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Sample records for catalytic component stoichiometries

  1. Molecular Components of Catalytic Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-07-02

    Selectivity, that is, to produce one molecule out of many other thermodynamically feasible product molecules, is the key concept to develop 'clean manufacturing' processes that do not produce byproducts (green chemistry). Small differences in potential energy barriers for elementary reaction steps control which reaction channel is more likely to yield the desired product molecule (selectivity), instead of the overall activation energy for the reaction that controls turnover rates (activity). Recent studies have demonstrated the atomic- or molecular-level tailoring of parameters such as the surface structures of active sites that give rise to nanoparticle size and shape dependence of turnover rates and reaction selectivities. Here, we highlight seven molecular components that influence reaction selectivities. These include: surface structure, adsorbate-induced restructuring, adsorbate mobility, reaction intermediates, surface composition, charge transport, and oxidation states for model metal single crystal and colloid nanoparticle catalysts. We show examples of their functioning and describe in-situ instruments that permit us to investigate their roles in surface reactions.

  2. Lego Stoichiometry.

    Science.gov (United States)

    Witzel, J. Eric

    2002-01-01

    Introduces a stoichiometry experiment using Legos or other building-block car kits. Determines the mass relationship between the required components and the final product. Includes both instructor information and a student activity sheet. (YDS)

  3. Lego Stoichiometry.

    Science.gov (United States)

    Witzel, J. Eric

    2002-01-01

    Introduces a stoichiometry experiment using Legos or other building-block car kits. Determines the mass relationship between the required components and the final product. Includes both instructor information and a student activity sheet. (YDS)

  4. Oxidation-reduction signalling components in regulatory pathways of state transitions and photosystem stoichiometry adjustment in chloroplasts.

    Science.gov (United States)

    Puthiyaveetil, Sujith; Ibrahim, Iskander M; Allen, John F

    2012-02-01

    State transitions and photosystem stoichiometry adjustment are two oxidation-reduction (redox)-regulated acclimatory responses in photosynthesis. State transitions are short-term adaptations that, in chloroplasts, involve reversible post-translational modification by phosphorylation of light-harvesting complex II (LHC II). Photosystem stoichiometry adjustments are long-term responses involving transcriptional regulation of reaction centre genes. Both responses are initiated by changes in light quality and are regulated by the redox state of plastoquinone (PQ). The LHC II kinase involved in the state 2 transition is a serine/threonine kinase known as STT7 in Chlamydomonas, and as STN7 in Arabidopsis. The phospho-LHC II phosphatase that produces the state 1 transition is a PP2C-type protein phosphatase currently termed both TAP38 and PPH1. In plants and algae, photosystem stoichiometry adjustment is governed by a modified two-component sensor kinase of cyanobacterial origin - chloroplast sensor kinase (CSK). CSK is a sensor of the PQ redox state. Chloroplast sigma factor 1 (SIG1) and plastid transcription kinase (PTK) are the functional partners of CSK in chloroplast gene regulation. We suggest a signalling pathway for photosystem stoichiometry adjustment. The signalling pathways of state transitions and photosystem stoichiometry adjustments are proposed to be distinct, with the two pathways sensing PQ redox state independently of each other.

  5. Uncovering the stoichiometry of Pyrococcus furiosus RNase P, a multi-subunit catalytic ribonucleoprotein complex, by surface-induced dissociation and ion mobility mass spectrometry.

    Science.gov (United States)

    Ma, Xin; Lai, Lien B; Lai, Stella M; Tanimoto, Akiko; Foster, Mark P; Wysocki, Vicki H; Gopalan, Venkat

    2014-10-20

    We demonstrate that surface-induced dissociation (SID) coupled with ion mobility mass spectrometry (IM-MS) is a powerful tool for determining the stoichiometry of a multi-subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg(2+). We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5' maturation. Previous step-wise, Mg(2+)-dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)2 complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM-MS in resolving conformational heterogeneity and yielding insights on RNP assembly.

  6. Component Development to Accelerate Commercial Implementation of Ultra-Low Emissions Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    McCarty, Jon; Berry, Brian; Lundberg, Kare; Anson, Orris

    2003-03-31

    This final report describes a 2000-2003 program for the development of components and processes to enhance the commercialization of ultra-low emissions catalytic combustion in industrial gas turbines. The range of project tasks includes: development of more durable, lower-cost catalysts and catalytic combustor components; development and design of a catalytic pre-burner and a catalytic pilot burner for gas turbines, and on-site fuel conversion processing for utilization of liquid fuel.

  7. Characterization of zinc-binding sites in human stromelysin-1: stoichiometry of the catalytic domain and identification of a cysteine ligand in the proenzyme.

    Science.gov (United States)

    Salowe, S P; Marcy, A I; Cuca, G C; Smith, C K; Kopka, I E; Hagmann, W K; Hermes, J D

    1992-05-19

    A determination of the zinc stoichiometry of the catalytic domain of the human matrix metalloproteinase stromelysin-1 has been carried out using enzyme purified from recombinant Escherichia coli that express C-terminally truncated protein. Atomic absorption spectrometry revealed that both the proenzyme (prostrom255) and the mature active form (strom255) contained nearly 2 mol of Zn/mol of protein. Full-length prostromelysin purified from a mammalian cell culture line also contained zinc in excess of 1 equiv. While zinc in prostrom255 could not be removed by dialysis against o-phenanthroline, similar treatment of mature strom255 resulted in the loss of one-half of the original zinc content. The peptidase activity of the zinc-depleted protein was reduced by greater than 85% but could be restored upon addition of Zn2+ or Co2+. Addition of a thiol-containing inhibitor to a CoZn hybrid enzyme resulted in marked spectral changes in both the visible and ultraviolet regions characteristic of sulfur ligation to Co2+. This direct evidence for an integral role in catalysis and inhibitor binding confirms the location of the exchangeable metal at the active site. To examine the environment of zinc in the proenzyme, a fully cobalt-substituted proenzyme was prepared by in vivo metal replacement. The absorbance features of dicobalt prostrom255 were consistent with metal coordination by the single cysteine present in the propeptide, although the data do not allow assignment to a particular zinc site.(ABSTRACT TRUNCATED AT 250 WORDS)

  8. Thermodynamic analysis of a process for producing high-octane gasoline components from catalytic cracking gas

    Science.gov (United States)

    Ismailova, Z. R.; Pirieva, Kh. B.; Kasimov, A. A.; Dzhamalova, S. A.; Gadzhizade, S. M.; Nuriev, Sh. A.; Zeinalova, S. Kh.; Dzhafarov, R. P.

    2016-03-01

    The results from a thermodynamic analysis of high-octane gasoline component production from catalytic cracking gases using zeolite catalyst OMNIKAT-210P modified with Ni, Co, Cr are presented. The equilibrium constants of the reactions assumed to occur in this process are calculated, along with the equilibrium yield of the reactions.

  9. Astrobiological Stoichiometry

    Science.gov (United States)

    Young, Patrick A.; Desch, Steven J.; Anbar, Ariel D.; Barnes, Rory; Hinkel, Natalie R.; Kopparapu, Ravikumar; Madhusudhan, Nikku; Monga, Nikhil; Pagano, Michael D.; Riner, Miriam A.; Scannapieco, Evan; Shim, Sang-Heon; Truitt, Amanda

    2014-07-01

    Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the "Stellar Stoichiometry" Workshop Without Walls hosted at Arizona State University April 11-12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors. The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ~2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.

  10. Astrobiological stoichiometry.

    Science.gov (United States)

    Young, Patrick A; Desch, Steven J; Anbar, Ariel D; Barnes, Rory; Hinkel, Natalie R; Kopparapu, Ravikumar; Madhusudhan, Nikku; Monga, Nikhil; Pagano, Michael D; Riner, Miriam A; Scannapieco, Evan; Shim, Sang-Heon; Truitt, Amanda

    2014-07-01

    Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the "Stellar Stoichiometry" Workshop Without Walls hosted at Arizona State University April 11-12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors. The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ∼ 2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.

  11. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  12. Catalytic Activity of Dual Metal Cyanide Complex in Multi-component Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    Anaswara RAVINDRAN; Rajendra SRIVASTAVA

    2011-01-01

    Several dual metal cyanide catalysts were prepared from potassium ferrocyanide,metal chloride (where metal =Zn2+,Mn2+,Ni2+,Co2+ and Fe2+),t-butanol (complexing agent) and PEG-4000 (co-complexing agent).The catalysts were characterized by elemental analysis (CHN and X-ray fluorescence),X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,Fourier-transform infiared spectroscopy,and UV-Visible spectroscopy.The dual metal cyanide catalysts were used in several acid catalyzed multi-component coupling reactions for the synthesis of pharmaceutically important organic derivatives.In all these reactions,the Fe-Fe containing dual metal cyanide catalyst was the best catalyst.The catalysts can be recycled without loss in catalytic activity.The advantage of this method is the use of mild,efficient and reusable catalysts for various reactions,which makes them candidates for commercial use.

  13. Convex Geometry and Stoichiometry

    CERN Document Server

    Jer-Chin,

    2011-01-01

    We demonstrate the benefits of a convex geometric perspective for questions on chemical stoichiometry. We show that the balancing of chemical equations, the use of "mixtures" to explain multiple stoichiometry, and the half-reaction for balancing redox actions all yield nice convex geometric interpretations. We also relate some natural questions on reaction mechanisms with the enumeration of lattice points in polytopes. Lastly, it is known that a given reaction mechanism imposes linear constraints on observed stoichiometries. We consider the inverse question of deducing reaction mechanism consistent with a given set of linear stoichiometric restrictions.

  14. Bridging the Stoichiometry Gap.

    Science.gov (United States)

    Gizara, Jeanne M.

    1981-01-01

    Discusses a method to solve problems in stoichiometry which can also be applied to other problems involving relationships between constituents in a chemical reaction. Students with little prior knowledge of chemistry can successfully use the method. (Author/SK)

  15. Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components

    Science.gov (United States)

    Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil product. Py/GC-MS was employed to study the catalytic fast pyrolysis of lignocellulosic biomass samples comprising oak, corn...

  16. Identifying the catalytic components of cellulose synthase and the maize mixed-linkage beta-glucan synthase

    Energy Technology Data Exchange (ETDEWEB)

    Nicholas C Carpita

    2009-04-20

    Five specific objectives of this project are to develop strategies to identify the genes that encode the catalytic components of "mixed-linkage" (1→3),(1→4)-beta-D-glucans in grasses, to determine the protein components of the synthase complex, and determine the biochemical mechanism of synthesis. We have used proteomic approaches to define intrinsic and extrinsic polypeptides of Golgi membranes that are associated with polysaccharide synthesis and trafficking. We were successful in producing recombinant catalytic domains of cellulose synthase genes and discovered that they dimerize upon concentration, indicating that two CesA proteins form the catalytic unit. We characterized a brittle stalk2 mutant as a defect in a COBRA-like protein that results in compromised lignin-cellulose interactions that decrease tissue flexibility. We used virus-induced gene silencing of barley cell wall polysaccharide synthesis by BSMV in an attempt to silence specific members of the cellulose synthase-like gene family. However, we unexpectedly found that regardless of the specificity of the target gene, whole gene interaction networks were silenced. We discovered the cause to be an antisense transcript of the cellulose synthase gene initiated small interfering RNAs that spread silencing to related genes.

  17. Stoichiometry of δ subunit containing GABAA receptors

    Science.gov (United States)

    Patel, B; Mortensen, M; Smart, T G

    2014-01-01

    Background and Purpose Although the stoichiometry of the major synaptic αβγ subunit-containing GABAA receptors has consensus support for 2α:2β:1γ, a clear view of the stoichiometry of extrasynaptic receptors containing δ subunits has remained elusive. Here we examine the subunit stoichiometry of recombinant α4β3δ receptors using a reporter mutation and a functional electrophysiological approach. Experimental Approach Using site-directed mutagenesis, we inserted a highly characterized 9′ serine to leucine mutation into the second transmembrane (M2) region of α4, β3 and δ subunits that increases receptor sensitivity to GABA. Whole-cell, GABA-activated currents were recorded from HEK-293 cells co-expressing different combinations of wild-type (WT) and/or mutant α4(L297S), β3(L284S) and δ(L288S) subunits. Key Results Recombinant receptors containing one or more mutant subunits showed increased GABA sensitivity relative to WT receptors by approximately fourfold, independent of the subunit class (α, β or δ) carrying the mutation. GABA dose–response curves of cells co-expressing WT subunits with their respective L9′S mutants exhibited multiple components, with the number of discernible components enabling a subunit stoichiometry of 2α, 2β and 1δ to be deduced for α4β3δ receptors. Varying the cDNA transfection ratio by 10-fold had no significant effect on the number of incorporated δ subunits. Conclusions and Implications Subunit stoichiometry is an important determinant of GABAA receptor function and pharmacology, and δ subunit-containing receptors are important mediators of tonic inhibition in several brain regions. Here we demonstrate a preferred subunit stoichiometry for α4β3δ receptors of 2α, 2β and 1δ. PMID:24206220

  18. Catalytically active telomerase holoenzyme is assembled in the dense fibrillar component of the nucleolus during S phase.

    Science.gov (United States)

    Lee, Ji Hoon; Lee, Yang Sin; Jeong, Sun Ah; Khadka, Prabhat; Roth, Jürgen; Chung, In Kwon

    2014-02-01

    The maintenance of human telomeres requires the ribonucleoprotein enzyme telomerase, which is composed of telomerase reverse transcriptase (TERT), telomerase RNA component, and several additional proteins for assembly and activity. Telomere elongation by telomerase in human cancer cells involves multiple steps including telomerase RNA biogenesis, holoenzyme assembly, intranuclear trafficking, and telomerase recruitment to telomeres. Although telomerase has been shown to accumulate in Cajal bodies for association with telomeric chromatin, it is unclear where and how the assembly and trafficking of catalytically active telomerase is regulated in the context of nuclear architecture. Here, we show that the catalytically active holoenzyme is initially assembled in the dense fibrillar component of the nucleolus during S phase. The telomerase RNP is retained in nucleoli through the interaction of hTERT with nucleolin, a major nucleolar phosphoprotein. Upon association with TCAB1 in S phase, the telomerase RNP is transported from nucleoli to Cajal bodies, suggesting that TCAB1 acts as an S-phase-specific holoenzyme component. Furthermore, depletion of TCAB1 caused an increase in the amount of telomerase RNP associated with nucleolin. These results suggest that the TCAB1-dependent trafficking of telomerase to Cajal bodies occurs in a step separate from the holoenzyme assembly in nucleoli. Thus, we propose that the dense fibrillar component is the provider of active telomerase RNP for supporting the continued proliferation of cancer and stem cells.

  19. The Arabidopsis cellulose synthase complex: a proposed hexamer of CESA trimers in an equimolar stoichiometry.

    Science.gov (United States)

    Hill, Joseph L; Hammudi, Mustafa B; Tien, Ming

    2014-12-01

    Cellulose is the most abundant renewable polymer on Earth and a major component of the plant cell wall. In vascular plants, cellulose synthesis is catalyzed by a large, plasma membrane-localized cellulose synthase complex (CSC), visualized as a hexameric rosette structure. Three unique cellulose synthase (CESA) isoforms are required for CSC assembly and function. However, elucidation of either the number or stoichiometry of CESAs within the CSC has remained elusive. In this study, we show a 1:1:1 stoichiometry between the three Arabidopsis thaliana secondary cell wall isozymes: CESA4, CESA7, and CESA8. This ratio was determined utilizing a simple but elegant method of quantitative immunoblotting using isoform-specific antibodies and (35)S-labeled protein standards for each CESA. Additionally, the observed equimolar stoichiometry was found to be fixed along the axis of the stem, which represents a developmental gradient. Our results complement recent spectroscopic analyses pointing toward an 18-chain cellulose microfibril. Taken together, we propose that the CSC is composed of a hexamer of catalytically active CESA trimers, with each CESA in equimolar amounts. This finding is a crucial advance in understanding how CESAs integrate to form higher order complexes, which is a key determinate of cellulose microfibril and cell wall properties.

  20. Stoichiometry and Turnover of the Stator and Rotor.

    Science.gov (United States)

    Morimoto, Yusuke V; Minamino, Tohru

    2017-01-01

    Fluorescence imaging techniques using green fluorescent protein (GFP) and related fluorescent proteins are utilized to monitor and analyze a wide range of biological processes in living cells. Stepwise photobleaching experiments can determine the stoichiometry of protein complexes. Fluorescence recovery after photobleaching (FRAP) experiments can reveal in vivo dynamics of biomolecules. In this chapter, we describe methods to detect the subcellular localization, stoichiometry, and turnovers of stator and rotor components of the Salmonella flagellar motor.

  1. Component Analysis of Deposits in Selective Catalytic Reduction System for Automotive Diesel Engine

    Directory of Open Access Journals (Sweden)

    Zhu Neng

    2016-01-01

    Full Text Available In this paper, deposits in exhaust pipes for automotive diesel engines were studied by various chemical analysis methods and a kind of analysis process to determine the compositions of organic matter was proposed. Firstly, the elements of the deposits were determined through the element analysis method. Then using characteristic absorption properties of organic functional groups to the infrared spectrum, the functional groups in the deposits were determined. Finally, by GC-MS (gas chromatography - mass spectrometry test, the content of each main component was determined quantitatively. Element analysis results indicated that the deposits adsorbed metal impurities from fuel oil, lubricating oil, mechanical wear and urea water solution. The result of GC-MS test showed that the area percentage of cyanuric acid was the biggest (about 85%, the second was urea (about 4%, and the content of biuret and biurea was scarce.

  2. Carbonic anhydrase IX, a hypoxia-induced catalytic component of the pH regulating machinery in tumors.

    Science.gov (United States)

    Sedlakova, Olga; Svastova, Eliska; Takacova, Martina; Kopacek, Juraj; Pastorek, Jaromir; Pastorekova, Silvia

    2014-01-08

    Acidic tissue microenvironment contributes to tumor progression via multiple effects including the activation of angiogenic factors and proteases, reduced cell-cell adhesion, increased migration and invasion, etc. In addition, intratumoral acidosis can influence the uptake of anticancer drugs and modulate the response of tumors to conventional therapy. Acidification of the tumor microenvironment often develops due to hypoxia-triggered oncogenic metabolism, which leads to the extensive production of lactate, protons, and carbon dioxide. In order to avoid intracellular accumulation of the acidic metabolic products, which is incompatible with the survival and proliferation, tumor cells activate molecular machinery that regulates pH by driving transmembrane inside-out and outside-in ion fluxes. Carbonic anhydrase IX (CA IX) is a hypoxia-induced catalytic component of the bicarbonate import arm of this machinery. Through its catalytic activity, CA IX directly participates in many acidosis-induced features of tumor phenotype as demonstrated by manipulating its expression and/or by in vitro mutagenesis. CA IX can function as a survival factor protecting tumor cells from hypoxia and acidosis, as a pro-migratory factor facilitating cell movement and invasion, as a signaling molecule transducing extracellular signals to intracellular pathways (including major signaling and metabolic cascades) and converting intracellular signals to extracellular effects on adhesion, proteolysis, and other processes. These functional implications of CA IX in cancer are supported by numerous clinical studies demonstrating the association of CA IX with various clinical correlates and markers of aggressive tumor behavior. Although our understanding of the many faces of CA IX is still incomplete, existing knowledge supports the view that CA IX is a biologically and clinically relevant molecule, exploitable in anticancer strategies aimed at targeting adaptive responses to hypoxia and/or acidosis.

  3. Stoichiometry of ATP hydrolysis and chlorophyllide formation of dark-operative protochlorophyllide oxidoreductase from Rhodobacter capsulatus

    Energy Technology Data Exchange (ETDEWEB)

    Nomata, Jiro [Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601 (Japan); Terauchi, Kazuki [Department of Life Sciences, Ritsumeikan University, Kusatsu, Shiga, 525-8577 (Japan); Fujita, Yuichi, E-mail: fujita@agr.nagoya-u.ac.jp [Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601 (Japan)

    2016-02-12

    Dark-operative protochlorophyllide (Pchlide) oxidoreductase (DPOR) is a nitrogenase-like enzyme catalyzing a reduction of the C17 = C18 double bond of Pchlide to form chlorophyllide a (Chlide) in bacteriochlorophyll biosynthesis. DPOR consists of an ATP-dependent reductase component, L-protein (a BchL dimer), and a catalytic component, NB-protein (a BchN–BchB heterotetramer). The L-protein transfers electrons to the NB-protein to reduce Pchlide, which is coupled with ATP hydrolysis. Here we determined the stoichiometry of ATP hydrolysis and the Chlide formation of DPOR. The minimal ratio of ATP to Chlide (ATP/2e{sup –}) was 4, which coincides with that of nitrogenase. The ratio increases with increasing molar ratio of L-protein to NB-protein. This profile differs from that of nitrogenase. These results suggest that DPOR has a specific intrinsic property, while retaining the common features shared with nitrogenase. - Highlights: • The stoichiometry of nitrogenase-like protochlorophyllide reductase was determined. • The minimal ATP/2e{sup –} ratio was 4, which coincides with that of nitrogenase. • The ATP/2e{sup –} ratio increases with increasing L-protein/NB-protein molar ratio. • DPOR has an intrinsic property, but retains features shared with nitrogenase.

  4. The Origin of Stoichiometry Problems

    Science.gov (United States)

    Jensen, William B.

    2003-11-01

    In response to a reader query, the column discusses the question of when quantitative stoichiometry problems first began to appear in introductory textbooks, and especially the role of the American chemist, Josiah Parsons Cooke, in this process.

  5. Overexpression, purification and characterization of the catalytic component of Oplophorus luciferase in the deep-sea shrimp, Oplophorus gracilirostris.

    Science.gov (United States)

    Inouye, Satoshi; Sasaki, Satoko

    2007-12-01

    The luciferase secreted by the deep-sea shrimp Oplophorus consists of 19 and 35kDa proteins. The 19-kDa protein (19kOLase), the catalytic component of luminescence reaction, was expressed in Escherichia coli using the cold-shock inducted expression system. 19kOLase, expressed as inclusion bodies, was solubilized with 6M urea and purified by urea-nickel chelate affinity chromatography. The yield of 19kOLase was 16 mg from 400 ml of cultured cells. 19kOLase in 6M urea could be refolded rapidly by dilution with 50mM Tris-HCl (pH 7.8)-10mM EDTA, and the refolded protein showed luminescence activity. The luminescence properties of refolded 19kOLase were characterized, in comparison with native Oplophorus luciferase. Luminescence intensity with bisdeoxycoelenterazine as a substrate was stimulated in the presence of organic solvents. The 19kOLase is a thermolabile protein and is 98 % inhibited by 1muM Cu2+. The cysteine residue of 19kOLase is not essential for catalysis of the luminescence reaction.

  6. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  7. Ordinary stoichiometry of extraordinary microorganisms.

    Science.gov (United States)

    Neveu, M; Poret-Peterson, A T; Anbar, A D; Elser, J J

    2016-01-01

    All life on Earth seems to be made of the same chemical elements in relatively conserved proportions (stoichiometry). Whether this stoichiometry is conserved in settings that differ radically in physicochemical conditions (extreme environments) from those commonly encountered elsewhere on the planet provides insight into possible stoichiometries for putative life beyond Earth. Here, we report measurements of elemental stoichiometry for extremophile microbes from hot springs of Yellowstone National Park (YNP). Phototrophic and chemotrophic microbes were collected in locations spanning large ranges of temperature (24 °C to boiling), pH (1.6-9.6), redox (0.1-7.2 mg L(-1) dissolved oxygen), and nutrient concentrations (0.01-0.25 mg L(-1) NO2-, 0.7-12.9 mg L(-1) NO3-, 0.01-42 mg L(-1) NH4 (+), 0.003-1.1 mg L(-1) P mostly as phosphate). Despite these extreme conditions, the microbial cells sampled had a major and trace element stoichiometry within the ranges commonly encountered for microbes living in the more moderate environments of lakes and surface oceans. The cells did have somewhat high C:P and N:P ratios that are consistent with phosphorus (P) limitation. Furthermore, chemotrophs and phototrophs had similar compositions with the exception of Mo content, which was enriched in cells derived from chemotrophic sites. Thus, despite the extraordinary physicochemical and biological diversity of YNP environments, life in these settings, in a stoichiometric sense, remains much the same as we know it elsewhere.

  8. Ecological Stoichiometry of Ocean Plankton.

    Science.gov (United States)

    Moreno, Allison R; Martiny, Adam C

    2017-08-30

    Marine plankton elemental stoichiometric ratios can deviate from the Redfield ratio (106C:16N:1P); here, we examine physiological and biogeochemical mechanisms that lead to the observed variation across lineages, regions, and seasons. Many models of ecological stoichiometry blend together acclimative and adaptive responses to environmental conditions. These two pathways can have unique molecular mechanisms and stoichiometric outcomes, and we attempt to disentangle the two processes. We find that interactions between environmental conditions and cellular growth are key to understanding stoichiometric regulation, but the growth rates of most marine plankton populations are poorly constrained. We propose that specific physiological mechanisms have a strong impact on plankton and community stoichiometry in nutrient-rich environments, whereas biogeochemical interactions are important for the stoichiometry of the oligotrophic gyres. Finally, we outline key areas with missing information that is needed to advance understanding of the present and future ecological stoichiometry of ocean plankton. Expected final online publication date for the Annual Review of Marine Science Volume 10 is January 3, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  9. Biodiversity effects on plant stoichiometry.

    Science.gov (United States)

    Abbas, Maike; Ebeling, Anne; Oelmann, Yvonne; Ptacnik, Robert; Roscher, Christiane; Weigelt, Alexandra; Weisser, Wolfgang W; Wilcke, Wolfgang; Hillebrand, Helmut

    2013-01-01

    In the course of the biodiversity-ecosystem functioning debate, the issue of multifunctionality of species communities has recently become a major focus. Elemental stoichiometry is related to a variety of processes reflecting multiple plant responses to the biotic and abiotic environment. It can thus be expected that the diversity of a plant assemblage alters community level plant tissue chemistry. We explored elemental stoichiometry in aboveground plant tissue (ratios of carbon, nitrogen, phosphorus, and potassium) and its relationship to plant diversity in a 5-year study in a large grassland biodiversity experiment (Jena Experiment). Species richness and functional group richness affected community stoichiometry, especially by increasing C:P and N:P ratios. The primacy of either species or functional group richness effects depended on the sequence of testing these terms, indicating that both aspects of richness were congruent and complementary to expected strong effects of legume presence and grass presence on plant chemical composition. Legumes and grasses had antagonistic effects on C:N (-27.7% in the presence of legumes, +32.7% in the presence of grasses). In addition to diversity effects on mean ratios, higher species richness consistently decreased the variance of chemical composition for all elemental ratios. The diversity effects on plant stoichiometry has several non-exclusive explanations: The reduction in variance can reflect a statistical averaging effect of species with different chemical composition or a optimization of nutrient uptake at high diversity, leading to converging ratios at high diversity. The shifts in mean ratios potentially reflect higher allocation to stem tissue as plants grew taller at higher richness. By showing a first link between plant diversity and stoichiometry in a multiyear experiment, our results indicate that losing plant species from grassland ecosystems will lead to less reliable chemical composition of forage for

  10. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Ruel, Bianca H.M.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    In PVC/NPOE ion-selective membranes of potentiometric sensors, the guest-host stoichiometry of the anion complex of H2PO4 - and F- selective uranyl salophene derivatives is 2:1. This stoichiometry is different from the stoichiometry observed in DMSO solution (1H NMR) or solid state (X-ray crystal

  11. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Ruel, Bianca H.M.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    In PVC/NPOE ion-selective membranes of potentiometric sensors, the guest-host stoichiometry of the anion complex of H2PO4 - and F- selective uranyl salophene derivatives is 2:1. This stoichiometry is different from the stoichiometry observed in DMSO solution (1H NMR) or solid state (X-ray crystal st

  12. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, Martijn M.G.; Snellink-Ruel, Bianca H.M.; Engbersen, Johan F.J.; Reinhoudt, David N.

    1998-01-01

    In PVC/NPOE ion-selective membranes of potentiometric sensors, the guest-host stoichiometry of the anion complex of H2PO4 - and F- selective uranyl salophene derivatives is 2:1. This stoichiometry is different from the stoichiometry observed in DMSO solution (1H NMR) or solid state (X-ray crystal st

  13. Optimization of biomass composition explains microbial growth-stoichiometry relationships

    Science.gov (United States)

    Franklin, O.; Hall, E.K.; Kaiser, C.; Battin, T.J.; Richter, A.

    2011-01-01

    Integrating microbial physiology and biomass stoichiometry opens far-reaching possibilities for linking microbial dynamics to ecosystem processes. For example, the growth-rate hypothesis (GRH) predicts positive correlations among growth rate, RNA content, and biomass phosphorus (P) content. Such relationships have been used to infer patterns of microbial activity, resource availability, and nutrient recycling in ecosystems. However, for microorganisms it is unclear under which resource conditions the GRH applies. We developed a model to test whether the response of microbial biomass stoichiometry to variable resource stoichiometry can be explained by a trade-off among cellular components that maximizes growth. The results show mechanistically why the GRH is valid under P limitation but not under N limitation. We also show why variability of growth rate-biomass stoichiometry relationships is lower under P limitation than under N or C limitation. These theoretical results are supported by experimental data on macromolecular composition (RNA, DNA, and protein) and biomass stoichiometry from two different bacteria. In addition, compared to a model with strictly homeostatic biomass, the optimization mechanism we suggest results in increased microbial N and P mineralization during organic-matter decomposition. Therefore, this mechanism may also have important implications for our understanding of nutrient cycling in ecosystems.

  14. Optimization of biomass composition explains microbial growth-stoichiometry relationships.

    Science.gov (United States)

    Franklin, Oskar; Hall, Edward K; Kaiser, Christina; Battin, Tom J; Richter, Andreas

    2011-02-01

    Integrating microbial physiology and biomass stoichiometry opens far-reaching possibilities for linking microbial dynamics to ecosystem processes. For example, the growth-rate hypothesis (GRH) predicts positive correlations among growth rate, RNA content, and biomass phosphorus (P) content. Such relationships have been used to infer patterns of microbial activity, resource availability, and nutrient recycling in ecosystems. However, for microorganisms it is unclear under which resource conditions the GRH applies. We developed a model to test whether the response of microbial biomass stoichiometry to variable resource stoichiometry can be explained by a trade-off among cellular components that maximizes growth. The results show mechanistically why the GRH is valid under P limitation but not under N limitation. We also show why variability of growth rate-biomass stoichiometry relationships is lower under P limitation than under N or C limitation. These theoretical results are supported by experimental data on macromolecular composition (RNA, DNA, and protein) and biomass stoichiometry from two different bacteria. In addition, compared to a model with strictly homeostatic biomass, the optimization mechanism we suggest results in increased microbial N and P mineralization during organic-matter decomposition. Therefore, this mechanism may also have important implications for our understanding of nutrient cycling in ecosystems.

  15. Stoichiometry of δ subunit containing GABA(A) receptors.

    Science.gov (United States)

    Patel, B; Mortensen, M; Smart, T G

    2014-02-01

    Although the stoichiometry of the major synaptic αβγ subunit-containing GABAA receptors has consensus support for 2α:2β:1γ, a clear view of the stoichiometry of extrasynaptic receptors containing δ subunits has remained elusive. Here we examine the subunit stoichiometry of recombinant α4β3δ receptors using a reporter mutation and a functional electrophysiological approach. Using site-directed mutagenesis, we inserted a highly characterized 9' serine to leucine mutation into the second transmembrane (M2) region of α4, β3 and δ subunits that increases receptor sensitivity to GABA. Whole-cell, GABA-activated currents were recorded from HEK-293 cells co-expressing different combinations of wild-type (WT) and/or mutant α4(L297S), β3(L284S) and δ(L288S) subunits. Recombinant receptors containing one or more mutant subunits showed increased GABA sensitivity relative to WT receptors by approximately fourfold, independent of the subunit class (α, β or δ) carrying the mutation. GABA dose-response curves of cells co-expressing WT subunits with their respective L9'S mutants exhibited multiple components, with the number of discernible components enabling a subunit stoichiometry of 2α, 2β and 1δ to be deduced for α4β3δ receptors. Varying the cDNA transfection ratio by 10-fold had no significant effect on the number of incorporated δ subunits. Subunit stoichiometry is an important determinant of GABAA receptor function and pharmacology, and δ subunit-containing receptors are important mediators of tonic inhibition in several brain regions. Here we demonstrate a preferred subunit stoichiometry for α4β3δ receptors of 2α, 2β and 1δ. © 2013 The British Pharmacological Society.

  16. Ordinary Stoichiometry of Extraordinary Microbes

    Science.gov (United States)

    Neveu, M.; Poret-Peterson, A. T.; Anbar, A. D.; Elser, J. J.

    2013-12-01

    Life on Earth seems to be composed of the same chemical elements in relatively conserved stoichiometric proportions. However, this observation is largely based on observations of biota from habitats spanning a moderate range of temperature and chemical composition (e.g., temperate lakes, forests, grasslands, oceanic phytoplankton). Whether this stoichiometry is conserved in settings that differ radically from such "normal" planetary settings may provide insight into the habitability of environments with radically different stoichiometries, and into possible stoichiometries for putative life beyond Earth. Here we report the first measurements of elemental stoichiometries of microbial extremophiles from hot springs of Yellowstone National Park (YNP). These phototrophic and chemotrophic microbes were collected in locations spanning large ranges of temperature (ambient to boiling) and pH (1 to 9). Microbial biomass was carefully extracted from hot spring sediment substrata following a procedure adapted from [1], which conserves cellular elemental abundances [2]. Their C and N contents were determined by Elemental Analysis Isotope Ratio Mass Spectrometry, and their P and trace element (Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and non-biogenic Al and Ti) contents were measured by Inductively Coupled Plasma Mass Spectrometry. Residual mineral contamination was an issue in some samples with low measured C and N; we eliminated these from our results. Even in the remaining samples, contamination sometimes prevented accurate determinations of cellular Mg, Ca, Mn, and Fe abundances; however, the cellular Ni, Cu, Zn, and Mo contents were several-fold above contamination level. Although hot spring water and sediment elemental abundances varied by orders of magnitude, the data showed that the extremophiles have a major and trace element stoichiometry similar to those previously measured in "normal" microbial biomass [3-6]. For example, biomass C:N:P ratios resembled those

  17. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  18. Synthesis of 1-alkyl triazolium triflate room temperature ionic liquids and their catalytic studies in multi-component Biginelli reaction

    Indian Academy of Sciences (India)

    Sankaranarayanan Nagarajan; Tanveer M Shaikh; Elango Kandasamy

    2015-09-01

    Synthesis of three Brønsted acid-based ionic liquids, namely, 1-ethyl-1,2,4-triazolium triflate (1a), 1-propyl-1,2,4-triazolium triflate (1b) and 1-butyl-1,2,4-triazolium triflate (1c), is described. These ionic liquids have been employed as catalysts for convenient and high-yielding one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones and 3,4-dihydropyrimidin-2(1H)-thiones, which are Biginelli reaction products. Advantages of the methodology are operational convenience, short reaction times, avoidance of chromatographic purification and non-production of toxic waste. Further, the catalysts are easily recovered and reused without any noticeable diminution in their catalytic activity.

  19. A two-component regulatory system in transcriptional control of photosystem stoichiometry: redox-dependent and sodium ion-dependent phosphoryl transfer from cyanobacterial histidine kinase Hik2 to response regulators Rre1 and RppA

    Directory of Open Access Journals (Sweden)

    Iskander Mohamed Ibrahim

    2016-02-01

    Full Text Available I hereby submit the above-titled manuscript for publication in Frontiers in Plant Science. The research reported is original and novel. No part of it is submitted for publication elsewhere.We report on regulation and interactions of a unique histidine sensor kinase, Hik2. Hik2 is found in all known cyanobacteria, but has no previously identified functional response regulator. Here we show that it transfers phosphate rapidly, in vitro, to two response regulators, termed Rre1 and RppA. Hik2 is of special importance in being indispensable to cyanobacteria, and in being the closest cyanobacterial homologue of the uniquely conserved Chloroplast Sensor Kinase (CSK, which couples photosynthetic electron transport to gene transcription. Hik2 function is so important that it has survived the transition from cyanobacterium to eukaryotic sub-cellular organelle. Hik2 is likely to be a redox sensor involved in adjustment of the stoichiometry of photosystems I and II of oxygenic photosynthesis. We show that Hik2 also responds to the specific presence of sodium ions. These regulatory controls and the bifurcated signal transduction pathway indicated by two response regulators lead to a proposal for integration of photosynthetic light-acclimation with response to salt stress.

  20. Estimating the stoichiometry of HIV neutralization.

    Science.gov (United States)

    Magnus, Carsten; Regoes, Roland R

    2010-03-19

    HIV-1 virions infect target cells by first establishing contact between envelope glycoprotein trimers on the virion's surface and CD4 receptors on a target cell, recruiting co-receptors, fusing with the cell membrane and finally releasing the genetic material into the target cell. Specific experimental setups allow the study of the number of trimer-receptor-interactions needed for infection, i.e., the stoichiometry of entry and also the number of antibodies needed to prevent one trimer from engaging successfully in the entry process, i.e., the stoichiometry of (trimer) neutralization. Mathematical models are required to infer the stoichiometric parameters from these experimental data. Recently, we developed mathematical models for the estimations of the stoichiometry of entry [1]. In this article, we show how our models can be extended to investigate the stoichiometry of trimer neutralization. We study how various biological parameters affect the estimate of the stoichiometry of neutralization. We find that the distribution of trimer numbers-which is also an important determinant of the stoichiometry of entry-influences the estimated value of the stoichiometry of neutralization. In contrast, other parameters, which characterize the experimental system, diminish the information we can extract from the data about the stoichiometry of neutralization, and thus reduce our confidence in the estimate. We illustrate the use of our models by re-analyzing previously published data on the neutralization sensitivity [2], which contains measurements of neutralization sensitivity of viruses with different envelope proteins to antibodies with various specificities. Our mathematical framework represents the formal basis for the estimation of the stoichiometry of neutralization. Together with the stoichiometry of entry, the stoichiometry of trimer neutralization will allow one to calculate how many antibodies are required to neutralize a virion or even an entire population of

  1. Enhanced formation of >C1 products in the electroreduction of CO2 by adding a carbon dioxide adsorption component to a gas diffusion layer-type catalytic electrode.

    Science.gov (United States)

    Marepally, Bhanu Chandra; Ampelli, Claudio; Genovese, Chiara; Saboo, Tapish; Perathoner, Siglinda; Wisser, Florian M; Veyre, Laurent; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Centi, Gabriele

    2017-09-18

    The addition of a CO2 adsorption component (substituted imidazolate-based SIM-1 crystals) to a gas diffusion layer (GDL) type catalytic electrode allows to enhance the activity and especially the selectivity to >C1 carbon chain products (ethanol, acetone and isopropanol) of a Pt-based electrocatalyst that is not able to form products of CO2 reduction involving C-C bond formation under conventional (liquid-phase) conditions. This indicates that the increase of the CO2 effective concentration at the electrode active surface is the factor controlling the formation of >C1 products rather than only the intrinsic properties of the electrocatalyst. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Inhibitory effects of seven components of danshen extract on catalytic activity of cytochrome P450 enzyme in human liver microsomes.

    Science.gov (United States)

    Qiu, Furong; Zhang, Rong; Sun, Jianguo; Jiye, A; Hao, Haiping; Peng, Ying; Ai, Hua; Wang, Guangji

    2008-07-01

    The potential for herb-drug interactions has recently received greater attention worldwide, considering the fact that the use of herbal products becomes more and more widespread. The goal of this work was to examine the potential for the metabolism-based drug interaction arising from seven active components (danshensu, protocatechuic aldehyde, protocatechuic acid, salvianolic acid B, tanshinone I, tanshinone IIA, and cryptotanshinone) of danshen extract. Probe substrates of cytochrome P450 enzymes were incubated in human liver microsomes (HLMs) with or without each component of danshen extract. IC(50) and K(i) values were estimated, and the types of inhibition were determined. Among the seven components of danshen extract, tanshinone I, tanshinone IIA, and cryptotanshinone were potent competitive inhibitors of CYP1A2 (K(i) = 0.48, 1.0, and 0.45 microM, respectively); danshensu was a competitive inhibitor of CYP2C9 (K(i) = 35 microM), and cryptotanshinone was a moderate mixed-type inhibitor of CYP2C9 (K(i) = 8 microM); cryptotanshinone inhibited weakly and in mixed mode against CYP2D6 activity (K(i) = 68 microM), and tanshinone I was a weak inhibitor of CYP2D6 (IC(50) = 120 microM); and protocatechuic aldehyde was a weak inhibitor of CYP3A4 (IC(50) = 130 and 160 microM for midazolam and testosterone, respectively). These findings provided some useful information for safe and effective use of danshen preparations in clinical practice. Our data indicated that it was necessary to study the in vivo interactions between drugs and pharmaceuticals with danshen extract.

  3. Catalytic bioreactors and methods of using same

    Energy Technology Data Exchange (ETDEWEB)

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  4. Acetylation dynamics and stoichiometry in Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Weinert, Brian Tate; Iesmantavicius, Vytautas; Moustafa, Tarek

    2014-01-01

    Lysine acetylation is a frequently occurring posttranslational modification; however, little is known about the origin and regulation of most sites. Here we used quantitative mass spectrometry to analyze acetylation dynamics and stoichiometry in Saccharomyces cerevisiae. We found that acetylation...... acetylation stoichiometry and found that the vast majority of mitochondrial and cytoplasmic acetylation had a very low stoichiometry. However, mitochondrial acetylation occurred at a significantly higher basal level than cytoplasmic acetylation, consistent with the distinct acetylation dynamics and higher...... acetyl-CoA concentration in mitochondria. High stoichiometry acetylation occurred mostly on histones, proteins present in histone acetyltransferase and deacetylase complexes, and on transcription factors. These data show that a majority of acetylation occurs at very low levels in exponentially growing...

  5. Thermal desorption study of catalytic systems. Communication 20. Adsorption of water vapors on the calcium aluminate components of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nissenbaum, V.D.; Danyushevskii, V.Y.; Golosman, E.Z.; Rubinstein, A.M.; Yakerson, V.I.

    1985-05-01

    Ca aluminates are used as a component of catalysts of gas-phase processes, some of which take place with the participation of water. Nickel calcium aluminate catalysts are thus used for hydrogenation of CO and CO/sub 2/ to CH/sub 4/ and water; zinc calcium aluminate catalysts are used for sulfur purification of process gases, where water is liberated during sulfiding of ZnO; and copper zinc calcium aluminate catalysts are used in low-temperature conversion of CO with water vapor. It is also known that Ca aluminates undergo various transformations in aqueous media with the formation of Ca hydroaluminates. This paper discusses the adsorption of water from the gas phase on calcium aluminate systems, which was investigated by the thermal desorption method. Samples of varying phase composition, different CaO/Al/sub 2/O/sub 3/ ratios, and specific surface areas were also studied and are reported on here.

  6. Component

    Directory of Open Access Journals (Sweden)

    Tibor Tot

    2011-01-01

    Full Text Available A unique case of metaplastic breast carcinoma with an epithelial component showing tumoral necrosis and neuroectodermal stromal component is described. The tumor grew rapidly and measured 9 cm at the time of diagnosis. No lymph node metastases were present. The disease progressed rapidly and the patient died two years after the diagnosis from a hemorrhage caused by brain metastases. The morphology and phenotype of the tumor are described in detail and the differential diagnostic options are discussed.

  7. New approach to develop ultra-high inhibitory drug using the power function of the stoichiometry of the targeted nanomachine or biocomplex.

    Science.gov (United States)

    Shu, Dan; Pi, Fengmei; Wang, Chi; Zhang, Peng; Guo, Peixuan

    2015-07-01

    To find methods for potent drug development by targeting to biocomplex with high copy number. Phi29 DNA packaging motor components with different stoichiometries were used as model to assay virion assembly with Yang Hui's Triangle [Formula: see text], where Z = stoichiometry, M = drugged subunits per biocomplex, p and q are the fraction of drugged and undrugged subunits in the population. Inhibition efficiency follows a power function. When number of drugged subunits to block the function of the complex K = 1, the uninhibited biocomplex equals q(z), demonstrating the multiplicative effect of stoichiometry on inhibition with stoichiometry 1000 > 6 > 1. Complete inhibition of virus replication was found when Z = 6. Drug inhibition potency depends on the stoichiometry of the targeted components of the biocomplex or nanomachine. The inhibition effect follows a power function of the stoichiometry of the target biocomplex.

  8. Unifying elemental stoichiometry and metabolic theory in predicting species abundances

    NARCIS (Netherlands)

    Ott, David; Digel, Christoph; Rall, Björn Christian; Maraun, Mark; Scheu, Stefan; Brose, Ulrich

    2014-01-01

    While metabolic theory predicts variance in population density within communities depending on population average body masses, the ecological stoichiometry concept relates density variation across communities to varying resource stoichiometry. Using a data set including biomass densities of 4959

  9. Unifying elemental stoichiometry and metabolic theory in predicting species abundances

    NARCIS (Netherlands)

    Ott, David; Digel, Christoph; Rall, Björn Christian; Maraun, Mark; Scheu, Stefan; Brose, Ulrich

    2014-01-01

    While metabolic theory predicts variance in population density within communities depending on population average body masses, the ecological stoichiometry concept relates density variation across communities to varying resource stoichiometry. Using a data set including biomass densities of 4959 pop

  10. Unifying elemental stoichiometry and metabolic theory in predicting species abundances

    NARCIS (Netherlands)

    Ott, David; Digel, Christoph; Rall, Björn Christian; Maraun, Mark; Scheu, Stefan; Brose, Ulrich

    2014-01-01

    While metabolic theory predicts variance in population density within communities depending on population average body masses, the ecological stoichiometry concept relates density variation across communities to varying resource stoichiometry. Using a data set including biomass densities of 4959 pop

  11. Fizzy Drinks: Stoichiometry You Can Taste.

    Science.gov (United States)

    Rohrig, Brian

    2000-01-01

    Presents an activity that is suitable for a high school chemistry or introductory college chemistry lab in which students create their own Fizzie-style carbonated beverage and use stoichiometry to calculate the correct mix of citric acid and baking soda. (Author/ASK)

  12. Ghanaian Teacher Trainees' Conceptual Understanding of Stoichiometry

    Science.gov (United States)

    Hanson, Ruby

    2016-01-01

    Chemical stoichiometry is a conceptual framework that encompasses other concepts such as the mole, writing of chemical equations in word and representative form, balancing of equations and the equilibrium concept. The underlying concepts enable students to understand relationships among entities of matter and required amounts for use when…

  13. Acetylation dynamics and stoichiometry in Saccharomyces cerevisiae.

    Science.gov (United States)

    Weinert, Brian T; Iesmantavicius, Vytautas; Moustafa, Tarek; Schölz, Christian; Wagner, Sebastian A; Magnes, Christoph; Zechner, Rudolf; Choudhary, Chunaram

    2014-01-01

    Lysine acetylation is a frequently occurring posttranslational modification; however, little is known about the origin and regulation of most sites. Here we used quantitative mass spectrometry to analyze acetylation dynamics and stoichiometry in Saccharomyces cerevisiae. We found that acetylation accumulated in growth-arrested cells in a manner that depended on acetyl-CoA generation in distinct subcellular compartments. Mitochondrial acetylation levels correlated with acetyl-CoA concentration in vivo and acetyl-CoA acetylated lysine residues nonenzymatically in vitro. We developed a method to estimate acetylation stoichiometry and found that the vast majority of mitochondrial and cytoplasmic acetylation had a very low stoichiometry. However, mitochondrial acetylation occurred at a significantly higher basal level than cytoplasmic acetylation, consistent with the distinct acetylation dynamics and higher acetyl-CoA concentration in mitochondria. High stoichiometry acetylation occurred mostly on histones, proteins present in histone acetyltransferase and deacetylase complexes, and on transcription factors. These data show that a majority of acetylation occurs at very low levels in exponentially growing yeast and is uniformly affected by exposure to acetyl-CoA.

  14. Ghanaian Teacher Trainees' Conceptual Understanding of Stoichiometry

    Science.gov (United States)

    Hanson, Ruby

    2015-01-01

    Chemical stoichiometry is a conceptual framework that encompasses other concepts such as the mole, writing of chemical equations in word and representative form, balancing of equations and the equilibrium concept. The underlying concepts enable students to understand relationships among entities of matter and required amounts for use when…

  15. Fizzy Drinks: Stoichiometry You Can Taste.

    Science.gov (United States)

    Rohrig, Brian

    2000-01-01

    Presents an activity that is suitable for a high school chemistry or introductory college chemistry lab in which students create their own Fizzie-style carbonated beverage and use stoichiometry to calculate the correct mix of citric acid and baking soda. (Author/ASK)

  16. Linking microbial and ecosystem ecology using ecological stoichiometry: a synthesis of conceptual and empirical approaches

    Science.gov (United States)

    Hall, E.K.; Maixner, F.; Franklin, O.; Daims, H.; Richter, A.; Battin, T.

    2011-01-01

    Currently, one of the biggest challenges in microbial and ecosystem ecology is to develop conceptual models that organize the growing body of information on environmental microbiology into a clear mechanistic framework with a direct link to ecosystem processes. Doing so will enable development of testable hypotheses to better direct future research and increase understanding of key constraints on biogeochemical networks. Although the understanding of phenotypic and genotypic diversity of microorganisms in the environment is rapidly accumulating, how controls on microbial physiology ultimately affect biogeochemical fluxes remains poorly understood. We propose that insight into constraints on biogeochemical cycles can be achieved by a more rigorous evaluation of microbial community biomass composition within the context of ecological stoichiometry. Multiple recent studies have pointed to microbial biomass stoichiometry as an important determinant of when microorganisms retain or recycle mineral nutrients. We identify the relevant cellular components that most likely drive changes in microbial biomass stoichiometry by defining a conceptual model rooted in ecological stoichiometry. More importantly, we show how X-ray microanalysis (XRMA), nanoscale secondary ion mass spectroscopy (NanoSIMS), Raman microspectroscopy, and in situ hybridization techniques (for example, FISH) can be applied in concert to allow for direct empirical evaluation of the proposed conceptual framework. This approach links an important piece of the ecological literature, ecological stoichiometry, with the molecular front of the microbial revolution, in an attempt to provide new insight into how microbial physiology could constrain ecosystem processes.

  17. Modified coprecipitation process of synthesizing Bi-system superconductor precursor powder and its stoichiometry

    Institute of Scientific and Technical Information of China (English)

    毛传斌; 杜泽华; 周廉

    1996-01-01

    A modified coprecipitation process is presented based on the stoichiometry study of oxalate coprecipitation process in water medium to synthesize Bi-Pb-Sr-Ca-Cu-O multi-component powder.Its characteristic is that the coprecipitation reaction takes place in a mixed solution medium composed of water and a kind of organic solvent (volume percentage >90%).Thus,it overcomes the serious shortcoming of inability to maintain stoichiometry in Bi-system superconductor powder synthesized by water-medium coprecipitation.The effects of pH value,oxalic acid concentration and aging time on stoichiometry maintenance in precipitate are systematically studied.Bulk material made from the powder prepared by the new modified coprecipitation also shows the success of the new process.

  18. Distinct Cellular Assembly Stoichiometry of Polycomb Complexes on Chromatin Revealed by Single-molecule Chromatin Immunoprecipitation Imaging*♦

    Science.gov (United States)

    Tatavosian, Roubina; Zhen, Chao Yu; Duc, Huy Nguyen; Balas, Maggie M.; Johnson, Aaron M.; Ren, Xiaojun

    2015-01-01

    Epigenetic complexes play an essential role in regulating chromatin structure, but information about their assembly stoichiometry on chromatin within cells is poorly understood. The cellular assembly stoichiometry is critical for appreciating the initiation, propagation, and maintenance of epigenetic inheritance during normal development and in cancer. By combining genetic engineering, chromatin biochemistry, and single-molecule fluorescence imaging, we developed a novel and sensitive approach termed single-molecule chromatin immunoprecipitation imaging (Sm-ChIPi) to enable investigation of the cellular assembly stoichiometry of epigenetic complexes on chromatin. Sm-ChIPi was validated by using chromatin complexes with known stoichiometry. The stoichiometry of subunits within a polycomb complex and the assembly stoichiometry of polycomb complexes on chromatin have been extensively studied but reached divergent views. Moreover, the cellular assembly stoichiometry of polycomb complexes on chromatin remains unexplored. Using Sm-ChIPi, we demonstrated that within mouse embryonic stem cells, one polycomb repressive complex (PRC) 1 associates with multiple nucleosomes, whereas two PRC2s can bind to a single nucleosome. Furthermore, we obtained direct physical evidence that the nucleoplasmic PRC1 is monomeric, whereas PRC2 can dimerize in the nucleoplasm. We showed that ES cell differentiation induces selective alteration of the assembly stoichiometry of Cbx2 on chromatin but not other PRC1 components. We additionally showed that the PRC2-mediated trimethylation of H3K27 is not required for the assembly stoichiometry of PRC1 on chromatin. Thus, these findings uncover that PRC1 and PRC2 employ distinct mechanisms to assemble on chromatin, and the novel Sm-ChIPi technique could provide single-molecule insight into other epigenetic complexes. PMID:26381410

  19. Distinct Cellular Assembly Stoichiometry of Polycomb Complexes on Chromatin Revealed by Single-molecule Chromatin Immunoprecipitation Imaging.

    Science.gov (United States)

    Tatavosian, Roubina; Zhen, Chao Yu; Duc, Huy Nguyen; Balas, Maggie M; Johnson, Aaron M; Ren, Xiaojun

    2015-11-20

    Epigenetic complexes play an essential role in regulating chromatin structure, but information about their assembly stoichiometry on chromatin within cells is poorly understood. The cellular assembly stoichiometry is critical for appreciating the initiation, propagation, and maintenance of epigenetic inheritance during normal development and in cancer. By combining genetic engineering, chromatin biochemistry, and single-molecule fluorescence imaging, we developed a novel and sensitive approach termed single-molecule chromatin immunoprecipitation imaging (Sm-ChIPi) to enable investigation of the cellular assembly stoichiometry of epigenetic complexes on chromatin. Sm-ChIPi was validated by using chromatin complexes with known stoichiometry. The stoichiometry of subunits within a polycomb complex and the assembly stoichiometry of polycomb complexes on chromatin have been extensively studied but reached divergent views. Moreover, the cellular assembly stoichiometry of polycomb complexes on chromatin remains unexplored. Using Sm-ChIPi, we demonstrated that within mouse embryonic stem cells, one polycomb repressive complex (PRC) 1 associates with multiple nucleosomes, whereas two PRC2s can bind to a single nucleosome. Furthermore, we obtained direct physical evidence that the nucleoplasmic PRC1 is monomeric, whereas PRC2 can dimerize in the nucleoplasm. We showed that ES cell differentiation induces selective alteration of the assembly stoichiometry of Cbx2 on chromatin but not other PRC1 components. We additionally showed that the PRC2-mediated trimethylation of H3K27 is not required for the assembly stoichiometry of PRC1 on chromatin. Thus, these findings uncover that PRC1 and PRC2 employ distinct mechanisms to assemble on chromatin, and the novel Sm-ChIPi technique could provide single-molecule insight into other epigenetic complexes.

  20. [Ecological stoichiometry and its application to medicinal plant resources].

    Science.gov (United States)

    Zhang, Ji; Jin, Hang; Zhang, Jin-Yu; Wang, Yuan-Zhong

    2013-01-01

    Ecological stoichiometry is a study of the balance of biological system's energy and the balance of multiple chemical elements. It focuses on the relationship of the element ratio in ecological processes. In this paper, the concept and main theoretical basis of ecological stoichiometry were introduced, and the status of stoichiometry in medicinal plant resources was reviewed. According to the recent development of ecological stoichiometry, the future directions of ecological stoichiometry of medicinal plants could be the study of the relationship between stoichiometric characteristic and growth and secondary metabolism of medicinal plants, and the influence of biotic (or abiotic) factors on the stoichiometric characteristic of medicinal plants.

  1. Differential Stoichiometry among Core Ribosomal Proteins

    Science.gov (United States)

    Slavov, Nikolai; Semrau, Stefan; Airoldi, Edoardo; Budnik, Bogdan; van Oudenaarden, Alexander

    2015-01-01

    Summary Understanding the regulation and structure of ribosomes is essential to understanding protein synthesis and its dysregulation in disease. While ribosomes are believed to have a fixed stoichiometry among their core ribosomal proteins (RPs), some experiments suggest a more variable composition. Testing such variability requires direct and precise quantification of RPs. We used mass spectrometry to directly quantify RPs across monosomes and polysomes of mouse embryonic stem cells (ESC) and budding yeast. Our data show that the stoichiometry among core RPs in wild-type yeast cells and ESC depends both on the growth conditions and on the number of ribosomes bound per mRNA. Furthermore, we find that the fitness of cells with a deleted RP-gene is inversely proportional to the enrichment of the corresponding RP in polysomes. Together, our findings support the existence of ribosomes with distinct protein composition and physiological function. PMID:26565899

  2. Biogeochemical stoichiometry of Antarctic Dry Valley ecosystems

    Science.gov (United States)

    Barrett, J. E.; Virginia, R. A.; Lyons, W. B.; McKnight, D. M.; Priscu, J. C.; Doran, P. T.; Fountain, A. G.; Wall, D. H.; Moorhead, D. L.

    2007-03-01

    Among aquatic and terrestrial landscapes of the McMurdo Dry Valleys, Antarctica, ecosystem stoichiometry ranges from values near the Redfield ratios for C:N:P to nutrient concentrations in proportions far above or below ratios necessary to support balanced microbial growth. This polar desert provides an opportunity to evaluate stoichiometric approaches to understand nutrient cycling in an ecosystem where biological diversity and activity are low, and controls over the movement and mass balances of nutrients operate over 10-106 years. The simple organisms (microbial and metazoan) comprising dry valley foodwebs adhere to strict biochemical requirements in the composition of their biomass, and when activated by availability of liquid water, they influence the chemical composition of their environment according to these ratios. Nitrogen and phosphorus varied significantly in terrestrial and aquatic ecosystems occurring on landscape surfaces across a wide range of exposure ages, indicating strong influences of landscape development and geochemistry on nutrient availability. Biota control the elemental ratio of stream waters, while geochemical stoichiometry (e.g., weathering, atmospheric deposition) evidently limits the distribution of soil invertebrates. We present a conceptual model describing transformations across dry valley landscapes facilitated by exchanges of liquid water and biotic processing of dissolved nutrients. We conclude that contemporary ecosystem stoichiometry of Antarctic Dry Valley soils, glaciers, streams, and lakes results from a combination of extant biological processes superimposed on a legacy of landscape processes and previous climates.

  3. Structural and evolutionary versatility in protein complexes with uneven stoichiometry.

    Science.gov (United States)

    Marsh, Joseph A; Rees, Holly A; Ahnert, Sebastian E; Teichmann, Sarah A

    2015-03-16

    Proteins assemble into complexes with diverse quaternary structures. Although most heteromeric complexes of known structure have even stoichiometry, a significant minority have uneven stoichiometry--that is, differing numbers of each subunit type. To adopt this uneven stoichiometry, sequence-identical subunits must be asymmetric with respect to each other, forming different interactions within the complex. Here we first investigate the occurrence of uneven stoichiometry, demonstrating that it is common in vitro and is likely to be common in vivo. Next, we elucidate the structural determinants of uneven stoichiometry, identifying six different mechanisms by which it can be achieved. Finally, we study the frequency of uneven stoichiometry across evolution, observing a significant enrichment in bacteria compared with eukaryotes. We show that this arises due to a general increased tendency for bacterial proteins to self-assemble and form homomeric interactions, even within the context of a heteromeric complex.

  4. 湿式催化氧化催化剂及其活性组分流失控制的研究%Research on Catalyst and Control of Active Catalyst Components Lossing in Catalytic Wet Air Oxidation

    Institute of Scientific and Technical Information of China (English)

    王锐; 尹华强; 李建军; 郭家秀; 任吉萍

    2011-01-01

    Catalytic Wet Air Oxidation is an efficient and feasible technology for high concentration and refractory organic wastewater treatment. But the lossing of the active components of catalyst induced decreased catalytic activity, shorter life, higher investment costs, etc. in industrial operation In the paper, the catalytic wet oxidation technology and catalyst applications were described. What's more, the loss mechanism of the catalyst, affecting factors and methods to improve catalyst stability were emphatically illustrated, at the same time, related experiments and the results obtained are introduced.%湿式催化氧化技术是一种处理高浓度、难降解有机废水的高效、可行的技术,但是在使用过程中,活性组分易流失,在工业化应用中带来催化活性降低、使用寿命变短、投资成本增高等问题。文中介绍了湿式催化氧化技术及催化剂研究,着重讲述催化剂流失机理、影响因素以及提高催化剂稳定的方法,同时对相关实验和成果也做了介绍。

  5. Volumetric determination of apolipoprotein stoichiometry of circulating HDL subspecies1[S

    Science.gov (United States)

    Segrest, Jere P.; Cheung, Marian C.; Jones, Martin K.

    2013-01-01

    Although HDL is inversely correlated with coronary heart disease, elevated HDL-cholesterol is not always protective. Additionally, HDL has biological functions that transcend any antiatherogenic role: shotgun proteomics show that HDL particles contain 84 proteins (latest count), many correlating with antioxidant and anti-inflammatory properties of HDL. ApoA-I has been suggested to serve as a platform for the assembly of these protein components on HDL with specific functions - the HDL proteome. However, the stoichiometry of apoA-I in HDL subspecies is poorly understood. Here we use a combination of immunoaffinity chromatography data and volumetric analysis to evaluate the size and stoichiometry of LpA-I and LpA-I,A-II particles. We conclude that there are three major LpA-I subspecies: two major particles, HDL[4] in the HDL3 size range (d = 85.0 ± 1.2 Å) and HDL[7] in the HDL2 size range (d = 108.5 ± 3.8 Å) with apoA-I stoichiometries of 3 and 4, respectively, and a small minor particle, HDL[1] (d = 73.8 ± 2.1Å) with an apoA-I stoichiometry of 2. Additionally, we conclude that the molar ratio of apolipoprotein to surface lipid is significantly higher in circulating HDL subspecies than in reconstituted spherical HDL particles, presumably reflecting a lack of phospholipid transfer protein in reconstitution protocols. PMID:23883582

  6. Kinetics and mechanism of catalytic hydroprocessing of components of coal-derived liquids. Twentieth quarterly report, February 16, 1984-May 15, 1984

    Energy Technology Data Exchange (ETDEWEB)

    Gates, B.C.; Olson, J.H.; Schuit, G.C.A.; Stiles, A.B.; Petrakis, L.

    1984-06-26

    Kinetics data have been determined for the catalytic hydroprocessing of the acidic fractions of a heavy distillate of a liquid derived from Powhatan No. 5 coal. A commercial, sulfided Ni-Mo/..gamma..-Al/sub 2/O/sub 3/ catalyst was used in the experiments, carried out at 350/sup 0/C and 120 atm with the coal liquid fractions dissolved in cyclohexane. The feed and hydrotreated products were analyzed by gas chromatography/mass spectrometry. The data were analyzed with group-type methods for compound classes, and results were also obtained for some individual organooxygen compounds. Catalytic hydroprocessing leads to a large increase in the number of compounds and a shift to lower boiling ranges. The data are broadly consistent with reaction networks determined with pure compounds; the most important reactions include aromatic ring hydrogenation, hydrodeoxygenation, and hydrodemethylation. Pseudo first-order rate constants for conversion of the predominant organooxygen compounds are on the order of 10/sup -4/ L/(g of catalyst.s); the reactivity decreases in the order cyclohexylphenol > dimethylhydroxyindane > tetrahydronaphthol > phenylphenol > 1-naphthol. 12 references, 15 figures, 5 tables.

