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.

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.

Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

PubMed

Pan, Yun-xiang; Zhuang, Huaqiang; Hong, Jindui; Fang, Zheng; Liu, Hai; Liu, Bin; Huang, Yizhong; Xu, Rong

2014-09-01

In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 μmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 μmol h(-1)), Pt/Ga2O3 (0.12 μmol h(-1)), and Pt/In2O3 (0.05 μmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Efficient whole cell biocatalyst for formate-based hydrogen production.

PubMed

Kottenhahn, Patrick; Schuchmann, Kai; Müller, Volker

2018-01-01

Molecular hydrogen (H 2 ) is an attractive future energy carrier to replace fossil fuels. Biologically and sustainably produced H 2 could contribute significantly to the future energy mix. However, biological H 2 production methods are faced with multiple barriers including substrate cost, low production rates, and low yields. The C1 compound formate is a promising substrate for biological H 2 production, as it can be produced itself from various sources including electrochemical reduction of CO 2 or from synthesis gas. Many microbes that can produce H 2 from formate have been isolated; however, in most cases H 2 production rates cannot compete with other H 2 production methods. We established a formate-based H 2 production method utilizing the acetogenic bacterium Acetobacterium woodii . This organism can use formate as sole energy and carbon source and possesses a novel enzyme complex, the hydrogen-dependent CO 2 reductase that catalyzes oxidation of formate to H 2 and CO 2 . Cell suspensions reached specific formate-dependent H 2 production rates of 71 mmol g protein -1 h -1 (30.5 mmol g CDW -1 h -1 ) and maximum volumetric H 2 evolution rates of 79 mmol L -1 h -1 . Using growing cells in a two-step closed batch fermentation, specific H 2 production rates reached 66 mmol g CDW -1 h -1 with a volumetric H 2 evolution rate of 7.9 mmol L -1  h -1 . Acetate was the major side product that decreased the H 2 yield. We demonstrate that inhibition of the energy metabolism by addition of a sodium ionophore is suitable to completely abolish acetate formation. Under these conditions, yields up to 1 mol H 2 per mol formate were achieved. The same ionophore can be used in cultures utilizing formate as specific switch from a growing phase to a H 2 production phase. Acetobacterium woodii reached one of the highest formate-dependent specific H 2 productivity rates at ambient temperatures reported so far for an organism without genetic modification and converted the substrate exclusively to H 2 . This makes this organism a very promising candidate for sustainable H 2 production and, because of the reversibility of the A. woodii enzyme, also a candidate for reversible H 2 storage.

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

KINETIC STUDIES RELATED TO THE LIMB (LIMESTONE INJECTION MULTISTAGE BURNER) BURNER

EPA Science Inventory

The report gives results of theoretical and experimental studies of subjects related to the limestone injection multistage burner (LIMB). The main findings include data on the rate of evolution of H2S from different coals and on the dependence of the rate of evolution on the dist...

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.

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.

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.

Hydrothermal growth of two dimensional hierarchical MoS2 nanospheres on one dimensional CdS nanorods for high performance and stable visible photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Chava, Rama Krishna; Do, Jeong Yeon; Kang, Misook

2018-03-01

The visible photocatalytic H2 production from water splitting considered as a clean and renewable energy source could solve the problem of greenhouse gas emission from fossil fuels. Despite tremendous efforts, the development of cost effective, highly efficient and more stable visible photocatalysts for splitting of water remains a great challenge. Here, we report the heteronanostructures consisting of hierarchical MoS2 nanospheres grown on 1D CdS nanorods referred to as CdS-MoS2 HNSs as a high performance visible photocatalyst for H2 evolution. The as-synthesized CdS-MoS2 HNSs exhibited ∼11 fold increment of H2 evolution rate when compared to pure CdS nanorods. This remarkable enhanced hydrogen evolution performance can be assigned to the positive synergetic effect from heteronanostructures formed between the CdS and MoS2 components which assist as an electron sink and source for abundant active edge sites and in turn increases the charge separation. This study presents a low-cost visible photocatalyst for solar energy conversion to achieve efficient H2.

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.

Facile synthesis of flake-like TiO2/C nano-composites for photocatalytic H2 evolution under visible-light irradiation

NASA Astrophysics Data System (ADS)

Yan, Baolin; Zhou, Juan; Liang, Xiaoyu; Song, Kainan; Su, Xintai

2017-01-01

The production of H2 by photocatalytic water splitting has become a promising approach for clean, economical, and renewable evolution of H2 by using solar energy. In spite of tremendous efforts, the present challenge for materials scientists is to build a highly active photocatalytic system with high efficiency and low cost. Here we report a facile method for the preparation of TiO2/C nano-flakes, which was used as an efficient visible-light photocatalyst for H2 evolution. This composite material was prepared by using a phase-transfer strategy combined with salt-template calcination treatment. The results showed that anatase TiO2 nanoparticles with the diameter of ∼10 nm were uniformly dispersed on the carbon nano-flakes. In addition, the samples prepared at 600 °C (denoted as T600) endowed a larger surface area of 196 m2 g-1 and higher light absorption, resulting in enhanced photocatalytic activity. Further, the T600 product reached a high H2 production rate of 57.2 μmol h-1 under visible-light irradiation. This unusual photocatalytic activity arose from the positive synergetic effect between the TiO2 and carbon in this hybrid catalyst. This work highlights the potential of TiO2/C nano-flakes in the field of photocatalytic H2 evolution under visible-light irradiation.

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.

Tuning Cu dopant of Zn 0.5 Cd 0.5 S nanocrystals enables high-performance photocatalytic H 2 evolution from water splitting under visible-light irradiation

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

Mei, Zongwei; Zhang, Bingkai; Zheng, Jiaxin

2016-08-01

Cu-doping into Zn1-xCdxS can greatly enhance the photocatalytic H2 evolution from water splitting under visible-light irradiation. However, it is still controversial for how the Cu-dopant improves this performance. Here, we report that appropriate Cu-doped Zn0.5Cd0.5S nanocrystals reach 21.4 mmol/h/g of H2 evolution rate without cocatalyst in the visible-light region, which is also 2.8 times as high as that of the undoped counterpart, and the corresponding apparent quantum efficiency is 18.8% at 428 nm. It is firstly confirmed that the Cu2+ changes into Cu+ after being doped by soft X-ray absorption spectroscopy (sXAS). We theoretically propose that the transformation of 2Cu2+more » to 2Cu+ results in one adjacent S2- vacancy (VS) in host during the doping process, while the Cu+-dopant and VS attract the photoexcited holes and electrons, respectively. Accordingly, the photocatalytic activity is improved due to the enhanced separation of photoexcited carriers accompanied with the enhanced light absorption resulting from the Cu+-dopant and 2Cu+/VS complex as possible active site for photocatalytic H2 evolution.« less

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.

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.

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.

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

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

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

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.

Phonon-mediated nuclear spin relaxation in H2O

NASA Astrophysics Data System (ADS)

Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

2017-03-01

A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

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.

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.

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

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.

Temporal and Geographical Distribution of Adamantane-Resistant H1N1 Virus and The Evolution Tree of MP Gene Mutation

NASA Astrophysics Data System (ADS)

He, W.; Dong, G.

2016-12-01

The adamantanamine, a kind of M2 inhibitor, is globally used to treat the infection of Influenza A(H1N1). But for the past decade, the H1N1 influenza virus becomes significantly resistant to adamantanamine owing to the mutation on site 26, 27, 30, 31 and 34. This study collects a number of 14823 M2 protein sequences of H1N1 virus strains from NCBI range from 1918 to April 12, 2016. We statistics the mutation rate of different hosts, mutation sites, countries and years to find out the change of mutation rate. The result shows that 60.53% H1N1 influenza virus affected Human have the resistance to adamantanamine and the S31N mutation should be the main reason. We also find that the mutation rate of S31N raised from 23.33% to 88.76%. The second aspect in this study is analyzing the MP gene sequence of H1N1 influenza virus to find out the evolution of H1N1 according to MP protein. This study collecting a great number of M2 protein sequences to find out the mutation situation of H1N1 have a signification to the surveillance of drug resistance and have a bit of guidance on using the adamantanamine.

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.

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.

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.

One-pot Synthesis of CdS Irregular Nanospheres Hybridized with Oxygen-Incorporated Defect-Rich MoS2 Ultrathin Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Zhang, Shouwei; Yang, Hongcen; Gao, Huihui; Cao, Ruya; Huang, Jinzhao; Xu, Xijin

2017-07-19

Robust and highly active photocatalysts, CdS@MoS 2 , for hydrogen evolution were successfully fabricated by one-step growth of oxygen-incorporated defect-rich MoS 2 ultrathin nanosheets on the surfaces of CdS with irregular fissures. Under optimized experimental conditions, the CdS@MoS 2 displayed a quantum yield of ∼24.2% at 420 nm and the maximum H 2 generation rate of ∼17203.7 umol/g/h using Na 2 S-Na 2 SO 3 as sacrificial agents (λ ≥ 420 nm), which is ∼47.3 and 14.7 times higher than CdS (∼363.8 μmol/g/h) and 3 wt % Pt/CdS (∼1173.2 μmol/g/h), respectively, and far exceeds all previous hydrogen evolution reaction photocatalysts with MoS 2 as co-catalysts using Na 2 S-Na 2 SO 3 as sacrificial agents. Large volumes of hydrogen bubbles were generated within only 2 s as the photocatalysis started, as demonstrated by the photocatalytic video. The high hydrogen evolution activity is attributed to several merits: (1) the intimate heterojunctions formed between the MoS 2 and CdS can effectively enhance the charge transfer ability and retard the recombination of electron-hole pairs; and (2) the defects in the MoS 2 provide additional active S atoms on the exposed edge sites, and the incorporation of O reduces the energy barrier for H 2 evolution and increases the electric conductivity of the MoS 2 . Considering its low cost and high efficiency, this highly efficient hybrid photocatalysts would have great potential in energy-generation and environment-restoration fields.

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.

[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.

Synthesis and characterization of Cu2O/TiO2 photocatalysts for H2 evolution from aqueous solution with different scavengers

NASA Astrophysics Data System (ADS)

Li, Yanping; Wang, Baowei; Liu, Sihan; Duan, Xiaofei; Hu, Zongyuan

2015-01-01

A series of Cu2O/TiO2 photocatalysts with different molar fraction of Cu2O were prepared by a facile modified ethanol-induced approach followed by a calcination process. The chemical state of copper compound was proved to be cuprous oxide by the characterization of X-ray photoelectron spectra (XPS). Furthermore, these composite oxides were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption desorption and UV-vis techniques to study the morphologies, structures, and optical properties of the as-prepared samples. The results indicated that the photocatalytic activity of n-type TiO2 was significantly enhanced by combined with p-type Cu2O, due to the efficient p-n heterojunction. The p-n heterojunction between Cu2O and TiO2 can enhance visible-light adsorption, efficiently suppress charge recombination, improve interfacial charge transfer, and especially provide plentiful reaction active sites on the surface of photocatalyst. As a consequence, the prepared 2.5-Cu2O/TiO2 photocatalyst exhibited the highest photocatalytic activity for H2 evolution rate and reached 2048.25 μmol/(g h), which is 14.48 times larger than that of pure P25. The apparent quantum yield (AQY) of the 2.5-Cu2O/TiO2 sample at 365 nm was estimated to be 4.32%. In addition, the influence of different scavengers, namely methanol, anhydrous ethanol, ethylene glycol and glycerol, on the photocatalytic activity for H2 evolution rate was discussed.

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

[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.

Wrinkle-free atomically thin CdS nanosheets for photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Pan, Ziwei; Li, Junnan; Zhou, Kebin

2018-05-01

Two-dimensional (2D) nanosheets of atomic thickness have attracted extensive research interest recently. In this work, atomically thin (0.7 nm) flat CdS (F-CdS) nanosheets of several tens of micrometers in lateral size were synthesized by a solvent-thermal method. The as-synthesized F-CdS could maintain flat morphology well in solution, while irreversible wrinkles could be generated after drying, forming wrinkled CdS (W-CdS) samples. It was revealed that the formation of wrinkles could reduce light absorbance, narrow the band gap, move down the conduction band position and accelerate electron–hole recombination. As photocatalysts, the F-CdS achieved a photocatalytic H2 evolution rate of 138.7 mmol g‑1 h‑1 without any co-catalyst under visible light, which was much higher than that of the W-CdS sample (with an H2 evolution rate of only 52.8 mmol g‑1 h‑1). This work demonstrates that great attention should be paid to the wrinkles in 2D materials as photocatalysts.

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 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

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

Does the Chemothermal Instability Have Any Role in the Fragmentation of Primordial Gas

NASA Astrophysics Data System (ADS)

Dutta, Jayanta

2015-10-01

The collapse of the primordial gas in the density regime ˜108-1010 cm-3 is controlled by the three-body H2 formation process, in which the gas can cool faster than free-fall time—a condition proposed as the chemothermal instability. We investigate how the heating and cooling rates are affected during the rapid transformation of atomic to molecular hydrogen. With a detailed study of the heating and cooling balance in a 3D simulation of Pop III collapse, we follow the chemical and thermal evolution of the primordial gas in two dark matter minihalos. The inclusion of sink particles in modified Gadget-2 smoothed particle hydrodynamics code allows us to investigate the long-term evolution of the disk that fragments into several clumps. We find that the sum of all the cooling rates is less than the total heating rate after including the contribution from the compressional heating (pdV). The increasing cooling rate during the rapid increase of the molecular fraction is offset by the unavoidable heating due to gas contraction. We conclude that fragmentation occurs because H2 cooling, the heating due to H2 formation and compressional heating together set a density and temperature structure in the disk that favors fragmentation, not the chemothermal instability.

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

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.

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.

Effect of Soret diffusion on lean hydrogen/air flames at normal and elevated pressure and temperature

NASA Astrophysics Data System (ADS)

Zhou, Zhen; Hernández-Pérez, Francisco E.; Shoshin, Yuriy; van Oijen, Jeroen A.; de Goey, Laurentius P. H.

2017-09-01

The influence of Soret diffusion on lean premixed flames propagating in hydrogen/air mixtures is numerically investigated with a detailed chemical and transport models at normal and elevated pressure and temperature. The Soret diffusion influence on the one-dimensional (1D) flame mass burning rate and two-dimensional (2D) flame propagating characteristics is analysed, revealing a strong dependency on flame stretch rate, pressure and temperature. For 1D flames, at normal pressure and temperature, with an increase of Karlovitz number from 0 to 0.4, the mass burning rate is first reduced and then enhanced by Soret diffusion of H2 while it is reduced by Soret diffusion of H. The influence of Soret diffusion of H2 is enhanced by pressure and reduced by temperature. On the contrary, the influence of Soret diffusion of H is reduced by pressure and enhanced by temperature. For 2D flames, at normal pressure and temperature, during the early phase of flame evolution, flames with Soret diffusion display more curved flame cells. Pressure enhances this effect, while temperature reduces it. The influence of Soret diffusion of H2 on the global consumption speed is enhanced at elevated pressure. The influence of Soret diffusion of H on the global consumption speed is enhanced at elevated temperature. The flame evolution is more affected by Soret diffusion in the early phase of propagation than in the long run due to the local enrichment of H2 caused by flame curvature effects. The present study provides new insights into the Soret diffusion effect on the characteristics of lean hydrogen/air flames at conditions that are relevant to practical applications, e.g. gas engines and turbines.

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.

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.

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

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.

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.

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.

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.

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

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.

Mathematical Modeling of Ni/H2 and Li-Ion Batteries

NASA Technical Reports Server (NTRS)

Weidner, John W.; White, Ralph E.; Dougal, Roger A.

2001-01-01

The modelling effort outlined in this viewgraph presentation encompasses the following topics: 1) Electrochemical Deposition of Nickel Hydroxide; 2) Deposition rates of thin films; 3) Impregnation of porous electrodes; 4) Experimental Characterization of Nickel Hydroxide; 5) Diffusion coefficients of protons; 6) Self-discharge rates (i.e., oxygen-evolution kinetics); 7) Hysteresis between charge and discharge; 8) Capacity loss on cycling; 9) Experimental Verification of the Ni/H2 Battery Model; 10) Mathematical Modeling Li-Ion Batteries; 11) Experimental Verification of the Li-Ion Battery Model; 11) Integrated Power System Models for Satellites; and 12) Experimental Verification of Integrated-Systems Model.

Composition and evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Donahue, Thomas (Principal Investigator)

1996-01-01

The contract year started by analyzing Jovian atmospheric data acquired by the Galileo Probe Mass Spectrometer (GPMS). Two Venus hydrogen projects got underway as well. The first study strives to understand how to reconcile the standard treatment of the evolution of the H2O and HDO resevoirs on Venus over 4.5 Gyr in the presence of H and D escape and injection by comets. The second study is calculating the charge exchange contribution to hydrogen loss rates, using realistic models for exospheric H, H(+), D, D(+), and ion temperature from PV data. This report includes the following papers as attachments and supporting data: 'The Galileo Probe Mass Spectrometer: Composition of Jupiter's Atmosphere'; 'Chemical Composition Measurements of the Atmosphere of Jupiter with the Galileo Probe Mass Spectrometer'; 'Ion/Neutral Escape of Hydrogen and Deuterium: Evolution of Water'; 'Hydrogen and Deuterium in the Thermosphere of Venus: Solar Cycle Variations and Escape'; and 'Solar Cycle Variations in H(+) and D(+) Densities in the Venus Ionosphere: Implications for Escape'.

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.

Evolution of the neuraminidase gene of seasonal influenza A and B viruses in Thailand between 2010 and 2015.

PubMed

Tewawong, Nipaporn; Vichiwattana, Preeyaporn; Korkong, Sumeth; Klinfueng, Sirapa; Suntronwong, Nungruthai; Thongmee, Thanunrat; Theamboonlers, Apiradee; Vongpunsawad, Sompong; Poovorawan, Yong

2017-01-01

The neuraminidase inhibitors (NAIs) oseltamivir and zanamivir are commonly used for the treatment and control of influenza A and B virus infection. However, the emergence of new influenza virus strains with reduced susceptibility to NAIs may appear with the use of these antivirals or even naturally. We therefore screened the neuraminidase (NA) sequences of seasonal influenza virus A(H1N1), A(H1N1)pdm09, A(H3N2), and influenza B virus strains identified in Thailand for the presence of substitutions previously reported to reduce susceptibility to NAIs. We initially examined oseltamivir resistance (characterized by the H275Y mutation in the NA gene) in 485 A(H1N1)pdm09 strains circulating in Thailand and found that 0.82% (4/485) had this substitution. To further evaluate the evolution of the NA gene, we also randomly selected 98 A(H1N1)pdm09, 158 A(H3N2), and 69 influenza B virus strains for NA gene amplification and sequencing, which revealed various amino acid mutations in the active site of the NA protein previously shown to be associated with reduced susceptibility to NAIs. Phylogenetic analysis of the influenza virus strains from this study and elsewhere around the world, together with the estimations of nucleotide substitution rates and selection pressure, and the predictions of B-cell epitopes and N-linked glycosylation sites all provided evidence for the ongoing evolution of NA. The overall rates of NA evolution for influenza A viruses were higher than for influenza B virus at the nucleotide level, although influenza B virus possessed more genealogical diversity than that of influenza A viruses. The continual surveillance of the antigenic changes associated with the NA protein will not only contribute to the influenza virus database but may also provide a better understanding of selection pressure exerted by antiviral use.

Evolution of the neuraminidase gene of seasonal influenza A and B viruses in Thailand between 2010 and 2015

PubMed Central

Tewawong, Nipaporn; Vichiwattana, Preeyaporn; Korkong, Sumeth; Klinfueng, Sirapa; Suntronwong, Nungruthai; Thongmee, Thanunrat; Theamboonlers, Apiradee; Vongpunsawad, Sompong; Poovorawan, Yong

2017-01-01

The neuraminidase inhibitors (NAIs) oseltamivir and zanamivir are commonly used for the treatment and control of influenza A and B virus infection. However, the emergence of new influenza virus strains with reduced susceptibility to NAIs may appear with the use of these antivirals or even naturally. We therefore screened the neuraminidase (NA) sequences of seasonal influenza virus A(H1N1), A(H1N1)pdm09, A(H3N2), and influenza B virus strains identified in Thailand for the presence of substitutions previously reported to reduce susceptibility to NAIs. We initially examined oseltamivir resistance (characterized by the H275Y mutation in the NA gene) in 485 A(H1N1)pdm09 strains circulating in Thailand and found that 0.82% (4/485) had this substitution. To further evaluate the evolution of the NA gene, we also randomly selected 98 A(H1N1)pdm09, 158 A(H3N2), and 69 influenza B virus strains for NA gene amplification and sequencing, which revealed various amino acid mutations in the active site of the NA protein previously shown to be associated with reduced susceptibility to NAIs. Phylogenetic analysis of the influenza virus strains from this study and elsewhere around the world, together with the estimations of nucleotide substitution rates and selection pressure, and the predictions of B-cell epitopes and N-linked glycosylation sites all provided evidence for the ongoing evolution of NA. The overall rates of NA evolution for influenza A viruses were higher than for influenza B virus at the nucleotide level, although influenza B virus possessed more genealogical diversity than that of influenza A viruses. The continual surveillance of the antigenic changes associated with the NA protein will not only contribute to the influenza virus database but may also provide a better understanding of selection pressure exerted by antiviral use. PMID:28410396

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

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

A novel twelve class fluctuation test reveals higher than expected mutation rates for influenza A viruses

PubMed Central

Pauly, Matthew D; Procario, Megan C; Lauring, Adam S

2017-01-01

Influenza virus’ low replicative fidelity contributes to its capacity for rapid evolution. Clonal sequencing and fluctuation tests have suggested that the influenza virus mutation rate is 2.7 × 10–6 - 3.0 × 10–5 substitutions per nucleotide per strand copied (s/n/r). However, sequencing assays are biased toward mutations with minimal fitness impacts and fluctuation tests typically investigate only a subset of all possible single nucleotide mutations. We developed a fluctuation test based on reversion to fluorescence in a set of virally encoded mutant green fluorescent proteins, which allowed us to measure the rates of selectively neutral mutations representative of the twelve different mutation types. We measured an overall mutation rate of 1.8 × 10–4 s/n/r for PR8 (H1N1) and 2.5 × 10–4 s/n/r for Hong Kong 2014 (H3N2) and a transitional bias of 2.7–3.6. Our data suggest that each replicated genome will have an average of 2–3 mutations and highlight the importance of mutational load in influenza virus evolution. DOI: http://dx.doi.org/10.7554/eLife.26437.001 PMID:28598328

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.

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.

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.

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

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.

Laser Measurements of the H Atom + Ozone Rate Constant at Atmospheric Temperatures

NASA Astrophysics Data System (ADS)

Liu, Y.; Smith, G. P.; Peng, J.; Reppert, K. J.; Callahan, S. L.

2015-12-01

The exothermic H + O3 reaction produces OH(v) Meinel band emissions, used to derive mesospheric H concentrations and chemical heating rates. We have remeasured its rate constant to reduce resulting uncertainties and the measurement extend to lower mesospheric temperatures using modern laser techniques. H atoms are produced by pulsed ultraviolet laser trace photolysis of O3, followed by reaction of O(D) with added H2. A second, delayed, frequency-mixed dye laser measures the reaction decay rate with the remaining ozone by laser induced fluorescence. We monitor either the H atom decay by 2 photon excitation at 205 nm and detection of red fluorescence, or the OH(v=9) product time evolution with excitation of the B-X (0,9) band at 237 nm and emission in blue B-A bands. By cooling the enclosed low pressure flow cell we obtained measurements from 146-305 K. Small kinetic modeling corrections are made for secondary regeneration of H atoms. The results fully confirm the current NASA JPL recommendation for this rate constant, and establish its extrapolation down to the lower temperatures of the mesosphere. This work was supported by the NSF Aeronomy Program and an NSF Physics summer REU student grant.

Dione and Rhea seasonal exospheres revealed by Cassini CAPS and INMS

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Waite, J. H.

2016-07-01

A Dione O2 and CO2 exosphere of similar composition and density to Rhea's is confirmed by Cassini spacecraft Ion Neutral Mass Spectrometer (INMS) flyby data. INMS results from three Dione and two Rhea flybys show exospheric spatial and temporal variability indicative of seasonal exospheres, modulated by winter polar gas adsorption and desorption at the equinoxes. Cassini Plasma Spectrometer (CAPS) pickup ion fluxes also show exospheric structure and evolution at Rhea consistent with INMS, after taking into consideration the anticipated charge exchange, electron impact, and photo-ionization rates. Data-model comparisons show the exospheric evolution to be consistent with polar frost diffusion into the surface regolith, which limits surface exposure and loss of the winter frost cap by sputtering. Implied O2 source rates of ∼45(7) × 1021 s-1 at Dione(Rhea) are ∼50(300) times less than expected from known O2 radiolysis yields from ion-irradiated pure water ice measured in the laboratory, ruling out secondary sputtering as a major exospheric contributor, and implying a nanometer scale surface refractory lag layer consisting of concentrated carbonaceous impurities. We estimate ∼30:1(2:1) relative O2:CO2 source rates at Dione(Rhea), consistent with a stoichiometric bulk composition below the lag layer of 0.01(0.13) C atoms per H2O molecule, deriving from endogenic constituents, implanted micrometeoritic organics, and (in particular at Dione) exogenous H2O delivery by E-ring grains. Impact deposition, gardening and vaporization may thereby control the global O2 source rates by fresh H2O ice exposure to surface radiolysis and trapped oxidant ejection.

Evolutionary dynamics of enzymes.

PubMed

Demetrius, L

1995-08-01

This paper codifies and rationalizes the large diversity in reaction rates and substrate specificity of enzymes in terms of a model which postulates that the kinetic properties of present-day enzymes are the consequence of the evolutionary force of mutation and selection acting on a class of primordial enzymes with poor catalytic activity and broad substrate specificity. Enzymes are classified in terms of their thermodynamic parameters, activation enthalpy delta H* and activation entropy delta S*, in their kinetically significant transition states as follows: type 1, delta H* > 0, delta S* < 0; type 2, delta H* < or = 0, delta S* < or = 0; type 3, delta H* > 0, delta S* > 0. We study the evolutionary dynamics of these three classes of enzymes subject to mutation, which acts at the level of the gene which codes for the enzyme and selection, which acts on the organism that contains the enzyme. Our model predicts the following evolutionary trends in the reaction rate and binding specificity for the three classes of molecules. In type 1 enzymes, evolution results in random, non-directional changes in the reaction rate and binding specificity. In type 2 and 3 enzymes, evolution results in a unidirectional increase in both the reaction rate and binding specificity. We exploit these results in order to codify the diversity in functional properties of present-day enzymes. Type 1 molecules will be described by intermediate reaction rates and broad substrate specificity. Type 2 enzymes will be characterized by diffusion-controlled rates and absolute substrate specificity. The type 3 catalysts can be further subdivided in terms of their activation enthalpy into two classes: type 3a (delta H* small) and type 3b (delta H* large). We show that type 3a will be represented by the same functional properties that identify type 2, namely, diffusion-controlled rates and absolute substrate specificity, whereas type 3b will be characterized by non-diffusion-controlled rates and absolute substrate specificity. We infer from this depiction of the three classes of enzymes, a general relation between the two functional properties, reaction rate and substrate specificity, namely, enzymes with diffusion-controlled rates have absolute substrate specificity. By appealing to energetic considerations, we furthermore show that enzymes with diffusion-controlled rates (types 2 and 3a) form a small subset of the class of all enzymes. This codification of present-day enzymes derived from an evolutionary model, essentially relates the structural properties of enzymes, as described by their thermodynamic parameters, to their functional properties, as represented by the reaction rate and substrate specificity.

Growth and photosynthetic responses of wheat plants grown in space

NASA Technical Reports Server (NTRS)

Tripathy, B. C.; Brown, C. S.; Levine, H. G.; Krikorian, A. D.

1996-01-01

Growth and photosynthesis of wheat (Triticum aestivum L. cv Super Dwarf) plants grown onboard the space shuttle Discovery for 10 d were examined. Compared to ground control plants, the shoot fresh weight of space-grown seedlings decreased by 25%. Postflight measurements of the O2 evolution/photosynthetic photon flux density response curves of leaf samples revealed that the CO2-saturated photosynthetic rate at saturating light intensities in space-grown plants declined 25% relative to the rate in ground control plants. The relative quantum yield of CO2-saturated photosynthetic O2 evolution measured at limiting light intensities was not significantly affected. In space-grown plants, the light compensation point of the leaves increased by 33%, which likely was due to an increase (27%) in leaf dark-respiration rates. Related experiments with thylakoids isolated from space-grown plants showed that the light-saturated photosynthetic electron transport rate from H2O through photosystems II and I was reduced by 28%. These results demonstrate that photosynthetic functions are affected by the microgravity environment.

Use of scanning calorimetry and microrespiration to determine effects of Bt toxin doses on Pandemis leafroller (Lepidoptera: Tortricidae) metabolism

USDA-ARS?s Scientific Manuscript database

Differential scanning calorimetry and microrespiration were used to determine the effects of the biopesticide, Bt toxin, on the metabolism of infected Pandemis leafroller, Pandemis purusana (Kearfott). The metabolic heat rate, CO2 evolution, O2 consumption of 2nd and 3rd instars following a 2 h expo...

Photocatalytic water oxidation by a pyrochlore oxide upon irradiation with visible light: rhodium substitution into yttrium titanate.

PubMed

Kiss, Borbala; Didier, Christophe; Johnson, Timothy; Manning, Troy D; Dyer, Matthew S; Cowan, Alexander J; Claridge, John B; Darwent, James R; Rosseinsky, Matthew J

2014-12-22

A stable visible-light-driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y2 Ti2 O7 is demonstrated by monitoring Vegard's law evolution of the unit-cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible-light active. The overall rate of oxygen evolution is comparable to WO3 but with superior light-harvesting and surface-area-normalized turnover rates, making Y2 Ti1.94 Rh0.06 O7 an excellent candidate for use in a Z-scheme water-splitting system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of phosphoric acid on the electrochemistry of lead electrodes in sulfuric acid electrolyte containing antimony

NASA Astrophysics Data System (ADS)

Venugopalan, S.

The influence of phosphoric acid (0 to 40 g 1 -1) on the Pb/PbSO 4 reaction and the kinetics of hydrogen evolution on pure, smooth lead and lead alloy electrodes is studied via galvanostatic polarization in the linear and Tafel domains with and without antimony (0 to 10 mg 1 -1) addition to the H 2SO 4 (3 to 10 M) electrolyte. Phosphoric acid is found to offset significantly the adverse effect of antimony. H 3PO 4 is also found to increase the hydrogen overpotential without affecting the Pb/PbSO 4 reaction. This implies that the open-circuit corrosion of lead and the consequent hydrogen evolution rate on lead are reduced in the presence of H 3PO 4. The beneficial effects of H 3PO 4 additive are found to be optimum at around 20 g 1 -1. Suppression of hydrogen evolution on the negative electrode, a crucial criterion for sealed cell operation, can be achieved using a H 3PO 4 additive.

Effect of various pretreatment methods on anaerobic mixed microflora to enhance biohydrogen production utilizing dairy wastewater as substrate.

PubMed

Venkata Mohan, S; Lalit Babu, V; Sarma, P N

2008-01-01

Influence of different pretreatment methods applied on anaerobic mixed inoculum was evaluated for selectively enriching the hydrogen (H(2)) producing mixed culture using dairy wastewater as substrate. The experimental data showed the feasibility of molecular biohydrogen generation utilizing dairy wastewater as primary carbon source through metabolic participation. However, the efficiency of H(2) evolution and substrate removal efficiency were found to be dependent on the type of pretreatment procedure adopted on the parent inoculum. Among the studied pretreatment methods, chemical pretreatment (2-bromoethane sulphonic acid sodium salt (0.2 g/l); 24 h) procedure enabled higher H(2) yield along with concurrent substrate removal efficiency. On the contrary, heat-shock pretreatment (100 degrees C; 1 h) procedure resulted in relatively low H(2) yield. Compared to control experiments all the adopted pretreatment methods documented higher H(2) generation efficiency. In the case of combination experiments, integration of pH (pH 3; adjusted with ortho-phosphoric acid; 24 h) and chemical pretreatment evidenced higher H(2) production. Data envelopment analysis (DEA), a frontier analysis technique model was successfully applied to enumerate the relative efficiency of different pretreatment methods studied by considered pretreatment procedures as input and cumulative H(2) production rate and substrate degradation rate as corresponding two outputs.

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

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 comparison of commercially available demineralized bone matrices with and without human mesenchymal stem cells in a rodent spinal fusion model.

PubMed

Hayashi, Tetsuo; Lord, Elizabeth L; Suzuki, Akinobu; Takahashi, Shinji; Scott, Trevor P; Phan, Kevin; Tian, Haijun; Daubs, Michael D; Shiba, Keiichiro; Wang, Jeffrey C

2016-07-01

OBJECTIVE The efficacy of some demineralized bone matrix (DBM) substances has been demonstrated in the spinal fusion of rats; however, no previous comparative study has reported the efficacy of DBM with human mesenchymal stem cells (hMSCs). There is an added cost to the products with stem cells, which should be justified by improved osteogenic potential. The purpose of this study is to prospectively compare the fusion rates of 3 different commercially available DBM substances, both with and without hMSCs. METHODS Posterolateral fusion was performed in 32 mature athymic nude rats. Three groups of 8 rats were implanted with 1 of 3 DBMs: Trinity Evolution (DBM with stem cells), Grafton (DBM without stem cells), or DBX (DBM without stem cells). A fourth group with no implanted material was used as a control group. Radiographs were obtained at 2, 4, and 8 weeks. The rats were euthanized at 8 weeks. Overall fusion was determined by manual palpation and micro-CT. RESULTS The fusion rates at 8 weeks on the radiographs for Trinity Evolution, Grafton, and DBX were 8 of 8 rats, 3 of 8 rats, and 5 of 8 rats, respectively. A significant difference was found between Trinity Evolution and Grafton (p = 0.01). The overall fusion rates as determined by micro-CT and manual palpation for Trinity Evolution, Grafton, and DBX were 4 of 8 rats, 3 of 8 rats, and 3 of 8 rats, respectively. The Trinity Evolution substance had the highest overall fusion rate, however no significant difference was found between groups. CONCLUSIONS The efficacies of these DBM substances are demonstrated; however, the advantage of DBM with hMSCs could not be found in terms of posterolateral fusion. When evaluating spinal fusion using DBM substances, CT analysis is necessary in order to not overestimate fusion.

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

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

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

Vibrational energy transfer in OH X 2Pi(i), v = 2 and 1

NASA Technical Reports Server (NTRS)

Raiche, George A.; Jeffries, Jay B.; Rensberger, Karen J.; Crosley, David R.

1990-01-01

Using an IR-pump/UV-probe method in a flow discharge cell, vibrational energy transfer in OH X 2Pi(i) has been studied. OH is prepared in v = 2 by overtone excitation, and the time evolution of population in v = 2 and 1 monitored by laser-induced fluorescence. Rate constants for vibrational relaxation by the colliders H2O, NH3, CO2, and CH4 were measured. Ratios of rate constants for removal from the two states, k2/k1, range from two to five.

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.

The quantitative genetics of maximal and basal rates of oxygen consumption in mice.

PubMed Central

Dohm, M R; Hayes, J P; Garland, T

2001-01-01

A positive genetic correlation between basal metabolic rate (BMR) and maximal (VO(2)max) rate of oxygen consumption is a key assumption of the aerobic capacity model for the evolution of endothermy. We estimated the genetic (V(A), additive, and V(D), dominance), prenatal (V(N)), and postnatal common environmental (V(C)) contributions to individual differences in metabolic rates and body mass for a genetically heterogeneous laboratory strain of house mice (Mus domesticus). Our breeding design did not allow the simultaneous estimation of V(D) and V(N). Regardless of whether V(D) or V(N) was assumed, estimates of V(A) were negative under the full models. Hence, we fitted reduced models (e.g., V(A) + V(N) + V(E) or V(A) + V(E)) and obtained new variance estimates. For reduced models, narrow-sense heritability (h(2)(N)) for BMR was <0.1, but estimates of h(2)(N) for VO(2)max were higher. When estimated with the V(A) + V(E) model, the additive genetic covariance between VO(2)max and BMR was positive and statistically different from zero. This result offers tentative support for the aerobic capacity model for the evolution of vertebrate energetics. However, constraints imposed on the genetic model may cause our estimates of additive variance and covariance to be biased, so our results should be interpreted with caution and tested via selection experiments. PMID:11560903

Modeling of neutrals in the Linac4 H- ion source plasma: Hydrogen atom production density profile and Hα intensity by collisional radiative model

NASA Astrophysics Data System (ADS)

Yamamoto, T.; Shibata, T.; Ohta, M.; Yasumoto, M.; Nishida, K.; Hatayama, A.; Mattei, S.; Lettry, J.; Sawada, K.; Fantz, U.

2014-02-01

To control the H0 atom production profile in the H- ion sources is one of the important issues for the efficient and uniform surface H- production. The purpose of this study is to construct a collisional radiative (CR) model to calculate the effective production rate of H0 atoms from H2 molecules in the model geometry of the radio-frequency (RF) H- ion source for Linac4 accelerator. In order to validate the CR model by comparison with the experimental results from the optical emission spectroscopy, it is also necessary for the model to calculate Balmer photon emission rate in the source. As a basic test of the model, the time evolutions of H0 production and the Balmer Hα photon emission rate are calculated for given electron energy distribution functions in the Linac4 RF H- ion source. Reasonable test results are obtained and basis for the detailed comparisons with experimental results have been established.

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.

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

Are H and O Being Lost From the Mars Atmosphere in the H2O Stoichiometric Ratio of 2:1?

NASA Astrophysics Data System (ADS)

Jakosky, B. M.; Chaffin, M.; Deighan, J.; Brain, D.; Halekas, J. S.

2017-12-01

Loss of gas from the Mars upper atmosphere to space has been a significant process in the evolution of the Mars atmosphere through time. H is derived from photodissociation of H2O, and is lost by Jeans (thermal) escape. O comes from photodissociation of either H2O or CO2, and is lost by non-thermal processes including dissociative recombination, ion pickup, or sputtering by pick-up ions impacting the atmosphere (in order of importance today). McElroy (1972) proposed that H and O are lost in the ratio of 2:1 that comes from photodissociation of H2O; any imbalance would result in build-up of the lesser-escaping atom that increases its loss rate until the rates were in balance. For the Mars year observed by MAVEN, the large seasonal variation in H loss rate makes this hypothesis difficult to evaluate; however, current best estimates of loss rates suggest that they could be in balance, given the observational uncertainties and seasonal variations (both of which are significant). Even if they are in balance over longer timescales, they still might not be during the "MAVEN" year due to: (i) complications resulting from the interplay between multiple loss processes for O beyond only photochemical loss as considered by McElroy, (ii) interannual and longer-term variations in the lower-atmosphere dust and water cycles that can change the escape rate, (iii) the variation in loss rate expected throughout the 11-year solar cycle, (iv) changes in lower-atmosphere forcing due to the changing orbital elements, or (v) loss of C, H, or O to the crust via reaction with surface minerals. The higher (and unequal) loss rates for all species early in history are likely to have kept H and O from being in balance over the 4-billion-year timescale.

An in situ mediator-free route to fabricate Cu2O/g-C3N4 type-II heterojunctions for enhanced visible-light photocatalytic H2 generation

NASA Astrophysics Data System (ADS)

Ji, Cong; Yin, Su-Na; Sun, Shasha; Yang, Shengyang

2018-03-01

Cu2O nanoparticles doped g-C3N4 are synthesized via an in situ method and investigated in detail by IR techniques, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet visible diffuse reflection spectroscopy, and photoluminescence spectroscopy. The as-prepared Cu2O/g-C3N4 hybrids demonstrate enhanced photocatalytic activity toward hydrogen generation compared to pure bulk g-C3N4, the effect of Cu2O content on the rate of visible light photocatalytic hydrogen evolution reveals the optimal hydrogen evolution rate can reach 33.2 μmol h-1 g-1, which is about 4 times higher that of pure g-C3N4. The enhanced photocatalytic activity can be attributed to the improved separation and transfer of photogenerated electron-hole pairs at the intimate interface between g-C3N4 and Cu2O. A possible photocatalytic mechanism of the Cu2O/g-C3N4 composite is also discussed. This mediator-free in situ chemical doping strategy developed in this work will contribute to the achievement of other multicomponent photocatalysts.

Galacti chemical evolution: Hygrogen through zinc

NASA Technical Reports Server (NTRS)

Timmes, F. X.; Woosley, S. E.; Weaver, Thomas A.

1995-01-01

Using the output from a grid of 60 Type II supernova models (Woosley & Weaver 1995) of varying mass (11 approx. less than (M/solar mass) approx. less than 40) and metallicity (0, 10(exp -4), 0.01, and 1 solar metallicity), the chemical evolution of 76 stable isotopes, from hydrogen to zinc, is calculated. The chemical evolution calculation employs a simple dynamical model for the Galaxy (infall with a 4 Gyr e-folding timescale onto a exponential dsk and 1/r(exp 2) bulge), and standard evolution parameters, such as a Salpeter initial mass function and a quadratic Schmidt star formation rate. The theoretical results are compared in detail with observed stellar abundances in stars with metallicities in the range -3.0 approx. less than (Fe/H) approx. less than 0.0 dex. While our discussion focuses on the solar neighborhood where there are the most observations, the supernova rates, an intrinsically Galactic quality, are also discussed.

[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.

INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Aggregation Behaviors of a Two-Species System with Lose-Lose Interactions

NASA Astrophysics Data System (ADS)

Song, Mei-Xia; Lin, Zhen-Quan; Li, Xiao-Dong; Ke, Jian-Hong

2010-06-01

We propose an aggregation evolution model of two-species (A- and B-species) aggregates to study the prevalent aggregation phenomena in social and economic systems. In this model, A- and B-species aggregates perform self-exchange-driven growths with the exchange rate kernels K (k,l) = Kkl and L(k,l) = Lkl, respectively, and the two species aggregates perform self-birth processes with the rate kernels J1(k) = J1k and J2(k) = J2k, and meanwhile the interaction between the aggregates of different species A and B causes a lose-lose scheme with the rate kernel H(k,l) = Hkl. Based on the mean-field theory, we investigated the evolution behaviors of the two species aggregates to study the competitions among above three aggregate evolution schemes on the distinct initial monomer concentrations A0 and B0 of the two species. The results show that the evolution behaviors of A- and B-species are crucially dominated by the competition between the two self-birth processes, and the initial monomer concentrations A0 and B0 play important roles, while the lose-lose scheme play important roles in some special cases.

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.

Semicontinuous Fenton oxidation of phenol in aqueous solution. A kinetic study.

PubMed

Zazo, J A; Casas, J A; Mohedano, A F; Rodriguez, J J

2009-09-01

This work investigates the Fenton oxidation of phenol in a semicontinuous reactor where the overall amount of H(2)O(2) is distributed as a continuous feed upon the reaction time. The experiments were carried out at 25 degrees C and atmospheric pressure, with 100mg/L initial phenol concentration and iron dosages from 1 to 100 mg/L. H(2)O(2) aqueous solution was continuously fed during 4h reaction time up to an overall dose varying within the range of 500-5000 mg/L. The results in terms of evolution of phenol, H(2)O(2) and intermediates, as well as TOC abatement were compared with those obtained in conventional batch operation. It was found that the oxidation rates for phenol and intermediates were lower when adding the H(2)O(2) continuously. However, a higher abatement of TOC was reached at the end of the 4-h reaction time, in spite of a similar overall H(2)O(2) consumption. This is the result of a more efficient OH generation throughout the semicontinuous process, favouring the reaction with the organic species and reducing the occurrence of competitive scavenging reactions involving Fe(2+), H(2)O(2) and OH. Two kinetic models were proposed, one for describing the evolution of phenol, aromatics and H(2)O(2) and the other for TOC. The influence of the operating conditions on the kinetic constants was also studied, looking for the optimal conditions in terms of both, environmental and economic points of view.

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.

Thermal evolution of a partially differentiated H chondrite parent body

NASA Astrophysics Data System (ADS)

Abrahams, J. N. H.; Bryson, J. F. J.; Weiss, B. P.; Nimmo, F.

2016-12-01

It has traditionally been assumed that planetesimals either melted entirely or remained completely undifferentiated as they accreted. The unmelted textures and cooling histories of chondrites have been used to argue that these meteorites originated from bodies that never differentiated. However, paleomagnetic measurements indicate that some chondrites (e.g., the H chondrite Portales Valley and several CV chondrites) were magnetized by a core dynamo magnetic field, implying that their parent bodies were partially differentiated. It has been unclear, however, whether planetesimal histories consistent with dynamo production can also be consistent with the diversity of chondrite cooling rates and ages. To address this, we modeled the thermal evolution of the H chondrite parent body, considering a variety of accretion histories and parent body radii. We considered partial differentiation using two-stage accretion involving the initial formation and differentiation of a small body, followed by the later addition of low thermal conductivity chondritic material that remains mostly unmelted. We were able to reproduce the measured thermal evolution of multiple H chondrites for a range of parent body parameters, including initial radii from 70-150 km, chondritic layer thicknesses from 50 km to over 100 km, and second stage accretion times of 2.5-3 Myr after solar system formation. Our predicted rates of core cooling and crystallization are consistent with dynamo generation by compositional convection beginning 60-200 Myr after solar system formation and lasting for at least tens of millions of years. This is consistent with magnetic studies of Portales Valley [Bryson et al., this meeting]. In summary, we find that thermal models of partial differentiation are consistent the radiometric ages, magnetization, and cooling rates of a diversity H chondrites.

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.

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.

The cosmological density of baryons from observations of 3He+ in the Milky Way.

PubMed

Bania, T M; Rood, Robert T; Balser, Dana S

2002-01-03

Primordial nucleosynthesis after the Big Bang can be constrained by the abundances of the light elements and isotopes 2H, 3He, 4He and 7Li (ref. 1). The standard theory of stellar evolution predicts that 3He is also produced by solar-type stars, so its abundance is of interest not only for cosmology, but also for understanding stellar evolution and the chemical evolution of the Galaxy. The 3He abundance in star-forming (H II) regions agrees with the present value for the local interstellar medium, but seems to be incompatible with the stellar production rates inferred from observations of planetary nebulae, which provide a direct test of stellar evolution theory. Here we develop our earlier observations, which, when combined with recent theoretical developments in our understanding of light-element synthesis and destruction in stars, allow us to determine an upper limit for the primordial abundance of 3He relative to hydrogen: 3He/H = (1.1 +/- 0.2) x 10(-5). The primordial density of all baryons determined from the 3He data is in excellent agreement with the densities calculated from other cosmological probes. The previous conflict is resolved because most solar-mass stars do not produce enough 3He to enrich the interstellar medium significantly.

The Cosmic Abundance of 3He: Green Bank Telescope Observations

NASA Astrophysics Data System (ADS)

Balser, Dana; Bania, Thomas

2018-01-01

The Big Bang theory for the origin of the Universe predicts that during the first ~1,000 seconds significant amounts of the light elements (2H, 3He, 4He, and 7Li) were produced. Many generations of stellar evolution in the Galaxy modifies these primordial abundances. Observations of the 3He+ hyperfine transition in Galactic HII regions reveals a 3He/H abundance ratio that is constant with Galactocentric radius to within the uncertainties, and is consistent with the primordial value as determined from cosmic microwave background experiments (e.g., WMAP). This "3He Plateau" indicates that the net production and destruction of 3He in stars is approximately zero. Recent stellar evolution models that include thermohaline mixing, however, predict that 3He/H abundance ratios should slightly decrease with Galactocentric radius, or in places in the Galaxy with lower star formation rates. Here we discuss sensitive Green Bank Telescope (GBT) observations of 3He+ at 3.46 cm in a subset of our HII region sample. We develop HII region models and derive accurate 3He/H abundance ratios to better constrain these new stellar evolution models.

Fragmentation during primordial star formation

NASA Astrophysics Data System (ADS)

Dutta, Jayanta

Understanding the physics of the very first stars in the universe, the so-called Population III (or Pop III) stars, is crucial in determining how the universe evolved into what we observe today. In the standard model of Pop III star formation, the baryonic matter, mainly atomic hydrogen, collapses gravitationally into small Dark Matter (DM) minihalos. However, so far there is little understanding on how the thermal, dynamical and chemical evolution of the primordial gas depend on the initial configuration of the minihalos (for example, rotation of the unstable clumps inside minihalos, turbulence, formation of molecular hydrogen and cosmic variance of the minihalos). We use the modified version of the Gadget-2 code, a three-dimensional smoothed particle hydrodynamics (SPH) simulations, to follow the evolution of the collapsing gas in both idealized as well as more realistic minihalos. Unlike some earlier cosmological calculations, the implementation of sink particles allows us to follow the evolution of the accretion disk that builds up in the centre of each minihalo and fragments. We find that the fragmentation behavior depends on the adopted choice of three-body H2 formation rate coefficient. The increasing cooling rate during rapid conversion of the atomic to molecular hydrogen is offset by the heating due to gas contraction. We propose that the H2 cooling, the heating due to H2 formation and compressional heating together set a density and temperature structure in the disk that favors fragmentation. We also find that the cloud's initial degree of rotation has a significant effect on the thermal and dynamical evolution of the collapsing gas. Clouds with higher rotation exhibit spiral-arm-like structures that become gravitationally unstable to fragmentation on several scales. These type of clouds tend to fragment more and have lower accretion rates compared to their slowly rotating counterparts. In addition, we find that the distribution of specific angular momentum (L) of the gas follows a power-law relation with the enclosed gas mass (M), L ∝ M1.125, which is controlled by the gravitational and pressure torque, and does not depend on the cloud's initial degree of rotation and turbulence.

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

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.

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.

