatalyzed reaction. PMID:25368146

Environmental and genetic sources of diversification in the timing of seed germination: implications for the evolution of bet hedging.

PubMed

Simons, Andrew M; Johnston, Mark O

2006-11-01

Environmental variation that is not predictably related to cues is expected to drive the evolution of bet-hedging strategies. The high variance observed in the timing of seed germination has led to it being the most cited diversification strategy in the theoretical bet-hedging literature. Despite this theoretical focus, virtually nothing is known about the mechanisms responsible for the generation of individual-level diversification. Here we report analyses of sources of variation in timing of germination within seasons, germination fraction over two generations and three sequential seasons, and the genetic correlation structure of these traits using almost 10,000 seeds from more than 100 genotypes of the monocarpic perennial Lobelia inflata. Microenvironmental analysis of time to germination suggests that extreme sensitivity to environmental gradients, or microplasticity, even within a homogeneous growth chamber, may act as an effective individual-level diversification mechanism and explains more than 30% of variance in time to germination. The heritability of within-season timing of germination was low (h(2) = 0.07) but significant under homogeneous conditions. Consistent with individual-level diversification, this low h(2) was attributable not to low additive genetic variance, but to an unusually high coefficient of residual variation in time to germination. Despite high power to detect additive genetic variance in within-season diversification, it was low and indistinguishable from zero. Restricted maximum likelihood detected significant genetic variation for germination fraction (h(2) = 0.18) under homogeneous conditions. Unexpectedly, this heritability was positive when measured within a generation by sibling analysis and negative when measured across generations by offspring-on-parent regression. The consistency of dormancy fraction over multiple delays, a major premise of Cohen's classic model, was supported by a strong genetic correlation (r = 0.468) observed for a cohort's germination fraction over two seasons. We discuss implications of the results for the evolution of bet hedging and highlight the need for further empirical study of the causal components of diversification.

NiFe (Oxy) Hydroxides Derived from NiFe Disulfides as an Efficient Oxygen Evolution Catalyst for Rechargeable Zn-Air Batteries: The Effect of Surface S Residues.

PubMed

Wang, Tanyuan; Nam, Gyutae; Jin, Yue; Wang, Xingyu; Ren, Pengju; Kim, Min Gyu; Liang, Jiashun; Wen, Xiaodong; Jang, Haeseong; Han, Jiantao; Huang, Yunhui; Li, Qing; Cho, Jaephil

2018-05-21

A facile H 2 O 2 oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm -2 after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The evolution of massive stars and their spectra. I. A non-rotating 60 M⊙ star from the zero-age main sequence to the pre-supernova stage

NASA Astrophysics Data System (ADS)

Groh, Jose H.; Meynet, Georges; Ekström, Sylvia; Georgy, Cyril

2014-04-01

For the first time, the interior and spectroscopic evolution of a massive star is analyzed from the zero-age main sequence (ZAMS) to the pre-supernova (SN) stage. For this purpose, we combined stellar evolution models using the Geneva code and stellar atmospheric/wind models using CMFGEN. With our approach, we were able to produce observables, such as a synthetic high-resolution spectrum and photometry, thereby aiding the comparison between evolution models and observed data. Here we analyze the evolution of a non-rotating 60 M⊙ star and its spectrum throughout its lifetime. Interestingly, the star has a supergiant appearance (luminosity class I) even at the ZAMS. We find the following evolutionary sequence of spectral types: O3 I (at the ZAMS), O4 I (middle of the H-core burning phase), B supergiant (BSG), B hypergiant (BHG), hot luminous blue variable (LBV; end of H-core burning), cool LBV (H-shell burning through the beginning of the He-core burning phase), rapid evolution through late WN and early WN, early WC (middle of He-core burning), and WO (end of He-core burning until core collapse). We find the following spectroscopic phase lifetimes: 3.22 × 106 yr for the O-type, 0.34 × 105 yr (BSG), 0.79 × 105 yr (BHG), 2.35 × 105 yr (LBV), 1.05 × 105 yr (WN), 2.57 × 105 yr (WC), and 3.80 × 104 yr (WO). Compared to previous studies, we find a much longer (shorter) duration for the early WN (late WN) phase, as well as a long-lived LBV phase. We show that LBVs arise naturally in single-star evolution models at the end of the MS when the mass-loss rate increases as a consequence of crossing the bistability limit. We discuss the evolution of the spectra, magnitudes, colors, and ionizing flux across the star's lifetime, and the way they are related to the evolution of the interior. We find that the absolute magnitude of the star typically changes by ~6 mag in optical filters across the evolution, with the star becoming significantly fainter in optical filters at the end of the evolution, when it becomes a WO just a few 104 years before the SN explosion. We also discuss the origin of the different spectroscopic phases (i.e., O-type, LBV, WR) and how they are related to evolutionary phases (H-core burning, H-shell burning, He-core burning). Tables 1, 4 and 5 are available in electronic form at http://www.aanda.orgSynthetic spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/564/A30

Molecular evolution and expression of oxygen transport genes in livebearing fishes (Poeciliidae) from hydrogen sulfide rich springs.

PubMed

Barts, Nicholas; Greenway, Ryan; Passow, Courtney N; Arias-Rodriguez, Lenin; Kelley, Joanna L; Tobler, Michael

2018-04-01

Hydrogen sulfide (H 2 S) is a natural toxicant in some aquatic environments that has diverse molecular targets. It binds to oxygen transport proteins, rendering them non-functional by reducing oxygen-binding affinity. Hence, organisms permanently inhabiting H 2 S-rich environments are predicted to exhibit adaptive modifications to compensate for the reduced capacity to transport oxygen. We investigated 10 lineages of fish of the family Poeciliidae that have colonized freshwater springs rich in H 2 S-along with related lineages from non-sulfidic environments-to test hypotheses about the expression and evolution of oxygen transport genes in a phylogenetic context. We predicted shifts in the expression of and signatures of positive selection on oxygen transport genes upon colonization of H 2 S-rich habitats. Our analyses indicated significant shifts in gene expression for multiple hemoglobin genes in lineages that have colonized H 2 S-rich environments, and three hemoglobin genes exhibited relaxed selection in sulfidic compared to non-sulfidic lineages. However, neither changes in gene expression nor signatures of selection were consistent among all lineages in H 2 S-rich environments. Oxygen transport genes may consequently be predictable targets of selection during adaptation to sulfidic environments, but changes in gene expression and molecular evolution of oxygen transport genes in H 2 S-rich environments are not necessarily repeatable across replicated lineages.

Challenges for accurate and prompt molecular diagnosis of clades of highly pathogenic avian influenza H5N1 viruses emerging in Vietnam.

PubMed

Slomka, Marek J; To, Thanh L; Tong, Hien H; Coward, Vivien J; Hanna, Amanda; Shell, Wendy; Pavlidis, Theo; Densham, Anstice L E; Kargiolakis, Georgios; Arnold, Mark E; Banks, Jill; Brown, Ian H

2012-01-01

Forty-six chickens and 48 ducks were sampled from four Vietnamese poultry premises in 2009 infected with H5N1 highly pathogenic avian influenza (HPAI) clade 2.3.2 and 2.3.4 viruses, which also differed by cleavage site (CS) sequences in their haemagglutinin (HA) genes. All clinical specimens (n=282), namely tracheal and cloacal swabs plus feathers, were tested by five Eurasian reverse-transcriptase AI RealTime polymerase chain reaction (RRT-PCR) methods. Bayesian modelling showed similar high sensitivity for the validated H5 HA2 RRT-PCR and a new modified M-gene RRT-PCR that utilizes lyophilized reagents. Both were more sensitive than the validated "wet" M-gene RRT-PCR. Another RRT-PCR, which targeted the H5-gene CS region, was effective for clade 2.3.4 detection, but severely compromised for clade 2.3.2 viruses. Reduced sensitivity of the H5 CS and "wet" M-gene RRT-PCRs correlated with mismatches between the target and the primer and/or probe sequences. However, the H5 HA2 RRT-PCR sensitively detected both clade 2.3.2 and 2.3.4 viruses, and agreed with N1 RRT-PCR results. Feather testing from diseased chicken and duck flocks by AI RRT-PCRs resulted in the most sensitive identification of H5N1 HPAI-infected birds. Evolution of new H5N1 HPAI clades remains a concern for currently affected Asian countries, but also for more distant regions where it is important to be prepared for new incursions of H5N1 HPAI viruses. Genetic evidence for adamantane resistance and sensitivity was also observed in isolates from both clades.

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Phase diagram for ammonia-water mixtures at high pressures - Implications for icy satellites

NASA Technical Reports Server (NTRS)

Cynn, H. C.; Boone, S.; Koumvakalis, A.; Nicol, M.; Stevenson, D. J.

1989-01-01

The (NH3)x(H2O)1-x phase diagram for X from 0 to 0.50 has been reexamined at temperatures from 125 K to 400 K and at pressures from 6.0 GPa using diamond anvil cells, and the implications of the findings for icy satellites are addressed. Titan is likely to have a thicker NH3-H2O ocean than previously suspected, because the stability field of NH3-H2O is found to be smaller than previously supposed. The implications for methane and ammonia volcanism on Titan are briefly discussed. The experimentally observed reactivity between the liquid and iron may also have implications for planetary and satellite evolution.

A Co2 P/WC Nano-Heterojunction Covered with N-Doped Carbon as Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Gao, Ya; Lang, Zhongling; Yu, Feiyang; Tan, Huaqiao; Yan, Gang; Wang, Yonghui; Ma, Yuanyuan; Li, Yangguang

2018-03-22

The hydrogen evolution reaction (HER) produces clean hydrogen through an electrochemical process. However, new nonprecious-metal electrocatalysts for the HER are required to reduce the consumption of energy. Herein, we report a new Co 2 P/WC nano-heterojunction that consists of Co 2 P and WC composite phases coated with a few-layer N-doped graphitic carbon shells (Co 2 P/WC@NC). The composite was prepared by a one-step annealing of the polyoxometalate Na 9 (NH 4 ) 5 [{(B-α-PW 9 O 34 )Co 3 (OH)(H 2 O) 2 (Ale)} 2 Co]⋅35 H 2 O (Co 7 P 6 W 18 ) and dicyandiamide (DCA). The preparation method consisted of the simultaneous phosphorization of Co and carbonization of W in a confined space to isolate a Co 2 P/WC nano-heterojunction phase for the first time. Co 2 P/WC@NC facilitated the generation of hydrogen in the electrolysis process, which had an overpotential of only 91 mV at a current density of 10 mA cm -2 in the acid solution; an excellent HER performance (2 H + +2 e - →H 2 ) and Tafel slope (40 mV dec -1 ) as well as durability over a period of 50 h were achieved. Theoretical calculations showed that the Co 2 P, WC, and N pyridinic C dopants in the material synergistically promoted the HER activity rather than the individual constituents. Furthermore, Co 2 P/WC@NC nano-heterojunctions showed good HER performance in the whole pH range of electrolytes and considerable durability in acidic media containing transition metal ions, which may attract more attention for the exploration and optimization of nano-heterojunction catalysts for the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

PubMed Central

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-01-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2. PMID:28485395

Infrared Observations of Hot Gas and Cold Ice Toward the Low Mass Protostar Elias 29

NASA Technical Reports Server (NTRS)

Boogert, A. C. A.; Tielens, A. G. G. M.; Ceccarelli, C.; Boonman, A. M. S.; vanDishoeck, E. F.; Keane, J. V.; Whittet, D. C. B.; deGraauw, T.

2000-01-01

We have obtained the full 1-200 micrometer spectrum of the low luminosity (36 solar luminosity Class I protostar Elias 29 in the rho Ophiuchi molecular cloud. It provides a unique opportunity to study the origin and evolution of interstellar ice and the interrelationship of interstellar ice and hot core gases around low mass protostars. We see abundant hot CO and H2O gas, as well as the absorption bands of CO, CO2, H2O and "6.85 micrometer" ices. We compare the abundances and physical conditions of the gas and ices toward Elias 29 with the conditions around several well studied luminous, high mass protostars. The high gas temperature and gas/solid ratios resemble those of relatively evolved high mass objects (e.g. GL 2591). However, none of the ice band profiles shows evidence for significant thermal processing, and in this respect Elias 29 resembles the least evolved luminous protostars, such as NGC 7538 : IRS9. Thus we conclude that the heating of the envelope of the low mass object Elias 29 is qualitatively different from that of high mass protostars. This is possibly related to a different density gradient of the envelope or shielding of the ices in a circumstellar disk. This result is important for our understanding of the evolution of interstellar ices, and their relation to cometary ices.

Ionic liquid-assisted synthesis of Br-modified g-C3N4 semiconductors with high surface area and highly porous structure for photoredox water splitting

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Wang, Yanyun; Zhou, Yuming; Qiu, Kaibo; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-12-01

Coping with the gradually increasing worldwide energy and environmental issues, it is urgent to develop efficient, cheap and visible-light-driven photocatalysts for hydrogen production. Here, we present a facile way to synthesize bromine doped graphitic carbon nitride (CN-BrX) with highly porous structure by using ionic liquid (1-butyl-3-vinylimidazolium bromide) as the Br source and soft-template for the first time, which applied in hydrogen evolution under visible light irradiation. A systematic study is conducted on the optimization in the doping amount. The results find that the as-fabricated CN-BrX photocatalysts possess a uniform porous network with thin walls due to the release of volatile domains and decomposition of ionic liquids. The highly porous structure with the large surface area (≤150 m2/g) benefits the exposure of active sites. Moreover, the bromine modification and porous structure can narrow the band gap, enhance the transportation capability of photogenerated electrons, improve the optical and conductive properties of CN, thus contribute to an outstanding H2 evolution rate under visible light irradiation (120 μmol h-1), which is about 3.6 times higher than pure CN. This work provides a new insight for designing the novel g-C3N4 based photocatalysts for hydrogen production, CO2 conversion and environmental remediation.

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

Directed evolution of an endoinulinase from Talaromyces purpureogenus toward efficient production of inulooligosaccharides.

PubMed

Afriat-Jurnou, Livnat; Cohen, Rami; Paluy, Irina; Ben-Adiva, Ran; Yadid, Itamar

2018-02-01

Inulinases are fructofuranosyl hydrolases that target the β-2,1 linkage of inulin and hydrolyze it into fructose, glucose and inulooligosaccharides (IOS), the latter are of growing interest as dietary fibers. Inulinases from various microorganisms have been purified, characterized and produced for industrial applications. However, there remains a need for inulinases with increased catalytic activity and better production yields to improve the hydrolysis process and fulfill the growing industrial demands for specific fibers. In this study, we used directed enzyme evolution to increase the yield and activity of an endoinulinase enzyme originated from the filamentous fungus Talaromyces purpureogenus (Penicillium purpureogenum ATCC4713). Our directed evolution approach yielded variants showing up to fivefold improvements in soluble enzyme production compared to the starting point which enabled high-yield production of highly purified recombinant enzyme. The distribution of the enzymatic reaction products demonstrated that after 24 h of incubation, the main product (57%) had a degree of polymerization of 3 (DP3). To the best of our knowledge, this is the first application of directed enzyme evolution to improve inulooligosaccharide production. The approach enabled the screening of large genetic libraries within short time frames and facilitated screening for improved enzymatic activities and properties, such as substrate specificity, product range, thermostability and pH optimum. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 2018. © 2018 American Institute of Chemical Engineers.

STELLAR POPULATIONS AND EVOLUTION OF EARLY-TYPE CLUSTER GALAXIES: CONSTRAINTS FROM OPTICAL IMAGING AND SPECTROSCOPY OF z = 0.5-0.9 GALAXY CLUSTERS

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

Jorgensen, Inger; Chiboucas, Kristin, E-mail: ijorgensen@gemini.edu, E-mail: kchiboucas@gemini.edu

2013-03-15

We present an analysis of stellar populations and evolutionary history of galaxies in three similarly rich galaxy clusters MS0451.6-0305 (z = 0.54), RXJ0152.7-1357 (z = 0.83), and RXJ1226.9+3332 (z = 0.89). Our analysis is based on high signal-to-noise ground-based optical spectroscopy and Hubble Space Telescope imaging for a total of 17-34 members in each cluster. Using the dynamical masses together with the effective radii and the velocity dispersions, we find no indication of evolution of sizes or velocity dispersions with redshift at a given galaxy mass. We establish the Fundamental Plane (FP) and scaling relations between absorption line indices andmore » velocity dispersions. We confirm that the FP is steeper at z Almost-Equal-To 0.86 compared to the low-redshift FP, indicating that under the assumption of passive evolution the formation redshift, z{sub form}, depends on the galaxy velocity dispersion (or alternatively mass). At a velocity dispersion of {sigma} = 125 km s{sup -1} (Mass = 10{sup 10.55} M{sub Sun }) we find z{sub form} = 1.24 {+-} 0.05, while at {sigma} = 225 km s{sup -1} (Mass = 10{sup 11.36} M{sub Sun }) the formation redshift is z{sub form} = 1.95{sup +0.3}{sub -0.2}, for a Salpeter initial mass function. The three clusters follow similar scaling relations between absorption line indices and velocity dispersions as those found for low-redshift galaxies. The zero point offsets for the Balmer lines depend on cluster redshifts. However, the offsets indicate a slower evolution, and therefore higher formation redshift, than the zero point differences found from the FP, if interpreting the data using a passive evolution model. Specifically, the strength of the higher order Balmer lines H{delta} and H{gamma} implies z{sub form} > 2.8. The scaling relations for the metal indices in general show small and in some cases insignificant zero point offsets, favoring high formation redshifts for a passive evolution model. Based on the absorption line indices and recent stellar population models from Thomas et al., we find that MS0451.6-0305 has a mean metallicity [M/H] approximately 0.2 dex below that of the other clusters and our low-redshift sample. We confirm our previous result that RXJ0152.7-1357 has a mean abundance ratio [{alpha}/Fe] approximately 0.3 dex higher than that of the other clusters. The differences in [M/H] and [{alpha}/Fe] between the high-redshift clusters and the low-redshift sample are inconsistent with a passive evolution scenario for early-type cluster galaxies over the redshift interval studied. Low-level star formation may be able to bring the metallicity of MS0451.6-0305 in agreement with the low-redshift sample, while we speculate whether galaxy mergers can lead to sufficiently large changes in the abundance ratios for the RXJ0152.7-1357 galaxies to allow them to reach the low-redshift sample values in the time available.« less

Hydrogen production by nitrogen-starved cultures of Anabaena cylindrica

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

Weissman, J.C.; Benemann, J.R.

Nitrogen-starved cultures of the alga Anabaena cylindrica 629 produced hydrogen and oxygen continuously for 7 to 19 days. Hydrogen production attained a maximum level after 1 to 2 days of starvation and was followed by a slow decline. The maximum rates were 30 ml of H/sub 2/ evolved per liter of culture per h or 32 ..mu..l of H/sub 2/ per mg of dry weight per h. In 5 to 7 days the rate of H/sub 2/ evolution by the more productive cultures fell to one-half its maximum value. The addition of 10/sup -4/ to 5 x 10/sup -4/ Mmore » ammonium increased the rate of oxygen evolution and the total hydrogen production of the cultures. H/sub 2/-O/sub 2/ ratios were 4:1 under conditions of complete nitrogen starvation and about 1.7:1 after the addition of ammonium. Thus, oxygen evolution was affected by the extent of the nitrogen starvation. Thermodynamic efficiencies of converting incident light energy to free energy of hydrogen via algal photosynthesis were 0.4 percent. Possible factors limiting hydrogen production were decline of reductant supply and filament breakage. Hydrogen production by filamentous, heterocystous blue-green algae could be used for development of a biophotolysis system.« less

Observing the metal-poor solar neighbourhood: a comparison of galactic chemical evolution predictions*†

NASA Astrophysics Data System (ADS)

Mishenina, T.; Pignatari, M.; Côté, B.; Thielemann, F.-K.; Soubiran, C.; Basak, N.; Gorbaneva, T.; Korotin, S. A.; Kovtyukh, V. V.; Wehmeyer, B.; Bisterzo, S.; Travaglio, C.; Gibson, B. K.; Jordan, C.; Paul, A.; Ritter, C.; Herwig, F.; NuGrid Collaboration

2017-08-01

Atmospheric parameters and chemical compositions for 10 stars with metallicities in the region of -2.2 < [Fe/H] < -0.6 were precisely determined using high-resolution, high signal-to-noise, spectra. For each star, the abundances, for 14-27 elements, were derived using both local thermodynamic equilibrium (LTE) and non-LTE (NLTE) approaches. In particular, differences by assuming LTE or NLTE are about 0.10 dex; depending on [Fe/H], Teff, gravity and element lines used in the analysis. We find that the O abundance has the largest error, ranging from 0.10 and 0.2 dex. The best measured elements are Cr, Fe, and Mn; with errors between 0.03 and 0.11 dex. The stars in our sample were included in previous different observational work. We provide a consistent data analysis. The data dispersion introduced in the literature by different techniques and assumptions used by the different authors is within the observational errors, excepting for HD103095. We compare these results with stellar observations from different data sets and a number of theoretical galactic chemical evolution (GCE) simulations. We find a large scatter in the GCE results, used to study the origin of the elements. Within this scatter as found in previous GCE simulations, we cannot reproduce the evolution of the elemental ratios [Sc/Fe], [Ti/Fe], and [V/Fe] at different metallicities. The stellar yields from core-collapse supernovae are likely primarily responsible for this discrepancy. Possible solutions and open problems are discussed.

Structure and evolution of fossil H II regions

NASA Technical Reports Server (NTRS)

Mccray, R.; Schwarz, J.

1971-01-01

The structure and evolution of a fossil H II region created by a burst of ionizing radiation from a supernova is considered. The cooling time scale for the shell is about 10 to the 6th power years. Superposition of million-year-old fossil H II regions may account for the temperature and ionization of the interstellar medium. Fossil H II regions are unstable to growth of thermal condensations. Highly ionized filamentary structures form and dissipate in about 10,000 years. Partially ionized clouds form and dissipate in about 10 to the 6th power years.

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid† †Electronic supplementary information (ESI) available: CVs for unary metal oxides deposition, electrochemical stability at higher current densities for unary metal oxides at pH 2.5, EDS maps for CoMnOx and CoPbOx, STEM images and PXRD of CoMnOx and CoFePbOx, high-resolution XPS of Fe 2p for CoFePbOx, Pourbaix diagrams (of Mn, Co, Pb, and Fe), and elemental analysis. See DOI: 10.1039/c7sc01239j Click here for additional data file.

PubMed Central

Huynh, Michael; Ozel, Tuncay; Liu, Chong; Lau, Eric C.

2017-01-01

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnOx) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnOx films. In acidic solutions (pH 2.5), CoMnOx exhibits the OER activity of electrodeposited Co oxide (CoOx) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnOx films for OER at 0.1 mA cm–2. Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbOx films that maintained the high OER activity of CoOx at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm–2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbOx exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts. PMID:29163926

Study of the Microstructure Evolution of Low-pH Cements Based on Ordinary Portland Cement (OPC) by Mid- and Near-Infrared Spectroscopy, and Their Influence on Corrosion of Steel Reinforcement.

PubMed

García Calvo, José Luis; Sánchez Moreno, Mercedes; Alonso Alonso, María Cruz; Hidalgo López, Ana; García Olmo, Juan

2013-06-18

Low-pH cements are designed to be used in underground repositories for high level waste. When they are based on Ordinary Portland Cements (OPC), high mineral admixture contents must be used which significantly modify their microstructure properties and performance. This paper evaluates the microstructure evolution of low-pH cement pastes based on OPC plus silica fume and/or fly ashes, using Mid-Infrared and Near-Infrared spectroscopy to detect cement pastes mainly composed of high polymerized C-A-S-H gels with low C/S ratios. In addition, the lower pore solution pH of these special cementitious materials have been monitored with embedded metallic sensors. Besides, as the use of reinforced concrete can be required in underground repositories, the influence of low-pH cementitious materials on steel reinforcement corrosion was analysed. Due to their lower pore solution pH and their different pore solution chemical composition a clear influence on steel reinforcement corrosion was detected.

Top-Down and Bottom-Up Approaches in Engineering 1 T Phase Molybdenum Disulfide (MoS2 ): Towards Highly Catalytically Active Materials.

PubMed

Chua, Chun Kiang; Loo, Adeline Huiling; Pumera, Martin

2016-09-26

The metallic 1 T phase of MoS2 has been widely identified to be responsible for the improved performances of MoS2 in applications including hydrogen evolution reactions and electrochemical supercapacitors. To this aim, various synthetic methods have been reported to obtain 1 T phase-rich MoS2 . Here, the aim is to evaluate the efficiencies of the bottom-up (hydrothermal reaction) and top-down (chemical exfoliation) approaches in producing 1 T phase MoS2 . It is established in this study that the 1 T phase MoS2 produced through the bottom-up approach contains a high proportion of 1 T phase and demonstrates excellent electrochemical and electrical properties. Its performance in the hydrogen evolution reaction and electrochemical supercapacitors also surpassed that of 1 T phase MoS2 produced through a top-down approach. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photocatalytic hydrogen evolution from in situ formation of few-layered MoS2/CdS nanosheet-based van der Waals heterostructures.

PubMed

Iqbal, Shahid; Pan, Ziwei; Zhou, Kebin

2017-05-25

Here we report for the first time that the H 2 bubbles generated by photocatalytic water splitting are effective in the layer-by-layer exfoliation of MoS 2 nanocrystals (NCs) into few layers. The as-obtained few layers can be in situ assembled with CdS nanosheets (NSs) into van der Waals heterostructures (vdWHs) of few-layered MoS 2 /CdS NSs which, in turn, are effective in charge separation and transfer, leading to enhanced photocatalytic H 2 production activity. The few-layered MoS 2 /CdS vdWHs exhibited a H 2 evolution rate of 140 mmol g (CdS) -1 h -1 and achieved an apparent quantum yield of 66% at 420 nm.

Effect of pressure on the tetragonal distortion in TiH2: a first-principles study

NASA Astrophysics Data System (ADS)

de Coss, R.; Quijano, R.; Singh, D. J.

2009-03-01

The transition metal dihydride TiH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Early electronic band structure calculations have shown that TiH2 in the cubic phase display a nearly flat double degenerated band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. Nevertheless, recently we have show that the instability of fcc-TiH2 is likely to be related with a van Hove singularity. In the present work, we have performed ab-initio calculations of the electronic structure and the tetragonal distortion for TiH2 under pressure (0-30 GPa). We found that the fcc-fct energy barrier and the tetragonal distortion increases with pressure. The evolution of the tetragonal distortion is analyzed in terms of the electronic band structure. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 49985.

Seroprevalence of H1N1, H3N2 and H1N2 influenza viruses in pigs in seven European countries in 2002-2003.

PubMed

Van Reeth, Kristien; Brown, Ian H; Dürrwald, Ralf; Foni, Emanuela; Labarque, Geoffrey; Lenihan, Patrick; Maldonado, Jaime; Markowska-Daniel, Iwona; Pensaert, Maurice; Pospisil, Zdenek; Koch, Guus

2008-05-01

Avian-like H1N1 and human-like H3N2 swine influenza viruses (SIV) have been considered widespread among pigs in Western Europe since the 1980s, and a novel H1N2 reassortant with a human-like H1 emerged in the mid 1990s. This study, which was part of the EC-funded 'European Surveillance Network for Influenza in Pigs 1', aimed to determine the seroprevalence of the H1N2 virus in different European regions and to compare the relative prevalences of each SIV between regions. Laboratories from Belgium, the Czech Republic, Germany, Italy, Ireland, Poland and Spain participated in an international serosurvey. A total of 4190 sow sera from 651 farms were collected in 2002-2003 and examined in haemagglutination inhibition tests against H1N1, H3N2 and H1N2. In Belgium, Germany, Italy and Spain seroprevalence rates to each of the three SIV subtypes were high (> or =30% of the sows seropositive) to very high (> or =50%), except for a lower H1N2 seroprevalence rate in Italy (13.8%). Most sows in these countries with high pig populations had antibodies to two or three subtypes. In Ireland, the Czech Republic and Poland, where swine farming is less intensive, H1N1 was the dominant subtype (8.0-11.7% seropositives) and H1N2 and H3N2 antibodies were rare (0-4.2% seropositives). Thus, SIV of H1N1, H3N2 and H1N2 subtype are enzootic in swine producing regions of Western Europe. In Central Europe, SIV activity is low and the circulation of H3N2 and H1N2 remains to be confirmed. The evolution and epidemiology of SIV throughout Europe is being further monitored through a second 'European Surveillance Network for Influenza in Pigs'.

Synthesis of BaW2O7-ethylene glycol inorganic-organic hybrid and its topochemical transformation to thin WS2 nanoplates

NASA Astrophysics Data System (ADS)

Afanasiev, Pavel

2018-02-01

A novel inorganic-organic hybrid barium tungstate - ethylene glycol Ba(C2H6O2)W2O7 phase has been prepared by non-aqueous precipitation and characterized. According to powder X-ray diffraction, the solid has an orthorhombic lattice (a = b = 6.415 Å, c = 13.05 Å) and represents a derivative of the H2W2O7 lamellar acid. The Ba(C2H6O2)W2O7 hybrid material is a layered solid and crystallizes as thin plates, which can be further topotacticaly transformed to few-layer WS2 nanoplates. Tungsten sulfide as obtained possesses high specific surface area and increased defectness of layers. Thin-layer WS2 materials as prepared show advantageous properties as hydrogen evolution electrocatalysts, or in combination with TiO2 as co-catalysts for photo catalytic hydrogen production from methanol.

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

Terai, Tsuyoshi; Itoh, Yoichi; Oasa, Yumiko

We present a measurement of H{sub 2}O ice crystallinity on the surface of trans-neptunian objects with near-infrared narrow-band imaging. The newly developed photometric technique allows us to efficiently determine the strength of a 1.65 μ m absorption feature in crystalline H{sub 2}O ice. Our data for three large objects—Haumea, Quaoar, and Orcus—which are known to contain crystalline H{sub 2}O ice on the surfaces, show a reasonable result with high fractions of the crystalline phase. It can also be pointed out that if the grain size of H{sub 2}O ice is larger than ∼20 μ m, the crystallinities of these objectsmore » are obviously below 1.0, which suggests the presence of the amorphous phase. In particular, Orcus exhibits a high abundance of amorphous H{sub 2}O ice compared to Haumea and Quaoar, possibly indicating a correlation between the bulk density of the bodies and the degree of surface crystallization. We also found the presence of crystalline H{sub 2}O ice on Typhon and 2008 AP{sub 129}, both of which are smaller than the minimum size limit for inducing cryovolcanism as well as a transition from amorphous to crystalline phase through thermal evolution due to the decay of long-lived isotopes.« less

Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-03-01

The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. A large number of gaps between 'cauliflower' like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

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

De Marco, Luigi; Department of Chemistry, James Frank Institute, and The Institute for Biophysical Dynamics, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637; Fournier, Joseph A.

Water’s extended hydrogen-bond network results in rich and complex dynamics on the sub-picosecond time scale. In this paper, we present a comprehensive analysis of the two-dimensional infrared (2D IR) spectrum of O–H stretching vibrations in liquid H{sub 2}O and their interactions with bending and intermolecular vibrations. By exploring the dependence of the spectrum on waiting time, temperature, and laser polarization, we refine our molecular picture of water’s complex ultrafast dynamics. The spectral evolution following excitation of the O–H stretching resonance reveals vibrational dynamics on the 50–300 fs time scale that are dominated by intermolecular delocalization. These O–H stretch excitons aremore » a result of the anharmonicity of the nuclear potential energy surface that arises from the hydrogen-bonding interaction. The extent of O–H stretching excitons is characterized through 2D depolarization measurements that show spectrally dependent delocalization in agreement with theoretical predictions. Furthermore, we show that these dynamics are insensitive to temperature, indicating that the exciton dynamics alone set the important time scales in the system. Finally, we study the evolution of the O–H stretching mode, which shows highly non-adiabatic dynamics suggestive of vibrational conical intersections. We argue that the so-called heating, commonly observed within ∼1 ps in nonlinear IR spectroscopy of water, is a nonequilibrium state better described by a kinetic temperature rather than a Boltzmann distribution. Our conclusions imply that the collective nature of water vibrations should be considered in describing aqueous solvation.« less

Facile sonochemical synthesis of amorphous NiFe-(oxy)hydroxide nanoparticles as superior electrocatalysts for oxygen evolution reaction.

PubMed

Lee, Eunjik; Park, Ah-Hyeon; Park, Hyun-Uk; Kwon, Young-Uk

2018-01-01

In this work, we present facile synthesis of amorphous Ni/Fe mixed (oxy)hydroxide (NiFe(H)) nanoparticles (NPs) and their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media. a-NiFe(H) NPs have received lots of attention as OER electrocatalysts with many desirable properties. By using a simple sonochemical route, we prepared amorphous Ni and Fe-alkoxide (NiFe(A)) NPs whose composition can be controlled in the entire composition range (Ni 100-x Fe x , 0≤x≤1). These samples are composed of extremely small NiFe(A) NPs with Ni and Fe atoms homogeneously distributed. NiFe(A) NPs are readily converted into corresponding electrocatalytically active NiFe(H) NP by a simple electrochemical treatment. Electrochemical analysis data show that the OER activity of amorphous NiFe(H) samples follows the volcano-type trend when plotted against the Fe content. Ni 70 Fe 30 (H) sample showed the lowest overpotential of 292mV at 10mAcm -2 geo and the lowest Tafel slope of 30.4mVdec -1 , outperforming IrO x /C (326mV, 41.7mVdec -1 ). Our samples are highly durable based on the chronopotentiometry data at the current density of 10mAcm -2 geo for 2h which show that Ni 70 Fe 30 sample maintains the steady-state potential, contrary to the time-varying IrO x /C. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural evolution of tunneling oxide passivating contact upon thermal annealing.