  7. Determination of the Stoichiometry of the Complete Bacterial Type III Secretion Needle Complex Using a Combined Quantitative Proteomic Approach*

    Science.gov (United States)

    Zilkenat, Susann; Franz-Wachtel, Mirita; Stierhof, York-Dieter; Galán, Jorge E.; Macek, Boris; Wagner, Samuel

    2016-01-01

    Precisely knowing the stoichiometry of their components is critical for investigating structure, assembly, and function of macromolecular machines. This has remained a technical challenge in particular for large, hydrophobic membrane-spanning protein complexes. Here, we determined the stoichiometry of a type III secretion system of Salmonella enterica serovar Typhimurium using two complementary protocols of gentle complex purification combined with peptide concatenated standard and synthetic stable isotope-labeled peptide-based mass spectrometry. Bacterial type III secretion systems are cell envelope-spanning effector protein-delivery machines essential for colonization and survival of many Gram-negative pathogens and symbionts. The membrane-embedded core unit of these secretion systems, termed the needle complex, is composed of a base that anchors the machinery to the inner and outer membranes, a hollow filament formed by inner rod and needle subunits that serves as conduit for substrate proteins, and a membrane-embedded export apparatus facilitating substrate translocation. Structural analyses have revealed the stoichiometry of the components of the base, but the stoichiometry of the essential hydrophobic export apparatus components and of the inner rod protein remain unknown. Here, we provide evidence that the export apparatus of type III secretion systems contains five SpaP, one SpaQ, one SpaR, and one SpaS. We confirmed that the previously suggested stoichiometry of nine InvA is valid for assembled needle complexes and describe a loose association of InvA with other needle complex components that may reflect its function. Furthermore, we present evidence that not more than six PrgJ form the inner rod of the needle complex. Providing this structural information will facilitate efforts to obtain an atomic view of type III secretion systems and foster our understanding of the function of these and related flagellar machines. Given that other virulence

  8. Determination of the Stoichiometry of the Complete Bacterial Type III Secretion Needle Complex Using a Combined Quantitative Proteomic Approach.

    Science.gov (United States)

    Zilkenat, Susann; Franz-Wachtel, Mirita; Stierhof, York-Dieter; Galán, Jorge E; Macek, Boris; Wagner, Samuel

    2016-05-01

    Precisely knowing the stoichiometry of their components is critical for investigating structure, assembly, and function of macromolecular machines. This has remained a technical challenge in particular for large, hydrophobic membrane-spanning protein complexes. Here, we determined the stoichiometry of a type III secretion system of Salmonella enterica serovar Typhimurium using two complementary protocols of gentle complex purification combined with peptide concatenated standard and synthetic stable isotope-labeled peptide-based mass spectrometry. Bacterial type III secretion systems are cell envelope-spanning effector protein-delivery machines essential for colonization and survival of many Gram-negative pathogens and symbionts. The membrane-embedded core unit of these secretion systems, termed the needle complex, is composed of a base that anchors the machinery to the inner and outer membranes, a hollow filament formed by inner rod and needle subunits that serves as conduit for substrate proteins, and a membrane-embedded export apparatus facilitating substrate translocation. Structural analyses have revealed the stoichiometry of the components of the base, but the stoichiometry of the essential hydrophobic export apparatus components and of the inner rod protein remain unknown. Here, we provide evidence that the export apparatus of type III secretion systems contains five SpaP, one SpaQ, one SpaR, and one SpaS. We confirmed that the previously suggested stoichiometry of nine InvA is valid for assembled needle complexes and describe a loose association of InvA with other needle complex components that may reflect its function. Furthermore, we present evidence that not more than six PrgJ form the inner rod of the needle complex. Providing this structural information will facilitate efforts to obtain an atomic view of type III secretion systems and foster our understanding of the function of these and related flagellar machines. Given that other virulence

  9. Unpacking students' atomistic uderstanding of stoichiometry

    Science.gov (United States)

    Baluyut, John Ysrael

    Despite the use by instructors of particulate nature of matter (PNOM) diagrams in the general chemistry classroom, misconceptions on stoichiometry continue to prevail among students tasked with conceptual problems on concepts of limiting and excess reagents, and reaction yields. This dissertation set out to explore students' understanding of stoichiometry at the microscopic level as they solved problems that using PNOM diagrams. In particular, the study investigated how students coordinated symbolic and microscopic representations to demonstrate their knowledge of stoichiometric concepts, quantified the prevalence and explained the nature of stoichiometric misconceptions in terms of dual processing and dual coding theories, and used eye tracking to identify visual behaviors that accompanied cognitive processes students used to solve conceptual stoichiometry problems with PNOM diagrams. Interviews with students asked to draw diagrams for specific stoichiometric situations showed dual processing systems were in play. Many students were found to have used these processing systems in a heuristic-analytic sequence. Heuristics, such as the factor-label method and the least amount misconception, were often used by students to select information for further processing in an attempt to reduce the cognitive load of the subsequent analytic stage of the solution process. Diagrams drawn by students were used then to develop an instrument administered over a much larger sample of the general chemistry student population. The robustness of the dual processing theory was manifested by response patterns observed with large proportions of the student samples. These response patterns suggest that many students seemed to rely on heuristics to respond to a specific item for one of two diagrams given for the same chemical context, and then used a more analytic approach in dealing with the same item for the other diagram. It was also found that many students incorrectly treated items

  10. Learning Stoichiometry: A Comparison of Text and Multimedia Formats

    Science.gov (United States)

    Evans, Karen L.; Yaron, David; Leinhardt, Gaea

    2008-01-01

    Even after repeated instruction, first year college chemistry students are often unable to apply stoichiometry knowledge to equilibrium and acid-base chemistry problems. The dynamic and interactive capabilities of online technology may facilitate stoichiometry instruction that promotes more meaningful learning. This study compares a…

  11. Learning Stoichiometry: A Comparison of Text and Multimedia Formats

    Science.gov (United States)

    Evans, Karen L.; Yaron, David; Leinhardt, Gaea

    2008-01-01

    Even after repeated instruction, first year college chemistry students are often unable to apply stoichiometry knowledge to equilibrium and acid-base chemistry problems. The dynamic and interactive capabilities of online technology may facilitate stoichiometry instruction that promotes more meaningful learning. This study compares a…

  12. Simplest Formula of Copper Iodide: A Stoichiometry Experiment.

    Science.gov (United States)

    MacDonald, D. J.

    1983-01-01

    Describes an experiment presented to students as a problem in determining the stoichiometry of "copper iodide" to decide whether it is cuprous iodide or cupric iodide. The experiment illustrates stoichiometry principles, providing experiences with laboratory techniques and numerical computation. Detailed outline (written for student use) is…

  13. Growth and stoichiometry of a common aquatic detritivore respond to changes in resource stoichiometry.

    Science.gov (United States)

    Fuller, Chris L; Evans-White, Michelle A; Entrekin, Sally A

    2015-03-01

    Consumer growth determines the quantity of nutrients transferred through food webs. The extent to which leaf composition and consumer physiology interact to constrain consumer production is not well understood. For example, detritivore growth, and thus material transfer, could change with detrital elemental composition. Detrital type and associated microbial biofilms can mediate the amount and rate of detritus consumed and used towards growth. Detritivore body stoichiometry or the threshold elemental ratio, the food ratio resulting in optimal growth, may predict taxon-specific growth response to stoichiometrically-altered detritus. Empirical measures of detritivore growth responses across a range of detrital stoichiometry are rare. We fed a common detritivore, Tipula abdominalis, maple or oak leaves that spanned a gradient of carbon:phosphorus (C:P) to examine how leaf identity and C:P interact to influence growth, consumption, assimilation efficiencies, and post-assimilatory processes. Tipula abdominalis growth and consumption varied with leaf type and stoichiometry. Individuals fed oak grew faster and ate more compared to individuals fed maple. Individuals fed maple grew faster and ate more as leaf C:P decreased. All individuals lost most of the material they assimilated through respiration and excretion regardless of leaf type or leaf stoichiometry. Consumption and growth rates of T. abdominalis increased with maple nutrient enrichment, but not oak, indicating leaf-specific nutrient enrichment affected leaf palatability. Slightly non-homeostatic T. abdominalis C:P was maintained by varied consumption, carbon assimilation, and P excretion. Our study underlines the importance of how detritivore consumption and post-assimilatory processing could influence whole-stream material storage and nutrient cycling in detrital-based ecosystems.

  14. Stoichiometry and assembly of mTOR complexes revealed by single-molecule pulldown.

    Science.gov (United States)

    Jain, Ankur; Arauz, Edwin; Aggarwal, Vasudha; Ikon, Nikita; Chen, Jie; Ha, Taekjip

    2014-12-16

    The mammalian target of rapamycin (mTOR) kinase is a master regulator of cellular, developmental, and metabolic processes. Deregulation of mTOR signaling is implicated in numerous human diseases including cancer and diabetes. mTOR functions as part of either of the two multisubunit complexes, mTORC1 and mTORC2, but molecular details about the assembly and oligomerization of mTORCs are currently lacking. We use the single-molecule pulldown (SiMPull) assay that combines principles of conventional pulldown assays with single-molecule fluorescence microscopy to investigate the stoichiometry and assembly of mTORCs. After validating our approach with mTORC1, confirming a dimeric assembly as previously reported, we show that all major components of mTORC2 exist in two copies per complex, indicating that mTORC2 assembles as a homodimer. Interestingly, each mTORC component, when free from the complexes, is present as a monomer and no single subunit serves as the dimerizing component. Instead, our data suggest that dimerization of mTORCs is the result of multiple subunits forming a composite surface. SiMPull also allowed us to distinguish complex disassembly from stoichiometry changes. Physiological conditions that abrogate mTOR signaling such as nutrient deprivation or energy stress did not alter the stoichiometry of mTORCs. On the other hand, rapamycin treatment leads to transient appearance of monomeric mTORC1 before complete disruption of the mTOR-raptor interaction, whereas mTORC2 stoichiometry is unaffected. These insights into assembly of mTORCs may guide future mechanistic studies and exploration of therapeutic potential.

  15. The Arabidopsis Cellulose Synthase Complex: A Proposed Hexamer of CESA Trimers in an Equimolar Stoichiometry

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Joseph L. [Pennsylvania State Univ., University Park, PA (United States); Hammudi, Mustafa B. [Pennsylvania State Univ., University Park, PA (United States); Tien, Ming [Pennsylvania State Univ., University Park, PA (United States)

    2014-12-01

    In this study, we show a 1:1:1 stoichiometry between the three Arabidopsis thaliana secondary cell wall isozymes: CESA4, CESA7, and CESA8. This ratio was determined utilizing a simple but elegant method of quantitative immunoblotting using isoform-specific antibodies and 35S-labeled protein standards for each CESA. Additionally, the observed equimolar stoichiometry was found to be fixed along the axis of the stem, which represents a developmental gradient. Our results complement recent spectroscopic analyses pointing toward an 18-chain cellulose microfibril. Taken together, we propose that the CSC is composed of a hexamer of catalytically active CESA trimers, with each CESA in equimolar amounts. This finding is a crucial advance in understanding how CESAs integrate to form higher order complexes, which is a key determinate of cellulose microfibril and cell wall properties.

  16. Effect of active component addition and support modification on catalytic activity of Ag/Al2O3 for the selective catalytic reduction of NOx by hydrocarbon - A review.

    Science.gov (United States)

    More, Pavan M

    2017-03-01

    The effect of active component addition and support modification of Ag/Al2O3 has been reviewed to examine their contribution to HC-SCR of NOx. This review has depicted the possible mechanisms of reduction of NO by hydrocarbon using metal/metal oxide doped Ag/Al2O3. The addition of second metal results in the maximum formation of well dispersed Agn(δ+) clusters. Specifically, addition of Au improves the low-temperature activity of the catalyst. However, the role of second metal also depends on the pretreatment to the catalyst and nature of the reductants. The support modification of Ag/Al2O3 by the addition of different metal oxides has also been reviewed. Modification by MgO showed improvement in activity besides sulfur tolerance. In situ DRIFT study demonstrates that the modification by MgO leads to the inhibition of sulfate formation of Ag and Al2O3. Enhancement in activity after second metal addition and support modification attributed to the synergistic effect and improved surface properties of Ag/Al2O3 catalyst.

  17. Experiences Teaching Stoichiometry to Students in Grades 10 and 11

    Science.gov (United States)

    Bridges, Cynthia Denise

    Many students have problems learning stoichiometry, a complex mathematical chemistry concept used to determine how much product will be produced or formed from a given quantity of reactants. The problem addressed in this study was teachers' lack of understanding of how to teach stoichiometry in a Midwestern urban school district. The conceptual framework of the study was based upon constructivist theory. A qualitative narrative approach was used to obtain the perceptions of 5 high school chemistry instructors related to their experiences, successful or unsuccessful, in teaching stoichiometry to students in Grades 10 and 11. Data were gathered through face-to-face interviews, which were analyzed via an inductive approach to reveal 6 themes: a difficult subject to teach, presentation of stoichiometry, relevancy, students' reactions, barriers, and gender differences. Findings suggested the need for teachers to be knowledgeable, creative, and resourceful in their subject areas to help their students to learn stoichiometry. Findings also revealed the need for teachers to adapt their instructional strategies and modes of delivery to reflect their students' individual learning styles. Understanding how the participating teachers explained stoichiometry to their students might help other chemistry teachers to examine and adapt their own instructional styles and delivery methods of the concept. This understanding might, in term, help to improve student achievement in stoichiometry in particular and chemistry in general.

  18. Stoichiometry of the KCNQ1 - KCNE1 ion channel complex.

    Science.gov (United States)

    Nakajo, Koichi; Ulbrich, Maximilian H; Kubo, Yoshihiro; Isacoff, Ehud Y

    2010-11-02

    The KCNQ1 voltage-gated potassium channel and its auxiliary subunit KCNE1 play a crucial role in the regulation of the heartbeat. The stoichiometry of KCNQ1 and KCNE1 complex has been debated, with some results suggesting that the four KCNQ1 subunits that form the channel associate with two KCNE1 subunits (a 42 stoichiometry), while others have suggested that the stoichiometry may not be fixed. We applied a single molecule fluorescence bleaching method to count subunits in many individual complexes and found that the stoichiometry of the KCNQ1 - KCNE1 complex is flexible, with up to four KCNE1 subunits associating with the four KCNQ1 subunits of the channel (a 44 stoichiometry). The proportion of the various stoichiometries was found to depend on the relative expression densities of KCNQ1 and KCNE1. Strikingly, both the voltage-dependence and kinetics of gating were found to depend on the relative densities of KCNQ1 and KCNE1, suggesting the heart rhythm may be regulated by the relative expression of the auxiliary subunit and the resulting stoichiometry of the channel complex.

  19. Synthesis and control of morphology, stoichiometry, and composition of transition metal oxides

    Science.gov (United States)

    Brier, Matthew Isaac

    Transition metal oxides (TMOs) are an important class of materials that have found uses in diverse applications, such as heterogeneous catalysts, sensors, and high temperature superconductors, due to their complex surface chemistry and high mobility of lattice oxygen atoms. Point defects such as oxygen and metal atom vacancies significantly perturb the electronic structure of TMOs and profoundly impact their electrical, optical, ferroelectric, photocatalytic, and other functional properties. As a result, significant research is being done to develop synthesis techniques that can produce metal oxides with controllable material properties. In this thesis, the use of hot wire chemical vapor deposition (HWCVD) was studied with the aim of precisely controlling the morphology, stoichiometry, and composition of TMOs. With molybdenum oxide as the model system, the control of morphology and stoichiometry was achieved by modulation of deposition parameters, such as filament power and gas phase composition. The study of HWCVD of MoOx led to the development of phase diagrams for the dependence of morphology and stoichiometry on deposition parameters. The knowledge gained studying the HWCVD of MoOx was then shown to translate to the deposition of other binary metal oxides by using tungsten, nickel, and vanadium metal filaments to synthesize their respective transition metal oxides. Additionally, NiMoO4 was synthesized as a proof-of-concept to show that HWCVD can be used to make ternary oxides. Nitridation of samples in an ammonia atmosphere was conducted to explore the potential for conversion of HWCVD grown TMOs to their respective metal nitrides, which are also reported to have catalytic properties. To examine the quality of TMOs grown by HWCVD, samples were electrochemically tested for their electrochromic properties and photoactivity with respect to splitting of water.

  20. A general method for determining secondary active transporter substrate stoichiometry.

    Science.gov (United States)

    Fitzgerald, Gabriel A; Mulligan, Christopher; Mindell, Joseph A

    2017-01-25

    The number of ions required to drive substrate transport through a secondary active transporter determines the protein's ability to create a substrate gradient, a feature essential to its physiological function, and places fundamental constraints on the transporter's mechanism. Stoichiometry is known for a wide array of mammalian transporters, but, due to a lack of readily available tools, not for most of the prokaryotic transporters for which high-resolution structures are available. Here, we describe a general method for using radiolabeled substrate flux assays to determine coupling stoichiometries of electrogenic secondary active transporters reconstituted in proteoliposomes by measuring transporter equilibrium potentials. We demonstrate the utility of this method by determining the coupling stoichiometry of VcINDY, a bacterial Na(+)-coupled succinate transporter, and further validate it by confirming the coupling stoichiometry of vSGLT, a bacterial sugar transporter. This robust thermodynamic method should be especially useful in probing the mechanisms of transporters with available structures.

  1. Unifying elemental stoichiometry and metabolic theory in predicting species abundances.

    Science.gov (United States)

    Ott, David; Digel, Christoph; Rall, Björn C; Maraun, Mark; Scheu, Stefan; Brose, Ulrich

    2014-10-01

    While metabolic theory predicts variance in population density within communities depending on population average body masses, the ecological stoichiometry concept relates density variation across communities to varying resource stoichiometry. Using a data set including biomass densities of 4959 populations of soil invertebrates across 48 forest sites we combined these two frameworks. We analyzed how the scaling of biomass densities with population-averaged body masses systematically interacts with stoichiometric variables. Simplified analyses employing either only body masses or only resource stoichiometry are highly context sensitive and yield variable and often misleading results. Our findings provide strong evidence that analyses of ecological state variables should integrate allometric and stoichiometric variables to explain deviations from predicted allometric scaling and avoid erroneous conclusions. In consequence, our study provides an important step towards unifying two prominent ecological theories, metabolic theory and ecological stoichiometry.

  2. Pulse-shaping based two-photon FRET stoichiometry.

    Science.gov (United States)

    Flynn, Daniel C; Bhagwat, Amar R; Brenner, Meredith H; Núñez, Marcos F; Mork, Briana E; Cai, Dawen; Swanson, Joel A; Ogilvie, Jennifer P

    2015-02-09

    Förster Resonance Energy Transfer (FRET) based measurements that calculate the stoichiometry of intermolecular interactions in living cells have recently been demonstrated, where the technique utilizes selective one-photon excitation of donor and acceptor fluorophores to isolate the pure FRET signal. Here, we present work towards extending this FRET stoichiometry method to employ two-photon excitation using a pulse-shaping methodology. In pulse-shaping, frequency-dependent phases are applied to a broadband femtosecond laser pulse to tailor the two-photon excitation conditions to preferentially excite donor and acceptor fluorophores. We have also generalized the existing stoichiometry theory to account for additional cross-talk terms that are non-vanishing under two-photon excitation conditions. Using the generalized theory we demonstrate two-photon FRET stoichiometry in live COS-7 cells expressing fluorescent proteins mAmetrine as the donor and tdTomato as the acceptor.

  3. The glycosylation stoichiometry of EWS species in neuronal cells.

    Science.gov (United States)

    Kamemura, Kazuo; Abe, Hiromi

    2017-01-01

    Although Ewing sarcoma protein (EWS) is known to be glycosylated by O-linked β-N-acetylglucosamine (O-GlcNAc), the dynamics and stoichiometry of its glycosylation remain obscure. Here, we report a dynamic change in the glycosylation stoichiometry of EWS species during neuronal differentiation of embryonic carcinoma P19 cells. Our findings suggest that O-GlcNAc glycosylation participates in the regulation of EWS functions in neuronal cells.

  4. SYNTHESIS OF cis-1, 4-POLYBUTADIENE WITH NICKEL CATALYST INVESTIGATIONS ON INTERACTIONS BETWEEN THE CATALYTIC COMPONENTS BY USING UV-VIS SPECTRUM

    Institute of Scientific and Technical Information of China (English)

    CHEN Dianbao; XU Guang; TANG Xuerning

    1987-01-01

    Ni(Ⅱ) naphthenate in hydrogenated gasoline or toluene will appear light green, which is the result of absorption in the red and blue bands of the spectrum. The three peaks caused by the spin-allowed d-d transitions are 403, 680, and 1170nm respectively, and are similar to those of Ni(H2O)6+2. The configuration of Ni(Ⅱ) complex is octahedral.In a two-component system of Ni(naph)2-Al(i-Bu)3, the naphthenate ligand attached to Ni(Ⅱ) can be exchanged for the alkyl group on tri-isobutylaluminium, if Al(i-Bu)3/Ni(naph)2 in a systemcontaining metalalkyl and naphthenate does not exceed the value of 0.53. At a higher ratio, Al(i-Bu)3/Ni(naph)2>0.53,Ni(Ⅱ) is reduced to Ni(Ⅰ) and Ni(O).In a two-component system Ni(naph)2-BF3·OEt2, a part of the naphthenate can be exchanged for halogen. A new Ni(Ⅱ) complex is formed, which consists of three new d-d bands in the region 360-1660 nm.

  5. "Why not stoichiometry" versus "stoichiometry--why not?" Part I: General context.

    Science.gov (United States)

    Michałowska-Kaczmarczyk, Anna Maria; Asuero, Agustin G; Michałowski, Tadeusz

    2015-01-01

    The elementary concepts involved with stoichiometry are considered from different viewpoints. Some examples of approximate calculations made according to the stoichiometric scheme are indicated, and correct resolution of the problems involved is presented. The principles of balancing chemical equations, based on their apparent similarities with algebraic equations, are criticized. The review concerns some peculiarities inherent in chemical reaction notation and its use (and abuse) in stoichiometric calculations that provide inconsistent results for various reasons. This "conventional" approach to stoichiometry is put in context with the generalized approach to electrolytic systems (GATES) established by Michałowski. The article contains a number of proposals that could potentially be taken into account and included in the next edition of the Orange Book. Notation of ions used in this article is not, deliberately, in accordance with actual IUPAC requirements in this respect. This article is intended to be provocative with the hope that some critical debate around the important topics treated should be generated and creatively expanded in the scientific community.

  6. Irradiation-induced effects of proton irradiation on zirconium carbides with different stoichiometries

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Y., E-mail: na.huang@materials.ox.ac.uk [Engineering Physics Department, University of Wisconsin-Madison, WI 53706 (United States); Maier, B.R. [Engineering Physics Department, University of Wisconsin-Madison, WI 53706 (United States); Allen, T.R. [Engineering Physics Department, University of Wisconsin-Madison, WI 53706 (United States); Idaho National Laboratory, Idaho Falls, ID 83415 (United States)

    2014-10-01

    Highlights: • ZrC{sub x} with four different stoichiometries (x = 0.9–1.2 with 0.1 step) were studied. • Proton irradiation at 800 °C introduced large amount of dislocation loops. • No voids were found before or after irradiation. • Dislocation loops size distribution and density varied with stoichiometry. - Abstract: Zirconium carbide (ZrC) is being considered for utilization in deep burn TRISO fuel particles for high-temperature, gas-cooled reactors. Zirconium carbide has a cubic B1 type crystal structure along with a very high melting point (3420 °C), exceptional hardness and good thermal and electrical conductivities. Understanding the ZrC irradiation response is crucial for establishing ZrC as an alternative component in TRISO fuel. Until now, very few studies on irradiation effects on ZrC have been released and fundamental aspects of defect evolution and kinetics are not well understood although some atomistic simulations and phenomenological studies have been performed. This work was carried out to understand the damage evolution in float-zone refined ZrC with different stoichiometries. Proton irradiations at 800 °C up to doses of 3 dpa were performed on ZrC{sub x} (where x ranges from 0.9 to 1.2) to investigate the damage evolution. The irradiation-induced defects, such as density of dislocation loops, at different stoichiometries and doses which were characterized by transmission electron microscopy (TEM) is presented and discussed.

  7. Catalytic properties of the resolved flavoprotein and cytochrome B components of the NADPH dependent O2- . generating oxidase from human neutrophils.

    Science.gov (United States)

    Gabig, T G; Lefker, B A

    1984-01-30

    The resolved flavoprotein and cytochrome b559 components of the NADPH dependent O2- . generating oxidase from human neutrophils were the subject of further study. The resolved flavoprotein, depleted of cytochrome b559, was reduced by NADPH under anaerobic conditions and reoxidized by oxygen. NADPH dependent O2- . generation by the resolved flavoprotein fraction was not detectable, however it was competent in the transfer of electrons from NADPH to artificial electron acceptors. The resolved cytochrome b559, depleted of flavoprotein, demonstrated no measureable NADPH dependent O2- . generating activity and was not reduced by NADPH under anaerobic conditions. The dithionite reduced form of the resolved cytochrome b559 was rapidly oxidized by oxygen, as was the cytochrome b559 in the intact oxidase.

  8. Morphological Dependence of Element Stoichiometry in the H. americanus Exoskeleton

    Science.gov (United States)

    Mergelsberg, S. T.; Ulrich, R. N.; Dove, P. M.

    2016-02-01

    The crustacean exoskeleton is a complex biocomposite of inorganic mineral and organic macromolecules that expresses highly divergent morphologies across different taxa. While the structures and compositions of the organic framework show complex links to environmental and developmental pressures, little is known about the mineral chemistry. Previous studies of the cuticle have assumed that magnesium, phosphorous, and other trace metals are largely contained in the inorganic mineral fraction. Due to analytical limitations of structural analyses and in situ spectroscopic methods, the stoichiometry of the organic and inorganic portions could not be resolved. For example, previous Raman and XRD studies conclude the higher concentrations of trace elements, such as P and Mg measured in reinforced structures, e.g. the claw and abdomen, are primarily determined by the mineral fraction. Using the American Lobster (Homarus americanus) as a model organism to establish relationships between body part function and cuticle composition, this study quantified the distributions of Mg and P in the mineral and organic fractions. The experiments were designed to dissolve the exoskeleton of 10 body parts using three types of solutions that were specific to extracting 1) the mineral phase, 2) protein, and 3) polysaccharide. Analysis of the solutions by ICP-OES shows the mineral phase contains magnesium and phosphorous at concentrations sufficient to support the formation of calcium-magnesium and phosphate minerals. The protein fraction of the body parts contains significantly more Mg and P than previously hypothesized, while the levels of P contained in the organic portion are fairly constant. The findings demonstrate the lobster cuticle contains a significant amount of non-mineralized P and Mg that is readily water-soluble in the protein component. However, for those body parts used for defense and food acquisition, such as the claw, the mineral component determines the overall

  9. ZSM-5催化生物质三组分和松木热解生物油组分分析%Component analysis of pyrolysis bio-oil from three major components of biomass andPinus yunnanensisby ZSM-5 catalytic

    Institute of Scientific and Technical Information of China (English)

    王霏; 郑云武; 黄元波; 杨晓琴; 刘灿; 徐高峰; 郑志锋

    2016-01-01

    In order to study the catalytic pyrolysis process of the three components(Cellulose, hemicellulose and lignin) with participation of mesoporous ZSM-5, Firstly the pyrolysis of three major components in biomass and wood powder ofPinus yunnanensis were conducted. Then catalytic pyrolysis of the three major components (microcrystalline cellulose, xylan and alkali lignin) and wood powder ofPinus yunnanensiswere carried out with the mesoporous ZSM-5 as catalyst. Compositions of the derived bio-oil were identified by gas chromatograph-mass spectrometer (GC-MS). By comparing the product distribution in bio-oil between pyrolysis and catalytic pyrolysis of three major components and wood powder, the catalytic pyrolysis mechanism of biomass was studied. What is more, ZSM-5 was analyzed by N2 adsorption-desorption and XRD diffraction, and ultimate analysis of bio-oil obtained were also identified. The results indicated that during catalytic pyrolysis of three major components andPinus yunnanensis, mesoporous ZSM-5 showed different performance. The results of XRD diffraction pattern and N2absorption/desorption demonstrated ZSM-5 used had abundant mesopores with mean pore size of 6.23nm. Through pyrolysis cellulose was mainly converted intoβ-D-allose (20.39%), furfural, 2,6-di-tert-butyl-4-methylphenol, 3-propyl glutaric acid, and 2,4-Pentadienoic acid. In the process of catalytic pyrolysis, ZSM-5 transformedβ-D-allose (20.39%), furfural, 3-Propyl glutaric acid, and 2,4-Pentadienoic acid into 1-methylnaphthalene and 2,6-dimethylnaphthalene. ZSM-5 performed the supreme catalytic activity for cellulose among 4 feedstocks, and the relative content of total aromatics in bio-oil obtained from catalytic pyrolysis of cellulose was 63.89%. The raw bio-oil from hemicellulose pyrolysis mainly contained furfural (67.78%) and 2,6-di-tert-butyl-4-methylphenol. But in the course of catalytic pyrolysis, the relative content of furfural reduced drastically to 2.66% while the relative content

  10. Catalytic microrotor driven by geometrical asymmetry

    Science.gov (United States)

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke

    2015-02-01

    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  11. Method and apparatus for monitoring a hydrocarbon-selective catalytic reduction device

    Science.gov (United States)

    Schmieg, Steven J; Viola, Michael B; Cheng, Shi-Wai S; Mulawa, Patricia A; Hilden, David L; Sloane, Thompson M; Lee, Jong H

    2014-05-06

    A method for monitoring a hydrocarbon-selective catalytic reactor device of an exhaust aftertreatment system of an internal combustion engine operating lean of stoichiometry includes injecting a reductant into an exhaust gas feedstream upstream of the hydrocarbon-selective catalytic reactor device at a predetermined mass flowrate of the reductant, and determining a space velocity associated with a predetermined forward portion of the hydrocarbon-selective catalytic reactor device. When the space velocity exceeds a predetermined threshold space velocity, a temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is determined, and a threshold temperature as a function of the space velocity and the mass flowrate of the reductant is determined. If the temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is below the threshold temperature, operation of the engine is controlled to regenerate the hydrocarbon-selective catalytic reactor device.

  12. Variable stoichiometry with thermodynamic control in ADM1.

    Science.gov (United States)

    Rodríguez, J; Lema, J M; van Loosdrecht, M C M; Kleerebezem, R

    2006-01-01

    The effect of a variable stoichiometry of the carbohydrate fermentation process in the IWA Anaerobic Digestion Model No.1 (ADM1) is investigated. Most existing anaerobic digestion models including ADM1 consider a fixed-stoichiometry for their conversion processes. The ADM1 model was first transformed into an only mol based model to remove some errors derived from the mixed COD-mol based standard model and to allow for implementation of the variable stoichiometry. Consequently, the values of the butyrate and acetate catabolic yields of carbohydrate fermentation are made dependent on the hydrogen concentration and the reactor pH according to the predictions of a recently developed mixed culture fermentation model based on thermodynamic considerations. The simulation results obtained showed no significantly different responses in terms of effluent quality and system robustness between the standard and the variable stoichiometry ADM1 under overload conditions, and for both single- and two-step anaerobic digestion configurations. This behaviour is explained by the non-limiting acetogenic activity that compensated for the changes in the acidogenic products, typical behaviour for serial processes close to equilibrium. Based on the results obtained, thermodynamic rather than kinetic control for these conversions is suggested. Depending on the objectives to be met, lumping of carbohydrate fermenters and oxidative acetogens into a single biomass group with a variable stoichiometry is proposed for further consideration.

  13. Possible involvement of membrane lipids peroxidation and oxidation of catalytically essential thiols of the cerebral transmembrane sodium pump as component mechanisms of iron-mediated oxidative stress-linked dysfunction of the pump's activity

    Directory of Open Access Journals (Sweden)

    T.I. Omotayo

    2015-04-01

    Full Text Available The precise molecular events defining the complex role of oxidative stress in the inactivation of the cerebral sodium pump in radical-induced neurodegenerative diseases is yet to be fully clarified and thus still open. Herein we investigated the modulation of the activity of the cerebral transmembrane electrogenic enzyme in Fe2+-mediated in vitro oxidative stress model. The results show that Fe2+ inhibited the transmembrane enzyme in a concentration dependent manner and this effect was accompanied by a biphasic generation of aldehydic product of lipid peroxidation. While dithiothreitol prevented both Fe2+ inhibitory effect on the pump and lipid peroxidation, vitamin E prevented only lipid peroxidation but not inhibition of the pump. Besides, malondialdehyde (MDA inhibited the pump by a mechanism not related to oxidation of its critical thiols. Apparently, the low activity of the pump in degenerative diseases mediated by Fe2+ may involve complex multi-component mechanisms which may partly involve an initial oxidation of the critical thiols of the enzyme directly mediated by Fe2+ and during severe progression of such diseases; aldehydic products of lipid peroxidation such as MDA may further exacerbate this inhibitory effect by a mechanism that is likely not related to the oxidation of the catalytically essential thiols of the ouabain-sensitive cerebral electrogenic pump.

  14. Detecting stoichiometry of macromolecular complexes in live cells using FRET

    Science.gov (United States)

    Ben-Johny, Manu; Yue, Daniel N.; Yue, David T.

    2016-01-01

    The stoichiometry of macromolecular interactions is fundamental to cellular signalling yet challenging to detect from living cells. Fluorescence resonance energy transfer (FRET) is a powerful phenomenon for characterizing close-range interactions whereby a donor fluorophore transfers energy to a closely juxtaposed acceptor. Recognizing that FRET measured from the acceptor's perspective reports a related but distinct quantity versus the donor, we utilize the ratiometric comparison of the two to obtain the stoichiometry of a complex. Applying this principle to the long-standing controversy of calmodulin binding to ion channels, we find a surprising Ca2+-induced switch in calmodulin stoichiometry with Ca2+ channels—one calmodulin binds at basal cytosolic Ca2+ levels while two calmodulins interact following Ca2+ elevation. This feature is curiously absent for the related Na channels, also potently regulated by calmodulin. Overall, our assay adds to a burgeoning toolkit to pursue quantitative biochemistry of dynamic signalling complexes in living cells. PMID:27922011

  15. Non-stoichiometry in U3Si2

    Science.gov (United States)

    Middleburgh, S. C.; Grimes, R. W.; Lahoda, E. J.; Stanek, C. R.; Andersson, D. A.

    2016-12-01

    Uranium silicides, in particular U3Si2, are being explored as an advanced nuclear fuel with increased accident tolerance as well as competitive economics compared to the baseline UO2 fuel. Here we use density functional theory calculations and thermochemical analysis to assess the stability of U3Si2 with respect to non-stoichiometry reactions in both the hypo- and hyper-stoichiometric regimes. We find that the degree of non-stoichiometry in U3Si2 is much smaller than in UO2 and at most reaches a few percent at high temperature. Non-stoichiometry impacts fuel performance by determining whether the loss of uranium due to fission leads to a non-stoichiometric U3Si2±x phase or precipitation of a second U-Si phase. We also investigate the U5Si4 phase as a candidate for the equilibrium phase diagram.

  16. Stoichiometries of remineralisation and denitrification in global biogeochemical ocean models

    Directory of Open Access Journals (Sweden)

    A. Paulmier

    2009-05-01

    Full Text Available Since the seminal paper of Redfield (1934, constant stoichiometric elemental ratios linking biotic carbon and nutrient fluxes are often assumed in marine biogeochemistry, and especially in coupled biogeochemical circulation models, to couple the global oxygen, carbon and nutrient cycles. However, when looking in more detail, some deviations from the classical Redfield stoichiometry have been reported, in particular with respect to remineralization of organic matter changing with depth or with ambient oxygen levels. We here compare the assumptions about the stoichiometry of organic matter and its remineralization that are used explicitly and implicitly in common biogeochemical ocean models. We find that the implicit assumptions made about the hydrogen content of organic matter can lead to inconsistencies in the modeled remineralization and denitrification stoichiometries. It is suggested that future marine biogeochemical models explicitly state the chemical composition assumed for the organic matter, including its oxygen and hydrogen content.

  17. Direct measurement of oxygen stoichiometry in perovskite films

    Science.gov (United States)

    Scola, J.; Benamar, A.; Berini, B.; Jomard, F.; Dumont, Y.

    2017-02-01

    We present a direct method to measure the oxygen stoichiometry in an oxide film with an accuracy of about 2%. It is based on a combination of 18O annealing and high mass resolution secondary ion mass spectroscopy. Calibration has been done on a LaNiO3 film whose electrical properties dependence on oxygen stoichiometry are well documented. The method is illustrated with a series of LaNiO3 films grown on SrTiO3 substrates prepared with different oxygen stoichiometries. The large influence of the surface state on oxygen exchange is evidenced in films grown on different substrate orientations or coated with a thin layer of LaAlO3. Oxygen surface exchange and bulk diffusion is then discussed for both LaNiO3 and SrVO3 films.

  18. Maximizing the efficiency of multienzyme process by stoichiometry optimization.

    Science.gov (United States)

    Dvorak, Pavel; Kurumbang, Nagendra P; Bendl, Jaroslav; Brezovsky, Jan; Prokop, Zbynek; Damborsky, Jiri

    2014-09-05

    Multienzyme processes represent an important area of biocatalysis. Their efficiency can be enhanced by optimization of the stoichiometry of the biocatalysts. Here we present a workflow for maximizing the efficiency of a three-enzyme system catalyzing a five-step chemical conversion. Kinetic models of pathways with wild-type or engineered enzymes were built, and the enzyme stoichiometry of each pathway was optimized. Mathematical modeling and one-pot multienzyme experiments provided detailed insights into pathway dynamics, enabled the selection of a suitable engineered enzyme, and afforded high efficiency while minimizing biocatalyst loadings. Optimizing the stoichiometry in a pathway with an engineered enzyme reduced the total biocatalyst load by an impressive 56 %. Our new workflow represents a broadly applicable strategy for optimizing multienzyme processes.

  19. The Single-Molecule Approach to Membrane Protein Stoichiometry.

    Science.gov (United States)

    Nichols, Michael G; Hallworth, Richard

    2016-01-01

    The advent of techniques for imaging solitary fluorescent molecules has made possible many new kinds of biological experiments. Here, we describe the application of single-molecule imaging to the problem of subunit stoichiometry in membrane proteins. A membrane protein of unknown stoichiometry, prestin, is coupled to the fluorescent enhanced green fluorescent protein (eGFP) and synthesized in the human embryonic kidney (HEK) cell line. We prepare adherent membrane fragments containing prestin-eGFP by osmotic lysis. The molecules are then exposed to continuous low-level excitation until their fluorescence reaches background levels. Their fluorescence decreases in discrete equal-amplitude steps, consistent with the photobleaching of single fluorophores. We count the number of steps required to photobleach each molecule. The molecular stoichiometry is then deduced using a binomial model.

  20. Revised Ion/Substrate Coupling Stoichiometry of GABA Transporters.

    Science.gov (United States)

    Eskandari, Sepehr; Willford, Samantha L; Anderson, Cynthia M

    2017-01-01

    The purpose of this review is to highlight recent evidence in support of a 3 Na(+): 1 Cl(-): 1 GABA coupling stoichiometry for plasma membrane GABA transporters (SLC6A1 , SLC6A11 , SLC6A12 , SLC6A13 ) and how the revised stoichiometry impacts our understanding of the contribution of GABA transporters to GABA homeostasis in synaptic and extrasynaptic regions in the brain under physiological and pathophysiological states. Recently, our laboratory probed the GABA transporter stoichiometry by analyzing the results of six independent measurements, which included the shifts in the thermodynamic transporter reversal potential caused by changes in the extracellular Na(+), Cl(-), and GABA concentrations, as well as the ratio of charge flux to substrate flux for Na(+), Cl(-), and GABA under voltage-clamp conditions. The shifts in the transporter reversal potential for a tenfold change in the external concentration of Na(+), Cl(-), and GABA were 84 ± 4, 30 ± 1, and 29 ± 1 mV, respectively. Charge flux to substrate flux ratios were 0.7 ± 0.1 charges/Na(+), 2.0 ± 0.2 charges/Cl(-), and 2.1 ± 0.1 charges/GABA. We then compared these experimental results with the predictions of 150 different transporter stoichiometry models, which included 1-5 Na(+), 0-5 Cl(-), and 1-5 GABA per transport cycle. Only the 3 Na(+): 1 Cl(-): 1 GABA stoichiometry model correctly predicts the results of all six experimental measurements. Using the revised 3 Na(+): 1 Cl(-): 1 GABA stoichiometry, we propose that the GABA transporters mediate GABA uptake under most physiological conditions. Transporter-mediated GABA release likely takes place under pathophysiological or extreme physiological conditions.

  1. Catalytic Chemistry on Oxide Nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Asthagiri, Aravind; Dixon, David A.; Dohnalek, Zdenek; Kay, Bruce D.; Rodriquez, Jose A.; Rousseau, Roger J.; Stacchiola, Dario; Weaver, Jason F.

    2016-05-29

    Metal oxides represent one of the most important and widely employed materials in catalysis. Extreme variability of their chemistry provides a unique opportunity to tune their properties and to utilize them for the design of highly active and selective catalysts. For bulk oxides, this can be achieved by varying their stoichiometry, phase, exposed surface facets, defect, dopant densities and numerous other ways. Further, distinct properties from those of bulk oxides can be attained by restricting the oxide dimensionality and preparing them in the form of ultrathin films and nanoclusters as discussed throughout this book. In this chapter we focus on demonstrating such unique catalytic properties brought by the oxide nanoscaling. In the highlighted studies planar models are carefully designed to achieve minimal dispersion of structural motifs and to attain detailed mechanistic understanding of targeted chemical transformations. Detailed level of morphological and structural characterization necessary to achieve this goal is accomplished by employing both high-resolution imaging via scanning probe methods and ensemble-averaged surface sensitive spectroscopic methods. Three prototypical examples illustrating different properties of nanoscaled oxides in different classes of reactions are selected.

  2. Determination of the upper and lower limits of the mechanistic stoichiometry of incompletely coupled fluxes. Stoichiometry of incompletely coupled reactions.

    Science.gov (United States)

    Beavis, A D; Lehninger, A L

    1986-07-15

    A rationale is formulated for the design of experiments to determine the upper and lower limits of the mechanistic stoichiometry of any two incompletely coupled fluxes J1 and J2. Incomplete coupling results when there is a branch at some point in the sequence of reactions or processes coupling the two fluxes. The upper limit of the mechanistic stoichiometry is given by the minimum value of dJ2/dJ1 obtained when the fluxes are systematically varied by changes in steps after the branch point. The lower limit is given by the maximum value of dJ2/dJ1 obtained when the fluxes are varied by changes in steps prior to the branch point. The rationale for determining these limits is developed from both a simple kinetic model and from a linear nonequilibrium thermodynamic treatment of coupled fluxes, using the mechanistic approach [Westerhoff, H. V. & van Dam, K. (1979) Curr. Top. Bioenerg. 9, 1-62]. The phenomenological stoichiometry, the flux ratio at level flow and the affinity ratio at static head of incompletely coupled fluxes are defined in terms of mechanistic conductances and their relationship to the mechanistic stoichiometry is discussed. From the rationale developed, experimental approaches to determine the mechanistic stoichiometry of mitochondrial oxidative phosphorylation are outlined. The principles employed do not require knowledge of the pathway or the rate of transmembrane leaks or slippage and may also be applied to analysis of the stoichiometry of other incompletely coupled systems, including vectorial H+/O and K+/O translocation coupled to mitochondrial electron transport.

  3. Assessment of the Stoichiometry of Multicomponent Crystals Using Only X-ray Powder Diffraction Data.

    Science.gov (United States)

    Maguire, Courtney K; Brunskill, Andrew P J

    2015-06-01

    Knowledge of the unit cell volume of a crystalline form and the expected space filling requirements of an API molecule can be used to determine if a crystalline material is likely to be multicomponent, such as a solvate, hydrate, salt, or a co-crystal. The unit cell information can be readily accessed from powder diffraction data alone utilizing powder indexing methodology. If the unit cell has additional space not likely attributable to the API entity, then there is either a void or another component within the crystal lattice. This "leftover" space can be used to determine the likely stoichiometry of the additional component. A simple approach for calculating the expected required volume for a given molecule within a crystal using an atom based additive approach will be discussed. Coupling this estimation with the actual unit cell volumes and space group information obtained from powder indexing allows for the rapid evaluation of the likely stoichiometry of multicomponent crystals using diffraction data alone. This approach is particularly useful for the early assessment of new phases during salt, co-crystal, and polymorph screening, and also for the characterization of stable and unstable solvates.

  4. Stoichiometry of a semi-aquatic plethodontid salamander: Intraspecific variation due to location, size and diet

    Science.gov (United States)

    Ecological stoichiometry provides a framework to investigate an organism's relationship to nutrient cycles. An organism's stoichiometry is thought to constrain its contribution to nutrient cycles (recycling or storage), and to limit its growth and reproduction. Factors that influ...

  5. Stoichiometry of a semi-aquatic plethodontid salamander: Intraspecific variation due to location, size and diet

    Science.gov (United States)

    Ecological stoichiometry provides a framework to investigate an organism's relationship to nutrient cycles. An organism's stoichiometry is thought to constrain its contribution to nutrient cycles (recycling or storage), and to limit its growth and reproduction. Factors that influ...

  6. Stoichiometry of the KCNQ1 − KCNE1 ion channel complex

    National Research Council Canada - National Science Library

    Koichi Nakajo; Maximilian H. Ulbrich; Yoshihiro Kubo; Ehud Y. Isacoff; Lily Yeh Jan

    2010-01-01

    .... The stoichiometry of KCNQ1 and KCNE1 complex has been debated, with some results suggesting that the four KCNQ1 subunits that form the channel associate with two KCNE1 subunits (a 4∶2 stoichiometry...

  7. Controlling the stoichiometry and doping of semiconductor materials

    Science.gov (United States)

    Albin, David; Burst, James; Metzger, Wyatt; Duenow, Joel; Farrell, Stuart; Colegrove, Eric

    2016-08-16

    Methods for treating a semiconductor material are provided. According to an aspect of the invention, the method includes annealing the semiconductor material in the presence of a compound that includes a first element and a second element. The first element provides an overpressure to achieve a desired stoichiometry of the semiconductor material, and the second element provides a dopant to the semiconductor material.

  8. Ecoenzymatic Stoichiometry of Stream Sediments with Comparison to Terrestrial Soils

    Science.gov (United States)

    In this study, we extend the development of ecoenzymatic stoichiometry to the surface sediments of stream ecosystems using data collected in a nationwide survey. The data set is larger and more comprehensive than those used in our previous studies. The data include the first broa...

  9. Stoichiometry controlled oxide thin film growth by pulsed laser deposition

    NARCIS (Netherlands)

    Groenen, Rik; Smit, Jasper; Orsel, Kasper; Vailionis, Arturas; Bastiaens, Bert; Huijben, Mark; Boller, Klaus; Rijnders, Guus; Koster, Gertjan

    2015-01-01

    The oxidation of species in the plasma plume during pulsed laser deposition controls both the stoichiometry as well as the growth kinetics of the deposited SrTiO3 thin films, instead of the commonly assumed mass distribution in the plasma plume and the kinetic energy of the arriving species. It was

  10. Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry

    Science.gov (United States)

    Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.

    2010-01-01

    Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…

  11. Quantitative Localization Microscopy: Effects of Photophysics and Labeling Stoichiometry

    NARCIS (Netherlands)

    Nieuwenhuizen, R.P.J.; Bates, M.; Szymborska, A.; Lidke, K.A.; Rieger, B.; Stallinga, S.

    2015-01-01

    Quantification in localization microscopy with reversibly switchable fluorophores is severely hampered by the unknown number of switching cycles a fluorophore undergoes and the unknown stoichiometry of fluorophores on a marker such as an antibody. We overcome this problem by measuring the average nu

  12. A general method for determining secondary active transporter substrate stoichiometry

    Science.gov (United States)

    Fitzgerald, Gabriel A; Mulligan, Christopher; Mindell, Joseph A

    2017-01-01

    The number of ions required to drive substrate transport through a secondary active transporter determines the protein’s ability to create a substrate gradient, a feature essential to its physiological function, and places fundamental constraints on the transporter’s mechanism. Stoichiometry is known for a wide array of mammalian transporters, but, due to a lack of readily available tools, not for most of the prokaryotic transporters for which high-resolution structures are available. Here, we describe a general method for using radiolabeled substrate flux assays to determine coupling stoichiometries of electrogenic secondary active transporters reconstituted in proteoliposomes by measuring transporter equilibrium potentials. We demonstrate the utility of this method by determining the coupling stoichiometry of VcINDY, a bacterial Na+-coupled succinate transporter, and further validate it by confirming the coupling stoichiometry of vSGLT, a bacterial sugar transporter. This robust thermodynamic method should be especially useful in probing the mechanisms of transporters with available structures. DOI: http://dx.doi.org/10.7554/eLife.21016.001 PMID:28121290

  13. Electrochemical determination of oxygen stoichiometry and entropy in oxides

    DEFF Research Database (Denmark)

    Zachau-Christiansen, Birgit; Jacobsen, Torben; Skaarup, Steen

    1996-01-01

    The oxygen stoichiometry of CeO2 and Ce0.82Gd0.18O1.91 is determined by a combination of cyclic voltammetry and coulometric titration. The electrochemical cell employed is an oxygen pumping cell, in which the oxide is subjected to different oxygen pressures corresponding to the potential imposed...

  14. Calcite growth kinetics: Modeling the effect of solution stoichiometry

    NARCIS (Netherlands)

    Wolthers, M.; Nehrke, G.; Gustafsson, J.P.; Van Cappellen, P.

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth rat

  15. Ecoenzymatic Stoichiometry of Stream Sediments with Comparison to Terrestrial Soils

    Science.gov (United States)

    In this study, we extend the development of ecoenzymatic stoichiometry to the surface sediments of stream ecosystems using data collected in a nationwide survey. The data set is larger and more comprehensive than those used in our previous studies. The data include the first broa...

  16. Quantitative Localization Microscopy: Effects of Photophysics and Labeling Stoichiometry

    NARCIS (Netherlands)

    Nieuwenhuizen, R.P.J.; Bates, M.; Szymborska, A.; Lidke, K.A.; Rieger, B.; Stallinga, S.

    2015-01-01

    Quantification in localization microscopy with reversibly switchable fluorophores is severely hampered by the unknown number of switching cycles a fluorophore undergoes and the unknown stoichiometry of fluorophores on a marker such as an antibody. We overcome this problem by measuring the average nu

  17. Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry

    Science.gov (United States)

    Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.

    2010-01-01

    Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…

  18. A simple nutrient-dependence mechanism for predicting the stoichiometry of marine ecosystems.

    Science.gov (United States)

    Galbraith, Eric D; Martiny, Adam C

    2015-07-07

    It is widely recognized that the stoichiometry of nutrient elements in phytoplankton varies within the ocean. However, there are many conflicting mechanistic explanations for this variability, and it is often ignored in global biogeochemical models and carbon cycle simulations. Here we show that globally distributed particulate P:C varies as a linear function of ambient phosphate concentrations, whereas the N:C varies with ambient nitrate concentrations, but only when nitrate is most scarce. This observation is consistent with the adjustment of the phytoplankton community to local nutrient availability, with greater flexibility of phytoplankton P:C because P is a less abundant cellular component than N. This simple relationship is shown to predict the large-scale, long-term average composition of surface particles throughout large parts of the ocean remarkably well. The relationship implies that most of the observed variation in N:P actually arises from a greater plasticity in the cellular P:C content, relative to N:C, such that as overall macronutrient concentrations decrease, N:P rises. Although other mechanisms are certainly also relevant, this simple relationship can be applied as a first-order basis for predicting organic matter stoichiometry in large-scale biogeochemical models, as illustrated using a simple box model. The results show that including variable P:C makes atmospheric CO2 more sensitive to changes in low latitude export and ocean circulation than a fixed-stoichiometry model. In addition, variable P:C weakens the relationship between preformed phosphate and atmospheric CO2 while implying a more important role for the nitrogen cycle.

  19. TECHNICAL SOLUTIONS OF COMPONENTS AND PARTS OF CATALYTIC SYSTEMS FOR ENERGY PRODUCTION AND CONVERSION Технические решения составных частей и узлов каталитических систем для производства и преобразования энергии

    Directory of Open Access Journals (Sweden)

    Medyakov A. A.

    2013-09-01

    Full Text Available The article provides a description of existing catalytic burning units, the rationale for improving the technical solutions of components and parts, and the catalytic burning unit proposed by the authors with a circulating bed of filler

  20. Irradiation-induced effects of proton irradiation on zirconium carbides with different stoichiometries

    Energy Technology Data Exchange (ETDEWEB)

    Y. Huang; B.R. Maier; T.R. Allen

    2014-10-01

    Zirconium carbide (ZrC) is being considered for utilization in deep burn TRISO fuel particles for hightemperature, gas-cooled reactors. Zirconium carbide has a cubic B1 type crystal structure along with a very high melting point (3420 ?C), exceptional hardness and good thermal and electrical conductivities. Understanding the ZrC irradiation response is crucial for establishing ZrC as an alternative component in TRISO fuel. Until now, very few studies on irradiation effects on ZrC have been released and fundamental aspects of defect evolution and kinetics are not well understood although some atomistic simulations and phenomenological studies have been performed. This work was carried out to understand the damage evolution in float-zone refined ZrC with different stoichiometries. Proton irradiations at 800 ?C up to doses of 3 dpa were performed on ZrCx (where x ranges from 0.9 to 1.2) to investigate the damage evolution. The irradiation-induced defects, such as density of dislocation loops, at different stoichiometries and doses which were characterized by transmission electron microscopy (TEM) is presented and discussed.

  1. 生物质焦油催化裂解过程中二次焦油成分%Secondary tar components in the catalytic cracking process of biomass tar

    Institute of Scientific and Technical Information of China (English)

    李永玲; 吴占松

    2015-01-01

    以秸秆热解产生的焦油为原料,在固定床反应器实验台上进行了催化裂解实验,研究了反应温度和催化剂种类对生物质焦油的裂解反应产物———二次焦油成分的影响规律。在高铝砖作为催化剂作用下,随着温度的升高,二次焦油构成有芳香化的趋势,多环芳烃的种类和含量都在增加。反应温度的提高有利于焦油的深度转化,二次焦油产率降低;但是高温下生成的二次焦油芳化程度更高,更容易引起催化剂积炭失活。当反应温度为900℃时,碱性催化剂白云石和石灰岩作用下二次焦油成分相似,以复杂的大分子环烃为主,而且焦油成分种类减少到10种左右;酸性催化剂高铝砖作用下焦油成分仍然很复杂,有将近30种,除了含有大分子环烃外,还含有部分石蜡烃,芳香族种类很多,多以双环、三环以及四环的形式存在。%Catalytic cracking experiments were carried out on biomass tar in a fixed-bed reactor to study the influence of reaction temperature and catalyst type on the cracking reaction product, secondary tar. The experimental results show that there is an aromatic trend in the secondary tar components, and the types and content of polycyclic aromatic hydrocarbons ( PAHs) both increase with the increase of reaction temperature when using the high-alumina brick as an acid catalyst. The rise of reaction temperature can not only improve the deep conversion of biomass tar and reduce the production rate of secondary tar, but also increase the aromatization degree of secondary tar, which is more likely to cause the catalyst deactivation with carbon deposition. When the reaction temperature is 900℃, the secondary tar components are similar with alkaline catalysts (dolomite or limestone), and their types reduce to about 10, which mainly include complex macromolecular hydrocarbon. However, the secondary tar components are still very complex

  2. Quantitative localization microscopy: effects of photophysics and labeling stoichiometry.

    Directory of Open Access Journals (Sweden)

    Robert P J Nieuwenhuizen

    Full Text Available Quantification in localization microscopy with reversibly switchable fluorophores is severely hampered by the unknown number of switching cycles a fluorophore undergoes and the unknown stoichiometry of fluorophores on a marker such as an antibody. We overcome this problem by measuring the average number of localizations per fluorophore, or generally per fluorescently labeled site from the build-up of spatial image correlation during acquisition. To this end we employ a model for the interplay between the statistics of activation, bleaching, and labeling stoichiometry. We validated our method using single fluorophore labeled DNA oligomers and multiple-labeled neutravidin tetramers where we find a counting error of less than 17% without any calibration of transition rates. Furthermore, we demonstrated our quantification method on nanobody- and antibody-labeled biological specimens.

  3. Influence of Physiological Stress on Nutrient Stoichiometry in Larval Amphibians.

    Science.gov (United States)

    Kirschman, Lucas J; Haslett, Savhannah; Fritz, Kelley A; Whiles, Matt R; Warne, Robin W

    2016-01-01

    Exposure to environmental stressors alters animal phenotypes as well as nutrient metabolism, assimilation, and excretion. While stress-induced shifts in nutrient processes are known to alter organismal carbon (C) and nitrogen (N) stoichiometry, there has been little exploration of how environmental factors influence phosphorous (P). A better understanding of how P cycling varies with animal physiological state may provide insight into across-scale processes, because P is essential to animal function and ecological processes such as production and decomposition. We tested the effects of predator stress and exogenous glucocorticoids on C∶N∶P stoichiometry of larval amphibians. Glucocorticoids altered nutrient stoichiometry, apparently by modulating ossification and renal function. This reduced whole-body P and significantly increased N∶P. Additionally, elevated glucocorticoids caused a long-term reduction in P excretion. This reduction may reflect an initial unmeasured loss of P that glucocorticoids induce over acute timescales. In contrast, exposure to predator cues had no effect on larval C∶N∶P stoichiometry, which highlights that different stressors have varied effects on the endocrine stress response. Predation, in particular, is ubiquitous in the environment; thus, larvae responding to predators have conserved mechanisms that likely prevent or minimize physiological disruption. These results demonstrate the differing physiological roles of N and P, distinct nutrient demands associated with amphibian metamorphosis, and the contrasting effects that different environmental factors have on the physiological stress response. Our results also suggest that anthropogenic changes to the environment that induce chronic stress in amphibians could affect the biogeochemistry of nutrient-poor environments where they may act as keystone species.

  4. Proton stoichiometry associated with human neutrophil respiratory-burst reactions.

    Science.gov (United States)

    Gabig, T G; Lefker, B A; Ossanna, P J; Weiss, S J

    1984-11-10

    Control of the intraphagosomal pH in neutrophils may be of importance in creating a microbicidal environment by regulating the activity of the O2-.-generating NADPH oxidase and the lysosomal enzymes discharged into this compartment. In this study, we examined the proton stoichiometry associated with the primary enzymatic reaction underlying the respiratory burst. A preparation of the neutrophil-derived, membrane oxidase consumed NADPH and generated O2-. with a stoichiometry of 1 NADPH:2 O2-. When the enzymatically produced O2-. was prevented from undergoing dismutation, net protons were released in an approximate 1:2 stoichiometry with O2-. generated. In contrast, when O2-. was allowed to dismutate to H2O2, net protons were consumed in a 1:1 stoichiometry with the accumulated H2O2. Thus, the delta pH associated with the NADPH oxidase-dependent production of O2-. was dictated by the fate of the generated radical. The consumption of the oxidase-generated H2O2 by the lysosomal enzyme myeloperoxidase resulted in the formation of HOCl which was trapped in the presence of taurine as the N-chloro derivative. The ratio of chlorinated product formed to H+ consumed was 1:1. The implications of these results are discussed in terms of the known intraphagosomal pH changes that occur following neutrophil stimulation. We conclude that the O2-.-generating oxidase plays a dual role in the phagosome by simultaneously creating an oxidizing environment that optimizes pH-dependent microbicidal processes.

  5. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  6. Learning stoichiometry: A comparison of text and multimedia instructional formats

    Science.gov (United States)

    Evans, Karen L.

    Even after multiple instructional opportunities, first year college chemistry students are often unable to apply stoichiometry knowledge in equilibrium and acid-base chemistry problem solving. Cognitive research findings suggest that for learning to be meaningful, learners need to actively construct their own knowledge by integrating new information into, and reorganizing, their prior understandings. Scaffolded inquiry in which facts, procedures, and principles are introduced as needed within the context of authentic problem solving may provide the practice and encoding opportunities necessary for construction of a memorable and usable knowledge base. The dynamic and interactive capabilities of online technology may facilitate stoichiometry instruction that promotes this meaningful learning. Entering college freshmen were randomly assigned to either a technology-rich or text-only set of cognitively informed stoichiometry review materials. Analysis of posttest scores revealed a significant but small difference in the performance of the two treatment groups, with the technology-rich group having the advantage. Both SAT and gender, however, explained more of the variability in the scores. Analysis of the posttest scores from the technology-rich treatment group revealed that the degree of interaction with the Virtual Lab simulation was significantly related to posttest performance and subsumed any effect of prior knowledge as measured by SAT scores. Future users of the online course should be encouraged to engage with the problem-solving opportunities provided by the Virtual Lab simulation through either explicit instruction and/or implementation of some level of program control within the course's navigational features.

  7. It is elemental: soil nutrient stoichiometry drives bacterial diversity.

    Science.gov (United States)

    Delgado-Baquerizo, Manuel; Reich, Peter B; Khachane, Amit N; Campbell, Colin D; Thomas, Nadine; Freitag, Thomas E; Abu Al-Soud, Waleed; Sørensen, Søren; Bardgett, Richard D; Singh, Brajesh K

    2017-03-01

    It is well established that resource quantity and elemental stoichiometry play major roles in shaping below and aboveground plant biodiversity, but their importance for shaping microbial diversity in soil remains unclear. Here, we used statistical modeling on a regional database covering 179 locations and six ecosystem types across Scotland to evaluate the roles of total carbon (C), nitrogen (N) and phosphorus (P) availabilities and ratios, together with land use, climate and biotic and abiotic factors, in determining regional scale patterns of soil bacterial diversity. We found that bacterial diversity and composition were primarily driven by variation in soil resource stoichiometry (total C:N:P ratios), itself linked to different land uses, and secondarily driven by other important biodiversity drivers such as climate, soil spatial heterogeneity, soil pH, root influence (plant-soil microbe interactions) and microbial biomass (soil microbe-microbe interactions). In aggregate, these findings provide evidence that nutrient stoichiometry is a strong predictor of bacterial diversity and composition at a regional scale. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

  8. Cerium reduction at the interface between ceria and yttria-stabilised zirconia and implications for interfacial oxygen non-stoichiometry

    Energy Technology Data Exchange (ETDEWEB)

    Song, Kepeng [Stuttgart Center for Electron Microscopy, Max Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart (Germany); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Wenhua Road 72, 110016 Shenyang (China); Schmid, Herbert [INM-Leibniz Institute for New Materials, Campus D2 2, D-66123 Saarbrücken (Germany); Srot, Vesna; Aken, Peter A. van, E-mail: vanaken@is.mpg.de [Stuttgart Center for Electron Microscopy, Max Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart (Germany); Gilardi, Elisa; Gregori, Giuliano; Maier, Joachim [Max Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart (Germany); Du, Kui [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Wenhua Road 72, 110016 Shenyang (China)

    2014-03-01

    Epitaxial CeO{sub 2} films with different thickness were grown on Y{sub 2}O{sub 3} stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO{sub 2} films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce{sup 4+} to Ce{sup 3+} at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also for understanding ceria catalytic properties.