Direct Simulation Monte Carlo modelling of the major species in the coma of comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Fougere, Nicolas; Altwegg, K.; Berthelier, J.-J.; Bieler, A.; Bockelée-Morvan, D.; Calmonte, U.; Capaccioni, F.; Combi, M. R.; De Keyser, J.; Debout, V.; Erard, S.; Fiethe, B.; Filacchione, G.; Fink, U.; Fuselier, S. A.; Gombosi, T. I.; Hansen, K. C.; Hässig, M.; Huang, Z.; Le Roy, L.; Leyrat, C.; Migliorini, A.; Piccioni, G.; Rinaldi, G.; Rubin, M.; Shou, Y.; Tenishev, V.; Toth, G.; Tzou, C.-Y.

2016-11-01

We analyse the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) - the Double Focusing Mass Spectrometer data between 2014 August and 2016 February to examine the effect of seasonal variations on the four major species within the coma of 67P/Churyumov-Gerasimenko (H2O, CO2, CO, and O2), resulting from the tilt in the orientation of the comet's spin axis. Using a numerical data inversion, we derive the non-uniform activity distribution at the surface of the nucleus for these species, suggesting that the activity distribution at the surface of the nucleus has not significantly been changed and that the differences observed in the coma are solely due to the variations in illumination conditions. A three-dimensional Direct Simulation Monte Carlo model is applied where the boundary conditions are computed with a coupling of the surface activity distributions and the local illumination. The model is able to reproduce the evolution of the densities observed by ROSINA including the changes happening at equinox. While O2 stays correlated with H2O as it was before equinox, CO2 and CO, which had a poor correlation with respect to H2O pre-equinox, also became well correlated with H2O post-equinox. The integration of the densities from the model along the line of sight results in column densities directly comparable to the VIRTIS-H observations. Also, the evolution of the volatiles' production rates is derived from the coma model showing a steepening in the production rate curves after equinox. The model/data comparison suggests that the seasonal effects result in the Northern hemisphere of 67P's nucleus being more processed with a layered structure while the Southern hemisphere constantly exposes new material.

Efficient Photocatalytic Hydrogen Evolution via Band Alignment Tailoring: Controllable Transition from Type-I to Type-II.

PubMed

Cheng, Zhongzhou; Wang, Fengmei; Shifa, Tofik Ahmed; Jiang, Chao; Liu, Quanlin; He, Jun

2017-11-01

Considering the sizable band gap and wide spectrum response of tin disulfide (SnS 2 ), ultrathin SnS 2 nanosheets are utilized as solar-driven photocatalyst for water splitting. Designing a heterostructure based on SnS 2 is believed to boost their catalytic performance. Unfortunately, it has been quite challenging to explore a material with suitable band alignment using SnS 2 nanomaterials for photocatalytic hydrogen generation. Herein, a new strategy is used to systematically tailor the band alignment in SnS 2 based heterostructure to realize efficient H 2 production under sunlight. A Type-I to Type-II band alignment transition is demonstrated via introducing an interlayer of Ce 2 S 3 , a potential photocatalyst for H 2 evolution, between SnS 2 and CeO 2 . Subsequently, this heterostructure demonstrates tunability in light absorption, charge transfer kinetics, and material stability. The optimized heterostructure (SnS 2 -Ce 2 S 3 -CeO 2 ) exhibits an incredibly strong light absorption ranging from deep UV to infrared light. Significantly, it also shows superior hydrogen generation with the rate of 240 µmol g -1 h -1 under the illumination of simulated sunlight with a very good stability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An EPR study of the pH dependence of formate effects on Photosystem II.

PubMed

Jajoo, Anjana; Katsuta, Nobuhiro; Kawamori, Asako

2006-04-01

Effects of formate on rates of O(2) evolution and electron paramagnetic resonance (EPR) signals were observed in the oxygen evolving PS II membranes as a function of pH. In formate treated PS II membranes, decrease in pH value resulted in the inhibition of the O(2) evolving activity, a decrease in the intensity of S(2) state multiline signal but an increase in the intensity of the Q(A)(-)Fe(2+) EPR signal. Time-resolved EPR study of the Y(Z)(*) decay kinetics showed that the light-induced intensity of Y(Z)(*) EPR signal was proportional to the formate concentration. The change in the pH affected both the light-induced intensities and the decay rates of Y(Z)(*), which was found to be faster at lower pH. At 253 K, t(1/e) value of Y(Z)(*) decay kinetics was found to be 8-10 s at pH 6.0 and 18-21 s at pH 5.0. The results presented here indicate that the extent of inhibition at the donor and the acceptor side of PS II due to formate is pH dependent, being more effective at lower pH.

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.; Marsik, S. J.

1974-01-01

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

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).

Loading Cd0.5Zn0.5S Quantum Dots onto Onion-Like Carbon Nanoparticles to Boost Photocatalytic Hydrogen Generation.

PubMed

Zhou, Xiaolong; Wang, Xina; Feng, Xi; Zhang, Kun; Peng, Xiaoniu; Wang, Hanbin; Liu, Chunlei; Han, Yibo; Wang, Hao; Li, Quan

2017-07-12

Carbon dots (C dots, size < 10 nm) have been conventionally decorated onto semiconductor matrixes for photocatalytic H 2 evolution, but the efficiency is largely limited by the low loading ratio of the C dots on the photocatalyst. Here, we propose an inverse structure of Cd 0.5 Zn 0.5 S quantum dots (QDs) loaded onto the onionlike carbon (OLC) matrix for noble metal-free photocatalytic H 2 evolution. Cd 0.5 Zn 0.5 S QDs (6.9 nm) were uniformly distributed on an OLC (30 nm) matrix with both upconverted and downconverted photoluminescence property. Such an inverse structure allows the full optimization of the QD/OLC interfaces for effective energy transfer and charge separation, both of which contribute to efficient H 2 generation. An optimized H 2 generation rate of 2018 μmol/h/g (under the irradiation of visible light) and 58.6 μmol/h/g (under the irradiation of 550-900 nm light) was achieved in the Cd 0.5 Zn 0.5 S/OLC composite samples. The present work shows that using the OLC matrix in such a reverse construction is a promising strategy for noble metal-free solar hydrogen production.

Preliminary conceptual model for mineral evolution in Yucca Mountain

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

Duffy, C.J.

1993-12-01

A model is presented for mineral alteration in Yucca Mountain, Nevada, that suggests that the mineral transformations observed there are primarily controlled by the activity of aqueous silica. The rate of these reactions is related to the rate of evolution of the metastable silica polymorphs opal-CT and cristobalite assuming that a{sub SiO{sub 2(aq)}} is fixed at the equilibrium solubility of the most soluble silica polymorph present. The rate equations accurately predict the present depths of disappearance of opal-CT and cristobalite. The rate equations have also been used to predict the extent of future mineral alteration that may result from emplacementmore » of a high-level nuclear waste repository in Yucca Mountain. Relatively small changes in mineralogy are predicted, but these predictions are based on the assumption that emplacement of a repository would not increase the pH of water in Yucca Mountain nor increase its carbonate content. Such changes may significantly increase mineral alteration. Some of the reactions currently occurring in Yucca Mountain consume H{sup +} and CO{sub 3}{sup 2{minus}}. Combining reaction rate models for these reactions with water chemistry data may make it possible to estimate water flux through the basal vitrophyre of the Topopah Spring Member and to help confirm the direction and rate of flow of groundwater in Yucca Mountain.« 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.

Multi-stage microbial system for continuous hydrogen production

DOEpatents

Kosourov, Sergey; Ghirardi, Maria L.; Seibert, Michael

2010-06-08

A method of using sequential chemostat culture vessels to provide continuous H.sub.2 production, in which photosynthetic O.sub.2 evolution and H.sub.2 photoproduction are separated physically into two separate bioreactors, comprising: a) growing a microorganism culture able to continuously generate H.sub.2 by photosynthetically producing cells at about the early-to-late log state in a first photobioreactor operating as a sulfur chemostat under aerobic and/or conditions; b) continuously feeding cells from the first photobioreactor to a second photobioreactor operating under anaerobic conditions and sulfur deprivation conditions resulting from constant uptake of sulfate in the first bioreactor and a low rate of culture flow between the first and second bioreactors, for induction of hydrogenase and H.sub.2 photoproduction to allow for continuous cultivation of the microorganism's cells in the first photobioreactor and constant H.sub.2 production in the second photobioreactor, and c) H.sub.2 gas from the second photobioreactor.

Release of hydrogen sulfide during microwave pyrolysis of sewage sludge: Effect of operating parameters and mechanism.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Yin, Linlin; Gong, Zhenlong; Zhang, Jie

2017-06-05

The effects of sludge characteristics, pyrolysis temperature, heating rate and catalysts on the release of H 2 S and mechanism of H 2 S formation during sludge pyrolysis were investigated in a microwave heating reactor (MHR). The evolution of sulfur-containing compounds in the pyrolysis chars obtained at temperature range of 400-800°C was characterized by XPS. For a given temperature, the maximum concentration of H 2 S appeared at moisture content of 80%. Compared to the influence of heating rate on the H 2 S yields, pyrolysis temperature and catalyst played a more significant role on the release of H 2 S during microwave pyrolysis process. The H 2 S concentration increased with increasing temperature from 400°C to 800°C while decreased with increasing heating rate. Both the Nickel-based catalyst and Dolomite displayed significant desulfurization effect and Ni-based catalyst exhibited the larger desulfurization capability than that of Dolomite. The organic sulfur compounds accounted for about 60% of the total sulfur in the sludge which was the main reason for the formation of H 2 S. The mechanism analysis indicated that the cleavage reactions of mercaptan and aromatic-S compounds at temperatures below 600°C and the cracking reaction of sulfate above 700°C respectively were responsible for the H 2 S release during sludge pyrolysis. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Understanding Combustion of H2/O2 Gases inside Nanobubbles Generated by Water Electrolysis Using Reactive Molecular Dynamic Simulations.

PubMed

Jain, S; Qiao, L

2018-06-21

This work explored the mechanism of spontaneous combustion of hydrogen-oxygen mixtures inside nanobubbles (which were generated by water electrolysis) using reactive molecular dynamic simulations based on the first-principles derived reactive force field ReaxFF. The effects of surface-assisted dissociation of H 2 and O 2 gases that produced H and O radicals were examined. Additionally, the ignition outcome and species evolution as a function of the initial system pressure (or bubble size) were studied. A significant amount of hydrogen peroxide (H 2 O 2 ), 6-140 times water (H 2 O), was observed in the combustion products. This was attributed to the low-temperature (∼300 K) and high-pressure (2-80 atm) conditions at which the chemical reactions were taking place. In addition, the rate of consumption of H 2 and O 2 molecules was found to increase with an increase in added H and O radical concentrations and initial system pressure. The rate at which heat was being lost from the combustion chamber (nanobubbles) was also compared to the rate at which heat was being released from the chemical reactions. Only a slight rise in the reaction temperature was observed (∼68 K), signifying that, at such small scales, heat losses dominate. The resulting chemistry was quite different from macroscopic combustion, which usually takes place at a much higher temperatures of above 1000 K.

Abundances and Evolution of Lithium in the Galactic Halo and Disk

NASA Astrophysics Data System (ADS)

Ryan, Sean G.; Kajino, Toshitaka; Beers, Timothy C.; Suzuki, Takeru Ken; Romano, Donatella; Matteucci, Francesca; Rosolankova, Katarina

2001-03-01

We have measured the Li abundance of 18 stars with -2<~[Fe/H]<~-1 and 6000<~Teff<~6400 K, a parameter range that was poorly represented in previous studies. We examine the Galactic chemical evolution (GCE) of this element, combining these data with previous samples of turnoff stars over the full range of halo metallicities. We find that A(Li) increases from a level of ~2.10 at [Fe/H]=-3.5 to ~2.40 at [Fe/H]=-1.0, where A(Li)=log10(n(Li)/n(H))+12.00. We compare the observations with several GCE calculations, including existing one-zone models and a new model developed in the framework of inhomogeneous evolution of the Galactic halo. We show that Li evolved at a constant rate relative to iron throughout the halo and old disk epochs but that during the formation of young disk stars, the production of Li relative to iron increased significantly. These observations can be understood in the context of models in which postprimordial Li evolution during the halo and old disk epochs is dominated by Galactic cosmic-ray fusion and spallation reactions, with some contribution from the ν-process in supernovae. The onset of more efficient Li production (relative to iron) in the young disk coincides with the appearance of Li from novae and asymptotic giant branch (AGB) stars. The major challenge facing the models is to reconcile the mild evolution of Li during the halo and old disk phases with the more efficient production (relative to iron) at [Fe/H]>-0.5. We speculate that cool-bottom processing (production) of Li in low-mass stars may provide an important late-appearing source of Li, without attendant Fe production, that might explain the Li production in the young disk. Based on observations obtained with the University College London échelle spectrograph (UCLES) on the Anglo-Australian Telescope (AAT) and the Utrecht échelle spectrograph (UES) on the William Herschel Telescope (WHT).

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.

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.

Kiloparsec-scale Simulations of Star Formation in Disk Galaxies. IV. Regulation of Galactic Star Formation Rates by Stellar Feedback

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

Butler, Michael J.; Tan, Jonathan C.; Teyssier, Romain

2017-06-01

Star formation from the interstellar medium of galactic disks is a basic process controlling the evolution of galaxies. Understanding the star formation rate (SFR) in a local patch of a disk with a given gas mass is thus an important challenge for theoretical models. Here we simulate a kiloparsec region of a disk, following the evolution of self-gravitating molecular clouds down to subparsec scales, as they form stars that then inject feedback energy by dissociating and ionizing UV photons and supernova explosions. We assess the relative importance of each feedback mechanism. We find that H{sub 2}-dissociating feedback results in themore » largest absolute reduction in star formation compared to the run with no feedback. Subsequently adding photoionization feedback produces a more modest reduction. Our fiducial models that combine all three feedback mechanisms yield, without fine-tuning, SFRs that are in excellent agreement with observations, with H{sub 2}-dissociating photons playing a crucial role. Models that only include supernova feedback—a common method in galaxy evolution simulations—settle to similar SFRs, but with very different temperatures and chemical states of the gas, and with very different spatial distributions of young stars.« less

New insights on the collisional escape of light neutrals from Mars

NASA Astrophysics Data System (ADS)

Gacesa, Marko; Zahnle, Kevin

2017-04-01

Photodissociative recombination (PDR) of atmospheric molecules on Mars is a major mechanism of production of hot (suprathermal) atoms with sufficient kinetic energy to either directly escape to space or to eject other atmospheric species. This collisional ejection mechanism is important for evaluating the escape rates of all light neutrals that are too heavy to escape via Jeans escape. In particular, it plays a role in estimating the total volume of escaped water constituents (i.e., O and H) from Mars, as well as influences evolution of the atmospheric [D]/[H] ratio1. We present revised estimates of total collisional escape rates of neutral light elements including H, He, and H2, based on recent (years 2015-2016) atmospheric density profiles obtained from the NASA Mars Atmosphere and Volatile Evolution (MAVEN) mission. We also estimate the contribution to the collisional escape from Energetic Neutral Atoms (ENAs) produced in charge-exchange of solar wind H+ and He+ ions with atmospheric gases2,3. Scattering of hot oxygen and atmospheric species of interest is modeled using fully-quantum reactive scattering formalism1,3. The escape rates are evaluated using a 1D model of the atmosphere supplemented with MAVEN measurements of the neutrals. Finally, new estimates of contributions of these non-thermal mechanisms to the estimated PDR escape rates from young Mars4 are presented. [1] M. Gacesa and V. Kharchenko, "Non-thermal escape of molecular hydrogen from Mars", Geophys. Res. Lett., 39, L10203 (2012). [2] N. Lewkow and V. Kharchenko, "Precipitation of Energetic Neutral Atoms and Escape Fluxes induced from the Mars Atmosphere", Astroph. J., 790, 98 (2014). [3] M. Gacesa, N. Lewkow, and V. Kharchenko, "Non-thermal production and escape of OH from the upper atmosphere of Mars", Icarus 284, 90 (2017). [4] J. Zhao, F. Tian, Y. Ni, and X. Huang, "DR-induced escape of O and C from early Mars", Icarus 284, 305 (2017).

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.

Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

PubMed

Chen, Qianjin; Luo, Long

2018-04-17

We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

The Mechanical and Microstructural Changes of Sn-Ag-Bi Solders with Cooling Rate and Bi Content Variations

NASA Astrophysics Data System (ADS)

Abd El-Rehim, A. F.; Zahran, H. Y.; AlFaify, S.

2018-02-01

The purpose of this study is to investigate the influence of cooling rate and Bi addition on the microstructure evolution and mechanical properties of Sn-3.5Ag alloy. A series of Sn-3.5Ag-xBi solders has been fabricated with Bi content in the range of 0.5-3.5 wt.%. After solution heat treatment at 170 °C for 24 h and subsequent aging heat treatment at 100 °C for 2 h, samples were divided into two groups. One group was rapidly quenched into iced water (water quenching) for the fast cooling rate (20 °C/s), while the second group was slowly cooled (furnace cooling) in the furnace for the slow cooling rate (0.2 °C/s) after the furnace reflow. The microstructural evolutions of the present solders have been investigated using x-ray diffraction and scanning electron microscopy. The microhardness was measured to correlate the mechanical properties to alloy compositions and cooling rate. It was found that the microhardness of Sn-3.5Ag-xBi solders increased with increasing cooling rate. The indentation creep curves have been evaluated from the obtained microhardness values. Results revealed the steady-state creep rate decreased with increasing Bi content exhibiting an anomalous behavior at 2.5Bi. The reason for improved creep resistance of Sn-3.5Ag-xBi solders is the result of the combination of the solid solution strengthening and precipitation strengthening of Bi. The mean values of stress exponent indicated that the operative creep mechanism is dislocation climb.

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

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.

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.

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.

Catalyst mixtures

DOEpatents

Masel, Richard I.; Rosen, Brian A.

2017-02-14

Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

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

On the pathways feeding the H2 production process in nutrient-replete, hypoxic conditions. Commentary on the article "Low oxygen levels contribute to improve photohydrogen production in mixotrophic non-stressed Chlamydomonas cultures", by Jurado-Oller et al., Biotechnology for Biofuels, published September 7, 2015; 8:149.

PubMed

Scoma, Alberto; Tóth, Szilvia Z

2017-01-01

Under low O 2 concentration (hypoxia) and low light, Chlamydomonas cells can produce H 2 gas in nutrient-replete conditions. This process is hindered by the presence of O 2 , which inactivates the [FeFe]-hydrogenase enzyme responsible for H 2 gas production shifting algal cultures back to normal growth. The main pathways accounting for H 2 production in hypoxia are not entirely understood, as much as culture conditions setting the optimal redox state in the chloroplast supporting long-lasting H 2 production. The reducing power for H 2 production can be provided by photosystem II (PSII) and photofermentative processes during which proteins are degraded via yet unknown pathways. In hetero- or mixotrophic conditions, acetate respiration was proposed to indirectly contribute to H 2 evolution, although this pathway has not been described in detail. Recently, Jurado-Oller et al. (Biotechnol Biofuels 8: 149, 7) proposed that acetate respiration may substantially support H 2 production in nutrient-replete hypoxic conditions. Addition of low amounts of O 2 enhanced acetate respiration rate, particularly in the light, resulting in improved H 2 production. The authors surmised that acetate oxidation through the glyoxylate pathway generates intermediates such as succinate and malate, which would be in turn oxidized in the chloroplast generating FADH 2 and NADH. The latter would enter a PSII-independent pathway at the level of the plastoquinone pool, consistent with the light dependence of H 2 production. The authors concluded that the water-splitting activity of PSII has a minor role in H 2 evolution in nutrient-replete, mixotrophic cultures under hypoxia. However, their results with the PSII inhibitor DCMU also reveal that O 2 or acetate additions promoted acetate respiration over the usually dominant PSII-dependent pathway. The more oxidized state experienced by these cultures in combination with the relatively short experimental time prevented acclimation to hypoxia, thus precluding the PSII-dependent pathway from contributing to H 2 production. In Chlamydomonas , continuous H 2 gas evolution is expected once low O 2 partial pressure and optimal reducing conditions are set. Under nutrient-replete conditions, the electrogenic processes involved in H 2 photoproduction may rely on various electron transport pathways. Understanding how physiological conditions select for specific metabolic routes is key to achieve economic viability of this renewable energy source.

Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase

NASA Astrophysics Data System (ADS)

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

2016-11-01

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 centres that catalyse 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-centred 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-1 s-1 turnover frequency of 250 s-1 at 10 mM H+ concentration) from mildly acidic solutions.

Enhancement in hydrogen evolution using Au-TiO2 hollow spheres with microbial devices modified with conjugated oligoelectrolytes

PubMed Central

Ngaw, Chee Keong; Wang, Victor Bochuan; Liu, Zhengyi; Zhou, Yi; Kjelleberg, Staffan; Zhang, Qichun; Tan, Timothy Thatt Yang; Loo, Say Chye Joachim

2015-01-01

Objective: Although photoelectrochemical (PEC) water splitting heralds the emergence of the hydrogen economy, the need for external bias and low efficiency stymies the widespread application of this technology. By coupling water splitting (in a PEC cell) to a microbial fuel cell (MFC) using Escherichia coli as the biocatalyst, this work aims to successfully demonstrate a sustainable hybrid PEC–MFC platform functioning solely by biocatalysis and solar energy, at zero bias. Through further chemical modification of the photo-anode (in the PEC cell) and biofilm (in the MFC), the performance of the hybrid system is expected to improve in terms of the photocurrent generated and hydrogen evolved. Methods: The hybrid system constitutes the interconnected PEC cell with the MFC. Both PEC cell and MFC are typical two-chambered systems housing the anode and cathode. Au-TiO2 hollow spheres and conjugated oligoelectrolytes were synthesised chemically and introduced to the PEC cell and MFC, respectively. Hydrogen evolution measurements were performed in triplicates. Results: The hybrid PEC–MFC platform generated a photocurrent density of 0.35 mA/cm2 (~70× enhancement) as compared with the stand-alone P25 standard PEC cell (0.005 mA/cm2) under one-sun illumination (100 mW/cm2) at zero bias (0 V vs. Pt). This increase in photocurrent density was accompanied by continuous H2 production. No H2 was observed in the P25 standard PEC cell whereas H2 evolution rate was ~3.4 μmol/h in the hybrid system. The remarkable performance is attributed to the chemical modification of E. coli through the incorporation of novel conjugated oligoelectrolytes in the MFC as well as the lower recombination rate and higher photoabsorption capabilities in the Au-TiO2 hollow spheres electrode. Conclusions: The combined strategy of photo-anode modification in PEC cells and chemically modified MFCs shows great promise for future exploitation of such synergistic effects between MFCs and semiconductor-based PEC water splitting. PMID:28721235

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.

Laboratory Measurements for H3+ Deuteration Reactions

NASA Astrophysics Data System (ADS)

Bowen, Kyle; Hillenbrand, Pierre-Michel; Urbain, Xavier; Savin, Daniel Wolf

2018-06-01

Deuterated molecules are important chemical tracers of protostellar cores. At the ~106 cm-3 particle densities and ~20 K temperatures typical for protostellar cores, most molecules freeze onto dust grains. A notable exception is H3+ and its isotopologues. These become important carriers of positive charge in the gas, can couple to any ambient magnetic field, and can thereby alter the cloud dynamics. Knowing the total abundance of H3+ and its isotopologues is important for studying the evolution of protostellar cores. However, H3+ and D3+ have no dipole moment. They lack a pure rotational spectrum and are not observable at protostellar core temperatures. Fortunately H2D+ and D2H+ have dipole moments and a pure rotational spectrum that can be excited in protostellar cores. Observations of these two molecules, combined with astrochemical models, provide information about the total abundance of H3+ and all its isotopologues. The inferred abundances, though, rely on accurate astrochemical data for the deuteration of H3+ and its isotopologues.Here we present laboratory measurements of the rate coefficients for three important deuterating reactions, namely D + H3+/H2D+/D2H+ → H + H2D+/ D2H+/D3+. Astrochemical models currently rely on rate coefficients from classical (Langevin) or semi-classical methods for these reactions, as fully quantum-mechanical calculations are beyond current computational capabilities. Laboratory studies are the most tractable means of providing the needed data. For our studies we used our novel dual-source, merged fast-beams apparatus, which enables us to study reactions of neutral atoms and molecular ions. Co-propagating beams allow us to measure experimental rate coefficients as a function of collision energy. We extract cross section data from these results, which we then convolve with a Maxwell-Boltzmann distribution to generate thermal rate coefficients. Here we present our results for these three reactions and discuss some implications.

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.

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.

Species-to-species rate coefficients for the H3+ + H2 reacting system

NASA Astrophysics Data System (ADS)

Sipilä, O.; Harju, J.; Caselli, P.

2017-10-01

Aims: We study whether or not rotational excitation can make a large difference to chemical models of the abundances of the H3+ isotopologs, including spin states, in physical conditions corresponding to starless cores and protostellar envelopes. Methods: We developed a new rate coefficient set for the chemistry of the H3+ isotopologs, allowing for rotational excitation, using previously published state-to-state rate coefficients. These new so-called species-to-species rate coefficients are compared with previously-used ground-state-to-species rate coefficients by calculating chemical evolution in variable physical conditions using a pseudo-time-dependent chemical code. Results: We find that the new species-to-species model produces different results to the ground state-to-species model at high density and toward increasing temperatures (T> 10 K). The most prominent difference is that the species-to-species model predicts a lower H3+ deuteration degree at high density owing to an increase of the rate coefficients of endothermic reactions that tend to decrease deuteration. For example at 20 K, the ground-state-to-species model overestimates the abundance of H2D+ by a factor of about two, while the abundance of D3+ can differ by up to an order of magnitude between the models. The spin-state abundance ratios of the various H3+ isotopologs are also affected, and the new model better reproduces recent observations of the abundances of ortho and para H2D+ and D2H+. The main caveat is that the applicability regime of the new rate coefficients depends on the critical densities of the various rotational transitions which vary with the abundances of the species and the temperature in dense clouds. Conclusions: The difference in the abundances of the H3+ isotopologs predicted by the species-to-species and ground state-to-species models is negligible at 10 K corresponding to physical conditions in starless cores, but inclusion of the excited states is very important in studies of deuteration at higher temperatures, for example in protostellar envelopes. The species-to-species rate coefficients provide a more realistic approach to the chemistry of the H3+ isotopologs than the ground-state-to-species rate coefficients do, and so the former should be adopted in chemical models describing the chemistry of the H3+ + H2 reacting system.

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

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

McAdam, Amy; Franz, Heather; Mahaffy, Paul R.; Eigenbrode, Jennifer L.; Stern, Jennifer C.; Brunner, Anna; Archer, Paul Douglas; Ming, Douglas W.; Morris, Richard V.; Atreya, Sushil K.

2013-01-01

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures < 500 C, and an evolution peak at higher temperatures near approx 750 C. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples

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...

Fabrication of 2D SnS2/g-C3N4 heterojunction with enhanced H2 evolution during photocatalytic water splitting.

PubMed

Liu, Enzhou; Chen, Jibing; Ma, Yongning; Feng, Juan; Jia, Jia; Fan, Jun; Hu, Xiaoyun

2018-08-15

In this work, the 2D SnS 2 /g-C 3 N 4 heterojunctions were successfully prepared by heating the homogeneous dispersion of SnS 2 nanosheets and g-C 3 N 4 nanosheets using a microwave muffle. SEM, TEM and HRTEM images indicated that the SnS 2 nanosheets were loaded on the surface of the g-C 3 N 4 nanosheets. The UV-vis spectra show that the absorption intensity of the as-prepared samples was increased and the absorption range was also extended from 420 nm to approximately 600 nm. The H 2 production rate over 5 wt% SnS 2 /g-C 3 N 4 can reach 972.6 μmol·h -1 ·g -1 under visible light irradiation (λ > 420 nm) using TEOA as the sacrifice agent and Pt as the electron trap, which is 2.9 and 25.6 times higher than those of the pristine g-C 3 N 4 and SnS 2 , respectively. According to the obtained PL spectra, photocurrent and EIS spectra, the enhanced performance for H 2 generation over the heterojunctions is primarily ascribed to the rapid charge transfer arising from the suitable band gap positions leading to an improved photocatalytic performance. The recycling experiments indicated that the as-prepared composites exhibit good stability in H 2 production. Additionally, a possible enhanced mechanism for H 2 evolution was deduced based on the results obtained by various characterization techniques. Copyright © 2018 Elsevier Inc. All rights reserved.

Global circulation patterns of seasonal influenza viruses vary with antigenic drift

PubMed Central

Bedford, Trevor; Riley, Steven; Barr, Ian G.; Broor, Shobha; Chadha, Mandeep; Cox, Nancy J.; Daniels, Rodney S.; Gunasekaran, C. Palani; Hurt, Aeron C.; Kelso, Anne; Lewis, Nicola S.; Li, Xiyan; McCauley, John W.; Odagiri, Takato; Potdar, Varsha; Rambaut, Andrew; Shu, Yuelong; Skepner, Eugene; Smith, Derek J.; Suchard, Marc A.; Tashiro, Masato; Wang, Dayan; Xu, Xiyan; Lemey, Philippe; Russell, Colin A.

2015-01-01

Understanding the spatio-temporal patterns of emergence and circulation of new human seasonal influenza virus variants is a key scientific and public health challenge. The global circulation patterns of influenza A/H3N2 viruses are well-characterized1-7 but the patterns of A/H1N1 and B viruses have remained largely unexplored. Here, based on analyses of 9,604 hemagglutinin sequences of human seasonal influenza viruses from 2000–2012, we show that the global circulation patterns of A/H1N1 (up to 2009), B/Victoria, and B/Yamagata viruses differ substantially from those of A/H3N2 viruses. While genetic variants of A/H3N2 viruses did not persist locally between epidemics and were reseeded from East and Southeast (E-SE) Asia, genetic variants of A/H1N1 and B viruses persisted across multiple seasons and exhibited complex global dynamics with E-SE Asia playing a limited role in disseminating new variants. The less frequent global movement of influenza A/H1N1 and B viruses coincided with slower rates of antigenic evolution, lower ages of infection, and smaller less frequent epidemics compared to A/H3N2 viruses. Detailed epidemic models support differences in age of infection, combined with the less frequent travel of children, as likely drivers of the differences in the patterns of global circulation, suggesting a complex interaction between virus evolution, epidemiology and human behavior. PMID:26053121

Global circulation patterns of seasonal influenza viruses vary with antigenic drift

NASA Astrophysics Data System (ADS)

Bedford, Trevor; Riley, Steven; Barr, Ian G.; Broor, Shobha; Chadha, Mandeep; Cox, Nancy J.; Daniels, Rodney S.; Gunasekaran, C. Palani; Hurt, Aeron C.; Kelso, Anne; Klimov, Alexander; Lewis, Nicola S.; Li, Xiyan; McCauley, John W.; Odagiri, Takato; Potdar, Varsha; Rambaut, Andrew; Shu, Yuelong; Skepner, Eugene; Smith, Derek J.; Suchard, Marc A.; Tashiro, Masato; Wang, Dayan; Xu, Xiyan; Lemey, Philippe; Russell, Colin A.

2015-07-01

Understanding the spatiotemporal patterns of emergence and circulation of new human seasonal influenza virus variants is a key scientific and public health challenge. The global circulation patterns of influenza A/H3N2 viruses are well characterized, but the patterns of A/H1N1 and B viruses have remained largely unexplored. Here we show that the global circulation patterns of A/H1N1 (up to 2009), B/Victoria, and B/Yamagata viruses differ substantially from those of A/H3N2 viruses, on the basis of analyses of 9,604 haemagglutinin sequences of human seasonal influenza viruses from 2000 to 2012. Whereas genetic variants of A/H3N2 viruses did not persist locally between epidemics and were reseeded from East and Southeast Asia, genetic variants of A/H1N1 and B viruses persisted across several seasons and exhibited complex global dynamics with East and Southeast Asia playing a limited role in disseminating new variants. The less frequent global movement of influenza A/H1N1 and B viruses coincided with slower rates of antigenic evolution, lower ages of infection, and smaller, less frequent epidemics compared to A/H3N2 viruses. Detailed epidemic models support differences in age of infection, combined with the less frequent travel of children, as probable drivers of the differences in the patterns of global circulation, suggesting a complex interaction between virus evolution, epidemiology, and human behaviour.

One-carbon substrate-based biohydrogen production: microbes, mechanism, and productivity.

PubMed

Rittmann, Simon K-M R; Lee, Hyun Sook; Lim, Jae Kyu; Kim, Tae Wan; Lee, Jung-Hyun; Kang, Sung Gyun

2015-01-01

Among four basic mechanisms for biological hydrogen (H2) production, dark fermentation has been considered to show the highest hydrogen evolution rate (HER). H2 production from one-carbon (C1) compounds such as formate and carbon monoxide (CO) is promising because formate is an efficient H2 carrier, and the utilization of CO-containing syngas or industrial waste gas may render the industrial biohydrogen production process cost-effective. A variety of microbes with the formate hydrogen lyase (FHL) system have been identified from phylogenetically diverse groups of archaea and bacteria, and numerous efforts have been undertaken to improve the HER for formate through strain optimization and bioprocess development. CO-dependent H2 production has been investigated to enhance the H2 productivity of various carboxydotrophs via an increase in CO gas-liquid mass transfer rates and the construction of genetically modified strains. Hydrogenogenic CO-conversion has been applied to syngas and by-product gas of the steel-mill process, and this low-cost feedstock has shown to be promising in the production of biomass and H2. Here, we focus on recent advances in the isolation of novel phylogenetic groups utilizing formate or CO, the remarkable genetic engineering that enhances H2 productivity, and the practical implementation of H2 production from C1 substrates. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Fermentative hydrogen production from liquid swine manure with glucose supplement using an anaerobic sequencing batch reactor

NASA Astrophysics Data System (ADS)

Wu, Xiao

2009-12-01

The idea of coupling renewable energy production and agricultural waste management inspired this thesis. The production of an important future fuel---hydrogen gas---from high strength waste stream-liquid swine manure---using anaerobic treatment processes makes the most sustainable sense for both wastewater utilization and energy generation. The objectives of this thesis were to develop a fermentation process for converting liquid swine manure to hydrogen and to maximize hydrogen productivity. Anaerobic sequencing batch reactor (ASBR) systems were constructed to carry out this fermentation process, and seed sludge obtained from a dairy manure anaerobic digester and pretreated by nutrient acclimation, heat and pH treatment was used as inoculum. High system stability was indicated by a short startup period of 12 days followed by stable hydrogen production, and successful sludge granulation occurred within 23 days of startup at a hydraulic retention time (HRT) of 24 hours. Operation at a progressively decreasing HRT from 24 to 8h gave rise to an increasing biogas production rate from 15.2-34.4L/d, while good linear relationships were observed between both total biogas and hydrogen production rates correlated to HRT, with R2 values of 0.993 and 0.997, respectively. The maximum hydrogen yield of 1.63 mol-H 2/mol-hexose-feed occurred at HRT of 16h, while the HRT of 12h was highly suggested to achieve both high production rate and efficient yield. Hexose utilization efficiencies over 98%, considerable hydrogen production rate up to 14.3 L/d and hydrogen percentage of off-gas up to 43% (i.e., a CO 2/H2 ratio of 1.2) with the absence of CH4 production throughout the whole course of experiment at a pH of 5.0 strongly validated the feasibility of the fermentative H2 production from liquid swine manure using an ASBR system. Ethanol as well as acetic, butyric and valeric acids were produced in the system accompanying the hydrogen production, with acetic acid being the dominant one, which contributed to 56-58% of the total soluble metabolite production, indicative of an acetic acid fermentation system, and acetate-to-butyrate ratio was found to be closely related to hydrogen yield. pH level influenced every aspect of the ASBR performance for hydrogen production. ASBR operation at five pHs ranging from 4.4 to 5.6 (4.4, 4.7, 5.0, 5.3, 5.6) showed distinct dynamic profiles of both biogas production and the changes of H2 and CH4 percentage in the biogas during a running period of 22 days. The H2 content in biogas, H 2 production rate and H2 yield were all pH-dependent, in the range of 5.1-36.9 %, 0.71-8.97 L/d and 0.12-1.50 mol-H2/mol-glucose, respectively, and maximum values for all three responses were simultaneously achieved at pH 5.0. Methanogens appeared to be significantly activated at pH of 5.3 or higher since significant CH4 evolution and concurrent reduction in H2 production was observed at pH 5.3 and 5.6. Acetate, propionate, butyrate, valerate, and ethanol were main aqueous products in all pH tests and their distribution was influenced by pH. Analysis of kinetic models developed from modified Gompertz equations for batch experiments showed that pH had a profound effect on all kinetic parameters for hydrogen production including hydrogen potential, maximum hydrogen production rate and the length of the lag phase, as well as the maximum substrate utilization rate. The low pH of 4.4 gave the highest hydrogen production potential but with the lowest hydrogen production rate. A contrast experiment was conducted with an initial pH of 5.3 but not controlled, came up with a rapid pH decline, leading to a low hexose degradation efficiency of 33.2% and a significantly suppressed H2 production, indicating the importance of pH control and the effect of pH on H2 production and substrate consumption. pH 5.0 was verified as the optimal for the proposed fermentation system by kinetic models. An extremely linear relationship (R2= 0.993) between the maximum H2 production rate and the maximum hexose degradation rate suggested that the pH inhibition on H2 production was a result of the suppression on the bacterial activity for substrate utilization due to an unfavorable pH level. System optimization was realized through experiments conducted according to a response surface methodology, with a central composite design and empirical quadratic response equations obtained for three responses including the hydrogen content in the biogas, hydrogen evolution rate and hydrogen yield, against three independent variables, pH (4.4-5.6), HRT (8-24h) and substrate glucose concentrations (Cg, 0-20 g/L). Contour plots revealed that all three responses were significantly impacted by the variable and squared pH. Furthermore, pH and Cg had a significant interaction effect on H2 production rate, while HRT and glucose concentration were interdependent, or they had a mildly significant interaction effect on H2 production rate. The hydrogen content decreased when pH was greater than 5.0 or less than 4.6 and a largest value of 42.7% could be obtained at pH 4.8, HRT 8 h, and Cg of 18.7 g/L. The highest hydrogen production rate of 26.1 L/d happened under a pH of 4.6, HRT of 8h, and Cg of 20 g/L; Lower HRT and higher Cg was found to benefit the H2 production rate because they provide elevated organic loading and food to microorganism ratio for the system. HRT shorter than 17h resulted in declined hydrogen yield, while the glucose concentration up to 20 g/L did not cause suppression on hydrogen yield. The revised optimal condition of pH 4.8, HRT 11h, and Cg of 20 g/L, which could achieve 85% of the maximum values of all three hydrogen productivity responses, was determined by surface response methodology. Highly reproducible results from confirming experiments at the optimal condition indicated that the results modeled in this study possessed a high reliability, while the results of H2 content, H2 production rate and yield were obtained as 40.3%, 23.16 L/d, and 1.36mol H2/mol hexose, respectively. Results obtained in this study indicated that ASBR system using swine manure based substrate had significant potential of fermentative hydrogen production. Key words: biohydrogen production, hydrogen fermentation, liquid swine manure, anaerobic sequencing batch reactor (ASBR), hydrogen content, hydrogen production rate, hydrogen yield

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Enhanced photocatalytic H2-production activity of C-dots modified g-C3N4/TiO2 nanosheets composites.

PubMed

Li, Yang; Feng, Xionghan; Lu, Zhexue; Yin, Hui; Liu, Fan; Xiang, Quanjun

2018-03-01

As a new carbon-based material, carbon dots (C-dots) have got widely preference because of its excellent electronic transfer capability. In this work, a novel ternary layered C-dots/g-C 3 N 4 /TiO 2 nanosheets (CGT) composite photocatalysts were prepared by impregnation precipitation methods. The optimal ternary CGT composite samples revealed high photocatalytic hydrogen evolution rate in triethanolamine aqueous solutions, which exceeded the rate of the optimal g-C 3 N 4 /TiO 2 composite sample by a factor of 5 times. The improved photocatalytic activity is owed to the positive effects of C-dots and layered heterojunction structure of TiO 2 nanosheets and g-C 3 N 4 sheets. C-dots in the CGT composites can serve as electron reservoirs to capture the photo-induced electrons. The well-defined layered heterojunction structure of CGT provides the intimate contact and the strong interaction of anatase TiO 2 nanosheets and g-C 3 N 4 sheets via face-to-face orientation, which restrains the recombination of photogenerated charge carriers, and thus enhances the photocatalytic H 2 -production activity. Electron paramagnetic resonance and transient photocurrent response proved the strong interaction and improved interfacial charge transfer of TiO 2 nanosheets and g-C 3 N 4 sheets, respectively. The mechanism of improving the photocatalytic H 2 -evolution activity was further confirmed by time-resolved fluorescence, electron paramagnetic resonance, transient photocurrent response and electrochemical impedance spectroscopy. Copyright © 2017 Elsevier Inc. All rights reserved.

Rotationally inelastic cross sections, rates and cooling times for para-H2 +, ortho-D2 + and HD+ in cold helium gas

NASA Astrophysics Data System (ADS)

Vera, Mario Hernández; Schiller, Stephan; Wester, Roland; Gianturco, Francesco Antonio

2017-05-01

In the present work we discuss the dynamical processes guiding the relaxation of the internal rotational energy of three diatomic ions, the para-H2+, the ortho-D2+ and the HD+ in collision with He atoms. The state-changing cross sections and rates for these Molecular Hydrogen Ions (MHIs) are obtained from Close Coupling quantum dynamics calculations and the decay times into their respective ground states are computed by further solving the relevant time-evolution equations. The comparison of the results from the three molecules allows us to obtain a detailed understanding, and a deep insight, on the relative efficiencies of the relaxation processes considered. Contribution to the Topical Issue "Dynamics of Molecular Systems (MOLEC 2016)", edited by Alberto Garcia-Vela, Luis Banares and Maria Luisa Senent.

THE EVOLUTION OF INNER DISK GAS IN TRANSITION DISKS

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

Hoadley, K.; France, K.; McJunkin, M.

2015-10-10

Investigating the molecular gas in the inner regions of protoplanetary disks (PPDs) provides insight into how the molecular disk environment changes during the transition from primordial to debris disk systems. We conduct a small survey of molecular hydrogen (H{sub 2}) fluorescent emission, using 14 well-studied Classical T Tauri stars at two distinct dust disk evolutionary stages, to explore how the structure of the inner molecular disk changes as the optically thick warm dust dissipates. We simulate the observed Hi-Lyman α-pumped H{sub 2} disk fluorescence by creating a 2D radiative transfer model that describes the radial distributions of H{sub 2} emissionmore » in the disk atmosphere and compare these to observations from the Hubble Space Telescope. We find the radial distributions that best describe the observed H{sub 2} FUV emission arising in primordial disk targets (full dust disk) are demonstrably different than those of transition disks (little-to-no warm dust observed). For each best-fit model, we estimate inner and outer disk emission boundaries (r{sub in} and r{sub out}), describing where the bulk of the observed H{sub 2} emission arises in each disk, and we examine correlations between these and several observational disk evolution indicators, such as n{sub 13–31}, r{sub in,} {sub CO}, and the mass accretion rate. We find strong, positive correlations between the H{sub 2} radial distributions and the slope of the dust spectral energy distribution, implying the behavior of the molecular disk atmosphere changes as the inner dust clears in evolving PPDs. Overall, we find that H{sub 2} inner radii are ∼4 times larger in transition systems, while the bulk of the H{sub 2} emission originates inside the dust gap radius for all transitional sources.« less

Highly efficient photocatalytic hydrogen evolution from nickel quinolinethiolate complexes under visible light irradiation

NASA Astrophysics Data System (ADS)

Rao, Heng; Yu, Wen-Qian; Zheng, Hui-Qin; Bonin, Julien; Fan, Yao-Ting; Hou, Hong-Wei

2016-08-01

Earth-abundant metal complexes have emerged as promising surrogates of platinum for catalyzing the hydrogen evolution reaction (HER). In this study, we report the design and synthesis of two novel nickel quinolinethiolate complexes, namely [Ni(Hqt)2(4, 4‧-Z-2, 2‧-bpy)] (Hqt = 8-quinolinethiol, Z = sbnd H [1] or sbnd CH3 [2], bpy = bipyridine). An efficient three-component photocatalytic homogeneous system for hydrogen generation working under visible light irradiation was constructed by using the target complexes as catalysts, triethylamine (TEA) as sacrificial electron donor and xanthene dyes as photosensitizer. We obtain turnover numbers (TON, vs. catalyst) for H2 evolution of 5923/7634 under the optimal conditions with 5.0 × 10-6 M complex 1/2 respectively, 1.0 × 10-3 M fluorescein and 5% (v/v) TEA at pH 12.3 in EtOH/H2O (1:1, v/v) mixture after 8 h irradiation (λ > 420 nm). We discuss the mechanism of H2 evolution in the homogeneous photocatalytic system based on fluorescence spectrum and cyclic voltammetry data.

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.

Hydrogen evolution using palladium sulfide (PdS) nanocorals as photoanodes in aqueous solution.

PubMed

Barawi, M; Ferrer, I J; Ares, J R; Sánchez, C

2014-11-26

Palladium sulfide (PdS) nanostructures are proposed to be used as photoanodes in photoelectrochemical cells (PECs) for hydrogen evolution due to their adequate transport and optical properties shown in previous works. Here, a complete morphological and electrochemical characterization of PdS films has been performed by different techniques. PdS flatband potential (Vfb=-0.65±0.05 V vs NHE) was determined by electrochemical impedance spectroscopy measurements in aqueous Na2SO3 electrolyte, providing a description of the energy levels scheme at the electrolyte-semiconductor interface. This energy levels scheme confirms PdS as a compound able to photogenerate hydrogen in a PEC. At last, photogenerated hydrogen rates are measured continuously by mass spectrometry as a function of the external bias potential under illumination, reaching values up to 4.4 μmolH2/h at 0.3 V vs Ag/AgCl.

En Route to Destruction: the Evolution in Composition of Ices in Comet D 2012 S1 (ISON) Between 1.2 and 0.34 Au from the Sun as Revealed at Infrared Wavelengths

NASA Technical Reports Server (NTRS)

Disanti, M. A.; Bonev, B. P.; Gibb, L. E.; Paganini, L.; Villanueva, G.; Mumma, M. J.; Keane, J. V.; Blake, G. A.; Dello Russo, N.; Meech, K. J.;

LAD Dissertation Prize Talk: Molecular Collisional Excitation in Astrophysical Environments

NASA Astrophysics Data System (ADS)

Walker, Kyle M.

2017-06-01

While molecular excitation calculations are vital in determining particle velocity distributions, internal state distributions, abundances, and ionization balance in gaseous environments, both theoretical calculations and experimental data for these processes are lacking. Reliable molecular collisional data with the most abundant species - H2, H, He, and electrons - are needed to probe material in astrophysical environments such as nebulae, molecular clouds, comets, and planetary atmospheres. However, excitation calculations with the main collider, H2, are computationally expensive and therefore various approximations are used to obtain unknown rate coefficients. The widely-accepted collider-mass scaling approach is flawed, and alternate scaling techniques based on physical and mathematical principles are presented here. The most up-to-date excitation data are used to model the chemical evolution of primordial species in the Recombination Era and produce accurate non-thermal spectra of the molecules H2+, HD, and H2 in a primordial cloud as it collapses into a first generation star.

Enhanced, robust light-driven H 2 generation by gallium-doped titania nanoparticles

DOE PAGES

Luo, Si; Nguyen-Phan, Thuy-Duong; Vovchok, Dimitriy; ...

2017-12-14

The splitting of water into molecular hydrogen and oxygen with the use of renewable solar energy is considered one of the most promising routes to yield sustainable fuel. In this paper, we report the H 2 evolution performance of gallium doped TiO 2 photocatalysts with varying degrees of Ga dopant. The gallium(III) ions induced significant changes in the structural, textural and electronic properties of TiO 2 nanoparticles, resulting in remarkably enhanced photocatalytic activity and good stability for H 2 production. Ga 3+ ions can act as hole traps that enable a large number of excited electrons to migrate towards themore » TiO 2 surface, thereby facilitating electron transfer and charge separation. Additionally, the cationic dopant and its induced defects might introduce a mid-gap state, promoting electron migration and prolonging the lifetime of charge carrier pairs. We have discovered that the optimal Ga dopant concentration was 3.125 at% and that the incorporation of platinum (0.5 wt%) as a co-catalyst further improved the H 2 evolution rate up to 5722 μmol g -1 h -1. Pt not only acts as an electron sink, drastically increasing the electron/hole pair lifetime, but it also creates an intimate contact at the heterojunction between Pt and Ga-TiO 2, thus improving the interfacial electron transfer process. Finally, these catalyst design strategies provide new ways of designing transition metal photocatalysts that improve green fuel production from renewable solar energy and water.« less

Evolutionary trend toward kinetic stability in the folding trajectory of RNases H

PubMed Central

Lim, Shion A.; Hart, Kathryn M.; Marqusee, Susan

2016-01-01

Proper folding of proteins is critical to producing the biological machinery essential for cellular function. The rates and energetics of a protein’s folding process, which is described by its energy landscape, are encoded in the amino acid sequence. Over the course of evolution, this landscape must be maintained such that the protein folds and remains folded over a biologically relevant time scale. How exactly a protein’s energy landscape is maintained or altered throughout evolution is unclear. To study how a protein’s energy landscape changed over time, we characterized the folding trajectories of ancestral proteins of the ribonuclease H (RNase H) family using ancestral sequence reconstruction to access the evolutionary history between RNases H from mesophilic and thermophilic bacteria. We found that despite large sequence divergence, the overall folding pathway is conserved over billions of years of evolution. There are robust trends in the rates of protein folding and unfolding; both modern RNases H evolved to be more kinetically stable than their most recent common ancestor. Finally, our study demonstrates how a partially folded intermediate provides a readily adaptable folding landscape by allowing the independent tuning of kinetics and thermodynamics. PMID:27799545

Effects of H2S/HS- on Stress Corrosion Cracking Behavior of X100 Pipeline Steel Under Simulated Sulfate-Reducing Bacteria Metabolite Conditions

NASA Astrophysics Data System (ADS)

Liu, Q.; Li, Z.; Liu, Z. Y.; Li, X. G.; Wang, S. Q.

