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Sample records for catalytic dynamic resolution

  1. Structural basis for catalytically restrictive dynamics of a high-energy enzyme state

    Science.gov (United States)

    Kovermann, Michael; Ådén, Jörgen; Grundström, Christin; Elisabeth Sauer-Eriksson, A.; Sauer, Uwe H.; Wolf-Watz, Magnus

    2015-07-01

    An emerging paradigm in enzymology is that transient high-energy structural states play crucial roles in enzymatic reaction cycles. Generally, these high-energy or `invisible' states cannot be studied directly at atomic resolution using existing structural and spectroscopic techniques owing to their low populations or short residence times. Here we report the direct NMR-based detection of the molecular topology and conformational dynamics of a catalytically indispensable high-energy state of an adenylate kinase variant. On the basis of matching energy barriers for conformational dynamics and catalytic turnover, it was found that the enzyme's catalytic activity is governed by its dynamic interconversion between the high-energy state and a ground state structure that was determined by X-ray crystallography. Our results show that it is possible to rationally tune enzymes' conformational dynamics and hence their catalytic power--a key aspect in rational design of enzymes catalysing novel reactions.

  2. Catalytic Kinetic Resolution of Saturated N-Heterocycles by Enantioselective Amidation with Chiral Hydroxamic Acids.

    Science.gov (United States)

    Kreituss, Imants; Bode, Jeffrey W

    2016-12-20

    The preparation of enantioenriched chiral compounds by kinetic resolution dates back to the laboratories of Louis Pasteur in the middle of the 19th century. Unlike asymmetric synthesis, this process can always deliver enantiopure material (ee > 99%) if the reactions are allowed to proceed to sufficient conversion and the selectivity of the process is not unity (s > 1). One of the most appealing and practical variants is acylative kinetic resolution, which affords easily separable reaction products, and several highly efficient enzymatic and small molecule catalysts are available. Unfortunately, this method is applicable to limited substrate classes such as alcohols and primary benzylamines. This Account focuses on our work in catalytic acylative kinetic resolution of saturated N-heterocycles, a class of molecules that has been notoriously difficult to access via asymmetric synthesis. We document the development of hydroxamic acids as suitable catalysts for enantioselective acylation of amines through relay catalysis. Alongside catalyst optimization and reaction development, we present mechanistic studies and theoretical calculation accounting for the origins of selectivity and revealing the concerted nature of many amide-bond forming reactions. Immobilization of the hydroxamic acid to form a polymer supported reagent allows simplification of the experimental setup, improvement in product purification, and extension of the substrate scope. The kinetic resolutions are operationally straight forward: reactions proceed at room temperature and open to air conditions, without generation of difficult-to-remove side products. This was utilized to achieve decagram scale resolution of antimalarial drug mefloquine to prepare more than 50 g of (+)-erythro-meflqouine (er > 99:1) from the racemate. The immobilized quasienantiomeric acyl hydroxamic acid reagents were also exploited for a rare practical implementation of parallel kinetic resolution that affords both enantiomers of

  3. Dynamic thermodynamic resolution: advantage by separation of equilibration and resolution.

    Science.gov (United States)

    Lee, Won Koo; Park, Yong Sun; Beak, Peter

    2009-02-17

    In the investigation of a chemical reaction, researchers typically survey variables such as time, temperature, and stoichiometry to optimize yields. This Account demonstrates how control of these variables, often in nontraditional ways, can provide significant improvements in enantiomeric ratios for asymmetric reactions. Dynamic thermodynamic resolution (DTR) offers a convenient method for the resolution of enantiomeric products in the course of a reaction. This process depends on an essential requirement: the equilibration of the penultimate diastereomers must be subject to external control. As a general case, the reaction of A(R), A(S) with B under the influence of the chiral species, L*, gives resolved products C(R) and C(S). In the first step of dynamic resolution under thermodynamic control, the enantiomeric reactants A(R) and A(S) and L* form the diastereomers A(R)/L* and A(S)/L*. The equilibrium between A(R) and A(S) can be rapid, slow, or not operative, and L* can represent a ligand, an auxiliary, or a crystallization process that provides a chiral environment. Second, the populations of the diastereomers are controlled, usually by thermal equilibration. Finally, the reaction of the diastereomers with a reagent B provides the enantiomeric products C(R) and C(S). The control of the diastereomeric equilibrium distinguishes DTR from other resolution techniques. By contrast, physical resolutions separate thermodynamically stable, nonequilibrating diastereomers, and dynamic kinetic resolutions utilize kinetic control for reactions of rapidly equilibrating diastereomers. The dynamic thermodynamic resolutions discussed in this Account illustrate cases of significantly improved enantioselectivities using this technique. Although many of the well-recognized cases come from organolithium chemistry, the principles are general, and we also present cases facilitated by other chemistries. This approach has been used to control enantioselectivities in a number of

  4. High-spatial-resolution mapping of catalytic reactions on single particles

    Science.gov (United States)

    Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; Bechtel, Hans A.; Martin, Michael C.; Toste, F. Dean; Gross, Elad

    2017-01-01

    The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles—which contain metal atoms with low coordination numbers—are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.

  5. Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution

    Science.gov (United States)

    Zhong, Jin-Hui; Jin, Xi; Meng, Lingyan; Wang, Xiang; Su, Hai-Sheng; Yang, Zhi-Lin; Williams, Christopher T.; Ren, Bin

    2016-11-01

    An atomic- and molecular-level understanding of heterogeneous catalysis is required to characterize the nature of active sites and improve the rational design of catalysts. Achieving this level of characterization requires techniques that can correlate catalytic performances to specific surface structures, so as to avoid averaging effects. Tip-enhanced Raman spectroscopy combines scanning probe microscopy with plasmon-enhanced Raman scattering and provides simultaneous topographical and chemical information at the nano/atomic scale from ambient to ultrahigh-vacuum and electrochemical environments. Therefore, it has been used to monitor catalytic reactions and is proposed to correlate the local structure and function of heterogeneous catalysts. Bimetallic catalysts, such as Pd-Au, show superior performance in various catalytic reactions, but it has remained challenging to correlate structure and reactivity because of their structural complexity. Here, we show that TERS can chemically and spatially probe the site-specific chemical (electronic and catalytic) and physical (plasmonic) properties of an atomically well-defined Pd(sub-monolayer)/Au(111) bimetallic model catalyst at 3 nm resolution in real space using phenyl isocyanide as a probe molecule (Fig. 1a). We observe a weakened N≡C bond and enhanced reactivity of phenyl isocyanide adsorbed at the Pd step edge compared with that at the Pd terrace. Density functional theory corroborates these observations by revealing a higher d-band electronic profile for the low-coordinated Pd step edge atoms. The 3 nm spatial resolution we demonstrate here is the result of an enhanced electric field and distinct electronic properties at the step edges.

  6. High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles**

    Science.gov (United States)

    Ristanović, Zoran; Kerssens, Marleen M; Kubarev, Alexey V; Hendriks, Frank C; Dedecker, Peter; Hofkens, Johan; Roeffaers, Maarten B J; Weckhuysen, Bert M

    2015-01-01

    Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50–150 μm-sized FCC spheres heavily influence their catalytic performance. Single-molecule fluorescence-based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super-resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub-micrometer zeolite ZSM-5 domains within real-life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM-5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity. PMID:25504139

  7. A Dynamic Supramolecular System Exhibiting Substrate Selectivity in the Catalytic Epoxidation of Olefins

    DEFF Research Database (Denmark)

    Jonsson, Stefan; Odille, Fabrice G. J.; Norrby, Per-Ola;

    2005-01-01

    A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction.......A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction....

  8. Resolution of structural heterogeneity in dynamic crystallography.

    Science.gov (United States)

    Ren, Zhong; Chan, Peter W Y; Moffat, Keith; Pai, Emil F; Royer, William E; Šrajer, Vukica; Yang, Xiaojing

    2013-06-01

    Dynamic behavior of proteins is critical to their function. X-ray crystallography, a powerful yet mostly static technique, faces inherent challenges in acquiring dynamic information despite decades of effort. Dynamic `structural changes' are often indirectly inferred from `structural differences' by comparing related static structures. In contrast, the direct observation of dynamic structural changes requires the initiation of a biochemical reaction or process in a crystal. Both the direct and the indirect approaches share a common challenge in analysis: how to interpret the structural heterogeneity intrinsic to all dynamic processes. This paper presents a real-space approach to this challenge, in which a suite of analytical methods and tools to identify and refine the mixed structural species present in multiple crystallographic data sets have been developed. These methods have been applied to representative scenarios in dynamic crystallography, and reveal structural information that is otherwise difficult to interpret or inaccessible using conventional methods.

  9. Dynamics of High-Resolution Networks

    DEFF Research Database (Denmark)

    Sekara, Vedran

    NETWORKS are everywhere. From the smallest confines of the cells within our bodies to the webs of social relations across the globe. Networks are not static, they constantly change, adapt, and evolve to suit new conditions. In order to understand the fundamental laws that govern networks we need...... the unprecedented amounts of information collected by mobile phones to gain detailed insight into the dynamics of social systems. This dissertation presents an unparalleled data collection campaign, collecting highly detailed traces for approximately 1000 people over the course of multiple years. The availability...

  10. Kinetic resolution and chemoenzymatic dynamic kinetic resolution of functionalized gamma-hydroxy amides.

    Science.gov (United States)

    Fransson, Ann-Britt L; Borén, Linnéa; Pàmies, Oscar; Bäckvall, Jan-E

    2005-04-01

    [reaction: see text] An efficient kinetic resolution of racemic gamma-hydroxy amides 1 was performed via Pseudomas cepacia lipase (PS-C)-catalyzed transesterification. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity (E values of up to >250). The combination of enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution. The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution yields the corresponding acetates in good yield and good to high enantioselectivity (ee's up to 98%). The synthetic utility of this procedure was illustrated by the practical synthesis of the versatile intermediate gamma-lactone (R)-5-methyltetrahydrofuran-2-one.

  11. Super-resolution optical microscopy of lipid plasma membrane dynamics.

    Science.gov (United States)

    Eggeling, Christian

    2015-01-01

    Plasma membrane dynamics are an important ruler of cellular activity, particularly through the interaction and diffusion dynamics of membrane-embedded proteins and lipids. FCS (fluorescence correlation spectroscopy) on an optical (confocal) microscope is a popular tool for investigating such dynamics. Unfortunately, its full applicability is constrained by the limited spatial resolution of a conventional optical microscope. The present chapter depicts the combination of optical super-resolution STED (stimulated emission depletion) microscopy with FCS, and why it is an important tool for investigating molecular membrane dynamics in living cells. Compared with conventional FCS, the STED-FCS approach demonstrates an improved possibility to distinguish free from anomalous molecular diffusion, and thus to give new insights into lipid-protein interactions and the traditional lipid 'raft' theory.

  12. Effects of FGFR2 kinase activation loop dynamics on catalytic activity.

    Science.gov (United States)

    Karp, Jerome M; Sparks, Samuel; Cowburn, David

    2017-02-01

    The structural mechanisms by which receptor tyrosine kinases (RTKs) regulate catalytic activity are diverse and often based on subtle changes in conformational dynamics. The regulatory mechanism of one such RTK, fibroblast growth factor receptor 2 (FGFR2) kinase, is still unknown, as the numerous crystal structures of the unphosphorylated and phosphorylated forms of the kinase domains show no apparent structural change that could explain how phosphorylation could enable catalytic activity. In this study, we use several enhanced sampling molecular dynamics (MD) methods to elucidate the structural changes to the kinase's activation loop that occur upon phosphorylation. We show that phosphorylation favors inward motion of Arg664, while simultaneously favoring outward motion of Leu665 and Pro666. The latter structural change enables the substrate to bind leading to its resultant phosphorylation. Inward motion of Arg664 allows it to interact with the γ-phosphate of ATP as well as the substrate tyrosine. We show that this stabilizes the tyrosine and primes it for the catalytic phosphotransfer, and it may lower the activation barrier of the phosphotransfer reaction. Our work demonstrates the value of including dynamic information gleaned from computer simulation in deciphering RTK regulatory function.

  13. Effects of FGFR2 kinase activation loop dynamics on catalytic activity

    Science.gov (United States)

    2017-01-01

    The structural mechanisms by which receptor tyrosine kinases (RTKs) regulate catalytic activity are diverse and often based on subtle changes in conformational dynamics. The regulatory mechanism of one such RTK, fibroblast growth factor receptor 2 (FGFR2) kinase, is still unknown, as the numerous crystal structures of the unphosphorylated and phosphorylated forms of the kinase domains show no apparent structural change that could explain how phosphorylation could enable catalytic activity. In this study, we use several enhanced sampling molecular dynamics (MD) methods to elucidate the structural changes to the kinase’s activation loop that occur upon phosphorylation. We show that phosphorylation favors inward motion of Arg664, while simultaneously favoring outward motion of Leu665 and Pro666. The latter structural change enables the substrate to bind leading to its resultant phosphorylation. Inward motion of Arg664 allows it to interact with the γ-phosphate of ATP as well as the substrate tyrosine. We show that this stabilizes the tyrosine and primes it for the catalytic phosphotransfer, and it may lower the activation barrier of the phosphotransfer reaction. Our work demonstrates the value of including dynamic information gleaned from computer simulation in deciphering RTK regulatory function. PMID:28151998

  14. Catalytic Features of the Botulinum Neurotoxin A Light Chain Revealed by High Resolution Structure of an Inhibitory Peptide Complex

    Energy Technology Data Exchange (ETDEWEB)

    Silvaggi,N.; Wilson, D.; Tzipori, S.; Allen, K.

    2008-01-01

    The Clostridium botulinum neurotoxin serotype A light chain (BoNT/A-LC) is a Zn(II)-dependent metalloprotease that blocks the release of acetylcholine at the neuromuscular junction by cleaving SNAP-25, one of the SNARE proteins required for exocytosis. Because of the potential for use of the toxin in bioterrorism and the increasingly widespread application of the toxin in the medical field, there is significant interest in the development of small-molecule inhibitors of the metalloprotease. Efforts to design such inhibitors have not benefited from knowledge of how peptides bind to the active site since the enzyme-peptide structures available previously either were not occupied in the vicinity of the catalytic Zn(II) ion or did not represent the product of SNAP-25 substrate cleavage. Herein we report the 1.4 Angstroms-resolution X-ray crystal structure of a complex between the BoNT/A-LC and the inhibitory peptide N-Ac-CRATKML, the first structure of the light chain with an inhibitory peptide bound at the catalytic Zn(II) ion. The peptide is bound with the Cys S? atom coordinating the metal ion. Surprisingly, the cysteine sulfur is oxidized to the sulfenic acid form. Given the unstable nature of this species in solution, is it likely that oxidation occurs on the enzyme. In addition to the peptide-bound structure, we report two structures of the unliganded light chain with and without the Zn(II) cofactor bound at 1.25 and 1.20 Angstroms resolution, respectively. The two structures are nearly identical, confirming that the Zn(II) ion plays a purely catalytic role. Additionally, the structure of the Zn(II)-bound uncomplexed enzyme allows identification of the catalytic water molecule and a second water molecule that occupies the same position as the peptidic oxygen in the tetrahedral intermediate. This observation suggests that the enzyme active site is prearranged to stabilize the tetrahedral intermediate of the protease reaction.

  15. Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process

    Institute of Scientific and Technical Information of China (English)

    胡永有; 徐巍华; 侯卫锋; 苏宏业; 褚健

    2005-01-01

    A first principles-based dynamic model for a continuous catalyst regeneration (CCR) platforming process, the UOP commercial naphtha catalytic reforming process, is developed in this paper. The lumping details of the naphtha feed and reaction scheme of the reaction model are given. The process model is composed of the reforming reaction model with catalyst deactivation, the furnace model and the separator model, which is capable of capturing the major dynamics that occurs in this process system. Dynamic simulations are performed based on Gear numerical algorithm and method of lines (MOL), a numerical technique dealing with partial differential equations (PDEs). The results of simulation are also presented. Dynamic responses caused by disturbances in the process system can be correctly predicted through simulations.

  16. Conserved water-mediated H-bonding dynamics of catalytic Asn 175 in plant thiol protease

    Indian Academy of Sciences (India)

    Tapas K Nandi; Hridoy R Bairagya; Bishnu P Mukhopadhyay; K Sekar; Dipankar Sukul; Asim K Bera

    2009-03-01

    The role of invariant water molecules in the activity of plant cysteine protease is ubiquitous in nature. On analysing the 11 different Protein DataBank (PDB) structures of plant thiol proteases, the two invariant water molecules W1 and W2 (W220 and W222 in the template 1PPN structure) were observed to form H-bonds with the Ob atom of Asn 175. Extensive energy minimization and molecular dynamics simulation studies up to 2 ns on all the PDB and solvated structures clearly revealed the involvement of the H-bonding association of the two water molecules in fixing the orientation of the asparagine residue of the catalytic triad. From this study, it is suggested that H-bonding of the water molecule at the W1 invariant site better stabilizes the Asn residue at the active site of the catalytic triad.

  17. High resolution, large dynamic range field map estimation

    Science.gov (United States)

    Dagher, Joseph; Reese, Timothy; Bilgin, Ali

    2013-01-01

    Purpose We present a theory and a corresponding method to compute high resolution field maps over a large dynamic range. Theory and Methods We derive a closed-form expression for the error in the field map value when computed from two echoes. We formulate an optimization problem to choose three echo times which result in a pair of maximally distinct error distributions. We use standard field mapping sequences at the prescribed echo times. We then design a corresponding estimation algorithm which takes advantage of the optimized echo times to disambiguate the field offset value. Results We validate our method using high resolution images of a phantom at 7T. The resulting field maps demonstrate robust mapping over both a large dynamic range, and in low SNR regions. We also present high resolution offset maps in vivo using both, GRE and MEGE sequences. Even though the proposed echo time spacings are larger than the well known phase aliasing cutoff, the resulting field maps exhibit a large dynamic range without the use of phase unwrapping or spatial regularization techniques. Conclusion We demonstrate a novel 3-echo field map estimation method which overcomes the traditional noise-dynamic range trade-off. PMID:23401245

  18. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  19. Cations and hydration in catalytic RNA: molecular dynamics of the hepatitis delta virus ribozyme.

    Science.gov (United States)

    Krasovska, Maryna V; Sefcikova, Jana; Réblová, Kamila; Schneider, Bohdan; Walter, Nils G; Sponer, Jirí

    2006-07-15

    The hepatitis delta virus (HDV) ribozyme is an RNA enzyme from the human pathogenic HDV. Cations play a crucial role in self-cleavage of the HDV ribozyme, by promoting both folding and chemistry. Experimental studies have revealed limited but intriguing details on the location and structural and catalytic functions of metal ions. Here, we analyze a total of approximately 200 ns of explicit-solvent molecular dynamics simulations to provide a complementary atomistic view of the binding of monovalent and divalent cations as well as water molecules to reaction precursor and product forms of the HDV ribozyme. Our simulations find that an Mg2+ cation binds stably, by both inner- and outer-sphere contacts, to the electronegative catalytic pocket of the reaction precursor, in a position to potentially support chemistry. In contrast, protonation of the catalytically involved C75 in the precursor or artificial placement of this Mg2+ into the product structure result in its swift expulsion from the active site. These findings are consistent with a concerted reaction mechanism in which C75 and hydrated Mg2+ act as general base and acid, respectively. Monovalent cations bind to the active site and elsewhere assisted by structurally bridging long-residency water molecules, but are generally delocalized.

  20. Molecular dynamics simulation and conformational analysis of some catalytically active peptides.

    Science.gov (United States)

    Honarparvar, Bahareh; Skelton, Adam A

    2015-04-01

    The design of stable and inexpensive artificial enzymes with potent catalytic activity is a growing field in peptide science. The first step in this design process is to understand the key factors that can affect the conformational preference of an enzyme and correlate them with its catalytic activity. In this work, molecular dynamics simulations in explicit water of two catalytically active peptides (peptide 1: Fmoc-Phe1-Phe2-His-CONH2; peptide 2: Fmoc-Phe1-Phe2-Arg-CONH2) were performed at temperatures of 300, 400, and 500 K. Conformational analysis of these peptides using Ramachandran plots identified the secondary structures of the amino acid residues involved (Phe1, Phe2, His, Arg) and confirmed their conformational flexibility in solution. Furthermore, Ramachandran maps revealed the intrinsic preference of the constituent residues of these compounds for a helical conformation. Long-range interaction distances and radius of gyration (R g) values obtained during 20 ns MD simulations confirmed their tendency to form folded conformations. Results showed a decrease in side-chain (Phe1, Phe2, His ring, and Arg) contacts as the temperature was raised from 300 to 400 K and then to 500 K. Finally, the radial distribution functions (RDF) of the water molecules around the nitrogen atoms in the catalytically active His and Arg residues of peptide 1 and peptide 2 revealed that the strongest water-peptide interaction occurred with the arginine nitrogen atoms in peptide 2. Our results highlight differences in the secondary structures of the two peptides that can be explained by the different arrangement of water molecules around the nitrogen atoms of Arg in peptide 2 as compared to the arrangement of water molecules around the nitrogen atoms of His in peptide 1. The results of this work thus provide detailed insight into peptide conformations which can be exploited in the future design of peptide analogs.

  1. Temperature-accelerated molecular dynamics gives insights into globular conformations sampled in the free state of the AC catalytic domain.

    Science.gov (United States)

    Selwa, Edithe; Huynh, Tru; Ciccotti, Giovanni; Maragliano, Luca; Malliavin, Thérèse E

    2014-10-01

    The catalytic domain of the adenyl cyclase (AC) toxin from Bordetella pertussis is activated by interaction with calmodulin (CaM), resulting in cAMP overproduction in the infected cell. In the X-ray crystallographic structure of the complex between AC and the C terminal lobe of CaM, the toxin displays a markedly elongated shape. As for the structure of the isolated protein, experimental results support the hypothesis that more globular conformations are sampled, but information at atomic resolution is still lacking. Here, we use temperature-accelerated molecular dynamics (TAMD) simulations to generate putative all-atom models of globular conformations sampled by CaM-free AC. As collective variables, we use centers of mass coordinates of groups of residues selected from the analysis of standard molecular dynamics (MD) simulations. Results show that TAMD allows extended conformational sampling and generates AC conformations that are more globular than in the complexed state. These structures are then refined via energy minimization and further unrestrained MD simulations to optimize inter-domain packing interactions, thus resulting in the identification of a set of hydrogen bonds present in the globular conformations.

  2. Origin of Kinetic Resolution of Hydroxy Esters through Catalytic Enantioselective Lactonization by Chiral Phosphoric Acids.

    Science.gov (United States)

    Changotra, Avtar; Sunoj, Raghavan B

    2016-08-05

    Kinetic resolution is a widely used strategy for separation and enrichment of enantiomers. Using density functional theory computations, the origin of how a chiral BINOL-phosphoric acid catalyzes the selective lactonization of one of the enantiomers of α-methyl γ-hydroxy ester is identified. In a stepwise mechanism, the stereocontrolling transition state for the addition of the hydroxyl group to the si face of the ester carbonyl in the case of the S isomer exhibits a network of more effective noncovalent interactions between the substrate and the chiral catalyst.

  3. GAS PHASE MOLECULAR DYNAMICS: HIGH-RESOLUTION SPECTROSCOPIC PROBES OF CHEMICAL DYNAMICS.

    Energy Technology Data Exchange (ETDEWEB)

    HALL, G.E.

    2006-05-30

    This research is carried out as part of the Gas Phase Molecular Dynamics group program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopic tools are developed and applied to problems in chemical dynamics. Recent topics have included the state-resolved studies of collision-induced electronic energy transfer, dynamics of barrierless unimolecular reactions, and the kinetics and spectroscopy of transient species.

  4. Dynamic simulation of industrial Fluidized-bed Catalytic Cracking - FCC unit

    Energy Technology Data Exchange (ETDEWEB)

    Secchi, Argimiro R.; Neumann, Gustavo A.; Trierweiler, Jorge O. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica]. E-mail: arge@enq.ufrgs.br; gneumann@enq.ufrgs.br; jorge@enq.ufrgs.br; Santos, Marlova G. [PETROBRAS S.A., Canoas, RS (Brazil). Refinaria Alberto Pasqualini]. E-mail: marlova@petrobras.com.br

    2000-07-01

    In this work a mathematical model for the dynamic simulation of the Fluidized-bed Catalytic Cracking (FCC) Reactor, to be used in the analysis, control, and optimization of this system is developed. Based on the full range of published data in FCC performance and kinetic rates, and adapted to the industrial unit of the PETROBRAS' Alberto Pasqualini Refinery (REFAP), an integrated dynamic model is build up. The model is sufficiently complex to capture the major dynamics effects that occur in this system. The regenerator is modeled as emulsion and bubble phases that exchange mass and heat. The riser is modeled as an adiabatic plug flow reactor. The fluid dynamic is taking into account for the catalyst circulation, and the dynamics of the gas phase and the riser are also considered into the model. The model, represented by a non-linear system of differential-algebraic equations, was written in language C and implemented in MATLAB/SIMULINK. The results are compared with the data obtained from the industrial plant of REFAP. (author)

  5. A Dynamical Resolution of the Sigma Term Puzzle

    CERN Document Server

    Ball, R D; Tigg, J; Ball, Richard D.; Forte, Stefano; Tigg, Jason

    1994-01-01

    We propose a resolution of the puzzle posed by the discrepancy between the pion-nucleon sigma term inferred from pion-nucleon scattering, and that deduced from baryon mass splittings using the Zweig rule. We show that there is a significant hypercharge-dependent dynamical contribution to baryon masses, not hitherto included in the analysis, which may be estimated using the scale Ward identity, and computed by solution of the Schwinger-Dyson equation for the quark self-energy. We find that the discrepancy is completely resolved without the need for any Zweig rule violation.

  6. Catalytic Mechanism of Perosamine N-Acetyltransferase Revealed by High-Resolution X-ray Crystallographic Studies and Kinetic Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Thoden, James B.; Reinhardt, Laurie A.; Cook, Paul D.; Menden, Patrick; Cleland, W.W.; Holden, Hazel M. (UW); (Mount Union); (UW-MED)

    2012-09-17

    N-Acetylperosamine is an unusual dideoxysugar found in the O-antigens of some Gram-negative bacteria, including the pathogenic Escherichia coli strain O157:H7. The last step in its biosynthesis is catalyzed by PerB, an N-acetyltransferase belonging to the left-handed {beta}-helix superfamily of proteins. Here we describe a combined structural and functional investigation of PerB from Caulobacter crescentus. For this study, three structures were determined to 1.0 {angstrom} resolution or better: the enzyme in complex with CoA and GDP-perosamine, the protein with bound CoA and GDP-N-acetylperosamine, and the enzyme containing a tetrahedral transition state mimic bound in the active site. Each subunit of the trimeric enzyme folds into two distinct regions. The N-terminal domain is globular and dominated by a six-stranded mainly parallel {beta}-sheet. It provides most of the interactions between the protein and GDP-perosamine. The C-terminal domain consists of a left-handed {beta}-helix, which has nearly seven turns. This region provides the scaffold for CoA binding. On the basis of these high-resolution structures, site-directed mutant proteins were constructed to test the roles of His 141 and Asp 142 in the catalytic mechanism. Kinetic data and pH-rate profiles are indicative of His 141 serving as a general base. In addition, the backbone amide group of Gly 159 provides an oxyanion hole for stabilization of the tetrahedral transition state. The pH-rate profiles are also consistent with the GDP-linked amino sugar substrate entering the active site in its unprotonated form. Finally, for this investigation, we show that PerB can accept GDP-3-deoxyperosamine as an alternative substrate, thus representing the production of a novel trideoxysugar.

  7. Catalytic performance and molecular dynamic simulation of immobilized CC bond hydrolase based on carbon nanotube matrix.

    Science.gov (United States)

    Zhou, Hao; Qu, Yuanyuan; Kong, Chunlei; Li, Duanxing; Shen, E; Ma, Qiao; Zhang, Xuwang; Wang, Jingwei; Zhou, Jiti

    2014-04-01

    Carbon nanotube (CNT) has been proved to be a kind of novel support for enzyme immobilization. In this study, we tried to find the relationship between conformation and catalytic performance of immobilized enzyme. Two CC bond hydrolases BphD and MfphA were immobilized on CNTs (SWCNT and MWCNT) via physical adsorption and covalent attachment. Among the conjugates, the immobilized BphD on chemically functionalized SWCNT (BphD-CSWCNT) retained the highest catalytic efficiency (kcat/Km value) compared to free BphD (92.9%). On the other hand, when MfphA bound to pristine SWCNT (MfphA-SWCNT), it was completely inactive. Time-resolved fluorescence spectrum indicated the formation of static ground complexes during the immobilization processes. Circular dichroism (CD) showed that the secondary structures of immobilized enzymes changed in varying degrees. In order to investigate the inhibition mechanism of MfphA by SWCNT, molecular dynamics simulation was employed to analyze the adsorption process, binding sites and time evolution of substrate tunnels. The results showed that the preferred binding sites (Trp201 and Met81) of MfphA for SWCNT blocked the main substrate access tunnel, thus making the enzyme inactive. The "tunnel-block" should be a novel possible inhibition mechanism for enzyme-nanotube conjugate.

  8. Molecular dynamics characterization of five pathogenic factor X mutants associated with decreased catalytic activity

    KAUST Repository

    Abdel-Azeim, Safwat

    2014-11-11

    Factor X (FX) is one of the major players in the blood coagulation cascade. Upon activation to FXa, it converts prothrombin to thrombin, which in turn converts fibrinogen into fibrin (blood clots). FXa deficiency causes hemostasis defects, such as intracranial bleeding, hemathrosis, and gastrointestinal blood loss. Herein, we have analyzed a pool of pathogenic mutations, located in the FXa catalytic domain and directly associated with defects in enzyme catalytic activity. Using chymotrypsinogen numbering, they correspond to D102N, T135M, V160A, G184S, and G197D. Molecular dynamics simulations were performed for 1.68 μs on the wild-type and mutated forms of FXa. Overall, our analysis shows that four of the five mutants considered, D102N, T135M, V160A, and G184S, have rigidities higher than those of the wild type, in terms of both overall protein motion and, specifically, subpocket S4 flexibility, while S1 is rather insensitive to the mutation. This acquired rigidity can clearly impact the substrate recognition of the mutants.

  9. Molecular dynamics and mutational analysis of the catalytic and translocation cycle of RNA polymerase

    Directory of Open Access Journals (Sweden)

    Kireeva Maria L

    2012-06-01

    Full Text Available Abstract Background During elongation, multi-subunit RNA polymerases (RNAPs cycle between phosphodiester bond formation and nucleic acid translocation. In the conformation associated with catalysis, the mobile “trigger loop” of the catalytic subunit closes on the nucleoside triphosphate (NTP substrate. Closing of the trigger loop is expected to exclude water from the active site, and dehydration may contribute to catalysis and fidelity. In the absence of a NTP substrate in the active site, the trigger loop opens, which may enable translocation. Another notable structural element of the RNAP catalytic center is the “bridge helix” that separates the active site from downstream DNA. The bridge helix may participate in translocation by bending against the RNA/DNA hybrid to induce RNAP forward movement and to vacate the active site for the next NTP loading. The transition between catalytic and translocation conformations of RNAP is not evident from static crystallographic snapshots in which macromolecular motions may be restrained by crystal packing. Results All atom molecular dynamics simulations of Thermus thermophilus (Tt RNAP reveal flexible hinges, located within the two helices at the base of the trigger loop, and two glycine hinges clustered near the N-terminal end of the bridge helix. As simulation progresses, these hinges adopt distinct conformations in the closed and open trigger loop structures. A number of residues (described as “switch” residues trade atomic contacts (ion pairs or hydrogen bonds in response to changes in hinge orientation. In vivo phenotypes and in vitro activities rendered by mutations in the hinge and switch residues in Saccharomyces cerevisiae (Sc RNAP II support the importance of conformational changes predicted from simulations in catalysis and translocation. During simulation, the elongation complex with an open trigger loop spontaneously translocates forward relative to the elongation complex with a

  10. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    Energy Technology Data Exchange (ETDEWEB)

    Hall,G.E.; Sears, T.J.

    2009-04-03

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopy, augmented by theoretical and computational methods, is used to investigate the structure and collision dynamics of chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry. Applications and methods development are equally important experimental components of this work.

  11. Atomic-scale investigations of the struct. and dynamics of complex catalytic materials

    Energy Technology Data Exchange (ETDEWEB)

    Karl Sohlberg, Drexel University

    2007-05-16

    By some accounts, catalysis impacts ≥ 30% of GDP in developed countries [Maxwell, I. E. Nature 394, 325-326 (1998)]. Catalysis is the enabling technology for petroleum production, for control of gaseous emissions from petroleum combustion, and for the production of industrial and consumer chemicals. Future applications of catalysis are potentially even more far reaching. There is an ever-growing need to move the economy from a fossil-fuel energy base to cleaner alternatives. Hydrogen-based combustion systems and fuel cells could play a dominant role, given a plentiful and inexpensive source of hydrogen. Photocatalysis is the most promising clean technology for hydrogen production, relying solely on water and sunlight, but performance enhancements in photocatalysis are needed to make this technology economically competitive. Given the enormously wide spread utilization of catalysts, even incremental performance enhancements would have far-reaching benefits for multiple end-use sectors. In the area of fuel and chemical production, such improvements would translate into vast reductions in energy consumption. At the consumption end, improvements in the catalysts involved would yield tremendous reductions in pollution. In the area of photocatalysis, such efficiency improvements could finally render hydrogen an economically viable fuel. Prerequisite to the non-empirical design and refinement of improved catalysts is the identification of the atomic-scale structure and properties of the catalytically active sites. This has become a major industrial research priority. The focus of this research program was to combine atomic-resolution Z-contrast electron microscopy with first-principles density functional theory calculations to deliver an atomic-scale description of heterogeneous catalytic systems that could form the basis for non-empirical design of improved catalysts with greater energy efficiency.

  12. High-Resolution Force Balance Analyses of Tidewater Glacier Dynamics

    Science.gov (United States)

    Enderlin, E. M.; Hamilton, G. S.; O'Neel, S.

    2015-12-01

    Changes in glacier velocity, thickness, and terminus position have been used to infer the dynamic response of tidewater glaciers to environmental perturbations, yet few analyses have attempted to quantify the associated variations in the glacier force balance. Where repeat high-resolution ice thickness and velocity estimates are available, force balance time series can be constructed to investigate the redistribution of driving and resistive forces associated with changes in terminus position. Comparative force balance analyses may, therefore, help us understand the variable dynamic response observed for glaciers in close proximity to each other. Here we construct force balance time series for Helheim Glacier, SE Greenland, and Columbia Glacier, SE Alaska, to investigate differences in dynamic sensitivity to terminus position change. The analysis relies on in situ and remotely sensed observations of ice thickness, velocity, and terminus position. Ice thickness time series are obtained from stereo satellite image-derived surface elevation and continuity-derived bed elevations that are constrained by airborne radar observations. Surface velocity time series are obtained from interferometric synthetic aperture radar (InSAR) observations. Approximately daily terminus positions are from a combination of satellite images and terrestrial time-lapse photographs. Helheim and Columbia glaciers are two of the best-studied Arctic tidewater glaciers with comprehensive high-resolution observational time series, yet we find that bed elevation uncertainties and poorly-constrained stress-coupling length estimates still hinder the analysis of spatial and temporal force balance variations. Here we use a new observationally-based method to estimate the stress-coupling length which successfully reduces noise in the derived force balance but preserves spatial variations that can be over-smoothed when estimating the stress-coupling length as a scalar function of the ice thickness

  13. Resolution enhancement in neural networks with dynamical synapses

    Directory of Open Access Journals (Sweden)

    C. C. Alan Fung

    2013-06-01

    Full Text Available Conventionally, information is represented by spike rates in the neural system. Here, we consider the ability of temporally modulated activities in neuronal networks to carry information extra to spike rates. These temporal modulations, commonly known as population spikes, are due to the presence of synaptic depression in a neuronal network model. We discuss its relevance to an experiment on transparent motions in macaque monkeys by Treue et al. in 2000. They found that if the moving directions of objects are too close, the firing rate profile will be very similar to that with one direction. As the difference in the moving directions of objects is large enough, the neuronal system would respond in such a way that the network enhances the resolution in the moving directions of the objects. In this paper, we propose that this behavior can be reproduced by neural networks with dynamical synapses when there are multiple external inputs. We will demonstrate how resolution enhancement can be achieved, and discuss the conditions under which temporally modulated activities are able to enhance information processing performances in general.

  14. Molecular dynamics study of the stability of a carbon nanotube atop a catalytic nanoparticle

    CERN Document Server

    Verkhovtsev, Alexey V; Solov'yov, Andrey V

    2014-01-01

    The stability of a single-walled carbon nanotube placed on top of a catalytic nickel nanoparticle is investigated by means of molecular dynamics simulations. As a case study, we consider the $(12,0)$ nanotube consisting of 720 carbon atoms and the icosahedral Ni$_{309}$ cluster. An explicit set of constant-temperature simulations is performed in order to cover a broad temperature range from 400 to 1200 K, at which a successful growth of carbon nanotubes has been achieved experimentally by means of chemical vapor deposition. The stability of the system depending on parameters of the involved interatomic interactions is analyzed. It is demonstrated that different scenarios of the nanotube dynamics atop the nanoparticle are possible depending on the parameters of the Ni-C potential. When the interaction is weak the nanotube is stable and resembles its highly symmetric structure, while an increase of the interaction energy leads to the abrupt collapse of the nanotube in the initial stage of simulation. In order t...

  15. Catalytic activation of pre-substrates via dynamic fragment assembly on protein templates.

    Science.gov (United States)

    Burda, Edyta; Rademann, Jörg

    2014-11-18

    Sensitive detection of small molecule fragments binding to defined sites of biomacromolecules is still a considerable challenge. Here we demonstrate that protein-binding fragments are able to induce enzymatic reactions on the protein surface via dynamic fragment ligation. Fragments binding to the S1 pocket of serine proteases containing a nitrogen, oxygen or sulphur nucleophile are found to activate electrophilic pre-substrates through a reversible, covalent ligation reaction. The dynamic ligation reaction positions the pre-substrate molecule at the active site of the protein thereby inducing its enzymatic cleavage. Catalytic activation of pre-substrates is confirmed by fluorescence spectroscopy and by high-performance liquid chromatography. The approach is investigated with 3 pre-substrates and 14 protein-binding fragments and the specific activation and the templating effect exerted by the enzyme is quantified for each protease-fragment-pre-substrate combination. The described approach enables the site-specific identification of protein-binding fragments, the functional characterization of enzymatic sites and the quantitative analysis of protein template-assisted ligation reactions.

  16. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    Energy Technology Data Exchange (ETDEWEB)

    Hall, G.E.

    2011-05-31

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  17. Determination of optimum rotational speed of heterogeneous catalytic reactor using computational fluid dynamic

    Directory of Open Access Journals (Sweden)

    Rungrote Kokoo

    2008-09-01

    Full Text Available Solid suspension in a stirrer tank reactor is relevant in many chemical process industries. For a heterogeneous catalyticreactor, the degree of solid suspension is a crucial parameter in the design and scaling-up processes. The suspension of solid catalysts at a minimum impeller speed can reduce the operating cost of processes. To ensure optimum conditions for suspension, a 3D simulation technique by Computational Fluid Dynamic (CFD was used to study flow characteristics in a heterogeneous catalytic reactor. A case study of a 200 milliliter cylindrical reactor was modeled together with equipped parts, i.e. a sampling port, 2 baffles, one thermocouple and a mechanical stirrer. The results show that the total velocity increases from the impeller’s center to the impeller’s tip and decreases from the impeller’s tip to the side wall of the reactor. The vertical velocity at the bottom of the impellers directs flow upward while the velocity at the top directs flow downward. These simulations provide a good preview of solid suspension without doing experiments. It is recommended that the vertical velocity at thebottom of the reactor is in the range between minimum fluidization velocity and terminal velocity to ensure solid suspension inthe system.

  18. A High-Resolution Sensor Network for Monitoring Glacier Dynamics

    Science.gov (United States)

    Edwards, S.; Murray, T.; O'Farrell, T.; Rutt, I. C.; Loskot, P.; Martin, I.; Selmes, N.; Aspey, R.; James, T.; Bevan, S. L.; Baugé, T.

    2013-12-01

    Changes in Greenland and Antarctic ice sheets due to ice flow/ice-berg calving are a major uncertainty affecting sea-level rise forecasts. Latterly GNSS (Global Navigation Satellite Systems) have been employed extensively to monitor such glacier dynamics. Until recently however, the favoured methodology has been to deploy sensors onto the glacier surface, collect data for a period of time, then retrieve and download the sensors. This approach works well in less dynamic environments where the risk of sensor loss is low. In more extreme environments e.g. approaching the glacial calving front, the risk of sensor loss and hence data loss increases dramatically. In order to provide glaciologists with new insights into flow dynamics and calving processes we have developed a novel sensor network to increase the robustness of data capture. We present details of the technological requirements for an in-situ Zigbee wireless streaming network infrastructure supporting instantaneous data acquisition from high resolution GNSS sensors thereby increasing data capture robustness. The data obtained offers new opportunities to investigate the interdependence of mass flow, uplift, velocity and geometry and the network architecture has been specifically designed for deployment by helicopter close to the calving front to yield unprecedented detailed information. Following successful field trials of a pilot three node network during 2012, a larger 20 node network was deployed on the fast-flowing Helheim glacier, south-east Greenland over the summer months of 2013. The utilisation of dual wireless transceivers in each glacier node, multiple frequencies and four ';collector' stations located on the valley sides creates overlapping networks providing enhanced capacity, diversity and redundancy of data 'back-haul', even close to ';floor' RSSI (Received Signal Strength Indication) levels around -100 dBm. Data loss through radio packet collisions within sub-networks are avoided through the

  19. Structure of a catalytic dimer of the α- and β-subunits of the F-ATPase from Paracoccus denitrificans at 2.3 Å resolution

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Ríos, Edgar; Montgomery, Martin G. [The Medical Research Council Mitochondrial Biology Unit, Cambridge Biomedical Campus, Hills Road, Cambridge CB2 0XY (United Kingdom); Leslie, Andrew G. W. [The Medical Research Council Laboratory of Molecular Biology, Cambridge Biomedical Campus, Francis Crick Avenue, Cambridge CB2 0QH (United Kingdom); García-Trejo, José J. [Universidad Nacional Autónoma de México, Mexico City (Mexico); Walker, John E., E-mail: walker@mrc-mbu.cam.ac.uk [The Medical Research Council Mitochondrial Biology Unit, Cambridge Biomedical Campus, Hills Road, Cambridge CB2 0XY (United Kingdom)

    2015-09-23

    The structure of the αβ heterodimer of the F-ATPase from the α-proteobacterium P. denitrificans has been determined at 2.3 Å resolution. It corresponds to the ‘open’ or ‘empty’ catalytic interface found in other F-ATPases. The structures of F-ATPases have predominantly been determined from mitochondrial enzymes, and those of the enzymes in eubacteria have been less studied. Paracoccus denitrificans is a member of the α-proteobacteria and is related to the extinct protomitochondrion that became engulfed by the ancestor of eukaryotic cells. The P. denitrificans F-ATPase is an example of a eubacterial F-ATPase that can carry out ATP synthesis only, whereas many others can catalyse both the synthesis and the hydrolysis of ATP. Inhibition of the ATP hydrolytic activity of the P. denitrificans F-ATPase involves the ζ inhibitor protein, an α-helical protein that binds to the catalytic F{sub 1} domain of the enzyme. This domain is a complex of three α-subunits and three β-subunits, and one copy of each of the γ-, δ- and ∊-subunits. Attempts to crystallize the F{sub 1}–ζ inhibitor complex yielded crystals of a subcomplex of the catalytic domain containing the α- and β-subunits only. Its structure was determined to 2.3 Å resolution and consists of a heterodimer of one α-subunit and one β-subunit. It has no bound nucleotides, and it corresponds to the ‘open’ or ‘empty’ catalytic interface found in other F-ATPases. The main significance of this structure is that it aids in the determination of the structure of the intact membrane-bound F-ATPase, which has been crystallized.

  20. Dynamic interplay between catalytic and lectin domains of GalNAc-transferases modulates protein O-glycosylation

    DEFF Research Database (Denmark)

    Lira-Navarrete, Erandi; de Las Rivas, Matilde; Compañón, Ismael;

    2015-01-01

    Protein O-glycosylation is controlled by polypeptide GalNAc-transferases (GalNAc-Ts) that uniquely feature both a catalytic and lectin domain. The underlying molecular basis of how the lectin domains of GalNAc-Ts contribute to glycopeptide specificity and catalysis remains unclear. Here we present...... the first crystal structures of complexes of GalNAc-T2 with glycopeptides that together with enhanced sampling molecular dynamics simulations demonstrate a cooperative mechanism by which the lectin domain enables free acceptor sites binding of glycopeptides into the catalytic domain. Atomic force microscopy...... and small-angle X-ray scattering experiments further reveal a dynamic conformational landscape of GalNAc-T2 and a prominent role of compact structures that are both required for efficient catalysis. Our model indicates that the activity profile of GalNAc-T2 is dictated by conformational heterogeneity...

  1. Impact of Mercury(II) on proteinase K catalytic center: investigations via classical and Born-Oppenheimer molecular dynamics.

    Science.gov (United States)

    Panek, Jarosław J; Mazzarello, Riccardo; Novič, Marjana; Jezierska-Mazzarello, Aneta

    2011-02-01

    Mercury(II) has a strong affinity for the thiol groups in proteins often resulting in the disruption of their biological functions. In this study we present classical and first-principles, DFT-based molecular dynamics (MD) simulations of a complex of Hg(II) and proteinase K, a well-known serine protease with a very broad and diverse enzymatic activity. It contains a catalytic triad formed by Asp39, His69, and Ser224, which is responsible for its biological activity. It was found previously by X-ray diffraction experiments that the presence of Hg(II) inhibits the enzymatic action of proteinase K by affecting the stereochemistry of the triad. Our simulations predict that (i) the overall structure as well as the protein backbone dynamics are only slightly affected by the mercury cation, (ii) depending on the occupied mercury site, the hydrogen bonds of the catalytic triad are either severely disrupted (both bonds for mercury at site 1, and the His69-Ser224 contact for mercury at site 2) or slightly strengthened (the Asp39-His69 bond when mercury is at site 2), (iii) the network of hydrogen bonds of the catalytic triad is not static but undergoes constant fluctuations, which are significantly modified by the presence of the Hg(II) cation, influencing in turn the triad's ability to carry out the enzymatic function--these facts explain the experimental findings on the inhibition of proteinase K by Hg(II).

  2. Dynamic interplay between catalytic and lectin domains of GalNAc-transferases modulates protein O-glycosylation

    Science.gov (United States)

    Lira-Navarrete, Erandi; de Las Rivas, Matilde; Compañón, Ismael; Pallarés, María Carmen; Kong, Yun; Iglesias-Fernández, Javier; Bernardes, Gonçalo J. L.; Peregrina, Jesús M.; Rovira, Carme; Bernadó, Pau; Bruscolini, Pierpaolo; Clausen, Henrik; Lostao, Anabel; Corzana, Francisco; Hurtado-Guerrero, Ramon

    2015-05-01

    Protein O-glycosylation is controlled by polypeptide GalNAc-transferases (GalNAc-Ts) that uniquely feature both a catalytic and lectin domain. The underlying molecular basis of how the lectin domains of GalNAc-Ts contribute to glycopeptide specificity and catalysis remains unclear. Here we present the first crystal structures of complexes of GalNAc-T2 with glycopeptides that together with enhanced sampling molecular dynamics simulations demonstrate a cooperative mechanism by which the lectin domain enables free acceptor sites binding of glycopeptides into the catalytic domain. Atomic force microscopy and small-angle X-ray scattering experiments further reveal a dynamic conformational landscape of GalNAc-T2 and a prominent role of compact structures that are both required for efficient catalysis. Our model indicates that the activity profile of GalNAc-T2 is dictated by conformational heterogeneity and relies on a flexible linker located between the catalytic and the lectin domains. Our results also shed light on how GalNAc-Ts generate dense decoration of proteins with O-glycans.