  9. Rhizosphere stoichiometry: are C : N : P ratios of plants, soils, and enzymes conserved at the plant species-level?

    Science.gov (United States)

    Bell, Colin; Carrillo, Yolima; Boot, Claudia M; Rocca, Jennifer D; Pendall, Elise; Wallenstein, Matthew D

    2014-01-01

    As a consequence of the tight linkages among soils, plants and microbes inhabiting the rhizosphere, we hypothesized that soil nutrient and microbial stoichiometry would differ among plant species and be correlated within plant rhizospheres. We assessed plant tissue carbon (C) : nitrogen (N) : phosphorus (P) ratios for eight species representing four different plant functional groups in a semiarid grassland during near-peak biomass. Using intact plant species-specific rhizospheres, we examined soil C : N : P, microbial biomass C : N, and soil enzyme C : N : P nutrient acquisition activities. We found that few of the plant species' rhizospheres demonstrated distinct stoichiometric properties from other plant species and unvegetated soil. Plant tissue nutrient ratios and components of below-ground rhizosphere stoichiometry predominantly differed between the C4 plant species Buchloe dactyloides and the legume Astragalus laxmannii. The rhizospheres under the C4 grass B. dactyloides exhibited relatively higher microbial C and lower soil N, indicative of distinct soil organic matter (SOM) decomposition and nutrient mineralization activities. Assessing the ecological stoichiometry among plant species' rhizospheres is a high-resolution tool useful for linking plant community composition to below-ground soil microbial and nutrient characteristics. By identifying how rhizospheres differ among plant species, we can better assess how plant-microbial interactions associated with ecosystem-level processes may be influenced by plant community shifts.

  10. O-GlcNAc glycosylation stoichiometry of the FET protein family: only EWS is glycosylated with a high stoichiometry.

    Science.gov (United States)

    Kamemura, Kazuo

    2017-03-01

    Of the FET (fused in sarcoma [FUS]/Ewing sarcoma protein [EWS]/TATA binding protein-associated factor 15 [TAF15]) family of heterogeneous nuclear ribonucleoprotein particle proteins, FUS and TAF15 are consistently and EWS variably found in inclusion bodies in neurodegenerative diseases such as frontotemporal lobar degeneration associated with FUS. It is speculated that dysregulation of FET proteins at the post-translational level is involved in their cytoplasmic deposition. Here, the O-linked β-N-acetylglucosamine (O-GlcNAc) glycosylation stoichiometry of the FET proteins was chemoenzymatically analyzed, and it was found that only EWS is dynamically glycosylated with a high stoichiometry in the neural cell lines tested and in mouse brain. It was also confirmed that EWS, but not FUS and TAF15, is glycosylated with a high stoichiometry not only in the neural cells but also in the non-neural cell lines tested. These results indicate that O-GlcNAc glycosylation imparts a physicochemical property on EWS that is distinct from that of the other FET proteins in most of cell lineages or tissues.

  11. Export stoichiometry and migrant-mediated flux of phosphorus in the North Pacific Subtropical Gyre

    Science.gov (United States)

    Hannides, Cecelia C. S.; Landry, Michael R.; Benitez-Nelson, Claudia R.; Styles, Renée M.; Montoya, Joseph P.; Karl, David M.

    2009-01-01

    Export processes play a major role in regulating global marine primary production by reducing the efficiency of nutrient cycling and turnover in surface waters. Most studies of euphotic zone export focus on passive fluxes, that is, sinking particles. However, active transport, the vertical transfer of material by migrating zooplankton, can also be an important component of carbon (C) and nitrogen (N) removal from the surface ocean. Here we demonstrate that active transport is an especially important mechanism for phosphorus (P) removal from the euphotic zone at Station ALOHA (Hawaii Ocean Time-series program; 22°45'N, 158°W), a P-stressed site in the North Pacific Subtropical Gyre. Migrant excretions in this region are P-rich (C 51:N 12:P 1) relative to sinking particles (C 250:N 31:P 1), and migrant-mediated P fluxes are almost equal in magnitude (82%) to P fluxes from sediment traps. Migrant zooplankton biomass and therefore the importance of this P removal pathway relative to sinking fluxes has increased significantly over the past 12 years, suggesting that active transport may be a major driving force for enhanced P-limitation of biological production in the NPSG. We further assess the C:N:P composition of zooplankton size fractions at Station ALOHA (C 88:N 18:P 1, on average) and discuss migrant-mediated P export in light of the balance between zooplankton and suspended particle stoichiometries. We conclude that, because active transport is such a large component of the total P flux and significantly impacts ecosystem stoichiometry, export processes involving migrant zooplankton must be included in large-scale efforts to understand biogeochemical cycles.

  12. Structure of Pyrazole Derivatives Impact their Affinity, Stoichiometry, and Cooperative Interactions for CYP2E1 Complexes

    Science.gov (United States)

    Hartman, Jessica H.; Bradley, Amber M.; Laddusaw, Ryan M; Perry, Martin D.; Miller, Grover P.

    2013-01-01

    CYP2E1 plays a critical role in detoxication and carcinogenic activation of drugs, pollutants, and dietary compounds; however, these metabolic processes can involve poorly characterized cooperative interactions that compromise the ability to understand and predict CYP2E1 metabolism. Herein, we employed an array of ten azoles with an emphasis on pyrazoles to establish the selectivity of catalytic and cooperative CYP2E1 sites through binding and catalytic studies. Spectral binding studies for monocyclic azoles suggested two binding events, while bicyclic azoles suggested one. Pyrazole had moderate affinity toward the CYP2E1 catalytic site that improved when a methyl group was introduced at either position 3 or 4. The presence of methyl groups simultaneously at positions 3 and 5 blocked binding, and a phenyl group at position 3 did not improve binding affinity. In contrast, pyrazole fusion to a benzene or cyclohexane ring greatly increased affinity. The consequences of these binding events on CYP2E1 catalysis were studied through inhibition studies with 4-nitrophenol, a substrate known to bind both sites. Most pyrazoles shared a common mixed cooperative inhibition mechanism in which pyrazole binding rescued CYP2E1 from substrate inhibition. Overall, inhibitor affinities toward the CYP2E1 catalytic site were similar to those reported in binding studies, and the same trend was observed for binding at the cooperative site. Taken together, these studies identified key structural determinants in the affinity and stoichiometry of azole interactions with CYP2E1 and consequences on catalysis that further advance an understanding of the relationship between structure and function for this enzyme. PMID:23811196

  13. Catalytic combustor for hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mercea, J.; Grecu, E.; Fodor, T.; Kreibik, S.

    1982-01-01

    The performance of catalytic combustors for hydrogen using platinum-supported catalysts is described. Catalytic plates of different sizes were constructed using fibrous and ceramic supports. The temperature distribution as well as the reaction efficiency as a function of the fuel input rate was determined, and a comparison between the performances of different plates is discussed.

  14. Analysis of the subunit stoichiometries in viral entry.

    Directory of Open Access Journals (Sweden)

    Carsten Magnus

    Full Text Available Virions of the Human Immunodeficiency Virus (HIV infect cells by first attaching with their surface spikes to the CD4 receptor on target cells. This leads to conformational changes in the viral spikes, enabling the virus to engage a coreceptor, commonly CCR5 or CXCR4, and consecutively to insert the fusion peptide into the cellular membrane. Finally, the viral and the cellular membranes fuse. The HIV spike is a trimer consisting of three identical heterodimers composed of the gp120 and gp41 envelope proteins. Each of the gp120 proteins in the trimer is capable of attaching to the CD4 receptor and the coreceptor, and each of the three gp41 units harbors a fusion domain. It is still under debate how many of the envelope subunits within a given trimer have to bind to the CD4 receptors and to the coreceptors, and how many gp41 protein fusion domains are required for fusion. These numbers are referred to as subunit stoichiometries. We present a mathematical framework for estimating these parameters individually by analyzing infectivity assays with pseudotyped viruses. We find that the number of spikes that are engaged in mediating cell entry and the distribution of the spike number play important roles for the estimation of the subunit stoichiometries. Our model framework also shows why it is important to subdivide the question of the number of functional subunits within one trimer into the three different subunit stoichiometries. In a second step, we extend our models to study whether the subunits within one trimer cooperate during receptor binding and fusion. As an example for how our models can be applied, we reanalyze a data set on subunit stoichiometries. We find that two envelope proteins have to engage with CD4-receptors and coreceptors and that two fusion proteins must be revealed within one trimer for viral entry. Our study is motivated by the mechanism of HIV entry but the experimental technique and the model framework can be extended to

  15. Bridging Food Webs, Ecosystem Metabolism, and Biogeochemistry Using Ecological Stoichiometry Theory.

    Science.gov (United States)

    Welti, Nina; Striebel, Maren; Ulseth, Amber J; Cross, Wyatt F; DeVilbiss, Stephen; Glibert, Patricia M; Guo, Laodong; Hirst, Andrew G; Hood, Jim; Kominoski, John S; MacNeill, Keeley L; Mehring, Andrew S; Welter, Jill R; Hillebrand, Helmut

    2017-01-01

    Although aquatic ecologists and biogeochemists are well aware of the crucial importance of ecosystem functions, i.e., how biota drive biogeochemical processes and vice-versa, linking these fields in conceptual models is still uncommon. Attempts to explain the variability in elemental cycling consequently miss an important biological component and thereby impede a comprehensive understanding of the underlying processes governing energy and matter flow and transformation. The fate of multiple chemical elements in ecosystems is strongly linked by biotic demand and uptake; thus, considering elemental stoichiometry is important for both biogeochemical and ecological research. Nonetheless, assessments of ecological stoichiometry (ES) often focus on the elemental content of biota rather than taking a more holistic view by examining both elemental pools and fluxes (e.g., organismal stoichiometry and ecosystem process rates). ES theory holds the promise to be a unifying concept to link across hierarchical scales of patterns and processes in ecology, but this has not been fully achieved. Therefore, we propose connecting the expertise of aquatic ecologists and biogeochemists with ES theory as a common currency to connect food webs, ecosystem metabolism, and biogeochemistry, as they are inherently concatenated by the transfer of carbon, nitrogen, and phosphorous through biotic and abiotic nutrient transformation and fluxes. Several new studies exist that demonstrate the connections between food web ecology, biogeochemistry, and ecosystem metabolism. In addition to a general introduction into the topic, this paper presents examples of how these fields can be combined with a focus on ES. In this review, a series of concepts have guided the discussion: (1) changing biogeochemistry affects trophic interactions and ecosystem processes by altering the elemental ratios of key species and assemblages; (2) changing trophic dynamics influences the transformation and fluxes of matter

  16. Bridging Food Webs, Ecosystem Metabolism, and Biogeochemistry Using Ecological Stoichiometry Theory

    Science.gov (United States)

    Welti, Nina; Striebel, Maren; Ulseth, Amber J.; Cross, Wyatt F.; DeVilbiss, Stephen; Glibert, Patricia M.; Guo, Laodong; Hirst, Andrew G.; Hood, Jim; Kominoski, John S.; MacNeill, Keeley L.; Mehring, Andrew S.; Welter, Jill R.; Hillebrand, Helmut

    2017-01-01

    Although aquatic ecologists and biogeochemists are well aware of the crucial importance of ecosystem functions, i.e., how biota drive biogeochemical processes and vice-versa, linking these fields in conceptual models is still uncommon. Attempts to explain the variability in elemental cycling consequently miss an important biological component and thereby impede a comprehensive understanding of the underlying processes governing energy and matter flow and transformation. The fate of multiple chemical elements in ecosystems is strongly linked by biotic demand and uptake; thus, considering elemental stoichiometry is important for both biogeochemical and ecological research. Nonetheless, assessments of ecological stoichiometry (ES) often focus on the elemental content of biota rather than taking a more holistic view by examining both elemental pools and fluxes (e.g., organismal stoichiometry and ecosystem process rates). ES theory holds the promise to be a unifying concept to link across hierarchical scales of patterns and processes in ecology, but this has not been fully achieved. Therefore, we propose connecting the expertise of aquatic ecologists and biogeochemists with ES theory as a common currency to connect food webs, ecosystem metabolism, and biogeochemistry, as they are inherently concatenated by the transfer of carbon, nitrogen, and phosphorous through biotic and abiotic nutrient transformation and fluxes. Several new studies exist that demonstrate the connections between food web ecology, biogeochemistry, and ecosystem metabolism. In addition to a general introduction into the topic, this paper presents examples of how these fields can be combined with a focus on ES. In this review, a series of concepts have guided the discussion: (1) changing biogeochemistry affects trophic interactions and ecosystem processes by altering the elemental ratios of key species and assemblages; (2) changing trophic dynamics influences the transformation and fluxes of matter

  17. Ecological Stoichiometry beyond Redfield: An Ionomic Perspective on Elemental Homeostasis

    Science.gov (United States)

    Jeyasingh, Punidan D.; Goos, Jared M.; Thompson, Seth K.; Godwin, Casey M.; Cotner, James B.

    2017-01-01

    Elemental homeostasis has been largely characterized using three important elements that were part of the Redfield ratio (i.e., carbon: nitrogen: phosphorus). These efforts have revealed substantial diversity in homeostasis among taxonomic groups and even within populations. Understanding the evolutionary basis, and ecological consequences of such diversity is a central challenge. Here, we propose that a more complete understanding of homeostasis necessitates the consideration of other elements beyond C, N, and P. Specifically, we posit that physiological complexity underlying maintenance of elemental homeostasis along a single elemental axis impacts processing of other elements, thus altering elemental homeostasis along other axes. Indeed, transcriptomic studies in a wide variety of organisms have found that individuals differentially express significant proportions of the genome in response to variability in supply stoichiometry in order to maintain varying levels of homeostasis. We review the literature from the emergent field of ionomics that has established the consequences of such physiological trade-offs on the content of the entire suite of elements in an individual. Further, we present experimental data on bacteria exhibiting divergent phosphorus homeostasis phenotypes demonstrating the fundamental interconnectedness among elemental quotas. These observations suggest that physiological adjustments can lead to unexpected patterns in biomass stoichiometry, such as correlated changes among suites of non-limiting microelements in response to limitation by macroelements. Including the entire suite of elements that comprise biomass will foster improved quantitative understanding of the links between chemical cycles and the physiology of organisms. PMID:28487686

  18. Using light scattering to determine the stoichiometry of protein complexes.

    Science.gov (United States)

    Mogridge, Jeremy

    2015-01-01

    The stoichiometry of a protein complex can be calculated from an accurate measurement of the complex's molecular weight. Multiangle laser light scattering in combination with size exclusion chromatography and interferometric refractometry provides a powerful means for determining the molecular weights of proteins and protein complexes. In contrast to conventional size exclusion chromatography and analytical centrifugation, measurements do not rely on the use of molecular weight standards and are not affected by the shape of the proteins. The technique is based on the direct relationship between the amount of light scattered by a protein in solution, and the product of its concentration and molecular weight. A typical experimental configuration includes a size exclusion column to fractionate the sample, a light scattering detector to measure scattered light, and an interferometric refractometer to measure protein concentration. The determination of the molecular weight of an anthrax toxin complex will be used to illustrate how multiangle laser light scattering can be used to determine the stoichiometry of protein complexes.

  19. Ecological Stoichiometry beyond Redfield: An Ionomic Perspective on Elemental Homeostasis

    Directory of Open Access Journals (Sweden)

    Punidan D. Jeyasingh

    2017-04-01

    Full Text Available Elemental homeostasis has been largely characterized using three important elements that were part of the Redfield ratio (i.e., carbon: nitrogen: phosphorus. These efforts have revealed substantial diversity in homeostasis among taxonomic groups and even within populations. Understanding the evolutionary basis, and ecological consequences of such diversity is a central challenge. Here, we propose that a more complete understanding of homeostasis necessitates the consideration of other elements beyond C, N, and P. Specifically, we posit that physiological complexity underlying maintenance of elemental homeostasis along a single elemental axis impacts processing of other elements, thus altering elemental homeostasis along other axes. Indeed, transcriptomic studies in a wide variety of organisms have found that individuals differentially express significant proportions of the genome in response to variability in supply stoichiometry in order to maintain varying levels of homeostasis. We review the literature from the emergent field of ionomics that has established the consequences of such physiological trade-offs on the content of the entire suite of elements in an individual. Further, we present experimental data on bacteria exhibiting divergent phosphorus homeostasis phenotypes demonstrating the fundamental interconnectedness among elemental quotas. These observations suggest that physiological adjustments can lead to unexpected patterns in biomass stoichiometry, such as correlated changes among suites of non-limiting microelements in response to limitation by macroelements. Including the entire suite of elements that comprise biomass will foster improved quantitative understanding of the links between chemical cycles and the physiology of organisms.

  20. Quantitative mass spectrometry measurements reveal stoichiometry of principal postsynaptic density proteins.

    Science.gov (United States)

    Lowenthal, Mark S; Markey, Sanford P; Dosemeci, Ayse

    2015-06-05

    Quantitative studies are presented of postsynaptic density (PSD) fractions from rat cerebral cortex with the ultimate goal of defining the average copy numbers of proteins in the PSD complex. Highly specific and selective isotope dilution mass spectrometry assays were developed using isotopically labeled polypeptide concatemer internal standards. Interpretation of PSD protein stoichiometry was achieved as a molar ratio with respect to PSD-95 (SAP-90, DLG4), and subsequently, copy numbers were estimated using a consensus literature value for PSD-95. Average copy numbers for several proteins at the PSD were estimated for the first time, including those for AIDA-1, BRAGs, and densin. Major findings include evidence for the high copy number of AIDA-1 in the PSD (144 ± 30)-equivalent to that of the total GKAP family of proteins (150 ± 27)-suggesting that AIDA-1 is an element of the PSD scaffold. The average copy numbers for NMDA receptor sub-units were estimated to be 66 ± 18, 27 ± 9, and 45 ± 15, respectively, for GluN1, GluN2A, and GluN2B, yielding a total of 34 ± 10 NMDA channels. Estimated average copy numbers for AMPA channels and their auxiliary sub-units TARPs were 68 ± 36 and 144 ± 38, respectively, with a stoichiometry of ∼1:2, supporting the assertion that most AMPA receptors anchor to the PSD via TARP sub-units. This robust, quantitative analysis of PSD proteins improves upon and extends the list of major PSD components with assigned average copy numbers in the ongoing effort to unravel the complex molecular architecture of the PSD.

  1. Catalytic distillation process

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  2. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  3. Catalytic Synthesis Lactobionic Acid

    Directory of Open Access Journals (Sweden)

    V.G. Borodina

    2014-07-01

    Full Text Available Gold nanoparticles are obtained, characterized and deposited on the carrier. Conducted catalytic synthesis of lactobionic acid from lactose. Received lactobionic acid identify on the IR spectrum.

  4. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)

    2009-01-01

    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the diffusi

  5. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)

    2009-01-01

    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the

  6. Thai Grade 10 and 11 Students' Understanding of Stoichiometry and Related Concepts

    Science.gov (United States)

    Dahsah, Chanyah; Coll, Richard Kevin

    2008-01-01

    The research reported in this case study explores the understanding of stoichiometry and related concepts of Thai science students in grades 10 and 11 after major national curriculum reforms. Students' conceptions and alternative conceptions were investigated using a questionnaire--the "Stoichiometry Concept Questionnaire" (SCQ) (N =…

  7. Absolute Phosphorylation Stoichiometry Analysis by Motif-Targeting Quantitative Mass Spectrometry.

    Science.gov (United States)

    Tsai, Chia-Feng; Ku, Wei-Chi; Chen, Yu-Ju; Ishihama, Yasushi

    2017-01-01

    Direct measurement of site-specific phosphorylation stoichiometry can unambiguously distinguish whether the degree of phosphorylation is regulated by upstream kinase/phosphatase activity or by transcriptional regulation to alter protein expression level. Here, we describe a motif-targeting quantitative proteomic approach that integrates dephosphorylation, isotope tag labeling, and enzymatic kinase reaction for large-scale phosphorylation stoichiometry measurement of the human proteome.

  8. Emiratii High School Students' Understandings of Stoichiometry and the Influence of Metacognition on Their Understanding

    Science.gov (United States)

    Haidar, Abdullateef H.; Al Naqabi, Ali K.

    2008-01-01

    The aim of this study is to investigate Emiratii high school students' understandings of stoichiometry, their use of metacognitive strategies, and the influence of students' use of metacognitive strategies on their understandings of stoichiometry. Two instruments were used in this study, the first to measure students' understandings of…

  9. Establishing a definitive stoichiometry for the Na+/monocarboxylate cotransporter SMCT1.

    Science.gov (United States)

    Coady, Michael J; Wallendorff, Bernadette; Bourgeois, Francis; Charron, Francois; Lapointe, Jean-Yves

    2007-10-01

    Several different stoichiometries have been proposed for the Na(+)/monocarboxylate cotransporter SMCT1, including variable Na(+)/substrate stoichiometry. In this work, we have definitively established an invariant 2:1 cotransport stoichiometry for SMCT1. By using two independent means of assay, we first showed that SMCT1 exhibits a 2:1 stoichiometry for Na(+)/lactate cotransport. Radiolabel uptake experiments proved that, unlike lactate, propionic acid diffuses passively through oocyte membranes and, consequently, propionate is a poor candidate for stoichiometric determination by these methods. Although we previously determined SMCT1 stoichiometry by measuring reversal potentials, this technique produced erroneous values, because SMCT1 simultaneously mediates both an inwardly rectifying cotransport current and an outwardly rectifying anionic leak current; the leak current predominates in the range where reversal potentials are observed. We therefore employed a method that compared the effect of halving the external Na(+) concentration to the effect of halving the external substrate concentration on zero-current potentials. Both lactate and propionate were cotransported through SMCT1 using 2:1 stoichiometries. The leak current passing through the protein has a 1 osmolyte/charge stoichiometry. Identification of cotransporter stoichiometry is not always a trivial task and it can lead to a much better understanding of the transport activity mediated by the protein in question.

  10. Thai Grade 10 and 11 Students' Understanding of Stoichiometry and Related Concepts

    Science.gov (United States)

    Dahsah, Chanyah; Coll, Richard Kevin

    2008-01-01

    The research reported in this case study explores the understanding of stoichiometry and related concepts of Thai science students in grades 10 and 11 after major national curriculum reforms. Students' conceptions and alternative conceptions were investigated using a questionnaire--the "Stoichiometry Concept Questionnaire" (SCQ) (N =…

  11. Thai Grade 10 and 11 Students' Conceptual Understanding and Ability to Solve Stoichiometry Problems

    Science.gov (United States)

    Dahsah, Chanyah; Coll, Richard K.

    2007-01-01

    Stoichiometry and related concepts are an important part of student learning in chemistry. In this interpretive-based inquiry, we investigated Thai Grade 10 and 11 students' conceptual understanding and ability to solve numerical problems for stoichiometry-related concepts. Ninety-seven participants completed a purpose-designed survey instrument…

  12. Emiratii High School Students' Understandings of Stoichiometry and the Influence of Metacognition on Their Understanding

    Science.gov (United States)

    Haidar, Abdullateef H.; Al Naqabi, Ali K.

    2008-01-01

    The aim of this study is to investigate Emiratii high school students' understandings of stoichiometry, their use of metacognitive strategies, and the influence of students' use of metacognitive strategies on their understandings of stoichiometry. Two instruments were used in this study, the first to measure students' understandings of…

  13. Evolving Phytoplankton Stoichiometry Fueled Diversification of the Marine Biosphere

    Directory of Open Access Journals (Sweden)

    Antonietta Quigg

    2012-05-01

    Full Text Available The availability of nutrients and the quantity and quality of food at the base of food webs have largely been ignored in discussions of the Phanerozoic record of biodiversity. We examine the role of nutrient availability and phytoplankton stoichiometry (the relative proportions of inorganic nutrients to carbon in the diversification of the marine biosphere. Nutrient availability and phytoplankton stoichiometry played a critical role in the initial diversification of the marine biosphere during the Neoproterozoic. Initial biosphere expansion during this time resulted in the massive sequestration of nutrients into biomass which, along with the geologically slow input of nutrients from land, set the stage for severe nutrient limitation and relatively constant marine biodiversity during the rest of the Paleozoic. Given the slow nutrient inputs from land and low recycling rates, the growth of early-to-middle Paleozoic metazoans remained limited by their having to expend energy to first “burn off” (respire excess carbon in food before the associated nutrients could be utilized for growth and reproduction; the relative equilibrium in marine biodiversity during the Paleozoic therefore appears to be real. Limited nutrient availability and the consequent nutrient imbalance may have delayed the appearance of more advanced carnivores until the Permo-Carboniferous, when widespread orogeny, falling sea level, the spread of forests, greater weathering rates, enhanced ocean circulation, oxygenation, and upwelling all combined to increase nutrient availability. During the Meso-Cenozoic, rising oxygen levels, the continued nutrient input from land, and, especially, increasing rates of bioturbation, enhanced nutrient availability, increasing the nutrient content of phytoplankton that fueled the diversification of the Modern Fauna.

  14. Ontogenetic variation in the body stoichiometry of two fish species.

    Science.gov (United States)

    Boros, Gergely; Sály, Péter; Vanni, Michael J

    2015-10-01

    One of the central questions of ecological stoichiometry theory is to what extent animal species maintain constant elemental composition in their bodies. Although several recent studies demonstrate intraspecific variation in animal elemental composition, relatively little is known about ontogenetic changes in vertebrates, especially during early life stages. We studied the intraspecific and interspecific ontogenetic variation in the body stoichiometry of two fish species in two different orders; fathead minnow (Pimephales promelas) and sheepshead minnow (Cyprinodon variegatus), reared under controlled laboratory conditions. During ontogeny, we measured the chemical composition of fish bodies, including carbon (C), nitrogen (N), phosphorus (P), calcium (Ca), and ribonucleic acid (RNA) contents. We found that N and RNA contents were relatively high in early life stages and declined substantially during development. In contrast, body C and C:N ratios were relatively low in embryos, post-embryos and larvae, and increased remarkably thereafter. Concentrations and ratios of some elements (e.g., Ca, P, Ca:P) did not exhibit consistent ontogenetic trends, but fluctuated dynamically between consecutive developmental stages in both species. Specific growth rates correlated significantly with RNA contents in both species. Analyses of the relative importance of different P pools at each developmental stage revealed that RNA was a considerable P pool in post-embryos, while bone-associated P was the dominant body P pool in later stages. Our results suggest that the elemental composition of fish bodies changes considerably during ontogeny. Each ontogenetic stage has its own stoichiometric signature, but the timing, magnitude and direction of ontogenetic changes can vary substantially between taxa.

  15. Environmental and organismal predictors of intraspecific variation in the stoichiometry of a neotropical freshwater fish.

    Science.gov (United States)

    El-Sabaawi, Rana W; Kohler, Tyler J; Zandoná, Eugenia; Travis, Joseph; Marshall, Michael C; Thomas, Steven A; Reznick, David N; Walsh, Matthew; Gilliam, James F; Pringle, Catherine; Flecker, Alexander S

    2012-01-01

    The elemental composition of animals, or their organismal stoichiometry, is thought to constrain their contribution to nutrient recycling, their interactions with other animals, and their demographic rates. Factors that affect organismal stoichiometry are generally poorly understood, but likely reflect elemental investments in morphological features and life history traits, acting in concert with the environmental availability of elements. We assessed the relative contribution of organismal traits and environmental variability to the stoichiometry of an insectivorous Neotropical stream fish, Rivulus hartii. We characterized the influence of body size, life history phenotype, stage of maturity, and environmental variability on organismal stoichiometry in 6 streams that differ in a broad suite of environmental variables. The elemental composition of R. hartii was variable, and overlapped with the wide range of elemental composition documented across freshwater fish taxa. Average %P composition was ∼3.2%(±0.6), average %N∼10.7%(±0.9), and average %C∼41.7%(±3.1). Streams were the strongest predictor of organismal stoichiometry, and explained up to 18% of the overall variance. This effect appeared to be largely explained by variability in quality of basal resources such as epilithon N:P and benthic organic matter C:N, along with variability in invertebrate standing stocks, an important food source for R. hartii. Organismal traits were weak predictors of organismal stoichiometry in this species, explaining when combined up to 7% of the overall variance in stoichiometry. Body size was significantly and positively correlated with %P, and negatively with N:P, and C:P, and life history phenotype was significantly correlated with %C, %P, C:P and C:N. Our study suggests that spatial variability in elemental availability is more strongly correlated with organismal stoichiometry than organismal traits, and suggests that the stoichiometry of carnivores may not be

  16. "Why not stoichiometry" versus "Stoichiometry--why not?" Part II: GATES in context with redox systems.

    Science.gov (United States)

    Michałowska-Kaczmarczyk, Anna Maria; Asuero, Agustin G; Toporek, Marcin; Michałowski, Tadeusz

    2015-01-01

    Redox equilibria and titration play an important role in chemical analysis, and the formulation of an accurate mathematical description is a challenge. This article is devoted to static and (mainly) dynamic redox systems; the dynamic systems are represented by redox titrations. An overview addresses earlier approaches to static redox systems (redox diagram plots, including Pourbaix diagrams) and to titration redox systems, thereby covering a gap in the literature. After this short review, the generalized approach to electrolytic systems (GATES) is introduced, with generalized electron balance (GEB) as its inherent part within GATES/GEB. Computer simulation, performed according to GATES/GEB, enables following the changes in potential and pH of the solution, together with chemical speciation at each step of a titration, thus providing better insight into this procedure. The undeniable advantages of GATES/GEB over earlier approaches are indicated. Formulation of GEB according to two approaches (I and II) is presented on the respective examples. A general criterion distinguishing between non-redox and redox systems is presented. It is indicated that the formulation of GEB according to Approach II does not need the knowledge of oxidation degrees of particular elements; knowledge of the composition, expressed by chemical formula of the species and its charge, is sufficient for this purpose. Approach I to GEB, known also as the "short" version of GEB, is applicable if oxidation degrees for all elements of the system are known beforehand. The roles of oxidants and reductants are not ascribed to particular components forming a system and to the species thus formed. This is the complete opposite of earlier approaches to redox titrations, based on the stoichiometric redox reaction, formulated for this purpose. GEB, perceived as a law of matter conservation, is fully compatible with other (charge and concentration) balances related to the system in question. The applicability

  17. [Study on catalytic oxidation of benzene by microwave heating].

    Science.gov (United States)

    Zhang, Yu-cai; Bo, Long-li; Wang, Xiao-hui; Liu, Hai-nan; Zhang, Hao

    2012-08-01

    The performance in catalytic oxidation of benzene was investigated in two different heating modes, microwave heating and conventional electric furnace heating. The effects of copper (Cu)-manganese (Mn) mass ratio, doping dose of cerium (Ce) and calcination temperature on the catalytic activity of Cu-Mn-Ce/molecular sieve catalyst were also checked in catalytic oxidation of benzene with microwave heating, and the catalysts were subsequently characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the catalyst had better catalytic activity for the oxidation of benzene under microwave heating than electric furnace heating, and high oxidation efficiency for benzene was reached due to the "local hot spots" and dipole polarization effect of microwave and stable bed reaction temperature. Under the conditions of Cu, Mn and Ce mass ratio 1:1:0.33 and calcination temperature 500 degrees C, the catalyst had the optimal catalytic activity for benzene oxidation, and its light-off temperature and complete combustion temperature were 165 degrees C and 230 degrees C, respectively. It was indicated by characteristics of XRD and SEM that the presence of copper and manganese oxides and Cu1.5Mn1.5O4 with spinel crystal improved the catalytic activity of the catalyst, and the doping of Ce promoted the dispersion and regularization of active components. High calcination temperature led to the sintering of the catalyst surface and agglomeration of active components, which decreased the catalytic activity of the catalyst in the catalytic oxidation

  18. Proteome-Wide Analysis of N-Glycosylation Stoichiometry Using SWATH Technology.

    Science.gov (United States)

    Yang, Xiangyun; Wang, Zhiyuan; Guo, Lin; Zhu, Zhengjiang; Zhang, Yaoyang

    2017-10-06

    N-glycosylation is a crucial post-translational modification (PTM) and plays essential roles in biological processes. Several methods have been developed for the relative quantification of N-glycosylation at the proteome scale. However, the proportion of N-glycosylated forms in a total protein population, or the "N-glycosylation stoichiometry", varies greatly among proteins or cellular states and is frequently missing due to the lack of robust technologies. In the present study, we developed a data-independent acquisition (DIA)-based strategy that enabled the in-depth measurement of N-glycosylation stoichiometry. A spectral library containing 3,509 N-glycosylated peptides and 17,525 fragment ions from human embryonic kidney cells 293 (HEK-293) cells was established from which the stoichiometries of 1,186 N-glycosites were calculated. These stoichiometric values differ greatly among different glycosites, and many glycosites tend to occur with low stoichiometry. We then investigated the N-glycosylation changes induced by tunicamycin in HEK-293 cells and by a temperature shift in Chinese hamster ovary (CHO) cells. Quantifying the proteome, N-glycoproteome, and N-glycosylation stoichiometry demonstrated that the regulation of N-glycosylation is primarily achieved by adjusting the N-glycosylation stoichiometry. In total, the stoichiometries of 2,274 glycosites were determined in the current study. Notably, our approach can be applied to other biological systems and other types of PTMs.

  19. Impact of stoichiometry on the electronic structure of PbS quantum dots.

    Science.gov (United States)

    Kim, Donghun; Kim, Dong-Ho; Lee, Joo-Hyoung; Grossman, Jeffrey C

    2013-05-10

    Although the stoichiometry of bulk lead sulfide (PbS) is exactly 1:1, that of quantum dots (QDs) can be considerably different from this crystalline limit. Employing first-principles calculations, we show that the impact of PbS QD stoichiometry on the electronic structure can be enormous, suggesting that control over the overall stoichiometry in the QD will play a critical role for improving the efficiency of optoelectronic devices made with PbS QDs. In particular, for bare PbS QDs, we find that: (i) stoichiometric PbS QDs are free from midgap states even without ligand passivation and independent of shape, (ii) off stoichiometry in PbS QDs introduces new states in the gap that are highly localized on certain surface atoms, and (iii) further deviations in stoichiometry lead to QDs with "metallic" behavior, with a dense number of energy states near the Fermi level. We further demonstrate that this framework holds for the case of passivated QDs by considering the attachment of ligand molecules as stoichiometry variations. Our calculations show that an optimal number of ligands makes the QD stoichiometric and heals unfavorable electronic structure, whereas too few or too many ligands cause effective off stoichiometry, resulting in QDs with defect states in the gap.

  20. Catalytic hydrotreating process

    Science.gov (United States)

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  1. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  2. Catalytic processes for space station waste conversion

    Science.gov (United States)

    Schoonover, M. W.; Madsen, R. A.

    1986-01-01

    Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.

  3. Molecular dynamics investigation on the deviation from stoichiometry in martensitic transformation

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Tetsuro, E-mail: tetsuro.suzuki@nifty.com [National Institute for Materials Science (Japan); Shimno, Masato; Otsuka, Kazuhiro; Ren, Xiaobing [National Institute for Materials Science (Japan); Saxena, Avadh [National Institute for Materials Science (Japan); Los Alamos National Laboratory (United States)

    2013-11-15

    Highlights: ► We have studied the martensitic transformation in Ti–Ni alloy near 50:50 stoichiometry. ► The atomistic process of the martensitic transformation is simulated by use of the molecular dynamics based on the 8-4 Lennard–Jones potential. ► The molecular dynamics provide atomistic picture when the formation of the martensite is suppressed for the deviation from 50:50 stoichiometry. -- Abstract: How the martensitic transformation in Ti–Ni alloy depends on the deviation from the stoichiometry is investigated by use of the molecular dynamics based on a simple model potential.

  4. Stoichiometry of the Human Glycine Receptor Revealed by Direct Subunit counting

    Science.gov (United States)

    Durisic, Nela; Godin, Antoine G.; Wever, Claudia M.; Heyes, Colin D.; Lakadamyali, Melike; Dent, Joseph A.

    2012-01-01

    The subunit stoichiometry of heteromeric glycine-gated channels (GlyRs) determines fundamental properties of these key inhibitory neurotransmitter receptors; however the ratio of α1 to β-subunits per receptor remains controversial. We used single molecule imaging and stepwise photobleaching in Xenopus oocytes to directly determine the subunit stoichiometry of a glycine receptor to be 3α1:2β. This approach allowed us to determine the receptor stoichiometry in mixed populations consisting of both heteromeric and homomeric channels, additionally revealing the quantitative proportions for the two populations. PMID:22973015

  5. Comparison of label-free quantification methods for the determination of protein complexes subunits stoichiometry

    Directory of Open Access Journals (Sweden)

    Bertrand Fabre

    2014-09-01

    Full Text Available Protein complexes are the main molecular machines that support all major cellular pathways and their in-depth characterization are essential to understand their functions. Determining the stoichiometry of the different subunits of a protein complex still remains challenging. Recently, many label-free quantitative proteomic approaches have been developed to study the composition of protein complexes. It is therefore of great interest to evaluate these different methods in a stoichiometry oriented objective. Here we compare the ability of four absolute quantitative label-free methods currently used in proteomic studies to determine the stoichiometry of a well-characterized protein complex, the 26S proteasome.

  6. Fundamental study of ash formation and deposition: Effect of reducing stoichiometry

    Energy Technology Data Exchange (ETDEWEB)

    Helble, J.J.; Bool, L.E.; Kang, S.G. [and others

    1995-11-01

    This project is designed to examine the effects of combustion stoichiometry on the fundamental aspects of ash formation and ash deposit initiation. Emphasis is being placed on reducing stoichiometries associated with low-NOx combustion, although a range of oxidant/fuel ratios are being considered. Previous work has demonstrated that ash formation depends strongly upon coal mineralogy, including mineral type, size, amount, and the presence of organically associated inorganic species. Combustion temperature and the oxidation state of iron also play a significant role. As these latter items will vary with changes in stoichiometry, research to determine the net effect on deposition is required.

  7. Functional dissection of the N-terminal sequence of Clostridium sp. G0005 glucoamylase: identification of components critical for folding the catalytic domain and for constructing the active site structure.

    Science.gov (United States)

    Sakaguchi, Masayoshi; Matsushima, Yudai; Nagamine, Yusuke; Matsuhashi, Tomoki; Honda, Shotaro; Okuda, Shoi; Ohno, Misa; Sugahara, Yasusato; Shin, Yongchol; Oyama, Fumitaka; Kawakita, Masao

    2017-03-01

    Clostridium sp. G0005 glucoamylase (CGA) is composed of a β-sandwich domain (BD), a linker, and a catalytic domain (CD). In the present study, CGA was expressed in Escherichia coli as inclusion bodies when the N-terminal region (39 amino acid residues) of the BD was truncated. To further elucidate the role of the N-terminal region of the BD, we constructed N-terminally truncated proteins (Δ19, Δ24, Δ29, and Δ34) and assessed their solubility and activity. Although all evaluated proteins were soluble, their hydrolytic activities toward maltotriose as a substrate varied: Δ19 and Δ24 were almost as active as CGA, but the activity of Δ29 was substantially lower, and Δ34 exhibited little hydrolytic activity. Subsequent truncation analysis of the N-terminal region sequence between residues 25 and 28 revealed that truncation of less than 26 residues did not affect CGA activity, whereas truncation of 26 or more residues resulted in a substantial loss of activity. Based on further site-directed mutagenesis and N-terminal sequence analysis, we concluded that the 26XaaXaaTrp28 sequence of CGA is important in exhibiting CGA activity. These results suggest that the N-terminal region of the BD in bacterial GAs may function not only in folding the protein into the correct structure but also in constructing a competent active site for catalyzing the hydrolytic reaction.

  8. Growth-induced non-stoichiometry in complex oxide systems

    Science.gov (United States)

    Breckenfeld, Eric

    Complex perovskite oxides have been studied extensively over the past few decades due to their wide range of functional properties and relative ease of epitaxial synthesis. These two factors have allowed such oxide systems to see a multitude of applications including sensors, memory, thermal management, and energy harvesting. The ability to access so many different functionalities is owed largely to the chemical diversity available to the perovskite unit cell, opening the door for metal-insulator-transitions, ferroelectricity, and superconductivity, to name a few. However, the same chemical diversity that enables so many potential applications also opens the door for a myriad of chemistry-related defects. Separating out the relative contributions of such extrinsic (or defect-driven) effects from the intrinsic material properties is crucial to enabling the use of these materials in high-performance, next-generation devices. In this work, we examine several model systems in order to explore the relationship between the pulsed laser deposition growth process, the film chemistry, and the subsequent effects on the defect landscape and film properties. We show that small changes to the laser fluence can have a marked impact on the chemical composition of the film, leading to cation stoichiometry deviations as large as 10% in SrTiO3, LaAlO3, and NdNiO3 systems. We demonstrate that such chemical deviations can lead to significant changes in the bulk thermal and dielectric properties of SrTiO3 and LaAlO3 films. We have also investigated the interface between SrTiO3 and LaAlO3, which has been studied extensively over the past 8 years due to the supposed presence of a 2-dimensional electron gas (2DEG). Our results indicate that the presence of cation defects in the LaAlO3 has a profound impact on the electronic properties of the 2DEG interface. Finally, we have similarly shown that cation non-stoichiometry can cause the metal-insulator-transition material NdNiO3 to behave

  9. Catalytic membrane in reduction of aqueous nitrates: operational principles and catalytic performance

    NARCIS (Netherlands)

    Ilinitch, O.M.; Cuperus, F.P.; Nosova, L.V.; Gribov, E.N.

    2000-01-01

    The catalytic membrane with palladium-copper active component supported over the macroporous ceramic membrane, and a series of γ-Al 2O 3 supported Pd-Cu catalysts were prepared and investigated. In reduction of nitrate ions by hydrogen in water at ambient temperature, pronounced internal diffusion

  10. 尿苷-5′-二磷酸葡萄糖醛酸转移酶对常见植物药组分的催化代谢及其相互作用%Catalytic metabolism and interaction of herbs and their components mediated by uridine 5′-diphosphate glucuronosyltransferases

    Institute of Scientific and Technical Information of China (English)

    高瑞; 陈昱; 张文; 夏春华; 张红; 黄世博; 熊玉卿

    2014-01-01

    尿苷-5′-二磷酸葡萄糖醛酸转移酶( UGT)是药物II相代谢反应最主要的酶,通过催化葡萄糖醛酸与内源性或外源性化学物质发生葡萄糖醛酸化反应,进而影响药物的药代动力学特征。许多植物药及其有效成分是UGT的底物,由UGT介导其催化代谢。本文概述了UGT酶介导某些植物药及其组分的催化代谢和对UGT酶活性的影响。%Uridine 5′-diphosphate glucuronosyltransferases ( UGT ) are the most important phase II drug metabolizing enzymes.They catalyze the glucuronidation of endogenous or exogenous chemicals , which then affect the pharmacokinetic characteristics of co -administrated drugs.Many herbs as well as their active ingredients are the substrates of UGT and their catalytic metabolism are mediated by UGT.This paper summarizes the catalytic metabolism of some herbs and their components mediated by UGT and their influence on UGT activity.

  11. Catalytic efficiency of designed catalytic proteins.

    Science.gov (United States)

    Korendovych, Ivan V; DeGrado, William F

    2014-08-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution.

  12. Catalytic efficiency of designed catalytic proteins

    Science.gov (United States)

    Korendovych, Ivan V; DeGrado, William F

    2014-01-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution. PMID:25048695

  13. Catalytic Phosphination and Arsination

    Institute of Scientific and Technical Information of China (English)

    Kwong Fuk Yee; Chan Kin Shing

    2004-01-01

    The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis.

  14. Influence of stoichiometry on the electrochromiccerium-titanium oxide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kullman, L.; Richardson, T.; Rubin, M.; Slack, J.; von Rottkay, K.

    1997-11-01

    CeO2-TiO2 finds use as passive counter-electrode in electrochromic devices. Thin films were produced by de-sputtering in a wide range of compositions. Influence of total pressure and oxygen partial pressure on the optical constants of TiO2 was investigated. Slightly substoichiometric Ti02 films exhibit a red-shift of the bandgap. The Ti02 content in the compound essentially determines the degree of cathodical coloring upon Li+ intercalation [1]. However, pure TiO2 films with comparable visible transmittance in the clear state behave differently during electrochemical cycling depending on oxygen stoichiometry. Films that are deposited at higher total pressure are more oxygen rich and require initial formatting until current voltage cycles become stable. CeO2-Ti02 films of intermediate compositions have the relatively highest charge capacity. Comparison with atomic force microscopy indicates a correlation of small grain size with high charge capacity.

  15. What Is the Overall Stoichiometry of a Complex Reaction?

    Science.gov (United States)

    Toby, Sidney; Tobias, Irwin

    2003-05-01

    The overall stoichiometry of a reaction having a multistep mechanism can be derived using methods based on either of the following two approaches: elemental-balance or extent of reaction. The extent of reaction method (ξ method) has been used for many years. We have recently shown (J.Chem. Educ. 2000, 77, 188) that integration of rate equations (the kinetic method) offers an alternative to the ξ method using methods that may be more familiar to many chemists. The two methods are, however, equivalent and give the same results, as pointed out in the Appendix. The elemental-balance method is the simplest of the three methods but, as we shall show, it does not always give as much information about the system being analyzed as do the other two methods. In this paper both elemental-balance and kinetic methods will be used to derive stoichiometric relationships and the results will be compared. We show that each method has its advantages and conclude that both methods are useful in different contexts.

  16. Complexation, Stability and Stoichiometry of Iron (III with Salbutamol

    Directory of Open Access Journals (Sweden)

    *N. Fatima

    2012-06-01

    Full Text Available Asthma is a wide speared disease all over the world. In this disease breathing is not smooth due to contraction of bronchitis. Ventolin is an effective drug for this purpose and is widely used. Its active ingredient is Salbutamol Sulphate, which is bronchodilator. Due to oxygen and nitrogen donor sites of Salbutamol (Fig I, it has been assumed that it may interact with metals present in the biological system, and therefore disturb the metals metabolism and imbalance the equilibrium. On the other hand two third of the body’s iron is found in hemoglobin which is an oxygen storage protein. Therefore may iron is chelated by the Salbutamol ion in the stomach. The chelation of iron by salbutamol, stability of the complex and Stoichiometry at acidic pH of the said complex is investigated implied Spectrophotometric technique. Salbutamol formed highly colored complex with iron having maximum absorbance at 550nm. A 1:3 complex formation in buffered and non buffered solutions at 30°C was found using mole ratio and slope ratio methods. Molar extinction coefficients were determined by calibration curve method and was found very high in non buffered solution comparative to buffered solutions. Stability constant of ML1 is found 6.3635, ML2 is 11.919 and ML3 is 16.858 in non buffered solution. Closer ln values were found in buffer of pH 3.0 and 3.5.

  17. Stoichiometry of Reducing Equivalents and Splitting of Water in the Citric Acid Cycle.

    Science.gov (United States)

    Madeira, Vitor M. C.

    1988-01-01

    Presents a solution to the problem of finding the source of extra reducing equivalents, and accomplishing the stoichiometry of glucose oxidation reactions. Discusses the citric acid cycle and glycolysis. (CW)

  18. Impact of stoichiometry representation on simulation of genotype-phenotype relationships in metabolic networks

    DEFF Research Database (Denmark)

    Brochado, Ana Rita; Andrejev, Sergej; Maranas, Costas D.

    2012-01-01

    linear combination of selected fluxes is widely used for formulating metabolic objective functions, we show that the resulting optimization problem is sensitive towards stoichiometry representation of the metabolic network. This undesirable sensitivity leads to different simulation results when using...... numerically different but biochemically equivalent stoichiometry representations and thereby makes biological interpretation intrinsically subjective and ambiguous. We hereby propose a new method, Minimization of Metabolites Balance (MiMBl), which decouples the artifacts of stoichiometry representation from...... the formulation of the desired objective functions, by casting objective functions using metabolite turnovers rather than fluxes. By simulating perturbed metabolic networks, we demonstrate that the use of stoichiometry representation independent algorithms is fundamental for unambiguously linking modeling results...

  19. Stoichiometry of excreta and excretion rates of a stream-dwelling plethodontid salamander

    Data.gov (United States)

    U.S. Environmental Protection Agency — Stoichiometry of excreta and excretion rates of a stream-dwelling plethodontid salamander in Cincinnati, OH, USA. This dataset is associated with the following...

  20. Management practices regulate the response of Moso bamboo foliar stoichiometry to nitrogen deposition.

    Science.gov (United States)

    Song, Xinzhang; Gu, Honghao; Wang, Meng; Zhou, Guomo; Li, Quan

    2016-04-07

    Moso bamboo, well known for its high growth rate, is being subjected to increasing amounts of nitrogen deposition. However, how anthropogenic management practices regulate the effects of N deposition on Moso bamboo stoichiometry remains poorly understood. We observed the effects of two years of simulated N deposition (30, 60 and 90 kg N ha(-1)yr(-1)) on the foliar stoichiometry of Moso bamboo plantations under conventional management (CM) and intensive management (IM). Young bamboo had significantly greater foliar N and P concentrations and N:P ratios than mature plants (P stoichiometry were influenced by management practices and bamboo growth stage. The effects of N deposition on foliar stoichiometry combined with anthropogenic management practices can influence ecosystem production, decomposition, and subsequent N and P cycles in Moso bamboo plantations.

  1. Scale-Dependent Carbon : Nitrogen : Phosphorus Seston Stoichiometry in Marine and Freshwaters

    National Research Council Canada - National Science Library

    Robert W. Sterner; Tom Andersen; James J. Elser; Dag O. Hessen; James M. Hood; Edward McCauley; Jotaro Urabe

    2008-01-01

    ... of >2,000 observations of the chemistry of particulate matter from small and large lakes, as well as near-and off-shore marine environments, we found that the best model to describe seston stoichiometry...

  2. Analysis of acetylation stoichiometry suggests that SIRT3 repairs nonenzymatic acetylation lesions

    DEFF Research Database (Denmark)

    Weinert, Brian T; Moustafa, Tarek; Iesmantavicius, Vytautas

    2015-01-01

    Acetylation is frequently detected on mitochondrial enzymes, and the sirtuin deacetylase SIRT3 is thought to regulate metabolism by deacetylating mitochondrial proteins. However, the stoichiometry of acetylation has not been studied and is important for understanding whether SIRT3 regulates...... or suppresses acetylation. Using quantitative mass spectrometry, we measured acetylation stoichiometry in mouse liver tissue and found that SIRT3 suppressed acetylation to a very low stoichiometry at its target sites. By examining acetylation changes in the liver, heart, brain, and brown adipose tissue...... of fasted mice, we found that SIRT3-targeted sites were mostly unaffected by fasting, a dietary manipulation that is thought to regulate metabolism through SIRT3-dependent deacetylation. Globally increased mitochondrial acetylation in fasted liver tissue, higher stoichiometry at mitochondrial acetylation...

  3. The effects of stoichiometry on the mechanical properties of icosahedral boron carbide under loading.

    Science.gov (United States)

    Taylor, DeCarlos E; McCauley, James W; Wright, T W

    2012-12-19

    The effects of stoichiometry on the atomic structure and the related mechanical properties of boron carbide (B(4)C) have been studied using density functional theory and quantum molecular dynamics simulations. Computational cells of boron carbide containing up to 960 atoms and spanning compositions ranging from 6.7% to 26.7% carbon were used to determine the effects of stoichiometry on the atomic structure, elastic properties, and stress-strain response as a function of hydrostatic, uniaxial, and shear loading paths. It was found that different stoichiometries, as well as variable atomic arrangements within a fixed stoichiometry, can have a significant impact on the yield stress of boron carbide when compressed uniaxially (by as much as 70% in some cases); the significantly reduced strength of boron carbide under shear loading is also demonstrated.

  4. Reprogramming factor stoichiometry influences the epigenetic state and biological properties of induced pluripotent stem cells

    NARCIS (Netherlands)

    Carey, B.W.; Markoulaki, S.; Hanna, J.H.; Faddah, D.A.; Buganim, Y.; Kim, J.; Ganz, K.; Steine, E.J.; Cassady, J.P.; Creyghton, M.P.; Welstead, G.G.; Gao, Q.; Jaenisch, R.

    2011-01-01

    We compared two genetically highly defined transgenic systems to identify parameters affecting reprogramming of somatic cells to a pluripotent state. Our results demonstrate that the level and stoichiometry of reprogramming factors during the reprogramming process strongly influence the resulting pl

  5. Stoichiometry of Reducing Equivalents and Splitting of Water in the Citric Acid Cycle.

    Science.gov (United States)

    Madeira, Vitor M. C.

    1988-01-01

    Presents a solution to the problem of finding the source of extra reducing equivalents, and accomplishing the stoichiometry of glucose oxidation reactions. Discusses the citric acid cycle and glycolysis. (CW)

  6. Variable nutrient stoichiometry (carbon:nitrogen:phosphorus) across trophic levels determines community and ecosystem properties in an oligotrophic mangrove system

    Science.gov (United States)

    Scharler, U.M.; Ulanowicz, Robert E.; Fogel, M.L.; Wooller, M.J.; Jacobson-Meyers, M.E.; Lovelock, C.E.; Feller, I.C.; Frischer, M.; Lee, R.; Mckee, Karen L.; Romero, I.C.; Schmit, J.P.; Shearer, C.

    2015-01-01

    Our study investigated the carbon:nitrogen:phosphorus (C:N:P) stoichiometry of mangrove island of the Mesoamerican Barrier Reef (Twin Cays, Belize). The C:N:P of abiotic and biotic components of this oligotrophic ecosystem was measured and served to build networks of nutrient flows for three distinct mangrove forest zones (tall seaward fringing forest, inland dwarf forests and a transitional zone). Between forest zones, the stoichiometry of primary producers, heterotrophs and abiotic components did not change significantly, but there was a significant difference in C:N:P, and C, N, and P biomass, between the functional groups mangrove trees, other primary producers, heterotrophs, and abiotic components. C:N:P decreased with increasing trophic level. Nutrient recycling in the food webs was highest for P, and high transfer efficiencies between trophic levels of P and N also indicated an overall shortage of these nutrients when compared to C. Heterotrophs were sometimes, but not always, limited by the same nutrient as the primary producers. Mangrove trees and the primary tree consumers were P limited, whereas the invertebrates consuming leaf litter and detritus were N limited. Most compartments were limited by P or N (not by C), and the relative depletion rate of food sources was fastest for P. P transfers thus constituted a bottleneck of nutrient transfer on Twin Cays. This is the first comprehensive ecosystem study of nutrient transfers in a mangrove ecosystem, illustrating some mechanisms (e.g. recycling rates, transfer efficiencies) which oligotrophic systems use in order to build up biomass and food webs spanning various trophic levels.

  7. Variable nutrient stoichiometry (carbon:nitrogen:phosphorus) across trophic levels determines community and ecosystem properties in an oligotrophic mangrove system.

    Science.gov (United States)

    Scharler, U M; Ulanowicz, R E; Fogel, M L; Wooller, M J; Jacobson-Meyers, M E; Lovelock, C E; Feller, I C; Frischer, M; Lee, R; McKee, K; Romero, I C; Schmit, J P; Shearer, C

    2015-11-01

    Our study investigated the carbon:nitrogen:phosphorus (C:N:P) stoichiometry of mangrove island of the Mesoamerican Barrier Reef (Twin Cays, Belize). The C:N:P of abiotic and biotic components of this oligotrophic ecosystem was measured and served to build networks of nutrient flows for three distinct mangrove forest zones (tall seaward fringing forest, inland dwarf forests and a transitional zone). Between forest zones, the stoichiometry of primary producers, heterotrophs and abiotic components did not change significantly, but there was a significant difference in C:N:P, and C, N, and P biomass, between the functional groups mangrove trees, other primary producers, heterotrophs, and abiotic components. C:N:P decreased with increasing trophic level. Nutrient recycling in the food webs was highest for P, and high transfer efficiencies between trophic levels of P and N also indicated an overall shortage of these nutrients when compared to C. Heterotrophs were sometimes, but not always, limited by the same nutrient as the primary producers. Mangrove trees and the primary tree consumers were P limited, whereas the invertebrates consuming leaf litter and detritus were N limited. Most compartments were limited by P or N (not by C), and the relative depletion rate of food sources was fastest for P. P transfers thus constituted a bottleneck of nutrient transfer on Twin Cays. This is the first comprehensive ecosystem study of nutrient transfers in a mangrove ecosystem, illustrating some mechanisms (e.g. recycling rates, transfer efficiencies) which oligotrophic systems use in order to build up biomass and food webs spanning various trophic levels.

  8. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System.

    Science.gov (United States)

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-10-26

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

  9. Lake nutrient stoichiometry is less predictable than nutrient concentrations at regional and sub-continental scales.

    Science.gov (United States)

    Collins, Sarah M; Oliver, Samantha K; Lapierre, Jean-Francois; Stanley, Emily H; Jones, John R; Wagner, Tyler; Soranno, Patricia A

    2017-07-01

    Production in many ecosystems is co-limited by multiple elements. While a known suite of drivers associated with nutrient sources, nutrient transport, and internal processing controls concentrations of phosphorus (P) and nitrogen (N) in lakes, much less is known about whether the drivers of single nutrient concentrations can also explain spatial or temporal variation in lake N:P stoichiometry. Predicting stoichiometry might be more complex than predicting concentrations of individual elements because some drivers have similar relationships with N and P, leading to a weak relationship with their ratio. Further, the dominant controls on elemental concentrations likely vary across regions, resulting in context dependent relationships between drivers, lake nutrients and their ratios. Here, we examine whether known drivers of N and P concentrations can explain variation in N:P stoichiometry, and whether explaining variation in stoichiometry differs across regions. We examined drivers of N:P in ~2,700 lakes at a sub-continental scale and two large regions nested within the sub-continental study area that have contrasting ecological context, including differences in the dominant type of land cover (agriculture vs. forest). At the sub-continental scale, lake nutrient concentrations were correlated with nutrient loading and lake internal processing, but stoichiometry was only weakly correlated to drivers of lake nutrients. At the regional scale, drivers that explained variation in nutrients and stoichiometry differed between regions. In the Midwestern U.S. region, dominated by agricultural land use, lake depth and the percentage of row crop agriculture were strong predictors of stoichiometry because only phosphorus was related to lake depth and only nitrogen was related to the percentage of row crop agriculture. In contrast, all drivers were related to N and P in similar ways in the Northeastern U.S. region, leading to weak relationships between drivers and stoichiometry

  10. Selective Catalytic Reduction of NO with Methane

    Institute of Scientific and Technical Information of China (English)

    Xiang Gao; Qi Yu; Limin Chen

    2003-01-01

    The removal of nitrogen oxides from exhaust gases has attracted great attention in recent years, and many approaches have been developed depending on the application. Methane, the main component of natural gas, has great potential as a NO reductant. In this paper, a number of catalysts previous reported for this catalytic reduction of NO have been reviewed, including a direct comparison of the relative activities and effective factors of the catalysts. Reaction mechanisms have also been explored preliminarily.

  11. The Effects of Nutrient Imbalances and Temperature on the Biomass Stoichiometry of Freshwater Bacteria.

    Science.gov (United States)

    Phillips, Katherine N; Godwin, Casey M; Cotner, James B

    2017-01-01

    Two contemporary effects of humans on aquatic ecosystems are increasing temperatures and increasing nutrient concentrations from fertilizers. The response of organisms to these perturbations has important implications for ecosystem processes. We examined the effects of phosphorus (P) supply and temperature on organismal carbon, nitrogen and phosphorus (C, N, and P) content, cell size and allocation into internal P pools in three strains of recently isolated bacteria (Agrobacterium sp., Flavobacterium sp., and Arthrobacter sp.). We manipulated resource C:P in chemostats and also manipulated temperatures from 10 to 30°C. Dilution rates were maintained for all the strains at ~25% of their temperature-specific maximum growth rate to simulate low growth rates in natural systems. Under these conditions, there were large effects of resource stoichiometry and temperature on biomass stoichiometry, element quotas, and cell size. Each strain was smaller when C-limited and larger when P-limited. Temperature had weak effects on morphology, little effect on C quotas, no effect on N quotas and biomass C:N, but had strong effects on P quotas, biomass N:P and C:P, and RNA. RNA content per cell increased with increasing temperature at most C:P supply ratios, but was more strongly affected by resource stoichiometry than temperature. Because we used a uniform relative growth rate across temperatures, these findings mean that there are important nutrient and temperature affects on biomass composition and stoichiometry that are independent of growth rate. Changes in biomass stoichiometry with temperature were greatest at low P availability, suggesting tighter coupling between temperature and biomass stoichiometry in oligotrophic ecosystems than in eutrophic systems. Because the C:P stoichiometry of biomass affects how bacteria assimilate and remineralize C, increased P availability could disrupt a negative feedback between biomass stoichiometry and C availability.

  12. Plant and soil nutrient stoichiometry along primary ecological successions: Is there any link?

    Science.gov (United States)

    Di Palo, Francesca; Fornara, Dario A

    2017-01-01

    Ecological stoichiometry suggests that plant Nitrogen (N)-to-Phosphorus (P) ratios respond to changes in both soil N:P stoichiometry and soil N and P availability. Thus we would expect that soil and plant N:P ratios be significantly related along natural gradients of soil development such as those associated with primary ecological successions. Here we explicitly search for linkages between plant and soil N:P stoichiometry along four primary successions distributed across Europe. We measured N and P content in soils and plant compartments (leaf, stem and root) of 72 wild plant species distributed along two sand dune and two glacier successions where soil age ranges from few to thousand years old. Overall we found that soil N:P ratios strongly increased along successional stages, however, plant N:P ratios were neither related to soil N:P stoichiometry nor to changes in soil N and P availability. Instead changes in plant nutrient stoichiometry were "driven" by plant-functional-group identity. Not only N:P ratios differed between legumes, grasses and forbs but each of these plant functional groups maintained N:P ratios relatively constant across pioneer, middle and advanced successional stages. Our evidence is that soil nutrient stoichiometry may not be a good predictor of changes in plant N:P stoichiometry along natural primary ecological successions, which have not reached yet a retrogressive stage. This could be because wild-plants rely on mechanisms of internal nutrient regulation, which make them less dependent to changes in soil nutrient availability under unpredictable environmental conditions. Further studies need to clarify what underlying evolutionary and eco-physiological mechanisms determine changes in nutrient stoichiometry in plant species distributed across natural environmental gradients.

  13. Fingerprint spectra in Laser Microprobe Mass Analysis of titanium oxides of different stoichiometry

    Science.gov (United States)

    Michiels, Eric; Gijbels, Renaat

    Micrometric particles of powdered titanium oxides of different stoichiometry (TiO 2, Ti 2O 3 and TiO) are examined by Laser Microprobe Mass Analysis (LAMMA). The stoichiometry of the compound can be correlated with the relative intensity distributions of the (positive or negative) cluster and atomic ions. Application of the "valence model" yields similar conclusions. Variations in laser energy density and in ion lens potential also effect the ion intensity distributions.

  14. The structure and continuous stoichiometry change of 1DTbBrx@SWCNTs.

    Science.gov (United States)

    Kiselev, N A; Kumskov, A S; Zhigalina, V G; Vasiliev, A L; Sloan, J; Falaleev, N S; Verbitskiy, N I; Eliseev, A A

    2016-04-01

    HRTEM and HAADF STEM of 1DTbBrx@SWCNT meta-nanotubes reveal three structural modifications of 1D nanocrystals within single wall carbon nanotube channels attributed to a different stoichiometry of the guest crystal. For SWCNTs with diameters Dm > 1.4 nm a most complete tetragonal unit cell is observed. When crystallization occurs inside SWCNT with Dm stoichiometry change in 1D nanocrystal indicating an average Tb:Br atomic ratio of 1:2.8 ± 0.1.