2017-04-01

The effect of H2S/HS-, which simulates the main metabolites of sulfate-reducing bacteria (SRB), on the electrochemical and stress corrosion cracking (SCC) behaviors of X100 steel was investigated in a near-neutral solution. The results showed that different H2S/HS- contents mainly affected the cathodic process of X100 electrochemical corrosion. As the concentration of H2S/HS- increased, the corrosion potential was shifted negatively, the corrosion current density was considerably increased, and the corrosion rate was linearly increased. Different rust layers with shifting structures were formed under different conditions and had different effects on electrochemical behaviors. However, sulfide mainly promoted local corrosion processes. With the synergistic effects of stress and H2S/HS-, SCC susceptibility was considerably enhanced. The accelerated process of hydrogen evolution by sulfide was crucial in enhancing SCC processes. In brief, the trace H2S/HS- generated by SRB metabolites played a positive role in promoting SCC.

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

NASA Astrophysics Data System (ADS)

McAdam, A.; Franz, H.; Mahaffy, P. R.; Eigenbrode, J. L.; Stern, J. C.; Brunner, A.; Sutter, B.; Archer, P. D.; Ming, D. W.; Morris, R. V.; Atreya, S. K.; Team, M.

2013-12-01

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise ~20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000oC and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures <500oC, and an evolution peak at higher temperatures near ~750oC. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the ~20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples (Mahaffy et al., this meeting).

Phenotypic plasticity of gas exchange pattern and water loss in Scarabaeus spretus (Coleoptera: Scarabaeidae): deconstructing the basis for metabolic rate variation.

PubMed

Terblanche, John S; Clusella-Trullas, Susana; Chown, Steven L

2010-09-01

Investigation of gas exchange patterns and modulation of metabolism provide insight into metabolic control systems and evolution in diverse terrestrial environments. Variation in metabolic rate in response to environmental conditions has been explained largely in the context of two contrasting hypotheses, namely metabolic depression in response to stressful or resource-(e.g. water) limited conditions, or elevation of metabolism at low temperatures to sustain life in extreme conditions. To deconstruct the basis for metabolic rate changes in response to temperature variation, here we undertake a full factorial study investigating the longer- and short-term effects of temperature exposure on gas exchange patterns. We examined responses of traits of gas exchange [standard metabolic rate (SMR); discontinuous gas exchange (DGE) cycle frequency; cuticular, respiratory and total water loss rate (WLR)] to elucidate the magnitude and form of plastic responses in the dung beetle, Scarabaeus spretus. Results showed that short- and longer-term temperature variation generally have significant effects on SMR and WLR. Overall, acclimation to increased temperature led to a decline in SMR (from 0.071+/-0.004 ml CO(2) h(-1) in 15 degrees C-acclimated beetles to 0.039+/-0.004 ml CO(2) h(-1) in 25 degrees C-acclimated beetles measured at 20 degrees C) modulated by reduced DGE frequency (15 degrees C acclimation: 0.554+/-0.027 mHz, 20 degrees C acclimation: 0.257+/-0.030 mHz, 25 degrees C acclimation: 0.208+/-0.027 mHz recorded at 20 degrees C), reduced cuticular WLRs (from 1.058+/-0.537 mg h(-1) in 15 degrees C-acclimated beetles to 0.900+/-0.400 mg h(-1) in 25 degrees C-acclimated beetles measured at 20 degrees C) and reduced total WLR (from 4.2+/-0.5 mg h(-1) in 15 degrees C-acclimated beetles to 3.1+/-0.5 mg h(-1) in 25 degrees C-acclimated beetles measured at 25 degrees C). Respiratory WLR was reduced from 2.25+/-0.40 mg h(-1) in 15 degrees C-acclimated beetles to 1.60+/-0.40 mg h(-1) in 25 degrees C-acclimated beetles measured at 25 degrees C, suggesting conservation of water during DGE bursts. Overall, this suggests water conservation is a priority for S. spretus exposed to longer-term temperature variation, rather than elevation of SMR in response to low temperature acclimation, as might be expected from a beetle living in a relatively warm, low rainfall summer region. These results are significant for understanding the evolution of gas exchange patterns and trade-offs between metabolic rate and water balance in insects and other terrestrial arthropods.

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.

Core thermal response and hydrogen generation of the N Reactor hydrogen mitigation design basis accident

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

White, M.D.; Lombardo, N.J.; Heard, F.J.

1988-04-01

Calculations were performed to determine core heatup, core damage, and subsequent hydrogen production of a hypothetical loss-of-cooling accident at the Department of Energy's N Reactor. The thermal transient response of the reactor core was solved using the TRUMP-BD computer program. Estimates of whole-core thermal damage and hydrogen production were made by weighting the results of multiple half-length pressure tube simulations at various power levels. The Baker-Just and Wilson parabolic rate equations for the metal-water chemical reactions modeled the key phenomena of chemical energy and hydrogen evolution. Unlimited steam was assumed available for continuous oxidation of exposed Zircaloy-2 surfaces and formore » uranium metal with fuel cladding beyond the failure temperature (1038 C). Intact fuel geometry was modeled. Maximum fuel temperatures (1181 C) in the cooled central regions of the core were predicted to occur one-half hour into the accident scenario. Maximum fuel temperatures of 1447 C occurred in the core GSCS-regions at the end of the 10-h transient. After 10-h 26% of the fuel inventory was predicted to have failed. Peak hydrogen evolution equaled 42 g/s, while 10-h integrated hydrogen evolution equaled 167 kg. 12 refs., 12 figs., 2 tabs.« less

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

Nucleation and growth of single layer graphene on electrodeposited Cu by cold wall chemical vapor deposition

NASA Astrophysics Data System (ADS)

Das, Shantanu; Drucker, Jeff

2017-03-01

The nucleation density and average size of graphene crystallites grown using cold wall chemical vapor deposition (CVD) on 4 μm thick Cu films electrodeposited on W substrates can be tuned by varying growth parameters. Growth at a fixed substrate temperature of 1000 °C and total pressure of 700 Torr using Ar, H2 and CH4 mixtures enabled the contribution of total flow rate, CH4:H2 ratio and dilution of the CH4/H2 mixture by Ar to be identified. The largest variation in nucleation density was obtained by varying the CH4:H2 ratio. The observed morphological changes are analogous to those that would be expected if the deposition rate were varied at fixed substrate temperature for physical deposition using thermal evaporation. The graphene crystallite boundary morphology progresses from irregular/jagged through convex hexagonal to regular hexagonal as the effective C deposition rate decreases. This observation suggests that edge diffusion of C atoms along the crystallite boundaries, in addition to H2 etching, may contribute to shape evolution of the graphene crystallites. These results demonstrate that graphene grown using cold wall CVD follows a nucleation and growth mechanism similar to hot wall CVD. As a consequence, the vast knowledge base relevant to hot wall CVD may be exploited for graphene synthesis by the industrially preferable cold wall method.

Hydrogen addition reactions of aliphatic hydrocarbons in comets

NASA Astrophysics Data System (ADS)

Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H.

2013-10-01

Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.

Chromospheres and mass loss in metal-deficient giant stars

NASA Technical Reports Server (NTRS)

Dupree, A. K.; Hartmann, L.; Avrett, E. H.

1984-01-01

Semiempirical atmospheric models indicate that the characteristic emission in the wings of the H-alpha line observed in Population II giant stars can arise naturally within static chromospheres. Radial expansion gives an asymmetric, blueshifted H-alpha core accompanied by greater emission in the red line wing than in the blue wing. Wind models with extended atmospheres suggest mass loss rates much smaller than 2 x 10 to the -9th solar mass per yr. Thus H-alpha provides no evidence that steady mass loss can significantly affect the evolution of stars on the red giant branch of globular clusters.

Decrease in hydrogen sulfide content during the final stage of beer fermentation due to involvement of yeast and not carbon dioxide gas purging.

PubMed

Oka, Kaneo; Hayashi, Teruhiko; Matsumoto, Nobuya; Yanase, Hideshi

2008-09-01

We observed a rapid decrease in hydrogen sulfide content in the final stage of beer fermentation that was attributed to yeast and not to the purging of carbon dioxide (CO(2)) gas. The well known immature off-flavor in beer due to hydrogen sulfide (H(2)S) behavior during beer fermentation was closely investigated. The H(2)S decrease occurred during the final stage of fermentation when the CO(2)-evolution rate was extremely small and there was a decrease in the availability of fermentable sugars, suggesting that the exhaustion of fermentable sugars triggered the decrease in H(2)S. An H(2)S-balance analysis suggested that the H(2)S decrease might have been caused due to sulfide uptake by yeast. Further investigation showed that the time necessary for H(2)S to decrease below the sensory threshold was related to the number of suspended yeast cells. This supported the hypothesis that yeast cells contributed to the rapid decrease in H(2)S during the final stage of beer fermentation.

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.

Estimating Collisionally-Induced Escape Rates of Light Neutrals from Early Mars

NASA Astrophysics Data System (ADS)

Gacesa, M.; Zahnle, K. J.

2016-12-01

Collisions of atmospheric gases with hot oxygen atoms constitute an important non-thermal mechanism of escape of light atomic and molecular species at Mars. In this study, we present revised theoretical estimates of non-thermal escape rates of neutral O, H, He, and H2 based on recent atmospheric density profiles obtained from the NASA Mars Atmosphere and Volatile Evolution (MAVEN) mission and related theoretical models. As primary sources of hot oxygen, we consider dissociative recombination of O2+ and CO2+ molecular ions. We also consider hot oxygen atoms energized in primary and secondary collisions with energetic neutral atoms (ENAs) produced in charge-exchange of solar wind H+ and He+ ions with atmospheric gases1,2. Scattering of hot oxygen and atmospheric species of interest is modeled using fully-quantum reactive scattering formalism3. This approach allows us to construct distributions of vibrationally and rotationally excited states and predict the products' emission spectra. In addition, we estimate formation rates of excited, translationally hot hydroxyl molecules in the upper atmosphere of Mars. The escape rates are calculated from the kinetic energy distributions of the reaction products using an enhanced 1D model of the atmosphere for a range of orbital and solar parameters. Finally, by considering different scenarios, we estimate the influence of these escape mechanisms on the evolution of Mars's atmosphere throughout previous epochs and their impact on the atmospheric D/H ratio. M.G.'s research was supported by an appointment to the NASA Postdoctoral Program at the NASA Ames Research Center, administered by Universities Space Research Association under contract with NASA. 1N. Lewkow and V. Kharchenko, "Precipitation of Energetic Neutral Atoms and Escape Fluxes induced from the Mars Atmosphere", Astroph. J., 790, 98 (2014) 2M. Gacesa, N. Lewkow, and V. Kharchenko, "Non-thermal production and escape of OH from the upper atmosphere of Mars", arXiv:1607.03602 (2016) 3M. Gacesa and V. Kharchenko, "Non-thermal escape of molecular hydrogen from Mars", Geophys. Res. Lett., 39, L10203 (2012).

Nitroxides protect horseradish peroxidase from H2O2-induced inactivation and modulate its catalase-like activity.

PubMed

Samuni, Amram; Maimon, Eric; Goldstein, Sara

2017-08-01

Horseradish peroxidase (HRP) catalyzes H 2 O 2 dismutation while undergoing heme inactivation. The mechanism underlying this process has not been fully elucidated. The effects of nitroxides, which protect metmyoglobin and methemoglobin against H 2 O 2 -induced inactivation, have been investigated. HRP reaction with H 2 O 2 was studied by following H 2 O 2 depletion, O 2 evolution and heme spectral changes. Nitroxide concentration was followed by EPR spectroscopy, and its reactions with the oxidized heme species were studied using stopped-flow. Nitroxide protects HRP against H 2 O 2 -induced inactivation. The rate of H 2 O 2 dismutation in the presence of nitroxide obeys zero-order kinetics and increases as [nitroxide] increases. Nitroxide acts catalytically since its oxidized form is readily reduced to the nitroxide mainly by H 2 O 2 . The nitroxide efficacy follows the order 2,2,6,6-tetramethyl-piperidine-N-oxyl (TPO)>4-OH-TPO>3-carbamoyl proxyl>4-oxo-TPO, which correlates with the order of the rate constants of nitroxide reactions with compounds I, II, and III. Nitroxide catalytically protects HRP against inactivation induced by H 2 O 2 while modulating its catalase-like activity. The protective role of nitroxide at μM concentrations is attributed to its efficient oxidation by P940, which is the precursor of the inactivated form P670. Modeling the dismutation kinetics in the presence of nitroxide adequately fits the experimental data. In the absence of nitroxide the simulation fits the observed kinetics only if it does not include the formation of a Michaelis-Menten complex. Nitroxides catalytically protect heme proteins against inactivation induced by H 2 O 2 revealing an additional role played by nitroxide antioxidants in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Documenting a significant relationship between macroevolutionary origination rates and Phanerozoic pCO2 levels.

PubMed

Cornette, James L; Lieberman, Bruce S; Goldstein, Robert H

2002-06-11

We show that the rates of diversification of the marine fauna and the levels of atmospheric CO(2) have been closely correlated for the past 545 million years. These results, using two of the fundamental databases of the Earth's biota and the Earth's atmospheric composition, respectively, are highly statistically significant (P < 0.001). The strength of the correlation suggests that one or more environmental variables controlling CO(2) levels have had a profound impact on evolution throughout the history of metazoan life. Comparing our work with highly significant correlations described by D. H. Rothman [Rothman, D. H. (2001) Proc. Natl. Acad. Sci. USA 98, 4305-4310] between total biological diversity and a measure of stable carbon isotope fractionation, we find that the rates of diversification rather than total diversification correlate with environmental variables, and that the rate of diversification follows the record of CO(2) projected by R. A. Berner and Z. Kothavala [Berner, R. A. & Kothavala, Z. (2001) Am. J. Sci. 301, 182-204] more closely than that predicted by Rothman.

Non-thermal escape rates of atmospheric H and D from Mars using MAVEN data

NASA Astrophysics Data System (ADS)

Gacesa, M.; Zahnle, K. J.

2017-12-01

Geological evidence suggests that an ocean of liquid water existed on Mars until at least middle to late Noachian era (4.1 to 3.8 Ga) and possibly, at least episodically, as late as Hesperian. Between 67% and 87% of the total primordial amount of water, equal to about 70 to 110 meters equivalent (spread over the entire Mars' surface), is believed to have escape to space, while about 35 meters remains on or beneath the surface as water ice. Establishing better constraints on these numbers and identifying the responsible atmospheric loss processes remains the major objective of NASA's Mars Atmosphere and Volatile EvolutioN (MAVEN) mission. The ratio of atmospheric Deuterium and Hydrogen (D/H) on Mars is one of the best indicators of water loss to space. While majority of H and D escape through thermal Jeans escape, up to 10% of D can escape to space via non-thermal mechanisms, such as collisions with superthermal neutral atoms. In this study, we present new estimates of non-thermal escape rates of light molecules of interest to the water evolution, including H2, HD, OH, and OD, based on recent measurements of atmospheric density and temperature profiles by MAVEN. The escape mechanisms considered include photochemical sources of hot O, as well as collisions with energetic neutral atoms produced in charge-exchange of solar wind ions with atmospheric gases1,2. Energy transport and escape rates are modeled using quantum reactive scattering formalism3 and seasonal variations are illustrated. Finally, a simple estimate of the role of the non-thermal escape mechanisms in previous eras is given. We conclude that D escape rates can be affected by the non-thermal processes with consequences on the estimates of primordial water inventory based on the D/H ratio. [1] N. Lewkow and V. Kharchenko, Astroph. J., 790, 98 (2014) [2] M. Gacesa, N. Lewkow, V. Kharchenko, Icarus 284, 90 (2017) [3] M. Gacesa and V. Kharchenko, Geophys. Res. Lett., 39, L10203 (2012)

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

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.

Dynamically Close Pairs of Galaxies Selected in the NIR

NASA Astrophysics Data System (ADS)

Keenan, Ryan C.; Foucaud, Sebastien; De Propris, Roberto; Lin, Jing-Hua

2013-07-01

Studies of dynamically close pairs of galaxies can serve as a powerful probe of the galaxy merger rate and its evolution. Here we present a large sample of dynamically close pairs of galaxies selected in the K-band from the UKIDSS LAS. These data span ~ 175 deg2 on the sky in the 2dFGRS equatorial region (10 h < RA < 14h). Combining the 2dFGRS redshifts with those from the SDSS, our K-band selected catalog is > 90% spectroscopically complete at K AB < 16.4. In this study, we focus on quantifying the relative contributions of wet, dry, and mixed mergers to the stellar mass buildup of galaxies over the past 1-2 Gyr.

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity.

PubMed

Semin, B К; Davletshina, L N; Seibert, M; Rubin, A B

2018-01-01

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2 Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH5.7) than at neutral pH (3Mn/RC are extracted at pH6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H 2 Q action, since H 2 Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H 2 Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O 2 at a low rate in the presence of exogenous Ca 2+ (at about 27% of the rate of O 2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O 2 by the 3Mn/1Fe cluster or apparent O 2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of collisional deactivation of O{sub 2}(b{sup 1}{Sigma}{sub g}{sup +}) molecules in a hydrogen-oxygen mixture at high temperatures using laser-induced gratings

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

Kozlov, D. N., E-mail: dnk@kapella.gpi.ru; Kobtsev, V. D.; Stel'makh, O. M.

2013-07-15

Collisional deactivation of O{sub 2}(b{sup 1}{Sigma}{sub g}{sup +}) molecules resonantly excited by a 10 ns pulse of laser radiation with a wavelength of 762 nm in H{sub 2}/O{sub 2} mixtures is experimentally studied. The radiation intensity and hence the molecule excitation efficiency have a spatially periodic modulation that leads to the formation of laser-induced gratings (LIGs) of the refractive index. The study of LIG temporal evolution allows collisional relaxation rates of molecular excited states and gas temperature to be determined. In this work, the b{sup 1}{Sigma}{sub g}{sup +} state of O{sub 2} molecules deactivation rates are measured in a 4.3more » vol % H{sub 2} mixture at the number density of 2 amg in the temperature range 291-850 K. The physical deactivation is shown to dominate in the collisions of H{sub 2} with O{sub 2}(b{sup 1}{Sigma}{sub g}{sup +}) and O{sub 2}(a{sup 1}{Delta}{sub g}) up to temperatures of 780-790 K at time delays up to 10 {mu}s after the excitation pulse. The parameters of the obtained temperature dependence of the (b{sup 1}{Sigma}{sub g}{sup +} state deactivation rate agree well with the data of independent measurements performed earlier at lower temperatures (200-400 K). Tunable diode laser absorption spectroscopy is used to measure the temperature dependence of the number density of the H{sub 2}O molecules which appear as the mixture, as the result of the dark gross reaction with O{sub 2} molecules in the ground state, O{sub 2} + 2H{sub 2} {yields} 2H{sub 2}O. The measurements show that this reaction results in complete transformation of H{sub 2} into H{sub 2}O at temperatures of 790-810 K.« less

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.

Enhanced photocatalytic activity towards degradation and H2 evolution over one dimensional TiO2@MWCNTs heterojunction

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Cao, Shuang; Wu, Zhijiao; Zhao, Suling; Piao, Lingyu

2017-04-01

With the distinct electronic and optical properties, multiwall carbon nanotubes (MWCNTs) are identified as an outstanding catalyst support, which can effectively improve the performance of the TiO2 photocatalysts. Herein, the unique one dimensional TiO2@MWCNTs nanocomposites have been prepared by a facile hydrothermal method. The TiO2 coating layers are extremely uniform and the thickness is adjustable for different nanocomposites. XPS measurements confirm that intimate electronic interactions are existed between MWCNTs and TiO2 via interfacial Tisbnd Osbnd C bond and the photoluminescence intensity of the TiO2@MWCNTs nanocomposites are effectively quenched compared with pure TiO2, suggesting the fast electron transfer rates. The thickness of TiO2 coating layers of the TiO2@MWCNTs nanocomposites plays a significant role in the photocatalytic degradation of organic pollutants, such as methylene blue (MB) and Rhodamine B (RhB), and photocatalytic H2 evolution from water. Due to the formation of one dimensional heterojunction of TiO2@MWCNTs nanocomposites and the positive synergistic effect between TiO2 and carbon nanotubes, it is found that the photocatalytic activity of the system is significantly improved.

Dynamical Effects on the Escape of H and D: Martian Water Reservoirs

NASA Technical Reports Server (NTRS)

Hartle, Richard E.; Einaudi, Franco (Technical Monitor)

2002-01-01

The evolution of water on Mars is dependent on the loss rates of H and D from its atmosphere, where the dominant loss mechanism for these constituents is Jeans escape. Throughout time, preferential escape of H over D has produced a deuterium rich atmosphere with a D/H ratio 5.2 times that of terrestrial water. Motion in the atmosphere of Mars is shown to change the Jeans escape rates of H and D in two important ways: (1) Atmospheric wind and rotation at the exobase increase the escape fluxes of H and D above the corresponding Jeans fluxes. (2) The percentage increase in escape flux due to motion is greatest for D. Recently, several models have been used to estimate the magnitudes of current and ancient crustal water reservoirs on Mars that freely exchange with its atmosphere. Differences in the reservoir sizes are influenced by differences in the composition at the exobase, thermal history of the atmosphere and the D/H ratio of earlier epochs as inferred from meteorites. When motion enhanced Jeans escape is applied to each of these models, it is shown in every case that factors (1) and (2) above lead to current and ancient crustal water reservoirs that are larger than those obtained without motion.

A green desulfurization technique: utilization of flue gas SO2 to produce H2 via a photoelectrochemical process based on Mo-doped BiVO4

NASA Astrophysics Data System (ADS)

Han, Jin; Li, Kejian; Cheng, Hanyun; Zhang, Liwu

2017-12-01

A green photoelectrochemical (PEC) process with simultaneous SO2 removal and H2 production has attracted an increasing attention. The proposed process uses flue gas SO2 to improve H2 production. The improvement of the efficiency of this process is necessary before it can become industrial viable. Herein, we reported a Mo modified BiVO4 photocatalysts for a simultaneous SO2 removal and H2 production. And the PEC performance could be significantly improved with doping and flue gas removal. The evolution rate of H2 and removal of SO2 could be enhanced by almost 3 times after Mo doping as compared with pristine BiVO4. The enhanced H2 production and SO2 removal is attributed to the improved bulk charge carrier transportation after Mo doping, and greatly enhanced oxidation reaction kinetics on the photoanode due to the formation of SO32- after SO2 absorption by the electrolyte. Due to the utilization of SO2 to improve the production of H2, the proposed PEC process may become a profitable desulfurization technique.

A Green Desulfurization Technique: Utilization of Flue Gas SO2 to Produce H2 via a Photoelectrochemical Process Based on Mo-Doped BiVO4

PubMed Central

Han, Jin; Li, Kejian; Cheng, Hanyun; Zhang, Liwu

2017-01-01

A green photoelectrochemical (PEC) process with simultaneous SO2 removal and H2 production has attracted an increasing attention. The proposed process uses flue gas SO2 to improve H2 production. The improvement of the efficiency of this process is necessary before it can become industrial viable. Herein, we reported a Mo modified BiVO4 photocatalysts for a simultaneous SO2 removal and H2 production. And the PEC performance could be significantly improved with doping and flue gas removal. The evolution rate of H2 and removal of SO2 could be enhanced by almost three times after Mo doping as compared with pristine BiVO4. The enhanced H2 production and SO2 removal is attributed to the improved bulk charge carrier transportation after Mo doping, and greatly enhanced oxidation reaction kinetics on the photoanode due to the formation of SO32− after SO2 absorption by the electrolyte. Due to the utilization of SO2 to improve the production of H2, the proposed PEC process may become a profitable desulfurization technique. PMID:29312924

A Green Desulfurization Technique: Utilization of Flue Gas SO2 to Produce H2 via a Photoelectrochemical Process Based on Mo-Doped BiVO4.

PubMed

Han, Jin; Li, Kejian; Cheng, Hanyun; Zhang, Liwu

2017-01-01

A green photoelectrochemical (PEC) process with simultaneous SO 2 removal and H 2 production has attracted an increasing attention. The proposed process uses flue gas SO 2 to improve H 2 production. The improvement of the efficiency of this process is necessary before it can become industrial viable. Herein, we reported a Mo modified BiVO 4 photocatalysts for a simultaneous SO 2 removal and H 2 production. And the PEC performance could be significantly improved with doping and flue gas removal. The evolution rate of H 2 and removal of SO 2 could be enhanced by almost three times after Mo doping as compared with pristine BiVO 4 . The enhanced H 2 production and SO 2 removal is attributed to the improved bulk charge carrier transportation after Mo doping, and greatly enhanced oxidation reaction kinetics on the photoanode due to the formation of [Formula: see text] after SO 2 absorption by the electrolyte. Due to the utilization of SO 2 to improve the production of H 2 , the proposed PEC process may become a profitable desulfurization technique.

Early age hydration of calcium sulfoaluminate (synthetic ye'elimite, C{sub 4}A{sub 3}S{sup ¯}) in the presence of gypsum and varying amounts of calcium hydroxide

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

Hargis, Craig W.; Kirchheim, Ana Paula; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

Suspensions of synthetic ye'elimite (C{sub 4}A{sub 3}S{sup ¯}) in a saturated gypsum (CS{sup ¯}H{sub 2}) and calcium hydroxide (CH) solution were examined in-situ in a wet cell by soft X-ray transmission microscopy and ex-situ by scanning electron microscopy. The most voluminous hydration product observed was ettringite. Ettringite commonly displayed acicular, filiform, reticulated, and stellate crystal habits. Additionally, pastes with C{sub 4}A{sub 3}S{sup ¯}, 15% CS{sup ¯}H{sub 2}, and varying amounts of CH were prepared and examined with X-ray diffraction (XRD) and isothermal calorimetry. The XRD experiments showed that increasing CH content caused more solid solution (SO{sub 4}{sup 2−}/OH{sup −}) AFmmore » phases to form at early ages (< 1 d) and more monosulfate to form at later ages (> 1 d). Calorimetry indicated that the increased production of solid solution AFm was accompanied with an increase in the initial (< 30 min) rate of heat evolution, and increasing CH generally reduced the time till the second maximum rate of heat evolution due to the formation of ettringite and monosulfate.« less

Electrochemical modification of a pyrolytic graphite sheet for improved negative electrode performance in the vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Kabir, Humayun; Gyan, Isaiah O.; Francis Cheng, I.

2017-02-01

The vanadium redox flow battery is a promising technology for buffering renewable energies. It is recognized that negative electrode is the limitation in this device where there are problems of slow heterogeneous electron transfer (HET) of V3+/2+ and parasitic H2 evolution. Any methods aimed at addressing one of these barriers must assess the effects on the other. We examine electrochemical enhancement of a common commercially available material. Treatment of Panasonic pyrolytic graphite sheets is through oxidation at 2.1 V vs. Ag/AgCl for 1 min in 1 M H2SO4. This increases the standard HET rate for V3+/2+ from 3.2 × 10-7 to 1 × 10-3 cm/s, one of the highest in literature and shifts voltammetric reductive peak potential from -1.0 V to -0.65 V in 50 mM V3+ in 1 M H2SO4. Infrared analysis of the surfaces indicates formation of Csbnd OH, Cdbnd O, and Csbnd O functionalities. These groups catalyze HET with V3+/2+ as hypothesized by Skyllas-Kasacos. Also of significance is that electrode modification decreases the fraction of the current directed towards H2 evolution. This proportion decreases by two orders of a magnitude from 12% to 0.1% as measured at the respective voltammetric peak potentials of -1.0 V (pristine) and -0.65 V (modified).

Photosystem II Peripheral Accessory Chlorophyll Mutants in Chlamydomonas reinhardtii. Biochemical Characterization and Sensitivity to Photo-Inhibition12

PubMed Central

Ruffle, Stuart V.; Wang, Jun; Johnston, Heather G.; Gustafson, Terry L.; Hutchison, Ronald S.; Minagawa, Jun; Crofts, Anthony; Sayre, Richard T.

2001-01-01

In addition to the four chlorophylls (Chls) involved in primary charge separation, the photosystem II (PSII) reaction center polypeptides, D1 and D2, coordinate a pair of symmetry-related, peripheral accessory Chls. These Chls are axially coordinated by the D1-H118 and D2-H117 residues and are in close association with the proximal Chl antennae proteins, CP43 and CP47. To gain insight into the function(s) of each of the peripheral Chls, we generated site-specific mutations of the amino acid residues that coordinate these Chls and characterized their energy and electron transfer properties. Our results demonstrate that D1-H118 and D2-H117 mutants differ with respect to: (a) their relative numbers of functional PSII complexes, (b) their relative ability to stabilize charge-separated states, (c) light-harvesting efficiency, and (d) their sensitivity to photo-inhibition. The D2-H117N and D2-H117Q mutants had reduced levels of functional PSII complexes and oxygen evolution capacity as well as reduced light-harvesting efficiencies relative to wild-type cells. In contrast, the D1-H118Q mutant was capable of near wild-type rates of oxygen evolution at saturating light intensities. The D1-H118Q mutant also was substantially more resistant to photo-inhibition than wild type. This reduced sensitivity to photo-inhibition is presumably associated with a reduced light-harvesting efficiency in this mutant. Finally, it is noted that the PSII peripheral accessory Chls have similarities to a to a pair of Chls also present in the PSI reaction center complex. PMID:11598237

Beyond Jcrit: a critical curve for suppression of H2-cooling in protogalaxies

NASA Astrophysics Data System (ADS)

Wolcott-Green, J.; Haiman, Z.; Bryan, G. L.

2017-08-01

Suppression of H2-cooling in early protogalaxies has important implications for the formation of supermassive black hole seeds, the first generation of stars and the epoch of reionization. This suppression can occur via photodissociation of H2 (by ultraviolet Lyman-Werner [LW] photons) or by photodetachment of H-, a precursor in H2 formation (by infrared [IR] photons). Previous studies have typically adopted idealized spectra, with a blackbody or a power-law shape, in modelling the chemistry of metal-free protogalaxies, and utilized a single parameter, the critical UV flux, or Jcrit, to determine whether H2-cooling is prevented. This can be misleading, as independent of the spectral shape, there is a critical curve in the (k_LW,k_H^-) plane, where kLW and k_H^- are the H2-dissocation rates by LW and IR photons, which determines whether a protogalaxy can cool below ˜1000 K. We use a one-zone model to follow the chemical and thermal evolution of gravitationally collapsing protogalactic gas, to compute this critical curve and provide an accurate analytical fit for it. We improve on previous works by considering a variety of more realistic Pop III or Pop II-type spectra from population synthesis models and perform fully frequency-dependent calculations of the H2-photodissociation rates for each spectrum. We compute the ratio k_LW/k_H^- for each spectrum, as well as the minimum stellar mass M*, for various IMFs and metallicities, required to prevent cooling in a neighbouring halo a distance d away. We provide critical M*/d2 values for suppression of H2-cooling, with analytic fits, which can be used in future studies.

Molecular dynamics investigation of dynamical properties of phosphatidylethanolamine lipid bilayers

NASA Astrophysics Data System (ADS)

Pitman, Michael C.; Suits, Frank; Gawrisch, Klaus; Feller, Scott E.

2005-06-01

We describe the dynamic behavior of a 1-stearoyl-2-oleoyl-phosphatidylethanolamine (SOPE) bilayer from a 20ns molecular dynamics simulation. The dynamics of individual molecules are characterized in terms of H2 spin-lattice relaxation rates, nuclear overhauser enhancement spectroscopy (NOESY) cross-relaxation rates, and lateral diffusion coefficients. Additionally, we describe the dynamics of hydrogen bonding through an analysis of hydrogen bond lifetimes and the time evolution of clusters of hydrogen bonded lipids. The simulated trajectory is shown to be consistent with experimental measures of internal, intermolecular, and diffusive motion. Consistent with our analysis of SOPE structure in the companion paper, we see hydrogen bonding dominating the dynamics of the interface region. Comparison of H2 T1 relaxation rates for chain methylene segments in phosphatidylcholine and phosphatidylethanolamine bilayers indicates that slower motion resulting from hydrogen bonding extends at least three carbons into the hydrophobic core. NOESY cross-relaxation rates compare well with experimental values, indicating the observed hydrogen bonding dynamics are realistic. Calculated lateral diffusion rates (4±1×10-8cm2/s) are comparable, though somewhat lower than, those determined by pulsed field gradient NMR methods.

Biochemical adaptation to ocean acidification.

PubMed

Stillman, Jonathon H; Paganini, Adam W

2015-06-01

The change in oceanic carbonate chemistry due to increased atmospheric PCO2  has caused pH to decline in marine surface waters, a phenomenon known as ocean acidification (OA). The effects of OA on organisms have been shown to be widespread among diverse taxa from a wide range of habitats. The majority of studies of organismal response to OA are in short-term exposures to future levels of PCO2 . From such studies, much information has been gathered on plastic responses organisms may make in the future that are beneficial or harmful to fitness. Relatively few studies have examined whether organisms can adapt to negative-fitness consequences of plastic responses to OA. We outline major approaches that have been used to study the adaptive potential for organisms to OA, which include comparative studies and experimental evolution. Organisms that inhabit a range of pH environments (e.g. pH gradients at volcanic CO2 seeps or in upwelling zones) have great potential for studies that identify adaptive shifts that have occurred through evolution. Comparative studies have advanced our understanding of adaptation to OA by linking whole-organism responses with cellular mechanisms. Such optimization of function provides a link between genetic variation and adaptive evolution in tuning optimal function of rate-limiting cellular processes in different pH conditions. For example, in experimental evolution studies of organisms with short generation times (e.g. phytoplankton), hundreds of generations of growth under future conditions has resulted in fixed differences in gene expression related to acid-base regulation. However, biochemical mechanisms for adaptive responses to OA have yet to be fully characterized, and are likely to be more complex than simply changes in gene expression or protein modification. Finally, we present a hypothesis regarding an unexplored area for biochemical adaptation to ocean acidification. In this hypothesis, proteins and membranes exposed to the external environment, such as epithelial tissues, may be susceptible to changes in external pH. Such biochemical systems could be adapted to a reduced pH environment by adjustment of weak bonds in an analogous fashion to biochemical adaptation to temperature. Whether such biochemical adaptation to OA exists remains to be discovered. © 2015. Published by The Company of Biologists Ltd.

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.

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.

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.

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.

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.

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

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

Li, Hui; Wen, Peng; Hoxie, Adam

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

DOE PAGES

Li, Hui; Wen, Peng; Hoxie, Adam; ...

2018-04-30

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Interface Engineering of Colloidal CdSe Quantum Dot Thin Films as Acid-Stable Photocathodes for Solar-Driven Hydrogen Evolution.

PubMed

Li, Hui; Wen, Peng; Hoxie, Adam; Dun, Chaochao; Adhikari, Shiba; Li, Qi; Lu, Chang; Itanze, Dominique S; Jiang, Lin; Carroll, David; Lachgar, Abdou; Qiu, Yejun; Geyer, Scott M

2018-05-23

Colloidal semiconductor quantum dot (CQD)-based photocathodes for solar-driven hydrogen evolution have attracted significant attention because of their tunable size, nanostructured morphology, crystalline orientation, and band gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM-1.5G, 100 mW/cm 2 ) at a potential of 0 V versus reversible hydrogen electrode (RHE) ( j 0 ) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V versus RHE and long-term stability with negligible degradation. In the acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited because of photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared with 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge-transfer rate, and faster reaction kinetics. We believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.

Glutathione-capped gold nanoclusters as photosensitizers. Visible light-induced hydrogen generation in neutral water.

PubMed

Chen, Yong-Siou; Kamat, Prashant V

2014-04-23

Glutathione-capped metal nanoclusters (Aux-GSH NCs) which exhibit molecular-like properties are employed as a photosensitizer for hydrogen generation in a photoelectrochemical cell (PEC) and a photocatalytic slurry reactor. The reversible reduction (E(0) = -0.63 V vs RHE) and oxidation (E(0) = 0.97 and 1.51 V vs RHE) potentials of these metal nanoclusters make them suitable for driving the water-splitting reaction. When a mesoscopic TiO2 film sensitized by Aux-GSH NCs is used as the photoanode with a Pt counter electrode in aqueous buffer solution (pH = 7), we observe significant photocurrent activity under visible light (400-500 nm) excitation. Additionally, sensitizing Pt/TiO2 nanoparticles with Aux-GSH NCs in an aqueous slurry system and irradiating with visible light produce H2 at a rate of 0.3 mmol of hydrogen/h/g of Aux-GSH NCs. The rate of H2 evolution is significantly enhanced (∼5 times) when a sacrificial donor, such as EDTA, is introduced into the system. Using metal nanoclusters as a photosensitizer for hydrogen generation lays the foundation for the future exploration of other metal nanoclusters with well-controlled numbers of metal atoms and capping ligands.

3D ordered porous MoxC (x = 1 or 2) for advanced hydrogen evolution and Li storage.

PubMed

Yu, Hong; Fan, Haosen; Wang, Jiong; Zheng, Yun; Dai, Zhengfei; Lu, Yizhong; Kong, Junhua; Wang, Xin; Kim, Young Jin; Yan, Qingyu; Lee, Jong-Min

2017-06-01

3D ordered porous structures of Mo x C are prepared with different Mo to C ratios and tested for two possible promising applications: hydrogen evolution reaction (HER) through water splitting and lithium ion batteries (LIBs). Mo 2 C and MoC with 3D periodic ordered structures are prepared with a similar process but different precursors. The 3D ordered porous MoC exhibits excellent cycling stability and rate performance as an anode material for LIBs. A discharge capacity of 450.9 mA h g -1 is maintained up to 3000 cycles at 10.0 A g -1 . The Mo 2 C with a similar ordered porous structure shows impressive electrocatalytic activity for the HER in neutral, alkaline and acidic pH solutions. In particular, Mo 2 C shows an onset potential of only 33 mV versus a reversible hydrogen electrode (RHE) and a Tafel slope of 42.5 mV dec -1 in a neutral aqueous solution (1.0 M phosphate buffer solution), which is approaching that of the commercial Pt/C catalyst.

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

Luo, Si; Nguyen-Phan, Thuy-Duong; Vovchok, Dimitriy

The splitting of water into molecular hydrogen and oxygen with the use of renewable solar energy is considered one of the most promising routes to yield sustainable fuel. In this paper, we report the H 2 evolution performance of gallium doped TiO 2 photocatalysts with varying degrees of Ga dopant. The gallium(III) ions induced significant changes in the structural, textural and electronic properties of TiO 2 nanoparticles, resulting in remarkably enhanced photocatalytic activity and good stability for H 2 production. Ga 3+ ions can act as hole traps that enable a large number of excited electrons to migrate towards themore » TiO 2 surface, thereby facilitating electron transfer and charge separation. Additionally, the cationic dopant and its induced defects might introduce a mid-gap state, promoting electron migration and prolonging the lifetime of charge carrier pairs. We have discovered that the optimal Ga dopant concentration was 3.125 at% and that the incorporation of platinum (0.5 wt%) as a co-catalyst further improved the H 2 evolution rate up to 5722 μmol g -1 h -1. Pt not only acts as an electron sink, drastically increasing the electron/hole pair lifetime, but it also creates an intimate contact at the heterojunction between Pt and Ga-TiO 2, thus improving the interfacial electron transfer process. Finally, these catalyst design strategies provide new ways of designing transition metal photocatalysts that improve green fuel production from renewable solar energy and water.« less

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 .

Hydrolytic properties of phenylalanyl- and N-acetylphenylalanyl adenylate anhydrides

NASA Technical Reports Server (NTRS)

Lacey, J. C., Jr.; Mullins, D. W., Jr.; Senaratne, N.

1984-01-01

The hydrolysis of phenylalynyl- and N-acetylephenylalanyl adenylate anhydrides (AcPhe-AMP) is studied experimentally using a new spectrophotometric method. The hydrolysis process was analyzed at low concentrations (0.0001 M), constant temperature of 25 C, constant buffer concentration (0.05 M), and as a function of pH. It is found that while Phe-AMP is susceptible to attack by OH(-), AcPhe-AMP is susceptible to acid decomposition as well. At a pH of 4 to 8, Phe-AMP hydolyzes faster than AcPhe-AMP, but at pH less than four or greater than eight, the blocked form hydrolyzes faster. Both forms are attacked by H2O at the same rate. The rate laws for the various hydrolytic mechanisms and the activation energies for the hydrolyses at pH 7.1 are given in a table, and the possible relevance of the findings to the origin and evolution of the process of protein synthesis is discussed.

Emission line galaxy pairs up to z=1.5 from the WISP survey

NASA Astrophysics Data System (ADS)

Teplitz, Harry I.; Dai, Yu Sophia; Malkan, Matthew Arnold; Scarlata, Claudia; Colbert, James W.; Atek, Hakim; Bagley, Micaela B.; Baronchelli, Ivano; Bedregal, Alejandro; Beck, Melanie; Bunker, Andrew; Dominguez, Alberto; Hathi, Nimish P.; Henry, Alaina L.; Mehta, Vihang; Pahl, Anthony; Rafelski, Marc; Ross, Nathaniel; Rutkowski, Michael J.; Siana, Brian D.; WISPs Team

2016-01-01

We present a sample of spectroscopically identified emission line galaxy pairs up to z=1.5 from WISPs (WFC3 Infrared Spectroscopic Parallel survey) using high resolution direct and grism images from HST. We searched ~150 fields with a covered area of ~600 arcmin^2, and a comoving volume of > 400 Gpc^3 at z=1-2, and found ~80 very close physical pairs (projected separation Dp < 50 h^{-1}kpc, relative velocity d_v < 500 kms^{-1}), and ~100 close physical pairs (50 < Dp < 100 h^{-1}kpc, d_v < 1000 kms^{-1}) of emission line galaxies, including two dozen triplets and quadruples. In this poster we present the multi-wavelength data, star formation rate (SFR), mass ratio, and study the merger rate evolution with this special galaxy pair sample.

Molecular Dynamics Studies of Thermal Induced Chemistry in Tatb

NASA Astrophysics Data System (ADS)

Quenneville, J.; Germann, T. C.; Thompson, A. P.; Kober, E. M.

2007-12-01

A reactive force field (ReaxFF) is used with molecular dynamics to probe the chemistry induced by intense heating (`accelerated cook-off') of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Large-system simulations are desired for TATB because of the high degree of carbon clustering expected in this material. Using small, 32-molecule simulations, we calculate the reaction rate as a function of temperature and compare the Arrhenius-predicted activation energy with experiment. Decomposition product evolution (mainly N2, H2O, CO2 and graphitic carbon clusters) is followed using a 576-molecule larger simulation, which also illustrates the effect of system size on both carbon clustering and reaction rate.

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

Visible light driven multifunctional photocatalysis in TeO2-based semiconductor glass ceramics

NASA Astrophysics Data System (ADS)

Kushwaha, Himmat Singh; Thomas, Paramanandam; Vaish, Rahul

2017-01-01

Photocatalytic xCaCu3Ti4O12-(100-x)TeO2 (x=0.25 mol% to 3 mol%), glass nanocomposites were fabricated and investigated for wastewater treatment, self-cleaning surfaces, and photocatalytic hydrogen evolution. Visible light active crystals of Cu-doped TiO2 and TiTe3O8 were grown by optimized crystallization of as-quenched glasses. The visible light photocatalytic activity of glass samples was investigated for estrogenic pharmaceutical pollutants, and the degradation rate was obtained as 168.56 min-1 m-2. A higher photocatalytic H2 production rate was observed (135 μmole h-1 g-1) for the crystallized CaCu3Ti4O12-TeO2 (x=3. 0) glass plate under visible light. The self-cleaning performance was observed using contact angle measurements for water under dark and light conditions. These visible light active glass ceramics are a cost effective sustainable solution for water treatment and self-cleaning applications.

Effect of aqueous Si/Mg ratio and pH on the nucleation and growth of sepiolite at 25 °C

NASA Astrophysics Data System (ADS)

Baldermann, Andre; Mavromatis, Vasileios; Frick, Paula M.; Dietzel, Martin

2018-04-01

Sepiolite [Mg4Si6O15(OH)2·6H2O] is a trioctahedral 2:1 Mg-silicate that has been often used to reconstruct the evolution of sedimentary environments and facies in the geological record. To date, however, the reaction paths underlying sepiolite formation are poorly constrained and most of the existing models are based on empirical observations. In order to shed light on the mechanisms controlling the formation of this mineral phase, in the present study, sepiolite was precipitated at 25 ± 1 °C from modified seawater and MgCl2 solutions undersaturated with respect to brucite and amorphous silica. Although a suite of hydrous Mg-silicates, such as kerolite, saponite, stevensite and talc, were oversaturated in the solutions at a higher level relative to sepiolite at any time of reaction, poorly crystallized, aluminous sepiolite was the only precipitate after 91 days. The precipitated sepiolite [Mg3.4-3.8Al0.1-0.4)∑3.8-3.9(Si5.9-6.0Al0-0.1)O15(OH)2·nH2O] shares a number of structural and chemical similarities with natural sepiolite, such as a fibrous crystal shape and an atomic Si/(Si + Mg+Al) ratio of ∼0.61. The proposed reaction path for the formation of sepiolite is based on the temporal evolution of the chemical compositions of the experimental solution and solids: (i) Nucleation and growth of Al-sepiolite occurred during the first 8 days of the experimental runs via condensation and polymerization of Sisbnd OH tetrahedra onto Mg-Al-O-OH template sheets at a precipitation rate of ∼2.19 ± 0.01 × 10-10 mol s-1. (ii) At decreasing pH and in the absence of [Al]aq this intermediate phase transformed into aluminous sepiolite at a slower crystal growth rate of ∼1.08 ± 0.02 × 10-12 mol s-1. This finding explains the high abundances of sepiolite in highly alkaline, evaporitic, lacustrine and soil environments, where the growth rates of sepiolite are considered faster (10-11 to 10-10 mol s-1, Brady, 1992). We propose that (i) low rates of Mg2+ ion dehydration and silica condensation and polymerization at the surface of the initial precipitate, (ii) the formation of MgS 040 aquo-complexes and (iii) the reduced sorption rates of [Si]aq and [Mg]aq at the active growth sites on sepiolite surfaces at pH ≤ 8.3 retard the precipitation of sepiolite in marine-diagenetic environments.

Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes

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

Brown, K. A.; Wilker, M. B.; Boehm, M.

2012-03-28

We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H{sup +} to H{sub 2} at a CaI turnover frequency of 380-900 s{sup -1} and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H{sub 2}. Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H{sub 2} evolution by CaI. Production of H{sub 2} by CdS:CaImore » was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H{sub 2} production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H{sub 2} production was limited by the rate of photon absorption ({approx}1 ms{sup -1}) and not by the turnover of CaI. Complexes were capable of H{sub 2} production for up to 4 h with a total turnover number of 106 before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.« less

H2 Production Under Visible Light Irradiation from Aqueous Methanol Solution on CaTiO3:Cu Prepared by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Lim, Sung Nam; Song, Shin Ae; Jeong, Yong-Cheol; Kang, Hyun Woo; Park, Seung Bin; Kim, Ki Young

2017-10-01

Perovskite-type photocatalysts of CaCu x Ti1- x O3 (0 ≤ x ≤ 0.02) powder were prepared by spray pyrolysis of aqueous solution or aqueous solution with polymeric additive. The effects of the amount of copper ions doped in the photocatalyst and the precursor type on the photocatalytic activity under visible-light irradiation were investigated. The crystal structure, oxidation state, and light adsorption properties of the prepared photocatalysts were analyzed using x-ray diffraction, x-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy, respectively. The doping of copper ions in CaTiO3 allowed visible-light absorption owing to a narrowing of the band gap energy of the host material through the formation of a new donor level for copper ions. Among the doped samples prepared from the aqueous precursor, CaTiO3 doped with 1 mol.% copper ions had the highest hydrogen evolution rate (140.7 μmol g-1 h-1). Notably, the hydrogen evolution rate of the photocatalyst doped with 1 mol.% copper ions prepared from the aqueous precursor with polymeric additive (295.0 μmol g-1 h-1) was two times greater than that prepared from the aqueous precursor, due to the morphology effect.

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.

Evolution of structure-reactivity correlations for the hydrogen abstraction reaction by chlorine atom.

PubMed

Poutsma, Marvin L

2013-01-31

Empirical structure-reactivity correlations are developed for log k(298), the gas-phase rate constants for the reaction (Cl(•) + HCR(3) → ClH + CR(3)(•)). It has long been recognized that correlation with Δ(r)H is weak. The poor performance of the linear Evans-Polanyi formulation is illustrated and was little improved by adding a quadratic term, for example, by making its slope smoothly dependent on Δ(r)H [η ≡ (Δ(r)H - Δ(r)H(min))/(Δ(r)H(max) - Δ(r)H(min))]. The "polar effect" ((δ-)Cl---H---CR(3)(δ+))(++) has also been long discussed, but there is no formalization of this dependence based on widely available independent variable(s). Using the sum of Hammett constants for the R substituents also gave at best modest correlations, either for σ(para) or for its dissection into F (field/inductive) and R (resonance) effects. Much greater success was achieved by combining these approaches with the preferred independent variable set being either [(Δ(r)H)(2), Δ(r)H, ΣF, and ΣR] or [η, Δ(r)H, ΣF, and ΣR]. For 64 rate constants that span 7 orders of magnitude, these correlation formulations give r(2) > 0.87 and a mean unsigned deviation of <0.5 log k units, with even better performance if primary, secondary, and tertiary reaction centers are treated separately.

Evolutionary and Biotechnological Implications of Robust Hydrogenase Activity in Halophilic Strains of Tetraselmis

PubMed Central

D'Adamo, Sarah; Jinkerson, Robert E.; Boyd, Eric S.; Brown, Susan L.; Baxter, Bonnie K.; Peters, John W.; Posewitz, Matthew C.