  3. Revealing structural dynamics in catalytic reactions using ultrafast transient x-ray absorption spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L. X.; Liu, D.; Chemical Sciences and Engineering Division; Northwestern Univ.

    2009-03-02

    Progression of a typical heterogeneous catalytic process as a function of a reaction parameter such as temperature can often be segmented, according to Fig. 1. Reactants first bind to active sites to form reaction intermediates with increases in temperature and kinetic energy (Region I). Further temperature increase leads to a full 'light-off' of the catalytic conversion and the reaction is dominated by the intra-particulate diffusion (Region II). The characteristic 'light-off' temperature at the boundary of region I and II often defines the activity of the catalyst. At even higher temperature enters the bulk diffusion region (III), where the catalytic reaction is limited mainly by mass transport between different phases. Significant efforts in practical catalyst design involve improving catalytic activities in the kinetic region (I) and reducing the 'light-off' temperature. Reaction rates at the kinetic region are defined by potential saddle points on top of which a series of 'transitional state' complexes are formed between the active sites and the adsorbed reactants (Fig. 2). Capturing structures of the 'transition state complexes' from the active center's perspective will provide ultimate understanding of catalytic mechanisms and insight into new catalyst design. Experimentally, however, it is a very challenging proposition.

  4. Extended-resolution structured illumination imaging of endocytic and cytoskeletal dynamics

    Science.gov (United States)

    Li, Dong; Shao, Lin; Chen, Bi-Chang; Zhang, Xi; Zhang, Mingshu; Moses, Brian; Milkie, Daniel E.; Beach, Jordan R.; Hammer, John A.; Pasham, Mithun; Kirchhausen, Tomas; Baird, Michelle A.; Davidson, Michael W.; Xu, Pingyong; Betzig, Eric

    2015-01-01

    Super-resolution fluorescence microscopy is distinct among nanoscale imaging tools in its ability to image protein dynamics in living cells. Structured illumination microscopy (SIM) stands out in this regard because of its high speed and low illumination intensities, but typically offers only a twofold resolution gain. We extended the resolution of live-cell SIM through two approaches: ultrahigh numerical aperture SIM at 84-nanometer lateral resolution for more than 100 multicolor frames, and nonlinear SIM with patterned activation at 45- to 62-nanometer resolution for approximately 20 to 40 frames. We applied these approaches to image dynamics near the plasma membrane of spatially resolved assemblies of clathrin and caveolin, Rab5a in early endosomes, and a-actinin, often in relationship to cortical actin. In addition, we examined mitochondria, actin, and the Golgi apparatus dynamics in three dimensions. PMID:26315442

  5. Some fundamental problems for an energy conserving adaptive resolution molecular dynamics scheme

    OpenAIRE

    Site, L. Delle

    2007-01-01

    Adaptive resolution molecular dynamics (MD) schemes allow for changing the number of degrees of freedom on the fly and preserve the free exchange of particles between regions of different resolution. There are two main alternatives on how to design the algorithm to switch resolution using auxiliary ''switching'' functions; force based and potential energy based approach. In this work we show that, in the framework of classical MD, the latter presents fundamental conceptual problems which make...

  6. Multi-Volume High Resolution RGB-D Mapping with Dynamic Volume Placement

    OpenAIRE

    Salvato, Michael; Finman, Ross; Leonard, John

    2015-01-01

    We present a novel RGB-D mapping system for generating 3D maps over spatially extended regions with higher resolution than current methods using multiple, dynamically placed mapping volumes. Our method takes in RGB-D frames and dynamically assigns multiple mapping volumes to the environment, exchanging mapping volumes between the CPU and GPU. Mapping volumes are added or removed as needed to allow for spatially extended, high resolution mapping. Our system is designed to maximize the resoluti...

  7. High-Resolution Crystal Structures of Streptococcus pneumoniae Nicotinamidase with Trapped Intermediates Provide Insights into the Catalytic Mechanism and Inhibition by Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Cen, Yana; Sauve, Anthony A.; Ealick, Steven E. (Cornell); (Weill-Med)

    2010-11-11

    Nicotinamidases are salvage enzymes that convert nicotinamide to nicotinic acid. These enzymes are essential for the recycling of nicotinamide into NAD{sup +} in most prokaryotes and most single-cell and multicellular eukaryotes, but not in mammals. The significance of these enzymes for nicotinamide salvage and for NAD{sup +} homeostasis has stimulated interest in nicotinamidases as possible antibiotic targets. Nicotinamidases are also regulators of intracellular nicotinamide concentrations, thereby regulating signaling of downstream NAD{sup +}-consuming enzymes, such as the NAD{sup +}-dependent deacetylases (sirtuins). Here, we report several high-resolution crystal structures of the nicotinamidase from Streptococcus pneumoniae (SpNic) in unliganded and ligand-bound forms. The structure of the C136S mutant in complex with nicotinamide provides details about substrate binding, while a trapped nicotinoyl thioester in a complex with SpNic reveals the structure of the proposed thioester reaction intermediate. Examination of the active site of SpNic reveals several important features, including a metal ion that coordinates the substrate and the catalytically relevant water molecule and an oxyanion hole that both orients the substrate and offsets the negative charge that builds up during catalysis. Structures of this enzyme with bound nicotinaldehyde inhibitors elucidate the mechanism of inhibition and provide further details about the catalytic mechanism. In addition, we provide a biochemical analysis of the identity and role of the metal ion that orients the ligand in the active site and activates the water molecule responsible for hydrolysis of the substrate. These data provide structural evidence of several proposed reaction intermediates and allow for a more complete understanding of the catalytic mechanism of this enzyme.

  8. Dynamic neuroanatomy at subcellular resolution in the zebrafish.

    Science.gov (United States)

    Faucherre, Adèle; López-Schier, Hernán

    2014-01-01

    Genetic means to visualize and manipulate neuronal circuits in the intact animal have revolutionized neurobiology. "Dynamic neuroanatomy" defines a range of approaches aimed at quantifying the architecture or subcellular organization of neurons over time during their development, regeneration, or degeneration. A general feature of these approaches is their reliance on the optical isolation of defined neurons in toto by genetically expressing markers in one or few cells. Here we use the afferent neurons of the lateral line as an example to describe a simple method for the dynamic neuroanatomical study of axon terminals in the zebrafish by laser-scanning confocal microscopy.

  9. Downscaling time series of MERIS full resolution data to monitor vegetation seasonal dynamics

    NARCIS (Netherlands)

    Zurita Milla, R.; Kaiser, G.; Clevers, J.G.P.W.; Schneider, W.; Schaepman, M.E.

    2009-01-01

    Monitoring vegetation dynamics is fundamental for improving Earth system models and for increasing our understanding of the terrestrial carbon cycle and the interactions between biosphere and climate. Medium spatial resolution sensors, like MERIS, exhibit a significant potential to study these dynam

  10. Data Driven Approach for High Resolution Population Distribution and Dynamics Models

    Energy Technology Data Exchange (ETDEWEB)

    Bhaduri, Budhendra L [ORNL; Bright, Eddie A [ORNL; Rose, Amy N [ORNL; Liu, Cheng [ORNL; Urban, Marie L [ORNL; Stewart, Robert N [ORNL

    2014-01-01

    High resolution population distribution data are vital for successfully addressing critical issues ranging from energy and socio-environmental research to public health to human security. Commonly available population data from Census is constrained both in space and time and does not capture population dynamics as functions of space and time. This imposes a significant limitation on the fidelity of event-based simulation models with sensitive space-time resolution. This paper describes ongoing development of high-resolution population distribution and dynamics models, at Oak Ridge National Laboratory, through spatial data integration and modeling with behavioral or activity-based mobility datasets for representing temporal dynamics of population. The model is resolved at 1 km resolution globally and describes the U.S. population for nighttime and daytime at 90m. Integration of such population data provides the opportunity to develop simulations and applications in critical infrastructure management from local to global scales.

  11. Dynamically-driven inactivation of the catalytic machinery of the SARS 3C-like protease by the N214A mutation on the extra domain.

    Science.gov (United States)

    Shi, Jiahai; Han, Nanyu; Lim, Liangzhong; Lua, Shixiong; Sivaraman, J; Wang, Lushan; Mu, Yuguang; Song, Jianxing

    2011-02-01

    Despite utilizing the same chymotrypsin fold to host the catalytic machinery, coronavirus 3C-like proteases (3CLpro) noticeably differ from picornavirus 3C proteases in acquiring an extra helical domain in evolution. Previously, the extra domain was demonstrated to regulate the catalysis of the SARS-CoV 3CLpro by controlling its dimerization. Here, we studied N214A, another mutant with only a doubled dissociation constant but significantly abolished activity. Unexpectedly, N214A still adopts the dimeric structure almost identical to that of the wild-type (WT) enzyme. Thus, we conducted 30-ns molecular dynamics (MD) simulations for N214A, WT, and R298A which we previously characterized to be a monomer with the collapsed catalytic machinery. Remarkably, three proteases display distinctive dynamical behaviors. While in WT, the catalytic machinery stably retains in the activated state; in R298A it remains largely collapsed in the inactivated state, thus implying that two states are not only structurally very distinguishable but also dynamically well separated. Surprisingly, in N214A the catalytic dyad becomes dynamically unstable and many residues constituting the catalytic machinery jump to sample the conformations highly resembling those of R298A. Therefore, the N214A mutation appears to trigger the dramatic change of the enzyme dynamics in the context of the dimeric form which ultimately inactivates the catalytic machinery. The present MD simulations represent the longest reported so far for the SARS-CoV 3CLpro, unveiling that its catalysis is critically dependent on the dynamics, which can be amazingly modulated by the extra domain. Consequently, mediating the dynamics may offer a potential avenue to inhibit the SARS-CoV 3CLpro.

  12. Dynamical quorum sensing and synchronization in collections of excitable and oscillatory catalytic particles

    Science.gov (United States)

    Tinsley, M. R.; Taylor, A. F.; Huang, Z.; Wang, F.; Showalter, K.

    2010-06-01

    We present experimental studies of interacting excitable and oscillatory catalytic particles in well-stirred and spatially distributed systems. A number of distinct paths to synchronized oscillatory behavior are described. We present an example of a Kuramoto type transition in a well-stirred system with a collective rhythm emerging on increasing the number density of oscillatory particles. Groups of spatially distributed oscillatory particles become entrained to a common frequency by organizing centers. Quorum sensing type transitions are found in populations of globally and locally coupled excitable particles, with a sharp transition from steady state to fully synchronized behavior at a critical density or group size.

  13. Practical Considerations for High Spatial and Temporal Resolution Dynamic Transmission Electron Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, M; Boyden, K; Browning, N D; Campbell, G H; Colvin, J D; DeHope, B; Frank, A M; Gibson, D J; Hartemann, F; Kim, J S; King, W E; LaGrange, T B; Pyke, B J; Reed, B W; Shuttlesworth, R M; Stuart, B C; Torralva, B R

    2006-05-01

    Although recent years have seen significant advances in the spatial resolution possible in the transmission electron microscope (TEM), the temporal resolution of most microscopes is limited to video rate at best. This lack of temporal resolution means that our understanding of dynamic processes in materials is extremely limited. High temporal resolution in the TEM can be achieved, however, by replacing the normal thermionic or field emission source with a photoemission source. In this case the temporal resolution is limited only by the ability to create a short pulse of photoexcited electrons in the source, and this can be as short as a few femtoseconds. The operation of the photo-emission source and the control of the subsequent pulse of electrons (containing as many as 5 x 10{sup 7} electrons) create significant challenges for a standard microscope column that is designed to operate with a single electron in the column at any one time. In this paper, the generation and control of electron pulses in the TEM to obtain a temporal resolution <10{sup -6} s will be described and the effect of the pulse duration and current density on the spatial resolution of the instrument will be examined. The potential of these levels of temporal and spatial resolution for the study of dynamic materials processes will also be discussed.

  14. A COMPARATIVE ANALYSIS OF DISPUTE RESOLUTION DYNAMICS IN ASIA

    Directory of Open Access Journals (Sweden)

    Pawel Voronin

    2014-01-01

    Full Text Available China’s rise to prominence in the international community following the end of the Cold War, the growth in economic power and population numbers project that China will become the leading world power within several decades, regardless of the course its government takes. The article aimes to contribute to answering the question whether this rise will be peaceful through a comparative analysis of resolved and unresolved territorial disputes between China and groups of neighbouring states between 1986 and 2013. While previous studies have focused rather exclusively on Chinese behaviour, this text will examine both sides of the dispute and the behavior of the parties in light of regional dynamics

  15. Improved ambiguity resolution for URTK with dynamic atmosphere constraints

    Science.gov (United States)

    Tang, Weiming; Liu, Wenjian; Zou, Xuan; Li, Zongnan; Chen, Liang; Deng, Chenlong; Shi, Chuang

    2016-12-01

    Raw observation processing method with prior knowledge of ionospheric delay could strengthen the ambiguity resolution (AR), but it does not make full use of the relatively longer wavelength of wide-lane (WL) observation. Furthermore, the accuracy of calculated atmospheric delays from the regional augmentation information has quite different in quality, while the atmospheric constraint used in the current methods is usually set to an empirical value. A proper constraint, which matches the accuracy of calculated atmospheric delays, can most effectively compensate the residual systematic biases caused by large inter-station distances. Therefore, the standard deviation of the residual atmospheric parameters should be fine-tuned. This paper presents an atmosphere-constrained AR method for undifferenced network RTK (URTK) rover, whose ambiguities are sequentially fixed according to their wavelengths. Furthermore, this research systematically analyzes the residual atmospheric error and finds that it mainly varies along the positional relationship between the rover and the chosen reference stations. More importantly, its ionospheric part of certain location will also be cyclically influenced every day. Therefore, the standard deviation of residual ionospheric error can be modeled by a daily repeated cosine or other functions with the help of data one day before, and applied by rovers as pseudo-observation. With the data collected at 29 stations from a continuously operating reference station network in Guangdong Province (GDCORS) in China, the efficiency of the proposed approach is confirmed by improving the success and error rates of AR for 10-20 % compared to that of the WL-L1-IF one, as well as making much better positioning accuracy.

  16. Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

    Science.gov (United States)

    Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  17. Coordinated Observations of X-ray and High-Resolution EUV Active Region Dynamics

    Science.gov (United States)

    Savage, Sabrina; Cirtain, Jonathan; Winebarger, Amy; Kobayashi, Ken; Golub, Leon; Korreck, Kelly

    2013-01-01

    The recently-launched High-resolution Coronal imager (Hi-C) sounding rocket provided the highest resolution images of coronal loops and other small-scale structures in the 193 Angstrom passband to date. With just 5 minutes of observations, the instrument recorded a variety of dynamic coronal events -- including even a small B-class flare. We will present our results comparing these extreme-ultraviolet (EUV) observations with X-ray imaging from Hinode/XRT as well as EUV AIA data to identify sources of hot plasma rooted in the photosphere and track their affect on the overall topology and dynamics of the active region.

  18. Charge to digital converter with constant resolution over the dynamic range

    Energy Technology Data Exchange (ETDEWEB)

    Nascetti, A. [Department of Aerospace and Astronautics Engineering, Sapienza University of Rome, via Eudossiana 16, 00184, Rome (Italy)

    2009-12-15

    A novel pixel-level charge to digital converter circuit suitable for multi-channel charge sensitive amplifiers or pixelated readout ICs for hybrid detectors is presented. The proposed circuit features large dynamic range operation with constant relative resolution over the whole dynamic range. These characteristics have been obtained by introducing the fractional charge packet counting concept. In particular, a solution has been proposed to obtain the analog-to-digital conversion with constant number of significant bits.

  19. Support influences in the Pd-catalyzed racemization and dynamic kinetic resolution of chiral benzylic amines

    NARCIS (Netherlands)

    Parvulescu, A.N.; Jacobs, P.A.; De Vos, D.E.

    2009-01-01

    The acid–base properties of the supports for Pd catalysts strongly affect their performance in racemization and dynamic kinetic resolution (DKR) of chiral benzylic amines. The need for a basic support was proven by comparing the racemization results obtained for Pd on silica, on LDH (layered double

  20. Nanometer resolution self-powered static and dynamic motion sensor based on micro-grated triboelectrification.

    Science.gov (United States)

    Zhou, Yu Sheng; Zhu, Guang; Niu, Simiao; Liu, Ying; Bai, Peng; Jing, Qingsheng; Wang, Zhong Lin

    2014-03-19

    A one-dimensional displacement and speed sensing technology that consists of a pair of micro-grating structures and utilizes the coupling between the triboelectric effect and electrostatic induction is demonstrated. Its distinct advantages, including being self-powered, high resolution, large dynamic range, and long detecting distance, show extensive potential applications in automation, manufacturing, process control, and portable devices.

  1. Super-resolution imaging in digital holography by using dynamic grating with a spatial light modulator

    Science.gov (United States)

    Lin, Qiaowen; Wang, Dayong; Wang, Yunxin; Rong, Lu; Chang, Shifeng

    2015-03-01

    A super-resolution imaging method using dynamic grating based on liquid-crystal spatial light modulator (SLM) is developed to improve the resolution of a digital holographic system. The one-dimensional amplitude cosine grating is loaded on the SLM, which is placed between the object and hologram plane in order to collect more high-frequency components towards CCD plane. The point spread function of the system is given to confirm the separation condition of reconstructed images for multiple diffraction orders. The simulation and experiments are carried out for a standard resolution test target as a sample, which confirms that the imaging resolution is improved from 55.7 μm to 31.3 μm compared with traditional lensless Fourier transform digital holography. The unique advantage of the proposed method is that the period of the grating can be programmably adjusted according to the separation condition.

  2. Experimental study of vaporization effect on steady state and dynamic behavior of catalytic pellets

    NARCIS (Netherlands)

    Kulikov, A.V.; Kuzin, N.A.; Shigarov, A.B.; Kirillov, V.A.; Kronberg, A.E.; Westerterp, K.R.

    2001-01-01

    The impact of the combined evaporation of the liquid phase and reaction on single catalyst pellet performance has been studied experimentally. The exothermic, catalyzed hydrogenation of α-methylstyrene (AMS) to cumene has been employed as a model reaction. Steady state and dynamic experiments have b

  3. Dynamical Response of Catalytic Systems in a CS Corrected Environmental Transmission Electron Microscope

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Dunin-Borkowski, Rafal E.; Boothroyd, Chris

    2010-01-01

    to chemical reactors, a conventional TEM is a high vacuum tool. Thus, observations do not always reflect the active state of materials. Environmental TEM (ETEM) provides the capability to expose samples to a gas atmosphere during imaging and analysis. Even though the gap between reactor and high...... nanoparticles up to 20nm in size. The particles were exposed to 1.3 mbar of H2 gas at 410°C in an image CS corrected FEI Titan 80-300 ETEM. Image sequences were acquired at 2 frames/s. Under these conditions, mobility of the particles was clearly visible, while maintaining lattice resolution of both the BN...

  4. Towards high resolution mapping of 3-D mesoscale dynamics from observations

    Directory of Open Access Journals (Sweden)

    B. Buongiorno Nardelli

    2012-10-01

    Full Text Available The MyOcean R&D project MESCLA (MEsoSCaLe dynamical Analysis through combined model, satellite and in situ data was devoted to the high resolution 3-D retrieval of tracer and velocity fields in the oceans, based on the combination of in situ and satellite observations and quasi-geostrophic dynamical models. The retrieval techniques were also tested and compared with the output of a primitive equation model, with particular attention to the accuracy of the vertical velocity field as estimated through the Q vector formulation of the omega equation. The project focused on a test case, covering the region where the Gulf Stream separates from the US East Coast. This work demonstrated that innovative methods for the high resolution mapping of 3-D mesoscale dynamics from observations can be used to build the next generations of operational observation-based products.

  5. Tropical Pacific internal atmospheric dynamics and resolution in a coupled GCM

    Science.gov (United States)

    Lopez, Hosmay; Kirtman, Ben P.

    2015-01-01

    A noise reduction technique, namely the interactive ensemble (IE) approach is adopted to reduce noise at the air-sea interface due to internal atmospheric dynamics in a state-of-the-art coupled general circulation model (CGCM). The IE technique uses multiple realization of atmospheric general circulation models coupled to a single ocean general circulation model. The ensembles mean fluxes from the atmospheric simulations are communicated to the ocean component. Each atmospheric simulation receives the same SST coming from the ocean component. The only difference among the atmospheric simulations comes from perturbed initial conditions, thus the atmospheric states are, in principle synoptically independent. The IE technique can be used to better understand the importance of weather noise forcing of natural variability such as El Niño Southern Oscillation (ENSO). To study the impact of weather noise and resolution in the context of a CGCM, two IE experiments are performed at different resolutions. Atmospheric resolution is an important issue since the noise statistics will depend on the spatial scales resolved. A simple formulation to extract atmospheric internal variability is presented. The results are compared to their respective control cases where internal atmospheric variability is left unchanged. The noise reduction has a major impact on the coupled simulation and the magnitude of this effect strongly depends on the horizontal resolution of the atmospheric component model. Specifically, applying the noise reduction technique reduces the overall climate variability more effectively at higher resolution. This suggests that "weather noise" is more important in sustaining climate variability as resolution increases. ENSO statistics, dynamics, and phase asymmetry are all modified by the noise reduction, in particular ENSO becomes more regular with less phase asymmetry when noise is reduced. All these effects are more marked for the higher resolution case. In

  6. Real-time high-resolution heterodyne-based measurements of spectral dynamics in fibre lasers

    Science.gov (United States)

    Sugavanam, Srikanth; Fabbri, Simon; Le, Son Thai; Lobach, Ivan; Kablukov, Sergey; Khorev, Serge; Churkin, Dmitry

    2016-03-01

    Conventional tools for measurement of laser spectra (e.g. optical spectrum analysers) capture data averaged over a considerable time period. However, the generation spectrum of many laser types may involve spectral dynamics whose relatively fast time scale is determined by their cavity round trip period, calling for instrumentation featuring both high temporal and spectral resolution. Such real-time spectral characterisation becomes particularly challenging if the laser pulses are long, or they have continuous or quasi-continuous wave radiation components. Here we combine optical heterodyning with a technique of spatio-temporal intensity measurements that allows the characterisation of such complex sources. Fast, round-trip-resolved spectral dynamics of cavity-based systems in real-time are obtained, with temporal resolution of one cavity round trip and frequency resolution defined by its inverse (85 ns and 24 MHz respectively are demonstrated). We also show how under certain conditions for quasi-continuous wave sources, the spectral resolution could be further increased by a factor of 100 by direct extraction of phase information from the heterodyned dynamics or by using double time scales within the spectrogram approach.

  7. An insight to conserved water molecular dynamics of catalytic and structural Zn(+2) ions in matrix metalloproteinase 13 of human.

    Science.gov (United States)

    Chakrabarti, Bornali; Bairagya, Hridoy R; Mallik, Payel; Mukhopadhyay, Bishnu P; Bera, Asim K

    2011-02-01

    Matrix Metalloproteinase (MMP)--13 or Collagenase--3 plays a significant role in the formation and remodeling of bone, tumor invasion and causes osteoarthritis. Water molecular dynamic studies of the five (1XUC, 1XUD, 1XUR, 456C, 830C) PDB and solvated structures of MMP-13 in human have been carried out upto 5 ns on assigning the differential charges (+2, +1, +0.5 e) to both the Zinc ions. The MM and MD-studies have revealed the coordination of three water molecules (W(H), W(I) and W(S)) to Zn(c) and one water to Zn(s). The transition of geometry around the Znc from tetrahedral to octahedral via trigonal bipyramidal, and for Zn(s) from tetrahedral to trigonal bipyramidal are seem interesting. Recognition of two zinc ions through water molecular bridging (Zn(c) - W(H) (W(1))...W(2)....W(3)....H(187) Zn(s)) and the stabilization of variable coordination geometries around metal ions may indicate the possible involvement of Zn(c) ...Zn(s) coupled mechanism in the catalytic process. So the hydrophilic topology and stereochemistry of water mediated coupling between Zn-ions may provide some plausible hope towards the design of some bidentate/polydentate bridging ligands or inhibitors for MMP-13.

  8. Dual enzymatic dynamic kinetic resolution by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase and Candida antarctica lipase B

    KAUST Repository

    Karume, Ibrahim

    2016-10-04

    The immobilization of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (TeSADH) using sol–gel method enables its use to racemize enantiopure alcohols in organic media. Here, we report the racemization of enantiopure phenyl-ring-containing secondary alcohols using xerogel-immobilized W110A TeSADH in hexane rather than the aqueous medium required by the enzyme. We further showed that this racemization approach in organic solvent was compatible with Candida antarctica lipase B (CALB)-catalyzed kinetic resolution. This compatibility, therefore, allowed a dual enzymatic dynamic kinetic resolution of racemic alcohols using CALB-catalyzed kinetic resolution and W110A TeSADH-catalyzed racemization of phenyl-ring-containing alcohols.

  9. Dynamic nuclear magnetic resonance field sensing with part-per-trillion resolution

    Science.gov (United States)

    Gross, Simon; Barmet, Christoph; Dietrich, Benjamin E.; Brunner, David O.; Schmid, Thomas; Pruessmann, Klaas P.

    2016-12-01

    High-field magnets of up to tens of teslas in strength advance applications in physics, chemistry and the life sciences. However, progress in generating such high fields has not been matched by corresponding advances in magnetic field measurement. Based mostly on nuclear magnetic resonance, dynamic high-field magnetometry is currently limited to resolutions in the nanotesla range. Here we report a concerted approach involving tailored materials, magnetostatics and detection electronics to enhance the resolution of nuclear magnetic resonance sensing by three orders of magnitude. The relative sensitivity thus achieved amounts to 1 part per trillion (10-12). To exemplify this capability we demonstrate the direct detection and relaxometry of nuclear polarization and real-time recording of dynamic susceptibility effects related to human heart function. Enhanced high-field magnetometry will generally permit a fresh look at magnetic phenomena that scale with field strength. It also promises to facilitate the development and operation of high-field magnets.

  10. DUSTER: dynamic contrast enhance up-sampled temporal resolution analysis method.

    Science.gov (United States)

    Liberman, Gilad; Louzoun, Yoram; Artzi, Moran; Nadav, Guy; Ewing, James R; Ben Bashat, Dafna

    2016-05-01

    Dynamic contrast enhanced (DCE) MRI using Tofts' model for estimating vascular permeability is widely accepted, yet inter-tissue differences in bolus arrival time (BAT) are generally ignored. In this work we propose a method, incorporating the BAT in the analysis, demonstrating its applicability and advantages in healthy subjects and patients. A method for DCE Up Sampled TEmporal Resolution (DUSTER) analysis is proposed which includes: baseline T1 map using DESPOT1 analyzed with flip angle (FA) correction; preprocessing; raw-signal-to-T1-to-concentration time curves (CTC) conversion; automatic arterial input function (AIF) extraction at temporal super-resolution; model fitting with model selection while incorporating BAT in the pharmacokinetic (PK) model, and fits contrast agent CTC while using exhaustive search in the BAT dimension in super-resolution. The method was applied to simulated data and to human data from 17 healthy subjects, six patients with glioblastoma, and two patients following stroke. BAT values were compared to time-to-peak (TTP) values extracted from dynamic susceptibility contrast imaging. Results show that the method improved the AIF estimation and allowed extraction of the BAT with a resolution of 0.8 s. In simulations, lower mean relative errors were detected for all PK parameters extracted using DUSTER compared to analysis without BAT correction (vp:5% vs. 20%, Ktrans: 9% vs. 24% and Kep: 8% vs. 17%, respectively), and BAT estimates demonstrated high correlations (r = 0.94, p resolution (2 s) and sub-sampled standard resolution data (6 s) (mean r = 0.85,p < 1e− 10). BAT and TTP values were significantly correlated in the different brain regions in healthy subjects (mean r = 0.72,p = < 1e− 3), as were voxel-wise comparisons in patients (mean r = 0.89, p < 1e− 10). In conclusion, incorporating BAT in DCE analysis improves estimation accuracy for the AIF and the PK parameters while providing an additional clinically important parameter.

  11. High resolution ultrasonic monitoring of muscle dynamics and novel approach to modelling

    OpenAIRE

    Muhammad, Zakir Hossain

    2013-01-01

    The presented work is concerned with the development and application of an ultrasonic detection scheme suitable for the monitoring of muscle dynamics with high temporal - down to 5 µs - and spatial resolution - down to 0.78 µm. A differential detection scheme has been developed to monitor the variations of the velocity of longitudinal polarized ultrasound waves travelling in contracting and relaxing muscle, compensating for variations of the path length by referencing to a frame. The observed...

  12. Towards a resolution of certain dilemmas in preon dynamics through local supersymmetry

    Science.gov (United States)

    Pati, Jogesh C.; Cveti, Mirjam; Sharatchandra, H. S.

    1987-03-01

    A resolution of one of the major dilemmas of preon dynamics, i.e., why (mq,ml)<<(1/r0)≡Λ0, is provided. In a class of models, supersymmetry (SUSY) in its local rather than global form permits a breaking of SUSY and also a generation of composite-fermion masses, but both with a severe damping by powers of (Λ0/MPlanck).

  13. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  14. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-09-30

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  15. High-resolution dynamic atomic force microscopy in liquids with different feedback architectures

    Directory of Open Access Journals (Sweden)

    John Melcher

    2013-02-01

    Full Text Available The recent achievement of atomic resolution with dynamic atomic force microscopy (dAFM [Fukuma et al., Appl. Phys. Lett. 2005, 87, 034101], where quality factors of the oscillating probe are inherently low, challenges some accepted beliefs concerning sensitivity and resolution in dAFM imaging modes. Through analysis and experiment we study the performance metrics for high-resolution imaging with dAFM in liquid media with amplitude modulation (AM, frequency modulation (FM and drive-amplitude modulation (DAM imaging modes. We find that while the quality factors of dAFM probes may deviate by several orders of magnitude between vacuum and liquid media, their sensitivity to tip–sample forces can be remarkable similar. Furthermore, the reduction in noncontact forces and quality factors in liquids diminishes the role of feedback control in achieving high-resolution images. The theoretical findings are supported by atomic-resolution images of mica in water acquired with AM, FM and DAM under similar operating conditions.

  16. FitEM2EM--tools for low resolution study of macromolecular assembly and dynamics.

    Directory of Open Access Journals (Sweden)

    Ziv Frankenstein

    Full Text Available Studies of the structure and dynamics of macromolecular assemblies often involve comparison of low resolution models obtained using different techniques such as electron microscopy or atomic force microscopy. We present new computational tools for comparing (matching and docking of low resolution structures, based on shape complementarity. The matched or docked objects are represented by three dimensional grids where the value of each grid point depends on its position with regard to the interior, surface or exterior of the object. The grids are correlated using fast Fourier transformations producing either matches of related objects or docking models depending on the details of the grid representations. The procedures incorporate thickening and smoothing of the surfaces of the objects which effectively compensates for differences in the resolution of the matched/docked objects, circumventing the need for resolution modification. The presented matching tool FitEM2EMin successfully fitted electron microscopy structures obtained at different resolutions, different conformers of the same structure and partial structures, ranking correct matches at the top in every case. The differences between the grid representations of the matched objects can be used to study conformation differences or to characterize the size and shape of substructures. The presented low-to-low docking tool FitEM2EMout ranked the expected models at the top.

  17. Dynamic imaging with high resolution time-of-flight pet camera - TOFPET I

    Energy Technology Data Exchange (ETDEWEB)

    Mullani, N.A.; Bristow, D.; Gaeta, J.; Gould, K.L.; Hartz, R.K.; Philipe, E.A.; Wong, W.H.; Yerian, K.

    1984-02-01

    One of the major design goals of the TOFPET I positron camera was to produce a high resolution whole body positron camera capable of dynamically imaging an organ such as the heart. TOFPET I is now nearing completion and preliminary images have been obtained to assess its dynamic and three dimensional imaging capabilities. Multiple gated images of the uptake of Rubidium in the dog heart and three dimensional surface displays of the distribution of the Rubidium-82 in the myocardium have been generated to demonstrate the three dimensional imaging properties. Fast dynamic images of the first pass of a bolus of radio-tracer through the heart have been collected with 4 second integration time and 50% gating (2 second equivalent integration time) with 18 mCi of Rb-82.

  18. Grand-Canonical Adaptive Resolution Centroid Molecular Dynamics: Implementation and Application

    CERN Document Server

    Agarwal, Animesh

    2016-01-01

    We have implemented the Centroid Molecular Dynamics scheme (CMD) into the Grand Canonical-like version of the Adaptive Resolution Simulation Molecular Dynamics (GC-AdResS) method. We have tested the implementation on two different systems, liquid parahydrogen at extreme thermodynamic conditions and liquid water at ambient conditions; the reproduction of structural as well as dynamical results of reference systems are highly satisfactory. The capability of performing GC-AdResS CMD simulations allows for the treatment of a system characterized by some quantum features and open boundaries. This latter characteristic not only is of computational convenience, allowing for equivalent results of much larger and computationally more expensive systems, but also suggests a tool of analysis so far not explored, that is the unambiguous identification of the essential (quantum) degrees of freedom required for a given property.

  19. Grand-Canonical Adaptive Resolution Centroid Molecular Dynamics: Implementation and application

    Science.gov (United States)

    Agarwal, Animesh; Delle Site, Luigi

    2016-09-01

    We have implemented the Centroid Molecular Dynamics scheme (CMD) into the Grand Canonical-like version of the Adaptive Resolution Simulation Molecular Dynamics (GC-AdResS) method. We have tested the implementation on two different systems, liquid parahydrogen at extreme thermodynamic conditions and liquid water at ambient conditions; the reproduction of structural as well as dynamical results of reference systems are highly satisfactory. The capability of performing GC-AdResS CMD simulations allows for the treatment of a system characterized by some quantum features and open boundaries. This latter characteristic not only is of computational convenience, allowing for equivalent results of much larger and computationally more expensive systems, but also suggests a tool of analysis so far not explored, that is the unambiguous identification of the essential degrees of freedom required for a given property.

  20. Adaptive resolution simulation of a biomolecule and its hydration shell: Structural and dynamical properties

    Science.gov (United States)

    Fogarty, Aoife C.; Potestio, Raffaello; Kremer, Kurt

    2015-05-01

    A fully atomistic modelling of many biophysical and biochemical processes at biologically relevant length- and time scales is beyond our reach with current computational resources, and one approach to overcome this difficulty is the use of multiscale simulation techniques. In such simulations, when system properties necessitate a boundary between resolutions that falls within the solvent region, one can use an approach such as the Adaptive Resolution Scheme (AdResS), in which solvent particles change their resolution on the fly during the simulation. Here, we apply the existing AdResS methodology to biomolecular systems, simulating a fully atomistic protein with an atomistic hydration shell, solvated in a coarse-grained particle reservoir and heat bath. Using as a test case an aqueous solution of the regulatory protein ubiquitin, we first confirm the validity of the AdResS approach for such systems, via an examination of protein and solvent structural and dynamical properties. We then demonstrate how, in addition to providing a computational speedup, such a multiscale AdResS approach can yield otherwise inaccessible physical insights into biomolecular function. We use our methodology to show that protein structure and dynamics can still be correctly modelled using only a few shells of atomistic water molecules. We also discuss aspects of the AdResS methodology peculiar to biomolecular simulations.

  1. Adaptive resolution simulation of a biomolecule and its hydration shell: Structural and dynamical properties

    Energy Technology Data Exchange (ETDEWEB)

    Fogarty, Aoife C., E-mail: fogarty@mpip-mainz.mpg.de; Potestio, Raffaello, E-mail: potestio@mpip-mainz.mpg.de; Kremer, Kurt, E-mail: kremer@mpip-mainz.mpg.de [Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany)

    2015-05-21

    A fully atomistic modelling of many biophysical and biochemical processes at biologically relevant length- and time scales is beyond our reach with current computational resources, and one approach to overcome this difficulty is the use of multiscale simulation techniques. In such simulations, when system properties necessitate a boundary between resolutions that falls within the solvent region, one can use an approach such as the Adaptive Resolution Scheme (AdResS), in which solvent particles change their resolution on the fly during the simulation. Here, we apply the existing AdResS methodology to biomolecular systems, simulating a fully atomistic protein with an atomistic hydration shell, solvated in a coarse-grained particle reservoir and heat bath. Using as a test case an aqueous solution of the regulatory protein ubiquitin, we first confirm the validity of the AdResS approach for such systems, via an examination of protein and solvent structural and dynamical properties. We then demonstrate how, in addition to providing a computational speedup, such a multiscale AdResS approach can yield otherwise inaccessible physical insights into biomolecular function. We use our methodology to show that protein structure and dynamics can still be correctly modelled using only a few shells of atomistic water molecules. We also discuss aspects of the AdResS methodology peculiar to biomolecular simulations.

  2. Super-resolution infrared time measurement method based on target dynamic characteristics

    Science.gov (United States)

    Li, Bin; Hu, Qiuping; Tang, Zili; Zhang, Sanxi; Zhang, Hua; Yue, Peng; Liu, Biao

    2016-10-01

    High precision time control in the use of weapons and equipment is an important part of product design and development. In order to satisfy the data acquisition requirement of high accuracy and reliability in the rapid flight process, the super-resolution time measurement method based on target dynamic characteristics was put forward and proved by the cabin opening time measurement experiment. First, the changes of explosion pressure wave and image in the cabin opening process were analyzed in detail. The change regulation of explosion flame shape was analyzed by the characteristics of typical pressure wave, and then the high frequency images of the explosion process were shot by high speed camera. The change regulation of the infrared image was obtained through the comparison of visible and infrared image mechanism. Then, combined with the target motion features, and the observed station parameters, the observation model of movement process was built. On the basis of the above research, the infrared characteristic and the movement characteristic were transformed, and the super resolution model was established. For test method, combined with the actual class time measuring process in experimental design, to obtain the special radar for measuring high precision open class time as the true value of the precision appraisal. Experimental results show that the infrared feature and motion feature can realize open class time super resolution measurement, can effectively improve the accuracy and reliability of the data, to achieve specific action of high accuracy measurement that plays an important role by making use of the target dynamic characteristics.

  3. Dynamic high-resolution ultrasound of the shoulder: how we do it.

    Science.gov (United States)

    Corazza, Angelo; Orlandi, Davide; Fabbro, Emanuele; Ferrero, Giulio; Messina, Carmelo; Sartoris, Riccardo; Perugin Bernardi, Silvia; Arcidiacono, Alice; Silvestri, Enzo; Sconfienza, Luca Maria

    2015-02-01

    Ultrasonography (US) is an established and well-accepted modality that can be used to evaluate articular and peri-articular structures around the shoulder. US has been proven to be useful in a wide range of rotator cuff diseases (tendon tears, tendinosis, and bursitis) as well as non-rotator cuff abnormalities (instability problems, synovial joint diseases, and nerve entrapment syndromes). Diagnostic accuracy of shoulder US when evaluating rotator cuff tears can reach 91-100% for partial and full thickness tears detection, respectively, having been reported to be as accurate as magnetic resonance imaging in experienced hands. US is cheap, readily available, capable to provide high-resolution images, and does not use ionizing radiations. In addition, US is the only imaging modality that allows performing dynamic evaluation of musculoskeletal structures, that may help to further increase diagnostic performance. In this setting, a standardized imaging protocol is essential for an exhaustive and efficient examination, also helping reducing the intrinsic dependence from operators of US. Furthermore, knowledge of pitfalls that can be encountered when examining the shoulder may help to avoid erroneous images interpretation. In this article we use detailed anatomic schemes and high-resolution US images to describe the normal US anatomy of soft tissues, articular, and para-articular structures located in and around the shoulder. Short video clips emphasizing the crucial role of dynamic maneuvers and dynamic real-time US examination of these structures are included as supplementary material.

  4. High-resolution dynamic pressure sensor array based on piezo-phototronic effect tuned photoluminescence imaging.

    Science.gov (United States)

    Peng, Mingzeng; Li, Zhou; Liu, Caihong; Zheng, Qiang; Shi, Xieqing; Song, Ming; Zhang, Yang; Du, Shiyu; Zhai, Junyi; Wang, Zhong Lin

    2015-03-24

    A high-resolution dynamic tactile/pressure display is indispensable to the comprehensive perception of force/mechanical stimulations such as electronic skin, biomechanical imaging/analysis, or personalized signatures. Here, we present a dynamic pressure sensor array based on pressure/strain tuned photoluminescence imaging without the need for electricity. Each sensor is a nanopillar that consists of InGaN/GaN multiple quantum wells. Its photoluminescence intensity can be modulated dramatically and linearly by small strain (0-0.15%) owing to the piezo-phototronic effect. The sensor array has a high pixel density of 6350 dpi and exceptional small standard deviation of photoluminescence. High-quality tactile/pressure sensing distribution can be real-time recorded by parallel photoluminescence imaging without any cross-talk. The sensor array can be inexpensively fabricated over large areas by semiconductor product lines. The proposed dynamic all-optical pressure imaging with excellent resolution, high sensitivity, good uniformity, and ultrafast response time offers a suitable way for smart sensing, micro/nano-opto-electromechanical systems.

  5. 工业催化重整过程动态建模与仿真%Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process

    Institute of Scientific and Technical Information of China (English)

    胡永有; 徐巍华; 侯卫锋; 苏宏业; 褚健

    2005-01-01

    A first principles-based dynamic model for a continuous catalyst regeneration (CCR) platforming process, the UOP commercial naphtha catalytic reforming process, is developed in this paper. The lumping details of the naphtha feed and reaction scheme of the reaction model are given. The process model is composed of the reforming reaction model with catalyst deactivation, the furnace model and the separator model, which is capable of capturing the major dynamics that occurs in this process system. Dynamic simulations are performed based on Gear numerical algorithm and method of lines (MOL), a numerical technique dealing with partial differential equations (PDEs). The results of simulation are also presented. Dynamic responses caused by disturbances in the process system can be correctly predicted through simulations.

  6. High resolution dynamic ocean topography in the Southern Ocean from GOCE

    Science.gov (United States)

    Albertella, A.; Savcenko, R.; Janjić, T.; Rummel, R.; Bosch, W.; Schröter, J.

    2012-08-01

    A mean dynamic ocean topography (MDT) has been computed using a high resolution GOCE (Gravity field and steady-state Ocean Circulation Explorer) gravity model and a new mean sea surface obtained from a combination of satellite altimetry covering the period 1992 October till 2010 April. The considered gravity model is GO-CONS-GCF-2-TIM-R3, which computes geoid using 12 months of GOCE gravity field data. The GOCE gravity data allow for more detailed and accurate estimates of MDT. This is illustrated in the Southern Ocean where the commission error is reduced from 20 to 5 cm compared to the MDT computed using the GRACE gravity field model ITG-Grace2010. As a result of the more detailed and accurate MDT, the calculation of geostrophic velocities from the MDT is now possible with higher accuracy and spatial resolution, and the error estimate is about 7 cm s-1 for the Southern Ocean.

  7. Validation of the Aura High Resolution Dynamics Limb Sounder geopotential heights

    Directory of Open Access Journals (Sweden)

    L. L. Smith

    2014-02-01

    Full Text Available Global satellite observations from the EOS Aura spacecraft's High Resolution Dynamics Limb Sounder (HIRDLS of temperature and geopotential height (GPH are discussed. The accuracy, resolution and precision of the HIRDLS version 7 algorithms are assessed and data screening recommendations are made. Comparisons with GPH from observations, reanalyses and models including European Center for Medium-Range Weather Forecasts Interim Reanalysis (ERA-Interim, National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR Reanalysis, Goddard Earth Observing System Model (GEOS version 5, and EOS Aura Microwave Limb Sounder (MLS illustrate the HIRDLS GPH have a precision ranging from 2 m to 30 m and an accuracy of ±100 m. Comparisons indicate HIRDLS GPH may have a slight low bias in the tropics and a slight high bias at high latitudes. Geostrophic winds computed with HIRDLS GPH qualitatively agree with winds from other data sources including ERA-Interim, NCEP and GEOS-5.

  8. Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

    Directory of Open Access Journals (Sweden)

    Bäckvall Jan-E

    2007-12-01

    Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

  9. Full dynamic resolution low lower DA-Converters for flat panel displays

    Directory of Open Access Journals (Sweden)

    C. Saas

    2006-01-01

    Full Text Available It has been shown that stepwise charging can reduce the power dissipated in the source drivers of a flat panel display. However the solution presented only provided a dynamic resolution of 3 bits which is not sufficient for obtaining a full color resolution display. In this work a further development of the basic idea is presented. The stepwise charging is increased to 4 bits and supplemented by a current source to provide an output signal which represents an 8 bit value with sufficient accuracy. Within this work the application is an AM-OLED flat panel display, but the concept can easily be applied to other display technologies like TFT-LCD as well.

  10. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I[alpha] photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a soft'' mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  11. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I{alpha} photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a ``soft`` mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  12. Impact of the lateral boundary conditions resolution on dynamical downscaling of precipitation in mediterranean spain

    Energy Technology Data Exchange (ETDEWEB)

    Amengual, A.; Romero, R.; Homar, V.; Ramis, C.; Alonso, S. [Universitat de les Illes Balears, Grup de Meteorologia, Departament de Fisica, Palma de Mallorca (Spain)

    2007-10-15

    Conclusions on the General Circulation Models (GCMs) horizontal and temporal optimum resolution for dynamical downscaling of rainfall in Mediterranean Spain are derived based on the statistical analysis of mesoscale simulations of past events. These events correspond to the 165 heavy rainfall days during 1984-1993, which are simulated with the HIRLAM mesoscale model. The model is nested within the European Centre for Medium-Range Weather Forecasts atmospheric grid analyses. We represent the spectrum of GCMs resolutions currently applied in climate change research by using varying horizontal and temporal resolutions of these analyses. Three sets of simulations are designed using input data with 1 , 2 and 3 horizontal resolutions (available at 6 h intervals), and three additional sets are designed using 1 horizontal resolution with less frequent boundary conditions updated every 12, 24 and 48 h. The quality of the daily rainfall forecasts is verified against rain-gauge observations using correlation and root mean square error analysis as well as Relative Operating Characteristic curves. Spatial distribution of average precipitation fields are also computed and verified against observations. For the whole Mediterranean Spain, model skill is not appreciably improved when using enhanced spatial input data, suggesting that there is no clear benefit in using high resolution data from General Circulation Model for the regional downscaling of precipitation under the conditions tested. However, significant differences are found in verification scores when boundary conditions are interpolated less frequently than 12 h apart. The analysis is particularized for six major rain bearing flow regimes that affect the region, and differences in model performance are found among the flow types, with slightly better forecasts for Atlantic and cold front passage flows. A remarkable spatial variability in forecast quality is found in the domain, with an overall tendency for higher

  13. Stereoselective nucleophilic fluoromethylation of aryl ketones: dynamic kinetic resolution of chiral α-fluoro carbanions.

    Science.gov (United States)

    Shen, Xiao; Miao, Wenjun; Ni, Chuanfa; Hu, Jinbo

    2014-01-13

    Although many methods are available for the synthesis of optically enriched monofluoromethyl secondary alcohols, synthesizing optically enriched monofluoromethyl tertiary alcohols remains a challenge. An efficient and easy-to-handle nucleophilic fluoromethylation protocol was developed. The current monofluoromethylation showed much higher facial selectivity than the corresponding difluoromethylation and proceeded via a different type of transition state. Excellent stereoselective control at the fluorinated carbon chiral center was found, an effect believed to be facilitated by the dynamic kinetic resolution of the chiral α-fluoro carbanions.

  14. Extended-Range High-Resolution Dynamical Downscaling over a Continental-Scale Domain

    Science.gov (United States)

    Husain, S. Z.; Separovic, L.; Yu, W.; Fernig, D.