PubMed

Choi, Sungjin; Min, Kwan Hong; Jeong, Myeong Sang; Lee, Jeong In; Kang, Min Gu; Song, Hee-Eun; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan; Kim, Ka-Hyun

2017-10-16

We report on the structural evolution of tunneling oxide passivating contact (TOPCon) for high efficient solar cells upon thermal annealing. The evolution of doped hydrogenated amorphous silicon (a-Si:H) into polycrystalline-silicon (poly-Si) by thermal annealing was accompanied with significant structural changes. Annealing at 600 °C for one minute introduced an increase in the implied open circuit voltage (V oc ) due to the hydrogen motion, but the implied V oc decreased again at 600 °C for five minutes. At annealing temperature above 800 °C, a-Si:H crystallized and formed poly-Si and thickness of tunneling oxide slightly decreased. The thickness of the interface tunneling oxide gradually decreased and the pinholes are formed through the tunneling oxide at a higher annealing temperature up to 1000 °C, which introduced the deteriorated carrier selectivity of the TOPCon structure. Our results indicate a correlation between the structural evolution of the TOPCon passivating contact and its passivation property at different stages of structural transition from the a-Si:H to the poly-Si as well as changes in the thickness profile of the tunneling oxide upon thermal annealing. Our result suggests that there is an optimum thickness of the tunneling oxide for passivating electron contact, in a range between 1.2 to 1.5 nm.

Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction.

PubMed

Chen, Dejian; Zou, Liling; Li, Shunxing; Zheng, Fengying

2016-02-01

Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g(-1) h(-1), which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications.

Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Chen, Dejian; Zou, Liling; Li, Shunxing; Zheng, Fengying

2016-02-01

Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g-1 h-1, which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications.

Blending Cr 2O 3 into a NiO-Ni electrocatalyst for sustained water splitting

DOE PAGES

Gong, Ming; Zhou, Wu; Kenney, Michael James; ...

2015-08-24

The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less

Hydrogen self-diffusion in single crystal olivine and electrical conductivity of the Earth’s mantle

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

Novella, Davide; Jacobsen, Benjamin; Weber, Peter K.

Nominally anhydrous minerals formed deep in the mantle and transported to the Earth’s surface contain tens to hundreds of ppm wt H 2O, providing evidence for the presence of dissolved water in the Earth’s interior. Even at these low concentrations, H 2O greatly affects the physico-chemical properties of mantle materials, governing planetary dynamics and evolution. The diffusion of hydrogen (H) controls the transport of H 2O in the Earth’s upper mantle, but is not fully understood for olivine ((Mg, Fe) 2SiO 4) the most abundant mineral in this region. Here we present new hydrogen self-diffusion coefficients in natural olivine singlemore » crystals that were determined at upper mantle conditions (2 GPa and 750–900 °C). Hydrogen self-diffusion is highly anisotropic, with values at 900 °C of 10 -10.9, 10 -12.8 and 10 -11.9 m 2/s along [100], [010] and [001] directions, respectively. Combined with the Nernst-Einstein relation, these diffusion results constrain the contribution of H to the electrical conductivity of olivine to be σH = 10 2.12S/m·C H2O·exp -187kJ/mol/(RT). Comparisons between the model presented in this study and magnetotelluric measurements suggest that plausible H 2O concentrations in the upper mantle (≤250 ppm wt) can account for high electrical conductivity values (10 -2–10 -1 S/m) observed in the asthenosphere.« less

Hydrogen self-diffusion in single crystal olivine and electrical conductivity of the Earth’s mantle

DOE PAGES

Novella, Davide; Jacobsen, Benjamin; Weber, Peter K.; ...

2017-07-13

Nominally anhydrous minerals formed deep in the mantle and transported to the Earth’s surface contain tens to hundreds of ppm wt H 2O, providing evidence for the presence of dissolved water in the Earth’s interior. Even at these low concentrations, H 2O greatly affects the physico-chemical properties of mantle materials, governing planetary dynamics and evolution. The diffusion of hydrogen (H) controls the transport of H 2O in the Earth’s upper mantle, but is not fully understood for olivine ((Mg, Fe) 2SiO 4) the most abundant mineral in this region. Here we present new hydrogen self-diffusion coefficients in natural olivine singlemore » crystals that were determined at upper mantle conditions (2 GPa and 750–900 °C). Hydrogen self-diffusion is highly anisotropic, with values at 900 °C of 10 -10.9, 10 -12.8 and 10 -11.9 m 2/s along [100], [010] and [001] directions, respectively. Combined with the Nernst-Einstein relation, these diffusion results constrain the contribution of H to the electrical conductivity of olivine to be σH = 10 2.12S/m·C H2O·exp -187kJ/mol/(RT). Comparisons between the model presented in this study and magnetotelluric measurements suggest that plausible H 2O concentrations in the upper mantle (≤250 ppm wt) can account for high electrical conductivity values (10 -2–10 -1 S/m) observed in the asthenosphere.« less

Hydrogen self-diffusion in single crystal olivine and electrical conductivity of the Earth's mantle.

PubMed

Novella, Davide; Jacobsen, Benjamin; Weber, Peter K; Tyburczy, James A; Ryerson, Frederick J; Du Frane, Wyatt L

2017-07-13

Nominally anhydrous minerals formed deep in the mantle and transported to the Earth's surface contain tens to hundreds of ppm wt H 2 O, providing evidence for the presence of dissolved water in the Earth's interior. Even at these low concentrations, H 2 O greatly affects the physico-chemical properties of mantle materials, governing planetary dynamics and evolution. The diffusion of hydrogen (H) controls the transport of H 2 O in the Earth's upper mantle, but is not fully understood for olivine ((Mg, Fe) 2 SiO 4 ) the most abundant mineral in this region. Here we present new hydrogen self-diffusion coefficients in natural olivine single crystals that were determined at upper mantle conditions (2 GPa and 750-900 °C). Hydrogen self-diffusion is highly anisotropic, with values at 900 °C of 10 -10.9 , 10 -12.8 and 10 -11.9 m 2 /s along [100], [010] and [001] directions, respectively. Combined with the Nernst-Einstein relation, these diffusion results constrain the contribution of H to the electrical conductivity of olivine to be σ H  = 10 2.12 S/m·C H2O ·exp -187kJ/mol/(RT) . Comparisons between the model presented in this study and magnetotelluric measurements suggest that plausible H 2 O concentrations in the upper mantle (≤250 ppm wt) can account for high electrical conductivity values (10 -2 -10 -1  S/m) observed in the asthenosphere.

A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

PubMed

Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

2017-07-18

The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

Chemistry through cocrystals: pressure-induced polymerization of C 2H 2·C 6H 6 to an extended crystalline hydrocarbon

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

Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li

The 1:1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.

Chemistry through cocrystals: pressure-induced polymerization of C 2H 2·C 6H 6 to an extended crystalline hydrocarbon

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

Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li

The 1 : 1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.

The Habitability of a Stagnant-Lid Earth

NASA Astrophysics Data System (ADS)

Tosi, N.; Godolt, M.; Stracke, B.; Ruedas, T.; Grenfell, L.; Höning, D.; Nikolaou, A.; Plesa, A. C.; Breuer, D.; Spohn, T.

2017-12-01

Plate tectonics is a fundamental component for the habitability of the Earth. Yet whether it is a recurrent feature of terrestrial bodies orbiting other stars or unique to the Earth is unknown. The stagnant lid may rather be the most common tectonic expression on such bodies. To understand whether a stagnant-lid planet can be habitable, i.e. host liquid water at its surface, we model the thermal evolution of the mantle, volcanic outgassing of H2O and CO2, and resulting climate of an Earth-like planet lacking plate tectonics. We used a 1D model of parameterized convection to simulate the evolution of melt generation and the build-up of an atmosphere of H2O and CO2 over 4.5 Gyr. We then employed a 1D radiative-convective atmosphere model to calculate the global mean atmospheric temperature and the boundaries of the habitable zone (HZ). The evolution of the interior is characterized by the initial production of a large amount of partial melt accompanied by a rapid outgassing of H2O and CO2. At 1 au, the obtained temperatures generally allow for liquid water on the surface nearly over the entire evolution. While the outer edge of the HZ is mostly influenced by the amount of outgassed CO2, the inner edge presents a more complex behaviour that is dependent on the partial pressures of both gases. At 1 au, the stagnant-lid planet considered would be regarded as habitable. The width of the HZ at the end of the evolution, albeit influenced by the amount of outgassed CO2, can vary in a non-monotonic way depending on the extent of the outgassed H2O reservoir. Our results suggest that stagnant-lid planets can be habitable over geological timescales and that joint modelling of interior evolution, volcanic outgassing, and accompanying climate is necessary to robustly characterize planetary habitability.

Superconducting order from disorder in 2H-TaSe2-xSx

NASA Astrophysics Data System (ADS)

Li, Lijun; Deng, Xiaoyu; Wang, Zhen; Liu, Yu; Abeykoon, Milinda; Dooryhee, Eric; Tomic, Aleksandra; Huang, Yanan; Warren, John B.; Bozin, Emil S.; Billinge, Simon J. L.; Sun, Yuping; Zhu, Yimei; Kotliar, Gabriel; Petrovic, Cedomir

2017-12-01

We report on the emergence of robust superconducting order in single crystal alloys of TaSe2-xSx (0 ≤ × ≤ 2). The critical temperature of the alloy is surprisingly higher than that of the two end compounds TaSe2 and TaS2. The evolution of superconducting critical temperature Tc(x) correlates with the full width at half maximum of the Bragg peaks and with the linear term of the high-temperature resistivity. The conductivity of the crystals near the middle of the alloy series is higher or similar than that of either one of the end members 2H-TaSe2 and/or 2H-TaS2. It is known that in these materials superconductivity is in close competition with charge density wave order. We interpret our experimental findings in a picture where disorder tilts this balance in favor of superconductivity by destroying the charge density wave order.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

PubMed

Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

2018-04-25

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Facile Modification of TiO2 with Nickel Sulfide and Sulfate Species for Photoreformation of Cellulose into H2.

PubMed

Hao, Hongchang; Zhang, Ling; Wang, Wenzhong; Zeng, Shuwen

2018-06-19

Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H2 evolution. However, the direct photoreformation still suffers from challenges such as the limited solubility of cellulose and dependence on catalytic activity of noble-metals. Herein, we reported a novel photoreformation of cellulose into H2 over TiO2 which is synchronously modified with nickel sulfide (NixSy) and chemisorbed sulfate species (SO42-) by a one-pot approach. A significant elevation in photocatalytic hydrogen evolution rate is achieved, with the maximal value of 3.02 mmol/g/h during the first three hours, almost 76-fold higher than that of P25 and comparable to Pt-P25. Aided by systematic investigation, it is proposed that nickel sulfide and sulfate modification synergistically contribute to the remarkably raised efficiency of biomass transformation. Specifically, NixSy serves as co-catalyst for photocatalytic H2 production, while SO42- ions are inferred to promote cellulose hydrolyzation and consequent accessibility of biomass to catalysts. Further, the accumulated formate intermediates are found to have a poison effect on catalysts, desorption of which can be controlled by tuning aqueous alkalinity. Overall, our strategy for modifying TiO2 with SO42- and NixSy provides a novel perspective of concurrently accelerating cellulose hydrolyzation process and supplementing hydrogen evolution sites, for efficient photocatalytic reformation of cellulose into H2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of high efficient Cu/TiO2 photocatalysts by grinding and their size-dependent photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Ni, Dawei; Shen, Haiyan; Li, Huiqiao; Ma, Ying; Zhai, Tianyou

2017-07-01

Recently, copper species have been extensively investigated to replace Pt as efficient co-catalysts for the evolution of H2 due to their low cost and relatively high activity. Cu nanoparticles less than 5 nm are successfully decorated on TiO2 surface in this work by an easy and mild milling process. These Cu nanoparticles are highly dispersed on TiO2 when the loading amount of Cu is no more than 10 wt%. The sizes of Cu nanoparticles can be controlled by changing the milling environment and decrease in the order of Cu-ethanol > Cu-water > Cu nanoparticles obtained through drying milling. The highest and stable hydrogen generation can be realized on Cu/TiO2 with 2.0 wt% Cu and sizes of Cu nanoparticles ranging from 2 to 4 nm, in which high and stable photocurrent confirms promoted photogenerated charge separation. Smaller Cu clusters are demonstrated to be detrimental to hydrogen evolution at same Cu content. High loading of Cu nanoparticles of 2-4 nm will benefit photogenerated electron-hole recombination and thus decrease the activity of Cu/TiO2. The results here demonstrate the key roles of Cu cluster size in addition to Cu coverage on photocatalytic activity of Cu/TiO2 composite photocatalysts.

Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

PubMed

Mozia, Sylwia; Kułagowska, Aleksandra; Morawski, Antoni W

2014-11-26

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

Evolution of the H9N2 influenza genotype that facilitated the genesis of the novel H7N9 virus

PubMed Central

Pu, Juan; Wang, Shuoguo; Yin, Yanbo; Zhang, Guozhong; Carter, Robert A.; Wang, Jinliang; Xu, Guanlong; Sun, Honglei; Wang, Min; Wen, Chu; Wei, Yandi; Wang, Dongdong; Zhu, Baoli; Lemmon, Gordon; Jiao, Yuannian; Duan, Susu; Wang, Qian; Du, Qian; Sun, Meng; Bao, Jinnan; Sun, Yipeng; Zhao, Jixun; Zhang, Hui; Wu, Gang; Liu, Jinhua; Webster, Robert G.

2015-01-01

The emergence of human infection with a novel H7N9 influenza virus in China raises a pandemic concern. Chicken H9N2 viruses provided all six of the novel reassortant’s internal genes. However, it is not fully understood how the prevalence and evolution of these H9N2 chicken viruses facilitated the genesis of the novel H7N9 viruses. Here we show that over more than 10 y of cocirculation of multiple H9N2 genotypes, a genotype (G57) emerged that had changed antigenicity and improved adaptability in chickens. It became predominant in vaccinated farm chickens in China, caused widespread outbreaks in 2010–2013 before the H7N9 viruses emerged in humans, and finally provided all of their internal genes to the novel H7N9 viruses. The prevalence and variation of H9N2 influenza virus in farmed poultry could provide an important early warning of the emergence of novel reassortants with pandemic potential. PMID:25548189

Evolution of the H9N2 influenza genotype that facilitated the genesis of the novel H7N9 virus.

PubMed

Pu, Juan; Wang, Shuoguo; Yin, Yanbo; Zhang, Guozhong; Carter, Robert A; Wang, Jinliang; Xu, Guanlong; Sun, Honglei; Wang, Min; Wen, Chu; Wei, Yandi; Wang, Dongdong; Zhu, Baoli; Lemmon, Gordon; Jiao, Yuannian; Duan, Susu; Wang, Qian; Du, Qian; Sun, Meng; Bao, Jinnan; Sun, Yipeng; Zhao, Jixun; Zhang, Hui; Wu, Gang; Liu, Jinhua; Webster, Robert G

2015-01-13

The emergence of human infection with a novel H7N9 influenza virus in China raises a pandemic concern. Chicken H9N2 viruses provided all six of the novel reassortant's internal genes. However, it is not fully understood how the prevalence and evolution of these H9N2 chicken viruses facilitated the genesis of the novel H7N9 viruses. Here we show that over more than 10 y of cocirculation of multiple H9N2 genotypes, a genotype (G57) emerged that had changed antigenicity and improved adaptability in chickens. It became predominant in vaccinated farm chickens in China, caused widespread outbreaks in 2010-2013 before the H7N9 viruses emerged in humans, and finally provided all of their internal genes to the novel H7N9 viruses. The prevalence and variation of H9N2 influenza virus in farmed poultry could provide an important early warning of the emergence of novel reassortants with pandemic potential.

CdS nanoparticles/CeO2 nanorods composite with high-efficiency visible-light-driven photocatalytic activity

NASA Astrophysics Data System (ADS)

You, Daotong; Pan, Bao; Jiang, Fan; Zhou, Yangen; Su, Wenyue

2016-02-01

Different mole ratios of CdS nanoparticles (NPs)/CeO2 nanorods (NRs) composites with effective contacts were synthesized through a two-step hydrothermal method. The crystal phase, microstructure, optical absorption properties, electrochemical properties and photocatalytic H2 production activity of these composites were investigated. It was concluded that the photogenerated charge carriers in the CdS NPs/CeO2 NRs composite with a proper mole ratio (1:1) exhibited the longest lifetime and highest separation efficiency, which was responsible for the highest H2-production rate of 8.4 mmol h-1 g-1 under visible-light irradiation (λ > 420 nm). The superior photocatalytic H2 evolution properties are attributed to the transfer of visible-excited electrons of CdS NPs to CeO2 NRs, which can effectively extend the light absorption range of wide-band gap CeO2 NRs. This work provides feasible routes to develop visible-light responsive CeO2-based nanomaterial for efficient solar utilization.

Structure, Dynamics, and Deuterium Fractionation of Massive Pre-stellar Cores

NASA Astrophysics Data System (ADS)

Goodson, Matthew D.; Kong, Shuo; Tan, Jonathan C.; Heitsch, Fabian; Caselli, Paola

2016-12-01

High levels of deuterium fraction in N2H+ are observed in some pre-stellar cores. Single-zone chemical models find that the timescale required to reach observed values ({D}{frac}{{{N}}2{{{H}}}+}\\equiv {{{N}}}2{{{D}}}+/{{{N}}}2{{{H}}}+≳ 0.1) is longer than the free-fall time, possibly 10 times longer. Here, we explore the deuteration of turbulent, magnetized cores with 3D magnetohydrodynamics simulations. We use an approximate chemical model to follow the growth in abundances of N2H+ and N2D+. We then examine the dynamics of the core using each tracer for comparison to observations. We find that the velocity dispersion of the core as traced by N2D+ appears slightly sub-virial compared to predictions of the Turbulent Core Model of McKee & Tan, except at late times just before the onset of protostar formation. By varying the initial mass surface density, the magnetic energy, the chemical age, and the ortho-to-para ratio of H2, we also determine the physical and temporal properties required for high deuteration. We find that low initial ortho-to-para ratios (≲ 0.01) and/or multiple free-fall times (≳ 3) of prior chemical evolution are necessary to reach the observed values of deuterium fraction in pre-stellar cores.

Synthesis of MoS2 and MoO2 for their applications in H2 generation and lithium ion batteries: a review.

PubMed

Zhao, Yufei; Zhang, Yuxia; Yang, Zhiyu; Yan, Yiming; Sun, Kening

2013-08-01

Scientists increasingly witness the applications of MoS 2 and MoO 2 in the field of energy conversion and energy storage. On the one hand, MoS 2 and MoO 2 have been widely utilized as promising catalysts for electrocatalytic or photocatalytic hydrogen evolution in aqueous solution. On the other hand, MoS 2 and MoO 2 have also been verified as efficient electrode material for lithium ion batteries. In this review, the synthesis, structure and properties of MoS 2 and MoO 2 are briefly summarized according to their applications for H 2 generation and lithium ion batteries. Firstly, we overview the recent advancements in the morphology control of MoS 2 and MoO 2 and their applications as electrocatalysts for hydrogen evolution reactions. Secondly, we focus on the photo-induced water splitting for H 2 generation, in which MoS 2 acts as an important co-catalyst when combined with other semiconductor catalysts. The newly reported research results of the significant functions of MoS 2 nanocomposites in photo-induced water splitting are presented. Thirdly, we introduce the advantages of MoS 2 and MoO 2 for their enhanced cyclic performance and high capacity as electrode materials of lithium ion batteries. Recent key achievements in MoS 2 - and MoO 2 -based lithium ion batteries are highlighted. Finally, we discuss the future scope and the important challenges emerging from these fascinating materials.

Preliminary 3D In-situ measurements of the texture evolution of strained H2O ice during annealing using neutron Laue diffractometry

NASA Astrophysics Data System (ADS)

Journaux, Baptiste; Montagnat, Maurine; Chauve, Thomas; Ouladdiaf, Bachir; Allibon, John

2015-04-01

Dynamic recrystallization (DRX) strongly affects the evolution of microstructure (grain size and shape) and texture (crystal preferred orientation) in materials during deformation at high temperature. Since texturing leads to anisotropic physical properties, predicting the effect of DRX is essential for industrial applications, for interpreting geophysical data and modeling geodynamic flows, and predicting ice sheet flow and climate evolution. A large amount of literature is available related to metallurgy, geology or glaciology, but there remains overall fundamental questions about the relationship between nucleation, grain boundary migration and texture development at the microscopic scale. Previous measurements of DRX in ice were either conducted using 2D ex-situ techniques such as AITA [1,2] or Electron Backscattering Diffraction (EBSD) [3], or using 3D statistical ex-situ [4] or in-situ [5] techniques. Nevertheless, all these techniques failed to observe at the scale of nucleation processes during DRX in full 3D. Here we present a new approach using neutron Laue diffraction, which enable to perform 3D measurements of in-situ texture evolution of strained polycrystalline H2O ice (>2% at 266 K) during annealing at the microscopic scale. Thanks the CYCLOPS instrument [6] (Institut Laue Langevin Grenoble, France) and the intrinsic low background of this setup, preliminary observations enabled us to follow, in H2O ice, the evolution of serrated grain boundaries, and kink-band during annealing. Our observations show a significant evolution of the texture and internal misorientation over the course of few hours at an annealing temperature of 268.5 K. In the contrary, ice kink-band structures seem to be very stable over time at near melting temperatures. The same samples have been analyzed ex-situ using EBSD for comparison. These results represent a first step toward in-situ microscopic measurements of dynamic recrystallization processes in ice during strain. This experiment has been conducted in the frame of the ANR-funded DREAM project that focuses on the recrystallization processes in anisotropic materials. References [1] D. S. Russell-Head and C.J.L. Wilson., 2001, Journal of Glaciology, 24, 117-130. [2] Wilson, C.J.L., Peternell, M., Piazolo, S., Luzin, V., 2014, Journal of Structural Geology, Microdynamics of Ice, 61, 50-77. [3] M. Montagnat, T. Chauve, F. Barou, A. Tommasi, B. Beausir, C. Fressengeas., in prep. [4] T. H. Jacka and J. Li., 2000, In T. Hondoh, editor, Physics of Ice Core Records, pages 83-102. Hokkaido University Press, Sapporo. [5] S. Piazolo, C. J. L. Wilson, V. Luzin, C. Brouzet, and M. Peternell., 2013, Geochemistry, Geophysics, Geosystems, 14, 4185-4194. [6] B. Ouladdiaf et al., 2011, Journal of Applied Crystallography, 44, 392-397.

Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

PubMed

Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

2013-04-07

Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

The behaviour of boron in a peraluminous granite-pegmatite system and associated hydrothermal solutions: a melt and fluid-inclusion study

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Förster, Hans-Jürgen; Heinrich, Wilhelm

2002-09-01

Detailed analyses of melt and fluid inclusions combined with an electron-microprobe survey of boron-bearing minerals reveal the evolution of boron in a highly evolved peraluminous granite-pegmatite complex and the associated high- and medium-temperature ore-forming hydrothermal fluids (Ehrenfriedersdorf, Erzgebirge, Germany). Melt inclusions in granite represent embryonic pegmatite-forming melts containing about 10 wt% H2O and 1.8 wt% B2O3. These melts are also enriched in F, P, and other incompatible elements such as Be, Sn, Rb, and Cs. Ongoing differentiation and volatile enrichment drove the system into a solvus, where two pegmatite-forming melts coexisted. The critical point is at about 712 °C, 100 MPa, 20 wt% H2O and 4.1 wt% B2O3. Cooling and concomitant fractional crystallisation from 700 to 500 °C induced development of two conjugate melts, an H2O-poor (A-melt) and an H2O-rich melt (B-melt) along the opening solvus. Boron is a major element in both melts and is preferentially partitioned into the H2O-rich melt. Temperature-dependent distribution coefficients $ D{boron}{{B - melt/A - melt}} $ are 1.3 at 650 °C, 1.5 at 600 °C, and 1.8 at 500 °C. In both melts, boron concentrations decreased during cooling because of exsolution of a boron-rich hypersaline brine throughout the pegmatitic stage. Boromuscovite containing up to 8.5 wt% was another sink for boron at this stage. The end of the melt-dominated pegmatitic stage was attained at a solidus temperature of around 490 °C. Fluid inclusions of the hydrothermal stage reveal trapping temperatures of 480 to 370 °C, along with varying densities and highly variable B2O3 contents ranging from 0.20 to 2.94 wt%. A boiling system evolved, indicating a complex interplay between closed- and open-system behaviour. Pressure switched from lithostatic to hydrostatic and back, generating hydrothermal convection cells where meteoric waters were introduced and mixed with magmatic fluids. Boron-rich solutions originated from magmatic fluids, whereas boron-depleted fluids were mainly of meteoric origin. This highlights the potential of boron for discriminating fluids of different origin. Tin is continuously enriched during the evolution because tin and boron are cross-linked by formation of boron-, fluorine- and tin-fluorine-bearing complexes and is finally deposited within quartz-cassiterite veins during the transition from closed- to open-system behaviour. Boron does not only trace the complex evolution of the Ehrenfriedersdorf complex but exerts, together with H2O, F and P, an important control on the physical and chemical properties of pegmatite-forming melts, and particularly on the formation of a two-melt solvus at low pressure. We discuss this with respect to experimental results on H2O solubility and the critical behaviour of the haplogranite-water system which contained variable concentrations of volatiles.

The behaviour of boron in a peraluminous granite-pegmatite system and associated hydrothermal solutions: a melt and fluid-inclusion study

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Förster, Hans-Jürgen; Heinrich, Wilhelm

Detailed analyses of melt and fluid inclusions combined with an electron-microprobe survey of boron-bearing minerals reveal the evolution of boron in a highly evolved peraluminous granite-pegmatite complex and the associated high- and medium-temperature ore-forming hydrothermal fluids (Ehrenfriedersdorf, Erzgebirge, Germany). Melt inclusions in granite represent embryonic pegmatite-forming melts containing about 10 wt% H2O and 1.8 wt% B2O3. These melts are also enriched in F, P, and other incompatible elements such as Be, Sn, Rb, and Cs. Ongoing differentiation and volatile enrichment drove the system into a solvus, where two pegmatite-forming melts coexisted. The critical point is at about 712 °C, 100 MPa, 20 wt% H2O and 4.1 wt% B2O3. Cooling and concomitant fractional crystallisation from 700 to 500 °C induced development of two conjugate melts, an H2O-poor (A-melt) and an H2O-rich melt (B-melt) along the opening solvus. Boron is a major element in both melts and is preferentially partitioned into the H2O-rich melt. Temperature-dependent distribution coefficients $ D{boron}{{B - melt/A - melt}} $ are 1.3 at 650 °C, 1.5 at 600 °C, and 1.8 at 500 °C. In both melts, boron concentrations decreased during cooling because of exsolution of a boron-rich hypersaline brine throughout the pegmatitic stage. Boromuscovite containing up to 8.5 wt% was another sink for boron at this stage. The end of the melt-dominated pegmatitic stage was attained at a solidus temperature of around 490 °C. Fluid inclusions of the hydrothermal stage reveal trapping temperatures of 480 to 370 °C, along with varying densities and highly variable B2O3 contents ranging from 0.20 to 2.94 wt%. A boiling system evolved, indicating a complex interplay between closed- and open-system behaviour. Pressure switched from lithostatic to hydrostatic and back, generating hydrothermal convection cells where meteoric waters were introduced and mixed with magmatic fluids. Boron-rich solutions originated from magmatic fluids, whereas boron-depleted fluids were mainly of meteoric origin. This highlights the potential of boron for discriminating fluids of different origin. Tin is continuously enriched during the evolution because tin and boron are cross-linked by formation of boron-, fluorine- and tin-fluorine-bearing complexes and is finally deposited within quartz-cassiterite veins during the transition from closed- to open-system behaviour. Boron does not only trace the complex evolution of the Ehrenfriedersdorf complex but exerts, together with H2O, F and P, an important control on the physical and chemical properties of pegmatite-forming melts, and particularly on the formation of a two-melt solvus at low pressure. We discuss this with respect to experimental results on H2O solubility and the critical behaviour of the haplogranite-water system which contained variable concentrations of volatiles.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Hydrogen-Treated Rutile TiO2 Shell in Graphite-Core Structure as a Negative Electrode for High-Performance Vanadium Redox Flow Batteries.

PubMed

Vázquez-Galván, Javier; Flox, Cristina; Fàbrega, Cristian; Ventosa, Edgar; Parra, Andres; Andreu, Teresa; Morante, Joan Ramón

2017-05-09

Hydrogen-treated TiO 2 as an electrocatalyst has shown to boost the capacity of high-performance all-vanadium redox flow batteries (VRFBs) as a simple and eco-friendly strategy. The graphite felt-based GF@TiO 2 :H electrode is able to inhibit the hydrogen evolution reaction (HER), which is a critical barrier for operating at high rate for long-term cycling in VRFBs. Significant improvements in charge/discharge and electron-transfer processes for the V 3+ /V 2+ reaction on the surface of reduced TiO 2 were achieved as a consequence of the formation of oxygen functional groups and oxygen vacancies in the lattice structure. Key performance indicators of VRFB have been improved, such as high capability rates and electrolyte-utilization ratios (82 % at 200 mA cm -2 ). Additionally, high coulombic efficiencies (ca. 100 % up to the 96th cycle, afterwards >97 %) were obtained, demonstrating the feasibility of achieving long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influenza H7N9 and H9N2 Viruses: Coexistence in Poultry Linked to Human H7N9 Infection and Genome Characteristics

PubMed Central

Yu, Xinfen; Jin, Tao; Cui, Yujun; Pu, Xiaoying; Li, Jun; Xu, Jin; Liu, Guang; Jia, Huijue; Liu, Dan; Song, Shili; Yu, Yang; Xie, Li; Huang, Renjie; Ding, Hua; Kou, Yu; Zhou, Yinyan; Wang, Yayu; Xu, Xun; Yin, Ye; Wang, Jian; Guo, Chenyi; Yang, Xianwei; Hu, Liangping; Wu, Xiaopeng; Wang, Hailong; Liu, Jun; Zhao, Guoqiu; Zhou, Jiyong; Gao, George F.; Yang, Ruifu; Wang, Jun

2014-01-01

ABSTRACT Avian influenza virus A of the novel H7N9 reassortant subtype was recently found to cause severe human respiratory infections in China. Live poultry markets were suspected locations of the human H7N9 infection sources, based on the cases' exposure histories and sequence similarities between viral isolates. To explore the role of live poultry markets in the origin of the novel H7N9 virus, we systematically examined poultry and environmental specimens from local markets and farms in Hangzhou, using real-time reverse transcription-PCR (RT-PCR) as well as high-throughput next-generation sequencing (NGS). RT-PCR identified specimens positive for the H7 and N9 genomic segments in all of the 12 poultry markets epidemiologically linked to 10 human H7N9 cases. Chickens, ducks, and environmental specimens from the markets contained heavily mixed subtypes, including H7, N9, H9, and N2 and sometimes H5 and N1. The idea of the coexistence of H7N9 and H9N2 subtypes in chickens was further supported by metagenomic sequencing. In contrast, human H7N9 infection cases (n = 31) were all negative for H9N2 virus according to real-time RT-PCR. The six internal segments were indistinguishable for the H7N9 and H9N2 viruses. The H9, N2, and internal-segment sequences were very close to the sequence of the H9N2 virus circulating in chickens in China recently. Our results provide direct evidence that H9N2 strains coexisted with the novel human-pathogenic H7N9 influenza virus in epidemiologically linked live poultry markets. Avian influenza A virus of the H9N2 subtype likely made a recent contribution to the evolution of the H7N9 virus and continues to do so. IMPORTANCE Our results suggest that avian influenza A virus of the H9N2 subtype likely made a recent contribution to the evolution of the H7N9 virus, a novel reassortant avian influenza virus A subtype, and continues to do so. The finding helps shed light on how the H7N9 virus emerged, spread, and transmitted to humans. It is of considerable interest for assessing the risk of the possible emergence of novel reassortant viruses with enhanced transmissibility to humans. PMID:24403589

Influenza H7N9 and H9N2 viruses: coexistence in poultry linked to human H7N9 infection and genome characteristics.