  15. Long-term macronutrient stoichiometry of UK ombrotrophic peatlands

    Science.gov (United States)

    Schillereff, Daniel; Boyle, John; Toberman, Hannah; Adams, Jessica; Tipping, Ed

    2016-04-01

    Ombrotrophic peatlands across northern latitudes represent a globally-important store for carbon (C), nitrogen (N) and phosphorus (P) through the Holocene. A key characteristic of ombrotrophic bogs is that N, P and other elements vital to their biogeochemical functioning are almost exclusively supplied by hydrological and biological inputs from the atmosphere. While different mechanisms regulating the atmospheric supply of N and P and their limiting effects on bog productivity have been widely studied, limited attention has been paid to the long-term patterns of, and controls on, macronutrient accumulation, cycling and stoichiometry in ombrotrophic peatlands. Indeed there is a dearth of C, N and P stoichiometric data from the UK despite decades of peatland research. Using data from 15 sites, we report the first estimates of millennial-scale macronutrient concentrations and accumulation rates in UK ombrotrophic peats. Carbon, nitrogen and phosphorus concentrations were measured on cores from five ombrotrophic blanket mires, spanning 4000-10000 years to present, and integrated with existing nutrient profiles from ten Scottish sites. Long-term C, N and P concentrations for the UK are 55.1, 1.55 and 0.037 wt%, similar to the few existing northern and tropical comparable sites worldwide. The uppermost peat (0 - 0.2 m) is more enriched in P and N (51.0, 1.86, and 0.070 wt%), while the deeper peat (0.5 - 1.25 m) is more depleted (56.6, 1.39, and 0.028 wt%). Long-term average (whole core) accumulation rates of carbon, nitrogen and phosphorus are 25.3±2.2 gC m-2 yr-1, 0.70±0.09 gN m-2 yr-1 and 0.018±0.004 gP m-2 yr-1, again similar to values reported elsewhere in the world. A number of significant findings can be drawn from our results: i) N and P concentrations in ombrotrophic peat are strongly associated, such that a regression model of N concentration on P concentration and mean annual precipitation, based on global meta data for surface peat samples, can explain 54

  16. CZTS stoichiometry effects on the band gap energy

    Energy Technology Data Exchange (ETDEWEB)

    Malerba, Claudia, E-mail: claudia.malerba-1@ing.unitn.it [University of Trento, Department of Civil, Environmental and Mechanical Engineering, via Mesiano 77, 38123 Trento (Italy); ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy); Biccari, Francesco [ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy); Azanza Ricardo, Cristy Leonor [University of Trento, Department of Civil, Environmental and Mechanical Engineering, via Mesiano 77, 38123 Trento (Italy); Valentini, Matteo [Sapienza – University of Rome, Department of Physics, p.le A. Moro 5, 00185 Roma (Italy); ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy); Chierchia, Rosa [ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy); Müller, Melanie [University of Trento, Department of Civil, Environmental and Mechanical Engineering, via Mesiano 77, 38123 Trento (Italy); Max Planck Institute for Solid State Research, Heisenberg str. 1, 70569 Stuttgart (Germany); Santoni, Antonino [ENEA, Frascati Research Center, via E. Fermi 45, 00044 Frascati (Italy); Esposito, Emilia [ENEA, Portici Research Center, Piazzale E. Fermi, 80055 Portici (Napoli) (Italy); Mangiapane, Pietro [ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy); Scardi, Paolo [University of Trento, Department of Civil, Environmental and Mechanical Engineering, via Mesiano 77, 38123 Trento (Italy); Mittiga, Alberto [ENEA, Casaccia Research Center, via Anguillarese 301, 00123 Roma (Italy)

    2014-01-05

    Highlights: • CZTS films with different compositions were grown from stacked-layer precursors. • The band-gap energy varies from 1.48 to 1.63 eV as the [Sn]/[Cu] ratio increases. • The Zn content seems not to be a critical parameter for the optical properties. • PDS data show an increase of the sub-gap absorption as the Sn content is reduced. • Formation of defects at low Sn content was proposed to explain the Eg variation. -- Abstract: The considerable spread of Cu{sub 2}ZnSnS{sub 4} (CZTS) optical properties reported in the literature is discussed in terms of material stoichiometry. To this purpose, kesterite thin films were prepared by sulfurization of multilayered precursors of ZnS, Cu and Sn, changing the relative amounts to obtain CZTS layers with different compositions. X-Ray Diffraction (XRD), Energy Dispersive X-Ray (EDX) spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Raman spectroscopy were used for structural and compositional analysis. XRD quantitative phase analysis provides the amount of spurious phases and information on Sn-site occupancy. The optical properties were investigated by spectrophotometric and Photothermal Deflection Spectroscopy (PDS) measurements to assess the absorption coefficient of samples with different compositions. The PDS data show an increase of the sub-band absorption as the Sn content decreases. The results are interpreted assuming the formation of additional defects as the tin content is reduced. Those defects can also be responsible for the decrease of the band gap energy value as the Sn/Cu ratio is decreased.

  17. Autotrophic stoichiometry emerging from optimality and variable co-limitation

    Directory of Open Access Journals (Sweden)

    Kai W Wirtz

    2016-11-01

    Full Text Available Autotrophic organisms reveal an astounding flexibility in their elemental stoichiometry, with potentially major implications on biogeochemical cycles and ecological functioning. Notwithstanding, stoichiometric regulation and co-limitation by multiple resources in autotrophs revt were in the past often described by heuristic formulations.In this study, we present a mechanistic model of autotroph growth, which features two major improvements over the existing schemes. First, we introduce the concept of metabolic network independence that defines the degree of phase-locking between accessory machines. Network independence is in particular suggested to be proportional to protein synthesis capability as quantified by variable intracellular N:C. Consequently, the degree of co-limitation becomes variable, contrasting with the dichotomous debate on the use of Liebig's law or the product rule, standing for constantly low and high co-limitation, respectively. Second, we resolve dynamic protein partitioning to light harvesting, carboxylation processes, and to an arbitrary number of nutrient acquisition machineries, as well as instantaneous activity regulation of nutrient uptake. For all regulatory processes we assume growth rate optimality, here extended by an explicit consideration of indirect feed-back effects.The combination of network independence and optimal regulation displays unprecedented skill in reproducing rich stoichiometric patterns collected from a large number of published chemostat experiments. This high skill indicates (1 that the current paradigm of fixed co-limitation is a critical short-coming of conventional models, and (2 that stoichiometric flexibility in autotrophs possibly reflects an optimality strategy. Numerical experiments furthermore show that regulatory mechanisms homogenize the effect of multiple stressors. Extended optimality alleviates the effect of the most limiting resource(s while down-regulating machineries for the

  18. Catalytic decarboxylations of fatty acids in immature oil source rocks

    Institute of Scientific and Technical Information of China (English)

    李哲; 张再龙; 孙燕华; 劳永新; 蔺五正; 吴卫芳

    2003-01-01

    Catalytic decarboxylations of fatty acids in immature oil source rock samples were examined in this study. The rock samples were obtained from seven oil fields in China. In order to clarify the effect of each mineral matter in the rock samples, both the Fe M?ssbauer effect and the X-ray diffraction (XRD) were used to determine the relative content of each mineral in the rock samples, and the catalytic activities of several minerals like clays, carbonates and pyrite were determined. The Fe M?ssbauer effect and the XRD studies show that clays are the main mineral components in the rock samples except for the samples from Biyang and Jianghan in which the main mineral component is ankerite. The other mineral components include calcite, plagioclase, quartz, feldspar, siderite, aragonite, pyrite, analcime, pyroxene and anhydrite. The studies of the catalytic decarboxylations of fatty acids suggest that carbonates and pyrite can make much greater contributions to the catalytic activities of the rock samples than clays. It is found that the overall catalytic activities of the rock samples are well related to the relative contents and the catalytic activities of clays, carbonates and pyrite in the rock samples.

  19. Electroanalytical Assessment of the Effect of Ni:Fe Stoichiometry and Architectural Expression on the Bifunctional Activity of Nanoscale NiyFe1-yOx.

    Science.gov (United States)

    Ko, Jesse S; Chervin, Christopher N; Vila, Mallory N; DeSario, Paul A; Parker, Joseph F; Long, Jeffrey W; Rolison, Debra R

    2017-09-19

    Electrocatalysis of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) was assessed for a series of Ni-substituted ferrites (NiyFe1-yOx, where y = 0.1 to 0.9) as expressed in porous, high-surface-area forms (ambigel and aerogel nanoarchitectures). We then correlate electrocatalytic activity with Ni:Fe stoichiometry as a function of surface area, crystallite size, and free volume. In order to ensure in-series comparisons, calcination at 350 °C/air was necessary to crystallize the respective NiyFe1-yOx nanoarchitectures, which index to the inverse spinel structure for Fe-rich materials (y ≤ 0.33), rock salt for the most Ni-rich material (y = 0.9), and biphasic for intermediate stoichiometry (0.5 ≤ y ≤ 0.67). In the intermediate Ni:Fe stoichiometric range (0.33 ≤ y ≤ 0.67), the OER current density at 390 mV increases monotonically with increasing Ni content and increasing surface area, but with different working curves for ambigels versus aerogels. At a common stoichiometry within this range, ambigels and aerogels yield comparable OER performance, but do so by expressing larger crystallite size (ambigel) versus higher surface area (aerogel). Effective OER activity can be achieved without requiring supercritical-fluid extraction as long as moderately high surface area, porous materials can be prepared. We find improved OER performance (η decreases from 390 to 373 mV) for Ni0.67Fe0.33Ox aerogel heat-treated at 300 °C/Ar, owing to an increase in crystallite size (2.7 to 4.1 nm). For the ORR, electrocatalytic activity favors Fe-rich NiyFe1-yOx materials; however, as the Ni-content increases beyond y = 0.5, a two-electron reduction pathway is still exhibited, demonstrating that bifunctional OER and ORR activity may be possible by choosing a nickel ferrite nanoarchitecture that provides high OER activity with sufficient ORR activity. Assessing the catalytic activity requires an appreciation of the multivariate interplay among Ni

  20. The upper and lower limits of the mechanistic stoichiometry of mitochondrial oxidative phosphorylation. Stoichiometry of oxidative phosphorylation.

    Science.gov (United States)

    Beavis, A D; Lehninger, A L

    1986-07-15

    Determination of the intrinsic or mechanistic P/O ratio of oxidative phosphorylation is difficult because of the unknown magnitude of leak fluxes. Applying a new approach developed to overcome this problem (see our preceding paper in this journal), the relationships between the rate of O2 uptake [( Jo)3], the net rate of phosphorylation (Jp), the P/O ratio, and the respiratory control ratio (RCR) have been determined in rat liver mitochondria when the rate of phosphorylation was systematically varied by three specific means. (a) When phosphorylation is titrated with carboxyatractyloside, linear relationships are observed between Jp and (Jo)3. These data indicate that the upper limit of the mechanistic P/O ratio is 1.80 for succinate and 2.90 for 3-hydroxybutyrate oxidation. (b) Titration with malonate or antimycin yields linear relationships between Jp and (Jo)3. These data give the lower limit of the mechanistic P/O ratio of 1.63 for succinate and 2.66 for 3-hydroxybutyrate oxidation. (c) Titration with a protonophore yields linear relationships between Jp, (Jo)3, and (Jo)4 and between P/O and 1/RCR. Extrapolation of the P/O ratio to 1/RCR = 0 yields P/O ratios of 1.75 for succinate and 2.73 for 3-hydroxybutyrate oxidation which must be equal to or greater than the mechanistic stoichiometry. When published values for the H+/O and H+/ATP ejection ratios are taken into consideration, these measurements suggest that the mechanistic P/O ratio is 1.75 for succinate oxidation and 2.75 for NADH oxidation.

  1. Consequences of Modification of Photosystem Stoichiometry and Amount in Cyanobacteria

    Energy Technology Data Exchange (ETDEWEB)

    Vermaas, Willem [Arizona State Univ., Tempe, AZ (United States)

    2016-12-13

    The proposed research seeks to address two interconnected, important questions that impact photosynthetic processes and that reflect key differences between the photosynthetic systems of cyanobacteria and plants or algae. The first question is what are the reasons and consequences of the high photosystem I / photosystem II (PS I/PS II) ratio in many cyanobacteria, vs. a ratio that is close to unity in many plants and algae. The corresponding hypothesis is that most of PS I functions in cyclic electron transport, and that reduction in PS I will result primarily in a shortage of ATP rather than reducing power. This hypothesis will be tested by reducing the amount of PS I by changing the promoter region of the psaAB operon in the cyanobacterium Synechocystis sp. PCC 6803 and generating a range of mutants with different PS I content and thereby different PS I/PS II ratios, with some of the mutants having a PS II/PS I ratio closer to that in plants. The resulting mutants will be probed in terms of their growth rates, electron transfer rates, and P700 redox kinetics. A second question relates to a Mehler-type reaction catalyzed by two flavoproteins, Flv1 and Flv3, that accept electrons from PS I and that potentially function as an electron safety valve leading to no useful purpose of the photosynthesis-generated electrons. The hypothesis to be tested is that Flv1 and Flv3 use the electrons for useful purposes such as cyclic electron flow around PS I. This hypothesis will be tested by analysis of a mutant strain lacking flv3, the gene for one of the flavoproteins. This research is important for a more detailed understanding of the consequences of photosystem stoichiometry and amounts in a living system. Such an understanding is critical for not only insights in the regulatory systems of the organism but also to guide the development of biological or bio-hybrid systems for solar energy conversion into fuels.

  2. Convergence of detrital stoichiometry predicts thresholds of nutrient-stimulated breakdown in streams.

    Science.gov (United States)

    Manning, David W P; Rosemond, Amy D; Gulis, Vladislav; Benstead, Jonathan P; Kominoski, John S; Maerz, John C

    2016-09-01

    Nutrient enrichment of detritus-based streams increases detrital resource quality for consumers and stimulates breakdown rates of particulate organic carbon (C). The relative importance of dissolved inorganic nitrogen (N) vs. phosphorus (P) for detrital quality and their effects on microbial- vs. detritivore-mediated detrital breakdown are poorly understood. We tested effects of experimental N and P additions on detrital stoichiometry (C:N, C:P) and total and microbial breakdown (i.e., with and without detritivorous shredders, respectively) of five detritus types (four leaf litter species and wood) with different initial C : nutrient content. We enriched five headwater streams continuously for two years at different relative availabilities of N and P and compared breakdown rates and detrital stoichiometry to pretreatment conditions. Total breakdown rates increased with nutrient enrichment and were predicted by altered detrital stoichiometry. Streamwater N and P, fungal biomass, and their interactions affected stoichiometry of detritus. Streamwater N and P decreased detrital C:N, whereas streamwater P had stronger negative effects on detrital C:P. Nutrient addition and fungal biomass reduced C:N by 70% and C:P by 83% on average after conditioning, compared to only 26% for C:N and 10% for C:P under pretreatment conditions. Detritus with lowest initial nutrient content changed the most and had greatest increases in total breakdown rates. Detrital stoichiometry was reduced and differences among detritus types were homogenized by nutrient enrichment. With enrichment, detrital nutrient content approached detritivore nutritional requirements and stimulated greater detritivore vs. microbial litter breakdown. We used breakpoint regression to estimate values of detrital stoichiometry that can potentially be used to indicate elevated breakdown rates. Breakpoint ratios for total breakdown were 41 (C:N) and 1518 (C:P), coinciding with total breakdown rates that were ~1.9

  3. Evolution of organismal stoichiometry in a long-term experiment with Escherichia coli.

    Science.gov (United States)

    Turner, Caroline B; Wade, Brian D; Meyer, Justin R; Sommerfeld, Brooke A; Lenski, Richard E

    2017-07-01

    Organismal stoichiometry refers to the relative proportion of chemical elements in the biomass of organisms, and it can have important effects on ecological interactions from population to ecosystem scales. Although stoichiometry has been studied extensively from an ecological perspective, much less is known about the rates and directions of evolutionary changes in elemental composition. We measured carbon, nitrogen and phosphorus content of 12 Escherichia coli populations that evolved under controlled carbon-limited, serial-transfer conditions for 50 000 generations. The bacteria evolved higher relative nitrogen and phosphorus content, consistent with selection for increased use of the more abundant elements. Total carbon assimilated also increased, indicating more efficient use of the limiting element. We also measured stoichiometry in one population repeatedly through time. Stoichiometry changed more rapidly in early generations than later on, similar to the trajectory seen for competitive fitness. Altogether, our study shows that stoichiometry evolved over long time periods, and that it did so in a predictable direction, given the carbon-limited environment.

  4. Plant fertilization interacts with life history: variation in stoichiometry and performance in nettle-feeding butterflies.

    Directory of Open Access Journals (Sweden)

    Hélène Audusseau

    Full Text Available Variation in food stoichiometry affects individual performance and population dynamics, but it is also likely that species with different life histories should differ in their sensitivity to food stoichiometry. To address this question, we investigated the ability of the three nettle-feeding butterflies (Aglais urticae, Polygonia c-album, and Aglais io to respond adaptively to induced variation in plant stoichiometry in terms of larval performance. We hypothesized that variation in larval performance between plant fertilization treatments should be functionally linked to species differences in host plant specificity. We found species-specific differences in larval performance between plant fertilization treatments that could not be explained by nutrient limitation. We showed a clear evidence of a positive correlation between food stoichiometry and development time to pupal stage and pupal mass in A. urticae. The other two species showed a more complex response. Our results partly supported our prediction that host plant specificity affects larval sensitivity to food stoichiometry. However, we suggest that most of the differences observed may instead be explained by differences in voltinism (number of generations per year. We believe that the potential of some species to respond adaptively to variation in plant nutrient content needs further attention in the face of increased eutrophication due to nutrient leakage from human activities.

  5. Stoichiometry of Site-specific Lysine Acetylation in an Entire Proteome*♦

    Science.gov (United States)

    Baeza, Josue; Dowell, James A.; Smallegan, Michael J.; Fan, Jing; Amador-Noguez, Daniel; Khan, Zia; Denu, John M.

    2014-01-01

    Acetylation of lysine ϵ-amino groups influences many cellular processes and has been mapped to thousands of sites across many organisms. Stoichiometric information of acetylation is essential to accurately interpret biological significance. Here, we developed and employed a novel method for directly quantifying stoichiometry of site-specific acetylation in the entire proteome of Escherichia coli. By coupling isotopic labeling and a novel pairing algorithm, our approach performs an in silico enrichment of acetyl peptides, circumventing the need for immunoenrichment. We investigated the function of the sole NAD+-dependent protein deacetylase, CobB, on both site-specific and global acetylation. We quantified 2206 peptides from 899 proteins and observed a wide distribution of acetyl stoichiometry, ranging from less than 1% up to 98%. Bioinformatic analysis revealed that metabolic enzymes, which either utilize or generate acetyl-CoA, and proteins involved in transcriptional and translational processes displayed the highest degree of acetylation. Loss of CobB led to increased global acetylation at low stoichiometry sites and induced site-specific changes at high stoichiometry sites, and biochemical analysis revealed altered acetyl-CoA metabolism. Thus, this study demonstrates that sirtuin deacetylase deficiency leads to both site-specific and global changes in protein acetylation stoichiometry, affecting central metabolism. PMID:24917678

  6. Plant Fertilization Interacts with Life History: Variation in Stoichiometry and Performance in Nettle-Feeding Butterflies

    Science.gov (United States)

    Audusseau, Hélène; Kolb, Gundula; Janz, Niklas

    2015-01-01

    Variation in food stoichiometry affects individual performance and population dynamics, but it is also likely that species with different life histories should differ in their sensitivity to food stoichiometry. To address this question, we investigated the ability of the three nettle-feeding butterflies (Aglais urticae, Polygonia c-album, and Aglais io) to respond adaptively to induced variation in plant stoichiometry in terms of larval performance. We hypothesized that variation in larval performance between plant fertilization treatments should be functionally linked to species differences in host plant specificity. We found species-specific differences in larval performance between plant fertilization treatments that could not be explained by nutrient limitation. We showed a clear evidence of a positive correlation between food stoichiometry and development time to pupal stage and pupal mass in A. urticae. The other two species showed a more complex response. Our results partly supported our prediction that host plant specificity affects larval sensitivity to food stoichiometry. However, we suggest that most of the differences observed may instead be explained by differences in voltinism (number of generations per year). We believe that the potential of some species to respond adaptively to variation in plant nutrient content needs further attention in the face of increased eutrophication due to nutrient leakage from human activities. PMID:25932628

  7. From Elements to Function: Toward Unifying Ecological Stoichiometry and Trait-Based Ecology

    Directory of Open Access Journals (Sweden)

    Cédric L. Meunier

    2017-05-01

    Full Text Available The theories developed in ecological stoichiometry (ES are fundamentally based on traits. Traits directly linked to cell/body stoichiometry, such as nutrient uptake and storage, as well as the associated trade-offs, have the potential to shape ecological interactions such as competition and predation within ecosystems. Further, traits that indirectly influence and are influenced by nutritional requirements, such as cell/body size and growth rate, are tightly linked to organismal stoichiometry. Despite their physiological and ecological relevance, traits are rarely explicitly integrated in the framework of ES and, currently, the major challenge is to more closely inter-connect ES with trait-based ecology (TBE. Here, we highlight four interconnected nutrient trait groups, i.e., acquisition, body stoichiometry, storage, and excretion, which alter interspecific competition in autotrophs and heterotrophs. We also identify key differences between producer-consumer interactions in aquatic and terrestrial ecosystems. For instance, our synthesis shows that, in contrast to aquatic ecosystems, traits directly influencing herbivore stoichiometry in forested ecosystems should play only a minor role in the cycling of nutrients. We furthermore describe how linking ES and TBE can help predict the ecosystem consequences of global change. The concepts we highlight here allow us to predict that increasing N:P ratios in ecosystems should shift trait dominances in communities toward species with higher optimal N:P ratios and higher P uptake affinity, while decreasing N retention and increasing P storage.

  8. The effect of resource quantity and resource stoichiometry on microbial carbon-use-efficiency

    Science.gov (United States)

    Kleiblinger, K.M.; Hall, E.K.; Wanek, W.; Szukics, U.; Hämmerle, I.; Ellersdorfer, G.; Böck, S.; Strauss, J.; Sterflinger, K.; Richter, A.; Zechmeister-Boltenstern, S.

    2010-01-01

    The carbon-use-efficiency (CUE) of microorganisms is an important parameter in determining ecosystem-level carbon (C) cycling; however, little is known about how variance in resources affects microbial CUE. To elucidate how resource quantity and resource stoichiometry affect microbial CUE, we cultured four microorganisms - two fungi (Aspergillus nidulans and Trichoderma harzianum) and two bacteria (Pectobacterium carotovorum and Verrucomicrobium spinosum) - under 12 unique C, nitrogen (N) and phosphorus (P) ratios. Whereas the CUE of A. nidulans was strongly affected by C, bacterial CUE was more strongly affected by mineral nutrients (N and P). Specifically, CUE in P. carotovorum was positively correlated with P, while CUE of V. spinosum primarily depended on N. This resulted in a positive relationship between fungal CUE and resource C : nutrient stoichiometry and a negative relationship between bacterial CUE and resource C : nutrient stoichiometry. The difference in the direction of the relationship between CUE and C : nutrient for fungi vs. bacteria was consistent with differences in biomass stoichiometry and suggested that fungi have a higher C demand than bacteria. These results suggest that the links between biomass stoichiometry, resource demand and CUE may provide a mechanism for commonly observed temporal and spatial patterns in microbial community structure and function in natural habitats.

  9. Stoichiometry of site-specific lysine acetylation in an entire proteome.

    Science.gov (United States)

    Baeza, Josue; Dowell, James A; Smallegan, Michael J; Fan, Jing; Amador-Noguez, Daniel; Khan, Zia; Denu, John M

    2014-08-01

    Acetylation of lysine ϵ-amino groups influences many cellular processes and has been mapped to thousands of sites across many organisms. Stoichiometric information of acetylation is essential to accurately interpret biological significance. Here, we developed and employed a novel method for directly quantifying stoichiometry of site-specific acetylation in the entire proteome of Escherichia coli. By coupling isotopic labeling and a novel pairing algorithm, our approach performs an in silico enrichment of acetyl peptides, circumventing the need for immunoenrichment. We investigated the function of the sole NAD(+)-dependent protein deacetylase, CobB, on both site-specific and global acetylation. We quantified 2206 peptides from 899 proteins and observed a wide distribution of acetyl stoichiometry, ranging from less than 1% up to 98%. Bioinformatic analysis revealed that metabolic enzymes, which either utilize or generate acetyl-CoA, and proteins involved in transcriptional and translational processes displayed the highest degree of acetylation. Loss of CobB led to increased global acetylation at low stoichiometry sites and induced site-specific changes at high stoichiometry sites, and biochemical analysis revealed altered acetyl-CoA metabolism. Thus, this study demonstrates that sirtuin deacetylase deficiency leads to both site-specific and global changes in protein acetylation stoichiometry, affecting central metabolism.

  10. Mathematical calculations of iron complex stoichiometry by direct UV-Vis spectrophotometry.

    Science.gov (United States)

    Filipský, Tomáš; Říha, Michal; Hrdina, Radomír; Vávrová, Kateřina; Mladěnka, Přemysl

    2013-08-01

    The effects of iron-chelating agents on miscellaneous pathologies are currently largely tested. Due to various indications, different properties for chelators are required. A stoichiometry of the complex in relation to pH is one of the crucial factors. Moreover, the published data on the stoichiometry, especially concerning flavonoids, are equivocal. In this study, a new complementary approach was employed for the determination of stoichiometry in 10 iron-chelating agents, including clinically used drugs, by UV-Vis spectrophotometry at relevant pH conditions and compared with the standard Job's method. This study showed that the simple approach based on absorbance at the wavelength of complex absorption maximum was sufficient when the difference between absorption maximum of substance and complex was high. However, in majority of substances this difference was much lower (9-73 nm). The novel complementary approach was able to determine the stoichiometry in all tested cases. The major benefit of this method compared to the standard Job's approach seems to be its capability to reveal a reaction stoichiometry in chelators with moderate affinity to iron. In conclusion, using this complementary method may explain several previous contradictory data and lead to a better understanding of the underlying mechanisms of chelator's action.

  11. The stoichiometry of the nucleoporin 62 subcomplex of the nuclear pore in solution.

    Science.gov (United States)

    Ulrich, Alexander; Partridge, James R; Schwartz, Thomas U

    2014-05-01

    The nuclear pore complex (NPC) regulates transport between the nucleus and cytoplasm. Soluble cargo-protein complexes navigate through the pore by binding to phenylalanine-glycine (FG)-repeat proteins attached to the channel walls. The Nup62 complex contains the FG-repeat proteins Nup62, Nup54, and Nup58 and is located in the center of the NPC. The three proteins bind each other via conserved coiled-coil segments. To determine the stoichiometry of the Nup62 complex, we undertook an in vitro study using gel filtration and analytical ultracentrifugation. Our results reveal a 1:1:1 stoichiometry of the Nup62 complex, where Nup54 is central with direct binding to Nup62 and Nup58. At high protein concentration, the complex forms larger assemblies while maintaining the Nup62:Nup54:Nup58 ratio. For the homologous Nsp1 complex from Saccharomyces cerevisiae, we determine the same stoichiometry, indicating evolutionary conservation. Furthermore, we observe that eliminating one binding partner can result in the formation of complexes with noncanonical stoichiometry, presumably because unpaired coiled-coil elements tend to find a promiscuous binding partner. We suggest that these noncanonical stoichiometries observed in vitro are unlikely to be physiologically relevant.

  12. Plant fertilization interacts with life history: variation in stoichiometry and performance in nettle-feeding butterflies.

    Science.gov (United States)

    Audusseau, Hélène; Kolb, Gundula; Janz, Niklas

    2015-01-01

    Variation in food stoichiometry affects individual performance and population dynamics, but it is also likely that species with different life histories should differ in their sensitivity to food stoichiometry. To address this question, we investigated the ability of the three nettle-feeding butterflies (Aglais urticae, Polygonia c-album, and Aglais io) to respond adaptively to induced variation in plant stoichiometry in terms of larval performance. We hypothesized that variation in larval performance between plant fertilization treatments should be functionally linked to species differences in host plant specificity. We found species-specific differences in larval performance between plant fertilization treatments that could not be explained by nutrient limitation. We showed a clear evidence of a positive correlation between food stoichiometry and development time to pupal stage and pupal mass in A. urticae. The other two species showed a more complex response. Our results partly supported our prediction that host plant specificity affects larval sensitivity to food stoichiometry. However, we suggest that most of the differences observed may instead be explained by differences in voltinism (number of generations per year). We believe that the potential of some species to respond adaptively to variation in plant nutrient content needs further attention in the face of increased eutrophication due to nutrient leakage from human activities.

  13. Teaching Reaction Stoichiometry: Exploring and Acknowledging Nigerian Chemistry Teachers Pedagogical Content Knowledge

    Directory of Open Access Journals (Sweden)

    Ayoade Ejiwale Okanlawon

    2010-06-01

    Full Text Available Although there is a growing interest in studies of students’ problem-solving strategies and difficulties, and misconceptionsregarding stoichiometry, little is known about the way teachers understand and teach reaction stoichiometry. This articlepresents a case study of pedagogical content knowledge put into actions by chemistry teachers when teaching the topic ofstoichiometry to second year senior secondary school students. Fourteen chemistry teachers with teaching experience rangingfrom 5 to 20 years were involved in this study. Research data were obtained from classroom observations and videotapedrecordings of classroom practice. Analyses of the teachers’ teaching activities revealed their skillfulness, resourcefulness, andweaknesses in terms of pedagogical content knowledge displayed when teaching stoichiometry. The results of this exploratorystudy offer insight into the knowledge systems that need to be expanded, enriched, and elaborated for teaching stoichiometry.To better understand the findings of this study, the results obtained were presented under two separate sections: (1 resultsconcerning introducing reaction stoichiometry to students and (2 results concerning leading students to identify limitingreagents. Implications for instruction and teachers’ professional development are offered.

  14. 铁基活性组分对COS的吸附及催化转化作用%Adsorption performance and catalytic conversion of iron-based active components on COS

    Institute of Scientific and Technical Information of China (English)

    任秀蓉; 王海堂; 常丽萍

    2011-01-01

    采用共沉淀法制备了脱硫用铁基吸附剂的主要活性组分Fe2O3,并对其进行还原处理,制备了不同价态的含铁组分Fe3O4和Fe。使用固定床反应装置分别考察了三者在400~500℃范围内、COS/N2和H2/COS/N2两种气氛下对COS的吸附和催化转化的行为。结果表明:在COS/N2气氛下,三者对COS均有吸附,其吸附能力随温度的变化而异,不同温度下三者对COS吸附的硫容顺序为:Fe2O3〉Fe3O4〉Fe(400℃和450℃);Fe3O4〉Fe2O3〉Fe(500℃)。在H2/COS/N2/气氛下,COS的氢解反应随着温度的升高而增强,各活性组分的硫化产物对COS的氢解反应都具有一定的催化作用,这对于抑制H2S向COS转化具有积极的作用。%The iron-based active component,Fe2O3,was prepared by co-precipitation method.Fe3O4 and Fe,were also prepared by reducing Fe2O3 at different temperature for different time.The adsorption behavior of them was investigated in COS/N2 and H2/COS/N2 gas streams using the fixed bed reactor at 400 ℃,450 ℃ and 500 ℃,respectively.The results show that all three active components can adsorb COS and their adsorption ability varies with temperature.At 500 ℃,the sulfur capacity of Fe3O4 is the highest,and that of Fe is the lowest.While at the temperatures of 450 ℃ and 400 ℃,the sulfur capacity has the following sequence:Fe2O3 Fe3O4 Fe.In H2/COS/N2 gas stream,the reaction of COS hydrogenolysis is enhanced by increasing temperature.The iron sulfides have certain catalysis on COS hydrogenolysis and it has an active influence on inhibition of conversion from H2S to COS.

  15. Nutrient Partitioning and Stoichiometry in Unburnt Sugarcane Ratoon at Varying Yield Levels

    Science.gov (United States)

    Leite, José M.; Ciampitti, Ignacio A.; Mariano, Eduardo; Vieira-Megda, Michele X.; Trivelin, Paulo C. O.

    2016-01-01

    Unraveling nutrient imbalances in contemporary agriculture is a research priority to improve whenever possible yield and nutrient use efficiency in sugarcane (Saccharum spp.) systems while minimizing the costs of cultivation (e.g., use of fertilizers) and environmental concerns. The main goal of this study was therefore to investigate biomass and nutrient [nitrogen (N), phosphorus (P), and potassium (K)] content, partitioning, stoichiometry and internal efficiencies in sugarcane ratoon at varying yield levels. Three sites were established on highly weathered tropical soils located in the Southeast region of Brazil. At all sites, seasonal biomass and nutrient uptake patterns were synthesized from four sampling times taken throughout the sugarcane ratoon season. In-season nutrient partitioning (in diverse plant components), internal efficiencies (yield to nutrient content ratio) and nutrient ratios (N:P and N:K) were determined at harvesting. Sugarcane exhibited three distinct phases of plant growth, as follows: lag, exponential–linear, and stationary. Across sites, nutrient requirement per unit of yield was 1.4 kg N, 0.24 kg P, and 2.7 kg K per Mg of stalk produced, but nutrient removal varied with soil nutrient status (based on soil plus fertilizer nutrient supply) and crop demand (potential yield). Dry leaves had lower nutrient content (N, P, and K) and broader N:P and N:K ratios when compared with tops and stalks plant fractions. Greater sugarcane yield and narrowed N:P ratio (6:1) were verified for tops of sugarcane when increasing both N and P content. High-yielding sugarcane systems were related to higher nutrient content and more balanced N:P (6:1) and N:K (0.5:1) ratios. PMID:27148297

  16. Nutrient Partitioning and Stoichiometry in Unburnt Sugarcane Ratoon at Varying Yield Levels

    Directory of Open Access Journals (Sweden)

    José Marcos Leite

    2016-04-01

    Full Text Available Unraveling nutrient imbalances in contemporary agriculture is a research priority to improve whenever possible yield and nutrient use efficiency in sugarcane (Saccharum spp. systems while minimizing the costs of cultivation (e.g., use of fertilizers and environmental concerns. The main goal of this study was therefore to investigate biomass and nutrient [nitrogen (N, phosphorus (P, and potassium (K] content, partitioning, stoichiometry and internal efficiencies in sugarcane ratoon at varying yield levels. Three sites were established on highly weathered tropical soils located in the Southeast region of Brazil. At all sites, seasonal biomass and nutrient uptake patterns were synthesized from four sampling times taken throughout the sugarcane ratoon season. At all sites, in-season nutrient partitioning (in diverse plant components, internal efficiencies (yield to nutrient content ratio and nutrient ratios (N:P and N:K were determined at harvesting. Sugarcane exhibited three distinct phases of plant growth, as follows: lag, exponential-linear, and stationary. Across sites, nutrient requirement per unit of yield was 1.4 kg N, 0.24 kg P, and 2.7 kg K per Mg of stalk produced, but nutrient removal varied with soil nutrient status (based on soil plus fertilizer nutrient supply and crop demand (potential yield. Dry leaves had lower nutrient content (N, P, and K and broader N:P and N:K ratios when compared with tops and stalks plant fractions. Greater sugarcane yield and narrowed N:P ratio (6:1 were verified for tops of sugarcane when increasing both N and P content. High-yielding sugarcane systems were related to higher nutrient content and more balanced N:P (6:1 and N:K (0.5:1 ratios.

  17. Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

    Directory of Open Access Journals (Sweden)

    Trung Dang-Bao

    2017-07-01

    Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

  18. Catalytic pyrolysis of waste mandarin over nanoporous materials.

    Science.gov (United States)

    Park, Young-Kwon; Kim, Jeong Wook; Park, Sung Hoon; Kim, Seong-Soo; Jeon, Jong-Ki; Lee, See Hoon

    2013-01-01

    Catalytic pyrolysis of waste mandarin was performed using nanoporous catalysts. AI-MCM-41 and Meso-MFI, which had different acid characteristics, were used. In addition, the characteristics of Pt/Meso-MFI were compared with those of Meso-MFI. To analyze the characteristics of the catalyst samples, Brunauer-Emmett-Teller surface area, temperature programmed desorption of NH3, and N2 adsorption-desorption analyses were performed. In addition, pyrolysis gas chromatography/mass spectrometry was used to facilitate the direct analysis of the pyrolytic products. The products obtained from catalytic pyrolysis contained a greater amount of valuable components than did those obtained from non-catalytic pyrolysis, indicating that catalytic pyrolysis improved the quality of the bio-oil. Additionally, valuable products such as furan and aromatic compounds were produced in greater quantities when Meso-MFI was used. When Pt/Meso-MFI was used, the amounts of furan and aromatic compounds produced increased even further.

  19. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  20. Dark field microscopic analysis of discrete Au nanostructures: Understanding the correlation of scattering with stoichiometry

    Science.gov (United States)

    Wang, Guoqing; Bu, Tong; Zako, Tamotsu; Watanabe-Tamaki, Ryoko; Tanaka, Takuo; Maeda, Mizuo

    2017-09-01

    Due to the potential of gold nanoparticle (AuNP)-based trace analysis, the discrimination of small AuNP clusters with different assembling stoichiometry is a subject of fundamental and technological importance. Here we prepare oligomerized AuNPs with controlled stoichiometry through DNA-directed assembly, and demonstrate that AuNP monomers, dimers and trimers can be clearly distinguished using dark field microscopy (DFM). The scattering intensity for of AuNP structures with stoichiometry ranging from 1 to 3 agrees well with our theoretical calculations. This study demonstrates the potential of utilizing the DFM approach in ultra-sensitive detection as well as the use of DNA-directed assembly for plasmonic nano-architectures.

  1. Elemental stoichiometry and compositions of weevil larvae and two acorn hosts under natural phosphorus variation.

    Science.gov (United States)

    Ji, Huawei; Du, Baoming; Liu, Chunjiang

    2017-04-05

    To understand how different trophic organisms in a parasite food chain adapt to the differences in soil nutrient conditions, we investigated stoichiometric variation and homeostasis of multiple elements in two acorn trees, Quercus variabilis and Quercus acutissima, and their parasite weevil larvae (Curculio davidi Fairmaire) at phosphorus (P)-deficient and P-rich sites in subtropical China where P-rich ores are scattered among dominant P-deficient soils. Results showed that elemental stoichiometry and compositions of both acorns and weevil larvae differed significantly between P-deficient and P-rich sites (p stoichiometry and compositions (p stoichiometry and composition and physiological regulations of nutritional needs in organisms and provide possible stoichiometric responses of both plants and animals to P loading, a worldwide issue from excess release of P into the environment.

  2. Effects of three global change drivers on terrestrial C:N:P stoichiometry

    DEFF Research Database (Denmark)

    Yue, Kai; Fornara, Dario A; Yang, Wanqin

    2017-01-01

    , and elevated CO2 ) on primary productivity and on the biogeochemistry of carbon (C), N and phosphorus (P) across different terrestrial ecosystems. Here we capitalize on this large amount of information by performing a comprehensive meta-analysis (>2000 case studies worldwide) to address how C:N:P stoichiometry...... of plants, soils and soil microbial biomass might respond to individual vs. combined effects of the three global change drivers. Our results show that (1) individual effects of N addition and elevated CO2 on C:N:P stoichiometry are stronger than warming, (2) combined effects of pairs of global change...... drivers (e.g., N addition + elevated CO2 , warming + elevated CO2 ) on C:N:P stoichiometry were generally weaker than the individual effects of each of these drivers, (3) additive interactions (i.e. when combined effects are equal to or no significantly different from the sum of individual effects) were...

  3. Effect of oxygen stoichiometry on T(sub c) of Bi-based superconductors

    Science.gov (United States)

    Zhao, J.; Seehra, M. S.

    1990-01-01

    The role of oxygen stoichiometry on T(sub c) is relatively well established on La2CuO(4+x) and the YBa2Cu3O(7-x) (123) superconductors, as compared to the Bi-based superconductors. Results are presented of investigations on the effects of oxygen stoichiometry on the transition temperature T(sub c) of Bi2Sr2CaCu2O(8+x) (2212 phase), and Pb-doped Bi2Sr2Ca2Cu3O(10+X) (2223 phase). It is shown that the effects of oxygen stoichiometry on T(sub c) of these two phases are very different. These results may be helpful in understanding the mechanism of superconductivity in the Bi-based superconductors.

  4. Contrasting effects of rising CO2 on primary production and ecological stoichiometry at different nutrient levels.

    Science.gov (United States)

    Verspagen, Jolanda M H; Van de Waal, Dedmer B; Finke, Jan F; Visser, Petra M; Huisman, Jef

    2014-08-01

    Although rising CO2 concentrations are thought to promote the growth and alter the carbon : nutrient stoichiometry of primary producers, several studies have reported conflicting results. To reconcile these contrasting results, we tested the following hypotheses: rising CO2 levels (1) will increase phytoplankton biomass more at high nutrient loads than at low nutrient loads, but (2) will increase their carbon : nutrient stoichiometry more at low than at high nutrient loads. We formulated a mathematical model to predict dynamic changes in phytoplankton population density, elemental stoichiometry and inorganic carbon chemistry in response to rising CO2 . The model was tested in chemostat experiments with the freshwater cyanobacterium Microcystis aeruginosa. The model predictions and experimental results confirmed the hypotheses. Our findings provide a novel theoretical framework to understand and predict effects of rising CO2 concentrations on primary producers and their nutritional quality as food for herbivores under different nutrient conditions.

  5. Shifts in leaf N:P stoichiometry during rehabilitation in highly alkaline bauxite processing residue sand.

    Science.gov (United States)

    Goloran, Johnvie B; Chen, Chengrong; Phillips, Ian R; Elser, James J

    2015-10-07

    Large quantities of sodic and alkaline bauxite residue are produced globally as a by-product from alumina refineries. Ecological stoichiometry of key elements [nitrogen (N) and phosphorus (P)] plays a critical role in establishing vegetation cover in bauxite residue sand (BRS). Here we examined how changes in soil chemical properties over time in rehabilitated sodic and alkaline BRS affected leaf N to P stoichiometry of native species used for rehabilitation. Both Ca and soil pH influenced the shifts in leaf N:P ratios of the study species as supported by consistently significant positive relationships (P stoichiometry can effectively provide a meaningful assessment on understanding nutrient limitation and productivity of native species used for vegetating highly sodic and alkaline BRS, and is a crucial indicator for assessing ecological rehabilitation performance.

  6. Aquatic heterotrophic bacteria have highly flexible phosphorus content and biomass stoichiometry.

    Science.gov (United States)

    Godwin, Casey M; Cotner, James B

    2015-10-01

    Bacteria are central to the cycling of carbon (C), nitrogen (N) and phosphorus (P) in every ecosystem, yet our understanding of how tightly these cycles are coupled to bacterial biomass composition is based upon data from only a few species. Bacteria are commonly assumed to have high P content, low biomass C:P and N:P ratios, and inflexible stoichiometry. Here, we show that bacterial assemblages from lakes exhibit unprecedented flexibility in their P content (3% to less than 0.01% of dry mass) and stoichiometry (C:N:P of 28: 7: 1 to more than 8500: 1200: 1). The flexibility in C:P and N:P stoichiometry was greater than any species or assemblage, including terrestrial and aquatic autotrophs, and suggests a highly dynamic role for bacteria in coupling multiple element cycles.

  7. Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

    DEFF Research Database (Denmark)

    Nielsen, A.H.; Vollertsen, Jes; Hvitved-jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...... parameters determined in a triplicate experiment. The kinetic parameters determined in 25 experiments on wastewater samples from a single site exhibited good constancy with a variation of the same order of magnitude as the precision of the method. It was found that the stoichiometry of the reaction could...... be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m...

  8. Low stoichiometry operation of a polymer electrolyte membrane fuel cell employing the interdigitated flow field design

    DEFF Research Database (Denmark)

    Berning, Torsten; Odgaard, Madeleine; Kær, Søren Knudsen

    2011-01-01

    Fuel cell operation on dry reactant gases under low stoichiometry conditions employing the interdigitated flow field is investigated using a multi-fluid model. It is assumed that the MEA contains a water uptake layer which facilitates water absorption to the membrane and hence prevents the anode...... stoichiometry may even be as low as 1.05. The effect of operation pressure and temperature on the membrane water content is studied. Finally, experiments are suggested to determine the kinetic absorption coefficient and the specific surface area of the electrolyte inside the catalyst layers....

  9. HYDROGEN TRANSFER IN CATALYTIC CRACKING

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Hydrogen transfer is an important secondary reaction of catalytic cracking reactions, which affects product yield distribution and product quality. It is an exothermic reaction with low activation energy around 43.3 kJ/mol. Catalyst properties and operation parameters in catalytic cracking greatly influence the hydrogen transfer reaction. Satisfactory results are expected through careful selection of proper catalysts and operation conditions.

  10. ``OPTICAL Catalytic Nanomotors''

    Science.gov (United States)

    Rosary-Oyong, Se, Glory

    D. Kagan, et.al, 2009:'' a motion-based chemical sensing involving fuel-driven nanomotors is demonstrated. The new protocol relies on the use of an optical microscope for tracking charge in the speed of nanowire motors in the presence of target analyte''. Synthetic nanomotors are propelled by catalytic decomposition of .. they do not require external electric, magnetic or optical fields as energy..pubs.acs.org/cen/science/83/i08/8308sci1.html>. Accompanying Fig 2.6(a) of optical micrograph of a partial monolayer of silica microbeads [J.Gibbs, 2011 ] retrieves WF Paxton:''rods were characterized by transmission electron & dark-field optical microscopy..'' & LF Valadares:''dimer due to the limited resolution of optical microscopy, however the result..'. Acknowledged to HE. Mr. Prof. SEDIONO M.P. TJONDRONEGORO.

  11. Catalytic quantum error correction

    CERN Document Server

    Brun, T; Hsieh, M H; Brun, Todd; Devetak, Igor; Hsieh, Min-Hsiu

    2006-01-01

    We develop the theory of entanglement-assisted quantum error correcting (EAQEC) codes, a generalization of the stabilizer formalism to the setting in which the sender and receiver have access to pre-shared entanglement. Conventional stabilizer codes are equivalent to dual-containing symplectic codes. In contrast, EAQEC codes do not require the dual-containing condition, which greatly simplifies their construction. We show how any quaternary classical code can be made into a EAQEC code. In particular, efficient modern codes, like LDPC codes, which attain the Shannon capacity, can be made into EAQEC codes attaining the hashing bound. In a quantum computation setting, EAQEC codes give rise to catalytic quantum codes which maintain a region of inherited noiseless qubits. We also give an alternative construction of EAQEC codes by making classical entanglement assisted codes coherent.

  12. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  13. Leaf N and P stoichiometry in relation to leaf shape and plant size for Quercus acutissima provenances across China.

    Science.gov (United States)

    Zhang, Hui; Yang, Xiuqing; Wang, Jingyuan; Wang, G Geoff; Yu, Mukui; Wu, Tonggui

    2017-04-10

    Plant stoichiometry in relation to the structure and function of biological systems has been investigated at multiple scales. However, few studies have focused on the roles of stoichiometry for a given species. In this study, we determined leaf N and P stoichiometry, leaf shape and plant size in three Quercus acutissima common gardens with different climatic and site conditions. In the three common gardens, leaf N and P stoichiometry was significantly correlated with leaf shape and plant size, suggesting that leaf N and P stoichiometry affects the morphological performance of the leaves and stem. The scaling slopes of the relationships between leaf N and P stoichiometry and leaf shape ranged from |0.12| to |1.00|, while the slopes of the relationships between leaf N and P stoichiometry and plant size ranged from |0.95| to |2.66|. These results suggest that non-functional tissues (stem) are more susceptible to leaf nutrition than functional tissues (leaves), and leaf stoichiometry is more important in the construction of non-functional tissues (stem). Between the northernmost and southernmost common gardens, leaf N and leaf width (W), N:P and stem height (H), and N:P and stem diameter (D) showed significant covariations, which indicates that leaf N and W, N:P and plant size exhibit similar plastic responses to environmental change.

  14. Enhancing Grade 10 Thai Students' Stoichiometry Understanding and Ability to Solve Numerical Problems via a Conceptual Change Perspective

    Science.gov (United States)

    Dahsah, Chanyah; Coll, Richard K.; Sung-ong, Sunan; Yutakom, Naruemon; Sanguanruang, Sudjit

    2008-01-01

    The international literature suggests students frequently resort to the use of formulae when solving stoichiometry problems without understanding the concepts. In prior work we identified Thai student alternative conceptions and ability to solve numerical problem for stoichiometry. The results indicate that many Thai students also hold alternative…

  15. Enhancing Grade 10 Thai Students' Stoichiometry Understanding and Ability to Solve Numerical Problems via a Conceptual Change Perspective

    Science.gov (United States)

    Dahsah, Chanyah; Coll, Richard K.; Sung-ong, Sunan; Yutakom, Naruemon; Sanguanruang, Sudjit

    2008-01-01

    The international literature suggests students frequently resort to the use of formulae when solving stoichiometry problems without understanding the concepts. In prior work we identified Thai student alternative conceptions and ability to solve numerical problem for stoichiometry. The results indicate that many Thai students also hold alternative…

  16. Catalytic pyrolysis of tars. A kinetic approach

    Energy Technology Data Exchange (ETDEWEB)

    Faundez, J.; Garcia, X.; Gordon, A. [Universidad de Concepcion (Chile). Dept. de Ingeniera Quimica

    1997-12-31

    A kinetic model to describe the catalytic pyrolysis of tars is proposed and validated through pyrolysis of two tars of different characteristics and origin. Calcinated limestone (11 m{sup 2}/g) was used as catalyst. The model assumes that tars are composed of two pseudo-components: (i) heavy tar, and (ii) light tar. Tar pyrolysis is described by two simultaneous chemical reactions; catalyst deactivation due to carbon deposition is also considered. After mathematical resolution, expressions for product`s concentration as functions of residence time, selectivity and the deactivation were obtained. (orig.)

  17. Root Responses to Altered Ecosystem N/P Stoichiometry in a Mediterranean Tree-Grass Ecosystem

    Science.gov (United States)

    Nair, Richard; Moreno, Gerado; Morris, Kendalynn; Schrumpf, Marion; Migliavacca, Mirco

    2017-04-01

    Biological components of the soil system (plant roots, fungi, microbes) may respond to biogeochemical drivers (e.g. nutrient status, water availability, C availability) in dissimilar ways due to differing scales, activities and access to resources. Understanding individual components and their phenology in the soil system is therefore critical to interpret overall fluxes. In seasonally dry systems, plants balance belowground investment with other growth and maintenance in life strategies where water limitations (in dry periods), nutrient limitations (in wet periods) and temperature/light limitations (in winter) interact, varying the need to invest in gaining these three resources throughout the year. Additionally, root growth may also be desynchronized with overall nutrient demand due to the ability to take up nutrients outside of seasonal periods of demand for storage and subsequent reallocation. We examined root responses to an ecosystem level stoichiometry (+N / +N+P) manipulation experiment at a highly instrumented site in a strongly seasonal semi-arid tree-grass ('dehesa') system (Majadas del Tietar, Spain). We are interested in whether root growth and phenology is affected by differing demand for nutrients/water both between sites and at tree and grass-dominated subsites. Many non-invasive, ecosystem-scale methods to measure changes in biogeochemical cycling focus only on integrated whole-system fluxes or above-ground change and it is difficult to extract a root signal. However, local soil respiration fluxes and root growth introduces a variety of method-dependent artefacts and drawbacks necessitating multiple approaches and careful interpretation. Therefore, in coordination with indirect measurements (subcanopy fluxes via eddy covariance, soil respiration chambers) we are using direct soil coring, ingrowth cores and repeatable measurements from custom-built minirhizotron systems to attempt to assess site-level variation in root biomass and phenology. In this

  18. Unsteady catalytic processes and sorption-catalytic technologies

    Energy Technology Data Exchange (ETDEWEB)

    Zagoruiko, A N [G.K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)

    2007-07-31

    Catalytic processes that occur under conditions of the targeted unsteady state of the catalyst are considered. The highest efficiency of catalytic processes was found to be ensured by a controlled combination of thermal non-stationarity and unsteady composition of the catalyst surface. The processes based on this principle are analysed, in particular, catalytic selective reduction of nitrogen oxides, deep oxidation of volatile organic impurities, production of sulfur by the Claus process and by hydrogen sulfide decomposition, oxidation of sulfur dioxide, methane steam reforming and anaerobic combustion, selective oxidation of hydrocarbons, etc.

  19. Component interactions in the soluble methane monooxygenase system from Methylococcus capsulatus (Bath).

    Science.gov (United States)

    Gassner, G T; Lippard, S J

    1999-09-28

    The soluble methane monooxygenase system of Methylococcus capsulatus (Bath) includes three protein components: a 251-kDa non-heme dinuclear iron hydroxylase (MMOH), a 39-kDa iron-sulfur- and FAD-containing reductase (MMOR), and a 16-kDa regulatory protein (MMOB). The thermodynamic stability and kinetics of formation of complexes between oxidized MMOH and MMOB or MMOR were measured by isothermal titration calorimetry and stopped-flow fluorescence spectroscopy at temperatures ranging from 3.3 to 45 degrees C. The results, in conjunction with data from equilibrium analytical ultracentrifugation studies of MMOR and MMOB, indicate that free MMOR and MMOB exist as monomers in solution and bind MMOH with 2:1 stoichiometry. The role of component interactions in the catalytic mechanism of sMMO was investigated through simultaneous measurement of oxidase and hydroxylase activities as a function of varied protein component concentrations during steady-state turnover. The partitioning of oxidase and hydroxylase activities of sMMO is highly dependent on both the MMOR concentration and the nature of the organic substrate. In particular, NADH oxidation is significantly uncoupled from methane hydroxylation at MMOR concentrations exceeding 20% of the hydroxylase concentration but remains tightly coupled to propylene epoxidation at MMOR concentrations ranging up to the MMOH concentration. The steady-state kinetic data were fit to numerical simulations of models that include both the oxidase activities of free MMOR and of MMOH/MMOR complexes and the hydroxylase activity of MMOH/MMOB complexes. The data were well described by a model in which MMOR and MMOB bind noncompetitively at distinct interacting sites on the hydroxylase. MMOB manifests its regulatory effects by differentially accelerating intermolecular electron transfer from MMOR to MMOH containing bound substrate and product in a manner consistent with its activating and inhibitory effects on the hydroxylase.

  20. Growth rate and resource imbalance interactively control biomass stoichiometry and elemental quotas of aquatic bacteria.

    Science.gov (United States)

    Godwin, Casey M; Whitaker, Emily A; Cotner, James B

    2017-03-01

    The effects of resource stoichiometry and growth rate on the elemental composition of biomass have been examined in a wide variety of organisms, but the interaction among these effects is often overlooked. To determine how growth rate and resource imbalance affect bacterial carbon (C): nitrogen (N): phosphorus (P) stoichiometry and elemental content, we cultured two strains of aquatic heterotrophic bacteria in chemostats at a range of dilution rates and P supply levels (C:P of 100:1 to 10,000:1). When growing below 50% of their maximum growth rate, P availability and dilution rate had strong interactive effects on biomass C:N:P, elemental quotas, cell size, respiration rate, and growth efficiency. In contrast, at faster growth rates, biomass stoichiometry was strongly homeostatic in both strains (C:N:P of 70:13:1 and 73:14:1) and elemental quotas of C, N, and P were tightly coupled (but not constant). Respiration and cell size increased with both growth rate and P limitation, and P limitation induced C accumulation and excess respiration. These results show that bacterial biomass stoichiometry is relatively constrained when all resources are abundant and growth rates are high, but at low growth rates resource imbalance is relatively more important than growth rate in controlling bacterial biomass composition. © 2016 by the Ecological Society of America.

  1. Stoichiometry and estimates of nutrient standing stocks of larval salamanders in Appalachian headwater streams

    Science.gov (United States)

    Joseph R. Milanovich; John C. Maerz; Amy D. Rosemond

    2015-01-01

    1.Because of their longevity and skeletal phosphorus demand, vertebrates can have distinct influences on the uptake, storage and recycling of nutrients in ecosystems. Quantification of body stoichiometry, combined with estimates of abundance or biomass, can provide insights into the effect of vertebrates on nutrient cycling. 2.We measured the nutrient content and...

  2. Modeling the Role of Epitope Arrangement on Antibody Binding Stoichiometry in Flaviviruses.

    Science.gov (United States)

    Ripoll, Daniel R; Khavrutskii, Ilja; Wallqvist, Anders; Chaudhury, Sidhartha

    2016-10-18

    Cryo-electron-microscopy (cryo-EM) structures of flaviviruses reveal significant variation in epitope occupancy across different monoclonal antibodies that have largely been attributed to epitope-level differences in conformation or accessibility that affect antibody binding. The consequences of these variations for macroscopic properties such as antibody binding and neutralization are the results of the law of mass action-a stochastic process of innumerable binding and unbinding events between antibodies and the multiple binding sites on the flavivirus in equilibrium-that cannot be directly imputed from structure alone. We carried out coarse-grained spatial stochastic binding simulations for nine flavivirus antibodies with epitopes defined by cryo-EM or x-ray crystallography to assess the role of epitope spatial arrangement on antibody-binding stoichiometry, occupancy, and neutralization. In our simulations, all epitopes were equally competent for binding, representing the upper limit of binding stoichiometry that results from epitope spatial arrangement alone. Surprisingly, our simulations closely reproduced the relative occupancy and binding stoichiometry observed in cryo-EM, without having to account for differences in epitope accessibility or conformation, suggesting that epitope spatial arrangement alone may be sufficient to explain differences in binding occupancy and stoichiometry between antibodies. Furthermore, we found that there was significant heterogeneity in binding configurations even at saturating antibody concentrations, and that bivalent antibody binding may be more common than previously thought. Finally, we propose a structure-based explanation for the stoichiometric threshold model of neutralization. Published by Elsevier Inc.

  3. Contrasting effects of rising CO2 on primary production and ecological stoichiometry at different nutrient levels

    NARCIS (Netherlands)

    Verspagen, J.M.H.; Van de Waal, D.B.; Finke, J.F; Visser, P.M.; Huisman, J.

    2014-01-01

    Although rising CO2 concentrations are thought to promote the growth and alter the carbon : nutrient stoichiometry of primary producers, several studies have reported conflicting results. To reconcile these contrasting results, we tested the following hypotheses: rising CO2 levels (1) will increase

  4. Students' Dilemmas in Reaction Stoichiometry Problem Solving: Deducing the Limiting Reagent in Chemical Reactions

    Science.gov (United States)

    Chandrasegaran, A. L.; Treagust, David F.; Waldrip, Bruce G.; Chandrasegaran, Antonia

    2009-01-01

    A qualitative case study was conducted to investigate the understanding of the limiting reagent concept and the strategies used by five Year 11 students when solving four reaction stoichiometry problems. Students' written problem-solving strategies were studied using the think-aloud protocol during problem-solving, and retrospective verbalisations…

  5. Using Audience Response Systems during Interactive Lectures to Promote Active Learning and Conceptual Understanding of Stoichiometry

    Science.gov (United States)

    Cotes, Sandra; Cotuá, José

    2014-01-01

    This article describes a method of instruction using an active learning strategy for teaching stoichiometry through a process of gradual knowledge building. Students identify their misconceptions and progress through a sequence of questions based on the same chemical equation. An infrared device and software registered as the TurningPoint Audience…

  6. Impact of Stoichiometry Representation on Simulation of Genotype-Phenotype Relationships in Metabolic Networks

    Science.gov (United States)

    Brochado, Ana Rita; Andrejev, Sergej; Maranas, Costas D.; Patil, Kiran R.

    2012-01-01

    Genome-scale metabolic networks provide a comprehensive structural framework for modeling genotype-phenotype relationships through flux simulations. The solution space for the metabolic flux state of the cell is typically very large and optimization-based approaches are often necessary for predicting the active metabolic state under specific environmental conditions. The objective function to be used in such optimization algorithms is directly linked with the biological hypothesis underlying the model and therefore it is one of the most relevant parameters for successful modeling. Although linear combination of selected fluxes is widely used for formulating metabolic objective functions, we show that the resulting optimization problem is sensitive towards stoichiometry representation of the metabolic network. This undesirable sensitivity leads to different simulation results when using numerically different but biochemically equivalent stoichiometry representations and thereby makes biological interpretation intrinsically subjective and ambiguous. We hereby propose a new method, Minimization of Metabolites Balance (MiMBl), which decouples the artifacts of stoichiometry representation from the formulation of the desired objective functions, by casting objective functions using metabolite turnovers rather than fluxes. By simulating perturbed metabolic networks, we demonstrate that the use of stoichiometry representation independent algorithms is fundamental for unambiguously linking modeling results with biological interpretation. For example, MiMBl allowed us to expand the scope of metabolic modeling in elucidating the mechanistic basis of several genetic interactions in Saccharomyces cerevisiae. PMID:23133362

  7. Nutrient stoichiometry in winter wheat: Element concentration pattern reflects developmental stage and weather.

    Science.gov (United States)

    Weih, M; Pourazari, F; Vico, G

    2016-10-24

    At least 16 nutrient elements are required by plants for growth and survival, but the factors affecting element concentration and their temporal evolution are poorly understood. The objective was to investigate i) element concentration pattern in winter wheat as affected by crop developmental stage and weather, and ii) whether, in the short term, element stoichiometry reflects the type of preceding crop. We assessed the temporal trajectories of element concentration pattern (N, P, K, Ca, Mg, S, Mn, Fe, Cu, Na, Zn) across the life cycle (from seed to seed) of winter wheat field-grown in cool-temperate Sweden during two years with contrasting weather and when cultivated in monoculture or after different non-wheat preceding crops. We found strong influence of developmental stage on concentration pattern, with the greatest deviation from grain concentrations found in plants at the start of stem elongation in spring. Inter-annual differences in weather affected stoichiometry, but no evidence was found for a short-term preceding-crop effect on element stoichiometry. Winter wheat element stoichiometry is similar in actively growing plant tissues and seeds. Nitrogen exerts a strong influence on the concentration pattern for all elements. Three groups of elements with concentrations changing in concert were identified.

  8. Oxygen non-stoichiometry determination of perovskite materials by a carbonation process

    NARCIS (Netherlands)

    Chen, Wei; Nijmeijer, Arian; Winnubst, Aloysius J.A.

    2012-01-01

    A new and easy method is developed to determine the oxygen non-stoichiometry of perovskite materials under equilibrium conditions. The method is based on the complete decomposition of the powder to stoichiometric metal oxides and/or metal carbonates by using CO2 as reacting gas. The oxygen

  9. Carbon, nitrogen, and phosphorus stoichiometry and eutrophication in River Thames Tributaries, UK

    Science.gov (United States)

    Primary productivity in aquatic systems relies on the availability of carbon (C), nitrogen (N) and phosphorus (P), with a preferred stoichiometric ratio of 106 C/16 N/1 P, known as the Redfield ratio. The intent of this paper is to present a methodology to visualize C/N/P stoichiometry and examine ...

  10. Teaching Lab Report Writing through Inquiry: A Green Chemistry Stoichiometry Experiment for General Chemistry

    Science.gov (United States)

    Cacciatore, Kristen L.; Sevian, Hannah

    2006-01-01

    We present an alternative to a traditional first-year chemistry laboratory experiment. This experiment has four key features: students utilize stoichiometry, learn and apply principles of green chemistry, engage in authentic scientific inquiry, and discover why each part of a scientific lab report is necessary. The importance and essential…

  11. Climate-driven changes in the ecological stoichiometry of aquatic ecosystems

    NARCIS (Netherlands)

    van de Waal, D.B.; Verschoor, A.M.; Verspagen, J.M.H.; van Donk, E.; Huisman, J.

    2010-01-01

    Advances in ecological stoichiometry, a rapidly expanding research field investigating the elemental composition of organisms and their environment, have shed new light on the impacts of climate change on freshwater and marine ecosystems. Current changes in the Earth's climate alter the availability

  12. Oxygen non-stoichiometry determination of perovskite materials by a carbonation process

    NARCIS (Netherlands)

    Chen, Wei; Nijmeijer, Arian; Winnubst, Aloysius J.A.