2014-01-01

Although significant advances in H2 photoproduction have recently been realized in fresh water algae (e.g. Chlamydomonas reinhardtii), relatively few studies have focused on H2 production and hydrogenase adaptations in marine or halophilic algae. Salt water organisms likely offer several advantages for biotechnological H2 production due to the global abundance of salt water, decreased H2 and O2 solubility in saline and hypersaline systems, and the ability of extracellular NaCl levels to influence metabolism. We screened unialgal isolates obtained from hypersaline ecosystems in the southwest United States and identified two distinct halophilic strains of the genus Tetraselmis (GSL1 and QNM1) that exhibit both robust fermentative and photo H2-production activities. The influence of salinity (3.5%, 5.5% and 7.0% w/v NaCl) on H2 production was examined during anoxic acclimation, with the greatest in vivo H2-production rates observed at 7.0% NaCl. These Tetraselmis strains maintain robust hydrogenase activity even after 24 h of anoxic acclimation and show increased hydrogenase activity relative to C. reinhardtii after extended anoxia. Transcriptional analysis of Tetraselmis GSL1 enabled sequencing of the cDNA encoding the FeFe-hydrogenase structural enzyme (HYDA) and its maturation proteins (HYDE, HYDEF and HYDG). In contrast to freshwater Chlorophyceae, the halophilic Tetraselmis GSL1 strain likely encodes a single HYDA and two copies of HYDE, one of which is fused to HYDF. Phylogenetic analyses of HYDA and concatenated HYDA, HYDE, HYDF and HYDG in Tetraselmis GSL1 fill existing knowledge gaps in the evolution of algal hydrogenases and indicate that the algal hydrogenases sequenced to date are derived from a common ancestor. This is consistent with recent hypotheses that suggest fermentative metabolism in the majority of eukaryotes is derived from a common base set of enzymes that emerged early in eukaryotic evolution with subsequent losses in some organisms. PMID:24465722

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

Whole Genome Characterization, Phylogenetic and Genome Signature Analysis of Human Pandemic H1N1 Virus in Thailand, 2009–2012

PubMed Central

Makkoch, Jarika; Suwannakarn, Kamol; Payungporn, Sunchai; Prachayangprecha, Slinporn; Cheiocharnsin, Thaweesak; Linsuwanon, Piyada; Theamboonlers, Apiradee; Poovorawan, Yong

2012-01-01

Background Three waves of human pandemic influenza occurred in Thailand in 2009–2012. The genome signature features and evolution of pH1N1 need to be characterized to elucidate the aspects responsible for the multiple waves of pandemic. Methodology/Findings Forty whole genome sequences and 584 partial sequences of pH1N1 circulating in Thailand, divided into 1st, 2nd and 3rd wave and post-pandemic were characterized and 77 genome signatures were analyzed. Phylogenetic trees of concatenated whole genome and HA gene sequences were constructed calculating substitution rate and dN/dS of each gene. Phylogenetic analysis showed a distinct pattern of pH1N1 circulation in Thailand, with the first two isolates from May, 2009 belonging to clade 5 while clades 5, 6 and 7 co-circulated during the first wave of pH1N1 pandemic in Thailand. Clade 8 predominated during the second wave and different proportions of the pH1N1 viruses circulating during the third wave and post pandemic period belonged to clades 8, 11.1 and 11.2. The mutation analysis of pH1N1 revealed many adaptive mutations which have become the signature of each clade and may be responsible for the multiple pandemic waves in Thailand, especially with regard to clades 11.1 and 11.2 as evidenced with V731I, G154D of PB1 gene, PA I330V, HA A214T S160G and S202T. The substitution rate of pH1N1 in Thailand ranged from 2.53×10−3±0.02 (M2 genes) to 5.27×10−3±0.03 per site per year (NA gene). Conclusions All results suggested that this virus is still adaptive, maybe to evade the host's immune response and tends to remain in the human host although the dN/dS were under purifying selection in all 8 genes. Due to the gradual evolution of pH1N1 in Thailand, continuous monitoring is essential for evaluation and surveillance to be prepared for and able to control future influenza activities. PMID:23251479

Revealing the relationship between the photocatalytic property and structure characteristic of reduced TiO2 by hydrogen and carbon monoxide treatment.

PubMed

Liu, Yunpeng; Li, Yuhang; Yang, Siyuan; Lin, Yuan; Zuo, Jianliang; Liang, Hong; Peng, Feng

2018-06-04

The hydrogenation (reduction) has been considered as an effective method to improve the photocatalytic activity of TiO2, however, the underlying relationship between structure and photocatalytic performance has still not been adequately unveiled so far. Herein, to obtain insight into the effect of structure on photocatalytic activity, two types of reduced TiO2 were prepared by CO (CO-TiO2) and H2 (H-TiO2), respectively. For H-TiO2, Ti-H bonds and oxygen vacancies are formed on the surface of H-TiO2, resulting in a more disorder surface lattice. However, for CO-TiO2, the more Ti-OH bonds are formed on the surface and the more bulk oxygen vacancies are introduced, the disorder layer of CO-TiO2 is relatively thin owing to the most of surface vacancies repaired by Ti-OH bonds. Under the simulated solar irradiation, the photocatalytic H2 evolution rate of CO-TiO2 reaches 7.17 mmol g-1 h-1, which is 4.14 and 1.50 times those of TiO2 and H-TiO2, respectively. The photocatalytic degradation rate constant of methyl orange on CO-TiO2 is 2.45 and 6.39 times those on H-TiO2 and TiO2. The superior photocatalytic activity of CO-TiO2 is attributed to the effective separation and transfer of the photo-generated electron-hole pairs, due to the synergistic effects of oxygen vacancies and surface Ti-OH bonds. This study reveals the relation between the photocatalytic property and structure, and provides a new method to prepare highly active TiO2 for H2 production and environmental treatment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adaptation of the autotrophic acetogen Sporomusa ovata to methanol accelerates the conversion of CO2 to organic products.

PubMed

Tremblay, Pier-Luc; Höglund, Daniel; Koza, Anna; Bonde, Ida; Zhang, Tian

2015-11-04

Acetogens are efficient microbial catalysts for bioprocesses converting C1 compounds into organic products. Here, an adaptive laboratory evolution approach was implemented to adapt Sporomusa ovata for faster autotrophic metabolism and CO2 conversion to organic chemicals. S. ovata was first adapted to grow quicker autotrophically with methanol, a toxic C1 compound, as the sole substrate. Better growth on different concentrations of methanol and with H2-CO2 indicated the adapted strain had a more efficient autotrophic metabolism and a higher tolerance to solvent. The growth rate on methanol was increased 5-fold. Furthermore, acetate production rate from CO2 with an electrode serving as the electron donor was increased 6.5-fold confirming that the acceleration of the autotrophic metabolism of the adapted strain is independent of the electron donor provided. Whole-genome sequencing, transcriptomic, and biochemical studies revealed that the molecular mechanisms responsible for the novel characteristics of the adapted strain were associated with the methanol oxidation pathway and the Wood-Ljungdahl pathway of acetogens along with biosynthetic pathways, cell wall components, and protein chaperones. The results demonstrate that an efficient strategy to increase rates of CO2 conversion in bioprocesses like microbial electrosynthesis is to evolve the microbial catalyst by adaptive laboratory evolution to optimize its autotrophic metabolism.

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

Galaxy Downsizing Evidenced by Hybrid Evolutionary Tracks

NASA Astrophysics Data System (ADS)

Firmani, C.; Avila-Reese, V.

2010-11-01

The stellar-dark halo mass relation of galaxies at different redshifts, M s(M h, z), encloses relevant features concerning their physical processes and evolution. This sequence of relations, defined in the range 0 < z < 4, together with average Λ cold dark matter (ΛCDM) halo mass aggregation histories (MAHs), is used here for inferring average galaxian hybrid evolutionary tracks (GHETs), where "hybrid" remarks on the combination of observational (M s) and theoretical (M h) ingredients. As a result of our approach, a unified picture of stellar and halo mass buildup, population migration, and downsizing of galaxies as a function of mass is presented. The inferred average M s growth histories (GHETs) of the highest and lowest mass galaxies are definitively quite different from the average MAHs, M h(z), of the corresponding dark halos. Depending on how a given M h(z) compares with the mass at which the M s-to-M h ratio curve peaks at the epoch z, M hp(z), two evolutionary phases are evidenced: (1) galaxies in an active regime of M s growth when M h < M hp and (2) galaxies in a quiescent or passive regime when M h>M hp. The typical M s at which galaxies transit from the active (star-forming) to the quiescent regime, M tran, increases with z, log(M tran/M sun) ≈10.30 + 0.55z, making evident a population downsizing phenomenon. This result agrees with independent observational determinations based on the evolution of the galaxy stellar mass function decomposition into blue and red galaxy populations. The specific star formation rate (SSFR) predicted from the derivative of the GHET is consistent with direct measures of the SSFR for galaxies at different redshifts, though both sets of observational inferences are independent. The average GHETs of galaxies smaller than M tran at z = 0 (M s ≈1010.3 M sun, M h ≈1011.8 M sun) did not reach the quiescent regime, and for them, the lower the mass, the faster the later M s growth rate (downsizing in SSFR). The GHETs allow us to predict the transition rate in the number density of active to passive population; the predicted values agree with direct estimates of the growth rate in the number density for the (massive) red population up to z ~ 1. We show that ΛCDM-based models of disk galaxy evolution, including feedback-driven outflows, are able to reproduce the low-mass side of the M s-M h relation at z ~ 0, but at higher z strongly disagree with the GHETs: models do not reproduce the strong downsizing in SSFR and the high SSFR of low-mass galaxies.

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.

Controlled Synthesis of CuS/TiO2 Heterostructured Nanocomposites for Enhanced Photocatalytic Hydrogen Generation through Water Splitting.

PubMed

Chandra, Moumita; Bhunia, Kousik; Pradhan, Debabrata

2018-04-16

Photocatalytic hydrogen (H 2 ) generation through water splitting has attracted substantial attention as a clean and renewable energy generation process that has enormous potential in converting solar-to-chemical energy using suitable photocatalysts. The major bottleneck in the development of semiconductor-based photocatalysts lies in poor light absorption and fast recombination of photogenerated electron-hole pairs. Herein we report the synthesis of CuS/TiO 2 heterostructured nanocomposites with varied TiO 2 contents via simple hydrothermal and solution-based process. The morphology, crystal structure, composition, and optical properties of the as-synthesized CuS/TiO 2 hybrids are evaluated in detail. Controlling the CuS/TiO 2 ratio to an optimum value leads to the highest photocatalytic H 2 production rate of 1262 μmol h -1 g -1 , which is 9.7 and 9.3 times higher than that of pristine TiO 2 nanospindles and CuS nanoflakes under irradiation, respectively. The enhancement in the H 2 evolution rate is attributed to increased light absorption and efficient charge separation with an optimum CuS coverage on TiO 2 . The photoluminescence and photoelectrochemical measurements further confirm the efficient separation of charge carriers in the CuS/TiO 2 hybrid. The mechanism and synergistic role of CuS and TiO 2 semiconductors for enhanced photoactivity is further delineated.

Photoelectrochemistry by Design: Tailoring the Nanoscale Structure of Pt/NiO Composites Leads to Enhanced Photoelectrochemical Hydrogen Evolution Performance

PubMed Central

2017-01-01

Photoelectrochemical hydrogen evolution is a promising avenue to store the energy of sunlight in the form of chemical bonds. The recent rapid development of new synthetic approaches enables the nanoscale engineering of semiconductor photoelectrodes, thus tailoring their physicochemical properties toward efficient H2 formation. In this work, we carried out the parallel optimization of the morphological features of the semiconductor light absorber (NiO) and the cocatalyst (Pt). While nanoporous NiO films were obtained by electrochemical anodization, the monodisperse Pt nanoparticles were synthesized using wet chemical methods. The Pt/NiO nanocomposites were characterized by XRD, XPS, SEM, ED, TEM, cyclic voltammetry, photovoltammetry, EIS, etc. The relative enhancement of the photocurrent was demonstrated as a function of the nanoparticle size and loading. For mass-specific surface activity the smallest nanoparticles (2.0 and 4.8 nm) showed the best performance. After deconvoluting the trivial geometrical effects (stemming from the variation of Pt particle size and thus the electroactive surface area), however, the intermediate particle sizes (4.8 and 7.2 nm) were found to be optimal. Under optimized conditions, a 20-fold increase in the photocurrent (and thus the H2 evolution rates) was observed for the nanostructured Pt/NiO composite, compared to the benchmark nanoparticulate NiO film. PMID:28620447

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.

Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

2014-12-01

C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.

On-line estimation of O2 production, CO2 uptake, and growth kinetics of microalgal cultures in a gas-tight photobioreactor

PubMed Central

Riisgård, Frederik Kier; Gunther, William Stuart; Lønsmann Iversen, Jens Jørgen

2006-01-01

Growth of the green algae Chlamydomonas reinhardtii and Chlorella sp. in batch cultures was investigated in a novel gas-tight photobioreactor, in which CO2, H2, and N2 were titrated into the gas phase to control medium pH, dissolved oxygen partial pressure, and headspace pressure, respectively. The exit gas from the reactor was circulated through a loop of tubing and re-introduced into the culture. CO2 uptake was estimated from the addition of CO2 as acidic titrant and O2 evolution was estimated from titration by H2, which was used to reduce O2 over a Pd catalyst. The photosynthetic quotient, PQ, was estimated as the ratio between O2 evolution and CO2 up-take rates. NH4+, NO2−, or NO3− was the final cell density limiting nutrient. Cultures of both algae were, in general, characterised by a nitrogen sufficient growth phase followed by a nitrogen depleted phase in which starch was the major product. The estimated PQ values were dependent on the level of oxidation of the nitrogen source. The PQ was 1 with NH4+ as the nitrogen source and 1.3 when NO3− was the nitrogen source. In cultures grown on all nitrogen sources, the PQ value approached 1 when the nitrogen source was depleted and starch synthesis became dominant, to further increase towards 1.3 over a period of 3–4 days. This latter increase in PQ, which was indicative of production of reduced compounds like lipids, correlated with a simultaneous increase in the degree of reduction of the biomass. When using the titrations of CO2 and H2 into the reactor headspace to estimate the up-take of CO2, the production of O2, and the PQ, the rate of biomass production could be followed, the stoichiometrical composition of the produced algal biomass could be estimated, and different growth phases could be identified. PMID:19396354

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.

Kinetics of nitrogenase of Klebsiella pneumoniae. Heterotropic interactions between magnesium-adenosine 5'-diphosphate and magnesium-adenosine 5'-triphosphate.

PubMed Central

Thorneley, R N; Cornish-Bowden, A

1977-01-01

The effects of MgADP and MgATP on the kinetics of a pre-steady-state electron-transfer reaction and on the steady-state kinetics of H2 evulution for nitrogenase proteins of K. pneumoniae were studied. MgADP was a competitive inhibitor of MgATP in the MgATP-induced electron transfer from the Fe-protein to the Mo-Fe-protein. A dissociation constant K'i = 20 micron was determined for MgADP. The release of MgADP or a coupled conformation change in the Fe-protein of K.pneumoniae occurred with a rate comparable with that of electron transfer, k approximately 2 X 10(2)S-1. Neither homotropic nor heterotropic interactions involving MgATP and MgADP were observed for this reaction. Steady-state kinetic data for H2 evolution exhibited heterotropic effects between MgADP and MgATP. The data have been fitted to symmetry and sequential-type models involving conformation changes in two identical subunits. The data suggest that the enzyme can bind up to molecules of either MgATP or MgADP, but is unable to bind both nucleotides simultaneously. The control of H2 evolution by the MgATP/MgADP ratio is not at the level of electron transfer between the Fe- and Mo-Fe-proteins. Images Fig. 2. PMID:336036

Songlines from Direct Collapse Seed Black Holes

NASA Astrophysics Data System (ADS)

Aykutalp, Aycin; Wise, John; Spaans, Marco; Meijerink, Rowin

2015-01-01

In the last decade, the growth of supermassive black holes (SMBHs) has been intricately linked to galaxy formation and evolution, and is a key ingredient in the assembly of galaxies. Observations of SMBHs with masses of 109 solar at high redshifts (z~7) poses challenges to the theory of seed black hole formation and their growth in young galaxies. Fundamental to understanding their existence within the first billion years after the Big Bang, is the identification of their formation processes, growth rate and evolution through cosmic time. We perform cosmological hydrodynamic simulations following the growth of direct collapse seed black holes (DCBH) including X-ray irradiation from the central black hole, stellar feedback both from metal-free and metal-rich stars and H2 self-shielding. These simulations demonstrate that X-ray irradiation from the central black hole regulates its growth and influence the formation of stellar population in the host halo. In particular, X-ray radiation enhances H2 formation in metal-free gas and initially induces the star formation in the halo. However, in the long term, X-ray irradiation from the accreting seed DCBH stifles the initial growth relative to the Eddington rate argument. This further complicates the explanation for the existence of SMBHs in the early universe.

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'.

The role of zonal flows and predator-prey oscillations in triggering the formation of edge and core transport barriers

NASA Astrophysics Data System (ADS)

Schmitz, L.; Zeng, L.; Rhodes, T. L.; Hillesheim, J. C.; Peebles, W. A.; Groebner, R. J.; Burrell, K. H.; McKee, G. R.; Yan, Z.; Tynan, G. R.; Diamond, P. H.; Boedo, J. A.; Doyle, E. J.; Grierson, B. A.; Chrystal, C.; Austin, M. E.; Solomon, W. M.; Wang, G.

2014-07-01

We present direct evidence of low frequency, radially sheared, turbulence-driven flows (zonal flows (ZFs)) triggering edge transport barrier formation preceding the L- to H-mode transition via periodic turbulence suppression in limit-cycle oscillations (LCOs), consistent with predator-prey dynamics. The final transition to edge-localized mode-free H-mode occurs after the equilibrium E × B flow shear increases due to ion pressure profile evolution. ZFs are also observed to initiate formation of an electron internal transport barrier (ITB) at the q = 2 rational surface via local suppression of electron-scale turbulence. Multi-channel Doppler backscattering (DBS) has revealed the radial structure of the ZF-induced shear layer and the E × B shearing rate, ωE×B, in both barrier types. During edge barrier formation, the shearing rate lags the turbulence envelope during the LCO by 90°, transitioning to anti-correlation (180°) when the equilibrium shear dominates the turbulence-driven flow shear due to the increasing edge pressure gradient. The time-dependent flow shear and the turbulence envelope are anti-correlated (180° out of phase) in the electron ITB. LCOs with time-reversed evolution dynamics (transitioning from an equilibrium-flow dominated to a ZF-dominated state) have also been observed during the H-L back-transition and are potentially of interest for controlled ramp-down of the plasma stored energy and pressure (normalized to the poloidal magnetic field) \\beta_{\\theta} =2\\mu_{0} n{( {T_{e} +T_{i}})}/{B_{\\theta}^{2}} in ITER.

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.

Rational construction of multiple interfaces in ternary heterostructure for efficient spatial separation and transfer of photogenerated carriers in the application of photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Jian-Wen; Ma, Dandan; Zou, Yajun; Fan, Zhaoyang; Shi, Jinwen; Cheng, Linhao; Ji, Xin; Niu, Chunming

2018-03-01

The design of efficient and stable photocatalyst plays a critical role in the photocatalytic hydrogen evolution from water splitting. Herein, we develop a novel ZnS/CdS/ZnO ternary heterostructure by the in-situ sulfuration of CdS/ZnO, which includes four contact interfaces: CdS-ZnS interface, ZnS-ZnO interface, CdS-ZnO interface and ZnS-CdS-ZnO ternary interface, forming three charge carrier-transfer modes (type-I, type-II and direct Z-scheme) through five carrier-transfer pathways. As a result, the separation and transfer of photoexcited electron-hole pairs are promoted significantly, resulting in a high hydrogen evolution rate of 44.70 mmol h-1 g-1, which is 2, 3.7 and 8 times higher than those of binary heterostructures, CdS/ZnO, CdS/ZnS and ZnS/ZnO, respectively, and 26.5, 280 and 298 times higher than those of single CdS, ZnO and ZnS, respectively. As a counterpart ternary heterostructure, CdS/ZnS/ZnO contains only two interfaces: CdS-ZnS interface and ZnS-ZnO interface, which form two charge carrier-transfer modes (type-I and type-II) through two carrier-transfer pathways, leading to its much lower hydrogen evolution rate (27.25 mmol h-1 g-1) than ZnS/CdS/ZnO ternary heterostructure. This work is relevant for understanding the charge-transfer pathways between multi-interfaces in multicomponent heterojunctions.

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.

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.

The clustering and bias of radio-selected AGN and star-forming galaxies in the COSMOS field

NASA Astrophysics Data System (ADS)

Hale, C. L.; Jarvis, M. J.; Delvecchio, I.; Hatfield, P. W.; Novak, M.; Smolčić, V.; Zamorani, G.

2018-03-01

Dark matter haloes in which galaxies reside are likely to have a significant impact on their evolution. We investigate the link between dark matter haloes and their constituent galaxies by measuring the angular two-point correlation function of radio sources, using recently released 3 GHz imaging over ˜2 deg2 of the Cosmological Evolution Survey (COSMOS) field. We split the radio source population into star-forming galaxies (SFGs) and active galactic nuclei (AGN), and further separate the AGN into radiatively efficient and inefficient accreters. Restricting our analysis to z < 1, we find SFGs have a bias, b = 1.5 ^{+0.1}_{-0.2}, at a median redshift of z = 0.62. On the other hand, AGN are significantly more strongly clustered with b = 2.1 ± 0.2 at a median redshift of 0.7. This supports the idea that AGN are hosted by more massive haloes than SFGs. We also find low accretion rate AGN are more clustered (b = 2.9 ± 0.3) than high accretion rate AGN (b = 1.8^{+0.4}_{-0.5}) at the same redshift (z ˜ 0.7), suggesting that low accretion rate AGN reside in higher mass haloes. This supports previous evidence that the relatively hot gas that inhabits the most massive haloes is unable to be easily accreted by the central AGN, causing them to be inefficient. We also find evidence that low accretion rate AGN appear to reside in halo masses of Mh ˜ 3-4 × 1013 h-1 M⊙ at all redshifts. On the other hand, the efficient accreters reside in haloes of Mh ˜ 1-2 × 1013 h-1 M⊙ at low redshift but can reside in relatively lower mass haloes at higher redshifts. This could be due to the increased prevalence of cold gas in lower mass haloes at z ≥ 1 compared to z < 1.

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.

New reaction rates for improved primordial D /H calculation and the cosmic evolution of deuterium

NASA Astrophysics Data System (ADS)

Coc, Alain; Petitjean, Patrick; Uzan, Jean-Philippe; Vangioni, Elisabeth; Descouvemont, Pierre; Iliadis, Christian; Longland, Richard

2015-12-01

Primordial or big bang nucleosynthesis (BBN) is one of the three historically strong evidences for the big bang model. Standard BBN is now a parameter-free theory, since the baryonic density of the Universe has been deduced with an unprecedented precision from observations of the anisotropies of the cosmic microwave background radiation. There is a good agreement between the primordial abundances of 4He, D, 3He, and 7Li deduced from observations and from primordial nucleosynthesis calculations. However, the 7Li calculated abundance is significantly higher than the one deduced from spectroscopic observations and remains an open problem. In addition, recent deuterium observations have drastically reduced the uncertainty on D /H , to reach a value of 1.6%. It needs to be matched by BBN predictions whose precision is now limited by thermonuclear reaction rate uncertainties. This is especially important as many attempts to reconcile Li observations with models lead to an increased D prediction. Here, we reevaluate the d (p ,γ )3He, d (d ,n ) 3H3, and d (d ,p ) 3H reaction rates that govern deuterium destruction, incorporating new experimental data and carefully accounting for systematic uncertainties. Contrary to previous evaluations, we use theoretical ab initio models for the energy dependence of the S factors. As a result, these rates increase at BBN temperatures, leading to a reduced value of D /H =(2.45 ±0.10 )×10-5 (2 σ ), in agreement with observations.

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%.

Modeling carbon production and transport during ELMs in DIII-D

NASA Astrophysics Data System (ADS)

Hogan, J.; Wade, M.; Coster, D.; Lasnier, C.

2004-11-01

Large-scale Type I ELM events could provide a significant C source in ITER, and C production rates depend on incident D flux density and surface temperature, quantities which can vary significantly during an ELM event. Recent progress on DIII-D has improved opportunities for code comparison. Fast time-scale measurements of divertor CIII evolution [1] and fast edge CER measurements of C profile evolution during low-density DIII-D LSN ELMy H-modes (type I) [2] have been modeled using the solps5.0/Eirene99 coupled edge code and time dependent thermal analysis codes. An ELM model based on characteristics of MHD peeling-ballooning modes reproduces the pedestal evolution. Qualitative agreement for the CIII evolution during an ELM event is found using the Roth et al annealing model for chemical sputtering and the sensitivity to other models is described. Significant ELM-to-ELM variations in observed maximum divertor target IR temperature during nominally identical ELMs are investigated with models for C emission from micron-scale dust particles. [1] M Groth, M Fenstermacher et al J Nucl Mater 2003, [2] M Wade, K Burrell et al PSI-16

Calculations of condensation and chemistry in an aircraft contrail

NASA Technical Reports Server (NTRS)

Miake-Lye, Richard C.; Brown, R. C.; Anderson, M. R.; Kolb, C. E.

1994-01-01

The flow field, chemistry, and condensation nucleation behind a transport airplane are calculated in two regimes using two separate reacting flow codes: first the axisymmetric plume, then the three dimensional vortex wake. The included chemical kinetics equations follow the evolution of the NO(y) and SO(x) chemical families. In the plume regime, the chemistry is coupled with the binary homogeneous formation of sulfate condensation nuclei, where the calculated nucleation rates predict that copious quantities of H2SO4/H2O nuclei are produced in subnanometer sizes. These sulfate aerosols could play a major role in the subsequent condensation of water vapor and the formation of contrails under favorable atmospheric conditions.

Flux dynamics and magnetovoltage measurements in a macroscopic cylindrical hole drilled in BSCCO

NASA Astrophysics Data System (ADS)

Yetiş, H.; Altinkok, A.; Olutaş, M.; Kiliç, A.; Kiliç, K.

2007-10-01

Slow transport relaxation measurements (V-t curves) and magnetovoltage measurements (V-H curves) were carried out in a polycrystalline sample of Bi1.7Pb0.3Sr2Ca2Cu3Ox (BSCCO) with a macroscopic cylindrically drilled hole (CH). The time evolution of quenched state in V-t curves was interpreted in terms of enhancement of the superconducting order parameter and the relaxation of moving entity. Upon cycling of the external magnetic field with different sweep rates, unusual counter clockwise hysteresis effects and asymmetry in V-H curves are observed in BSCCO sample with CH, which can also be correlated to the trapping of the macroscopic flux bundles in CH.

GeSn growth kinetics in reduced pressure chemical vapor deposition from Ge2H6 and SnCl4

NASA Astrophysics Data System (ADS)

Aubin, J.; Hartmann, J. M.

2018-01-01

We have investigated the low temperature epitaxy of high Sn content GeSn alloys in a 200 mm industrial Reduced Pressure - Chemical Vapor Deposition tool from Applied Materials. Gaseous digermane (Ge2H6) and liquid tin tetrachloride (SnCl4) were used as the Ge and Sn precursors, respectively. The impact of temperature (in the 300-350 °C range), Ge2H6 and SnCl4 mass-flows on the GeSn growth kinetics at 100 Torr has been thoroughly explored. Be it at 300 °C or 325 °C, a linear GeSn growth rate increase together with a sub-linear Sn concentration increase occurred as the SnCl4 mass-flow increased, irrespective of the Ge2H6 mass flow (fixed or varying). The Sn atoms seemed to catalyze H desorption from the surface, resulting in higher GeSn growth rates for high SnCl4 mass-flows (in the 4-21 nm min-1 range). The evolution of the Sn content x with the F (SnCl4) 2 ·/F (Ge2H6) mass-flow ratio was fitted by x2/(1 - x) = n ·F (SnCl4) 2 ·/F (Ge2H6), with n = 0.25 (325 °C) and 0.60 (300 °C). We have otherwise studied the impact of temperature, in the 300-350 °C range, on the GeSn growth kinetics. The GeSn growth rate exponentially increased with the temperature, from 15 up to 32 nm min-1. The associated activation energy was low, i.e. Ea = 10 kcal mol-1. Meanwhile, the Sn content decreased linearly as the growth temperature increased, from 15% at 300 °C down to 6% at 350 °C.

MUFASA: galaxy formation simulations with meshless hydrodynamics

NASA Astrophysics Data System (ADS)

Davé, Romeel; Thompson, Robert; Hopkins, Philip F.

2016-11-01

We present the MUFASA suite of cosmological hydrodynamic simulations, which employs the GIZMO meshless finite mass (MFM) code including H2-based star formation, nine-element chemical evolution, two-phase kinetic outflows following scalings from the Feedback in Realistic Environments zoom simulations, and evolving halo mass-based quenching. Our fiducial (50 h-1 Mpc)3 volume is evolved to z = 0 with a quarter billion elements. The predicted galaxy stellar mass functions (GSMFs) reproduces observations from z = 4 → 0 to ≲ 1.2σ in cosmic variance, providing an unprecedented match to this key diagnostic. The cosmic star formation history and stellar mass growth show general agreement with data, with a strong archaeological downsizing trend such that dwarf galaxies form the majority of their stars after z ˜ 1. We run 25 and 12.5 h-1 Mpc volumes to z = 2 with identical feedback prescriptions, the latter resolving all hydrogen-cooling haloes, and the three runs display fair resolution convergence. The specific star formation rates broadly agree with data at z = 0, but are underpredicted at z ˜ 2 by a factor of 3, re-emphasizing a longstanding puzzle in galaxy evolution models. We compare runs using MFM and two flavours of smoothed particle hydrodynamics, and show that the GSMF is sensitive to hydrodynamics methodology at the ˜×2 level, which is sub-dominant to choices for parametrizing feedback.

Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation.

PubMed

Tran, Camly T; Williard, Paul G; Kim, Eunsuk

2014-08-27

The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H(•) (e(-)/H(+)). Nitrosylation of (NEt4)2[Fe2S2(SPh)4] (1) in the presence of PhSH or (t)Bu3PhOH results in the formation of (NEt4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or (t)Bu3PhO(•). The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H(•) donor. Employment of clusters with electron-donating groups or H(•) donors from thiols leads to a larger amount of H2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology.

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

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

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.

Convergent evolution of ribonuclease h in LTR retrotransposons and retroviruses.

PubMed

Ustyantsev, Kirill; Novikova, Olga; Blinov, Alexander; Smyshlyaev, Georgy

2015-05-01

Ty3/Gypsy long terminals repeat (LTR) retrotransposons are structurally and phylogenetically close to retroviruses. Two notable structural differences between these groups of genetic elements are 1) the presence in retroviruses of an additional envelope gene, env, which mediates infection, and 2) a specific dual ribonuclease H (RNH) domain encoded by the retroviral pol gene. However, similar to retroviruses, many Ty3/Gypsy LTR retrotransposons harbor additional env-like genes, promoting concepts of the infective mode of these retrotransposons. Here, we provide a further line of evidence of similarity between retroviruses and some Ty3/Gypsy LTR retrotransposons. We identify that, together with their additional genes, plant Ty3/Gypsy LTR retrotransposons of the Tat group have a second RNH, as do retroviruses. Most importantly, we show that the resulting dual RNHs of Tat LTR retrotransposons and retroviruses emerged independently, providing strong evidence for their convergent evolution. The convergent resemblance of Tat LTR retrotransposons and retroviruses may indicate similar selection pressures acting on these diverse groups of elements and reveal potential evolutionary constraints on their structure. We speculate that dual RNH is required to accelerate retrotransposon evolution through increased rates of strand transfer events and subsequent recombination events. © The Author 2015. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Fabrication of efficient TiO2-RGO heterojunction composites for hydrogen generation via water-splitting: Comparison between RGO, Au and Pt reduction sites

NASA Astrophysics Data System (ADS)

El-Bery, Haitham M.; Matsushita, Yoshihisa; Abdel-moneim, Ahmed

2017-11-01

A facile one-step synthesis approach of M/TiO2/RGO (M = Au or Pt) ternary composite by hydrothermal treatment for hydrogen generation via water-splitting was investigated. Photocurrent response measurements revealed that TiO2 (P25) nanoparticles anchored on the reduced graphene oxide (RGO) surface exhibited a p-n heterojunction interface by changing the photocurrent direction with the applied bias from reverse to forward potential. H2 evolution rate of TiO2/RGO (5 wt.%) composite was substantially enhanced by 12-fold in comparison to bare TiO2 under simulated solar light irradiation. Cyclic volatmmetry measurements manifested, that the optimized 0.3 wt.% of platinum metal loaded on TiO2/RGO composite was the most active catalytic reduction sites for hydrogen generation reaction with an initial hydrogen rate of 670 μmol h-1. This study sheds the light on the tunable semiconductor type of TiO2/RGO composite fabricated by solution mixing pathway and its merits to improve the photocatalytic activity.

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.

Exponential growth and selection in self-replicating materials from DNA origami rafts

NASA Astrophysics Data System (ADS)

He, Xiaojin; Sha, Ruojie; Zhuo, Rebecca; Mi, Yongli; Chaikin, Paul M.; Seeman, Nadrian C.

2017-10-01

Self-replication and evolution under selective pressure are inherent phenomena in life, and but few artificial systems exhibit these phenomena. We have designed a system of DNA origami rafts that exponentially replicates a seed pattern, doubling the copies in each diurnal-like cycle of temperature and ultraviolet illumination, producing more than 7 million copies in 24 cycles. We demonstrate environmental selection in growing populations by incorporating pH-sensitive binding in two subpopulations. In one species, pH-sensitive triplex DNA bonds enable parent-daughter templating, while in the second species, triplex binding inhibits the formation of duplex DNA templating. At pH 5.3, the replication rate of species I is ~1.3-1.4 times faster than that of species II. At pH 7.8, the replication rates are reversed. When mixed together in the same vial, the progeny of species I replicate preferentially at pH 7.8 similarly at pH 5.3, the progeny of species II take over the system. This addressable selectivity should be adaptable to the selection and evolution of multi-component self-replicating materials in the nanoscopic-to-microscopic size range.

[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 kinetic and thermodynamic understanding of O2 tolerance in [NiFe]-hydrogenases

PubMed Central

Cracknell, James A.; Wait, Annemarie F.; Lenz, Oliver; Friedrich, Bärbel; Armstrong, Fraser A.

2009-01-01

In biology, rapid oxidation and evolution of H2 is catalyzed by metalloenzymes known as hydrogenases. These enzymes have unusual active sites, consisting of iron complexed by carbonyl, cyanide, and thiolate ligands, often together with nickel, and are typically inhibited or irreversibly damaged by O2. The Knallgas bacterium Ralstonia eutropha H16 (Re) uses H2 as an energy source with O2 as a terminal electron acceptor, and its membrane-bound uptake [NiFe]-hydrogenase (MBH) is an important example of an “O2-tolerant” hydrogenase. The mechanism of O2 tolerance of Re MBH has been probed by measuring H2 oxidation activity in the presence of O2 over a range of potential, pH and temperature, and comparing with the same dependencies for individual processes involved in the attack by O2 and subsequent reactivation of the active site. Most significantly, O2 tolerance increases with increasing temperature and decreasing potentials. These trends correlate with the trends observed for reactivation kinetics but not for H2 affinity or the kinetics of O2 attack. Clearly, the rate of recovery is a crucial factor. We present a kinetic and thermodynamic model to account for O2 tolerance in Re MBH that may be more widely applied to other [NiFe]-hydrogenases. PMID:19934053

Evolution of the Blue and Far-Infrared Galaxy Luminosity Functions

NASA Technical Reports Server (NTRS)

Lonsdale, Carol J.; Chokshi, Arati

1993-01-01

The space density of blue-selected galaxies at moderate redshifts is determined here directly by deriving the luminosity function. Evidence is found for density evolution for moderate luminosity galaxies at a rate of (1+z) exp delta, with a best fit of delta + 4 +/- 2, between the current epoch and Z greater than about 0.1. At M(b) less than -22 evidence is found for about 0.5-1.5 mag of luminosity evolution in addition to the density evolution, corresponding to an evolutionary rate of about (1+z) exp gamma, with gamma = 0.5-2.5, but a redshift of about 0.4. Assuming a steeper faint end slope of alpha = -1.3 similar to that observed in the Virgo cluster, could explain the data with a luminosity evolution rate of gamma = 1-2, without need for any density evolution. Acceptable fits are found by comparing composite density and luminosity evolution models to faint IRAS 60 micron source counts, implying that the blue and far-IR evolutionary rates may be similar.

Desorption induced by solar wind electrons analogs in methanol ice

NASA Astrophysics Data System (ADS)

Bergantini, A. S.; Pilling, Sergio; Andrade, Diana; Boechat-Roberty, Heloisa Maria; Rocco, Maria Luiza M.

2012-07-01

Methanol (CH _{3}OH) has been detected in several environments in space, such as comets, asteroids, grains of interstellar dust and protostars forming regions such as W33A and RAFGL 7009. CH _{3}OH is the most abundant molecule (after H _{2}O) found in solid state in these objects. The action of ionizing agents in such environments induces changes in methanol ice which lead to the formation ionic species, reactive radicals and new compounds. In this experiment, frozen methanol (142 K) was irradiated with an electron beam (energies from 650 to 1500 eV) inside an ultra-high vacuum chamber (˜ 1×10^{-10} mbar), at the Surface Chemistry Laboratory of Federal University of Rio de Janeiro (LaQuiS/ UFRJ). The beam simulates the action of electrons from solar wind in frozen surfaces like as comets, asteroids and moons. Results show the desorption of several new ionized species such as (CH _{3}OH)H ^{+}, H _{2}COH ^{+}, C _{2}H _{3} ^{+}, HCO ^{+}, CO ^{+}, O ^{+}, C ^{+}, H ^{+}. The individual desorbed ion rate was calculated. The determined half-life of frozen methanol in Earth orbit due to the electron bombardment was about 4.2 yr. The ionic desorption rate is an important parameter in surface chemistry, since these parameters are often approximated in chemical evolution models of astrophysical environments, due to the lack of laboratory data.

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.

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

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

Chen, Li; Wang, Mengyi; Kang, Qinjun

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

DOE PAGES

Chen, Li; Wang, Mengyi; Kang, Qinjun; ...

2018-04-26

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

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.

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.

Investigation into the disparate origin of CO 2 and H 2O outgassing for comet 67P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; VIRTIS Team

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma.We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ~5.0% and ~2.5% for Feb. 28 and April 27 respectively. Because of the highly variable nature of the CO2 evolution we do not believe that these numbers are diagnostic of the comets bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's geometric shape, illumination and past orbital history.Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the sun is 2.5x1026 molecules/s while for April 27 at 1.76 AU it is 4.65x1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the night side. A rough estimate of the water surface evaporation rate of the illuminated nucleus for April 27 yields about 5x1019 molecules/s m2.

Different Endosymbiotic Interactions in Two Hydra Species Reflect the Evolutionary History of Endosymbiosis.

PubMed

Ishikawa, Masakazu; Yuyama, Ikuko; Shimizu, Hiroshi; Nozawa, Masafumi; Ikeo, Kazuho; Gojobori, Takashi

2016-08-03

Endosymbiosis is an important evolutionary event for organisms, and there is widespread interest in understanding the evolution of endosymbiosis establishment. Hydra is one of the most suitable organisms for studying the evolution of endosymbiosis. Within the genus Hydra, H. viridissima and H. vulgaris show endosymbiosis with green algae. Previous studies suggested that the endosymbiosis in H. vulgaris took place much more recently than that in H. viridissima, noting that the establishment of the interaction between H. vulgaris and its algae is not as stable as in H. viridissima. To investigate the on-going process of endosymbiosis, we first compared growth and tolerance to starvation in symbiotic and aposymbiotic polyps of both species. The results revealed that symbiotic H. viridissima had a higher growth rate and greater tolerance to starvation than aposymbiotic polyps. By contrast, growth of symbiotic H. vulgaris was identical to that of aposymbiotic polyps, and symbiotic H. vulgaris was less tolerant to starvation. Moreover, our gene expression analysis showed a pattern of differential gene expression in H. viridissima similar to that in other endosymbiotically established organisms, and contrary to that observed in H. vulgaris We also showed that H. viridissima could cope with oxidative stress that caused damage, such as cell death, in H. vulgaris These observations support the idea that oxidative stress related genes play an important role in the on-going process of endosymbiosis evolution. The different evolutionary stages of endosymbiosis studied here provide a deeper insight into the evolutionary processes occurring toward a stable endosymbiosis. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Effects of cattle slurry acidification on ammonia and methane evolution during storage.

PubMed

Petersen, Søren O; Andersen, Astrid J; Eriksen, Jørgen

2012-01-01

Slurry acidification before storage is known to reduce NH(3) emissions, but recent observations have indicated that CH(4) emissions are also reduced. We investigated the evolution of CH(4) from fresh and aged cattle slurry during 3 mo of storage as influenced by pH adjustment to 5.5 with sulfuric acid. In a third storage experiment, cattle slurry acidified with commercial equipment on two farms was incubated. In the manipulation experiments, effects of acid and sulfate were distinguished by adding hydrochloric acid and potassium sulfate separately or in combination, rather than sulfuric acid. In one experiment sulfur was also added to slurry as the amino acid methionine in separate treatments. In each treatment 20-kg portions of slurry (n = 4) were stored for 95 d. All samples were subsampled nine to 10 times for determination of NH(3) and CH(4) evolution rates using a 2-L flow-through system. In all experiments, the pH of acidified cattle slurry increased gradually to between 6.5 and 7. Acidification of slurry reduced the evolution of CH(4) by 67 to 87%. The greatest reduction was observed with aged cattle slurry, which had a much higher potential for CH(4) production than fresh slurry. Sulfate and methionine amendment to cattle slurry without pH adjustment also significantly inhibited methanogenesis, probably as a result of sulfide production. The study suggests that complex microbial interactions involving sulfur transformations and pH determine the potential for CH(4) emission during storage of cattle slurry, and that slurry acidification may be a cost-effective greenhouse gas mitigation option. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

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.

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.

A Metal-Organic Framework Approach toward Highly Nitrogen-Doped Graphitic Carbon as a Metal-Free Photocatalyst for Hydrogen Evolution.

PubMed

Zhao, Xiuxia; Yang, Hao; Jing, Peng; Shi, Wei; Yang, Guangming; Cheng, Peng

2017-03-01

Zeolitic imidazolate framework-8 (ZIF-8)-derived N-doped graphene analogous polyhedrons (ZNGs) obtained via the direct carbonation of ZIF-8 are applied to photocatalytic hydrogen evolution for the first time. The contents of different types of nitrogen atoms in ZNGs can be fine-tuned via the calcination temperature, which significantly influences the hydrogen evolution rate of the ZNGs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insights into highly improved solar-driven photocatalytic oxygen evolution over integrated Ag3PO4/MoS2 heterostructures

NASA Astrophysics Data System (ADS)

Cui, Xingkai; Yang, Xiaofei; Xian, Xiaozhai; Tian, Lin; Tang, Hua; Liu, Qinqin

2018-04-01

Oxygen evolution has been considered as the rate-determining step in photocatalytic water splitting due to its sluggish four-electron half-reaction rate, the development of oxygen-evolving photocatalysts with well-defined morphologies and superior interfacial contact is highly important for achieving high-performance solar water splitting. Herein, we report the fabrication of Ag3PO4/MoS2 nanocomposites and, for the first time, their use in photocatalytic water splitting into oxygen under LED light illumination. Ag3PO4 nanoparticles were found to be anchored evenly on the surface of MoS2 nanosheets, confirming an efficient hybridization of two semiconductor materials. A maximum oxygen-generating rate of 201.6 mol L-1 g-1 h-1 was determined when 200 mg MoS2 nanosheets were incorporated into Ag3PO4 nanoparticles, which is around 5 times higher than that of bulk Ag3PO4. Obvious enhancements in light-harvesting property, as well as electron-hole separation and charge transportation are revealed by the combination of different characterizations. ESR analysis verified that more active oxygen-containing radicals generate over illuminated Ag3PO4/MoS2 composite photocatalysts rather than irradiated Ag3PO4. The improvement in oxygen evolution performance of Ag3PO4/MoS2 composite photocatalysts is ascribed to wide spectra response in the visible-light region, more efficient charge separation and enhanced oxidation capacity in the valence band (VB). This study provides new insights into the design and development of novel composite photocatalytic materials for solar-to-fuel conversion.

Coupling of diversification and pH adaptation during the evolution of terrestrial Thaumarchaeota.

PubMed

Gubry-Rangin, Cécile; Kratsch, Christina; Williams, Tom A; McHardy, Alice C; Embley, T Martin; Prosser, James I; Macqueen, Daniel J

2015-07-28

The Thaumarchaeota is an abundant and ubiquitous phylum of archaea that plays a major role in the global nitrogen cycle. Previous analyses of the ammonia monooxygenase gene amoA suggest that pH is an important driver of niche specialization in these organisms. Although the ecological distribution and ecophysiology of extant Thaumarchaeota have been studied extensively, the evolutionary rise of these prokaryotes to ecological dominance in many habitats remains poorly understood. To characterize processes leading to their diversification, we investigated coevolutionary relationships between amoA, a conserved marker gene for Thaumarchaeota, and soil characteristics, by using deep sequencing and comprehensive environmental data in Bayesian comparative phylogenetics. These analyses reveal a large and rapid increase in diversification rates during early thaumarchaeotal evolution; this finding was verified by independent analyses of 16S rRNA. Our findings suggest that the entire Thaumarchaeota diversification regime was strikingly coupled to pH adaptation but less clearly correlated with several other tested environmental factors. Interestingly, the early radiation event coincided with a period of pH adaptation that enabled the terrestrial Thaumarchaeota ancestor to initially move from neutral to more acidic and alkaline conditions. In contrast to classic evolutionary models, whereby niches become rapidly filled after adaptive radiation, global diversification rates have remained stably high in Thaumarchaeota during the past 400-700 million years, suggesting an ongoing high rate of niche formation or switching for these microbes. Our study highlights the enduring importance of environmental adaptation during thaumarchaeotal evolution and, to our knowledge, is the first to link evolutionary diversification to environmental adaptation in a prokaryotic phylum.

Coupling of diversification and pH adaptation during the evolution of terrestrial Thaumarchaeota

PubMed Central

Gubry-Rangin, Cécile; Kratsch, Christina; Williams, Tom A.; McHardy, Alice C.; Embley, T. Martin; Prosser, James I.; Macqueen, Daniel J.

2015-01-01

The Thaumarchaeota is an abundant and ubiquitous phylum of archaea that plays a major role in the global nitrogen cycle. Previous analyses of the ammonia monooxygenase gene amoA suggest that pH is an important driver of niche specialization in these organisms. Although the ecological distribution and ecophysiology of extant Thaumarchaeota have been studied extensively, the evolutionary rise of these prokaryotes to ecological dominance in many habitats remains poorly understood. To characterize processes leading to their diversification, we investigated coevolutionary relationships between amoA, a conserved marker gene for Thaumarchaeota, and soil characteristics, by using deep sequencing and comprehensive environmental data in Bayesian comparative phylogenetics. These analyses reveal a large and rapid increase in diversification rates during early thaumarchaeotal evolution; this finding was verified by independent analyses of 16S rRNA. Our findings suggest that the entire Thaumarchaeota diversification regime was strikingly coupled to pH adaptation but less clearly correlated with several other tested environmental factors. Interestingly, the early radiation event coincided with a period of pH adaptation that enabled the terrestrial Thaumarchaeota ancestor to initially move from neutral to more acidic and alkaline conditions. In contrast to classic evolutionary models, whereby niches become rapidly filled after adaptive radiation, global diversification rates have remained stably high in Thaumarchaeota during the past 400–700 million years, suggesting an ongoing high rate of niche formation or switching for these microbes. Our study highlights the enduring importance of environmental adaptation during thaumarchaeotal evolution and, to our knowledge, is the first to link evolutionary diversification to environmental adaptation in a prokaryotic phylum. PMID:26170282

Influence of electron storing, transferring and shuttling assets of reduced graphene oxide at the interfacial copper doped TiO2 p-n heterojunction for increased hydrogen production.

PubMed

Babu, Sundaram Ganesh; Vinoth, Ramalingam; Kumar, Dharani Praveen; Shankar, Muthukonda V; Chou, Hung-Lung; Vinodgopal, Kizhanipuram; Neppolian, Bernaurdshaw

2015-05-07

Herein we report simple, low-cost and scalable preparation of reduced graphene oxide (rGO) supported surfactant-free Cu2O-TiO2 nanocomposite photocatalysts by an ultrasound assisted wet impregnation method. Unlike the conventional preparation techniques, simultaneous reduction of Cu(2+) (in the precursor) to Cu(+) (Cu2O), and graphene oxide (GO) to rGO is achieved by an ultrasonic method without the addition of any external reducing agent; this is ascertained by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. UV-visible diffused reflectance spectroscopy (DRS) studies (Tauc plots) provide evidence for the loading of Cu2O tailoring the optical band gap of the photocatalyst from 3.21 eV to 2.87 eV. The photoreactivity of the as-prepared Cu2O-TiO2/rGO samples is determined via H2 evolution from water in the presence of glycerol as a hole (h(+)) scavenger under visible light irradiation. Very interestingly, the addition of rGO augments the carrier mobility at the Cu2O-TiO2 p-n heterojunction, which is evidenced by the significantly reduced luminescence intensity of the Cu2O-TiO2/rGO photocatalyst. Hence rGO astonishingly enhances the photocatalytic activity compared with pristine TiO2 nanoparticles (NPs) and Cu2O-TiO2, by factors of ∼14 and ∼7, respectively. A maximum H2 production rate of 110 968 μmol h(-1) gcat(-1) is obtained with a 1.0% Cu and 3.0% GO photocatalyst composition; this is significantly higher than previously reported graphene based photocatalysts. Additionally, the present H2 production rate is much higher than those of precious/noble metal (especially Pt) assisted (as co-catalysts) graphene based photocatalysts. Moreover, to the best of our knowledge, this is the highest H2 production rate (110 968 μmol h(-1) gcat(-1)) achieved by a graphene based photocatalyst through the splitting of water under visible light irradiation.