PubMed

Yu, Xinfen; Jin, Tao; Cui, Yujun; Pu, Xiaoying; Li, Jun; Xu, Jin; Liu, Guang; Jia, Huijue; Liu, Dan; Song, Shili; Yu, Yang; Xie, Li; Huang, Renjie; Ding, Hua; Kou, Yu; Zhou, Yinyan; Wang, Yayu; Xu, Xun; Yin, Ye; Wang, Jian; Guo, Chenyi; Yang, Xianwei; Hu, Liangping; Wu, Xiaopeng; Wang, Hailong; Liu, Jun; Zhao, Guoqiu; Zhou, Jiyong; Pan, Jingcao; Gao, George F; Yang, Ruifu; Wang, Jun

2014-03-01

Avian influenza virus A of the novel H7N9 reassortant subtype was recently found to cause severe human respiratory infections in China. Live poultry markets were suspected locations of the human H7N9 infection sources, based on the cases' exposure histories and sequence similarities between viral isolates. To explore the role of live poultry markets in the origin of the novel H7N9 virus, we systematically examined poultry and environmental specimens from local markets and farms in Hangzhou, using real-time reverse transcription-PCR (RT-PCR) as well as high-throughput next-generation sequencing (NGS). RT-PCR identified specimens positive for the H7 and N9 genomic segments in all of the 12 poultry markets epidemiologically linked to 10 human H7N9 cases. Chickens, ducks, and environmental specimens from the markets contained heavily mixed subtypes, including H7, N9, H9, and N2 and sometimes H5 and N1. The idea of the coexistence of H7N9 and H9N2 subtypes in chickens was further supported by metagenomic sequencing. In contrast, human H7N9 infection cases (n = 31) were all negative for H9N2 virus according to real-time RT-PCR. The six internal segments were indistinguishable for the H7N9 and H9N2 viruses. The H9, N2, and internal-segment sequences were very close to the sequence of the H9N2 virus circulating in chickens in China recently. Our results provide direct evidence that H9N2 strains coexisted with the novel human-pathogenic H7N9 influenza virus in epidemiologically linked live poultry markets. Avian influenza A virus of the H9N2 subtype likely made a recent contribution to the evolution of the H7N9 virus and continues to do so. Our results suggest that avian influenza A virus of the H9N2 subtype likely made a recent contribution to the evolution of the H7N9 virus, a novel reassortant avian influenza virus A subtype, and continues to do so. The finding helps shed light on how the H7N9 virus emerged, spread, and transmitted to humans. It is of considerable interest for assessing the risk of the possible emergence of novel reassortant viruses with enhanced transmissibility to humans.

Hydrogen Peroxide Formation and pH Changes at Rock-Water Interface during Stressing

NASA Astrophysics Data System (ADS)

Xie, S.; Kulahci, I.; Cyr, G.; Tregloan-Reed, J.; Balk, M.; Rothschild, L. J.; Freund, F. T.

2008-12-01

Common igneous and high-grade metamorphic rocks contain dormant defects, which become activated when stressed. They release electronic charge carriers, in particular defect electrons associated with O- states in a matrix of O2-. Known as 'positive holes' or pholes for short, the O- states can spread out of the stressed rock volume, travel along stress gradients over distances on the order of meters in the lab and probably over kilometers in the field. They carry a current, which can flow through meters of rock in the laboratory, probably tens of kilometers in the field. At rock-water interfaces the O- states turn into O radicals, which subtract H from H2O, forming OH- in the rock surface and PH radicals in the water. Two OH combine to H2O2. In the process the pH becomes more acidic. The discovery of H2O2 formation at rock-water interfaces as part of stress- activated currents on the tectonically active Earth may help us better understand the oxidation of the early Earth and the evolution of early Life.

Highly Pathogenic H5N1 Avian Influenza Viruses Exhibit Few Barriers to Gene Flow in Vietnam

PubMed Central

Carrel, Margaret; Wan, Xiu-Feng; Nguyen, Tung; Emch, Michael

2013-01-01

Locating areas where genetic change is inhibited can illuminate underlying processes that drive evolution of pathogens. The persistence of highly pathogenic H5N1 avian influenza in Vietnam since 2003, and the continuous molecular evolution of Vietnamese avian influenza viruses, indicates that local environmental factors are supportive not only of incidence but also of viral adaptation. This article explores whether gene flow is constant across Vietnam, or whether there exist boundary areas where gene flow exhibits discontinuity. Using a dataset of 125 highly pathogenic H5N1 avian influenza viruses, principal components analysis and wombling analysis are used to indicate the location, magnitude, and statistical significance of genetic boundaries. Results show that a small number of geographically minor boundaries to gene flow in highly pathogenic H5N1 avian influenza viruses exist in Vietnam, but that overall there is little division in genetic exchange. This suggests that differences in genetic characteristics of viruses from one region to another are not the result of barriers to H5N1 viral exchange in Vietnam, and that H5N1 avian influenza is able to spread relatively unimpeded across the country. PMID:22350419

Evolution of fluid geochemistry at the Turrialba volcano (Costa Rica) from 1998 to 2008

NASA Astrophysics Data System (ADS)

Vaselli, O.; Tassi, Franco; Duarte, E.; Fernandez, E.; Poreda, R. J.; Huertas, A. Delgado

2010-05-01

Turrialba (10°02'N, 83°45'W) is a 3,349-m high stratovolcano belonging to the Holocene “Cordillera Central” volcanic belt of Costa Rica. The summit consists of three EW-oriented craters (East, Central, and West). Since its last eruptive phase (1864-1866), the Central and West craters have displayed modest fumarolic activity, with outlet temperatures clustering around 90°C. In 2001, seismic swarms, ground deformation, and increasing fumarolic activity occurred. From 2005 to 2008, new fumarolic vents opened between and within the Central and West craters, and along the western and southwestern outer flanks of the volcanic edifice. These physical changes were accompanied by a drastic modification in the gas chemistry that can be divided in three stages: (1) hydrothermal (from 1998 to autumn 2001), characterized by the presence of H2O, CO2, H2S, and, to a very minor extent, HCl and HF; (2) hydrothermal/magmatic (autumn 2001-2007), with the appearance of SO2 and a significant increase of HCl and HF; and (3) magmatic-dominated (2007-2008), characterized by increased SO2 content, SO2/H2S > 100, and temperatures up to 282°C. Accordingly, gas equilibrium in the CO2-CH4-H2 system suggests a progressive evolution of the deep fluid reservoir toward higher temperatures and more oxidizing conditions. The chemical-physical modifications of Turrialba in the last decade can be interpreted as part of a cyclic mechanism controlling the balance between the hydrothermal and the magmatic systems. Nevertheless, the risk of rejuvenation of the volcanic activity cannot be excluded, and an appropriate seismic, ground deformation, and geochemical monitoring program is highly recommended. Turrialba lies at a distance of 35 and 15 km from San José and Cartago, respectively, the two largest cities in Costa Rica.

Kinetics of hydrogen-evolution reaction on lead and lead-alloy electrodes in sulfuric acid electrolyte with phosphoric acid and antimony additives

NASA Astrophysics Data System (ADS)

Venugopalan, S.

1994-03-01

The kinetics of the hydrogen-evolution reaction (HER) on smooth Pb, PbCaSn and PbSbSe alloy electrodes is studied in H 2SO 4 (3-10 M) electrolyte that contains phosphoric acid (0-40 g l -1) and antimony (0-10 mg l -1) using galvanostatic polarization in the Tafel domain. A direct correlation is found between iO,H and icor on lead and lead-alloy electrodes with varying concentrations of H 3PO 4 and Sb(III) in H 2SO 4. The maximum suppression of the HER occurs with 20 g l -1 H 3PO 4 in H 2SO 4 for both lead and lead alloys. The data are explained in the light of a model that employs adsorption of H 3PO 4 at the electrode/ electrolyte interface.

Semiconductive Copper(I)-Organic Frameworks for Efficient Light-Driven Hydrogen Generation Without Additional Photosensitizers and Cocatalysts.

PubMed

Shi, Dongying; Zheng, Rui; Sun, Ming-Jun; Cao, Xinrui; Sun, Chun-Xiao; Cui, Chao-Jie; Liu, Chun-Sen; Zhao, Junwei; Du, Miao

2017-11-13

As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost-effective Cu 2 I 2 -based MOF, Cu-I-bpy (bpy=4,4'-bipyridine) exhibited highly efficient photocatalytic hydrogen production (7.09 mmol g -1  h -1 ). Density functional theory (DFT) calculations established the electronic structures of Cu-I-bpy with a narrow band gap of 2.05 eV, indicating its semiconductive behavior, which is consistent with the experimental value of 2.00 eV. The proposed mechanism demonstrates that Cu 2 I 2 clusters of Cu-I-bpy serve as photoelectron generators to accelerate the copper(I) hydride interaction, providing redox reaction sites for hydrogen evolution. The highly stable cocatalyst-free and self-sensitized Cu-I-bpy provides new insights into the future design of cost-effective d 10 -based MOFs for highly efficient and long-term solar fuels production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenated amorphous carbon films on steel balls and Si substrates: Nanostructural evolutions and their trigging tribological behaviors

NASA Astrophysics Data System (ADS)

Wang, Yongfu; Wang, Yan; Zhang, Xingkai; Shi, Jing; Gao, Kaixiong; Zhang, Bin; Zhang, Junyan

2017-10-01

In this study, we prepared hydrogenated amorphous carbon films on steel balls and Si substrates (steel ball- and Si substrate-films) with different deposition time, and discussed their carbon nanostructural evolutions and tribological behaviors. The steel ball-film structure started to be graphite-like structure and then gradually transformed into fullerene-like (FL) structure. The Si substrate-film structure began in FL structure and kept it through the thickness. The difference may be result from the competition between high starting substrate temperature after additional nitriding applied on the steel balls (its supply power is higher than that in the film deposition), and relaxation of compressive stress from energized ion bombardment in film deposition process. The FL structural film friction couples could achieve ultra-low friction in open air. In particular, the Si substrate-film with 3 h, against the steel ball-film with 2 h and 3 h, exhibited super-low friction (∼0.009) and superlong wear life (∼5.5 × 105 cycles). Our result could widen the superlubricity scope from previously high load and velocity, to middle load and velocity.

Amorphous Nickel-Cobalt-Borate Nanosheet Arrays for Efficient and Durable Water Oxidation Electrocatalysis under Near-Neutral Conditions.

PubMed

Chen, Lanlan; Ren, Xiang; Teng, Wanqing; Shi, Pengfei

2017-07-21

Electrolytic hydrogen generation needs earth-abundant oxygen evolution reaction electrocatalysts that perform efficiently at mild pH. Here, the development of amorphous nickel-cobalt-borate nanosheet arrays on macroporous nickel foam (NiCo-Bi/NF) as a 3D catalyst electrode for high-performance water oxidation in near-neutral media is reported. To drive a current density of 10 mA cm -2 , the resulting NiCo-Bi/NF demands an overpotential of only 430 mV in 0.1 m potassium borate (K-Bi, pH 9.2). Moreover, it also shows long-term electrochemical durability with maintenance of catalytic activity for 20 h, achieving a high turnover frequency of 0.21 s -1 at an overpotential of 550 mV. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

PubMed

Feng, Jin-Xian; Tong, Si-Yao; Tong, Ye-Xiang; Li, Gao-Ren

2018-04-18

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H + and hamper the ability of H + to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H + from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Development of Inorganic Nanomaterials as Photocatalysts for the Water Splitting Reaction

NASA Astrophysics Data System (ADS)

Frame, Fredrick Andrew

The photochemical water splitting reaction is of great interest for converting solar energy into usable fuels. This dissertation focuses on the development of inorganic nanoparticle catalysts for solar energy driven conversion of water into hydrogen and oxygen. The results from these selected studies have allowed greater insight into nanoparticle chemistry and the role of nanoparticles in photochemical conversion of water in to hydrogen and oxygen. Chapter 2 shows that CdSe nanoribbons have photocatalytic activity for hydrogen production from water in the presence of Na2S/Na2SO 3 as sacrificial electron donors in both UV and visible light. Quantum confinement of this material leads to an extended bandgap of 2.7 eV and enables the photocatalytic activity of this material. We report on the photocatalytic H2 evolution, and its dependence on platinum co-catalysts, the concentration of the electron donor, and the wavelength of incident radiation. Transient absorption measurements reveal decay of the excited state on multiple timescales, and an increase of lifetimes of trapped electrons due to the sacrificial electron donors. In chapter 3, we explore the catalytic activity of citrate-capped CdSe quantum dots. We show that the process is indeed catalytic for these dots in aqueous 0.1 M Na2S:Na2SO3, but not in pure water. Furthermore, optical spectroscopy was used to report electronic transitions in the dots and electron microscopy was used to obtain morphology of the catalyst. Interestingly, an increasing catalytic rate is noted for undialyzed catalyst. Dynamic light scattering experiments show an increased hydrodynamic radius in the case of undialyzed CdSe dots in donor solution. In chapter 4 we show that CdSe:MoS2 nanoparticle composites with improved catalytic activity can be assembled from CdSe and MoS2 nanoparticle building units. We report on the photocatalytic H 2 evolution, quantum efficiency using LED irriadiation, and its dependence on the co-catalyst loading. Furthermore, optical spectroscopy, cyclic voltammetry, and electron microscopy were used to obtain morphology, optical properties, and electronic structure of the catalysts. In chapter 5, illumination with visible light (lambda > 400 nm) photoconverts a red V2O5 gel in aqueous methanol solution into a green VO2 gel. The presence of V(4+) in the green VO2 gel is supported by Electron Energy Loss Spectra. High-resolution electron micrographs, powder X-ray diffraction, and selective area electron diffraction (SAED) data show that the crystalline structure of the V2O5 gel is retained upon reduction. After attachment of colloidal Pt nanoparticles, H2 evolution proceeds catalytically on the VO2 gel. The Pt nanoparticles reduce the H2 evolution overpotential. However, the activity of the new photocatalyst remains limited by the VO2 conduction band edge just below the proton reduction potential. Chapter 6 studies the ability of IrO2 to evolve oxygen from aqueous solutions under UV irradiation. We show that visible illumination (lambda > 400 nm) of iridium dioxide (IrO2) nanocrystals capped in succinic acid in aqueous sodium persulfate solution leads to catalytic oxygen evolution. While the majority of catalytic hydrogen evolution comes from UV light, the process can still be driven with visible light. Morphology, optical properties, surface photovoltage measurements, and oxygen evolution rates are discussed.

MUFASA: the strength and evolution of galaxy conformity in various tracers

NASA Astrophysics Data System (ADS)

Rafieferantsoa, Mika; Davé, Romeel

2018-03-01

We investigate galaxy conformity using the MUFASA cosmological hydrodynamical simulation. We show a bimodal distribution in galaxy colour with radius, albeit with too many low-mass quenched satellite galaxies compared to observations. MUFASA produces conformity in observed properties such as colour, specific star formation rate (sSFR), and H I content, i.e. neighbouring galaxies have similar properties. We see analogous trends in other properties such as in environment, stellar age, H2 content, and metallicity. We introduce quantifying conformity using S(R), measuring the relative difference in upper and lower quartile properties of the neighbours. We show that low-mass and non-quenched haloes have weak conformity (S(R)≲ 0.5) extending to large projected radii R in all properties, while high-mass and quenched haloes have strong conformity (S(R)˜ 1) that diminishes rapidly with R and disappears at R ≳ 1 Mpc. S(R) is strongest for environment in low-mass haloes, and sSFR (or colour) in high-mass haloes, and is dominated by one-halo conformity with the exception of H I in small haloes. Metallicity shows a curious anticonformity in massive haloes. Tracking the evolution of conformity for z = 0 galaxies back in time shows that conformity broadly emerges as a late-time (z ≲ 1) phenomenon. However, for fixed halo mass bins, conformity is fairly constant with redshift out to z ≳ 2. These trends are consistent with the idea that strong conformity only emerges once haloes grow above MUFASA's quenching mass scale of ˜1012 M⊙. A quantitative measure of conformity in various properties, along with its evolution, thus represents a new and stringent test of the impact of quenching on environment within current galaxy formation models.

Evolutionary analysis of FAM83H in vertebrates.

PubMed

Huang, Wushuang; Yang, Mei; Wang, Changning; Song, Yaling

2017-01-01

Amelogenesis imperfecta is a group of disorders causing abnormalities in enamel formation in various phenotypes. Many mutations in the FAM83H gene have been identified to result in autosomal dominant hypocalcified amelogenesis imperfecta in different populations. However, the structure and function of FAM83H and its pathological mechanism have yet to be further explored. Evolutionary analysis is an alternative for revealing residues or motifs that are important for protein function. In the present study, we chose 50 vertebrate species in public databases representative of approximately 230 million years of evolution, including 1 amphibian, 2 fishes, 7 sauropsidas and 40 mammals, and we performed evolutionary analysis on the FAM83H protein. By sequence alignment, conserved residues and motifs were indicated, and the loss of important residues and motifs of five special species (Malayan pangolin, platypus, minke whale, nine-banded armadillo and aardvark) was discovered. A phylogenetic time tree showed the FAM83H divergent process. Positive selection sites in the C-terminus suggested that the C-terminus of FAM83H played certain adaptive roles during evolution. The results confirmed some important motifs reported in previous findings and identified some new highly conserved residues and motifs that need further investigation. The results suggest that the C-terminus of FAM83H contain key conserved regions critical to enamel formation and calcification.

Net light-induced oxygen evolution in photosystem I deletion mutants of the cyanobacterium Synechocystis sp. PCC 6803.

PubMed

Wang, Qing Jun; Singh, Abhay; Li, Hong; Nedbal, Ladislav; Sherman, Louis A; Govindjee; Whitmarsh, John

2012-05-01

Oxygenic photosynthesis in cyanobacteria, algae, and plants requires photosystem II (PSII) to extract electrons from H(2)O and depends on photosystem I (PSI) to reduce NADP(+). Here we demonstrate that mixotrophically-grown mutants of the cyanobacterium Synechocystis sp. PCC 6803 that lack PSI (ΔPSI) are capable of net light-induced O(2) evolution in vivo. The net light-induced O(2) evolution requires glucose and can be sustained for more than 30 min. Utilizing electron transport inhibitors and chlorophyll a fluorescence measurements, we show that in these mutants PSII is the source of the light-induced O(2) evolution, and that the plastoquinone pool is reduced by PSII and subsequently oxidized by an unidentified electron acceptor that does not involve the plastoquinol oxidase site of the cytochrome b(6)f complex. Moreover, both O(2) evolution and chlorophyll a fluorescence kinetics of the ΔPSI mutants are highly sensitive to KCN, indicating the involvement of a KCN-sensitive enzyme(s). Experiments using (14)C-labeled bicarbonate show that the ΔPSI mutants assimilate more CO(2) in the light compared to the dark. However, the rate of the light-minus-dark CO(2) assimilation accounts for just over half of the net light-induced O(2) evolution rate, indicating the involvement of unidentified terminal electron acceptors. Based on these results we suggest that O(2) evolution in ΔPSI cells can be sustained by an alternative electron transport pathway that results in CO(2) assimilation and that includes PSII, the platoquinone pool, and a KCN-sensitive enzyme. Copyright © 2012 Elsevier B.V. All rights reserved.

Recurrent Loss of APOBEC3H Activity during Primate Evolution.

PubMed

Garcia, Erin I; Emerman, Michael

2018-06-20

Genes in the APOBEC3 family encode cytidine deaminases that provide a barrier against viral infection and retrotransposition. Of all APOBEC3 genes in humans, APOBEC3H ( A3H ) is the most polymorphic: some haplotypes encode stable and active A3H proteins, while others are unstable and poorly antiviral. Such variation in human A3H affects interactions with the lentiviral antagonist Vif, which counteracts A3H via proteasomal degradation. In order to broaden our understanding of A3H-Vif interactions, as well as its evolution in Old World monkeys, we characterized A3H variation within four African green monkey (AGM) subspecies. We found that A3H is highly polymorphic in AGMs and has lost antiviral activity in multiple Old World monkeys. This loss of function was partially related to protein expression levels but was also influenced by amino acid mutations in the N-terminus. Moreover, we demonstrate that the evolution of A3H in the primate lineages leading to AGMs was not driven by Vif. Our work suggests that activity of A3H is evolutionarily dynamic and may have a negative effect on host fitness, resulting in its recurrent loss in primates. IMPORTANCE Adaptation of viruses to their hosts is critical for transmission of viruses between different species. Previous studies had identified changes in a protein from the APOBEC3 family that influenced species-specificity of simian immunodeficiency viruses (SIVs) in African green monkeys. We studied the evolution of a related protein in the same system, APOBEC3H, which has experienced a loss of function in humans. This evolutionary approach revealed that recurrent loss of APOBEC3H activity has taken place during primate evolution suggesting that APOBEC3H places a fitness cost on hosts. The variability of APOBEC3H activity between different primates highlights the differential selective pressures on the APOBEC3 gene family. Copyright © 2018 American Society for Microbiology.

A Unified Picture of Pinatubo Aerosol Global-to Micro-Scale Evolution, From Space, Air, and Ground Measurements

NASA Technical Reports Server (NTRS)

Russell, Philip B.; Livingston, J. M.; Pueschel, R. F.; Pollack, J. B.; Brooks, S.; Hamill, P.; Hughes, J.; Thomason, L.; Stowe, L.; Deshler, T.;

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

DOE PAGES

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira; ...

2016-11-30

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

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

To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of amore » regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less

Directed evolution of enzymes using microfluidic chips

NASA Astrophysics Data System (ADS)

Pilát, Zdeněk.; Ježek, Jan; Šmatlo, Filip; Kaůka, Jan; Zemánek, Pavel

2016-12-01

Enzymes are highly versatile and ubiquitous biological catalysts. They can greatly accelerate large variety of reactions, while ensuring appropriate catalytic activity and high selectivity. These properties make enzymes attractive biocatalysts for a wide range of industrial and biomedical applications. Over the last two decades, directed evolution of enzymes has transformed the field of protein engineering. We have devised microfluidic systems for directed evolution of haloalkane dehalogenases in emulsion droplets. In such a device, individual bacterial cells producing mutated variants of the same enzyme are encapsulated in microdroplets and supplied with a substrate. The conversion of a substrate by the enzyme produced by a single bacterium changes the pH in the droplet which is signalized by pH dependent fluorescence probe. The droplets with the highest enzymatic activity can be separated directly on the chip by dielectrophoresis and the resultant cell lineage can be used for enzyme production or for further rounds of directed evolution. This platform is applicable for fast screening of large libraries in directed evolution experiments requiring mutagenesis at multiple sites of a protein structure.

The Effects of Tidal Dissipation on the Thermal Evolution of Triton

NASA Astrophysics Data System (ADS)

Gaeman, J.; Hier-Majumder, S.; Roberts, J. H.

2009-12-01

This work explores the coupled structural, thermal, and orbital evolution of Neptune's icy satellite, Triton. Recent geyser activity, ridge formation, and volatile transport, observed on Triton's surface, indicate possible activity within Triton's interior [1,2]. Triton is hypothesized to have been captured from an initially heliocentric orbit. During the circularization of Triton's orbit following its capture by Neptune, intense tidal heating likely contributed to the formation of a subsurface ocean [3]. Although the time of Triton's capture is not exactly known, it is likely that the event took place earlier in the history of our solar system, when the probability of binary capture was higher [4, 5]. This work examines the thermal evolution of Triton by employing a coupled tidal and two-phase thermal evolution model, for both an early and late capture scenario. Thermal evolution of a solid crust underlain by an H2O-NH3 mushy layer is driven by the evolution of tidal heating, as Triton's orbital eccentricity evolves following its capture. The governing equations for tidal heating are solved using the propagator matrix method [6, 7], while the governing equation for the coupled crust-multiphase layer thermal evolution were numerically solved using a finite volume discretization. The results indicate that the existence of a subsurface ocean is strongly dependent on ammonia content as larger concentrations of ammonia influence liquidus temperature and density contrast between solid and liquid phases [8]. Preliminary results indicate that an ocean likely exists for compositions containing a relatively high percentage of ammonia for both early and late capture of the satellite. In contrast, the subsurface ocean freezes completely for lower ammonia content. [1] Brown, R. H., Kirk, R. L. (1994). Journal of Geophysical Research 99, 1965-981. [2] Prockter, L. M., Nimmo, F., Pappalardo, R. T. (2005). Geophysical Research Letters 32, L14202. [3] Ross, M. N., Schubert, G. (1990). Geophysical Research Letters 17, 1749-752. [4] Agnor, C. B., Hamilton, D. P. (2006). Nature 441, 192-94. [5] Schenk, P. M., Zahnle, K. (2007). Icarus 192, 135-49. [6] Roberts, J. H., Nimmo, F. (2008). Icarus 194, 675-689. [7] Sabadini, R., Vermeersen, B., (2004). Global Dynamics of the Earth. Kluwer Academic Publishers. [8] Hogenboom, D. L., Kargel, J. S., Concolmagno, G. J., Holden, T. C., Lee, L., Buyyounouski, M. (1997). Icarus 128, 171-80.

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

Berto, Tobias F.; Sanwald, Kai E.; Byers, J. Paige

Photocatalytic overall water splitting requires co-catalysts that efficiently promote the generation of H-2 but do not catalyze its reverse oxidation. We demonstrate that CO chemisorbed on metal co-catalysts (Rh, Pt, Pd) suppresses the back reaction while maintaining the rate of H-2 evolution. On Rh/GaN:ZnO, the highest H-2 production rates were obtained with 4-40 mbar of CO, the back reaction remaining suppressed below 7 mbar of O-2. The O-2 and H-2 evolution rates compete with CO oxidation and the back reaction. The rates of all reactions increased with increasing photon absorption. However, due to different dependencies on the rate of chargemore » carrier generation, the selectivities for O-2 and H-2 formation increased in comparison to CO oxidation and the back reaction with increasing photon flux and/or quantum efficiency. Under optimum conditions, the impact of CO to prevent the back reaction is identical to that of a Cr2O3 layer covering the active metal particle.« less

The relative influence of H2O and CO2 on the primitive surface conditions and evolution of rocky planets

NASA Astrophysics Data System (ADS)

Salvador, A.; Massol, H.; Davaille, A.; Marcq, E.; Sarda, P.; Chassefière, E.

2017-07-01

How the volatile content influences the primordial surface conditions of terrestrial planets and, thus, their future geodynamic evolution is an important question to answer. We simulate the secular convective cooling of a 1-D magma ocean (MO) in interaction with its outgassed atmosphere. The heat transfer in the atmosphere is computed either using the grey approximation or using a k-correlated method. We vary the initial CO2 and H2O contents (respectively from 0.1 × 10-2 to 14 × 10-2 wt % and from 0.03 to 1.4 times the Earth Ocean current mass) and the solar distance—from 0.63 to 1.30 AU. A first rapid cooling stage, where efficient MO cooling and degassing take place, producing the atmosphere, is followed by a second quasi steady state where the heat flux balance is dominated by the solar flux. The end of the rapid cooling stage (ERCS) is reached when the mantle heat flux becomes negligible compared to the absorbed solar flux. The resulting surface conditions at ERCS, including water ocean's formation, strongly depend both on the initial volatile content and solar distance D. For D > DC, the "critical distance," the volatile content controls water condensation and a new scaling law is derived for the water condensation limit. Although today's Venus is located beyond DC due to its high albedo, its high CO2/H2O ratio prevents any water ocean formation. Depending on the formation time of its cloud cover and resulting albedo, only 0.3 Earth ocean mass might be sufficient to form a water ocean on early Venus.

Oxygen and hydrogen peroxide in the early evolution of life on earth: in silico comparative analysis of biochemical pathways.

PubMed

Slesak, Ireneusz; Slesak, Halina; Kruk, Jerzy

2012-08-01

In the Universe, oxygen is the third most widespread element, while on Earth it is the most abundant one. Moreover, oxygen is a major constituent of all biopolymers fundamental to living organisms. Besides O(2), reactive oxygen species (ROS), among them hydrogen peroxide (H(2)O(2)), are also important reactants in the present aerobic metabolism. According to a widely accepted hypothesis, aerobic metabolism and many other reactions/pathways involving O(2) appeared after the evolution of oxygenic photosynthesis. In this study, the hypothesis was formulated that the Last Universal Common Ancestor (LUCA) was at least able to tolerate O(2) and detoxify ROS in a primordial environment. A comparative analysis was carried out of a number of the O(2)-and H(2)O(2)-involving metabolic reactions that occur in strict anaerobes, facultative anaerobes, and aerobes. The results indicate that the most likely LUCA possessed O(2)-and H(2)O(2)-involving pathways, mainly reactions to remove ROS, and had, at least in part, the components of aerobic respiration. Based on this, the presence of a low, but significant, quantity of H(2)O(2) and O(2) should be taken into account in theoretical models of the early Archean atmosphere and oceans and the evolution of life. It is suggested that the early metabolism involving O(2)/H(2)O(2) was a key adaptation of LUCA to already existing weakly oxic zones in Earth's primordial environment.

Nanoplasmonically Engineered Interfaces on Amorphous TiO2 for Highly Efficient Photocatalysis in Hydrogen Evolution.

PubMed

Liang, Huijun; Meng, Qiuxia; Wang, Xiaobing; Zhang, Hucheng; Wang, Jianji

2018-04-25

The nanoplasmonic metal-driven photocatalytic activity depends heavily on the spacing between metal nanoparticles (NPs) and semiconductors, and this work shows that ethylene glycol (EG) is an ideal candidate for interface spacer. Controlling the synthetic systems at pH 3, the composite of Ag NPs with EG-stabilized amorphous TiO 2 (Ag/TiO 2 -3) was synthesized by the facile light-induced reduction. It is verified that EG spacers can set up suitable geometric arrangement in the composite: the twin hydroxyls act as stabilizers to bind Ag NPs and TiO 2 together and the nonconductive alkyl chains consisting only of two CH 2 are able to separate the two building blocks completely and also provide the shortest channels for an efficient transfer of radiation energies to reach TiO 2 . Employed as photocatalysts in hydrogen evolution under visible light, amorphous TiO 2 hardly exhibits the catalytic activity due to high defect density, whereas Ag/TiO 2 -3 represents a remarkably high catalytic efficiency. The enhancement mechanism of the reaction rate is proposed by the analysis of the compositional, structural, and optical properties from a series of Ag/TiO 2 composites.

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

DOE PAGES

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

2017-09-25

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

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

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

Rapid and broad detection of H5 hemagglutinin by an immunochromatographic kit using novel monoclonal antibody against highly pathogenic avian influenza virus belonging to the genetic clade 2.3.4.4.

PubMed

Nguyen, Lam Thanh; Nakaishi, Kazunari; Motojima, Keiko; Ohkawara, Ayako; Minato, Erina; Maruyama, Junki; Hiono, Takahiro; Matsuno, Keita; Okamatsu, Masatoshi; Kimura, Takashi; Takada, Ayato; Kida, Hiroshi; Sakoda, Yoshihiro

2017-01-01

Highly pathogenic avian influenza viruses (HPAIVs) of H5 subtype have persistently caused outbreaks in domestic poultry and wild birds worldwide and sporadically infected humans. Rapid and accurate diagnosis is one of the key strategies for the control of H5 HPAIVs. However, the sensitivity of the diagnosis of H5 HPAIVs has gradually reduced due to extensive antigenic variation during their evolution. Particularly, the previously developed immunochromatographic diagnosis kit for H5 viruses, Linjudge Flu A/H5, exhibits reduced detection of H5 HPAIVs isolated in recent years. In the present study, we established a new advanced H5 rapid immunochromatographic detection kit (New Linjudge Flu A/H5) by a combination of two anti-H5 hemagglutinin monoclonal antibodies, A64/1 previously applied in the Linjudge Flu A/H5 and A32/2, a novel monoclonal antibody generated from a clade 2.3.4.4 H5 HPAIV. The new kit broadly detected all classical and recent H5 influenza viruses and showed a higher specificity and sensitivity than the original Linjudge Flu A/H5 with recently circulating H5 HPAIVs. Furthermore, the applicability of the New Linjudge Flu A/H5 was demonstrated by detecting antigens from the swabs and tissue homogenates of naturally infected birds and experimentally infected chickens with H5N6 HPAIVs belonging to the genetic clade 2.3.4.4. Our study, therefore, can provide an effective point-of-care rapid antigen detection kit for the surveillance of H5 avian influenza viruses and as a prompt countermeasure against the current widespread of the clade 2.3.4.4 H5 HPAIVs in domestic and wild birds.

Acidification, not carbonation, is the major regulator of carbon fluxes in the coccolithophore Emiliania huxleyi.

PubMed

Kottmeier, Dorothee M; Rokitta, Sebastian D; Rost, Björn

2016-07-01

A combined increase in seawater [CO2 ] and [H(+) ] was recently shown to induce a shift from photosynthetic HCO3 (-) to CO2 uptake in Emiliania huxleyi. This shift occurred within minutes, whereas acclimation to ocean acidification (OA) did not affect the carbon source. To identify the driver of this shift, we exposed low- and high-light acclimated E. huxleyi to a matrix of two levels of dissolved inorganic carbon (1400, 2800 μmol kg(-1) ) and pH (8.15, 7.85) and directly measured cellular O2 , CO2 and HCO3 (-) fluxes under these conditions. Exposure to increased [CO2 ] had little effect on the photosynthetic fluxes, whereas increased [H(+) ] led to a significant decline in HCO3 (-) uptake. Low-light acclimated cells overcompensated for the inhibition of HCO3 (-) uptake by increasing CO2 uptake. High-light acclimated cells, relying on higher proportions of HCO3 (-) uptake, could not increase CO2 uptake and photosynthetic O2 evolution consequently became carbon-limited. These regulations indicate that OA responses in photosynthesis are caused by [H(+) ] rather than by [CO2 ]. The impaired HCO3 (-) uptake also provides a mechanistic explanation for lowered calcification under OA. Moreover, it explains the OA-dependent decrease in photosynthesis observed in high-light grown phytoplankton. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

H5N1-SeroDetect EIA and rapid test: a novel differential diagnostic assay for serodiagnosis of H5N1 infections and surveillance.