    2012-01-01

    A new and easy method is developed to determine the oxygen non-stoichiometry of perovskite materials under equilibrium conditions. The method is based on the complete decomposition of the powder to stoichiometric metal oxides and/or metal carbonates by using CO2 as reacting gas. The oxygen non-stoic

  13. Na+ : Aspartate Coupling Stoichiometry in the Glutamate Transporter Homologue Glt(Ph)

    NARCIS (Netherlands)

    Groeneveld, Maarten; Slotboom, Dirk-Jan

    2010-01-01

    The Na+ aspartate symporter Glt(Ph) from Pyrococcus horikoshil is the only member of the glutamate transporter family for which crystal structures have been determined. The cation:aspartate coupling stoichiometry is unknown, thus hampering the elucidation of the ion coupling mechanism. Here we measu

  14. Global biodiversity, stoichiometry and ecosystem function responses to human-induced C-N-P imbalances.

    Science.gov (United States)

    Carnicer, Jofre; Sardans, Jordi; Stefanescu, Constantí; Ubach, Andreu; Bartrons, Mireia; Asensio, Dolores; Peñuelas, Josep

    2015-01-01

    Global change analyses usually consider biodiversity as a global asset that needs to be preserved. Biodiversity is frequently analysed mainly as a response variable affected by diverse environmental drivers. However, recent studies highlight that gradients of biodiversity are associated with gradual changes in the distribution of key dominant functional groups characterized by distinctive traits and stoichiometry, which in turn often define the rates of ecosystem processes and nutrient cycling. Moreover, pervasive links have been reported between biodiversity, food web structure, ecosystem function and species stoichiometry. Here we review current global stoichiometric gradients and how future distributional shifts in key functional groups may in turn influence basic ecosystem functions (production, nutrient cycling, decomposition) and therefore could exert a feedback effect on stoichiometric gradients. The C-N-P stoichiometry of most primary producers (phytoplankton, algae, plants) has been linked to functional trait continua (i.e. to major axes of phenotypic variation observed in inter-specific analyses of multiple traits). In contrast, the C-N-P stoichiometry of higher-level consumers remains less precisely quantified in many taxonomic groups. We show that significant links are observed between trait continua across trophic levels. In spite of recent advances, the future reciprocal feedbacks between key functional groups, biodiversity and ecosystem functions remain largely uncertain. The reported evidence, however, highlights the key role of stoichiometric traits and suggests the need of a progressive shift towards an ecosystemic and stoichiometric perspective in global biodiversity analyses. Copyright © 2014 Elsevier GmbH. All rights reserved.

  15. Management practices regulate the response of Moso bamboo foliar stoichiometry to nitrogen deposition

    Science.gov (United States)

    Song, Xinzhang; Gu, Honghao; Wang, Meng; Zhou, Guomo; Li, Quan

    2016-04-01

    Moso bamboo, well known for its high growth rate, is being subjected to increasing amounts of nitrogen deposition. However, how anthropogenic management practices regulate the effects of N deposition on Moso bamboo stoichiometry remains poorly understood. We observed the effects of two years of simulated N deposition (30, 60 and 90 kg N ha‑1yr‑1) on the foliar stoichiometry of Moso bamboo plantations under conventional management (CM) and intensive management (IM). Young bamboo had significantly greater foliar N and P concentrations and N:P ratios than mature plants (P bamboo and P concentrations of mature bamboo but decreased mature bamboo foliar N:P ratios (P bamboo plantations, but the positive effects were diminished when the addition rate exceeded 60 kg N ha‑1yr‑1. Nitrogen increased foliar N concentrations but aggravated P deficiency in CM bamboo plantations. The positive effects of N deposition on foliar stoichiometry were influenced by management practices and bamboo growth stage. The effects of N deposition on foliar stoichiometry combined with anthropogenic management practices can influence ecosystem production, decomposition, and subsequent N and P cycles in Moso bamboo plantations.

  16. Introductory College Chemistry Students' Understanding of Stoichiometry: Connections between Conceptual and Computational Understandings and Instruction.

    Science.gov (United States)

    Wolfer, Adam J.; Lederman, Norman G.

    Many studies of college chemistry students have found a gap between students' success in solving computational chemistry problems and their success in solving conceptual chemistry problems. This paper examines college students' understanding of the concept of stoichiometry, the particulate nature of matter, and chemistry problem solving. This…

  17. Investigating the Effect of Complexity Factors in Stoichiometry Problems Using Logistic Regression and Eye Tracking

    Science.gov (United States)

    Tang, Hui; Kirk, John; Pienta, Norbert J.

    2014-01-01

    This paper includes two experiments, one investigating complexity factors in stoichiometry word problems, and the other identifying students' problem-solving protocols by using eye-tracking technology. The word problems used in this study had five different complexity factors, which were randomly assigned by a Web-based tool that we developed. The…

  18. Growth and properties of strained VOx thin films with controlled stoichiometry

    NARCIS (Netherlands)

    Rata, AD; Chezan, AR; Haverkort, MW; Hsieh, HH; Lin, HJ; Chen, CT; Tjeng, LH; Hibma, T

    2004-01-01

    We have succeeded in growing epitaxial films of rocksalt VOx on MgO(001) substrates. The oxygen content as a function of oxygen flux was determined using O-18(2)-Rutherford backscattering spectrometry and the vanadium valence using x-ray-absorption spectroscopy. The upper and lower stoichiometry lim

  19. Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

    DEFF Research Database (Denmark)

    Nielsen, A.H.; Vollertsen, Jes; Hvitved-jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...

  20. Nutrient stoichiometry in winter wheat: Element concentration pattern reflects developmental stage and weather

    Science.gov (United States)

    Weih, M.; Pourazari, F.; Vico, G.

    2016-10-01

    At least 16 nutrient elements are required by plants for growth and survival, but the factors affecting element concentration and their temporal evolution are poorly understood. The objective was to investigate i) element concentration pattern in winter wheat as affected by crop developmental stage and weather, and ii) whether, in the short term, element stoichiometry reflects the type of preceding crop. We assessed the temporal trajectories of element concentration pattern (N, P, K, Ca, Mg, S, Mn, Fe, Cu, Na, Zn) across the life cycle (from seed to seed) of winter wheat field-grown in cool-temperate Sweden during two years with contrasting weather and when cultivated in monoculture or after different non-wheat preceding crops. We found strong influence of developmental stage on concentration pattern, with the greatest deviation from grain concentrations found in plants at the start of stem elongation in spring. Inter-annual differences in weather affected stoichiometry, but no evidence was found for a short-term preceding–crop effect on element stoichiometry. Winter wheat element stoichiometry is similar in actively growing plant tissues and seeds. Nitrogen exerts a strong influence on the concentration pattern for all elements. Three groups of elements with concentrations changing in concert were identified.

  1. Low stoichiometry operation of a polymer electrolyte membrane fuel cell employing the interdigitated flow field design

    DEFF Research Database (Denmark)

    Berning, Torsten; Odgaard, Madeleine; Kær, Søren Knudsen

    2011-01-01

    Fuel cell operation on dry reactant gases under low stoichiometry conditions employing the interdigitated flow field is investigated using a multi-fluid model. It is assumed that the MEA contains a water uptake layer which facilitates water absorption to the membrane and hence prevents the anode...

  2. Sequential Block Copolymer Self-Assemblies Controlled by Metal-Ligand Stoichiometry.

    Science.gov (United States)

    Yin, Liyuan; Wu, Hongwei; Zhu, Mingjie; Zou, Qi; Yan, Qiang; Zhu, Liangliang

    2016-06-28

    While numerous efforts have been devoted to developing easy-to-use probes based on block copolymers for detecting analytes due to their advantages in the fields of self-assembly and sensing, a progressive response on block copolymers in response to a continuing chemical event is not readily achievable. Herein, we report the self-assembly of a 4-piperazinyl-1,8-naphthalimide based functional block copolymer (PS-b-PN), whose self-assembly and photophysics can be controlled by the stoichiometry-dependent metal-ligand interaction upon the side chain. The work takes advantages of (1) stoichiometry-controlled coordination-structural transformation of the piperazinyl moiety on PS-b-PN toward Fe(3+) ions, thereby resulting in a shrinkage-expansion conversion of the self-assembled nanostructures in solution as well as in thin film, and (2) stoichiometry-controlled competition between photoinduced electron transfer and spin-orbital coupling process upon naphthalimide fluorophore leading to a boost-decline emission change of the system. Except Fe(3+) ions, such a stoichiometry-dependent returnable property cannot be observed in the presence of other transition ions. The strategy for realizing the dual-channel sequential response on the basis of the progressively alterable nanomorphologies and emissions might provide deeper insights for the further development of advanced polymeric sensors.

  3. Students' Dilemmas in Reaction Stoichiometry Problem Solving: Deducing the Limiting Reagent in Chemical Reactions

    Science.gov (United States)

    Chandrasegaran, A. L.; Treagust, David F.; Waldrip, Bruce G.; Chandrasegaran, Antonia

    2009-01-01

    A qualitative case study was conducted to investigate the understanding of the limiting reagent concept and the strategies used by five Year 11 students when solving four reaction stoichiometry problems. Students' written problem-solving strategies were studied using the think-aloud protocol during problem-solving, and retrospective verbalisations…

  4. Using Audience Response Systems during Interactive Lectures to Promote Active Learning and Conceptual Understanding of Stoichiometry

    Science.gov (United States)

    Cotes, Sandra; Cotuá, José

    2014-01-01

    This article describes a method of instruction using an active learning strategy for teaching stoichiometry through a process of gradual knowledge building. Students identify their misconceptions and progress through a sequence of questions based on the same chemical equation. An infrared device and software registered as the TurningPoint Audience…

  5. Oxygen non-stoichiometry determination of perovskite materials by a carbonation process

    NARCIS (Netherlands)

    Chen, W.; Nijmeijer, A.; Winnubst, A.J.A.

    2012-01-01

    A new and easy method is developed to determine the oxygen non-stoichiometry of perovskite materials under equilibrium conditions. The method is based on the complete decomposition of the powder to stoichiometric metal oxides and/or metal carbonates by using CO2 as reacting gas. The oxygen non-stoic

  6. Analysis of acetylation stoichiometry suggests that SIRT3 repairs nonenzymatic acetylation lesions.

    Science.gov (United States)

    Weinert, Brian T; Moustafa, Tarek; Iesmantavicius, Vytautas; Zechner, Rudolf; Choudhary, Chunaram

    2015-11-03

    Acetylation is frequently detected on mitochondrial enzymes, and the sirtuin deacetylase SIRT3 is thought to regulate metabolism by deacetylating mitochondrial proteins. However, the stoichiometry of acetylation has not been studied and is important for understanding whether SIRT3 regulates or suppresses acetylation. Using quantitative mass spectrometry, we measured acetylation stoichiometry in mouse liver tissue and found that SIRT3 suppressed acetylation to a very low stoichiometry at its target sites. By examining acetylation changes in the liver, heart, brain, and brown adipose tissue of fasted mice, we found that SIRT3-targeted sites were mostly unaffected by fasting, a dietary manipulation that is thought to regulate metabolism through SIRT3-dependent deacetylation. Globally increased mitochondrial acetylation in fasted liver tissue, higher stoichiometry at mitochondrial acetylation sites, and greater sensitivity of SIRT3-targeted sites to chemical acetylation in vitro and fasting-induced acetylation in vivo, suggest a nonenzymatic mechanism of acetylation. Our data indicate that most mitochondrial acetylation occurs as a low-level nonenzymatic protein lesion and that SIRT3 functions as a protein repair factor that removes acetylation lesions from lysine residues.

  7. Na+ : Aspartate Coupling Stoichiometry in the Glutamate Transporter Homologue Glt(Ph)

    NARCIS (Netherlands)

    Groeneveld, Maarten; Slotboom, Dirk-Jan

    2010-01-01

    The Na+ aspartate symporter Glt(Ph) from Pyrococcus horikoshil is the only member of the glutamate transporter family for which crystal structures have been determined. The cation:aspartate coupling stoichiometry is unknown, thus hampering the elucidation of the ion coupling mechanism. Here we measu

  8. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase...

  9. Investigating the Effect of Complexity Factors in Stoichiometry Problems Using Logistic Regression and Eye Tracking

    Science.gov (United States)

    Tang, Hui; Kirk, John; Pienta, Norbert J.

    2014-01-01

    This paper includes two experiments, one investigating complexity factors in stoichiometry word problems, and the other identifying students' problem-solving protocols by using eye-tracking technology. The word problems used in this study had five different complexity factors, which were randomly assigned by a Web-based tool that we developed. The…

  10. Impact of stoichiometry representation on simulation of genotype-phenotype relationships in metabolic networks.

    Science.gov (United States)

    Brochado, Ana Rita; Andrejev, Sergej; Maranas, Costas D; Patil, Kiran R

    2012-01-01

    Genome-scale metabolic networks provide a comprehensive structural framework for modeling genotype-phenotype relationships through flux simulations. The solution space for the metabolic flux state of the cell is typically very large and optimization-based approaches are often necessary for predicting the active metabolic state under specific environmental conditions. The objective function to be used in such optimization algorithms is directly linked with the biological hypothesis underlying the model and therefore it is one of the most relevant parameters for successful modeling. Although linear combination of selected fluxes is widely used for formulating metabolic objective functions, we show that the resulting optimization problem is sensitive towards stoichiometry representation of the metabolic network. This undesirable sensitivity leads to different simulation results when using numerically different but biochemically equivalent stoichiometry representations and thereby makes biological interpretation intrinsically subjective and ambiguous. We hereby propose a new method, Minimization of Metabolites Balance (MiMBl), which decouples the artifacts of stoichiometry representation from the formulation of the desired objective functions, by casting objective functions using metabolite turnovers rather than fluxes. By simulating perturbed metabolic networks, we demonstrate that the use of stoichiometry representation independent algorithms is fundamental for unambiguously linking modeling results with biological interpretation. For example, MiMBl allowed us to expand the scope of metabolic modeling in elucidating the mechanistic basis of several genetic interactions in Saccharomyces cerevisiae.

  11. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  12. Simultaneous regulation of antenna size and photosystem I/II stoichiometry in Arabidopsis thaliana.

    Science.gov (United States)

    Jia, Ting; Ito, Hisashi; Tanaka, Ayumi

    2016-11-01

    The photosystem I/II ratio increased when antenna size was enlarged by transient induction of CAO in chlorophyll b -less mutants, thus indicating simultaneous regulation of antenna size and photosystem I/II stoichiometry. Regulation of antenna size and photosystem I/II stoichiometry is an indispensable strategy for plants to acclimate to changes to light environments. When plants grown in high-light conditions are transferred to low-light conditions, the peripheral antennae of photosystems are enlarged. A change in the photosystem I/II ratio is also observed under the same light conditions. However, our knowledge of the correlation between antenna size modulation and variation in photosystem I/II stoichiometry remains limited. In this study, chlorophyll a oxygenase was transiently induced in Arabidopsis thaliana chlorophyll b-less mutants, ch1-1, to alter the antenna size without changing environmental conditions. In addition to the accumulation of chlorophyll b, the levels of the peripheral antenna complexes of both photosystems gradually increased, and these were assembled to the core antenna of both photosystems. However, the antenna size of photosystem II was greater than that of photosystem I. Immunoblot analysis of core antenna proteins showed that the number of photosystem I increased, but not that of photosystem II, resulting in an increase in the photosystem I/II ratio. These results clearly indicate that antenna size adjustment was coupled with changes in photosystem I/II stoichiometry. Based on these results, the physiological importance of simultaneous regulation of antenna size and photosystem I/II stoichiometry is discussed in relation to acclimation to light conditions.

  13. Evidence for a Revised Ion/Substrate Coupling Stoichiometry of GABA Transporters.

    Science.gov (United States)

    Willford, Samantha L; Anderson, Cynthia M; Spencer, Shelly R; Eskandari, Sepehr

    2015-08-01

    Plasma membrane γ-aminobutyric acid (GABA) transporters (GATs) are electrogenic transport proteins that couple the cotranslocation of Na(+), Cl(-), and GABA across the plasma membrane of neurons and glia. A fundamental property of the transporter that determines its ability to concentrate GABA in cells and, hence, regulate synaptic and extra-synaptic GABA concentrations, is the ion/substrate coupling stoichiometry. Here, we scrutinized the currently accepted 2 Na(+):1 Cl(-):1 GABA stoichiometry because it is inconsistent with the measured net charge translocated per co-substrate (Na(+), Cl(-), and GABA). We expressed GAT1 and GAT3 in Xenopus laevis oocytes and utilized thermodynamic and uptake under voltage-clamp measurements to determine the stoichiometry of the GABA transporters. Voltage-clamped GAT1-expressing oocytes were internally loaded with GABA, and the reversal potential (V rev) of the transporter-mediated current was recorded at different external concentrations of Na(+), Cl(-), or GABA. The shifts in V rev for a tenfold change in the external Na(+), Cl(-), and GABA concentration were 84 ± 4, 30 ± 1, and 29 ± 1 mV, respectively. To determine the net charge translocated per Na(+), Cl(-), and GABA, we measured substrate fluxes under voltage clamp in cells expressing GAT1 or GAT3. Charge flux to substrate flux ratios were 0.7 ± 0.1 charge/Na(+), 2.0 ± 0.2 charges/Cl(-), and 2.1 ± 0.1 charges/GABA. Altogether, our results strongly suggest a 3 Na(+):1 Cl(-):1 GABA coupling stoichiometry for the GABA transporters. The revised stoichiometry has important implications for understanding the contribution of GATs to GABAergic signaling in health and disease.

  14. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)

    2013-11-01

    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  15. Catalytic gasification of biomass

    Science.gov (United States)

    Robertus, R. J.; Mudge, L. K.; Sealock, L. J., Jr.; Mitchell, D. H.; Weber, S. L.

    1981-12-01

    Methane and methanol synthesis gas can be produced by steam gasification of biomass in the presence of appropriate catalysts. This concept is to use catalysts in a fluidized bed reactor which is heated indirectly. The objective is to determine the technical and economic feasibility of the concept. Technically the concept has been demonstrated on a 50 lb per hr scale. Potential advantages over conventional processes include: no oxygen plant is needed, little tar is produced so gas and water treatment are simplified, and yields and efficiencies are greater than obtained by conventional gasification. Economic studies for a plant processing 2000 T/per day dry wood show that the cost of methanol from wood by catalytic gasification is competitive with the current price of methanol. Similar studies show the cost of methane from wood is competitive with projected future costs of synthetic natural gas. When the plant capacity is decreased to 200 T per day dry wood, neither product is very attractive in today's market.

  16. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    洪文明; 王梓坤

    2000-01-01

    The longtime behavior of the immigration process associated with a catalytic super-Brown-ian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d = 3.

  17. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The longtime behavior of the immigration process associated with a catalytic super-Brownian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d=3.

  18. Stoichiometry of the large conductance bacterial mechanosensitive channel of E. coli. A biochemical study

    Science.gov (United States)

    Sukharev, S. I.; Schroeder, M. J.; McCaslin, D. R.

    1999-01-01

    MscL, a 15 kDa transmembrane protein, is the only component involved in the formation of a 3 nS channel in the inner membrane of Escherichia coli that opens in response to mechanical or osmotic stress. While previous data had suggested that the functional MscL complex might be a hexamer, a recent crystallographic study of the MscL homologue from M. tuberculosis reveals a pentameric structure. The present work further examines the stoichiometry of the E. coli MscL using a variety of biochemical approaches. Detergent-purified 6His-MscL in solution and MscL in the membrane could be chemically crosslinked with the products displaying ladderlike patterns on SDS gels. Three crosslinking agents (EDC, DMS, and DMA) used at saturating concentrations invariably generated pentamers as the largest product. DSS produced additional bands corresponding to larger complexes although the pentamer band appeared to be the predominant product at high levels of crosslinker. It is not clear whether these extra bands reflect a difference in the crosslinking chemistry of DSS or whether its spacer arm is the longest of those used, or a combination of both facts. For the detergent-solubilized 6His-MscL both sedimentation equilibrium and gel chromatography showed the presence of multiple species. Thus the longer spacer arm could permit both intra- and intercomplex linkages. Nonetheless, the patterns obtained with all agents are consistent with and strongly suggest a pentameric organization for the MscL channel. Expression of MscL as genetically engineered double or triple subunit tandems yields low numbers of functional channels as compared to expressed monomers. The double-tandem assemblies must have an even number of subunits and crosslinking in the membrane confirmed hexamerization. Gel chromatography clearly demonstrated that the channels formed from the double tandems were larger than those formed from WT MscL, consistent with the native channel being pentameric. The observation that

  19. Looking inside the box: using Raman microspectroscopy to deconstruct microbial biomass stoichiometry one cell at a time.

    Science.gov (United States)

    Hall, Edward K; Singer, Gabriel A; Pölzl, Marvin; Hämmerle, Ieda; Schwarz, Christian; Daims, Holger; Maixner, Frank; Battin, Tom J

    2011-02-01

    Stoichiometry of microbial biomass is a key determinant of nutrient recycling in a wide variety of ecosystems. However, little is known about the underlying causes of variance in microbial biomass stoichiometry. This is primarily because of technological constraints limiting the analysis of macromolecular composition to large quantities of microbial biomass. Here, we use Raman microspectroscopy (MS), to analyze the macromolecular composition of single cells of two species of bacteria grown on minimal media over a wide range of resource stoichiometry. We show that macromolecular composition, determined from a subset of identified peaks within the Raman spectra, was consistent with macromolecular composition determined using traditional analytical methods. In addition, macromolecular composition determined by Raman MS correlated with total biomass stoichiometry, indicating that analysis with Raman MS included a large proportion of a cell's total macromolecular composition. Growth phase (logarithmic or stationary), resource stoichiometry and species identity each influenced each organism's macromolecular composition and thus biomass stoichiometry. Interestingly, the least variable peaks in the Raman spectra were those responsible for differentiation between species, suggesting a phylogenetically specific cellular architecture. As Raman MS has been previously shown to be applicable to cells sampled directly from complex environments, our results suggest Raman MS is an extremely useful application for evaluating the biomass stoichiometry of environmental microorganisms. This includes the ability to partition microbial biomass into its constituent macromolecules and increase our understanding of how microorganisms in the environment respond to resource heterogeneity.

  20. Looking inside the box: using Raman microspectroscopy to deconstruct microbial biomass stoichiometry one cell at a time

    Science.gov (United States)

    Hall, Edward K.; Singer, Gabriel A.; Pölzl, Marvin; Hämmerle, Ieda; Schwarz, Christian; Daims, Holger; Maixner, Frank; Battin, Tom J.

    2011-01-01

    Stoichiometry of microbial biomass is a key determinant of nutrient recycling in a wide variety of ecosystems. However, little is known about the underlying causes of variance in microbial biomass stoichiometry. This is primarily because of technological constraints limiting the analysis of macromolecular composition to large quantities of microbial biomass. Here, we use Raman microspectroscopy (MS), to analyze the macromolecular composition of single cells of two species of bacteria grown on minimal media over a wide range of resource stoichiometry. We show that macromolecular composition, determined from a subset of identified peaks within the Raman spectra, was consistent with macromolecular composition determined using traditional analytical methods. In addition, macromolecular composition determined by Raman MS correlated with total biomass stoichiometry, indicating that analysis with Raman MS included a large proportion of a cell's total macromolecular composition. Growth phase (logarithmic or stationary), resource stoichiometry and species identity each influenced each organism's macromolecular composition and thus biomass stoichiometry. Interestingly, the least variable peaks in the Raman spectra were those responsible for differentiation between species, suggesting a phylogenetically specific cellular architecture. As Raman MS has been previously shown to be applicable to cells sampled directly from complex environments, our results suggest Raman MS is an extremely useful application for evaluating the biomass stoichiometry of environmental microorganisms. This includes the ability to partition microbial biomass into its constituent macromolecules and increase our understanding of how microorganisms in the environment respond to resource heterogeneity.

  1. Stoichiometry and kinetics of mercury uptake by photosynthetic bacteria.

    Science.gov (United States)

    Kis, Mariann; Sipka, Gábor; Maróti, Péter

    2017-05-01

    Mercury adsorption on the cell surface and intracellular uptake by bacteria represent the key first step in the production and accumulation of highly toxic mercury in living organisms. In this work, the biophysical characteristics of mercury bioaccumulation are studied in intact cells of photosynthetic bacteria by use of analytical (dithizone) assay and physiological photosynthetic markers (pigment content, fluorescence induction, and membrane potential) to determine the amount of mercury ions bound to the cell surface and taken up by the cell. It is shown that the Hg(II) uptake mechanism (1) has two kinetically distinguishable components, (2) includes co-opted influx through heavy metal transporters since the slow component is inhibited by Ca(2+) channel blockers, (3) shows complex pH dependence demonstrating the competition of ligand binding of Hg(II) ions with H(+) ions (low pH) and high tendency of complex formation of Hg(II) with hydroxyl ions (high pH), and (4) is not a passive but an energy-dependent process as evidenced by light activation and inhibition by protonophore. Photosynthetic bacteria can accumulate Hg(II) in amounts much (about 10(5)) greater than their own masses by well-defined strong and weak binding sites with equilibrium binding constants in the range of 1 (μM)(-1) and 1 (mM)(-1), respectively. The strong binding sites are attributed to sulfhydryl groups as the uptake is blocked by use of sulfhydryl modifying agents and their number is much (two orders of magnitude) smaller than the number of weak binding sites. Biofilms developed by some bacteria (e.g., Rvx. gelatinosus) increase the mercury binding capacity further by a factor of about five. Photosynthetic bacteria in the light act as a sponge of Hg(II) and can be potentially used for biomonitoring and bioremediation of mercury-contaminated aqueous cultures.

  2. Abstract: Stoichiometry, Vibrational Modes and Structures of Molten Nb2O5-K2S2O7 Mixtures

    DEFF Research Database (Denmark)

    Boghosian, S.; Borup, F.; Berg, Rolf W.

    1998-01-01

    High temperature Raman spectroscopy is used tostudy the vibrational modes and structures of the Nb205-K2S207(0 mixtures at 450-700 oC under static equilibria conditions. Band assignments and Raman band intensity correlations with complex stoichiometry are performed...... in order to characterise the complex(es) formed. The determination of stoichiometry is done following a general procedure which is based on a simple formalism correlating measurements of relative Raman band intensities with the stoichiometry of solutes in molten salt solvents....

  3. Interrelationships between trans-Plasma Membrane Electron/Proton Transfer Stoichiometry, Organic Acid Metabolism, and Nitrate Reduction in Dwarf Bean (Phaseolus vulgaris).

    Science.gov (United States)

    Van Beusichem, M L; Nelemans, J A; Bienfait, H F

    1988-05-01

    Iron deficiency in dwarf bean (Phaseolus vulgaris L.) induces an increased activity of a system in the rhizodermal cells, which reduces extracellular ferric salts, and an active proton efflux from the roots, which is coupled to accumulation of citrate and malate in the roots and subsequent export of these compounds in the xylem. During reduction of extracellular ferricyanide by Fe-deficient plants, the stoichiometry of electron transport to proton efflux is 2e(-)/1H(+), and citrate and malate levels in the roots are strongly decreased. Reduction of ferricyanide by Fe-sufficient plants has no influence on root and shoot levels of citrate and malate, but in such plants the process is characterized by a e(-)/H(+) efflux stoichiometry close to unity. Apparently, organic acid metabolism and transport are closely associated with the e(-)/H(+) efflux ratio. To assess the significance of organic acid metabolism as one of the direct intracellular components of the induced unbalanced e(-)/H(+) efflux by roots, we studied NO(3) (-) reduction in shoots and roots of Fe-deficient and Fe-sufficient plants. Nitrate reductase activity in the roots was positively correlated with the level of citrate and malate, whereas the enzyme activity in the leaves responded positively to the import of these organic acid anions.

  4. Research Update: Stoichiometry controlled oxide thin film growth by pulsed laser deposition

    Directory of Open Access Journals (Sweden)

    Rik Groenen

    2015-07-01

    Full Text Available The oxidation of species in the plasma plume during pulsed laser deposition controls both the stoichiometry as well as the growth kinetics of the deposited SrTiO3 thin films, instead of the commonly assumed mass distribution in the plasma plume and the kinetic energy of the arriving species. It was observed by X-ray diffraction that SrTiO3 stoichiometry depends on the composition of the background gas during deposition, where in a relative small pressure range between 10−2 mbars and 10−1 mbars oxygen partial pressure, the resulting film becomes fully stoichiometric. Furthermore, upon increasing the oxygen (partial pressure, the growth mode changes from 3D island growth to a 2D layer-by-layer growth mode as observed by reflection high energy electron diffraction.

  5. Compensation mechanism in liquid encapsulated Czochralski GaAs Importance of melt stoichiometry

    Science.gov (United States)

    Holmes, D. E.; Chen, R. T.; Elliott, K. R.; Kirkpatrick, C. G.; Yu, P. W.

    1982-01-01

    It is shown that the key to reproducible growth of undoped semi-insulating GaAs by the liquid encapsulated Czochralski (LEC) technique is the control over the melt stoichiometry. Twelve crystals were grown from stoichiometric and nonstoichiometric melts. The material was characterized by secondary ion mass spectrometry, localized vibrational mode far infrared spectroscopy, Hall-effect measurements, optical absorption, and photoluminescence. A quantitative model for the compensation mechanism in the semi-insulating material was developed based on these measurements. The free carrier concentration is controlled by the balance between EL2 deep donors and carbon acceptors; furthermore, the incorporation of EL2 is controlled by the melt stoichiometry, increasing as the As atom fraction in the melt increases. As a result, semi-insulating material can be grown only from melts above a critical As composition. The practical significance of these results is discussed in terms of achieving high yield and reproducibility in the crystal growth process.

  6. Spore production of Penicillium roqueforti by solid state fermentation: Stoichiometry, growth and sporulation behavior.

    Science.gov (United States)

    Desfarges, C; Larroche, C; Gros, J B

    1987-06-01

    The development of Penicillium roqueforti on buckwheat seeds proceeds roughly into four steps, involving a lag phase and three growth phases. First, it appears as a spore germination and external colonization of the grains by the mycelium. Then, mainly external sporulation and internal colonization of the seeds occur and finally internal sporulation takes place. The Stoichiometry of the growth and the sporulation is established. Kinetic experiments performed in a fixed bed reactor show that the growth of the microorganism (biomass production) may be estimated by the protein content of the medium. This growth occurs with a very low mu(max) value close to 0.030 h(-1). The chitin content of the medium is an indicator of the sporulation, just as the metabolic liquor (mainly water) produced during the course of a cultivation. The values of the observed respiratory quotient are close to those predicted by stoichiometry.

  7. Effects of cation stoichiometry on electronic and structural properties of LaNiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Cole R.; Lang, Andrew C.; Taheri, Mitra L.; May, Steven J., E-mail: smay@coe.drexel.edu [Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104 (United States); Shutthanandan, Vaithiyalingam [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

    2015-07-15

    LaNiO{sub 3} films with varying La:Ni ratios were deposited onto SrTiO{sub 3} (001) substrates via molecular beam epitaxy to elucidate the effects of cation off-stoichiometry. The physical properties of La-deficient films are found to differ substantially from those of Ni-deficient films, with La-deficient films exhibiting lower electrical resistivities and smaller c-axis parameters than Ni-deficient films. No evidence of secondary phases is observed; however, transmission electron microscopy reveals an abundance of defects, the nature of which differs in lanthanum- and nickel-deficient films. This work illustrates the nontrivial role that cation stoichiometry can play on the functional properties of complex oxides.

  8. Research Update: Stoichiometry controlled oxide thin film growth by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Groenen, Rik; Smit, Jasper; Orsel, Kasper; Vailionis, Arturas; Bastiaens, Bert; Huijben, Mark; Boller, Klaus; Rijnders, Guus; Koster, Gertjan, E-mail: g.koster@utwente.nl [Faculty of Science and Technology and MESA+ Institute for Nanotechnology, University of Twente, 7500 AE Enschede (Netherlands)

    2015-07-01

    The oxidation of species in the plasma plume during pulsed laser deposition controls both the stoichiometry as well as the growth kinetics of the deposited SrTiO{sub 3} thin films, instead of the commonly assumed mass distribution in the plasma plume and the kinetic energy of the arriving species. It was observed by X-ray diffraction that SrTiO{sub 3} stoichiometry depends on the composition of the background gas during deposition, where in a relative small pressure range between 10{sup −2} mbars and 10{sup −1} mbars oxygen partial pressure, the resulting film becomes fully stoichiometric. Furthermore, upon increasing the oxygen (partial) pressure, the growth mode changes from 3D island growth to a 2D layer-by-layer growth mode as observed by reflection high energy electron diffraction.

  9. Simulated terrestrial runoff triggered a phytoplankton succession and changed seston stoichiometry in coastal lagoon mesocosms.

    Science.gov (United States)

    Deininger, A; Faithfull, C L; Lange, K; Bayer, T; Vidussi, F; Liess, A

    2016-08-01

    Climate change scenarios predict intensified terrestrial storm runoff, providing coastal ecosystems with large nutrient pulses and increased turbidity, with unknown consequences for the phytoplankton community. We conducted a 12-day mesocosm experiment in the Mediterranean Thau Lagoon (France), adding soil (simulated runoff) and fish (different food webs) in a 2 × 2 full factorial design and monitored phytoplankton composition, shade adaptation and stoichiometry. Diatoms (Chaetoceros) increased four-fold immediately after soil addition, prymnesiophytes and dinoflagellates peaked after six- and 12 days, respectively. Soil induced no phytoplankton shade adaptation. Fish reduced the positive soil effect on dinoflagellates (Scripsiella, Glenodinium), and diatom abundance in general. Phytoplankton community composition drove seston stoichiometry. In conclusion, pulsed terrestrial runoff can cause rapid, low quality (high carbon: nutrient) diatom blooms. However, bloom duration may be short and reduced in magnitude by fish. Thus, climate change may shift shallow coastal ecosystems towards famine or feast dynamics.

  10. Effects of three global change drivers on terrestrial C:N:P stoichiometry: a global synthesis.

    Science.gov (United States)

    Yue, Kai; Fornara, Dario A; Yang, Wanqin; Peng, Yan; Li, Zhijie; Wu, Fuzhong; Peng, Changhui

    2017-06-01

    Over the last few decades, there has been an increasing number of controlled-manipulative experiments to investigate how plants and soils might respond to global change. These experiments typically examined the effects of each of three global change drivers [i.e., nitrogen (N) deposition, warming, and elevated CO2 ] on primary productivity and on the biogeochemistry of carbon (C), N, and phosphorus (P) across different terrestrial ecosystems. Here, we capitalize on this large amount of information by performing a comprehensive meta-analysis (>2000 case studies worldwide) to address how C:N:P stoichiometry of plants, soils, and soil microbial biomass might respond to individual vs. combined effects of the three global change drivers. Our results show that (i) individual effects of N addition and elevated CO2 on C:N:P stoichiometry are stronger than warming, (ii) combined effects of pairs of global change drivers (e.g., N addition + elevated CO2 , warming + elevated CO2 ) on C:N:P stoichiometry were generally weaker than the individual effects of each of these drivers, (iii) additive interactions (i.e., when combined effects are equal to or not significantly different from the sum of individual effects) were more common than synergistic or antagonistic interactions, (iv) C:N:P stoichiometry of soil and soil microbial biomass shows high homeostasis under global change manipulations, and (v) C:N:P responses to global change are strongly affected by ecosystem type, local climate, and experimental conditions. Our study is one of the first to compare individual vs. combined effects of the three global change drivers on terrestrial C:N:P ratios using a large set of data. To further improve our understanding of how ecosystems might respond to future global change, long-term ecosystem-scale studies testing multifactor effects on plants and soils are urgently required across different world regions. © 2017 John Wiley & Sons Ltd.

  11. Growth of III-V films by control of MBE growth front stoichiometry

    Science.gov (United States)

    Grunthaner, Frank J. (Inventor); Liu, John K. (Inventor); Hancock, Bruce R. (Inventor)

    1992-01-01

    For the growth of strain-layer materials and high quality single and multiple quantum wells, the instantaneous control of growth front stoichiometry is critical. The process of the invention adjusts the offset or phase of molecular beam epitaxy (MBE) control shutters to program the instantaneous arrival or flux rate of In and As4 reactants to grow InAs. The interrupted growth of first In, then As4, is also a key feature.

  12. Preparation of Bimetallic PtnPdm Supported Clusters with Well-Defined Stoichiometry

    Science.gov (United States)

    Rousset, J. L.; Cadrot, A. M.; Aires, F. Santos; Renouprez, A.; Mélinon, P.; Perez, A.; Pellarin, M.; Vialle, J. L.; Broyer, M.

    Supported bimetallic Pd-Pt clusters with a well-defined stoichiometry are produced using a laser-vaporization source. Free clusters are also studied by time-of-flight mass spectrometry and photofragmentation. The supported clusters are characterized by energy dispersive x-ray analysis. The low binding energy of palladium atoms compared to that of platinum is clearly demonstrated in both free and supported clusters. The reactivity is briefly discussed.

  13. Evolution of the conductivity type in germania by varying the stoichiometry

    Energy Technology Data Exchange (ETDEWEB)

    Islamov, D. R., E-mail: damir@isp.nsc.ru [A. V. Rzhanov Institute of Semiconductor Physics, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Gritsenko, V. A., E-mail: grits@isp.nsc.ru [A. V. Rzhanov Institute of Semiconductor Physics, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Cheng, C. H. [Department of Mechatronic Technology, National Taiwan Normal University, Taipei 106, Taiwan (China); Chin, A., E-mail: albert-achin@hotmail.com [National Chiao Tung University, Hsinchu 300, Taiwan (China)

    2013-12-02

    Information regarding the conductivity type of Si/GeO{sub x}/Ni structures with various stoichiometry has been obtained using experiments on injection of minority carriers from n- and p-type silicon. Results show that non-stoichiometric GeO{sub x} films exhibit bipolar conductivity, that is, holes as well as electrons contribute to the charge transport. Stoichiometric GeO{sub 2} films exhibit unipolar electron conductivity.

  14. Study of the anaerobic decomposition of valeric acid using variable stoichiometry and thermodynamic control

    OpenAIRE

    Fluvià Sabio, Sergi

    2014-01-01

    The stoichiometry of biological decomposition reactions of many organic compounds depends on the environmental conditions and the relative concentrations of reactants and products, making that, often the calculation models based on constant stoichiometric coefficients are not able to describe experimental values. This is the case of proteins in anaerobic medium, for which an effective and realistic method for expressing the dynamics of aminoacids reactions has not been found yet. A methodolog...

  15. Proton translocation stoichiometry of cytochrome oxidase: use of a fast-responding oxygen electrode.

    OpenAIRE

    Reynafarje, B; Alexandre, A.; Davies, P.; Lehninger, A L

    1982-01-01

    The mechanistic stoichiometry of vectorial H+ ejection coupled to electron transport from added ferrocytochrome c to oxygen by the cytochrome oxidase (EC 1.9.3.1) of rat liver mitoplasts was determined from measurements of the initial rates of electron flow and H+ ejection in the presence of K+ (with valinomycin). Three different methods of measuring electron flow were used: (a) dual-wavelength spectrophotometry of ferrocytochrome c oxidation, (b) uptake of scalar H+ for the reduction of O2 i...

  16. Multiple vs. single phytoplankton species alter stoichiometry of trophic interaction with zooplankton.

    Science.gov (United States)

    Plum, Christoph; Hüsener, Matthias; Hillebrand, Helmut

    2015-11-01

    Despite the progress made in explaining trophic interactions through the stoichiometric interplay between consumers and resources, it remains unclear how the number of species in a trophic group influences the effects of elemental imbalances in food webs. Therefore, we conducted a laboratory experiment to test the hypothesis that multispecies producer assemblages alter the nutrient dynamics in a pelagic community. Four algal species were reared in mono- and polycultures under a 2 x 2 factorial combination of light and nutrient supply, thereby contrasting the stoichiometry of trophic interactions involving single vs. multiple producer species. After 9 d, these cultures were fed to the calanoid copepod Acartia tonsa, and we monitored biomass, resource use, and C:N:P stoichiometry in both phyto- and zooplankton. According to our expectations, light and N supply resulted in gradients of phytoplankton biomass and nutrient composition (C:N:P). Significant net diversity effects for algal biomass and C:N:P ratios reflected the greater responsiveness of the phytoplankton polyculture to altered resource supply compared to monocultures. These alterations of elemental ratios were common, and were partly triggered by changes in species frequency in the mixtures and partly by diversity-related changes in resource use. Copepod individual biomass increased under high light (HL) and N-reduced (-N) conditions, when food was high in C:N but low in C:P and N:P, whereas copepod growth was obviously P limited, and copepod stoichiometry was not affected by phytoplankton elemental composition. Correspondingly, copepod individual biomass reflected significant net diversity effects: compared to expectations- derived from monocultures, copepod individuals feeding on algal polycultures remained smaller than predicted under HL and N-sufficient (+N) conditions but grew larger than predicted under HL, -N and low light +N conditions. In conclusion, multiple producer species altered the

  17. Fire alters ecosystem carbon and nutrients but not plant nutrient stoichiometry or composition in tropical savanna.

    Science.gov (United States)

    Pellegrini, Adam F A; Hedin, Lars O; Staver, A Carla; Govender, Navashni

    2015-05-01

    Fire and nutrients interact to influence the global distribution and dynamics of the savanna biome, but the results of these interactions are both complex and poorly known. A critical but unresolved question is whether short-term losses of carbon and nutrients caused by fire can trigger long-term and potentially compensatory responses in the nutrient stoichiometry of plants, or in the abundance of dinitrogen-fixing trees. There is disagreement in the literature about the potential role of fire on savanna nutrients, and, in turn, on plant stoichiometry and composition. A major limitation has been the lack of fire manipulations over time scales sufficiently long for these interactions to emerge. We use a 58-year, replicated, large-scale, fire manipulation experiment in Kruger National Park (South Africa) in savanna to quantify the effect of fire on (1) distributions of carbon, nitrogen, and phosphorus at the ecosystem scale; (2) carbon: nitrogen: phosphorus stoichiometry of above- and belowground tissues of plant species; and (3) abundance of plant functional groups including nitrogen fixers. Our results show dramatic effects of fire on the relative distribution of nutrients in soils, but that individual plant stoichiometry and plant community composition remained unexpectedly resilient. Moreover, measures of nutrients and carbon stable isotopes allowed us to discount the role of tree cover change in favor of the turnover of herbaceous biomass as the primary mechanism that mediates a transition from low to high 'soil carbon and nutrients in the absence of fire. We conclude that, in contrast to extra-tropical grasslands or closed-canopy forests, vegetation in the savanna biome may be uniquely adapted to nutrient losses caused by recurring fire.

  18. Non-stoichiometry and optical spectra of Nd(III) substituted PbTiO3

    NARCIS (Netherlands)

    Bouwma, J.; Heilbron, M.A.

    1976-01-01

    The non-stoichiometry of the perovskite (ABO3)-type phase in the system PbO---TiO2---Nd2O3 has been studied. Monophasic compounds of composition Pb1−αxNdxTiO3+x(1.5−α) with x 0.21 and 0.09 α 1.5 were prepared. The ferroelectric Curie temperature (Tc) shows a decrease of 18.5 K/at% Nd with increas

  19. Determination of Stoichiometry of Solutes in Molten Salt Solvents by Correlations of Relative Raman Band Intensities

    DEFF Research Database (Denmark)

    Boghosian, Soghomon; Berg, Rolf W.

    1999-01-01

    Raman spectroscopy has been used to determine the stoichiometry of solute complexes in molten salts at high temperatures under static equilibrium conditions, A simple formalism is derived for correlating relative Raman band intensities with stoichiometric coefficients. The experimental procedures...... and sets of experiments required for establishing the stoichiometry are described, The proposed method was applied for studying the dissolution reactions of V2O5 in molten Cs2S2O7 and of Nb2O5 or MoO3 in molten K2S2O7 at temperatures in the range 430-700 degrees C: (1) V2O5 + nS(2)O(7)(2-) (1) --> X-2n- (1......); (2) Nb2O5 + nS(2)O(7)(2-) (1) --> Y2n- (1); (3) MoO3 + nS(2)O(7)(2-) (1) --> Z(2n)- (1). It is shown that the solute complex species formed in the studied reactions have, respectively, the following stoichiometries: (1) n = 2, (VO)(2)O(SO4)(4)(4-); (2) n = 3, NbO(SO4)(3)(3-); (3) n = 1, MoO(SO4)(2)(2-)....

  20. Stoichiometry of natural bacterial assemblages from lakes located across an elevational gradient.

    Science.gov (United States)

    Stenzel, Birgit; Rofner, Carina; Pérez, Maria Teresa; Sommaruga, Ruben

    2017-07-19

    Heterotrophic bacteria are thought to be phosphorus-rich organisms with relatively homeostatic stoichiometry, but the elemental composition of natural bacterial communities has rarely been assessed. Here we tested whether bacterial stoichiometry changes with the trophic status of lakes by assessing the elemental composition of the bacterial-dominated (hereafter microbial) fraction together with that of the dissolved and seston fractions in 11 lakes situated along an elevational gradient. The stoichiometry of these three size-fractions was analyzed during the thermal stratification and mixing periods in composite water samples and in the water layer of the deep chlorophyll-a maximum. In addition, we analyzed the relative abundance of the most common bacterial groups in the lakes. Our results show that the microbial fraction was always enriched in phosphorus compared to the dissolved fraction, irrespectively of the lake trophic status. Further, they indicate that the elemental composition of bacteria in mountain lakes is at least seasonally very dynamic, resulting not only from changes in the nutrient ratios of the resource itself, but probably from changes in the composition of the dominant bacterial taxa too, though at the taxonomic level analyzed, we did not find evidence for this.

  1. Carbon:Nitrogen:Phosphorus Stoichiometry in Fungi: A Meta-Analysis.

    Science.gov (United States)

    Zhang, Ji; Elser, James J

    2017-01-01

    Surveys of carbon:nitrogen:phosphorus ratios are available now for major groups of biota and for various aquatic and terrestrial biomes. However, while fungi play an important role in nutrient cycling in ecosystems, relatively little is known about their C:N:P stoichiometry and how it varies across taxonomic groups, functional guilds, and environmental conditions. Here we present the first systematic compilation of C:N:P data for fungi including four phyla (Ascomycota, Basidiomycota, Glomeromycota, and Zygomycota). The C, N, and P contents (percent of dry mass) of fungal biomass varied from 38 to 57%, 0.23 to 15%, and 0.040 to 5.5%, respectively. Median C:N:P stoichiometry for fungi was 250:16:1 (molar), remarkably similar to the canonical Redfield values. However, we found extremely broad variation in fungal C:N:P ratios around the central tendencies in C:N:P ratios. Lower C:P and N:P ratios were found in Ascomycota fungi than in Basidiomycota fungi while significantly lower C:N ratios (p stoichiometry in the mycelium.

  2. Intraspecific N and P stoichiometry of Phragmites australis: geographic patterns and variation among climatic regions.

    Science.gov (United States)

    Hu, Yu-Kun; Zhang, Ya-Lin; Liu, Guo-Fang; Pan, Xu; Yang, Xuejun; Li, Wen-Bing; Dai, Wen-Hong; Tang, Shuang-Li; Xiao, Tao; Chen, Ling-Yun; Xiong, Wei; Song, Yao-Bin; Dong, Ming

    2017-02-24

    Geographic patterns in leaf stoichiometry reflect plant adaptations to environments. Leaf stoichiometry variations along environmental gradients have been extensively studied among terrestrial plants, but little has been known about intraspecific leaf stoichiometry, especially for wetland plants. Here we analyzed the dataset of leaf N and P of a cosmopolitan wetland species, Phragmites australis, and environmental (geographic, climate and soil) variables from literature and field investigation in natural wetlands distributed in three climatic regions (subtropical, temperate and highland) across China. We found no clear geographic patterns in leaf nutrients of P. australis across China, except for leaf N:P ratio increasing with altitude. Leaf N and N:P decreased with mean annual temperature (MAT), and leaf N and P were closely related to soil pH, C:N ratio and available P. Redundancy analysis showed that climate and soil variables explained 62.1% of total variation in leaf N, P and N:P. Furthermore, leaf N in temperate region and leaf P in subtropical region increased with soil available P, while leaf N:P in subtropical region decreased with soil pH. These patterns in P. australis different from terrestrial plants might imply that changes in climate and soil properties can exert divergent effects on wetland and terrestrial ecosystems.

  3. Effect of ordering energy and stoichiometry in {Sigma} = 5 boundaries in B2 compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mutasa, B.; Farkas, D. [Virginia Polytechnic Inst. and State Univ., Blacksburg, VA (United States). Dept. of Materials Science and Engineering

    1998-11-01

    The relaxed atomistic grain boundary structures in B2 aluminides were investigated using molecular statics and embedded atom potentials in order to explore general trends for a series of B2 compounds. The authors studied free surface energies and grain boundary structures in three compounds: FeAl, NiAl and CoAl. These alloys represent a series of materials with increasing antiphase boundary energies. The misorientations chosen for detailed study correspond to the {Sigma}5(31) and {Sigma}5(210) symmetrical tilt grain boundaries. The effects of both boundary stoichiometry and bulk simulation block stoichiometry on grain boundary energetics were investigated in detail. The structures obtained for the three alloys are very similar. Defect energies were calculated for boundaries contained in both stoichiometric and off-stoichiometric bulks. The surface energies for these B2 aluminides were also calculated so that trends concerning the cohesive energy of the boundaries could be studied. The implications of the increasing ordering energy, stoichiometry, and multiplicity of possible structures for grain boundary brittleness are discussed.

  4. Climate change effects on macrofaunal litter decomposition: the interplay of temperature, body masses and stoichiometry.

    Science.gov (United States)

    Ott, David; Rall, Björn C; Brose, Ulrich

    2012-11-05

    Macrofauna invertebrates of forest floors provide important functions in the decomposition process of soil organic matter, which is affected by the nutrient stoichiometry of the leaf litter. Climate change effects on forest ecosystems include warming and decreasing litter quality (e.g. higher C : nutrient ratios) induced by higher atmospheric CO(2) concentrations. While litter-bag experiments unravelled separate effects, a mechanistic understanding of how interactions between temperature and litter stoichiometry are driving decomposition rates is lacking. In a laboratory experiment, we filled this void by quantifying decomposer consumption rates analogous to predator-prey functional responses that include the mechanistic parameters handling time and attack rate. Systematically, we varied the body masses of isopods, the environmental temperature and the resource between poor (hornbeam) and good quality (ash). We found that attack rates increased and handling times decreased (i) with body masses and (ii) temperature. Interestingly, these relationships interacted with litter quality: small isopods possibly avoided the poorer resource, whereas large isopods exhibited increased, compensatory feeding of the poorer resource, which may be explained by their higher metabolic demands. The combination of metabolic theory and ecological stoichiometry provided critically important mechanistic insights into how warming and varying litter quality may modify macrofaunal decomposition rates.

  5. Stoichiometry and thickness dependence of superconducting properties of niobium nitride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Beebe, Melissa R., E-mail: mrbeebe@email.wm.edu; Beringer, Douglas B.; Burton, Matthew C.; Yang, Kaida; Lukaszew, R. Alejandra [Department of Physics, The College of William & Mary, Small Hall, 300 Ukrop Way, Williamsburg, Virginia 23185 (United States)

    2016-03-15

    The current technology used in linear particle accelerators is based on superconducting radio frequency (SRF) cavities fabricated from bulk niobium (Nb), which have smaller surface resistance and therefore dissipate less energy than traditional nonsuperconducting copper cavities. Using bulk Nb for the cavities has several advantages, which are discussed elsewhere; however, such SRF cavities have a material-dependent accelerating gradient limit. In order to overcome this fundamental limit, a multilayered coating has been proposed using layers of insulating and superconducting material applied to the interior surface of the cavity. The key to this multilayered model is to use superconducting thin films to exploit the potential field enhancement when these films are thinner than their London penetration depth. Such field enhancement has been demonstrated in MgB{sub 2} thin films; here, the authors consider films of another type-II superconductor, niobium nitride (NbN). The authors present their work correlating stoichiometry and superconducting properties in NbN thin films and discuss the thickness dependence of their superconducting properties, which is important for their potential use in the proposed multilayer structure. While there are some previous studies on the relationship between stoichiometry and critical temperature T{sub C}, the authors are the first to report on the correlation between stoichiometry and the lower critical field H{sub C1}.

  6. Stoichiometry for α-bungarotoxin block of α7 acetylcholine receptors

    Science.gov (United States)

    Dacosta, Corrie J. B.; Free, Chris R.; Sine, Steven M.

    2015-08-01

    α-Bungarotoxin (α-Btx) binds to the five agonist binding sites on the homopentameric α7-acetylcholine receptor, yet the number of bound α-Btx molecules required to prevent agonist-induced channel opening remains unknown. To determine the stoichiometry for α-Btx blockade, we generate receptors comprised of wild-type and α-Btx-resistant subunits, tag one of the subunit types with conductance mutations to report subunit stoichiometry, and following incubation with α-Btx, monitor opening of individual receptor channels with defined subunit stoichiometry. We find that a single α-Btx-sensitive subunit confers nearly maximal suppression of channel opening, despite four binding sites remaining unoccupied by α-Btx and accessible to the agonist. Given structural evidence that α-Btx locks the agonist binding site in an inactive conformation, we conclude that the dominant mechanism of antagonism is non-competitive, originating from conformational arrest of the binding sites, and that the five α7 subunits are interdependent and maintain conformational symmetry in the open channel state.

  7. Interactive effects of predation risk and conspecific density on the nutrient stoichiometry of prey.

    Science.gov (United States)

    Guariento, Rafael D; Carneiro, Luciana S; Jorge, Jaqueiuto S; Borges, Angélica N; Esteves, Francisco A; Caliman, Adriano

    2015-11-01

    The mere presence of predators (i.e., predation risk) can alter consumer physiology by restricting food intake and inducing stress, which can ultimately affect prey-mediated ecosystem processes such as nutrient cycling. However, many environmental factors, including conspecific density, can mediate the perception of risk by prey. Prey conspecific density has been defined as a fundamental feature that modulates perceived risk. In this study, we tested the effects of predation risk on prey nutrient stoichiometry (body and excretion). Using a constant predation risk, we also tested the effects of varying conspecific densities on prey responses to predation risk. To answer these questions, we conducted a mesocosm experiment using caged predators (Belostoma sp.), and small bullfrog tadpoles (Lithobates catesbeianus) as prey. We found that L. catesbeianus tadpoles adjust their body nutrient stoichiometry in response to predation risk, which is affected by conspecific density. We also found that the prey exhibited strong morphological responses to predation risk (i.e., an increase in tail muscle mass), which were positively correlated to body nitrogen content. Thus, we pose the notion that in risky situations, adaptive phenotypic responses rather than behavioral ones might partially explain why prey might have a higher nitrogen content under predation risk. In addition, the interactive roles of conspecific density and predation risk, which might result in reduced perceived risk and physiological restrictions in prey, also affected how prey stoichiometry responded to the fear of predation.

  8. Hydrogen peroxide catalytic decomposition

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2010-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

  9. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Vivek V Ranade

    2014-03-01

    Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heterogeneous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  10. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  11. The Effects of Trace Contaminants on Catalytic Processing of Biomass-Derived Feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.; Peterson, Keith L.; Muzatko, Danielle S.; Alderson, Eric V.; Hart, Todd R.; Neuenschwander, Gary G.

    2004-03-25

    Trace components in biomass feedstocks are potential catalyst poisons when catalytically processing these materials to value-added chemical products. Trace components include inorganic elements such as alkali metals and alkaline earths, phosphorus or sulfur, aluminum or silicon, chloride, or transition metals. Protein components in biomass feedstocks can lead to formation of peptide fractions (from hydrolysis) or ammonium ions (from more severe breakdown) both of which might interfere with catalysis. The effects of these components on catalytic hydrogenation processing has been studied in batch reactor processing tests

  12. Stoichiometry of chromatin-associated protein complexes revealed by label-free quantitative mass spectrometry-based proteomics.

    Science.gov (United States)

    Smits, Arne H; Jansen, Pascal W T C; Poser, Ina; Hyman, Anthony A; Vermeulen, Michiel

    2013-01-07

    Many cellular proteins assemble into macromolecular protein complexes. The identification of protein-protein interactions and quantification of their stoichiometry is therefore crucial to understand the molecular function of protein complexes. Determining the stoichiometry of protein complexes is usually achieved by mass spectrometry-based methods that rely on introducing stable isotope-labeled reference peptides into the sample of interest. However, these approaches are laborious and not suitable for high-throughput screenings. Here, we describe a robust and easy to implement label-free relative quantification approach that combines the detection of high-confidence protein-protein interactions with an accurate determination of the stoichiometry of the identified protein-protein interactions in a single experiment. We applied this method to two chromatin-associated protein complexes for which the stoichiometry thus far remained elusive: the MBD3/NuRD and PRC2 complex. For each of these complexes, we accurately determined the stoichiometry of the core subunits while at the same time identifying novel interactors and their stoichiometry.

  13. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations......The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...

  14. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations......The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... and quantum state merging, and leads to a resource theory of decoupling....

  15. Resource stoichiometry and availability modulate species richness and biomass of tropical litter macro-invertebrates.

    Science.gov (United States)

    Jochum, Malte; Barnes, Andrew D; Weigelt, Patrick; Ott, David; Rembold, Katja; Farajallah, Achmad; Brose, Ulrich

    2017-09-01

    High biodiversity and biomass of soil communities are crucial for litter decomposition in terrestrial ecosystems such as tropical forests. However, the leaf litter that these communities consume is of particularly poor quality as indicated by elemental stoichiometry. The impact of resource quantity, quality and other habitat parameters on species richness and biomass of consumer communities is often studied in isolation, although much can be learned from simultaneously studying both community characteristics. Using a dataset of 780 macro-invertebrate consumer species across 32 sites in tropical lowland rain forest and agricultural systems on Sumatra, Indonesia, we investigated the effects of basal resource stoichiometry (C:X ratios of N, P, K, Ca, Mg, Na, S in local leaf litter), litter mass (basal resource quantity and habitat space), plant species richness (surrogate for litter habitat heterogeneity), and soil pH (acidity) on consumer species richness and biomass across different consumer groups (i.e. 3 feeding guilds and 10 selected taxonomic groups). In order to distinguish the most important predictors of consumer species richness and biomass, we applied a standardised model averaging approach investigating the effects of basal resource stoichiometry, litter mass, plant species richness and soil pH on both consumer community characteristics. This standardised approach enabled us to identify differences and similarities in the magnitude and importance of such effects on consumer species richness and biomass. Across consumer groups, we found litter mass to be the most important predictor of both species richness and biomass. Resource stoichiometry had a more pronounced impact on consumer species richness than on their biomass. As expected, taxonomic groups differed in which resource and habitat parameters (basal resource stoichiometry, litter mass, plant species richness and pH) were most important for modulating their community characteristics. The importance

  16. Warming reinforces nonconsumptive predator effects on prey growth, physiology, and body stoichiometry.

    Science.gov (United States)

    Janssens, Lizanne; Van Dievel, Marie; Stoks, Robby

    2015-12-01

    While nonconsumptive effects of predators may strongly affect prey populations, little is known how future warming will modulate these effects. Such information would be especially relevant with regard to prey physiology and resulting changes in prey stoichiometry. We investigated in Enallagma cyathigerum damselfly larvae the effects of a 4°C warming (20°C vs. 24°C) and predation risk on growth rate, physiology and body stoichiometry, for the first time including all key mechanisms suggested by the general stress paradigm (GSP) on how stressors shape changes in body stoichiometry. Growth rate and energy storage were higher at 24°C. Based on thermodynamic principles and the growth rate hypothesis, we could demonstrate predictable reductions in body C:P under warming and link these to the increase in P-rich RNA; the associated warming-induced decrease in C:N may be explained by the increased synthesis of N-rich proteins. Yet, under predation risk, growth rate instead decreased with warming and the warming-induced decreases in C:N and C:P disappeared. As predicted by the GSP, larvae increased body C:N and C:P at 24°C under predation risk. Notably, we did not detect the assumed GSP-mechanisms driving these changes: despite an increased metabolic rate there was neither an increase of C-rich biomolecules (instead fat and sugar contents decreased under predation risk), nor a decrease of N-rich proteins. We hypothesize that the higher C:N and N:P under predation risk are caused by a higher investment in morphological defense. This may also explain the stronger predator-induced increase in C:N under warming. The expected higher C:P under predation risk was only present under warming and matched the observed growth reduction and associated reduction in P-rich RNA. Our integrated mechanistic approach unraveled novel pathways of how warming and predation risk shape body stoichiometry. Key findings that (1) warming effects on elemental stoichiometry were predictable and

  17. Stoichiometries and affinities of interacting proteins from concentration series of solution scattering data: decomposition by least squares and quadratic optimization.

    Science.gov (United States)

    Chandola, Himanshu; Williamson, Tim E; Craig, Bruce A; Friedman, Alan M; Bailey-Kellogg, Chris

    2014-06-01

    In studying interacting proteins, complementary insights are provided by analyzing both the association model (the stoichiometry and affinity constants of the intermediate and final complexes) and the quaternary structure of the resulting complexes. Many current methods for analyzing protein interactions either give a binary answer to the question of association and no information about quaternary structure or at best provide only part of the complete picture. Presented here is a method to extract both types of information from X-ray or neutron scattering data for a series of equilibrium mixtures containing the initial components at different concentrations. The method determines the association pathway and constants, along with the scattering curves of the individual members of the mixture, so as to best explain the scattering data for the mixtures. The derived curves then enable reconstruction of the intermediate and final complexes. Using simulated solution scattering data for four hetero-oligomeric complexes with different structures, molecular weights and association models, it is demonstrated that this method accurately determines the simulated association model and scattering profiles for the initial components and complexes. Recognizing that experimental mixtures contain static contaminants and nonspecific complexes with the lowest affinities (inter-particle interference) as well as the desired specific complex(es), a new analytical method is also employed to extend this approach to evaluating the association models and scattering curves in the presence of static contaminants, testing both a nonparticipating monomer and a large homo-oligomeric aggregate. It is demonstrated that the method is robust to both random noise and systematic noise from such contaminants, and the treatment of nonspecific complexes is discussed. Finally, it is shown that this method is applicable over a large range of weak association constants typical of specific but transient

  18. Catalytic carbon membranes for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Damle, A.S.; Gangwal, S.K.

    1992-01-01

    Commercial carbon composite microfiltration membranes may be modified for gas separation applications by providing a gas separation layer with pores in the 1- to 10-nm range. Several organic polymeric precursors and techniques for depositing a suitable layer were investigated in this project. The in situ polymerization technique was found to be the most promising, and pure component permeation tests with membrane samples prepared with this technique indicated Knudsen diffusion behavior. The gas separation factors obtained by mixed-gas permeation tests were found to depend strongly on gas temperature and pressure indicating significant viscous flow at high-pressure conditions. The modified membranes were used to carry out simultaneous water gas shift reaction and product hydrogen separation. These tests indicated increasing CO conversions with increasing hydrogen separation. A simple process model was developed to simulate a catalytic membrane reactor. A number of simulations were carried out to identify operating conditions leading to product hydrogen concentrations over 90 percent. (VC)

  19. Simple, chemoselective, catalytic olefin isomerization.

    Science.gov (United States)

    Crossley, Steven W M; Barabé, Francis; Shenvi, Ryan A

    2014-12-01

    Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  20. Catalytic Asymmetric Bromocyclization of Polyenes.

    Science.gov (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi

    2017-02-01

    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  1. High temperature catalytic membrane reactors

    Energy Technology Data Exchange (ETDEWEB)

    1990-03-01

    Current state-of-the-art inorganic oxide membranes offer the potential of being modified to yield catalytic properties. The resulting modules may be configured to simultaneously induce catalytic reactions with product concentration and separation in a single processing step. Processes utilizing such catalytically active membrane reactors have the potential for dramatically increasing yield reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity. Examples of commercial interest include hydrogenation, dehydrogenation, partial and selective oxidation, hydrations, hydrocarbon cracking, olefin metathesis, hydroformylation, and olefin polymerization. A large portion of the most significant reactions fall into the category of high temperature, gas phase chemical and petrochemical processes. Microporous oxide membranes are well suited for these applications. A program is proposed to investigate selected model reactions of commercial interest (i.e. dehydrogenation of ethylbenzene to styrene and dehydrogenation of butane to butadiene) using a high temperature catalytic membrane reactor. Membranes will be developed, reaction dynamics characterized, and production processes developed, culminating in laboratory-scale demonstration of technical and economic feasibility. As a result, the anticipated increased yield per reactor pass economic incentives are envisioned. First, a large decrease in the temperature required to obtain high yield should be possible because of the reduced driving force requirement. Significantly higher conversion per pass implies a reduced recycle ratio, as well as reduced reactor size. Both factors result in reduced capital costs, as well as savings in cost of reactants and energy.