Influence of electron storing, transferring and shuttling assets of reduced graphene oxide at the interfacial copper doped TiO2 p-n heterojunction for increased hydrogen production

NASA Astrophysics Data System (ADS)

Babu, Sundaram Ganesh; Vinoth, Ramalingam; Praveen Kumar, Dharani; Shankar, Muthukonda V.; Chou, Hung-Lung; Vinodgopal, Kizhanipuram; Neppolian, Bernaurdshaw

2015-04-01

Herein we report simple, low-cost and scalable preparation of reduced graphene oxide (rGO) supported surfactant-free Cu2O-TiO2 nanocomposite photocatalysts by an ultrasound assisted wet impregnation method. Unlike the conventional preparation techniques, simultaneous reduction of Cu2+ (in the precursor) to Cu+ (Cu2O), and graphene oxide (GO) to rGO is achieved by an ultrasonic method without the addition of any external reducing agent; this is ascertained by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. UV-visible diffused reflectance spectroscopy (DRS) studies (Tauc plots) provide evidence for the loading of Cu2O tailoring the optical band gap of the photocatalyst from 3.21 eV to 2.87 eV. The photoreactivity of the as-prepared Cu2O-TiO2/rGO samples is determined via H2 evolution from water in the presence of glycerol as a hole (h+) scavenger under visible light irradiation. Very interestingly, the addition of rGO augments the carrier mobility at the Cu2O-TiO2 p-n heterojunction, which is evidenced by the significantly reduced luminescence intensity of the Cu2O-TiO2/rGO photocatalyst. Hence rGO astonishingly enhances the photocatalytic activity compared with pristine TiO2 nanoparticles (NPs) and Cu2O-TiO2, by factors of ~14 and ~7, respectively. A maximum H2 production rate of 110 968 μmol h-1 gcat-1 is obtained with a 1.0% Cu and 3.0% GO photocatalyst composition; this is significantly higher than previously reported graphene based photocatalysts. Additionally, the present H2 production rate is much higher than those of precious/noble metal (especially Pt) assisted (as co-catalysts) graphene based photocatalysts. Moreover, to the best of our knowledge, this is the highest H2 production rate (110 968 μmol h-1 gcat-1) achieved by a graphene based photocatalyst through the splitting of water under visible light irradiation.

Evolution of spreading rate and H2 production by serpentinization at mid-ocean ridges from 200 Ma to Present

NASA Astrophysics Data System (ADS)

Andreani, M.; García del Real, P.; Daniel, I.; Wright, N.; Coltice, N.

2017-12-01

Mid-oceanic ridge (MOR) spreading rate spatially varies today from 20 to 200 mm/yr and geological records attest of important temporal variations, at least during the past 200 My. The spreading rate has a direct impact on the mechanisms accomodating extension (magmatic vs tectonic), hence on the nature of the rocks forming the oceanic lithosphere. The latter is composed of variable amount of magmatic and mantle rocks, that dominate at fast and (ultra-) slow spreading ridges, respectively. Serpentinization of mantle rocks contributes to global fluxes and notably to those of hydrogen and carbon by providing a pathways for dihydrogen (H2) production, carbone storage by mineralization, and carbon reduction to CH4 and possibly complex organic compounds. Quantification of the global chemical impact of serpentinization through geological time requires a coupling of geochemical parameters with plate-tectonic reconstructions. Here we quantify serpentinization extent and concurrent H2 production at MOR from the Jurassic (200 Ma) to present day (0 Ma). We coupled mean values of relevant petro-chemical parameters such as the proportion of mantle rocks, initial iron in olivine, iron redox state in serpentinites, % of serpentinization to high-resolution models of plate motion within the GPlates infrastructure to estimate the lengths in 1 Myr intervals for the global MOR plate boundary (spreading and transform components), and spreading ridges as a function of their rate. The model sensitivity to selected parameters has been tested. The results show that fragmentation of Pangea resulted in elevated H2 rates (>1012 to 1013 mol/yr) starting at 160 Ma compared to Late Mesozoic (<160 Ma) rates (<1011-1012 mol/yr). From 160 Ma to present, the coupled opening of the Atlantic and Indian oceans as well as the variation in spreading rates maintained H2 generation in the 1012 mol/yr level, but with significant excursions mainly related to the length of ultra-slow spreading segments. For the first time, this model offers a framework toward flux modeling at MOR through time. The model can be further implemented by adding supplementary geochemical parameters or serve other geochemical issues.

Process-based modeling of silicate mineral weathering responses to increasing atmospheric CO2 and climate change

NASA Astrophysics Data System (ADS)

Banwart, Steven A.; Berg, Astrid; Beerling, David J.

2009-12-01

A mathematical model describes silicate mineral weathering processes in modern soils located in the boreal coniferous region of northern Europe. The process model results demonstrate a stabilizing biological feedback mechanism between atmospheric CO2 levels and silicate weathering rates as is generally postulated for atmospheric evolution. The process model feedback response agrees within a factor of 2 of that calculated by a weathering feedback function of the type generally employed in global geochemical carbon cycle models of the Earth's Phanerozoic CO2 history. Sensitivity analysis of parameter values in the process model provides insight into the key mechanisms that influence the strength of the biological feedback to weathering. First, the process model accounts for the alkalinity released by weathering, whereby its acceleration stabilizes pH at values that are higher than expected. Although the process model yields faster weathering with increasing temperature, because of activation energy effects on mineral dissolution kinetics at warmer temperature, the mineral dissolution rate laws utilized in the process model also result in lower dissolution rates at higher pH values. Hence, as dissolution rates increase under warmer conditions, more alkalinity is released by the weathering reaction, helping maintain higher pH values thus stabilizing the weathering rate. Second, the process model yields a relatively low sensitivity of soil pH to increasing plant productivity. This is due to more rapid decomposition of dissolved organic carbon (DOC) under warmer conditions. Because DOC fluxes strongly influence the soil water proton balance and pH, this increased decomposition rate dampens the feedback between productivity and weathering. The process model is most sensitive to parameters reflecting soil structure; depth, porosity, and water content. This suggests that the role of biota to influence these characteristics of the weathering profile is as important, if not more important, than the role of biota to influence mineral dissolution rates through changes in soil water chemistry. This process-modeling approach to quantify the biological weathering feedback to atmospheric CO2 demonstrates the potential for a far more mechanistic description of weathering feedback in simulations of the global geochemical carbon cycle.

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.

Active Cocatalysts for Photocatalytic Hydrogen Evolution Derived from Nickel or Cobalt Amine Complexes.

PubMed

Huang, Yi; Zhang, Bin

2017-11-20

A cost-effective and robust strategy for the anchoring of molecular hydrogen evolution cocatalysts onto semiconductors has recently been reported. The composite materials were highly efficient and stable towards photocatalytic H 2 evolution. This study provides guidance for the design and construction of highly active heterogeneous photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Self-discharge performance of Ni-MH battery by using electrodes with hydrophilic/hydrophobic surface

NASA Astrophysics Data System (ADS)

Li, Xiaofeng; Wang, Xiaojie; Dong, Huichao; Xia, Tongchi; Wang, Lizhen; Song, Yanhua

2013-12-01

The polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC) film is separately coated on the surface of the metal hydride (MH) and Ni(OH)2 electrodes to obtain the electrodes with hydrophobic or hydrophilic surface. The effects of the surface treatment on the oxygen and hydrogen evolution from the electrodes are studied by using cyclic voltammetry tests. Although the positive and negative active materials of the Ni-MH batteries show a lower self-decomposition rate after the CMC treatment, the self-discharge rate of the batteries show little change. On the contrary, the self-discharge rate of the batteries decreases from 35.9% to 27.1% by using the PTFE-treated Ni(OH)2 electrodes, which might be related to the suppression of the reaction between NiOOH and H2 by the hydrophobic film.

Numerical Study of Microstructural Evolution During Homogenization of Al-Si-Mg-Fe-Mn Alloys

NASA Astrophysics Data System (ADS)

Priya, Pikee; Johnson, David R.; Krane, Matthew J. M.

2016-09-01

Microstructural evolution during homogenization of Al-Si-Mg-Fe-Mn alloys occurs in two stages at different length scales: while holding at the homogenization temperature (diffusion on the scale of the secondary dendrite arm spacing (SDAS) in micrometers) and during quenching to room temperature (dispersoid precipitation at the nanometer to submicron scale). Here a numerical study estimates microstructural changes during both stages. A diffusion-based model developed to simulate evolution at the SDAS length scale predicts homogenization times and microstructures matching experiments. That model is coupled with a Kampmann Wagner Neumann-based precipitate nucleation and growth model to study the effect of temperature, composition, as-cast microstructure, and cooling rates during posthomogenization quenching on microstructural evolution. A homogenization schedule of 853 K (580 °C) for 8 hours, followed by cooling at 250 K/h, is suggested to optimize microstructures for easier extrusion, consisting of minimal α-Al(FeMn)Si, no β-AlFeSi, and Mg2Si dispersoids <1 μm size.

Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential.

PubMed

Wang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng

2018-05-15

Electrochemical reduction of N 2 to NH 3 provides an alternative to the Haber-Bosch process for sustainable, distributed production of NH 3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N 2 reduction. Here we report efficient electroreduction of N 2 to NH 3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH 3 yield rate of ~4.5 μg mg -1 Pd h -1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N 2 hydrogenation to *N 2 H, the rate-limiting step for NH 3 electrosynthesis.

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.

Pore scale study of multiphase multicomponent reactive transport during CO2 dissolution trapping

NASA Astrophysics Data System (ADS)

Chen, Li; Wang, Mengyi; Kang, Qinjun; Tao, Wenquan

2018-06-01

Solubility trapping is crucial for permanent CO2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO2-water two-phase flow, multicomponent (CO2(aq), H+, HCO3-, CO32- and OH-) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO2(aq) concentration, scCO2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is required by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Finally, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.

Evolutionary Dynamics and Global Diversity of Influenza A Virus.

PubMed

Rejmanek, Daniel; Hosseini, Parviez R; Mazet, Jonna A K; Daszak, Peter; Goldstein, Tracey

2015-11-01

The increasing number of zoonotic infections caused by influenza A virus (IAV) subtypes of avian origin (e.g., H5N1 and H7N9) in recent years underscores the need to better understand the factors driving IAV evolution and diversity. To evaluate the current feasibility of global analyses to contribute to this aim, we evaluated information in the public domain to explore IAV evolutionary dynamics, including nucleotide substitution rates and selection pressures, using 14 IAV subtypes in 32 different countries over a 12-year period (2000 to 2011). Using geospatial information from 39,785 IAV strains, we examined associations between subtype diversity and socioeconomic, biodiversity, and agricultural indices. Our analyses showed that nucleotide substitution rates for 11 of the 14 evaluated subtypes tended to be higher in Asian countries, particularly in East Asia, than in Canada and the United States. Similarly, at a regional level, subtypes H5N1, H5N2, and H6N2 exhibited significantly higher substitution rates in East Asia than in North America. In contrast, the selection pressures (measured as ratios of nonsynonymous to synonymous evolutionary changes [dN/dS ratios]) acting on individual subtypes showed little geographic variation. We found that the strongest predictors for the detected subtype diversity at the country level were reporting effort (i.e., total number of strains reported) and health care spending (an indicator of economic development). Our analyses also identified major global gaps in IAV reporting (including a lack of sequences submitted from large portions of Africa and South America and a lack of geolocation information) and in broad subtype testing which, until addressed, will continue to hinder efforts to track the evolution and diversity of IAV around the world. In recent years, an increasing number of influenza A virus (IAV) subtypes, including H5N1, H7N9, and H10N8, have been detected in humans. High fatality rates have led to an increased urgency to better understand where and how novel pathogenic influenza virus strains emerge. Our findings showed that mutational rates of 11 commonly encountered subtypes were higher in East Asian countries than in North America, suggesting that there may be a greater risk for the emergence of novel pathogenic strains in East Asia. In assessing the potential drivers of IAV subtype diversity, our analyses confirmed that reporting effort and health care spending were the best predictors of the observed subtype diversity at the country level. These findings underscore the need to increase sampling and reporting efforts for all subtypes in many undersampled countries throughout the world. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Study of low-defect and strain-relaxed GeSn growth via reduced pressure CVD in H2 and N2 carrier gas

NASA Astrophysics Data System (ADS)

Margetis, J.; Mosleh, A.; Al-Kabi, S.; Ghetmiri, S. A.; Du, W.; Dou, W.; Benamara, M.; Li, B.; Mortazavi, M.; Naseem, H. A.; Yu, S.-Q.; Tolle, J.

2017-04-01

High quality, thick (up to 1.1 μm), strain relaxed GeSn alloys were grown on Ge-buffered Si (1 0 0) in an ASM Epsilon® chemical vapor deposition system using SnCl4 and low-cost commercial GeH4 precursors. The significance of surface chemistry in regards to growth rate and Sn-incorporation is discussed by comparing growth kinetics data in H2 and N2 carrier gas. The role of carrier gas is also explored in the suppression of Sn surface segregation and evolution of layer composition and strain profiles via secondary ion mass spectrometry and X-ray diffraction. Transmission electron microscopy revealed the spontaneous compositional splitting and formation of a thin intermediate layer in which dislocations are pinned. This intermediate layer enables the growth of a thick, strain relaxed, and defect-free epitaxial layer on its top. Last, we present photoluminescence results which indicate that both N2 and H2 growth methods produce optoelectronic device quality material.

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.

Adaptation of the autotrophic acetogen Sporomusa ovata to methanol accelerates the conversion of CO2 to organic products

PubMed Central

Tremblay, Pier-Luc; Höglund, Daniel; Koza, Anna; Bonde, Ida; Zhang, Tian

2015-01-01

Acetogens are efficient microbial catalysts for bioprocesses converting C1 compounds into organic products. Here, an adaptive laboratory evolution approach was implemented to adapt Sporomusa ovata for faster autotrophic metabolism and CO2 conversion to organic chemicals. S. ovata was first adapted to grow quicker autotrophically with methanol, a toxic C1 compound, as the sole substrate. Better growth on different concentrations of methanol and with H2-CO2 indicated the adapted strain had a more efficient autotrophic metabolism and a higher tolerance to solvent. The growth rate on methanol was increased 5-fold. Furthermore, acetate production rate from CO2 with an electrode serving as the electron donor was increased 6.5-fold confirming that the acceleration of the autotrophic metabolism of the adapted strain is independent of the electron donor provided. Whole-genome sequencing, transcriptomic, and biochemical studies revealed that the molecular mechanisms responsible for the novel characteristics of the adapted strain were associated with the methanol oxidation pathway and the Wood-Ljungdahl pathway of acetogens along with biosynthetic pathways, cell wall components, and protein chaperones. The results demonstrate that an efficient strategy to increase rates of CO2 conversion in bioprocesses like microbial electrosynthesis is to evolve the microbial catalyst by adaptive laboratory evolution to optimize its autotrophic metabolism. PMID:26530351

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.

Rates of Decomposition of Ribose and other Sugars: Implications for Chemical Evolution

NASA Technical Reports Server (NTRS)

Larralde, Rosa; Robertson, Michael P.; Miller, Stanley L.

1995-01-01

The existence of the RNA world, in which RNA acted as a catalyst as well as an informational macromolecule, assumes a large prebiotic source of ribose or the existence of pre-RNA molecules with backbones different from ribose-phosphate. The generally accepted prebiotic synthesis of ribose, the formose reaction, yields numerous sugars without any selectivity. Even if there were a selective synthesis of ribose, there is still the problem of stability. Sugars are known to be unstable in strong acid or base, but there are few data for neutral solutions. Therefore, we have measured the rate of decomposition of ribose between pH 4 and pH 8 from 40 C to 120 C. The ribose half-lives are very short (73 min at pH 7.0 and 100 C and 44 years at pH 7.0 and 0 C). The other aldopentoses and aldohexoses have half-lives within an order of magnitude of these values, as do 2-deoxyribose, ribose 5-phosphate, and ribose 2,4bisphosphate. These results suggest that the backbone of the first genetic material could not have contained ribose or other sugars because of their instability.

Crystallisation regimes and kinetics in experimentally decompressed dacitic magma

NASA Astrophysics Data System (ADS)

Blum-Oeste, N.; Schmidt, B. C.; Webb, S. L.

2011-12-01

Kinetic processes during magma ascent may have a strong influence on the eruption style. In water bearing dacitic magmas decompression induced exsolution of water and accompanying crystallisation of plagioclase are the main processes which drive the system towards a new equilibrium state. We present new data on the evolution of residual glass composition and crystal size distributions of plagioclase from decompression experiments. Experiments have been conducted in cold seal pressure vessels at 850°C on a natural dacite composition from Taapaca volcano (N. Chile). After an initial equilibration at 2kbar decompression rates between 6.3 and 450bar/h were applied to final pressures between 50 and 1550bar where samples were rapidly quenched. Complementary equilibrium experiments were done at corresponding pressures. The glass composition evolves from the initial state towards the equilibrium at the final pressure. The completeness of this re-equilibration depends on run duration and reaction rates. We introduce the "re-equilibration index" (REI), a fraction between 0 (initial state) and 1 (final state) which allows comparison of chemical components in terms of re-equilibration at different decompression rates. REI divided by the decompression duration gives the "re-equilibration rate" (RER). The REI varies among oxides and it decreases with increasing decompression rate. The highest REIs of ~0.9 have been found for MgO, K2O and Al2O3 at 6.3bar/h whereas Na2O shows the lowest number with 0.25 at this decompression rate. Towards faster decompression all REIs tend to decrease which shows a decreasing completeness of re-equilibration. At 450bar/h the highest REIs are ~0.25. RERs increase from below ~0.005/h at 6.3bar/h up to almost 0.08/h for Al2O3 at 450bar/h. The variability of RERs of different oxides also increases with decompression rates. At 450bar/h the RERs reach from <0.005/h up to 0.08/h. Although RERs strongly increase from low to high decompression rates, this does not compensate for the decreasing duration available for re-equilibration as REIs clearly show. The volume fraction of plagioclase decreases from ~21% at 6.3bar/h to ~16% at 450bar/h which fits the decrease in REIs. The population density of small crystals decreases whereas the population density of larger crystals increases from slow to fast decompression. This reflects a transition from nucleation controlled crystallisation at slow decompression to a growth dominated regime at fast decompression. As RERs show re-equilibration is faster in the growth dominated regime. Although this transition in nucleation processes might be counter-intuitive it can be explained by the observation of slightly higher water concentrations at fast decompression rates resulting in higher liquidus temperatures and thus lower undercooling.

SILCC-Zoom: the dynamic and chemical evolution of molecular clouds

NASA Astrophysics Data System (ADS)

Seifried, D.; Walch, S.; Girichidis, P.; Naab, T.; Wünsch, R.; Klessen, R. S.; Glover, S. C. O.; Peters, T.; Clark, P.

2017-12-01

We present 3D 'zoom-in' simulations of the formation of two molecular clouds out of the galactic interstellar medium. We model the clouds - identified from the SILCC simulations - with a resolution of up to 0.06 pc using adaptive mesh refinement in combination with a chemical network to follow heating, cooling and the formation of H2 and CO including (self-) shielding. The two clouds are assembled within a few million years with mass growth rates of up to ∼10-2 M⊙ yr-1 and final masses of ∼50 000 M⊙. A spatial resolution of ≲0.1 pc is required for convergence with respect to the mass, velocity dispersion and chemical abundances of the clouds, although these properties also depend on the cloud definition such as based on density thresholds, H2 or CO mass fraction. To avoid grid artefacts, the progressive increase of resolution has to occur within the free-fall time of the densest structures (1-1.5 Myr) and ≳200 time-steps should be spent on each refinement level before the resolution is progressively increased further. This avoids the formation of spurious, large-scale, rotating clumps from unresolved turbulent flows. While CO is a good tracer for the evolution of dense gas with number densities n ≥ 300 cm-3, H2 is also found for n ≲ 30 cm-3 due to turbulent mixing and becomes dominant at column densities around 30-50 M⊙ pc-2. The CO-to-H2 ratio steadily increases within the first 2 Myr, whereas XCO ≃ 1-4 × 1020 cm-2 (K km s-1)-1 is approximately constant since the CO(1-0) line quickly becomes optically thick.

Rapid divergence of histones in Hydrozoa (Cnidaria) and evolution of a novel histone involved in DNA damage response in hydra.

PubMed

Reddy, Puli Chandramouli; Ubhe, Suyog; Sirwani, Neha; Lohokare, Rasika; Galande, Sanjeev

2017-08-01

Histones are fundamental components of chromatin in all eukaryotes. Hydra, an emerging model system belonging to the basal metazoan phylum Cnidaria, provides an ideal platform to understand the evolution of core histone components at the base of eumetazoan phyla. Hydra exhibits peculiar properties such as tremendous regenerative capacity, lack of organismal senescence and rarity of malignancy. In light of the role of histone modifications and histone variants in these processes it is important to understand the nature of histones themselves and their variants in hydra. Here, we report identification of the complete repertoire of histone-coding genes in the Hydra magnipapillata genome. Hydra histones were classified based on their copy numbers, gene structure and other characteristic features. Genomic organization of canonical histone genes revealed the presence of H2A-H2B and H3-H4 paired clusters in high frequency and also a cluster with all core histones along with H1. Phylogenetic analysis of identified members of H2A and H2B histones suggested rapid expansion of these groups in Hydrozoa resulting in the appearance of unique subtypes. Amino acid sequence level comparisons of H2A and H2B forms with bilaterian counterparts suggest the possibility of a highly mobile nature of nucleosomes in hydra. Absolute quantitation of transcripts confirmed the high copy number of histones and supported the canonical nature of H2A. Furthermore, functional characterization of H2A.X.1 and a unique variant H2A.X.2 in the gastric region suggest their role in the maintenance of genome integrity and differentiation processes. These findings provide insights into the evolution of histones and their variants in hydra. Copyright © 2017 Elsevier GmbH. All rights reserved.

Physical characterization of fast rotator NEOs

NASA Astrophysics Data System (ADS)

Kikwaya Eluo, Jean-Baptiste; Hergenrother, Carl W.

2015-08-01

Understanding the physical characteristics of fast rotator NEOs (sub-km sizes with H > 22) is important for two reasons: to establish properties that can constraint models of their potential hazard, and to learn about the origin and the evolution of the solar system. Technically it is difficult to cover different ranges of wavelengths using one telescope with one instrument. Setting up a network of telescopes with different instruments observing simultaneously the same object will efficiently contribute to the characterization of NEOs.ART (Arizona Robotic Telescope) is a University of Arizona initiative whose goal is to use local 2-m size telescopes to provide near real-time observations of Target of Opportunity objects covering the visible and the near- infrared wavelengths. We plan to use three telescopes of the ART project to observe fast rotator NEOs: 1) VATT (Vatican Advanced Technology Telescope) at Mount Graham (longitude: -109.8719, latitude: 32.7016, elevation: 10469 feet) with VATT-4K optical imager for photometry to estimate colors, lightcurves to get the rotation rate, and estimate the phase angle function of NEOs, 2) Bok 2.3 m at Kitt Peak (longitude: -111.6004, latitude: 31.9629, elevation: 6795 feet) with BCSpec (Boller & Chivens Spectrograph) for visible spectroscopy, and 3) Kuiper 1.5-m at Mount Bigelow (longitude: -110.7345, latitude: 32.4165, elevation: 8235 feet) with a near-infrared instrument.We report here the preliminary results of several NEOs whose rotation rate, color, and type have been estimated using photometry with images recorded with VATT-4K. 2009 SQ104 has a rotation rate of 6.85+/- 0.03 h, 2014 AY28 has a rotation rate of 0.91 +/- 0.02 h, 2014 EC of 0.54 +/-0.04 h, 2014 FA44 of 3.45 +/- 0.05 h, 2014 KS40 of 1.11 +/- 0.06 h, 2011 PT of 0.17 +/- 0.05 h, 2014 SC324 of 0.36 +/- 0.43 h, 2014 WF201 of 1.00 +/- 0.03 h. Of these objects, 2014 HM2, 2014 FA, 2014 SB145, 2011 PT fall among X-type asteroids; 2014 KS, 2014 WF are likely to be C-type; and 2014 SC 324 is a D-type.

Characterisation of the magmatic signature in gas emissions from Turrialba Volcano, Costa Rica

NASA Astrophysics Data System (ADS)

Moussallam, Y.; Peters, N.; Ramírez, C.; Oppenheimer, C.; Aiuppa, A.; Giudice, G.

2014-12-01

The equilibrium composition of volcanic gases with their magma is often overprinted by interaction with a shallow hydrothermal system. Identifying the magmatic signature of volcanic gases is critical to relate their composition to properties of the magma (temperature, fO2, gas-melt segregation depth). We report measurements of the chemical composition and flux of the major gas species emitted from Turrialba Volcano during March 2013. Measurements were made of two vents in the summit region, one of which opened in 2010 and the other in 2012. We determined an average SO2 flux of 5.2 ± 1.9 kg s-1 using scanning ultraviolet spectroscopy, and molar proportions of H2O, CO2, SO2, HCl, CO and H2 gases of 94.16, 4.03, 1.56, 0.23, 0.003 and 0.009% respectively by open-path Fourier transform infrared (FTIR) spectrometry and a multi-species gas-sensing system. Together, these data imply fluxes of 88, 8, 0.44, 5 × 10-3 and 1 × 10-3 kg s-1 for H2O, CO2, HCl, CO and H2 respectively. Although H2S was detected, its concentration could not be resolved. HF was not detected. The chemical signature of the gas from both vents was found to be broadly similar. Following the opening of the 2010 and 2012 vents we found limited to negligible interaction of the magmatic gas with the hydrothermal system has occurred and the gas composition of the volcanic plume is broadly representative of equilibrium with the magma. The time evolution of the gas composition, the continuous emission of large quantities of SO2, and the physical evolution of the summit area with new vent openings and more frequent eruptions all point towards a continuous drying of the hydrothermal system at Turrialba's summit at an apparently increasing rate.

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.

How does a tidal embayment morphodynamically react on sea level rise?

NASA Astrophysics Data System (ADS)

van der Wegen, Mick

2010-05-01

Conditions for (assumed) equilibrium in tidal embayments have been studied extensively in the past years with morphodynamic 1D models (Van Dongeren and De Vriend, 1994; Schuttelaars and de Swart, 1996, 2000; Lanzoni and Seminara, 2002) and 2D models (Hibma et al. [2003], Van der Wegen and Roelvink [2008]) Van der Wegen et al 2008). The current research addresses the impact of sea level rise on tidal embayments. Although effects of sea level rise may only become apparent after decades, the character of the embayment can change considerably. Examples are the (dis)appearance or re-allocation of intertidal flats, increased tidal resonance, shift from sediment export to import, deepening of channel area and other related (ecological) parameters. The research applies a 2D morphodynamic model (Delft3D) in an idealized environment. The model is based on the 2 D shallow water equations, the Engelund -Hansen transport formula and includes bed slope effects, drying and flooding procedures and an advanced morphodynamic update scheme (Roelvink 2006). The initial condition of the bathymetry is generated by 3000 years of morphodynamic calculations in a 80 km long and 2.5 km wide rectangular tidal embayment under constant M2 tidal forcing conditions (Van der Wegen and Roelvink [2008]). After this period sea level rise gradually developing towards a rate of 0.4 m/century is added to the boundary conditions. Model results describe development towards less intertidal area and a transition from an exporting system to a importing system. Model results are evaluated in terms of M2, M4 and M6 tidal constituents as well as against Vs/Vc (shoal volume over channel volume) versus a/h (amplitude over water depth) relationship as proposed by Friedrichs and Aubrey (1988). Although the model describes morphodynamic development in a strongly idealized environment the results can provide an excellent tool to systematically study the impact of sea level rise in tidal embayments as well as the time scales of dominant underlying resulting transport mechanisms and processes. DISSANAYAKE, D.M.P.K; RANASINGHE, R. and ROELVINK, J.A., 2009. Effect of Sea Level Rise in tidal inlet evolution: a numerical modelling approach. Journal of Coastal Research, SI 56 (Proceedings of the 10th International Coastal Symposium), pg - pg. Lisbon, Portugal. Friedrichs, C. T., and D. G. Aubrey (1988), Non-linear tidal distortion in shallow well mixed estuaries: A synthesis, Estuarine Coastal Shelf Sci.,27, 521- 545, doi:10.1016/0272-7714(88)90082-0. Hibma, A., H.M. Schuttelaars, and H. J. de Vriend (2003b), Initial formation and long-term evolution of channel-shoal patterns in estuaries, in Proc. 3rd RCEM conf.edited by A. Sánchez -Acrilla and A. Bateman, pp. 740-760, IAHR., Barcelona, Spain. Lanzoni, S., and G. Seminara (2002), Long-term evolution and morphodynamic equilibrium of tidal channels, J. Geophys. Res., 107(C1), 3001, doi:10.1029/2000JC000468. Roelvink, J. A. (2006), Coastal morphodynamic evolution techniques, J. Coastal Eng., 53, 177-187. Schuttelaars, H. M., and H. E. De Swart (1996), An idealized long termmorphodynamic model of a tidal embayment, Eur. J. Mech. B Fluids, 15(1), 55-80. Schuttelaars, H. M., and H. E. De Swart (2000), Multiple morphodynamic equilibria in tidal embayments, J. Geophys. Res., 105(C10), 24,105 - 24,118. Van Dongeren, A. D., and H. J. De Vriend (1994), A model of morphological behaviour of tidal basins, Coastal Eng., 22, 287- 310. van der Wegen, M., and J. A. Roelvink (2008), Long-term morphodynamic evolution of a tidal embayment using a twodimensional, process-based model, J. Geophys. Res., 113, C03016, doi:10.1029/2006JC003983 van der Wegen, M., Z. B. Wang, H. H. G. Savenije, and J. A. Roelvink (2008), Long-term morphodynamic evolution and energy dissipation in a coastal plain, tidal embayment, J. Geophys. Res., 113, F03001, doi:10.1029/2007JF000898

Convergent Evolution of Ribonuclease H in LTR Retrotransposons and Retroviruses

PubMed Central

Ustyantsev, Kirill; Novikova, Olga; Blinov, Alexander; Smyshlyaev, Georgy

2015-01-01

Ty3/Gypsy long terminals repeat (LTR) retrotransposons are structurally and phylogenetically close to retroviruses. Two notable structural differences between these groups of genetic elements are 1) the presence in retroviruses of an additional envelope gene, env, which mediates infection, and 2) a specific dual ribonuclease H (RNH) domain encoded by the retroviral pol gene. However, similar to retroviruses, many Ty3/Gypsy LTR retrotransposons harbor additional env-like genes, promoting concepts of the infective mode of these retrotransposons. Here, we provide a further line of evidence of similarity between retroviruses and some Ty3/Gypsy LTR retrotransposons. We identify that, together with their additional genes, plant Ty3/Gypsy LTR retrotransposons of the Tat group have a second RNH, as do retroviruses. Most importantly, we show that the resulting dual RNHs of Tat LTR retrotransposons and retroviruses emerged independently, providing strong evidence for their convergent evolution. The convergent resemblance of Tat LTR retrotransposons and retroviruses may indicate similar selection pressures acting on these diverse groups of elements and reveal potential evolutionary constraints on their structure. We speculate that dual RNH is required to accelerate retrotransposon evolution through increased rates of strand transfer events and subsequent recombination events. PMID:25605791

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.

Kinetic measurement and prediction of the hydrogen outgassing from the polycrystalline LiH/Li 2O/LiOH system

NASA Astrophysics Data System (ADS)

Dinh, L. N.; Grant, D. M.; Schildbach, M. A.; Smith, R. A.; Siekhaus, W. J.; Balazs, B.; Leckey, J. H.; Kirkpatrick, J. R.; McLean, W.

2005-12-01

Due to the exothermic reaction of lithium hydride (LiH) salt with water during transportation and handling, there is always a thin film of lithium hydroxide (LiOH) present on the LiH surface. In dry or vacuum storage, this thin LiOH film slowly decomposes. The technique of temperature-programmed reaction/decomposition (TPR) was employed in combination with the isoconversion method of thermal analysis to determine the outgassing kinetics of H 2O from pure LiOH and H 2 and H 2O from this thin LiOH film. H 2 production via the reaction of LiH with LiOH, forming a lithium oxide (Li 2O) interlayer, is thermodynamically favored, with the rate of further reaction limited by diffusion through the Li 2O and the stability of the decomposing LiOH. Lithium hydroxide at the LiOH/vacuum interface also decomposes easily to Li 2O, releasing H 2O which subsequently reacts with LiH in a closed system to form H 2. At the onset of dry decomposition, where H 2 is the predominant product, the activation energy for outgassing from a thin LiOH film is lower than that for bulk LiOH. However, as the reactions at the LiH/Li 2O/LiOH and at the LiOH/vacuum interfaces proceed, the overall activation energy barrier for the outgassing approaches that of bulk LiOH decomposition. The kinetics developed here predict a hydrogen evolution profile in good agreement with hydrogen release observed during long term isothermal storage.

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

NASA Astrophysics Data System (ADS)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral-water interface.

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.

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

Bockris, J.O.; Devanathan, M.A.V.

The galvanostatic double charging method was applied to determine the coverage of Ni cathodes with adsorbed atomic H in 2 N NaOH solutions. Anodic current densities were varied from 0.05 to 1.8 amp/sq cm. The plateau indicating absence of readsorption was between 0.6 and 1.8 amp/sq cm, for a constant cathodic c.d. of 1/10,000 amp/sq cm. The variation of the adsorbed H over cathodic c.d.'s ranging from 10 to the -6th power to 1/10 at a constant anodic c.d. of 1 amp/sq cm were calculated and the coverage calculated. The mechanism of the H evolution reaction was elucidated. The ratemore » determining step is discharge from a water molecules followed by rapid Tafel recombination. The rate constants for these processes and the rate constant for the ionisation, calculated with the extrapolated value of coverage for the reversible H electrode, were determined. A modification of the Tafel equation which takes into account both coverage and ionisation is in harmony with the results. A new method for the determination of coverage suitable for corrodible metals is described which involves the measurement of the rate of permeation of H by electrochemical techniques which enhances the sensitivity of the method. (Author)« less

Bioelectrochemical oxidation of water.

PubMed

Pita, Marcos; Mate, Diana M; Gonzalez-Perez, David; Shleev, Sergey; Fernandez, Victor M; Alcalde, Miguel; De Lacey, Antonio L

2014-04-23

The electrolysis of water provides a link between electrical energy and hydrogen, a high energy density fuel and a versatile energy carrier, but the process is very expensive. Indeed, the main challenge is to reduce energy consumption for large-scale applications using efficient renewable catalysts that can be produced at low cost. Here we present for the first time that laccase can catalyze electrooxidation of H2O to molecular oxygen. Native and laboratory-evolved laccases immobilized onto electrodes serve as bioelectrocatalytic systems with low overpotential and a high O2 evolution ratio against H2O2 production during H2O electrolysis. Our results open new research ground on H2O splitting, as they overcome serious practical limitations associated with artificial electrocatalysts currently used for O2 evolution.

Climatic response of annual tree-rings

NASA Astrophysics Data System (ADS)

Ageev, Boris G.; Gruzdev, Aleksandr N.; Ponomarev, Yurii N.; Sapozhnikova, Valeria A.

2014-11-01

Extensive literature devoted to investigations into the influence of environmental conditions on the plant respiration and respiration rate. It is generally accepted that the respired CO2 generated in a stem completely diffuses into the atmosphere. Results obtained from explorations into the CO2 content in disc tree rings by the method proposed in this work shows that a major part of CO2 remains in tree stems and exhibits inter-annual variability. Different methods are used to describe of CO2 and H2O distributions in disc tree rings. The relation of CO2 and H2O variations in a Siberian stone pine disc to meteorological parameters are analyzed with use of wavelet, spectral and cross-spectral techniques. According to a multiple linear regression model, the time evolution of the width of Siberian stone pine rings can be partly explained by a combined influence of air temperature, precipitation, cloudiness and solar activity. Conclusions are made regarding the response of the CO2 and H2O content in coniferous tree disc rings to various climatic factors. Suggested method of CO2, (CO2+H2O) detection can be used for studying of a stem respiration in ecological risk areas.

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.

RRKM and master equation kinetic analysis of parallel addition reactions of isomeric radical intermediates in hydrocarbon flames

NASA Astrophysics Data System (ADS)

Winter, Pierre M.; Rheaume, Michael; Cooksy, Andrew L.

2017-08-01

We have calculated the temperature-dependent rate coefficients of the addition reactions of butadien-2-yl (C4H5) and acroylyl (C3H3O) radicals with ethene (C2H4), carbon monoxide (CO), formaldehyde (H2CO), hydrogen cyanide (HCN), and ketene (H2CCO), in order to explore the balance between kinetic and thermodynamic control in these combustion-related reactions. For the C4H5 radical, the 1,3-diene form of the addition products is more stable than the 1,2-diene, but the 1,2-diene form of the radical intermediate is stabilized by an allylic delocalization, which may influence the relative activation energies. For the reactions combining C3H3O with C2H4, CO, and HCN, the opposite is true: the 1,2-enone form of the addition products is more stable than the 1,3-enone, whereas the 1,3-enone is the slightly more stable radical species. Optimized geometries and vibrational modes were computed with the QCISD/aug-cc-pVDZ level and basis, followed by single-point CCSD(T)-F12a/cc-pVDZ-F12 energy calculations. Our findings indicate that the kinetics in all cases favor reaction along the 1,3 pathway for both the C4H5 and C3H3O systems. The Rice-Ramsperger-Kassel-Marcus (RRKM) microcanonical rate coefficients and subsequent solution of the chemical master equation were used to predict the time-evolution of our system under conditions from 500 K to 2000 K and from 10-5 bar to 10 bars. Despite the 1,3 reaction pathway being more favorable for the C4H5 system, our results predict branching ratios of the 1,2 to 1,3 product as high as 0.48 at 1 bar. Similar results hold for the acroylyl system under these combustion conditions, suggesting that under kinetic control the branching of these reactions may be much more significant than the thermodynamics would suggest. This effect may be partly attributed to the low energy difference between 1,2 and 1,3 forms of the radical intermediate. No substantial pressure-dependence is found for the overall forward reaction rates until pressures decrease below 0.1 bar.

Two-dimensional porous architecture of protonated GCN and reduced graphene oxide via electrostatic self-assembly strategy for high photocatalytic hydrogen evolution under visible light

NASA Astrophysics Data System (ADS)

Pu, Chenchen; Wan, Jun; Liu, Enzhou; Yin, Yunchao; Li, Juan; Ma, Yongning; Fan, Jun; Hu, Xiaoyun

2017-03-01

Herein, porous protonated graphitic carbon nitride (pGCN) is prepared from bulk g-C3N4 (GCN) directly by acidic cutting and hydrothermal process. The holey structure not only provides a lot of bounds on the accelerated and photo induced charge transfer and thus reduce the aggregation, but also endows the GCN with more exposure to the active site. The pGCN is obtained with an increased band gap of 2.91 eV together with a higher specific surface area of 82.76 m2g-1. Meanwhile, the positively charged GCN resulted from the protonation pretreatment is beneficial for improving the interaction with negatively charged GO sheets. Compared with GCN, pGCN-rGO displays a significant decrease of PL intensities and an apparently enhancement of visible-light absorption, resulting a lower charge recombination rate and a better light absorption. Besides, the enhanced charge separation is demonstrated by photoluminescence emission spectroscopy and the transient photocurrent measurement. The photocatalytic performance studies for the degradation of MB indicate that pGCN-rGO exhibits the highest adsorption ability towards dye molecules. In addition, the pGCN-5 wt% rGO composite shows the optimal photocatalytic activity, the photodegradation rate of MB is 99.4% after 80 min of irradiation and the H2 evolution performance up to 557 μmol g-1h-1 under visible light, which is much higher than the other control samples.

Growth modelling of Nitrosomonas europaea ATCC® 19718 and Nitrobacter winogradskyi ATCC® 25391: A new online indicator of the partial nitrification.

PubMed

Cruvellier, Nelly; Poughon, Laurent; Creuly, Catherine; Dussap, C-Gilles; Lasseur, Christophe

2016-11-01

The aim of the present work was to study the growth of two nitrifying bacteria. For modelling the nitrifying subsystem of the MELiSSA loop, Nitrosomonas europaea ATCC® 19718 and Nitrobacter winogradskyi ATCC® 25931 were grown separately and in cocultures. The kinetic parameters of a stoichiometric mass balanced Pirt model were identified: μmax=0.054h(-1), decay rate b=0.003h(-1) and maintenance rate m=0.135gN-NH4(+)·gX(-1)·h(-1) for Nitrosomonas europaea; μmax=0.024h(-1), b=0.001h(-1) and m=0.467gN-NO2(-)·gX(-1)·h(-1) for Nitrobacter winogradskyi. A predictive structured model of nitrification in co-culture was developed. The online evolution of the addition of KOH is correlated to the nitritation; the dissolved oxygen concentration is correlated to both nitritation and nitratation. The model suitably represents these two variables so that transient partial nitrification is assessed. This is a clue for avoiding partial nitrification by predictive functional control. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evolution of camel CYP2E1 and its associated power of binding toxic industrial chemicals and drugs.

PubMed

Kandeel, Mahmoud; Altaher, Abdullah; Kitade, Yukio; Abdelaziz, Magdi; Alnazawi, Mohamed; Elshazli, Kamal

2016-10-01

Camels are raised in harsh desert environment for hundreds of years ago. By modernization of live and the growing industrial revolution in camels rearing areas, camels are exposed to considerable amount of chemicals, industrial waste, environmental pollutions and drugs. Furthermore, camels have unique gene evolution of some genes to withstand living in harsh environments. In this work, the camel cytochrome P450 2E1 (CYP2E1) is compromised to detect its evolution rate and its power to bind with various chemicals, protoxins, procarcinogens, industrial toxins and drugs. In comparison with human CYP2E1, camel CYP2E1 more efficiently binds to small toxins as aniline, benzene, catechol, amides, butadiene, toluene and acrylamide. Larger compounds were more preferentially bound to the human CYP2E1 in comparison with camel CYP2E1. The binding of inhalant anesthetics was almost similar in both camel and human CYP2E1 coinciding with similar anesthetic effect as well as toxicity profiles. Furthermore, evolutionary analysis indicated the high evolution rate of camel CYP2E1 in comparison with human, farm and companion animals. The evolution rate of camel CYP2E1 was among the highest evolution rate in a subset of 57 different organisms. These results indicate rapid evolution and potent toxin binding power of camel CYP2E1. Copyright © 2016. Published by Elsevier Ltd.

Production of Hydrogen by Electrocatalysis: Making the H-H Bond by Combining Protons and Hydrides

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

Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.

2014-03-25

Generation of hydrogen by reduction of two protons by two electrons can be catalysed by molecular electrocatalysts. Determination of the thermodynamic driving force for elimination of H2 from molecular complexes is important for the rational design of molecular electrocatalysts, and allows the design of metal complexes of abundant, inexpensive metals rather than precious metals (“Cheap Metals for Noble Tasks”). The rate of H2 evolution can be dramatically accelerated by incorporating pendant amines into diphosphine ligands. These pendant amines in the second coordination sphere function as protons relays, accelerating intramolecular and intermolecular proton transfer reactions. The thermodynamics of hydride transfer frommore » metal hydrides and the acidity of protonated pendant amines (pKa of N-H) contribute to the thermodynamics of elimination of H2; both of the hydricity and acidity can be systematically varied by changing the substituents on the ligands. A series of Ni(II) electrocatalysts with pendant amines have been developed. In addition to the thermochemical considerations, the catalytic rate is strongly influenced by the ability to deliver protons to the correct location of the pendant amine. Protonation of the amine endo to the metal leads to the N-H being positioned appropriately to favor rapid heterocoupling with the M-H. Designing ligands that include proton relays that are properly positioned and thermodynamically tuned is a key principle for molecular electrocatalysts for H2 production as well as for other multi-proton, multi-electron reactions important for energy conversions. The research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Krishna, Nanda Gopala; Kim, Dong-Ik

2015-10-01

Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr2O4 and MnCr2O4 along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

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;

Physiological response of a red tide alga (Skeletonema costatum) to nitrate enrichment, with special reference to inorganic carbon acquisition.

PubMed

Gao, Guang; Xia, Jianrong; Yu, Jinlan; Zeng, Xiaopeng

2018-02-01

A classical red tide alga Skeletonema costatum was cultured under various nitrate levels to investigate its physiological response to nitrate enrichment combined with CO 2 limitation. The higher nitrate levels increased content of photosynthetic pigments (Chl a and Chl c), electron transport rate in photosystem II, photosynthetic O 2 evolution, and thus growth rate in S. costatum. On the other hand, the lower CO 2 levels (3.5-4.4 μmol kg -1 seawater) and higher pH (8.56-8.63) values in seawater were observed under higher nitrate conditions. Redox activity of plasma membrane and carbonic anhydrase in S. costatum was enhanced to address the reduced CO 2 level at higher nitrate levels. In addition, the pH compensation point was enhanced and direct HCO 3 - use was induced at higher nitrate levels. These findings indicate that nitrate enrichment would stimulate the breakout of S. costatum dominated red tides via enhancing its photosynthetic performances, and maintain a quick growth rate under CO 2 limitation conditions through improving its inorganic carbon acquisition capability. Our study sheds light on the mechanisms of S. costatum defeating CO 2 limitation during algal bloom. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

Light-enhanced dark respiration in leaves, isolated cells and protoplasts of various types of C4 plants.

PubMed

Parys, Eugeniusz; Jastrzebski, Hubert

2006-04-01

The rate of respiratory CO2 evolution from the leaves of Zea mays, Panicum miliaceum, and Panicum maximum, representing NADP-ME, NAD-ME, and PEP-CK types of C4 plants, respectively, was increased by approximately two to four times after a period of photosynthesis. This light-enhanced dark respiration (LEDR) was a function of net photosynthetic rate specific to plant species, and was depressed by 1% O2. When malate, aspartate, oxaloacetate or glycine solution at 50 mM concentration was introduced into the leaves instead of water, the rate of LEDR was enhanced, far less in Z. mays (by 10-25%) than in P. miliaceum (by 25-35%) or P. maximum (by 40-75%). The enhancement of LEDR under glycine was relatively stable over a period of 1 h, whereas the remaining metabolites caused its decrease following a transient increase. The metabolites reduced the net photosynthesis rate in the two Panicum species, but not in Z. mays, where this process was stimulated by glycine. The bundle sheath cells from P. miliaceum exhibited a higher rate of LEDR than those of Z. mays and P. maximum. Glycine had no effect on the respiration rate of the cells, but malate increased in cells of Z. mays and P. miliaceum by about 50% and 30%, respectively. With the exception of aspartate, which stimulated both the O2 evolution and O2 uptake in P. maximum, the remaining metabolites reduced photosynthetic O2 evolution from bundle sheath cells in Panicun species. The net O2 exchange in illuminated cells of Z. mays did not respond to CO2 or metabolites. Leaf mesophyll protoplasts of Z. mays and P. miliaceum, and bundle sheath protoplasts of Z. mays, which are unable to fix CO2 photosynthetically, also produced LEDR, but the mesophyll protoplasts, compared with bundle sheath protoplasts, required twice the time of illumination to obtain the maximal rate. The results suggest that the substrates for LEDR in C4 plants are generated during a period of illumination not only via the Calvin cycle reactions, but also by the conversion of endogenous compounds present in leaf cells. The stimulation of LEDR under glycine is discussed in relation to its direct or indirect effect on mitochondrial respiration.

Mantle redox evolution and the oxidation state of the Archean atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.; Eggler, D. H.; Raeburn, S. P.

1993-01-01

Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.

Molecular evolution of H5N1 in Thailand between 2004 and 2008.

PubMed

Suwannakarn, Kamol; Amonsin, Alongkorn; Sasipreeyajan, Jiroj; Kitikoon, Pravina; Tantilertcharoen, Rachod; Parchariyanon, Sujira; Chaisingh, Arunee; Nuansrichay, Bandit; Songserm, Thaweesak; Theamboonlers, Apiradee; Poovorawan, Yong

2009-09-01

Highly pathogenic avian influenza (HPAI) H5N1 viruses have seriously affected the Asian poultry industry since their occurrence in 2004. Thailand has been one of those countries exposed to HPAI H5N1 outbreaks. This project was designed to compare the molecular evolution of HPAI H5N1 in Thailand between 2004 and 2008. Viruses with clade 1 hemagglutinin (HA) were first observed in early 2004 and persisted until 2008. Viruses with clade 2.3.4 HA were first observed in the northeastern region of Thailand between 2006 and 2007. Phylogenetic analysis among Thai isolates indicated that clade 1 viruses in Thailand consist of three distinct lineages: CUK2-like, PC168-like, and PC170-like viruses. The CUK2-like virus represents the predominant lineage and has been circulating throughout the course of the 4-year outbreaks. Analysis of recently isolated viruses has shown that the genetic distance was slightly different from viruses of the early outbreak and that CUK2-like viruses comprise the native strain. Between 2005 and 2007, PC168-like and PC170-like viruses were first observed in several areas around central and lower northern Thailand. In 2008, viruses reassorted from these two lineages, PC168-like and PC170-like viruses, were initially isolated in the lower northern provinces of Thailand and subsequently spread to the upper central part of Thailand. On the other hand, CUK2-like viruses were still detected around the lower northern and the upper central part of Thailand. Furthermore, upon emergence of the reassorted viruses, the PC168-like and PC170-like lineages could not be detected, suggesting that the only predominant strains still circulating in Thailand were CUK2-like and reassorted viruses. The substitution rate among clade 1 viruses in Thailand was lower. The virus being limited to the same area might explain the lower nucleotide substitution rate. This study has demonstrated that nationwide attempts to monitor the virus may help curb access and propagation of new HPAI viral genes.

Mediated water electrolysis in biphasic systems.