PubMed

Khurana, Surender; Sasono, Pretty; Fox, Annette; Nguyen, Van Kinh; Le, Quynh Mai; Pham, Quang Thai; Nguyen, Tran Hien; Nguyen, Thanh Liem; Horby, Peter; Golding, Hana

2011-12-01

Continuing evolution of highly pathogenic (HP) H5N1 influenza viruses in wild birds with transmission to domestic poultry and humans poses a pandemic threat. There is an urgent need for a simple and rapid serological diagnostic assay which can differentiate between antibodies to seasonal and H5N1 strains and that could provide surveillance tools not dependent on virus isolation and nucleic acid technologies. Here we describe the establishment of H5N1 SeroDetect enzyme-linked immunosorbent assay (ELISA) and rapid test assays based on three peptides in HA2 (488-516), PB1-F2 (2-75), and M2e (2-24) that are highly conserved within H5N1 strains. These peptides were identified by antibody repertoire analyses of H5N1 influenza survivors in Vietnam using whole-genome-fragment phage display libraries (GFPDLs). To date, both platforms have demonstrated high levels of sensitivity and specificity in detecting H5N1 infections (clade 1 and clade 2.3.4) in Vietnamese patients as early as 7 days and up to several years postinfection. H5N1 virus-uninfected individuals in Vietnam and the United States, including subjects vaccinated with seasonal influenza vaccines or with confirmed seasonal virus infections, did not react in the H5N1-SeroDetect assays. Moreover, sera from individuals vaccinated with H5N1 subunit vaccine with moderate anti-H5N1 neutralizing antibody titers did not react positively in the H5N1-SeroDetect ELISA or rapid test assays. The simple H5N1-SeroDetect ELISA and rapid tests could provide an important tool for large-scale surveillance for potential exposure to HP H5N1 strains in both humans and birds.

Remotely Distinguishing and Mapping Endogenic Water on the Moon

NASA Technical Reports Server (NTRS)

Klima, Rachel L.; Petro, Noah E.

2017-01-01

Water and/or hydroxyl detected remotely on the lunar surface originates from several sources: (i) comets and other exogenous debris; (ii) solar wind implantation; (iii) the lunar interior. While each of these sources is interesting in its own right, distinguishing among them is critical for testing hypotheses for the origin and evolution of the Moon and our Solar System. Existing spacecraft observations are not of high enough spectral resolution to uniquely characterize the bonding energies of the hydroxyl molecules that have been detected. Nevertheless, the spatial distribution and associations of H, OH- or H2O with specific lunar lithologies provide some insight into the origin of lunar hydrous materials. The global distribution of OH-/H2O as detected using infrared spectroscopic measurements from orbit is here examined, with particular focus on regional geological features that exhibit OH-/H2O absorption band strengths that differ from their immediate surroundings.

Investigation on thermodynamics of ion-slicing of GaN and heterogeneously integrating high-quality GaN films on CMOS compatible Si(100) substrates.

PubMed

Huang, Kai; Jia, Qi; You, Tiangui; Zhang, Runchun; Lin, Jiajie; Zhang, Shibin; Zhou, Min; Zhang, Bo; Yu, Wenjie; Ou, Xin; Wang, Xi

2017-11-08

Die-to-wafer heterogeneous integration of single-crystalline GaN film with CMOS compatible Si(100) substrate using the ion-cutting technique has been demonstrated. The thermodynamics of GaN surface blistering is in-situ investigated via a thermal-stage optical microscopy, which indicates that the large activation energy (2.5 eV) and low H ions utilization ratio (~6%) might result in the extremely high H fluence required for the ion-slicing of GaN. The crystalline quality, surface topography and the microstructure of the GaN films are characterized in detail. The full width at half maximum (FWHM) for GaN (002) X-ray rocking curves is as low as 163 arcsec, corresponding to a density of threading dislocation of 5 × 10 7  cm -2 . Different evolution of the implantation-induced damage was observed and a relationship between the damage evolution and implantation-induced damage is demonstrated. This work would be beneficial to understand the mechanism of ion-slicing of GaN and to provide a platform for the hybrid integration of GaN devices with standard Si CMOS process.

Electrocatalytic H2 production from seawater over Co, N-codoped nanocarbons.

PubMed

Gao, Shuang; Li, Guo-Dong; Liu, Yipu; Chen, Hui; Feng, Liang-Liang; Wang, Yun; Yang, Min; Wang, Dejun; Wang, Shan; Zou, Xiaoxin

2015-02-14

One of the main barriers blocking sustainable hydrogen production is the use of expensive platinum-based catalysts to produce hydrogen from water. Herein we report the cost-effective synthesis of catalytically active, nitrogen-doped, cobalt-encased carbon nanotubes using inexpensive starting materials-urea and cobalt chloride hexahydrate (CoCl2·6H2O). Moreover, we show that the as-obtained nanocarbon material exhibits a remarkable electrocatalytic activity toward the hydrogen evolution reaction (HER); and thus it can be deemed as a potential alternative to noble metal HER catalysts. In particular, the urea-derived carbon nanotubes synthesized at 900 °C (denoted as U-CNT-900) show a superior catalytic activity for HER with low overpotential and high current density in our study. Notably also, U-CNT-900 has the ability to operate stably at all pH values (pH 0-14), and even in buffered seawater (pH 7). The possible synergistic effects between carbon-coated cobalt nanoparticles and the nitrogen dopants can be proposed to account for the HER catalytic activity of U-CNT-900. Given the high natural abundance, ease of synthesis, and high catalytic activity and durability in seawater, this U-CNT-900 material is promising for hydrogen production from water in industrial applications.

Cobalt encapsulated N-doped defect-rich carbon nanotube as pH universal hydrogen evolution electrocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Suyun; Xiao, Xinxin; Lv, Taotao; Lv, Xiaomeng; Liu, Botao; Wei, Wei; Liu, Jun

2018-07-01

Exploring efficient and economical Pt-free electrocatalysts is of great significance for the electrocatalytic hydrogen evolution reaction (HER). However, the rational design on an industrial scale is a formidable challenge. Herein, we reported a facile calcination at controlled temperatures to fabricate rationally assembled cobalt nanoparticles embedded in defect-rich N-doped carbon nanotubes (Co-NCNTs), which was derived from low-cost dicyanadiamide thermally polymerized with cobalt precursor forming metal-organic frameworks, then further calculation leading to final products. The as-obtained samples were endowed with high content of N as electrocatalytic active site, defect-rich structure and excellent synergistic effect between cobalt nanoparticles and carbon nanotubes toward electrocatalytic HER. As expected, Co-NCNTs were highly active and long-term stable with onset potentials of c.a. 15 mV in acidic electrolytes (0.5 M H2SO4), 70 mV in alkaline (1 M KOH) and 300 mV in neutral media (pH 7). Specially, to achieve the current density of 10 mA cm-2, the overpotential of 103 mV in acid, 204 mV in alkaline and 337 mV in neutral media was obtained. The enhanced HER performance was discussed in detail by adjusting the molar ratio of precursor and metal species. Moreover, the present synthetic route is easy to scale up and expand to other non-noble metal and alloy.

Highly efficient D2 generation by dehydrogenation of formic acid in D2O through H+/D+ exchange on an iridium catalyst: application to the synthesis of deuterated compounds by transfer deuterogenation.

PubMed

Wang, Wan-Hui; Hull, Jonathan F; Muckerman, James T; Fujita, Etsuko; Hirose, Takuji; Himeda, Yuichiro

2012-07-23

Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D(2)) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H(+)/D(+) exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D(2) evolution (purity up to 89 %) was achieved by using HCO(2)H as an electron source and D(2)O as a deuterium source; a rhodium analogue provided HD gas (98 %) under similar conditions. Furthermore, pressurized D(2) (98 %) without CO gas was generated by using DCO(2)D in D(2)O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO(2)H in D(2)O. Mechanistic studies show that the H(+)/D(+) exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Yung, Y. L.

1981-01-01

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, and the results of recent laboratory studies. The model satisfactorily accounts for the observations of CO, O2, (1) and SO2 in the stratosphere. Oxygen, derived from CO2 photolysis, is primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen radicals essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere, with the O-O bond broken by S + O2 and SO + HO2. The sensitivity of stratospheric chemistry to ambient H2 abundance was studied and the model prefers the high value (1 10 ppm) recently inferred from the Pioneer Venus ionospheric measurements. The importance of the photochemical production of S2O, (SO)2, S2, H2S2O2 and H2S2O3 is speculated. A number of previously unsuspected similarities between the chemistry of the stratospheres of Venus and the Earth, presented and discussed.

Spatial transmission of H5N6 highly pathogenic avian influenza viruses among wild birds in Ibaraki Prefecture, Japan, 2016-2017.

PubMed

Tsunekuni, Ryota; Yaguchi, Yuji; Kashima, Yuki; Yamashita, Kaoru; Takemae, Nobuhiro; Mine, Junki; Tanikawa, Taichiro; Uchida, Yuko; Saito, Takehiko

2018-05-01

From 29 November 2016 to 24 January 2017, sixty-three cases of H5N6 highly pathogenic avian influenza virus (HPAIV) infections were detected in wild birds in Ibaraki Prefecture, Japan. Here, we analyzed the genetic, temporal, and geographic correlations of these 63 HPAIVs to elucidate their dissemination throughout the prefecture. Full-genome sequence analysis of the Ibaraki isolates showed that 7 segments (PB2, PB1, PA, HA, NP, NA, NS) were derived from G1.1.9 strains while the M segment was from G1.1 strains; both groups of strains circulated in south China. Pathological studies revealed severe systemic infection in dead swans (the majority of dead birds and the only species necropsied), thus indicating high susceptibility to H5N6 HPAIVs. Coalescent phylogenetic analysis using the 7 G1.1.9-derived segments enabled detailed analysis of the short-term evolution of these highly homologous HPAIVs. This analysis revealed that the H5N6 HPAIVs isolated from wild birds in Ibaraki Prefecture were divided into 7 groups. Spatial analysis demonstrated that most of the cases concentrated around Senba Lake originated from a single source, and progeny viruses were transmitted to other locations after the infection expanded in mute swans. In contrast, within just a 5-km radius of the area in which cases were concentrated, three different intrusions of H5N6 HPAIVs were evident. Multi-segment analysis of short-term evolution showed that not only was the invading virus spread throughout Ibaraki Prefecture but also that, despite the small size of this region, multiple invasions had occurred during winter 2016-2017.

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

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

Jiang, Kun; Kharel, Priti; Peng, Yande

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

DOE PAGES

Jiang, Kun; Kharel, Priti; Peng, Yande; ...

2017-09-12

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

Integrating influenza antigenic dynamics with molecular evolution

PubMed Central

Bedford, Trevor; Suchard, Marc A; Lemey, Philippe; Dudas, Gytis; Gregory, Victoria; Hay, Alan J; McCauley, John W; Russell, Colin A; Smith, Derek J; Rambaut, Andrew

2014-01-01

Influenza viruses undergo continual antigenic evolution allowing mutant viruses to evade host immunity acquired to previous virus strains. Antigenic phenotype is often assessed through pairwise measurement of cross-reactivity between influenza strains using the hemagglutination inhibition (HI) assay. Here, we extend previous approaches to antigenic cartography, and simultaneously characterize antigenic and genetic evolution by modeling the diffusion of antigenic phenotype over a shared virus phylogeny. Using HI data from influenza lineages A/H3N2, A/H1N1, B/Victoria and B/Yamagata, we determine patterns of antigenic drift across viral lineages, showing that A/H3N2 evolves faster and in a more punctuated fashion than other influenza lineages. We also show that year-to-year antigenic drift appears to drive incidence patterns within each influenza lineage. This work makes possible substantial future advances in investigating the dynamics of influenza and other antigenically-variable pathogens by providing a model that intimately combines molecular and antigenic evolution. DOI: http://dx.doi.org/10.7554/eLife.01914.001 PMID:24497547

A Rapid Microwave-Assisted Thermolysis Route to Highly Crystalline Carbon Nitrides for Efficient Hydrogen Generation.

PubMed

Guo, Yufei; Li, Jing; Yuan, Yupeng; Li, Lu; Zhang, Mingyi; Zhou, Chenyan; Lin, Zhiqun

2016-11-14

Highly crystalline graphitic carbon nitride (g-C 3 N 4 ) with decreased structural imperfections benefits from the suppression of electron-hole recombination, which enhances its hydrogen generation activity. However, producing such g-C 3 N 4 materials by conventional heating in an electric furnace has proven challenging. Herein, we report on the synthesis of high-quality g-C 3 N 4 with reduced structural defects by judiciously combining the implementation of melamine-cyanuric acid (MCA) supramolecular aggregates and microwave-assisted thermolysis. The g-C 3 N 4 material produced after optimizing the microwave reaction time can effectively generate H 2 under visible-light irradiation. The highest H 2 evolution rate achieved was 40.5 μmol h -1 , which is two times higher than that of a g-C 3 N 4 sample prepared by thermal polycondensation of the same supramolecular aggregates in an electric furnace. The microwave-assisted thermolysis strategy is simple, rapid, and robust, thereby providing a promising route for the synthesis of high-efficiency g-C 3 N 4 photocatalysts. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Significant Enhancement of H2 Formation in Disk Galaxies under Strong Ram Pressure

NASA Astrophysics Data System (ADS)

Henderson, Benjamin; Bekki, Kenji

2016-05-01

We show for the first time that H2 formation on dust grains can be enhanced in disk galaxies under strong ram pressure (RP). We numerically investigate how the time evolution of H I and H2 components in disk galaxies orbiting a group/cluster of galaxies can be influenced by the hydrodynamical interaction between the gaseous components of the galaxies and the hot intracluster medium. We find that compression of H I caused by RP increases H2 formation in disk galaxies before RP rapidly strips H I, cutting off the fuel supply and causing a drop in H2 density. We also find that the level of this H2 formation enhancement in a disk galaxy under RP depends on the mass of its host cluster dark matter halo, the initial positions and velocities of the disk galaxy, and the disk inclination angle with respect to the orbital plane. We demonstrate that dust growth is a key factor in the evolution of the H I and H2 mass in disk galaxies under strong RP. We discuss how the correlation between H2 fractions and surface gas densities of disk galaxies evolves with time in the galaxies under RP. We also discuss whether galaxy-wide star formation rates (SFRs) in cluster disk galaxies can be enhanced by RP if the SFRs depend on H2 densities.

Detailed study of SiOxNy:H/Si interface properties for high quality surface passivation of crystalline silicon

NASA Astrophysics Data System (ADS)

Dong, Peng; Lei, Dong; Yu, Xuegong; Huang, Chunlai; Li, Mo; Dai, Gang; Zhang, Jian; Yang, Deren

2018-01-01

In this work, we present a detailed study on the interface and passivation properties of the hydrogenated silicon oxynitride (SiOxNy:H) on the crystalline silicon (c-Si) and their correlations with the film composition. The SiOxNy:H films were synthesized by plasma enhanced chemical vapor deposition (PECVD) at various N2O flow rates, which results in different film composition, in particular the different H-related bonds, such as Sisbnd H and Nsbnd H bonds. Fourier transform infrared spectroscopy measurements show that the concentration of Nsbnd H bonds increases with the N2O flows from 0 to 30 sccm, while drops below the detection limit at N2O flows above 30 sccm. This changing trend of Nsbnd H bonds correlates well with the evolution of carrier lifetime of silicon substrate passivated by SiOxNy:H film, indicating the crucial role of Nsbnd H bonds in surface passivation. It is inferred that during the film deposition and forming gas anneal (FGA) a considerable amount of hydrogen atoms are liberated from the weak type of Nsbnd H bonds rather than Sisbnd H bonds, and then passivate the dangling bonds at the interface, thus resulting in the significant reduction of interface state density and the improved passivation quality. In detail, the interface state density is reduced from ∼5 × 1012 to ∼2 × 1012 cm-2 eV-1 after the FGA, as derived from the high frequency capacitance-voltage (Csbnd V) measurements.

Evolution of trace elements in the planetary boundary layer in southern China: Effects of dust storms and aerosol-cloud interactions

NASA Astrophysics Data System (ADS)

Li, Tao; Wang, Yan; Zhou, Jie; Wang, Tao; Ding, Aijun; Nie, Wei; Xue, Likun; Wang, Xinfeng; Wang, Wenxing

2017-03-01

Aerosols and cloud water were analyzed at a mountaintop in the planetary boundary layer in southern China during March-May 2009, when two Asian dust storms occurred, to investigate the effects of aerosol-cloud interactions (ACIs) on chemical evolution of atmospheric trace elements. Fe, Al, and Zn predominated in both coarse and fine aerosols, followed by high concentrations of toxic Pb, As, and Cd. Most of these aerosol trace elements, which were affected by dust storms, exhibited various increases in concentrations but consistent decreases in solubility. Zn, Fe, Al, and Pb were the most abundant trace elements in cloud water. The trace element concentrations exhibited logarithmic inverse relationships with the cloud liquid water content and were found highly pH dependent with minimum concentrations at the threshold of pH 5.0. The calculation of Visual MINTEQ model showed that 80.7-96.3% of Fe(II), Zn(II), Pb(II), and Cu(II) existed in divalent free ions, while 71.7% of Fe(III) and 71.5% of Al(III) were complexed by oxalate and fluoride, respectively. ACIs could markedly change the speciation distributions of trace elements in cloud water by pH modification. The in-cloud scavenging of aerosol trace elements likely reached a peak after the first 2-3 h of cloud processing, with scavenging ratios between 0.12 for Cr and 0.57 for Pb. The increases of the trace element solubility (4-33%) were determined in both in-cloud aerosols and postcloud aerosols. These results indicated the significant importance of aerosol-cloud interactions to the evolution of trace elements during the first several cloud condensation/evaporation cycles.

High-Temperature Annealing Induced He Bubble Evolution in Low Energy He Ion Implanted 6H-SiC

NASA Astrophysics Data System (ADS)

Liu, Yu-Zhu; Li, Bing-Sheng; Zhang, Li

2017-05-01

Bubble evolution in low energy and high dose He-implanted 6H-SiC upon thermal annealing is studied. The < 0001> -oriented 6H-SiC wafers are implanted with 15 keV helium ions at a dose of 1× 1017 cm-2 at room temperature. The samples with post-implantation are annealed at temperatures of 1073, 1173, 1273, and 1473 K for 30 min. He bubbles in the wafers are examined via cross-sectional transmission electron microscopy (XTEM) analysis. The results present that nanoscale bubbles are almost homogeneously distributed in the damaged layer of the as-implanted sample, and no significant change is observed in the He-implanted sample after 1073 K annealing. Upon 1193 K annealing, almost full recrystallization of He-implantation-induced amorphization in 6H-SiC is observed. In addition, the diameters of He bubbles increase obviously. With continually increasing temperatures to 1273 K and 1473 K, the diameters of He bubbles increase and the number density of lattice defects decreases. The growth of He bubbles after high temperature annealing abides by the Ostwald ripening mechanism. The mean diameter of He bubbles located at depths of 120-135 nm as a function of annealing temperature is fitted in terms of a thermal activated process which yields an activation energy of 1.914+0.236 eV. Supported by the National Natural Science Foundation of China under Grant No 11475229.

ELLIPSOMETRIC STUDY OF a-Si:H NUCLEATION, GROWTH, AND INTERFACES

NASA Astrophysics Data System (ADS)

Collins, R. W.

Recent in situ and spectroscopic ellipsometry investigations of hydrogenated amorphous silicon (a-Si:H) nucleation behavior, microstructural evolution, and interface formation are reviewed. An outline of the commonly applied experimental techniques and data analysis is also presented. In situ ellipsometry reveals a nuclei formation and convergence sequence in the first 50Å of a-Si:H growth by rf plasma deposition from silane on c-Si and metal substrates. This sequence provides evidence of favorable growth chemistry that results in material with a low density of structural defects. The influence of deposition parameters and processes on the nucleation and subsequent microstructural evolution of a-Si:H is covered in detail. Among the other topics discussed include: nucleation of microcrystalline Si, evolution of surface roughness on a-Si:H, inert and reactive gas plasma modification of a-Si:H, and formation of a-Si:H heterostructures with SiO2, wide band gap alloys, and Bdoped a-Si:H.

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of graphene

NASA Astrophysics Data System (ADS)

Wang, Faze; Zheng, Maojun; Zhu, Changqing; Zhang, Bin; Chen, Wen; Ma, Li; Shen, Wenzhong

2015-08-01

Visible light photocatalytic H2 production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet, which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H2-production rate of 7.42 μmol h-1 g-1, eight times more than the pure ZnS sample. This high visible-light photocatalytic H2 production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H2 evolution.

Visible light photocatalytic H2-production activity of wide band gap ZnS nanoparticles based on the photosensitization of grapheme.

PubMed

Wang, Faze; Zheng, Maojun; Zhu, Changqing; Zhang, Bin; Chen, Wen; Ma, Li; Shen, Wenzhong

2015-08-28

Visible light photocatalytic H(2) production from water splitting is considered an attractive way to solve the increasing global energy crisis in modern life. In this study, a series of zinc sulfide nanoparticles and graphene (GR) sheet composites were synthesized by a two-step hydrothermal method, which used zinc chloride, sodium sulfide, and graphite oxide (GO) as the starting materials. The as-prepared ZnS-GR showed highly efficient visible light photocatalytic activity in hydrogen generation. The morphology and structure of the composites obtained by transmission electron microscope and x-ray diffraction exhibited a small crystallite size and a good interfacial contact between the ZnS nanoparticles and the two-dimensional (2D) GR sheet,which were beneficial for the photocatalysis. When the content of the GR in the catalyst was 0.1%, the ZG0.1 sample exhibited the highest H(2)-production rate of 7.42 μmol h(−1) g(−1), eight times more than the pure ZnS sample. This high visible-light photocatalytic H(2) production activity is attributed to the photosensitization of GR. Irradiated by visible light, the electrons photogenerated from GR transfer to the conduction band of ZnS to participate in the photocatalytic process. This study presents the visible-light photocatalytic activity of wide bandgap ZnS and its application in H(2) evolution.

Molybdenum Carbide Nanoparticles Coated into the Graphene Wrapping N-Doped Porous Carbon Microspheres for Highly Efficient Electrocatalytic Hydrogen Evolution Both in Acidic and Alkaline Media.

PubMed

Wei, Huifang; Xi, Qiaoya; Chen, Xi'an; Guo, Daying; Ding, Feng; Yang, Zhi; Wang, Shun; Li, Juan; Huang, Shaoming

2018-03-01

Molybdenum carbide (Mo 2 C) is recognized as an alternative electrocatalyst to noble metal for the hydrogen evolution reaction (HER). Herein, a facile, low cost, and scalable method is provided for the fabrication of Mo 2 C-based eletrocatalyst (Mo 2 C/G-NCS) by a spray-drying, and followed by annealing. As-prepared Mo 2 C/G-NCS electrocatalyst displays that ultrafine Mo 2 C nanopartilces are uniformly embedded into graphene wrapping N-doped porous carbon microspheres derived from chitosan. Such designed structure offer several favorable features for hydrogen evolution application: 1) the ultrasmall size of Mo 2 C affords a large exposed active sites; 2) graphene-wrapping ensures great electrical conductivity; 3) porous structure increases the electrolyte-electrode contact points and lowers the charge transfer resistance; 4) N-dopant interacts with H + better than C atoms and favorably modifies the electronic structures of adjacent Mo and C atoms. As a result, the Mo 2 C/G-NCS demonstrates superior HER activity with a very low overpotential of 70 or 66 mV to achieve current density of 10 mA cm -2 , small Tafel slope of 39 or 37 mV dec -1 , respectively, in acidic and alkaline media, and high stability, indicating that it is a great potential candidate as HER electrocatalyst.

Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

PubMed

Gao, Yu-Ji; Yang, Yichen; Li, Xu-Bing; Wu, Hao-Lin; Meng, Shu-Lin; Wang, Yang; Guo, Qing; Huang, Mao-Yong; Tung, Chen-Ho; Wu, Li-Zhu

2018-05-08

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 μmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.

Genotype patterns of contemporary reassorted H3N2 virus in U.S. swine

USDA-ARS?s Scientific Manuscript database

To understand the evolution of H3N2v influenza viruses that have infected 288 humans since July 2011, we performed the largest phylogenetic analysis at a whole genome scale of influenza viruses from North American swine to date (n = 200). At least ten distinct reassorted H3N2/pandemic H1N1 (rH3N2p)...

Carbon and hydrogen metabolism of green algae in light and dark

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

Not Available

1990-01-01

After adaptation to a hydrogen metabolism, Chlamydomonas reinhardtii can photoanaerobically metabolize acetate with the evolution of H{sub 2} and CO{sub 2}. An enzyme profile of the chloroplastic, cytoplasmic, and mitochondrial fractions were obtained with a cellular fractionation procedure that incorporated cell wall removal by autolysine, digestion of the plasmalemma with digitonin and fractionation by differential centrifugation on a Percoll step gradient. The sequence of events leading to the photo-evolution of H{sub 2} from acetate includes the conversion of acetate into succinate via the extraplastidic glyoxylate cycle, the oxidation of succinate to fumarate by chloroplastic succinic dehydrogenase and the oxidation ofmore » malate to oxaloacetate in the chloroplast by NAD dependent malate dehydrogenase. The level of potential activity of the enzymes was sufficient to accommodate the observed rate of gas evolution. The isolated darkened chloroplast evolves aerobically CO{sub 2} from glucose indicating a chloroplastic respiratory pathway. Evolution of CO{sub 2} is blocked by mitochondrial inhibitors.« less

On the Role of Dissolved Gases in the Atmosphere Retention of Low-mass Low-density Planets

NASA Astrophysics Data System (ADS)

Chachan, Yayaati; Stevenson, David J.

2018-02-01

Low-mass low-density planets discovered by Kepler in the super-Earth mass regime typically have large radii for their inferred masses, implying the presence of H2–He atmospheres. These planets are vulnerable to atmospheric mass loss due to heating by the parent star’s XUV flux. Models coupling atmospheric mass loss with thermal evolution predicted a bimodal distribution of planetary radii, which has gained observational support. However, a key component that has been ignored in previous studies is the dissolution of these gases into the molten core of rock and iron that constitute most of their mass. Such planets have high temperatures (>2000 K) and pressures (∼kbars) at the core-envelope boundary, ensuring a molten surface and a subsurface reservoir of hydrogen that can be 5–10 times larger than the atmosphere. This study bridges this gap by coupling the thermal evolution of the planet and the mass loss of the atmosphere with the thermodynamic equilibrium between the dissolved H2 and the atmospheric H2 (Henry’s law). Dissolution in the interior allows a planet to build a larger hydrogen repository during the planet formation stage. We show that the dissolved hydrogen outgasses to buffer atmospheric mass loss. The slow cooling of the planet also leads to outgassing because solubility decreases with decreasing temperature. Dissolution of hydrogen in the interior therefore increases the atmosphere retention ability of super-Earths. The study highlights the importance of including the temperature- and pressure-dependent solubility of gases in magma oceans and coupling outgassing to planetary evolution models.

Human infection with a highly pathogenic avian influenza A (H5N6) virus in Yunnan province, China.

PubMed

Xu, Wen; Li, Hong; Jiang, Li

2016-01-01

Highly pathogenic avian influenza A H5N6 virus has caused four human infections in China. This study reports the preliminary findings of the first known human case of H5N6 in Yunnan province. The patient initially developed symptoms of sore throat and coughing on 27 January 2015. The disease rapidly progressed to severe pneumonia, multiple organ dysfunctions and acute respiratory distress syndrome and the patient died on 6 February. Virological analysis determined that the virus belonged to H5 clade 2.3.4.4 and it has obtained partial ability for mammalian adaptation and amantadine resistance. Environmental investigation found H5 in 63% of the samples including poultry faeces, tissues, cage surface swabs and sewage from local live poultry markets by real-time RT-PCR. These findings suggest that the expanding and enhancing of surveillance in both avian and humans are necessary to monitor the evolution of H5 influenza virus and to facilitate early detection of suspected cases.

A genetically engineered H5 protein expressed in insect cells confers protection against different clades of H5N1 highly pathogenic avian influenza viruses in chickens.

PubMed

Oliveira Cavalcanti, Marcia; Vaughn, Eric; Capua, Ilaria; Cattoli, Giovanni; Terregino, Calogero; Harder, Timm; Grund, Christian; Vega, Carlos; Robles, Francisco; Franco, Julio; Darji, Ayub; Arafa, Abdel-Satar; Mundt, Egbert

2017-04-01

The evolution of highly pathogenic H5N1 avian influenza viruses (HPAI-H5N1) has resulted in the appearance of a number of diverse groups of HPAI-H5N1 based on the presence of genetically similar clusters of their haemagglutinin sequences (clades). An H5 antigen encoded by a recombinant baculovirus and expressed in insect cells was used for oil-emulsion-based vaccine prototypes. In several experiments, vaccination was performed at 10 days of age, followed by challenge infection on day 21 post vaccination (PV) with HPAI-H5N1 clades 2.2, 2.2.1, and 2.3.2. A further challenge infection with HPAI-H5N1 clade 2.2.1 was performed at day 42 PV. High haemagglutination inhibition titres were observed for the recH5 vaccine antigen, and lower haemagglutination inhibition titres for the challenge virus antigens. Nevertheless, the rate of protection from mortality and clinical signs was 100% when challenged at 21 days PV and 42 days PV, indicating protection over the entire broiler chicken rearing period without a second vaccination. The unvaccinated control chickens mostly died between two and five days after challenge infection. A low level of viral RNA was detected by reverse transcription followed by a quantitative polymerase chain reaction in a limited number of birds for a short period after challenge infection, indicating a limited spread of HPAI-H5N1 at flock level. Furthermore, it was observed that the vaccine can be used in a differentiation infected from vaccinated animals (DIVA) approach, based on the detection of nucleoprotein antibodies in vaccinated/challenged chickens. The vaccine fulfilled all expectations of an inactivated vaccine after one vaccination against challenge with different clades of H5N1-HPAI and is suitable for a DIVA approach.

MnMoO4 nanosheet array: an efficient electrocatalyst for hydrogen evolution reaction with enhanced activity over a wide pH range.

PubMed

Wen, Lulu; Sun, Yiqiang; Zhang, Tao; Bai, Yu; Li, Xinyang; Lyu, Xianjun; Cai, Weiping; Li, Yue

2018-08-17

We report the preparation of MnMoO 4 nanosheet array on nickel foam (MnMoO 4 NSA/NF) as an excellent 3D hydrogen evolution reaction (HER) electrocatalyst with good catalytic performance applied under basic, acidic and neutral conditions. In 0.5 M H 2 SO 4 , this MnMoO 4 NSA/NF electrode needs an overpotential of 89 mV to drive current densities of 10 mA cm -2 , to achieve the same current density, it demands overpotentials of 105 mV in 1.0 M KOH, 161 mV in 1.0 M PBS (pH = 7), respectively. After continuous CV scanning for 1000 cycles under different pH conditions, it also demonstrates an excellent stability with ignorable activity decrease. Such preeminent HER performance may be derived from the synergistic effect between manganese (Mn) and molybdenum (Mo) atoms, exposure of more active sites on the nanosheets and effective electron transport along the nanosheets. This MnMoO 4 NSA/NF electrocatalyst provides us a highly efficient material for water splitting devices for industrial hydrogen production.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effects of copper fining on the wine content in sulfur off-odors and on their evolution during accelerated anoxic storage.

PubMed

Vela, Eduardo; Hernández-Orte, Purificación; Franco-Luesma, Ernesto; Ferreira, Vicente

2017-09-15

Three different red wines with reductive character have been treated with two different doses of copper sulfate (0.06 and 0.5mg/L) and with a commercial copper-containing product at the recommended dose (0.6mg/L). Wines were in contact with copper one week, centrifuged and stored at 50°C in strict anoxia for 2weeks (up to 7 in one case). Brine-releasable (BR-) and free fractions of Volatile Sulfur Compounds were determined throughout the process. Relevant increases of BR-H 2 S suggest that those wines contained other H 2 S precursors non-detectable by the brine dilution method. Copper treatments had two major effects: 1) immediate decrease the levels of free H 2 S and methanethiol (MeSH); 2) slow the rate at which free H 2 S (not MeSH) increases during anoxic storage. After 7weeks of anoxia levels of free H 2 S and MeSH were high and similar regardless of the copper treatment. Higher copper doses could induce the accumulation of BR-H 2 S. Copyright © 2017 Elsevier Ltd. All rights reserved.

Introduction and enzootic of A/H5N1 in Egypt: Virus evolution, pathogenicity and vaccine efficacy ten years on.