    2014-12-01

    High-resolution mesoscale simulations, when applied for downscaling meteorological fields over large spatial domains and for extended time periods, can provide valuable information for many practical application scenarios including the weather-dependent renewable energy industry. In the present study, a strategy has been proposed to dynamically downscale coarse-resolution meteorological fields from Environment Canada's regional analyses for a period of multiple years over the entire Canadian territory. The study demonstrates that a continuous mesoscale simulation over the entire domain is the most suitable approach in this regard. Large-scale deviations in the different meteorological fields pose the biggest challenge for extended-range simulations over continental scale domains, and the enforcement of the lateral boundary conditions is not sufficient to restrict such deviations. A scheme has therefore been developed to spectrally nudge the simulated high-resolution meteorological fields at the different model vertical levels towards those embedded in the coarse-resolution driving fields derived from the regional analyses. A series of experiments were carried out to determine the optimal nudging strategy including the appropriate nudging length scales, nudging vertical profile and temporal relaxation. A forcing strategy based on grid nudging of the different surface fields, including surface temperature, soil-moisture, and snow conditions, towards their expected values obtained from a high-resolution offline surface scheme was also devised to limit any considerable deviation in the evolving surface fields due to extended-range temporal integrations. The study shows that ensuring large-scale atmospheric similarities helps to deliver near-surface statistical scores for temperature, dew point temperature and horizontal wind speed that are better or comparable to the operational regional forecasts issued by Environment Canada. Furthermore, the meteorological fields

  15. WRF high resolution dynamical downscaling of ERA-Interim for Portugal

    Energy Technology Data Exchange (ETDEWEB)

    Soares, Pedro M.M. [University of Lisbon, Instituto Dom Luiz, Lisbon (Portugal); Faculdade de Ciencias da Universidade de Lisboa, Lisbon (Portugal); Cardoso, Rita M.; Miranda, Pedro M.A.; Medeiros, Joana de [University of Lisbon, Instituto Dom Luiz, Lisbon (Portugal); Belo-Pereira, Margarida; Espirito-Santo, Fatima [Instituto de Meteorologia, Lisbon (Portugal)

    2012-11-15

    This study proposes a dynamically downscaled climatology of Portugal, produced by a high resolution (9 km) WRF simulation, forced by 20 years of ERA-Interim reanalysis (1989-2008), nested in an intermediate domain with 27 km of resolution. The Portuguese mainland is characterized by large precipitation gradients, with observed mean annual precipitation ranging from about 400 to over 2,200 mm, with a very wet northwest and rather dry southeast, largely explained by orographic processes. Model results are compared with all available stations with continuous records, comprising daily information in 32 stations for temperature and 308 for precipitation, through the computation of mean climatologies, standard statistical errors on daily to seasonally timescales, and distributions of extreme events. Results show that WRF at 9 km outperforms ERA-Interim in all analyzed variables, with good results in the representation of the annual cycles in each region. The biases of minimum and maximum temperature are reduced, with improvement of the description of temperature variability at the extreme range of its distribution. The largest gain of the high resolution simulations is visible in the rainiest regions of Portugal, where orographic enhancement is crucial. These improvements are striking in the high ranking percentiles in all seasons, describing extreme precipitation events. WRF results at 9 km compare favorably with published results supporting its use as a high-resolution regional climate model. This higher resolution allows a better representation of extreme events that are of major importance to develop mitigation/adaptation strategies by policy makers and downstream users of regional climate models in applications such as flash floods or heat waves. (orig.)

  16. Studying Vortex Dynamics of Rotating Convection with High-resolution PIV Measurement

    Science.gov (United States)

    Fu, Hao; Sun, Shiwei; Wang, Yu; Zhou, Bowen; Wang, Yuan

    2016-11-01

    A novel experimental setup for studying vortex dynamics in rotating Rayleigh-Benard convection has been made in School of Atmospheric Sciences, Nanjing University. With water as the working fluid, three lasers with different frequencies and the corresponding three CCDs have been placed to complete 2D2C (two dimensions, two components) PIV measurement. The lasers are fixed on two crossing guiding ways and can move up and down to scan the flow field. An algorithm has been made to reconstruct 3D velocity field based on multiple 2D2C PIV data. This time, we are going to present the details of this new machine and algorithm, as well as some scientific understanding of vortex dynamics owing to this high-resolution velocity measurement system. This work was supported by "LMSWE Lab Funding No. 14380001".

  17. Dynamic high-resolution ultrasound of the shoulder: How we do it

    Energy Technology Data Exchange (ETDEWEB)

    Corazza, Angelo, E-mail: angelcoraz@libero.it [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Orlandi, Davide, E-mail: theabo@libero.it [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Fabbro, Emanuele, E-mail: emanuele.fabbro@gmail.com [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Ferrero, Giulio, E-mail: giulio.ferrero@gmail.com [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Messina, Carmelo, E-mail: carmelomessina.md@gmail.com [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Milano, Piazza Malan 2, 20097 San Donato Milanese (Italy); Sartoris, Riccardo, E-mail: riccardo.sartoris@hotmail.it [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Perugin Bernardi, Silvia, E-mail: silvy-86-@hotmail.it [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Arcidiacono, Alice, E-mail: a.arcidiacono84@gmail.com [Scuola di Specializzazione in Radiodiagnostica, Università degli Studi di Genova, Via Alberti 4, 16132 Genova (Italy); Silvestri, Enzo, E-mail: silvi.enzo@gmail.com [Dipartimento di Radiologia, Ospedale Evangelico Internazionale, Corso Solferino 29A, 16121 Genova (Italy); and others

    2015-02-15

    Highlights: • This paper shows how to apply US technique to image soft tissues around the shoulder. • Readers will learn to recognize normal US anatomy of tendons of the shoulder. • Readers will learn to apply dynamic maneuvers to improve rotator cuff visibility. - Abstract: Ultrasonography (US) is an established and well-accepted modality that can be used to evaluate articular and peri-articular structures around the shoulder. US has been proven to be useful in a wide range of rotator cuff diseases (tendon tears, tendinosis, and bursitis) as well as non-rotator cuff abnormalities (instability problems, synovial joint diseases, and nerve entrapment syndromes). Diagnostic accuracy of shoulder US when evaluating rotator cuff tears can reach 91–100% for partial and full thickness tears detection, respectively, having been reported to be as accurate as magnetic resonance imaging in experienced hands. US is cheap, readily available, capable to provide high-resolution images, and does not use ionizing radiations. In addition, US is the only imaging modality that allows performing dynamic evaluation of musculoskeletal structures, that may help to further increase diagnostic performance. In this setting, a standardized imaging protocol is essential for an exhaustive and efficient examination, also helping reducing the intrinsic dependence from operators of US. Furthermore, knowledge of pitfalls that can be encountered when examining the shoulder may help to avoid erroneous images interpretation. In this article we use detailed anatomic schemes and high-resolution US images to describe the normal US anatomy of soft tissues, articular, and para-articular structures located in and around the shoulder. Short video clips emphasizing the crucial role of dynamic maneuvers and dynamic real-time US examination of these structures are included as supplementary material.

  18. Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

    DEFF Research Database (Denmark)

    Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram

    2012-01-01

    Pd/Al2O3 catalysts oscillate between ignition and extinction of the catalytic partial oxidation of methane when they are exposed to a 2:1 reaction mixture of methane and oxygen. The oscillations of the catalytic performance and the structure of Pd/Al2O3 catalysts in a fixed-bed reactor were...... of the Pd particles at increasing age of the catalyst was observed, which leads to a lower oscillation frequency. Effects of particle size, oven temperature, and oxygen/methane ratio on the oscillation behavior were studied in detail. The deactivation period (reoxidation of Pd) was much less influenced...... by the oven temperature than the ignition behavior of the catalytic partial oxidation of methane. This indicates that deactivation is caused by an autoreduction of the palladium at the beginning of the catalyst bed due to the high temperature achieved by total oxidation of methane....

  19. Bending Dynamics of Fluctuating Biopolymers Probed by Automated High-Resolution Filament Tracking

    Science.gov (United States)

    Brangwynne, Clifford P.; Koenderink, Gijsje H.; Barry, Ed; Dogic, Zvonimir; MacKintosh, Frederick C.; Weitz, David A.

    2007-01-01

    Microscope images of fluctuating biopolymers contain a wealth of information about their underlying mechanics and dynamics. However, successful extraction of this information requires precise localization of filament position and shape from thousands of noisy images. Here, we present careful measurements of the bending dynamics of filamentous (F-)actin and microtubules at thermal equilibrium with high spatial and temporal resolution using a new, simple but robust, automated image analysis algorithm with subpixel accuracy. We find that slender actin filaments have a persistence length of ∼17 μm, and display a q−4-dependent relaxation spectrum, as expected from viscous drag. Microtubules have a persistence length of several millimeters; interestingly, there is a small correlation between total microtubule length and rigidity, with shorter filaments appearing softer. However, we show that this correlation can arise, in principle, from intrinsic measurement noise that must be carefully considered. The dynamic behavior of the bending of microtubules also appears more complex than that of F-actin, reflecting their higher-order structure. These results emphasize both the power and limitations of light microscopy techniques for studying the mechanics and dynamics of biopolymers. PMID:17416612

  20. Investigating sub-spine actin dynamics in rat hippocampal neurons with super-resolution optical imaging.

    Directory of Open Access Journals (Sweden)

    Vedakumar Tatavarty

    Full Text Available Morphological changes in dendritic spines represent an important mechanism for synaptic plasticity which is postulated to underlie the vital cognitive phenomena of learning and memory. These morphological changes are driven by the dynamic actin cytoskeleton that is present in dendritic spines. The study of actin dynamics in these spines traditionally has been hindered by the small size of the spine. In this study, we utilize a photo-activation localization microscopy (PALM-based single-molecule tracking technique to analyze F-actin movements with approximately 30-nm resolution in cultured hippocampal neurons. We were able to observe the kinematic (physical motion of actin filaments, i.e., retrograde flow and kinetic (F-actin turn-over dynamics of F-actin at the single-filament level in dendritic spines. We found that F-actin in dendritic spines exhibits highly heterogeneous kinematic dynamics at the individual filament level, with simultaneous actin flows in both retrograde and anterograde directions. At the ensemble level, movements of filaments integrate into a net retrograde flow of approximately 138 nm/min. These results suggest a weakly polarized F-actin network that consists of mostly short filaments in dendritic spines.

  1. Temporal dynamics of motivation-cognitive control interactions revealed by high-resolution pupillometry

    Directory of Open Access Journals (Sweden)

    Kimberly Sarah Chiew

    2013-01-01

    Full Text Available Motivational manipulations, such as the presence of performance-contingent reward incentives, can have substantial influences on cognitive control. Previous evidence suggests that reward incentives may enhance cognitive performance specifically through increased preparatory, or proactive, control processes. The present study examined reward influences on cognitive control dynamics in the AX-Continuous Performance Task (AX-CPT, using high-resolution pupillometry. In the AX-CPT, contextual cues must be actively maintained over a delay in order to appropriately respond to ambiguous target probes. A key feature of the task is that it permits dissociable characterization of preparatory, proactive control processes (i.e., utilization of context and reactive control processes (i.e., target-evoked interference resolution. Task performance profiles suggested that reward incentives enhanced proactive control (context utilization. Critically, pupil dilation was also increased on reward incentive trials during context maintenance periods, suggesting trial-specific shifts in proactive control, particularly when context cues indicated the need to overcome the dominant target response bias. Reward incentives had both transient (i.e., trial-by-trial and sustained (i.e., block-based effects on pupil dilation, which may reflect distinct underlying processes. The transient pupillary effects were present even when comparing against trials matched in task performance, suggesting a unique motivational influence of reward incentives. These results suggest that pupillometry may be a useful technique for investigating reward motivational signals and their dynamic influence on cognitive control.

  2. Temporal dynamics of motivation-cognitive control interactions revealed by high-resolution pupillometry.

    Science.gov (United States)

    Chiew, Kimberly S; Braver, Todd S

    2013-01-01

    Motivational manipulations, such as the presence of performance-contingent reward incentives, can have substantial influences on cognitive control. Previous evidence suggests that reward incentives may enhance cognitive performance specifically through increased preparatory, or proactive, control processes. The present study examined reward influences on cognitive control dynamics in the AX-Continuous Performance Task (AX-CPT), using high-resolution pupillometry. In the AX-CPT, contextual cues must be actively maintained over a delay in order to appropriately respond to ambiguous target probes. A key feature of the task is that it permits dissociable characterization of preparatory, proactive control processes (i.e., utilization of context) and reactive control processes (i.e., target-evoked interference resolution). Task performance profiles suggested that reward incentives enhanced proactive control (context utilization). Critically, pupil dilation was also increased on reward incentive trials during context maintenance periods, suggesting trial-specific shifts in proactive control, particularly when context cues indicated the need to overcome the dominant target response bias. Reward incentives had both transient (i.e., trial-by-trial) and sustained (i.e., block-based) effects on pupil dilation, which may reflect distinct underlying processes. The transient pupillary effects were present even when comparing against trials matched in task performance, suggesting a unique motivational influence of reward incentives. These results suggest that pupillometry may be a useful technique for investigating reward motivational signals and their dynamic influence on cognitive control.

  3. High-resolution polypeptide structure and dynamics in anisotropic environments: The gramicidin channel

    Energy Technology Data Exchange (ETDEWEB)

    Cross, T.A.; Lee, K.C.; Ketchem, R.R.; Hu, W.; Lazo, N.D.; Huo, S. [Florida State Univ., Tallahassee, FL (United States)

    1994-12-01

    To understand the details of macromolecular function, high-resolution structural and dynamic detail is essential. The polypeptide fold of the gramicidin channel has been effectively modeled for the past 20 years, yet the functional changes in conductance and channel lifetime associated with amino acid substitutions cannot be predicted. To accomplish this goal, high-resolution electrostatic modeling and the precise orientation of all dipoles are required. Furthermore, an enhanced knowledge of the complex molecular environment of this membrane-bound peptide is needed. An aqueous environment is relatively uniform and achiral. The membrane environment is very heterogenous and chiral. A knowledge of the interactions, specific and nonspecific, between peptide and lipid will aid in developing a better understanding of this environment. To accomplish this goal, it is necessary to study the peptide in an extended lipid bilayer, rather than in a vesicular or micellar form. These latter environments are likely to possess increased dynamics, increased water penetration, and distorted interactions between the polypeptide and membrane surface. To perform NMR studies on bilayer bound peptides, solid state NMR methods are required, and for specific site information, isotopic labels are incorporated using solid phase peptide synthesis.

  4. Super-resolution restoration applied to the characterisation of dynamic surface changes on the Martian surface

    Science.gov (United States)

    Tao, Yu; Muller, Jan-Peter

    2016-10-01

    Higher spatial resolution imaging data is always desirable to the international community of planetary scientists interested in improving understanding of surface formation processes. We have previously developed a novel Super-resolution restoration (SRR) technique using Gotcha sub-pixel matching [Shin & Muller, PR, 2012], orthorectification, segmentation, and 4th order PDE-TV, called GPT SRR [Tao & Muller, PSS, 2016]. This technique is able to restore 5cm-12.5cm near rover scale images (Navcam at a range of ≥5m) from multi-angle repeat-pass 25cm resolution MRO HiRISE images [Tao & Muller, ISPRS, 2016].We have successfully applied the GPT-SRR to the MER and MSL missions (http://www.progisweb.eu), as well as the alleged site of the Beagle-2 spacecraft (https://www.flickr.com/photos/uclnews/albums/72157667609698345). In this work, we further apply GPT-SRR on areas with known dynamic changes, including Recurring Slope Lineae (RSL), Gullies, and Polar Dune Flows. We restore static surface and meanwhile track the dynamic features to characterise the "change", including directions and speed of the changes. We also demonstrate that such repeat images can be used to image the MER-A rover stuck in the sands.AcknowledgementsThe research leading to these results has received funding from the European Union's Seventh Framework Programme (FP7/2007-2013) under iMars grant agreement no. 607379 as well as partial funding from the STFC "MSSL Consolidated Grant" ST/K000977/1.

  5. Atomistic resolution structure and dynamics of lipid bilayers in simulations and experiments.

    Science.gov (United States)

    Ollila, O H Samuli; Pabst, Georg

    2016-10-01

    Accurate details on the sampled atomistic resolution structures of lipid bilayers can be experimentally obtained by measuring C-H bond order parameters, spin relaxation rates and scattering form factors. These parameters can be also directly calculated from the classical atomistic resolution molecular dynamics simulations (MD) and compared to the experimentally achieved results. This comparison measures the simulation model quality with respect to 'reality'. If agreement is sufficient, the simulation model gives an atomistic structural interpretation of the acquired experimental data. Significant advance of MD models is made by jointly interpreting different experiments using the same structural model. Here we focus on phosphatidylcholine lipid bilayers, which out of all model membranes have been studied mostly by experiments and simulations, leading to the largest available dataset. From the applied comparisons we conclude that the acyl chain region structure and rotational dynamics are generally well described in simulation models. Also changes with temperature, dehydration and cholesterol concentration are qualitatively correctly reproduced. However, the quality of the underlying atomistic resolution structural changes is uncertain. Even worse, when focusing on the lipid bilayer properties at the interfacial region, e.g. glycerol backbone and choline structures, and cation binding, many simulation models produce an inaccurate description of experimental data. Thus extreme care must be applied when simulations are applied to understand phenomena where the interfacial region plays a significant role. This work is done by the NMRlipids Open Collaboration project running at https://nmrlipids.blogspot.fi and https://github.com/NMRLipids. This article is part of a Special Issue entitled: Biosimulations edited by Ilpo Vattulainen and Tomasz Róg.

  6. Evaluation of the variable depth resolution of active dynamic thermography on human skin

    Science.gov (United States)

    Prindeze, Nicholas J.; Hoffman, Hilary A.; Carney, Bonnie C.; Moffatt, Lauren T.; Loew, Murray H.; Shupp, Jeffrey W.

    2015-06-01

    Active dynamic thermography (ADT) is an imaging technique capable of characterizing the non-homogenous thermal conductance of damaged tissues. The purpose of this study was to determine optimal stimulation parameters and quantify the optical resolution of ADT through various depths of human skin. Excised tissue from plastic surgery operations was collected immediately following excision. A total of 12 thin to thick split-thickness grafts were harvested from 3 patients. Grafts were placed on top of a 3D printed resolution chart and thermal stimulation was applied from a 300W halogen lamp array for between 0.5-10 seconds to determine optimal parameters. Video was captured with a thermal camera, and analysis was performed by reconstructing an image from thermal gradients. In this study ADT resolved 0.445+/-0 lp/mm at a depth of 0.010", 0.356+/-0.048 lp/mm at a depth of 0.015", 0.334+/-0.027 lp/mm at a depth of 0.020" and 0.265+/-0.022 lp/mm at a depth of 0.025". The stimulus energy required for maximum resolution at each depth was 3- 4s, 8s, 12s and 12s respectively. ADT is a sensitive technique for imaging dermal structure, capable of resolving detail as fine as 1124 μm, 1427 μm, 1502 μm and 1893 μm in thin to thick split-thickness skin grafts respectively. This study has characterized a correlation between stimulus input and maximal resolution at differing depths of skin. It has also defined the functional imaging depth of ADT to below the sub-cutis, well below conventional spectrophotometric techniques.

  7. Daniel K. Inouye Solar Telescope: High-resolution observing of the dynamic Sun

    Science.gov (United States)

    Tritschler, A.; Rimmele, T. R.; Berukoff, S.; Casini, R.; Kuhn, J. R.; Lin, H.; Rast, M. P.; McMullin, J. P.; Schmidt, W.; Wöger, F.; DKIST Team

    2016-11-01

    The 4-m aperture Daniel K. Inouye Solar Telescope (DKIST) formerly known as the Advanced Technology Solar Telescope (ATST) is currently under construction on Haleakalā (Maui, Hawai'i) projected to start operations in 2019. At the time of completion, DKIST will be the largest ground-based solar telescope providing unprecedented resolution and photon collecting power. The DKIST will be equipped with a set of first-light facility-class instruments offering unique imaging, spectroscopic and spectropolarimetric observing opportunities covering the visible to infrared wavelength range. This first-light instrumentation suite will include: a Visible Broadband Imager (VBI) for high-spatial and -temporal resolution imaging of the solar atmosphere; a Visible Spectro-Polarimeter (ViSP) for sensitive and accurate multi-line spectropolarimetry; a Fabry-Pérot based Visible Tunable Filter (VTF) for high-spatial resolution spectropolarimetry; a fiber-fed Diffraction-Limited Near Infra-Red Spectro-Polarimeter (DL-NIRSP) for two-dimensional high-spatial resolution spectropolarimetry (simultaneous spatial and spectral information); and a Cryogenic Near Infra-Red Spectro-Polarimeter (Cryo-NIRSP) for coronal magnetic field measurements and on-disk observations of, e.g., the CO lines at 4.7 μm. We will provide an overview of the DKIST's unique capabilities with strong focus on the first-light instrumentation suite, highlight some of the additional properties supporting observations of transient and dynamic solar phenomena, and touch on some operational strategies and the DKIST critical science plan.

  8. Substrate binding and catalytic mechanism in phospholipase C from Bacillus cereus. a molecular mechanics and molecular dynamics study

    DEFF Research Database (Denmark)

    da Graça Thrige, D; Buur, J R; Jørgensen, Flemming Steen

    1997-01-01

    For the first time a consistent catalytic mechanism of phospholipase C from Bacillus cereus is reported based on molecular mechanics calculations. We have identified the position of the nucleophilic water molecule, which is directly involved in the hydrolysis of the natural substrate phosphatidyl...

  9. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  10. Dynamic high-resolution US of ankle and midfoot ligaments: normal anatomic structure and imaging technique.

    Science.gov (United States)

    Sconfienza, Luca Maria; Orlandi, Davide; Lacelli, Francesca; Serafini, Giovanni; Silvestri, Enzo

    2015-01-01

    The ankle is the most frequently injured major joint in the body, and ankle sprains are frequently encountered in individuals playing football, basketball, and other team sports, in addition to occurring in the general population. Imaging plays a crucial role in the evaluation of ankle ligaments. Magnetic resonance imaging has been proven to provide excellent evaluation of ligaments around the ankle, with the ability to show associated intraarticular abnormalities, joint effusion, and bone marrow edema. Ultrasonography (US) performed with high-resolution broadband linear-array probes has become increasingly important in the assessment of ligaments around the ankle because it is low cost, fast, readily available, and free of ionizing radiation. US can provide a detailed depiction of normal anatomic structures and is effective for evaluating ligament integrity. In addition, US allows the performance of dynamic maneuvers, which may contribute to increased visibility of normal ligaments and improved detection of tears. In this article, the authors describe the US techniques for evaluation of the ankle and midfoot ligaments and include a brief review of the literature related to their basic anatomic structures and US of these structures. Short video clips showing dynamic maneuvers and dynamic real-time US of ankle and midfoot structures and their principal pathologic patterns are included as supplemental material. Use of a standardized imaging technique may help reduce the intrinsic operator dependence of US. Online supplemental material is available for this article.

  11. Dynamics of genomic clones in breast cancer patient xenografts at single cell resolution

    Science.gov (United States)

    Eirew, Peter; Steif, Adi; Khattra, Jaswinder; Ha, Gavin; Yap, Damian; Farahani, Hossein; Gelmon, Karen; Chia, Stephen; Mar, Colin; Wan, Adrian; Laks, Emma; Biele, Justina; Shumansky, Karey; Rosner, Jamie; McPherson, Andrew; Nielsen, Cydney; Roth, Andrew J. L.; Lefebvre, Calvin; Bashashati, Ali; de Souza, Camila; Siu, Celia; Aniba, Radhouane; Brimhall, Jazmine; Oloumi, Arusha; Osako, Tomo; Bruna, Alejandra; Sandoval, Jose; Algara, Teresa; Greenwood, Wendy; Leung, Kaston; Cheng, Hongwei; Xue, Hui; Wang, Yuzhuo; Lin, Dong; Mungall, Andrew J.; Moore, Richard; Zhao, Yongjun; Lorette, Julie; Nguyen, Long; Huntsman, David; Eaves, Connie J.; Hansen, Carl; Marra, Marco A.; Caldas, Carlos; Shah, Sohrab P.; Aparicio, Samuel

    2016-01-01

    Human cancers, including breast cancers, are comprised of clones differing in mutation content. Clones evolve dynamically in space and time following principles of Darwinian evolution1,2, underpinning important emergent features such as drug resistance and metastasis3–7. Human breast cancer xenoengraftment is used as a means of capturing and studying tumour biology, and breast tumour xenografts are generally assumed to be reasonable models of the originating tumours8–10. However the consequences and reproducibility of engraftment and propagation on the genomic clonal architecture of tumours has not been systematically examined at single cell resolution. Here we show by both deep genome and single cell sequencing methods, the clonal dynamics of initial engraftment and subsequent serial propagation of primary and metastatic human breast cancers in immunodeficient mice. In all 15 cases examined, clonal selection on engraftment was observed in both primary and metastatic breast tumours, varying in degree from extreme selective engraftment of minor (<5% of starting population) clones to moderate, polyclonal engraftment. Furthermore, ongoing clonal dynamics during serial passaging is a feature of tumours experiencing modest initial selection. Through single cell sequencing, we show that major mutation clusters estimated from tumour population sequencing relate predictably to the most abundant clonal genotypes, even in clonally complex and rapidly evolving cases. Finally, we show that similar clonal expansion patterns can emerge in independent grafts of the same starting tumour population, indicating that genomic aberrations can be reproducible determinants of evolutionary trajectories. Our results show that measurement of genomically defined clonal population dynamics will be highly informative for functional studies utilizing patient-derived breast cancer xenoengraftment. PMID:25470049

  12. In vitro high-resolution structural dynamics of single germinating bacterial spores

    Energy Technology Data Exchange (ETDEWEB)

    Plomp, M; Leighton, T; Wheeler, K; Malkin, A

    2006-11-14

    Although significant progress has been achieved in understanding the genetic and biochemical bases of the spore germination process, the structural basis for breaking the dormant spore state remains poorly understood. We have used atomic force microscopy (AFM) to probe the high-resolution structural dynamics of single Bacillus atrophaeus spores germinating under native conditions. Here we show that AFM can reveal previously unrecognized germination-induced alterations in spore coat architecture and topology as well as the disassembly of outer spore coat rodlet structures. These results and previous studies in other microorganisms suggest that the spore coat rodlets are structurally similar to amyloid fibrils. AFM analysis of the nascent surface of the emerging germ cell revealed a porous network of peptidoglycan fibers. The results are consistent with a honeycomb model structure for synthetic peptidoglycan oligomers determined by nuclear magnetic resonance. AFM is a promising experimental tool for investigating the morphogenesis of spore germination and cell wall peptidoglycan structure.

  13. In vitro high-resolution structural dynamics of single germinating bacterial spores

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence Livermore National Laboratory

    2006-12-11

    Although significant progress has been achieved in understanding the genetic and biochemical bases of the spore germination process, the structural basis for breaking the dormant spore state remains poorly understood. We have used atomic force microscopy (AFM) to probe the high-resolution structural dynamics of single Bacillus atrophaeus spores germinating under native conditions. Here we show that AFM can reveal previously unrecognized germination-induced alterations in spore coat architecture and topology as well as the disassembly of outer spore coat rodlet structures. These results and previous studies in other microorganisms suggest that the spore coat rodlets are structurally similar to amyloid fibrils. AFM analysis of the nascent surface of the emerging germ cell revealed a porous network of peptidoglycan fibers. The results are consistent with a honeycomb model structure for synthetic peptidoglycan oligomers determined by nuclear magnetic resonance. AFM is a promising experimental tool for investigating the morphogenesis of spore germination and cell wall peptidoglycan structure.

  14. Detection and Extraction of Roads from High Resolution Satellites Images with Dynamic Programming

    Science.gov (United States)

    Benzouai, Siham; Smara, Youcef

    2010-12-01

    The advent of satellite images allows now a regular and a fast digitizing and update of geographic data, especially roads which are very useful for Geographic Information Systems (GIS) applications such as transportation, urban pollution, geomarketing, etc. For this, several studies have been conducted to automate roads extraction in order to minimize the manual processes [4]. In this work, we are interested in roads extraction from satellite imagery with high spatial resolution (at best equal to 10 m). The method is semi automatic and follows a linear approach where road is considered as a linear object. As roads extraction is a pattern recognition problem, it is useful, above all, to characterize roads. After, we realize a pre-processing by applying an Infinite Size Edge Filter -ISEF- and processing method based on dynamic programming concept, in particular, Fishler algorithm designed by F*.

  15. Glycation promoted by dynamic high pressure microfluidisation pretreatment revealed by high resolution mass spectrometry.

    Science.gov (United States)

    Huang, Xiaoqin; Tu, Zongcai; Wang, Hui; Zhang, Qiuting; Hu, Yueming; Zhang, Lan; Niu, Peipei; Shi, Yan; Xiao, Hui

    2013-12-01

    The effect of dynamic high pressure microfluidisation (DHPM) pretreatment on the glycation of bovine serum albumin (BSA) was investigated. A detailed glycation map was obtained from high resolution mass spectrometry. Without DHPM pretreatment, only 7 glycation sites were identified, whereas the numbers were increased to 10, 11 and 11 when BSA-glucose was pretreated with DHPM at 50, 100 and 200 MPa, respectively, suggesting that DHPM pretreatment can significantly promote the Maillard reaction. Average degree of substitution per peptide molecule BSA (DSP) was used to further evaluate the glycation level under various DHPM conditions. All the DHPM pretreated samples exhibited elevated glycation level compared to the un-pretreated sample. With 100 MPa DHPM pretreatment, the protein showed the most significantly enhanced glycation extent. In addition, our results suggest that Maillard-type glycation followed by mass spectrometry analysis can be used to study the conformational changes when proteins are disturbed by external forces.

  16. Unraveling the molecular structure of the catalytic domain of matrix metalloproteinase-2 in complex with a triple-helical peptide by means of molecular dynamics simulations.

    Science.gov (United States)

    Díaz, Natalia; Suárez, Dimas; Valdés, Haydeé

    2013-11-26

    Herein, we present the results of a computational study that employed various simulation methodologies to build and validate a series of molecular models of a synthetic triple-helical peptide (fTHP-5) both in its native state and in a prereactive complex with the catalytic domain of the MMP-2 enzyme. First, the structure and dynamical properties of the fTHP-5 substrate are investigated by means of molecular dynamics (MD) simulations. Then, the propensity of each of the three peptide chains in fTHP-5 to be distorted around the scissile peptide bond is assessed by carrying out potential of mean force calculations. Subsequently, the distorted geometries of fTHP-5 are docked within the MMP-2 active site following a semirigid protocol, and the most stable docked structures are fully relaxed and characterized by extensive MD simulations in explicit solvent. Following a similar approach, we also investigate a hypothetical ternary complex formed between two MMP-2 catalytic units and a single fTHP-5 molecule. Overall, our models for the MMP-2/fTHP-5 complexes unveil the extent to which the triple helix is distorted to allow the accommodation of an individual peptide chain within the MMP active site.

  17. Super-resolution chemical imaging with dynamic placement of plasmonic hotspots

    Science.gov (United States)

    Olson, Aeli P.; Ertsgaard, Christopher T.; McKoskey, Rachel M.; Rich, Isabel S.; Lindquist, Nathan C.

    2015-08-01

    We demonstrate dynamic placement of plasmonic "hotspots" for super-resolution chemical imaging via Surface Enhanced Raman Spectroscopy (SERS). A silver nanohole array surface was coated with biological samples and illuminated with a laser. Due to the large plasmonic field enhancements, blinking behavior of the SERS hotspots was observed and processed using a Stochastic Optical Reconstruction Microscopy (STORM) algorithm enabling localization to within 10 nm. However, illumination of the sample with a single static laser beam (i.e., a slightly defocused Gaussian beam) only produced SERS hotspots in fixed locations on the surface, leaving noticeable gaps in any final image. But, by using a spatial light modulator (SLM), the illumination profile of the beam could be altered, shifting any hotspots across the nanohole array surface in sub-wavelength steps. Therefore, by properly structuring an illuminating light field with the SLM, we show the possibility of positioning plasmonic hotspots over a metallic nanohole surface on-the-fly. Using this and our SERS-STORM imaging technique, we show potential for high-resolution chemical imaging without the noticeable gaps that were present with static laser illumination. Interestingly, even illuminating the surface with randomly shifting SLM phase profiles was sufficient to completely fill in a wide field of view for super-resolution SERS imaging of a single strand of 100-nm thick collagen protein fibrils. Images were then compared to those obtained with a scanning electron microscope (SEM). Additionally, we explored alternative methods of phase shifting other than holographic illumination through the SLM to create localization of hotspots necessary for SERS-STORM imaging.

  18. Image derived input functions for dynamic High Resolution Research Tomograph PET brain studies.

    Science.gov (United States)

    Mourik, Jurgen E M; van Velden, Floris H P; Lubberink, Mark; Kloet, Reina W; van Berckel, Bart N M; Lammertsma, Adriaan A; Boellaard, Ronald

    2008-12-01

    The High Resolution Research Tomograph (HRRT) is a dedicated human brain positron emission tomography (PET) scanner. The aim of the present study was to validate the use of image derived input functions (IDIF) as an alternative for arterial sampling for HRRT human brain studies. To this end, IDIFs were extracted from 3D ordinary Poisson ordered subsets expectation maximization (OP-OSEM) and reconstruction based partial volume corrected (PVC) OP-OSEM images. IDIFs, either derived directly from regions of interest or further calibrated using manual samples taken during scans, were evaluated for dynamic [(11)C]flumazenil data (n=6). Results obtained with IDIFs were compared with those obtained using blood sampler input functions (BSIF). These comparisons included areas under the curve (AUC) for peak (0-3.3 min) and tail (3.3-55.0 min). In addition, slope, intercept and Pearson's correlation coefficient of tracer kinetic analysis results based on IDIF and BSIF were calculated for each subject. Good peak AUC ratios (0.83+/-0.21) between IDIF and BSIF were found for calibrated IDIFs extracted from OP-OSEM images. This combination of IDIFs and images also provided good slope values (1.07+/-0.11). Improved resolution, as obtained with PVC OP-OSEM, changed AUC ratios to 1.14+/-0.35 and, for tracer kinetic analysis, slopes changed to 0.95+/-0.13. For all reconstructions, non-calibrated IDIFs gave poorer results (>61+/-34% higher slopes) compared with calibrated IDIFs. The results of this study indicate that the use of IDIFs, extracted from OP-OSEM or PVC OP-OSEM images, is feasible for dynamic HRRT data, thereby obviating the need for online arterial sampling.

  19. Carbon budget estimation of a subarctic catchment using a dynamic ecosystem model at high spatial resolution

    Science.gov (United States)

    Tang, J.; Miller, P. A.; Persson, A.; Olefeldt, D.; Pilesjo, P.; Heliasz, M.; Jackowicz-Korczynski, M.; Yang, Z.; Smith, B.; Callaghan, T. V.; Christensen, T. R.

    2015-05-01

    A large amount of organic carbon is stored in high-latitude soils. A substantial proportion of this carbon stock is vulnerable and may decompose rapidly due to temperature increases that are already greater than the global average. It is therefore crucial to quantify and understand carbon exchange between the atmosphere and subarctic/arctic ecosystems. In this paper, we combine an Arctic-enabled version of the process-based dynamic ecosystem model, LPJ-GUESS (version LPJG-WHyMe-TFM) with comprehensive observations of terrestrial and aquatic carbon fluxes to simulate long-term carbon exchange in a subarctic catchment at 50 m resolution. Integrating the observed carbon fluxes from aquatic systems with the modeled terrestrial carbon fluxes across the whole catchment, we estimate that the area is a carbon sink at present and will become an even stronger carbon sink by 2080, which is mainly a result of a projected densification of birch forest and its encroachment into tundra heath. However, the magnitudes of the modeled sinks are very dependent on future atmospheric CO2 concentrations. Furthermore, comparisons of global warming potentials between two simulations with and without CO2 increase since 1960 reveal that the increased methane emission from the peatland could double the warming effects of the whole catchment by 2080 in the absence of CO2 fertilization of the vegetation. This is the first process-based model study of the temporal evolution of a catchment-level carbon budget at high spatial resolution, including both terrestrial and aquatic carbon. Though this study also highlights some limitations in modeling subarctic ecosystem responses to climate change, such as aquatic system flux dynamics, nutrient limitation, herbivory and other disturbances, and peatland expansion, our study provides one process-based approach to resolve the complexity of carbon cycling in subarctic ecosystems while simultaneously pointing out the key model developments for capturing

  20. High resolution field study of sediment dynamics on a strongly heterogeneous bed

    Science.gov (United States)

    Bailly Du Bois, P.; Blanpain, O.; Lafite, R.; Cugier, P.; Lunven, M.

    2010-12-01

    Extensive field measurements have been carried out at several stations in a macrotidal inner continental shelf in the English Channel (around 25 m depth) during spring tide period. The strong tidal current measured (up to 1.6 m.s-1) allowed sediment dynamics on a bed characterised by a mixture of size with coarse grains to be dominant. Data acquired in such hydro-sedimentary conditions are scarce. A new instrument, the DYnamic Sediment Profile Imagery (DySPI) system, was specifically conceived and implemented in-situ to observe and measure, with a high temporal resolution, the dynamics of a strongly heterogeneous mixture of particles in a grain-size scale. The data collected covered: 1) grain size range (side scan sonar, video observations, Shipeck grab samples, DySPI images) and vertical sorting (stratigraphic sampling by divers) of sediment cover, 2) hydrodynamic features (acoustic Doppler velocimeter, acoustic Doppler profiler), 3) suspended load nature and dynamics (optical backscatter, chlorophyll fluorometer, particle size analyser, Niskin bottles, scanning electron microscopy), 4) sand and gravel bedload transport estimates (DySPI image processing), 5) transfer dynamics of fine grains within a coarse matrix and their depth of penetration (radionuclides measurements in stratigraphic samples). The four stations present different grain size vertical sorting from a quasi-permanent armouring to a homogenous distribution. The sediment cover condition is directly linked to hydrodynamic capacity and sediment availability. Fine grain ratio within deep sediment layers (up to 10 cm) is higher when the bed armouring is durable. However, fine sediments are not permanently depth trapped: deep layers are composed of few years-old radionuclide tracers fixed on fine grains and a vertical mixing coefficient has been evaluated for each sediment cover. Fine grain dynamics within a coarse matrix is inversely proportional to the robustness of the armour layer. For current

  1. Hybrid Young interferometer for high resolution measurement of dynamic speckle using high birefringence liquid crystal

    Science.gov (United States)

    Bennis, N.; Holdynski, Z.; Merta, I.; Marc, P.; Kula, P.; Mazur, R.; Piecek, W.; Jaroszewicz, L. R.

    2015-08-01

    It is well known that the Young interference experiment is the fundamental setup to combine two beams and to construct the phase modulated light. Moreover, homodyne phase demodulator is based on signal decoding in back Fourier focal plane using bicell photodetector (B-PD). On the above base, we propose a novel experimental approach to the signals demodulation by using the optical interferometer which operates in homodyne mode, combined with liquid crystal spatial light modulators operating both phase as speckle modulator. Dynamic phase changes between the two beams can be controlled by monopixel liquid crystals cell placed in one branch of the interferometer. A phase modulation effect in a signal arm of interferometer is observed as a dynamic shift of the speckle pattern. Simple arithmetic combination of signals from B-PD placed in speckle pattern plane is only one necessary numerical manipulation to obtain exactly phase difference. Concept of signals demodulation in the Fourier focal plane can be only used for exactly defined geometrical (B-PD as well as Young interferometer) and physical parameters (polarization, wavelength). We optimize the setup geometry to obtain extremely high measurement resolution. In this paper we focus on the principles of operation of each part of the system as well as discussion their requirement in order to increase the signal to noise ratio.

  2. Sarcomere dynamics in single myocardial cells as revealed by high-resolution light diffractometry.

    Science.gov (United States)

    Leung, A F

    1983-08-01

    A specially designed diffractometer with a high spatial and temporal resolution recorded the diffraction of a laser beam by single enzymatically isolated myocardial cells. The fine structures within the first-order diffraction were resolved and each structure was interpreted as the diffraction from a group of sarcomeres of nearly equal length. During activation of the cell dynamics of each discrete group of sarcomeres was uniform and independent of the other groups. However, a small nonuniform component in the sarcomere dynamics was observed and attributed to the coupling between the shortening tension and the radial stress resulting from the expansion of the myofibrillar cross-section. The time-course of the diffraction fine structures during contractile activity revealed (1) the period of the contraction-relaxation cycle, (2) the latent period, (3) the shortening and relengthening speeds and (4) the variation in the line width and intensity of the fine structure. Measurements showed that the latent period was dependent on the free Ca2+ of the cell's bathing solution while the initial shortening speed was not. The diffraction line width and intensity of the shortening cell were explained by the grating model.

  3. Bond dissociation mechanism of ethanol during carbon nanotube synthesis via alcohol catalytic CVD technique: Ab initio molecular dynamics simulation

    Science.gov (United States)

    Oguri, Tomoya; Shimamura, Kohei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

    2014-03-01

    Dissociation of ethanol on a nickel cluster is investigated by ab initio molecular dynamics simulation to reveal the bond dissociation mechanism of carbon source molecules during carbon nanotube synthesis. C-C bonds in only CHxCO fragments are dissociated on the nickel cluster, whereas there is no preferential structure among the fragments for C-O bond dissociation. The dissociation preference is uncorrelated with the bond dissociation energy of corresponding bonds in freestanding molecules but is correlated with the energy difference between fragment molecules before and after dissociation on the nickel surface. Moreover, carbon-chain formation occurs after C-C bond dissociation in a continuous simulation. What determines the chirality of CNTs? What happens at the dissociation stage of carbon source molecules? Regarding the former question, many researchers have pointed out the good epitaxial relationship between a graphite network and a close-packed facet (i.e., fcc(1 1 1) or hcp(0 0 0 1)) of transition metals [17-19]. Therefore, the correlation between the chirality of CNTs and the angle of the step edge on metal (or metal carbide) surfaces has been closely investigated [20-22]. In association with this geometric matching, the epitaxial growth of graphene on Cu(1 1 1) and Ni(1 1 1) surfaces has recently been achieved via CCVD technique [23-25], which is a promising technique for the synthesis of large-area and monolayer graphene.Regarding the latter question, it is empirically known that the yield and quality of CNT products strongly depend on the choice of carbon source molecules and additives. For example, it is well known that the use of ethanol as carbon source molecules yields a large amount of SWNTs without amorphous carbons (called the alcohol CCVD (ACCVD) technique) compared with the CCVD process using hydrocarbons [4]. Moreover, the addition of a small amount of water dramatically enhances the activity and lifetime of the catalytic metal (called the

  4. Cross-Species Analysis of Protein Dynamics Associated with Hydride and Proton Transfer in the Catalytic Cycle of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase.

    Science.gov (United States)

    Hoeven, Robin; Hardman, Samantha J O; Heyes, Derren J; Scrutton, Nigel S

    2016-02-16

    Experimental interrogation of the relationship between protein dynamics and enzyme catalysis is challenging. Light-activated protochlorophyllide oxidoreductase (POR) is an excellent model for investigating this relationship because photoinitiation of the reaction cycle enables coordinated turnover in a "dark-assembled" ternary enzyme-substrate complex. The catalytic cycle involves sequential hydride and proton transfers (from NADPH and an active site tyrosine residue, respectively) to the substrate protochlorophyllide. Studies with a limited cross-species subset of POR enzymes (n = 4) have suggested that protein dynamics associated with hydride and proton transfer are distinct [Heyes, D. J., Levy, C., Sakuma, M., Robertson, D. L., and Scrutton, N. S. (2011) J. Biol. Chem. 286, 11849-11854]. Here, we use steady-state assays and single-turnover laser flash spectroscopy to analyze hydride and proton transfer dynamics in an extended series of POR enzymes taken from many species, including cyanobacteria, algae, embryophytes, and angiosperms. Hydride/proton transfer in all eukaryotic PORs is faster compared to prokaryotic PORs, suggesting active site architecture has been optimized in eukaryotic PORs following endosymbiosis. Visible pump-probe spectroscopy was also used to demonstrate a common photoexcitation mechanism for representative POR enzymes from different branches of the phylogenetic tree. Dynamics associated with hydride transfer are localized to the active site of all POR enzymes and are conserved. However, dynamics associated with proton transfer are variable. Protein dynamics associated with proton transfer are also coupled to solvent dynamics in cyanobacterial PORs, and these networks are likely required to optimize (shorten) the donor-acceptor distance for proton transfer. These extended networks are absent in algal and plant PORs. Our analysis suggests that extended networks of dynamics are disfavored, possibly through natural selection. Implications for

  5. Realistic initiation and dynamics of the Madden-Julian Oscillation in a coarse resolution aquaplanet GCM

    Science.gov (United States)

    Ajayamohan, R. S.; Khouider, Boualem; Majda, Andrew J.

    2013-12-01

    The main mechanisms for the initiation and propagation of the Madden-Julian Oscillation (MJO) are still widely debated. The capacity of operational global climate models (GCMs) to correctly simulate the MJO is hindered by the inadequacy of the underlying cumulus parameterizations. Here we show that a coarse resolution GCM, coupled to a simple multicloud model parameterization mimicking the observed dynamics and physical structure of organized tropical convection, simulates the MJO in an idealized setting of an aquaplanet without ocean dynamics. We impose a fixed nonhomogeneous sea-surface temperature replicating the Indian Ocean/Western Pacific warm pool. This results in a succession of MJOs with realistic phase speed, amplitude, and physical structure. Each MJO event is initiated at a somewhat random location over the warm pool and dies sometimes near the eastern boundary of the warm pool and sometimes at a random location way beyond the warm pool. Also occasionally the MJO events stall at the center of maximum heating. This is reminiscent of the fact that in nature some MJOs stall over the maritime continent while others reach the central Pacific Ocean and beyond. The initiation mechanism in the model is believed to be a combination of persistent intermittent convective events interacting with observed large-scale flow patterns and internal tropical dynamics. The large-scale flow patterns are associated with planetary-scale dry Kelvin waves that are triggered by preceding MJO events and circle the globe, while congestus cloud decks on the flanks of the warm pool are believed to force Rossby gyres which then funnel moisture toward the equatorial region.

  6. Millisecond dynamics in glutaredoxin during catalytic turnover is dependent on substrate binding and absent in the resting states

    DEFF Research Database (Denmark)

    Jensen, Kristine Steen; Winther, Jakob R; Teilum, Kaare

    2011-01-01

    on the time scale of catalytic turnover were not observed for the enzyme in the resting states, implying that alternative conformers do not accumulate to significant concentrations. These results infer that the turnover rate in glutaredoxin is governed by formation of a productive enzyme-substrate encounter...... to the glutathione exchange rate was observed for 23 residues. Binding of reduced glutathione resulted in competitive inhibition of the reduced enzyme having kinetics similar to that of the reaction. This observation couples the motions observed during catalysis directly to substrate binding. Backbone motions...

  7. Enzymatic dynamic kinetic resolution of racemic N-formyl- and N-carbamoyl-amino acids using immobilized L-N-carbamoylase and N-succinyl-amino acid racemase.

    Science.gov (United States)

    Soriano-Maldonado, Pablo; Las Heras-Vazquez, Francisco Javier; Clemente-Jimenez, Josefa María; Rodriguez-Vico, Felipe; Martínez-Rodríguez, Sergio

    2015-01-01

    Taking advantage of the catalytic promiscuity of L-carbamoylase from Geobacillus stearothermophilus CECT43 (BsLcar) and N-succinyl-amino acid racemase from Geobacillus kaustophilus CECT4264 (GkNSAAR), we have evaluated the production of different optically pure L-α-amino acids starting from different racemic N-formyl- and N-carbamoyl-amino acids using a dynamic kinetic resolution approach. The enzymes were immobilized on two different solid supports, resulting in improved stability of the enzymes in terms of thermostability and storage when compared to the enzymes in solution. The bienzymatic system retained up to 80% conversion efficiency after 20 weeks at 4 °C and up to 90% after 1 week at 45 °C. The immobilization process also resulted in a great enhancement of the activity of BsLcar toward N-formyl-tryptophan, showing for the first time that substrate specificity of L-carbamoylases can be influenced by this approach. The system was effective for the biosynthesis of natural and unnatural L-amino acids (enantiomeric excess (e.e.) >99.5%), such as L-methionine, L-alanine, L-tryptophan, L-homophenylalanine, L-aminobutyric acid, and L-norleucine, with a higher performance toward N-formyl-α-amino acid substrates. Biocatalyst reuse was studied, and after 10 reaction cycles, over 75% activity remained.

  8. The impact of resolution on the dynamics of the martian global atmosphere: Varying resolution studies with the MarsWRF GCM

    Science.gov (United States)

    Toigo, Anthony D.; Lee, Christopher; Newman, Claire E.; Richardson, Mark I.