PubMed

Scanlon, Micheál D; Peljo, Pekka; Rivier, Lucie; Vrubel, Heron; Girault, Hubert H

2017-08-30

The concept of efficient electrolysis by linking photoelectrochemical biphasic H 2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H 2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp 2 *Fe (III) ] + ) to neutral decamethylferrocene (Cp 2 *Fe (II) ) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp 2 *Fe (II) to form the corresponding hydride species, [Cp 2 *Fe (IV) (H)] + . Subsequently, [Cp 2 *Fe (IV) (H)] + spontaneously undergoes a chemical reaction in the oil phase to evolve hydrogen gas (H 2 ) and regenerate [Cp 2 *Fe (III) ] + , whereupon this catalytic Electrochemical, Chemical, Chemical (ECC') cycle is repeated. During biphasic electrolysis, the stability and recyclability of the [Cp 2 *Fe (III) ] + /Cp 2 *Fe (II) redox couple were confirmed by chronoamperometric measurements and, furthermore, the steady-state concentration of [Cp 2 *Fe (III) ] + monitored in situ by UV/vis spectroscopy. Post-biphasic electrolysis, the presence of H 2 in the headspace of the cathodic compartment was established by sampling with gas chromatography. The rate of the biphasic hydrogen evolution reaction (HER) was enhanced by redox electrocatalysis in the presence of floating catalytic molybdenum carbide (Mo 2 C) microparticles at the immiscible water/oil interface. The use of a superhydrophobic organic electrolyte salt was critical to ensure proton transfer from water to oil, and not anion transfer from oil to water, in order to maintain electroneutrality after electron transfer. The design, testing and successful optimisation of the operation of the biphasic electrolysis cell under dark conditions with Cp 2 *Fe (II) lays the foundation for the achievement of photo-induced biphasic water electrolysis at low overpotentials using another metallocene, decamethylrutheneocene (Cp 2 *Ru (II) ). Critically, Cp 2 *Ru (II) may be recycled at a potential more positive than that of proton reduction in DCE.

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.

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.

Thiol-catalyzed formation of lactate and glycerate from glyceraldehyde. [significance in molecular evolution

NASA Technical Reports Server (NTRS)

Weber, A. L.

1983-01-01

The rate of lactate formation from glyceraldehyde, catalyzed by N-acetyl-cysteine at ambient temperature in aqueous sodium phosphate (pH 7.0), is more rapid at higher sodium phosphate concentrations and remains essentially the same in the presence and absence of oxygen. The dramatic increase in the rate of glycerate formation that is brought about by this thiol, N-acetylcysteine, is accompanied by commensurate decreases in the rates of glycolate and formate production. It is suggested that the thiol-dependent formation of lactate and glycerate occurs by way of their respective thioesters. Attention is given to the significance of these reactions in the context of molecular evolution.

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction.

PubMed

Ritzert, Nicole L; Moffat, Thomas P

2016-12-08

The interaction between electrodeposition of Ni and electrolyte breakdown, namely the hydrogen evolution reaction (HER) via H 3 O + and H 2 O reduction, was investigated under well-defined mass transport conditions using ultramicroelectrodes (UME's) coupled with optical imaging, generation/collection scanning electrochemical microscopy (G/C-SECM), and preliminary microscale pH measurements. For 5 mmol/L NiCl 2 + 0.1 mol/L NaCl, pH 3.0, electrolytes, the voltammetric current at modest overpotentials, i.e. , between -0.6 V and -1.4 V vs. Ag/AgCl, was distributed between metal deposition and H 3 O + reduction, with both reactions reaching mass transport limited current values. At more negative potentials, an unusual sharp current spike appeared upon the onset of H 2 O reduction that was accompanied by a transient increase in H 2 production. The peak potential of the current spike was a function of both [Ni(H 2 O) 6 ] 2+ (aq) concentration and pH. The sharp rise in current was ascribed to the onset of autocatalytic H 2 O reduction, where electrochemically generated OH - species induce heterogeneous nucleation of Ni(OH) 2(ads) islands, the perimeter of which is reportedly active for H 2 O reduction. As the layer coalesces, further metal deposition is quenched while H 2 O reduction continues albeit at a decreased rate as fewer of the most reactive sites, e.g. , Ni/Ni(OH) 2 island edges, are available. At potentials below -1.5 V vs. Ag/AgCl, H 2 O reduction is accelerated, leading to homogeneous precipitation of bulk Ni(OH) 2 · x H 2 O within the nearly hemispherical diffusion layer of the UME.

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.

Improved constraints on the expansion rate of the Universe up to z ∼ 1.1 from the spectroscopic evolution of cosmic chronometers

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

Moresco, M.; Cimatti, A.; Jimenez, R.

2012-08-01

We present new improved constraints on the Hubble parameter H(z) in the redshift range 0.15 < z < 1.1, obtained from the differential spectroscopic evolution of early-type galaxies as a function of redshift. We extract a large sample of early-type galaxies ( ∼ 11000) from several spectroscopic surveys, spanning almost 8 billion years of cosmic lookback time (0.15 < z < 1.42). We select the most massive, red elliptical galaxies, passively evolving and without signature of ongoing star formation. Those galaxies can be used as standard cosmic chronometers, as firstly proposed by Jimenez and Loeb (2002), whose differential age evolutionmore » as a function of cosmic time directly probes H(z). We analyze the 4000 Å break (D4000) as a function of redshift, use stellar population synthesis models to theoretically calibrate the dependence of the differential age evolution on the differential D4000, and estimate the Hubble parameter taking into account both statistical and systematical errors. We provide 8 new measurements of H(z), and determine its change in H(z) to a precision of 5–12% mapping homogeneously the redshift range up to z ∼ 1.1; for the first time, we place a constraint on H(z) at z≠0 with a precision comparable with the one achieved for the Hubble constant (about 5–6% at z ∼ 0.2), and covered a redshift range (0.5 < z < 0.8) which is crucial to distinguish many different quintessence cosmologies. These measurements have been tested to best match a ΛCDM model, clearly providing a statistically robust indication that the Universe is undergoing an accelerated expansion. This method shows the potentiality to open a new avenue in constrain a variety of alternative cosmologies, especially when future surveys (e.g. Euclid) will open the possibility to extend it up to z ∼ 2.« less

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.

Electron Irradiation of Kuiper Belt Surface Ices: Ternary N2-CH4-CO Mixtures as a Case Study

NASA Astrophysics Data System (ADS)

Kim, Y. S.; Kaiser, R. I.

2012-10-01

The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH4) and carbon monoxide (CO) doped nitrogen (N2) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N2-CH4 and CO-CH4 systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH2N2), and its radical fragment (HCN2); oxygen-bearing products were of acetaldehyde (CH3CHO), formyl radical (HCO), and formaldehyde (H2CO). As in the pure ices, the methyl radical (CH3) and ethane (C2H6) were also detected, as were carbon dioxide (CO2) and the azide radical (N3). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

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.

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.

High-resolution mineralogical characterization and biogeochemical modeling of uranium reaction pathways at the FRC

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

Chen Zhu

2006-06-15

High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the Oak Ridge Field-Research Center (FRC) Chen Zhu, Indiana University, David R. Veblen, Johns Hopkins University We have successfully completed a proof-of-concept, one-year grant on a three-year proposal from the former NABIR program, and here we seek additional two-year funding to complete and publish the research. Using a state-of-the-art 300-kV, atomic resolution, Field Emission Gun Transmission Electron Microscope (TEM), we have successfully identified three categories of mineral hosts for uranium in contaminated soils: (1) iron oxides; (2) mixed manganese-iron oxides; and (3) uranium phosphates. Method development using parallel electronmore » energy loss spectroscopy (EELS) associated with the TEM shows great promise for characterizing the valence states of immobilized U during bioremediation. We have also collected 27 groundwater samples from two push-pull field biostimulation tests, which form two time series from zero to approximately 600 hours. The temporal evolution in major cations, anions, trace elements, and the stable isotopes 34S, 18O in sulfate, 15N in nitrate, and 13C in dissolved inorganic carbon (DIC) clearly show that biostimulation resulted in reduction of nitrate, Mn(IV), Fe(III), U(VI), sulfate, and Tc(VII), and these reduction reactions were intimately coupled with a complex network of inorganic reactions evident from alkalinity, pH, Na, K, Mg, and Ca concentrations. From these temporal trends, apparent zero order rates were regressed. However, our extensive suite of chemical and isotopic data sets, perhaps the first and only comprehensive data set available at the FRC, show that the derived rates from these field biostimulation experiments are composite and lump-sum rates. There were several reactions that were occurring at the same time but were masked by these pseudo-zero order rates. A reaction-path model comprising a total of nine redox couples (NO3–/NH4+, MnO2(s)/Mn2+, Fe(OH)3(s) /Fe2+, TcO4–/TcO2(s), UO22+/UO2(s), SO42–/HS–, CO2/CH4, ethanol/acetate, and H+/H2.) is used to simulate the temporal biogeochemical evolution observed in the field tests. Preliminary results show that the models based on thermodynamics and more complex rate laws can generate the apparent zero order rates when several concurrent or competing reactions occur. Professor Alex Halliday of Oxford University, UK, and his postdoctoral associates are measuring the uranium isotopes in our groundwater samples. Newly developed state-of-the-art analytical techniques in measuring variability in 235U/238U offer the potential to distinguish biotic and abiotic uranium reductive mechanisms.« less

The evolution of multiple isotypic IgM heavy chain genes in the shark.

PubMed

Lee, Victor; Huang, Jing Li; Lui, Ming Fai; Malecek, Karolina; Ohta, Yuko; Mooers, Arne; Hsu, Ellen

2008-06-01

The IgM H chain gene organization of cartilaginous fishes consists of 15-200 miniloci, each with a few gene segments (V(H)-D1-D2-J(H)) and one C gene. This is a gene arrangement ancestral to the complex IgH locus that exists in all other vertebrate classes. To understand the molecular evolution of this system, we studied the nurse shark, which has relatively fewer loci, and characterized the IgH isotypes for organization, functionality, and the somatic diversification mechanisms that act upon them. Gene numbers differ slightly between individuals ( approximately 15), but five active IgM subclasses are always present. Each gene undergoes rearrangement that is strictly confined within the minilocus; in B cells there is no interaction between adjacent loci located > or =120 kb apart. Without combinatorial events, the shark IgM H chain repertoire is based on junctional diversity and, subsequently, somatic hypermutation. We suggest that the significant contribution by junctional diversification reflects the selected novelty introduced by RAG in the early vertebrate ancestor, whereas combinatorial diversity coevolved with the complex translocon organization. Moreover, unlike other cartilaginous fishes, there are no germline-joined VDJ at any nurse shark mu locus, and we suggest that such genes, when functional, are species-specific and may have specialized roles. With an entire complement of IgM genes available for the first time, phylogenetic analyses were performed to examine how the multiple Ig loci evolved. We found that all domains changed at comparable rates, but V(H) appears to be under strong positive selection for increased amino acid sequence diversity, and surprisingly, so does Cmicro2.

Effect of heavy ion irradiation on microstructural evolution in CF8 cast austenitic stainless steel

DOE PAGES

Chen, Wei-Ying; Li, Meimei; Kirk, Marquis A.; ...

2015-08-21

The microstructural evolution in ferrite and austenitic in cast austenitic stainless steel (CASS) CF8, as received or thermally aged at 400 °C for 10,000 h, was followed under TEM with in situ irradiation of 1 MeV Kr ions at 300 and 350 °C to a fluence of 1.9 × 10 15 ions/cm 2 (~3 dpa) at the IVEM-Tandem Facility. For the unaged CF8, the irradiation-induced dislocation loops appeared at a much lower dose in the austenite than in the ferrite. At the end dose, the austenite formed a well-developed dislocation network microstructure, while the ferrite exhibited an extended dislocation structuremore » as line segments. Compared to the unaged CF8, the aged specimen appeared to have lower rate of damage accumulation. The rate of microstructural evolution under irradiation in the ferrite was significantly lower in the aged specimen than in the unaged. Finally, we attributed this difference to the different initial microstructures in the unaged and aged specimens, which implies that thermal aging and irradiation are not independent but interconnected damage processes.« less

Klaus - an exceptional winter storm over Northern Iberia and Southern France

NASA Astrophysics Data System (ADS)

Liberato, M. R. L.; Pinto, J. G.; Trigo, I. F.; Trigo, R. M.

2010-09-01

The synoptic evolution and impacts of storm Klaus that swept through northern Iberia and southern France on 23-24 January 2009, are assessed. Klaus followed an unusual southern path and was the costliest weather hazard event worldwide during 2009. In particular, it was the most intense and damaging wind storm in the region in a decade, provoked more than 20 casualties and insured losses of several billion Euros. Several long-term records of maximum wind speed gust were broken, including Bordeaux, Narbonne and Perpignan. Storm Klaus first developed close to the Bermudas, traveled fast eastwards and underwent explosive development near the Iberian Peninsula. Its development was supported by an extended and intensified polar jet which stretched down to Western Europe and strong upper-air divergence associated with a second jet streak. Afterwards, it steered southeastwards across Southern France into Northern Italy and the Adriatic. The evolution of "Klaus" is analysed using two standard cyclone detecting and tracking schemes. Results show that both tracks exhibited similar features and positions throughout almost all of their lifecycles, with minor minor discrepancies. These are likely associated to the fields used by each method for storm identification (near surface geopotential height and geostrophic vorticity, respectively) and to different handling of the spatio-temporal evolution of multiple cyclone candidates. In its strengthening phase, "Klaus" presents deepening rates above 37 hPa/24h, a value that after geostrophically adjusted to the reference latitude of 60°N increases to 44 hPa/24h, implying an exceptional event with bomb characteristics. During the maximum intensification phase, the laplacian of surface pressure increased by 1.165hPa/(deglat)2 within 24 hours.

Muscovite dissolution kinetics as a function of pH at elevated temperature

DOE PAGES

Lammers, Kristin; Smith, Megan M.; Carroll, Susan A.

2017-06-07

We report that mineral reactivity can play an important role in fracture-controlled fluid networks where maintaining or increasing permeability is a goal, such as enhanced geothermal systems. In these systems, dissolution generates new void space, removes cement and physically transports less reactive mineral grains, while secondary precipitation acts to narrow or seal off fluid pathways. Sheet silicate mineral reactivity is likely to affect permeability evolution at the elevated temperatures of geothermal reservoirs because of the high reactive surface area and prevalence of these minerals in hydrothermal zones. To better describe the reactivity of one common sheet silicate, muscovite, we conducted kinetic dissolution experiments using flow-through reactors at temperatures of 100–280 °C and a pH range of 2–9. Surface area-normalized muscovite dissolution rates ranged from 0.17–155 · 10 - 11 mol m - 2 s - 1 over this temperature range, but showed little variation with pH above 150 °C. Aluminum was released to solution nonstoichiometrically with respect to dissolved silica, most likely resulting from secondary precipitation of an aluminum oxy-hydroxide identified as boehmite (γ-AlO(OH)( s)) by X-ray diffraction in reaction products from experiments conducted at pH ≤ 6. Surface area-normalized muscovite dissolution rates, Rate mus (mol m - 2 s - 1), can be described from 25 to 280 °C with the following kinetic rate equation: Rate mus = ([3∙10 -3∙e -44 /R∙T∙amore » $$0.8\\atop{H+}$$] + [9∙10 -6∙e- 45/R∙T] + [5∙10 -1∙ e-61/R∙T ∙a$$0.6\\atop{OH-}$$] ∙ (1-e -ΔGr/RT) where the rate and pre-exponential factors are in mol m - 2 s - 1; the activation energies, E, are in kJ mol - 1; a H+ and a OH- represent the activities of H + and OH -, respectively; R (kJ mol - 1 K - 1) is the gas constant; T is the temperature in Kelvins; and ΔG r (kJ mol - 1) is a measure of how close the aqueous solution is to muscovite equilibrium. The rate equation is constrained by our new data literature rates and has been evaluated against previous formulations with varying dependence on reaction affinity. Although 150 °C muscovite rates from Oelkers et al. (2008) show a systematic dependence on reaction affinity, incorporating this dependence did not accurately reproduce the higher-temperature rates. In conclusion, we recommend the rate equation shown above, with an affinity term that slows reaction rates only when solutions are close to equilibrium, for simulating the dissolution of muscovite under geothermal conditions.« less

Muscovite dissolution kinetics as a function of pH at elevated temperature

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

Lammers, Kristin; Smith, Megan M.; Carroll, Susan A.

We report that mineral reactivity can play an important role in fracture-controlled fluid networks where maintaining or increasing permeability is a goal, such as enhanced geothermal systems. In these systems, dissolution generates new void space, removes cement and physically transports less reactive mineral grains, while secondary precipitation acts to narrow or seal off fluid pathways. Sheet silicate mineral reactivity is likely to affect permeability evolution at the elevated temperatures of geothermal reservoirs because of the high reactive surface area and prevalence of these minerals in hydrothermal zones. To better describe the reactivity of one common sheet silicate, muscovite, we conducted kinetic dissolution experiments using flow-through reactors at temperatures of 100–280 °C and a pH range of 2–9. Surface area-normalized muscovite dissolution rates ranged from 0.17–155 · 10 - 11 mol m - 2 s - 1 over this temperature range, but showed little variation with pH above 150 °C. Aluminum was released to solution nonstoichiometrically with respect to dissolved silica, most likely resulting from secondary precipitation of an aluminum oxy-hydroxide identified as boehmite (γ-AlO(OH)( s)) by X-ray diffraction in reaction products from experiments conducted at pH ≤ 6. Surface area-normalized muscovite dissolution rates, Rate mus (mol m - 2 s - 1), can be described from 25 to 280 °C with the following kinetic rate equation: Rate mus = ([3∙10 -3∙e -44 /R∙T∙amore » $$0.8\\atop{H+}$$] + [9∙10 -6∙e- 45/R∙T] + [5∙10 -1∙ e-61/R∙T ∙a$$0.6\\atop{OH-}$$] ∙ (1-e -ΔGr/RT) where the rate and pre-exponential factors are in mol m - 2 s - 1; the activation energies, E, are in kJ mol - 1; a H+ and a OH- represent the activities of H + and OH -, respectively; R (kJ mol - 1 K - 1) is the gas constant; T is the temperature in Kelvins; and ΔG r (kJ mol - 1) is a measure of how close the aqueous solution is to muscovite equilibrium. The rate equation is constrained by our new data literature rates and has been evaluated against previous formulations with varying dependence on reaction affinity. Although 150 °C muscovite rates from Oelkers et al. (2008) show a systematic dependence on reaction affinity, incorporating this dependence did not accurately reproduce the higher-temperature rates. In conclusion, we recommend the rate equation shown above, with an affinity term that slows reaction rates only when solutions are close to equilibrium, for simulating the dissolution of muscovite under geothermal conditions.« 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.

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.

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.

Cosmic evolution and metal aversion in superluminous supernova host galaxies

NASA Astrophysics Data System (ADS)

Schulze, S.; Krühler, T.; Leloudas, G.; Gorosabel, J.; Mehner, A.; Buchner, J.; Kim, S.; Ibar, E.; Amorín, R.; Herrero-Illana, R.; Anderson, J. P.; Bauer, F. E.; Christensen, L.; de Pasquale, M.; de Ugarte Postigo, A.; Gallazzi, A.; Hjorth, J.; Morrell, N.; Malesani, D.; Sparre, M.; Stalder, B.; Stark, A. A.; Thöne, C. C.; Wheeler, J. C.

2018-01-01

The SUperluminous Supernova Host galaxIES survey aims to provide strong new constraints on the progenitors of superluminous supernovae (SLSNe) by understanding the relationship to their host galaxies. We present the photometric properties of 53 H-poor and 16 H-rich SLSN host galaxies out to z ∼ 4. We model their spectral energy distributions to derive physical properties, which we compare with other galaxy populations. At low redshift, H-poor SLSNe are preferentially found in very blue, low-mass galaxies with high average specific star formation rates. As redshift increases, the host population follows the general evolution of star-forming galaxies towards more luminous galaxies. After accounting for secular evolution, we find evidence for differential evolution in galaxy mass, but not in the B band and the far-ultraviolet luminosity (3σ confidence). Most remarkable is the scarcity of hosts with stellar masses above 1010 M⊙ for both classes of SLSNe. In case of H-poor SLSNe, we attribute this to a stifled production efficiency above ∼0.4 solar metallicity. However, we argue that, in addition to low metallicity, a short-lived stellar population is also required to regulate the SLSN production. H-rich SLSNe are found in a very diverse population of star-forming galaxies. Still, the scarcity of massive hosts suggests a stifled production efficiency above ∼0.8 solar metallicity. The large dispersion of the H-rich SLSNe host properties is in stark contrast to those of gamma-ray burst, regular core-collapse SN, and H-poor SLSNe host galaxies. We propose that multiple progenitor channels give rise to this subclass.

Corotation lag limit on mass-loss rate from Io

NASA Astrophysics Data System (ADS)

Huang, T. S.; Siscoe, G. L.

1987-08-01

Considering rapid escape of H2O from Io during an early hot evolutionary epoch, an H2O plasma torus is constructed by balancing dissociation and ionization products against centrifugally driven diffusion, including for the first time the effects of corotation lag resulting from mass loading. Two fundamental limits are found as the mass injection rate increases: (1) an 'ignition' limit of 1.1 x 10 to the 6th kg/s, beyond which the torus cannot ionize itself and photoionization dominates; and (2) the ultimate mass loading limit of 1.3 x 10 to the 7th kg/s, which occurs when neutrals newly created by charge exchange and recombination cannot leave the torus, thereby bringing magnetospherically driven transport to a halt. Connecting this limit with the variations of Io's temperature in its early evolution epoch gives an estimate of the upper limit on the total mass loss from Io, about 3.0 x 10 to the 20th kg (for high-opacity nebula) and about 8.9 x 10 to the 20th kg (for low-opacity nebula). These limits correspond to eroding 8 km and 22 km of H2O from the surface. It is concluded that compared to the other Galilean satellites, Io was created basically dry.

The Influence of MgH2 on the Assessment of Electrochemical Data to Predict the Degradation Rate of Mg and Mg Alloys

PubMed Central

Mueller, Wolf-Dieter; Hornberger, Helga

2014-01-01

Mg and Mg alloys are becoming more and more of interest for several applications. In the case of biomaterial applications, a special interest exists due to the fact that a predictable degradation should be given. Various investigations were made to characterize and predict the corrosion behavior in vitro and in vivo. Mostly, the simple oxidation of Mg to Mg2+ ions connected with adequate hydrogen development is assumed, and the negative difference effect (NDE) is attributed to various mechanisms and electrochemical results. The aim of this paper is to compare the different views on the corrosion pathway of Mg or Mg alloys and to present a neglected pathway based on thermodynamic data as a guideline for possible reactions combined with experimental observations of a delay of visible hydrogen evolution during cyclic voltammetry. Various reaction pathways are considered and discussed to explain these results, like the stability of the Mg+ intermediate state, the stability of MgH2 and the role of hydrogen overpotential. Finally, the impact of MgH2 formation is shown as an appropriate base for the prediction of the degradation behavior and calculation of the corrosion rate of Mg and Mg alloys. PMID:24972140

First time-dependent study of H{sub 2} and H{sub 3}{sup +} ortho-para chemistry in the diffuse interstellar medium: Observations meet theoretical predictions

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

Albertsson, T.; Semenov, D.; Henning, Th.

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H{sub 3}{sup +}. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H{sub 3}{sup +}, unlike H{sub 2}, seems to be outmore » of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H{sub 3}{sup +} and find that the destruction of the lowest rotational states of H{sub 3}{sup +} by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H{sub 3}{sup +} is assumed. Additionally, an increased cosmic-ray ionization rate to 10{sup –15} s{sup –1} further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H{sub 3}{sup +} under interstellar conditions.« less

First Time-dependent Study of H2 and H_3^+ Ortho-Para Chemistry in the Diffuse Interstellar Medium: Observations Meet Theoretical Predictions

NASA Astrophysics Data System (ADS)

Albertsson, T.; Indriolo, N.; Kreckel, H.; Semenov, D.; Crabtree, K. N.; Henning, Th.

2014-05-01

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H_3^+. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H2 and H_3^+ in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H_3^+, unlike H2, seems to be out of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H2 and H_3^+ in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H_3^+ and find that the destruction of the lowest rotational states of H_3^+ by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H_3^+ is assumed. Additionally, an increased cosmic-ray ionization rate to 10-15 s-1 further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H_{3}^{+} under interstellar conditions. Partly based on observations collected at the European Organization for Astronomical Research in the Southern Hemisphere, Chile, as part of program 088.C-0351.

Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

PubMed Central

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2016-01-01

Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids. PMID:26801026

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.

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.

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.

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;

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy

PubMed Central

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-01-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER. PMID:27034988

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

PubMed

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-03-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

In Vitro Evolution and Affinity-Maturation with Coliphage Qβ Display

PubMed Central

Skamel, Claudia; Aller, Stephen G.; Bopda Waffo, Alain

2014-01-01

The Escherichia coli bacteriophage, Qβ (Coliphage Qβ), offers a favorable alternative to M13 for in vitro evolution of displayed peptides and proteins due to high mutagenesis rates in Qβ RNA replication that better simulate the affinity maturation processes of the immune response. We describe a benchtop in vitro evolution system using Qβ display of the VP1 G-H loop peptide of foot-and-mouth disease virus (FMDV). DNA encoding the G-H loop was fused to the A1 minor coat protein of Qβ resulting in a replication-competent hybrid phage that efficiently displayed the FMDV peptide. The surface-localized FMDV VP1 G-H loop cross-reacted with the anti-FMDV monoclonal antibody (mAb) SD6 and was found to decorate the corners of the Qβ icosahedral shell by electron microscopy. Evolution of Qβ-displayed peptides, starting from fully degenerate coding sequences corresponding to the immunodominant region of VP1, allowed rapid in vitro affinity maturation to SD6 mAb. Qβ selected under evolutionary pressure revealed a non-canonical, but essential epitope for mAb SD6 recognition consisting of an Arg-Gly tandem pair. Finally, the selected hybrid phages induced polyclonal antibodies in guinea pigs with good affinity to both FMDV and hybrid Qβ-G-H loop, validating the requirement of the tandem pair epitope. Qβ-display emerges as a novel framework for rapid in vitro evolution with affinity-maturation to molecular targets. PMID:25393763

Elucidating hydrogen oxidation/evolution kinetics in base and acid by enhanced activities at the optimized Pt shell thickness on the Ru core

DOE PAGES

Elbert, Katherine; Hu, Jue; Ma, Zhong; ...

2015-10-05

Hydrogen oxidation and evolution on Pt in acid are facile processes, while in alkaline electrolytes, they are 2 orders of magnitude slower. Thus, developing catalysts that are more active than Pt for these two reactions is important for advancing the performance of anion exchange membrane fuel cells and water electrolyzers. Herein, we detail a 4-fold enhancement of Pt mass activity that we achieved using single-crystalline Ru@Pt core–shell nanoparticles with two-monolayer-thick Pt shells, which doubles the activity on Pt–Ru alloy nanocatalysts. For Pt specific activity, the two- and one-monolayer-thick Pt shells exhibited enhancement factors of 3.1 and 2.3, respectively, compared tomore » the Pt nanocatalysts in base, differing considerably from the values of 1 and 0.4, respectively, in acid. To explain such behavior and the orders of magnitude difference in activity on going from acid to base, we performed kinetic analyses of polarization curves over a wide range of potential from –250 to 250 mV using the dual-pathway kinetic equation. From acid to base, the activation free energies increase the most for the Volmer reaction, resulting in a switch of the rate-determining step from the Tafel to the Volmer reaction, and a shift to a weaker optimal hydrogen binding energy. Furthermore, the much higher activation barrier for the Volmer reaction in base than in acid is ascribed to one or both of the two catalyst-insensitive factors: slower transport of OH – than H + in water and a stronger O–H bond in water molecules (HO–H) than in hydrated protons (H 2O–H +).« less

Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

PubMed Central

2017-01-01

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

The influence of sperm concentration, length of the gamete co-culture and the evolution of different sperm parameters on the in vitro fertilization of prepubertal goat oocytes.

PubMed

Palomo, M J; Mogas, T; Izquierdo, D; Paramio, M T

2010-11-01

The aims of the present study were: (1) to evaluate the influence of sperm concentration (ranging from 0.5 × 10(6) to 4 × 10(6) spermatozoa/ml) and length of the gamete co-incubation time (2, 4, 6, 8, 10, 12, 16, 20, 24 or 28 h) on in vitro fertilization (IVF), assessing the sperm penetration rate; (2) to investigate the kinetics of different semen parameters as motility, viability and acrosome status during the co-culture period; and (3) to analyse the effect of the presence of cumulus-oocytes complexes (COCs) on these parameters. To achieve these objectives, several experiments were carried out using in vitro matured oocytes from prepubertal goats. The main findings of this work are that: (1) in our conditions, the optimum sperm concentration is 4 × 10(6) sperm/ml, as this sperm:oocyte ratio (approximately 28,000) allowed us to obtain the highest penetration rate, without increasing polyspermy incidence; (2) the highest percentage of viable acrosome-reacted spermatozoa is observed between 8-12 h of gamete co-culture, while the penetration rate is maximum at 12 h of co-incubation; and (3) the presence of COCs seems to favour the acrosome reaction of free spermatozoa on IVF medium, but not significantly. In conclusion, we suggest that a gamete co-incubation for 12-14 h, with a concentration of 4 × 10(6) sperm/ml, would be sufficient to obtain the highest rate of penetration, reducing the exposure of oocytes to high levels of reactive oxygen species produced by spermatozoa, especially when a high sperm concentration is used to increase the caprine IVF outcome.

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.

Process intensification through microbial strain evolution: mixed glucose-xylose fermentation in wheat straw hydrolyzates by three generations of recombinant Saccharomyces cerevisiae

PubMed Central

2014-01-01

Background Lignocellulose hydrolyzates present difficult substrates for ethanol production by the most commonly applied microorganism in the fermentation industries, Saccharomyces cerevisiae. High resistance towards inhibitors released during pretreatment and hydrolysis of the feedstock as well as efficient utilization of hexose and pentose sugars constitute major challenges in the development of S. cerevisiae strains for biomass-to-ethanol processes. Metabolic engineering and laboratory evolution are applied, alone and in combination, to adduce desired strain properties. However, physiological requirements for robust performance of S. cerevisiae in the conversion of lignocellulose hydrolyzates are not well understood. The herein presented S. cerevisiae strains IBB10A02 and IBB10B05 are descendants of strain BP10001, which was previously derived from the widely used strain CEN.PK 113-5D through introduction of a largely redox-neutral oxidoreductive xylose assimilation pathway. The IBB strains were obtained by a two-step laboratory evolution that selected for fast xylose fermentation in combination with anaerobic growth before (IBB10A02) and after adaption in repeated xylose fermentations (IBB10B05). Enzymatic hydrolyzates were prepared from up to 15% dry mass pretreated (steam explosion) wheat straw and contained glucose and xylose in a mass ratio of approximately 2. Results With all strains, yield coefficients based on total sugar consumed were high for ethanol (0.39 to 0.40 g/g) and notably low for fermentation by-products (glycerol: ≤0.10 g/g; xylitol: ≤0.08 g/g; acetate: 0.04 g/g). In contrast to the specific glucose utilization rate that was similar for all strains (qGlucose ≈ 2.9 g/gcell dry weight (CDW)/h), the xylose consumption rate was enhanced by a factor of 11.5 (IBB10A02; qXylose = 0.23 g/gCDW/h) and 17.5 (IBB10B05; qXylose = 0.35 g/gCDW/h) as compared to the qXylose of the non-evolved strain BP10001. In xylose-supplemented (50 g/L) hydrolyzates prepared from 5% dry mass, strain IBB10B05 displayed a qXylose of 0.71 g/gCDW/h and depleted xylose in 2 days with an ethanol yield of 0.30 g/g. Under the conditions used, IBB10B05 was also capable of slow anaerobic growth. Conclusions Laboratory evolution of strain BP10001 resulted in effectively enhanced qXylose at almost complete retention of the fermentation capabilities previously acquired by metabolic engineering. Strain IBB10B05 is a sturdy candidate for intensification of lignocellulose-to-bioethanol processes. PMID:24708666

Co-composting of vegetable wastes and carton: Effect of carton composition and parameter variations.

PubMed

Rawoteea, Soonita Anjeena; Mudhoo, Ackmez; Kumar, Sunil

2017-03-01

The aim of the study was to investigate the effects of carton in the composting process of mixed vegetable wastes using an experimental composter of capacity 80L. Three different mixes were set-up (Mixes 1, 2 and 3) which consisted of vegetable wastes, 2.0kg paper and bulking agents, vegetable wastes, 1.5kg carton and bulking agents, vegetable wastes, 4.5kg carton and bulking agents, respectively. Temperature evolution, pH trends, moisture levels, respiration rates, percentage volatile solids and electrical conductivity were monitored for a period of 50days. The system remained under thermophilic conditions for a very short period due to the small size of the reactor. The three mixes did not exceed a temperature of 55°C, where sanitization takes place by the destruction of pathogens. The highest peak of CO 2 evolution was observed in Mix 2 indicating that maximum microbial degradation took place in that mix. Copyright © 2016. Published by Elsevier Ltd.

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.

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

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Different Endosymbiotic Interactions in Two Hydra Species Reflect the Evolutionary History of Endosymbiosis

PubMed Central

Ishikawa, Masakazu; Yuyama, Ikuko; Shimizu, Hiroshi; Nozawa, Masafumi; Ikeo, Kazuho; Gojobori, Takashi

2016-01-01

Endosymbiosis is an important evolutionary event for organisms, and there is widespread interest in understanding the evolution of endosymbiosis establishment. Hydra is one of the most suitable organisms for studying the evolution of endosymbiosis. Within the genus Hydra, H. viridissima and H. vulgaris show endosymbiosis with green algae. Previous studies suggested that the endosymbiosis in H. vulgaris took place much more recently than that in H. viridissima, noting that the establishment of the interaction between H. vulgaris and its algae is not as stable as in H. viridissima. To investigate the on-going process of endosymbiosis, we first compared growth and tolerance to starvation in symbiotic and aposymbiotic polyps of both species. The results revealed that symbiotic H. viridissima had a higher growth rate and greater tolerance to starvation than aposymbiotic polyps. By contrast, growth of symbiotic H. vulgaris was identical to that of aposymbiotic polyps, and symbiotic H. vulgaris was less tolerant to starvation. Moreover, our gene expression analysis showed a pattern of differential gene expression in H. viridissima similar to that in other endosymbiotically established organisms, and contrary to that observed in H. vulgaris. We also showed that H. viridissima could cope with oxidative stress that caused damage, such as cell death, in H. vulgaris. These observations support the idea that oxidative stress related genes play an important role in the on-going process of endosymbiosis evolution. The different evolutionary stages of endosymbiosis studied here provide a deeper insight into the evolutionary processes occurring toward a stable endosymbiosis. PMID:27324918

The Effect of N2 Photoabsorption Cross Section Resolution on C2H6 Production in Titan’s Ionosphere

NASA Astrophysics Data System (ADS)

Luspay-Kuti, Adrienn; Mandt, Kathleen E.; Plessis, Sylvain; Greathouse, Thomas K.

2014-11-01

Titan’s rich organic chemistry begins with the photochemistry of only two molecules: N2 and CH4. The details on how higher-order hydrocarbons and nitriles are formed from these molecules have key implications for both the structure and evolution of Titan’s atmosphere, and for its surface-atmosphere interactions. Of high importance is the production of C2H6, which is a sink for CH4, and a main component in the polar lakes. Results of photochemical models, though, may be sensitive to the choice of input parameters, such as the N2 photoabsorption cross section resolution, as previously shown for nitrogen (Liang et al. (2007) ApJL 664, 115-118), and CH4 (Lavvas et al. (2011) Icarus 213, 233-251). Here we investigate the possibility of the same effect on the production rates of C2H6. We modeled production and loss rates, as well as mixing ratio and density profiles between an altitude of 600 and 1600 km for low and high resolution N2 cross sections via a coupled ion-neutral-thermal model (De La Haye et al. (2008) Icarus 197, 110-136; Mandt et al. (2012) JGR 117, E10006). Our results show a clear impact of photoabsorption cross section resolution used on all neutral and ion species contributing to C2H6 production. The magnitude of the influence varies amongst species. Ethane production profiles exhibit a significant increase with better resolution; a factor of 1.2 between 750 and 950 km, and a factor of 1.1 in the total column-integrated production rate. These values are lower limits, as additional reactions involving C2H5 not included in the model may also contribute to the production rates. The clear effect on C2H6 (which is not a parent molecule, nor does it bear nitrogen) may have important implications for other molecules in Titan’s atmosphere as well. The possible non-negligible impact of an isotope of nitrogen may argue for the inclusion of isotopes in photochemical models. For future analysis, development of a more efficient and streamlined model called Planet-INC is underway. This open source model is a high-performance probabilistic planetary model that includes detailed uncertainty analysis capabilities.

On the rates of type Ia supernovae originating from white dwarf collisions in quadruple star systems

NASA Astrophysics Data System (ADS)

Hamers, Adrian S.

2018-04-01

We consider the evolution of stellar hierarchical quadruple systems in the 2+2 (two binaries orbiting each other's barycentre) and 3+1 (triple orbited by a fourth star) configurations. In our simulations, we take into account the effects of secular dynamical evolution, stellar evolution, tidal evolution and encounters with passing stars. We focus on type Ia supernovae (SNe Ia) driven by collisions of carbon-oxygen (CO) white dwarfs (WDs). Such collisions can arise from several channels: (1) collisions due to extremely high eccentricities induced by secular evolution, (2) collisions following a dynamical instability of the system, and (3) collisions driven by semisecular evolution. The systems considered here have initially wide inner orbits, with initial semilatus recti larger than 12 {au}, implying no interaction if the orbits were isolated. However, taking into account dynamical evolution, we find that ≈0.4 (≈0.6) of 2+2 (3+1) systems interact. In particular, Roche Lobe overflow can be triggered possibly in highly eccentric orbits, dynamical instability can ensue due to mass-loss-driven orbital expansion or secular evolution, or a semisecular regime can be entered. We compute the delay-time distributions (DTDs) of collision-induced SNe Ia, and find that they are flatter compared to the observed DTD. Moreover, our combined SNe Ia rates are (3.7± 0.7) × 10^{-6} M_⊙^{-1} and (1.3± 0.2) × 10^{-6} M_⊙^{-1} for 2+2 and 3+1 systems, respectively, three orders of magnitude lower compared to the observed rate, of order 10^{-3} M_⊙^{-1}. The low rates can be ascribed to interactions before the stars evolve to CO WDs. However, our results are lower limits given that we considered a subset of quadruple systems.

On the rates of Type Ia supernovae originating from white dwarf collisions in quadruple star systems

NASA Astrophysics Data System (ADS)

Hamers, Adrian S.

2018-07-01

We consider the evolution of stellar hierarchical quadruple systems in the 2+2 (two binaries orbiting each other's barycentre) and 3+1 (triple orbited by a fourth star) configurations. In our simulations, we take into account the effects of secular dynamical evolution, stellar evolution, tidal evolution, and encounters with passing stars. We focus on Type Ia supernovae (SNe Ia) driven by collisions of carbon-oxygen (CO) white dwarfs (WDs). Such collisions can arise from several channels: (1) collisions due to extremely high eccentricities induced by secular evolution, (2) collisions following a dynamical instability of the system, and (3) collisions driven by semisecular evolution. The systems considered here have initially wide inner orbits, with initial semilatus recti larger than 12 au, implying no interaction if the orbits were isolated. However, taking into account dynamical evolution, we find that ≈0.4 (≈0.6) of 2+2 (3+1) systems interact. In particular, Roche lobe overflow can be triggered possibly in highly eccentric orbits, dynamical instability can ensue due to mass-loss-driven orbital expansion or secular evolution, or a semisecular regime can be entered. We compute the delay-time distributions (DTDs) of collision-induced SNe Ia, and find that they are flatter compared to the observed DTD. Moreover, our combined SNe Ia rates are (3.7± 0.7) × 10^{-6} M_{⊙}^{-1} and (1.3± 0.2) × 10^{-6} M_{⊙}^{-1} for 2+2 and 3+1 systems, respectively, three orders of magnitude lower compared to the observed rate, of the order of 10^{-3} M_{⊙}^{-1}. The low rates can be ascribed to interactions before the stars evolve to CO WDs. However, our results are lower limits given that we considered a subset of quadruple systems.

Orbital evolution and escape of Martian Trojans due to the Yarkovsky effect

NASA Astrophysics Data System (ADS)

Christou, Apostolos

2017-06-01

Recently it was shown that the Yarkovsky effect can lead to significant orbit change for Trojans of Mars [1,2] and that the orbital distribution of observed Trojans is consistent with a negative along-track acceleration of the same functional form as seasonal yarkovsky; this feature was used to constrain the age of the Eureka family of Mars Trojan asteroids [2]. In contrast, the Yarkovsky effect appears to have a negligible role in shaping observed families of Jupiter Trojans [3].To explore the evolution and end states of Trojans evolved by the Yarkosky effect, I have numerically integrated test particles under a model of the diurnal variant and for different values of the acceleration strength up to 10-2 AU/Myr for da/dt outside the resonance. I use as a starting point the orbits of the three largest Martian Trojans: 5261 Eureka, (101429) 1998 VF31 and (121514) 1999 UJ7.I find, as in [2], that the evolution of the inclination I and the libration amplitude L depends on the sign of the acceleration and is essentially deterministic. Considering the rate of change of the Tisserand constant [5,6] leads to a simple analytical expression that reproduces well the inclination evolution of the Trojans. The evolution of e is somewhat more stochastic, probably due to chaotic diffusion [4] and/or the influence of Mars’ eccentricity [2].Trojans escape upon reaching the boundaries of stability domains mapped out in [4], demarcated by resonances with principal secular modes and the Kozai resonance. The mechanism of escape is by increasing e and/or the libration amplitude to the point of allowing close encounters with Mars.During the presentation I will describe the ensemble evolution of Trojans under Yarkovsky, how it is related to the lifetime in the 1:1 resonance and discuss the implications for Trojan stability at Earth and Jupiter.[1] Christou, A.A., 2013, Icarus, 224, 144.[2] Ćuk, M., Christou, A.A., Hamilton, D.P., 2015, Icarus, 252, 339.[3] Milani, A., Knezević, Z., Spoto, F., Cellino, A., Novaković, B., Tsirvoulis, G., 2017, Icarus, 288, 240.[4] Scholl, H., Marzari, F., Tricarico, P., 2005, Icarus, 175, 397.[5] Hamilton, D.P., 1994, Icarus, 109, 221[6] Liou, J. C., Zook, H. A., 1997, Icarus, 128, 354.

Regional oxygen reduction and denitrification rates in groundwater from multi-model residence time distributions, San Joaquin Valley, USA

USGS Publications Warehouse

Green, Christopher T.; Jurgens, Bryant; Zhang, Yong; Starn, Jeffrey; Singleton, Michael J.; Esser, Bradley K.

2016-01-01

Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary and covary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into the characteristics of residence times and rates of O2 reduction and denitrification (NO3− reduction) by comparing reaction rates using multi-model analytical residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwater age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The RTD approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF6, CFCs, 3H, He from 3H (tritiogenic He),14C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variances than those produced by individual RTD models. The set of multi-model RTDs was used in combination with NO3− and dissolved gas data to estimate zero order and first order rates of O2 reduction and denitrification. Results indicated that O2 reduction and denitrification rates followed approximately log-normal distributions. Rates of O2 and NO3− reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O2 reduction rates. Estimated historical NO3− trends were similar to historical measurements. Results show that the multi-model approach can improve estimation of age distributions, and that relatively easily measured O2 rates can provide information about trends in denitrification rates, which are more difficult to estimate.

Regional oxygen reduction and denitrification rates in groundwater from multi-model residence time distributions, San Joaquin Valley, USA

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

Green, Christopher T.; Jurgens, Bryant C.; Zhang, Yong

Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary and covary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into the characteristics of residence times and rates of O 2 reduction and denitrification (NO 3 – reduction) by comparing reaction rates using multi-model analytical residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwatermore » age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The RTD approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF 6, CFCs, 3H, He from 3H (tritiogenic He), 14C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variances than those produced by individual RTD models. The set of multi-model RTDs was used in combination with NO 3 – and dissolved gas data to estimate zero order and first order rates of O 2 reduction and denitrification. Results indicated that O 2 reduction and denitrification rates followed approximately log-normal distributions. Rates of O 2 and NO 3 – reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O 2 reduction rates. Estimated historical NO 3 – trends were similar to historical measurements. Here, results show that the multi-model approach can improve estimation of age distributions, and that relatively easily measured O 2 rates can provide information about trends in denitrification rates, which are more difficult to estimate.« less

Regional oxygen reduction and denitrification rates in groundwater from multi-model residence time distributions, San Joaquin Valley, USA

DOE PAGES

Green, Christopher T.; Jurgens, Bryant C.; Zhang, Yong; ...

2016-05-14

Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary and covary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into the characteristics of residence times and rates of O 2 reduction and denitrification (NO 3 – reduction) by comparing reaction rates using multi-model analytical residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwatermore » age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The RTD approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF 6, CFCs, 3H, He from 3H (tritiogenic He), 14C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variances than those produced by individual RTD models. The set of multi-model RTDs was used in combination with NO 3 – and dissolved gas data to estimate zero order and first order rates of O 2 reduction and denitrification. Results indicated that O 2 reduction and denitrification rates followed approximately log-normal distributions. Rates of O 2 and NO 3 – reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O 2 reduction rates. Estimated historical NO 3 – trends were similar to historical measurements. Here, results show that the multi-model approach can improve estimation of age distributions, and that relatively easily measured O 2 rates can provide information about trends in denitrification rates, which are more difficult to estimate.« less

Evolution of the Campanian Ignimbrite Magmatic System I: Constraints on Compositional Zonation and Eruption Probability Imposed By Phase Equilibria

NASA Astrophysics Data System (ADS)

Fowler, S.; Spera, F.; Bohrson, W.; Belkin, H.; Devivo, B.

2005-12-01

The eruption and deposition of the ~39.3 ka Campanian Ignimbrite (CI), a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite, is the dominant event in the history of the Campi Flegrei volcanic field near Naples, Italy. In an effort to comprehend its petrological evolution, we have conducted ~~110 MELTS (Ghiorso, 1997) phase equilibria simulations of the major element evolution of parental CI magma. The goals of this work are to approximate oxygen fugacity (fO2), initial dissolved water content and pressure at which isobaric closed system fractional crystallization of parental melt most accurately captures the observed liquid line of descent and to study the implications of heat extraction from parental CI magma with respect to the origin of compositional zonation and the probability of explosive eruption. Although the CI magma body did not evolve as a perfectly closed system, this assumption allows quantitative insight into magma-host rock mass exchange using trace element and isotopic data (see companion contribution by Bohrson et al.). The parental melt composition was reconstructed using data for melt inclusions trapped within CI clinopyroxene phenocrysts reported by Webster et al. (2003), while allowing for reaction between parental melt and clinopyroxene host. The inferred parental melt is a basaltic trachyandesite. The search space for pressure, (fO2) and initial dissolved H2O was 0.1-0.5 in 0.05 GPa increments, QFM-1 to QFM+3 and 1, 2 and 3 wt. % H2O, respectively. The criteria used to judge the quality of a simulation include correspondence of the MELTS prediction with CI liquid and phenocryst compositions. Results indicate that a good first-order model involves evolution from a basaltic trachyandesite parent by isobaric (~0.15 GPa) crystal fractionation initially containing ~3 wt% dissolved H2O along the QFM+1 buffer. H2O first saturates at 1127°C at 0.15 GPa when the dissolved water content is ~4 wt %. A striking result is the discovery of a pseudo-invariant point at ~883°C (Tip) and 0.15 GPa. The fraction of melt changes abruptly from ~0.5 to ~0.1 at Tip due to the simultaneous crystallization of alkali feldspar, plagioclase, spinel, biotite and apatite. At Tip, there is a dramatic decrease in the viscosity of melt (by a factor of four) and magma density (~5%) and an increase in the dissolved H2O content of the melt (from 4.4-5.1 wt%) and in the volume fraction,θ, of supercritical fluid in the multiphase system. In particular, θ increases from ~0.05 at 885°C to ~0.6 at 882°C. The liquid composition also changes discontinuously at Tip with Si, Na, and H2O increasing and K and Al decreasing as temperature falls below Tip. The marked variations in composition and properties of volatile-saturated melt and magma were the trigger that led to the catastrophic eruption and formation of the compositionally-zoned CI magma. Because phase equilibria modeling provides information on the enthalpy changes associated with fractional crystallization and because the dimensions of the CI magma chamber and heat extraction rate can be approximated, a time scale for CI magmatic evolution can be derived. The estimated crystallization duration (τ) is10-100 ka and 75% of τ is spent at or near Tip.

The H I content of non-isolated galaxies

NASA Technical Reports Server (NTRS)

Zasov, Anatoli V.

1990-01-01

It seems obvious that the evolution of star formation rate and hence of gas content in galaxies strongly depends on their environment. It reveals itself in particular in enhanced star formation or even in a strong burst of activity of massive stars often observed in interacting galaxies. Nevertheless it should be noted that the time scale for the gas to be exhausted in these galaxies is unknown even approximately. To clarify a role of surroundings in the evolution of disk galaxies we should compare the H I content of isolated and non-isolated galaxies otherwise similar by their properties. It is concluded that there are no systematic differences between H I content in isolated and non-isolated late-type galaxies; in spite of the differences of star formation rates their hydrogen mass is determined by slowly evolving kinematic parameters of the disk. Enhanced star formation in interacting galaxies, if it lasts long enough, must have an initial mass function enriched in massive stars in order not to significantly reduce the supply of gas. Certainly these conclusions are not valid for galaxies which are members of rich clusters such as Virgo or Coma, where H I-deficiency really exists, possibly due to the interaction of interstellar H I with hot intergalactic gas.

Protonated ions as systemic trapping agents for noble gases: From electronic structure to radiative association.