PubMed

Abdelwhab, E M; Hassan, M K; Abdel-Moneim, A S; Naguib, M M; Mostafa, A; Hussein, I T M; Arafa, A; Erfan, A M; Kilany, W H; Agour, M G; El-Kanawati, Z; Hussein, H A; Selim, A A; Kholousy, S; El-Naggar, H; El-Zoghby, E F; Samy, A; Iqbal, M; Eid, A; Ibraheem, E M; Pleschka, S; Veits, J; Nasef, S A; Beer, M; Mettenleiter, T C; Grund, C; Ali, M M; Harder, T C; Hafez, H M

2016-06-01

It is almost a decade since the highly pathogenic H5N1 avian influenza virus (A/H5N1) of clade 2.2.1 was introduced to Egypt in 2005, most likely, via wild birds; marking the longest endemic status of influenza viruses in poultry outside Asia. The endemic A/H5N1 in Egypt still compromises the poultry industry, poses serious hazards to public health and threatens to become potentially pandemic. The control strategies adopted for A/H5N1 in Egyptian poultry using diverse vaccines in commercialized poultry neither eliminated the virus nor did they decrease its evolutionary rate. Several virus clades have evolved, a few of them disappeared and others prevailed. Disparate evolutionary traits in both birds and humans were manifested by accumulation of clade-specific mutations across viral genomes driven by a variety of selection pressures. Viruses in vaccinated poultry populations displayed higher mutation rates at the immunogenic epitopes, promoting viral escape and reducing vaccine efficiency. On the other hand, viruses isolated from humans displayed changes in the receptor binding domain, which increased the viral affinity to bind to human-type glycan receptors. Moreover, viral pathogenicity exhibited several patterns in different hosts. This review aims to provide an overview of the viral evolution, pathogenicity and vaccine efficacy of A/H5N1 in Egypt during the last ten years. Copyright © 2016 Elsevier B.V. All rights reserved.

Elevated atmospheric escape of atomic hydrogen from Mars induced by high-altitude water

NASA Astrophysics Data System (ADS)

Chaffin, M. S.; Deighan, J.; Schneider, N. M.; Stewart, A. I. F.

2017-01-01

Atmospheric loss has controlled the history of Martian habitability, removing most of the planet’s initial water through atomic hydrogen and oxygen escape from the upper atmosphere to space. In standard models, H and O escape in a stoichiometric 2:1 ratio because H reaches the upper atmosphere via long-lived molecular hydrogen, whose abundance is regulated by a photochemical feedback sensitive to atmospheric oxygen content. The relatively constant escape rates these models predict are inconsistent with known H escape variations of more than an order of magnitude on seasonal timescales, variation that requires escaping H to have a source other than H2. The best candidate source is high-altitude water, detected by the Mars Express spacecraft in seasonally variable concentrations. Here we use a one-dimensional time-dependent photochemical model to show that the introduction of high-altitude water can produce a large increase in the H escape rate on a timescale of weeks, quantitatively linking these observations. This H escape pathway produces prompt H loss that is not immediately balanced by O escape, influencing the oxidation state of the atmosphere for millions of years. Martian atmospheric water loss may be dominated by escape via this pathway, which may therefore potentially control the planet’s atmospheric chemistry. Our findings highlight the influence that seasonal atmospheric variability can have on planetary evolution.

The Second Most Distant Cluster of Galaxies in the Extended Medium Sensitivity Survey

NASA Technical Reports Server (NTRS)

Donahue, Megan; Voit, G. Mark; Scharf, Caleb A.; Gioia, Isabella M.; Mullis, Christopher R.; Hughes, John P.; Stocke, John T.

1999-01-01

We report on our ASCA, Keck, and ROSAT observations of MS 1137.5+6625, the second most distant cluster of galaxies in the Einstein Extended Medium Sensitivity Survey (EMSS), at redshift 0.78. We now have a full set of X-ray temperatures, optical velocity dispersions, and X-ray images for a complete, high-redshift sample of clusters of galaxies drawn from the EMSS. Our ASCA observations of MS 1137.5 +6625 yield a temperature of 5.7 (+2.1)(-1.1) keV and a metallicity of 0.43 (+40)(-3.7) solar, with 90% confidence limits. Keck II spectroscopy of 22 cluster members reveals a velocity dispersion of 884 (+185)(-124) km 24/s. This cluster is the most distant in the sample with a detected iron line. We also derive a mean abundance at z = 0.8 by simultaneously fitting X-ray data for the two z = 0.8 clusters, and obtain an abundance of Z(sub Fe) = 0.33 (+.26)(-.23). Our ROSAT observations show that MS 1137.5+6625 is regular and highly centrally concentrated. Fitting of a Beta model to the X-ray surface brightness yields a core radius of only 71/h kpc (q(sub o) = 0.1) with Beta = 0.70(+.45)(-.15) The gas mass interior to 0.5/h Mpc is thus 1.2 (+0.2)(-0.3) X 10(exp 13) h(exp - 5/2) Solar Mass (q(sub o) = 0.1). If the cluster's gas is nearly isothermal and in hydrostatic equilibrium with the cluster potential, the total mass of the cluster within this same region is 2.1(+1.5)(-0.8) X 10exp 14)/h Solar Mass, giving a gas fraction of 0.06 +/-0.04 h (exp -3/2). This cluster is the highest redshift EMSS cluster showing evidence for a possible cooling flow (about 20-400 Solar Mass/yr). The velocity dispersion, temperature, gas fraction, and iron abundance of MS 1137.5+6625 are all statistically the same as those properties in lower red- shift clusters of similar luminosity. With this cluster's temperature now in hand, we derive a high-redshift temperature function for EMSS clusters at 0.5 < z < 0.9 and compare it with temperature functions at lower redshifts, showing that the evolution of the temperature function is relatively modest. Supplementing our high-redshift sample with other data from the literature, we demonstrate that neither the cluster luminosity-temperature relation, nor cluster metallicities, nor the cluster gas evolved with redshift. The very modest degree of evolution in the luminosity-temperature relation inferred from these data is inconsistent with the absence of evolution in the X-ray luminosity functions derived from ROSAT cluster surveys if a critical density structure formation model is assumed.

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

Pan, Zhichen; Li, Di; Qian, Lei

We present 2.5-square-degree C{sub 2}H N = 1–0 and N{sub 2}H{sup +} J = 1–0 maps of the ρ Ophiuchi molecular cloud complex. These are the first large-scale maps of the ρ Ophiuchi molecular cloud complex with these two tracers. The C{sub 2}H emission is spatially more extended than the N{sub 2}H{sup +} emission. One faint N{sub 2}H{sup +} clump, Oph-M, and one C{sub 2}H ring, Oph-RingSW, are identified for the first time. The observed C{sub 2}H-to-N{sub 2}H{sup +} abundance ratio ([C{sub 2}H]/[N{sub 2}H{sup +}]) varies between 5 and 110. We modeled the C{sub 2}H and N{sub 2}H{sup +} abundancesmore » with 1D chemical models, which show a clear decline of [C{sub 2}H]/[N{sub 2}H{sup +}] with chemical age. Such an evolutionary trend is little affected by temperatures when they are below 40 K. At high density ( n {sub H} > 10{sup 5} cm{sup −3}), however, the time it takes for the abundance ratio to drop at least one order of magnitude becomes less than the dynamical time (e.g., turbulence crossing time of ∼10{sup 5} yr). The observed [C{sub 2}H]/[N{sub 2}H{sup +}] difference between L1688 and L1689 can be explained by L1688 having chemically younger gas in relatively less dense regions. The observed [C{sub 2}H]/[N{sub 2}H{sup +}] values are the results of time evolution, accelerated at higher densities. For the relatively low density regions in L1688 where only C{sub 2}H emission was detected, the gas should be chemically younger.« less

Hydrogen isotope fractionation between C-H-O species in magmatic fluids

NASA Astrophysics Data System (ADS)

Foustoukos, D. I.; Mysen, B. O.

2012-12-01

Constraining the hydrogen isotope fractionation between H-bearing volatiles (e.g. H2, CH4, hydrocarbons, H2O) as function of temperature and pressure helps to promote our understanding of the isotopic composition of evolved magmatic fluids and the overall mantle-cycling of water and reduced C-O-H volatiles. To describe the thermodynamics of the exchange reactions between the different H/D isotopologues of H2 and CH4 under supercritical water conditions, a novel experimental technique has been developed by combining vibrational Raman spectroscopy with hydrothermal diamond anvil cell designs (HDAC), which offers a method to monitor the in-situ evolution of H/D containing species. To this end, the equilibrium relationship between H2-D2-HD in supercritical fluid was investigated at temperatures ranging from 300 - 800 oC and pressures ~ 0.3 - 1.3 GPa [1]. Experimental results obtained in-situ and ex-situ show a significant deviation from the theoretical values of the equilibrium constant predicted for ideal-gas reference state, and with an apparent negative temperature effect triggered by the enthalpy contributions due to mixing in supercritical water. Here, we present a series of HDAC experiments conducted to evaluate the role of supercritical water on the isotopic equilibrium between H/D methane isotopologues at 600 - 800 oC and 409 - 1622 MPa. In detail, tetrakis-silane (Si5C12H36) was reacted with H2O-D2O aqueous solution in the presence of either Ni or Pt metal catalyst, resulting to the formation of deuterated methane species such as CH3D, CHD3, CH2D2 and CD4. Two distinctly different set of experiments ("gas phase"; "liquid phase") were performed by adjusting the silane/water proportions. By measuring the relative intensities of Raman vibrational modes of species, experimental results demonstrate distinctly different thermodynamic properties for the CH4-CH3D-CHD3-CH2D2 equilibrium in gas and liquid-water-bearing systems. In addition, the D/H molar ratio of methane in the liquid is twice that recorded in the gas phase. Accordingly, condensed-phase isotope effects are inferred to govern the evolution of H/D isotopologues, induced by differences in the solubility of the isotopic molecules driven by excess energy/entropy developed during the mixing of non-polar species in the supercritical water structure. On the contrary, at such high temperatures/-pressures statistical thermodynamic models, based on the vibrational zero point energy distributions and high-temperature anharmonicity for isotopic molecules in ideal-gas reference state, predict minimal isotope exchange. Data, therefore, demonstrate that the solvation mechanism of H-D-bearing species in magmatic fluids can impose substantial D/H fractionation effects governing the δD composition of coexisting species even at lower-crust/upper-mantle temperature conditions. 1. Foustoukos D.I. and B.O. Mysen, (2012) D/H isotopic fractionation in the H2-H2O system at supercritical water conditions: Composition and hydrogen bonding effects, Geochim. Cosmochim. Acta, 86, 88-102.

The new galaxy evolution paradigm revealed by the Herschel surveys

NASA Astrophysics Data System (ADS)

Eales, Stephen; Smith, Dan; Bourne, Nathan; Loveday, Jon; Rowlands, Kate; van der Werf, Paul; Driver, Simon; Dunne, Loretta; Dye, Simon; Furlanetto, Cristina; Ivison, R. J.; Maddox, Steve; Robotham, Aaron; Smith, Matthew W. L.; Taylor, Edward N.; Valiante, Elisabetta; Wright, Angus; Cigan, Philip; De Zotti, Gianfranco; Jarvis, Matt J.; Marchetti, Lucia; Michałowski, Michał J.; Phillipps, Steven; Viaene, Sebastien; Vlahakis, Catherine

2018-01-01

The Herschel Space Observatory has revealed a very different galaxyscape from that shown by optical surveys which presents a challenge for galaxy-evolution models. The Herschel surveys reveal (1) that there was rapid galaxy evolution in the very recent past and (2) that galaxies lie on a single Galaxy Sequence (GS) rather than a star-forming 'main sequence' and a separate region of 'passive' or 'red-and-dead' galaxies. The form of the GS is now clearer because far-infrared surveys such as the Herschel ATLAS pick up a population of optically red star-forming galaxies that would have been classified as passive using most optical criteria. The space-density of this population is at least as high as the traditional star-forming population. By stacking spectra of H-ATLAS galaxies over the redshift range 0.001 < z < 0.4, we show that the galaxies responsible for the rapid low-redshift evolution have high stellar masses, high star-formation rates but, even several billion years in the past, old stellar populations - they are thus likely to be relatively recent ancestors of early-type galaxies in the Universe today. The form of the GS is inconsistent with rapid quenching models and neither the analytic bathtub model nor the hydrodynamical EAGLE simulation can reproduce the rapid cosmic evolution. We propose a new gentler model of galaxy evolution that can explain the new Herschel results and other key properties of the galaxy population.

High phase-purity 1T'-MoS2- and 1T'-MoSe2-layered crystals

NASA Astrophysics Data System (ADS)

Yu, Yifu; Nam, Gwang-Hyeon; He, Qiyuan; Wu, Xue-Jun; Zhang, Kang; Yang, Zhenzhong; Chen, Junze; Ma, Qinglang; Zhao, Meiting; Liu, Zhengqing; Ran, Fei-Rong; Wang, Xingzhi; Li, Hai; Huang, Xiao; Li, Bing; Xiong, Qihua; Zhang, Qing; Liu, Zheng; Gu, Lin; Du, Yonghua; Huang, Wei; Zhang, Hua

2018-06-01

Phase control plays an important role in the precise synthesis of inorganic materials, as the phase structure has a profound influence on properties such as conductivity and chemical stability. Phase-controlled preparation has been challenging for the metallic-phase group-VI transition metal dichalcogenides (the transition metals are Mo and W, and the chalcogens are S, Se and Te), which show better performance in electrocatalysis than their semiconducting counterparts. Here, we report the large-scale preparation of micrometre-sized metallic-phase 1T'-MoX2 (X = S, Se)-layered bulk crystals in high purity. We reveal that 1T'-MoS2 crystals feature a distorted octahedral coordination structure and are convertible to 2H-MoS2 following thermal annealing or laser irradiation. Electrochemical measurements show that the basal plane of 1T'-MoS2 is much more active than that of 2H-MoS2 for the electrocatalytic hydrogen evolution reaction in an acidic medium.

Genetic characterization of low-pathogenic avian influenza viruses isolated on the Izumi plain in Japan: possible association of dynamic movements of wild birds with AIV evolution.

PubMed

Nakagawa, Hiroko; Okuya, Kosuke; Kawabata, Toshiko; Matsuu, Aya; Takase, Kozo; Kuwahara, Masakazu; Toda, Shigehisa; Ozawa, Makoto

2018-04-01

The Izumi plain in Kagoshima Prefecture, Japan, is an overwintering site of endangered cranes (hooded cranes and white-naped cranes) and of many other migratory birds (including wild ducks) that are considered carriers of avian influenza viruses (AIVs). To assess the risks of a highly pathogenic avian influenza outbreak in the crane populations, we tested various environmental samples for AIVs in this area. In the 2014-2015 winter season, we isolated one AIV of the H6N2 subtype from the cranes' roost water and two AIVs of the H11N9 subtype from a crane fecal sample and a cloacal swab of a dead spot-billed duck. Genetic analysis of these AIV isolates indicated that our H6N2 isolate is genetically close to AIVs isolated from wild birds in Southeast Asian countries, except that the PB1 and NS genes belong to the North American virus lineage. All genes of the two H11N9 isolates are related to AIVs belonging to the Eurasian virus lineage. Notably, in our phylogenetic trees, H11 HA and N9 NA genes showing high sequence similarity to the corresponding genes of isolates from wild birds in South Africa and Spain, respectively, did not cluster in the major groups with recent wild-bird isolates from East Asia. These results suggest that AIVs with viral gene segments derived from various locations and bird species have been brought to the Izumi plain. These findings imply a possible association of dynamic movements of wild birds with AIV evolution.

N-glycan profiles in H9N2 avian influenza viruses from chicken eggs and human embryonic lung fibroblast cells.

PubMed

Chen, Wentian; Zhong, Yaogang; Su, Rui; Qi, Huicai; Deng, Weina; Sun, Yu; Ma, Tianran; Wang, Xilong; Yu, Hanjie; Wang, Xiurong; Li, Zheng

2017-11-01

N-glycosylation can affect the host specificity, virulence and infectivity of influenza A viruses (IAVs). In this study, the distribution and evolution of N-glycosylation sites in the hemagglutinin (HA) and neuraminidase (NA) of H9N2 virus were explored using phylogenetic analysis. Then, one strain of the H9N2 subtypes was proliferated in the embryonated chicken eggs (ECE) and human embryonic lung fibroblast cells (MRC-5) system. The proliferated viral N-glycan profiles were analyzed by a glycomic method that combined the lectin microarray and MALDI-TOF/TOF-MS. As a result, HA and NA of H9N2 viruses prossess six and five highly conserved N-glycosylation sites, respectively. Sixteen lectins (e.g., MAL-II, SNA and UEA-I) had increased expression levels of the glycan structures in the MRC-5 compared with the ECE system; however, 6 lectins (e.g., PHA-E, PSA and DSA) had contrasting results. Eleven glycans from the ECE system and 13 glycans from the MRC-5 system were identified. Our results showed that the Fucα-1,6GlcNAc(core fucose) structure was increased, and pentaantennary N-glycans were only observed in the ECE system. The SAα2-3/6Gal structures were highly expressed and Fucα1-2Galβ1-4GlcNAc structures were only observed in the MRC-5 system. We conclude that the existing SAα2-3/6Gal sialoglycans make the offspring of the H9N2 virus prefer entially attach to each other, which decreases the virulence. Alterations in the glycosylation sites for the evolution and role of IAVs have been widely described; however, little is known about the exact glycan structures for the same influenza strain from different hosts. Our findings may provide a novel way for further discussing the molecular mechanism of the viral transmission and virulence associated with viral glycosylation in avian and human hosts as well as vital information for designing a vaccine against influenza and other human viruses. Copyright © 2017. Published by Elsevier B.V.

Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: An efficient electrocatalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei

2018-02-01

The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.

Copper Nanowires: A Substitute for Noble Metals to Enhance Photocatalytic H2 Generation.

PubMed

Xiao, Shuning; Liu, Peijue; Zhu, Wei; Li, Guisheng; Zhang, Dieqing; Li, Hexing

2015-08-12

Microwave-assisted hydrothermal approach was developed as a general strategy to decorate copper nanowires (CuNWs) with nanorods (NRs) or nanoparticles (NPs) of metal oxides, metal sulfides, and metal organic frameworks (MOFs). The microwave irradiation induced local "super hot" dots generated on the CuNWs surface, which initiated the adsorption and chemical reactions of the metal ions, accompanied by the growth and assembly of NPs building blocks along the metal nanowires' surfaces. This solution-processed approach enables the NRs (NPs) @CuNWs hybrid structure to exhibit three unique characteristics: (1) high coverage density of NRs (NPs) per NWs with the morphology of NRs (NPs) directly growing from the CuNWs core, (2) intimate contact between CuNWs and NRs (NPs), and (3) flexible choices of material composition. Such hybrid structures also increased light absorption by light scattering. In general, the TiO2/CuNWs showed excellent photocatalytic activity for H2 generation. The corresponding hydrogen production rate is 5104 μmol h(-1) g(-1) with an apparent quantum yield (AQY) of 17.2%, a remarkably high AQY among the noble-metal free TiO2 photocatalysts. Such performance may be associated with the favorable geometry of the hybrid system, which is characterized by a large contact area between the photoactive materials (TiO2) and the H2 evolution cocatalyst (Cu), the fast and short diffusion paths of photogenerated electrons transferring from the TiO2 to the CuNWs. This study not only shows a possibility for the utilization of low cost copper nanowires as a substitute for noble metals in enhanced solar photocatalytic H2 generation but also exhibits a general strategy for fabricating other highly active H2 production photocatalysts by a facile microwave-assisted solution approach.

Molybdenum-independent nitrogenases of Azotobacter vinelandii: a functional species of alternative nitrogenase-3 isolated from a molybdenum-tolerant strain contains an iron-molybdenum cofactor.

PubMed Central

Pau, R N; Eldridge, M E; Lowe, D J; Mitchenall, L A; Eady, R R

1993-01-01

Nitrogenase-3 of Azotobacter vinelandii is synthesized under conditions of molybdenum and vanadium deficiency. The minimal metal requirement for its synthesis, and its metal content, indicated that the only transition metal in nitrogenase-3 was iron [Chisnell, Premakumar and Bishop (1988) J. Bacteriol. 170, 27-33; Pau, Mitchenall and Robson (1989) J. Bacteriol. 171, 124-129]. A new species of nitrogenase-3 has been purified from a strain of A. vinelandii (RP306) lacking structural genes for the Mo- and V-nitrogenases and containing a mutation which enables nitrogenase-3 to be synthesized in the presence of molybdenum. SDS/PAGE showed that component 1 contained a 15 kDa polypeptide which N-terminal amino acid sequence determination showed to be encoded by anfG. This confirms that nitrogenase-3, like V-nitrogenase, comprises three subunits. Preparations of the nitrogenase-3 from strain RP306 contained 24 Fe atoms and 1 Mo atom per molecule. Characterization of the cofactor centre of the enzyme by e.p.r. spectroscopy and an enzymic cofactor assay, together with stimulation of the growth of strain RP306 by Mo, showed that nitrogenase-3 can incorporate the Mo-nitrogenase cofactor (FeMoco) to form a functional enzyme. The specific activities (nmol of product produced/min per mg of protein) determined from activity titration curves were: under N2, NH3 formation 110, with concomitant H2 evolution of 220; under argon, H2 evolution 350; under 10% acetylene (C2H2) in argon, ethylene (C2H4) 58, ethane (C2H6) 26, and concomitant H2 evolution 226. The rate of formation of C2H6 was non-linear, and the C2H6/C2H4 ratio strongly dependent on the ratio of nitrogenase components. PMID:8392330

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Genomic anatomy of Escherichia coli O157:H7 outbreaks

PubMed Central

Eppinger, Mark; Mammel, Mark K.; Leclerc, Joseph E.; Ravel, Jacques; Cebula, Thomas A.

2011-01-01

The rapid emergence of Escherichia coli O157:H7 from an unknown strain in 1982 to the dominant hemorrhagic E. coli serotype in the United States and the cause of widespread outbreaks of human food-borne illness highlights a need to evaluate critically the extent to which genomic plasticity of this important enteric pathogen contributes to its pathogenic potential and its evolution as well as its adaptation in different ecological niches. Aimed at a better understanding of the evolution of the E. coli O157:H7 pathogenome, the present study presents the high-quality sequencing and comparative phylogenomic analysis of a comprehensive panel of 25 E. coli O157:H7 strains associated with three nearly simultaneous food-borne outbreaks of human disease in the United States. Here we present a population genetic analysis of more than 200 related strains recovered from patients, contaminated produce, and zoonotic sources. High-resolution phylogenomic approaches allow the dynamics of pathogenome evolution to be followed at a high level of phylogenetic accuracy and resolution. SNP discovery and study of genome architecture and prophage content identified numerous biomarkers to assess the extent of genetic diversity within a set of clinical and environmental strains. A total of 1,225 SNPs were identified in the present study and are now available for typing of the E. coli O157:H7 lineage. These data should prove useful for the development of a refined phylogenomic framework for forensic, diagnostic, and epidemiological studies to define better risk in response to novel and emerging E. coli O157:H7 resistance and virulence phenotypes. PMID:22135463

Ultraviolet Irradiation of Naphthalene in H2O Ice: Implications for Meteorites and Biogenesis

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Dworkin, Jason; Sandford, Scott A.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

Sunlight-promoted photocatalytic hydrogen gas evolution from water-suspended cellulose: a systematic study.

PubMed

Speltini, Andrea; Sturini, Michela; Dondi, Daniele; Annovazzi, Enrico; Maraschi, Federica; Caratto, Valentina; Profumo, Antonella; Buttafava, Armando

2014-10-01

This work presents a systematic study of cellulose (CLS) as a sacrificial biomass for photocatalytic H2 evolution from water. The idea is indeed to couple a largely available and not expensive biomass, and water, with a renewable energy like solar radiation. An aqueous CLS suspension irradiated either at 366 nm (UV-A) or under sunlight in the presence of Pt/TiO2 behaves as a H2 evolving system. The effects of irradiation time, catalyst and CLS concentrations, pH and water salinity are studied. Addition of CLS to the sample significantly improved H2 evolution from water splitting, with yields up to ten fold higher than those observed in neat water. The mechanism of the photocatalytic process relies on the TiO2-mediated CLS hydrolysis, under irradiation. The polysaccharide depolymerisation generates water-soluble species and intermediates, among them 5-hydroxymethylfurfural (HMF) was identified. These intermediates are readily oxidized following the glucose photoreforming, thus enhancing water hydrogen ion reduction to give gas-phase H2. The formation of "colored" by-products from HMF self-polymerization involves a sort of "in situ dye sensitization" that allows an effective photoreaction even under solar light. The procedure is evaluated and successfully extended on cellulosic biomasses, i.e. rice husk and alfalfa (Medicago sativa) stems, not previously investigated for this application.

First-Principles Study of the Jahn-Teller Distortion in the Ti1-XVXH2 and Zr1-XNbxH2 Alloys

NASA Astrophysics Data System (ADS)

Quijano, Ramiro; de Coss, Romeo; Singh, David

2008-03-01

The transition metal dihydrides TiH2 and ZrH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Electronic band structure calculations have shown that TiH2 and ZrH2 in the cubic phase display a very flat band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. In order to understand the role of band filling in controlling the structural instability of the transition metal dihydrides, we have performed a first-principles total energy study of the Ti1-XVxH2 and Zr1-xNbxH2 alloys. The calculations were performed using FP-LAPW method within the (DFT) and we use the GGA for exchange correlation functional energy. The critical concentration for which the Jahn-Teller effect is suppressed, was determined from the evolution of the tetragonal-cubic energy barrier. We discuss the electronic mechanism of the structural-instability, in terms of the band filling. From the obtained results we conclude that the tetragonal distortion in TiH2 and ZrH2 is not produced only by a Jahn-Teller Effect. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 43830-F.

Enzootic genotype S of H9N2 avian influenza viruses donates internal genes to emerging zoonotic influenza viruses in China.

PubMed

Gu, Min; Chen, Hongzhi; Li, Qunhui; Huang, Junqing; Zhao, Mingjun; Gu, Xiaobing; Jiang, Kaijun; Wang, Xiaoquan; Peng, Daxin; Liu, Xiufan

2014-12-05

Avian influenza viruses of subtype H9N2 are widely prevalent in poultry in many Asian countries, and the segmented nature of the viral genome results in multiple distinct genotypes via reassortment. In this study, genetic evolution of H9N2 viruses circulating in eastern China during 2007-2013 was analyzed. The results showed that the diversity of the gene constellations generated six distinct genotypes, in which a novel genotype (S) bearing the backbone of A/chicken/Shanghai/F/98-like viruses by acquiring A/quail/Hong Kong/G1/97-like polymerase basic subunit 2 and matrix genes has gradually established its ecological niche and been consistently prevalent in chicken flocks in eastern China since its first detection in 2007. Furthermore, genotype S possessed the peculiarity to donate most of its gene segments to other emerging influenza A viruses in China, including the novel reassortant highly pathogenic avian influenza H5N2, the 2013 novel H7N7, H7N9 and the latest reassortant H10N8 viruses, with potential threat to poultry industry and human health. Copyright © 2014 Elsevier B.V. All rights reserved.

GOLDRUSH. II. Clustering of galaxies at z ˜ 4-6 revealed with the half-million dropouts over the 100 deg2 area corresponding to 1 Gpc3

NASA Astrophysics Data System (ADS)

Harikane, Yuichi; Ouchi, Masami; Ono, Yoshiaki; Saito, Shun; Behroozi, Peter; More, Surhud; Shimasaku, Kazuhiro; Toshikawa, Jun; Lin, Yen-Ting; Akiyama, Masayuki; Coupon, Jean; Komiyama, Yutaka; Konno, Akira; Lin, Sheng-Chieh; Miyazaki, Satoshi; Nishizawa, Atsushi J.; Shibuya, Takatoshi; Silverman, John

2018-01-01

We present clustering properties from 579492 Lyman-break galaxies (LBGs) at z ˜ 4-6 over the 100 deg2 sky (corresponding to a 1.4 Gpc3 volume) identified in early data of the Hyper Suprime-Cam (HSC) Subaru Strategic Program survey. We derive angular correlation functions (ACFs) for the HSC LBGs with unprecedentedly high statistical accuracies at z ˜ 4-6, and compare them with the halo occupation distribution (HOD) models. We clearly identify significant ACF excesses in 10″ < θ < 90″, the transition scale between one- and two-halo terms, suggestive of the existence of the non-linear halo bias effect. Combining the HOD models and previous clustering measurements of faint LBGs at z ˜ 4-7, we investigate the dark matter halo mass (Mh) of the z ˜ 4-7 LBGs and its correlation with various physical properties including the star formation rate (SFR), the stellar-to-halo mass ratio (SHMR), and the dark matter accretion rate (\\dot{M}_{ h}) over a wide mass range of Mh/M⊙ = 4 × 1010-4 × 1012. We find that the SHMR increases from z ˜ 4 to 7 by a factor of ˜4 at Mh ≃ 1 × 1011 M⊙ , while the SHMR shows no strong evolution in the similar redshift range at Mh ≃ 1 × 1012 M⊙ . Interestingly, we identify a tight relation of SFR/\\dot{M}_{ h}-Mh showing no significant evolution beyond 0.15 dex in this wide mass range over z ˜ 4-7. This weak evolution suggests that the SFR/\\dot{M}_{ h}-Mh relation is a fundamental relation in high-redshift galaxy formation whose star formation activities are regulated by the dark matter mass assembly. Assuming this fundamental relation, we calculate the cosmic star formation rate densities (SFRDs) over z = 0-10 (a.k.a. the Madau-Lilly plot). The cosmic SFRD evolution based on the fundamental relation agrees with the one obtained by observations, suggesting that the cosmic SFRD increase from z ˜ 10 to 4 - 2 (decrease from z ˜ 4-2 to 0) is mainly driven by the increase of the halo abundance (the decrease of the accretion rate).

Acid-adapted strains of Escherichia coli K-12 obtained by experimental evolution.

PubMed

Harden, Mark M; He, Amanda; Creamer, Kaitlin; Clark, Michelle W; Hamdallah, Issam; Martinez, Keith A; Kresslein, Robert L; Bush, Sean P; Slonczewski, Joan L

2015-03-01

Enteric bacteria encounter a wide range of pHs throughout the human intestinal tract. We conducted experimental evolution of Escherichia coli K-12 to isolate clones with increased fitness during growth under acidic conditions (pH 4.5 to 4.8). Twenty-four independent populations of E. coli K-12 W3110 were evolved in LBK medium (10 g/liter tryptone, 5 g/liter yeast extract, 7.45 g/liter KCl) buffered with homopiperazine-N,N'-bis-2-(ethanosulfonic acid) and malate at pH 4.8. At generation 730, the pH was decreased to 4.6 with HCl. By 2,000 generations, all populations had achieved higher endpoint growth than the ancestor at pH 4.6 but not at pH 7.0. All evolving populations showed a progressive loss of activity of lysine decarboxylase (CadA), a major acid stress enzyme. This finding suggests a surprising association between acid adaptation and moderation of an acid stress response. At generation 2,000, eight clones were isolated from four populations, and their genomes were sequenced. Each clone showed between three and eight missense mutations, including one in a subunit of the RNA polymerase holoenzyme (rpoB, rpoC, or rpoD). Missense mutations were found in adiY, the activator of the acid-inducible arginine decarboxylase (adiA), and in gcvP (glycine decarboxylase), a possible acid stress component. For tests of fitness relative to that of the ancestor, lacZ::kan was transduced into each strain. All acid-evolved clones showed a high fitness advantage at pH 4.6. With the cytoplasmic pH depressed by benzoate (at external pH 6.5), acid-evolved clones showed decreased fitness; thus, there was no adaptation to cytoplasmic pH depression. At pH 9.0, acid-evolved clones showed no fitness advantage. Thus, our acid-evolved clones showed a fitness increase specific to low external pH. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Acid-Adapted Strains of Escherichia coli K-12 Obtained by Experimental Evolution

PubMed Central

Harden, Mark M.; He, Amanda; Creamer, Kaitlin; Clark, Michelle W.; Hamdallah, Issam; Martinez, Keith A.; Kresslein, Robert L.; Bush, Sean P.

2015-01-01

Enteric bacteria encounter a wide range of pHs throughout the human intestinal tract. We conducted experimental evolution of Escherichia coli K-12 to isolate clones with increased fitness during growth under acidic conditions (pH 4.5 to 4.8). Twenty-four independent populations of E. coli K-12 W3110 were evolved in LBK medium (10 g/liter tryptone, 5 g/liter yeast extract, 7.45 g/liter KCl) buffered with homopiperazine-N,N′-bis-2-(ethanosulfonic acid) and malate at pH 4.8. At generation 730, the pH was decreased to 4.6 with HCl. By 2,000 generations, all populations had achieved higher endpoint growth than the ancestor at pH 4.6 but not at pH 7.0. All evolving populations showed a progressive loss of activity of lysine decarboxylase (CadA), a major acid stress enzyme. This finding suggests a surprising association between acid adaptation and moderation of an acid stress response. At generation 2,000, eight clones were isolated from four populations, and their genomes were sequenced. Each clone showed between three and eight missense mutations, including one in a subunit of the RNA polymerase holoenzyme (rpoB, rpoC, or rpoD). Missense mutations were found in adiY, the activator of the acid-inducible arginine decarboxylase (adiA), and in gcvP (glycine decarboxylase), a possible acid stress component. For tests of fitness relative to that of the ancestor, lacZ::kan was transduced into each strain. All acid-evolved clones showed a high fitness advantage at pH 4.6. With the cytoplasmic pH depressed by benzoate (at external pH 6.5), acid-evolved clones showed decreased fitness; thus, there was no adaptation to cytoplasmic pH depression. At pH 9.0, acid-evolved clones showed no fitness advantage. Thus, our acid-evolved clones showed a fitness increase specific to low external pH. PMID:25556191

Clade 2.3.4.4 avian influenza A (H5N8) outbreak in commercial poultry, Iran, 2016: the first report and update data.