    2012-09-01

    latitudes at equinox, even the lowest model resolution considered here appears to do a good job for the southern winter and southern equinoctial pole (although in detail some discrepancies remain). These results suggest that studies of the northern winter jet (e.g., transient waves and cyclogenesis) will be more sensitive to global model resolution that those of the south (e.g., the confining dynamics of the southern polar vortex relevant to studies of argon transport). For surface winds, the major effect of increased horizontal resolution is in the superposition of circulations forced by local-scale topography upon the large-scale surface wind patterns. While passive predictions of dust lifting are generally insensitive to model horizontal resolution when no lifting threshold is considered, increasing the stress threshold produces significantly more lifting in higher resolution simulations with the generation of finer-scale, higher-stress winds due primarily to better-resolved topography. Considering the positive feedbacks expected for radiatively active dust lifting, we expect this bias to increase when such feedbacks are permitted.

  9. High resolution simulations of energy absorption in dynamically loaded cellular structures

    Science.gov (United States)

    Winter, R. E.; Cotton, M.; Harris, E. J.; Eakins, D. E.; McShane, G.

    2017-03-01

    Cellular materials have potential application as absorbers of energy generated by high velocity impact. CTH, a Sandia National Laboratories Code which allows very severe strains to be simulated, has been used to perform very high resolution simulations showing the dynamic crushing of a series of two-dimensional, stainless steel metal structures with varying architectures. The structures are positioned to provide a cushion between a solid stainless steel flyer plate with velocities ranging from 300 to 900 m/s, and an initially stationary stainless steel target. Each of the alternative architectures under consideration was formed by an array of identical cells each of which had a constant volume and a constant density. The resolution of the simulations was maximised by choosing a configuration in which one-dimensional conditions persisted for the full period over which the specimen densified, a condition which is most readily met by impacting high density specimens at high velocity. It was found that the total plastic flow and, therefore, the irreversible energy dissipated in the fully densified energy absorbing cell, increase (a) as the structure becomes more rodlike and less platelike and (b) as the impact velocity increases. Sequential CTH images of the deformation processes show that the flow of the cell material may be broadly divided into macroscopic flow perpendicular to the compression direction and jetting-type processes (microkinetic flow) which tend to predominate in rod and rodlike configurations and also tend to play an increasing role at increased strain rates. A very simple analysis of a configuration in which a solid flyer impacts a solid target provides a baseline against which to compare and explain features seen in the simulations. The work provides a basis for the development of energy absorbing structures for application in the 200-1000 m/s impact regime.

  10. Magnetic dynamics studied by high-resolution electron spectroscopy and time-resolved electron microscopy

    Science.gov (United States)

    Jayaraman, Rajeswari

    Future information technology requires an increased magnetically encoded data density and novel electromagnetic modes of data transfer. While to date magnetic properties are observed and characterized mostly statically, the need emerges to monitor and capture their fast dynamics. In this talk, I will focus on the spin dynamics i.e. spin wave excitations and the dynamics of a new topological distribution of spins termed ``skyrmions''. Wave packets of spin waves offer the unique capability to transport a quantum bit, the spin, without the transport of charge or mass. Here, large wave-vector spin waves are of particular interest as they admit spin localization within a few nanometers. By using our recently developed electron energy loss spectrometer, we could study such spin waves in ultrathin films with an unprecedented energy resolution of 4 meV. By virtue of the finite penetration depth of low energy electrons, spin waves localized at interfaces between a substrate and a thin capping layer can be been studied yielding information about the exchange coupling between atoms at the interface. The quantization of spin waves with wave vectors perpendicular to the film gives rise to standing modes to which EELS has likewise access. Such studies when carried out as function of the film thickness again yield information on the layer dependence of the exchange coupling. Magnetic skyrmions are promising candidates as information carriers in logic or storage devices. Currently, little is known about the influence of disorder, defects, or external stimuli on the spatial distribution and temporal evolution of the skyrmion lattice. In this talk, I will describe the dynamical role of disorder in a large and flat thin film of Cu2OSeO3, exhibiting a skyrmion phase in an insulating material. We image up to 70,000 skyrmions by means of cryo-Lorentz Transmission Electron Microscopy as a function of the applied magnetic field. In the skyrmion phase, dislocations are shown to cause the

  11. Prediction of gasoline yield in a fluid catalytic cracking (FCC riser using k-epsilon turbulence and 4-lump kinetic models: A computational fluid dynamics (CFD approach

    Directory of Open Access Journals (Sweden)

    Muhammad Ahsan

    2015-07-01

    Full Text Available Fluid catalytic cracking (FCC is an essential process for the conversion of gas oil to gasoline. This study is an effort to model the phenomenon numerically using commercial computational fluid dynamics (CFD software, heavy density catalyst and 4-lump kinetic model. Geometry, boundary conditions and dimensions of industrial riser for catalytic cracking unit are conferred for 2D simulation using commercial CFD code FLUENT 6.3. Continuity, momentum, energy and species transport equations, applicable to two phase solid and gas flow, are used to simulate the physical phenomenon as efficient as possible. This study implements and predicts the use of the granular Eulerian multiphase model with species transport. Time accurate transient problem is solved with the prediction of mass fraction profiles of gas oil, gasoline, light gas and coke. The output curves demonstrate the breaking of heavy hydrocarbon in the presence of catalyst. An approach proposed in this study shows good agreement with the experimental and numerical data available in the literature.

  12. Using very high resolution satellite images to identify coastal zone dynamics at North Western Black Sea

    Science.gov (United States)

    Florin Zoran, Liviu; Ionescu Golovanov, Carmen; Zoran, Maria

    2010-05-01

    The availability of updated information about the extension and characteristics of land cover is a crucial issue in the perspective of a correct landscape planning and management of marine coastal zones. Satellite remote sensing data can provide accurate information about land coverage at different scales and the recent availability of very high resolution images definitely improved the precision of coastal zone spatio-temporal changes. The Romanian North Western coastal and shelf zones of the Black Sea and Danube delta are a mosaic of complex, interacting ecosystems, rich natural resources and socio-economic activity. Dramatic changes in the Black Sea's ecosystem and resources are due to natural and anthropogenic causes (increase in the nutrient and pollutant load of rivers input, industrial and municipal wastewater pollution along the coast, and dumping on the open sea). A scientific management system for protection, conservation and restoration must be based on reliable information on bio-geophysical and geomorphologic processes, coastal erosion, sedimentation dynamics, mapping of macrophyte fields, water quality, and climatic change effects. Use of satellite images is of great help for coastal zone monitoring and environmental impact assessment. Synergetic use of in situ measurements with multisensors satellite data could provide a complex assessment of spatio-temporal changes. In this study was developed a method for extracting coastal zone features information as well as landcover dynamics from IKONOS, very high resolution images for North-Western Black Sea marine coastal zone. The main objective was obtaining reliable data about the spatio-temporal coastal zone changes in two study areas located in Constanta urban area and Danube Delta area. We used an object-oriented approach based on preliminary segmentation and classification of the resulting object. First of all, segmentation parameters were tested and selected comparing segmented polygons with

  13. Interaction networks in protein folding via atomic-resolution experiments and long-time-scale molecular dynamics simulations

    DEFF Research Database (Denmark)

    Sborgi, Lorenzo; Verma, Abhinav; Piana, Stefano;

    2015-01-01

    The integration of atomic-resolution experimental and computational methods offers the potential for elucidating key aspects of protein folding that are not revealed by either approach alone. Here, we combine equilibrium NMR measurements of thermal unfolding and long molecular dynamics simulation...

  14. Refinement of horizontal resolution in dynamical downscaling of climate information using WRF: Costs, benefits, and lessons learned

    Science.gov (United States)

    Dynamical downscaling techniques have previously been developed by the U.S. Environmental Protection Agency (EPA) using a nested WRF at 108- and 36-km. Subsequent work extended one-way nesting down to 12-km resolution. Recently, the EPA Office of Research and Development used com...

  15. High-Resolution Modeling Disturbance-Induced Forest Carbon Dynamics with Lidar and Landsat Observations

    Science.gov (United States)

    Zhao, M.; Huang, C.; Hurtt, G. C.; Dubayah, R.; Fisk, J.; Sahajpal, R.; Flanagan, S.; Swatantran, A.; Huang, W.; Tang, H.; ONeil-Dunne, J.; Johnson, K. D.

    2015-12-01

    Forest stands are dynamic in a status from severely, partially disturbed, or undisturbed to different stages of recovery towards maturity and equilibrium. Forest ecosystem models generally use potential biomass (an assumption of equilibrium status) as initial biomass, which is unrealistic and could result in unreliable estimates of disturbance-induced carbon changes. To accurately estimate spatiotemporal changes of forest carbon stock and fluxes, it requires accurate information on initial biomass, the extent and severity of disturbance, and following land use. We demonstrate a prototype system to achieve this goal by integrating 1-m small footprint Lidar acquired in year 2004, 30-m Landsat disturbances from 1984 to 2011, and an individual-based structure height Ecosystem Demography (ED) model. Lidar provides critical information on forest canopy height, improving the accuracy of initial forest biomass estimates; impervious surfaces data and yearly disturbance data from Landsat provide information on wall-to-wall yearly natural and anthropogenic disturbances and their severity (on average 0.32% for the natural and 0.19% for the anthropogenic for below test area); ED model plays a central role by linking both Lidar canopy height and Landsat disturbances with ecosystem processes. We tested the system at 90-m spatial resolution in Charles County, Maryland, by running ED model for six experiments, the combinations of three initial biomass (potential, moderate and low initial biomass constrained by Lidar canopy height) with two disturbance scenarios (with and without anthropogenic disturbances). Our experiments show that estimated changes of carbon stock and flux are sensitive to initial biomass status and human-induced land cover change. Our prototype system can assess regional carbon dynamics at local scale under changing climate and disturbance regimes, and provide useful information for forest management and land use policies.

  16. High-resolution isotope measurements resolve rapid ecohydrological dynamics at the soil-plant interface.

    Science.gov (United States)

    Volkmann, Till H M; Haberer, Kristine; Gessler, Arthur; Weiler, Markus

    2016-05-01

    Plants rely primarily on rainfall infiltrating their root zones - a supply that is inherently variable, and fluctuations are predicted to increase on most of the Earth's surface. Yet, interrelationships between water availability and plant use on short timescales are difficult to quantify and remain poorly understood. To overcome previous methodological limitations, we coupled high-resolution in situ observations of stable isotopes in soil and transpiration water. We applied the approach along with Bayesian mixing modeling to track the fate of (2) H-labeled rain pulses following drought through soil and plants of deciduous tree ecosystems. We resolve how rainwater infiltrates the root zones in a nonequilibrium process and show that tree species differ in their ability to quickly acquire the newly available source. Sessile oak (Quercus petraea) adjusted root uptake to vertical water availability patterns under drought, but readjustment toward the rewetted topsoil was delayed. By contrast, European beech (Fagus sylvatica) readily utilized water from all soil depths independent of water depletion, enabling faster uptake of rainwater. Our results demonstrate that species-specific plasticity and responses to water supply fluctuations on short timescales can now be identified and must be considered to predict vegetation functional dynamics and water cycling under current and future climatic conditions.

  17. Sub-Airy disk angular resolution with high dynamic range in the near-infrared

    Directory of Open Access Journals (Sweden)

    Richichi A.

    2011-07-01

    Full Text Available Lunar occultations (LO are a simple and effective high angular resolution method, with minimum requirements in instrumentation and telescope time. They rely on the analysis of the diffraction fringes created by the lunar limb. The diffraction phenomen occurs in space, and as a result LO are highly insensitive to most of the degrading effects that limit the performance of traditional single telescope and long-baseline interferometric techniques used for direct detection of faint, close companions to bright stars. We present very recent results obtained with the technique of lunar occultations in the near-IR, showing the detection of companions with very high dynamic range as close as few milliarcseconds to the primary star. We discuss the potential improvements that could be made, to increase further the current performance. Of course, LO are fixed-time events applicable only to sources which happen to lie on the Moon’s apparent orbit. However, with the continuously increasing numbers of potential exoplanets and brown dwarfs beign discovered, the frequency of such events is not negligible. I will list some of the most favorable potential LO in the near future, to be observed from major observatories.

  18. Carbon budget estimation of a subarctic catchment using a dynamic ecosystem model at high spatial resolution

    Directory of Open Access Journals (Sweden)

    J. Tang

    2015-01-01

    Eriophorum, Sphagnum and then tundra heath during the observation periods. The catchment-level carbon fluxes from aquatic systems are dominated by CO2 emissions from streams. Integrated across the whole catchment, we estimate that the area is a carbon sink at present, and will become an even stronger carbon sink by 2080, which is mainly a result of a projected densification of birch forest and its encroachment into tundra heath. However, the magnitudes of the modelled sinks are very dependent on future atmospheric CO2 concentrations. Furthermore, comparisons of global warming potentials between two simulations with and without CO2 increase since 1960 reveal that the increased methane emission from the peatland could double the warming effects of the whole catchment by 2080 in the absence of CO2 fertilization of the vegetation. This is the first process-based model study of the temporal evolution of a catchment-level carbon budget at high spatial resolution, integrating comprehensive and diverse fluxes including both terrestrial and aquatic carbon. Though this study also highlights some limitations in modelling subarctic ecosystem responses to climate change including aquatic system flux dynamics, nutrient limitation, herbivory and other disturbances and peatland expansion, our application provides a mechanism to resolve the complexity of carbon cycling in subarctic ecosystems while simultaneously pointing out the key model developments for capturing complex subarctic processes.

  19. Expanding the linear dynamic range for quantitative liquid chromatography-high resolution mass spectrometry utilizing natural isotopologue signals

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hanghui, E-mail: Hanghui.Liu@senomyx.com [Senomyx Inc. 4767 Nexus Centre Dr., San Diego, CA 92121 (United States); Lam, Lily; Yan, Lin; Chi, Bert [Senomyx Inc. 4767 Nexus Centre Dr., San Diego, CA 92121 (United States); Dasgupta, Purnendu K., E-mail: Dasgupta@uta.edu [Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019-0065 (United States)

    2014-11-19

    Highlights: • Less abundant isotopologue ions were utilized to decrease detector saturation. • A 25–50 fold increase in the upper limit of dynamic range was demonstrated. • Linear dynamic range was expanded without compromising mass resolution. - Abstract: The linear dynamic range (LDR) for quantitative liquid chromatography–mass spectrometry can be extended until ionization saturation is reached by using a number of target isotopologue ions in addition to the normally used target ion that provides the highest sensitivity. Less abundant isotopologue ions extend the LDR: the lower ion abundance decreases the probability of ion detector saturation. Effectively the sensitivity decreases and the upper limit of the LDR increases. We show in this paper that the technique is particularly powerful with a high resolution time of flight mass spectrometer because the data for all ions are automatically acquired, and we demonstrated this for four small organic molecules; the upper limits of LDRs increased by 25–50 times.

  20. Qualitative Aspects of the Solutions of a Mathematical Model for the Dynamic Analysis of the Reversible Chemical Reaction SO2(g)+1/2O2(g)<=>SO3(g) in a Catalytic Reactor

    CERN Document Server

    Wilfredo, Angulo

    2014-01-01

    We present some qualitative aspects concerning the solution to the mathematical model describing the dynamical behavior of the reversible chemical reaction SO2(g)+1/2O2(g)SO3(g) carried out in a catalytic reactor used in the process of sulfuric acid production.

  1. High-resolution dynamic angiography using flat-panel volume CT: feasibility demonstration for neuro and lower limb vascular applications

    Energy Technology Data Exchange (ETDEWEB)

    Mehndiratta, Amit [Massachusetts General Hospital, Department of Radiology, Harvard Medical School, Boston, MA (United States); University of Oxford, Institute of Biomedical Engineering and Keble College, Oxford (United Kingdom); Indian Institute of Technology Delhi and All India Institute of Medical Science, Centre for Biomedical Engineering, New Delhi (India); Rabinov, James D. [Massachusetts General Hospital, Interventional Neuroradiology, Harvard Medical School, Boston, MA (United States); Grasruck, Michael [Siemens Medical Solutions, Forchheim (Germany); Liao, Eric C. [Massachusetts General Hospital, Department of Plastic and Reconstructive Surgery and Center for Regenerative Medicine, Harvard Medical School, Boston, MA (United States); Crandell, David [Spaulding Rehabilitation Hospital, Department of Physical Medicine and Rehabilitation, Harvard Medical School, Charlestown, MA (United States); Gupta, Rajiv [Massachusetts General Hospital, Department of Radiology, Harvard Medical School, Boston, MA (United States)

    2015-07-15

    This paper evaluates a prototype flat-panel volume CT (fpVCT) for dynamic in vivo imaging in a variety of neurovascular and lower limb applications. Dynamic CTA was performed on 12 patients (neuro = 8, lower limb = 4) using an fpVCT with 120 kVp, 50 mA, rotation time varying from 8 to 19 s, and field of view of 25 x 25 x 18 cm{sup 3}. Four-dimensional data sets (i.e. 3D images over time) were reconstructed and reviewed. Dynamic CTA demonstrated sufficient spatio-temporal resolution to elucidate first-pass and recirculation dynamics of contrast bolus through neurovasclar pathologies and phasic blood flow though lower-limb vasculature and grafts. The high spatial resolution of fpVCT resulted in reduced partial volume and metal beam-hardening artefacts. This facilitated assessment of vascular lumen in the presence of calcified plaque and evaluation of fractures, especially in the presence of fixation hardware. Evaluation of arteriovenous malformation using dynamic fpVCT angiography was of limited utility. Dynamic CTA using fpVCT can visualize time-varying phenomena in neuro and lower limb vascular applications and has sufficient diagnostic imaging quality to evaluate a number of pathologies affecting these regions. (orig.)

  2. Crystallization-induced dynamic resolution R-epimer from 25-OCH3-PPD epimeric mixture.

    Science.gov (United States)

    Zhang, Sainan; Tang, Yun; Cao, Jiaqing; Zhao, Chen; Zhao, Yuqing

    2015-11-15

    25-OCH3-PPD is a promising antitumor dammarane sapogenin isolated from the total saponin-hydrolyzed extract of Panax ginseng berry and Panax notoginseng leaves. 20(R)-25-OCH3-PPD was more potent as an anti-cancer agent than 20(S)-25-OCH3-PPD and epimeric mixture of 25-OCH3-PPD. This paper describes the rapid separation process of the R-epimer of 25-OCH3-PPD from its epimeric mixture by crystallization-induced dynamic resolution (CIDR). The optimized CIDR process was based on single factor analysis and nine well-planned orthogonal design experiments (OA9 matrix). A rapid and sensitive reverse phase high-performance liquid chromatographic (HPLC) method with evaporative light-scattering detector (ELSD) was developed and validated for the quantitation of 25-OCH3-PPD epimeric mixture and crystalline product. Separation and quantitation were achieved with a silica column using a mobile phase consisting of methanol and water (87:13, v/v) at a flow rate of 1.0mL/min. The ELSD detection was performed at 50°C and 3L/min. Under conditions involving 3mL of 95% ethanol, 8% HCl, and a hermetically sealed environment for 72h, the maximum production of 25(R)-OCH3-PPD was achieved with a chemical purity of 97% and a total yield of 87% through the CIDR process. The 25(R)-OCH3-PPD was nearly completely separated from the 220mg 25-OCH3-PPD epimeric mixture. Overall, a simple and steady small-batch purification process for the large-scale production of 25(R)-OCH3-PPD from 25-OCH3-PPD epimeric mixture was developed.

  3. A novel xenograft model in zebrafish for high-resolution investigating dynamics of neovascularization in tumors.

    Directory of Open Access Journals (Sweden)

    Chengjian Zhao

    Full Text Available Tumor neovascularization is a highly complex process including multiple steps. Understanding this process, especially the initial stage, has been limited by the difficulties of real-time visualizing the neovascularization embedded in tumor tissues in living animal models. In the present study, we have established a xenograft model in zebrafish by implanting mammalian tumor cells into the perivitelline space of 48 hours old Tg(Flk1:EGFP transgenic zebrafish embryos. With this model, we dynamically visualized the process of tumor neovascularization, with unprecedented high-resolution, including new sprouts from the host vessels and the origination from VEGFR2(+ individual endothelial cells. Moreover, we quantified their contributions during the formation of vascular network in tumor. Real-time observations revealed that angiogenic sprouts in tumors preferred to connect each other to form endothelial loops, and more and more endothelial loops accumulated into the irregular and chaotic vascular network. The over-expression of VEGF165 in tumor cells significantly affected the vascularization in xenografts, not only the number and size of neo-vessels but the abnormalities of tumor vascular architecture. The specific inhibitor of VEGFR2, SU5416, significantly inhibited the vascularization and the growth of melanoma xenografts, but had little affects to normal vessels in zebrafish. Thus, this zebrafish/tumor xenograft model not only provides a unique window to investigate the earliest events of tumoral neoangiogenesis, but is sensitive to be used as an experimental platform to rapidly and visually evaluate functions of angiogenic-related genes. Finally, it also offers an efficient and cost-effective means for the rapid evaluation of anti-angiogenic chemicals.

  4. Dynamics of the MAP IOP 15 severe Mistral event: Observations and high-resolution numerical simulations

    Science.gov (United States)

    Guénard, V.; Drobinski, P.; Caccia, J. L.; Tedeschi, G.; Currier, P.

    2006-04-01

    This paper investigates the fundamental processes involved in a severe Mistral event that occurred during the Mesoscale Alpine Program (from 6 to 9 November 1999). The Mistral refers to a violent north/north-westerly wind blowing in south-eastern France from the Rhône valley to the French Riviera. The study is based on measurements from radiosoundings launched from Lyon and Nîmes and from two UHF wind profilers located near Marseille and Toulon allowing a good description of the flow in the complex terrain formed by the south-western Alps. Observational results are compared with RAMS non-hydrostatic numerical simulations performed with 27 km, 9 km and 3 km nested grids. The numerical simulations capture the flow complexity both upstream of the Alps and in the coastal area affected by the Mistral. They correctly reproduce horizontal wind speeds and directions, vertical velocities, virtual potential temperature and relative humidity documented by the observational network. The simulations are used to point out the main dynamical processes generating the Mistral. It is found that flow splitting around the Alps and around the isolated peaks bordering the south-eastern part of the Rhône valley (Mont Ventoux 1909 m, Massif du Lubéron 1425 m) induces the low-level jet observed near Marseille that lasts for 36 hours. The high-resolution simulation indicates that the transient low-level jet lasting for only 9 hours observed at Toulon is due to a gravity wave breaking over local topography (the Sainte Baume 1147 m) where hydraulic jumps are involved. A mountain wake with two opposite-sign potential-vorticity banners is generated. The mesoscale wake explains the westward progression of the large-scale Alpine wake.

  5. 2.0A resolution crystal structures of the ternary complexes of human phenylalanine hydroxylase catalytic domain with tetrahydrobiopterin and 3-(2-thienyl)-L-alanine or L-norleucine: substrate specificity and molecular motions related to substrate binding.

    Science.gov (United States)

    Andersen, Ole Andreas; Stokka, Anne J; Flatmark, Torgeir; Hough, Edward

    2003-10-31

    The crystal structures of the catalytic domain of human phenylalanine hydroxylase (hPheOH) in complex with the physiological cofactor 6(R)-L-erythro-5,6,7,8-tetrahydrobiopterin (BH(4)) and the substrate analogues 3-(2-thienyl)-L-alanine (THA) or L-norleucine (NLE) have been determined at 2.0A resolution. The ternary THA complex confirms a previous 2.5A structure, and the ternary NLE complex shows that similar large conformational changes occur on binding of NLE as those observed for THA. Both structures demonstrate that substrate binding triggers structural changes throughout the entire protomer, including the displacement of Tyr138 from a surface position to a buried position at the active site, with a maximum displacement of 20.7A for its hydroxyl group. Two hinge-bending regions, centred at Leu197 and Asn223, act in consort upon substrate binding to create further large structural changes for parts of the C terminus. Thus, THA/L-Phe binding to the active site is likely to represent the epicentre of the global conformational changes observed in the full-length tetrameric enzyme. The carboxyl and amino groups of THA and NLE are positioned identically in the two structures, supporting the conclusion that these groups are of key importance in substrate binding, thus explaining the broad non-physiological substrate specificity observed for artificially activated forms of the enzyme. However, the specific activity with NLE as the substrate was only about 5% of that with THA, which is explained by the different affinities of binding and different catalytic turnover.

  6. Features of the Jovian DAM radiation dynamic spectra as observed by modern receivers with high frequency-temporal resolution

    Science.gov (United States)

    Litvinenko, G.; Konovalenko, A.; Zakharenko, V.; Vinogradov, V.; Shaposhnikov, V.; Zarka, Ph.

    2012-09-01

    One of the promising approaches to investigating features of the Jovian decameter radio emission (DAM) is application of novel experimental techniques with a further detailed analysis of the obtained data using both well-known and modern mathematical methods. Several observational campaigns were performed in November 2009 with the use of the UTR-2 radio telescope (Kharkov, Ukraine) and efficient registration systems with high frequency and temporal resolutions (the antenna effective area is about 105 m2, the frequency resolution is 4 kHz, the temporal resolution is 0.25 ms, and the dynamic range is 70 dB) [1]. The main goal of these campaigns was to experimentally investigate new properties of the Jovian DAM emission which could be detected using the above mentioned equipment. Also an original software package was developed for control the digital receiver and for off-line data analysis at the postprocessing stage.

  7. High Spatio-Temporal-Resolution Detection of Chlorophyll Fluorescence Dynamics from a Single Chloroplast with Confocal Imaging Fluorometer

    CERN Document Server

    Tseng, Yi-Chin

    2016-01-01

    Chlorophyll fluorescence (CF) is a key indicator to study plant physiology or photosynthesis efficiency. Conventionally, CF is characterized by fluorometers, which only allows ensemble measurement through wide-field detection. For imaging fluorometers, the typical spatial and temporal resolutions are on the order of millimeter and second, far from enough to study cellular/sub-cellular CF dynamics. In addition, due to the lack of optical sectioning capability, conventional imaging fluorometers cannot identify CF from a single cell or even a single chloroplast. Here we demonstrated a novel fluorometer based on confocal imaging, that not only provides high contrast images, but also allows CF measurement with spatiotemporal resolution as high as micrometer and millisecond. CF transient (the Kautsky curve) from a single chloroplast is successfully obtained, with both the temporal dynamics and the intensity dependences corresponding well to the ensemble measurement from conventional studies. The significance of con...

  8. Dynamic atomic scale in situ electron microscopy in the development of an efficient heterogeneous catalytic process for pharmaceutical NSAIDS

    NARCIS (Netherlands)

    N.R. Shiju; K. Yoshida; E.D. Boyes; D.R. Brown; P.L. Gai

    2011-01-01

    In heterogeneous catalysis the identification of the active site and crucially its location to prevent unwanted sintering and deactivation during the transformation of the precursor to active catalyst require the integration of dynamic in situ imaging at the atomic level and reactivity studies. We r

  9. Applying High Resolution Imagery to Understand the Role of Dynamics in the Diminishing Arctic Sea Ice Cover

    Science.gov (United States)

    2015-09-30

    Role of Dynamics in the Diminishing Arctic Sea Ice Cover ” Dr. Sinead L. Farrell University of Maryland, ESSIC, 5825 University Research Court...day Arctic ice cover , enabling the improvement of models used to forecast ice drift. APPROACH Our research is centered on the application of...resolution visible band imagery for deriving geophysical information on the sea ice pack of the Arctic Ocean , and improve understanding of key

  10. Time-resolved PIV technique for high temporal resolution measurement of mechanical prosthetic aortic valve fluid dynamics.

    Science.gov (United States)

    Kaminsky, R; Morbiducci, U; Rossi, M; Scalise, L; Verdonck, P; Grigioni, M

    2007-02-01

    Prosthetic heart valves (PHVs) have been used to replace diseased native valves for more than five decades. Among these, mechanical PHVs are the most frequently implanted. Unfortunately, these devices still do not achieve ideal behavior and lead to many complications, many of which are related to fluid mechanics. The fluid dynamics of mechanical PHVs are particularly complex and the fine-scale characteristics of such flows call for very accurate experimental techniques. Adequate temporal resolution can be reached by applying time-resolved PIV, a high-resolution dynamic technique which is able to capture detailed chronological changes in the velocity field. The aim of this experimental study is to investigate the evolution of the flow field in a detailed time domain of a commercial bileaflet PHV in a mock-loop mimicking unsteady conditions, by means of time-resolved 2D Particle Image Velocimetry (PIV). The investigated flow field corresponded to the region immediately downstream of the valve plane. Spatial resolution as in "standard" PIV analysis of prosthetic valve fluid dynamics was used. The combination of a Nd:YLF high-repetition-rate double-cavity laser with a high frame rate CMOS camera allowed a detailed, highly temporally resolved acquisition (up to 10000 fps depending on the resolution) of the flow downstream of the PHV. Features that were observed include the non-homogeneity and unsteadiness of the phenomenon and the presence of large-scale vortices within the field, especially in the wake of the valve leaflets. Furthermore, we observed that highly temporally cycle-resolved analysis allowed the different behaviors exhibited by the bileaflet valve at closure to be captured in different acquired cardiac cycles. By accurately capturing hemodynamically relevant time scales of motion, time-resolved PIV characterization can realistically be expected to help designers in improving PHV performance and in furnishing comprehensive validation with experimental data

  11. Capturing the multiscale dynamics of membrane protein complexes with all-atom, mixed-resolution, and coarse-grained models.

    Science.gov (United States)

    Liao, Chenyi; Zhao, Xiaochuan; Liu, Jiyuan; Schneebeli, Severin T; Shelley, John C; Li, Jianing

    2017-03-20

    The structures and dynamics of protein complexes are often challenging to model in heterogeneous environments such as biological membranes. Herein, we meet this fundamental challenge at attainable cost with all-atom, mixed-resolution, and coarse-grained models of vital membrane proteins. We systematically simulated five complex models formed by two distinct G protein-coupled receptors (GPCRs) in the lipid-bilayer membrane on the ns-to-μs timescales. These models, which suggest the swinging motion of an intracellular loop, for the first time, provide the molecular details for the regulatory role of such a loop. For the models at different resolutions, we observed consistent structural stability but various levels of speed-ups in protein dynamics. The mixed-resolution and coarse-grained models show two and four times faster protein diffusion than the all-atom models, in addition to a 4- and 400-fold speed-up in the simulation performance. Furthermore, by elucidating the strengths and challenges of combining all-atom models with reduced resolution models, this study can serve as a guide to simulating other complex systems in heterogeneous environments efficiently.

  12. Modeling Carbon Dynamics in Paddy Soils in Jiangsu Province of China with Soil Databases Differing in Spatial Resolution

    Institute of Scientific and Technical Information of China (English)

    XU Sheng-Xiang; SHI Xue-Zheng; ZHAO Yong-Cun; YU Dong-Sheng; WANG Shi-Hang; ZHANG Li-Ming; C. S. LI; TAN Man-Zhi

    2011-01-01

    A number of process-based models have been developed for quantifying carbon (C) sequestration in ago-ecosystems.The DeNitrification-DeComposition (DNDC) model was used to simulate and quantify long-term (1980-2008) soil organic carbon (SOC) dynamics in the important rice-producing province,Jiangsu,China.Changes in SOC storages were estimated from two soil databases differing in spatial resolution:a county database consisting of 68 polygons and a soil patch-based database of 701 polygons for all 3.7 Mha of rice fields in Jiangsu.The simulated SOC storage with the coarse resolution county database ranged between 131.0-320.6 Tg C in 1980 and 170.3-305.1 Tg C in 2008,respectively,while that estimated with the fine resolution database was 201.6 and 216.2 Tg C in 1980 and 2008,respectively.The results modeled with the soil databases differing in spatial resolution indicated that using the soil input data with higher resolution substantially increased the accuracy of the modeled results; and when lacking detailed soil datasets,the DNDC model,parameterized with the most sensitive factor (MSF) method to cope with attribute uncertainty,could still produce acceptable results although with deviations of up to 60% for the case study reported in this paper.

  13. Adaptive Resolution Simulation as a Grand Canonical Molecular Dynamics Scheme: Principles, Applications and Perspectives

    CERN Document Server

    Site, Luigi Delle; Junghans, Christoph; Wang, Han

    2014-01-01

    We describe the adaptive resolution multiscale method AdResS. The conceptual evolution as well as the improvements of its technical efficiency are described step by step, with an explicit reference to current limitations and open problems.

  14. Inhibition of lactoperoxidase by its own catalytic product: crystal structure of the hypothiocyanate-inhibited bovine lactoperoxidase at 2.3-A resolution.

    Science.gov (United States)

    Singh, A K; Singh, Nagendra; Sharma, Sujata; Shin, Kouichirou; Takase, Mitsunori; Kaur, Punit; Srinivasan, A; Singh, T P

    2009-01-01

    To the best of our knowledge, this is the first report on the structure of product-inhibited mammalian peroxidase. Lactoperoxidase is a heme containing an enzyme that catalyzes the inactivation of a wide range of microorganisms. In the presence of hydrogen peroxide, it preferentially converts thiocyanate ion into a toxic hypothiocyanate ion. Samples of bovine lactoperoxidase containing thiocyanate (SCN(-)) and hypothiocyanate (OSCN(-)) ions were purified and crystallized. The structure was determined at 2.3-A resolution and refined to R(cryst) and R(free) factors of 0.184 and 0.221, respectively. The determination of structure revealed the presence of an OSCN(-) ion at the distal heme cavity. The presence of OSCN(-) ions in crystal samples was also confirmed by chemical and spectroscopic analysis. The OSCN(-) ion interacts with the heme iron, Gln-105 N(epsilon1), His-109 N(epsilon2), and a water molecule W96. The sulfur atom of the OSCN(-) ion forms a hypervalent bond with a nitrogen atom of the pyrrole ring D of the heme moiety at an S-N distance of 2.8 A. The heme group is covalently bound to the protein through two ester linkages involving carboxylic groups of Glu-258 and Asp-108 and the modified methyl groups of pyrrole rings A and C, respectively. The heme moiety is significantly distorted from planarity, whereas pyrrole rings A, B, C, and D are essentially planar. The iron atom is displaced by approximately 0.2 A from the plane of the heme group toward the proximal site. The substrate channel resembles a long tunnel whose inner walls contain predominantly aromatic residues such as Phe-113, Phe-239, Phe-254, Phe-380, Phe-381, Phe-422, and Pro-424. A phosphorylated Ser-198 was evident at the surface, in the proximity of the calcium-binding channel.

  15. Hamming distance geometry of a protein conformational space. Application to the clustering of a 4 ns molecular dynamics trajectory of the HIV-1 integrase catalytic core

    CERN Document Server

    Laboulais, C; Le Bret, M; Gabarro-Arpa, J; Laboulais, Cyril; Ouali, Mohammed; Bret, Marc Le; Gabarro-Arpa, Jacques

    2001-01-01

    Protein structures can be encoded into binary sequences, these are used to define a Hamming distance in conformational space: the distance between two different molecular conformations is the number of different bits in their sequences. Each bit in the sequence arises from a partition of conformational space in two halves. Thus, the information encoded in the binary sequences is also used to characterize the regions of conformational space visited by the system. We apply this distance and their associated geometric structures, to the clustering and analysis of conformations sampled during a 4 ns molecular dynamics simulation of the HIV-1 integrase catalytic core. The cluster analysis of the simulation shows a division of the trajectory into two segments of 2.6 and 1.4 ns length, which are qualitatively different: the data points to the fact that equilibration is only reached at the end of the first segment. Some length of the paper is devoted to compare the Hamming distance to the r.m.s. deviation measure. Th...

  16. Dynamically-driven enhancement of the catalytic machinery of the SARS 3C-like protease by the S284-T285-I286/A mutations on the extra domain.

    Directory of Open Access Journals (Sweden)

    Liangzhong Lim

    Full Text Available Previously we revealed that the extra domain of SARS 3CLpro mediated the catalysis via different mechanisms. While the R298A mutation completely abolished the dimerization, thus resulting in the inactive catalytic machinery, N214A inactivated the enzyme by altering its dynamics without significantly perturbing its structure. Here we studied another mutant with S284-T285-I286 replaced by Ala (STI/A with a 3.6-fold activity increase and slightly enhanced dimerization. We determined its crystal structure, which still adopts the dimeric structure almost identical to that of the wild-type (WT, except for slightly tighter packing between two extra-domains. We then conducted 100-ns molecular dynamics (MD simulations for both STI/A and WT, the longest reported so far for 3CLpro. In the simulations, two STI/A extra domains become further tightly packed, leading to a significant volume reduction of the nano-channel formed by residues from both catalytic and extra domains. The enhanced packing appears to slightly increase the dynamic stability of the N-finger and the first helix residues, which subsequently triggers the redistribution of dynamics over residues directly contacting them. This ultimately enhances the dynamical stability of the residues constituting the catalytic dyad and substrate-binding pockets. Further correlation analysis reveals that a global network of the correlated motions exists in the protease, whose components include all residues identified so far to be critical for the dimerization and catalysis. Most strikingly, the N214A mutation globally decouples this network while the STI/A mutation alters the correlation pattern. Together with previous results, the present study establishes that besides the classic structural allostery, the dynamic allostery also operates in the SARS 3CLpro, which is surprisingly able to relay the perturbations on the extra domain onto the catalytic machinery to manifest opposite catalytic effects. Our

  17. Dynamically-driven enhancement of the catalytic machinery of the SARS 3C-like protease by the S284-T285-I286/A mutations on the extra domain.

    Science.gov (United States)

    Lim, Liangzhong; Shi, Jiahai; Mu, Yuguang; Song, Jianxing

    2014-01-01

    Previously we revealed that the extra domain of SARS 3CLpro mediated the catalysis via different mechanisms. While the R298A mutation completely abolished the dimerization, thus resulting in the inactive catalytic machinery, N214A inactivated the enzyme by altering its dynamics without significantly perturbing its structure. Here we studied another mutant with S284-T285-I286 replaced by Ala (STI/A) with a 3.6-fold activity increase and slightly enhanced dimerization. We determined its crystal structure, which still adopts the dimeric structure almost identical to that of the wild-type (WT), except for slightly tighter packing between two extra-domains. We then conducted 100-ns molecular dynamics (MD) simulations for both STI/A and WT, the longest reported so far for 3CLpro. In the simulations, two STI/A extra domains become further tightly packed, leading to a significant volume reduction of the nano-channel formed by residues from both catalytic and extra domains. The enhanced packing appears to slightly increase the dynamic stability of the N-finger and the first helix residues, which subsequently triggers the redistribution of dynamics over residues directly contacting them. This ultimately enhances the dynamical stability of the residues constituting the catalytic dyad and substrate-binding pockets. Further correlation analysis reveals that a global network of the correlated motions exists in the protease, whose components include all residues identified so far to be critical for the dimerization and catalysis. Most strikingly, the N214A mutation globally decouples this network while the STI/A mutation alters the correlation pattern. Together with previous results, the present study establishes that besides the classic structural allostery, the dynamic allostery also operates in the SARS 3CLpro, which is surprisingly able to relay the perturbations on the extra domain onto the catalytic machinery to manifest opposite catalytic effects. Our results thus imply a

  18. The nonlinear dynamics of family problem solving in adolescence: the predictive validity of a peaceful resolution attractor.

    Science.gov (United States)

    Dishion, Thomas J; Forgatch, Marion; Van Ryzin, Mark; Winter, Charlotte

    2012-07-01

    In this study we examined the videotaped family interactions of a community sample of adolescents and their parents. Youths were assessed in early to late adolescence on their levels of antisocial behavior. At age 16-17, youths and their parents were videotaped interacting while completing a variety of tasks, including family problem solving. The interactions were coded and compared for three developmental patterns of antisocial behavior: early onset, persistent; adolescence onset; and typically developing. The mean duration of conflict bouts was the only interaction pattern that discriminated the 3 groups. In the prediction of future antisocial behavior, parent and youth reports of transition entropy and conflict resolution interacted to account for antisocial behavior at age 18-19. Families with low entropy and peaceful resolutions predicted low levels of youth antisocial behavior at age 18-19. These findings suggest the need to study both attractors and repellers to understand family dynamics associated with health and social and emotional development.

  19. High resolution polarimeter-interferometer system for fast equilibrium dynamics and MHD instability studies on Joint-TEXT tokamak (invited)

    Energy Technology Data Exchange (ETDEWEB)

    Chen, J.; Zhuang, G., E-mail: ge-zhuang@hust.edu.cn; Li, Q.; Liu, Y.; Gao, L.; Zhou, Y. N.; Jian, X.; Xiong, C. Y.; Wang, Z. J. [State Key Laboratory of Advanced Electromagnetic Engineering and Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Brower, D. L.; Ding, W. X. [Department of Physics and Astronomy, University of California Los Angeles, Los Angeles, California 90095 (United States)

    2014-11-15

    A high-performance Faraday-effect polarimeter-interferometer system has been developed for the J-TEXT tokamak. This system has time response up to 1 μs, phase resolution < 0.1° and minimum spatial resolution ∼15 mm. High resolution permits investigation of fast equilibrium dynamics as well as magnetic and density perturbations associated with intrinsic Magneto-Hydro-Dynamic (MHD) instabilities and external coil-induced Resonant Magnetic Perturbations (RMP). The 3-wave technique, in which the line-integrated Faraday angle and electron density are measured simultaneously by three laser beams with specific polarizations and frequency offsets, is used. In order to achieve optimum resolution, three frequency-stabilized HCOOH lasers (694 GHz, >35 mW per cavity) and sensitive Planar Schottky Diode mixers are used, providing stable intermediate-frequency signals (0.5–3 MHz) with S/N > 50. The collinear R- and L-wave probe beams, which propagate through the plasma poloidal cross section (a = 0.25–0.27 m) vertically, are expanded using parabolic mirrors to cover the entire plasma column. Sources of systematic errors, e.g., stemming from mechanical vibration, beam non-collinearity, and beam polarization distortion are individually examined and minimized to ensure measurement accuracy. Simultaneous density and Faraday measurements have been successfully achieved for 14 chords. Based on measurements, temporal evolution of safety factor profile, current density profile, and electron density profile are resolved. Core magnetic and density perturbations associated with MHD tearing instabilities are clearly detected. Effects of non-axisymmetric 3D RMP in ohmically heated plasmas are directly observed by polarimetry for the first time.

  20. Double domain wavelength multiplexed Fizeau interferometer with high resolution dynamic sensing and absolute length detection

    Science.gov (United States)

    Antonacci, Julián; Arenas, Gustavo F.; Duchowicz, Ricardo

    2017-04-01

    In this work, we present a simple photonic instrument that has the ability of measuring positions, distances and vibrations with very high resolution by means of two Fizeau interferometers (FI), both using the same optical fiber end as a probe tip itself. On the one hand we have a time domain FI powered with a 1310 nm laser and monitored by an InGaAs detector providing displacement information with resolution around a tenth of nm but regardless of the absolute position of object and of the displacement sense. On the other, a spectral domain FI version based on a super luminescent source (SLED) centred at 800 nm with bandwidth of nearly 40 nm is analysed in real time by means of a digital spectrometer. Each spectrum is acquired in a very small time interval and provides information of both length of the cavity as well as its correct sense of evolution. Resolution of this system is lower than its complementary temporal case, but distance and sense measurements are absolute and can be determined successfully by adequate processing of spectral signal.Both interferometers are optically coupled to a single fiber optic probe and are wavelength modulated.Therefore, combination of both sensors results in a new one which allows the correct knowledge of an object or surfaces under test, i.e. a high resolution of displacement data plus its absolute position and true sense of movement.

  1. Dynamic Resolution in GPU-Accelerated Volume Rendering to Autostereoscopic Multiview Lenticular Displays

    Directory of Open Access Journals (Sweden)

    Daniel Ruijters

    2008-09-01

    Full Text Available The generation of multiview stereoscopic images of large volume rendered data demands an enormous amount of calculations. We propose a method for hardware accelerated volume rendering of medical data sets to multiview lenticular displays, offering interactive manipulation throughout. The method is based on buffering GPU-accelerated direct volume rendered visualizations of the individual views from their respective focal spot positions, and composing the output signal for the multiview lenticular screen in a second pass. This compositing phase is facilitated by the fact that the view assignment per subpixel is static, and therefore can be precomputed. We decoupled the resolution of the individual views from the resolution of the composited signal, and adjust the resolution on-the-fly, depending on the available processing resources, in order to maintain interactive refresh rates. The optimal resolution for the volume rendered views is determined by means of an analysis of the lattice of the output signal for the lenticular screen in the Fourier domain.

  2. High-resolution modeling of atmospheric dynamics in the Nepalese Himalaya

    NARCIS (Netherlands)

    Collier, Emily; Immerzeel, Walter W.

    2015-01-01

    High-altitude meteorological processes in the Himalaya are influenced by complex interactions between the topography and the monsoon and westerly circulation systems. In this study, we use the Weather Research and Forecasting model configured with high spatial resolution to understand seasonal patte

  3. Measuring the dynamics of second-order photon correlation functions inside a pulse with picosecond time resolution

    DEFF Research Database (Denmark)

    Assmann, Marc; Veit, Franziska; Tempel, Jean-Sebastian;

    2010-01-01

    We present a detailed discussion of a recently demonstrated experimental technique capable of measuring the orrelation function of a pulsed light source with picosecond time resolution. The measurement involves a streak camera in single photon counting mode, which is modified such that a signal...... at a fixed repetition rate, and well defined energy, can be monitored after each pulsed laser excitation. The technique provides further insight into the quantum optical properties of pulsed light emission from semiconductor nanostructures, and the dynamics inside a pulse, on the subnanosecond time scale....

  4. Improving the off-axis spatial resolution and dynamic range of the NIF X-ray streak cameras (invited).

    Science.gov (United States)

    MacPhee, A G; Dymoke-Bradshaw, A K L; Hares, J D; Hassett, J; Hatch, B W; Meadowcroft, A L; Bell, P M; Bradley, D K; Datte, P S; Landen, O L; Palmer, N E; Piston, K W; Rekow, V V; Hilsabeck, T J; Kilkenny, J D

    2016-11-01

    We report simulations and experiments that demonstrate an increase in spatial resolution of the NIF core diagnostic x-ray streak cameras by at least a factor of two, especially off axis. A design was achieved by using a corrector electron optic to flatten the field curvature at the detector plane and corroborated by measurement. In addition, particle in cell simulations were performed to identify the regions in the streak camera that contribute the most to space charge blurring. These simulations provide a tool for convolving synthetic pre-shot spectra with the instrument function so signal levels can be set to maximize dynamic range for the relevant part of the streak record.

  5. Chemical Dynamic Thermodynamic Resolution and S/R Interconversion of Unprotected Unnatural Tailor-made α-Amino Acids.

    Science.gov (United States)

    Wang, Shuni; Zhou, Shengbin; Wang, Jiang; Nian, Yong; Kawashima, Aki; Moriwaki, Hiroki; Aceña, José L; Soloshonok, Vadim A; Liu, Hong

    2015-10-16

    Described here is an advanced, general method for purely chemical dynamic thermodynamic resolution and S/R interconversion of unprotected tailor-made α-amino acids (α-AAs) through intermediate formation of the corresponding nickel(II)-chelated Schiff bases. The method features virtually complete stereochemical outcome, broad substrate generality (35 examples), and operationally convenient conditions allowing for large-scale preparation of the target α-AAs in enantiomerically pure form. Furthermore, the new type of nonracemizable axially chiral ligands can be quantitatively recycled and reused, rendering the whole process economically and synthetically attractive.

  6. Improving the off-axis spatial resolution and dynamic range of the NIF X-ray streak cameras (invited)

    Science.gov (United States)

    MacPhee, A. G.; Dymoke-Bradshaw, A. K. L.; Hares, J. D.; Hassett, J.; Hatch, B. W.; Meadowcroft, A. L.; Bell, P. M.; Bradley, D. K.; Datte, P. S.; Landen, O. L.; Palmer, N. E.; Piston, K. W.; Rekow, V. V.; Hilsabeck, T. J.; Kilkenny, J. D.