PubMed

Ozgurel, O; Pauzat, F; Pilmé, J; Ellinger, Y; Bacchus-Montabonel, M-C; Mousis, O

2017-10-07

The deficiencies of argon, krypton, and xenon observed in the atmosphere of Titan as well as anticipated in some comets might be related to a scenario of sequestration by H 3 + in the gas phase at the early evolution of the solar nebula. The chemical process implied is a radiative association, evaluated as rather efficient in the case of H 3 + , especially for krypton and xenon. This mechanism of chemical trapping might not be limited to H 3 + only, considering that the protonated ions produced in the destruction of H 3 + by its main competitors present in the primitive nebula, i.e., H 2 O, CO, and N 2 , might also give stable complexes with the noble gases. However the effective efficiency of such processes is still to be proven. Here, the reactivity of the noble gases Ar, Kr, and Xe, with all protonated ions issued from H 2 O, CO, and N 2 , expected to be present in the nebula with reasonably high abundances, has been studied with quantum simulation method dynamics included. All of them give stable complexes and the rate coefficients of their radiative associations range from 10 -16 to 10 -19 cm 3 s -1 , which is reasonable for such reactions and has to be compared to the rates of 10 -16 to 10 -18 cm 3 s -1 , obtained with H 3 + . We can consider this process as universal for all protonated ions which, if present in the primitive nebula as astrophysical models predict, should act as sequestration agents for all three noble gases with increasing efficiency from Ar to Xe.

Potentiostatic activation of as-made graphene electrodes for high-rate performance in supercapacitors

NASA Astrophysics Data System (ADS)

Senthilkumar, Krishnan; Jeong, Seok; Lah, Myoung Soo; Sohn, Kee-Sun; Pyo, Myoungho

2016-10-01

A thermally expanded graphene oxide (EGO) electrode is electrochemically activated to simultaneously introduce electrolyte-accessible mesopores and oxygen functional groups. The former is produced via O2 evolution and the latter is incorporated by the intermediate hydroxyl radicals generated during the potentiostatic oxidation of H2O in 1 M H2SO4 at 1.2 V (vs. Ag/AgCl). When applied as a supercapacitor, the potentiostatically treated EGO (EGO-PS) shows significant enhancement in an electric-double layer (EDL) process with a noticeable Faradaic reaction and delivers high capacitance at fast charge/discharge (C/D) rates (334 F g-1 at 0.1 A g-1 and 230 F g-1 at 50 A g-1). In contrast to EGO-PS, EGO that is oxidized potentiodynamically (EGO-PD) shows negligible enhancement in EDL currents. EGO that is subjected to successive potential pulses also shows behaviors similar to EGO-PD, which indicates the importance of hydroxyl radical accumulation via a potentiostatic method for simultaneous functionalization and microstructural control of graphenes. The potentiostatic post-treatment presented here is a convenient post-treatment strategy that could be used to readily increase capacitance and simultaneously improve the high-rate performance of carbon-based electrodes.

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.

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.

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.

Characterization and evaluation of cadmium indate photocatalysts for solar hydrogen conversion

NASA Astrophysics Data System (ADS)

Thornton, Jason M.

Alternative energy sources are needed to respond to the continued increase in the global energy needs and a potential decrease in the future supplies of fossil fuels. Solar hydrogen conversion in which sunlight is harnessed to split water into H2 fuel and O2 is a promising source of energy because it is renewable and produces no CO2. A number of semiconducting oxide materials have shown promise for overall water splitting for the generation of hydrogen over the years. In this work we focus on the synthesis and analysis of undoped and C-doped cadmium indate (CdIn2O 4) thin films and nanoparticle powders, and their evaluation for hydrogen evolution via water splitting. The catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis, scanning electron microscopy (SEM), and BET surface adsorption measurements. Spray and sol-gel pyrolysis methods were used for the synthesis of the materials. Doping C into CdIn 2O4 leads to enhancement in light absorption and the band gap was determined to be 2.3 eV in the nanoparticle powders. Carbon doping improves the photocurrent density by 33% and the H2 evolution rate by a factor of two. The performance of C-doped CdIn2O4 were optimized with respect to several synthetic parameters, including the In:Cd molar ratio and glucose concentration, calcination temperature, and the film thickness while the nanoparticles were additionally optimized to F127 concentration and platinum cocatalyst loading. Hydrogen generation activity was evaluated under UV-visible irradiation without the use of a sacrificial reagent and using bandpass filters the quantum efficiency was determined. Compared to platinized TiO2 in methanol C-CdIn2O4 showed a 4-fold increase in hydrogen production. The material was capable of hydrogen generation using visible light only and with good efficiency even at 510 nm. Using natural sunlight illumination, the material evolved hydrogen at a rate of 17 micromol h-1. These studies show carbon-doped cadmium indate to be a promising catalyst for solar hydrogen conversion.

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.

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.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

NASA Astrophysics Data System (ADS)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations and to elucidate the stoichiometry of the reaction. After the implementation of (i) the obtained f(ΔGr) term in the K-montmorillonte dissolution rate law, (ii) a fraction of highly reactive particles and surfaces and (iii) the cation exchange reactions between the interlayer K+ and the released Al3+, Mg2+, Ca2+ and H+, the simulations agreed with the experimental concentrations at the outlet. This match indicates that fast dissolution of fine particles and highly reactive sites and exchange between the interlayer K and dissolved structural cations (Al and Mg) and protons are responsible for the temporary incongruency of the K-montmorillonite dissolution reaction. As long as dissolution of the bulk sample predominates, the reaction is stoichiometric.

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.

Expansion Rate Scaling and Energy Evolution in the Electron Diffusion Gauge Experiment.

NASA Astrophysics Data System (ADS)

Morrison, Kyle; Davidson, Ronald; Paul, Stephen; Jenkins, Thomas

2001-10-01

The expansion of the Electron Diffusion Gauge (EDG) pure electron plasma resulting from collisions with background neutral gas atoms is characterized by the pressure and magnetic field scalings of the profile expansion rate (d/dt) < r^2 >. The measured expansion rate in the higher pressure regime is found to be in good agreement with the classical estimate [ fracddt< r^2 > = frac2 NL e^2 ν_enm ω_c^2 (1+frac2TNL e^2). ] Expansion rate data is obtained for smaller initial plasmas (with outer diameter 1/4 of the trap wall diameter) generated with an improved filament installed in the EDG device, and the data is compared with previous results for larger-filament plasmas. The dynamic energy evolution of the plasma, including electrostatic energy and inferred temperature evolution for several of the measurements, is discussed.

Investigation into the disparate origin of CO2 and H2O outgassing for Comet 67/P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Bieler, André; Capaccioni, Fabrizio; Bockelée-Morvan, Dominique; Filacchione, Gianrico; Erard, Stephane; Leyrat, Cedric; Blecka, Maria; Capria, Maria Teresa; Combi, Michael; Crovisier, Jacques; De Sanctis, Maria Cristina; Fougere, Nicolas; Taylor, Fred; Migliorini, Alessandra; Piccioni, Giuseppe

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma. We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ∼5.0% and ∼2.5% for Feb. 28 and April 27, respectively. Because of the highly variable nature of the CO2 evolution from the surface we do not believe that these numbers are diagnostic of the comet's bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's rotational orientation combined with its complex geometric shape which can result in quite variable rates of erosion for different surface areas such as the northern and southern hemisphere. Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the Sun is 2.5 × 1026 molecules/s while for April 27 at 1.76 AU it is 4.65 × 1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the night side. We also make an attempt to obtain the fraction of the H2O production coming from the highly active neck of the comet versus the rest of the illuminated surface from the pole-on view of Feb. 28 and estimate that about 60% of the H2O derives from the neck area. A rough estimate of the water surface evaporation rate of the illuminated nucleus for April 27 yields about 5 × 1019 molecules/s/m2. Spatial radial profiles of H2O on April 27 on the illuminated side of the comet, extending from 1.78 to 6.47 km from the nucleus center, show that water follows model predictions quite well, with the gas accelerating as it expands into the coma. Our dayside radial profile allows us to make an empirical determination of the expansion velocity of water. On the night side the spatial profile of water follows 1/ρ. The CO2 profiles do not exhibit any acceleration into the coma but are closely matched by a 1/ρ profile.

The role of zonal flows and predator–prey oscillations in triggering the formation of edge and core transport barriers

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

Schmitz, Lothar; Zeng, Lei; Rhodes, Terry L.

2014-04-24

Here, we present direct evidence of low frequency, radially sheared, turbulence-driven flows (zonal flows (ZFs)) triggering edge transport barrier formation preceding the L- to H-mode transition via periodic turbulence suppression in limit-cycle oscillations (LCOs), consistent with predator–prey dynamics. The final transition to edge-localized mode-free H-mode occurs after the equilibrium E × B flow shear increases due to ion pressure profile evolution. ZFs are also observed to initiate formation of an electron internal transport barrier (ITB) at the q = 2 rational surface via local suppression of electron-scale turbulence. Multi-channel Doppler backscattering (DBS) has revealed the radial structure of the ZF-induced shear layer and the E × B shearing rate, ω E×B, in both barrier types. During edge barrier formation, the shearing rate lags the turbulence envelope during the LCO by 90°, transitioning to anti-correlation (180°) when the equilibrium shear dominates the turbulence-driven flow shear due to the increasing edge pressure gradient. The time-dependent flow shear and the turbulence envelope are anti-correlated (180° out of phase) in the electron ITB. LCOs with time-reversed evolution dynamics (transitioning from an equilibrium-flow dominated to a ZF-dominated state) have also been observed during the H–L back-transition and are potentially of interest for controlled ramp-down of the plasma stored energy and pressure (normalized to the poloidal magnetic field)more » $$\\beta_{\\theta} =2\\mu_{0} n{( {T_{{\\rm e}} +T_{{\\rm i}}})}/{B_{\\theta}^{2}}$$ in ITER.« less

On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon Chemistry

NASA Astrophysics Data System (ADS)

Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

2014-07-01

The chemical processing of ethylene ices (C2H4) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

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.

Evolution of vitamin B2 biosynthesis: structural and functional similarity between pyrimidine deaminases of eubacterial and plant origin.

PubMed

Fischer, Markus; Römisch, Werner; Saller, Sabine; Illarionov, Boris; Richter, Gerald; Rohdich, Felix; Eisenreich, Wolfgang; Bacher, Adelbert

2004-08-27

The Arabidopsis thaliana open reading frame At4g20960 predicts a protein whose N-terminal part is similar to the eubacterial 2,5-diamino-6-ribosylamino-4(3H)-pyrimidinone 5'-phosphate deaminase domain. A synthetic open reading frame specifying a pseudomature form of the plant enzyme directed the synthesis of a recombinant protein which was purified to apparent homogeneity and was shown by NMR spectroscopy to convert 2,5-diamino-6-ribosylamino-4(3H)-pyrimidinone 5'-phosphate into 5-amino-6-ribosylamino-2,4(1H,3H)-pyrimidinedione 5'-phosphate at a rate of 0.9 micromol mg(-1) min(-1). The substrate and product of the enzyme are both subject to spontaneous anomerization of the ribosyl side chain as shown by (13)C NMR spectroscopy. The protein contains 1 eq of Zn(2+)/subunit. The deaminase activity could be assigned to the N-terminal section of the plant protein. The deaminase domains of plants and eubacteria share a high degree of similarity, in contrast to deaminases from fungi. These data show that the riboflavin biosynthesis in plants proceeds by the same reaction steps as in eubacteria, whereas fungi use a different pathway.

Photocatalytic degradation of E. coliform in water.

PubMed

Sun, Darren Delai; Tay, Joo Hwa; Tan, Koh Min

2003-08-01

This study aims to further investigate the total mineralization of the bacteria to the extent of death and cell-mass inactivation using a TiO2-Fe2O3 membrane photocatalytic oxidation reactor. Experimental results clearly indicated that dissolved oxygen (DO), hydraulic retention time (HRT) and concentration of the model bacteria (Escherichia coliform) affected the removal efficiency. It was found that the ultimate removal efficiency was 99% at DO level of 21.34 mg/l, HRT at 60s and high concentration of E. coli at 10(9)CFU/ml. The morphologic studies also showed that E. coliform could be further mineralized into CO2 and H2O. Dissolved organic carbon, pH and gas chromatograph analysis had justified most importantly the evolution of CO2. Experimental results revealed that the photomineralization rate of E. coliform followed pseudo-first-order kinetics by the role of DO. The derived empirical models were found consistent with the proposed reaction pathways of a combined UV breakdown on mass cell and a dual-site Langmuir-Hinshelwood mechanism where the rate-controlling step is the surface interaction between the adsorbed cleavage bacterial cells and hydroxyl radicals.

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.

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.

Treatment of Symptomatic Severe Aortic Stenosis With a Novel Resheathable Supra-Annular Self-Expanding Transcatheter Aortic Valve System.

PubMed

Manoharan, Ganesh; Walton, Antony S; Brecker, Stephen J; Pasupati, Sanjeevan; Blackman, Daniel J; Qiao, Hongyan; Meredith, Ian T

2015-08-24

The purpose of this study was to prospectively evaluate the safety and clinical performance of the CoreValve Evolut R transcatheter aortic valve replacement (TAVR) system (Medtronic, Inc., Minneapolis, Minnesota) in a single-arm, multicenter pivotal study in high- or extreme-risk patients with symptomatic aortic valve stenosis. Although outcomes following TAVR are improving, challenges still exist. The repositionable 14-F equivalent CoreValve Evolut R TAVR system was developed to mitigate some of these challenges. Suitable patients (n = 60) underwent TAVR with a 26- or 29-mm Evolut R valve. Primary safety endpoints were mortality and stroke at 30 days. Primary clinical performance endpoints were device success per the VARC-2 (Valve Academic Research Consortium-2) and the percent of patients with mild or less aortic regurgitation 24 h to 7 days post-procedure. Patients (66.7% female; mean age 82.8 ± 6.1 years; Society of Thoracic Surgeons Score 7.0 ± 3.7%) underwent TAVR via the transfemoral route in 98.3%, using a 29-mm valve in 68.3% of patients. All attempts at repositioning were successful. No death or stroke was observed up to 30 days. The VARC-2 overall device success rate was 78.6%. Paravalvular regurgitation post TAVR was mild or less in 96.6%, moderate in 3.4%, and severe in 0% at 30 days. Major vascular complications occurred in 8.3%, and permanent pacemaker implantation was required in 11.7% of patients. The repositionable 14-F equivalent Evolut R TAVR system is safe and effective at treating high-risk symptomatic aortic stenosis patients. Repositioning was successful when required in all patients, with low rates of moderate or severe paravalvular aortic regurgitation and low permanent pacemaker implantation. (The Medtronic CoreValve™ Evolut R™ CE Mark Clinical Study; NCT01876420). Copyright © 2015 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

DNA DSB measurements and modelling approaches based on gamma-H2AX foci time evolution

NASA Astrophysics Data System (ADS)

Esposito, Giuseppe; Campa, Alessandro; Antonelli, Francesca; Mariotti, Luca; Belli, Mauro; Giardullo, Paola; Simone, Giustina; Antonella Tabocchini, Maria; Ottolenghi, Andrea

DNA double strand breaks (DSBs) induced by ionising radiation are considered the main dam-age related to the deleterious consequences in the cells. Unrepaired or mis-repaired DSBs can cause mutations or loss of chromosome regions which can eventually lead to cell death or neo-plastic transformation. Quantification of the number and complexity of DSBs induced by low doses of radiation remains a complex problem. About ten years ago Rogakou et al. proposed an immunofluorescent technique able to detect even a single DSB per cell. This approach is based on the serine 139 phosphorylation of many molecules (up to 2000) of histone H2AX (γg-H2AX) following the induction of a DSB in the DNA. DSB can be visualized as foci by immunofluores-cence by using phospho-specific antibodies, so that enumeration of foci can be used to measure DSB induction and processing. It is still not completely clear how γ-H2AX dephosphorylation takes place; however it has been related with DSB repair, in particular with the efficiency of DSB repair. In this work we analyse the H2AX phosphorylation-dephosphorylation kinetics after irradiation of primary human fibroblasts (AG1522 cell line) with radiation of differing quality, that is γ-rays and α-particles (125 keV/µm), with the aim of comparing the time evolution of γ-H2AX foci. Our results show that, after a dose of 0.5 Gy, both γ-rays and α-particles induce the maximum number of γ-H2AX foci within 30 minutes from irradiation, that this number depends on the radiation type and is consistent with the number of track traversal in α-irradiated nuclei, that the dephosphorylation kinetics are very different, being the α-induced foci rate of disappearence slower than that of γ-induced foci. In this work a modellistic approach to estimate the number of DSB induced by γ-rays detectable by using the γ-H2AX assay is presented. The competing processes of appearance and disappearance of visible foci will be modeled taking into account the phosphorylation and dephosphorylation phenomena. The effect of possible overlapping DSB induced at short distance (within 2 Mbp) will be also taken into account. Moreover, for charged particles (in particular for α-particles) the average number of DSB per focus is calculated.

Amp Synthesis in Aqueous Solution of Adenosine and Phosphorus Pentoxide

NASA Astrophysics Data System (ADS)

Yamagata, Y.; Kojima, H.; Ejiri, K.; Inomata, K.

1982-12-01

Possible formation of a P4O10 molecule in magma, the stability of the molecule in hydrous volcanic gas at high temperatures and a possible prebiotic phosphate cycle were discussed in relation to chemical evolution. To demonstrate the utility of phosphorus pentoxide as a phosphorylating agent, aqueous solutions of adenosine (0.02M) and phosphorus pentoxide (0.2M) were incubated at 37°C for 5 months. The pH of the solutions was adjusted every day or every few days to each fixed value (9.0, 10.5, 11.5, 12.5) with 10 N NaOH. The HPLC analysis showed the formation of 2'-AMP, 3'-AMP, 5'-AMP, cyclic (2' 3')-AMP and cyclic (3' 5')-AMP. The main components of the products were 2'- and 3'-AMP, though cyclic (2' 3')-AMP was the main component in the early period of the incubation at pH 9.0. The yields (conversion rate of adenosine to AMPs) were increased almost linearly with the incubation time for 5 months in the case of pH 9.0. The final yields were about 3% (pH 9.0), 6% (pH 9.0, 1 M NaCl), 5% (pH 9.0, 0.01 M CaCl2, 0.01 M MgCl2), 7% (pH 9.0, 0.5 M NaCl, 0.01 M CaCl2, 0.01 M MgCl2), 9% (pH 9.0, 1 M NaCl, 0.01 M CaCl2, 0.01 M MgCl2), 32% (pH 10.5), 43% (pH 11.5), 35% (pH 12.5).

Continuous Monitoring of Photolysis Products by Thz Spectroscopy

NASA Astrophysics Data System (ADS)

Omar, Abdelaziz; Cuisset, Arnaud; Mouret, Gaël; Hindle, Francis; Eliet, Sophie; Bocquet, Robin

2015-06-01

We demonstrate the potential of THz spectroscopy to monitor the real time evolution of the gas phase concentration of photolysis products and determine the kinetic reaction rate constant. In the primary work, we have chosen to examine the photolysis of formaldehyde (H_2CO). Exposure of H_2CO to a UVB light (250 to 360 nm) in a single pass of 135 cm length cell leads to decomposition via two mechanisms: the radical channel with production of HCO and the molecular channel with production of CO. A commercial THz source (frequency multiplication chain) operating in the range 600-900 GHz was used to detect and quantify the various chemical species as a function of time. Monitoring the concentrations of CO and H_2CO via rotational transitions, allowed the kinetic rate of H_2CO consummation to be obtained, and an estimation of the rate constants for both the molecular and radical photolysis mechanisms. We have modified our experimental setup to increase the sensitivity of the spectrometer and changed sample preparation protocol specifically to quantify the HCO concentration. Acetaldehyde was used as the precursor for photolysis by UVC resulting in the decompositon mechanism can be described by: CH_3CHO+hν→ CH_3 + HCO → CH_4 + CO Frequency modulation of the source and Zeeman modulation is used to achieve the high sensitivity required. Particular attention has been paid to the mercury photosensitization effect that allowed us to increase the HCO production enabling quantification of the monitored radical. We quantify the HCO radical and start a spectroscopic study of the line positions. H. M. Pickett and T. L. Boyd, Chem. Phys. Lett, Vol 58, 446-449, (1978) S. Eliet, A. Cuisset, M Guinet, F. Hindle, G. Mouret, R. Bocquet, and J. Demaison, Journal of Molecular Spectroscopy, Vol 279, 12-15 (2012). G. Mouret, M. Guinet, A. Cuisset, L. Croizé, S. Eliet, R. Bocquet and F. Hindle, Sensors Journal. IEEE, Vol 13, 133 - 138, (2013)

Properties of a new type Al/Pb-0.3%Ag alloy composite anode for zinc electrowinning

NASA Astrophysics Data System (ADS)

Yang, Hai-tao; Liu, Huan-rong; Zhang, Yong-chun; Chen, Bu-ming; Guo, Zhong-cheng; Xu, Rui-dong

2013-10-01

An Al/Pb-0.3%Ag alloy composite anode was produced via composite casting. Its electrocatalytic activity for the oxygen evolution reaction and corrosion resistance was evaluated by anodic polarization curves and accelerated corrosion test, respectively. The microscopic morphologies of the anode section and anodic oxidation layer during accelerated corrosion test were obtained by scanning electron microscopy. It is found that the composite anode (hard anodizing) displays a more compact interfacial combination and a better adhesive strength than plating tin. Compared with industrial Pb-0.3%Ag anodes, the oxygen evolution overpotentials of Al/Pb-0.3%Ag alloy (hard anodizing) and Al/Pb-0.3%Ag alloy (plating tin) at 500 A·m-2 were lower by 57 and 14 mV, respectively. Furthermore, the corrosion rates of Pb-0.3%Ag alloy, Al/Pb-0.3%Ag alloy (hard anodizing), and Al/Pb-0.3%Ag alloy (plating tin) were 13.977, 9.487, and 11.824 g·m-2·h-1, respectively, in accelerated corrosion test for 8 h at 2000 A·m-2. The anodic oxidation layer of Al/Pb-0.3%Ag alloy (hard anodizing) is more compact than Pb-0.3%Ag alloy and Al/Pb-0.3%Ag alloy (plating tin) after the test.

Synthesis and structure of a ferric complex of 2,6-di(1H-pyrazol-3-yl)pyridine and its excellent performance in the redox-controlled living ring-opening polymerization of ε-caprolactone.

PubMed

Fang, Yang-Yang; Gong, Wei-Jie; Shang, Xiu-Juan; Li, Hong-Xi; Gao, Jun; Lang, Jian-Ping

2014-06-14

The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.

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.

The Impact of Nuclear Reaction Rate Uncertainties on the Evolution of Core-collapse Supernova Progenitors

NASA Astrophysics Data System (ADS)

Fields, C. E.; Timmes, F. X.; Farmer, R.; Petermann, I.; Wolf, William M.; Couch, S. M.

2018-02-01

We explore properties of core-collapse supernova progenitors with respect to the composite uncertainties in the thermonuclear reaction rates by coupling the probability density functions of the reaction rates provided by the STARLIB reaction rate library with MESA stellar models. We evolve 1000 models of 15{M}ȯ from the pre-main sequence to core O-depletion at solar and subsolar metallicities for a total of 2000 Monte Carlo stellar models. For each stellar model, we independently and simultaneously sample 665 thermonuclear reaction rates and use them in a MESA in situ reaction network that follows 127 isotopes from 1H to 64Zn. With this framework we survey the core mass, burning lifetime, composition, and structural properties at five different evolutionary epochs. At each epoch we measure the probability distribution function of the variations of each property and calculate Spearman rank-order correlation coefficients for each sampled reaction rate to identify which reaction rate has the largest impact on the variations on each property. We find that uncertainties in the reaction rates of {}14{{N}}{({{p}},γ )}15{{O}}, triple-α, {}12{{C}}{(α ,γ )}16{{O}}, 12C(12C,p)23Na, 12C(16O, p)27Al, 16O(16O,n)31S, 16O(16O, p)31P, and 16O(16O,α)28Si dominate the variations of the properties surveyed. We find that variations induced by uncertainties in nuclear reaction rates grow with each passing phase of evolution, and at core H-, He-depletion they are of comparable magnitude to the variations induced by choices of mass resolution and network resolution. However, at core C-, Ne-, and O-depletion, the reaction rate uncertainties can dominate the variation, causing uncertainty in various properties of the stellar model in the evolution toward iron core-collapse.

Degassing of basaltic magma: decompression experiments and implications for interpreting the textures of volcanic rocks

NASA Astrophysics Data System (ADS)

Le Gall, Nolwenn; Pichavant, Michel; Cai, Biao; Lee, Peter; Burton, Mike

2017-04-01

Decompression experiments were performed to simulate the ascent of basaltic magma, with the idea of approaching the textural features of volcanic rocks to provide insights into degassing processes. The experiments were conducted in an internally heated pressure vessel between NNO-1.4 and +0.9. H2O-only (4.9 wt%) and H2O-CO2-bearing (0.71-2.45 wt% H2O, 818-1094 ppm CO2) melts, prepared from Stromboli pumice, were synthesized at 1200°C and 200 MPa, continuously decompressed between 200 and 25 MPa at a rate of either 39 or 78 kPa/s (or 1.5 and 3 m/s, respectively), and rapidly quenched. Run products were characterized both texturally (by X-ray computed tomography and scanning electron microscopy) and chemically (by IR spectroscopy and electron microprobe analysis), and then compared with products from basaltic Plinian eruptions and Stromboli paroxysms (bubble textures, glass inclusions). The obtained results demonstrate that textures are controlled by the kinetics of nucleation, growth, coalescence and outgassing of the bubbles, as well as by fragmentation, which largely depend on the presence of CO2 in the melt and the achievement in chemical equilibrium. Textures of the H2O-only melts result from two nucleation events, the first at high pressure (200 < P < 150 MPa) and the second at low pressure (50 < P < 25 MPa), preceding fragmentation. Both events, restricted to narrow P intervals, are driven by melt H2O supersaturation. In contrast, textures of the H2O-CO2-bearing basaltic melts result from continuous bubble nucleation, which is driven by the generation of melts supersaturated in CO2. This persistent non-equilibrium degassing causes the bubbles to evolve through power law distributions, as small bubbles continue to form and grow. This is what is observed in Plinian products. From our results, the evolution to mixed power law-exponential distributions, as found in Stromboli products, is indicative of the prevalence of bubble coalescence and an evolution toward chemical equilibrium. In line with this, a strong correlation was found between experimental and natural bubble textures (bubble number densities, shapes, sizes and distributions), having implications for interpreting bubbles in volcanic rocks and quantifying magma ascent rates. Next step will be to perform in situ decompression experiments to simulate both degassing and crystallization of basaltic magma during ascent in the shallow volcanic conduit (P < 50 MPa), using synchrotron X-ray imaging. The obtained 4D (3D + time) data will help us refine our understanding of magma ascent processes. This experimental programme requires first technology adaptation and development, which is in progress.

Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

PubMed

Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

2018-04-26

Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

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.

Characterizing precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during artificial aging and non-isothermal heat treatments by in situ electrical resistivity monitoring

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

Jiang, Fulin; Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L7; Zurob, Hatem S., E-mail: zurobh@mcmaster.ca

In situ electrical resistivity monitoring technique was employed to continuously evaluate the precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during typical artificial aging treatments. The effects of artificial aging on the precipitates stability during non-isothermal heat treatments were also explored. Conventional hardness test, transmission electron microscopy and differential scanning calorimetry were also adopted to verify the electrical resistivity results. The results indicated that both the precipitation process and its timely rate could be followed by the monitored electrical resistivity during artificial aging treatments. The electrical resistivity results gave overall information on continuous precipitation and dissolution processes, especially under high heatingmore » rates. Samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h presented more stable state and coarser precipitates than the samples only artificial aging heat treated at 120 °C for 24 h or triple artificial aging heat treated at 120 °C/24 h + 195 °C/15 min + 120 °/24 h. While the incoherent η precipitates in the samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h were more easiness to coarsening and dissolve during non-isothermal heat treatments as well. - Highlights: • In situ electrical resistivity monitoring technique was employed on an Al-Zn-Mg-Cu alloy. • The precipitate evolution during typical artificial aging treatments was studied. • The precipitate stability during non-isothermal heat treatments was explored. • The electrical resistivity wonderfully monitored continuous precipitation and dissolution. • The alloy submitted to a T7 treatment presents a more stable state during heating due to incoherent η precipitates.« less

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.

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

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.

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

USDA-ARS?s Scientific Manuscript database

Novel subtypes of Eurasian-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 subsequently evolved into four genetically distinct groups (A – D) of clade 2.3.4.4...

Cosmic CARNage I: on the calibration of galaxy formation models

NASA Astrophysics Data System (ADS)

Knebe, Alexander; Pearce, Frazer R.; Gonzalez-Perez, Violeta; Thomas, Peter A.; Benson, Andrew; Asquith, Rachel; Blaizot, Jeremy; Bower, Richard; Carretero, Jorge; Castander, Francisco J.; Cattaneo, Andrea; Cora, Sofía A.; Croton, Darren J.; Cui, Weiguang; Cunnama, Daniel; Devriendt, Julien E.; Elahi, Pascal J.; Font, Andreea; Fontanot, Fabio; Gargiulo, Ignacio D.; Helly, John; Henriques, Bruno; Lee, Jaehyun; Mamon, Gary A.; Onions, Julian; Padilla, Nelson D.; Power, Chris; Pujol, Arnau; Ruiz, Andrés N.; Srisawat, Chaichalit; Stevens, Adam R. H.; Tollet, Edouard; Vega-Martínez, Cristian A.; Yi, Sukyoung K.

2018-04-01

We present a comparison of nine galaxy formation models, eight semi-analytical, and one halo occupation distribution model, run on the same underlying cold dark matter simulation (cosmological box of comoving width 125h-1 Mpc, with a dark-matter particle mass of 1.24 × 109h-1M⊙) and the same merger trees. While their free parameters have been calibrated to the same observational data sets using two approaches, they nevertheless retain some `memory' of any previous calibration that served as the starting point (especially for the manually tuned models). For the first calibration, models reproduce the observed z = 0 galaxy stellar mass function (SMF) within 3σ. The second calibration extended the observational data to include the z = 2 SMF alongside the z ˜ 0 star formation rate function, cold gas mass, and the black hole-bulge mass relation. Encapsulating the observed evolution of the SMF from z = 2 to 0 is found to be very hard within the context of the physics currently included in the models. We finally use our calibrated models to study the evolution of the stellar-to-halo mass (SHM) ratio. For all models, we find that the peak value of the SHM relation decreases with redshift. However, the trends seen for the evolution of the peak position as well as the mean scatter in the SHM relation are rather weak and strongly model dependent. Both the calibration data sets and model results are publicly available.

Comparative mapping and rapid karyotypic evolution in the genus helianthus.

PubMed Central

Burke, John M; Lai, Zhao; Salmaso, Marzia; Nakazato, Takuya; Tang, Shunxue; Heesacker, Adam; Knapp, Steven J; Rieseberg, Loren H

2004-01-01

Comparative genetic linkage maps provide a powerful tool for the study of karyotypic evolution. We constructed a joint SSR/RAPD genetic linkage map of the Helianthus petiolaris genome and used it, along with an integrated SSR genetic linkage map derived from four independent H. annuus mapping populations, to examine the evolution of genome structure between these two annual sunflower species. The results of this work indicate the presence of 27 colinear segments resulting from a minimum of eight translocations and three inversions. These 11 rearrangements are more than previously suspected on the basis of either cytological or genetic map-based analyses. Taken together, these rearrangements required a minimum of 20 chromosomal breakages/fusions. On the basis of estimates of the time since divergence of these two species (750,000-1,000,000 years), this translates into an estimated rate of 5.5-7.3 chromosomal rearrangements per million years of evolution, the highest rate reported for any taxonomic group to date. PMID:15166168

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.

Mathematical model for carbon dioxide evolution from the thermophilic composting of synthetic food wastes made of dog food

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

Chang, J.I.; Tsai, J.J.; Wu, K.H.

2005-07-01

The impacts of the aeration and the agitation on the composting process of synthetic food wastes made of dog food were studied in a laboratory-scale reactor. Two major peaks of CO{sub 2} evolution rate were observed. Each peak represented an independent stage of composting associated with the activities of thermophilic bacteria. CO{sub 2} evolutions known to correlate well with microbial activities and reactor temperatures were fitted successfully to a modified Gompertz equation, which incorporated three biokinetic parameters, namely, CO{sub 2} evolution potential, specific CO{sub 2} evolution rate, and lag phase time. No parameters that describe the impact of operating variablesmore » are involved. The model is only valid for the specified experimental conditions and may look different with others. The effects of operating parameters such as aeration and agitation were studied statistically with multivariate regression technique. Contour plots were constructed using regression equations for the examination of the dependence of CO{sub 2} evolution potentials on aeration and agitation. In the first stage, a maximum CO{sub 2} evolution potential was found when the aeration rate and the agitation parameter were set at 1.75 l/kg solids-min and 0.35, respectively. In the second stage, a maximum existed when the aeration rate and the agitation parameter were set at 1.8 l/kg solids-min and 0.5, respectively. The methods presented here can also be applied for the optimization of large-scale composting facilities that are operated differently and take longer time.« less

A Thermal Evolution Model of the Earth Including the Biosphere, Continental Growth and Mantle Hydration

NASA Astrophysics Data System (ADS)

Höning, D.; Spohn, T.

2014-12-01

By harvesting solar energy and converting it to chemical energy, photosynthetic life plays an important role in the energy budget of Earth [2]. This leads to alterations of chemical reservoirs eventually affecting the Earth's interior [4]. It further has been speculated [3] that the formation of continents may be a consequence of the evolution life. A steady state model [1] suggests that the Earth without its biosphere would evolve to a steady state with a smaller continent coverage and a dryer mantle than is observed today. We present a model including (i) parameterized thermal evolution, (ii) continental growth and destruction, and (iii) mantle water regassing and outgassing. The biosphere enhances the production rate of sediments which eventually are subducted. These sediments are assumed to (i) carry water to depth bound in stable mineral phases and (ii) have the potential to suppress shallow dewatering of the underlying sediments and crust due to their low permeability. We run a Monte Carlo simulation for various initial conditions and treat all those parameter combinations as success which result in the fraction of continental crust coverage observed for present day Earth. Finally, we simulate the evolution of an abiotic Earth using the same set of parameters but a reduced rate of continental weathering and erosion. Our results suggest that the origin and evolution of life could have stabilized the large continental surface area of the Earth and its wet mantle, leading to the relatively low mantle viscosity we observe at present. Without photosynthetic life on our planet, the Earth would be geodynamical less active due to a dryer mantle, and would have a smaller fraction of continental coverage than observed today. References[1] Höning, D., Hansen-Goos, H., Airo, A., Spohn, T., 2014. Biotic vs. abiotic Earth: A model for mantle hydration and continental coverage. Planetary and Space Science 98, 5-13. [2] Kleidon, A., 2010. Life, hierarchy, and the thermodynamic machinery of planet Earth. Phys. Life Rev. 7, 428-460. [3] Rosing, M .T., et al., 2006. The rise of continents - an essay on the geologic consequences of photosynthesis. Paleogeogr., Paleoclimatol., Paleoecol. 232, 99-113. [4] Sleep, N.H., Bird, D.K., Pope, E., 2012. Paleontology of Earth's mantle. Annu. Rev. Earth Planet. Sci. 40, 277-300.

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.

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)...

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.

Imidazole modified g-C3N4 photocatalyst: Structural characterization and versatile energy applications

NASA Astrophysics Data System (ADS)

Zhang, Lu; Liu, Qianqian; Chai, Yuanyuan; Ren, Jia; Dai, Wei-Lin

2018-02-01

Novel imidazole modified g-C3N4 were firstly synthesized via a facile one-pot thermo-induced co-condensation method. Characterization results showed that imidazole modification can improve the visible light harvesting, interfacial charge transfer and separation of g-C3N4, without destroying its pristine framework structure. The as-obtained imidazole modified g-C3N4 showed remarkably enhanced and rather stable photocatalytic performance in H2 evolution, photo-degradation of water contaminants and selective photo-oxidation of benzyl alcohol, demonstrating its all-round applications as a versatile photocatalyst. The weight ratio between imidazole and urea was well tuned and the optimal photocatalytic activity was obtained, which shows CNU-I50 sample (50 mg imidazole in 15 g urea) possesses the highest hydrogen evolution rate of 2150 μmol g-1 h-1, superior to most of the previous reported g-C3N4 materials. These results suggest that those imidazole modified g-C3N4 materials are potential photocatalyst when applied to solar energy conversion, water purification and selective photosynthesis reactions.

In situ photodeposition of cobalt on CdS nanorod for promoting photocatalytic hydrogen production under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Yanhong; Liu, Mei; Gao, Li; Mao, Liqun; Fan, Zeyun; Shangguan, Wenfeng

2018-06-01

Non-noble metal Co were loaded on CdS for enhancing photocatalytic activity of water splitting by a simple and efficient in situ photodeposition method. The Co particles with diameter ca. 5 nm were photoreduced and then loaded on the surface of CdS. The loading of Co can not only effectively promote the separation of electrons and holes photoexcited by CdS, but reduce the overpotential of hydrogen evolution as well, thus enhancing photocatalytic activity of water splitting. The highest photocatalytic H2 evolution rate of Co/CdS reaches up to 1299 μmol h-1 under visible light irradiation(λ > 420 nm) when the amount of loading is 1.0 wt%, which is 17 times of that of pure CdS and achieves 80% of that of 0.5 wt%Pt/CdS. This work not only exhibits a pathway to obtain photocatalysts with high photocatalytic activity for hydrogen production, but provides a possibility for the utilization of low cost Co as a substitute for noble metals in photocatalytic hydrogen production.

Ozonation of the pharmaceutical compound ranitidine: reactivity and kinetic aspects.

PubMed

Rivas, Javier; Gimeno, Olga; Encinas, Angel; Beltrán, Fernando

2009-07-01

Ranitidine has been ozonated under different operating conditions of pH, applied ozone dose, initial ranitidine concentration and presence or absence of free radical inhibitors. Results of ranitidine evolution with time indicate a high reactivity of this compound with molecular ozone. Mineralization levels achieved in the order of 20-25% suggest that the (CH3)2-N-CH2- moiety bonded to the furan ring could be separated from the rest of the ranitidine structure and further mineralized. Only alkaline conditions (pH=11) are capable of increasing TOC conversion up to values close to 70%. Determination of the direct ozonation rate constant for ranitidine by means of competitive kinetics reveals an unacceptable dependence of the aforementioned constant with the reference compound reactivity. It is hypothesised that only reference compounds with reactivity similar to the target species should be used.

Real-time and post-plasma studies of influence of low levels of tungsten on carbon erosion and surface evolution behaviour in D2 plasma

NASA Astrophysics Data System (ADS)

Weilnboeck, F.; Fox-Lyon, N.; Oehrlein, G. S.; Doerner, R. P.

2010-02-01

A profound influence of monolayer tungsten coverage of hard carbon films on the evolution of carbon surface erosion behaviour, surface chemistry and morphology in D2 plasma has been established by real-time ellipsometry, x-ray photoelectron spectroscopy and atomic force microscopy measurements. The erosion of tungsten-covered carbon showed two distinct stages of plasma material interactions: rapid tungsten removal during the initial erosion period and steady-state amorphous carbon removal accompanied by large-scale surface roughness development. The initial removal of tungsten takes place at a rate that significantly exceeds typical sputter yields at the ion energies used here and is attributed to elimination of weakly bonded tungsten from the surface. The tungsten remaining on the a-C : H film surface causes surface roughness development of the eroding carbon surface by a masking effect, and simultaneously leads to a seven fold reduction of the steady-state carbon erosion rate for long plasma surface interaction times (~100 s). Results presented are of direct relevance for material transport and re-deposition, and the interaction of those films with plasma in the divertor region and on mirror surfaces of fusion devices.

Ultraviolet and optical observations of metal deficient red giants and chromospheric models

NASA Technical Reports Server (NTRS)

Duprele, A. K.; Avrett, E. H.; Hartmann, L.; Smith, G.

1984-01-01

Three metal deficient field stars were observed in the ultraviolet and optical spectral regions: HD 165195, HD 110281, and HD 232078. High dispersion spectra near H alpha, and low dispersion, long wavelength IUE spectra were obtained. The H alpha profiles have strong asymmetric emission with absorption cores that are frequently asymmetric. The surface flux of Mg II lines is similar to that of luminous Pop I stars in spite of the lower metal abundance. Semi-empirical atmospheric models suggest that the characteristic emission in the wings of the H alpha line can arise within static chromospheres. Radial expansion gives an asymmetric, blue-shifted H alpha core accompanied by greater emission in the red line wing than the blue wing. Wind models with extended atmospheres suggest mass loss rates - 2 billion M/yr. Thus H alpha provides no evidence that steady mass loss is substantial enough to significantly affect the evolution of stars on the red giant branch of globular clusters.

Modeling of the flow behavior of SAE 8620H combing microstructure evolution in hot forming

NASA Astrophysics Data System (ADS)

Fu, Xiaobin; Wang, Baoyu; Tang, Xuefeng

2017-10-01

With the development of net-shape forming technology, hot forming process is widely applied to manufacturing gear parts, during which, materials suffer severe plastic distortion and microstructure changes continually. In this paper, to understand and model the flow behavior and microstructure evolution, SAE 8620H, a widely used gear steel, is selected as the object and the flow behavior and microstructure evolution are observed by an isothermal hot compression tests at 1273-1373 K with a strain rate of 0.1-10 s-1. Depending on the results of the compression test, a set of internal-state-variable based unified constitutive equations is put forward to describe the flow behavior and microstructure evaluation of SAE 8620H. Moreover, the evaluation of the dislocation density and the fraction of dynamic recrystallization based on the theory of thermal activation is modeled and reincorporated into the constitutive law. The material parameters in the constitutive model are calculated based on the measured flow stress and dynamic recrystallization fraction. The predicted flow stress under different deformation conditions has a good agreement with the measured results.

Evolution of a Cell Culture-Derived Genotype 1a Hepatitis C Virus (H77S.2) during Persistent Infection with Chronic Hepatitis in a Chimpanzee

PubMed Central

Yi, MinKyung; Hu, Fengyu; Joyce, Michael; Saxena, Vikas; Welsch, Christoph; Chavez, Deborah; Guerra, Bernadette; Yamane, Daisuke; Veselenak, Ronald; Pyles, Rick; Walker, Christopher M.; Tyrrell, Lorne; Bourne, Nigel; Lanford, Robert E.

2014-01-01

ABSTRACT Persistent infection is a key feature of hepatitis C virus (HCV). However, chimpanzee infections with cell culture-derived viruses (JFH1 or related chimeric viruses that replicate efficiently in cell culture) have been limited to acute-transient infections with no pathogenicity. Here, we report persistent infection with chronic hepatitis in a chimpanzee challenged with cell culture-derived genotype 1a virus (H77S.2) containing 6 cell culture-adaptive mutations. Following acute-transient infection with a chimeric H77/JFH1 virus (HJ3-5), intravenous (i.v.) challenge with 106 FFU H77S.2 virus resulted in immediate seroconversion and, following an unusual 4- to 6-week delay, persistent viremia accompanied by alanine aminotransferase (ALT) elevation, intrahepatic innate immune responses, and diffuse hepatopathy. This first persistent infection with cell culture-produced HCV provided a unique opportunity to assess evolution of cell culture-adapted virus in vivo. Synonymous and nonsynonymous nucleotide substitution rates were greatest during the first 8 weeks of infection. Of 6 cell culture-adaptive mutations in H77S.2, Q1067R (NS3) had reverted to Q1067 and S2204I (NS5A) was replaced by T2204 within 8 weeks of infection. By 62 weeks, 4 of 6 mutations had reverted to the wild-type sequence, and all reverted to the wild-type sequence by 194 weeks. The data suggest H77S.2 virus has greater potential for persistence and pathogenicity than JFH1 and demonstrate both the capacity of a nonfit virus to persist for weeks in the liver in the absence of detectable viremia as well as strong selective pressure against cell culture-adaptive mutations in vivo. IMPORTANCE This study shows that mutations promoting the production of infectious genotype 1a HCV in cell culture have the opposite effect and attenuate replication in the liver of the only fully permissive animal species other than humans. It provides the only example to date of persistent infection in a chimpanzee challenged with cell culture-produced virus and provides novel insight into the forces shaping molecular evolution of that virus during 5 years of persistent infection. It demonstrates that a poorly fit virus can replicate for weeks within the liver in the absence of detectable viremia, an observation that expands current concepts of HCV pathogenesis and that is relevant to relapses observed with direct-acting antiviral therapies. PMID:24429362

Abundances of Volatile - Bearing Species from Evolved Gas Analysis of Samples from the Rocknest Aeolian Bedform in Gale Crater

NASA Technical Reports Server (NTRS)

Archer, P. D., Jr.; Franc, H. B.; Sutter, B.; McAdam, A.; Ming, D. W.; Morris, R. V.; Mahaffy, P. R.

2013-01-01

The Sample Analysis at Mars (SAM) instrument suite on board the Mars Science Laboratory (MSL) recently ran four samples from an aeolian bedform named Rocknest. SAM detected the evolution of H2O, CO2, O2, and SO2, indicative of the presence of multiple volatile bearing species (Fig 1). The Rocknest bedform is a windblown deposit selected as representative of both the windblown material in Gale crater as well as the globally-distributed martian dust. Four samples of Rocknest material were analyzed by SAM, all from the fifth scoop taken at this location. The material delivered to SAM passed through a 150 m sieve and is assumed to have been well mixed during the sample acquisition/preparation/handoff process. SAM heated the Rocknest samples to approx.835 C at a ramp rate of 35 C/min with a He carrier gas flow rate of apprx.1.5 standard cubic centimeters per minute and at an oven pressure of 30 mbar [1]. Evolved gases were detected by a quadrupole mass spectrometer (QMS). This abstract presents the molar abundances of H2O, CO2, O2, and SO2 as well as their concentration in rocknest samples using an estimated sample mass.

A theoretical study of three gas-phase reactions involving the production or loss of methane cations.

PubMed

Baptista, Leonardo; da Silveira, Enio F

2014-10-21

Hydrocarbon ions are important species in flames, spectroscopy and the interstellar medium. Their importance is reflected in the extensive body of literature on the structure and reactivity of carbocations. However, the geometry, electronic structure and reactivity of carbocations are difficult to assess. This study aims to contribute to the current knowledge of this subject by presenting a quantum mechanics description of methane cation dissociation using multiconfigurational methods. The geometric and electronic parameters of the minimum structure were determined for three main reaction paths: the dissociation CH4(+)→ CH2(+) + H2 and the dissociation-recombination processes CH4(+)↔ CH3(+) + H. The electronic and energetic effects of these reactions were analyzed, and it was found that each reaction path has a strong dependence on the methodology used as well as a strong multiconfigurational character during dissociation. The first doublet excited states are inner-shell excited states and may correspond to the ions that are expected to be formed after electron detachment. The rate coefficient for each reaction path was determined using variational transition state theory and RRKM/master equation calculations. The major dissociation paths, with their rate coefficients at the high-pressure limit, are CH4(+)(X(~)(2)B1) → CH3(+)(A(2)A1') + H((2)S) (k∞(T) = 1.42 × 10(+14) s(-1) exp(-37.12/RT)) and CH4(+)(X(~)(2)B1) → CH2(+)(A(2)A1) + H2((2)Σg(+)) (k∞(T) = 9.18 × 10(+14) s(-1) exp(-55.77/RT)). Our findings help to explain the abundance of ions formed from CH4 in the interstellar medium and to build models of chemical evolution.

The Global Evolution of Giant Molecular Clouds. I. Model Formulation and Quasi-Equilibrium Behavior

NASA Astrophysics Data System (ADS)

Krumholz, Mark R.; Matzner, Christopher D.; McKee, Christopher F.

2006-12-01

We present semianalytic dynamical models for giant molecular clouds evolving under the influence of H II regions launched by newborn star clusters. In contrast to previous work, we neither assume that clouds are in virial or energetic equilibrium, nor do we ignore the effects of star formation feedback. The clouds, which we treat as spherical, can expand and contract homologously. Photoionization drives mass ejection; the recoil of cloud material both stirs turbulent motions and leads to an effective confining pressure. The balance between these effects and the decay of turbulent motions through isothermal shocks determines clouds' dynamical and energetic evolution. We find that for realistic values of the rates of turbulent dissipation, photoevaporation, and energy injection by H II regions, the massive clouds where most molecular gas in the Galaxy resides live for a few crossing times, in good agreement with recent observational estimates that large clouds in Local Group galaxies survive roughly 20-30 Myr. During this time clouds remain close to equilibrium, with virial parameters of 1-3 and column densities near 1022 H atoms cm-2, also in agreement with observed cloud properties. Over their lives they convert 5%-10% of their mass into stars, after which point most clouds are destroyed when a large H II region unbinds them. In contrast, small clouds like those found in the solar neighborhood only survive ~1 crossing time before being destroyed.

Micro-evolution of the hepatitis B virus genome in hepatitis B e-antigen-positive carriers: comparison of genotypes B and C at various immune stages.

PubMed

Liu, Chun-Jen; Chen, Ting-Chih; Chen, Pei-Jer; Wang, Hurng-Yi; Tseng, Tai-Chung; Cheng, Huei-Ru; Liu, Chen-Hua; Chen, Ding-Shinn; Kao, Jia-Horng

2015-01-01

Patients with hepatitis B virus (HBV) genotype B infection experience hepatitis B e-antigen (HBeAg) seroconversion at an earlier stage than do patients with genotype C infection. Therefore, this study investigated whether the differential phenotypes are related to HBV genomic evolution. Thirty-three HBeAg-positive patients with a mean follow-up of 3.1 years were enrolled: 16 at the immune tolerance stage (group I) and 17 at the immune clearance stage (group II). The evolution rates of paired viral genomes at enrollment and at the final follow-up in the full-length genome (μf), nonoverlapping regions (synonymous [μs] and nonsynonymous [μa]), and overlapping regions (μ) were calculated. The evolution rates were then compared according to serum alanine aminotransferase (ALT) levels and HBV genotype. The overall μf evolution rate was lower in group I than in group II (1.4 × 10(-5)  ± 3.3 × 10(-5) vs 1.2 × 10(-3)  ± 1.2 × 10(-3) nucleotide substitution/site/year, P < 0.001). We observed similar results for the μs, μa, and μ evolution rates. All evolution parameters were comparable between genotypes B and C. We determined a positive correlation between μa/y and the area under the average ALT time curve in genotype B (R(2)  = 0.6935, P < 0.0001), but not in genotype C (R(2)  = 0.1606, P = 0.124). The evolution rate of the HBV genome is higher at the immune clearance stage than at the immune tolerance stage. Host immune selection might play a role in triggering evolution of genotype B. © 2014 Journal of Gastroenterology and Hepatology Foundation and Wiley Publishing Asia Pty Ltd.