PubMed

Ghafouri, Seyed Ali; GhalyanchiLangeroudi, Arash; Maghsoudloo, Hossein; Kh Farahani, Reza; Abdollahi, Hamed; Tehrani, Farshad; Fallah, Mohammad Hossein

2017-06-01

In 2010, H5N8 highly pathogenic avian influenza (HPAI) viruses of the A/Goose/Guangdong/1/1996 lineage dramatically affected poultry and wild birds in Asia, Europe, and North America. In November 2016, HPAI H5N8 was detected in a commercial layer farm in Tehran province. The diagnosis was based on real-time reverse transcriptase PCR (RRT-PCR) and sequencing of haemaglutinin (HA) and neuraminidase (NA) genes from suspected samples. Genetic and phylogenetic analysis of the HA gene demonstrated that the Iranian HPAI H5N8 viruses belong to the HPAI H5 virus clade 2.3.4.4 and cluster within group B (Gochang-like). In particular, the highest similarity was found with the sequences of the HPAI H5N8 identified in Russia in 2016. To our knowledge, this clade has not been previously detected in Iran. Previous HPAI A (H5) epidemic in Iran occurred in 2015 and involved exclusively viruses of clade 2.3.2.1c. These findings indicate that Iran is at high risk of introduction of HPAI H5 of the A/Goose/Guangdong/1/1996 lineage from East Asia and highlight the need to maintain adequate monitoring activities in target wild and domestic bird species for HPAI early detection. This study is useful for better understanding the genetic and antigenic evolution of H5 HPAI viruses in the region and the world.

Highly efficient photocatalytic H2 evolution using TiO2 nanoparticles integrated with electrocatalytic metal phosphides as cocatalysts

NASA Astrophysics Data System (ADS)

Song, Rui; Zhou, Wu; Luo, Bing; Jing, Dengwei

2017-09-01

In this work, electrocatalysts like the metal phosphides Ni2P, NiCoP, and FeP, can serve as cocatalysts of TiO2 to form efficient composite photocatalysts for hydrogen generation from an aqueous methanol solution. On comparing Ni2P, NiCoP, and FeP and optimizing their proportions, the NiCoP(1 wt%)/TiO2 composite was found to exhibit the highest activity toward photocatalytic H2 production (1.54 μmol h-1 mg-1), which is about thirteen times that of the naked TiO2 nanoparticles. Mott-Schottky (MS) analysis indicated that the large upward shift or band bending of the Fermi energy level (EF) in metal phosphides was responsible for the enhanced activity of the composites. The steady-state photoluminescence (PL) spectra and photocurrent transient response further confirmed that the enhanced photoinduced charge transfer and band separation after TiO2 was integrated with the metal phosphides. Thus, these electrocatalysts were shown to be efficient cocatalysts that can replace noble metals as low-cost photocatalytic H2 production.

Interaction between ATP, metal ions, glycine, and several minerals

NASA Technical Reports Server (NTRS)

Rishpon, J.; Ohara, P. J.; Lawless, J. G.; Lahav, N.

1982-01-01

Interactions between ATP, glycine and montmorillonite and kaolinite clay minerals in the presence of various metal cations are investigated. The adsorption of adenine nucleotides on clays and Al(OH)3 was measured as a function of pH, and glycine condensation was followed in the presence of ATP, ZnCl2, MgCl2 and either kaolinite or montmorillonite. The amounts of ATP and ADP adsorbed are found to decrease with increasing Ph, and to be considerably enhanced in experiments with Mg(2+)- and Zn(2+)-montmorillonite with respect to Na(+)-montmorillonite. The effects of divalent cations are less marked in kaolinite. Results for Al(OH)3 show the importance of adsorption at clay platelet edges at high pH. The decomposition of ATP during drying at high temperature is observed to be inhibited by small amounts of clay, vacuum, or Mg(2+) or Zn(2+) ions, and to be accompanied by peptide formation in the presence of glycine. Results suggest the importance of Zn(2+) and Mg(2+) in chemical evolution.

Microstructural evolution during thermal annealing of ice-Ih

NASA Astrophysics Data System (ADS)

Hidas, Károly; Tommasi, Andréa; Mainprice, David; Chauve, Thomas; Barou, Fabrice; Montagnat, Maurine

2017-06-01

We studied the evolution of the microstructure of ice-Ih during static recrystallization by stepwise annealing experiments. We alternated thermal annealing and electron backscatter diffraction (EBSD) analyses on polycrystalline columnar ice pre-deformed in uniaxial compression at temperature of -7 °C to macroscopic strains of 3.0-5.2. Annealing experiments were carried out at -5 °C and -2 °C up to a maximum of 3.25 days, typically in 5-6 steps. EBSD crystal orientation maps obtained after each annealing step permit the description of microstructural changes. Decrease in average intragranular misorientation at the sample scale and modification of the misorientation across subgrain boundaries provide evidence for recovery from the earliest stages of annealing. This initial evolution is similar for all studied samples irrespective of their initial strain or annealing temperature. After an incubation period ≥1.5 h, recovery is accompanied by recrystallization (nucleation and grain boundary migration). Grain growth proceeds at the expense of domains with high intragranular misorientations, consuming first the most misorientated parts of primary grains. Grain growth kinetics fits the parabolic growth law with grain growth exponents in the range of 2.4-4.0. Deformation-induced tilt boundaries and kink bands may slow down grain boundary migration. They are stable features during early stages of static recrystallization, only erased by normal growth, which starts after >24 h of annealing.

Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

NASA Astrophysics Data System (ADS)

Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

2009-04-01

Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

Loss of genes implicated in gastric function during platypus evolution.

PubMed

Ordoñez, Gonzalo R; Hillier, Ladeana W; Warren, Wesley C; Grützner, Frank; López-Otín, Carlos; Puente, Xose S

2008-01-01

The duck-billed platypus (Ornithorhynchus anatinus) belongs to the mammalian subclass Prototheria, which diverged from the Theria line early in mammalian evolution. The platypus genome sequence provides a unique opportunity to illuminate some aspects of the biology and evolution of these animals. We show that several genes implicated in food digestion in the stomach have been deleted or inactivated in platypus. Comparison with other vertebrate genomes revealed that the main genes implicated in the formation and activity of gastric juice have been lost in platypus. These include the aspartyl proteases pepsinogen A and pepsinogens B/C, the hydrochloric acid secretion stimulatory hormone gastrin, and the alpha subunit of the gastric H+/K+-ATPase. Other genes implicated in gastric functions, such as the beta subunit of the H+/K+-ATPase and the aspartyl protease cathepsin E, have been inactivated because of the acquisition of loss-of-function mutations. All of these genes are highly conserved in vertebrates, reflecting a unique pattern of evolution in the platypus genome not previously seen in other mammalian genomes. The observed loss of genes involved in gastric functions might be responsible for the anatomical and physiological differences in gastrointestinal tract between monotremes and other vertebrates, including small size, lack of glands, and high pH of the monotreme stomach. This study contributes to a better understanding of the mechanisms that underlie the evolution of the platypus genome, might extend the less-is-more evolutionary model to monotremes, and provides novel insights into the importance of gene loss events during mammalian evolution.

Loss of genes implicated in gastric function during platypus evolution

PubMed Central

Ordoñez, Gonzalo R; Hillier, LaDeana W; Warren, Wesley C; Grützner, Frank; López-Otín, Carlos; Puente, Xose S

2008-01-01

Background The duck-billed platypus (Ornithorhynchus anatinus) belongs to the mammalian subclass Prototheria, which diverged from the Theria line early in mammalian evolution. The platypus genome sequence provides a unique opportunity to illuminate some aspects of the biology and evolution of these animals. Results We show that several genes implicated in food digestion in the stomach have been deleted or inactivated in platypus. Comparison with other vertebrate genomes revealed that the main genes implicated in the formation and activity of gastric juice have been lost in platypus. These include the aspartyl proteases pepsinogen A and pepsinogens B/C, the hydrochloric acid secretion stimulatory hormone gastrin, and the α subunit of the gastric H+/K+-ATPase. Other genes implicated in gastric functions, such as the β subunit of the H+/K+-ATPase and the aspartyl protease cathepsin E, have been inactivated because of the acquisition of loss-of-function mutations. All of these genes are highly conserved in vertebrates, reflecting a unique pattern of evolution in the platypus genome not previously seen in other mammalian genomes. Conclusion The observed loss of genes involved in gastric functions might be responsible for the anatomical and physiological differences in gastrointestinal tract between monotremes and other vertebrates, including small size, lack of glands, and high pH of the monotreme stomach. This study contributes to a better understanding of the mechanisms that underlie the evolution of the platypus genome, might extend the less-is-more evolutionary model to monotremes, and provides novel insights into the importance of gene loss events during mammalian evolution. PMID:18482448

Determining pre-eruptive compositions of late Paleozoic magma from kaolinized volcanic ashes: Analysis of glass inclusions in quartz microphenocrysts from tonsteins

NASA Astrophysics Data System (ADS)

Webster, James D.; Congdon, Roger D.; Lyons, Paul C.

1995-02-01

Glass inclusions in quartz microphenocrysts were analyzed for major and minor elements by electron microprobe and H, Li, Be, B, Rb, Sr, Y, Nb, Mo, Sn, Cs, Ce, Th, and U by ion microprobe. The phenocrysts and inclusions occur as fresh relicts in about eleven strongly kaolinized, air-fall volcanic ash units (tonsteins) that outcrop in five states located in the central Appalachian basin; the ashes were erupted during the Pennsylvanian. Even though the whole-rock tonstein samples are extremely altered, the glass trapped in quartz microphenocrysts preserves pre-eruptive melt compositions, and, consequently, the inclusions are useful for determining compositions of source magmas and identifying geochemical trends indicative of magmatic evolution. Interpretation of inclusion compositions indicates the strongly altered tonsteins were derived from potassium-enriched, metaluminous to mildly peraluminous magma(s). The tonsteins can be divided into two groups on the basis of trapped melt compositions: older tonsteins that have inclusions with high Sr and normative quartz contents and comparatively low concentrations of U, Th, Rb, Y, Cs, Nb, F, and Cl (±Be) and younger tonsteins whose inclusions contain low Sr and normative quartz and high concentrations of U, Th, Rb, Y, Cs, Nb, F, and Cl (±Be). In general, as concentrations of Sr decreased, the magmatic abundances of Rb, Y, Cs, Nb, U, Th, Cl, and F (±Be) increased. The associated magma or magmas were highly evolved, volatile enriched, and contained Rb, Nb, and Y abundances characteristic of continental within-plate granites; compositions ranged from high-silica rhyolite to topaz rhyolite. Pre-eruptive volatile abundances in the source magma(s) were generally high but also highly variable. Chlorine contents of melt(s) ranged from 0.02-0.23 wt%, and F ranged from 0.01-0.7 wt%. Concentrations of H 2O in melt(s) ranged from 1.6-6.5 wt%. The high pre-eruptive H 2O contents are consistent with large eruptive volumes indicating the precursor rhyolites, which weathered to tonsteins, were a result of plinian eruptions. Even though pre-eruptive water concentrations exhibit no recognizable trends with any elements studied, magmatic evolution appears to have been a strong function of F and H 2O in melt(s); the thermal stabilities of quartz and feldspar were controlled by F and H 2O activities at pressures of approximately 0.5-1 kbar.

Co-regulation of dark and light reactions in three biochemical subtypes of C(4) species.

PubMed

Kiirats, Olavi; Kramer, David M; Edwards, Gerald E

2010-08-01

Regulation of light harvesting in response to changes in light intensity, CO(2) and O(2) concentration was studied in C(4) species representing three different metabolic subtypes: Sorghum bicolor (NADP-malic enzyme), Amaranthus edulis (NAD-malic enzyme), and Panicum texanum (PEP-carboxykinase). Several photosynthetic parameters were measured on the intact leaf level including CO(2) assimilation rates, O(2) evolution, photosystem II activities, thylakoid proton circuit and dissipation of excitation energy. Gross rates of O(2) evolution (J(O)₂'), measured by analysis of chlorophyll fluorescence), net rates of O(2) evolution and CO(2) assimilation responded in parallel to changes in light and CO(2) levels. The C(4) subtypes had similar energy requirements for photosynthesis since there were no significant differences in maximal quantum efficiencies for gross rates of O(2) evolution (average value = 0.072 O(2)/quanta absorbed, approximately 14 quanta per O(2) evolved). At saturating actinic light intensities, when photosynthesis was suppressed by decreasing CO(2), ATP synthase proton conductivity (g (H) (+)) responded strongly to changes in electron flow, decreasing linearly with J(O)₂', which was previously observed in C(3) plants. It is proposed that g (H) (+) is controlled at the substrate level by inorganic phosphate availability. The results suggest development of nonphotochemical quenching in C(4) plants is controlled by a decrease in g (H) (+), which causes an increase in proton motive force by restricting proton efflux from the lumen, rather than by cyclic or pseudocyclic electron flow.

Superconducting order from disorder in 2H-TaSe 2-xS x

DOE PAGES

Li, Lijun; Deng, Xiaoyu; Wang, Zhen; ...

2017-02-24

Here, we report on the emergence of robust superconducting order in single crystal alloys of TaSe 2$ -$x S x (0 ≤ × ≤2). The critical temperature of the alloy is surprisingly higher than that of the two end compounds TaSe2 and TaS2. The evolution of superconducting critical temperature T c(x) correlates with the full width at half maximum of the Bragg peaks and with the linear term of the high-temperature resistivity. The conductivity of the crystals near the middle of the alloy series is higher or similar than that of either one of the end members 2H-TaSe 2 and/ormore » 2H-TaS 2. It is known that in these materials superconductivity is in close competition with charge density wave order. We interpret our experimental findings in a picture where disorder tilts this balance in favor of superconductivity by destroying the charge density wave order.« less

Unified Description of the Optical Phonon Modes in N-Layer MoTe2

NASA Astrophysics Data System (ADS)

Froehlicher, Guillaume; Lorchat, Etienne; Fernique, François; Joshi, Chaitanya; Molina-Sánchez, Alejandro; Wirtz, Ludger; Berciaud, Stéphane

N -layer transition metal dichalcogenides (denoted MX2) provide a unique platform to investigate the evolution of the physical properties between the bulk (3D) and monolayer (quasi-2D) limits. Here, we present a unified analysis of the optical phonon modes in N-layer 2 H -MX2. The 2 H -phase (or hexagonal phase) is the most common polytype for semiconducting MX2 (such as MoS2). Using Raman spectroscopy, we have measured the manifold of low-frequency (rigid layer), mid-frequency (involving intralayer displacement of the chalcogen atoms only), and high-frequency (involving intralayer displacements of all atoms) Raman-active modes in N = 1 to 12 layer 2 H -molybdenenum ditelluride (MoTe2). For each monolayer mode, the N-dependent phonon frequencies give rise to fan diagrams that are quantitatively fit to a force constant model. This analysis allows us to deduce the frequencies of all the bulk (including silent) optical phonon modes.

Escape and fractionation of volatiles and noble gases: from Mars-sized planetary embryos to growing protoplanets

NASA Astrophysics Data System (ADS)

Odert, Petra; Lammer, Helmut; Erkaev, Nikolai V.; Nikolaou, Athanasia; Lichtenegger, Herbert I. M.; Johnstone, Colin P.; Kislyakova, Kristina G.; Leitzinger, Martin; Tosi, Nicola

2017-04-01

Planetary embryos form larger planetary objects via collisions. Such Moon- to Mars-sized bodies can have magma oceans. During the solidification of their magma oceans planetary embryos may therefore degas significant amounts of their volatiles, forming H2O/CO2 dominated steam atmospheres. Such atmospheres may escape efficiently due to the low gravity of these objects and the high EUV emission of the young host star. Planets forming from such building blocks could therefore be drier than expected. We model the energy-limited outflow of hydrogen which is able to drag along heavier species such as O and CO2. We take into account different stellar EUV evolution tracks to investigate the loss of steam atmospheres from Mars-sized planetary embryos at different orbital distances. We find that the estimated envelopes are typically lost within a few to a few tens of Myr. Moreover, we address the influence on protoplanet evolution using Venus as an example. We investigate different early evolution scenarios and constrain realistic cases by comparing modeled noble gas isotope ratios with presently observed ones. We are able to reproduce current ratios by assuming either a pure steam atmosphere or a mixture with accreted hydrogen from the protoplanetary nebula. Despite being able to find solutions for different parameter combinations, our results favor a low-activity Sun with possibly a small amount of residual H from the protoplanetary nebula. In other cases too much CO2 is lost during evolution, which is inconsistent with Venus' present atmosphere. A critical issue is likely the time at which the initial steam atmosphere is outgassed.

Study of the gas contents of rocks: An approach to the evolution of atmospheres on the earth and planets

NASA Technical Reports Server (NTRS)

Barker, C.

1972-01-01

A high vacuum system was built for extracting volatiles from rocks either by heating or crushing, and preliminary analyses of the volatiles were made for selected terrestrial basalts and granites. The apparatus and experimental procedures are described, and the major problems associated with water measurement and choice of argon to replace neon as the internal standard are discussed. Preliminary analyses of granites and basalts indicate the following: All analyses lie in the H2O-CO2-CO triangle on a C-H-O ternary diagram. The compositions of the volatiles plot in distinct, but overlapping, areas of the C-H-O diagram. Pre-Cambrian granites have a higher volatile content than younger granites. Continental basalts have a higher volatile content than oceanic basalts.

Thermally induced evolution of hydrogenated amorphous carbon

NASA Astrophysics Data System (ADS)

Mangolini, Filippo; Rose, Franck; Hilbert, James; Carpick, Robert W.

2013-10-01

The thermally induced structural evolution of hydrogenated amorphous carbon (a-C:H) films was investigated in situ by X-ray photoelectron spectroscopy for annealing temperatures up to 500 °C. A model for the conversion of sp3- to sp2-hybridized carbon in a-C:H vs. temperature and time was developed and applied to determine the ranges of activation energies for the thermally activated processes occurring. The energies are consistent with ordering and clustering of sp2 carbon, scission of sp3 carbon-hydrogen bonds and formation of sp2 carbon, and direct transformation of sp3- to sp2-hybridized carbon.

Application of Fe-Ti oxide dissolution experiments to the petrogenesis of the Ekati Diamond Mine kimberlites, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Kressall, R.; Fedortchouk, Y.; McCammon, C. A.

2015-12-01

Composition of kimberlites is ambiguous due to assimilation and fractional crystallization. We propose that the evolution history of minerals can be used to decipher the magmatic history of kimberlites. We use Fe-Ti oxides (chromite and ilmenite) from six kimberlites from the Ekati Diamond Mine and dissolution experiments to elucidate the petrogenesis of kimberlites. Experiments at 0.1 MPa and variable ƒO2s in a diopside-anorthite melt show that the dissolution rate of ilmenite is highly sensitive to ƒO2. No significant difference was observed in chromite. Zoning in chromite is related to the Fe-content and oxidation state of the melt. Experiments at 1 GPa explore the development of chromite surface resorption features in the system Ca-Mg-Si-H-C-O. Five kimberlites contain a low abundance of ilmenite, owing to a relatively high ƒO2, though ilmenite constituted 65% of oxide macocrysts in one kimberlite. Chromite compositions evolve from Mg-chromite to magnesio-ulvöspinel-magnetite (MUM) in all but one kimberlite where chromite evolves to a pleonaste composition perhaps as a result of rapid emplacement. The high abundance of MUM spinel and low abundance of ilmenite in the matrix could be related to the change in the stable Ti-phase with increasing ƒO2. Core compositions of macrocrysts vary for different mantle sources but rims converge to a composition slightly more oxidized and Mg-rich than chromite from depleted peridotite. Ilmenite commonly has rims composed of perovskite, titanite and MUM. We suggest a model where the kimberlite melt composition is controlled by the co-dissolution and co-precipitation of silicates (predominantly orthopyroxene and olivine) to explain chromite evolution in kimberlites. Resorption-related surface features on chromite macrocrysts show trigon protrusions-depressions on {111} faces and step-like features along the crystal edges resembling products of experiments in H2O fluid. We propose predominantly H2O magmatic fluid in Ekati kimberlites.

In-Situ Sampling Analysis of a Jupiter Trojan Asteroid by High Resolution Mass Spectrometry in the Solar Power Sail Mission

NASA Astrophysics Data System (ADS)

Kebukawa, Y.; Aoki, J.; Ito, M.; Kawai, Y.; Okada, T.; Matsumoto, J.; Yano, H.; Yurimoto, H.; Terada, K.; Toyoda, M.; Yabuta, H.; Nakamura, R.; Cottin, H.; Grand, N.; Mori, O.

2017-12-01

The Solar Power Sail (SPS) mission is one of candidates for the upcoming strategic middle-class space exploration to demonstrate the first outer Solar System journey of Japan. The mission concept includes in-situ sampling analysis of the surface and subsurface (up to 1 m) materials of a Jupiter Trojan asteroid using high resolution mass spectrometry (HRMS). The candidates for the HRMS are multi-turn time-of-flight mass spectrometer (MULTUM) type and Cosmorbitrap type. We plan to analyze isotopic and elemental compositions of volatile materials from organic matter, hydrated minerals, and ice (if any), in order to understand origin and evolution of the Jupiter Trojan asteroids. It will provide insights into planet formation/migration theories, evolution and distribution of volatiles in the Solar System, and missing link between asteroids and comets on evolutional. The HRMS system allows to measure H, N, C, O isotopic compositions and elemental compositions of molecules prepared by various pre-MS procedures including stepwise heating up to 600ºC, gas chromatography (GC), and high-temperature pyrolysis with catalyst to decompose the samples into simple gaseous molecules (e.g., H2, CO, and N2) for isotopic ratio analysis. The required mass resolution should be at least 30,000 for analyzing isotopic ratios for simple gaseous molecules. For elemental compositions, mass accuracy of 10 ppm is required to determine elemental compositions for molecules with m/z up to 300 (as well as compound specific isotopic compositions for smaller molecules). Our planned analytical sequences consist of three runs for both surface and subsurface samples. In addition, `sniff mode' which simply introduces environmental gaseous molecules into a HRMS will be done by the system.

Ultra-low cost and highly stable hydrated FePO4 anodes for aqueous sodium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Yuesheng; Feng, Zimin; Laul, Dharminder; Zhu, Wen; Provencher, Manon; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-01-01

The growing demands for large-scale energy storage devices have put a spotlight on aqueous sodium-ion batteries, which possess a number of highly desirable features, such as sodium abundance, low cost and safety over organic electrolytes. While lots of cathode materials were reported, only few candidate materials like active carbon and NaTi2(PO4)3 were proposed as anodes. It is a long-standing common knowledge that the low cost, non-toxicity, and highly reversible FePO4·2H2O is known as an attractive cathode material for non-aqueous lithium- and sodium-ion batteries, but we demonstrate for the first time that nano-size non-carbon coated amorphous FePO4·2H2O can be used as the anode for an aqueous sodium-ion battery. Its optimum operating voltage (∼2.75 V vs. Na+/Na) avoids hydrogen evolution. The capacity is as high as 80 mAh/g at a rate of 0.5 C in a three-electrode system. The full cell, using the Na0.44MnO2 as cathode, maintained 90% of the capacity at 300 cycles at a rate of 3 C. The calculations also show that its volume change during the intercalation of Na ions is below 2%. Its low cost, high safety, along with its outstanding electrochemical performance makes amorphous FePO4·2H2O a promising anode material for aqueous sodium-ion batteries.

Massive stars: Their lives in the interstellar medium; Proceedings of the Symposium, ASP Annual Meeting, 104th, Univ. of Wisconsin, Madison, June 23-25, 1992

NASA Astrophysics Data System (ADS)

Cassinelli, Joseph P.; Churchwell, Edward B.

1993-01-01

Various papers on massive stars and their relationship to the interstellar medium are presented. Individual topics addressed include: observations of newly formed massive stars, star formation with nonthermal motions, embedded stellar clusters in H II regions, a Milky Way concordance, NH3 and H2O masers, PIGs in the Trapezium, star formation in photoevaporating molecular clouds, massive star evolution, mass loss from cool supergiant stars, massive runaway stars, CNO abundances in three A-supergiants, mass loss from late-type supergiants, OBN stars and blue supergiant supernovae, the most evolved W-R stars, X-ray variability in V444 Cygni, highly polarized stars in Cassiopeia, H I bubbles around O stars, interstellar H I LY-alpha absorption, shocked ionized gas in 30 Doradus, wind mass and energy deposition. Also discussed are: stellar wind bow shocks, O stars giant bubbles in M33, Eridanus soft X-ray enhancement, wind-blown bubbles in ejecta medium, nebulae around W-R stars, highly ionized gas in the LMC, cold ionized gas around hot H II regions, initial mass function in the outer Galaxy, late stages in SNR evolution, possible LBV in NGC 1313, old SN-pulsar association, cold bright matter near SN1987A, starbursts in the nearby universe, giant H II regions, powering the superwind in NGC 253, obscuration effects in starburst Galactic nuclei, starburst propagation in dwarf galaxies, 30 Doradus, W-R content of NGC 595 and NGC 604, Cubic Cosmic X-ray Background Experiment.

Evolution of thick domain walls in de Sitter universe

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

Dolgov, A.D.; Godunov, S.I.; Rudenko, A.S., E-mail: dolgov@fe.infn.it, E-mail: sgodunov@itep.ru, E-mail: a.s.rudenko@inp.nsk.su

We consider thick domain walls in a de Sitter universe following paper by Basu and Vilenkin. However, we are interested not only in stationary solutions found therein, but also investigate the general case of domain wall evolution with time. When the wall thickness parameter, δ{sub 0}, is smaller than H {sup −1}/√2, where H is the Hubble parameter in de Sitter space-time, then the stationary solutions exist, and initial field configurations tend with time to the stationary ones. However, there are no stationary solutions for δ{sub 0} ≥ H {sup −1}/√2. We have calculated numerically the rate of the wallmore » expansion in this case and have found that the width of the wall grows exponentially fast for δ{sub 0} >> H {sup −1}. An explanation for the critical value δ{sub 0} {sub c} = H {sup −1}/√2 is also proposed.« less

SIGNIFICANT ENHANCEMENT OF H{sub 2} FORMATION IN DISK GALAXIES UNDER STRONG RAM PRESSURE

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

Henderson, Benjamin; Bekki, Kenji

We show for the first time that H{sub 2} formation on dust grains can be enhanced in disk galaxies under strong ram pressure (RP). We numerically investigate how the time evolution of H i and H{sub 2} components in disk galaxies orbiting a group/cluster of galaxies can be influenced by the hydrodynamical interaction between the gaseous components of the galaxies and the hot intracluster medium. We find that compression of H i caused by RP increases H{sub 2} formation in disk galaxies before RP rapidly strips H i, cutting off the fuel supply and causing a drop in H{sub 2}more » density. We also find that the level of this H{sub 2} formation enhancement in a disk galaxy under RP depends on the mass of its host cluster dark matter halo, the initial positions and velocities of the disk galaxy, and the disk inclination angle with respect to the orbital plane. We demonstrate that dust growth is a key factor in the evolution of the H i and H{sub 2} mass in disk galaxies under strong RP. We discuss how the correlation between H{sub 2} fractions and surface gas densities of disk galaxies evolves with time in the galaxies under RP. We also discuss whether galaxy-wide star formation rates (SFRs) in cluster disk galaxies can be enhanced by RP if the SFRs depend on H{sub 2} densities.« less

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

NASA Astrophysics Data System (ADS)

Roy, Nitish; Hirano, Yuiri; Kuriyama, Haruo; Sudhagar, Pitchaimuthu; Suzuki, Norihiro; Katsumata, Ken-Ichi; Nakata, Kazuya; Kondo, Takeshi; Yuasa, Makoto; Serizawa, Izumi; Takayama, Tomoaki; Kudo, Akihiko; Fujishima, Akira; Terashima, Chiaki

2016-11-01

Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-doped diamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at -1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion.

Petrology of blueschist from the Western Himalaya (Ladakh, NW India): Exploring the complex behavior of a lawsonite-bearing system in a paleo-accretionary setting

NASA Astrophysics Data System (ADS)

Groppo, Chiara; Rolfo, Franco; Sachan, Himanshu K.; Rai, Santosh K.

2016-05-01

Although the Himalaya is the archetype of collisional orogens, formed as a consequence of the closure of the Neo-Tethyan ocean separating India from Asia, high-pressure metamorphic rocks are rare. Beside few eclogites, corresponding to the metamorphosed continental Indian crust dragged below Asia or underthrusted beneath southern Tibet, blueschists occur seldom along the Yarlung-Tsangpo Suture zone, i.e. the suture marking the India-Asia collision. These blueschists, mostly interpreted as related to paleo-accretionary prisms formed in response to the subduction of the Neo-Tethyan ocean below the Asian plate, are crucial for constraining the evolution of the India-Asia convergence zone during the closure of the Neo-Tethyan Ocean. In the Western Himalaya, the best occurrence of blueschist is that of the Sapi-Shergol Ophiolitic Mélange in Ladakh. This unit is dominated by volcanoclastic sequences rich in mafic material with subordinate interbedding of metasediments, characterized by very fresh lawsonite blueschist-facies assemblages. In this paper, the lawsonite blueschist-facies metasediments have been petrologically investigated with the aims of (i) constraining the P-T evolution of the Sapi-Shergol Ophiolitic Mélange, (ii) evaluating the influence of Fe2O3 and of H2O on the stability of the high-pressure mineral assemblages, (iii) understanding the processes controlling lawsonite formation and preservation, and (iv) interpreting the P-T evolution of the Sapi-Shergol blueschists in the framework of India-Asia collision. Our results indicate that (i) the Sapi-Shergol blueschists experienced a cold subduction history along a low thermal gradient, up to peak conditions of ca. 470 °C, 19 kbar; furthermore, in order to preserve lawsonite in the studied lithologies, exhumation must have been coupled with significant cooling, i.e. the resulting P-T path is characterized by a clockwise hairpin loop along low thermal gradients (< 8-9 °C/km); (ii) the presence of ferric iron in the investigated system has a non-negligible (lowering) effect on pressure estimates, whereas temperatures estimates are not influenced by the oxidation state of the system; (iii) the observed sequence of mineral growth (i.e. simultaneous growth of lawsonite and garnet) suggests that (a) the system was initially H2O-undersaturated and lawsonite growth was triggered by a protracted H2O influx at high pressure (equilibrium approach), or (b) the system was H2O-saturated since the beginning, but lawsonite growth was delayed due to the predominance of kinetic factors over equilibrium dynamics (nonequilibrium approach); (iv) the inferred P-T evolution is consistent with a cold subduction zone system in an intra-oceanic subduction setting. Moreover, the estimated peak P-T conditions roughly coincide with the maximum P-T estimates predicted by thermo-mechanical models for the metasediments exhumed in accretionary wedges, and with the maximum P-T conditions recorded by natural occurrences of blueschist accretionary complexes worldwide.

Faster Electron Injection and More Active Sites for Efficient Photocatalytic H2 Evolution in g-C3 N4 /MoS2 Hybrid.

PubMed

Shi, Xiaowei; Fujitsuka, Mamoru; Kim, Sooyeon; Majima, Tetsuro

2018-03-01

Herein, the structural effect of MoS 2 as a cocatalyst of photocatalytic H 2 generation activity of g-C 3 N 4 under visible light irradiation is studied. By using single-particle photoluminescence (PL) and femtosecond time-resolved transient absorption spectroscopies, charge transfer kinetics between g-C 3 N 4 and two kinds of nanostructured MoS 2 (nanodot and monolayer) are systematically investigated. Single-particle PL results show the emission of g-C 3 N 4 is quenched by MoS 2 nanodots more effectively than MoS 2 monolayers. Electron injection rate and efficiency of g-C 3 N 4 /MoS 2 -nanodot hybrid are calculated to be 5.96 × 10 9 s -1 and 73.3%, respectively, from transient absorption spectral measurement, which are 4.8 times faster and 2.0 times higher than those of g-C 3 N 4 /MoS 2 -monolayer hybrid. Stronger intimate junction between MoS 2 nanodots and g-C 3 N 4 is suggested to be responsible for faster and more efficient electron injection. In addition, more unsaturated terminal sulfur atoms can serve as the active site in MoS 2 nanodot compared with MoS 2 monolayer. Therefore, g-C 3 N 4 /MoS 2 nanodot exhibits a 7.9 times higher photocatalytic activity for H 2 evolution (660 µmol g- 1 h -1 ) than g-C 3 N 4 /MoS 2 monolayer (83.8 µmol g -1 h -1 ). This work provides deep insight into charge transfer between g-C 3 N 4 and nanostructured MoS 2 cocatalysts, which can open a new avenue for more rationally designing MoS 2 -based catalysts for H 2 evolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photocatalytic activity for H2 evolution under irradiation of UV-vis light by Au-modified nitrogen-doped TiO2.