    2016-11-01

    We report simulations and experiments that demonstrate an increase in spatial resolution of the NIF core diagnostic x-ray streak cameras by at least a factor of two, especially off axis. A design was achieved by using a corrector electron optic to flatten the field curvature at the detector plane and corroborated by measurement. In addition, particle in cell simulations were performed to identify the regions in the streak camera that contribute the most to space charge blurring. These simulations provide a tool for convolving synthetic pre-shot spectra with the instrument function so signal levels can be set to maximize dynamic range for the relevant part of the streak record.

  7. Production of solar radiation bankable datasets from high-resolution solar irradiance derived with dynamical downscaling Numerical Weather prediction model

    Directory of Open Access Journals (Sweden)

    Yassine Charabi

    2016-11-01

    Full Text Available A bankable solar radiation database is required for the financial viability of solar energy project. Accurate estimation of solar energy resources in a country is very important for proper siting, sizing and life cycle cost analysis of solar energy systems. During the last decade an important progress has been made to develop multiple solar irradiance database (Global Horizontal Irradiance (GHI and Direct Normal Irradiance (DNI, using satellite of different resolution and sophisticated models. This paper assesses the performance of High-resolution solar irradiance derived with dynamical downscaling Numerical Weather Prediction model with, GIS topographical solar radiation model, satellite data and ground measurements, for the production of bankable solar radiation datasets. For this investigation, NWP model namely Consortium for Small-scale Modeling (COSMO is used for the dynamical downscaling of solar radiation. The obtained results increase confidence in solar radiation data base obtained from dynamical downscaled NWP model. The mean bias of dynamical downscaled NWP model is small, on the order of a few percents for GHI, and it could be ranked as a bankable datasets. Fortunately, these data are usually archived in the meteorological department and gives a good idea of the hourly, monthly, and annual incident energy. Such short time-interval data are valuable in designing and operating the solar energy facility. The advantage of the NWP model is that it can be used for solar radiation forecast since it can estimate the weather condition within the next 72–120 hours. This gives a reasonable estimation of the solar radiation that in turns can be used to forecast the electric power generation by the solar power plant.

  8. Molecular dynamics simulations and structure-guided mutagenesis provide insight into the architecture of the catalytic core of the ectoine hydroxylase.

    Science.gov (United States)

    Widderich, Nils; Pittelkow, Marco; Höppner, Astrid; Mulnaes, Daniel; Buckel, Wolfgang; Gohlke, Holger; Smits, Sander H J; Bremer, Erhard

    2014-02-06

    Many bacteria amass compatible solutes to fend-off the detrimental effects of high osmolarity on cellular physiology and water content. These solutes also function as stabilizers of macromolecules, a property for which they are referred to as chemical chaperones. The tetrahydropyrimidine ectoine is such a compatible solute and is widely synthesized by members of the Bacteria. Many ectoine producers also synthesize the stress protectant 5-hydroxyectoine from the precursor ectoine, a process that is catalyzed by the ectoine hydroxylase (EctD). The EctD enzyme is a member of the non-heme-containing iron(II) and 2-oxoglutarate-dependent dioxygenase superfamily. A crystal structure of the EctD protein from the moderate halophile Virgibacillus salexigens has previously been reported and revealed the coordination of the iron catalyst, but it lacked the substrate ectoine and the co-substrate 2-oxoglutarate. Here we used this crystal structure as a template to assess the likely positioning of the ectoine and 2-oxoglutarate ligands within the active site by structural comparison, molecular dynamics simulations, and site-directed mutagenesis. Collectively, these approaches suggest the positioning of the iron, ectoine, and 2-oxoglutarate ligands in close proximity to each other and with a spatial orientation that will allow the region-selective and stereo-specific hydroxylation of (4S)-ectoine to (4S,5S)-5-hydroxyectoine. Our study thus provides a view into the catalytic core of the ectoine hydroxylase and suggests an intricate network of interactions between the three ligands and evolutionarily highly conserved residues in members of the EctD protein family.

  9. 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.

  10. Varying the resolution of the Rouse model on temporal and spatial scales: application to multiscale modelling of DNA dynamics

    CERN Document Server

    Rolls, Edward; Erban, Radek

    2016-01-01

    A multi-resolution bead-spring model for polymer dynamics is developed as a generalization of the Rouse model. A polymer chain is described using beads of variable sizes connected by springs with variable spring constants. A numerical scheme which can use different timesteps to advance the positions of different beads is presented and analyzed. The position of a particular bead is only updated at integer multiples of the timesteps associated with its connecting springs. This approach extends the Rouse model to a multiscale model on both spatial and temporal scales, allowing simulations of localized regions of a polymer chain with high spatial and temporal resolution, while using a coarser modelling approach to describe the rest of the polymer chain. A method for changing the model resolution on-the-fly is developed using the Metropolis-Hastings algorithm. It is shown that this approach maintains key statistics of the end-to-end distance and diffusion of the polymer filament and makes computational savings whe...

  11. Unraveling the Architecture and Structural Dynamics of Pathogens by High-Resolution in vitro Atomic Force Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Malkin, A J; Plomp, M; Leighton, T J; McPherson, A; Wheeler, K E

    2005-04-12

    Progress in structural biology very much depends upon the development of new high-resolution techniques and tools. Despite decades of study of viruses, bacteria and bacterial spores and their pressing importance in human medicine and biodefense, many of their structural properties are poorly understood. Thus, characterization and understanding of the architecture of protein surface and internal structures of pathogens is critical to elucidating mechanisms of disease, immune response, physicochemical properties, environmental resistance and development of countermeasures against bioterrorist agents. Furthermore, even though complete genome sequences are available for various pathogens, the structure-function relationships are not understood. Because of their lack of symmetry and heterogeneity, large human pathogens are often refractory to X-ray crystallographic analysis or reconstruction by cryo-electron microscopy (cryo-EM). An alternative high-resolution method to examine native structure of pathogens is atomic force microscopy (AFM), which allows direct visualization of macromolecular assemblies at near-molecular resolution. The capability to image single pathogen surfaces at nanometer scale in vitro would profoundly impact mechanistic and structural studies of pathogenesis, immunobiology, specific cellular processes, environmental dynamics and biotransformation.

  12. High spatial resolution three-dimensional mapping of vegetation spectral dynamics using computer vision and hobbyist unmanned aerial vehicles

    Science.gov (United States)

    Dandois, J. P.; Ellis, E. C.

    2013-12-01

    High spatial resolution three-dimensional (3D) measurements of vegetation by remote sensing are advancing ecological research and environmental management. However, substantial economic and logistical costs limit this application, especially for observing phenological dynamics in ecosystem structure and spectral traits. Here we demonstrate a new aerial remote sensing system enabling routine and inexpensive aerial 3D measurements of canopy structure and spectral attributes, with properties similar to those of LIDAR, but with RGB (red-green-blue) spectral attributes for each point, enabling high frequency observations within a single growing season. This 'Ecosynth' methodology applies photogrammetric ''Structure from Motion'' computer vision algorithms to large sets of highly overlapping low altitude (greenness were highly correlated (R2 = 0.88) with MODIS NDVI time series for the same area and vertical differences in canopy color revealed the early green up of the dominant canopy species, Liriodendron tulipifera, strong evidence that Ecosynth time series measurements capture vegetation structural and spectral dynamics at the spatial scale of individual trees. Observing canopy phenology in 3D at high temporal resolutions represents a breakthrough in forest ecology. Inexpensive user-deployed technologies for multispectral 3D scanning of vegetation at landscape scales (< 1 km2) heralds a new era of participatory remote sensing by field ecologists, community foresters and the interested public.

  13. Improved resolution and reliability in dynamic PET using Bayesian regularization of MRTM2

    DEFF Research Database (Denmark)

    Agn, Mikael; Svarer, Claus; Frokjaer, Vibe G.;

    2014-01-01

    This paper presents a mathematical model that regularizes dynamic PET data by using a Bayesian framework. We base the model on the well known two-parameter multilinear reference tissue method MRTM2 and regularize on the assumption that spatially close regions have similar parameters. The developed...

  14. Simulation of macromolecular liquids with the adaptive resolution molecular dynamics technique

    Science.gov (United States)

    Peters, J. H.; Klein, R.; Delle Site, L.

    2016-08-01

    We extend the application of the adaptive resolution technique (AdResS) to liquid systems composed of alkane chains of different lengths. The aim of the study is to develop and test the modifications of AdResS required in order to handle the change of representation of large molecules. The robustness of the approach is shown by calculating several relevant structural properties and comparing them with the results of full atomistic simulations. The extended scheme represents a robust prototype for the simulation of macromolecular systems of interest in several fields, from material science to biophysics.

  15. A multicrystal diffraction data-collection approach for studying structural dynamics with millisecond temporal resolution

    Directory of Open Access Journals (Sweden)

    Robin Schubert

    2016-11-01

    Full Text Available Many biochemical processes take place on timescales ranging from femtoseconds to seconds. Accordingly, any time-resolved experiment must be matched to the speed of the structural changes of interest. Therefore, the timescale of interest defines the requirements of the X-ray source, instrumentation and data-collection strategy. In this study, a minimalistic approach for in situ crystallization is presented that requires only a few microlitres of sample solution containing a few hundred crystals. It is demonstrated that complete diffraction data sets, merged from multiple crystals, can be recorded within only a few minutes of beamtime and allow high-resolution structural information of high quality to be obtained with a temporal resolution of 40 ms. Global and site-specific radiation damage can be avoided by limiting the maximal dose per crystal to 400 kGy. Moreover, analysis of the data collected at higher doses allows the time-resolved observation of site-specific radiation damage. Therefore, our approach is well suited to observe structural changes and possibly enzymatic reactions in the low-millisecond regime.

  16. Gelation-driven Dynamic Systemic Resolution: in situ Generation and Self-Selection of an Organogelator

    Science.gov (United States)

    Hu, Lei; Zhang, Yang; Ramström, Olof

    2015-06-01

    An organogelator was produced and identified from a dynamic imine system, resolved and amplified by selective gelation. The formation of the organogel was monitored in situ by 1H NMR, showing the existence of multiple reversible reactions operating simultaneously, and the redistribution of the involved species during gelation. The formed organogelator proved effective with a range of organic solvents, including DMSO, toluene, and longer, linear alcohols.

  17. Observations of movement dynamics of flying insects using high resolution lidar

    DEFF Research Database (Denmark)

    Kirkeby, Carsten Thure; Wellenreuther, Maren; Brydegaard, Mikkel

    2016-01-01

    could distinguish three insect clusters based on morphology and found that two contained insects predominantly recorded above the field in the evening, whereas the third was formed by insects near the forest at around 21:30. Together our results demonstrate the capability of lidar for distinguishing......Insects are fundamental to ecosystem functioning and biodiversity, yet the study of insect movement, dispersal and activity patterns remains a challenge. Here we present results from a novel high resolution laser-radar (lidar) system for quantifying flying insect abundance recorded during one...... summer night in Sweden. We compare lidar recordings with data from a light trap deployed alongside the lidar. A total of 22808 insect were recorded, and the relative temporal quantities measured matched the quantities recorded with the light trap within a radius of 5 m. Lidar records showed that small...

  18. High Resolution Angle Resolved Photoemission Studies on Quasi-Particle Dynamics in Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Leem, C.S.

    2010-06-02

    We obtained the spectral function of the graphite H point using high resolution angle resolved photoelectron spectroscopy (ARPES). The extracted width of the spectral function (inverse of the photo-hole lifetime) near the H point is approximately proportional to the energy as expected from the linearly increasing density of states (DOS) near the Fermi energy. This is well accounted by our electron-phonon coupling theory considering the peculiar electronic DOS near the Fermi level. And we also investigated the temperature dependence of the peak widths both experimentally and theoretically. The upper bound for the electron-phonon coupling parameter is 0.23, nearly the same value as previously reported at the K point. Our analysis of temperature dependent ARPES data at K shows that the energy of phonon mode of graphite has much higher energy scale than 125K which is dominant in electron-phonon coupling.

  19. Dynamics of Saturn’s 2010 Great White Spot from high-resolution Cassini ISS observations

    Science.gov (United States)

    Hueso, Ricardo; Sánchez-Lavega, A.; del Río-Gaztelurrutia, T.

    2012-10-01

    On December 5th 2010 a storm erupted in Saturn’s North Temperate latitudes which were experiencing early spring season. The storm quickly developed to a planet-wide disturbance of the Great White Spot type. The ISS instrument onboard Cassini acquired its first images of the storm on 23th December 2010 and performed repeated observations with a variety of spatial resolutions over the nearly 10 months period the storm continued active. Here we present an analysis of two of the image sequences with better spatial resolution of the mature storm when it was fully developed and very active. We used an image correlation algorithm to measure the cloud motions obtained from images separated 20 minutes and obtained 16,000 wind tracers in a domain of 60 degrees longitude per 20 degrees in latitude. Intense zonal and meridional motions accompanied the storm and reached values of 120 m/s in particular regions of the active storm. The storm released a chain of anticyclonic and cyclonic vortices at planetocentric latitudes of 36° and 32° respectively. The short time difference between the images results in estimated wind uncertainties of 15 m/s that did not allow to perform a complete analysis of the turbulence and kinetic spectrum of the motions. We identify locations of the updrafts and link those with the morphology in different observing filters. The global behaviour of the storm was examined in images separated by 10 hours confirming the intensity of the winds and the global behaviour of the vortices. Acknowledgments: This work was supported by the Spanish MICIIN project AYA2009-10701 with FEDER funds, by Grupos Gobierno Vasco IT-464-07 and by Universidad País Vasco UPV/EHU through program UFI11/55.

  20. Resolution of Ibuprofen Ester by Catalytic Antibodies in Water-miscible Organic-solvents%水-有机溶剂混溶体系中催化抗体催化拆分布洛芳脂

    Institute of Scientific and Technical Information of China (English)

    杨根生; 应黎; 欧志敏; 姚善泾

    2009-01-01

    The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonatc hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and TV, .N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 umol, 0.2 mol·L-1 phosphate buffer, pH 8) at 37℃ for 10 h, a good conversion (48.7%) and high cnantiomeric excess (>99%) could be reached. The kinetic analysis of the cata-lytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (kcat/km) was enhanced to 151.91 L·mmol-1·min-1, twice as large as that for the buffer solution only.

  1. Analog filtering of large solvent signals for improved dynamic range in high-resolution NMR.

    Science.gov (United States)

    Redfield, A G; Kunz, S D

    1998-01-01

    The large solvent signal from samples in H2O solvent still challenges the dynamic range capability of any spectrometer. The solvent signal can be largely removed with a pair of simple resistor-capacitor (RC) high-pass filters when the solvent frequency is set at center band (zero frequency) using quadrature detection, with RC approximately 0.5 ms. However, an approximately 0.5-ms transient remains at initial time, which we reduce fourfold for a short time only, just before the A/D converter, by means of a variable-gain amplifier, and later restore with software. This modification can result in a nearly fourfold increase in dynamic range. When we converted to a frequency-shifted mode (A. G. Redfield and S. D. Kunz, 1994, J. Magn. Reson. A 108, 234-237) we replaced the RC high-pass filter with a quadrature feedback notch filter tuned to the solvent frequency (5.06 kHz). This filter is an example of a class of two-input/two-output filters which maintain the spectral integrity (image-free character) of quadrature signals. Digital filters of the same type are also considered briefly. We discuss the implications of these ideas for spectrometer input design, including schemes for elimination of radiation damping, and effects of probe bandwidth on extreme oversampling.

  2. Path Integral Molecular Dynamics within the Grand Canonical-like Adaptive Resolution Technique: Quantum-Classical Simulation of Liquid Water

    CERN Document Server

    Agarwal, Animesh

    2015-01-01

    Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to investigate properties induced by spatial delocalization of atoms; however computationally this technique is very demanding. The abovementioned limitation implies the restriction of PIMD applications to relatively small systems and short time scales. One possible solution to overcome size and time limitation is to introduce PIMD algorithms into the Adaptive Resolution Simulation Scheme (AdResS). AdResS requires a relatively small region treated at path integral level and embeds it into a large molecular reservoir consisting of generic spherical coarse grained molecules. It was previously shown that the realization of the idea above, at a simple level, produced reasonable results for toy systems or simple/test systems like liquid parahydrogen. Encouraged by previous results, in this ...

  3. DYNAMIC SOFTWARE TESTING MODELS WITH PROBABILISTIC PARAMETERS FOR FAULT DETECTION AND ERLANG DISTRIBUTION FOR FAULT RESOLUTION DURATION

    Directory of Open Access Journals (Sweden)

    A. D. Khomonenko

    2016-07-01

    Full Text Available Subject of Research.Software reliability and test planning models are studied taking into account the probabilistic nature of error detection and discovering. Modeling of software testing enables to plan the resources and final quality at early stages of project execution. Methods. Two dynamic models of processes (strategies are suggested for software testing, using error detection probability for each software module. The Erlang distribution is used for arbitrary distribution approximation of fault resolution duration. The exponential distribution is used for approximation of fault resolution discovering. For each strategy, modified labeled graphs are built, along with differential equation systems and their numerical solutions. The latter makes it possible to compute probabilistic characteristics of the test processes and states: probability states, distribution functions for fault detection and elimination, mathematical expectations of random variables, amount of detected or fixed errors. Evaluation of Results. Probabilistic characteristics for software development projects were calculated using suggested models. The strategies have been compared by their quality indexes. Required debugging time to achieve the specified quality goals was calculated. The calculation results are used for time and resources planning for new projects. Practical Relevance. The proposed models give the possibility to use the reliability estimates for each individual module. The Erlang approximation removes restrictions on the use of arbitrary time distribution for fault resolution duration. It improves the accuracy of software test process modeling and helps to take into account the viability (power of the tests. With the use of these models we can search for ways to improve software reliability by generating tests which detect errors with the highest probability.

  4. Observations of movement dynamics of flying insects using high resolution lidar.

    Science.gov (United States)

    Kirkeby, Carsten; Wellenreuther, Maren; Brydegaard, Mikkel

    2016-07-04

    Insects are fundamental to ecosystem functioning and biodiversity, yet the study of insect movement, dispersal and activity patterns remains a challenge. Here we present results from a novel high resolution laser-radar (lidar) system for quantifying flying insect abundance recorded during one summer night in Sweden. We compare lidar recordings with data from a light trap deployed alongside the lidar. A total of 22808 insect were recorded, and the relative temporal quantities measured matched the quantities recorded with the light trap within a radius of 5 m. Lidar records showed that small insects (wing size 2.5 mm(2) in cross-section) were most abundant near the lidar beam before 22:00 and then moved towards the light trap between 22:00 and 23:30. We could distinguish three insect clusters based on morphology and found that two contained insects predominantly recorded above the field in the evening, whereas the third was formed by insects near the forest at around 21:30. Together our results demonstrate the capability of lidar for distinguishing different types of insect during flight and quantifying their movements.

  5. Observations of movement dynamics of flying insects using high resolution lidar

    Science.gov (United States)

    Kirkeby, Carsten; Wellenreuther, Maren; Brydegaard, Mikkel

    2016-07-01

    Insects are fundamental to ecosystem functioning and biodiversity, yet the study of insect movement, dispersal and activity patterns remains a challenge. Here we present results from a novel high resolution laser-radar (lidar) system for quantifying flying insect abundance recorded during one summer night in Sweden. We compare lidar recordings with data from a light trap deployed alongside the lidar. A total of 22808 insect were recorded, and the relative temporal quantities measured matched the quantities recorded with the light trap within a radius of 5 m. Lidar records showed that small insects (wing size insects (wing size >2.5 mm2 in cross-section) were most abundant near the lidar beam before 22:00 and then moved towards the light trap between 22:00 and 23:30. We could distinguish three insect clusters based on morphology and found that two contained insects predominantly recorded above the field in the evening, whereas the third was formed by insects near the forest at around 21:30. Together our results demonstrate the capability of lidar for distinguishing different types of insect during flight and quantifying their movements.

  6. The high-resolution architecture and structural dynamics of Bacillus spores

    Energy Technology Data Exchange (ETDEWEB)

    Plomp, M; Leighton, T J; Wheeler, K E; Malkin, A J

    2004-05-06

    The capability to image single microbial cell surfaces at nanometer scale under native conditions would profoundly impact mechanistic and structural studies of pathogenesis, immunobiology, environmental resistance and biotransformation. We report here that advances in atomic force microscopy (AFM) have allowed us to directly visualize high-resolution native structures of bacterial endospores, including the exosporium and spore coats of four Bacillus species in air and water environments. The dimensions of individual Bacillus atrophaeus spores were found to decrease reversibly by 12% in response to a change in the environment from aqueous to aerial phase. Intraspecies spore size distribution analyses revealed that spore length could vary by a factor of 2 while the absolute deviation is 7 - 13% in length and 4 - 6 % in width. AFM analysis also demonstrated that the mechanisms of spore coat self-assembly are similar to those described for inorganic and macromolecular crystallization. These results establish AFM as a powerful new tool for the analysis of molecular architecture and variability as a function of spatial, temporal and developmental organizational scales.

  7. High resolution polarimeter-interferometer system for fast equilibrium dynamics and MHD instability studies on Joint-TEXT tokamak (invited).

    Science.gov (United States)

    Chen, J; Zhuang, G; Li, Q; Liu, Y; Gao, L; Zhou, Y N; Jian, X; Xiong, C Y; Wang, Z J; Brower, D L; Ding, W X

    2014-11-01

    A high-performance Faraday-effect polarimeter-interferometer system has been developed for the J-TEXT tokamak. This system has time response up to 1 μs, phase resolution dynamics as well as magnetic and density perturbations associated with intrinsic Magneto-Hydro-Dynamic (MHD) instabilities and external coil-induced Resonant Magnetic Perturbations (RMP). The 3-wave technique, in which the line-integrated Faraday angle and electron density are measured simultaneously by three laser beams with specific polarizations and frequency offsets, is used. In order to achieve optimum resolution, three frequency-stabilized HCOOH lasers (694 GHz, >35 mW per cavity) and sensitive Planar Schottky Diode mixers are used, providing stable intermediate-frequency signals (0.5-3 MHz) with S/N > 50. The collinear R- and L-wave probe beams, which propagate through the plasma poloidal cross section (a = 0.25-0.27 m) vertically, are expanded using parabolic mirrors to cover the entire plasma column. Sources of systematic errors, e.g., stemming from mechanical vibration, beam non-collinearity, and beam polarization distortion are individually examined and minimized to ensure measurement accuracy. Simultaneous density and Faraday measurements have been successfully achieved for 14 chords. Based on measurements, temporal evolution of safety factor profile, current density profile, and electron density profile are resolved. Core magnetic and density perturbations associated with MHD tearing instabilities are clearly detected. Effects of non-axisymmetric 3D RMP in ohmically heated plasmas are directly observed by polarimetry for the first time.

  8. Fluid dynamics and convective heat transfer in impinging jets through implementation of a high resolution liquid crystal technique

    Science.gov (United States)

    Kim, K.; Wiedner, B.; Camci, C.

    1993-01-01

    A combined convective heat transfer and fluid dynamics investigation in a turbulent round jet impinging on a flat surface is presented. The experimental study uses a high resolution liquid crystal technique for the determination of the convective heat transfer coefficients on the impingement plate. The heat transfer experiments are performed using a transient heat transfer method. The mean flow and the character of turbulent flow in the free jet is presented through five hole probe and hot wire measurements, respectively. The flow field character of the region near the impingement plate plays an important role in the amount of convective heat transfer. Detailed surveys obtained from five hole probe and hot wire measurements are provided. An extensive validation of the liquid crystal based heat transfer method against a conventional technique is also presented. After a complete documentation of the mean and turbulent flow field, the convective heat transfer coefficient distributions on the impingement plate are presented. The near wall of the impingement plate and the free jet region is treated separately. The current heat transfer distributions are compared to other studies available from the literature. The present paper contains complete sets of information on the three dimensional mean flow, turbulent velocity fluctuations, and convective heat transfer to the plate. The experiments also prove that the present nonintrusive heat transfer method is highly effective in obtaining high resolution heat transfer maps with a heat transfer coefficient uncertainty of 5.7 percent.

  9. Dynamic fault trees resolution: A conscious trade-off between analytical and simulative approaches

    Energy Technology Data Exchange (ETDEWEB)

    Chiacchio, F., E-mail: chiacchio@dmi.unict.it [Dipartimento di Matematica e Informatica-DMI, Universita degli Studi di Catania (Italy); Compagno, L., E-mail: lco@diim.unict.it [Dipartimento di Ingegneria Industriale e Meccanica-DIIM, Universita degli Studi di Catania (Italy); D' Urso, D., E-mail: ddurso@diim.unict.it [Dipartimento di Ingegneria Industriale e Meccanica-DIIM, Universita degli Studi di Catania (Italy); Manno, G., E-mail: gmanno@dmi.unict.it [Dipartimento di Matematica e Informatica-DMI, Universita degli Studi di Catania (Italy); Trapani, N., E-mail: ntrapani@diim.unict.it [Dipartimento di Ingegneria Industriale e Meccanica-DIIM, Universita degli Studi di Catania (Italy)

    2011-11-15

    Safety assessment in industrial plants with 'major hazards' requires a rigorous combination of both qualitative and quantitative techniques of RAMS. Quantitative assessment can be executed by static or dynamic tools of dependability but, while the former are not sufficient to model exhaustively time-dependent activities, the latter are still too complex to be used with success by the operators of the industrial field. In this paper we present a review of the procedures that can be used to solve quite general dynamic fault trees (DFT) that present a combination of the following characteristics: time dependencies, repeated events and generalized probability failure. Theoretical foundations of the DFT theory are discussed and the limits of the most known DFT tools are presented. Introducing the concept of weak and strong hierarchy, the well-known modular approach is adapted to study a more generic class of DFT. In order to quantify the approximations introduced, an ad-hoc simulative environment is used as benchmark. In the end, a DFT of an accidental scenario is analyzed with both analytical and simulative approaches. Final results are in good agreement and prove how it is possible to implement a suitable Monte Carlo simulation with the features of a spreadsheet environment, able to overcome the limits of the analytical tools, thus encouraging further researches along this direction. - Highlights: > Theoretical foundations of the DFT are reviewed and the limits of the analytical techniques are assessed. > Hierarchical technique is discussed, introducing the concepts of weak and strong equivalence. > Simulative environment developed with a spreadsheet electronic document is tested. > Comparison between the simulative and the analytical results is performed. > Classification of which technique is more suitable is provided, depending on the complexity of the DFT.

  10. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...... and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...

  11. Toolbox for Urban Mobility Simulation: High Resolution Population Dynamics for Global Cities

    Science.gov (United States)

    Bhaduri, B. L.; Lu, W.; Liu, C.; Thakur, G.; Karthik, R.

    2015-12-01

    In this rapidly urbanizing world, unprecedented rate of population growth is not only mirrored by increasing demand for energy, food, water, and other natural resources, but has detrimental impacts on environmental and human security. Transportation simulations are frequently used for mobility assessment in urban planning, traffic operation, and emergency management. Previous research, involving purely analytical techniques to simulations capturing behavior, has investigated questions and scenarios regarding the relationships among energy, emissions, air quality, and transportation. Primary limitations of past attempts have been availability of input data, useful "energy and behavior focused" models, validation data, and adequate computational capability that allows adequate understanding of the interdependencies of our transportation system. With increasing availability and quality of traditional and crowdsourced data, we have utilized the OpenStreetMap roads network, and has integrated high resolution population data with traffic simulation to create a Toolbox for Urban Mobility Simulations (TUMS) at global scale. TUMS consists of three major components: data processing, traffic simulation models, and Internet-based visualizations. It integrates OpenStreetMap, LandScanTM population, and other open data (Census Transportation Planning Products, National household Travel Survey, etc.) to generate both normal traffic operation and emergency evacuation scenarios. TUMS integrates TRANSIMS and MITSIM as traffic simulation engines, which are open-source and widely-accepted for scalable traffic simulations. Consistent data and simulation platform allows quick adaption to various geographic areas that has been demonstrated for multiple cities across the world. We are combining the strengths of geospatial data sciences, high performance simulations, transportation planning, and emissions, vehicle and energy technology development to design and develop a simulation

  12. Numerical modeling of permafrost dynamics in Alaska using a high spatial resolution dataset

    Directory of Open Access Journals (Sweden)

    E. E. Jafarov

    2012-01-01

    Full Text Available Climate projections for the 21st century indicate that there could be a pronounced warming and permafrost degradation in the Arctic and sub-Arctic regions. Climate warming is likely to cause permafrost thawing with subsequent effects on surface albedo, hydrology, soil organic matter storage and greenhouse gas emissions. To assess possible changes in the permafrost thermal state and active layer thickness, we implemented the GIPL2-MPI transient numerical model for the entire Alaska permafrost domain. Input parameters to the model are spatial datasets of mean monthly air temperature and precipitation, prescribed thermal properties of the multilayered soil column, and water content which are specific for each soil class and geographical location. As a climate forcing we used the composite of five IPCC Global Circulation Models that has been downscaled to 2 by 2 km spatial resolution by Scenarios Network for Alaska Planning (SNAP group.

    In this paper we present the preliminary modeling results based on input of five-model composite with A1B carbon emission scenario. The model has been calibrated according to the annual borehole temperature measurements for the State of Alaska. We also performed more detailed calibration for fifteen shallow borehole stations where high quality data are available on daily basis. To validate the model performance we compared simulated active layer thicknesses with observed data from CALM active layer monitoring stations. Calibrated model was used to address possible ground temperature changes for the 21st century. The model simulation results show the widespread permafrost degradation in Alaska could begin in 2040–2099 time frame within the vast area southward from the Brooks Range except for the high altitudes of the Alaska Range and Wrangell Mountains.

  13. Numerical modeling of permafrost dynamics in Alaska using a high spatial resolution dataset

    Directory of Open Access Journals (Sweden)

    E. E. Jafarov

    2012-06-01

    Full Text Available Climate projections for the 21st century indicate that there could be a pronounced warming and permafrost degradation in the Arctic and sub-Arctic regions. Climate warming is likely to cause permafrost thawing with subsequent effects on surface albedo, hydrology, soil organic matter storage and greenhouse gas emissions.

    To assess possible changes in the permafrost thermal state and active layer thickness, we implemented the GIPL2-MPI transient numerical model for the entire Alaska permafrost domain. The model input parameters are spatial datasets of mean monthly air temperature and precipitation, prescribed thermal properties of the multilayered soil column, and water content that are specific for each soil class and geographical location. As a climate forcing, we used the composite of five IPCC Global Circulation Models that has been downscaled to 2 by 2 km spatial resolution by Scenarios Network for Alaska Planning (SNAP group.

    In this paper, we present the modeling results based on input of a five-model composite with A1B carbon emission scenario. The model has been calibrated according to the annual borehole temperature measurements for the State of Alaska. We also performed more detailed calibration for fifteen shallow borehole stations where high quality data are available on daily basis. To validate the model performance, we compared simulated active layer thicknesses with observed data from Circumpolar Active Layer Monitoring (CALM stations. The calibrated model was used to address possible ground temperature changes for the 21st century. The model simulation results show widespread permafrost degradation in Alaska could begin between 2040–2099 within the vast area southward from the Brooks Range, except for the high altitude regions of the Alaska Range and Wrangell Mountains.

  14. High-resolution ocean pH dynamics in four subtropical Atlantic benthic habitats

    Science.gov (United States)

    Hernández, C. A.; Clemente, S.; Sangil, C.; Hernández, J. C.

    2015-12-01

    Oscillations of ocean pH are largely unknown in coastal environments and ocean acidification studies often do not account for natural variability yet most of what is known about marine species and populations is found out via studies conducted in near shore environments. Most experiments designed to make predictions about future climate change scenarios are carried out in coastal environments with no research that takes into account the natural pH variability. In order to fill this knowledge gap and to provide reliable measures of pH oscillation, seawater pH was measured over time using moored pH sensors in four contrasting phytocenoses typical of the north Atlantic subtropical region. Each phytocenosis was characterized by its predominant engineer species: (1) Cystoseira abies-marina, (2) a mix of gelidiales and geniculate corallines, (3) Lobophora variegata, and (4) encrusting corallines. The autonomous pH measuring systems consisted of a pH sensor; a data logger and a battery encased in a waterproof container and allowed the acquisition of high-resolution continuous pH data at each of the study sites. The pH variation observed ranged by between 0.09 and 0.24 pHNBS units. A clear daily variation in seawater pH was detected at all the studied sites (0.04-0.12 pHNBS units). Significant differences in daily pH oscillations were also observed between phytocenoses, which shows that macroalgal communities influence the seawater pH in benthic habitats. Natural oscillations in pH must be taken into account in future ocean acidification studies to put findings in perspective and for any ecological recommendations to be realistic.

  15. Advancing Access to New Technology for Sustained High Resolution Observations of Plankton: From Bloom Dynamics to Climate Change

    Science.gov (United States)

    Sosik, H. M.; Olson, R. J.

    2012-12-01

    The combination of ocean observatory infrastructure and automated submersible flow cytometry can provide unprecedented capability for sustained high resolution time series of plankton, including taxa that are harmful or early indicators of ecosystem response to environmental change. Over the past decade, we have developed the FlowCytobot series of instruments that exemplify this capability. FlowCytobot and Imaging FlowCytobot use a combination of laser-based scattering and fluorescence measurements and video imaging of individual particles to enumerate and characterize cells ranging from picocyanobacteria to large chaining-forming diatoms. The process of developing these complex instruments was streamlined by access to the Martha's Vineyard Coastal Observatory (MVCO), a cabled facility on the New England Shelf, where real time two-way communications and access to shore power expedited cycles of instrument evaluation and design refinement. Repeated deployments at MVCO, typically 6 months in duration, have produced multi-year high resolution (hourly to daily) time series that are providing new insights into dynamics of community structure such as blooms, seasonality, and possibly even trends linked to regional climate change. The high temporal resolution observations of single cell properties make it possible not only to characterize taxonomic composition and size structure, but also to quantify taxon-specific growth rates. To meet the challenge of broadening access to this enabling technology, we have taken a two-step approach. First, we are partnering with a few scientific collaborators interested in using the instruments in different environments and to address different applications, notably the detection and characterization of harmful algal bloom events. Collaboration at this stage ensured that these first users outside the developers' lab had access to technical know-how required for successful outcomes; it also provided additional feedback that could be

  16. Towards a microchannel-based X-ray detector with two-dimensional spatial and time resolution and high dynamic range.

    Science.gov (United States)

    Adams, Bernhard W; Mane, Anil U; Elam, Jeffrey W; Obaid, Razib; Wetstein, Matthew; Chollet, Matthieu

    2015-09-01

    X-ray detectors that combine two-dimensional spatial resolution with a high time resolution are needed in numerous applications of synchrotron radiation. Most detectors with this combination of capabilities are based on semiconductor technology and are therefore limited in size. Furthermore, the time resolution is often realised through rapid time-gating of the acquisition, followed by a slower readout. Here, a detector technology is realised based on relatively inexpensive microchannel plates that uses GHz waveform sampling for a millimeter-scale spatial resolution and better than 100 ps time resolution. The technology is capable of continuous streaming of time- and location-tagged events at rates greater than 10(7) events per cm(2). Time-gating can be used for improved dynamic range.

  17. Towards a microchannel-based X-ray detector with two-dimensional spatial and time resolution and high dynamic range

    Energy Technology Data Exchange (ETDEWEB)

    Adams, Bernhard W.; Mane, Anil; Elam, Jeffrey; Obaid, Razib; Wetstein, Matthew J.

    2015-09-01

    X-ray detectors that combine two-dimensional spatial resolution with a high time resolution are needed in numerous applications of synchrotron radiation. Most detectors with this combination of capabilities are based on semiconductor technology and are therefore limited in size. Furthermore, the time resolution is often realised through rapid time-gating of the acquisition, followed by a slower readout. Here, a detector technology is realised based on relatively inexpensive microchannel plates that uses GHz waveform sampling for a millimeter-scale spatial resolution and better than 100 ps time resolution. The technology is capable of continuous streaming of time- and location-tagged events at rates greater than 10(7) events per cm(2). Time-gating can be used for improved dynamic range.

  18. High-Resolution Imaging of Structure and Dynamics of the Lowermost Mantle

    Science.gov (United States)

    Zhao, Chunpeng

    This research investigates Earth structure in the core-mantle boundary (CMB) region, where the solid rocky mantle meets the molten iron alloy core. At long wavelengths, the lower mantle is characterized by two nearly antipodal large low shear velocity provinces (LLSVPs), one beneath the Pacific Ocean the other beneath Africa and the southern Atlantic Ocean. However, fine-scale LLSVP structure as well as its relationship with plate tectonics, mantle convection, hotspot volcanism, and Earth's outer core remains poorly understood. The recent dramatic increase in seismic data coverage due to the EarthScope experiment presents an unprecedented opportunity to utilize large concentrated datasets of seismic data to improve resolution of lowermost mantle structures. I developed an algorithm that identifies anomalously broadened seismic waveforms to locate sharp contrasts in shear velocity properties across the margins of the LLSVP beneath the Pacific. The result suggests that a nearly vertical mantle plume underlies Hawaii that originates from a peak of a chemically distinct reservoir at the base of the mantle, some 600-900 km above the CMB. Additionally, acute horizontal Vs variations across and within the northern margin of the LLSVP beneath the central Pacific Ocean are inferred from forward modeling of differential travel times between S (and Sdiff) and SKS, and also between ScS and S. I developed a new approach to expand the geographic detection of ultra-low velocity zones (ULVZs) with a new ScS stacking approach that simultaneously utilizes the pre- and post-cursor wavefield. Strong lateral variations in ULVZ thicknesses and properties are found across the LLSVP margins, where ULVZs are thicker and stronger within the LLSVP than outside of it, consistent with convection model predictions. Differential travel times, amplitude ratios, and waveshapes of core waves SKKS and SKS are used to investigate CMB topography and outermost core velocity structure. 1D and 2D

  19. Investigating Forest Harvest Effects on DOC Concentration and Quality: An In Situ, High Resolution Approach to Quantifying DOC Export Dynamics

    Science.gov (United States)

    Jollymore, A. J.; Johnson, M. S.; Hawthorne, I.

    2013-12-01

    Justification: Forest harvest effects on water quality can signal alterations in hydrologic and ecologic processes incurred as a result of forest harvest activities. Organic matter (OM), specifically dissolved organic carbon (DOC), plays a number of important roles mediating UV-light penetration, redox reactivity and microbial activity within aquatic ecosystems. Quantification of DOC is typically pursued via grab sampling followed by chemical or spectrophotometric analysis, limiting the temporal resolution obtained as well as the accuracy of export calculations. The advent of field-deployable sensors capable of measuring DOC concentration and certain quality characteristics in situ provides the ability to observe dynamics at temporal scales necessary for accurate calculation of DOC flux, as well as the observation of dynamic changes in DOC quality on timescales impossible to observe through grab sampling. Methods: This study utilizes a field deployable UV-Vis spectrophotometer (spectro::lyzer, s::can, Austria) to investigate how forest harvest affects DOC export. The sensor was installed at an existing hydrologic monitoring site at the outlet of a headwater stream draining a small (91 hectare) second growth Douglasfir-dominated catchment near Campbell River on Vancouver Island, British Columbia. Measurement began late in 2009, prior to forest harvest and associated activities such as road building (which commenced in October 2010 and ended in early 2011), and continues to present. During this time - encompassing the pre, during and post-harvest conditions - the absorbance spectrum of stream water from 200 to 750 nm was measured. DOC concentration and spectroscopic indices related to DOC quality (including SUVA, which relates to the concentration of aromatic carbon, and spectral slope) were subsequently calculated for each spectra obtained at 30-minute intervals. Results and conclusions: High frequency measurements of DOC show that overall export of OM increased in

  20. Investigations into the Structure and Dynamics of Chalcogenide Glasses using High-Resolution Nuclear Magnetic Resonance Spectroscopy

    Science.gov (United States)

    Kaseman, Derrick Charles

    Chalcogenide glasses constitute an important class of materials that are sulfides, selenides or tellurides of group IV and/or V elements, namely Ge, As, P and Si with minor concentrations of other elements such as Ga, Sb, In. Because of their infrared transparency that can be tuned by changing chemistry and can be actively altered by exposure to band gap irradiation, chalcogenide glasses find use in passive and active optical devices for applications in the areas of photonics, remote sensing and memory technology. Therefore, it is important to establish predictive models of structure-property relationships for these materials for optimization of their physical properties for various applications. Structural elucidation of chalcogenide glasses is experimentally challenging and in order to make predictive structural models, structural units at both short and intermediate -range length scales must be identified and quantified. Nuclear Magnetic Resonance (NMR) spectroscopy is an element-specific structural probe that is uniquely suited for this task, but resolution and sensitivity issues have severely limited the applications of such techniques in the past. The recent development of multi-dimensional solid-state NMR techniques, such as Phase Adjusted Spinning Sidebands (PASS) and Magic Angle Turning (MAT) can potentially alleviate such issues. In this study novel two-dimensional, high-resolution 77Se and 125Te MATPASS NMR spectroscopic techniques are utilized to elucidate quantitatively the compositional evolution of the short- and intermediate- range atomic structure in three binary chalcogenide glass-forming systems, namely: GexSe100-x, AsxSe100-x , and AsxTe100-x. The spectroscopic results provide unambiguous site speciation and quantification for short- and intermediate-range structural motifs present in these glasses. In turn, for all systems, robust structural models and the corresponding structure-property relationships are successfully established as a function

  1. High-Resolution Monitoring of Glacier Dynamics During Calving Events at Helheim Glacier South-East Greenland

    Science.gov (United States)

    Murray, T.; Rutt, I. C.; O'Farrell, T.; Edwards, S.; Selmes, N.; Martin, I.; James, T.; Aspey, R.; Bevan, S. L.; Loskot, P.; Baugé, T.

    2013-12-01

    By bringing together expertise in glaciology, GNSS (Global Navigation Satellite System) technology and processing, and wireless networks we have designed, installed and operated a wireless network of GNSS sensors very close to the margin of the heavily crevassed and fast-flowing Helheim Glacier in south-east Greenland. In 2012, we undertook field trials installing 3 GNSS sensors on the glacier's flowline, and observed the dynamic effects of a major calving event. In 2013, a full 20 node wireless network was installed together with 5 oblique cameras, instrumenting an area ~16 km^2 of the glacier margin. The network will run throughout the summer months. In combination with auxiliary data, such as airborne lidar measurement of surface topography, crevasse spacing and calving rates, oblique photogrammetry, and DEMs and velocity fields from TanDEM-X satellite imagery, the network provides velocity and elevation data of unprecedented resolution in time and space for the key marginal area of the glacier, where recent changes in glacier dynamics appear to have initiated. We present data showing the glacier's dynamic and topographic response to calving events. These data will provide rich opportunities for testing calving models and to improve understanding of the controls on the contribution of these tidewater glaciers to sea-level rise. The network has low energy consumption and a novel base-station topology providing diversity and redundancy: it is also robust to the loss of nodes as the glacier calves. Such a network would also be suitable for data collection in a number of harsh environmental settings such as earthquake, landslide or volcano monitoring.

  2. Monitoring early fusion dynamics of human immunodeficiency virus type 1 at single-molecule resolution.

    Science.gov (United States)

    Dobrowsky, Terrence M; Zhou, Yan; Sun, Sean X; Siliciano, Robert F; Wirtz, Denis

    2008-07-01

    The fusion of human immunodeficiency virus type 1 (HIV-1) to host cells is a dynamic process governed by the interaction between glycoproteins on the viral envelope and the major receptor, CD4, and coreceptor on the surface of the cell. How these receptors organize at the virion-cell interface to promote a fusion-competent site is not well understood. Using single-molecule force spectroscopy, we map the tensile strengths, lifetimes, and energy barriers of individual intermolecular bonds between CCR5-tropic HIV-1 gp120 and its receptors CD4 and CCR5 or CXCR4 as a function of the interaction time with the cell. According to the Bell model, at short times of contact between cell and virion, the gp120-CD4 bond is able to withstand forces up to 35 pN and has an initial lifetime of 0.27 s and an intermolecular length of interaction of 0.34 nm. The initial bond also has an energy barrier of 6.7 k(B)T (where k(B) is Boltzmann's constant and T is absolute temperature). However, within 0.3 s, individual gp120-CD4 bonds undergo rapid destabilization accompanied by a shortened lifetime and a lowered tensile strength. This destabilization is significantly enhanced by the coreceptor CCR5, not by CXCR4 or fusion inhibitors, which suggests that it is directly related to a conformational change in the gp120-CD4 bond. These measurements highlight the instability and low tensile strength of gp120-receptor bonds, uncover a synergistic role for CCR5 in the progression of the gp120-CD4 bond, and suggest that the cell-virus adhesion complex is functionally arranged about a long-lived gp120-coreceptor bond.

  3. Resolution of Two Sub-Populations of Conformers and Their Individual Dynamics by Time Resolved Ensemble Level FRET Measurements.

    Directory of Open Access Journals (Sweden)

    Gil Rahamim

    Full Text Available Most active biopolymers are dynamic structures; thus, ensembles of such molecules should be characterized by distributions of intra- or intermolecular distances and their fast fluctuations. A method of choice to determine intramolecular distances is based on Förster resonance energy transfer (FRET measurements. Major advances in such measurements were achieved by single molecule FRET measurements. Here, we show that by global analysis of the decay of the emission of both the donor and the acceptor it is also possible to resolve two sub-populations in a mixture of two ensembles of biopolymers by time resolved FRET (trFRET measurements at the ensemble level. We show that two individual intramolecular distance distributions can be determined and characterized in terms of their individual means, full width at half maximum (FWHM, and two corresponding diffusion coefficients which reflect the rates of fast ns fluctuations within each sub-population. An important advantage of the ensemble level trFRET measurements is the ability to use low molecular weight small-sized probes and to determine nanosecond fluctuations of the distance between the probes. The limits of the possible resolution were first tested by simulation and then by preparation of mixtures of two model peptides. The first labeled polypeptide was a relatively rigid Pro7 and the second polypeptide was a flexible molecule consisting of (Gly-Ser7 repeats. The end to end distance distributions and the diffusion coefficients of each peptide were determined. Global analysis of trFRET measurements of a series of mixtures of polypeptides recovered two end-to-end distance distributions and associated intramolecular diffusion coefficients, which were very close to those determined from each of the pure samples. This study is a proof of concept study demonstrating the power of ensemble level trFRET based methods in resolution of subpopulations in ensembles of flexible macromolecules.

  4. Dynamic Cluster Analysis: An Unbiased Method for Identifying A+2 Element Containing Compounds in Liquid Chromatographic High-Resolution TOF Mass Spectrometric Data

    DEFF Research Database (Denmark)

    Andersen, Aaron John Christian; Hansen, Per Juel; Jørgensen, Kevin

    2016-01-01

    Dynamic Cluster Analysis (DCA) is an automated, unbiased technique which can identify Cl, Br, S, and other A+2 element containing metabolites in liquid chromatographic high resolution mass spectrometric data. DCA is based on three features, primarily the previously unutilised A+1 to A+2 isotope c...

  5. Dynamic Feedbacks Between Flow, Erosion and Evolving River Bank Roughness Revealed Through Repeat High-Resolution Topographic Surveys

    Science.gov (United States)

    Leyland, J.; Darby, S. E.; Rinaldi, M.; Teruggi, L. B.; Ostuni, D.

    2012-12-01

    Bank erosion is a key process in fluvial dynamics, with significant fractions of the total sediment load being sourced from river banks. Studies have shown that hydraulic erosion of the bank toe is a driving factor of long term rates of bank retreat. Fluvial bank erosion rates are often quantified using an excess shear stress model where the erosion rate is a function of the boundary shear stress applied by the flow above a critical threshold. Research has shown that the form roughness induced by natural topographic bank features such as slumps, spurs and embayments, is a major component of the spatially-averaged total shear stress. The skin friction component of this shear stress is typically an order of magnitude less than the total, meaning that the form roughness provides an important control on bank erosion rates. However, measuring the relative components of the total shear stress for a natural system is not straightforward. In this research we apply the method of Kean and Smith [2006, J. Geophys. Res., 111(4), F04009, doi:10.1029/2006JF000467] to partition the form and skin drag components of river bank roughness for an eroding bank of the Cecina River in central Italy. This method approximates the form drag component of the roughness along a longitudinal bank profile as a series of user defined Gaussian curves, with the skin friction component estimated through analysis of the deviations of the data from the fitted curves. For our site, a temporal sequence (2003 - 2011) of high-resolution topographic surveys has been collected through a combination of photogrammetry and Terrestrial Laser Scanning. For each survey five vertically equidistant profiles are extracted and analysed alongside DEMs of difference and associated flow data modelled using the distributed hydrological model MOBIDIC. The data are used to explore the dynamic feedbacks that exist between river discharge, bank erosion processes and bank form roughness, revealing insights into the self

  6. High-resolution simulations of the final assembly of Earth-like planets 1: terrestrial accretion and dynamics

    CERN Document Server

    Raymond, S N; Lunine, J I; Raymond, Sean N.; Quinn, Thomas; Lunine, Jonathan I.