  2. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion.

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W; Liu, Yan; Walter, Nils G; Yan, Hao

    2016-02-10

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.

  3. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

    2016-01-01

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology. PMID:26861509

  4. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh

    2013-06-30

    Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

  5. OPERATING SPECIFICATIONS OF CATALYTIC CLEANING OF GAS FROM BIOMASS GASIFICATION

    Directory of Open Access Journals (Sweden)

    Martin Lisý

    2015-12-01

    Full Text Available The paper focuses on the theoretical description of the cleaning of syngas from biomass and waste gasification using catalytic methods, and on the verification of the theory through experiments. The main obstruction to using syngas from fluid gasification of organic matter is the presence of various high-boiling point hydrocarbons (i.e., tar in the gas. The elimination of tar from the gas is a key factor in subsequent use of the gas in other technologies for cogeneration of electrical energy and heat. The application of a natural or artificial catalyst for catalytic destruction of tar is one of the methods of secondary elimination of tar from syngas. In our experiments, we used a natural catalyst (dolomite or calcium magnesium carbonate from Horní Lánov with great mechanical and catalytic properties, suitable for our purposes. The advantages of natural catalysts in contrast to artificial catalysts include their availability, low purchase prices and higher resilience to the so-called catalyst poison. Natural calcium catalysts may also capture undesired compounds of sulphure and chlorine. Our paper presents a theoretical description and analysis of catalytic destruction of tar into combustible gas components, and of the impact of dolomite calcination on its efficiency. The efficiency of the technology is verified in laboratories. The facility used for verification was a 150 kW pilot gasification unit with a laboratory catalytic filter. The efficiency of tar elimination reached 99.5%, the tar concentration complied with limits for use of the gas in combustion engines, and the tar content reached approximately 35 mg/mn3. The results of the measurements conducted in laboratories helped us design a pilot technology for catalytic gas cleaning.

  6. Electronic components

    CERN Document Server

    Colwell, Morris A

    1976-01-01

    Electronic Components provides a basic grounding in the practical aspects of using and selecting electronics components. The book describes the basic requirements needed to start practical work on electronic equipment, resistors and potentiometers, capacitance, and inductors and transformers. The text discusses semiconductor devices such as diodes, thyristors and triacs, transistors and heat sinks, logic and linear integrated circuits (I.C.s) and electromechanical devices. Common abbreviations applied to components are provided. Constructors and electronics engineers will find the book useful

  7. Quantification of Lysine Acetylation and Succinylation Stoichiometry in Proteins Using Mass Spectrometric Data-Independent Acquisitions (SWATH).

    Science.gov (United States)

    Meyer, Jesse G; D'Souza, Alexandria K; Sorensen, Dylan J; Rardin, Matthew J; Wolfe, Alan J; Gibson, Bradford W; Schilling, Birgit

    2016-11-01

    Post-translational modification of lysine residues by NƐ-acylation is an important regulator of protein function. Many large-scale protein acylation studies have assessed relative changes of lysine acylation sites after antibody enrichment using mass spectrometry-based proteomics. Although relative acylation fold-changes are important, this does not reveal site occupancy, or stoichiometry, of individual modification sites, which is critical to understand functional consequences. Recently, methods for determining lysine acetylation stoichiometry have been proposed based on ratiometric analysis of endogenous levels to those introduced after quantitative per-acetylation of proteins using stable isotope-labeled acetic anhydride. However, in our hands, we find that these methods can overestimate acetylation stoichiometries because of signal interferences when endogenous levels of acylation are very low, which is especially problematic when using MS1 scans for quantification. In this study, we sought to improve the accuracy of determining acylation stoichiometry using data-independent acquisition (DIA). Specifically, we use SWATH acquisition to comprehensively collect both precursor and fragment ion intensity data. The use of fragment ions for stoichiometry quantification not only reduces interferences but also allows for determination of site-level stoichiometry from peptides with multiple lysine residues. We also demonstrate the novel extension of this method to measurements of succinylation stoichiometry using deuterium-labeled succinic anhydride. Proof of principle SWATH acquisition studies were first performed using bovine serum albumin for both acetylation and succinylation occupancy measurements, followed by the analysis of more complex samples of E. coli cell lysates. Although overall site occupancy was low (<1%), some proteins contained lysines with relatively high acetylation occupancy. Graphical Abstract ᅟ.

  8. Quantification of Lysine Acetylation and Succinylation Stoichiometry in Proteins Using Mass Spectrometric Data-Independent Acquisitions (SWATH)

    Science.gov (United States)

    Meyer, Jesse G.; D'Souza, Alexandria K.; Sorensen, Dylan J.; Rardin, Matthew J.; Wolfe, Alan J.; Gibson, Bradford W.; Schilling, Birgit

    2016-09-01

    Post-translational modification of lysine residues by NƐ-acylation is an important regulator of protein function. Many large-scale protein acylation studies have assessed relative changes of lysine acylation sites after antibody enrichment using mass spectrometry-based proteomics. Although relative acylation fold-changes are important, this does not reveal site occupancy, or stoichiometry, of individual modification sites, which is critical to understand functional consequences. Recently, methods for determining lysine acetylation stoichiometry have been proposed based on ratiometric analysis of endogenous levels to those introduced after quantitative per-acetylation of proteins using stable isotope-labeled acetic anhydride. However, in our hands, we find that these methods can overestimate acetylation stoichiometries because of signal interferences when endogenous levels of acylation are very low, which is especially problematic when using MS1 scans for quantification. In this study, we sought to improve the accuracy of determining acylation stoichiometry using data-independent acquisition (DIA). Specifically, we use SWATH acquisition to comprehensively collect both precursor and fragment ion intensity data. The use of fragment ions for stoichiometry quantification not only reduces interferences but also allows for determination of site-level stoichiometry from peptides with multiple lysine residues. We also demonstrate the novel extension of this method to measurements of succinylation stoichiometry using deuterium-labeled succinic anhydride. Proof of principle SWATH acquisition studies were first performed using bovine serum albumin for both acetylation and succinylation occupancy measurements, followed by the analysis of more complex samples of E. coli cell lysates. Although overall site occupancy was low (<1%), some proteins contained lysines with relatively high acetylation occupancy.

  9. Functional Analysis of Orai1 Concatemers Supports a Hexameric Stoichiometry for the CRAC Channel.

    Science.gov (United States)

    Yen, Michelle; Lokteva, Ludmila A; Lewis, Richard S

    2016-11-01

    Store-operated Ca(2+) entry occurs through the binding of the endoplasmic reticulum (ER) Ca(2+) sensor STIM1 to Orai1, the pore-forming subunit of the Ca(2+) release-activated Ca(2+) (CRAC) channel. Although the essential steps leading to channel opening have been described, fundamental questions remain, including the functional stoichiometry of the CRAC channel. The crystal structure of Drosophila Orai indicates a hexameric stoichiometry, while studies of linked Orai1 concatemers and single-molecule photobleaching suggest that channels assemble as tetramers. We assessed CRAC channel stoichiometry by expressing hexameric concatemers of human Orai1 and comparing in detail their ionic currents to those of native CRAC channels and channels generated from monomeric Orai1 constructs. Cell surface biotinylation results indicated that Orai1 channels in the plasma membrane were assembled from intact hexameric polypeptides and not from truncated protein products. In addition, the L273D mutation depressed channel activity equally regardless of which Orai1 subunit in the concatemer carried the mutation. Thus, functional channels were generated from intact Orai1 hexamers in which all subunits contributed equally. These hexameric Orai1 channels displayed the biophysical fingerprint of native CRAC channels, including the distinguishing characteristics of gating (store-dependent activation, Ca(2+)-dependent inactivation, open probability), permeation (ion selectivity, affinity for Ca(2+) block, La(3+) sensitivity, unitary current magnitude), and pharmacology (enhancement and inhibition by 2-aminoethoxydiphenyl borate). Because permeation characteristics depend strongly on pore geometry, it is unlikely that hexameric and tetrameric pores would display identical Ca(2+) affinity, ion selectivity, and unitary current magnitude. Thus, based on the highly similar pore properties of the hexameric Orai1 concatemer and native CRAC channels, we conclude that the CRAC channel functions as a

  10. Carbon:Nitrogen:Phosphorus Stoichiometry in Fungi: A Meta-Analysis

    Directory of Open Access Journals (Sweden)

    Ji Zhang

    2017-07-01

    Full Text Available Surveys of carbon:nitrogen:phosphorus ratios are available now for major groups of biota and for various aquatic and terrestrial biomes. However, while fungi play an important role in nutrient cycling in ecosystems, relatively little is known about their C:N:P stoichiometry and how it varies across taxonomic groups, functional guilds, and environmental conditions. Here we present the first systematic compilation of C:N:P data for fungi including four phyla (Ascomycota, Basidiomycota, Glomeromycota, and Zygomycota. The C, N, and P contents (percent of dry mass of fungal biomass varied from 38 to 57%, 0.23 to 15%, and 0.040 to 5.5%, respectively. Median C:N:P stoichiometry for fungi was 250:16:1 (molar, remarkably similar to the canonical Redfield values. However, we found extremely broad variation in fungal C:N:P ratios around the central tendencies in C:N:P ratios. Lower C:P and N:P ratios were found in Ascomycota fungi than in Basidiomycota fungi while significantly lower C:N ratios (p < 0.05 and higher N:P ratios (p < 0.01 were found in ectomycorrhizal fungi than in saprotrophs. Furthermore, several fungal stoichiometric ratios were strongly correlated with geographic and abiotic environmental factors, especially latitude, precipitation, and temperature. The results have implications for understanding the roles that fungi play in function in symbioses and in soil nutrient cycling. Further work is needed on the effects of actual in situ growth conditions of fungal growth on stoichiometry in the mycelium.

  11. Stoichiometry as key to ferroelectricity in compressively strained SrTiO{sub 3} films

    Energy Technology Data Exchange (ETDEWEB)

    Haislmaier, R. C.; Engel-Herbert, R.; Gopalan, V. [Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2016-07-18

    While strain is a powerful tuning parameter for inducing ferroelectricity in thin film oxides, the role of stoichiometry control is critical, but far less explored. A series of compressively strained SrTiO{sub 3} films on (001) (LaAlO{sub 3}){sub 0.3}(Sr{sub 2}AlTaO{sub 6}){sub 0.35} substrates were grown by hybrid molecular beam epitaxy where the Ti cation was supplied using a metal-organic titanium tetraisopropoxide molecule that helps systematically and precisely control Sr:Ti stoichiometry in the resulting films. A stoichiometric growth window is located through X-ray diffraction and in-situ reflection high-energy electron diffraction measurements, which show a minimum out-of-plane lattice parameter as well as constant growth rate within the stoichiometric growth window range. Using temperature dependent optical second harmonic generation (SHG) characterization, a ferroelectric-to-paraelectric transition at T ∼ 180 K is observed for a stoichiometric SrTiO{sub 3} film, as well as a higher temperature structural transition at T ∼ 385 K. Using SHG polarimetry modeling, the polar point group symmetry is determined to be tetragonal 4mm with the polarization pointing out-of-plane of the film. The SHG coefficients, d{sub 31}/d{sub 15}=3 and d{sub 33}/d{sub 15}=21, were determined at 298 K. The ferroelectric transition disappears in films grown outside the growth window, thus proving the critical role of stoichiometry control in realizing strain-induced ferroelectricity.

  12. PIP Water Transport and Its pH Dependence Are Regulated by Tetramer Stoichiometry.

    Science.gov (United States)

    Jozefkowicz, Cintia; Sigaut, Lorena; Scochera, Florencia; Soto, Gabriela; Ayub, Nicolás; Pietrasanta, Lía Isabel; Amodeo, Gabriela; González Flecha, F Luis; Alleva, Karina

    2016-03-29

    Many plasma membrane channels form oligomeric assemblies, and heterooligomerization has been described as a distinctive feature of some protein families. In the particular case of plant plasma membrane aquaporins (PIPs), PIP1 and PIP2 monomers interact to form heterotetramers. However, the biological properties of the different heterotetrameric configurations formed by PIP1 and PIP2 subunits have not been addressed yet. Upon coexpression of tandem PIP2-PIP1 dimers in Xenopus oocytes, we can address, for the first time to our knowledge, the functional properties of single heterotetrameric species having 2:2 stoichiometry. We have also coexpressed PIP2-PIP1 dimers with PIP1 and PIP2 monomers to experimentally investigate the localization and biological activity of each tetrameric assembly. Our results show that PIP2-PIP1 heterotetramers can assemble with 3:1, 1:3, or 2:2 stoichiometry, depending on PIP1 and PIP2 relative expression in the cell. All PIP2-PIP1 heterotetrameric species localize at the plasma membrane and present the same water transport capacity. Furthermore, the contribution of any heterotetrameric assembly to the total water transport through the plasma membrane doubles the contribution of PIP2 homotetramers. Our results also indicate that plasma membrane water transport can be modulated by the coexistence of different tetrameric species and by intracellular pH. Moreover, all the tetrameric species present similar cooperativity behavior for proton sensing. These findings throw light on the functional properties of PIP tetramers, showing that they have flexible stoichiometry dependent on the quantity of PIP1 and PIP2 molecules available. This represents, to our knowledge, a novel regulatory mechanism to adjust water transport across the plasma membrane.

  13. Phase Stability and Stoichiometry in Thin Film Iron Pyrite: Impact on Electronic Transport Properties.

    Science.gov (United States)

    Zhang, Xin; Scott, Tom; Socha, Tyler; Nielsen, David; Manno, Michael; Johnson, Melissa; Yan, Yuqi; Losovyj, Yaroslav; Dowben, Peter; Aydil, Eray S; Leighton, Chris

    2015-07-01

    The use of pyrite FeS2 as an earth-abundant, low-cost, nontoxic thin film photovoltaic hinges on improved understanding and control of certain physical and chemical properties. Phase stability, phase purity, stoichiometry, and defects, are central in this respect, as they are frequently implicated in poor solar cell performance. Here, phase-pure polycrystalline pyrite FeS2 films, synthesized by ex situ sulfidation, are subject to systematic reduction by vacuum annealing (to 550 °C) to assess phase stability, stoichiometry evolution, and their impact on transport. Bulk probes reveal the onset of pyrrhotite (Fe(1-δ)S) around 400 °C, rapidly evolving into the majority phase by 425 °C. This is supported by X-ray photoelectron spectroscopy on (001) crystals, revealing surface Fe(1-δ)S formation as low as 160 °C, with rapid growth near 400 °C. The impact on transport is dramatic, with Fe(1-δ)S minority phases leading to a crossover from diffusive transport to hopping (due to conductive Fe(1-δ)S nanoregions in an FeS2 matrix), followed by metallicity when Fe(1-δ)S dominates. Notably, the crossover to hopping leads to an inversion of the sign, and a large decrease in magnitude of the Hall coefficient. By tracking resistivity, magnetotransport, magnetization, and structural/chemical parameters vs annealing, we provide a detailed picture of the evolution in properties with stoichiometry. A strong propensity for S-deficient minority phase formation is found, with no wide window where S vacancies control the FeS2 carrier density. These findings have important implications for FeS2 solar cell development, emphasizing the need for (a) nanoscale chemical homogeneity, and (b) caution in interpreting carrier types and densities.

  14. [Stoichiometry of cytochromes and oxygen tension in skeletal muscles of marine fish].

    Science.gov (United States)

    Soldatov, A A; Parfenova, I A

    2014-01-01

    The character of oxygen tension distribution and peculiarities of cytochromes stoichiometry in skeletal muscles of bottom and pelagic species of marine fish were compared. It is shown, that the limitation of muscle activity increases the number of hypoxic zones in the muscle tissue. The mitochondrial electron-transporting chain then obtain the uncompensated type of organization, expressed in the increase of the share of the terminal complex aa3 on the background of general reduction of cytochromes content in the muscles. The reaction is of an adaptive character and can be implemented by pelagic fish species in conditions of experimental hypokinesia.

  15. The influence of stoichiometry on electrical properties of silicon carbide grown by physical vapor transport process

    Science.gov (United States)

    Li, Qiang

    The purposes of this thesis were to investigate the influence of the vapor phase stoichiometry in the ambient on electrical properties of silicon carbide grown by physical vapor transport (PVT) process in order to provide a better understanding of the nature of the compensation mechanisms in semi-insulating SiC crystals. Standard PVT and hydrogen-assisted PVT processes have been used to grow SiC single crystals. Chemical elemental analysis, contactless resistivity mapping (COREMA), temperature dependent Hall measurements (TDH), deep level transient spectroscopy (DLTS), and minority diffusion length measurements were performed to characterize the properties of SiC wafers. The nitrogen contamination, the net carrier concentrations, and the concentrations of the major deep traps in the undoped and nitrogen-doped SiC crystals were found to substantially decrease during the standard PVT growth when moving from seed to tail of the crystal. Addition of hydrogen to the growth ambient changed all the properties in the same direction. As a consequence of the doping and deep traps variations, the electrical properties including resistivity, Fermi energy, and minority carrier lifetime continuously changed during the growth. The results of the hydrogen-assisted PVT growth and the virtual reactor growth modeling indicated that the electrical properties change as a function of stoichiometry in the vapor phase, and the carbon transport efficiency can be enhanced by the reactions of hydrogen with the SiC charge material and the graphite parts of the crucible. Thermodynamic calculation of the vapor phase stoichiometry and the studies of the properties of H2-assisted PVT-grown crystals have shown that hydrogen can be used as a key factor controlling the vapor phase stoichiometry in the PVT process; in this manner the purity, electrical uniformities and the yield of the semi-insulating wafers can be improved to a great extent. The electron mobility values were found unusually low in

  16. Impact of stoichiometry on the linear and nonlinear optical response of SnOx thin films

    Science.gov (United States)

    Li, Zhong-guo; Liang, Ling-yan; Cao, Hong-tao; Song, Ying-lin

    2017-06-01

    SnO is a promising p-type oxide semiconductor materials for applications such as transparent electronics and solar cells. However, further improvement of its performance is hindered by its diverse stoichiometry. We investigated the nonlinear and saturable absorption characteristics of pristine SnO and O-rich SnOx films by femtosecond degenerate pump-probe measurements at 515 nm. UV-Vis absorption data indicate bandgap blueshift with increasing oxygen concentration. Pristine SnO film exhibit saturable absorption while nonlinear absorption is observed in O-rich SnOx films. Our results shed light on the utilization of SnO in future device applications.

  17. Copper(II) ions and the Alzheimer's amyloid-β peptide: Affinity and stoichiometry of binding

    Science.gov (United States)

    Tõugu, Vello; Friedemann, Merlin; Tiiman, Ann; Palumaa, Peep

    2014-10-01

    Deposition of amyloid beta (Aβ) peptides into amyloid plaques is the hallmark of Alzheimer's disease. According to the amyloid cascade hypothesis this deposition is an early event and primary cause of the disease, however, the mechanisms that cause this deposition remain elusive. An increasing amount of evidence shows that the interactions of biometals can contribute to the fibrillization and amyloid formation by amyloidogenic peptides. From different anions the copper ions deserve the most attention since it can contribute not only toamyloid formation but also to its toxicity due to the generation of ROS. In this thesis we focus on the affinity and stoichiometry of copper(II) binding to the Aβ molecule.

  18. Thin-Film Transistor-Based Biosensors for Determining Stoichiometry of Biochemical Reactions

    Science.gov (United States)

    Wang, Yi-Wen; Chen, Ting-Yang; Yang, Tsung-Han; Chang, Cheng-Chung; Yang, Tsung-Lin; Lo, Yu-Hwa

    2016-01-01

    The enzyme kinetic in a biochemical reaction is critical to scientific research and drug discovery but can hardly be determined experimentally from enzyme assays. In this work, a charge-current transducer (a transistor) is proposed to evaluate the status of biochemical reaction by monitoring the electrical charge changes. Using the malate-aspartate shuttle as an example, a thin-film transistor (TFT)-based biosensor with an extended gold pad is demonstrated to detect the biochemical reaction between NADH and NAD+. The drain current change indicates the status of chemical equilibrium and stoichiometry. PMID:28033412

  19. Report on a NASA astrobiology institute-funded workshop without walls: stellar stoichiometry.

    Science.gov (United States)

    Desch, Steven J; Young, Patrick A; Anbar, Ariel D; Hinkel, Natalie; Pagano, Michael; Truitt, Amanda; Turnbull, Margaret

    2014-04-01

    We report on the NASA Astrobiology Institute-funded Workshop Without Walls entitled "Stellar Stoichiometry," hosted by the "Follow the Elements" team at Arizona State University in April 2013. We describe several innovative practices we adopted that made effective use of the Workshop Without Walls videoconferencing format, including use of information technologies, assignment of scientific tasks before the workshop, and placement of graduate students in positions of authority. A companion article will describe the scientific results arising from the workshop. Our intention here is to suggest best practices for future Workshops Without Walls.

  20. Catalytic wet oxidation of aqueous methylamine: comparative study on the catalytic performance of platinum-ruthenium, platinum, and ruthenium catalysts supported on titania.

    Science.gov (United States)

    Song, Aiying; Lu, Gongxuan

    2015-01-01

    Promotion of the dispersion of Ru species supported on TiO2 was achieved by introduction of Pt component and the role of Pt in enhancing the catalytic performances of Pt-Ru was investigated with catalytic wet air oxidation of methylamine used as a probing reaction. It was found that Pt-Ru/TiO2 displayed a much better catalytic performance compared with Pt/TiO2 and Ru/TiO2 catalysts due to having the highest dispersion of active species. Both high total organic carbon conversion and nitrogen selectivity (∼100%) over Pt-Ru/TiO2 catalyst were achieved at low temperature (200 °C). X-ray photoelectron spectroscopy characterization indicated that there were strong interactions between metal particles and the support, which may increase the catalytic performance of catalysts.

  1. Structured materials for catalytic and sensing applications

    Science.gov (United States)

    Hokenek, Selma

    been synthesized and characterized to establish the effects of nanoparticle size on catalytic activity in methanol decomposition. The physicochemical properties of the synthesized palladium-nickel nanoparticles will be discussed, as a function of the synthesis parameters. The optical characteristics of the Ag and Pd nanoparticles will be determined, with a view toward tuning the response of the nanoparticles for incorporation in sensors. Analysis of the monometallic palladium particles revealed a dependence of syngas production on nanoparticle size. The peak and steady state TOFs increased roughly linearly with the average nanoparticle diameter. The amount of coke deposited on the particle surfaces was found to be independent on the size of the nanoparticles. Shape control of the nickel-palladium nanoparticles with a high selectivity for (100) and (110) facets (≤ 80%) has been demonstrated. The resulting alloy nanoparticles were found to have homogeneous composition throughout their volume and maintain FCC crystal structure. Substitution of Ni atoms in the Pd lattice at a 1:3 molar ratio was found to induce lattice strains of ~1%. The Ag nanocubes synthesized exhibited behavior very similar to literature values, when taken on their own, exhibiting a pair of distinct absorbance peaks at 350 nm and 455 nm. In physical mixtures with the Pd nanoparticles synthesized, their behavior showed that the peak position of the Ag nanocubes' absorbance in UV-Vis could be tuned based on the relative proportions of the Ag and Pd nanoparticles present in the suspension analysed. The Ag polyhedra synthesized for comparison showed a broad doublet peak throughout the majority of the visible range before testing as a component in a physical mixture with the Pd nanoparticles. The addition of Pd nanoparticles to form a physical mixture resulted in some damping of the doublet peak observed as well as a corresponding shift in the baseline absorbance proportional to the amount of Pd added to

  2. Foliar nitrogen and phosphorus stoichiometry of three wetland plants distributed along an elevation gradient in Dongting Lake, China.

    Science.gov (United States)

    Li, Feng; Gao, Han; Zhu, Lianlian; Xie, Yonghong; Yang, Guishan; Hu, Cong; Chen, Xinsheng; Deng, Zhengmiao

    2017-06-06

    We examined foliar nitrogen (N) and phosphorus (P) stoichiometry of 3 wetland plants (Phalaris arundinacea, Miscanthus sacchariflorus, and Carex brevicuspis) distributed along an elevation gradient in the Dongting Lake, China, and how this stoichiometry is related to soil physico-chemical characteristics, elevation, and flooding days. Plant and soil samples were collected from 3 lakeshore sites. Total N and P concentrations of plants and six physico-chemical characteristics of the soil were measured, in addition to the elevation and flooding days. P. arundinacea and M. sacchariflorus had higher total N and P concentrations than C. brevicuspis. The foliar N:P ratio decreased with increasing elevation, and only increased with increasing foliar total N concentration. Canonical correspondence analysis indicated that the foliar stoichiometry was primarily regulated by soil water content, followed by soil nutrient concentration. The foliar N and P stoichiometry of the 3 wetland plants was insignificantly correlated with soil total P concentration. However, foliar stoichiometric characteristics and soil total N concentration significantly differed among the 3 species. These results demonstrate that spatial variation of foliar stoichiometry in wetland plants exists along an elevation gradient, with this information being useful for the conservation and management of wetland plants in this lake.

  3. Template electrodeposition of catalytic nanomotors.

    Science.gov (United States)

    Wang, Joseph

    2013-01-01

    The combination of nanomaterials with electrode materials has opened new horizons in electroanalytical chemistry, and in electrochemistry in general. Over the past two decades we have witnessed an enormous activity aimed at designing new electrochemical devices based on nanoparticles, nanotubes or nanowires, and towards the use of electrochemical routes--particularly template-assisted electrodeposition--for preparing nanostructured materials. The power of template-assisted electrochemical synthesis is demonstrated in this article towards the preparation and the realization of self-propelled catalytic nanomotors, ranging from Pt-Au nanowire motors to polymer/Pt microtube engines. Design considerations affecting the propulsion behavior of such catalytic nanomotors are discussed along with recent bioanalytical and environmental applications. Despite recent major advances, artificial nanomotors have a low efficiency compared to their natural counterparts. Hopefully, the present Faraday Discussion will stimulate other electrochemistry teams to contribute to the fascinating area of artificial nanomachines.

  4. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  5. The influence of microscopic and macroscopic non-stoichiometry on interfacial planarity during the solid-phase epitaxial growth of amorphized GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Belay, K.B.; Ridgway, M.C.; Llewellyn, D.J. [Australian National Univ., Canberra, ACT (Australia). Dept. of Physics

    1996-12-31

    The influence of microscopic and macroscopic non-stoichiometry on the Solid-Phase Epitaxial Growth of GaAs has been studied. Ion implantation has been employed to produce microscopic non-stoichiometry via Ga and As implants and macroscopic non-stoichiometry via Ga or As implants. In-situ Time Resolved Reflectivity and Transmission Electron Microscopy and ex-situ Rutherford Backscattering Spectroscopy and Channeling have been used to investigate the regrowth of amorphized GaAs layers. As non-stoichiometry shifts from microscopic to macroscopic the interface loses its planar nature and subsequently gets rougher. 7 refs., 3 figs.

  6. Radiation/Catalytic Augmented Combustion.

    Science.gov (United States)

    1980-09-01

    NATIO& NAk H(fJI At tl TANUAHTOb 19 A ~omm.81-0287 LVL RADIATION/CATALYTIC AUGMENTED COMBUST ION MOSHE LAVID CORPORATE RESEARCH-TECHNOLOGY FEASIBILITY...refinements as necessary. i. Perform cannular combustor experiments to Investigate ignition and flame attachment in flowing, liquid -fuel, unpremixed...stabilizer, with a sintered metal disk on the downstream side through which hot gases or products of partial fuel oxidation can be passed. Experimental

  7. Catalytic polarographic currents of oxidizers

    Energy Technology Data Exchange (ETDEWEB)

    Zajtsev, P.M.; Zhdanov, S.I.; Nikolaeva, T.D. (Vsesoyuznyj Nauchno-Issledovatel' skij Inst. Khimicheskikh Reaktivov i Osobo Chistykh Veshchestv, Moscow (USSR))

    1982-06-01

    The state of theory and practice of an important direction in polarography, i.e. catalytic currents of oxidizers-substrates that have found a wide application in the development of highly sensitive methods of determination of a large number of substrates, catalysts and polarographically nonactive ligands, is considered. Transition and some non-transition elements serve as catalysts of reactions that cause catalytic polarographic currents of substrates. Catalytic activity of an inorganic catalyst increases with the increase in the number of its d-orbit. Complex formation in most cases leads to the increase of catalyst activity, however, sometimes a reverse phenomenon takes place. For many catalysts the maximum activity is observed at pH values close to pK value of their hydrolysis. The properties of oxidizers-substrates is revealed by H/sub 2/O/sub 2/, ClO/sub 3//sup -/, BrO/sub 3//sup -/, IO/sub 3//sup -/, ClO/sub 4//sup -/, IO/sub 4//sup -/, NO/sub 2//sup -/, NO/sub 3//sup -/, NH/sub 2/OH, V(5), V(4), S/sub 2/O/sub 8//sup 2 -/, H/sub 2/SO/sub 4/, H/sub 2/C/sub 2/O/sub 4/, COHCOOH, alkenes compounds, organic halogen , sulfur- and amine-containing compounds.

  8. Thermodynamics of catalytic nanoparticle morphology

    Science.gov (United States)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  9. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1997-12-31

    The aim of this work was to study the catalytic cleaning of gasification gas from tars and ammonia. In addition, factors influencing catalytic activity in industrial applications were studied, as well as the effects of different operation conditions and limits. Also the catalytic reactions of tar and ammonia with gasification gas components were studied. The activities of different catalyst materials were measured with laboratory-scale reactors fed by slip streams taken from updraft and fluid bed gasifiers. Carbonate rocks and nickel catalysts proved to be active tar decomposing catalysts. Ammonia decomposition was in turn facilitated by nickel catalysts and iron materials like iron sinter and iron dolomite. Temperatures over 850 deg C were required at 2000{sup -1} space velocity at ambient pressure to achieve almost complete conversions. During catalytic reactions H{sub 2} and CO were formed and H{sub 2}O was consumed in addition to decomposing hydrocarbons and ammonia. Equilibrium gas composition was almost achieved with nickel catalysts at 900 deg C. No deactivation by H{sub 2}S or carbon took place in these conditions. Catalyst blocking by particulates was avoided by using a monolith type of catalyst. The apparent first order kinetic parameters were determined for the most active materials. The activities of dolomite, nickel catalyst and reference materials were measured in different gas atmospheres using laboratory apparatus. This consisted of nitrogen carrier, toluene as tar model compound, ammonia and one of the components H{sub 2}, H{sub 2}O, CO, CO{sub 2}, CO{sub 2}+H{sub 2}O or CO+CO{sub 2}. Also synthetic gasification gas was used. With the dolomite and nickel catalyst the highest toluene decomposition rates were measured with CO{sub 2} and H{sub 2}O. In gasification gas, however, the rate was retarded due to inhibition by reaction products (CO, H{sub 2}, CO{sub 2}). Tar decomposition over dolomite was modelled by benzene reactions with CO{sub 2}, H

  10. Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

    Science.gov (United States)

    Song, Hyunjoon

    2015-03-17

    In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple

  11. Synthesis, structure, morphology and stoichiometry characterization of cluster and nano magnetite

    Energy Technology Data Exchange (ETDEWEB)

    Singh, L. Herojit; Pati, S.S. [Institute of Physics, University of Brasilia, 70919-970, Brasilia, DF (Brazil); Guimarães, Edi M. [Institute of Geoscience, University of Brasilia, 70910-900, Brasilia, DF (Brazil); Rodrigues, P.A.M.; Oliveira, Aderbal C. [Institute of Physics, University of Brasilia, 70919-970, Brasilia, DF (Brazil); Garg, V.K., E-mail: vijgarg@gmail.com [Institute of Physics, University of Brasilia, 70919-970, Brasilia, DF (Brazil)

    2016-08-01

    We have studied the stoichiometry of magnetite nanoparticles using three spectroscopic techniques: Mössbauer, photoacoustic and ferromagnetic resonance (FMR). By varying the weight ratio of the Fe precursor to the reducing agent (sodium acetate) and a post-synthesis annealing, we were able to synthesize samples with different amounts of Fe vacancies, from stoichiometric Fe{sub 3}O{sub 4} to γ-Fe{sub 2}O{sub 3}. By synthesizing magnetite in the presence of zeolite we obtained nanoparticles within the 3–10 nm diameter range. The spectroscopic results show that there is a correlation between the amount of Fe vacancies and (i) the optical absorption and (ii) the g-values from the Electron paramagnetic resonance EPR spectra of the nanoparticles. - Highlights: • Magnetite nanoparticles and cluster synthesized. • Photoacoustic spectroscopy is effective in determining the stoichiometry. • Particles with 9 nm size has 0 < δ < 0.14. • Less than 9 nm gives 0.14 < δ < 0.3 and size <3 nm have δ = 0.33 (i.e. γ-Fe{sub 2}O{sub 3}).

  12. Effect of microbial enzyme allocation strategies on stoichiometry of soil organic matter (SOM) decomposition

    Science.gov (United States)

    Wutzler, Thomas

    2014-05-01

    We explored different strategies of soil microbial community to invest resources into extracellular enzymes by conceptual modelling. Similar to the EEZY model by Moorhead et al. (2012), microbial community can invest into two separate pools of enzymes that depolymerize two different SOM pools. We show that with assuming that a fixed fraction of substrate uptake is allocated to enzymes, the microbial dynamics decouples from decomposition dynamics. We propose an alternative formulation where investment into enzymes is proportional to microbial biomass. Next, we show that the strategy of optimizing stoichiometry of decomposition flux according to microbial biomass stoichiometry yield less microbial growth than the strategy of optimizing revenue of the currently limiting element. However, both strategies result in better usage of the resources, i.e. less C overflow or N mineralization, than the strategy of equal allocation to both enzymes. Further, we discuss effects of those strategies on decomposition of SOM and priming at different time scales and discuss several abstractions from the detailed model dynamics for usage in larger scale models.

  13. Non-stoichiometry Defects and Radiation Hardness of Lead Tungstate Crystals PbWO4

    CERN Document Server

    Devitsin, E G; Kozlov, V A; Nefedov, L; Polyansky, E V; Potashov, S Yu; Terkulov, A R; Zadneprovski, B I

    2001-01-01

    It has been stated many times that the formation of radiation infringements in PbWO4 is to big extent stipulated by non-stoichiometry defects of the crystals, arising in the process of their growth and annealing. To refine the idea of characteristics of non-stoichiometry defects and their effect on the radiation hardness of PbWO4 the current study is aimed at the melt composition infringements during its evaporation and at optical transmission of crystals obtained in these conditions after their irradiation (137Cs source). In the optical transmission measurements along with traditional techniques a method "in situ" was used, which provided the measurements in fixed points of the spectrum (380, 470 and 535 nm) directly in the process of the irradiation. X-ray phase and fluorescence analysis of condensation products of vapours over PbWO4 melt has found PbWO4 phase in their content as well as compounds rich in lead, PbO, Pb2WO5, with overall ratio Pb/W = 3.2. Correspondingly the lack of lead and variations in th...

  14. Perovskite Hollow Fibers with Precisely Controlled Cation Stoichiometry via One-Step Thermal Processing.

    Science.gov (United States)

    Zhu, Jiawei; Zhang, Guangru; Liu, Gongping; Liu, Zhengkun; Jin, Wanqin; Xu, Nanping

    2017-05-01

    The practical applications of perovskite hollow fibers (HFs) are limited by challenges in producing these easily, cheaply, and reliably. Here, a one-step thermal processing approach is reported for the efficient production of high performance perovskite HFs, with precise control over their cation stoichiometry. In contrast to traditional production methods, this approach directly uses earth-abundant raw chemicals in a single thermal process. This approach can control cation stoichiometry by avoiding interactions between the perovskites and polar solvents/nonsolvents, optimizes sintering, and results in high performance HFs. Furthermore, this method saves much time and energy (≈ 50%), therefore pollutant emissions are greatly reduced. One successful example is Ba0.5Sr0.5Co0.8Fe0.2O3-δ HFs, which are used in an oxygen-permeable membrane. This exhibits high oxygen permeation flux values that exceed desired commercial targets and compares favorably with previously reported oxygen-permeable membranes. Studies on other perovskites have produced similarly successful results. Overall, this approach could lead to energy efficient, solid-state devices for industrial application in energy and environmental fields. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Stoichiometry, Metabolism and Nutrient Limitation Across the Periodic Table in Natural Flowing-Water Chemostats

    Science.gov (United States)

    Cohen, M. J.; Nifong, R. L.; Kurz, M. J.; Cropper, W. P.; Martin, J. B.

    2014-12-01

    Relative supplies of macro and micronutrients (C,N,P, various metals), along with light and water, controls ecosystem metabolism, trophic energy transfer and community structure. Here we test the hypothesis, using measurements from 41 spring-fed rivers in Florida, that tissue stoichiometry indicates autotroph nutrient limitation status. Low variation in discharge, temperature and chemical composition within springs, but large variation across springs creates an ideal setting to assess the relationship between limitation and resource supply. Molar N:P ranges from 0.4 to 90, subjecting autotrophs to dramatically different nutrient supply. Over this gradient, species-specific autotroph tissue C:N:P ratios are strictly homeostatic, and with no evidence that nutrient supply affects species composition. Expanding to include 19 metals and micronutrients revealed autotrophs are more plastic in response to micronutrient variation, particularly for iron and manganese whose supply fluxes are small compared to biotic demand. Using a Droop model modified to reflect springs conditions (benthic production, light limitation, high hydraulic turnover), we show that tissue stoichiometry transitions from homeostatic to plastic with the onset of nutrient limitation, providing a potentially powerful new tool for predicting nutrient limitation and thus eutrophication in flowing waters.

  16. Biogeographic bases for a shift in crop C : N : P stoichiometries during domestication.

    Science.gov (United States)

    Delgado-Baquerizo, Manuel; Reich, Peter B; García-Palacios, Pablo; Milla, Rubén

    2016-05-01

    We lack both a theoretical framework and solid empirical data to understand domestication impacts on plant chemistry. We hypothesised that domestication increased leaf N and P to support high plant production rates, but biogeographic and climate patterns further influenced the magnitude and direction of changes in specific aspects of chemistry and stoichiometry. To test these hypotheses, we used a data set of leaf C, N and P from 21 herbaceous crops and their wild progenitors. Domestication increased leaf N and/or P for 57% of the crops. Moreover, the latitude of the domestication sites (negatively related to temperature) modulated the domestication effects on P (+), C (-), N : P (-) and C : P (-) ratios. Further results from a litter decomposition assay showed that domestication effects on litter chemistry affected the availability of soil N and P. Our findings draw attention to evolutionary effects of domestication legacies on plant and soil stoichiometry and related ecosystem services (e.g. plant yield and soil fertility).

  17. Effect of A-site Non-stoichiometry on LSCF Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Templeton, Jared W.; Lu, Zigui; Stevenson, Jeffry W.; Hardy, John S.

    2011-09-01

    LSCF Cathodes were explored when effected with A-site non-stoichiometry. At 700-800 C, the operating temperatures of intermediate temperature (IT-) SOFCs have enabled the use of stainless steels in the SOFC framework and current collectors, allowing significant reductions in cost. However, the lower operating temperatures of IT-SOFC's also result in significant decreases in power densities of cells with LSM cathodes due to their high activation energies. LSCF is a mixed ionic electronic conducting perovskite that exhibits higher performance than LSM/YSZ composites and shows potential as a replacement cathode. This study investigates the effect of A-site stoichiometry on the performance of LSCF cathodes. Cell tests showed that A-site and Sr-deficient LSCF cathodes consistently outperformed stoichiometric LSCF cathodes, exhibiting up to 10% higher cell power densities. It was also observed that all stoichiometric, A-site, and Sr-deficient LSCF cathodes degraded over time at similar rates. Contributions of ohmic and electrode polarization losses to cell degradation rates were similar regardless of cathode composition.

  18. Phosphorus Availability Alters the Effects of Silver Nanoparticles on Periphyton Growth and Stoichiometry.

    Directory of Open Access Journals (Sweden)

    Beth C Norman

    Full Text Available Exposure to silver nanoparticles (AgNPs may alter the structure and function of freshwater ecosystems. However, there remains a paucity of studies investigating the effects of AgNP exposure on freshwater communities in the natural environment where interactions with the ambient environment may modify AgNP toxicity. We used nutrient diffusing substrates to determine the interactive effects of AgNP exposure and phosphorus (P enrichment on natural assemblages of periphyton in three Canadian Shield lakes. The lakes were all phosphorus poor and spanned a gradient of dissolved organic carbon availability. Ag slowly accumulated in the exposed periphyton, which decreased periphyton carbon and chlorophyll a content and increased periphyton C:P and N:P in the carbon rich lakes. We found significant interactions between AgNP and P treatments on periphyton carbon, autotroph standing crop and periphyton stoichiometry in the carbon poor lake such that P enhanced the negative effects of AgNPs on chlorophyll a and lessened the impact of AgNP exposure on periphyton stoichiometry. Our results contrast with those of other studies demonstrating that P addition decreases metal toxicity for phytoplankton, suggesting that benthic and pelagic primary producers may react differently to AgNP exposure and highlighting the importance of in situ assays when assessing potential effects of AgNPs in fresh waters.

  19. Silicon supply modifies C:N:P stoichiometry and growth of Phragmites australis.

    Science.gov (United States)

    Schaller, J; Brackhage, C; Gessner, M O; Bäuker, E; Gert Dudel, E

    2012-03-01

    Silicon is a non-essential element for plant growth. Nevertheless, it affects plant stress resistance and in some plants, such as grasses, it may substitute carbon (C) compounds in cell walls, thereby influencing C allocation patterns and biomass production. How variation in silicon supply over a narrow range affects nitrogen (N) and phosphorus (P) uptake by plants has also been investigated in some detail. However, little is known about effects on the stoichiometric relationships between C, N and P when silicon supply varies over a broader range. Here, we assessed the effect of silicon on aboveground biomass production and C:N:P stoichiometry of common reed, Phragmites australis, in a pot experiment in which three widely differing levels of silicon were supplied. Scanning electron microscopy (SEM) showed that elevated silicon supply promoted silica deposition in the epidermis of Phragmites leaves. This resulted in altered N:P ratios, whereas C:N ratios changed only slightly. Plant growth was slightly (but not significantly) enhanced at intermediate silicon supply levels but significantly decreased at high levels. These findings point to the potential of silicon to impact plant growth and elemental stoichiometry and, by extension, to affect biogeochemical cycles in ecosystems dominated by Phragmites and other grasses and sedges.

  20. FluxExplorer: A general platform for modeling and analyses of metabolic networks based on stoichiometry

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Stoichiometry-based analyses of meta- bolic networks have aroused significant interest of systems biology researchers in recent years. It is necessary to develop a more convenient modeling platform on which users can reconstruct their network models using completely graphical operations, and explore them with powerful analyzing modules to get a better understanding of the properties of metabolic systems. Herein, an in silico platform, FluxExplorer, for metabolic modeling and analyses based on stoichiometry has been developed as a publicly available tool for systems biology research. This platform integrates various analytic approaches, in- cluding flux balance analysis, minimization of meta- bolic adjustment, extreme pathways analysis, shadow prices analysis, and singular value decom- position, providing a thorough characterization of the metabolic system. Using a graphic modeling process, metabolic networks can be reconstructed and modi- fied intuitively and conveniently. The inconsistencies of a model with respect to the FBA principles can be proved automatically. In addition, this platform sup- ports systems biology markup language (SBML). FluxExplorer has been applied to rebuild a metabolic network in mammalian mitochondria, producing meaningful results. Generally, it is a powerful and very convenient tool for metabolic network modeling and analysis.

  1. The Effects of Nutrient Stoichiometry on Bacterial Community Composition in Streams

    Science.gov (United States)

    Rubin, M. A.; Leff, L. G.

    2005-05-01

    Bacterial biofilm community composition in streams may be affected by the nutrient stoichiometry of the surrounding water. Specifically, varying nitrogen to phosphorus (N:P) molar ratios potentially can select for or against different taxa, such as various subclasses of Proteobacteria, and thus alter community structure. In this study, bacterial communities at three sites along the Mahoning River (Ohio) with different inorganic nutrient concentrations were compared. Bacteria in biofilms on cobbles were enumerated using fluorescent in situ hybridization (FISH) to determine the abundance of alpha-, beta-, and gamma-Proteobacteria, and the Cytophaga-Flavobacterium-cluster. Nitrate, ammonia, and soluble reactive phosphate (SRP) concentrations in the water ranged from undetectable to 0.05 g/L of SRP and 0.3 g/L of ammonia. Beta-Proteobacteria appeared to be the most affected by N:P (ranging from 11 to 150) showing a positive correlation between their abundance and the N:P ratio. The Cytophaga-Flavobacterium showed effects that were nearly opposite of the beta-Proteobacteria. These findings provide evidence that limitation by single nutrients may not be as good a predictor of bacterial community structure as the molar ratios of these nutrients. Also, the nutrient stoichiometry could have a bottom up effect on stream ecosystems because of the central role that microbes play in stream food webs.

  2. Quantitative Analysis of Various Metalloprotein Compositional Stoichiometries with Simultaneous PIXE and NRA

    Science.gov (United States)

    McCubbin, Andrew; Deyoung, Paul; Peaslee, Graham; Sibley, Megan; Warner, Joshua

    2013-04-01

    Stoichiometric characterization has been carried out on multiple metalloproteins using a combination of Ion Beam Analysis methods and a newly modified preparation technique. Particle Induced X-ray emission (PIXE) spectroscopy is a non-destructive ion beam analysis technique well suited to determine the concentrations of heavy elements. Nuclear Reaction Analysis (NRA) is a technique which measures the areal density of a thin target from scattering cross sections of 3.4 MeV protons. A combination of NRA and PIXE has been developed to provide a quantitative technique for the determination of stoichiometric metal ion ratios in metalloproteins. About one third of all proteins are metalloproteins, and most do not have well determined stoichiometric compositions for the metals they contain. Current work focuses on establishing a standard method in which to prepare protein samples. The method involves placing drops of protein solutions on aluminized polyethylene terephthalate (Mylar) and allowing them to dry. This technique has been tested for several proteins of known stoichiometry to determine cofactor content and has proven to be a reliable analysis method, accurately determining metal stoichiometry in cytochrome c, superoxide dismutase, concanavalin A, vitamin B12, and hemoglobin.

  3. Assembly Stoichiometry of the GluK2/GluK5 Kainate Receptor Complex

    Directory of Open Access Journals (Sweden)

    Andreas Reiner

    2012-03-01

    Full Text Available Ionotropic glutamate receptors assemble as homo- or heterotetramers. One well-studied heteromeric complex is formed by the kainate receptor subunits GluK2 and GluK5. Retention motifs prevent trafficking of GluK5 homomers to the plasma membrane, but coassembly with GluK2 yields functional heteromeric receptors. Additional control over GluK2/GluK5 assembly seems to be exerted by the amino-terminal domains, which preferentially assemble into heterodimers as isolated domains. However, the stoichiometry of the full-length GluK2/GluK5 receptor complex has yet to be determined, as is the case for all non-NMDA glutamate receptors. Here, we address this question, using a single-molecule imaging technique that enables direct counting of the number of each GluK subunit type in homomeric and heteromeric receptors in the plasma membranes of live cells. We show that GluK2 and GluK5 assemble with 2:2 stoichiometry. This is an important step toward understanding the assembly mechanism, architecture, and functional consequences of heteromer formation in ionotropic glutamate receptors.

  4. The cascade of C:N:P stoichiometry in an ombrotrophic peatland: from plants to peat

    Science.gov (United States)

    Wang, Meng; Moore, Tim R.; Talbot, Julie; Richard, Pierre J. H.

    2014-01-01

    Northern peatlands are important carbon (C) sinks and while the patterns of C accumulation have been frequently investigated, nitrogen (N) and phosphorus (P) accumulation are often neglected. Here we link the C:N:P stoichiometry from foliar plant tissues, through senescent litters to peat, and determine C, N and P accumulation rates at Mer Bleue Bog, eastern Canada. Average C:N:P ratios changed from 794:17:1 in the foliar tissues to 911:10:1 in litter and 1285:32:1 in acrotelm peat. The increase in C:N and C:P ratios from mature to senescent tissues is related to nutrient resorption. The increase in C:P and N:P ratios in peat, which was contrary to that observed in Canadian forest soils, may be related to plant/mycorrhizae uptake of P. The long-term apparent rates of C, N and P accumulation were 29.5 ± 2.1 (SE) g C, 0.87 ± 0.01 g N and 0.017 ± 0.002 g P m-2 yr-1, respectively. The significant correlation between the accumulation rates of N and P and that of C suggests more attention be placed on C:N:P stoichiometry in peatland biogeochemistry, in particular in understanding why C:P ratios are so large in the lower parts of the profile.

  5. Non-stoichiometry defects and radiation hardness of lead tungstate crystals PbWO sub 4

    CERN Document Server

    Devitsin, E G; Potashov, S Yu; Terkulov, A R; Nefedov, V A; Polyansky, E V; Zadneprovski, B I; Kjellberg, P; Korbel, V

    2002-01-01

    It has been stated many times that the formation of radiation infringements in PbWO sub 4 is to a big extent stipulated by the non-stoichiometry defects of the crystals, arising in the process of their growth and annealing. To refine the idea of characteristics of the non-stoichiometry defects and their effect on the radiation hardness of PbWO sub 4 , the current study is aimed at the melt composition infringements during its evaporation and at optical transmission of crystals obtained in these conditions after their irradiation ( sup 1 sup 3 sup 7 Cs source). In the optical transmission measurements along with traditional techniques a method 'in situ' was used, which provided the measurements in fixed points of the spectrum (380, 470 and 535 nm) directly in the process of the irradiation. X-ray phase and fluorescence analysis of condensation products of vapours over PbWO sub 4 melt has found PbWO sub 4 phase in their content as well as compounds rich in lead PbO, Pb sub 2 WO sub 5 with overall ratio Pb/W (3....

  6. Stoichiometry and kinetics of the anaerobic ammonium oxidation (Anammox) with trace hydrazine addition.

    Science.gov (United States)

    Yao, Zongbao; Lu, Peili; Zhang, Daijun; Wan, Xinyu; Li, Yulian; Peng, Shuchan

    2015-12-01

    Purpose of this study is to investigate the stoichiometry and kinetics of anaerobic ammonium oxidation (Anammox) with trace hydrazine addition. The stoichiometry was established based on the electron balance of Anammox process with trace N2H4 addition. The stoichiometric coefficients were determined by the proton consumption and the changes in substrates and products. It was found that trace N2H4 addition can increase the yield of Anammox bacteria (AnAOB) and reduce NO3(-) yield, which enhances the Anammox. Subsequently, kinetic model of Anammox with trace N2H4 addition was developed, and the parameters of the anaerobic degradation model of N2H4 were obtained for the first time. The maximum specific substrate utilization rate, half-saturation constant and inhibition constant of N2H4 were 25.09mgN/g VSS/d, 10.42mgN/L and 1393.88mgN/L, respectively. These kinetic parameters might provide important information for the engineering applications of Anammox with trace N2H4 addition.

  7. Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

    Science.gov (United States)

    Goodwill, Joseph E; Mai, Xuyen; Jiang, Yanjun; Reckhow, David A; Tobiason, John E

    2016-09-01

    Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment.

  8. The development of a single molecule fluorescence standard and its application in estimating the stoichiometry of the nuclear pore complex.

    Science.gov (United States)

    Tie, Hieng Chiong; Madugula, Viswanadh; Lu, Lei

    2016-09-30

    We report here an image-based method to quantify the stoichiometry of diffraction-limited sub-cellular protein complexes in vivo under spinning disk confocal microscopy. A GFP single molecule fluorescence standard was first established by immobilizing His-tagged GFP molecules onto the glass surface via nickel nitrilotriacetic acid functionalized polyethylene glycol. When endogenous nucleoporins were knocked down and replaced by the exogenously expressed and knockdown-resistant GFP-nucleoporins, the stoichiometry of the nucleoporin was estimated by the ratio of its fluorescence intensity to that of the GFP single molecules. Our measured stoichiometry of Nup35, Nup93, Nup133 and Nup88 is 23, 18, 14 and 9 and there are possibly16 copies of Nup107-160 complex per nuclear pore complex.

  9. Plasma dynamics and cations off-stoichiometry in LaAlO3 films grown in high pressures regimes

    Science.gov (United States)

    Sambri, A.; Khare, Amit; Mirabella, S.; Di Gennaro, E.; Safeen, Akif; Di Capua, F.; Campajola, L.; Scotti di Uccio, U.; Amoruso, S.; Miletto Granozio, F.

    2016-12-01

    The indirect effect of oxygen background gas on the La/Al ratio during the growth of LaAlO3 (LAO) films by pulsed laser deposition (PLD) is analyzed, in a pressure range between 10-3 and 10-1 mbar. We resort to two complementary investigation methods: Rutherford backscattering spectroscopy and spectrally resolved, time-gated imaging of the laser plume. The first technique allows us to analyze the stoichiometry of the deposited films, and the latter allows us to analyze the plume expansion phase of the PLD process by collecting chemically resolved two-dimensional images of the relevant atomic/molecular species. The comparison between the results obtained by the two techniques allows us to highlight the role of the plume-gas interaction in affecting cations stoichiometry. Our results indicate that, in the considered pressure range, the background oxygen pressure affects the cations stoichiometry of the LAO films, besides determining their oxygen content.

  10. Extreme thermodynamic conditions: novel stoichiometries, violations of textbook chemistry, and intriguing possibilities for the synthesis of new materials

    Science.gov (United States)

    Stavrou, Elissaios

    As evidenced by numerous experimental and theoretical studies, application of high pressure can dramatically modify the atomic arrangement and electronic structures of both elements and compounds. However, the great majority of research has been focused on the effect of pressure on compounds with constant stoichiometries (typically those stable under ambient conditions). Recent theoretical predictions, using advanced search algorithms, suggest that composition is another important variable in the search for stable compounds, i.e. that the more stable stoichiometry at elevated pressures is not a priory the same as that at ambient pressure. Indeed, thermodynamically stable compounds with novel compositions were theoretically predicted and experimentally verified even in relatively simple chemical systems including: Na-Cl, C-N, Li-H, Na-H, Cs-N, H-N, Na-He, Xe-Fe. These materials are stable due to the formation of novel chemical bonds that are absent, or even forbidden, at ambient conditions. Tuning the composition of the system thus represents another important, but poorly explored approach to the synthesis of novel materials. By varying the stoichiometry one can design novel materials with enhanced properties (e.g. high energy density, hardness, superconductivity etc.), that are metastable at ambient conditions and synthesized at thermodynamic conditions less extreme than that those required for known stoichiometries. Moreover, current outstanding questions, ``anomalies'' and ``paradoxes'' in geo- and planetary science (e.g. the Xenon paradox) could be addressed based on the stability of surprising, stoichiometries that challenge our traditional ``textbook'' picture. In this talk, I will briefly present recent results and highlight the need of close synergy between experimental and theoretical efforts to understand the challenging and complex field of variable stoichiometry under pressure. Finally, possible new routes for the synthesis of novel materials will be

  11. Land-use and soil depth affect resource and microbial stoichiometry in a tropical mountain rainforest region of southern Ecuador.

    Science.gov (United States)

    Tischer, Alexander; Potthast, Karin; Hamer, Ute

    2014-05-01

    Global change phenomena, such as forest disturbance and land-use change, significantly affect elemental balances as well as the structure and function of terrestrial ecosystems. However, the importance of shifts in soil nutrient stoichiometry for the regulation of belowground biota and soil food webs have not been intensively studied for tropical ecosystems. In the present account, we examine the effects of land-use change and soil depth on soil and microbial stoichiometry along a land-use sequence (natural forest, pastures of different ages, secondary succession) in the tropical mountain rainforest region of southern Ecuador. Furthermore, we analyzed (PLFA-method) whether shifts in the microbial community structure were related to alterations in soil and microbial stoichiometry. Soil and microbial stoichiometry were affected by both land-use change and soil depth. After forest disturbance, significant decreases of soil C:N:P ratios at the pastures were followed by increases during secondary succession. Microbial C:N ratios varied slightly in response to land-use change, whereas no fixed microbial C:P and N:P ratios were observed. Shifts in microbial community composition were associated with soil and microbial stoichiometry. Strong positive relationships between PLFA-markers 18:2n6,9c (saprotrophic fungi) and 20:4 (animals) and negative associations between 20:4 and microbial N:P point to land-use change affecting the structure of soil food webs. Significant deviations from global soil and microbial C:N:P ratios indicated a major force of land-use change to alter stoichiometric relationships and to structure biological systems. Our results support the idea that soil biotic communities are stoichiometrically flexible in order to adapt to alterations in resource stoichiometry.

  12. Stoichiometry of monoclonal antibody neutralization of T-cell line-adapted human immunodeficiency virus type 1

    DEFF Research Database (Denmark)

    Schønning, Kristian; Lund, O; Lund, O S

    1999-01-01

    In order to study the stoichiometry of monoclonal antibody (MAb) neutralization of T-cell line-adapted human immunodeficiency virus type 1 (HIV-1) in antibody excess and under equilibrium conditions, we exploited the ability of HIV-1 to generate mixed oligomers when different env genes are coexpr......In order to study the stoichiometry of monoclonal antibody (MAb) neutralization of T-cell line-adapted human immunodeficiency virus type 1 (HIV-1) in antibody excess and under equilibrium conditions, we exploited the ability of HIV-1 to generate mixed oligomers when different env genes...

  13. Oxygen Stoichiometry in Cation Deficient (La,Sr)_{1-z}MnO_3 SOFC Cathode Materials

    DEFF Research Database (Denmark)

    Zachau-Christiansen, Birgit; Jacobsen, Torben; Skaarup, Steen

    1997-01-01

    The variation of oxygen stoichiometry with oxygen partial pressure is determined for perovskites, ABO3, with the general composition: (La1-xSrx)_{1-z}MnO_{3+y}. The measurements are performed as linear sweep voltammetry on an oxygen pumping cell, where the oxygen partial pressure is controlled...... by the imposed potential.It is found that the oxygen stoichiometry and hence the defect chemistry is different whether A-site charge deficiency is established by Sr-doping or by A-site vacancies. Furthermore,A-site deficient lanthanum strontium manganates expel a secondary phase of manganese oxide when exposed...

  14. Stoichiometry of monoclonal antibody neutralization of T-cell line-adapted human immunodeficiency virus type 1

    DEFF Research Database (Denmark)

    Schønning, Kristian; Lund, O; Lund, O S;

    1999-01-01

    In order to study the stoichiometry of monoclonal antibody (MAb) neutralization of T-cell line-adapted human immunodeficiency virus type 1 (HIV-1) in antibody excess and under equilibrium conditions, we exploited the ability of HIV-1 to generate mixed oligomers when different env genes are coexpr......In order to study the stoichiometry of monoclonal antibody (MAb) neutralization of T-cell line-adapted human immunodeficiency virus type 1 (HIV-1) in antibody excess and under equilibrium conditions, we exploited the ability of HIV-1 to generate mixed oligomers when different env genes...

  15. Coupling between catalytic loop motions and enzyme global dynamics.

    Directory of Open Access Journals (Sweden)

    Zeynep Kurkcuoglu

    Full Text Available Catalytic loop motions facilitate substrate recognition and binding in many enzymes. While these motions appear to be highly flexible, their functional significance suggests that structure-encoded preferences may play a role in selecting particular mechanisms of motions. We performed an extensive study on a set of enzymes to assess whether the collective/global dynamics, as predicted by elastic network models (ENMs, facilitates or even defines the local motions undergone by functional loops. Our dataset includes a total of 117 crystal structures for ten enzymes of different sizes and oligomerization states. Each enzyme contains a specific functional/catalytic loop (10-21 residues long that closes over the active site during catalysis. Principal component analysis (PCA of the available crystal structures (including apo and ligand-bound forms for each enzyme revealed the dominant conformational changes taking place in these loops upon substrate binding. These experimentally observed loop reconfigurations are shown to be predominantly driven by energetically favored modes of motion intrinsically accessible to the enzyme in the absence of its substrate. The analysis suggests that robust global modes cooperatively defined by the overall enzyme architecture also entail local components that assist in suitable opening/closure of the catalytic loop over the active site.

  16. Dynamic Responsive Systems for Catalytic Function.

    Science.gov (United States)

    Vlatković, Matea; Collins, Beatrice S L; Feringa, Ben L

    2016-11-21

    Responsive systems have recently gained much interest in the scientific community in attempts to mimic dynamic functions in biological systems. One of the fascinating potential applications of responsive systems lies in catalysis. Inspired by nature, novel responsive catalytic systems have been built that show analogy with allosteric regulation of enzymes. The design of responsive catalytic systems allows control of catalytic activity and selectivity. In this Review, advances in the field over the last four decades are discussed and a comparison is made amongst the dynamic responsive systems based on the principles underlying their catalytic mechanisms. The catalyst systems are sorted according to the triggers used to achieve control of the catalytic activity and the distinct catalytic reactions illustrated. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  18. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  19. Flexible subunit stoichiometry of functional human P2X2/3 heteromeric receptors.

    Science.gov (United States)

    Kowalski, Maria; Hausmann, Ralf; Schmid, Julia; Dopychai, Anke; Stephan, Gabriele; Tang, Yong; Schmalzing, Günther; Illes, Peter; Rubini, Patrizia

    2015-12-01

    The aim of the present work was to clarify whether heterotrimeric P2X2/3 receptors have a fixed subunit stoichiometry consisting of one P2X2 and two P2X3 subunits as previously suggested, or a flexible stoichiometry containing also the inverse subunit composition. For this purpose we transfected HEK293 cells with P2X2 and P2X3 encoding cDNA at the ratios of 1:2 and 4:1, and analysed the biophysical and pharmacological properties of the generated receptors by means of the whole-cell patch-clamp technique. The concentration-response curves for the selective agonist α,β-meATP did not differ from each other under the two transfection ratios. However, co-expression of an inactive P2X2 mutant and the wild type P2X3 subunit and vice versa resulted in characteristic distortions of the α,β-meATP concentration-response relationships, depending on which subunit was expressed in excess, suggesting that HEK293 cells express mixtures of (P2X2)1/(P2X3)2 and (P2X2)2/(P2X3)1 receptors. Whereas the allosteric modulators H+ and Zn2+ failed to discriminate between the two possible heterotrimeric receptor variants, the α,β-meATP-induced responses were blocked more potently by the competitive antagonist A317491, when the P2X2 subunit was expressed in deficit of the P2X3 subunit. Furthermore, blue-native PAGE analysis of P2X2 and P2X3 subunits co-expressed in Xenopus laevis oocytes and HEK293 cells revealed that plasma membrane-bound P2X2/3 receptors appeared in two clearly distinct heterotrimeric complexes: a (P2X2-GFP)2/(P2X3)1 complex and a (P2X2-GFP)1/(P2X3)2 complex. These data strongly indicate that the stoichiometry of the heteromeric P2X2/3 receptor is not fixed, but determined in a permutational manner by the relative availability of P2X2 and P2X3 subunits.

  20. Some Aspects of the Catalytic Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Anil; K.Saikia

    2007-01-01

    1 Results Catalytic reactions are gaining importance due to its low cost, operational simplicity, high efficiency and selectivity. It is also getting much attention in green synthesis. Many useful organic reactions, including the acylation of alcohols and aldehydes, carbon-carbon, carbon-nitrogen, carbon-sulfur bond forming and oxidation reactions are carried out by catalyst. We are exploring the catalytic acylation of alcohols and aldehydes in a simple and efficient manner. Catalytic activation of unr...