PubMed

Zhao, Weirong; Ai, Zhuyu; Dai, Jiusong; Zhang, Meng

2014-01-01

Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H2 evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO2 by N doping and Au loading. Au/N-doped TiO2 photocatalysts were synthesized and successfully used for photocatalytic water splitting for H2 evolution under irradiation of UV and UV-vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations. DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO2 > Au/N-doped TiO2 > TiO2 > N-doped TiO2. While under irradiation of UV-vis light, the N-TiO2 and Au/N-TiO2 samples show higher H2 evolution than their corresponding nitrogen-free samples (TiO2 and Au/TiO2). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO2. Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO2 and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV-vis light.

Synthetic nebular emission from massive galaxies - I: origin of the cosmic evolution of optical emission-line ratios

NASA Astrophysics Data System (ADS)

Hirschmann, Michaela; Charlot, Stephane; Feltre, Anna; Naab, Thorsten; Choi, Ena; Ostriker, Jeremiah P.; Somerville, Rachel S.

2017-12-01

Galaxies occupy different regions of the [O III]λ5007/H β-versus-[N II]λ6584/H α emission-line ratio diagram in the distant and local Universe. We investigate the origin of this intriguing result by modelling self-consistently, for the first time, nebular emission from young stars, accreting black holes (BHs) and older, post-asymptotic giant branch (post-AGB) stellar populations in galaxy formation simulations in a full cosmological context. In post-processing, we couple new-generation nebular-emission models with high-resolution, cosmological zoom-in simulations of massive galaxies to explore which galaxy physical properties drive the redshift evolution of the optical-line ratios [O III]λ5007/H β, [N II]λ6584/H α, [S II]λλ6717, 6731/H α and [O I]λ6300/H α. The line ratios of simulated galaxies agree well with observations of both star-forming and active local Sloan Digital Sky Survey galaxies. Towards higher redshifts, at fixed galaxy stellar mass, the average [O III]/H β is predicted to increase and [N II]/H α, [S II]/H α and [O I]/H α to decrease - widely consistent with observations. At fixed stellar mass, we identify star formation history, which controls nebular emission from young stars via the ionization parameter, as the primary driver of the cosmic evolution of [O III]/H β and [N II]/H α. For [S II]/H α and [O I]/H α, this applies only to redshifts greater than z = 1.5, the evolution at lower redshift being driven in roughly equal parts by nebular emission from active galactic nuclei and post-AGB stellar populations. Instead, changes in the hardness of ionizing radiation, ionized-gas density, the prevalence of BH accretion relative to star formation and the dust-to-metal mass ratio (whose impact on the gas-phase N/O ratio we model at fixed O/H) play at most a minor role in the cosmic evolution of simulated galaxy line ratios.

Genetic characterization of influenza A viruses circulating in pigs and isolated in north-east Spain during the period 2006-2007.

PubMed

Baratelli, Massimiliano; Córdoba, Lorena; Pérez, Lester J; Maldonado, Jaime; Fraile, Lorenzo; Núñez, José I; Montoya, Maria

2014-04-01

Swine influenza virus is one of the most important pathogens involved in the swine respiratory disease complex. Recent serological surveys showed a high prevalence of swine influenza strains belonging to the H1N1, H1N2 and H3N2 subtypes circulating in pigs in Spain. However, little is known about their genome sequence. Five swine influenza strains were isolated from some unrelated outbreaks occurred during 2006-2007, and their complete genome sequences were determined. Phylogenetic analysis revealed that they belonged to the lineages "Avian-Like" H1N1, "Human-Like" H3N2, and "Human-Like" H1N2, showing tight relationships with early or contemporary strains described in Europe. Notably, one virus of the H1N2 subtype showed genetic and antigenic divergence with the European contemporary strains or vaccinal strains of the same subtype, suggesting that some local and divergent clusters of the virus may pass unnoticed in routinary subtyping. Finally, analysis on the entire pattern of genome segments suggested that a second reassortment event could have influenced the evolution of that divergent H1N2 strain. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evolution of highly pathogenic avian influenza H5N1 viruses in Egypt indicating progressive adaptation

USDA-ARS?s Scientific Manuscript database

Highly pathogenic avian influenza (HPAI) virus of the H5N1 subtype was first diagnosed in poultry in Egypt in 2006, and since then the disease became enzootic in poultry throughout the country affecting the poultry industry and village poultry as well as infecting humans. Vaccination has been used ...

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

2017-05-01

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

GUM 48d: AN EVOLVED H II REGION WITH ONGOING STAR FORMATION

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

Karr, J. L.; Ohashi, N.; Manoj, P.

2009-05-20

High-mass star formation and the evolution of H II regions have a substantial impact on the morphology and star formation history of molecular clouds. The H II region Gum 48d, located in the Centaurus Arm at a distance of 3.5 kpc, is an old, well evolved H II region whose ionizing stars have moved off the main sequence. As such, it represents a phase in the evolution of H II regions that is less well studied than the earlier, more energetic, main-sequence phase. In this paper, we use multiwavelength archive data from a variety of sources to perform a detailedmore » study of this interesting region. Morphologically, Gum 48d displays a ring-like faint H II region associated with diffuse emission from the associated photodissociation region, and is formed from part of a large, massive molecular cloud complex. There is extensive ongoing star formation in the region, at scales ranging from low to high mass, which is consistent with triggered star formation scenarios. We investigate the dynamical history and evolution of this region, and conclude that the original H II region was once larger and more energetic than the faint region currently seen. The proposed history of this molecular cloud complex is one of multiple, linked generations of star formation, over a period of 10 Myr. Gum 48d differs significantly in morphology and star formation from the other H II regions in the molecular cloud; these differences are likely the result of the advanced age of the region, and its different evolutionary status.« less

Physical conditions of the interstellar medium in high-redshift submillimetre bright galaxies

NASA Astrophysics Data System (ADS)

Yang, Chentao

2017-12-01

The discovery of a population of high- redshift dust-obscured submillimeter galaxies (SMGs) from ground-based submm cameras has revolutionised our understanding of galaxy evolution and star formation in extreme conditions. They are the strongest starbursts in the Universe approaching the Eddington limit and are believed to be the progenitors of the most massive galaxies today. However, theoretical models of galaxy evolution have even been challenged by a large number of detections of high-redshift SMGs. A very few among them are gravitationally lensed by an intervening galaxy. Recent wide-area extragalactic surveys have discovered hundreds of such strongly lensed SMGs, opening new exciting opportunities for observing the interstellar medium in these exceptional objects. We have thus carefully selected a sample of strongly gravitational lensed SMGs based on the submillimeter flux limit from the Herschel-ATLAS sample. Using IRAM telescopes, we have built a rich H2O-line-detected sample of 16 SMGs. We found a close-to-linear tight correlation between the H2O line and total infrared luminosity. This indicates the importance of far-IR pumping to the excitation of the H2O lines. Using a far-IR pumping model, we have derived the physical properties of the H2O gas and the dust. We showed that H2O lines trace a warm dense gas that may be closely related to the active star formation. Along with the H2O lines, several H2O+ lines have also been detected in three of our SMGs. We also find a tight correlation between the luminosity of the lines of H2O and H2O+ from local ULIRGs to high-redshift SMGs. The flux ratio between H2O+ and H2O suggests that cosmic rays from strong star forming activities are possibly driving the related oxygen chemistry. Another important common molecular gas tracer is the CO line. We have observed multiple transitions of the CO lines in each of our SMGs with IRAM 30m telescope. By analysing the CO line profile, we discovered a significant differential lensing effect that might cause underestimation of the linewidth by a factor of 2. Using LVG modelling and fitting the multi-J CO fluxes via a Bayesian approach, we derived gas densities and temperature, and CO column density per unit velocity gradient. We then found a correlation between the gas thermal pressure and the star formation efficiency. We have also studied the global properties of the molecular gas and its relationship with star formation. We have derived the gas to dust mass ratio and the gas depletion time, they show no difference compared with other SMGs. With the detections of atomic carbon lines in our SMGs, we extended the local linear correlation between the CO and CI line luminosity. Finally, we compared the linewidths of the CO and H2O emission line, which agree very well with each other. This suggests that the emitting regions of these two molecules are likely to be co-spatially located. In order to understand the properties of molecular emission in high-redshift SMGs, and more generally, the structure and the dynamical properties of these galaxies, it is crucial to acquire high-resolution images. We thus observed two of our brightest sources with ALMA and NOEMA interferometers using their high spatial resolution configuration. These images have allowed us to reconstruct the intrinsic morphology of the sources. We compared the CO, H2O and dust emission. The cold dust emission has a smaller size compared with the CO and H2O gas, while the latter two are similar in size. By fitting the dynamical model to the CO data of the source, we have shown that the source can be modelled with a rotating disk. We derived the projected dynamical mass and the effective radius of those sources. With the future NOEMA and ALMA, we will be able to extend such kind of observations to a larger sample lensed SMGs and even to unlensed SMGs, to study various gas tracers, and to understand the physical conditions of the ISM and their relation to the star formation.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces.Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces. Electronic supplementary information (ESI) available: TEM and HRTEM images of hematite seeds and iron oxide/SnO2 (12 h and 36 h). See DOI: 10.1039/c1nr10728c

Ab initio molecular dynamics simulations reveal localization and time evolution dynamics of an excess electron in heterogeneous CO2-H2O systems.

PubMed

Liu, Ping; Zhao, Jing; Liu, Jinxiang; Zhang, Meng; Bu, Yuxiang

2014-01-28

In view of the important implications of excess electrons (EEs) interacting with CO2-H2O clusters in many fields, using ab initio molecular dynamics simulation technique, we reveal the structures and dynamics of an EE associated with its localization and subsequent time evolution in heterogeneous CO2-H2O mixed media. Our results indicate that although hydration can increase the electron-binding ability of a CO2 molecule, it only plays an assisting role. Instead, it is the bending vibrations that play the major role in localizing the EE. Due to enhanced attraction of CO2, an EE can stably reside in the empty, low-lying π(*) orbital of a CO2 molecule via a localization process arising from its initial binding state. The localization is completed within a few tens of femtoseconds. After EE trapping, the ∠OCO angle of the core CO2 (-) oscillates in the range of 127°∼142°, with an oscillation period of about 48 fs. The corresponding vertical detachment energy of the EE is about 4.0 eV, which indicates extreme stability of such a CO2-bound solvated EE in [CO2(H2O)n](-) systems. Interestingly, hydration occurs not only on the O atoms of the core CO2 (-) through formation of O⋯H-O H-bond(s), but also on the C atom, through formation of a C⋯H-O H-bond. In the latter binding mode, the EE cloud exhibits considerable penetration to the solvent water molecules, and its IR characteristic peak is relatively red-shifted compared with the former. Hydration on the C site can increase the EE distribution at the C atom and thus reduce the C⋯H distance in the C⋯H-O H-bonds, and vice versa. The number of water molecules associated with the CO2 (-) anion in the first hydration shell is about 4∼7. No dimer-core (C2O4 (-)) and core-switching were observed in the double CO2 aqueous media. This work provides molecular dynamics insights into the localization and time evolution dynamics of an EE in heterogeneous CO2-H2O media.

Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

PubMed

Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

2008-01-01

The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

THE XMM-NEWTON WIDE FIELD SURVEY IN THE COSMOS FIELD: REDSHIFT EVOLUTION OF AGN BIAS AND SUBDOMINANT ROLE OF MERGERS IN TRIGGERING MODERATE-LUMINOSITY AGNs AT REDSHIFTS UP TO 2.2

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

Allevato, V.; Hasinger, G.; Salvato, M.

2011-08-01

We present a study of the redshift evolution of the projected correlation function of 593 X-ray selected active galactic nuclei (AGNs) with I{sub AB} < 23 and spectroscopic redshifts z < 4, extracted from the 0.5-2 keV X-ray mosaic of the 2.13 deg{sup 2} XMM- Cosmic Evolution Survey (COSMOS). We introduce a method to estimate the average bias of the AGN sample and the mass of AGN hosting halos, solving the sample variance using the halo model and taking into account the growth of the structure over time. We find evidence of a redshift evolution of the bias factor formore » the total population of XMM-COSMOS AGNs from b-bar (z-bar =0.92)=2.30{+-}0.11 to b-bar (z-bar =1.94)=4.37{+-}0.27 with an average mass of the hosting dark matter (DM) halos log M{sub 0}(h{sup -1} M{sub sun}) {approx} 13.12 {+-} 0.12 that remains constant at all z < 2. Splitting our sample into broad optical line AGNs (BL), AGNs without broad optical lines (NL), and X-ray unobscured and obscured AGNs, we observe an increase of the bias with redshift in the range z-bar = 0.7-2.25 and z-bar = 0.6-1.5 which corresponds to a constant halo mass of log M{sub 0}(h{sup -1} M{sub sun}) {approx} 13.28 {+-} 0.07 and log M{sub 0}(h{sup -1} M{sub sun}) {approx} 13.00 {+-} 0.06 for BL/X-ray unobscured AGNs and NL/X-ray obscured AGNs, respectively. The theoretical models, which assume a quasar phase triggered by major mergers, cannot reproduce the high bias factors and DM halo masses found for X-ray selected BL AGNs with L{sub BOL} {approx} 2 x 10{sup 45} erg s{sup -1}. Our work extends up to z {approx} 2.2 the z {approx}< 1 statement that, for moderate-luminosity X-ray selected BL AGNs, the contribution from major mergers is outnumbered by other processes, possibly secular ones such as tidal disruptions or disk instabilities.« less

Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption

NASA Astrophysics Data System (ADS)

Zheng, Xueli; Zhang, Bo; de Luna, Phil; Liang, Yufeng; Comin, Riccardo; Voznyy, Oleksandr; Han, Lili; García de Arquer, F. Pelayo; Liu, Min; Dinh, Cao Thang; Regier, Tom; Dynes, James J.; He, Sisi; Xin, Huolin L.; Peng, Huisheng; Prendergast, David; Du, Xiwen; Sargent, Edward H.

2018-02-01

The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. We took the view that generating transition-metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Here, using density functional theory, we find that the formation energy of desired Ni4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal P. We therefore synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics with in situ soft X-ray absorption spectroscopy (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni4+ under low overpotential conditions. The NiCoFeP catalyst outperforms IrO2 and retains its performance following 100 h of operation. We showcase NiCoFeP in a membrane-free CO2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm-2, reducing CO2 into CO and oxidizing H2O to O2 with a 64% electricity-to-chemical-fuel efficiency.

Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption.

PubMed

Zheng, Xueli; Zhang, Bo; De Luna, Phil; Liang, Yufeng; Comin, Riccardo; Voznyy, Oleksandr; Han, Lili; García de Arquer, F Pelayo; Liu, Min; Dinh, Cao Thang; Regier, Tom; Dynes, James J; He, Sisi; Xin, Huolin L; Peng, Huisheng; Prendergast, David; Du, Xiwen; Sargent, Edward H

2018-02-01

The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. We took the view that generating transition-metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Here, using density functional theory, we find that the formation energy of desired Ni 4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal P. We therefore synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics with in situ soft X-ray absorption spectroscopy (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni 4+ under low overpotential conditions. The NiCoFeP catalyst outperforms IrO 2 and retains its performance following 100 h of operation. We showcase NiCoFeP in a membrane-free CO 2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm -2 , reducing CO 2 into CO and oxidizing H 2 O to O 2 with a 64% electricity-to-chemical-fuel efficiency.

Evolution of substrate specificity for the bile salt transporter ASBT (SLC10A2)[S

PubMed Central

Lionarons, Daniël A.; Boyer, James L.; Cai, Shi-Ying

2012-01-01

The apical Na+-dependent bile salt transporter (ASBT/SLC10A2) is essential for maintaining the enterohepatic circulation of bile salts. It is not known when Slc10a2 evolved as a bile salt transporter or how it adapted to substantial changes in bile salt structure during evolution. We characterized ASBT orthologs from two primitive vertebrates, the lamprey that utilizes early 5α-bile alcohols and the skate that utilizes structurally different 5β-bile alcohols, and compared substrate specificity with ASBT from humans who utilize modern 5β-bile acids. Everted gut sacs of skate but not the more primitive lamprey transported 3H-taurocholic acid (TCA), a modern 5β-bile acid. However, molecular cloning identified ASBT orthologs from both species. Cell-based assays using recombinant ASBT/Asbt's indicate that lamprey Asbt has high affinity for 5α-bile alcohols, low affinity for 5β-bile alcohols, and lacks affinity for TCA, whereas skate Asbt showed high affinity for 5α- and 5β-bile alcohols but low affinity for TCA. In contrast, human ASBT demonstrated high affinity for all three bile salt types. These findings suggest that ASBT evolved from the earliest vertebrates by gaining affinity for modern bile salts while retaining affinity for older bile salts. Also, our results indicate that the bile salt enterohepatic circulation is conserved throughout vertebrate evolution. PMID:22669917

ZnO-dotted porous ZnS cluster microspheres for high efficient, Pt-free photocatalytic hydrogen evolution.

PubMed

Wu, Aiping; Jing, Liqiang; Wang, Jianqiang; Qu, Yang; Xie, Ying; Jiang, Baojiang; Tian, Chungui; Fu, Honggang

2015-03-09

The Pt-free photocatalytic hydrogen evolution (PHE) has been the focus in the photocatalysis field. Here, the ZnO-dotted porous ZnS cluster microsphere (PCMS) is designed for high efficient, Pt-free PHE. The PCMS is designed through an easy "controlling competitive reaction" strategy by selecting the thiourea as S(2-) source and Zn(Ac)₂·2H₂O as Zn source in ethylene glycol medium. Under suitable conditions, one of the PCMS, named PCMS-1, with high SBET specific area of 194 m(2)g(-1), microsphere size of 100 nm and grain size of 3 nm can be obtained. The formation of PCMS is verified by TEM, XAES, XPS, Raman and IR methods. Importantly, a series of the experiments and theoretical calculation demonstrate that the dotting of ZnO not only makes the photo-generated electrons/hole separate efficiently, but also results in the formation of the active catalytic sites for PHE. As a result, the PCMS-1 shows the promising activity up to 367 μmol h(-1) under Pt-free condition. The PHE activity has no obvious change after addition 1 wt.% Pt, implying the presence of active catalytic sites for hydrogen evolution in the PCMS-1. The easy synthesis process, low preparation cost of the PCMS makes their large potential for Pt-free PHE.

A statistical study towards high-mass BGPS clumps with the MALT90 survey

NASA Astrophysics Data System (ADS)

Liu, Xiao-Lan; Xu, Jin-Long; Ning, Chang-Chun; Zhang, Chuan-Peng; Liu, Xiao-Tao

2018-01-01

In this work, we perform a statistical investigation towards 50 high-mass clumps using data from the Bolocam Galactic Plane Survey (BGPS) and Millimetre Astronomy Legacy Team 90-GHz survey (MALT90). Eleven dense molecular lines (N2H+(1–0), HNC(1–0), HCO+(1–0), HCN(1–0), HN13C(1–0), H13CO+(1–0), C2H(1–0), HC3N(10–9), SiO(2–1), 13CS(2–1)and HNCO(44,0 ‑ 30,3)) are detected. N2H+ and HNC are shown to be good tracers for clumps in various evolutionary stages since they are detected in all the fields. The detection rates of N-bearing molecules decrease as the clumps evolve, but those of O-bearing species increase with evolution. Furthermore, the abundance ratios [N2H+]/[HCO+] and log([HC3N]/[HCO+]) decline with log([HCO+]) as two linear functions, respectively. This suggests that N2H+ and HC3N transform to HCO+ as the clumps evolve. We also find that C2H is the most abundant molecule with an order of magnitude 10‑8. In addition, three new infall candidates, G010.214–00.324, G011.121–00.128 and G012.215–00.118(a), are discovered to have large-scale infall motions and infall rates with an order of magnitude 10‑3 M ⊙ yr‑1.

Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand

PubMed Central

2015-01-01

The cobalt complex [CoIIIN4H(Br)2]+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (fCO= 45% ± 6.4) near the CoI/0 redox couple for [CoIIIN4H(Br)2]+ (E1/2 = −1.88 V FeCp2+/0) with simultaneous H2 evolution (fH2= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal CoI/0redox couple, and attempts were made to isolate the triply reduced compound (“[Co0N4H]”). Instead, the doubly reduced (“CoI”) compounds [CoN4] and [CoN4H(MeCN)]+ were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H2 evolution and CO2 reduction electrocatalysis. PMID:24773584

Laser-Induced Graphene Formation on Wood.

PubMed

Ye, Ruquan; Chyan, Yieu; Zhang, Jibo; Li, Yilun; Han, Xiao; Kittrell, Carter; Tour, James M

2017-10-01

Wood as a renewable naturally occurring resource has been the focus of much research and commercial interests in applications ranging from building construction to chemicals production. Here, a facile approach is reported to transform wood into hierarchical porous graphene using CO 2 laser scribing. Studies reveal that the crosslinked lignocellulose structure inherent in wood with higher lignin content is more favorable for the generation of high-quality graphene than wood with lower lignin content. Because of its high electrical conductivity (≈10 Ω per square), graphene patterned on wood surfaces can be readily fabricated into various high-performance devices, such as hydrogen evolution and oxygen evolution electrodes for overall water splitting with high reaction rates at low overpotentials, and supercapacitors for energy storage with high capacitance. The versatility of this technique in formation of multifunctional wood hybrids can inspire both research and industrial interest in the development of wood-derived graphene materials and their nanodevices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Escape and fractionation of volatiles and noble gases from Mars-sized planetary embryos and growing protoplanets

NASA Astrophysics Data System (ADS)

Odert, P.; Lammer, H.; Erkaev, N. V.; Nikolaou, A.; Lichtenegger, H. I. M.; Johnstone, C. P.; Kislyakova, K. G.; Leitzinger, M.; Tosi, N.

2018-06-01

Planetary embryos form protoplanets via mutual collisions, which can lead to the development of magma oceans. During their solidification, significant amounts of the mantles' volatile contents may be outgassed. The resulting H2O/CO2 dominated steam atmospheres may be lost efficiently via hydrodynamic escape due to the low gravity of these Moon- to Mars-sized objects and the high stellar EUV luminosities of the young host stars. Protoplanets forming from such degassed building blocks after nebula dissipation could therefore be drier than previously expected. We model the outgassing and subsequent hydrodynamic escape of steam atmospheres from such embryos. The efficient outflow of H drags along heavier species like O, CO2, and noble gases. The full range of possible EUV evolution tracks of a young solar-mass star is taken into account to investigate the atmospheric escape from Mars-sized planetary embryos at different orbital distances. The estimated envelopes are typically lost within a few to a few tens of Myr. Furthermore, we study the influence on protoplanetary evolution, exemplified by Venus. In particular, we investigate different early evolution scenarios and constrain realistic cases by comparing modeled noble gas isotope ratios with present observations. Isotope ratios of Ne and Ar can be reproduced, starting from solar values, under hydrodynamic escape conditions. Solutions can be found for different solar EUV histories, as well as assumptions about the initial atmosphere, assuming either a pure steam atmosphere or a mixture with accreted hydrogen from the protoplanetary nebula. Our results generally favor an early accretion scenario with a small amount of residual hydrogen from the protoplanetary nebula and a low-activity Sun, because in other cases too much CO2 is lost during evolution, which is inconsistent with Venus' present atmosphere. Important issues are likely the time at which the initial steam atmosphere is outgassed and/or the amount of CO2 which may still be delivered at later evolutionary stages. A late accretion scenario can only reproduce present isotope ratios for a highly active young Sun, but then unrealistically massive steam atmospheres (few kbar) would be required.

Modelling of transitions between L- and H-mode in JET high plasma current plasmas and application to ITER scenarios including tungsten behaviour

NASA Astrophysics Data System (ADS)

Koechl, F.; Loarte, A.; Parail, V.; Belo, P.; Brix, M.; Corrigan, G.; Harting, D.; Koskela, T.; Kukushkin, A. S.; Polevoi, A. R.; Romanelli, M.; Saibene, G.; Sartori, R.; Eich, T.; Contributors, JET

2017-08-01

The dynamics for the transition from L-mode to a stationary high Q DT H-mode regime in ITER is expected to be qualitatively different to present experiments. Differences may be caused by a low fuelling efficiency of recycling neutrals, that influence the post transition plasma density evolution on the one hand. On the other hand, the effect of the plasma density evolution itself both on the alpha heating power and the edge power flow required to sustain the H-mode confinement itself needs to be considered. This paper presents results of modelling studies of the transition to stationary high Q DT H-mode regime in ITER with the JINTRAC suite of codes, which include optimisation of the plasma density evolution to ensure a robust achievement of high Q DT regimes in ITER on the one hand and the avoidance of tungsten accumulation in this transient phase on the other hand. As a first step, the JINTRAC integrated models have been validated in fully predictive simulations (excluding core momentum transport which is prescribed) against core, pedestal and divertor plasma measurements in JET C-wall experiments for the transition from L-mode to stationary H-mode in partially ITER relevant conditions (highest achievable current and power, H 98,y ~ 1.0, low collisionality, comparable evolution in P net/P L-H, but different ρ *, T i/T e, Mach number and plasma composition compared to ITER expectations). The selection of transport models (core: NCLASS  +  Bohm/gyroBohm in L-mode/GLF23 in H-mode) was determined by a trade-off between model complexity and efficiency. Good agreement between code predictions and measured plasma parameters is obtained if anomalous heat and particle transport in the edge transport barrier are assumed to be reduced at different rates with increasing edge power flow normalised to the H-mode threshold; in particular the increase in edge plasma density is dominated by this edge transport reduction as the calculated neutral influx across the separatrix remains unchanged (or even slightly decreases) following the H-mode transition. JINTRAC modelling of H-mode transitions for the ITER 15 MA / 5.3 T high Q DT scenarios with the same modelling assumptions as those being derived from JET experiments has been carried out. The modelling finds that it is possible to access high Q DT conditions robustly for additional heating power levels of P AUX  ⩾  53 MW by optimising core and edge plasma fuelling in the transition from L-mode to high Q DT H-mode. An initial period of low plasma density, in which the plasma accesses the H-mode regime and the alpha heating power increases, needs to be considered after the start of the additional heating, which is then followed by a slow density ramp. Both the duration of the low density phase and the density ramp-rate depend on boundary and operational conditions and can be optimised to minimise the resistive flux consumption in this transition phase. The modelling also shows that fuelling schemes optimised for a robust access to high Q DT H-mode in ITER are also optimum for the prevention of the contamination of the core plasma by tungsten during this phase.

One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

PubMed

Chen, Junze; Wu, Xue-Jun; Yin, Lisha; Li, Bing; Hong, Xun; Fan, Zhanxi; Chen, Bo; Xue, Can; Zhang, Hua

2015-01-19

Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An investigation on microstructure and mechanical property of thermally aged stainless steel weld overlay cladding

NASA Astrophysics Data System (ADS)

Cao, X. Y.; Zhu, P.; Ding, X. F.; Lu, Y. H.; Shoji, T.

2017-04-01

Microstructural evolution and mechanical property change of E308L stainless steel weld overlay cladding aged at 400 °C for 400, 1000 and 5000 h were investigated by transmission electron microscope (TEM) and small punch test (SPT). The results indicated that thermal aging had no obvious effect on the volume fraction of ferrite, but can cause microstructural evolution by spinodal decomposotion and G-phase precipitation in the ferrite phase. Spinodal decomposition took place after aging up to 1000 h, while G-phase formed along dislocations, and growed up to 2-11 nm after aging for 5000 h. The total energy for inducing deformation and fracture by the small punch tests decreased with the increase of thermal aging time, and this decline was associated with spinodal decomposition and G-phase precipitation. Plastic deformation of the aged ferrite proceeded via formation of curvilinear slip bands. Nucleation of microcracks occurred at the δ/γ interface along the slip bands. The hardening of the ferrite and high stress concentration on δ/γ phase interface resulted in brittle fracture and phase boundary separation after thermal aging.

M Gene Reassortment in H9N2 Influenza Virus Promotes Early Infection and Replication: Contribution to Rising Virus Prevalence in Chickens in China.

PubMed

Pu, Juan; Sun, Honglei; Qu, Yi; Wang, Chenxi; Gao, Weihua; Zhu, Junda; Sun, Yipeng; Bi, Yuhai; Huang, Yinhua; Chang, Kin-Chow; Cui, Jie; Liu, Jinhua

2017-04-15

Segment reassortment and base mutagenesis of influenza A viruses are the primary routes to the rapid evolution of high-fitness virus genotypes. We recently described a predominant G57 genotype of avian H9N2 viruses that caused countrywide outbreaks in chickens in China during 2010 to 2013, which led to the zoonotic emergence of H7N9 viruses. One of the key features of the G57 genotype is the replacement of the earlier A/chicken/Beijing/1/1994 (BJ/94)-like M gene with the A/quail/Hong Kong/G1/1997 (G1)-like M gene of quail origin. We report here the functional significance of the G1-like M gene in H9N2 viruses in conferring increased infection severity and infectivity in primary chicken embryonic fibroblasts and chickens. H9N2 virus housing the G1-like M gene, in place of the BJ/94-like M gene, showed an early surge in viral mRNA and viral RNA (vRNA) transcription that was associated with enhanced viral protein production and with an early elevated release of progeny virus comprising largely spherical rather than filamentous virions. Importantly, H9N2 virus with the G1-like M gene conferred extrapulmonary virus spread in chickens. Five highly represented signature amino acid residues (37A, 95K, 224N, and 242N in the M1 protein and 21G in the M2 protein) encoded by the prevalent G1-like M gene were demonstrated to be prime contributors to enhanced infectivity. Therefore, the genetic evolution of the M gene in H9N2 virus increases reproductive virus fitness, indicating its contribution to the rising virus prevalence in chickens in China. IMPORTANCE We recently described the circulation of a dominant genotype (genotype G57) of H9N2 viruses in countrywide outbreaks in chickens in China, which was responsible, through reassortment, for the emergence of H7N9 viruses that cause severe human infections. A key feature of the genotype G57 H9N2 virus is the presence of the quail-origin G1-like M gene, which had replaced the earlier BJ/94-like M gene. We found that H9N2 virus with the G1-like M gene, but not the BJ/94-like M gene, showed an early surge in progeny virus production and more severe pathology and extrapulmonary virus spread in chickens. Five highly represented amino acid residues in the M1 and M2 proteins derived from the G1-like M gene were shown to mediate enhanced virus infectivity. These observations enhance what we currently know about the roles of reassortment and mutations in virus fitness and have implications for assessing the potential of variant influenza viruses that can cause a rising prevalence in chickens. Copyright © 2017 American Society for Microbiology.

M Gene Reassortment in H9N2 Influenza Virus Promotes Early Infection and Replication: Contribution to Rising Virus Prevalence in Chickens in China

PubMed Central

Pu, Juan; Sun, Honglei; Qu, Yi; Wang, Chenxi; Gao, Weihua; Zhu, Junda; Sun, Yipeng; Bi, Yuhai; Huang, Yinhua; Chang, Kin-Chow

2017-01-01

ABSTRACT Segment reassortment and base mutagenesis of influenza A viruses are the primary routes to the rapid evolution of high-fitness virus genotypes. We recently described a predominant G57 genotype of avian H9N2 viruses that caused countrywide outbreaks in chickens in China during 2010 to 2013, which led to the zoonotic emergence of H7N9 viruses. One of the key features of the G57 genotype is the replacement of the earlier A/chicken/Beijing/1/1994 (BJ/94)-like M gene with the A/quail/Hong Kong/G1/1997 (G1)-like M gene of quail origin. We report here the functional significance of the G1-like M gene in H9N2 viruses in conferring increased infection severity and infectivity in primary chicken embryonic fibroblasts and chickens. H9N2 virus housing the G1-like M gene, in place of the BJ/94-like M gene, showed an early surge in viral mRNA and viral RNA (vRNA) transcription that was associated with enhanced viral protein production and with an early elevated release of progeny virus comprising largely spherical rather than filamentous virions. Importantly, H9N2 virus with the G1-like M gene conferred extrapulmonary virus spread in chickens. Five highly represented signature amino acid residues (37A, 95K, 224N, and 242N in the M1 protein and 21G in the M2 protein) encoded by the prevalent G1-like M gene were demonstrated to be prime contributors to enhanced infectivity. Therefore, the genetic evolution of the M gene in H9N2 virus increases reproductive virus fitness, indicating its contribution to the rising virus prevalence in chickens in China. IMPORTANCE We recently described the circulation of a dominant genotype (genotype G57) of H9N2 viruses in countrywide outbreaks in chickens in China, which was responsible, through reassortment, for the emergence of H7N9 viruses that cause severe human infections. A key feature of the genotype G57 H9N2 virus is the presence of the quail-origin G1-like M gene, which had replaced the earlier BJ/94-like M gene. We found that H9N2 virus with the G1-like M gene, but not the BJ/94-like M gene, showed an early surge in progeny virus production and more severe pathology and extrapulmonary virus spread in chickens. Five highly represented amino acid residues in the M1 and M2 proteins derived from the G1-like M gene were shown to mediate enhanced virus infectivity. These observations enhance what we currently know about the roles of reassortment and mutations in virus fitness and have implications for assessing the potential of variant influenza viruses that can cause a rising prevalence in chickens. PMID:28148803

Combined cosmological tests of a bivalent tachyonic dark energy scalar field model

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

Keresztes, Zoltán; Gergely, László Á., E-mail: zkeresztes@titan.physx.u-szeged.hu, E-mail: gergely@physx.u-szeged.hu

A recently investigated tachyonic scalar field dark energy dominated universe exhibits a bivalent future: depending on initial parameters can run either into a de Sitter exponential expansion or into a traversable future soft singularity followed by a contraction phase. We also include in the model (i) a tiny amount of radiation, (ii) baryonic matter (Ω{sub b}h{sup 2} = 0.022161, where the Hubble constant is fixed as h = 0.706) and (iii) cold dark matter (CDM). Out of a variety of six types of evolutions arising in a more subtle classification, we identify two in which in the past the scalar field effectively degenerates intomore » a dust (its pressure drops to an insignificantly low negative value). These are the evolutions of type IIb converging to de Sitter and type III hitting the future soft singularity. We confront these background evolutions with various cosmological tests, including the supernova type Ia Union 2.1 data, baryon acoustic oscillation distance ratios, Hubble parameter-redshift relation and the cosmic microwave background (CMB) acoustic scale. We determine a subset of the evolutions of both types which at 1σ confidence level are consistent with all of these cosmological tests. At perturbative level we derive the CMB temperature power spectrum to find the best agreement with the Planck data for Ω{sub CDM} = 0.22. The fit is as good as for the ΛCDM model at high multipoles, but the power remains slightly overestimated at low multipoles, for both types of evolutions. The rest of the CDM is effectively generated by the tachyonic field, which in this sense acts as a combined dark energy and dark matter model.« less

Hydrogen production by photoelectrolytic decomposition of H2O using solar energy

NASA Technical Reports Server (NTRS)

Rauh, R. D.; Alkaitis, S. A.; Buzby, J. M.; Schiff, R.