    2005-01-01

    The final stage in the formation of terrestrial planets consists of the accumulation of ~1000-km ``planetary embryos'' and a swarm of billions of 1-10 km ``planetesimals.'' During this process, water-rich material is accreted by the terrestrial planets via impacts of water-rich bodies from beyond roughly 2.5 AU. We present results from five high-resolution dynamical simulations. These start from 1000-2000 embryos and planetesimals, roughly 5-10 times more particles than in previous simulations. Each simulation formed 2-4 terrestrial planets with masses between 0.4 and 2.6 Earth masses. The eccentricities of most planets were ~0.05, lower than in previous simulations, but still higher than for Venus, Earth and Mars. Each planet accreted at least the Earth's current water budget. We demonstrate several new aspects of the accretion process: 1) The feeding zones of terrestrial planets change in time, widening and moving outward. Even in the presence of Jupiter, water-rich material from beyond 2.5 AU is not accret...

  7. Path integral molecular dynamics within the grand canonical-like adaptive resolution technique: Simulation of liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Animesh, E-mail: animesh@zedat.fu-berlin.de; Delle Site, Luigi, E-mail: dellesite@fu-berlin.de [Institute for Mathematics, Freie Universität Berlin, Berlin (Germany)

    2015-09-07

    Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to investigate properties induced by spatial delocalization of atoms; however, computationally this technique is very demanding. The above mentioned limitation implies the restriction of PIMD applications to relatively small systems and short time scales. One of the possible solutions to overcome size and time limitation is to introduce PIMD algorithms into the Adaptive Resolution Simulation Scheme (AdResS). AdResS requires a relatively small region treated at path integral level and embeds it into a large molecular reservoir consisting of generic spherical coarse grained molecules. It was previously shown that the realization of the idea above, at a simple level, produced reasonable results for toy systems or simple/test systems like liquid parahydrogen. Encouraged by previous results, in this paper, we show the simulation of liquid water at room conditions where AdResS, in its latest and more accurate Grand-Canonical-like version (GC-AdResS), is merged with two of the most relevant PIMD techniques available in the literature. The comparison of our results with those reported in the literature and/or with those obtained from full PIMD simulations shows a highly satisfactory agreement.

  8. Path integral molecular dynamics within the grand canonical-like adaptive resolution technique: Simulation of liquid water

    Science.gov (United States)

    Agarwal, Animesh; Delle Site, Luigi

    2015-09-01

    Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to investigate properties induced by spatial delocalization of atoms; however, computationally this technique is very demanding. The above mentioned limitation implies the restriction of PIMD applications to relatively small systems and short time scales. One of the possible solutions to overcome size and time limitation is to introduce PIMD algorithms into the Adaptive Resolution Simulation Scheme (AdResS). AdResS requires a relatively small region treated at path integral level and embeds it into a large molecular reservoir consisting of generic spherical coarse grained molecules. It was previously shown that the realization of the idea above, at a simple level, produced reasonable results for toy systems or simple/test systems like liquid parahydrogen. Encouraged by previous results, in this paper, we show the simulation of liquid water at room conditions where AdResS, in its latest and more accurate Grand-Canonical-like version (GC-AdResS), is merged with two of the most relevant PIMD techniques available in the literature. The comparison of our results with those reported in the literature and/or with those obtained from full PIMD simulations shows a highly satisfactory agreement.

  9. Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields.

    Science.gov (United States)

    Klinkusch, Stefan; Tremblay, Jean Christophe

    2016-05-14

    In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

  10. Spatial-Temporal Dynamics of High-Resolution Animal Networks: What Can We Learn from Domestic Animals?

    Directory of Open Access Journals (Sweden)

    Shi Chen

    Full Text Available Animal social network is the key to understand many ecological and epidemiological processes. We used real-time location system (RTLS to accurately track cattle position, analyze their proximity networks, and tested the hypothesis of temporal stationarity and spatial homogeneity in these networks during different daily time periods and in different areas of the pen. The network structure was analyzed using global network characteristics (network density, subgroup clustering (modularity, triadic property (transitivity, and dyadic interactions (correlation coefficient from a quadratic assignment procedure at hourly level. We demonstrated substantial spatial-temporal heterogeneity in these networks and potential link between indirect animal-environment contact and direct animal-animal contact. But such heterogeneity diminished if data were collected at lower spatial (aggregated at entire pen level or temporal (aggregated at daily level resolution. The network structure (described by the characteristics such as density, modularity, transitivity, etc. also changed substantially at different time and locations. There were certain time (feeding and location (hay that the proximity network structures were more consistent based on the dyadic interaction analysis. These results reveal new insights for animal network structure and spatial-temporal dynamics, provide more accurate descriptions of animal social networks, and allow more accurate modeling of multiple (both direct and indirect disease transmission pathways.

  11. The influence of vegetation covers on soil moisture dynamics at high temporal resolution in scattered tree woodlands of Mediterranean climate

    Science.gov (United States)

    Lozano-Parra, Javier; Schnabel, Susanne; Ceballos-Barbancho, Antonio

    2015-04-01

    Soil water is a key factor that controls the organization and functioning of dryland ecosystems. However, in spite of its great importance in ecohydrological processes, most of the studies focus on daily or longer timescales, while its dynamics at shorter timescales are very little known. The main objective of this work was to determine the role of vegetation covers (grassland and tree canopy) in the soil hydrological response using measurements with high temporal resolution in evergreen oak woodland with Mediterranean climate. For this, soil water content was monitored continuously with a temporal resolution of 30 minutes and by means of capacitance sensors, mainly for the hydrological years 2010-2011 and 2011-2012. They were installed at 5, 10 and 15 cm, and 5 cm above the bedrock and depending on soil profile. This distribution along the soil profile is justified because soils are generally very shallow and most of the roots are concentrated in the upper layer. The sensors were gathered in 8 soil moisture stations in two contrasting situations characterized by different vegetation covers: under tree canopy and in open spaces or grasslands. Soil moisture variations were calculated at rainfall event scale at top soil layer and deepest depth by the difference between the final and initial soil moisture registered by a sensor at the finish and the beginning of the rainfall event, respectively. Besides, as soil moisture changes are strongly influenced by antecedent conditions, different antecedent soil moisture conditions or states, from driest to wettest, were also defined. The works were carried out in 3 experimental farms of the Spanish region of Extremadura. Results obtained revealed that rainwater amount bypassing vegetation covers and reaching the soil may temporarily be modified by covers according to precipitation properties and antecedent environmental conditions (from dry to wet) before the rain episode. Rainfall amounts triggering a positive soil

  12. Lacustrine particle dynamics in high-altitude Estany Redó (Spain - a high resolution sediment trap study

    Directory of Open Access Journals (Sweden)

    Michael STURM

    2006-08-01

    Full Text Available Particle fluxes were measured from 2000 to 2001 with 3 integrating open traps (O-traps and a sequencing trap (S-trap in the 73-m deep, oligotrophic, high-mountain Estany (Lake Redó (2240 m a.s.l. over a period of 558 days. O-traps were deployed at 26, 46, and 66 m water depth to measure overall sedimentation rates, while the S-trap was deployed at 66 m water depth to detect dynamics of seasonal particle fluxes with a resolution of 4 days (during ice break-up, summer, ice formation to 21 days (during ice cover. Our results show a high degree of seasonal variability in particle dynamics. Total particle fluxes vary from almost zero to more than 600 mg m-2 d-1. The highest fluxes occur during short time windows after ice-break-up (minerogenic particles, during spring (planktonic biomass, and during fall overturn (chrysophycean cysts. Particle fluxes also differed markedly from year to year in absolute values (2000: 644 mg m-2 d-1, 2001: 370 mg m-2 d-1 as well as in average values (2000: 76 mg m-2 d-1, 2001: 44 mg m-2 d-1. Annual and seasonal meteorological changes and events have a clear influence on the lake system and on the amount and composition of particles. C/N ratios during April and May increased significantly from 2000 (6-14 to 2001 (>28, reflecting the more intense soil erosion and transport of terrestrial plant remains into the lake caused by heavy precipitation in 2001. Air temperature strongly influences the timing of the occurrence of the main bio-productivity peak. Strong wind events shorten the period of ice cover. Our investigation shows that sediment trap studies lasting more than one limnological cycle are useful in studying the effects of short-term meteorological changes and weather events on high mountain lakes. However, long-term particle flux measurements would be necessary to determine amplitudes of natural seasonal cycles and for the interpretation of the decadal-scale environmental changes occurring in such lakes.

  13. Ultrafast probing of the x-ray-induced lattice and electron dynamics in graphite at atomic-resolution

    Energy Technology Data Exchange (ETDEWEB)

    Hau-Riege, S

    2010-10-07

    We used LCLS pulses to excite thin-film and bulk graphite with various different microstructures, and probed the ultrafast ion and electron dynamics through Bragg and x-ray Thomson scattering (XRTS). We pioneered XRTS at LCLS, making this technique viable for other users. We demonstrated for the first time that the LCLS can be used to characterize warm-dense-matter through Bragg and x-ray Thomson scattering. The warm-dense-matter conditions were created using the LCLS beam. Representative examples of the results are shown in the Figure above. In our experiment, we utilized simultaneously both Bragg and two Thomson spectrometers. The Bragg measurements as a function of x-ray fluence and pulse length allows us to characterize the onset of atomic motion at 2 keV with the highest resolution to date. The Bragg detector was positioned in back-reflection, providing us access to scattering data with large scattering vectors (nearly 4{pi}/{lambda}). We found a clear difference between the atomic dynamics for 70 and 300 fs pulses, and we are currently in the process of comparing these results to our models. The outcome of this comparison will have important consequences for ultrafast diffractive imaging, for which it is still not clear if atomic resolution can truly be achieved. The backward x-ray Thomson scattering data suggests that the average graphite temperature and ionization was 10 eV and 1.0, respectively, which agrees with our models. In the forward scattering data, we observed an inelastic feature in the Thomson spectrum that our models currently do not reproduce, so there is food for thought. We are in the process of writing these results up. Depending on if we can combine the Bragg and Thomson data or not, we plan to publish them in a single paper (e.g. Nature or Science) or as two separate papers (e.g. two Phys. Rev. Lett.). We will present the first analysis of the results at the APS Plasma Meeting in November 2010. We had a fantastic experience performing our

  14. Formation of {open_quotes}metal wool{close_quotes} structures and dynamics of catalytic etching of platinum surfaces during ammonia oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Lyubovsky, M.R.; Barelko, V.V. [Institute of Chemical Physics in Chernogolovka, Moscow (Russian Federation)

    1994-09-01

    Reconstruction of a clean surface of a platinum catalyst and a platinum surface covered with gold during ammonia oxidation was studied by SEM observations. It was found that the process of catalytic etching had two sequential stages in which different crystal structures with different rates of growth formed on the surface. The first stage was the formation of parallel facets, and the second stage was the formation of individual microcrystals with perfect crystal faces. It was also found that the second state had a threshold character, beginning after some delay from the start of the reaction. A structure resembling metal wool and consisting of interlaced platinum filaments was found to form on the surface of gold-covered platinum catalysts. Characteristic features of this structure`s development are reported. The growth of filaments is attributed to the vapor-liquid-solid mechanism of whisker growth. On the basis of the observed platinum whisker formation and behavior during ammonia oxidation, a mechanism of catalyst surface reconstruction that explains observed characteristic features of the process of catalytic etching is proposed. 25 refs., 8 figs.

  15. Development of a Dynamic Barrier Island (Sylt, Eastern North Sea) Based on High-Resolution Aerial Photographs and GIS

    Science.gov (United States)

    Dolch, T.; Hass, H. C.

    2004-12-01

    Wind and currents are the driving forces for the morphological development of coastlines and islands by giving them their shape, run and structure. This is especially true in highly dynamic areas such as the Wadden Sea in North-Western Europe. In this unique environment changes are continuous and distinct developments can be noticed within decades. The Island of Sylt, located in the Wadden Sea near the German-Danish border, is a sandy barrier island that protects the mainland against storm floods and waves. Thus, it experiences strong erosion (about 1 m coastal retreat per year). The North Atlantic Oscillation (NAO), that controls the atmospheric circulation over the North Sea, and northerly currents are the driving forces for the morphological development. Rising sea-level due to global change amplifies the erosion processes and forces people to protect the coastline (in this case beach nourishment). The Koenigshafen, a protected, semi-enclosed bay in the north of the Island of Sylt, can be regarded as representative for the study of many coastal processes that affect the island. In this case study, a long-term series of high resolution aerial photographs of the Koenigshafen (starting in 1936) shows the development of the survey area. Wind and currents affect not only the run of the coastline but also sediment composition and biodynamics in the bay. Looking at the hydrodynamics governing the bay, it should have mostly muddy sediments. Strong westerly winds, however, supply the bay with large amounts of sand from inland dunes and create sandy tidal flats. The long-term development of seagrass and mussel beds can also be retrieved from aerial photographs. In both cases a distinct decline in size can be noticed. Remote sensing and GIS techniques allow monitoring the conditions as well as to reconstruct the past development and to predict future developments.

  16. Dynamic time warping assessment of high-resolution melt curves provides a robust metric for fungal identification

    Science.gov (United States)

    Phatak, Sayali S.; Li, Dongmei; Luka, Janos; Calderone, Richard A.

    2017-01-01

    Fungal infections are a global problem imposing considerable disease burden. One of the unmet needs in addressing these infections is rapid, sensitive diagnostics. A promising molecular diagnostic approach is high-resolution melt analysis (HRM). However, there has been little effort in leveraging HRM data for automated, objective identification of fungal species. The purpose of these studies was to assess the utility of distance methods developed for comparison of time series data to classify HRM curves as a means of fungal species identification. Dynamic time warping (DTW), first introduced in the context of speech recognition to identify temporal distortion of similar sounds, is an elastic distance measure that has been successfully applied to a wide range of time series data. Comparison of HRM curves of the rDNA internal transcribed spacer (ITS) region from 51 strains of 18 fungal species using DTW distances allowed accurate classification and clustering of all 51 strains. The utility of DTW distances for species identification was demonstrated by matching HRM curves from 243 previously identified clinical isolates against a database of curves from standard reference strains. The results revealed a number of prior misclassifications, discriminated species that are not resolved by routine phenotypic tests, and accurately identified all 243 test strains. In addition to DTW, several other distance functions, Edit Distance on Real sequence (EDR) and Shape-based Distance (SBD), showed promise. It is concluded that DTW-based distances provide a useful metric for the automated identification of fungi based on HRM curves of the ITS region and that this provides the foundation for a robust and automatable method applicable to the clinical setting. PMID:28264030

  17. Imaging of radiocesium uptake dynamics in a plant body by using a newly developed high-resolution gamma camera.

    Science.gov (United States)

    Kawachi, Naoki; Yin, Yong-Gen; Suzui, Nobuo; Ishii, Satomi; Yoshihara, Toshihiro; Watabe, Hiroshi; Yamamoto, Seiichi; Fujimaki, Shu

    2016-01-01

    We developed a new gamma camera specifically for plant nutritional research and successfully performed live imaging of the uptake and partitioning of (137)Cs in intact plants. The gamma camera was specially designed for high-energy gamma photons from (137)Cs (662 keV). To obtain reliable images, a pinhole collimator made of tungsten heavy alloy was used to reduce penetration and scattering of gamma photons. A single-crystal scintillator, Ce-doped Gd3Al2Ga3O12, with high sensitivity, no natural radioactivity, and no hygroscopicity was used. The array block of the scintillator was coupled to a high-quantum efficiency position sensitive photomultiplier tube to obtain accurate images. The completed gamma camera had a sensitivity of 0.83 count s(-1) MBq(-1) for (137)Cs with an energy window from 600 keV to 730 keV, and a spatial resolution of 23.5 mm. We used this gamma camera to study soybean plants that were hydroponically grown and fed with 2.0 MBq of (137)Cs for 6 days to visualize and investigate the transport dynamics in aerial plant parts. (137)Cs gradually appeared in the shoot several hours after feeding, and then accumulated preferentially and intensively in growing pods and seeds; very little accumulation was observed in mature leaves. Our results also suggested that this gamma-camera method may serve as a practical analyzing tool for breeding crops and improving cultivation techniques resulting in low accumulation of radiocesium into the consumable parts of plants.

  18. 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.

  19. Single-wavelength-controlled in situ dynamic super-resolution fluorescence imaging for block copolymer nanostructures via blue-light-switchable FRAP.

    Science.gov (United States)

    Gong, Wen-Liang; Yan, Jie; Zhao, Ling-Xi; Li, Chong; Huang, Zhen-Li; Tang, Ben Zhong; Zhu, Ming-Qiang

    2016-11-02

    Photoswitchable fluorophores are promising in single-molecule optical devices and super-resolution fluorescence imaging, especially in single-molecule photo-activated localization microscopy (PALM) or stochastic optical reconstruction microscopy (STORM). However, the scarcity of current photoswitchable fluorophores stimulates researchers to develop complicated optical systems and processing software, in accordance with the limited photoswitchable fluorescent proteins and organic fluorophores. Previous efforts to develop synthetic photoswitchable fluorophores have exhibited their promising potential in super-resolution fluorescence imaging. Here, we have designed and synthesized a fluorescence molecular switch with reversible green emission, a napthalimide-hexaarylbiimidazole conjugate (NI-N-HABI), which exhibits strong fluorescence in the emissive state, with fast thermal fading of the photochromism and spontaneous fluorescence recovery after photobleaching (FRAP) induced by blue-light. The photoswitchable fluorophore enables the red-edge wavelength of the optical response to red-shift from the initial near-UV region at less than 400 nm, to 500 nm. The relatively fast fading speed of NI-N-HABI and its sensitivity to longer blue-light irradiation (400-500 nm) have allowed simplification of the optical microscopic system from a two-wavelength laser source to a single-wavelength laser. We applied NI-N-HABI in single-wavelength-controlled in situ dynamic super-resolution fluorescence imaging for the self-assembly and solvent annealing of amphiphilic block polymers, with 50 nm of optical resolution. Single-wavelength-controlled dynamic super-resolution fluorescence imaging facilitates nanoscale optical visualization for the dynamic physical and chemical fluctuation processes of stimuli-responsive nanostructures.

  20. Dynamic Contacts of U2, RES, Cwc25, Prp8 and Prp45 Proteins with the Pre-mRNA Branch-Site and 3' Splice Site during Catalytic Activation and Step 1 Catalysis in Yeast Spliceosomes.

    Directory of Open Access Journals (Sweden)

    Cornelius Schneider

    Full Text Available Little is known about contacts in the spliceosome between proteins and intron nucleotides surrounding the pre-mRNA branch-site and their dynamics during splicing. We investigated protein-pre-mRNA interactions by UV-induced crosslinking of purified yeast B(act spliceosomes formed on site-specifically labeled pre-mRNA, and analyzed their changes after conversion to catalytically-activated B* and step 1 C complexes, using a purified splicing system. Contacts between nucleotides upstream and downstream of the branch-site and the U2 SF3a/b proteins Prp9, Prp11, Hsh49, Cus1 and Hsh155 were detected, demonstrating that these interactions are evolutionarily conserved. The RES proteins Pml1 and Bud13 were shown to contact the intron downstream of the branch-site. A comparison of the B(act crosslinking pattern versus that of B* and C complexes revealed that U2 and RES protein interactions with the intron are dynamic. Upon step 1 catalysis, Cwc25 contacts with the branch-site region, and enhanced crosslinks of Prp8 and Prp45 with nucleotides surrounding the branch-site were observed. Cwc25's step 1 promoting activity was not dependent on its interaction with pre-mRNA, indicating it acts via protein-protein interactions. These studies provide important insights into the spliceosome's protein-pre-mRNA network and reveal novel RNP remodeling events during the catalytic activation of the spliceosome and step 1 of splicing.

  1. Integrating real-time and manual monitored data to predict hillslope soil moisture dynamics with high spatio-temporal resolution using linear and non-linear models

    Science.gov (United States)

    Zhu, Qing; Zhou, Zhiwen; Duncan, Emily W.; Lv, Ligang; Liao, Kaihua; Feng, Huihui

    2017-02-01

    Spatio-temporal variability of soil moisture (θ) is a challenge that remains to be better understood. A trade-off exists between spatial coverage and temporal resolution when using the manual and real-time θ monitoring methods. This restricted the comprehensive and intensive examination of θ dynamics. In this study, we integrated the manual and real-time monitored data to depict the hillslope θ dynamics with good spatial coverage and temporal resolution. Linear (stepwise multiple linear regression-SMLR) and non-linear (support vector machines-SVM) models were used to predict θ at 39 manual sites (collected 1-2 times per month) with θ collected at three real-time monitoring sites (collected every 5 mins). By comparing the accuracies of SMLR and SVM for each depth and manual site, an optimal prediction model was then determined at this depth of this site. Results showed that θ at the 39 manual sites can be reliably predicted (root mean square errors model. The subsurface flow dynamics was an important factor that determined whether the relationship was linear or non-linear. Depth to bedrock, elevation, topographic wetness index, profile curvature, and θ temporal stability influenced the selection of prediction model since they were related to the subsurface soil water distribution and movement. Using this approach, hillslope θ spatial distributions at un-sampled times and dates can be predicted. Missing information of hillslope θ dynamics can be acquired successfully.

  2. Modelling Vegetation Cover Dynamics of the Niger Floodplain in Mali, Westafrica, Using Multitemporal MERIS Full Resolution and TERRA -ASTER Data

    Science.gov (United States)

    Seiler, Ralf

    well as seasonal distribution of the annual rainfall in the catchment areas and the resulting water supply contributed by the river system. Due to the relatively good availability of (surface) water, the Niger Inland Ecosystem serves as stop-over for many migrating birds and other wildlife species as well as an eonomic base for farmers and pastoral people. As a consequence, the entire Niger Inland Delta has been declared as protected RAMSAR site in 2004. Interaction among pre-flood, flood and post-flood conditions strongly affect the patterns of landcover in and around the delta as vegetation cover is strongly correlated with the availability of surface water. The Inland Delta is dominantly covered by (irrigated) fields or grasslands during flood and post-flood periods (October to January), while most of the photosynthetically active vegetation withers during the rest of the year. This yields in highly vibrant vegetation cover, although the vegetation cover density remains low even during flood period for most of the Inland Delta. This study analyses the intra-annual dynamics as well as changes in vegetation cover between individual years by interpreting 17 MERIS full resolution data over the period from Aug. 2002 to June 2005. MERIS sensor provides measurements from 15 spectral bands within the VIS and NIR part of the EMS with 300 m spatial resolution. Thus allowing for analyses at a regional scale level with high sensitivity for the amount of green vegetation. Short time dynamics of vegetation are related to changes in vegetation cover density. These changes were modelled with Vegetation Indices (VI) as parameter. To overcome well known problems related with NDVIs dependence of illumination and viewing angle, background signal (soil brightness) and changes in humidity, the MGVI was used as indix to derive more sophisticated biophysical information in addition to the classical NDVI. Soil types influence the remotely sensed signal significantly due to the overall

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Dynamic Observation of the Three-Dimensional Distribution of Labeled Liposomes Using the Novel High-Resolution Single-Photon Emission Computed Tomography

    Directory of Open Access Journals (Sweden)

    Andreas Wirrwar

    2008-09-01

    Full Text Available The aim of this study was to show that the multipinhole technique (high-resolution single-photon emission computed tomography [HiSPECT] is suitable for dynamic imaging of both biodistribution and temporal uptake behavior of radiolabeled cationic liposomes in Balb/c-mice. HiSPECT uses multipinhole collimators adapted to a clinical SPECT scanner, together with a dedicated iterative reconstruction program. This technique provides both high spatial resolution and an improvement in sensitivity. Six male Balb/c mice received 9.8 ± 4.0 MBq of the In 111-labeled liposomes. The measurements started directly after the injection and tomographic data were acquired in steps of 5 minutes. The regional evaluation displayed a high initial uptake of liposomes in the lungs (45.4%, which decreased to 25.1% after 30 minutes and to below 2% after 48 hours. In contrast, liver uptake increased in the first 30 minutes from 13.1 to 21.2% and remained relatively stable at 24.4% (24 hours and 18.8% (48 hours. The data are interpreted as a slow shift of liposomes from the lungs into the liver and later to other organs such as the spleen and bladder. This study shows that the HiSPECT technique is capable of dynamically visualizing the uptake behavior of radioactively labeled liposomes in vivo with high temporal and spatial resolution.

  10. Investigation of subcellular localization and dynamics of membrane proteins in living bacteria by combining optical micromanipulation and high-resolution microscopy (Conference Presentation)

    Science.gov (United States)

    Barroso Peña, Álvaro; Nieves, Marcos; Teper, Konrad; Wedlich-Soldner, Roland; Denz, Cornelia

    2016-09-01

    The plasma membrane serves as protective interface between cells and their environment. It also constitutes a hub for selective nutrient uptake and signal transduction. Increasing evidence over the last years indicates that, similar to eukaryotic cells, lateral membrane organization plays an important role in the regulation of prokaryotic signaling pathways. However, the mechanisms underlying this phenomenon are still poorly understood. Spatiotemporal characterization of bacterial signal transduction demands very sensitive high-resolution microscopy techniques due to the low expression levels of most signaling proteins and the small size of bacterial cells. In addition, direct study of subcellular confinement and dynamics of bacterial signaling proteins during the different stages of the signal transduction also requires immobilization in order to avoid cell displacement caused by Brownian motion, local fluid flows and bacterial self-propulsion. In this work we present a novel approach based on the combination of high resolution imaging and optical manipulation that enables the investigation of the distribution and dynamics of proteins at the bacterial plasma membrane. For this purpose, we combine the versatility of holographic optical tweezers (HOT) with the sensitivity and resolution of total internal reflection fluorescence (TIRF) microscopy. Furthermore, we discuss the implementation of microfluidic devices in our integrated HOT+TIRF system for the control of growth conditions of bacterial cells. The capabilities of our workstation provides thus new valuable insights into the fundamental cellular and physical mechanisms underlying the regulation of bacterial signal transduction.

  11. Re-evaluation of low-resolution crystal structures via interactive molecular-dynamics flexible fitting (iMDFF): a case study in complement C4.

    Science.gov (United States)

    Croll, Tristan Ian; Andersen, Gregers Rom

    2016-09-01

    While the rapid proliferation of high-resolution structures in the Protein Data Bank provides a rich set of templates for starting models, it remains the case that a great many structures both past and present are built at least in part by hand-threading through low-resolution and/or weak electron density. With current model-building tools this task can be challenging, and the de facto standard for acceptable error rates (in the form of atomic clashes and unfavourable backbone and side-chain conformations) in structures based on data with dmax not exceeding 3.5 Å reflects this. When combined with other factors such as model bias, these residual errors can conspire to make more serious errors in the protein fold difficult or impossible to detect. The three recently published 3.6-4.2 Å resolution structures of complement C4 (PDB entries 4fxg, 4fxk and 4xam) rank in the top quartile of structures of comparable resolution both in terms of Rfree and MolProbity score, yet, as shown here, contain register errors in six β-strands. By applying a molecular-dynamics force field that explicitly models interatomic forces and hence excludes most physically impossible conformations, the recently developed interactive molecular-dynamics flexible fitting (iMDFF) approach significantly reduces the complexity of the conformational space to be searched during manual rebuilding. This substantially improves the rate of detection and correction of register errors, and allows user-guided model building in maps with a resolution lower than 3.5 Å to converge to solutions with a stereochemical quality comparable to atomic resolution structures. Here, iMDFF has been used to individually correct and re-refine these three structures to MolProbity scores of <1.7, and strategies for working with such challenging data sets are suggested. Notably, the improved model allowed the resolution for complement C4b to be extended from 4.2 to 3.5 Å as demonstrated by paired refinement.

  12. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X......-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation...

  13. Effect of Noise and Flow Field Resolution on the Evaluation of Fluid Dynamic Forces on Bodies Using only the Velocity Field and its Derivatives

    Science.gov (United States)

    Breda, Maria Cecilia; Krueger, Paul S.

    2010-11-01

    Determining unsteady fluid dynamic forces on bodies using only measurements of the velocity field and its derivatives is essential in many investigations, including studies of freely swimming or flying animals. In this project, all terms in a control-volume force equation utilizing only the velocity field and its derivatives discussed by Noca et al. (J. Fluids Struct., 13, 551 - 578) will be analyzed with regard to the influence of flow field noise and resolution to determine which terms dominate the error in the computed force and which factor has the greatest effect on the error. Using analytical and computational flow fields for which the lift and drag forces are known, irregularities found in real experimental results including noise and reduced spatial/temporal resolution will be added to assess their effect on the computed forces. Results for several canonical flows will be presented.

  14. High-resolution monitoring of root water uptake dynamics in laboratory conditions using full-wave inversion of near-field radar

    Science.gov (United States)

    Mourmeaux, Nicolas; Meunier, Félicien; Tran, Phuong Anh; Draye, Xavier; Lambot, Sébastien

    2014-05-01

    Root water uptake dynamics at local scale can be studied in laboratory conditions by growing plants in rhizotron containing sand and by imaging the water content evolution of the medium using light transmission. This technique allows to retrieve the water content with high resolution but cannot be applied in opaque media such as leaf-mold or clay, which is a major limitation for more realistic applications. Recently, ground-penetrating radar (GPR) has proven to be one of the most promising techniques for high-resolution digital soil mapping at the field scale. Particularly, by using full-wave inverse modeling of near-field GPR data with a high frequency antenna, the electrical properties of soil and their correlated water content can be reconstructed with a high spatiotemporal resolution. In this study, we applied the approach by using an ultra-wideband frequency-domain radar with a transmitting and receiving horn antenna operating in the frequency range 3-6 GHz for imaging, in near-field conditions, a rhizotron containing sand subject to different water content conditions. Synthetic radar data were also generated to examine the well-posedness of the full-waveform inverse problem at high frequencies. Finally, we compared the water content obtained by GPR and light transmission measurements. The results have shown that the near-field modeled and measured GPR data match very well in the frequency and time domains for both dry and wet sands. In the case of the dry sand, the estimated water content based on GPR and light transmission data was retrieved with small differences. This research shows the potential of the GPR system and near-field full-wave antenna-medium model to accurately estimate the water content of soils with a high spatial resolution. Future studies will focus on the use of GPR to monitor root water uptake dynamics of plants in field conditions. This abstract is of interest for COST Action TU1208.

  15. Reconstruction of climate dynamics in an Arctic fjord environment: evidence from a multi-proxy high resolution marine record.

    Science.gov (United States)

    MacLachlan, S. E.; Howe, J.

    2012-12-01

    The cryosphere is a crucial component of the Earth's climate system, and comprises sea ice, snow, glaciers, ice cap, ice shelves, river and lake ice, ice sheets and frozen ground. The cryosphere has shown ice growth and decay on many timescales associated both with 100,000 year ice age cycles and with shorter-term (Ice Age. Crucially the cyosphere acts as a barometer for climate change because it provides a visible means of assessing the impacts of recent climate warming. Coastal Arctic regions are particularly sensitive to climate change, and records of glacier fluctuations can be used to infer past climate. The western Svalbard margin is a climatically sensitive region presently influenced by the warm and saline Atlantic water of the West Spitsbergen Current. This current is the northernmost extension of the Norwegian Atlantic Current that transports significant quantities of heat northward, maintaining the seas west of the Svalbard shelf increasingly ice free. For the Svalbard area there are currently a number of low-resolution (centennial to multi-decadal) marine records that span the Holocene. Despite their low resolution, several studies have highlighted abrupt environmental shifts and fluctuating glacial conditions during the Holocene. A few low-resolution lake records and other sporadic terrestrial datasets also exist providing a limited insight into the terrestrial environmental changes over the last two millennia. We have generated the first sub-decadal resolution late Holocene climatic record, in order to determine the nature and timing of environmental changes across transient climate events at an unprecedented temporal scale for this region. XRF analyses provides the high-resolution data series, which has been integrated with sedimentological data to better define the environmental processes; thus providing the basis for the reconstruction of climate change in this glaciated fjordic environment.

  16. 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.

  17. Asymmetric Synthesis of Substituted Thiolanes through Domino Thia-Michael-Henry Dynamic Covalent Systemic Resolution using Lipase Catalysis.

    Science.gov (United States)

    Zhang, Yan; Vongvilai, Pornrapee; Sakulsombat, Morakot; Fischer, Andreas; Ramström, Olof

    2014-03-24

    Dynamic systems based on consecutive thia-Michael and Henry reactions were generated and transformed using lipase-catalyzed asymmetric transformation. Substituted thiolane structures with three contiguous stereocenters were resolved in the process in high yields and high enantiomeric excesses.

  18. Dynamics of a Coupled System: Multi-Resolution Remote Sensing in Assessing Social-Ecological Responses during 25 Years of Gas Field Development in Arctic Russia

    Directory of Open Access Journals (Sweden)

    Florian Stammler

    2012-04-01

    Full Text Available Hydrocarbon exploration has been underway in the north of West Siberia for several decades. Giant gas fields on the Yamal Peninsula are expected to begin feeding the Nord Stream pipeline to Western Europe in late 2012. Employing a variety of high- to very high-resolution satellite-based sensors, we have followed the establishment and spread of Bovanenkovo, the biggest and first field to be developed. Extensive onsite field observations and measurements of land use and land cover changes since 1985 have been combined with intensive participant observation in all seasons among indigenous Nenets reindeer herders and long-term gas field workers during 2004–2007 and 2010–2011. Time series and multi-resolution imagery was used to build a chronology of the gas field’s development. Large areas of partially or totally denuded tundra and most forms of expanding infrastructure are readily tracked with Landsat scenes (1985, 1988, 2000, 2009, 2011. SPOT (1993, 1998 and ASTER (2001 were also used. Quickbird-2 (2004 and GeoEye (2010 were most successful in detecting small-scale anthropogenic disturbances as well as individual camps of nomadic herders moving in the vicinity of the gas field. For assessing gas field development the best results are obtained by combining lower resolution with Very High Resolution (VHR imagery (spatial resolution < 5 m and fieldwork. Nenets managing collective and privately owned herds of reindeer have proven adept in responding to a broad range of intensifying industrial impacts at the same time as they have been dealing with symptoms of a warming climate. Here we detail both the spatial extent of gas field growth and the dynamic relationship between Nenets nomads and their rapidly evolving social-ecological system.

  19. Seismic Study of the Subsurface Structure and Dynamics of the Solar Interior from High Spatial Resolution Observations

    Science.gov (United States)

    Korzennik, Sylvain G.

    1997-01-01

    We have carried out the data reduction and analysis of Mt. Wilson 60' solar tower high spatial resolution observations. The reduction of the 100-day-long summer of 1990 observation campaign in terms of rotational splittings was completed leading to an excess of 600,000 splittings. The analysis of these splittings lead to a new inference of the solar internal rotation rate as a function of depth and latitude.

  20. 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.

  1. Stochasticity of Road Traffic Dynamics: Comprehensive Linear and Nonlinear Time Series Analysis on High Resolution Freeway Traffic Records

    CERN Document Server

    Siegel, H; Siegel, Helge; Belomestnyi, Dennis

    2006-01-01

    The dynamical properties of road traffic time series from North-Rhine Westphalian motorways are investigated. The article shows that road traffic dynamics is well described as a persistent stochastic process with two fixed points representing the freeflow (non-congested) and the congested state regime. These traffic states have different statistical properties, with respect to waiting time distribution, velocity distribution and autocorrelation. Logdifferences of velocity records reveal non-normal, obviously leptocurtic distribution. Further, linear and nonlinear phase-plane based analysis methods yield no evidence for any determinism or deterministic chaos to be involved in traffic dynamics on shorter than diurnal time scales. Several Hurst-exponent estimators indicate long-range dependence for the free flow state. Finally, our results are not in accordance to the typical heuristic fingerprints of self-organized criticality. We suggest the more simplistic assumption of a non-critical phase transition between...

  2. Automated method for relating regional pulmonary structure and function: integration of dynamic multislice CT and thin-slice high-resolution CT

    Science.gov (United States)

    Tajik, Jehangir K.; Kugelmass, Steven D.; Hoffman, Eric A.

    1993-07-01

    We have developed a method utilizing x-ray CT for relating pulmonary perfusion to global and regional anatomy, allowing for detailed study of structure to function relationships. A thick slice, high temporal resolution mode is used to follow a bolus contrast agent for blood flow evaluation and is fused with a high spatial resolution, thin slice mode to obtain structure- function detail. To aid analysis of blood flow, we have developed a software module, for our image analysis package (VIDA), to produce the combined structure-function image. Color coded images representing blood flow, mean transit time, regional tissue content, regional blood volume, regional air content, etc. are generated and imbedded in the high resolution volume image. A text file containing these values along with a voxel's 3-D coordinates is also generated. User input can be minimized to identifying the location of the pulmonary artery from which the input function to a blood flow model is derived. Any flow model utilizing one input and one output function can be easily added to a user selectable list. We present examples from our physiologic based research findings to demonstrate the strengths of combining dynamic CT and HRCT relative to other scanning modalities to uniquely characterize pulmonary normal and pathophysiology.

  3. Clinical application of bilateral high temporal and spatial resolution dynamic contrast-enhanced magnetic resonance imaging of the breast at 7 T

    Energy Technology Data Exchange (ETDEWEB)

    Pinker, K.; Baltzer, P.; Bernathova, M.; Weber, M.; Leithner, D.; Helbich, T.H. [Medical University Vienna, Department of Biomedical Imaging and Image-guided Therapy, Division of Molecular and Gender Imaging, Waehringer Guertel 18-20, 1090, Vienna (Austria); Bogner, W.; Trattnig, S.; Gruber, S.; Zaric, O. [Medical University Vienna, Department of Biomedical Imaging and Image-guided Therapy, MR Centre of Excellence, Vienna (Austria); Abeyakoon, O. [King' s College, Department of Radiology, London (United Kingdom); Dubsky, P. [Medical University Vienna, Department of Surgery, Vienna (Austria); Bago-Horvath, Z. [Medical University Vienna, Department of Pathology, Vienna (Austria)

    2014-04-15

    The objective of our study was to evaluate the clinical application of bilateral high spatial and temporal resolution dynamic contrast-enhanced magnetic resonance imaging (HR DCE-MRI) of the breast at 7 T. Following institutional review board approval 23 patients with a breast lesion (BIRADS 0, 4-5) were included in our prospective study. All patients underwent bilateral HR DCE-MRI of the breast at 7 T (spatial resolution of 0.7 mm{sup 3} voxel size, temporal resolution of 14 s). Two experienced readers (r1, r2) and one less experienced reader (r3) independently assessed lesions according to BI-RADS registered. Image quality, lesion conspicuity and artefacts were graded from 1 to 5. Sensitivity, specificity and diagnostic accuracy were assessed using histopathology as the standard of reference. HR DCE-MRI at 7 T revealed 29 lesions in 23 patients (sensitivity 100 % (19/19); specificity of 90 % (9/10)) resulting in a diagnostic accuracy of 96.6 % (28/29) with an AUC of 0.95. Overall image quality was excellent in the majority of cases (27/29) and examinations were not hampered by artefacts. There was excellent inter-reader agreement for diagnosis and image quality parameters (κ = 0.89-1). Bilateral HR DCE-MRI of the breast at 7 T is feasible with excellent image quality in clinical practice and allows accurate breast cancer diagnosis. (orig.)

  4. Monitoring of the Spatial Distribution and Temporal Dynamics of the Green Vegetation Fraction of Croplands in Southwest Germany Using High-Resolution RapidEye Satellite Images

    Science.gov (United States)

    Imukova, Kristina; Ingwersen, Joachim; Streck, Thilo

    2014-05-01

    The green vegetation fraction (GVF) is a key input variable to the evapotranspiration scheme applied in the widely used NOAH land surface model (LSM). In standard applications of the NOAH LSM, the GVF is taken from a global map with a 15 km×15 km resolution. The central objective of the present study was (a) to derive gridded GVF data in a high spatial and temporal resolution from RapidEye images for a region in Southwest Germany, and (b) to improve the representation of the GVF dynamics of croplands in the NOAH LSM for a better simulation of water and energy exchange between land surface and atmosphere. For the region under study we obtained monthly RapidEye satellite images with a resolution 5 m×5 m by the German Aerospace Center (DLR). The images hold five spectral bands: blue, green, red, red-edge and near infrared (NIR). The GVF dynamics were determined based on the Normalized Difference Vegetation Index (NDVI) calculated from the red and near-infrared bands of the satellite images. The satellite GVF data were calibrated and validated against ground truth measurements. Digital colour photographs above the canopy were taken with a boom-mounted digital camera at fifteen permanently marked plots (1 m×1 m). Crops under study were winter wheat, winter rape and silage maize. The GVF was computed based on the red and the green band of the photographs according to Rundquist's method (2002). Based on the obtained calibration scheme GVF maps were derived in a monthly resolution for the region. Our results confirm a linear relationship between GVF and NDVI and demonstrate that it is possible to determine the GVF of croplands from RapidEye images based on a simple two end-member mixing model. Our data highlight the high variability of the GVF in time and space. At the field scale, the GVF was normally distributed with a coefficient of variation of about 32%. Variability was mainly caused by soil heterogeneities and management differences. At the regional scale the GVF

  5. Direct current (DC) resistivity and Induced Polarization (IP) monitoring of active layer dynamics at high temporal resolution

    DEFF Research Database (Denmark)

    Doetsch, J.; Fiandaca, G.; Ingeman-Nielsen, Thomas;

    2015-01-01

    With permafrost thawing and changes in active layer dynamics induced by climate change, interactions between biogeochemical and thermal processes in the ground are of great importance. Here, active layer dynamics have been monitored using direct current (DC) resistivity and induced polarization (IP...... the soil freezing as a strong increase in resistivity. While the freezing horizon generally moves deeper with time, some variations in the freezing depth are observed along the profile. Comparison with depth-specific soil temperature indicates an exponential relationship between resistivity and below...

  6. 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.

  7. 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.

  8. High resolution measurements of methane and carbon dioxide in surface waters over a natural seep reveal dynamics of dissolved phase air-sea flux.

    Science.gov (United States)

    Du, Mengran; Yvon-Lewis, Shari; Garcia-Tigreros, Fenix; Valentine, David L; Mendes, Stephanie D; Kessler, John D

    2014-09-01

    Marine hydrocarbon seeps are sources of methane and carbon dioxide to the ocean, and potentially to the atmosphere, though the magnitude of the fluxes and dynamics of these systems are poorly defined. To better constrain these variables in natural environments, we conducted the first high-resolution measurements of sea surface methane and carbon dioxide concentrations in the massive natural seep field near Coal Oil Point (COP), California. The corresponding high resolution fluxes were calculated, and the total dissolved phase air-sea fluxes over the surveyed plume area (∼363 km(2)) were 6.66 × 10(4) to 6.71 × 10(4) mol day(-1) with respect to CH4 and -6.01 × 10(5) to -5.99 × 10(5) mol day(-1) with respect to CO2. The mean and standard deviation of the dissolved phase air-sea fluxes of methane and carbon dioxide from the contour gridding analysis were estimated to be 0.18 ± 0.19 and -1.65 ± 1.23 mmol m(-2) day(-1), respectively. This methane flux is consistent with previous, lower-resolution estimates and was used, in part, to conservatively estimate the total area of the dissolved methane plume at 8400 km(2). The influx of carbon dioxide to the surface water refutes the hypothesis that COP seep methane appreciably influences carbon dioxide dynamics. Seeing that the COP seep field is one of the biggest natural seeps, a logical conclusion could be drawn that microbial oxidation of methane from natural seeps is of insufficient magnitude to change the resulting plume area from a sink of atmospheric carbon dioxide to a source.

  9. High-resolution precipitation data derived from dynamical downscaling using the WRF model for the Heihe River Basin, northwest China

    Science.gov (United States)

    Zhang, Xuezhen; Xiong, Zhe; Zheng, Jingyun; Ge, Quansheng

    2017-01-01

    The community of climate change impact assessments and adaptations research needs regional high-resolution (spatial) meteorological data. This study produced two downscaled precipitation datasets with spatial resolutions of as high as 3 km by 3 km for the Heihe River Basin (HRB) from 2011 to 2014 using the Weather Research and Forecast (WRF) model nested with Final Analysis (FNL) from the National Center for Environmental Prediction (NCEP) and ERA-Interim from the European Centre for Medium-Range Weather Forecasts (ECMWF) (hereafter referred to as FNLexp and ERAexp, respectively). Both of the downscaling simulations generally reproduced the observed spatial patterns of precipitation. However, users should keep in mind that the two downscaled datasets are not exactly the same in terms of observations. In comparison to the remote sensing-based estimation, the FNLexp produced a bias of heavy precipitation centers. In comparison to the ground gauge-based measurements, for the warm season (May to September), the ERAexp produced more precipitation (root-mean-square error (RMSE) = 295.4 mm, across the 43 sites) and more heavy rainfall days, while the FNLexp produced less precipitation (RMSE = 115.6 mm) and less heavy rainfall days. Both the ERAexp and FNLexp produced considerably more precipitation for the cold season (October to April) with RMSE values of 119.5 and 32.2 mm, respectively, and more heavy precipitation days. Along with simulating a higher number of heavy precipitation days, both the FNLexp and ERAexp also simulated stronger extreme precipitation. Sensitivity experiments show that the bias of these simulations is much more sensitive to micro-physical parameterizations than to the spatial resolution of topography data. For the HRB, application of the WSM3 scheme may improve the performance of the WRF model.

  10. Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Criswell, L.; Fuhrmann, D;

    2004-01-01

    Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of similar to0.1-4 ns. We present evidence that these rel...

  11. Physics and dynamics coupling across scales in the next generation CESM: Meeting the challenge of high resolution. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Vincent E.

    2015-02-21

    This is a final report for a SciDAC grant supported by BER. The project implemented a novel technique for coupling small-scale dynamics and microphysics into a community climate model. The technique uses subcolumns that are sampled in Monte Carlo fashion from a distribution of subgrid variability. The resulting global simulations show several improvements over the status quo.

  12. 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.

  13. A dynamic model of interactions of Ca2+, calmodulin, and catalytic subunits of Ca2+/calmodulin-dependent protein kinase II.

    Directory of Open Access Journals (Sweden)

    Shirley Pepke

    2010-02-01

    Full Text Available During the acquisition of memories, influx of Ca2+ into the postsynaptic spine through the pores of activated N-methyl-D-aspartate-type glutamate receptors triggers processes that change the strength of excitatory synapses. The pattern of Ca2+influx during the first few seconds of activity is interpreted within the Ca2+-dependent signaling network such that synaptic strength is eventually either potentiated or depressed. Many of the critical signaling enzymes that control synaptic plasticity,including Ca2+/calmodulin-dependent protein kinase II (CaMKII, are regulated by calmodulin, a small protein that can bindup to 4 Ca2+ ions. As a first step toward clarifying how the Ca2+-signaling network decides between potentiation or depression, we have created a kinetic model of the interactions of Ca2+, calmodulin, and CaMKII that represents our best understanding of the dynamics of these interactions under conditions that resemble those in a postsynaptic spine. We constrained parameters of the model from data in the literature, or from our own measurements, and then predicted time courses of activation and autophosphorylation of CaMKII under a variety of conditions. Simulations showed that species of calmodulin with fewer than four bound Ca2+ play a significant role in activation of CaMKII in the physiological regime,supporting the notion that processing of Ca2+ signals in a spine involves competition among target enzymes for binding to unsaturated species of CaM in an environment in which the concentration of Ca2+ is fluctuating rapidly. Indeed, we showed that dependence of activation on the frequency of Ca2+ transients arises from the kinetics of interaction of fluctuating Ca2+with calmodulin/CaMKII complexes. We used parameter sensitivity analysis to identify which parameters will be most beneficial to measure more carefully to improve the accuracy of predictions. This model provides a quantitative base from which to build more complex dynamic

  14. Prolonged applied potential to anode facilitate selective enrichment of bio-electrochemically active Proteobacteria for mediating electron transfer: microbial dynamics and bio-catalytic analysis.