Post-recombination early Universe cooling by translation-internal inter-conversion: The role of minor constituents.

PubMed

McCaffery, Anthony J

2015-09-14

Little is known of the mechanism by which H and H2, the principal constituents of the post-re-combination early Universe, cooled sufficiently to permit cluster formation, nucleosynthesis, and, eventually, the formation of structured objects. Radiative decay primarily cools the internal modes of H2, as Δj = - 2 jumps accompany quadrupolar emission. This, however, would be a self-limiting mechanism. In this work, a translational energy cooling mechanism based on collision-induced, translation-to-internal mode conversion, is extended, following an earlier study [A. J. McCaffery and R. J. Marsh, J. Chem. Phys. 139, 234310 (2013)] of ensembles comprising H2 in a H atom bath gas. Here, the possible influence of minor species, such as HD, on this cooling mechanism is investigated. Results suggest that the influence of HD is small but not insignificant. Conversion is very rapid and an overall translation-to-internal energy conversion efficiency of some 5% could be expected. This finding may be of use in the further development of models of this complex phase of early Universe evolution. An unexpected finding in this study was that H2 + HD ensembles are capable of very rapid translation-to-internal conversion with efficiencies of >40% and relaxation rates that appear to be relatively slow. This may have potential as an energy storage mechanism.

Post-recombination early Universe cooling by translation–internal inter-conversion: The role of minor constituents

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

McCaffery, Anthony J., E-mail: A.J.McCaffery@sussex.ac.uk

Little is known of the mechanism by which H and H{sub 2}, the principal constituents of the post-re-combination early Universe, cooled sufficiently to permit cluster formation, nucleosynthesis, and, eventually, the formation of structured objects. Radiative decay primarily cools the internal modes of H{sub 2}, as Δj = − 2 jumps accompany quadrupolar emission. This, however, would be a self-limiting mechanism. In this work, a translational energy cooling mechanism based on collision-induced, translation-to-internal mode conversion, is extended, following an earlier study [A. J. McCaffery and R. J. Marsh, J. Chem. Phys. 139, 234310 (2013)] of ensembles comprising H{sub 2} in amore » H atom bath gas. Here, the possible influence of minor species, such as HD, on this cooling mechanism is investigated. Results suggest that the influence of HD is small but not insignificant. Conversion is very rapid and an overall translation-to-internal energy conversion efficiency of some 5% could be expected. This finding may be of use in the further development of models of this complex phase of early Universe evolution. An unexpected finding in this study was that H{sub 2} + HD ensembles are capable of very rapid translation-to-internal conversion with efficiencies of >40% and relaxation rates that appear to be relatively slow. This may have potential as an energy storage mechanism.« less

A Stable Plasmonic Cu@Cu2 O/ZnO Heterojunction for Enhanced Photocatalytic Hydrogen Generation.

PubMed

Lou, Yongbing; Zhang, Yake; Cheng, Lin; Chen, Jinxi; Zhao, Yixin

2018-05-09

The localized surface plasmon resonance (LSPR) effect has been widely utilized in photocatalysis, but most reported LSPR materials are based on noble metals of gold or silver with high chemical stability. Plasmonic copper nanoparticles that exhibit an LSPR absorbance at 600 nm are promising for many applications, such as photocatalysis. Unfortunately, plasmonic copper nanoparticles are affected by serious surface oxidation in air. Herein, a novel lollipop-shaped Cu@Cu 2 O/ZnO heterojunction nanostructure was designed, for the first time, to stabilize the plasmonic Cu core by decorating Cu@Cu 2 O core-shell structures with ZnO nanorods. This Cu@Cu 2 O/ZnO nanostructure exhibited significantly enhanced stability than that of regular Cu@Cu 2 O, which accounted for the remarkably enhanced photocatalytic H 2 evolution rate through water splitting, relative to pristine ZnO nanorods, over an extended wavelength range due to the plasmonic Cu core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative study of diethyl phthalate degradation by UV/H2O2 and UV/TiO2: kinetics, mechanism, and effects of operational parameters.

PubMed

Song, Chengjie; Wang, Liping; Ren, Jie; Lv, Bo; Sun, Zhonghao; Yan, Jing; Li, Xinying; Liu, Jingjing

2016-02-01

The photodegradation of diethyl phthalate (DEP) by UV/H2O2 and UV/TiO2 is studied. The DEP degradation kinetics and multiple crucial factors effecting the clearance of DEP are investigated, including initial DEP concentration ([DEP]0), initial pH values (pH0), UV light intensity, anions (Cl(-), NO(3-), SO4 (2-), HCO3 (-), and CO3 (2-)), cations (Mg(2+), Ca(2+), Mn(2+), and Fe(3+)), and humic acid (HA). Total organic carbon (TOC) removal is tested by two treatments. And, cytotoxicity evolution of DEP degradation intermediates is detected. The relationship between molar ratio ([H2O2]/[DEP] or [TiO2]/[DEP]) and degradation kinetic constant (K) is also studied. And, the cytotoxicity tests of DEP and its degradation intermediates in UV/H2O2 and UV/TiO2 treatments are researched. The DEP removal efficiency of UV/H2O2 treatment is higher than UV/TiO2 treatment. The DEP degradation fitted a pseudo-first-order kinetic pattern under experimental conditions. The K linearly related with molar ratio in UV/H2O2 treatment while nature exponential relationship is observed in the case of UV/TiO2. However, K fitted corresponding trends better in H2O2 treatment than in TiO2 treatment. The Cl(-) is in favor of the DEP degradation in UV/H2O2 treatment; in contrast, it is disadvantageous to the DEP degradation in UV/TiO2 treatment. Other anions are all disadvantageous to the DEP degradation in two treatments. Fe(3+) promotes the degradation rates significantly. And, all other cations in question inhibit the degradation of DEP. HA hinders DEP degradation in two treatments. The intermediates of DEP degradation in UV/TiO2 treatment are less toxic to biological cell than that in UV/H2O2 treatment.

Thermal decomposition and oxidation of CH3OH.

PubMed

Lee, Pei-Fang; Matsui, Hiroyuki; Xu, Ding-Wei; Wang, Niann-Shiah

2013-01-24

Thermal decomposition of CH(3)OH diluted in Ar has been studied by monitoring H atoms behind reflected shock waves of 100 ppm CH(3)OH + Ar. The total decomposition rate k(1) for CH(3)OH + M → products obtained in this study is expressed as, ln(k(1)/cm(3) molecule(-1) s(-1)) = -(14.81 ± 1.22) - (38.86 ± 1.82) × 10(3)/T, over 1359-1644 K. The present result on k(1) is indicated to be substantially smaller than the extrapolation of the most of the previous experimental data but consistent with the published theoretical results [Faraday Discuss. 2002, 119, 191-205 and J. Phys. Chem. A 2007, 111, 3932-3950]. Oxidation of CH(3)OH has been studied also by monitoring H atoms behind shock waves of (0.35-100) ppm CH(3)OH + (100-400) ppm O(2) + Ar. For the low concentration CH(3)OH (below 10 ppm) + O(2) mixtures, the initial concentration of CH(3)OH is evaluated by comparing evolutions of H atoms in the same concentration of CH(3)OH with addition of 300 ppm H(2) diluted in Ar. The branching fraction for CH(3)OH + Ar → (1)CH(2) + H(2)O + Ar has been quantitatively evaluated from this comparative measurements with using recent experimental result on the yield of H atoms in the reaction of (1,3)CH(2) + O(2) [J. Phys. Chem. A 2012, 116, 9245-9254]; i.e., the branching fraction for the above reaction is evaluated as, φ(1a) = 0.20 ± 0.04 at T = 1880-2050 K, in the 1.3 and 3.5 ppm CH(3)OH + 100 ppm O(2) samples. An extended reaction mechanism for the pyrolysis and oxidation of CH(3)OH is constructed based on the results of the present study combined with the oxidation mechanism of natural gas [GRI-Mech 3.0]; evolution of H atoms can be predicted very well with this new reaction scheme over a wide concentration range for the pyrolysis (0.36-100 ppm CH(3)OH), and oxidation (0.36-100 ppm CH(3)OH + 100/400 ppm O(2)) of methanol.

Distinct Physiological Roles of the Three [NiFe]-Hydrogenase Orthologs in the Hyperthermophilic Archaeon Thermococcus kodakarensis ▿ †

PubMed Central

Kanai, Tamotsu; Matsuoka, Ryoji; Beppu, Haruki; Nakajima, Akihito; Okada, Yoshihiro; Atomi, Haruyuki; Imanaka, Tadayuki

2011-01-01

Hydrogenases catalyze the reversible oxidation of molecular hydrogen (H2) and play a key role in the energy metabolism of microorganisms in anaerobic environments. The hyperthermophilic archaeon Thermococcus kodakarensis KOD1, which assimilates organic carbon coupled with the reduction of elemental sulfur (S0) or H2 generation, harbors three gene operons encoding [NiFe]-hydrogenase orthologs, namely, Hyh, Mbh, and Mbx. In order to elucidate their functions in vivo, a gene disruption mutant for each [NiFe]-hydrogenase ortholog was constructed. The Hyh-deficient mutant (PHY1) grew well under both H2S- and H2-evolving conditions. H2S generation in PHY1 was equivalent to that of the host strain, and H2 generation was higher in PHY1, suggesting that Hyh functions in the direction of H2 uptake in T. kodakarensis under these conditions. Analyses of culture metabolites suggested that significant amounts of NADPH produced by Hyh are used for alanine production through glutamate dehydrogenase and alanine aminotransferase. On the other hand, the Mbh-deficient mutant (MHD1) showed no growth under H2-evolving conditions. This fact, as well as the impaired H2 generation activity in MHD1, indicated that Mbh is mainly responsible for H2 evolution. The copresence of Hyh and Mbh raised the possibility of intraspecies H2 transfer (i.e., H2 evolved by Mbh is reoxidized by Hyh) in this archaeon. In contrast, the Mbx-deficient mutant (MXD1) showed a decreased growth rate only under H2S-evolving conditions and exhibited a lower H2S generation activity, indicating the involvement of Mbx in the S0 reduction process. This study provides important genetic evidence for understanding the physiological roles of hydrogenase orthologs in the Thermococcales. PMID:21515783

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.

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.

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.

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.

Hierarchically 3D assembled strontium titanate nanomaterials for water splitting application

NASA Astrophysics Data System (ADS)

Moniruddin, Md; Afroz, Khurshida; Shabdan, Yerkin; Bizri, Baraa; Nuraje, Nurxat

2017-10-01

Water splitting is an important technique to store solar energy in the simple form of chemical energy, such as hydrogen. Strontium titanate (SrTiO3) is one of the most promising photocatalysts to produce hydrogen gas from water splitting. In this research, an electrospinning technique in combination with sol-gel method was developed to synthesize 3D porous SrTiO3 nanostructures. Different crystallite sizes of SrTiO3-nanofibers (STO-NFs) were produced by varying the synthesis parameters including precursor concentration and calcination temperature. The synthesized nanofibers were characterized using DSC, TGA, XRD, SEM, and TEM. The crystallite size of STO-NFs decreases with increasing precursor concentration (3.03-15.78 vol.%) and gradually increases as the calcination temperature increases within the range of 600-800 °C. The photocatalytic activity of different STO-NFs (based on crystallite size) was also evaluated by the amount of H2 production from water splitting under UV irradiation. The H2 evolution study demonstrated that the photocatalytic activity of the STO-NFs strongly depends on the crystallite size of the nanofibers, precursor concentration, and calcination temperature. The H2 production rate increases with increasing crystallite size and temperature, whereas it decreases with increasing precursor concentration. The photocatalytic performance of the STO-NFs was also compared with the commercial SrTiO3 nanoparticles (STO-NPs) after Pt addition as a cocatalyst, where the synthesized nanofibers showed 2 times higher H2 production rate (1.14 mmol/g-h) than that of the nanoparticles. This synthesis technique provides a good example to produce other inorganic photocatalytic 3D porous structure materials.

Improving the photocatalytic hydrogen production of Ag/g-C3N4 nanocomposites by dye-sensitization under visible light irradiation

NASA Astrophysics Data System (ADS)

Qin, Jiayi; Huo, Jingpei; Zhang, Piyong; Zeng, Jian; Wang, Tingting; Zeng, Heping

2016-01-01

Ag nanoparticles were deposited on the surface of g-C3N4 by a chemical reduction method to increase visible-light absorption via the localized surface plasmon resonance effect, resulting in the reduced recombination of photo-generated electron-holes and enhanced photocatalytic activity. The Ag/g-C3N4 composite with a Ag loading of 3 wt% has the optimum photoactivity that is almost 3.6 and 3.4 times higher than pure g-C3N4 and the same photocatalysis system which has been reported, respectively. Fluorescein was introduced as a photosensitizer and H2 evolution soared to 2014.20 μmol g-1 h-1 and the rate is even about 4.8 times higher than that of the 3 wt% Ag/g-C3N4 composite. The chemical structure, composites, morphologies and optical properties of the obtained products are well-characterized by XRD, FTIR, TEM, EDS, XPS and UV-Vis DRS. Meanwhile, the photocatalyst exhibits high stability and reusability.Ag nanoparticles were deposited on the surface of g-C3N4 by a chemical reduction method to increase visible-light absorption via the localized surface plasmon resonance effect, resulting in the reduced recombination of photo-generated electron-holes and enhanced photocatalytic activity. The Ag/g-C3N4 composite with a Ag loading of 3 wt% has the optimum photoactivity that is almost 3.6 and 3.4 times higher than pure g-C3N4 and the same photocatalysis system which has been reported, respectively. Fluorescein was introduced as a photosensitizer and H2 evolution soared to 2014.20 μmol g-1 h-1 and the rate is even about 4.8 times higher than that of the 3 wt% Ag/g-C3N4 composite. The chemical structure, composites, morphologies and optical properties of the obtained products are well-characterized by XRD, FTIR, TEM, EDS, XPS and UV-Vis DRS. Meanwhile, the photocatalyst exhibits high stability and reusability. Electronic supplementary information (ESI) available: TEM images, TGA curves, PXRD and FTIR spectra, the recycling experiment of 3% Ag/g-C3N4, the specific process for H2 production, the diagram for the rate of hydrogen generation vs. the amount of fluorescein, the figure for the photocatalytic hydrogen production testing system, tables of contrast experiments for photocatalytic hydrogen generation and elemental composition of the CN in all the samples. See DOI: 10.1039/c5nr06346a

Characterization and application of the hetero-junction ZnFe2O4/TiO2 for Cr(VI) reduction under visible light

NASA Astrophysics Data System (ADS)

Rekhila, G.; Trari, M.; Bessekhouad, Y.

2017-06-01

The spinel ZnFe2O4 prepared by nitrate route is used as dispersed photons collector capable to sensitize TiO2 under visible light and to reduce Cr(VI) into trivalent state. The transport properties, optical and photo-electrochemical characterizations are correlated, to build the energetic diagram of the hetero-system ZnFe2O4/TiO2/CrO4 - solution. A gap of 1.97 eV is obtained for the spinel from the diffuse reflectance. The conduction band of ZnFe2O4 (-1.47 V SCE) favors the electrons injection into TiO2, permitting a physical separation of the charge carriers. The oxidation of oxalic acid by photoholes prevents the corrosion of the spinel. The best configuration ZnFe2O4 (75 %)/TiO2 (25 %) is used to catalyze the downhill reaction (2HCrO4 - + 3C2H4O4 + 1.5O2 + 8H+ → 2Cr3+ + 6CO2 + 11 H2O, Δ G° = -557 kcal mol-1). 60 % of Cr(VI) are reduced after 3 h of visible light illumination and the photoactivity follows a first-order kinetic with a half-life of 70 min. The water reduction competes with the HCrO4 - reduction which is the reason in the regression of the photoactivity; a hydrogen evolution rate of 24 µmol mg-1 h-1 is obtained.

H1N1 seasonal influenza virus evolutionary rate changed over time.

PubMed

Suptawiwat, Ornpreya; Kongchanagul, Alita; Boonarkart, Chompunuch; Auewarakul, Prasert

2018-05-02

It was previously shown that the seasonal H1N1 influenza virus antigenic drift occurred at a slower rate than the seasonal H3N2 virus during the first decade of the 21th century. It was hypothesized that the slower antigenic evolution led to a decrease in average ages of infection, which in turn resulted in lower level of global viral circulation. It is unclear what caused the difference between the two viruses, but a plausible explanation may be related to the fact that the H1N1 virus had been in human population for much longer than the H3N2 virus. This would suggest that H1N1 antigenic drift in an earlier period may have been different from a more recent period. To test this hypothesis, we analyzed seasonal H1N1 influenza sequences during various time periods. In comparison to more recent H1N1 virus, the older H1N1 virus during the first half of the 20th century showed evidences of higher nonsynnonymous/synonymous ration (dN/dS) in its hemagglutinin (HA) gene. We compared amino acid sequence changes in the HA epitopes for each outbreak season and found that there were less changes in later years. Amino acid sequence diversity in the epitopes as measured by sequence entropy became smaller for each passing decade. These suggest that there might be some limit to the antigenic drift. The longer an influenza virus has drifted in human population, the less flexibility it may become. With less flexibility to adapt and escape the host immunity, the virus may have to rely more on younger naïve population. Copyright © 2018 Elsevier B.V. All rights reserved.

Investigation of nucleation kinetics in H2SO4 vapor through modeling of gas phase kinetics coupled with particle dynamics

NASA Astrophysics Data System (ADS)

Carlsson, Philip T. M.; Zeuch, Thomas

2018-03-01

We have developed a new model utilizing our existing kinetic gas phase models to simulate experimental particle size distributions emerging in dry supersaturated H2SO4 vapor homogeneously produced by rapid oxidation of SO2 through stabilized Criegee-Intermediates from 2-butene ozonolysis. We use a sectional method for simulating the particle dynamics. The particle treatment in the model is based on first principles and takes into account the transition from the kinetic to the diffusion-limited regime. It captures the temporal evolution of size distributions at the end of the ozonolysis experiment well, noting a slight underrepresentation of coagulation effects for larger particle sizes. The model correctly predicts the shape and the modes of the experimentally observed particle size distributions. The predicted modes show an extremely high sensitivity to the H2SO4 evaporation rates of the initially formed H2SO4 clusters (dimer to pentamer), which were arbitrarily restricted to decrease exponentially with increasing cluster size. In future, the analysis presented in this work can be extended to allow a direct validation of quantum chemically predicted stabilities of small H2SO4 clusters, which are believed to initiate a significant fraction of atmospheric new particle formation events. We discuss the prospects and possible limitations of the here presented approach.

One-pot synthesis of K-doped g-C3N4 nanosheets with enhanced photocatalytic hydrogen production under visible-light irradiation

NASA Astrophysics Data System (ADS)

Wang, Yanyun; Zhao, Shuo; Zhang, Yiwei; Fang, Jiasheng; Zhou, Yuming; Yuan, Shenhao; Zhang, Chao; Chen, Wenxia

2018-05-01

Graphite carbon nitride (g-C3N4), as a promising low cost, visible light driven conjugated polymer semiconductor photocatalyst, has attracted wide attentions from researchers. However, low light absorption efficiency and inadequate charge separation limit the potential applications of g-C3N4. This paper exhibits K-doped g-C3N4 prepared by a facile thermal polymerization with KBr as the K source. The experiments of photocatalytic hydrogen evolution demonstrate that KBr content strongly affects the activity of the catalyst. XRD, FT-IR, XPS, SEM, TEM, UV-vis diffuse reflectance spectra, photoluminescence (PL) characterization methods are used to study the effects of potassium on the catalyst performance. The results find that K-modified g-C3N4 has a narrower band gap and enhanced light harvesting properties. Moreover, the photocatalytic hydrogen evolution rate (HER) of the optimized K-doped g-C3N4 nanosheets (10 wt % KBr) reaches 1337.2 μmol g-1h-1, which is about 5.6 times in comparison with that of pure g-C3N4 (239.8 μmol g-1h-1). The doping of the potassium may increase the π-conjugated systems and accelerate the electron transport rate, then improve the photocatalytic properties. Based on the results of the analysis, a possible mechanism is proposed.

The Rate of Core Collapse Supernovae to Redshift 2.5 from the CANDELS and CLASH Supernova Surveys

NASA Astrophysics Data System (ADS)

Strolger, Louis-Gregory; Dahlen, Tomas; Rodney, Steven A.; Graur, Or; Riess, Adam G.; McCully, Curtis; Ravindranath, Swara; Mobasher, Bahram; Shahady, A. Kristin

2015-11-01

The Cosmic Assembly Near-infrared Deep Extragalactic Legacy Survey and Cluster Lensing And Supernova survey with Hubble multi-cycle treasury programs with the Hubble Space Telescope (HST) have provided new opportunities to probe the rate of core-collapse supernovae (CCSNe) at high redshift, now extending to z≈ 2.5. Here we use a sample of approximately 44 CCSNe to determine volumetric rates, RCC, in six redshift bins in the range 0.1\\lt z\\lt 2.5. Together with rates from our previous HST program, and rates from the literature, we trace a more complete history of {R}{CC}(z), with {R}{CC}=0.72+/- 0.06 yr-1 Mpc-3 10-4{h}703 at z\\lt 0.08, and increasing to {3.7}-1.6+3.1 yr-1 Mpc-3 10-4{h}703 to z≈ 2.0. The statistical precision in each bin is several factors better than than the systematic error, with significant contributions from host extinction, and average peak absolute magnitudes of the assumed luminosity functions for CCSN types. Assuming negligible time delays from stellar formation to explosion, we find these composite CCSN rates to be in excellent agreement with cosmic star formation rate density (SFRs) derived largely from dust-corrected rest-frame UV emission, with a scaling factor of k=0.0091+/- 0.0017 {M}⊙ -1, and inconsistent (to \\gt 95% confidence) with SFRs from IR luminous galaxies, or with SFR models that include simple evolution in the initial mass function over time. This scaling factor is expected if the fraction of the IMF contributing to CCSN progenitors is in the 8-50 M⊙ range. It is not supportive, however, of an upper mass limit for progenitors at \\lt 20 {M}⊙ .

Temporal evolution of the anthropogenic CO2 and acidification of the northwestern Mediterranean Sea, from the mid-1990s to the mid-2000s

NASA Astrophysics Data System (ADS)

Savy, J.-P.; Yao, K. M.; Touratier, F.; Goyet, C.

2012-04-01

Since the beginning of the industrial era, humankind consumption of fossil fuels at increasing rates has led to increases in atmospheric CO2 concentrations by approximately 105 ppm. In the same time, the Mediterranean coastal regions experienced a brutal population growth, from 94 million habitants in 1950 to 274 million in 2000, generating a strong anthropogenic pressure on the Mediterranean marine ecosystems. To follow the man-induced changes on the Mediterranean carbonate system properties (pH; total alkalinity, AT; total inorganic carbon CT, and CO2 partial pressure, pCO2), an entire body-research has recently emerged in order to quantify both the present and future penetration of anthropogenic carbon (CANT) in the Mediterranean Sea and the inferred acidification of its waters. From monthly observations accumulated over more than a decade (from 1993 to 2005) at DYFAMED time-series station (DYnamique des Flux Atmosphériques en MEDiterranée) located in the central part of the Ligurian Sea, Touratier and Goyet (2009) have estimated the temporal evolution of CANT of the western Mediterranean Sea. This study highlights that concentrations of anthropogenic CO2 are much higher at DYFAMED site (> 50 mol.kg-1) than those found in the Atlantic Ocean. Our study, conducted with measurements performed at 10 meters depth from 1995 to 2011 at the same location, allowed us to investigate the temporal evolution of CANT into the upper seawater layer. Our results indicate an averaged annual CANT increase of 3 µmol.kg-1 and a linked pH drop of 0.0032 per year confirming the ongoing acidification of the Mediterranean water masses. These results suggest the vulnerability and the endangerment of the Mediterranean ecosystems by the massive human-induced CO2 emissions. Touratier F. and C. Goyet (2009). Decadal evolution of anthropogenic CO2 in the north western Mediterranean Sea (at the Dyfamed site) from the mid-1990's to the mid-2000's. Deep Sea Research Part I, 56, 1708-1716

Autoignition of hydrogen in shear flows

NASA Astrophysics Data System (ADS)

Kalbhor, Abhijit; Chaudhuri, Swetaprovo; Chitilappilly, Lazar

2018-05-01

In this paper, we compare the autoignition characteristics of laminar, nitrogen-diluted hydrogen jets in two different oxidizer flow configurations: (a) co-flowing heated air and (b) wake of heated air, using two-dimensional numerical simulations coupled with detailed chemical kinetics. In both cases, autoignition is observed to initiate at locations with low scalar dissipation rates and high HO2 depletion rates. It is found that the induction stage prior to autoignition is primarily dominated by chemical kinetics and diffusion while the improved scalar mixing imparted by the large-scale flow structures controls the ignition progress in later stages. We further investigate the ignition transience and its connection with mixing by varying the initial wake conditions and fuel jet to oxidizer velocity ratios. These studies reveal that the autoignition delay times are independent of initial wake flow conditions. However, with increased jet velocity ratios, the later stages of ignition are accelerated, mainly due to enhanced mixing facilitated by the higher scalar dissipation rates. Furthermore, the sensitivity studies for the jet in wake configuration show a significant reduction in ignition delay even for about 0.14% (by volume) hydrogen dilution in the oxidizer. In addition, the detailed autoignition chemistry and the relative roles of certain radical species in the initiation of the autoignition process in these non-premixed jets are investigated by tracking the evolution of important chain reactions using a Lagrangian particle tracking approach. The reaction H2 + O2 ↔ HO2 + H is recognized to be the dominant chain initiation reaction that provides H radicals essential for the progress of subsequent elementary reactions during the pre-ignition stage.

Coupling of thermal evolution and despinning of early Iapetus

NASA Astrophysics Data System (ADS)

Robuchon, G.; Choblet, G.; Tobie, G.; Čadek, O.; Sotin, C.; Grasset, O.

2010-06-01

The Cassini mission revealed two spectacular characteristics of Iapetus: (1) a geologically old and high equatorial ridge, which is unique in the Solar System and (2) a large flattening of 35 km consistent with the equilibrium figure for a hydrostatic body rotating with a period of 16 h, whereas the current spin period is 79.33 days. This study describes three-dimensional simulations of solid-state convection within an undifferentiated Iapetus. It investigates the implications for the evolution of the interior thermal structure and its spin rate and global shape using radially layered viscoelastic models. The role of the concentration in the short-lived radiogenic element [ 26Al], just after accretion is completed, is specifically addressed. The first result is to show that whatever the [ 26Al] value, convection occurs. As suggested by Castillo-Rogez et al. [Castillo-Rogez, J., Matson, D., Sotin, C., Johnson, T., Lunine, J., Thomas, P. [2007] Icarus, 190, 179-202], convection reduces the warming of the interior compared to the conductive evolution and therefore limits the conditions for despinning. In our calculations, two conceptual linear viscoelastic models are used. When considering a Maxwell rheology, the interior temperature (viscosity) never reaches a value high (low) enough to induce despinning. In order to promote dissipation at low temperature, a Burgers rheology, which includes an additional dissipation peak, is introduced. For favorable parameter values, this latter rheology leads to despinning. However, only models associated with large amounts of short-lived radiogenic elements ([26Al]⩾25ppb) lead to the observed flattening. This suggests that the accretion process needs to be completed shortly after the formation of CAIs (Calcium-Aluminum-rich Inclusions) (⩽4 Myr). For [ 26Al] varying between 72 and 46 ppb, the observed flattening is obtained only for a limited range of initial spin period, between 9.5 and 10.2 h. For [ 26Al] ranging between 30 and 15 ppb, initial spin rates smaller than 8.5 h are required. For smaller values of [ 26Al], the body is too cold and viscous to acquire a significant flattening even if a rotation period close to the body disruption limit is considered. Even with a thin lithosphere during the early stage, our simulations show that Iapetus never reaches the equilibrium figure for a hydrostatic body due to the non-zero rigidity of the lithosphere. The 35 km value of the flattening is the result of the partial relaxation of an ancient larger flattening ranging between 45 and 80 km, depending on the evolution of the lithosphere thickness mainly controlled by the radiogenic content. A thin lithosphere is consistent with an early building of the equatorial ridge. The lithosphere thickening due to interior cooling can explain the preservation of the ridge throughout the remaining evolution of Iapetus.

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.

Experimental Evolution of Escherichia coli K-12 at High pH and RpoS Induction.

PubMed

Hamdallah, Issam; Torok, Nadia; Bischof, Katarina M; Majdalani, Nadim; Chadalavada, Sriya; Mdluli, Nonto; Creamer, Kaitlin E; Clark, Michelle; Holdener, Chase; Basting, Preston J; Gottesman, Susan; Slonczewski, Joan L

2018-05-25

Experimental evolution of Escherichia coli K-12 W3110 by serial dilutions for 2,200 generations at high pH extended the range of sustained growth from pH 9.0 to pH 9.3. pH 9.3-adapted isolates showed mutations in DNA-binding regulators and envelope proteins. One population showed an IS1 knockout of phoB (positive regulator of the phosphate regulon). A phoB :: kanR knockout increased growth at high pH. phoB mutants are known to increase production of fermentation acids, which could enhance fitness at high pH. Mutations in pcnB (poly(A) polymerase) also increased growth at high pH. Three out of four populations showed deletions of torI, an inhibitor of TorR, which activates expression of torCAD (trimethylamine N-oxide respiration) at high pH. All populations showed point mutations affecting the stationary-phase sigma RpoS, either in the coding gene or in regulators of RpoS expression. RpoS is required for survival in extreme base. In our microplate assay, rpoS deletion slightly decreased growth at pH 9.1. RpoS protein accumulated faster at pH 9 than at pH 7. The RpoS accumulation at high pH required the presence of one or more antiadapters that block degradation (IraM, IraD, and IraP). Other genes with mutations after high pH evolution encode regulators such as yobG ( mgrB ) (PhoPQ regulator), rpoN (nitrogen starvation sigma), malI , and purR ; as well as envelope proteins ompT and yahO Overall, E. coli evolution at high pH selects for mutations in key transcriptional regulators, including phoB and the stationary-phase sigma RpoS. IMPORTANCE Escherichia coli in its native habitat encounters high pH stress such as that of pancreatic secretions. Experimental evolution over 2,000 generations showed selection for mutations in regulatory factors, such as deletion of the phosphate regulator PhoB and mutations that alter function of the global stress regulator RpoS. RpoS is induced at high pH via multiple mechanisms. Copyright © 2018 American Society for Microbiology.

Scale Invariance in Landscape Evolution Models Using Stream Power Laws

NASA Astrophysics Data System (ADS)

Kwang, J. S.; Parker, G.

2014-12-01

Landscape evolution models (LEM) commonly utilize stream power laws to simulate river incision with formulations such as E = KAmSn, where E is a vertical incision rate [L/T], K is an erodibility constant [L1-2m/T], A is an upstream drainage area [L2], S is a local channel gradient [-], and m and n are positive exponents that describe the basin hydrology. In our reduced complexity model, the landscape approached equilibrium by balancing an incision rate with a constant, uniform, vertical rock uplift rate at every location in the landscape. From our simulations, for a combination of m and n, the landscape exhibited scale invariance. That is, regardless of the size and scale of the basin, the relief and vertical structure of the landscape remained constant. Therefore, the relief and elevation profile of the landscape at equilibrium were only dependent on the coefficients for erodibility and uplift and an equation that described how upstream area, A, increased as the length of a stream increased. In our analytical 1D models, we utilized two equations that described upslope area, (a) A = Bl, where B is the profile width [L], and l is the stream length from the ridge [L] and (b) A = Clh, Hack's Law, where C is a constant [L2-h] and h is a positive exponent. With these equations, (a) m = n and (b) hm = n resulted in scale invariance. In our numerical 2D models, the relationship between A and l was inherent in the actual structure of the drainage network. From our numerical 2D results, scale invariance occurred when 2m = n. Additionally, using reasonable values from the literature for exponents, n, m and h, resulted in singularities at the ridges in the landscape, which caused truncation error. In consequence, the elevation of the ridge increased as the number of grid cells in the domain increased in the numerical model, and the model was unable to converge. These singularities at the ridges appeared when (a) m ≥ n and (b) hm ≥ n in the analytical model and 2m ≥ n in the numerical model. Here we present (1) 1D analytical solutions and (2) 2D numerical solutions that demonstrate scale invariance in LEMs and (3) the consequences of the singularity in 2D LEM numerical simulations. These results will help provide insight about the structure and dynamics of landscapes and drainage networks and shed light on geomorphological empirical relationships.

Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

PubMed

Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

2016-10-06

The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H 2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h -1 and a TON of 449 000 for H 2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

PubMed

Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

2015-04-21

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2O in alkaline electrolytes

DOE PAGES

Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros; ...

2018-03-23

Ammonia (NH 3) is considered an important chemical for both agriculture fertilizer and renewable energy. The conventional Haber-Bosh process to produce NH 3 is energy intensive and leads to significant CO 2 emission. Alternatively, electrochemical synthesis of ammonia (ESA) through the nitrogen reduction reaction (NRR) by using renewable electricity has recently attracted significant attention. Herein, we report a metal-organic framework-derived nitrogen-doped nanoporous carbon as an electrocatalyst for the NRR. It exhibits a remarkable production rate of NH 3 up to 3.4 ×10 –6 mol cm –2 h –1 with a Faradaic efficiency (FE) of 10.2% at –0.3 V vs. RHEmore » under room temperature and ambient pressure using aqueous 0.1 M KOH electrolyte. Increasing the temperature to 60 °C further improves production rates to 7.3 × 10 –6 mol cm –2 h –1. The stability of the nitrogen-doped carbon electrocatalyst was demonstrated during an 18-h continuous test with constant production rates. First principles calculations were used to elucidate the possible active sites and reaction pathway. The moiety, which consists of three pyridinic N atoms (N 3) adjacent with one carbon vacancy embedded in a carbon layer, is able to strongly adsorb N 2 and further realize N≡N triple bond dissociation for the subsequent protonation process. The rate-determining step of the NRR is predicted to be the adsorption and bond activation of N 2 molecule. Increasing overpotentials is favorable for the protonation process during NH 3 generation. Further doping Fe into the nitrogen-doped carbon likely blocks the N 3 active sites and facilitates the hydrogen evolution reaction, a strong competitor to the NRR, thus yielding negative effect on ammonia production. Furthermore, this work provides a new insight into the rational design and synthesis of nitrogen-doped and defect-rich carbon as efficient NRR catalysts for NH 3 synthesis at ambient conditions.« less

Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2O in alkaline electrolytes

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

Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros

Ammonia (NH 3) is considered an important chemical for both agriculture fertilizer and renewable energy. The conventional Haber-Bosh process to produce NH 3 is energy intensive and leads to significant CO 2 emission. Alternatively, electrochemical synthesis of ammonia (ESA) through the nitrogen reduction reaction (NRR) by using renewable electricity has recently attracted significant attention. Herein, we report a metal-organic framework-derived nitrogen-doped nanoporous carbon as an electrocatalyst for the NRR. It exhibits a remarkable production rate of NH 3 up to 3.4 ×10 –6 mol cm –2 h –1 with a Faradaic efficiency (FE) of 10.2% at –0.3 V vs. RHEmore » under room temperature and ambient pressure using aqueous 0.1 M KOH electrolyte. Increasing the temperature to 60 °C further improves production rates to 7.3 × 10 –6 mol cm –2 h –1. The stability of the nitrogen-doped carbon electrocatalyst was demonstrated during an 18-h continuous test with constant production rates. First principles calculations were used to elucidate the possible active sites and reaction pathway. The moiety, which consists of three pyridinic N atoms (N 3) adjacent with one carbon vacancy embedded in a carbon layer, is able to strongly adsorb N 2 and further realize N≡N triple bond dissociation for the subsequent protonation process. The rate-determining step of the NRR is predicted to be the adsorption and bond activation of N 2 molecule. Increasing overpotentials is favorable for the protonation process during NH 3 generation. Further doping Fe into the nitrogen-doped carbon likely blocks the N 3 active sites and facilitates the hydrogen evolution reaction, a strong competitor to the NRR, thus yielding negative effect on ammonia production. Furthermore, this work provides a new insight into the rational design and synthesis of nitrogen-doped and defect-rich carbon as efficient NRR catalysts for NH 3 synthesis at ambient conditions.« less

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.

Selection during crop diversification involves correlated evolution of the circadian clock and ecophysiological traits in Brassica rapa.

PubMed

Yarkhunova, Yulia; Edwards, Christine E; Ewers, Brent E; Baker, Robert L; Aston, Timothy Llewellyn; McClung, C Robertson; Lou, Ping; Weinig, Cynthia

2016-04-01

Crop selection often leads to dramatic morphological diversification, in which allocation to the harvestable component increases. Shifts in allocation are predicted to impact (as well as rely on) physiological traits; yet, little is known about the evolution of gas exchange and related anatomical features during crop diversification. In Brassica rapa, we tested for physiological differentiation among three crop morphotypes (leaf, turnip, and oilseed) and for correlated evolution of circadian, gas exchange, and phenological traits. We also examined internal and surficial leaf anatomical features and biochemical limits to photosynthesis. Crop types differed in gas exchange; oilseed varieties had higher net carbon assimilation and stomatal conductance relative to vegetable types. Phylogenetically independent contrasts indicated correlated evolution between circadian traits and both gas exchange and biomass accumulation; shifts to shorter circadian period (closer to 24 h) between phylogenetic nodes are associated with higher stomatal conductance, lower photosynthetic rate (when CO2 supply is factored out), and lower biomass accumulation. Crop type differences in gas exchange are also associated with stomatal density, epidermal thickness, numbers of palisade layers, and biochemical limits to photosynthesis. Brassica crop diversification involves correlated evolution of circadian and physiological traits, which is potentially relevant to understanding mechanistic targets for crop improvement. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Photochemical modelling of Venus clouds using Pioneer Venus data

NASA Technical Reports Server (NTRS)

Mcelroy, Michael B.

1985-01-01

In order to understand the evolution of water on Venus, we must know the hydrogen escape flux as a function of the tropospheric water abundance. We have studied the connection between total stratospheric hydrogen and exobase hydrogen available to non-thermal escape processes and examined the details of the photochemical trap for water at the Venus cloud tops. Our immediate goal is to calculate the stratospheric water abundance as a function of the tropospheric water abundance. Photochemical production of H2SO4 acts as a sink for both water and sulfur and is capable of keeping stratospheric abundances low if a proper balance exists between the tropospheric abundances. If production of H2SO4 were the only sink for H2O and SO2, the excess in tropospheric abundance of one over the other would reach the stratosphere, and the functional dependence of stratospheric H2O on tropospheric H2O would be linear near the present state. On Venus, however, sulfuric acid condenses at cloud top temperatures and the resulting aerosols can absorb additional water of hydration. This complicates the water budget, increasing the efficiency of sulfur as a sink for water. We have investigated the balance between tropospheric H2O and SO2 and how delicate the balance is. Our major conclusions from this work are the following: (1) H2O and SO2 are mutually limiting if proper tropospheric balance is maintained; (2) changes in tropospheric abundances on the order of 5 ppm are significant; and (3) changes in mixing rates near the cloud tops can cause dramatic changes in SO2 without causing dramatic changes in H2O.

Accretion flow dynamics during 1999 outburst of XTE J1859+226—modeling of broadband spectra and constraining the source mass

NASA Astrophysics Data System (ADS)

Nandi, Anuj; Mandal, S.; Sreehari, H.; Radhika, D.; Das, Santabrata; Chattopadhyay, I.; Iyer, N.; Agrawal, V. K.; Aktar, R.

2018-05-01

We examine the dynamical behavior of accretion flow around XTE J1859+226 during the 1999 outburst by analyzing the entire outburst data (˜166 days) from RXTE Satellite. Towards this, we study the hysteresis behavior in the hardness intensity diagram (HID) based on the broadband (3-150 keV) spectral modeling, spectral signature of jet ejection and the evolution of Quasi-periodic Oscillation (QPO) frequencies using the two-component advective flow model around a black hole. We compute the flow parameters, namely Keplerian accretion rate (\\dot{m}d), sub-Keplerian accretion rate (\\dot{m}h), shock location (rs) and black hole mass (M_{bh}) from the spectral modeling and study their evolution along the q-diagram. Subsequently, the kinetic jet power is computed as L^{obs}_{jet} ˜3-6 ×10^{37} erg s^{-1} during one of the observed radio flares which indicates that jet power corresponds to 8-16% mass outflow rate from the disc. This estimate of mass outflow rate is in close agreement with the change in total accretion rate (˜14%) required for spectral modeling before and during the flare. Finally, we provide a mass estimate of the source XTE J1859+226 based on the spectral modeling that lies in the range of 5.2-7.9 M_{⊙} with 90% confidence.

Solution and surface chemistry of the Se(IV)-Fe(0) reactions: Effect of initial solution pH.

PubMed

Xia, Xuefen; Ling, Lan; Zhang, Wei-Xian

2017-02-01

Aspects of solution and solid-phase reactions between selenite (Se(IV)) and nanoscale zero-valent iron (nZVI) were investigated. Experimental results on the effects of initial solution pH, formation and evolution of nZVI corrosion products, and speciation of selenium in nZVI were presented. In general, the rate of Se(IV) removal decreases with increasing initial pH. The observed rate constants of Se(IV) removal decreased from 0.3530 to 0.0364 min -1 as pH increased from 4.0 to 10.0. Composition and morphology of nZVI corrosion products and selenium species were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Results confirmed that Se(IV) was reduced to Se(0) and Se(-II) by nZVI. Lower solution pH favored further reduction of Se(0) to Se(-II). Amorphous FeOOH, magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ) and ferrous hydroxide (Fe(OH) 2 ) were identified as the main corrosion products. Under alkaline conditions, the corrosion products were mainly of Fe(OH) 2 along with small amounts of Fe 3 O 4 , while nZVI in acidic solutions was oxidized to mostly Fe 3 O 4 and amorphous FeOOH. Furthermore, these corrosion products acted as intermediates for electron transfer and reactive/sorptive sites for Se(IV) adsorption and reduction, thus played a crucial role in the removal of aqueous Se(IV). Copyright © 2016. Published by Elsevier Ltd.

Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

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

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2016-01-21

Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and themore » use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t{sub 1} and t{sub 3} periods, respectively. In addition to through-space and through-bond {sup 13}C/{sup 1}H and {sup 13}C/{sup 13}C chemical shift correlations, the 3D {sup 1}H/{sup 13}C/{sup 1}H experiment also provides a COSY-type {sup 1}H/{sup 1}H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ({sup 1}H/{sup 1}H chemical shift correlation spectrum) at different {sup 13}C chemical shift frequencies from the 3D {sup 1}H/{sup 13}C/{sup 1}H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D {sup 1}H/{sup 13}C/{sup 1}H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids.« less

Comparison of different advanced oxidation processes for the degradation of two fluoroquinolone antibiotics in aqueous solutions.

PubMed

Bobu, Maria; Yediler, Ayfer; Siminiceanu, Ilie; Zhang, Feifang; Schulte-Hostede, Sigurd

2013-01-01

In this study a comparative assessment using various advanced oxidation processes (UV/H(2)O(2), UV/H(2)O(2)/Fe(II), O(3), O(3)/UV, O(3)/UV/H(2)O(2) and O(3)/UV/H(2)O(2)/Fe(II)) was attempted to degrade efficiently two fluoroquinolone drugs ENR [enrofloxacin (1-Cyclopropyl-7-(4-ethyl-1-piperazinyl)-6-fluoro-1,4-dihydro-4-oxo-3-quinolonecarboxylic acid)] and CIP [ciprofloxacin (1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)-quinoline-3-carboxylic acid)] in aqueous solutions at a concentrations of 0.15 mM for each drug. The efficiency of the applied oxidation processes (AOPs) has been estimated by the conversion of the original substrate (X(ENR) and X(CIP)) and the reduction of chemical oxygen demand (COD), total organic carbon (TOC). Special emphasis was laid on the effect of varying reaction pH as well as of the applied oxidant doses on the observed reaction kinetics for each advanced oxidation processes. High degradation efficiencies, particularly in terms of rates of TOC and COD abatement, were obtained for photo-Fenton assisted ozonation [O(3)/UV/H(2)O(2)/Fe(II)], compared to other advanced oxidation processes. At pH 3 and 25°C best results for the degradation of both investigated drugs were achieved when 10 mM H(2)O(2), 0.5 mM Fe(II) and an initial dose of 8.5 mg L(-1) ozone were applied. In addition, the evolution of toxicity of the reaction mixtures for different AOPs has been studied by the bioluminescence test (LUMIStox 300).

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.

Ascorbate accumulation during sulphur deprivation and its effects on photosystem II activity and H2 production of the green alga Chlamydomonas reinhardtii.

PubMed

Nagy, Valéria; Vidal-Meireles, André; Tengölics, Roland; Rákhely, Gábor; Garab, Győző; Kovács, László; Tóth, Szilvia Z

2016-07-01

In nature, H2 production in Chlamydomonas reinhardtii serves as a safety valve during the induction of photosynthesis in anoxia, and it prevents the over-reduction of the photosynthetic electron transport chain. Sulphur deprivation of C. reinhardtii also triggers a complex metabolic response resulting in the induction of various stress-related genes, down-regulation of photosynthesis, the establishment of anaerobiosis and expression of active hydrogenase. Photosystem II (PSII) plays dual role in H2 production because it supplies electrons but the evolved O2 inhibits the hydrogenase. Here, we show that upon sulphur deprivation, the ascorbate content in C. reinhardtii increases about 50-fold, reaching the mM range; at this concentration, ascorbate inactivates the Mn-cluster of PSII, and afterwards, it can donate electrons to tyrozin Z(+) at a slow rate. This stage is followed by donor-side-induced photoinhibition, leading to the loss of charge separation activity in PSII and reaction centre degradation. The time point at which maximum ascorbate concentration is reached in the cell is critical for the establishment of anaerobiosis and initiation of H2 production. We also show that ascorbate influenced H2 evolution via altering the photosynthetic electron transport rather than hydrogenase activity and starch degradation. © 2015 John Wiley & Sons Ltd.

On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

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

Zhou, Li; Maity, Surajit; Abplanalp, Matt

2014-07-20

The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) andmore » n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.« less

Effect of UV and UV/H2O2 in the presence of chloramines on NDMA formation potential of tramadol.

PubMed

Radjenovic, Jelena; Farré, Maria José; Gernjak, Wolfgang

2012-08-07

This study evaluates the effect of UV-C and UV-C/H(2)O(2) in the presence of chloramines on the N-nitrosodimethylamine formation potential (NDMA FP) of tramadol as a model precursor. The experiments were performed at high initial concentrations of TMDL (i.e., 20 mg/L) in order to elucidate the structures of TMDL byproducts. Twenty-four byproducts were identified in UV-C, UV-C/monochloramine, and UV/H(2)O(2)/monochloramine oxidation of tramadol using MS(3) capabilities of a hybrid quadrupole-linear ion trap mass spectrometer, combined with online hydrogen/deuterium (H/D) exchange experiments. Oxidative cleavage of methoxy and methoxybenzene moiety, O-demethylation, hydroxylation, and cyclohexane ring-opening were identified as major reaction mechanisms of tramadol in UV oxidation. Addition of monochloramine decreased the degradation rates of tramadol and its byproducts and yielded several monochlorinated derivatives. The oxidation rates were significantly enhanced in the presence of H(2)O(2), and byproducts of oxidative benzene ring-opening were detected. The majority of the identified byproducts are likely to have a higher NDMA FP than the parent compound due to a reduced steric hindrance and/or insertion of electron-donating hydroxyl groups in the N,N-dimethylamine side chain. This was confirmed by the results of NDMA FP tests, which showed that the formation of NDMA was enhanced up to four times depending on the process conditions in UV alone and in UV and UV/H(2)O(2) in the presence of monochloramine. Prolonged oxidation by hydroxyl radicals in UV/H(2)O(2)/monochloramine process mineralized some of the byproducts and slightly reduced the NDMA FP at the end of the treatment. The obtained degradation pathway of tramadol allowed the correlation of changes in NDMA FP during oxidation with its major oxidative transformation reactions. This manuscript demonstrates the significance of oxidation byproducts as NDMA precursors and emphasizes the need for their consideration when evaluating the evolution of NDMA FP during oxidative treatment.

Enhanced Photocatalytic Hydrogen Evolution by Loading Cd0.5Zn0.5S QDs onto Ni2P Porous Nanosheets.

PubMed

Xiao, Lingfeng; Su, Tong; Wang, Zhuo; Zhang, Kun; Peng, Xiaoniu; Han, Yibo; Li, Quan; Wang, Xina

2018-02-02

Ni 2 P has been decorated on CdS nanowires or nanorods for efficient photocatalytic H 2 production, whereas the specific surface area remains limited because of the large size. Here, the composites of Cd 0.5 Zn 0.5 S quantum dots (QDs) on thin Ni 2 P porous nanosheets with high specific surface area were constructed for noble metal-free photocatalytic H 2 generation. The porous Ni 2 P nanosheets, which were formed by the interconnection of 15-30 nm-sized Ni 2 P nanoparticles, allowed the uniform loading of 7 nm-sized Cd 0.5 Zn 0.5 S QDs and the loading density being controllable. By tuning the content of Ni 2 P, H 2 generation rates of 43.3 μM h - 1 (1 mg photocatalyst) and 700 μM h - 1 (100 mg photocatalyst) and a solar to hydrogen efficiency of 1.5% were achieved for the Ni 2 P-Cd 0.5 Zn 0.5 S composites. The effect of Ni 2 P content on the light absorption, photoluminescence, and electrochemical property of the composite was systematically studied. Together with the band structure calculation based on density functional theory, the promotion of Ni 2 P in charge transfer and HER activity together with the shading effect on light absorption were revealed. Such a strategy can be applied to other photocatalysts toward efficient solar hydrogen generation.