  1. Catalytic Combustion for Ultra-Low NOx Hydrogen Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Etemad, Shahrokh; Baird, Benjamin; Alavandi, Sandeep

    2011-06-30

    Precision Combustion, Inc., (PCI) in close collaboration with Solar Turbines, Incorporated, has developed and demonstrated a combustion system for hydrogen fueled turbines that reduces NOx to low single digit level while maintaining or improving current levels of efficiency and eliminating emissions of carbon dioxide. Full scale Rich Catalytic Hydrogen (RCH1) injector was developed and successfully tested at Solar Turbines, Incorporated high pressure test facility demonstrating low single digit NOx emissions for hydrogen fuel in the range of 2200F-2750F. This development work was based on initial subscale development for faster turnaround and reduced cost. Subscale testing provided promising results for 42% and 52% H2 with NOx emissions of less than 2 ppm with improved flame stability. In addition, catalytic reactor element testing for substrate oxidation, thermal cyclic injector testing to simulate start-stop operation in a gas turbine environment, and steady state 15 atm. operation testing were performed successfully. The testing demonstrated stable and robust catalytic element component life for gas turbine conditions. The benefit of the catalytic hydrogen combustor technology includes capability of delivering near-zero NOx without costly post-combustion controls and without requirement for added sulfur control. In addition, reduced acoustics increase gas turbine component life. These advantages advances Department of Energy (DOE’s) objectives for achievement of low single digit NOx emissions, improvement in efficiency vs. postcombustion controls, fuel flexibility, a significant net reduction in Integrated Gasification Combined Cycle (IGCC) system net capital and operating costs, and a route to commercialization across the power generation field from micro turbines to industrial and utility turbines.

  2. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  3. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase II project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  4. Possibilities Of Metals Extracton From Spent Metallic Automotive Catalytic Converters By Using Biometallurgical Method

    Directory of Open Access Journals (Sweden)

    Willner J.

    2015-09-01

    Full Text Available The main task of automotive catalytic converters is reducing the amount of harmful components of exhaust gases. Metallic catalytic converters are an alternative to standard ceramic catalytic converters. Metallic carriers are usually made from FeCrAl steel, which is covered by a layer of Precious Group Metals (PGMs acting as a catalyst. There are many methods used for recovery of platinum from ceramic carriers in the world, but the issue of platinum and other metals recovery from metallic carriers is poorly described. The article presents results of preliminary experiments of metals biooxidation (Fe, Cr and Al from spent catalytic converters with metallic carrier, using bacteria of the Acidithiobacillus genus.

  5. Catalytic reforming feed characterisation technique

    Energy Technology Data Exchange (ETDEWEB)

    Larraz Mora, R.; Arvelo Alvarez, R. [Univ. of La Laguna, Chemical Engineering Dept., La Laguna (Spain)

    2002-09-01

    The catalytic reforming of naphtha is one of the major refinery processes, designed to increase the octane number of naphtha or to produce aromatics. The naphtha used as catalytic reformer feedstock usually contains a mixture of paraffins, naphthenes, and aromatics in the carbon number range C{sub 6} to C{sub 10}. The detailed chemical composition of the feed is necessary to predict the aromatics and hydrogen production as well as the operation severity. The analysis of feed naphtha is usually reported in terms of its ASTM distillation curve and API or specific gravity. Since reforming reactions are described in terms of lumped chemical species (paraffins, naphthenes and aromatics), a feed characterisation technique should be useful in order to predict reforming operating conditions and detect feed quality changes. Unfortunately online analyzer applications as cromatography or recently introduced naphtha NMR [1] are scarce in most of refineries. This work proposes an algorithmic characterisation method focusing on its main steps description. The method could help on the subjects previously described, finally a calculation example is shown. (orig.)

  6. Stoichiometry in Context: Inquiry-Guided Problems of Chemistry for Encouraging Critical Thinking in Engineering Students

    Directory of Open Access Journals (Sweden)

    Gabriel Pinto

    2013-01-01

    Full Text Available This paper focuses on examples of educational tools concerning the learning of chemistry for engineering students through different daily life cases. These tools were developed during the past few years for enhancing the active role of students. They refer to cases about mineral water, medicaments, dentifrices and informative panels about solar power, where an adequate quantitative treatment through stoichiometry calculations allows the interpretation of data and values announced by manufacturers. These cases were developed in the context of an inquiry-guided instruction model. By bringing tangible chemistry examples into the classroom we provide an opportunity for engineering students to apply this science to familiar products in hopes that they will appreciate chemistry more, will be motivated to study concepts in greater detail, and will connect the relevance of chemistry to everyday life.

  7. Manipulating the drug/proton antiport stoichiometry of the secondary multidrug transporter MdfA.

    Science.gov (United States)

    Tirosh, Osnat; Sigal, Nadejda; Gelman, Amir; Sahar, Nadav; Fluman, Nir; Siemion, Shira; Bibi, Eitan

    2012-07-31

    Multidrug transporters are integral membrane proteins that use cellular energy to actively extrude antibiotics and other toxic compounds from cells. The multidrug/proton antiporter MdfA from Escherichia coli exchanges monovalent cationic substrates for protons with a stoichiometry of 1, meaning that it translocates only one proton per antiport cycle. This may explain why transport of divalent cationic drugs by MdfA is energetically unfavorable. Remarkably, however, we show that MdfA can be easily converted into a divalent cationic drug/≥ 2 proton-antiporter, either by random mutagenesis or by rational design. The results suggest that exchange of divalent cationi c drugs with two (or more) protons requires an additional acidic residue in the multidrug recognition pocket of MdfA. This outcome further illustrates the exceptional promiscuous capabilities of multidrug transporters.

  8. Optimization of dicarboxylic acid cellulose synthesis: reaction stoichiometry and role of hypochlorite scavengers.

    Science.gov (United States)

    Sirviö, Juho Antti; Liimatainen, Henrikki; Visanko, Miikka; Niinimäki, Jouko

    2014-12-19

    The reaction conditions in terms of reaction time, sodium chlorite stoichiometry, and the effect of hypochlorite scavengers on the chlorite oxidation of dialdehyde cellulose (DAC) was studied. The impact of storage on the reactivity of DAC fibers was also investigated. It was found that chlorite oxidation of DAC is a rapid reaction, resulting in oxidation of 71% of the aldehyde after only 8 min when 2.5 times excess of sodium chlorite compared to aldehyde groups was used. Reactivity of DAC was observed to decrease quickly during the storage and only 68% of the aldehyde groups reacted after two weeks storage compared to the reaction performed with freshly prepared DAC. Hydrogen peroxide and sulfamic acid were observed to increase the reaction efficiency of chlorite oxidation by reducing the amount of side-reactions between chlorite and hypochlorite. A minor amount of sulfamic acid can be used to replace acetic acid as a catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Dry Etching of Copper Phthalocyanine Thin Films: Effects on Morphology and Surface Stoichiometry

    Directory of Open Access Journals (Sweden)

    Michael J. Brett

    2012-08-01

    Full Text Available We investigate the evolution of copper phthalocyanine thin films as they are etched with argon plasma. Significant morphological changes occur as a result of the ion bombardment; a planar surface quickly becomes an array of nanopillars which are less than 20 nm in diameter. The changes in morphology are independent of plasma power, which controls the etch rate only. Analysis by X-ray photoelectron spectroscopy shows that surface concentrations of copper and oxygen increase with etch time, while carbon and nitrogen are depleted. Despite these changes in surface stoichiometry, we observe no effect on the work function. The absorbance and X-ray diffraction spectra show no changes other than the peaks diminishing with etch time. These findings have important implications for organic photovoltaic devices which seek nanopillar thin films of metal phthalocyanine materials as an optimal structure.

  10. A method to quantify FRET stoichiometry with phasor plot analysis and acceptor lifetime ingrowth.

    Science.gov (United States)

    Chen, WeiYue; Avezov, Edward; Schlachter, Simon C; Gielen, Fabrice; Laine, Romain F; Harding, Heather P; Hollfelder, Florian; Ron, David; Kaminski, Clemens F

    2015-03-10

    FRET is widely used for the study of protein-protein interactions in biological samples. However, it is difficult to quantify both the FRET efficiency (E) and the affinity (Kd) of the molecular interaction from intermolecular FRET signals in samples of unknown stoichiometry. Here, we present a method for the simultaneous quantification of the complete set of interaction parameters, including fractions of bound donors and acceptors, local protein concentrations, and dissociation constants, in each image pixel. The method makes use of fluorescence lifetime information from both donor and acceptor molecules and takes advantage of the linear properties of the phasor plot approach. We demonstrate the capability of our method in vitro in a microfluidic device and also in cells, via the determination of the binding affinity between tagged versions of glutathione and glutathione S-transferase, and via the determination of competitor concentration. The potential of the method is explored with simulations.

  11. THE EFFECT OF A-SITE STOICHIOMETRY ON LSCF CATHODE PERFORMANCE AND STABILITY

    Energy Technology Data Exchange (ETDEWEB)

    Templeton, Jared W.; Hardy, John S.; Lu, Zigui; Stevenson, Jeffry W.

    2011-11-01

    Anode-supported solid oxide fuel cells (SOFCs) were prepared and tested identically except for variations in the A-site stoichiometry of the LSCF cathode. A commercial supplier provided lanthanum strontium cobalt ferrite (LSCF) powders that were stoichiometric [La0.6Sr0.4Co0.2Fe0.8O3-δ], A-site deficient [(La0.6Sr0.4)1-xCo0.2Fe0.8O3-δ], and Sr-deficient [La0.6Sr0.4-xCo0.2Fe0.8O3-δ], in which the imposed deficiency (x) was 0.02, 0.05, and 0.1 in the non-stoichiometric cases. Multiple 1,000 hour tests were run using each LSCF cathode composition. The performance and stability of the cells will be discussed.

  12. Branch-point stoichiometry can generate weak links in metabolism: the case of glycine biosynthesis

    Indian Academy of Sciences (India)

    Enrique Meléndez-Hevia; Patricia D E Paz-Lugo

    2008-12-01

    Although the metabolic network permits conversion between almost any pair of metabolites, this versatility fails at certain sites because of chemical constraints (kinetic, thermodynamic and stoichiometric) that seriously restrict particular conversions. We call these sites weak links in metabolism, as they can interfere harmfully with management of matter and energy if the network as a whole does not include adequate safeguards. A critical weak link is created in glycine biosynthesis by the stoichiometry of the reaction catalyzed by glycine hydroxymethyltransferase (EC 2.1.2.1), which converts serine into glycine plus one C1 unit: this produces an absolute dependence of the glycine production flux on the utilization of C1 units for other metabolic pathways that do not work coordinately with glycine use. It may not be possible, therefore, to ensure that glycine is always synthesized in sufficient quantities to meet optimal metabolic requirements.

  13. Effect of K(+) on the Stoichiometry of Carbonated Hydroxyapatite Obtained by the Hydrolysis of Monetite.

    Science.gov (United States)

    De Maeyer, Erna A. P.; Verbeeck, Ronald M. H.; Pieters, Ilse Y.

    1996-02-14

    This study investigates the stoichiometry and the thermal stability of K(+)- and CO(3)(2)(-)-containing apatites (KCAp's) obtained by the hydrolysis of monetite. The analysis results of the samples after drying reveal that the KCAp's start to lose carbonate at temperatures V(Ca) + CO(3)(2)(-) + V(OH)] and [Ca(2+) + PO(4)(3)(-) K(+) + CO(3)(2)(-)], where V(X) stands for a vacancy in the X-sublattice. Moreover, a small part of the CO(3)(2)(-) ions are presumably incorporated according to [Ca(2+) + 2PO(4)(3)(-) V(Ca) + 2CO(3)(2)(-)]. A comparison of the contributions of these fundamental mechanisms with the results for precipitated Na(+)- and CO(3)(2)(-)-containing apatites shows that no intrinsic coupling whatsoever exists between these mechanisms.

  14. A cell-free assay to determine the stoichiometry of plasma membrane proteins.

    Science.gov (United States)

    Trigo, Cesar; Vivar, Juan P; Gonzalez, Carlos B; Brauchi, Sebastian

    2013-04-01

    Plasma membrane receptors, transporters, and ion channel molecules are often found as oligomeric structures that participate in signaling cascades essential for cell survival. Different states of protein oligomerization may play a role in functional control and allosteric regulation. Stochastic GFP-photobleaching (SGP) has emerged as an affordable and simple method to determine the stoichiometry of proteins at the plasma membrane. This non-invasive optical approach can be useful for total internal reflection of fluorescence microscopy (TIRFM), where signal-to-noise ratio is very high at the plasma membrane. Here, we report an alternative methodology implemented on a standard laser scanning confocal microscope (LSCM). The simplicity of our method will allow for its implementation in any epifluorescence microscope of choice.

  15. Elemental stoichiometry and compositions of weevil larvae and two acorn hosts under natural phosphorus variation

    Science.gov (United States)

    Ji, Huawei; Du, Baoming; Liu, Chunjiang

    2017-04-01

    To understand how different trophic organisms in a parasite food chain adapt to the differences in soil nutrient conditions, we investigated stoichiometric variation and homeostasis of multiple elements in two acorn trees, Quercus variabilis and Quercus acutissima, and their parasite weevil larvae (Curculio davidi Fairmaire) at phosphorus (P)-deficient and P-rich sites in subtropical China where P-rich ores are scattered among dominant P-deficient soils. Results showed that elemental stoichiometry and compositions of both acorns and weevil larvae differed significantly between P-deficient and P-rich sites (p plants and animals to P loading, a worldwide issue from excess release of P into the environment.

  16. Dry etching of copper phthalocyanine thin films: effects on morphology and surface stoichiometry.

    Science.gov (United States)

    Van Dijken, Jaron G; Brett, Michael J

    2012-08-24

    We investigate the evolution of copper phthalocyanine thin films as they are etched with argon plasma. Significant morphological changes occur as a result of the ion bombardment; a planar surface quickly becomes an array of nanopillars which are less than 20 nm in diameter. The changes in morphology are independent of plasma power, which controls the etch rate only. Analysis by X-ray photoelectron spectroscopy shows that surface concentrations of copper and oxygen increase with etch time, while carbon and nitrogen are depleted. Despite these changes in surface stoichiometry, we observe no effect on the work function. The absorbance and X-ray diffraction spectra show no changes other than the peaks diminishing with etch time. These findings have important implications for organic photovoltaic devices which seek nanopillar thin films of metal phthalocyanine materials as an optimal structure.

  17. Quantitative analysis of a metalloprotein compositional stoichiometry with PIXE and PESA

    Science.gov (United States)

    Warner, J. D.; DeYoung, P. A.; Ellsworth, L. A.; Kiessel, L. M.; Rycenga, M. J.; Peaslee, G. F.

    2010-05-01

    An absolute measurement of the heavy element concentrations in a dried sample of aqueous protein solution has been combined with the absolute measurement of protein molecular concentration in the same sample. The ratio of these two measurements yields the metal-to-protein compositional stoichiometry of the metalloprotein. This combination of two Ion Beam Analysis techniques (Particle-Induced X-ray Emission and Proton Elastic Scattering Analysis) allows quantitative assessment of the metal atom to protein ratio in metalloproteins without direct measurement of sulfur atoms within the protein for the first time. While these results only demonstrate success with a single well-known metalloprotein, this combination of measurement ratios holds promise for future Ion Beam Analysis studies of metalloproteins.

  18. Quantitative analysis of a metalloprotein compositional stoichiometry with PIXE and PESA

    Energy Technology Data Exchange (ETDEWEB)

    Warner, J.D. [Department of Chemistry, Hope College, Holland, MI 49422-9000 (United States); Department of Physics, Hope College, Holland, MI 49422-9000 (United States); DeYoung, P.A., E-mail: deyoung@hope.ed [Department of Chemistry, Hope College, Holland, MI 49422-9000 (United States); Department of Physics, Hope College, Holland, MI 49422-9000 (United States); Ellsworth, L.A.; Kiessel, L.M.; Rycenga, M.J.; Peaslee, G.F. [Department of Chemistry, Hope College, Holland, MI 49422-9000 (United States); Department of Physics, Hope College, Holland, MI 49422-9000 (United States)

    2010-05-15

    An absolute measurement of the heavy element concentrations in a dried sample of aqueous protein solution has been combined with the absolute measurement of protein molecular concentration in the same sample. The ratio of these two measurements yields the metal-to-protein compositional stoichiometry of the metalloprotein. This combination of two Ion Beam Analysis techniques (Particle-Induced X-ray Emission and Proton Elastic Scattering Analysis) allows quantitative assessment of the metal atom to protein ratio in metalloproteins without direct measurement of sulfur atoms within the protein for the first time. While these results only demonstrate success with a single well-known metalloprotein, this combination of measurement ratios holds promise for future Ion Beam Analysis studies of metalloproteins.

  19. Action of DCCD on the H+/O stoichiometry of mitoplast cytochrome c oxidase.

    Science.gov (United States)

    Lehninger, A L; Reynafarje, B; Costa, L

    1985-01-01

    The mechanistic H+/O ejection stoichiometry of the cytochrome c oxidase reaction in rat liver mitoplasts is close to 4 at level flow when the reduced oxidase is pulsed with O2. Dicyclohexylcarbodiimide (DCCD) up to 30 nmol/mg protein fails to influence the rate of electron flow through the mitoplast oxidase, but inhibits H+ ejection. The inhibition of H+ ejection appears to be biphasic; ejection of 2-3 H+ per O is completely inhibited by very low DCCD, whereas inhibition of the remaining H+ ejection requires very much higher concentrations of DCCD. This effect suggests the occurrence of two types of H+ pumps in the native cytochrome oxidase of mitoplasts.

  20. Response of sheep to supplementation of Probio-catalytic in the diets

    Directory of Open Access Journals (Sweden)

    B Haryanto

    2008-12-01

    significantly different than that of the control group. The molar proportion of volatile fatty acid components was within the normal values. Based on the results of the present experiment, it was concluded that addition of probio-catalytic supplement A at 0.5% was advantageous and it could be suggested to be included in the diet to improve the productive performance of sheep.

  1. Consequences of warming and resource quality on the stoichiometry and nutrient cycling of a stream shredder.

    Science.gov (United States)

    Mas-Martí, Esther; Romaní, Anna M; Muñoz, Isabel

    2015-01-01

    As a result of climate change, streams are warming and their runoff has been decreasing in most temperate areas. These changes can affect consumers directly by increasing their metabolic rates and modifying their physiology and indirectly by changing the quality of the resources on which organisms depend. In this study, a common stream detritivore (Echinogammarus berilloni Catta) was reared at two temperatures (15 and 20°C) and fed Populus nigra L. leaves that had been conditioned either in an intermittent or permanent reach to evaluate the effects of resource quality and increased temperatures on detritivore performance, stoichiometry and nutrient cycling. The lower quality (i.e., lower protein, soluble carbohydrates and higher C:P and N:P ratios) of leaves conditioned in pools resulted in compensatory feeding and lower nutrient retention capacity by E. berilloni. This effect was especially marked for phosphorus, which was unexpected based on predictions of ecological stoichiometry. When individuals were fed pool-conditioned leaves at warmer temperatures, their growth rates were higher, but consumers exhibited less efficient assimilation and higher mortality. Furthermore, the shifts to lower C:P ratios and higher lipid concentrations in shredder body tissues suggest that structural molecules such as phospholipids are preserved over other energetic C-rich macromolecules such as carbohydrates. These effects on consumer physiology and metabolism were further translated into feces and excreta nutrient ratios. Overall, our results show that the effects of reduced leaf quality on detritivore nutrient retention were more severe at higher temperatures because the shredders were not able to offset their increased metabolism with increased consumption or more efficient digestion when fed pool-conditioned leaves. Consequently, the synergistic effects of impaired food quality and increased temperatures might not only affect the physiology and survival of detritivores but

  2. Consequences of warming and resource quality on the stoichiometry and nutrient cycling of a stream shredder.

    Directory of Open Access Journals (Sweden)

    Esther Mas-Martí

    Full Text Available As a result of climate change, streams are warming and their runoff has been decreasing in most temperate areas. These changes can affect consumers directly by increasing their metabolic rates and modifying their physiology and indirectly by changing the quality of the resources on which organisms depend. In this study, a common stream detritivore (Echinogammarus berilloni Catta was reared at two temperatures (15 and 20°C and fed Populus nigra L. leaves that had been conditioned either in an intermittent or permanent reach to evaluate the effects of resource quality and increased temperatures on detritivore performance, stoichiometry and nutrient cycling. The lower quality (i.e., lower protein, soluble carbohydrates and higher C:P and N:P ratios of leaves conditioned in pools resulted in compensatory feeding and lower nutrient retention capacity by E. berilloni. This effect was especially marked for phosphorus, which was unexpected based on predictions of ecological stoichiometry. When individuals were fed pool-conditioned leaves at warmer temperatures, their growth rates were higher, but consumers exhibited less efficient assimilation and higher mortality. Furthermore, the shifts to lower C:P ratios and higher lipid concentrations in shredder body tissues suggest that structural molecules such as phospholipids are preserved over other energetic C-rich macromolecules such as carbohydrates. These effects on consumer physiology and metabolism were further translated into feces and excreta nutrient ratios. Overall, our results show that the effects of reduced leaf quality on detritivore nutrient retention were more severe at higher temperatures because the shredders were not able to offset their increased metabolism with increased consumption or more efficient digestion when fed pool-conditioned leaves. Consequently, the synergistic effects of impaired food quality and increased temperatures might not only affect the physiology and survival of

  3. Lysine acetylation stoichiometry and proteomics analyses reveal pathways regulated by sirtuin 1 in human cells.

    Science.gov (United States)

    Gil, Jeovanis; Ramírez-Torres, Alberto; Chiappe, Diego; Luna-Peñaloza, Juan; Fernandez-Reyes, Francis C; Arcos-Encarnación, Bolivar; Contreras, Sandra; Encarnación-Guevara, Sergio

    2017-09-11

    Lysine acetylation is a widespread posttranslational modification (PTM) affecting many biological pathways. Recent studies indicate that acetylated lysine residues mainly exhibit low acetylation occupancy, but challenges in sample preparation and analysis make it difficult to confidently assign these numbers, limiting understanding of their biological significance. Here, we tested three common sample preparation methods to determine their suitability for assessing acetylation stoichiometry in three human cell lines, identifying the acetylation occupancy in more than 1,300 proteins from each cell line. The stoichiometric analysis in combination with quantitative proteomics also enabled us to explore their functional roles. We found that higher abundance of the deacetylase sirtuin 1 (SIRT1) correlated with lower acetylation occupancy and lower levels of ribosomal proteins including those involved in ribosome biogenesis and rRNA processing. Treatment with the SIRT1 inhibitor EX-527 confirmed SIRT1's role in the regulation of pre-rRNA synthesis and processing. Specifically, proteins involved in pre-rRNA transcription, including subunits of the Pol 1 and SL1 complexes and the RNA polymerase I specific transcription initiation factor RRN3 were up-regulated after SIRT1 inhibition. Moreover, many protein effectors and regulators of pre-rRNA processing needed for rRNA maturation were also up-regulated after EX-527 treatment, with the outcome that pre-rRNA and 28S rRNA levels also increased. More generally, we found that SIRT1 inhibition down-regulates metabolic pathways including glycolysis and pyruvate metabolism. Together, these results provide the largest dataset thus far of lysine acetylation stoichiometry (available via ProteomeXchange with identifier PXD005903) and set the stage for further biological investigations of this central PTM. Copyright © 2017, The American Society for Biochemistry and Molecular Biology.

  4. Forest wildfire increases soil microbial biomass C:N:P stoichiometry in long-term effects

    Science.gov (United States)

    Zhou, Xuan

    2017-04-01

    Boreal forest fire strongly influences carbon (C) stock in permafrost soil by thawing permafrost table which accelerated microbe decomposition process. We studied soil microbial biomass stoichiometry in a gradient of four (3 yr, 25 yr, 46 yr and more than 100 yr) ages since fire in Canada boreal forest. Soil microbial biomass (MB) in long-term after fire is significantly higher than in short-term. MB C and nitrogen (N) were mainly dominated by corresponding soil element concentration and inorganic P, while MB phosphorus (P) changes were fully explained by soil N. Fire ages and soil temperature positively increased MB N and P, indicating the negative impact by fire. Microbial C:N:P gradually increased with fire ages from 15:2:1 to 76:6:1 and then drop down to 17:2:1 in the oldest fire ages. The degree of homeostasis of microbial C, N and P are close to 1 indicates non-homoeostasis within microbial elements, while it of C:N:P is close to 8 shows a strong homeostasis within element ratios and proved microbial stoichiometric ratio is not driven by soil element ratios. In conclusion, i) microbial biomass elements highly depends on soil nutrient supply rather than fire ages; ii) wildfire decreased microbial stoichiometry immediate after fire but increased with years after fire (YF) which at least 3 times higher than > 100 fire ages; iii) microbial biomass C, N and P deviated from strict homeostasis but C:N:P ratio reflects stronger homeostasis.

  5. [Characteristics of leaf carbon, nitrogen and phosphorus stoichiometry in relation to plant size of Machilus pauhoi].

    Science.gov (United States)

    Zhang, Lei-lei; Zhong, Quan-lin; Cheng, Dong-liang; Zhang, Zhong-rui; Fei, Ling; Xu, Chao-bin; He, Li-zhong; Wang, Wei-jun

    2015-07-01

    To explore the effects of stand age on variation patterns of leaf C, N, P stoichiometric characteristics of Machilus pauhoi, two stands, i.e., 9 and 13 years old, were selected. The relationships between leaf nutrient contents (C, N and P) and diameters at breast height (DBH) of individual plants were analyzed. The data revealed that the individual variations of seedlings in M. pauhoi stands were strengthened with the stand development. The stand age had significant effects on leaf C, N, P contents and C:N ratio but not on C:P and N: P ratios. Specifically, the mean values of leaf C, N, P contents and N:P ratio in the 9-year-old stand were lower than those in the 13-year-old stand, whereas, inverse pattern of C:N and C:P ratios were found in the two stands. Furthermore, leaf N and P stoichiometry varied significantly within the stand. Specifically, leaf N and P contents, as well as their stoichiometric ratios, linearly correlated with DBH in the 9-year-old stand. On the contrary, leaf N and P stoichiometry showed quadratic correlation in 13-year-old stand (except leaf C:N which linearly correlated with DBH). Lastly, nutrient transfer rates of leaf N and P in the 9-year-old stand were higher than that in 13-year-old stand, and the discrepancies of leaf nutrient transfer strategy between growing and non-growing seasons were caused by the different growth phases and environmental conditions.

  6. [Effects of stand density on Oligostachyum lubricum leaf carbon, nitrogen, and phosphorus stoichiometry and nutrient resorption].

    Science.gov (United States)

    Guo, Zi-Wu; Chen, Shuang-Lin; Yang, Qing-Ping; Li, Ying-chun

    2013-04-01

    Taking pure Oligostachyum lubricum forest as test object, this paper studied the matured and withered leaves carbon (C), nitrogen (N), and phosphorus (P) stoichiometry and N and P resorption patterns of 1-3 years old stands at the densities of 24600-29800 stem hm-2 (D, ), 37500-42600 stem hm-2 (D2 ), 46500 - 52800 stem hm-2 (D3), and 76500 - 85500 stem hm-2 (D4). With increasing stand density, the matured leaves C, N, and P contents and withered leaves C and P contents had an overall decrease, the withered leaves N content decreased after an initial increase, and the matured leaves C content at density )4 decreased dramatically. The leaf C/N and C/P ratio increased with increasing stand density, whereas the leaf N/P ratio increased first but decreased then. At stand densities D3 and D4, the leaf N and P utilization efficiencies were significantly higher than those at D, and D2. With increasing stand density, the leaf N resorption capacity increased after an initial decrease, while the leaf P resorption capacity increased steadily. At stand densities D,-D3, the matured leaves N/P ratio was 16.24-19.37, suggesting that the P limitation occurred, leaf establishment increased, and population increase and expansion enhanced. At density D4, the matured leaves N/P ratio was 13.42-15.74, implying that the N limitation strengthened, leaf withering and defoliation increased, and population increase inhibited. All the results indicated that O. lubricum could regulate its leaf C, N and P contents and stoichiometry and enhance the leaf N and P utilization efficiency and resorption capacity to adapt to the severe competition of environment resources at high stand density. In our experimental condition, 46500-52800 stem hm-2 could be the appropriate stand density for O. lubricum management.

  7. Proton translocation stoichiometry of cytochrome oxidase: use of a fast-responding oxygen electrode.

    Science.gov (United States)

    Reynafarje, B; Alexandre, A; Davies, P; Lehninger, A L

    1982-12-01

    The mechanistic stoichiometry of vectorial H+ ejection coupled to electron transport from added ferrocytochrome c to oxygen by the cytochrome oxidase (EC 1.9.3.1) of rat liver mitoplasts was determined from measurements of the initial rates of electron flow and H+ ejection in the presence of K+ (with valinomycin). Three different methods of measuring electron flow were used: (a) dual-wavelength spectrophotometry of ferrocytochrome c oxidation, (b) uptake of scalar H+ for the reduction of O2 in the presence of a protonophore, and (c) a fast-responding membraneless oxygen electrode. The reliability of the rate measurements was first established against the known stoichiometry of the scalar reaction of cytochrome oxidase (2ferrocytochrome c + 2H+ + 1/2O2 leads to 2ferricytochrome c + H2O) in the presence of excess protonophore. With all three methods the directly observed vectorial H+/O ejection ratios in the presence of K+ + valinomycin significantly exceeded 3.0. However, because the rate of backflow of the ejected H+ into the mitoplasts is very high and increases with the increasing delta pH generated across the membrane, there is a very rapid decline in the observed H+/O ratio from the beginning of the reaction. Kinetic analysis of ferrocytochrome c oxidation by the mitoplasts, carried out with a fast-responding membraneless oxygen electrode, showed the reaction to be first order in O2 and allowed accurate extrapolation of the rates of O2 uptake and H+ ejection to zero time. At this point, at which there is zero delta pH across the membrane, the H+/O ejection ratio of the cytochrome oxidase reaction, obtained from the rates at zero time, is close to 4.0.

  8. Use of stoichiometry to predict the abundance and functioning of root symbioses

    Science.gov (United States)

    Johnson, N. C.

    2012-04-01

    Plants form nutritional symbioses with fungi and bacteria and the importance of these partnerships varies with the mineral fertility of soil. There is strong evidence that plants acclimate and adapt to their local soil conditions through root symbioses; nitrogen limitation is ameliorated by symbiosis with diazotrophic prokaryotes and mycorrhizas ameliorate phosphorus limitation. Corollaries of ecological stoichiometry may be useful for predicting the abundance and functioning of mycorrhizas and N-fixation symbioses. A series of field experiments show that arbuscular mycorrhizal (AM) symbioses in grasslands in North America and in the African Serengeti are most beneficial to plant nutrition when plants are phosphorus limited and have sufficient nitrogen and carbon. A reciprocal inoculation experiment shows that locally adapted communities of AM fungi, associated soil organisms and plants arise such that mutualistic benefits are maximized; both AM fungi and plants grew best in their "home" soil-symbiont combination compared to "away" soil-symbiont combinations. Plants in their home combination acquired more limiting resource (either phosphorus or nitrogen) and consequently grew larger; similarly, AM fungi in their home combination formed more arbuscules and extraradical hyphae. Genetic analysis of the AM fungi inside plant roots indicate that these results correspond to variation in the community composition of AM fungi and also to variation in the symbiotic performance of local isolates of one particular species of AM fungus. The next step is to conduct landscape scale studies of root symbioses to test the hypothesis that plants cultivate microbial communities in and around their roots such that the species and ecotypes of microorganisms within these communities is customized for optimal nutrient acquisition under site-specific environmental conditions. If locally adapted communities of root and rhizosphere organisms are common, then plants may be optimizing their

  9. Accurate Quantification of Site-specific Acetylation Stoichiometry Reveals the Impact of Sirtuin Deacetylase CobB on the E. coli Acetylome.

    Science.gov (United States)

    Weinert, Brian Tate; Satpathy, Shankha; Hansen, Bogi Karbech; Lyon, David; Jensen, Lars Juhl; Choudhary, Chunaram

    2017-05-01

    Lysine acetylation is a protein posttranslational modification (PTM) that occurs on thousands of lysine residues in diverse organisms from bacteria to humans. Accurate measurement of acetylation stoichiometry on a proteome-wide scale remains challenging. Most methods employ a comparison of chemically acetylated peptides to native acetylated peptides, however, the potentially large differences in abundance between these peptides presents a challenge for accurate quantification. Stable isotope labeling by amino acids in cell culture (SILAC)-based mass spectrometry (MS) is one of the most widely used quantitative proteomic methods. Here we show that serial dilution of SILAC-labeled peptides (SD-SILAC) can be used to identify accurately quantified peptides and to estimate the quantification error rate. We applied SD-SILAC to determine absolute acetylation stoichiometry in exponentially-growing and stationary-phase wild-type and Sirtuin deacetylase CobB-deficient cells. To further analyze CobB-regulated sites under conditions of globally increased or decreased acetylation, we measured stoichiometry in phophotransacetylase (ptaΔ) and acetate kinase (ackAΔ) mutant strains in the presence and absence of the Sirtuin inhibitor nicotinamide. We measured acetylation stoichiometry at 3,669 unique sites and found that the vast majority of acetylation occurred at a low stoichiometry. Manipulations that cause increased nonenzymatic acetylation by acetyl-phosphate (AcP), such as stationary-phase arrest and deletion of ackA, resulted in globally increased acetylation stoichiometry. Comparison to relative quantification under the same conditions validated our stoichiometry estimates at hundreds of sites, demonstrating the accuracy of our method. Similar to Sirtuin deacetylase 3 (SIRT3) in mitochondria, CobB suppressed acetylation to lower than median stoichiometry in WT, ptaΔ, and ackAΔ cells. Together, our results provide a detailed view of acetylation stoichiometry in E. coli

  10. Differences in General Cognitive Abilities and Domain-Specific Skills of Higher-and Lower-Achieving Students in Stoichiometry

    Science.gov (United States)

    Gulacar, Ozcan; Eilks, Ingo; Bowman, Charles R.

    2014-01-01

    This paper reports a comparison of a group of higher-and lower-achieving undergraduate chemistry students, 17 in total, as separated on their ability in stoichiometry. This exploratory study of 17 students investigated parallels and differences in the students' general and domain-specific cognitive abilities. Performance, strategies, and mistakes…

  11. Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

    Science.gov (United States)

    Journal of Chemical Education, 2015

    2015-01-01

    This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

  12. Effectiveness of Inquiry-Based Lessons Using Particulate Level Models to Develop High School Students' Understanding of Conceptual Stoichiometry

    Science.gov (United States)

    Kimberlin, Stephanie; Yezierski, Ellen

    2016-01-01

    Students' inaccurate ideas about what is represented by chemical equations and concepts underlying stoichiometry are well documented; however, there are few classroom-ready instructional solutions to help students build scientifically accurate ideas about these topics central to learning chemistry. An intervention (two inquiry-based activities)…

  13. Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

    Science.gov (United States)

    Journal of Chemical Education, 2015

    2015-01-01

    This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

  14. The Effects of Mixing, Reaction Rates, and Stoichiometry on Yield for Mixing Sensitive Reactions—Part II: Design Protocols

    Directory of Open Access Journals (Sweden)

    Syed Imran A. Shah

    2012-01-01

    Full Text Available Competitive-consecutive and competitive-parallel reactions are both mixing sensitive reactions where the yield of desired product depends on how fast the reactants are brought together. Recent experimental results have suggested that the magnitude of the mixing effect may depend strongly on the stoichiometry of the reactions. To investigate this, a 1D, dimensionless, reaction-diffusion model was developed at the micromixing scale, yielding a single general Damköhler number. Dimensionless reaction rate ratios were derived for both reaction schemes. A detailed investigation of the effects of initial mixing condition (striation thickness, dimensionless reaction rate ratio, and reaction stoichiometry on the yield of desired product showed that the stoichiometry has a considerable effect on yield. All three variables were found to interact strongly. Model results for 12 stoichiometries are used to determine the mixing scale and relative rate ratio needed to achieve a specified yield for each reaction scheme. The results show that all three variables need to be considered when specifying reactors for mixing sensitive reactions.

  15. A Study Comparing the Efficacy of a Mole Ratio Flow Chart to Dimensional Analysis for Teaching Reaction Stoichiometry.

    Science.gov (United States)

    Wagner, Eugene P.

    2001-01-01

    Reaction stoichiometry calculations have always been difficult for students. Offers the use of a mole ratio flow chart (MRFC) as a logistical sequence of steps that incorporates molar proportions as alternative problem solving techniques to improve student understanding. Indicates that MRFC users performed as well on exam problems covering…

  16. Effectiveness of Inquiry-Based Lessons Using Particulate Level Models to Develop High School Students' Understanding of Conceptual Stoichiometry

    Science.gov (United States)

    Kimberlin, Stephanie; Yezierski, Ellen

    2016-01-01

    Students' inaccurate ideas about what is represented by chemical equations and concepts underlying stoichiometry are well documented; however, there are few classroom-ready instructional solutions to help students build scientifically accurate ideas about these topics central to learning chemistry. An intervention (two inquiry-based activities)…

  17. Influence of stoichiometry on the optical and electrical properties of chemical vapor deposition derived MoS2.

    Science.gov (United States)

    Kim, In Soo; Sangwan, Vinod K; Jariwala, Deep; Wood, Joshua D; Park, Spencer; Chen, Kan-Sheng; Shi, Fengyuan; Ruiz-Zepeda, Francisco; Ponce, Arturo; Jose-Yacaman, Miguel; Dravid, Vinayak P; Marks, Tobin J; Hersam, Mark C; Lauhon, Lincoln J

    2014-10-28

    Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. The optoelectronic properties of CVD grown monolayer MoS2 have been intensively investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS2 during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoOx species. As MoS2-δ is reduced (increasing δ), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes nonuniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ∼ 0 V. We conclude that the electrical and optical properties of monolayer MoS2 crystals can be tuned via stoichiometry engineering to meet the requirements of various applications.

  18. Accurate determination of peptide phosphorylation stoichiometry via automated diagonal capillary electrophoresis coupled with mass spectrometry: proof of principle.

    Science.gov (United States)

    Mou, Si; Sun, Liangliang; Dovichi, Norman J

    2013-11-19

    While reversible protein phosphorylation plays an important role in many cellular processes, simple and reliable measurement of the stoichiometry of phosphorylation can be challenging. This measurement is confounded by differences in the ionization efficiency of phosphorylated and unphosphorylated sites during analysis by mass spectrometry. Here, we demonstrate diagonal capillary electrophoresis-mass spectrometry for the accurate determination of this stoichiometry. Diagonal capillary electrophoresis is a two-dimensional separation method that incorporates an immobilized alkaline phosphatase microreactor at the distal end of the first capillary and employs identical electrophoretic separation modes in both dimensions. The first dimension is used to separate a mixture of the phosphorylated and unphosphorylated forms of a peptide. Fractions are parked in the reactor where they undergo complete dephosphorylation. The products are then periodically transferred to the second capillary and analyzed by mass spectrometry (MS). Because the phosphorylated and unphosphorylated forms differ in charge, they are well resolved in the first dimension separation. Because the unphosphorylated and dephosphorylated peptides are identical, there is no bias in ionization efficiency, and phosphorylation stoichiometry can be determined by the ratio of the signal of the two forms. A calibration curve was generated from mixtures of a phosphorylated standard peptide and its unphosphorylated form, prepared in a bovine serum albumin tryptic digest. This proof of principle experiment demonstrated a linear response across nearly 2 orders of magnitude in stoichiometry.

  19. Differences in General Cognitive Abilities and Domain-Specific Skills of Higher-and Lower-Achieving Students in Stoichiometry

    Science.gov (United States)

    Gulacar, Ozcan; Eilks, Ingo; Bowman, Charles R.

    2014-01-01

    This paper reports a comparison of a group of higher-and lower-achieving undergraduate chemistry students, 17 in total, as separated on their ability in stoichiometry. This exploratory study of 17 students investigated parallels and differences in the students' general and domain-specific cognitive abilities. Performance, strategies, and mistakes…

  20. Oxygen Stoichiometry in Cation Deficient (La,Sr)_{1-z}MnO_3 SOFC Cathode Materials

    DEFF Research Database (Denmark)

    Zachau-Christiansen, Birgit; Jacobsen, Torben; Skaarup, Steen

    1997-01-01

    The variation of oxygen stoichiometry with oxygen partial pressure is determined for perovskites, ABO3, with the general composition: (La1-xSrx)_{1-z}MnO_{3+y}. The measurements are performed as linear sweep voltammetry on an oxygen pumping cell, where the oxygen partial pressure is controlled...

  1. Catalytic hydrolysis of cellulose into furans

    Science.gov (United States)

    Shi, Chengmei; Tao, Furong; Cui, Yuezhi

    2016-12-01

    Chromium chloride in 4-(3-methylimidazolium-1-yl)butane-1-sulfonic acid hydrogen sulfate (IL-1) was found to effectively catalyze the hydrolysis of microcrystalline cellulose (MCC) at 150°C for 300 min to achieve 87.8% conversion to a slate of products. With a catalytic amount of CrCl3, the yields of 5-hydroxymethyl furfural (HMF) and furfural were up to 32.4 and 15.2%, respectively, small molecules levulinic acid (LA, 10.8%) and the total reducing sugars (TRS, 10.7%) were also generated. Through LC-MSD analysis and mass spectra, dimer of furan compounds as the main by-products were speculated, and the components of gas products were methane, ethane, CO, CO2, and H2. We suggested that IL-1 and CrCl3 exhibited a coordination interaction; the formation of the intermediate via the hydride shift played a key role in the formation of HMF. The catalyst was recycled and exhibited constant activity for five successive trials.

  2. Stoichiometry and geometry of the CXC chemokine receptor 4 complex with CXC ligand 12: Molecular modeling and experimental validation

    Science.gov (United States)

    Kufareva, Irina; Stephens, Bryan S.; Holden, Lauren G.; Qin, Ling; Zhao, Chunxia; Kawamura, Tetsuya; Abagyan, Ruben; Handel, Tracy M.

    2014-01-01

    Chemokines and their receptors regulate cell migration during development, immune system function, and in inflammatory diseases, making them important therapeutic targets. Nevertheless, the structural basis of receptor:chemokine interaction is poorly understood. Adding to the complexity of the problem is the persistently dimeric behavior of receptors observed in cell-based studies, which in combination with structural and mutagenesis data, suggest several possibilities for receptor:chemokine complex stoichiometry. In this study, a combination of computational, functional, and biophysical approaches was used to elucidate the stoichiometry and geometry of the interaction between the CXC-type chemokine receptor 4 (CXCR4) and its ligand CXCL12. First, relevance and feasibility of a 2:1 stoichiometry hypothesis was probed using functional complementation experiments with multiple pairs of complementary nonfunctional CXCR4 mutants. Next, the importance of dimers of WT CXCR4 was explored using the strategy of dimer dilution, where WT receptor dimerization is disrupted by increasing expression of nonfunctional CXCR4 mutants. The results of these experiments were supportive of a 1:1 stoichiometry, although the latter could not simultaneously reconcile existing structural and mutagenesis data. To resolve the contradiction, cysteine trapping experiments were used to derive residue proximity constraints that enabled construction of a validated 1:1 receptor:chemokine model, consistent with the paradigmatic two-site hypothesis of receptor activation. The observation of a 1:1 stoichiometry is in line with accumulating evidence supporting monomers as minimal functional units of G protein-coupled receptors, and suggests transmission of conformational changes across the dimer interface as the most probable mechanism of altered signaling by receptor heterodimers. PMID:25468967

  3. Changes in N:P Supply Ratios Affect the Ecological Stoichiometry of a Toxic Cyanobacterium and Its Fungal Parasite.

    Science.gov (United States)

    Frenken, Thijs; Wierenga, Joren; Gsell, Alena S; van Donk, Ellen; Rohrlack, Thomas; Van de Waal, Dedmer B

    2017-01-01

    Human activities have dramatically altered nutrient fluxes from the landscape into receiving waters. As a result, not only the concentration of nutrients in surface waters has increased, but also their elemental ratios have changed. Such shifts in resource supply ratios will alter autotroph stoichiometry, which may in turn have consequences for higher trophic levels, including parasites. Here, we hypothesize that parasite elemental composition will follow changes in the stoichiometry of its host, and that its reproductive success will decrease with host nutrient limitation. We tested this hypothesis by following the response of a host-parasite system to changes in nitrogen (N) and phosphorus (P) supply in a controlled laboratory experiment. To this end, we exposed a fungal parasite (the chytrid Rhizophydium megarrhizum) to its host (the freshwater cyanobacterium Planktothrix rubescens) under control, low N:P and high N:P conditions. Host N:P followed treatment conditions, with a decreased N:P ratio under low N:P supply, and an increased N:P ratio under high N:P supply, as compared to the control. Shifts in host N:P stoichiometry were reflected in the parasite stoichiometry. Furthermore, at low N:P supply, host intracellular microcystin concentration was lowered as compared to high N:P supply. In contrast to our hypothesis, zoospore production decreased at low N:P and increased at high N:P ratio as compared to the control. These findings suggest that fungal parasites have a relatively high N, but low P requirement. Furthermore, zoospore elemental content, and thereby presumably their size, decreased at high N:P ratios. From these results we hypothesize that fungal parasites may exhibit a trade-off between zoospore size and production. Since zooplankton can graze on chytrid zoospores, changes in parasite production, stoichiometry and cell size may have implications for aquatic food web dynamics.

  4. α4β2 Nicotinic Acetylcholine Receptors: RELATIONSHIPS BETWEEN SUBUNIT STOICHIOMETRY AND FUNCTION AT THE SINGLE CHANNEL LEVEL.

    Science.gov (United States)

    Mazzaferro, Simone; Bermudez, Isabel; Sine, Steven M

    2017-02-17

    Acetylcholine receptors comprising α4 and β2 subunits are the most abundant class of nicotinic acetylcholine receptor in the brain. They contribute to cognition, reward, mood, and nociception and are implicated in a range of neurological disorders. Previous measurements of whole-cell macroscopic currents showed that α4 and β2 subunits assemble in two predominant pentameric stoichiometries, which differ in their sensitivity to agonists, antagonists, and allosteric modulators. Here we compare agonist-elicited single channel currents from receptors assembled with an excess of either the α4 or β2 subunit, forming receptor populations biased toward one or the other stoichiometry, with currents from receptors composed of five concatemeric subunits in which the subunit stoichiometry is predetermined. Our results associate each subunit stoichiometry with a unique single channel conductance, mean open channel lifetime, and sensitivity to the allosteric potentiator 3-[3-(3-pyridinyl)-1,2,4-oxadiazol-5-yl]benzonitrile (NS-9283). Receptors with the composition (α4β2)2α4 exhibit high single channel conductance, brief mean open lifetime, and strong potentiation by NS-9283, whereas receptors with the composition (α4β2)2β2 exhibit low single channel conductance and long mean open lifetime and are not potentiated by NS-9283. Thus single channel current measurements reveal bases for the distinct functional and pharmacological properties endowed by different stoichiometries of α4 and β2 subunits and establish pentameric concatemers as a means to delineate interactions between subunits that confer these properties. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  5. Stoichiometry and geometry of the CXC chemokine receptor 4 complex with CXC ligand 12: molecular modeling and experimental validation.

    Science.gov (United States)

    Kufareva, Irina; Stephens, Bryan S; Holden, Lauren G; Qin, Ling; Zhao, Chunxia; Kawamura, Tetsuya; Abagyan, Ruben; Handel, Tracy M

    2014-12-16

    Chemokines and their receptors regulate cell migration during development, immune system function, and in inflammatory diseases, making them important therapeutic targets. Nevertheless, the structural basis of receptor:chemokine interaction is poorly understood. Adding to the complexity of the problem is the persistently dimeric behavior of receptors observed in cell-based studies, which in combination with structural and mutagenesis data, suggest several possibilities for receptor:chemokine complex stoichiometry. In this study, a combination of computational, functional, and biophysical approaches was used to elucidate the stoichiometry and geometry of the interaction between the CXC-type chemokine receptor 4 (CXCR4) and its ligand CXCL12. First, relevance and feasibility of a 2:1 stoichiometry hypothesis was probed using functional complementation experiments with multiple pairs of complementary nonfunctional CXCR4 mutants. Next, the importance of dimers of WT CXCR4 was explored using the strategy of dimer dilution, where WT receptor dimerization is disrupted by increasing expression of nonfunctional CXCR4 mutants. The results of these experiments were supportive of a 1:1 stoichiometry, although the latter could not simultaneously reconcile existing structural and mutagenesis data. To resolve the contradiction, cysteine trapping experiments were used to derive residue proximity constraints that enabled construction of a validated 1:1 receptor:chemokine model, consistent with the paradigmatic two-site hypothesis of receptor activation. The observation of a 1:1 stoichiometry is in line with accumulating evidence supporting monomers as minimal functional units of G protein-coupled receptors, and suggests transmission of conformational changes across the dimer interface as the most probable mechanism of altered signaling by receptor heterodimers.

  6. Changes in N:P Supply Ratios Affect the Ecological Stoichiometry of a Toxic Cyanobacterium and Its Fungal Parasite

    Directory of Open Access Journals (Sweden)

    Thijs Frenken

    2017-06-01

    Full Text Available Human activities have dramatically altered nutrient fluxes from the landscape into receiving waters. As a result, not only the concentration of nutrients in surface waters has increased, but also their elemental ratios have changed. Such shifts in resource supply ratios will alter autotroph stoichiometry, which may in turn have consequences for higher trophic levels, including parasites. Here, we hypothesize that parasite elemental composition will follow changes in the stoichiometry of its host, and that its reproductive success will decrease with host nutrient limitation. We tested this hypothesis by following the response of a host–parasite system to changes in nitrogen (N and phosphorus (P supply in a controlled laboratory experiment. To this end, we exposed a fungal parasite (the chytrid Rhizophydium megarrhizum to its host (the freshwater cyanobacterium Planktothrix rubescens under control, low N:P and high N:P conditions. Host N:P followed treatment conditions, with a decreased N:P ratio under low N:P supply, and an increased N:P ratio under high N:P supply, as compared to the control. Shifts in host N:P stoichiometry were reflected in the parasite stoichiometry. Furthermore, at low N:P supply, host intracellular microcystin concentration was lowered as compared to high N:P supply. In contrast to our hypothesis, zoospore production decreased at low N:P and increased at high N:P ratio as compared to the control. These findings suggest that fungal parasites have a relatively high N, but low P requirement. Furthermore, zoospore elemental content, and thereby presumably their size, decreased at high N:P ratios. From these results we hypothesize that fungal parasites may exhibit a trade-off between zoospore size and production. Since zooplankton can graze on chytrid zoospores, changes in parasite production, stoichiometry and cell size may have implications for aquatic food web dynamics.

  7. Catalytic Radical Domino Reactions in Organic Synthesis.

    Science.gov (United States)

    Sebren, Leanne J; Devery, James J; Stephenson, Corey R J

    2014-02-07

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes.

  8. Catalytic gasification of dry and wet biomass

    NARCIS (Netherlands)

    van Rossum, G.; Potic, B.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

    2009-01-01

    Catalytic gasification of dry biomass and of wet biomass streams in hot compressed water are reviewed and discussed as potential technologies for the production of synthesis gas, hydrogen- and methane-rich gas. Next to literature data also new experimental results from our laboratory on catalytic

  9. System Study of Rich Catalytic/Lean burn (RCL) Catalytic Combustion for Natural Gas and Coal-Derived Syngas Combustion Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Shahrokh Etemad; Lance Smith; Kevin Burns

    2004-12-01

    Rich Catalytic/Lean burn (RCL{reg_sign}) technology has been successfully developed to provide improvement in Dry Low Emission gas turbine technology for coal derived syngas and natural gas delivering near zero NOx emissions, improved efficiency, extending component lifetime and the ability to have fuel flexibility. The present report shows substantial net cost saving using RCL{reg_sign} technology as compared to other technologies both for new and retrofit applications, thus eliminating the need for Selective Catalytic Reduction (SCR) in combined or simple cycle for Integrated Gasification Combined Cycle (IGCC) and natural gas fired combustion turbines.

  10. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  11. Catalytic Graphitization of Phenolic Resin

    Institute of Scientific and Technical Information of China (English)

    Mu Zhao; Huaihe Song

    2011-01-01

    The catalytic graphitization of thermal plastic phenolic-formaldehyde resin with the aid of ferric nitrate (FN) was studied in detail. The morphologies and structural features of the products including onion-like carbon nanoparticles and bamboo-shaped carbon nanotubes were investigated by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction and Raman spectroscopy measurements. It was found that with the changes of loading content of FN and residence time at 1000℃, the products exhibited various morphologies. The TEM images showed that bamboo-shaped carbon nanotube consisted of tens of bamboo sticks and onion-like carbon nanoparticle was made up of quasi-spherically concentrically closed carbon nanocages.

  12. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  13. Non-catalytic recuperative reformer

    Energy Technology Data Exchange (ETDEWEB)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  14. Unsteady processes in catalytic reactors

    Energy Technology Data Exchange (ETDEWEB)

    Matros, Yu.Sh.

    1985-01-01

    In recent years a realization has occurred that reaction and reactor dynamics must be considered when designing and operating catalytic reactors. In this book, the author has focussed on both the processes occurring on individual porous-catalyst particles as well as the phenomena displayed by collections of these particles in fixed-bed reactors. The major topics discussed include the effects of unsteady-state heat and mass transfer, the influence of inhomogeneities and stagnant regions in fixed beds, and reactor operation during forced cycling of operating conditions. Despite the title of the book, attention is also paid to the determination of the number and stability of fixed-bed steady states, with the aim of describing the possibility of controlling reactors at unstable steady states. However, this development is somewhat dated, given the recent literature on multiplicity phenomena and process control.

  15. Method of fabricating a catalytic structure

    Science.gov (United States)

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2009-09-22

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

  16. Cathlean: catalytic, hybrid, lean-premixed burner for gas turbines

    Energy Technology Data Exchange (ETDEWEB)

    Carroni, Richard; Griffin, Timothy [Alstom Power Technology Ltd., Baden-Daettwil (Switzerland); Kelsall, Greg [Alstom Power Technology Centre, Whetstone (United Kingdom)

    2004-08-01

    Cathlean (an EU FP5 project) addresses the research and development of an advanced, ultra-low NO{sub x}, hybrid burner for gas turbines (present and future), that combines catalytic and lean-premix combustion components. Such a hybrid design enables this new technology to be introduced in a lower-risk manner. The catalytic elements serve to pretreat the fuel in order to enhance performance in terms of emissions <3 ppmv NO{sub x} and <10 ppmv CO at 15% O{sub 2} and 50-100% load, for natural gas fuel), part-load stability (reducing the lean blow-out temperature by over 100 deg C) and thermoacoustic phenomena (pulsations << 0.3% of pressure). The principle scientific objective is to quantify the advantages of the hybrid burner in terms of the above-mentioned criteria, relative to traditional, lean-premixed combustors. The present paper describes the technical and organisational aspects of the project, including an outline of state-of-the-art catalytic combustion technology, technical specification of the advanced burner and a description of the methods used to attain project goals. (Author)

  17. Stoichiometries of U2AF35, U2AF65 and U2 snRNP reveal new early spliceosome assembly pathways.

    Science.gov (United States)

    Chen, Li; Weinmeister, Robert; Kralovicova, Jana; Eperon, Lucy P; Vorechovsky, Igor; Hudson, Andrew J; Eperon, Ian C

    2017-02-28

    The selection of 3΄ splice sites (3΄ss) is an essential early step in mammalian RNA splicing reactions, but the processes involved are unknown. We have used single molecule methods to test whether the major components implicated in selection, the proteins U2AF35 and U2AF65 and the U2 snRNP, are able to recognize alternative candidate sites or are restricted to one pre-specified site. In the presence of adenosine triphosphate (ATP), all three components bind in a 1:1 stoichiometry with a 3΄ss. Pre-mRNA molecules with two alternative 3΄ss can be bound concurrently by two molecules of U2AF or two U2 snRNPs, so none of the components are restricted. However, concurrent occupancy inhibits splicing. Stoichiometric binding requires conditions consistent with coalescence of the 5΄ and 3΄ sites in a complex (I, initial), but if this cannot form the components show unrestricted and stochastic association. In the absence of ATP, when complex E forms, U2 snRNP association is unrestricted. However, if protein dephosphorylation is prevented, an I-like complex forms with stoichiometric association of U2 snRNPs and the U2 snRNA is base-paired to the pre-mRNA. Complex I differs from complex A in that the formation of complex A is associated with the loss of U2AF65 and 35. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

  18. Phosphate supply explains variation in nucleic acid allocation but not C : P stoichiometry in the western North Atlantic

    Science.gov (United States)

    Zimmerman, A. E.; Martiny, A. C.; Lomas, M. W.; Allison, S. D.

    2014-03-01

    Marine microbial communities mediate many biogeochemical transformations in the ocean. Consequently, processes such as primary production and carbon (C) export are linked to nutrient regeneration and are influenced by the resource demand and elemental composition of marine microbial biomass. Laboratory studies have demonstrated that differential partitioning of element resources to various cellular components can directly influence overall cellular elemental ratios, especially with respect to growth machinery (i.e., ribosomal RNA) and phosphorus (P) allocation. To investigate whether allocation to RNA is related to biomass P content and overall C : P biomass composition in the open ocean, we characterized patterns of P allocation and C : P elemental ratios along an environmental gradient of phosphate supply in the North Atlantic subtropical gyre (NASG) from 35.67° N, 64.17° W to 22.676° N, 65.526° W. Because the NASG is characterized as a P-stressed ecosystem, we hypothesized that biochemical allocation would reflect sensitivity to bioavailable phosphate, such that greater phosphate supply would result in increased allocation toward P-rich RNA for growth. We predicted these changes in allocation would also result in lower C : P ratios with increased phosphate supply. However, bulk C : P ratios were decoupled from allocation to nucleic acids and did not appear to vary systematically across a phosphate supply gradient of 2.2-14.7 μmol m-2 d-1. Overall, we found that C : P ratios ranged from 188 to 306 along the transect, and RNA represented only 6-12% of total particulate P, whereas DNA represented 11-19%. We did find that allocation to RNA was positively correlated with phosphate supply rate, suggesting a consistent physiological response in biochemical allocation to resource supply within the whole community. These results suggest that community composition and/or nonnucleic acid P pools may influence ecosystem-scale variation in C : P stoichiometry more than

  19. Catalytic synthesis of long-chained alcohols from syngas

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt

    This work has been an investigation of the catalytic conversion of syngas into mixed alcohols with Mo-based catalysts. The primary focus has been on the use of alkali promoted cobalt-molybdenum sulfide as a catalyst for the alcohol synthesis. The alcohol synthesis is a possibility...... the user to employ a less thorough and therefore less costly syngas cleaning. To evaluate, to which extent a removal of other components in the raw syngas is necessary, the influence of NH3 and H2O in the feed has also been investigated. Ammonia (741 ppmv) in the feed is observed to cause a general...

  20. Revolutionary systems for catalytic combustion and diesel catalytic particulate traps.

    Energy Technology Data Exchange (ETDEWEB)

    Stuecker, John Nicholas; Witze, Peter O.; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward

    2004-12-01

    This report is a summary of an LDRD project completed for the development of materials and structures conducive to advancing the state of the art for catalyst supports and diesel particulate traps. An ancillary development for bio-medical bone scaffolding was also realized. Traditionally, a low-pressure drop catalyst support, such as a ceramic honeycomb monolith, is used for catalytic reactions that require high flow rates of gases at high-temperatures. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. ''Robocasting'' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low-pressure drops. These alternative 3-dimensional geometries may also provide a foundation for the development of self-regenerating supports capable of trapping and combusting soot particles from a diesel engine exhaust stream. This report describes the structures developed and characterizes the improved catalytic performance that can result. The results show that, relative to honeycomb monolith supports, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application. Practical applications include the combustion of natural gas for power generation, production of syngas, and hydrogen reforming reactions. The robocast lattice structures also show practicality for diesel particulate trapping. Preliminary results for trapping efficiency are reported as well as the development of electrically resistive lattices that can regenerate the structure

  1. C : N : P stoichiometry at the Bermuda Atlantic Time-series Study station in the North Atlantic Ocean

    Directory of Open Access Journals (Sweden)

    A. Singh

    2015-06-01

    Full Text Available Nitrogen (N and phosphorus (P availability determine the strength of the ocean's carbon (C uptake, and variation in the N : P ratio in inorganic nutrients is key to phytoplankton growth. A similarity between C : N : P ratios in the plankton biomass and deep-water nutrients was observed by Alfred C. Redfield around 80 years ago and suggested that biological processes in the surface ocean controlled deep ocean chemistry. Recent studies have emphasized the role of inorganic N : P ratios in governing biogeochemical processes, particularly the C : N : P ratio in suspended particulate organic matter (POM, with somewhat less attention given to exported POM and dissolved organic matter (DOM. Herein, we extend the discussion on ecosystem C : N : P stoichiometry but also examine temporal variation of stoichiometric relationships. We have analysed elemental stoichiometry in the suspended POM and total (POM + DOM organic matter (TOM pools in the upper 100 m, and in the exported POM and sub-euphotic zone (100–500 m inorganic nutrient pools from the monthly data collected at the Bermuda Atlantic Time-series Study (BATS site located in the western part of the North Atlantic Ocean. C : N : P ratios in the TOM pool were more than twice that in the POM pool. Observed C : N ratios in suspended POM were approximately equal to the canonical Redfield Ratio (C : N : P = 106 : 16 : 1, while N : P and C : P ratios in the same pool were more than twice the Redfield Ratio. Average N : P ratios in the subsurface inorganic nutrient pool were ~ 26 : 1, squarely between the suspended POM ratio and the Redfield ratio. We have further linked variation in elemental stoichiometry with that of phytoplankton cell abundance observed at the BATS site. Findings from this study suggest that the variation elemental ratios with depth in the euphotic zone was mainly due to different growth rates of cyanobacterial cells. These time-series data have also allowed us to examine the

  2. Topological entropy of catalytic sets: Hypercycles revisited

    Science.gov (United States)

    Sardanyés, Josep; Duarte, Jorge; Januário, Cristina; Martins, Nuno

    2012-02-01

    The dynamics of catalytic networks have been widely studied over the last decades because of their implications in several fields like prebiotic evolution, virology, neural networks, immunology or ecology. One of the most studied mathematical bodies for catalytic networks was initially formulated in the context of prebiotic evolution, by means of the hypercycle theory. The hypercycle is a set of self-replicating species able to catalyze other replicator species within a cyclic architecture. Hypercyclic organization might arise from a quasispecies as a way to increase the informational containt surpassing the so-called error threshold. The catalytic coupling between replicators makes all the species to behave like a single and coherent evolutionary multimolecular unit. The inherent nonlinearities of catalytic interactions are responsible for the emergence of several types of dynamics, among them, chaos. In this article we begin with a brief review of the hypercycle theory focusing on its evolutionary implications as well as on different dynamics associated to different types of small catalytic networks. Then we study the properties of chaotic hypercycles with error-prone replication with symbolic dynamics theory, characterizing, by means of the theory of topological Markov chains, the topological entropy and the periods of the orbits of unimodal-like iterated maps obtained from the strange attractor. We will focus our study on some key parameters responsible for the structure of the catalytic network: mutation rates, autocatalytic and cross-catalytic interactions.

  3. Pelagic community production and carbon-nutrient stoichiometry under variable ocean acidification in an Arctic fjord

    Directory of Open Access Journals (Sweden)

    A. Silyakova

    2013-07-01

    clear that the pelagic ecosystem response to increasing CO2 is more complex than that represented in previous work, e.g. Bellerby et al. (2008. Carbon and nutrient uptake representation in models should, where possible, be more focused on individual plankton functional types as applying a single stoichiometry to a biogeochemical model with regard to the effect of increasing pCO2 may not always be optimal. The phase variability in NCP and stoichiometry may be better understood if CO2 sensitivities of the plankton's functional type biogeochemical uptake kinetics and trophic interactions are better constrained.