    Science.gov (United States)

    Kannaiah Goud, R; Mohan, S Venkata

    2013-06-01

    Prolonged application of poised potential to anode was evaluated to understand the influence of applied potentials [500 mV (E500); 1000 mV (E1000); 2000 mV (E2000)] on bio-electrogenic activity of microbial fuel cell (MFC) and the resulting dynamics in microbial community in comparison to control operation. E1000 system documented higher electrogenic activity (309 mW/m(2)) followed by E500 (143 mW/m(2)), E2000 (112 mW/m(2)) and control (65 mW/m(2)) operations. The improved power output at optimum applied potential (1000mV) might be attributed to the enrichment of electrochemically active bacteria majorly belonging to the phylum Proteobacteria with less extent of Firmicutes which helped in effective electron (mediated) transfer through release of exogenous shuttlers. Improved bio-electrogenic activity due to enrichment at 1000mV applied potential also correlated well with the observed cyctochrome-c peaks on the voltamatogram, lower ion ohmic losses and bio-electro kinetic analysis. Electric-shock at higher applied potential (E2000) resulted in the survival of less number of microbial species leading to lower electrogenesis.

  15. Direct current (DC) resistivity and induced polarization (IP) monitoring of active layer dynamics at high temporal resolution

    DEFF Research Database (Denmark)

    Doetsch, Joseph; Ingeman-Nielsen, Thomas; Christiansen, Anders V.

    2015-01-01

    With permafrost thawing and changes in active layer dynamics induced by climate change, interactions between biogeochemical and thermal processes in the ground are of great importance. Here, active layer dynamics have been monitored using direct current (DC) resistivity and induced polarization (IP...... and subsurface temperatures supplemented the DC-IP measurements. A time-lapse DC-IP monitoring system has been acquiring at least six datasets per day on a 42-electrode profile with 0.5. m electrode spacing since July 2013. Remote control of the data acquisition system enables interactive adaptation...... of the measurement schedule, which is critically important to acquire data in the winter months, where extremely high contact resistances increase the demands on the resistivity meter. Data acquired during the freezing period of October 2013 to February 2014 clearly image the soil freezing as a strong increase...

  16. Modelling hen harrier dynamics to inform human-wildlife conflict resolution: a spatially-realistic, individual-based approach.

    Directory of Open Access Journals (Sweden)

    Johannes P M Heinonen

    Full Text Available Individual-based models have gained popularity in ecology, and enable simultaneous incorporation of spatial explicitness and population dynamic processes to understand spatio-temporal patterns of populations. We introduce an individual-based model for understanding and predicting spatial hen harrier (Circus cyaneus population dynamics in Great Britain. The model uses a landscape with habitat, prey and game management indices. The hen harrier population was initialised according to empirical census estimates for 1988/89 and simulated until 2030, and predictions for 1998, 2004 and 2010 were compared to empirical census estimates for respective years. The model produced a good qualitative match to overall trends between 1989 and 2010. Parameter explorations revealed relatively high elasticity in particular to demographic parameters such as juvenile male mortality. This highlights the need for robust parameter estimates from empirical research. There are clearly challenges for replication of real-world population trends, but this model provides a useful tool for increasing understanding of drivers of hen harrier dynamics and focusing research efforts in order to inform conflict management decisions.

  17. Observing and modeling the dynamic atmosphere of the low mass-loss C-star R Sculptoris at high angular resolution

    CERN Document Server

    Sacuto, Stéphane; Hron, Josef; Nowotny, Walter; Paladini, Claudia; Verhoelst, Tijl; Höfner, Susanne

    2010-01-01

    We study the circumstellar environment of the carbon-rich star R Scl using the near- and mid-infrared high spatial resolution observations from the ESO-VLTI instruments VINCI and MIDI. These observations aim at increasing our knowledge of the dynamic processes in play within the very close circumstellar environment where the mass loss of AGB stars is initiated. Data are interpreted using a self-consistent dynamic model. Interferometric observations do not show any significant variability effect at the 16 m baseline between phases 0.17 and 0.23 in the K band, and for both the 15 m baseline between phases 0.66 and 0.97 and the 31 m baseline between phases 0.90 and 0.97 in the N band. We find fairly good agreement between the dynamic model and the spectrophotometric data from 0.4 to 25 $\\mu$m. The model agrees well with the time-dependent flux data at 8.5 $\\mu$m, whereas it is too faint at 11.3 and 12.5 $\\mu$m. The VINCI visibilities are reproduced well, meaning that the extension of the model is suitable in the...

  18. High resolution Dopplerimetry of correlated angular and quantum state-resolved CO(2) scattering dynamics at the gas-liquid interface.

    Science.gov (United States)

    Perkins, Bradford G; Nesbitt, David J

    2010-11-14

    Full three dimensional (3D) translational distributions for quantum state-resolved scattering dynamics at the gas-liquid interface are presented for experimental and theoretical studies of CO(2) + perfluorinated surfaces. Experimentally, high resolution absorption profiles are measured as a function of incident (θ(inc)) and scattering (θ(scat)) angles for CO(2) that has been scattered from a 300 K perfluorinated polyether surface (PFPE) with an incident energy of E(inc) = 10.6(8) kcal mol(-1). Line shape analysis of the absorption profiles reveals non-equilibrium dynamics that are characterized by trapping-desorption (TD) and impulsive scattering (IS) components, with each channel simply characterized by an effective "temperature" that compares very well with previous results from rotational state analysis [Perkins and Nesbitt, J. Phys. Chem. A, 2008, 112, 9324]. From a theoretical perspective, molecular dynamics (MD) simulations of CO(2) + fluorinated self-assembled monolayer surface (F-SAMs) yield translational probability distributions that are also compared with experimental results. Trajectories are parsed by θ(scat) and J, with the results rigorously corrected by flux-to-density transformation and providing comparisons in near quantitative agreement with experiment. 3D flux and velocity distributions obtained from MD simulations are also presented to illustrate the role of in- and out-of-plane scattering.

  19. Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

    Science.gov (United States)

    Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

    2016-01-01

    This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

  20. Tracking in real time the crawling dynamics of adherent living cells with a high resolution surface plasmon microscope

    Science.gov (United States)

    Streppa, L.; Berguiga, L.; Boyer Provera, E.; Ratti, F.; Goillot, E.; Martinez Torres, C.; Schaeffer, L.; Elezgaray, Juan; Arneodo, A.; Argoul, F.

    2016-03-01

    We introduce a high resolution scanning surface plasmon microscope for long term imaging of living adherent mouse myoblast cells. The coupling of a high numerical aperture objective lens with a fibered heterodyne interferometer provides both enhanced sensitivity and long term stability. This microscope takes advantage of the plasmon resonance excitation and the amplification of the electromagnetic field in near-field distance to the gold coated coverslip. This plasmon enhanced evanescent wave microscopy is particularly attractive for the study of cell adhesion and motility since it can be operated without staining of the biological sample. We show that this microscope allows very long-term imaging of living samples, and that it can capture and follow the temporal deformation of C2C12 myoblast cell protusions (lamellipodia), during their migration on a at surface.

  1. Nanoscale mapping of catalytic activity using tip-enhanced Raman spectroscopy.

    Science.gov (United States)

    Kumar, N; Stephanidis, B; Zenobi, R; Wain, A J; Roy, D

    2015-04-28

    Chemical mapping of a photocatalytic reaction with nanoscale spatial resolution is demonstrated for the first time using tip-enhanced Raman spectroscopy (TERS). An ultrathin alumina film applied to the Ag-coated TERS tip blocks catalytic interference whilst maintaining near-field electromagnetic enhancement, thus enabling spectroscopic imaging of catalytic activity on nanostructured Ag surfaces.

  2. Re-evaluation of low-resolution crystal structures via interactive molecular-dynamics flexible fitting (iMDFF)

    DEFF Research Database (Denmark)

    Croll, Tristan Ian; Andersen, Gregers Rom

    2016-01-01

    interactive molecular-dynamics flexible fitting (iMDFF) approach significantly reduces the complexity of the conformational space to be searched during manual rebuilding. This substantially improves the rate of detection and correction of register errors, and allows user-guided model building in maps...... density. With current model-building tools this task can be challenging, and the de facto standard for acceptable error rates (in the form of atomic clashes and unfavourable backbone and side-chain conformations) in structures based on data with dmax not exceeding 3.5 Å reflects this. When combined...

  3. Detecting Rock Glacier Dynamics in Southern Carpathians Mountains Using High-Resolution Optical and Multi-Temporal SAR Satellite Imagery .....

    Science.gov (United States)

    Necsoiu, M.; Onaca, A.

    2015-12-01

    This research provided the first documented assessment of the dynamics of rock glaciers in Southern Carpathian Mountains over almost half a century (1968-2014). The dynamics of four representative rock glaciers were assessed using complementary satellite-based optical and radar remote sensing techniques. We investigated the dynamics of the area using co-rectification of paired optical satellite datasets acquired by SPOT5, WV-1, Pléiades, and Corona to estimate short term (7 years) and longer term changes (44 years). Accurately rectifying and co-registering Corona KH-4B imagery allowed us to expand the time horizon over which changes in this alpine environment could be analyzed. The displacements revealed by this analysis correlate with variations in local slope of the rock glaciers, and presence or absence of permafrost. For radar analysis, nine ascending ALOS-1 PALSAR images were used based clear sky and absence of snow groundcover (i.e. June-October). Although decorrelation limits the ability to perform quantitative InSAR analyses, loss of coherence was useful in detecting subtle changes in active rock glacier environments, as well as other mass movements including rock falls, rock avalanches, debris flows, creep of permafrost, and solifluction. Small Baseline Subset (SBAS) InSAR analysis successfully quantified rates of change for unstable areas. The results of this investigation, although based on limited archived imagery, demonstrate that correlation analysis, coherence analysis, and multitemporal InSAR techniques can yield useful information for detecting creeping permafrost in a complex mountain environment, such as Retezat Mountains. Our analyses showed that rock glaciers in the Southern Carpathian Mountains are experiencing very slow annual movement of only a few cm per year. Results of the remote sensing analyses are consistent with field observations of permafrost occurrence at these sites (for more, please see Abstract ID# 68413). The combined optical

  4. Sediment dynamics in paired High Arctic lakes revealed from high-resolution swath bathymetry and acoustic stratigraphy surveys

    Science.gov (United States)

    Normandeau, A.; Lamoureux, S. F.; Lajeunesse, P.; Francus, P.

    2016-09-01

    High Arctic lakes are commonly used for paleoclimatic reconstructions because they are particularly sensitive to climate variability. However, the processes leading to sediment deposition and distribution in these lakes are often poorly understood. Here for the first time in the Canadian High Arctic, we present original data resulting from swath bathymetry and subbottom surveys carried out on two lakes at Cape Bounty, Melville Island. The results reveal the dynamic nature of the lakes, in which mass movement deposits and bedforms on the deltas reflect frequent slope instabilities and hyperpycnal flow activity. The analysis of the mass movement deposits reveals that small blocky debris flows/avalanches, debris flows, and a slide occurred during the Holocene. These mass movements are believed to have been triggered by earthquakes and potentially by permafrost thawing along the shoreline. Altogether, these mass movement deposits cover more than 30% of the lake floors. Additionally, the river deltas on both lakes were mapped and reveal the presence of several gullies and bedforms. The presence of gullies along the delta front indicates that hyperpycnal flows generated at the river mouth can transport sediment in different trajectories downslope, resulting in a different sediment accumulation pattern and record. The dynamic nature of these two lakes suggests that further analysis on sediment transport and distribution within Arctic lakes is required in order to improve paleoclimatic reconstructions.

  5. Flash-and-freeze: coordinating optogenetic stimulation with rapid freezing to visualize membrane dynamics at synapses with millisecond resolution

    Directory of Open Access Journals (Sweden)

    Shigeki Watanabe

    2016-08-01

    Full Text Available Electron microscopy depicts subcellular structures at synapses exquisitely but only captures static images. To visualize membrane dynamics, we have developed a novel technique, called flash-and-freeze, which induces neuronal activity with a flash of light and captures the membrane dynamics by rapid freezing. For characterizing membrane movements during synaptic transmission, a light-sensitive cation channel, channelrhodopsin, is heterologously expressed in mouse hippocampal neurons or in Caenorhabditis elegans motor neurons. A brief pulse of blue light activates channelrhodopsin and induces an action potential, leading to synaptic transmission. Following the light stimulation, neurons are frozen at different time intervals ranging from 10 ms to 20 s. Electron micrographs are then acquired from each time point to visualize the morphological changes. Using this approach, we have characterized a novel form of endocytosis, ultrafast endocytosis, which rapidly removes excess membrane added to the surface during neurotransmission. The flash-and-freeze approach can be adapted to study other cellular phenomena that can be induced by light-sensitive genetic or pharmacological tools.

  6. Flash-and-Freeze: Coordinating Optogenetic Stimulation with Rapid Freezing to Visualize Membrane Dynamics at Synapses with Millisecond Resolution

    Science.gov (United States)

    Watanabe, Shigeki

    2016-01-01

    Electron microscopy depicts subcellular structures at synapses exquisitely but only captures static images. To visualize membrane dynamics, we have developed a novel technique, called flash-and-freeze, which induces neuronal activity with a flash of light and captures the membrane dynamics by rapid freezing. For characterizing membrane movements during synaptic transmission, a light-sensitive cation channel, channelrhodopsin, is heterologously expressed in mouse hippocampal neurons or in Caenorhabditis elegans motor neurons. A brief pulse of blue light activates channelrhodopsin and induces an action potential, leading to synaptic transmission. Following the light stimulation, neurons are frozen at different time intervals ranging from 10 ms to 20 s. Electron micrographs are then acquired from each time point to visualize the morphological changes. Using this approach, we have characterized a novel form of endocytosis, ultrafast endocytosis, which rapidly removes excess membrane added to the surface during neurotransmission. The flash-and-freeze approach can be adapted to study other cellular phenomena that can be induced by light-sensitive genetic or pharmacological tools. PMID:27594835

  7. Drosophila pupal macrophages--a versatile tool for combined ex vivo and in vivo imaging of actin dynamics at high resolution.

    Science.gov (United States)

    Sander, Moritz; Squarr, Anna Julia; Risse, Benjamin; Jiang, Xiaoyi; Bogdan, Sven

    2013-01-01

    Molecular understanding of actin dynamics requires a genetically traceable model system that allows live cell imaging together with high-resolution microscopy techniques. Here, we used Drosophila pupal macrophages that combine many advantages of cultured cells with a genetic in vivo model system. Using structured illumination microscopy together with advanced spinning disk confocal microscopy we show that these cells provide a powerful system for single gene analysis. It allows forward genetic screens to characterize the regulatory network controlling cell shape and directed cell migration in a physiological context. We knocked down components regulating lamellipodia formation, including WAVE, single subunits of Arp2/3 complex and CPA, one of the two capping protein subunits and demonstrate the advantages of this model system by imaging mutant macrophages ex vivo as well as in vivo upon laser-induced wounding.

  8. Integration of reactive membrane extraction with lipase-hydrolysis dynamic kinetic resolution of naproxen 2,2,2-trifluoroethyl thioester in isooctane.

    Science.gov (United States)

    Lu, Chu-Hsun; Cheng, Yu-Chi; Tsai, Shau-Wei

    2002-07-20

    Lipases immobilized on polypropylene powders have been used as the biocatalyst in the enantioselective hydrolysis of (S)-naproxen from racemic naproxen thioesters in isooctane, in which trioctylamine was added to perform in situ racemization of the remaining (R)-thioester substrate. A detailed study of the kinetics for hydrolysis and racemization indicates that increasing the trioctylamine concentration can activate and stabilize the lipase as well as enhance the racemization and non-stereoselective hydrolysis of the thioester. Effects of the aqueous pH value and trioctylamine concentration on (S)-naproxen dissociation and partitioning in the aqueous phase as well as the transportation in a hollow fiber membrane were further investigated. Good agreements between the experimental data and theoretical results were obtained when the dynamic kinetic resolution process was integrated with a hollow fiber membrane to reactively extract the desired (S)-naproxen out of the reaction medium.

  9. High resolution polarimeter-interferometer system for fast equilibrium dynamics and MHD instability studies on Joint-TEXT tokamak (invited)a)

    Science.gov (United States)

    Chen, J.; Zhuang, G.; Li, Q.; Liu, Y.; Gao, L.; Zhou, Y. N.; Jian, X.; Xiong, C. Y.; Wang, Z. J.; Brower, D. L.; Ding, W. X.

    2014-11-01

    A high-performance Faraday-effect polarimeter-interferometer system has been developed for the J-TEXT tokamak. This system has time response up to 1 μs, phase resolution dynamics as well as magnetic and density perturbations associated with intrinsic Magneto-Hydro-Dynamic (MHD) instabilities and external coil-induced Resonant Magnetic Perturbations (RMP). The 3-wave technique, in which the line-integrated Faraday angle and electron density are measured simultaneously by three laser beams with specific polarizations and frequency offsets, is used. In order to achieve optimum resolution, three frequency-stabilized HCOOH lasers (694 GHz, >35 mW per cavity) and sensitive Planar Schottky Diode mixers are used, providing stable intermediate-frequency signals (0.5-3 MHz) with S/N > 50. The collinear R- and L-wave probe beams, which propagate through the plasma poloidal cross section (a = 0.25-0.27 m) vertically, are expanded using parabolic mirrors to cover the entire plasma column. Sources of systematic errors, e.g., stemming from mechanical vibration, beam non-collinearity, and beam polarization distortion are individually examined and minimized to ensure measurement accuracy. Simultaneous density and Faraday measurements have been successfully achieved for 14 chords. Based on measurements, temporal evolution of safety factor profile, current density profile, and electron density profile are resolved. Core magnetic and density perturbations associated with MHD tearing instabilities are clearly detected. Effects of non-axisymmetric 3D RMP in ohmically heated plasmas are directly observed by polarimetry for the first time.

  10. High-resolution high-speed dynamic mechanical spectroscopy of cells and other soft materials with the help of atomic force microscopy.

    Science.gov (United States)

    Dokukin, M; Sokolov, I

    2015-07-28

    Dynamic mechanical spectroscopy (DMS), which allows measuring frequency-dependent viscoelastic properties, is important to study soft materials, tissues, biomaterials, polymers. However, the existing DMS techniques (nanoindentation) have limited resolution when used on soft materials, preventing them from being used to study mechanics at the nanoscale. The nanoindenters are not capable of measuring cells, nanointerfaces of composite materials. Here we present a highly accurate DMS modality, which is a combination of three different methods: quantitative nanoindentation (nanoDMA), gentle force and fast response of atomic force microscopy (AFM), and Fourier transform (FT) spectroscopy. This new spectroscopy (which we suggest to call FT-nanoDMA) is fast and sensitive enough to allow DMS imaging of nanointerfaces, single cells, while attaining about 100x improvements on polymers in both spatial (to 10-70 nm) and temporal resolution (to 0.7 s/pixel) compared to the current art. Multiple frequencies are measured simultaneously. The use of 10 frequencies are demonstrated here (up to 300 Hz which is a rather relevant range for biological materials and polymers, in both ambient conditions and liquid). The method is quantitatively verified on known polymers and demonstrated on cells and polymers blends. Analysis shows that FT-nanoDMA is highly quantitative. The FT-nanoDMA spectroscopy can easily be implemented in the existing AFMs.

  11. High-resolution high-speed dynamic mechanical spectroscopy of cells and other soft materials with the help of atomic force microscopy

    Science.gov (United States)

    Dokukin, M.; Sokolov, I.

    2015-01-01

    Dynamic mechanical spectroscopy (DMS), which allows measuring frequency-dependent viscoelastic properties, is important to study soft materials, tissues, biomaterials, polymers. However, the existing DMS techniques (nanoindentation) have limited resolution when used on soft materials, preventing them from being used to study mechanics at the nanoscale. The nanoindenters are not capable of measuring cells, nanointerfaces of composite materials. Here we present a highly accurate DMS modality, which is a combination of three different methods: quantitative nanoindentation (nanoDMA), gentle force and fast response of atomic force microscopy (AFM), and Fourier transform (FT) spectroscopy. This new spectroscopy (which we suggest to call FT-nanoDMA) is fast and sensitive enough to allow DMS imaging of nanointerfaces, single cells, while attaining about 100x improvements on polymers in both spatial (to 10–70 nm) and temporal resolution (to 0.7s/pixel) compared to the current art. Multiple frequencies are measured simultaneously. The use of 10 frequencies are demonstrated here (up to 300 Hz which is a rather relevant range for biological materials and polymers, in both ambient conditions and liquid). The method is quantitatively verified on known polymers and demonstrated on cells and polymers blends. Analysis shows that FT-nanoDMA is highly quantitative. The FT-nanoDMA spectroscopy can easily be implemented in the existing AFMs. PMID:26218346

  12. Semi-crosslinked polyacrylamides as high-resolution and dynamic self-coating sieving matrices for protein capillary electrophoresis

    Institute of Scientific and Technical Information of China (English)

    ZHOU Jin; XU JianDong; XIE Yao; QU Feng; DENG YuLin; GENG LiNa

    2008-01-01

    This paper describes non-gel capillary sieving electrophoresis employing semi-crosslinked poly-acrylamide as a high performance and low viscous replaceable separation matrix for separation of non-denatured protein separation. Arising from the fine sieving and dynamic coating ability of this polymer, a mixture of basic proteins lysozyme, cytochrome C, ribonuclease A, and trypsin was resolved with excellent reproducibility. Mixing different semi-crosslinked polyacrylamides together further im-proves the separation. The separtion mechanism was analyzed. With network structure developed to an intermediate state between crosslinked gel and linear polymer solutions, these semi-crosslinked polyacrylamide polymers demonstrate a promise as a new class of size sieving separation medium, not only in capillary electrophoresis, but also in microfluidic chip separation schemes.

  13. 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.

  14. Evaluation of Dynamical Downscaling Resolution Effect on Wind Energy Forecast Value for a Wind Farm in Central Sweden

    Science.gov (United States)

    Rosgaard, Martin; Hahmann, Andrea; Skov Nielsen, Torben; Giebel, Gregor; Ejnar Sørensen, Poul; Madsen, Henrik

    2014-05-01

    For any energy system relying on wind power, accurate forecasts of wind fluctuations are essential for efficient integration into the power grid. Increased forecast precision allows end-users to plan day-ahead operation with reduced risk of penalties which in turn supports the feasibility of wind energy. This study aims to quantify value added to wind energy forecasts in the 12-48 hour leadtime by downscaling global numerical weather prediction (NWP) data using a limited-area NWP model. The accuracy of statistical wind power forecasting tools depends strongly on this NWP input. Typical performance metrics are mean absolute error or root mean square error for predicted- against observed wind power production, and these metrics are closely related to wind speed forecast bias and correlation with observations. Wind speed bias can be handled in the statistical wind power forecasting model, though it is entirely up to it's NWP input to describe the wind speed correlation correctly. The basis of comparison for forecasts is data from the Stor-Rotliden wind farm in central Sweden. The surrounding forest adds to the forecasting challenge, thus motivating the downscaling experiment as the potential for wind power forecast improvement is higher in complex terrain. The 40 Vestas V90 turbines were erected in 2009 and correspond to 78MWe installed electrical capacity. Forecasts from global and limited-area NWP models, together covering five different horizontal computational grid spacings of ~50km down to ~1km, are studied for a yearlong, continuous time period. The preliminary results shown quantify forecast strengths and weaknesses for each NWP model resolution.

  15. Production of a Dynamic Cropland Mask by Processing Remote Sensing Image Series at High Temporal and Spatial Resolutions

    Directory of Open Access Journals (Sweden)

    Silvia Valero

    2016-01-01

    Full Text Available The exploitation of new high revisit frequency satellite observations is an important opportunity for agricultural applications. The Sentinel-2 for Agriculture project S2Agri (http://www.esa-sen2agri.org/SitePages/Home.aspx is designed to develop, demonstrate and facilitate the Sentinel-2 time series contribution to the satellite EO component of agriculture monitoring for many agricultural systems across the globe. In the framework of this project, this article studies the construction of a dynamic cropland mask. This mask consists of a binary “annual-cropland/no-annual-cropland” map produced several times during the season to serve as a mask for monitoring crop growing conditions over the growing season. The construction of the mask relies on two classical pattern recognition techniques: feature extraction and classification. One pixel- and two object-based strategies are proposed and compared. A set of 12 test sites are used to benchmark the methods and algorithms with regard to the diversity of the agro-ecological context, landscape patterns, agricultural practices and actual satellite observation conditions. The classification results yield promising accuracies of around 90% at the end of the agricultural season. Efforts will be made to transition this research into operational products once Sentinel-2 data become available.

  16. Mapping and Characterization of Hydrological Dynamics in a Coastal Marsh Using High Temporal Resolution Sentinel-1A Images

    Directory of Open Access Journals (Sweden)

    Cécile Cazals

    2016-07-01

    Full Text Available In Europe, water levels in wetlands are widely controlled by environmental managers and farmers. However, the influence of these management practices on hydrodynamics and biodiversity remains poorly understood. This study assesses advantages of using radar data from the recently launched Sentinel-1A satellite to monitor hydrological dynamics of the Poitevin marshland in western France. We analyze a time series of 14 radar images acquired in VV and HV polarizations from December 2014 to May 2015 with a 12-day time step. Both polarizations are used with a hysteresis thresholding algorithm which uses both spatial and temporal information to distinguish open water, flooded vegetation and non-flooded grassland. Classification results are compared to in situ piezometric measurements combined with a Digital Terrain Model derived from LiDAR data. Results reveal that open water is successfully detected, whereas flooded grasslands with emergent vegetation and fine-grained patterns are detected with moderate accuracy. Five hydrological regimes are derived from the flood duration and mapped. Analysis of time steps in the time series shows that decreased temporal repetitivity induces significant differences in estimates of flood duration. These results illustrate the great potential to monitor variations in seasonal floods with the high temporal frequency of Sentinel-1A acquisitions.

  17. Prediction of prostate cancer extracapsular extension with high spatial resolution dynamic contrast-enhanced 3-T MRI

    Energy Technology Data Exchange (ETDEWEB)

    Bloch, B.N. [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of Radiology, Boston, MA (United States); Boston Medical Center and Boston University, Department of Radiology, Boston, MA (United States); Genega, Elizabeth M. [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of Pathology, Boston, MA (United States); Costa, Daniel N.; Pedrosa, Ivan; Rofsky, Neil M. [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of Radiology, Boston, MA (United States); University of Texas Southwestern Medical Center, Department of Radiology, Dallas, TX (United States); Smith, Martin P.; Kressel, Herbert Y. [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of Radiology, Boston, MA (United States); Ngo, Long [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of General Medicine, Boston, MA (United States); Sanda, Martin G.; DeWolf, William C. [Beth Israel Deaconess Medical Center and Harvard Medical School, Department of Division of Urology, Boston, MA (United States)

    2012-10-15

    To assess the value of dynamic contrast-enhanced (DCE) combined with T2-weighted (T2W) endorectal coil (ERC) magnetic resonance imaging (MRI) at 3 T for determining extracapsular extension (ECE) of prostate cancer. In this IRB-approved study, ERC 3-T MRI of the prostate was performed in 108 patients before radical prostatectomy. T2W fast spin-echo and DCE 3D gradient echo images were acquired. The interpretations of readers with varied experience were analysed. MRI-based staging results were compared with radical prostatectomy histology. Descriptive statistics were generated for prediction of ECE and staging accuracies were determined by the area under the receiver-operating characteristic curve. The overall sensitivity, specificity, positive predictive value and negative predictive value for ECE were 75 %, 92 %, 79 % and 91 %, respectively. Diagnostic accuracy for staging was 86 %, 80 % and 91 % for all readers, experienced and less experienced readers, respectively. ERC 3-T MRI of the prostate combining DCE and T2W imaging is an accurate pretherapeutic staging tool for assessment of ECE in clinical practice across varying levels of reader experience. (orig.)

  18. The glass transition in cured epoxy thermosets: A comparative molecular dynamics study in coarse-grained and atomistic resolution

    Energy Technology Data Exchange (ETDEWEB)

    Langeloth, Michael; Böhm, Michael C.; Müller-Plathe, Florian [Eduard-Zintl-Institut für Anorganische und Physikalische Chemie and Center of Smart Interfaces, Technische Universität Darmstadt, Alarich Weiss Straße 4, D-64287 Darmstadt (Germany); Sugii, Taisuke, E-mail: taisuke.sugii.zs@hitachi.com [Center for Technology Innovation – Mechanical Engineering, Research & Development Group, Hitachi, Ltd., 832-2, Horiguchi, Hitachinaka, Ibaraki 312-0034 (Japan)

    2015-12-28

    We investigate the volumetric glass transition temperature T{sub g} in epoxy thermosets by means of molecular dynamics simulations. The epoxy thermosets consist of the resin bisphenol A diglycidyl ether and the hardener diethylenetriamine. A structure based coarse-grained (CG) force field has been derived using iterative Boltzmann inversion in order to facilitate simulations of larger length scales. We observe that T{sub g} increases clearly with the degree of cross-linking for all-atomistic (AA) and CG simulations. The transition T{sub g} in CG simulations of uncured mixtures is much lower than in AA-simulations due to the soft nature of the CG potentials, but increases all the more with the formation of rigid cross-links. Additional simulations of the CG mixtures in contact with a surface show the existence of an interphase region of about 3 nm thickness in which the network properties deviate significantly from the bulk. In accordance to experimental studies, we observe that T{sub g} is reduced in this interphase region and gradually increases to its bulk value with distance from the surface. The present study shows that the glass transition is a local phenomenon that depends on the network structure in the immediate environment.

  19. Continuous monitoring bed-level dynamics on an intertidal flat: introducing novel stand-alone high-resolution SED-sensors

    Science.gov (United States)

    Hu, Zhan; Lenting, Walther; van der Wal, Daphne; Bouma, Tjeerd

    2015-04-01

    Tidal flat morphology is continuously shaped by hydrodynamic force, resulting in highly dynamic bed elevations. The knowledge of short-term bed-level changes is important both for understanding sediment transport processes as well as for assessing critical ecological processes such as e.g. vegetation recruitment chances on tidal flats. Due to the labour involved, manual discontinuous measurements lack the ability to continuously monitor bed-elevation changes. Existing methods for automated continuous monitoring of bed-level changes lack vertical accuracy (e.g., Photo-Electronic Erosion Pin sensor and resistive rod) or limited in spatial application by using expensive technology (e.g., acoustic bed level sensors). A method provides sufficient accuracy with a reasonable cost is needed. In light of this, a high-accuracy sensor (2 mm) for continuously measuring short-term Surface-Elevation Dynamics (SED-sensor) was developed. This SED-sensor makes use of photovoltaic cells and operates stand-alone using internal power supply and data logging system. The unit cost and the labour in deployments is therefore reduced, which facilitates monitoring with a number of units. In this study, the performance of a group of SED-sensors is tested against data obtained with precise manual measurements using traditional Sediment Erosion Bars (SEB). An excellent agreement between the two methods was obtained, indicating the accuracy and precision of the SED-sensors. Furthermore, to demonstrate how the SED-sensors can be used for measuring short-term bed-level dynamics, two SED-sensors were deployed for 1 month at two sites with contrasting wave exposure conditions. Daily bed-level changes were obtained including a severe storm erosion event. The difference in observed bed-level dynamics at both sites was statistically explained by their different hydrodynamic conditions. Thus, the stand-alone SED-sensor can be applied to monitor sediment surface dynamics with high vertical and temporal

  20. Genome-wide dynamic transcriptional profiling in clostridium beijerinckii NCIMB 8052 using single-nucleotide resolution RNA-Seq

    Directory of Open Access Journals (Sweden)

    Wang Yi

    2012-03-01

    Full Text Available Abstract Background Clostridium beijerinckii is a prominent solvent-producing microbe that has great potential for biofuel and chemical industries. Although transcriptional analysis is essential to understand gene functions and regulation and thus elucidate proper strategies for further strain improvement, limited information is available on the genome-wide transcriptional analysis for C. beijerinckii. Results The genome-wide transcriptional dynamics of C. beijerinckii NCIMB 8052 over a batch fermentation process was investigated using high-throughput RNA-Seq technology. The gene expression profiles indicated that the glycolysis genes were highly expressed throughout the fermentation, with comparatively more active expression during acidogenesis phase. The expression of acid formation genes was down-regulated at the onset of solvent formation, in accordance with the metabolic pathway shift from acidogenesis to solventogenesis. The acetone formation gene (adc, as a part of the sol operon, exhibited highly-coordinated expression with the other sol genes. Out of the > 20 genes encoding alcohol dehydrogenase in C. beijerinckii, Cbei_1722 and Cbei_2181 were highly up-regulated at the onset of solventogenesis, corresponding to their key roles in primary alcohol production. Most sporulation genes in C. beijerinckii 8052 demonstrated similar temporal expression patterns to those observed in B. subtilis and C. acetobutylicum, while sporulation sigma factor genes sigE and sigG exhibited accelerated and stronger expression in C. beijerinckii 8052, which is consistent with the more rapid forespore and endspore development in this strain. Global expression patterns for specific gene functional classes were examined using self-organizing map analysis. The genes associated with specific functional classes demonstrated global expression profiles corresponding to the cell physiological variation and metabolic pathway switch. Conclusions The results from this

  1. Monitoring Early Fusion Dynamics of Human Immunodeficiency Virus Type 1 at Single-Molecule Resolution ▿ †

    Science.gov (United States)

    Dobrowsky, Terrence M.; Zhou, Yan; Sun, Sean X.; Siliciano, Robert F.; Wirtz, Denis

    2008-01-01

    The fusion of human immunodeficiency virus type 1 (HIV-1) to host cells is a dynamic process governed by the interaction between glycoproteins on the viral envelope and the major receptor, CD4, and coreceptor on the surface of the cell. How these receptors organize at the virion-cell interface to promote a fusion-competent site is not well understood. Using single-molecule force spectroscopy, we map the tensile strengths, lifetimes, and energy barriers of individual intermolecular bonds between CCR5-tropic HIV-1 gp120 and its receptors CD4 and CCR5 or CXCR4 as a function of the interaction time with the cell. According to the Bell model, at short times of contact between cell and virion, the gp120-CD4 bond is able to withstand forces up to 35 pN and has an initial lifetime of 0.27 s and an intermolecular length of interaction of 0.34 nm. The initial bond also has an energy barrier of 6.7 kBT (where kB is Boltzmann's constant and T is absolute temperature). However, within 0.3 s, individual gp120-CD4 bonds undergo rapid destabilization accompanied by a shortened lifetime and a lowered tensile strength. This destabilization is significantly enhanced by the coreceptor CCR5, not by CXCR4 or fusion inhibitors, which suggests that it is directly related to a conformational change in the gp120-CD4 bond. These measurements highlight the instability and low tensile strength of gp120-receptor bonds, uncover a synergistic role for CCR5 in the progression of the gp120-CD4 bond, and suggest that the cell-virus adhesion complex is functionally arranged about a long-lived gp120-coreceptor bond. PMID:18480458

  2. Site-directed spectroscopic probes of actomyosin structural dynamics.

    Science.gov (United States)

    Thomas, David D; Kast, David; Korman, Vicci L

    2009-01-01

    Spectroscopy of myosin and actin has entered a golden age. High-resolution crystal structures of isolated actin and myosin have been used to construct detailed models for the dynamic actomyosin interactions that move muscle. Improved protein mutagenesis and expression technologies have facilitated site-directed labeling with fluorescent and spin probes. Spectroscopic instrumentation has achieved impressive advances in sensitivity and resolution. Here we highlight the contributions of site-directed spectroscopic probes to understanding the structural dynamics of myosin II and its actin complexes in solution and muscle fibers. We emphasize studies that probe directly the movements of structural elements within the myosin catalytic and light-chain domains, and changes in the dynamics of both actin and myosin due to their alternating strong and weak interactions in the ATPase cycle. A moving picture emerges in which single biochemical states produce multiple structural states, and transitions between states of order and dynamic disorder power the actomyosin engine.

  3. Rapid Calibration of High Resolution Geologic Models to Dynamic Data Using Inverse Modeling: Field Application and Validation

    Energy Technology Data Exchange (ETDEWEB)

    Akhil Datta-Gupta

    2008-03-31

    Streamline-based assisted and automatic history matching techniques have shown great potential in reconciling high resolution geologic models to production data. However, a major drawback of these approaches has been incompressibility or slight compressibility assumptions that have limited applications to two-phase water-oil displacements only. We propose an approach to history matching three-phase flow using a novel compressible streamline formulation and streamline-derived analytic sensitivities. First, we utilize a generalized streamline model to account for compressible flow by introducing an 'effective density' of total fluids along streamlines. Second, we analytically compute parameter sensitivities that define the relationship between the reservoir properties and the production response, viz. water-cut and gas/oil ratio (GOR). These sensitivities are an integral part of history matching, and streamline models permit efficient computation of these sensitivities through a single flow simulation. We calibrate geologic models to production data by matching the water-cut and gas/oil ratio using our previously proposed generalized travel time inversion (GTTI) technique. For field applications, however, the highly non-monotonic profile of the gas/oil ratio data often presents a challenge to this technique. In this work we present a transformation of the field production data that makes it more amenable to GTTI. Further, we generalize the approach to incorporate bottom-hole flowing pressure during three-phase history matching. We examine the practical feasibility of the method using a field-scale synthetic example (SPE-9 comparative study) and a field application. Recently Ensemble Kalman Filtering (EnKF) has gained increased attention for history matching and continuous reservoir model updating using data from permanent downhole sensors. It is a sequential Monte-Carlo approach that works with an ensemble of reservoir models. Specifically, the method

  4. 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.

  5. Imaging of radiocesium uptake dynamics in a plant body using a newly developed high-resolution gamma camera for radiocesium

    Energy Technology Data Exchange (ETDEWEB)

    Kawachi, Naoki; Yin, Yong-Gen; Suzui, Nobuo; Ishii, Satomi; Fujimaki, Shu [Radiotracer Imaging Gr., Quantum Beam Science Directorate, Japan Atomic Energy Agency (JAEA), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Yoshihara, Toshihiro [Plant Molecular Biology, Laboratory of Environmental Science, Central Research Institute of Electric Power Industry (CRIEPI), 1646 Abiko, Chiba 270-1194 (Japan); Watabe, Hiroshi [Cyclotron and Radioisotope Center (CYRIC), Tohoku University, 6-3Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8578 (Japan); Yamamoto, Seiichi [Department of Radiological and Medical Laboratory Sciences, Nagoya University Graduate School of Medicine, 1-1-20 Daiko-Minami, Higashi-ku, Nagoya 461-8673 (Japan)

    2014-07-01

    Vast agricultural and forest areas around the Tokyo Electric Power Company Fukushima Daiichi Nuclear Power Station in Japan were contaminated with radiocesium (Cs-134 and Cs-137) after the accident following the earthquake and tsunami in March 2011. A variety of agricultural studies, such as fertilizer management and plant breeding, have been undertaken intensively for reduction of radiocesium uptake in crops, or, enhancement of uptake in phyto-remediation. In this study, we newly developed a gamma camera specific for plant nutritional research, and performed quantitative analyses on uptake and partitioning of radiocesium in intact plant bodies. In general, gamma camera is a common technology in medical imaging, but it is not applicable to high-energy gamma rays such as emissions from Cs-137 (662 keV). Therefore, we designed our new gamma camera to prevent the penetration and scattering of the high-energy gamma rays. A single-crystal scintillator, Ce-doped Gd{sub 3}Al{sub 2}Ga{sub 3}O{sub 12} (Ce:GAGG), was employed, which has a relatively high density, a large light output, no natural radioactivity and no hygroscopicity. A 44 x 44 matrix of the Ce:GAGG pixels, with dimensions of 0.85 mm x 0.85 mm x 10 mm for each pixel, was coupled to a high-quantum efficiency position sensitive photomultiplier tube. This gamma detector unit was encased in a 20-mm-thick tungsten container with a tungsten pinhole collimator on the front. By using this gamma camera, soybean plants (Glycine max), grown in hydroponic solutions and fed with 1-2 MBq of Cs-137, were imaged for 6.5 days in maximum to investigate and visualize the uptake dynamics into/within the areal part. As a result, radiocesium gradually appeared in the shoot several hours after feeding of Cs-137, and then accumulated intensively in the maturing pods and seeds in a characteristic pattern. Our results also demonstrated that this gamma-camera method enables quantitative evaluation of plant ability to absorb, transport

  6. A statistical-dynamical scheme for reconstructing ocean forcing in the Atlantic. Part II: methodology, validation and application to high-resolution ocean models

    Energy Technology Data Exchange (ETDEWEB)

    Minvielle, Marie; Cassou, Christophe; Terray, Laurent; Najac, Julien [CERFACS/CNRS, Climate Modelling and Global Change Team, Toulouse (France); Bourdalle-Badie, Romain [CERFACS/CNRS, Climate Modelling and Global Change Team, Toulouse (France); MERCATOR Parc Technologique du Canal, Ramonville St Agne (France)

    2011-02-15

    A novel statistical-dynamical scheme has been developed to reconstruct the sea surface atmospheric variables necessary to force an ocean model. Multiple linear regressions are first built over a so-called learning period and over the entire Atlantic basin from the observed relationship between the surface wind conditions, or predictands, and the anomalous large scale atmospheric circulations, or predictors. The latter are estimated in the extratropics by 500 hPa geopotential height weather regimes and in the tropics by low-level wind classes. The transfer function further combined to an analog step is then used to reconstruct all the surface variables fields over 1958-2002. We show that the proposed hybrid scheme is very skillful in reproducing the mean state, the seasonal cycle and the temporal evolution of all the surface ocean variables at interannual timescale. Deficiencies are found in the level of variance especially in the tropics. It is underestimated for 2-m temperature and humidity as well as for surface radiative fluxes in the interannual frequency band while it is slightly overestimated at higher frequency. Decomposition in empirical orthogonal function (EOF) shows that the spatial and temporal coherence of the forcing fields is however very well captured by the reconstruction method. For dynamical downscaling purposes, reconstructed fields are then interpolated and used to carry out a high-resolution oceanic simulation using the NATL4 (1/4 ) model integrated over 1979-2001. This simulation is compared to a reference experiment where the original observed forcing fields are prescribed instead. Mean states between the two experiments are virtually undistinguishable both in terms of surface fluxes and ocean dynamics estimated by the barotropic and the meridional overturning streamfunctions. The 3-dimensional variance of the simulated ocean is well preserved at interannual timescale both for temperature and salinity except in the tropics where it is

  7. High-resolution Average Forest Phenology and Annual Residuals for Quantifying the Start of Spring and Summer Leaf-area Dynamics

    Science.gov (United States)

    Elmore, A. J.; Guinn, S. M.

    2009-12-01

    Land surface phenology (LSP) is the seasonal pattern of vegetation dynamics that occur each spring and fall. Multiple drivers of spatial variation in LSP and its variation over time have been analyzed using satellite remote sensing. Until recently, these observations have been restricted to moderate- and low-resolution data, as it is only at these spatial resolutions for which temporally continuous data is available. However, understanding small scale variation in LSP over space and time may be key to linking pattern to process, and in particular, could be used to understand how ecological processes at the stand level scale to landscapes and continents. Through utilization of the large, and now free, Landsat record, recent research has led to the development of robust methods for calculating average phenological patterns at 30-m resolution by stacking two decades worth of data by acquisition day of year (DOY). Here we have extended these techniques to calculate the deviation from the average LSP for any given acquisition DOY-year combination. We model the average LSP as two sigmoid functions, one increasing in spring and a second decreasing in fall, connected by a sloped line representing gradual summer leaf area changes (see Figure). Deviation from the average LSP is considered here to take two forms: (1) residual vegetation cover in mid- to late-summer represent locations in which disturbance, drought, or (alternatively) better than average growing conditions have resulted a separation (either negative or positive) from the average vegetation cover for that DOY, and (2) climate conditions that result in an earlier or later onset of greenness, exhibited as a separation from the average spring onset of greenness curve in the DOY direction (either early or late.) Our study system for this work is the deciduous forests of the mid-Atlantic, USA, where we show that late summer vegetation cover is tied to edaphic properties governing the site specific soil moisture

  8. Advances in monitoring dynamic hydrologic conditions in the vadose zone through automated high-resolution ground-penetrating radar imaging and analysis

    Science.gov (United States)

    Mangel, Adam R.

    This body of research focuses on resolving physical and hydrological heterogeneities in the subsurface with ground-penetrating radar (GPR). Essentially, there are two facets of this research centered on the goal of improving the collective understanding of unsaturated flow processes: i) modifications to commercially available equipment to optimize hydrologic value of the data and ii) the development of novel methods for data interpretation and analysis in a hydrologic context given the increased hydrologic value of the data. Regarding modifications to equipment, automation of GPR data collection substantially enhances our ability to measure changes in the hydrologic state of the subsurface at high spatial and temporal resolution (Chapter 1). Additionally, automated collection shows promise for quick high-resolution mapping of dangerous subsurface targets, like unexploded ordinance, that may have alternate signals depending on the hydrologic environment (Chapter 5). Regarding novel methods for data inversion, dispersive GPR data collected during infiltration can constrain important information about the local 1D distribution of water in waveguide layers (Chapters 2 and 3), however, more data is required for reliably analyzing complicated patterns produced by the wetting of the soil. In this regard, data collected in 2D and 3D geometries can further illustrate evidence of heterogeneous flow, while maintaining the content for resolving wave velocities and therefore, water content. This enables the use of algorithms like reflection tomography, which show the ability of the GPR data to independently resolve water content distribution in homogeneous soils (Chapter 5). In conclusion, automation enables the non-invasive study of highly dynamic hydrologic processes by providing the high resolution data required to interpret and resolve spatial and temporal wetting patterns associated with heterogeneous flow. By automating the data collection, it also allows for the novel

  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. 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.

  11. An evaluation of dynamical downscaling of Central Plains summer precipitation using a WRF-based regional climate model at a convection-permitting 4 km resolution

    Science.gov (United States)

    Sun, Xuguang; Xue, Ming; Brotzge, Jerald; McPherson, Renee A.; Hu, Xiao-Ming; Yang, Xiu-Qun

    2016-12-01

    A significant challenge with dynamical downscaling of climate simulations is the ability to accurately represent convection and precipitation. The use of convection-permitting resolutions avoids cumulus parameterization, which is known to be a large source of uncertainty. A regional climate model (RCM) based on the Weather Research and Forecasting model is configured with a 4 km grid spacing and applied to the U.S. Great Plains, a region characterized by many forms of weather and climate extremes. The 4 km RCM is evaluated by running it in a hindcast mode over the central U.S. region for a 10 year period, forced at the boundary by the 32 km North America Regional Reanalysis. The model is also run at a 25 km grid spacing, but with cumulus parameterization turned on for comparison. The 4 km run more successfully reproduces certain observed features of the Great Plains May-through-August precipitation. In particular, the magnitude of extreme precipitation and the diurnal cycle of precipitation over the Great Plains are better simulated. The 4 km run more realistically simulates the low-level jet and related atmospheric circulations that transport and redistribute moisture from Gulf of Mexico. The convection-permitting RCM may therefore produce better dynamical downscaling of future climate when nested within global model climate projections, especially for extreme precipitation magnitudes. The 4 km and 25 km simulations do share similar precipitation biases, including low biases over the central Great Plains and high biases over the Rockies. These biases appear linked to circulation biases in the simulations, but determining of the exact causes will require extensive, separate studies.