1980-01-01

Photoelectrochemical systems for the efficient decomposition of water are discussed. Semiconducting d band oxides which would yield the combination of stability, low electron affinity, and moderate band gap essential for an efficient photoanode are sought. The materials PdO and Fe-xRhxO3 appear most likely. Oxygen evolution yields may also be improved by mediation of high energy oxidizing agents, such as CO3(-). Examination of several p type semiconductors as photocathodes revealed remarkable stability for p-GaAs, and also indicated p-CdTe as a stable H2 photoelectrode. Several potentially economical schemes for photoelectrochemical decomposition of water were examined, including photoelectrochemical diodes and two stage, four photon processes.

Fluid evolution during burial and Variscan deformation in the Lower Devonian rocks of the High-Ardenne slate belt (Belgium): sources and causes of high-salinity and C-O-H-N fluids

NASA Astrophysics Data System (ADS)

Kenis, I.; Muchez, Ph.; Verhaert, G.; Boyce, A.; Sintubin, M.

2005-08-01

Fluid inclusions in quartz veins of the High-Ardenne slate belt have preserved remnants of prograde and retrograde metamorphic fluids. These fluids were examined by petrography, microthermometry and Raman analysis to define the chemical and spatial evolution of the fluids that circulated through the metamorphic area of the High-Ardenne slate belt. The earliest fluid type was a mixed aqueous/gaseous fluid (H2O-NaCl-CO2-(CH4-N2)) occurring in growth zones and as isolated fluid inclusions in both the epizonal and anchizonal part of the metamorphic area. In the central part of the metamorphic area (epizone), in addition to this mixed aqueous/gaseous fluid, primary and isolated fluid inclusions are also filled with a purely gaseous fluid (CO2-N2-CH4). During the Variscan orogeny, the chemical composition of gaseous fluids circulating through the Lower Devonian rocks in the epizonal part of the slate belt, evolved from an earlier CO2-CH4-N2 composition to a later composition enriched in N2. Finally, a late, Variscan aqueous fluid system with a H2O-NaCl composition migrated through the Lower Devonian rocks. This latest type of fluid can be observed in and outside the epizonal metamorphic part of the High-Ardenne slate belt. The chemical composition of the fluids throughout the metamorphic area, shows a direct correlation with the metamorphic grade of the host rock. In general, the proportion of non-polar species (i.e. CO2, CH4, N2) with respect to water and the proportion of non-polar species other than CO2 increase with increasing metamorphic grade within the slate belt. In addition to this spatial evolution of the fluids, the temporal evolution of the gaseous fluids is indicative for a gradual maturation due to metamorphism in the central part of the basin. In addition to the maturity of the metamorphic fluids, the salinity of the aqueous fluids also shows a link with the metamorphic grade of the host-rock. For the earliest and latest fluid inclusions in the anchizonal part of the High-Ardenne slate belt the salinity varies respectively between 0 and 3.5 eq.wt% NaCl and between 0 and 2.7 eq.wt% NaCl, while in the epizonal part the salinity varies between 0.6 and 17 eq.wt% NaCl and between 3 and 10.6 eq.wt% for the earliest and latest aqueous fluid inclusions, respectively. Although high salinity fluids are often attributed to the original sedimentary setting, the increasing salinity of the fluids that circulated through the Lower Devonian rocks in the High-Ardenne slate belt can be directly attributed to regional metamorphism. More specifically the salinity of the primary fluid inclusions is related to hydrolysis reactions of Cl-bearing minerals during prograde metamorphism, while the salinity of the secondary fluid inclusions is rather related to hydration reactions during retrograde metamorphism. The temporal and spatial distribution of the fluids in the High-Ardenne slate belt are indicative for a closed fluid flow system present in the Lower Devonian rocks during burial and Variscan deformation, where fluids were in thermal and chemical equilibrium with the host rock. Such a closed fluid flow system is confirmed by stable isotope study of the veins and their adjacent host rock for which uniform δ180 values of both the veins and their host rock demonstrate a rock-buffered fluid flow system.

Continuing evolution of H9N2 avian influenza virus in South Korea

USDA-ARS?s Scientific Manuscript database

The H9N2 low pathogenic avian influenza (LPAI) has caused great economic losses in Korean poultry industry since the first outbreak in 1996. Although the hemagglutinin gene of early H9N2 viruses were closely related to Chinese Y439-like lineage virus, it evolved into a unique Korean lineage after ...

Poultry vaccination directed evolution of H9N2 low pathogenicity avian influenza viruses in Korea

USDA-ARS?s Scientific Manuscript database

Significant economic losses in the poultry industries have resulted from H9N2 low pathogenic avian influenza virus infections across North Africa, the Middle East and Asia. The present study investigated the evolutionary dynamics of H9N2 viruses circulating in Korea from 1996 to 2012. Our analysis o...

A chemical model for the interstellar medium in galaxies

NASA Astrophysics Data System (ADS)

Bovino, S.; Grassi, T.; Capelo, Pedro R.; Schleicher, D. R. G.; Banerjee, R.

2016-05-01

Aims: We present and test chemical models for three-dimensional hydrodynamical simulations of galaxies. We explore the effect of changing key parameters such as metallicity, radiation, and non-equilibrium versus equilibrium metal cooling approximations on the transition between the gas phases in the interstellar medium. Methods: The microphysics was modelled by employing the public chemistry package KROME, and the chemical networks were tested to work in a wide range of densities and temperatures. We describe a simple H/He network following the formation of H2 and a more sophisticated network that includes metals. Photochemistry, thermal processes, and different prescriptions for the H2 catalysis on dust are presented and tested within a one-zone framework. The resulting network is made publicly available on the KROME webpage. Results: We find that employing an accurate treatment of the dust-related processes induces a faster HI-H2 transition. In addition, we show when the equilibrium assumption for metal cooling holds and how a non-equilibrium approach affects the thermal evolution of the gas and the HII-HI transition. Conclusions: These models can be employed in any hydrodynamical code via an interface to KROME and can be applied to different problems including isolated galaxies, cosmological simulations of galaxy formation and evolution, supernova explosions in molecular clouds, and the modelling of star-forming regions. The metal network can be used for a comparison with observational data of CII 158 μm emission both for high-redshift and for local galaxies.

Evolution-informed forecasting of seasonal influenza A (H3N2)

PubMed Central

Du, Xiangjun; King, Aaron A.; Woods, Robert J.; Pascual, Mercedes

2018-01-01

Inter-pandemic or seasonal influenza exacts an enormous annual burden both in terms of human health and economic impact. Incidence prediction ahead of season remains a challenge largely because of the virus’ antigenic evolution. We propose here a forecasting approach that incorporates evolutionary change into a mechanistic epidemiological model. The proposed models are simple enough that their parameters can be estimated from retrospective surveillance data. These models link amino-acid sequences of hemagglutinin epitopes with a transmission model for seasonal H3N2 influenza, also informed by H1N1 levels. With a monthly time series of H3N2 incidence in the United States over 10 years, we demonstrate the feasibility of prediction ahead of season and an accurate real-time forecast for the 2016/2017 influenza season. PMID:29070700

Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4.

PubMed

Long, Ran; Li, Yu; Liu, Yan; Chen, Shuangming; Zheng, Xusheng; Gao, Chao; He, Chaohua; Chen, Nanshan; Qi, Zeming; Song, Li; Jiang, Jun; Zhu, Junfa; Xiong, Yujie

2017-03-29

Photocatalytic conversion of CO 2 to CH 4 , a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H 2 by side reactions. The design of catalytic sites for CO 2 adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO 2 to CH 4 by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO 2 -to-CH 4 conversion: (1) providing the paired Cu-Pd sites for the enhanced CO 2 adsorption and the suppressed H 2 evolution; and (2) elevating the d-band center of Cu sites for the improved CO 2 activation. As a result, the Pd 7 Cu 1 -TiO 2 photocatalyst achieves the high selectivity of 96% for CH 4 production with a rate of 19.6 μmol g cat -1 h -1 . This work provides fresh insights into the catalytic site design for selective photocatalytic CO 2 conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction

DOE PAGES

Favaro, Marco; Drisdell, Walter S.; Marcus, Matthew A.; ...

2016-12-27

The oxygen evolution reaction (OER) is a critical component of industrial processes such as electrowinning of metals and the chlor-alkali process. It also plays a central role in the development of a renewable energy field for generation a solar fuels by providing both the protons and electrons needed to generate fuels such as H 2 or reduced hydrocarbons from CO 2. To improve these processes, it is necessary to expand the fundamental understanding of catalytically active species at low overpotential, which will further the development of electrocatalysts with high activity and durability. In this context, performing experimental investigations of themore » electrocatalysts under realistic working regimes (i.e., under operando conditions) is of crucial importance. In this paper, we study a highly active quinary transition-metal-oxide-based OER electrocatalyst by means of operando ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy performed at the solid/liquid interface. We observe that the catalyst undergoes a clear chemical-structural evolution as a function of the applied potential with Ni, Fe, and Co oxyhydroxides comprising the active catalytic species. Finally, while CeO 2 is redox inactive under catalytic conditions, its influence on the redox processes of the transition metals boosts the catalytic activity at low overpotentials, introducing an important design principle for the optimization of electrocatalysts and tailoring of high-performance materials.« less

Structural differences between the avian and human H7N9 hemagglutinin proteins are attributable to modifications in salt bridge formation: a computational study with implications in viral evolution.

PubMed

Cueno, Marni E; Imai, Kenichi; Tamura, Muneaki; Ochiai, Kuniyasu

2013-01-01

Influenza A hemagglutinin (HA) is a homotrimeric glycoprotein composed of a fibrous globular stem supporting a globular head containing three sialic acid binding sites responsible for infection. The H7N9 strain has consistently infected an avian host, however, the novel 2013 strain is now capable of infecting a human host which would imply that the HA in both strains structurally differ. A better understanding of the structural differences between the avian and human H7N9 strains may shed light into viral evolution and transmissibility. In this study, we elucidated the structural differences between the avian and human H7N9 strains. Throughout the study, we generated HA homology models, verified the quality of each model, superimposed HA homology models to determine structural differences, and, likewise, elucidated the probable cause for these structural differences. We detected two different types of structural differences between the novel H7N9 human and representative avian strains, wherein, one type (Pattern-1) showed three non-overlapping regions while the other type (Pattern-2) showed only one non-overlapping region. In addition, we found that superimposed HA homology models exhibiting Pattern-1 contain three non-overlapping regions designated as: Region-1 (S1571-A1601); Region-3 (R2621-S2651); and Region-4 (S2701-D2811), whereas, superimposed HA homology models showing Pattern-2 only contain one non-overlapping region designated as Region-2 (S1371-S1451). We attributed the two patterns we observed to either the presence of salt bridges involving the E1141 residue or absence of the R1411:D771 salt bridge. Interestingly, comparison between the human H7N7 and H7N9 HA homology models showed high structural similarity. We propose that the putative absence of the R1411:D771 salt bridge coupled with the putative presence of the E1141:R2621 and E1141:K2641 salt bridges found in the 2013 H7N9 HA homology model is associated to human-type receptor binding. This highlights the possible significance of HA salt bridge formation modifications in viral infectivity, immune escape, transmissibility and evolution.

3-Phenylpropanoic acid-based phosphotyrosine (pTyr) mimetics: hit evolution to a novel orally active protein tyrosine phosphatase 1B (PTP1B) inhibitor.

PubMed

Tang, Yan-Bo; Liu, Jun-Zheng; Zhang, Shu-En; Du, Xin; Nie, Feilin; Tian, Jin-Ying; Ye, Fei; Huang, Kai; Hu, Jin-Ping; Li, Yan; Xiao, Zhiyan

2014-05-01

Protein tyrosine phosphatase 1B (PTP1B) is a promising therapeutic target for type 2 diabetes. Herein, we report the evolution of a previously identified 3-phenylpropanoic acid-based PTP1B inhibitor to an orally active lead compound. A series of 3-phenylpropanoic acid-based PTP1B inhibitors were synthesized, and three of them, 3-(4-(9H-carbazol-9-yl)phenyl)-5-(3,5-di-tert-butyl-4-methoxyphenyl)-5-oxopentanoic acid (9), 3-(4-(9H-carbazol-9-yl)phenyl)-5-(4'-bromo-[1,1'-biphenyl]-4-yl)-5-oxopentanoic acid (10) and 3-(4-(9H-carbazol-9-yl)-2-fluorophenyl)-5-(4-cyclohexylphenyl)-5-oxopentanoic acid (16), showed IC50 values at sub-micromolar level. Further in vivo evaluation indicated the sodium salt of 9 not only exhibited significant insulin-sensitizing and hypoglycemia effects, but also decreased the serum levels of triglyceride and total cholesterol in high-fat-diet-induced insulin resistance model mice. Preliminary in vivo pharmacokinetic studies on the sodium salt of 9 revealed its pharmacokinetic profile after oral administration in rats. These results provide proof-of-concept for the dual effects of PTP1B inhibitors on both glucose and lipid metabolisms. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A unique mode of tissue oxygenation and the adaptive radiation of teleost fishes.

PubMed

Randall, D J; Rummer, J L; Wilson, J M; Wang, S; Brauner, C J

2014-04-15

Teleost fishes constitute 95% of extant aquatic vertebrates, and we suggest that this is related in part to their unique mode of tissue oxygenation. We propose the following sequence of events in the evolution of their oxygen delivery system. First, loss of plasma-accessible carbonic anhydrase (CA) in the gill and venous circulations slowed the Jacobs-Stewart cycle and the transfer of acid between the plasma and the red blood cells (RBCs). This ameliorated the effects of a generalised acidosis (associated with an increased capacity for burst swimming) on haemoglobin (Hb)-O2 binding. Because RBC pH was uncoupled from plasma pH, the importance of Hb as a buffer was reduced. The decrease in buffering was mediated by a reduction in the number of histidine residues on the Hb molecule and resulted in enhanced coupling of O2 and CO2 transfer through the RBCs. In the absence of plasma CA, nearly all plasma bicarbonate ultimately dehydrated to CO2 occurred via the RBCs, and chloride/bicarbonate exchange was the rate-limiting step in CO2 excretion. This pattern of CO2 excretion across the gills resulted in disequilibrium states for CO2 hydration/dehydration reactions and thus elevated arterial and venous plasma bicarbonate levels. Plasma-accessible CA embedded in arterial endothelia was retained, which eliminated the localized bicarbonate disequilibrium forming CO2 that then moved into the RBCs. Consequently, RBC pH decreased which, in conjunction with pH-sensitive Bohr/Root Hbs, elevated arterial oxygen tensions and thus enhanced tissue oxygenation. Counter-current arrangement of capillaries (retia) at the eye and later the swim bladder evolved along with the gas gland at the swim bladder. Both arrangements enhanced and magnified CO2 and acid production and, therefore, oxygen secretion to those specialised tissues. The evolution of β-adrenergically stimulated RBC Na(+)/H(+) exchange protected gill O2 uptake during stress and further augmented plasma disequilibrium states for CO2 hydration/dehydration. Finally, RBC organophosphates (e.g. NTP) could be reduced during hypoxia to further increase Hb-O2 affinity without compromising tissue O2 delivery because high-affinity Hbs could still adequately deliver O2 to the tissues via Bohr/Root shifts. We suggest that the evolution of this unique mode of tissue O2 transfer evolved in the Triassic/Jurassic Period, when O2 levels were low, ultimately giving rise to the most extensive adaptive radiation of extant vertebrates, the teleost fishes.

Boosting heterosubtypic neutralization antibodies in recipients of 2009 pandemic H1N1 influenza vaccine.

PubMed

Qiu, Chao; Huang, Yang; Wang, Qian; Tian, Di; Zhang, Wanju; Hu, Yunwen; Yuan, Zhenghong; Zhang, Xiaoyan; Xu, Jianqing

2012-01-01

A mass vaccination has been implemented to prevent the spread of 2009 pandemic influenza virus in China. Highly limited information is available on whether this vaccine induces cross-reactive neutralization antibodies against other subtypes of influenza viruses. We employed pseudovirus-based assays to analyze heterosubtypic neutralization responses in serum samples of 23 recipients of 2009 pandemic influenza vaccine. One dose of pandemic vaccine not only stimulated good neutralization antibodies against cognate influenza virus 2009 influenza A (H1N1), but also raised broad cross-reactive neutralization activities against seasonal H3N2 and highly pathogenic avian influenza virus H5N1 and lesser to H2N2. The cross-reactive neutralization activities were completely abolished after the removal of immunoglobin G (IgG). In contrast, H1N1 vaccination alone in influenza-naive mice elicited only vigorous homologous neutralizing activities but not cross-reactive neutralization activities. Our data suggest that the cross-reactive neutralization epitopes do exist in this vaccine and could elicit significant cross-reactive neutralizing IgG antibodies in the presence of preexisting responses. The exposure to H1N1 vaccine is likely to modify the hierarchical order of preexisting immune responses to influenza viruses. These findings provide insights into the evolution of human immunity to influenza viruses after experiencing multiple influenza virus infections and vaccinations.

INFRARED STUDY OF UV/EUV IRRADIATION OF NAPHTHALENE IN H2O+NH3 ICE

NASA Astrophysics Data System (ADS)

Chen, Y.-J.; Nuevo, M.; Yeh, F.-C.; Yih, T.-S.; Sun, W.-H.; Ip, W.-H.; Fung, H.-S.; Lee, Y.-Y.; Wu, C.-Y. R.

We have carried out photon irradiation study of naphthalene (C10H8), the smallest polycyclic aromatic hydrocarbon (PAH) in water and ammonia ice mixtures. Photons provided by a synchrotron radiation light source in two broad-band energy ranges in the ultraviolet/near extreme ultraviolet (4-20 eV) and the extreme ultraviolet (13-45 eV) ranges were used for the irradiation of H2O+NH3+C10H8 = 1:1:1 ice mixtures at 15K. We could identify several photo-products, namely CH4, C2H6, C3H8, CO, CO2, HNCO, OCN-, and probably quinoline (C9H7N) and phenanthridine (C13H9N). We found that the light hydrocarbons are preferably produced for the ice mixture subjected to 4-20 eV photons. However, the production yields of CO, CO2, and OCN- species seem to be higher for the mixture subjected to EUV photons (13-45 eV). Therefore, naphthalene and its photo-products appear to be more efficiently destroyed when high energy photons (E > 20 eV) are used. This has important consequences on the photochemical evolution of PAHs in astrophysical environments.

Epidemiology, ecology and gene pool of influenza A virus in Egypt: will Egypt be the epicentre of the next influenza pandemic?

PubMed

Abdelwhab, E M; Abdel-Moneim, Ahmed S

2015-01-01

Outside Asia, Egypt is considered to be an influenza H5N1 epicentre and presents a far greater pandemic risk than other countries. The long-term endemicity of H5N1 and the recent emergence of H9N2 in poultry call attention to the need for unravelling the epidemiology, ecology and highly diverse gene pool of influenza A virus (IAV) in Egypt which is the aim of this review. Isolation of a considerable number of IAV subtypes from several avian and mammalian hosts was described. Co-infections of poultry with H5N1 and H9N2 and subclinical infections of pigs and humans with H1N1 and H5N1 may raise the potential for the reassortment of these viruses. Moreover, the adjustment of IAV genomes, particularly H5N1, to optimize their evolution toward efficient transmission in human is progressing in Egypt. Understanding the present situation of influenza viruses in Egypt will help in the control of the disease and can potentially prevent a possible pandemic.

Crystallization behaviour of hydroxide cobalt carbonates by aging: Environmental implications.

NASA Astrophysics Data System (ADS)

González-López, Jorge; Fernández-González, Angeles; Jimenez, Amalia

2014-05-01

Cobalt is a naturally occurring element widely distributed in water, sediments and air that is essential for living species, since it is a component of B12 vitamin and it is also a strategic and critical element used in a number of commercial, industrial and military applications. However, relatively high accumulations of cobalt in environment can be toxic for human and animal health. Cobalt usually occurs as Co2+ and Co3+ in aqueous solutions, where Co2+ is the most soluble and hence its mobility in water is higher. The study of the precipitation of cobalt carbonates is of great interest due to the abundance of carbonate minerals in contact with surface water and groundwater which can be polluted with Co2+. Previous works have demonstrated that the formation of Co-bearing calcium carbonates and Co-rich low crystallinity phases takes place at ambient conditions. With the aim of investigating the crystallization behavior of Co- bearing carbonates at ambient temperature, macroscopic batch-type experiments have been carried out by mixing aqueous solutions of CoCl2 (0.05M) and Na2CO3 (0.05M) during increasing reaction times (5 minutes and 1, 5, 24, 48, 96, 168, 720 and 1440 hours). The main goals of this work were (i) to analyse the physicochemical evolution of the system and (ii) to study the evolution of the crystallinity of the solid phases during aging. After a given reaction period, pH, alkalinity and dissolved Co2+ in the aqueous solutions were analysed. The evolution of the morphology and chemical composition of the solids with aging time was examined by SEM and TEM. The precipitates were also analyzed by X-ray powder diffraction (XRD) and the crystallinity degree was followed by the intensity and the full width at high medium (FWHM) of the main peaks. The results show that a low crystallinity phase was obtained at the very beginning of aging. This phase evolves progressively to form hydroxide carbonate cobalt (Co2CO3(OH)2) which crystallize with the spatial group P21/a (monoclinic system) after about 4 days. At the same time, the most important fall of cobalt content takes place, but pH and alkalinity values do not show significant changes. The evolution of the aqueous solutions is closely related to the increases of crystallinity degree. TEM study confirms the evolution of the shape of crystals, which exhibit platelet morphology at the end of aging time.

PAH-Mineral Interactions. A Laboratory Approach to Astrophysical Catalysis

NASA Astrophysics Data System (ADS)

Adolfo Cruz Diaz, Gustavo; Mattioda, Andrew

2017-06-01

Polycyclic Aromatic Hydrocarbon (PAH) molecules carry the infrared emission features which dominate the spectra of most galactic and extragalactic sources. Our study investigates the chemical evolution, chemical properties, physical properties, thermal stability, and photostability of samples produced from the UV-irradiation of simulated mineral dust grains coated with aromatics and astrobiologically relevant ices, using infrared spectroscopy. We investigate the chemical evolution of aromatic organics via anhydrous (no H2O ice) and hydrous (H2O ice) mechanisms. The anhydrous mechanism involves UV-induced catalytic reactions between organics and dense-cloud mineral grains, whereas the hydrous mechanism incorporates H2O-rich ice mixtures with the minerals and organics. These investigations identify the chemical and physical interactions occurring between the organic species, the dust grains and water-rich ices.These laboratory simulations also generate observable IR spectroscopic parameters for future astronomical observations with infrared telescopes such as SOFIA and JWST as well as provide empirical parameters for input into astronomical models of the early stages of planetary formation. These studies give us a deeper understanding of the potential catalytic pathways mineral surfaces provide and a deeper understanding of the role of ice-organic compositions in the chemical reaction pathways and how these processes fit into the formation of new planetary systems.In order to achieve these goals we use the Harrick ‘Praying Mantis’ Diffuse Reflectance Accessory (DRIFTS), which allows FTIR measurements of dust samples under ambient conditions by measuring the light scattered by the dust sample. We have also incorporated a low -temperature reaction chamber permitting the DRIFTS measurements at low temperatures and high-vacuum. This set-up permits the analysis of the solid particles surfaces revealing the chemical species adsorbed as well as their chemical evolution via the introduction of reactant gases, UV irradiation, temperature change, etc.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

[Genetic evolution and substitution frequency of avian influenza virus HA gene in chicken H9N2 subtype in China in the last 20 years].

PubMed

Meng, Fang; Xu, Huaiying; Zhang, Wei; Huang, Dihai; Zhang, Zaihui; Liu, Xia; Chang, Weishan; Qin, Zhuoming

2016-01-04

Low pathogenic avian influenza (LPAI) H9N2 subtype virus has been prevalent in domestic poultry in China over two decades. This study was to determine the genetic evolution trend of H9N2 avian influenza virus (AIV) under immune pressure of vaccine. H9 HA sequences of 40 isolates from the present study and 136 pandemic strains and 7 classical strains from China downloaded from GenBank, were genetically analyzed to determine evolution, molecular characteristic, and mutation frequency. Phylogenetic trees analysis suggested that H9N2 subtypes AIV could be clustered into 5 distinct lineages: G1-like, BJ94-like, Y280-like, S2-like and Americans lineages. Most H9N2 isolates in 2005-2014 belonged to S2-like sub-genotype, suggesting that this genotype was the dominate isolates in China. Further more, comparison based on the amino acid sequence showed that different lineages have their distinct characteristics, and significant accumulations of amino acid variation were also found. In addition, in comparison with reference Ck/BJ/1/1994 HA gene, average annual substitution rates of H9N2 pandemic strain nucleotide and amino acid were 5.73 x 10⁻³ and 4.25 x 10⁻³ from 1994 to 2014, respectively. Substitution rate during 2011-2014 were 6.35 x 10⁻³ and 5.32 x 10⁻³, higher than that during the period of 2006-2010 (5.22 x 10⁻³ and 3.70 x 10⁻³) and even much higher than that during the 1999-2005 (0.74 x 10⁻³ and 0.50 x 10⁻³), when the vaccines were initially applied in the field. Overall, these data indicate that the mismatch between H9N2 vaccine strains and pandemic strains drives the virus to quickly mutate.

Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

PubMed

Zhang, Zhicheng; Liu, Guigao; Cui, Xiaoya; Chen, Bo; Zhu, Yihan; Gong, Yue; Saleem, Faisal; Xi, Shibo; Du, Yonghua; Borgna, Armando; Lai, Zhuangchai; Zhang, Qinghua; Li, Bing; Zong, Yun; Han, Yu; Gu, Lin; Zhang, Hua

2018-06-07

The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm -2 , and the turnover frequency reaches 18.63 H 2 s -1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Emergence and evolution of avian H5N2 influenza viruses in chickens in Taiwan.

PubMed

Lee, Chang-Chun David; Zhu, Huachen; Huang, Pei-Yu; Peng, Liuxia; Chang, Yun-Cheng; Yip, Chun-Hung; Li, Yao-Tsun; Cheung, Chung-Lam; Compans, Richard; Yang, Chinglai; Smith, David K; Lam, Tommy Tsan-Yuk; King, Chwan-Chuen; Guan, Yi

2014-05-01

Sporadic activity by H5N2 influenza viruses has been observed in chickens in Taiwan from 2003 to 2012. The available information suggests that these viruses were generated by reassortment between a Mexican-like H5N2 virus and a local enzootic H6N1 virus. Yet the origin, prevalence, and pathogenicity of these H5N2 viruses have not been fully defined. Following the 2012 highly pathogenic avian influenza (HPAI) outbreaks, surveillance was conducted from December 2012 to July 2013 at a live-poultry wholesale market in Taipei. Our findings showed that H5N2 and H6N1 viruses cocirculated at low levels in chickens in Taiwan. Phylogenetic analyses revealed that all H5N2 viruses had hemagglutinin (HA) and neuraminidase (NA) genes derived from a 1994 Mexican-like virus, while their internal gene complexes were incorporated from the enzootic H6N1 virus lineage by multiple reassortment events. Pathogenicity studies demonstrated heterogeneous results even though all tested viruses had motifs (R-X-K/R-R) supportive of high pathogenicity. Serological surveys for common subtypes of avian viruses confirmed the prevalence of the H5N2 and H6N1 viruses in chickens and revealed an extraordinarily high seroconversion rate to an H9N2 virus, a subtype that is not found in Taiwan but is prevalent in mainland China. These findings suggest that reassortant H5N2 viruses, together with H6N1 viruses, have become established and enzootic in chickens throughout Taiwan and that a large-scale vaccination program might have been conducted locally that likely led to the introduction of the 1994 Mexican-like virus to Taiwan in 2003. H5N2 avian influenza viruses first appeared in chickens in Taiwan in 2003 and caused a series of outbreaks afterwards. Phylogenetic analyses show that the chicken H5N2 viruses have H5 and N2 genes that are closely related to those of a vaccine strain originating from Mexico in 1994, while the contemporary duck H5N2 viruses in Taiwan belong to the Eurasian gene pool. The unusually high similarity of the chicken H5N2 viruses to the Mexican vaccine strain suggests that these viruses might have been introduced to Taiwan by using inadequately inactivated or attenuated vaccines. These chicken H5N2 viruses are developing varying levels of pathogenicity that could lead to significant consequences for the local poultry industry. These findings emphasize the need for strict quality control and competent oversight in the manufacture and usage of avian influenza virus vaccines and indicate that alternatives to widespread vaccination may be desirable.

Emergence and Evolution of Avian H5N2 Influenza Viruses in Chickens in Taiwan

PubMed Central

Lee, Chang-Chun David; Zhu, Huachen; Huang, Pei-Yu; Peng, Liuxia; Chang, Yun-Cheng; Yip, Chun-Hung; Li, Yao-Tsun; Cheung, Chung-Lam; Compans, Richard; Yang, Chinglai; Smith, David K.; Lam, Tommy Tsan-Yuk

2014-01-01

ABSTRACT Sporadic activity by H5N2 influenza viruses has been observed in chickens in Taiwan from 2003 to 2012. The available information suggests that these viruses were generated by reassortment between a Mexican-like H5N2 virus and a local enzootic H6N1 virus. Yet the origin, prevalence, and pathogenicity of these H5N2 viruses have not been fully defined. Following the 2012 highly pathogenic avian influenza (HPAI) outbreaks, surveillance was conducted from December 2012 to July 2013 at a live-poultry wholesale market in Taipei. Our findings showed that H5N2 and H6N1 viruses cocirculated at low levels in chickens in Taiwan. Phylogenetic analyses revealed that all H5N2 viruses had hemagglutinin (HA) and neuraminidase (NA) genes derived from a 1994 Mexican-like virus, while their internal gene complexes were incorporated from the enzootic H6N1 virus lineage by multiple reassortment events. Pathogenicity studies demonstrated heterogeneous results even though all tested viruses had motifs (R-X-K/R-R) supportive of high pathogenicity. Serological surveys for common subtypes of avian viruses confirmed the prevalence of the H5N2 and H6N1 viruses in chickens and revealed an extraordinarily high seroconversion rate to an H9N2 virus, a subtype that is not found in Taiwan but is prevalent in mainland China. These findings suggest that reassortant H5N2 viruses, together with H6N1 viruses, have become established and enzootic in chickens throughout Taiwan and that a large-scale vaccination program might have been conducted locally that likely led to the introduction of the 1994 Mexican-like virus to Taiwan in 2003. IMPORTANCE H5N2 avian influenza viruses first appeared in chickens in Taiwan in 2003 and caused a series of outbreaks afterwards. Phylogenetic analyses show that the chicken H5N2 viruses have H5 and N2 genes that are closely related to those of a vaccine strain originating from Mexico in 1994, while the contemporary duck H5N2 viruses in Taiwan belong to the Eurasian gene pool. The unusually high similarity of the chicken H5N2 viruses to the Mexican vaccine strain suggests that these viruses might have been introduced to Taiwan by using inadequately inactivated or attenuated vaccines. These chicken H5N2 viruses are developing varying levels of pathogenicity that could lead to significant consequences for the local poultry industry. These findings emphasize the need for strict quality control and competent oversight in the manufacture and usage of avian influenza virus vaccines and indicate that alternatives to widespread vaccination may be desirable. PMID:24623422