  4. Natural off-stoichiometry causes carrier doping in half-Heusler filled tetrahedral structures

    Science.gov (United States)

    Yu, Yonggang G.; Zhang, Xiuwen; Zunger, Alex

    2017-02-01

    The half-Heusler filled tetrahedral structures (FTSs) are zinc-blende-like compounds, where an additional atom is filling its previously empty interstitial site. The FTSs having 18 valence electrons per formula unit are an emerging family of functional materials, whose intrinsic doping trends underlying a wide range of electronic functionalities are yet to be understood. Interestingly, even pristine compounds without any attempt at impurity/chemical doping exhibit intriguing trends in the free carriers they exhibit. Applying the first principles theory of doping to a few prototype compounds in the AIVBXCIV and AIVBIXCV groups, we describe the key ingredients controlling the materials' propensity for both intrinsic and extrinsic doping: (a) The spontaneous deviations from 1:1:1 stoichiometry reflect predictable thermodynamic stability of specific competing phases. (b) Bulk ABC compounds containing 3 d elements in the B position (ZrNiSn and ZrCoSb) are predicted to be naturally 3 d rich. The B =3 d interstitials are the prevailing shallow donors, whereas the potential acceptors (e.g., Zr vacancy and Sn-on-Zr antisite) are ineffective electron killers, resulting in an overall uncompensated n -type character, even without any chemical doping. In these materials, the band edges are "natural impurity bands" due to non-Daltonian off-stoichiometry, such as B interstitials, not intrinsic bulk controlled states as in a perfect crystal. (c) Bulk ABC compounds containing 5 d elements in the B position (ZrPtSn, ZrIrSb, and TaIrGe) are predicted to be naturally C rich and A poor. This promotes the hole-producing C -on-A antisite defects rather than B -interstitial donors. The resultant p -type character (without chemical doping) therein is "latent" for C =Sn and Sb; however, as the C -on-A hole-producing acceptors are rather deep and p typeness is manifest only at high temperature or via impurity doping. In contrast, in TaIrGe (B =Ir , 5 d ) , the prevailing hole-producing Ge

  5. High-frequency fire alters C : N : P stoichiometry in forest litter.

    Science.gov (United States)

    Toberman, Hannah; Chen, Chengrong; Lewis, Tom; Elser, James J

    2014-07-01

    Fire is a major driver of ecosystem change and can disproportionately affect the cycling of different nutrients. Thus, a stoichiometric approach to investigate the relationships between nutrient availability and microbial resource use during decomposition is likely to provide insight into the effects of fire on ecosystem functioning. We conducted a field litter bag experiment to investigate the long-term impact of repeated fire on the stoichiometry of leaf litter C, N and P pools, and nutrient-acquiring enzyme activities during decomposition in a wet sclerophyll eucalypt forest in Queensland, Australia. Fire frequency treatments have been maintained since 1972, including burning every 2 years (2yrB), burning every 4 years (4 yrB) and no burning (NB). C : N ratios in freshly fallen litter were 29-42% higher and C : P ratios were 6-25% lower for 2 yrB than NB during decomposition, with correspondingly lower 2yrB N : P ratios (27-32) than for NB (34-49). Trends in litter soluble and microbial N : P ratios were similar to the overall litter N : P ratios across fire treatments. Consistent with these, the ratio of activities for N-acquiring to P-acquiring enzymes in litter was higher for 2 yrB than NB, whereas 4 yrB was generally intermediate between 2 yrB and NB. Decomposition rates of freshly fallen litter were significantly lower for 2 yrB (72 ± 2% mass remaining at the end of experiment) than for 4 yrB (59 ± 3%) and NB (62 ± 3%), a difference that may be related to effects of N limitation, lower moisture content, and/or litter C quality. Results for older mixed-age litter were similar to those for freshly fallen litter although treatment differences were less pronounced. Overall, these findings show that frequent fire (2 yrB) decoupled N and P cycling, as manifested in litter C : N : P stoichiometry and in microbial biomass N : P ratio and enzymatic activities. Furthermore, these data indicate that fire induced a transient shift to N-limited ecosystem conditions

  6. Development of Catalytic Cooking Plates

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin; Silversand, Fredrik [CATATOR AB, Lund (Sweden); Tena, Emmanuel; Berger, Marc [Gaz de France (France)

    2004-04-01

    Gas catalytic combustion for gas stoves or cooking plates (closed catalytic burner system with ceramic plates) is a very promising technique in terms of ease of cleaning, power modulation and emissions. Previous investigations show that wire mesh catalysts, prepared and supplied by Catator AB (CAT), seem to be very well suited for such applications. Beside significantly reducing the NOx-emissions, these catalysts offer important advantages such as good design flexibility, low pressure drop and high heat transfer capacity, where the latter leads to a quick thermal response. Prior to this project, Gaz de France (GdF) made a series of measurements with CAT's wire mesh catalysts in their gas cooking plates and compared the measured performance with similar results obtained with theirs cordierite monolith catalysts. Compared to the monolith catalyst, the wire mesh catalyst was found to enable very promising results with respect to both emission levels (<10 mg NO{sub x} /kWh, <5 mg CO/kWh) and life-time (>8000 h vs. 700 h at 200 kW/m{sup 2}). It was however established that the radiation and hence, the thermal efficiency of the cooking plate, was significantly less than is usually measured in combination with the monolith (15 % vs. 32 %). It was believed that the latter could be improved by developing new burner designs based on CAT's wire mesh concept. As a consequence, a collaboration project between GdF, CAT and the Swedish Gas Technology AB was created. This study reports on the design, the construction and the evaluation of new catalytic burners, based on CAT's wire mesh catalysts, used for the combustion of natural gas in gas cooking stoves. The evaluation of the burners was performed with respect to key factors such as thermal efficiency, emission quality and pressure drop, etc, by the use of theoretical simulations and experimental tests. Impacts of parameters such as the the wire mesh number, the wire mesh structure (planar or folded), the

  7. Catalytic allylation of phenols : chloride-free route towards epoxy resins

    NARCIS (Netherlands)

    Rijn, Jimmy Antonius van

    2010-01-01

    An industrially applicable process was developed for the synthesis of epoxy resin components. A catalytic reaction was explored towards allyl phenyl ethers that prevents the use of chloride-containing starting materials and thus formation of chloride-containing side products. The preferred allylatin

  8. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.

    2016-01-01

    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic buil

  9. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions durin

  10. Catalytic C-C Bond Cleavage for the Production of Chemicals from Lignin

    NARCIS (Netherlands)

    Jastrzebski, R.|info:eu-repo/dai/nl/338017747

    2016-01-01

    Lignin is a major component of lignocellulosic biomass and could be an important renewable feedstock in industry for the production of (aromatic) bulk and fine chemicals. To this end, the development of new catalytic processes is required; both to depolymerise the biopolymer into small aromatic

  11. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  12. Halogen Chemistry on Catalytic Surfaces.

    Science.gov (United States)

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling.

  13. Effects of stoichiometry and substitution in quasi-one-dimensional iron chalcogenide BaFe2S3

    Science.gov (United States)

    Hirata, Yasuyuki; Maki, Sachiko; Yamaura, Jun-ichi; Yamauchi, Touru; Ohgushi, Kenya

    2015-11-01

    The effects of off-stoichiometry and elemental substitution on electronic properties of iron-based ladder compound BaFe2S3 are investigated. Resistivity and magnetization are revealed to be quite sensitive to the stoichiometry of Fe atoms, and 10% deficiency at Fe sites reduces the antiferromagnetic transition temperature by 40 K. The antiferromagnetic transition temperature decreases even faster and collapses to zero with hole doping through 10% K substitution at the Ba site, while the antiferromagnetic ordering phase remains with electron doping through 20% Co substitution at the Fe site. Such electron-hole asymmetry is opposite to two-dimensional iron-based superconductors, and can be explained on the basis of both itinerant and localized electronic pictures.

  14. Urbanization and agriculture increase exports and differentially alter elemental stoichiometry of dissolved organic matter (DOM) from tropical catchments

    DEFF Research Database (Denmark)

    Gücker, Björn; Silva, Ricky C. S.; Graeber, Daniel

    2016-01-01

    ) concentrations, but consistent effects on DOM elemental stoichiometry have not yet been reported. Here, we studied stream water DOC concentrations, catchment DOC exports, and DOM elemental stoichiometry in 20 tropical catchments at the Cerrado–Atlantic rainforest transition, dominated by natural vegetation......, pasture, intensive agriculture, and urban land cover. Streams draining pasture could be distinguished from those draining natural catchments by their lower DOC concentrations, with lower DOM C:N and C:P ratios. Catchments with intensive agriculture had higher DOC exports and lower DOM C:P ratios than...... natural catchments. Finally, with the highest DOC concentrations and exports, as well as the highest DOM C:P and N:P ratios, but the lowest C:N ratios among all land-use types, urbanized catchments had the strongest effects on catchment DOM. Thus, urbanization may have alleviated N limitation...

  15. Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys Ml(Ni0.71Co0.15-Al0.06Mn0.08)x (Ml=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.

  16. Control and Study of the Stoichiometry in Evaporated Perovskite Solar Cells.

    Science.gov (United States)

    Teuscher, Joël; Ulianov, Alexey; Müntener, Othmar; Grätzel, Michael; Tétreault, Nicolas

    2015-11-01

    Herein, we present the precise stoichiometric control of methlyammonium lead iodide perovskite thin-films using high vacuum dual-source vapor-phase deposition. We found that UV/Vis absorption and emission spectra were inadequate for assessing precisely the perovskite composition. Alternatively, inductively coupled plasma mass spectrometry (ICP-MS) is used to give precise, reproducible, quantitative measurements of the I/Pb ratio without systematic errors that often result from varying device thicknesses and morphologies. This controlled deposition method enables better understanding of the evaporation and deposition processes; methylammonium iodide evaporation appears omnidirectional, controlled using the chamber pressure and incorporated in the film through interaction with the unidirectionally evaporated PbI2. Furthermore, these thin-films were incorporated into solar cell device architectures with the best photovoltaic performance and reproducibility obtained for devices made with stoichiometric perovskite active layers. Additionally, and particularly pertinent to the field of perovskite photovoltaics, we found that the I-V hysteresis was unaffected by varying the film stoichiometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Predicting nutrient excretion of aquatic animals with metabolic ecology and ecological stoichiometry: a global synthesis.

    Science.gov (United States)

    Vanni, Michael J; McIntyre, Peter B

    2016-12-01

    The metabolic theory of ecology (MTE) and ecological stoichiometry (ES) are both prominent frameworks for understanding energy and nutrient budgets of organisms. We tested their separate and joint power to predict nitrogen (N) and phosphorus (P) excretion rates of ectothermic aquatic invertebrate and vertebrate animals (10,534 observations worldwide). MTE variables (body size, temperature) performed better than ES variables (trophic guild, vertebrate classification, body N:P) in predicting excretion rates, but the best models included variables from both frameworks. Size scaling coefficients were significantly lower than predicted by MTE (<0.75), were lower for P than N, and varied greatly among species. Contrary to expectations under ES, vertebrates excreted both N and P at higher rates than invertebrates despite having more nutrient-rich bodies, and primary consumers excreted as much nutrients as carnivores despite having nutrient-poor diets. Accounting for body N:P hardly improved upon predictions from treating vertebrate classification categorically. We conclude that basic data on body size, water temperature, trophic guild, and vertebrate classification are sufficient to make general estimates of nutrient excretion rates for any animal taxon or aquatic ecosystem. Nonetheless, dramatic interspecific variation in size-scaling coefficients and counter-intuitive patterns with respect to diet and body composition underscore the need for field data on consumption and egestion rates. Together, MTE and ES provide a powerful conceptual basis for interpreting and predicting nutrient recycling rates of aquatic animals worldwide. © 2016 by the Ecological Society of America.

  18. Stoichiometry-controlled compensation in liquid encapsulated Czochralski GaAs

    Science.gov (United States)

    Holmes, D. E.; Chen, R. T.; Elliott, K. R.; Kirkpatrick, C. G.

    1982-01-01

    It is shown that the electrical compensation of undoped GaAs grown by the liquid encapsulated Czochralski technique is controlled by the melt stoichiometry. The concentration of the deep donor EL2 in the crystal depends on the As concentration in the melt, increasing from about 5 x 10 to the 15th per cu cm to 1.7 x 10 to the 16th per cu cm as the As atom fraction increases from 0.48 to 0.51. Furthermore, it is shown that the free-carrier concentration of semi-insulating GaAs is determined by the relative concentrations of EL2 and carbon acceptors. As a result, semi-insulating material can be obtained only above a critical As concentration (0.475-atom fraction in the material here) where the concentration of EL2 is sufficient to compensate residual acceptors. Below the critical As concentration the material is p type due to excess acceptors.

  19. Non-Redfield, nutrient synergy and flexible internal elemental stoichiometry in a marine bacterium

    Science.gov (United States)

    Trautwein, Kathleen; Feenders, Christoph; Hulsch, Reiner; Ruppersberg, Hanna S.; Strijkstra, Annemieke; Kant, Mirjam; Vagts, Jannes; Wünsch, Daniel; Michalke, Bernhard; Maczka, Michael; Schulz, Stefan; Hillebrand, Helmut; Blasius, Bernd

    2017-01-01

    Abstract The stoichiometric constraints of algal growth are well understood, whereas there is less knowledge for heterotrophic bacterioplankton. Growth of the marine bacterium Phaeobacter inhibens DSM 17395, belonging to the globally distributed Roseobacter group, was studied across a wide concentration range of NH4+ and PO43−. The unique dataset covers 415 different concentration pairs, corresponding to 207 different molar N:P ratios (from 10−2 to 105). Maximal growth (by growth rate and biomass yield) was observed within a restricted concentration range at N:P ratios (∼50−120) markedly above Redfield. Experimentally determined growth parameters deviated to a large part from model predictions based on Liebig's law of the minimum, thus implicating synergistic co-limitation due to biochemical dependence of resources. Internal elemental ratios of P. inhibens varied with external nutrient supply within physiological constraints, thus adding to the growing evidence that aquatic bacteria can be flexible in their internal elemental composition. Taken together, the findings reported here revealed that P. inhibens is well adapted to fluctuating availability of inorganic N and P, expected to occur in its natural habitat (e.g. colonized algae, coastal areas). Moreover, this study suggests that elemental variability in bacterioplankton needs to be considered in the ecological stoichiometry of the oceans. PMID:28486660

  20. Reproducibility and off-stoichiometry issues in nickelate thin films grown by pulsed laser deposition

    Science.gov (United States)

    Preziosi, Daniele; Sander, Anke; Barthélémy, Agnès; Bibes, Manuel

    2017-01-01

    Rare-earth nickelates are strongly correlated oxides displaying a metal-to-insulator transition at a temperature tunable by the rare-earth ionic radius. In PrNiO3 and NdNiO3, the transition is very sharp and shows an hysteretic behavior akin to a first-order transition. Both the temperature at which the transition occurs and the associated resistivity change are extremely sensitive to doping and therefore to off-stoichiometry issues that may arise during thin film growth. Here we report that strong deviations in the transport properties of NdNiO3 films can arise in films grown consecutively under nominally identical conditions by pulsed laser deposition; some samples show a well-developed transition with a resistivity change of up to five orders of magnitude while others are metallic down to low temperatures. Through a detailed analysis of in-situ X-ray photoelectron spectroscopy data, we relate this behavior to large levels of cationic off-stoichoimetry that also translate in changes in the Ni valence and bandwidth. Finally, we demonstrate that this lack of reproducibility can be remarkably alleviated by using single-phase NdNiO3 targets.

  1. The control of stoichiometry in Epitaxial semiconductor structures. Interfacial Chemistry: Property relations. A workshop review

    Science.gov (United States)

    Bachmann, Klaus J.

    1995-01-01

    A workshop on the control of stoichiometry in epitaxial semiconductor structures was held on August 21-26, 1995 in the hotel Stutenhaus at Vesser in Germany. The secluded location of the workshop in the forest of Thuringia and its informal style stimulated extensive private discussions among the participants and promoted new contacts between young scientists from Eastern and Western Europe and the USA. Topics addressed by the presentations were interactions of precursors to heteroepitaxy and doping with the substrate surface, the control of interfacial properties under the conditions of heteroepitaxy for selected materials systems, methods of characterization of interfaces and native point defects in semiconductor heterostructures and an in depth evaluation of the present status of the control and characterization of the point defect chemistry for one specific semiconductor (ZnGeP2), including studies of both heterostructures and bulk single crystals. The selected examples of presentations and comments given here represent individual choices - made by the author to highlight major points of the discussions.

  2. Thermal annealing of SiC thin films with varying stoichiometry

    Energy Technology Data Exchange (ETDEWEB)

    Kuenle, Matthias [Fraunhofer Institute for Solar Energy Systems, Heidenhofstrasse 2, 79110 Freiburg (Germany)], E-mail: matthias.kuenle@ise.fraunhofer.de; Janz, Stefan [Fraunhofer Institute for Solar Energy Systems, Heidenhofstrasse 2, 79110 Freiburg (Germany); Eibl, Oliver [Eberhard-Karls-Universitaet, Tuebingen, Institute for Applied Physics, Auf der Morgenstelle 10, 72076 Tuebingen (Germany); Berthold, Christoph; Presser, Volker; Nickel, Klaus-Georg [Eberhard-Karls-Universitaet, Tuebingen, Institute for Geoscience, Applied Mineralogy, Wilhelmstrasse 56, 72074 Tuebingen (Germany)

    2009-03-15

    Thin films of amorphous hydrogenated silicon carbide (a-SiC:H) with varying stoichiometry of silicon and carbon were prepared by Plasma Enhanced Chemical Vapour Deposition (PECVD). After deposition a subsequent rapid thermal annealing was carried out at 900, 1100 and 1300 deg. C. The as-deposited and annealed SiC thin films were investigated by X-ray diffraction (XRD), cross-section and plane view transmission electron microscopy (TEM), Fourier-Transformed Infrared (FTIR) and Raman spectroscopy. The deposited films were amorphous directly after deposition and became nanocrystalline after annealing at 1300 deg. C. This was verified by XRD measurements. Microvoids were found in all films investigated by TEM. Densification and crystallisation as well as cooling introduced tensile stresses within the annealed SiC film and lead eventually to crack formation in the film. The annealed stoichiometric SiC film shows v-shaped extended defects at the Si-SiC interface likely formed during the annealing at high temperatures. FTIR and Raman spectroscopy showed a strong influence of initial film properties such as hydrogen content and binding structure on the internal structure of the SiC thin films after annealing.

  3. Predicting Thin Film Stoichiometry In V-O2 Reactive Sputtering

    Directory of Open Access Journals (Sweden)

    He Yu

    2015-06-01

    Full Text Available The electrical, optical and mechanical properties of compound oxides film depend strongly on the composition of the film, especially for vanadium oxide thin films, since the vanadium-oxygen phase diagram includes mixed valence oxides with two or more oxidation states. Therefore, it is interesting to predict the film stoichiometry in VOx films. However, it has not, to any great extent yet, been possible to predict the composition of vanadium oxides films. In this article, we present a model that enables us to predict film composition of vanadium oxides prepared by reactive sputtering. Based on this model, the fraction ratio of V, V2O3, VO2 and V2O5 in the substrate surface as a function of oxygen flow is investigated. It is concluded that the presented theoretical model for the involved reactions and composition of VOx thin film during reactive sputtering process is in qualitative agreement with the XPS results from experiment and can be used to find optimum processing conditions for deposition of films of a desired composition.DOI: http://dx.doi.org/10.5755/j01.ms.21.2.6910

  4. Teaching reactions and stoichiometry: A comparison of guided inquiry and traditional laboratory activities

    Science.gov (United States)

    Meister Thomas, Lynn

    There is a major movement in science education towards the inclusion of science inquiry and process. Guided-inquiry instruction is expected to have a positive impact on students' concrete and conceptual knowledge along with their ability to engage in the practices of science. This study examined the impact of inquiry-based teaching on student achievement. The topics of reactions and stoichiometry were taught in two different periods of first-year secondary honors chemistry. Both classes received the same lectures and assignments for this curriculum and both classes performed the same laboratory activities. However, one class received traditional, step-by-step (often called "cookbook") laboratory instructions while the other class developed their own procedures and made decisions about data to complete the laboratory activities. Pre- and post-tests were given to each class, followed by a test of retention after ten weeks. The results of this study indicate that inquiry-based instruction has a positive impact on student achievement. A significant increase between pre- and post- test scores for the experimental group as opposed to the scores for the control group suggests that achievement was correlated with guided inquiry instruction methods. Additionally, a notable trend suggested that guided inquiry instruction has a positive effect on learning retention.

  5. Stoichiometry of H+ ejection during respiration-dependent accumulation of Ca2+ by rat liver mitochondria.

    Science.gov (United States)

    Brand, M D; Chen, C H; Lehninger, A L

    1976-02-25

    We have investigated the energy-dependent uptake of Ca2+ by rat liver mitochondria with succinate as respiratory substrate with rotenone added to block NAD-linked electron transport. In the presence of 3-hydroxybutyric or other permeant monocarboxylic acids Ca2+ was taken up to extents approaching those seen in the presence of phosphate. The quantitative relationship between cation and anion uptake was determined from the slope of a plot of 3-hydroxybutyrate uptake against Ca2+ uptake, a method which allowed determination of the stoichiometry without requiring ambiguous corrections for early nonenergized or nonstoichiometric binding events. This procedure showed that 2 molecules of 3-hydroxtbutyrate were accumulated with each Ca2+ ion. Under these conditions close to 2 Ca2+ ions and 4 molecules of 3-hydroxybutyrate were accumulated per pair of electrons per energy-conserving site of the respiratory chain. Since 3-hydroxybutyrate must be protonated to pass the membrane as the undissociated free acid, it is concluded that 4 protons were ejected (and subsequently reabsorbed) per pair of electrons per energy-conserving site, in contrast to the value 2.0 postulated by the chemiosmotic hypothesis.

  6. Stoichiometry of mitochondrial H+ translocation coupled to succinate oxidation at level flow.

    Science.gov (United States)

    Costa, L E; Reynafarje, B; Lehninger, A L

    1984-04-25

    The mechanistic stoichiometry of vectorial H+ translocation coupled to succinate oxidation by rat liver mitochondria in the presence of a permeant cation has been determined under level flow conditions with a membraneless fast responding O2 electrode kinetically matched with a glass pH electrode. The reactions were initiated by rapid injection of O2 into the anaerobically preincubated test system under conditions in which interfering H+ backflow was minimized. The rates of O2 uptake and H+ ejection, obtained from computer-fitted regression lines, were monotonic and first order over 75% of the course of O2 consumption. Extrapolation of the observed rates to zero time, at which zero delta mu H+ and thus level flow prevails, yielded vectorial H+/O flow ratios above 7 and closely approaching 8. The mitochondria undergo no irreversible change and give identical H+/O ratios on repeated tests. In a further refinement, the lower and upper limits of the mechanistic H+/O ratio were determined to be 7.55 and 8.56, respectively, from plots of the rates of O2 uptake versus H+ ejection at increasing malonate and increasing valinomycin concentrations, respectively. It is therefore concluded that the mechanistic H+/O ratio for energy-conserving sites 2 + 3 is 8, in confirmation of earlier measurements. KCl concentration is critical for maximal observed H+/O ratios. Optimum conditions and possible errors in determination of mechanistic H+/O translocation ratios are discussed.

  7. Stoichiometry control of complex oxides by sequential pulsed-laser deposition from binary-oxide targets

    Energy Technology Data Exchange (ETDEWEB)

    Herklotz, A. [ORNL, Materials Science and Technology Division, Bethel Valley Road, Oak Ridge, Tennessee 37831-6056 (United States); Martin Luther University Halle-Wittenberg, Institute for Physics, Von-Danckelmann-Platz 3, 06120 Halle (Germany); Dörr, K. [Martin Luther University Halle-Wittenberg, Institute for Physics, Von-Danckelmann-Platz 3, 06120 Halle (Germany); Ward, T. Z.; Eres, G. [ORNL, Materials Science and Technology Division, Bethel Valley Road, Oak Ridge, Tennessee 37831-6056 (United States); Christen, H. M.; Biegalski, M. D. [ORNL, Center for Nanophase Materials Sciences, Bethel Valley Road, Oak Ridge, Tennessee 37831-6496 (United States)

    2015-03-30

    To have precise atomic layer control over interfaces, we examine the growth of complex oxides through the sequential deposition from binary targets by pulsed laser deposition. In situ reflection high-energy electron diffraction (RHEED) is used to control the growth and achieve films with excellent structural quality. The growth from binary oxide targets is fundamentally different from single target growth modes and shows more similarities to shuttered growth by molecular beam epitaxy. The RHEED intensity oscillations of non-stoichiometric growth are consistent with a model of island growth and accumulation of excess material on the surface that can be utilized to determine the correct stoichiometry for growth. Correct monolayer doses can be determined through an envelope frequency in the RHEED intensity oscillations. In order to demonstrate the ability of this growth technique to create complex heterostructures, the artificial n = 2 and 3 Sr{sub n+1}Ti{sub n}O{sub 3n+1} Ruddlesden-Popper phases are grown with good long-range order. This method enables the precise unit-cell level control over the structure of perovskite-type oxides, and thus the growth of complex materials with improved structural quality and electronic functionality.

  8. Nitrogen addition alters elemental stoichiometry within soil aggregates in a temperate steppe

    Science.gov (United States)

    Yin, Jinfei; Wang, Ruzhen; Liu, Heyong; Feng, Xue; Xu, Zhuwen; Jiang, Yong

    2016-11-01

    Ongoing increases in anthropogenic nitrogen (N) inputs have largely affected soil carbon (C) and nutrient cycling in most terrestrial ecosystems. Numerous studies have concerned the effects of elevated N inputs on soil dissolved organic carbon (DOC), dissolved inorganic N (DIN), available phosphorus (AP), exchangeable calcium (Ca) and magnesium (Mg), and available iron (Fe) and manganese (Mn). However, few have emphasized the stoichiometric traits of these soil parameters, especially within different soil aggregate fractions. In a semiarid grassland of Inner Mongolia, we studied the effect of N addition on the ratios of DOC : DIN, DOC : AP, DIN : AP, exchangeable Ca : Mg, available Fe : Mn within three soil aggregate classes of large macroaggregates (> 2000 µm), small macroaggregates (250-2000 µm), and microaggregates (soil aggregates. The soil DOC : AP ratio significantly decreased along with increasing N gradients within large macroaggregates and microaggregates. Nitrogen significantly decreased the ratio of exchangeable Ca : Mg within soil macroaggregates. The ratio of available Fe : Mn decreased with N addition within three soil aggregate classes. Alteration of elemental stoichiometry within soil fractions that are characterized by different nutrient retention capacity will influence the chemical composition of soil microorganisms and plant quality.

  9. Nitrate uptake across biomes and the influence of elemental stoichiometry: A new look at LINX II

    Science.gov (United States)

    Wymore, Adam S.; Coble, Ashley A.; Rodríguez-Cardona, Bianca; McDowell, William H.

    2016-08-01

    Considering recent increases in anthropogenic N loading, it is essential to identify the controls on N removal and retention in aquatic ecosystems because the fate of N has consequences for water quality in streams and downstream ecosystems. Biological uptake of nitrate (NO3-) is a major pathway by which N is removed from these ecosystems. Here we used data from the second Lotic Intersite Nitrogen eXperiment (LINX II) in a multivariate analysis to identify the primary drivers of variation in NO3- uptake velocity among biomes. Across 69 study watersheds in North America, dissolved organic carbon:NO3- ratios and photosynthetically active radiation were identified as the two most important predictor variables in explaining NO3- uptake velocity. However, within a specific biome the predictor variables of NO3- uptake velocity varied and included various physical, chemical, and biological attributes. Our analysis demonstrates the broad control of elemental stoichiometry on NO3- uptake velocity as well as the importance of biome-specific predictors. Understanding this spatial variation has important implications for biome-specific watershed management and the downstream export of NO3-, as well as for development of spatially explicit global models that describe N dynamics in streams and rivers.

  10. Assessing the oxygen stoichiometry during the sintering of (U, Pu)O2 fuel

    Science.gov (United States)

    Vaudez, Stéphane; Léchelle, Jacques; Berzati, Ségolène; Heintz, Jean-Marc

    2015-05-01

    Diffusion phenomena occurring in ceramics such as (U, Pu)O2 during sintering are affected by the oxygen content in the atmosphere. The latter sets the nature and the concentration of point defects which govern diffusion mechanisms in the bulk of the material. The oxygen partial pressure, pO2, of the sintering gas in equilibrium with mixed oxide (MOX) pellets needs to be precisely controlled; otherwise it may induce a large dispersion in the critical parameters for fuel manufacturing (Gauche, 2013; Matzke, 1987). It is crucial to understand the relation between the sintering atmosphere and the fuel throughout the thermal cycle. In this study, the oxygen potential of the sintering gas was monitored by measuring the oxygen partial pressure (pO2) at the outlet of a dilatometer by means of a zirconia probe. Coupling the thermal cycle with an outlet gas pO2 measurement makes it possible to identify different redox phenomena. Variations in the oxygen stoichiometry can be determined during the sintering of (U, Pu)O2, as well as can its final O/M. Our results make it possible to recommend a sintering atmosphere and sintering thermal cycle in order to obtain an O/M ratio that is as close as possible to the target value.

  11. Assessment of the stoichiometry and efficiency of CO2 fixation coupled to reduced sulfur oxidation

    Directory of Open Access Journals (Sweden)

    Judith M Klatt

    2015-05-01

    Full Text Available Chemolithoautotrophic sulfur oxidizing bacteria (SOB couple the oxidation of reduced sulfur compounds to the production of biomass. Their role in the cycling of carbon, sulfur, oxygen and nitrogen is, however, difficult to quantify due to the complexity of sulfur oxidation pathways. We describe a generic theoretical framework for linking the stoichiometry and energy conservation efficiency of autotrophic sulfur oxidation while accounting for the partitioning of the reduced sulfur pool between the energy generating and energy conserving steps as well as between the main possible products (sulfate versus elemental sulfur. Using this framework, we show that the energy conservation efficiency varies widely among SOB with no apparent relationship to their phylogeny. Aerobic SOB equipped with reverse dissimilatory sulfite reductase tend to have higher efficiency than those relying on the complete Sox pathway, whereas for anaerobic SOB the presence of membrane-bound, as opposed to periplasmic, nitrate reductase systems appears to be linked to higher efficiency. We employ the framework to also show how limited rate measurements can be used to estimate the primary productivity of SOB without the knowledge of the sulfate-to-elemental-sulfur production ratio. Finally, we discuss how the framework can help researchers gain new insights into the activity of SOB and their niches.

  12. Ecological stoichiometry quantitatively predicts responses of tadpoles to a food quality gradient.

    Science.gov (United States)

    Stephens, Jeffrey P; Berven, Keith A; Tiegs, Scott D; Raffel, Thomas R

    2015-08-01

    Ecological stoichiometry (ES) uses elemental ratios and mass balance to explain organismal growth, an important parameter in ecological systems. In this study, we tested quantitative predictions of the ES "minimal model" for the growth rates of two tadpole species (wood frogs, Lithobates sylvaticus and American toads, Anaxyrus americanus), by manipulating light and the quality of a leaf litter mixture in a seminatural mesocosm experiment. We predicted that wood frogs, which consume leaf litter as a resource, would respond more strongly to leaf litter quality than toads, which forage on periphyton and algae. The ES minimal model, parameterized from literature values, provided strikingly accurate quantitative predictions of nonlinear wood frog growth patterns across gradients of leaf litter quality, both in this experiment and when applied to previously published data on wood frog growth responses to various leaf litter species. In contrast, toad growth was best explained by the biomass of periphyton, which was driven primarily by light availability and only indirectly influenced by litter-derived soluble polyphenols. This study demonstrates the power of ES to predict organism growth rates, and highlights potential applications of this theory to predicting population- and community-level responses to changing forest environments.

  13. Modeling the effect of substrate stoichiometry on microbial carbon use efficiency and soil C cycling

    Science.gov (United States)

    Abramoff, R. Z.; Tang, J.; Georgiou, K.; Brodie, E.; Torn, M. S.; Riley, W. J.

    2015-12-01

    Microorganisms degrade soil organic matter (SOM) and apportion newly acquired substrates into enzyme production, biomass growth, and respiration. The fraction of acquired substrate that is released into the atmosphere as heterotrophic respiration is determined by the microbial carbon use efficiency (CUE), commonly defined as the fraction of carbon uptake that is allocated to microbial growth and enzyme production. Despite recent demonstrations that changes in CUE can greatly affect predictions of global soil C stocks, most models do not incorporate process-level representation of CUE or how it varies with substrate stoichiometry. Here we introduce coupled C and N cycling into a prognostic CUE model that uses the dynamic energy budget theory to predict CUE at each time step. We solve this model over a range of substrate C:N to simulate the effects of N addition on CUE, and test the model against previously published measurements of CUE after nutrient enrichment with a range of substrates. We find that CUE declines with microbial N limitation due to C overflow and acquisition strategies that favor N immobilization. We also demonstrate that including an intracellular reserve pool in the model alleviates decreases in CUE by allowing excess C to be stored during periods of N limitation. Consistent with previous studies, we find that predictions of soil C stocks are highly sensitive to CUE. Furthermore, we show that interactive effects between substrate inputs and temperature result in a wide range of possible CUE values under global change scenarios.

  14. Evidence for the formation of a covalent thiosulfinate intermediate with peroxiredoxin in the catalytic mechanism of sulfiredoxin.

    Science.gov (United States)

    Roussel, Xavier; Béchade, Guillaume; Kriznik, Alexandre; Van Dorsselaer, Alain; Sanglier-Cianferani, Sarah; Branlant, Guy; Rahuel-Clermont, Sophie

    2008-08-15

    The typical 2-Cys peroxiredoxins are thiol-peroxidases involved in the physiology of hydrogen peroxide not only as a toxic but also as a signaling molecule. Coordination of these functions depends on the sulfinylation of the catalytic Cys, a modification reversed by ATP-dependent sulfiredoxin, which specifically reduces the sulfinic acid group of overoxidized 2-Cys peroxiredoxins into a sulfenic acid. Sulfiredoxin was originally proposed to operate by covalent catalysis, with formation of a peroxiredoxin-sulfiredoxin intermediate linked by a thiosulfinate bond between the catalytic Cys of both partners, a hypothesis rejected by a study of the human enzyme. To settle the argument, we investigated the catalytic mechanism of Saccharomyces cerevisiae sulfiredoxin, by the characterization of the nature and kinetics of formation of the protein species formed between sulfiredoxin and its substrate in the presence of ATP, using mutants of the non-essential Cys residues of both proteins. We observed the formation of a dithiothreitol-reducible peroxiredoxin-sulfiredoxin species using SDS-PAGE and Western blot analysis, and its mass was shown to correspond to a thiosulfinate complex by high resolution mass spectrometry coupled to liquid chromatography. We next measured indirectly and directly a rate constant of formation of the thiosulfinate species of approximately 2 min(-1), for both wild-type and mutant sulfiredoxins, at least equal to the steady-state rate constant of the reaction, with a stoichiometry of 1:1 relative to peroxiredoxin. Taken altogether, our results strongly argue in favor of the formation of a covalent thiosulfinate peroxiredoxin-sulfiredoxin species as an intermediate on the catalytic pathway.

  15. Determination of binding constants and stoichiometries of short-range, hydrogen-bonding solvation by use of a proton-transfer indicator reaction

    Science.gov (United States)

    Schullery, Stephen E.; Wojdyla, Stephen M.; Ostroski, Robert A.; Scott, Ronald M.

    1997-10-01

    A recent method for determination of stoichiometries and binding constants for short-range, hydrogen bonding solvation is reviewed and new results are presented. The method exploits the sensitivity of a proton-transfer equilibrium, KPT to changes in solvent composition. Solvation numbers and binding constants for primary and secondary stages of solvation of an aminephenol proton-transfer adduct and the phenol and amine are determined as adjustable parameters when model isotherms are fitted to KPT versus [ S] data, where [ S] is the concentration of a hydrogen-bonding minor component of a mixed solvent, Results for most of the twenty-three aprotic solvents investigated are modeled by bifurcation-type hydrogen bonding of two or more electron pairs to a single polar hydrogen. Results for the seven protic solvents studied, including new data for ethanol, 2-choloroethanol, and 2,2-dichloroethanol, are modeled by two, or possibly three, successive stages of solvation, assumed to involve hydrogen-bonded chains. Preliminary results indicate that solvation by water is amenable to this analysis.

  16. Nucleotide sequence, DNA damage location and protein stoichiometry influence base excision repair outcome at CAG/CTG repeats

    Science.gov (United States)

    Goula, Agathi-Vasiliki; Pearson, Christopher E.; Della Maria, Julie; Trottier, Yvon; Tomkinson, Alan E.; Wilson, David M.; Merienne, Karine

    2012-01-01

    Expansion of CAG/CTG repeats is the underlying cause of >fourteen genetic disorders, including Huntington’s disease (HD) and myotonic dystrophy. The mutational process is ongoing, with increases in repeat size enhancing the toxicity of the expansion in specific tissues. In many repeat diseases the repeats exhibit high instability in the striatum, whereas instability is minimal in the cerebellum. We provide molecular insights as to how base excision repair (BER) protein stoichiometry may contribute to the tissue-selective instability of CAG/CTG repeats by using specific repair assays. Oligonucleotide substrates with an abasic site were mixed with either reconstituted BER protein stoichiometries mimicking the levels present in HD mouse striatum or cerebellum, or with protein extracts prepared from HD mouse striatum or cerebellum. In both cases, repair efficiency at CAG/CTG repeats and at control DNA sequences was markedly reduced under the striatal conditions, likely due to the lower level of APE1, FEN1 and LIG1. Damage located towards the 5’ end of the repeat tract was poorly repaired accumulating incompletely processed intermediates as compared to an AP lesion in the centre or at the 3’ end of the repeats or within a control sequences. Moreover, repair of lesions at the 5’ end of CAG or CTG repeats involved multinucleotide synthesis, particularly under the cerebellar stoichiometry, suggesting that long-patch BER processes lesions at sequences susceptible to hairpin formation. Our results show that BER stoichiometry, nucleotide sequence and DNA damage position modulate repair outcome, and suggest that a suboptimal LP-BER activity promotes CAG/CTG repeat instability. PMID:22497302

  17. Stoichiometry and Life-History Interact to Determine the Magnitude of Cross-Ecosystem Element and Biomass Fluxes.

    Science.gov (United States)

    Luhring, Thomas M; DeLong, John P; Semlitsch, Raymond D

    2017-01-01

    Ecosystems are linked through the transfer of materials and energy. Studies examining material fluxes across habitat boundaries frequently quantify unidirectional flows of nutrients and energy. However, material fluxes can be multidirectional, and we lack a conceptual framework to describe how their quantity and stoichiometry influence the net transfer of individual elements between ecosystems. Here we develop a zero net transfer isocline (ZNTI) framework that integrates the relative mass and stoichiometry of fluxes into and out of an ecosystem. We then use case studies with amphibians and salmon to elucidate how life history, ontogenetic shifts in stoichiometry, and trophic interactions shape relative fluxes of nutrients between aquatic and terrestrial ecosystems. Because they increase in both size and Ca content from ova to metamorphs, amphibian life histories strongly bias them toward net Ca export into the terrestrial environment. Because amphibian biomass, C, P, and Ca ZNTIs do not overlap, there is no value of survivorship where the net flux of biomass, C, P, and Ca are simultaneously balanced between terrestrial and aquatic habitats. The degree of iteroparity and semelparity in salmon strongly affects both the magnitude of net biomass and P flux between riverine and marine environments. While the net direction of biomass flux generally remains strongly biased toward import into the riverine system, net P flux can reach net export into the marine environment because of increasing adult breeding survival leading to reduced mass and %P of what they deposit in rivers (e.g., ova vs. whole carcasses). These examples highlight how ontogenetic shifts in body size and stoichiometry result in asymmetric fluxes of elements and biomass that can lead to simultaneous net imports and exports of different elements within the same system. Furthermore, they demonstrate how changes in life-history characteristics and stage-specific survivorship can lead to changes in net

  18. Interactions between growth-dependent changes in cell size, nutrient supply and cellular elemental stoichiometry of marine Synechococcus.

    Science.gov (United States)

    Garcia, Nathan S; Bonachela, Juan A; Martiny, Adam C

    2016-11-01

    The factors that control elemental ratios within phytoplankton, like carbon:nitrogen:phosphorus (C:N:P), are key to biogeochemical cycles. Previous studies have identified relationships between nutrient-limited growth and elemental ratios in large eukaryotes, but little is known about these interactions in small marine phytoplankton like the globally important Cyanobacteria. To improve our understanding of these interactions in picophytoplankton, we asked how cellular elemental stoichiometry varies as a function of steady-state, N- and P-limited growth in laboratory chemostat cultures of Synechococcus WH8102. By combining empirical data and theoretical modeling, we identified a previously unrecognized factor (growth-dependent variability in cell size) that controls the relationship between nutrient-limited growth and cellular elemental stoichiometry. To predict the cellular elemental stoichiometry of phytoplankton, previous theoretical models rely on the traditional Droop model, which purports that the acquisition of a single limiting nutrient suffices to explain the relationship between a cellular nutrient quota and growth rate. Our study, however, indicates that growth-dependent changes in cell size have an important role in regulating cell nutrient quotas. This key ingredient, along with nutrient-uptake protein regulation, enables our model to predict the cellular elemental stoichiometry of Synechococcus across a range of nutrient-limited conditions. Our analysis also adds to the growth rate hypothesis, suggesting that P-rich biomolecules other than nucleic acids are important drivers of stoichiometric variability in Synechococcus. Lastly, by comparing our data with field observations, our study has important ecological relevance as it provides a framework for understanding and predicting elemental ratios in ocean regions where small phytoplankton like Synechococcus dominates.

  19. Metaproteome analysis of the microbial community during leaf litter decomposition - the impact of stoichiometry and temperature perturbations

    Science.gov (United States)

    Keiblinger, K. M.; Schneider, T.; Leitner, S.; Hämmerle, I.; Riedel, K.; Zechmeister-Boltenstern, S.

    2012-04-01

    Leaf litter decomposition is the breakdown of dead plant material, a terrestrial ecosystem process of paramount importance. Nutrients released during decomposition play a key role for microbial growth and plant productivity. These processes are controlled by abiotic factors, such as climate, and by biotic factors, such as litter nutrient concentration and stoichiometry (carbon:nutrient ratio) and activity of soil organisms. Future climate change scenarios predict temperature perturbations, therefore following changes of microbial community composition and possible feedbacks on ecosystem processes are of key interest; especially as our knowledge about the microbial regulation of these processes is still scarce. Our aim was to elucidate how temperature perturbations and leaf litter stoichiometry affect the composition of the microbial decomposer community. To this end a terrestrial microcosm experiment using beech (Fagus sylvatica) litter with different stoichiometry was conducted. In a semi-quantitative metaproteomics approach (1D-SDS PAGE combined with liquid chromatography and tandem mass spectrometry; unique spectral counting) we used the intrinsic metabolic function of proteins to relate specific microbial activities to their phylogenetic origin in multispecies communities. Decomposer communities varied on litter with different stoichiometry so that microbial decomposers (fungi and bacteria) were favoured in litter with narrow C:nutrient ratios. The fungal community was dominated by Ascomycota (Eurotiomycetes, Sordariomycetes) and Basidiomycota (Agaricomycetes) and the bacterial community was dominated by Proteobacteria, Actinobacteria and Firmicutes. The extracellular enzymes we detected belonged mainly to classes of xylanases, pectinases, cellulases and proteases and were almost exclusively of fungal origin (particularly Ascomycota). Temperature stress (heat and frost) evoked strong changes in community composition, enzyme activities, dissolved organic

  20. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.

    2015-01-01

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  1. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...... of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social...... work with new possibilities of development of the work, but also suggestions for development of the concept of catalytic processes....

  2. Catalytic converters as a source of platinum

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2011-10-01

    Full Text Available The increase of Platinum Group Metals demand in automotive industry is connected with growing amount of cars equipped with the catalytic converters. The paper presents the review of available technologies during recycling process. The possibility of removing platinum from the used catalytic converters applying pyrometallurgical and hyrdometallurgical methods were also investigated. Metals such as Cu, Pb, Ca, Mg, Cd were used in the pyrometallurgical research (catalytic converter was melted with Cu, Pb and Ca or Mg and Cd vapours were blown through the whole carrier. In hydrometallurgical research catalytic converters was dissolved in aqua regia. Analysis of Pt contents in the carrier before and after the process was performed by means of atomic absorption spectroscopy. Obtained result were discussed.

  3. A Comparative Discussion of the Catalytic Activity and CO2-Selectivity of Cu-Zr and Pd-Zr (Intermetallic Compounds in Methanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Norbert Köpfle

    2017-02-01

    Full Text Available The activation and catalytic performance of two representative Zr-containing intermetallic systems, namely Cu-Zr and Pd-Zr, have been comparatively studied operando using methanol steam reforming (MSR as test reaction. Using an inverse surface science and bulk model catalyst approach, we monitored the transition of the initial metal/intermetallic compound structures into the eventual active and CO2-selective states upon contact to the methanol steam reforming mixture. For Cu-Zr, selected nominal stoichiometries ranging from Cu:Zr = 9:2 over 2:1 to 1:2 have been prepared by mixing the respective amounts of metallic Cu and Zr to yield different Cu-Zr bulk phases as initial catalyst structures. In addition, the methanol steam reforming performance of two Pd-Zr systems, that is, a bulk system with a nominal Pd:Zr = 2:1 stoichiometry and an inverse model system consisting of CVD-grown ZrOxHy layers on a polycrystalline Pd foil, has been comparatively assessed. While the CO2-selectivity and the overall catalytic performance of the Cu-Zr system is promising due to operando formation of a catalytically beneficial Cu-ZrO2 interface, the case for Pd-Zr is different. For both Pd-Zr systems, the low-temperature coking tendency, the high water-activation temperature and the CO2-selectivity spoiling inverse WGS reaction limit the use of the Pd-Zr systems for selective MSR applications, although alloying of Pd with Zr opens water activation channels to increase the CO2 selectivity.

  4. Influence of oxygen non-stoichiometry on physical properties of NdSr2Mn2O7±δ

    Institute of Scientific and Technical Information of China (English)

    A.M. Yankin; A.V. Fetisov; O.M. Fedorova; S.A. Uporov; V.Ya. Mitrofanov

    2015-01-01

    NdSr2Mn2O7+δ compounds were synthesized by ceramic method under three different cooling conditions. The NdSr2Mn2O7+δ samples were characterized by powder X-ray diffraction (XRD). Oxygen non-stoichiometry data for the studied pow-ders were determined by using gravimetric and X-ray photoelectron spectroscopy (XPS) methods. The correlation of cooling method and oxygen as non-stoichiometry was established. The electroconductivity in samples was studied by using four-point probe method, and the strong correlation with non-stoichiometry was found out. Magnetization measurements were carried out. It was found that the magnetic and transport properties of the samples were also influenced by oxygen non-stoichiometry. The evolution of the magnetic properties could be explained by the formation of magnetic clusters in the vicinity of oxygen vacancies (OV) and strong competition between the superexchange and double exchange interactions.

  5. Changes in Stoichiometry, Cellular RNA, and Alkaline Phosphatase Activity of Chlamydomonas in Response to Temperature and Nutrients.

    Science.gov (United States)

    Hessen, Dag O; Hafslund, Ola T; Andersen, Tom; Broch, Catharina; Shala, Nita K; Wojewodzic, Marcin W

    2017-01-01

    Phytoplankton may respond both to elevated temperatures and reduced nutrients by changing their cellular stoichiometry and cell sizes. Since increased temperatures often cause increased thermal stratification and reduced vertical flux of nutrients into the mixed zone, it is difficult to disentangle these drivers in nature. In this study, we used a factorial design with high and low levels of phosphorus (P) and high and low temperature to assess responses in cellular stoichiometry, levels of RNA, and alkaline phosphatase activity (APA) in the chlorophyte Chlamydomonas reinhardtii. Growth rate, C:P, C:N, N:P, RNA, and APA all responded primarily to P treatment, but except for N:P and APA, also temperature contributed significantly. For RNA, the contribution from temperature was particularly strong with higher cellular levels of RNA at low temperatures, suggesting a compensatory allocation to ribosomes to maintain protein synthesis and growth. These experiments suggest that although P-limitation is the major determinant of growth rate and cellular stoichiometry, there are pronounced effects of temperature also via interaction with P. At the ecosystem level, nutrients and temperature will thus interact, but temperatures would likely exert a stronger impact on these phytoplankton traits indirectly via its force on stratification regimes and vertical nutrient fluxes.

  6. Concise Whole-Cell Modeling of BKCa-CaV Activity Controlled by Local Coupling and Stoichiometry.

    Science.gov (United States)

    Montefusco, Francesco; Tagliavini, Alessia; Ferrante, Marco; Pedersen, Morten Gram

    2017-06-06

    Large-conductance Ca(2+)-dependent K(+) (BKCa) channels are important regulators of electrical activity. These channels colocalize and form ion channel complexes with voltage-dependent Ca(2+) (CaV) channels. Recent stochastic simulations of the BKCa-CaV complex with 1:1 stoichiometry have given important insight into the local control of BKCa channels by fluctuating nanodomains of Ca(2+). However, such Monte Carlo simulations are computationally expensive, and are therefore not suitable for large-scale simulations of cellular electrical activity. In this work we extend the stochastic model to more realistic BKCa-CaV complexes with 1:n stoichiometry, and analyze the single-complex model with Markov chain theory. From the description of a single BKCa-CaV complex, using arguments based on timescale analysis, we derive a concise model of whole-cell BKCa currents, which can readily be analyzed and inserted into models of cellular electrical activity. We illustrate the usefulness of our results by inserting our BKCa description into previously published whole-cell models, and perform simulations of electrical activity in various cell types, which show that BKCa-CaV stoichiometry can affect whole-cell behavior substantially. Our work provides a simple formulation for the whole-cell BKCa current that respects local interactions in BKCa-CaV complexes, and indicates how local-global coupling of ion channels may affect cell behavior. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  7. Discovery of a new method for potent drug development using power function of stoichiometry ofhomomeric biocomplexes or biological nanomotors

    Science.gov (United States)

    Pi, Fengmei; Vieweger, Mario; Zhao, Zhengyi; Wang, Shaoying; Guo, Peixuan

    2015-01-01

    Introduction Multidrug resistance and the appearance of incurable diseases inspire the quest for potent therapeutics. Areas Covered We review a new methodology in designing potent drugs by targeting multi-subunit homomeric biological motors, machines, or complexes with Z>1 and K=1, where Z is the stoichiometry of the target, and K is the number of drugged subunits required to block the function of the complex. The condition is similar to a series, electrical circuit of Christmas decorations; failure of one light bulb causes the entire lighting system to lose power. In most multisubunit, homomeric biological systems, a sequential coordination or cooperative action mechanism is utilized, thus K equals 1. Drug inhibition depends on the ratio of drugged to nondrugged complexes. When K=1, and Z>1, the inhibition effect follows a power law with respect to Z, leading to enhanced drug potency. The hypothesis that the potency of drug inhibition depends on the stoichiometry of the targeted biological complexes was recently quantified by Yang-Hui's Triangle (or binomial distribution), and proved using a highly sensitive in vitro phi29 viral DNA packaging system. Examples of targeting homomeric bio-complexes with high stoichiometry for potent drug discovery are discussed. Expert Opinion Biomotors with multiple subunits are widespread in viruses, bacteria, and cells, making this approach generally applicable in the development of inhibition drugs with high efficiency. PMID:26307193

  8. The c-ring stoichiometry of ATP synthase is adapted to cell physiological requirements of alkaliphilic Bacillus pseudofirmus OF4

    Science.gov (United States)

    Preiss, Laura; Klyszejko, Adriana L.; Hicks, David B.; Liu, Jun; Fackelmayer, Oliver J.; Yildiz, Özkan; Krulwich, Terry A.; Meier, Thomas

    2013-01-01

    The c-rings of ATP synthases consist of individual c-subunits, all of which harbor a conserved motif of repetitive glycine residues (GxGxGxG) important for tight transmembrane α-helix packing. The c-ring stoichiometry determines the number of ions transferred during enzyme operation and has a direct impact on the ion-to-ATP ratio, a cornerstone parameter of cell bioenergetics. In the extreme alkaliphile Bacillus pseudofirmus OF4, the glycine motif is replaced by AxAxAxA. We performed a structural study on two mutants with alanine-to-glycine changes using atomic force microscopy and X-ray crystallography, and found that mutants form smaller c12 rings compared with the WT c13. The molar growth yields of B. pseudofirmus OF4 cells on malate further revealed that the c12 mutants have a considerably reduced capacity to grow on limiting malate at high pH. Our results demonstrate that the mutant ATP synthases with either c12 or c13 can support ATP synthesis, and also underscore the critical importance of an alanine motif with c13 ring stoichiometry for optimal growth at pH >10. The data indicate a direct connection between the precisely adapted ATP synthase c-ring stoichiometry and its ion-to-ATP ratio on cell physiology, and also demonstrate the bioenergetic challenges and evolutionary adaptation strategies of extremophiles. PMID:23613590

  9. Changes in Stoichiometry, Cellular RNA, and Alkaline Phosphatase Activity of Chlamydomonas in Response to Temperature and Nutrients

    Science.gov (United States)

    Hessen, Dag O.; Hafslund, Ola T.; Andersen, Tom; Broch, Catharina; Shala, Nita K.; Wojewodzic, Marcin W.

    2017-01-01

    Phytoplankton may respond both to elevated temperatures and reduced nutrients by changing their cellular stoichiometry and cell sizes. Since increased temperatures often cause increased thermal stratification and reduced vertical flux of nutrients into the mixed zone, it is difficult to disentangle these drivers in nature. In this study, we used a factorial design with high and low levels of phosphorus (P) and high and low temperature to assess responses in cellular stoichiometry, levels of RNA, and alkaline phosphatase activity (APA) in the chlorophyte Chlamydomonas reinhardtii. Growth rate, C:P, C:N, N:P, RNA, and APA all responded primarily to P treatment, but except for N:P and APA, also temperature contributed significantly. For RNA, the contribution from temperature was particularly strong with higher cellular levels of RNA at low temperatures, suggesting a compensatory allocation to ribosomes to maintain protein synthesis and growth. These experiments suggest that although P-limitation is the major determinant of growth rate and cellular stoichiometry, there are pronounced effects of temperature also via interaction with P. At the ecosystem level, nutrients and temperature will thus interact, but temperatures would likely exert a stronger impact on these phytoplankton traits indirectly via its force on stratification regimes and vertical nutrient fluxes. PMID:28167934

  10. One-step electrodeposition for targeted off-stoichiometry Cu2ZnSnS4 thin films

    Science.gov (United States)

    Tang, Aiyue; Liu, Jingjun; Ji, Jing; Dou, Meiling; Li, Zhilin; Wang, Feng

    2016-10-01

    Cu2ZnSnS4 (CZTS) is a promising quaternary compound suitable for absorber layer of thin film solar cells. The precise control of the atomic ratio of the films are difficult for the electrodeposition of CZTS thin films. Here, we reported targeted off-stoichiometry CZTS thin films synthesized by one-step electrodeposition. We obtained Cu-poor thin films and the chemical composition of the as-deposited thin films were tailored to targeted off-stoichiometry. Based on the different kinetics of the metallic ion reduction, we successfully controlled the chemical composition by varying deposition time. After annealing, pure kesterite structure was obtained and the electronic interactions between Cu and Sn was verified in the films, which contributes to high carrier mobility. The band gap of the thin films were in the range of 1.43-1.52 eV, which is suitable for absorber layers of thin film solar cells. The carrier mobility reached a value of 28.20 cm2/V s with carrier concentration of 2.09 × 1018 cm-3 when Cu/(Zn + Sn) and Zn/Sn ratios were 0.97 and 1.13, respectively. This work paves a way for synthesizing targeted off-stoichiometry compounds by controlling kinetics and reaction time in large scale.

  11. Discovery of a new method for potent drug development using power function of stoichiometry of homomeric biocomplexes or biological nanomotors.

    Science.gov (United States)

    Pi, Fengmei; Vieweger, Mario; Zhao, Zhengyi; Wang, Shaoying; Guo, Peixuan

    2016-01-01

    Multidrug resistance and the appearance of incurable diseases inspire the quest for potent therapeutics. We review a new methodology in designing potent drugs by targeting multi-subunit homomeric biological motors, machines or complexes with Z > 1 and K = 1, where Z is the stoichiometry of the target, and K is the number of drugged subunits required to block the function of the complex. The condition is similar to a series electrical circuit of Christmas decorations: failure of one light bulb causes the entire lighting system to lose power. In most multi-subunit, homomeric biological systems, a sequential coordination or cooperative action mechanism is utilized, thus K equals 1. Drug inhibition depends on the ratio of drugged to non-drugged complexes. When K = 1, and Z > 1, the inhibition effect follows a power law with respect to Z, leading to enhanced drug potency. The hypothesis that the potency of drug inhibition depends on the stoichiometry of the targeted biological complexes was recently quantified by Yang-Hui's Triangle (or binomial distribution), and proved using a highly sensitive in vitro phi29 viral DNA packaging system. Examples of targeting homomeric bio-complexes with high stoichiometry for potent drug discovery are discussed. Biomotors with multiple subunits are widespread in viruses, bacteria and cells, making this approach generally applicable in the development of inhibition drugs with high efficiency.

  12. Stoichiometry, Length, and Wall Thickness Optimization of TiO2 Nanotube Array for Efficient Alcohol Sensing.

    Science.gov (United States)

    Hazra, A; Bhowmik, B; Dutta, K; Chattopadhyay, P P; Bhattacharyya, P

    2015-05-13

    The present study concerns development of an efficient alcohol sensor by controlling the stoichiometry, length, and wall thickness of electrochemically grown TiO2 nanotube array for its use as the sensing layer. Judicious variation of H2O content (0, 2, 10 and 100% by volume) in the mixed electrolyte comprising ethylene glycol and NH4F resulted into the desired variation of stoichiometry. The sensor study was performed within the temperature range of 27 to 250 °C for detecting the alcohols in the concentration range of 10-1000 ppm. The nanotubes grown with the electrolyte containing 2 vol % H2O offered the maximum response magnitude. For this stoichiometry, variation of corresponding length (1.25-2.4 μm) and wall thickness (19.8-9 nm) of the nanotubes was achieved by varying the anodization time (4-16 h) and temperatures (42-87 °C), respectively. While the variation of length influenced the sensing parameters insignificantly, the best response magnitude was achieved for ∼13 nm wall thickness. The underlying sensing mechanism was correlated with the experimental findings on the basis of structural parameters of the nanotubes.

  13. Growth control of oxygen stoichiometry in homoepitaxial SrTiO3 films by pulsed laser epitaxy in high vacuum.

    Science.gov (United States)

    Lee, Ho Nyung; Ambrose Seo, Sung S; Choi, Woo Seok; Rouleau, Christopher M

    2016-01-29

    In many transition metal oxides, oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that, through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects even in high vacuum. We use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well.

  14. Measuring Conceptual Change on Stoichiometry Using Mental Models and IllStructured Problems In a Flipped Classroom Environment

    Directory of Open Access Journals (Sweden)

    Norrie E. Gayeta

    2017-05-01

    Full Text Available This study aimed to measure conceptual change on stoichiometry using mental models and ill-structured problems in flipped classroom environment. This study examined the level of conceptual understanding of students on stoichiometry before and after exposure to flipped and traditional lecture method. It also covered the type of conceptual change, and students’ description in flipped classroom environment. Qualitative and quantitative research methods were used in the study. Respondents were two sections of third year Bachelor of Secondary Education, Biological Science. Frequency, percentage, ranking, mean, standard deviation, Hake factor test, and t-test were the statistical tools applied to answer specific questions. Results showed profound increase towards conceptual change representing a shift from intuitive understanding to correct incomplete understanding level. Thus, change for the better, in theoretical type was determined from pretest to posttest of students exposed to flipped and traditional instruction. Results also indicated that there is no significant difference on students’ conceptual change on stoichiometry exposed to flipped and traditional lecture method. Furthermore, students strongly agreed that flipped classroom instruction helped them develop positive attitude towards chemistry and appropriate for learning college chemistry.

  15. MOBILE COMPLEX FOR CATALYTIC THERMAL WASTE TREATMENT

    Directory of Open Access Journals (Sweden)

    Vedi V.E.

    2012-12-01

    Full Text Available The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  16. Chemical and catalytic properties of elemental carbon

    Energy Technology Data Exchange (ETDEWEB)

    Chang, S.G.; Brodzinsky, R.; Gundel, L.A.; Novakov, T.

    1980-10-01

    Elemental carbon particles resulting from incomplete combustion of fossil fuel are one of the major constituents of airborne particulate matter. These particles are a chemically and catalytically active material and can be an effective carrier for other toxic air pollutants through their adsorptive capability. The chemical, adsorptive, and catalytic behaviors of carbon particles depend very much on their crystalline structure, surface composition, and electronic properties. This paper discusses these properties and examines their relevance to atmospheric chemistry.

  17. Catalytic Radical Domino Reactions in Organic Synthesis

    Science.gov (United States)

    Sebren, Leanne J.; Devery, James J.; Stephenson, Corey R.J.

    2014-01-01

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes. PMID:24587964

  18. Temperature Modulation of a Catalytic Gas Sensor

    OpenAIRE

    Eike Brauns; Eva Morsbach; Sebastian Kunz; Marcus Baeumer; Walter Lang

    2014-01-01

    The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additi...

  19. Disentangling evolutionary signals: conservation, specificity determining positions and coevolution. Implication for catalytic residue prediction

    DEFF Research Database (Denmark)

    Teppa, Elin; Wilkins, Angela D.; Nielsen, Morten

    2012-01-01

    to the prediction system. Conclusions: This work contributes to the understanding of the different signals of evolution and also shows that it is possible to improve the detection of catalytic residues by integrating structural and higher order sequence evolutionary information with sequence conservation....... predictive potential compared to others when it comes to, in particular, the identification of catalytic residues (CR) in proteins. Using a large set of enzymatic protein families and measures based on different evolutionary signals, we sought to break up the different components of the information content...

  20. The altitudinal patterns of leaf C∶N∶P stoichiometry are regulated by plant growth form, climate and soil on Changbai Mountain, China.

    Science.gov (United States)

    Zhao, Ning; He, Nianpeng; Wang, Qiufeng; Zhang, Xinyu; Wang, Ruili; Xu, Zhiwei; Yu, Guirui

    2014-01-01

    Understanding the geographic patterns and potential drivers of leaf stoichiometry is critical for modelling the nutrient fluxes of ecosystems and to predict the responses of ecosystems to global changes. This study aimed to explore the altitudinal patterns and potential drivers of leaf C∶N∶P stoichiometry. We measured the concentrations of leaf C, N and P in 175 plant species as well as soil nutrient concentrations along an altitudinal transect (500-2300 m) on the northern slope of Changbai Mountain, China to explore the response of leaf C∶N∶P stoichiometry to plant growth form (PGF), climate and soil. Leaf C, N, P and C∶N∶P ratios showed significant altitudinal trends. In general, leaf C and C∶N∶P ratios increased while leaf N and P decreased with elevation. Woody and herbaceous species showed different responses to altitudinal gradients. Trees had the largest variation in leaf C, C∶N and C∶P ratios, while herbs showed the largest variation in leaf N, P and N∶P ratio. PGF, climate and soil jointly regulated leaf stoichiometry, explaining 17.6% to 52.1% of the variation in the six leaf stoichiometric traits. PGF was more important in explaining leaf stoichiometry variation than soil and climate. Our findings will help to elucidate the altitudinal patterns of leaf stoichiometry and to model ecosystem nutrient cycling.