  12. High Resolution He I 10830 AA Narrow-band Imaging of an M-class Flare. I - Analysis of Sunspot Dynamics during Flaring

    Science.gov (United States)

    Wang, Ya; Su, Yingna; Hong, Zhenxiang; Zeng, Zhicheng; Ji, Kaifan; Goode, Philip R.; Cao, Wenda; Ji, Haisheng

    2016-12-01

    In this paper, we report our first-step results of high resolution He i 10830 Å narrow-band imaging (bandpass: 0.5 Å) of an M1.8 class two-ribbon flare on 2012 July 5. The flare was observed with the 1.6 m aperture New Solar Telescope at Big Bear Solar Observatory. For this unique data set, sunspot dynamics during flaring were analyzed for the first time. By directly imaging the upper chromosphere, running penumbral waves are clearly seen as an outward extension of umbral flashes; both take the form of absorption in the 10830 Å narrow-band images. From a space-time image made of a slit cutting across a flare ribbon and the sunspot, we find that the dark lanes for umbral flashes and penumbral waves are obviously broadened after the flare. The most prominent feature is the sudden appearance of an oscillating absorption strip inside the ribbon when it sweeps into the sunspot’s penumbral and umbral regions. During each oscillation, outwardly propagating umbral flashes and subsequent penumbral waves rush out into the inwardly sweeping ribbon, followed by a return of the absorption strip with similar speed. We tentatively explain the phenomena as the result of a sudden increase in the density of ortho-helium atoms in the area of the sunspot being excited by the flare’s extreme ultraviolet illumination. This explanation is based on the observation that 10830 Å absorption around the sunspot area gets enhanced during the flare. Nevertheless, questions are still open and we need further well-devised observations to investigate the behavior of sunspot dynamics during flares.

  13. 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.

  14. Warm Absorbers in X-rays (WAX), a comprehensive high resolution grating spectral study of a sample of Seyfert Galaxies: II. Warm Absorber dynamics and feedback to galaxies

    CERN Document Server

    Laha, Sibasish; Chakravorty, Susmita; Dewangan, Gulab C; Kembhavi, Ajit K

    2016-01-01

    This paper is a sequel to the extensive study of warm absorber (WA) in X-rays carried out using high resolution grating spectral data from XMM-Newton satellite (WAX-I). Here we discuss the global dynamical properties as well as the energetics of the WA components detected in the WAX sample. The slope of WA density profile ($n\\propto r^{-\\alpha}$) estimated from the linear regression slope of ionization parameter $\\xi$ and column density $N_H$ in the WAX sample is $\\alpha=1.236\\pm 0.034$. We find that the WA clouds possibly originate as a result of photo-ionised evaporation from the inner edge of the torus (torus wind). They can also originate in the cooling front of the shock generated by faster accretion disk outflows, the ultra-fast outflows (UFO), impinging onto the interstellar medium or the torus. The acceleration mechanism for the WA is complex and neither radiatively driven wind nor MHD driven wind scenario alone can describe the outflow acceleration. However, we find that radiative forces play a signi...

  15. High resolution He I 10830 \\AA\\ narrow-band imaging of an M-class flare. I - analysis of sunspot dynamics during flaring

    CERN Document Server

    Wang, Ya; Hong, Zhenxiang; Zeng, Zhicheng; Ji, Kaifan; Goode, Philip R; Cao, Wenda; Ji, Haisheng

    2016-01-01

    In this paper, we report our first-step results of high resolution He\\,\\textsc{i} 10830 \\AA\\ narrow-band imaging (bandpass: 0.5 {\\AA}) of an M1.8 class two-ribbon flare on July 5, 2012. The flare was observed with the 1.6 meter aperture New Solar Telescope at Big Bear Solar Observatory. For this unique data set, sunspot dynamics during flaring were analyzed for the first time. By directly imaging the upper chromosphere, running penumbral waves are clearly seen as an outward extension of umbral flashes, both take the form of absorption in the 10830 \\AA\\ narrow-band images. From a space-time image made of a slit cutting across a flare ribbon and the sunspot, we find that the dark lanes for umbral flashes and penumbral waves are obviously broadened after the flare. The most prominent feature is the sudden appearance of an oscillating absorption strip inside the ribbon when it sweeps into the sunspot's penumbral and umbral regions. During each oscillation, outwardly propagating umbral flashes and subsequent penum...

  16. Probing molecular dynamics in chromatographic systems using high-resolution 1H magic-angle-spinning NMR spectroscopy: interaction between p-Xylene and C18-bonded silica.

    Science.gov (United States)

    Coen, Muireann; Wilson, Ian D; Nicholson, Jeremy K; Tang, Huiru; Lindon, John C

    2004-06-01

    The exact nature of the interaction between small molecules and chromatographic solid phases has been the subject of much research, but detailed understanding of the molecular dynamics in such systems remains elusive. High-resolution (1)H magic-angle-spinning (MAS) NMR spectroscopy has been applied to the investigation of C18-bonded silica material as used in chromatographic separation techniques together with an adsorbed model analyte, p-xylene. Two distinct p-xylene and water environments were identified within the C18-bonded silica through the measurement of (1)H NMR chemical shifts, T(1) and T(2) relaxation times and diffusion coefficients, including their temperature dependence. The results have been analyzed in terms of two environments, p-xylene within the C18 chains, in slow exchange on the NMR time scale with p-xylene in a more mobile state adsorbed as a layer in close proximity to the C18 particles, but which is distinct from free liquid p-xylene. The techniques used here could have more general applications, including the study of drug molecules bound into phospholipid membranes in micelles or vesicles.

  17. 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.

  18. Dynamics of the Gong windstorm (Jan 2013) in the context of a 20-year high-resolution simulation of Iberian climate

    Science.gov (United States)

    Miranda, Pedro M. A.; João Chinita, Maria; Cardoso, Rita; Soares, Pedro; Viterbo, Pedro; Pinto, Paulo; Mendes, Manuel

    2014-05-01

    state. The Oeste storm is also poorly simulated in both simulations. Xinthia and Klaus, on the other hand, are both well represented in the continuous RCM simulation. The Oeste storm was earlier diagnosed as a sting-jet storm, using Doppler radar techniques, corresponding to the conceptual model of Browning (2004). The present case study simulation shows that the same applies to the Gong storm, although the latter has a somewhat larger horizontal scale. An increased relevance of this extreme storm dynamics in recent and future European storms is an intriguing possibility. The sensitivity of these storms to details in the synoptic environment is a very relevant issue in the analysis of storm trends in future climate scenarios. Acknowledgements. Study supported by FCT through Grants PTDC/CTE-ATM/119922/2010 and PEST/OE/CTE/LA0019-2013-2014. References Browning, K.A., 2004: The sting at the end of the tail: Damaging winds associated with extratropical cyclones. Q. J. R. Meteorol. Soc., 130, 375-399 Cardoso RM, Soares PMM, Miranda PMA, Belo-Pereira M (2013) WRF high resolution simulation of Iberian mean and extreme precipitation climate, International Journal of Climatology, 33, 2591-2608, DOI: 10.1002/joc.3616 Soares PMM, Cardoso RM, Miranda PMA, Viterbo P, Belo-Pereira M, Viterbo P (2012) Assessment of the ENSEMBLES regional climate models in the representation of precipitation variability and extremes over Portugal. J Geophys Res (Atmospheres), 117, D07114, doi:10.1029/2011JD016768

  19. Design parameters for measurements of local catalytic activity on surfaces

    DEFF Research Database (Denmark)

    Johansson, Martin; Johannessen, Tue; Jørgensen, Jan Hoffmann;

    2006-01-01

    Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward...

  20. 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

  1. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-04-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  2. Dynamics of explosive paroxysms at open andesitic systems: high-resolution mass distribution analyses of 2006 tephra from Tungurahua volcano (Ecuador)

    Science.gov (United States)

    Le Pennec, J.; Eychenne, J.; Ramon, P.; Yepes, H.

    2012-12-01

    Many andesitic volcanoes at subduction plate margins can experience in the course of their evolution periods of sub-continuous eruption during years, decades, or centuries. Such long-lived periods may embrace more or less intense outgassing events, extrusion of viscous lava flows and domes (e.g. Colima in Mexico, Merapi in Indonesia, Arenal in Costa Rica), and explosive activity of uneven intensity (e.g. Semeru in Indonesia, Sakurajima in Japan, Sangay in Ecuador). In addition, strong explosive events of short duration may occur, with potential generation of pyroclastic flows on the flanks and beyond, which can pose significant hazards in populated regions. The origin and dynamics of such violent eruptions remain poorly known and may involve a combination of different factors. Tungurahua volcano, Ecuador, reawaken in 1999 and is an example of such open-system behaviour that experienced a strong and deadly andesitic pyroclastic flow-forming event in August 2006. Inspection of the deposits suggested that the event could have been triggered by magma mixing (silicic pumices in the tephra), magma-water interaction (presence of xenolithic clasts) or deep andesitic magma reinjection (based on mineral chemistry). Here we investigate these options by performing a high-resolution mass budget analysis of the scoria fall deposit. This is achieved by analysing componentry compositions and their mass distribution pattern in the layer, which allow us to document and integrate exponential and power laws mass decay rates over wide areas. The results yield a total mass for the tephra layer of ~2 x 1010kg. The pumice mass fraction is far too small (< 0.4 %) to account for the high explosivity of the 2006 event. Similarly, the xenoclastic mass fraction is small (0.2%) and suggests limited magma-water interaction. Instead, we interpret these xenoclasts as a result of upper conduit erosion at a rate of ~30 cm/hour during the paroxysm. Altogether our results support an explosive event

  3. Dynamics in mangroves assessed by high-resolution and multi-temporal satellite data: a case study in Zhanjiang Mangrove National Nature Reserve (ZMNNR), P. R. China

    Science.gov (United States)

    Leempoel, K.; Satyaranayana, B.; Bourgeois, C.; Zhang, J.; Chen, M.; Wang, J.; Bogaert, J.; Dahdouh-Guebas, F.

    2013-08-01

    Mangrove forests are declining across the globe, mainly because of human intervention, and therefore require an evaluation of their past and present status (e.g. areal extent, species-level distribution, etc.) to implement better conservation and management strategies. In this paper, mangrove cover dynamics at Gaoqiao (P. R. China) were assessed through time using 1967, 2000 and 2009 satellite imagery (sensors Corona KH-4B, Landsat ETM+, GeoEye-1 respectively). Firstly, multi-temporal analysis of satellite data was undertaken, and secondly biotic and abiotic differences were analysed between the different mangrove stands, assessed through a supervised classification of a high-resolution satellite image. A major decline in mangrove cover (-36%) was observed between 1967 and 2009 due to rice cultivation and aquaculture practices. Moreover, dike construction has prevented mangroves from expanding landward. Although a small increase of mangrove area was observed between 2000 and 2009 (+24%), the ratio mangrove / aquaculture kept decreasing due to increased aquaculture at the expense of rice cultivation in the vicinity. From the land-use/cover map based on ground-truth data (5 × 5 m plot-based tree measurements) (August-September, 2009) as well as spectral reflectance values (obtained from pansharpened GeoEye-1), both Bruguiera gymnorrhiza and small Aegiceras corniculatum are distinguishable at 73-100% accuracy, whereas tall A. corniculatum was correctly classified at only 53% due to its mixed vegetation stands with B. gymnorrhiza (overall classification accuracy: 85%). In the case of sediments, sand proportion was significantly different between the three mangrove classes. Overall, the advantage of very high resolution satellite images like GeoEye-1 (0.5 m) for mangrove spatial heterogeneity assessment and/or species-level discrimination was well demonstrated, along with the complexity to provide a precise classification for non-dominant species (e.g. Kandelia obovata

  4. Dynamics in mangroves assessed by high-resolution and multi-temporal satellite data: a case study in Zhanjiang Mangrove National Nature Reserve (ZMNNR, P. R. China

    Directory of Open Access Journals (Sweden)

    K. Leempoel

    2013-08-01

    Full Text Available Mangrove forests are declining across the globe, mainly because of human intervention, and therefore require an evaluation of their past and present status (e.g. areal extent, species-level distribution, etc. to implement better conservation and management strategies. In this paper, mangrove cover dynamics at Gaoqiao (P. R. China were assessed through time using 1967, 2000 and 2009 satellite imagery (sensors Corona KH-4B, Landsat ETM+, GeoEye-1 respectively. Firstly, multi-temporal analysis of satellite data was undertaken, and secondly biotic and abiotic differences were analysed between the different mangrove stands, assessed through a supervised classification of a high-resolution satellite image. A major decline in mangrove cover (−36% was observed between 1967 and 2009 due to rice cultivation and aquaculture practices. Moreover, dike construction has prevented mangroves from expanding landward. Although a small increase of mangrove area was observed between 2000 and 2009 (+24%, the ratio mangrove / aquaculture kept decreasing due to increased aquaculture at the expense of rice cultivation in the vicinity. From the land-use/cover map based on ground-truth data (5 × 5 m plot-based tree measurements (August–September, 2009 as well as spectral reflectance values (obtained from pansharpened GeoEye-1, both Bruguiera gymnorrhiza and small Aegiceras corniculatum are distinguishable at 73–100% accuracy, whereas tall A. corniculatum was correctly classified at only 53% due to its mixed vegetation stands with B. gymnorrhiza (overall classification accuracy: 85%. In the case of sediments, sand proportion was significantly different between the three mangrove classes. Overall, the advantage of very high resolution satellite images like GeoEye-1 (0.5 m for mangrove spatial heterogeneity assessment and/or species-level discrimination was well demonstrated, along with the complexity to provide a precise classification for non-dominant species (e

  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. 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.

  7. 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.)

  8. X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes

    NARCIS (Netherlands)

    Kalirai, Samanbir; Boesenberg, Ulrike; Falkenberg, Gerald; Meirer, Florian; Weckhuysen, Bert M.

    2015-01-01

    Microprobe X-ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life-stages. 3D multi-element imaging, at submicron resolution was achieved by using a large

  9. 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.

  10. 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.

  11. Long-term hydrological dynamics and fire history over the last 2000 years in CE Europe reconstructed from a high-resolution peat archive

    Science.gov (United States)

    Marcisz, Katarzyna; Tinner, Willy; Colombaroli, Daniele; Kołaczek, Piotr; Słowiński, Michał; Fiałkiewicz-Kozieł, Barbara; Łokas, Edyta; Lamentowicz, Mariusz

    2015-03-01

    Sphagnum peatlands in the oceanic-continental transition zone of Poland are currently influenced by climatic and anthropogenic factors that lead to peat desiccation and susceptibility to fire. Little is known about the response of Sphagnum peatland testate amoebae (TA) to the combined effects of drought and fire. To understand the relationships between hydrology and fire dynamics, we used high-resolution multi-proxy palaeoecological data to reconstruct 2000 years of mire history in northern Poland. We employed a new approach for Polish peatlands - joint TA-based water table depth and charcoal-inferred fire activity reconstructions. In addition, the response of most abundant TA hydrological indicators to charcoal-inferred fire activity was assessed. The results show four hydrological stages of peatland development: moderately wet (from ˜35 BC to 800 AD), wet (from ˜800 to 1390 AD), dry (from ˜1390 to 1700 AD) and with an instable water table (from ˜1700 to 2012 AD). Fire activity has increased in the last millennium after constant human presence in the mire surroundings. Higher fire activity caused a rise in the water table, but later an abrupt drought appeared at the onset of the Little Ice Age. This dry phase is characterized by high ash contents and high charcoal-inferred fire activity. Fires preceded hydrological change and the response of TA to fire was indirect. Peatland drying and hydrological instability was connected with TA community changes from wet (dominance of Archerella flavum, Hyalosphenia papilio, Amphitrema wrightianum) to dry (dominance of Cryptodifflugia oviformis, Euglypha rotunda); however, no clear fire indicator species was found. Anthropogenic activities can increase peat fires and cause substantial hydrology changes. Our data suggest that increased human fire activity was one of the main factors that influenced peatland hydrology, though the mire response through hydrological changes towards drier conditions was delayed in relation to

  12. The evolution of model catalytic systems; studies of structure, bonding and dynamics from single crystal metal surfaces to nanoparticles, and from low pressure (10(-3) Torr) to liquid interfaces.

    Science.gov (United States)

    Somorjai, Gabor A; York, Roger L; Butcher, Derek; Park, Jeong Y

    2007-07-21

    The material and pressure gap has been a long standing challenge in the field of heterogeneous catalysis and have transformed surface science and biointerfacial research. In heterogeneous catalysis, the material gap refers to the discontinuity between well-characterized model systems and industrially relevant catalysts. Single crystal metal surfaces have been useful model systems to elucidate the role of surface defects and the mobility of reaction intermediates in catalytic reactivity and selectivity. As nanoscience advances, we have developed nanoparticle catalysts with lithographic techniques and colloidal syntheses. Nanoparticle catalysts on oxide supports allow us to investigate several important ingredients of heterogeneous catalysis such as the metal-oxide interface and the influence of noble metal particle size and surface structure on catalytic selectivity. Monodispersed nanoparticle and nanowire arrays were fabricated for use as model catalysts by lithographic techniques. Platinum and rhodium nanoparticles in the 1-10 nm range were synthesized in colloidal solutions in the presence of polymer capping agents. The most catalytically active systems are employed at high pressure or at solid-liquid interfaces. In order to study the high pressure and liquid interfaces on the molecular level, experimental techniques with which we bridged the pressure gap in catalysis have been developed. These techniques include the ultrahigh vacuum system equipped with high pressure reaction cell, high pressure Sum Frequency Generation (SFG) vibration spectroscopy, High Pressure Scanning Tunneling Microscopy (HP-STM), and High Pressure X-ray Photoemission Spectroscopy (HP-XPS), and Quartz Crystal Microbalance (QCM). In this article, we overview the development of experimental techniques and evolution of the model systems for the research of heterogeneous catalysis and biointerfacial studies that can shed light on the long-standing issues of materials and pressure gaps.

  13. 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.

  14. 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....

  15. Dynamics

    CERN Document Server

    Goodman, Lawrence E

    2001-01-01

    Beginning text presents complete theoretical treatment of mechanical model systems and deals with technological applications. Topics include introduction to calculus of vectors, particle motion, dynamics of particle systems and plane rigid bodies, technical applications in plane motions, theory of mechanical vibrations, and more. Exercises and answers appear in each chapter.

  16. Resolution propositions; Proposition de resolution

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-05-01

    To put a resolution to the meeting in relation with the use of weapons made of depleted uranium is the purpose of this text. The situation of the use of depleted uranium by France during the Gulf war and other recent conflicts will be established. This resolution will give the most strict recommendations face to the eventual sanitary and environmental risks in the use of these kind of weapons. (N.C.)

  17. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    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...... 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...... and quantum state merging, and leads to a resource theory of decoupling....

  18. Three-dimensional simulation and modeling of a catalytic cracking fluidized bed reactor - cluster formation; Modelagem e simulacao tridimensional de um reator de craqueamento catalitico em leito fluidizado - formacao de clusters

    Energy Technology Data Exchange (ETDEWEB)

    Georg, Ivan Carlos; Maliska, Clovis Raimundo [Santa Catarina Univ., Florianopolis, SC (Brazil). Programa de Pos-graduacao em Engenharia Mecanica. Lab. de Simulacao Numerica em Mecanica dos Fluidos e Transferencia de Calor]. E-mail: ivan@sinmec.ufsc; maliska@sinmec.ufsc.br; Porto, Luismar Marques [Santa Catarina Univ., Florianopolis, SC (Brazil). Programa de Pos-graduacao em Engenharia Quimica e Alimentos. Lab. de Tecnologias Integradas]. E-mail: luismar@enq.ufsc.br

    2003-07-01

    Fluid catalytic cracking (FCC) is an industrial process that converts heavy hydrocarbons to lower molecular-weight products that are more profit. A multiphase model are developed to describe de gas-solid flow with a 3D high resolution grid, which have the finality to capture the meso-scale structures. This structures influence the transfer mechanisms of mass, momentum, energy and the rate of the reactions. The aim of this work is to present numerical results to demonstrate that the fluid dynamic model suggested here can capture the clusters of particles. (author)

  19. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)

    VLADIMIR LESKOVAC

    2008-04-01

    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

  20. 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.

  1. 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.

  2. Contrast-enhanced dynamic MRI protocol with improved spatial and time resolution for in vivo microimaging of the mouse with a 1.5-T body scanner and a superconducting surface coil.

    Science.gov (United States)

    Ginefri, Jean-Christophe; Poirier-Quinot, Marie; Robert, Philippe; Darrasse, Luc

    2005-02-01

    Magnetic resonance imaging (MRI) is well suited for small animal model investigations to study various human pathologies. However, the assessment of microscopic information requires a high-spatial resolution (HSR) leading to a critical problem of signal-to-noise ratio limitations in standard whole-body imager. As contrast mechanisms are field dependent, working at high field do not allow to derive MRI criteria that may apply to clinical settings done in standard whole-body systems. In this work, a contrast-enhanced dynamic MRI protocol with improved spatial and time resolution was used to perform in vivo tumor model imaging on the mouse at 1.5 T. The needed sensitivity is provided by the use of a 12-mm superconducting surface coil operating at 77 K. High quality in vivo images were obtained and revealed well-defined internal structures of the tumor. A 3-D HSR sequence with voxels of 59x59x300 microm3 encoded within 6.9 min and a 2-D sequence with subsecond acquisition time and isotropic in-plane resolution of 234 microm were used to analyze the contrast enhancement kinetics in tumoral structures at long and short time scales. This work is a first step to better characterize and differentiate the dynamic behavior of tumoral heterogeneities.

  3. First-principles investigations for the catalytic dissociation and oxidation of methane on the Cu surfaces

    Science.gov (United States)

    Li, Ying; Mahadevan, Jagan; Wang, Sanwu

    2010-03-01

    The catalytic reactions of dissociation and oxidation of methane on the copper surfaces play a key role in, for example, the development of high-performance solid oxide fuel cells. We used first-principles quantum theory and large-scale parallel calculations to investigate the atomic-scale mechanism of the catalytic chemical reactions. We report the calculated results, which provide fundamental information and understanding about the atomic-scale dynamics and electronic structures pertinent to the reactions and specifically the catalytic role of the Cu(100) and Cu(111) surfaces. We also report comparison of our results with available experimental data and previous theoretical investigations.

  4. High-Resolution X-Ray Spectroscopy of a Low-Luminosity Active Galactic Nucleus: The Structure and Dynamics of M81*

    NARCIS (Netherlands)

    Young, A.J.; Nowak, M.A.; Markoff, S.; Marshall, H.L.; Canizares, C.R.

    2007-01-01

    We present Chandra HETGS observations of the low-luminosity active galactic nucleus (LLAGN) of M81. The HETGS is unique in providing high-resolution spectroscopy of the central 1" of M81, including the iron K bandpass. The continuum is a power law of photon index Gamma=1.8, similar to that seen in h

  5. The influence of platinum washing-out time on its recovery from used auto catalytic converters

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2014-07-01

    Full Text Available The used catalytic converters contain small amounts of precious metals. Recovery of these metals is essential for environmental and economic reasons. This work presents a method of Platinum Group Metals (PGM recovery from auto catalytic converters in which they are washed out by a liquid metal. The magneto-hydro-dynamic pump was used to force circulation of liquid metal under the influence of electromagnetic fields The influence of process time on platinum recovery was also carried out.

  6. Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Xiao Wu

    2016-01-01

    Full Text Available The catalytic synthesis of cyclic carbonates using carbon dioxide as a C1-building block is a highly active area of research. Here, we review the catalytic production of enantiomerically enriched cyclic carbonates via kinetic resolution of racemic epoxides catalysed by metal-containing catalyst systems.

  7. Toward a High-Resolution Monitoring of Continental Surface Water Extent and Dynamics, at Global Scale: from GIEMS (Global Inundation Extent from Multi-Satellites) to SWOT (Surface Water Ocean Topography)

    Science.gov (United States)

    Prigent, Catherine; Lettenmaier, Dennis P.; Aires, Filipe; Papa, Fabrice

    2016-03-01

    Up to now, high-resolution mapping of surface water extent from satellites has only been available for a few regions, over limited time periods. The extension of the temporal and spatial coverage was difficult, due to the limitation of the remote sensing technique [e.g., the interaction of the radiation with vegetation or cloud for visible observations or the temporal sampling with the synthetic aperture radar (SAR)]. The advantages and the limitations of the various satellite techniques are reviewed. The need to have a global and consistent estimate of the water surfaces over long time periods triggered the development of a multi-satellite methodology to obtain consistent surface water all over the globe, regardless of the environments. The Global Inundation Extent from Multi-satellites (GIEMS) combines the complementary strengths of satellite observations from the visible to the microwave, to produce a low-resolution monthly dataset (0.25^circ × 0.25^circ) of surface water extent and dynamics. Downscaling algorithms are now developed and applied to GIEMS, using high-spatial-resolution information from visible, near-infrared, and synthetic aperture radar (SAR) satellite images, or from digital elevation models. Preliminary products are available down to 500-m spatial resolution. This work bridges the gaps and prepares for the future NASA/CNES Surface Water Ocean Topography (SWOT) mission to be launched in 2020. SWOT will delineate surface water extent estimates and their water storage with an unprecedented spatial resolution and accuracy, thanks to a SAR in an interferometry mode. When available, the SWOT data will be adopted to downscale GIEMS, to produce a long time series of water surfaces at global scale, consistent with the SWOT observations.

  8. Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

    Science.gov (United States)

    Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.

    2016-05-01

    Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4–fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.

  9. 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.

  10. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune;

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...... by dynamic thermal limitations of the reactor. (c) 2007 Elsevier B.V. All rights reserved....

  11. 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

  12. 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.

  13. 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.

  14. Structural Basis for the Catalytic Activity of Human SER/THR Protein Phosphatase-5

    Science.gov (United States)

    Swingle, M. R.; Honkanen, R.; Ciszak, E.

    2004-01-01

    Serinekhreonine protein phosphatase-5 (PP5) affects many signaling networks that regulate cell growth. Here we report the 1.6 Angstrom resolution crystal structure of PP5 catalytic domain with metal and phosphate ions in the active site. The structure reveals a mechanism for PPS-mediated catalysis that requires the precise positioning of two metal ions within a conserved Asp(sup 271)-M(sub 1),-M(sub 2)-His(sup 427)-W(sup 2)-His(sup 304)-Asp(sup 274) catalytic motif, and provides a structural basis for the exceptional catalytic proficiency of protein phosphatases placing them among the most powerful catalysts. Resolution of the entire C-terminus revealed a novel subdomain, and the structure of PP5 should aid development of specific inhibitors.

  15. Structural Basis for the Catalytic Activity of Human Serine/Threonine Protein Phosphatase-5

    Science.gov (United States)

    Swingle, M. R.; Honkanen, R.; Ciszak, E. M.

    2004-01-01

    Serinehhreonine protein phosphatase-5 (PP5) affects many signaling networks that regulate cell growth and cellular responses to stress. Here we report the crystal structure of the PP5 catalytic domain (PP5c) at a resolution of 1.6 A. From this structure we resolved the mechanism for PP5-mediated hydrolysis of phosphoprotein substrates, which requires the precise positioning of two metal ions within a con served Aspn-271-M(sub 1):M(sub 2)-W(sup 1)-His-427-His-304-Asp-274 catalytic motif. The structure of PPSc provides a structural basis for explaining the exceptional catalytic proficiency of protein phosphatases, which are among the most powerful known catalysts. Resolution of the entire C-terminus revealed a novel subdomain, and the structure of the PP5c should also aid development of type-specific inhibitors.

  16. High resolution study of the H+D 2 → HD+D reaction dynamics at a collision energy of 2.2 eV

    Science.gov (United States)

    Wrede, E.; Schnieder, L.; Welge, K. H.; Aoiz, F. J.; Bañares, L.; Herrero, V. J.

    1997-01-01

    The reactivity of H + D 2( v = 0, j = 0) → HD( v', j') + D has been investigated in a high resolution crossed molecular beam experiment at a collision energy of 2.2 eV. Time-of-flight (TOF) spectra of D atoms at different laboratory (LAB) scattering angles and their total angular distribution were measured using the technique of Rydberg atom TOF spectroscopy. The resolution of this technique allows the identification of individual rovibrational states of the corresponding HD product molecule at the different LAB angles. A detailed simulation of the experimental measurements has been performed by using state resolved differential cross sections from quasiclassical trajectory (QCT) calculations on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) and on the double-many-body-expansion (DMBE) potential energy surfaces (PES). A general good agreement between experiment and theory is found, although there are some discrepancies which are discussed.

  17. Linking benthic dynamics and cold-water coral occurrences: A high-resolution model study at three carbonate mound provinces in the NE Atlantic

    OpenAIRE

    2012-01-01

    We used the 3-D ocean circulation model with grid refinement ROMS-AGRIF to describe the hydrodynamic conditions at three cold-water coral provinces in the NE Atlantic (Logachev Mounds, Arc Mounds and Belgica Mounds). Modelled fields of currents, temperature and salinity were analysed for observed occurrences and presence/absence of living coral frameworks, living coral colonies within each province. The central model grid has a horizontal resolution of approximately 250 m, except for the Arc ...

  18. Water erosion as a cause for agricultural soil loss: modeling of dynamic processes using high-resolution ground based LiDAR measurements

    Science.gov (United States)

    Oz, Imri; Filin, Sagi; Assouline, Shmuel; Shtain, Zachi; Furman, Alexander

    2016-04-01

    Soil erosion by rainfall and water flow is a frequent natural geomorphic process shaping the earth's surface at various scales. Conventional agrotechnical methods enhance soil erosion at the field scale and are at the origin of the reduction of the upper soil layer depth. This reduction is expressed in two aspects: decrease of soil depth, mainly due to erosion, and the diminution of soil quality, mainly due to the loss of fine material, nutrients and organic matter. Rain events, not even the most extremes, cause detachment and transport of fertile soil rich in organic matter and nutrients away from the fields, filling and plugging drainage channels, blocking infrastructure and contaminating water sources. Empirical, semi-empirical and mechanistic models are available to estimate soil erosion by water flow and sediment transport (e.g. WEPP, KINEROSS, EUROSEM). Calibration of these models requires data measured at high spatial and temporal resolutions. Development of high-resolution measurement tools (for both spatial and temporal aspects) should improve the calibration of functions related to particles detachment and transport from the soil surface. In addition, despite the great impact of different tillage systems on the soil erosion process, the vast majority of the models ignore this fundamental factor. The objective of this study is to apply high-resolution ground-based LiDAR measurements to different tillage schemes and scales to improve the ability of models to accurately describe the process of soil erosion induced by rainfall and overland flow. Ground-based laser scans provide high resolution accurate and subtle geomorphic changes, as well as larger-scale deformations. As such, it allows frequent monitoring, so that even the effect of a single storm can be measured, thus improving the calibration of the erosion models. Preliminary results for scans made in the field show the potential and limitations of ground-based LiDAR, and at this point qualitatively can

  19. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    OpenAIRE

    E. Smit; Creemer, J.F.; Zandbergen, H. W.; Weckhuysen, B. M.; Groot, F.M.F. de

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the...

  20. Unary resolution

    DEFF Research Database (Denmark)

    Aubert, Clément; Bagnol, Marc; Seiller, Thomas

    2016-01-01

    of the cut-elimination procedure of linear logic known as the geometry of interaction . This framework is restricted to terms (logic programs, rewriting rules) using only unary symbols, and this restriction is shown to be complete for polynomial time computation by encoding pushdown automata. Soundness w......We give a characterization of deterministic polynomial time computation based on an algebraic structure called the resolution semiring, whose elements can be understood as logic programs or sets of rewriting rules over first-order terms. This construction stems from an interactive interpretation...

  1. In-situ scanning transmission X-ray microscopy of catalytic materials under reaction conditions

    NARCIS (Netherlands)

    de Smit, E.; Creemer, J.F.; Zandbergen, H.W.; Weckhuysen, B.M.; de Groot, F.M.F.

    2009-01-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant

  2. Chemical imaging of molecular changes in a hydrated single cell by dynamic secondary ion mass spectrometry and super-resolution microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Xin; Szymanski, Craig J.; Wang, Zhaoying; Zhou, Yufan; Ma, Xiang; Yu, Jiachao; Evans, James E.; Orr, Galya; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-05-15

    Chemical imaging of single cells is important in capturing biological dynamics. Single cell correlative imaging is realized between structured illumination microscopy (SIM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) using System for Analysis at the Liquid Vacuum Interface (SALVI), a multimodal microreactor. SIM characterized cells and guided subsequent ToF-SIMS analysis. Dynamic ToF-SIMS provided time- and space-resolved cell molecular mapping. Lipid fragments were identified in the hydrated cell membrane. Principal component analysis was used to elucidate chemical component differences among mouse lung cells that uptake zinc oxide nanoparticles. Our results provided submicron chemical spatial mapping for investigations of cell dynamics at the molecular level.

  3. 动态动力学拆分在手性药物合成中的应用%Application of Dynamic Kinetic Resolution in the Preparation of Chiral Drugs

    Institute of Scientific and Technical Information of China (English)

    林义; 吕力琼; 黄俊; 蒋成君

    2016-01-01

    动态动力学拆分是合成手性化合物最方便和最有效的方法之一,该方法的主要特征是用酶催化拆分和金属催化原位外消旋化未反应的底物,克服了经典动力学拆分最高产率只有50%的缺陷,理论上可以达到100%的收率。本文概述了动态动力学拆分技术在手性药物合成中的应用。%The dynamic kinetic resolution (DKR) of racemic compounds provides one of the most conve-nient and efficient routes to a wide range of chiral molecules. A key feature of this methodology is the use of metal catalysts for the in situ racemization of enzymatically unreactive enantiomers in the enzymatic resolu-tion of racemic substrates. It overcomes the limitation of the maximum 50% yield in the traditional kinetic resolution. In this way, all of the substrate could be converted into a single product isomer with a 100%theo-retical yield. In this review and the latest research progress as well as the application in preparation of chiral drugs are also presented.

  4. High-Resolution Dynamical Downscaling of ERA-Interim Using the WRF Regional Climate Model for the Area of Poland. Part 1: Model Configuration and Statistical Evaluation for the 1981-2010 Period

    Science.gov (United States)

    Kryza, Maciej; Wałaszek, Kinga; Ojrzyńska, Hanna; Szymanowski, Mariusz; Werner, Małgorzata; Dore, Anthony J.

    2017-02-01

    In this work, we present the results of high-resolution dynamical downscaling of air temperature, relative humidity, wind speed and direction, for the area of Poland, with the Weather Research and Forecasting (WRF) model. The model is configured using three nested domains, with spatial resolution of 45 km × 45 km, 15 km × 15 km and 5 km × 5 km. The ERA-Interim database is used for boundary conditions. The results are evaluated by comparison with station measurements for the period 1981-2010. The model is capable of reproducing the main climatological features of the study area. The results are in very close agreement with the measurements, especially for the air temperature. For all four meteorological variables, the model performance captures seasonal and daily cycles. For the air temperature and winter season, the model underestimates the measurements. For summer, the model shows higher values, compared with the measurements. The opposite is the case for relative humidity. There is a strong diurnal pattern in mean error, which changes seasonally. The agreement with the measurements is worse for the seashore and mountain areas, which suggests that the 5 km × 5 km grid might still have an insufficient spatial resolution. There is no statistically significant temporal trend in the model performance. The larger year-to-year changes in the model performance, e.g. for the years 1982 and 2010 for the air temperature should therefore be linked with the natural variability of meteorological conditions.

  5. 260 frames-per-second 648x488 resolution division-of-focal-plane polarimeter with structural dynamics and tracking applications.

    Science.gov (United States)

    York, Timothy; Marinov, Radoslav; Gruev, Viktor

    2016-04-18

    We have designed an image sensor that can capture the first three Stokes parameters at 648 by 488 spatial resolution at 260 frames per second. The sensor consists of a CCD image sensor monolithically integrated with pixel pitch-matched aluminum nanowire polarization filters. The sensor demonstrates a Malus law response over all pixels, and has a relatively uniform diattenuation over the visible spectrum. We demonstrate two potential applications for the sensor. The first uses circular polarization in transmission mode to observe high-speed stress failure in polycarbonate. The second uses polarization in reflected mode to track high speed automobile traffic.

  6. High-resolution multi-proxy reconstruction of Lake Ighiel (Western Carpathians, Romania): processes and controlling factors of lacustrine dynamics during the mid and late Holocene

    Science.gov (United States)

    Haliuc, Aritina; Veres, Daniel; Hubay, Katalin; Begy, Robert; Brauer, Achim; Hutchinson, Simon; Braun, Mihaly

    2016-04-01

    Concerns about current and prospective environmental change have increased the interest in past climate variability and its impact on the bio-hydro-atmosphere and human society. Acting as high-resolution terrestrial archives, lacustrine sediments are the result of the complex interaction between internal and external forcing and an important tool in efforts to resolve questions related to the palaeoclimatic and palaeoenvironmental conditions of the recent past. Here we discuss a new, high-resolution sedimentary record from the Romanian Carpathians (central-eastern Europe). Lake Ighiel (46° 10'50"N, 23° 22'00"E) is a small lake located in a mid-altitude mountain belt (Trascau Mountains) at an altitude of 924 m ( lake maximum depth 9 m; catchment area 487 ha). We employ detailed 210Pb and 14C dating coupled with high-resolution X-ray fluorescence scanning (μ-XRF) measurements, long-core sedimentary logging, environmental magnetic proxies (susceptibility, natural and induced remanences) in an attempt to trace the 6000 years evolution of lake-catchment system. More specifically, we discuss: i) the temporal evolution of the main sedimentation phases of the lake based on sedimentological, geochemical and magnetic proxies; ii) the amplitude and interplay of processes (natural and/or anthropogenic) controlling the depositional environment through time; iii) assess the contribution of each controlling factors and reconstruct the evolution of lacustrine system and palaeoclimate forcing using multivariate statistics. The sedimentary record can be divided into six phases based on alternating high and low detrital fluxes, oscillating lacustrine productivity and redox conditions. A series of detrital events (5200; 4800; 5400; 5250; 4500; 4050; 3800; 3500; 3250; 3050; 2650; 2350; 2250; 1400; 1100; 500; 100 cal yr BP) were identified by microfacies analyses and X-ray fluorescence scanning (μ-XRF) analysis. These events are reflected in most of the parameters and appear

  7. Shape tailored green synthesis and catalytic properties of gold nanocrystals.

    Science.gov (United States)

    Rajan, Anish; MeenaKumari, M; Philip, Daizy

    2014-01-24

    The use of environmentally benign procedures is highly desirable for the synthesis of nanoparticles. Here we report a simple, versatile, economic, ecofriendly and reproducible green method for the size-tunable synthesis of stable and crystalline gold nanoparticles of varied shape using aqueous extract of Garcinia Combogia fruit. The predominant anisotropic nature in the morphology of synthesized particles at lower quantities of extract gradually shifted to spherical particles with larger quantity of extract and increase of temperature. The onset of reduction, the time-evolution of the Surface Plasmon Resonance (SPR) and the catalytic activity are studied using UV-Visible spectroscopy. The Selected Area Diffraction (SAED) pattern, the lattice fringes in the High Resolution Transmission Electron Microscopic (HRTEM) image and the X-ray Diffraction (XRD) pattern clearly show the pure crystalline nature of the synthesized gold nanoparticles. The role of carboxyl group present in Garcinia Combogia fruit extract in the reduction of chloroaurate ions is established using Fourier Transform Infrared (FTIR) spectra. The size dependent catalytic activity of the green synthesized gold nanoparticles on the reduction of 4-Nitrophenol to 4-Aminophenol using sodium borohydride is studied and reported for the first time. The first order kinetics is fitted and rate constants are calculated. Catalytically active green synthesized gold nanoparticles with controllable size and shape presents an advanced step in future biomedical and chemical applications.

  8. Current use pesticide and legacy organochlorine pesticide dynamics at the ocean-sea ice-atmosphere interface in resolute passage, Canadian Arctic, during winter-summer transition.

    Science.gov (United States)

    Pućko, Monika; Stern, Gary A; Burt, Alexis E; Jantunen, Liisa M; Bidleman, Terry F; Macdonald, Robie W; Barber, David G; Geilfus, Nicolas-X; Rysgaard, Søren

    2017-02-15

    Here, we present the first detailed analysis of processes by which various current use pesticides (CUPs) and legacy organochlorine pesticides (OCPs) are concentrated in melt ponds that form on Arctic sea ice in the summer, when surface snow is melting and ice eventually breaks up. Four current use pesticides (dacthal, chlorpyrifos, trifluralin, and pentachloronitrobenzene) and one legacy organochlorine pesticide (α-hexachlorocyclohexane) were detected in ponds in Resolute Passage, Canadian Arctic, in 2012. Melt-pond concentrations changed over time as a function of gas exchange, precipitation, and dilution with melting sea ice. Observed increases in melt-pond concentrations for all detected pesticides were associated with precipitation events. Dacthal reached the highest concentration of all current use pesticides in ponds (95±71pgL(-1)), a value exceeding measured concentrations in the under-ice (0m) and 5m seawater by >10 and >16 times, respectively. Drainage of dacthal-enriched pond water to the ocean during ice break-up provides an important ice-mediated annual delivery route, adding ~30% of inventory in the summer Mixed Layer (ML; 10m) in the Resolute Passage, and a concentrating mechanism with potential implications for exposures to organisms such as ice algae, and phytoplankton.

  9. Catalyst dynamics: consequences for classical kinetic descriptions of reactors

    DEFF Research Database (Denmark)

    Johannessen, Tue; Larsen, Jane Hvolbæk; Chorkendorff, Ib

    2001-01-01

    The modelling of catalytic reactions/reactors has undergone great improvements since the introduction of empirical power-law kinetics in chemical reaction engineering and micro-kinetic models based on insight into the nature of elementary steps have appeared for many reactions. However, recent...... of the dynamical behaviour of some catalytic systems and discuss the corresponding Limitations in existing models for catalytic reactions and reactors. Catalytic reactors operated in non-steady-state are becoming more frequent in industry. The additional efforts needed to accurately simulate these types...... of reactors are discussed. Finally, we discuss the role of computational fluid dynamics (CFD) as a tool for detailed simulation of catalytic reactors....

  10. 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

  11. 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.

  12. 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...

  13. HIRES the high-resolution spectrograph for the E-ELT: dynamics and control of the repositioning mechanism for the E-ELT HIRES polarimeter

    Science.gov (United States)

    Di Varano, I.; Strassmeier, K. G.; Woche, M.

    2016-08-01

    A full Stokes dual channel polarimeter for the E-ELT HIRES spectrograph has been envisioned for the intermediate focus f/4.4, operating within a spectral range of 0.4-1.6 μ. It will feed the EELT- HIRES instrument located on the Nasmyth platform via two pairs of dedicated fibers: one fibre pair optimized for the BVRI, the other one optimized for the JH band or any other feasible combination. The instrument must be retractable within a workspace in fulfillment with the ESO requirements on the allocated volume and the dynamic response of the AO tower. For such purpose a swinging arm has been designed with a rotation provided by 5 revolute joints and a jackscrew. Moreover repeatability in repositioning has to be guaranteed by a parallel manipulator, performing an alignment procedure mainly along 5 axes. Dynamics and control criteria with a feed forward chain to compensate for vibration forces and feedback chain for tracking procedure are hereafter presented.

  14. An Efficient Single-Molecule Resolution Method for Simulating Spatio-Temporal Dynamics of Protein Interaction Networks that Involve the Cell Membranes

    Science.gov (United States)

    Yogurtcu, Osman N.; Johnson, Margaret E.

    A significant number of the cellular protein interaction networks, such as the receptor mediated signaling and vesicle trafficking pathways, includes membranes as a molecular assembly platform. Computer simulations can provide insight into the dynamics of complex formation and help identify the principles that govern recruitment and assembly on the membranes. Here, we introduce the Free-Propagator Re-weighting (FPR) algorithm, a recently developed method that efficiently simulates the spatio-temporal dynamics of multiprotein complex formation both in the solution and on the membranes. In the FPR, the position of each protein is propagated using the Brownian motion and the reactions between pairs of proteins can occur upon collisions. Depending on the dimensionality of the interaction, the association probabilities are determined by solving the Smoluchowski diffusion equations in 2D or 3D and trajectory reweighting allows us to obtain the exact association rates for all the reactive pairs. Using the FPR, in this presentation, we investigate the interaction dynamics of the receptor mediated endocytic network as a case study and discuss the possible effects of membrane binding and molecular crowding on the formation of complexes. Supported by the NIGMS/NIH under R00GM098371.

  15. 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.

  16. 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...

  17. 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...

  18. Assessing resolution in super-resolution imaging.

    Science.gov (United States)

    Demmerle, Justin; Wegel, Eva; Schermelleh, Lothar; Dobbie, Ian M

    2015-10-15

    Resolution is a central concept in all imaging fields, and particularly in optical microscopy, but it can be easily misinterpreted. The mathematical definition of optical resolution was codified by Abbe, and practically defined by the Rayleigh Criterion in the late 19th century. The limit of conventional resolution was also achieved in this period, and it was thought that fundamental constraints of physics prevented further increases in resolution. With the recent development of a range of super-resolution techniques, it is necessary to revisit the concept of optical resolution. Fundamental differences in super-resolution modalities mean that resolution is not a directly transferrable metric between techniques. This article considers the issues in resolution raised by these new technologies, and presents approaches for comparing resolution between different super-resolution methods.

  19. 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).

  20. 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.)

  1. New insight into the dynamic properties and the active site architecture of H-Ras p21 revealed by X-ray crystallography at very high resolution

    Directory of Open Access Journals (Sweden)

    Klink Björn U

    2010-10-01

    Full Text Available Abstract Background In kinetic crystallography, the usually static method of X-ray diffraction is expanded to allow time-resolved analysis of conformational rearrangements in protein structures. To achieve this, reactions have to be triggered within the protein crystals of interest, and optical spectroscopy can be used to monitor the reaction state. For this approach, a modified form of H-Ras p21 was designed which allows reaction initiation and fluorescence readout of the initiated GTPase reaction within the crystalline state. Rearrangements within the crystallized protein due to the progressing reaction and associated heterogeneity in the protein conformations have to be considered in the subsequent refinement processes. Results X-ray diffraction experiments on H-Ras p21 in different states along the reaction pathway provide detailed information about the kinetics and mechanism of the GTPase reaction. In addition, a very high data quality of up to 1.0 Å resolution allowed distinguishing two discrete subconformations of H-Ras p21, expanding the knowledge about the intrinsic flexibility of Ras-like proteins, which is important for their function. In a complex of H-Ras•GppNHp (guanosine-5'-(β,γ-imido-triphosphate, a second Mg2+ ion was found to be coordinated to the γ-phosphate group of GppNHp, which positions the hydrolytically active water molecule very close to the attacked γ-phosphorous atom. Conclusion For the structural analysis of very high-resolution data we have used a new 'two-chain-isotropic-refinement' strategy. This refinement provides an alternative and easy to interpret strategy to reflect the conformational variability within crystal structures of biological macromolecules. The presented fluorescent form of H-Ras p21 will be advantageous for fluorescence studies on H-Ras p21 in which the use of fluorescent nucleotides is not feasible.

  2. The short-chain oxidoreductase Q9HYA2 from Pseudomonas aeruginosa PAO1 contains an atypical catalytic center.

    Science.gov (United States)

    Huether, Robert; Mao, Qilong; Duax, William L; Umland, Timothy C

    2010-05-01

    The characteristic oxidation or reduction reaction mechanisms of short-chain oxidoreductase (SCOR) enzymes involve a highly conserved Asp-Ser-Tyr-Lys catalytic tetrad. The SCOR enzyme Q9HYA2 from the pathogenic bacterium Pseudomonas aeruginosa was recognized to possess an atypical catalytic tetrad composed of Lys118-Ser146-Thr159-Arg163. Orthologs of Q9HYA2 containing the unusual catalytic tetrad along with conserved substrate and cofactor recognition residues were identified in 27 additional species, the majority of which are bacterial pathogens. However, this atypical catalytic tetrad was not represented within the Protein Data Bank. The crystal structures of unligated and NADPH-complexed Q9HYA2 were determined at 2.3 A resolution. Structural alignment to a polyketide ketoreductase (KR), a typical SCOR, demonstrated that Q9HYA2's Lys118, Ser146, and Arg163 superimposed upon the KR's catalytic Asp114, Ser144, and Lys161, respectively. However, only the backbone of Q9HYA2's Thr159 overlapped KR's catalytic Tyr157. The Thr159 hydroxyl in apo Q9HYA2 is poorly positioned for participating in catalysis. In the Q9HYA2-NADPH complex, the Thr159 side chain was modeled in two alternate rotamers, one of which is positioned to interact with other members of the tetrad and the bound cofactor. A chloride ion is bound at the position normally occupied by the catalytic tyrosine hydroxyl. The putative active site of Q9HYA2 contains a chemical moiety at each catalytically important position of a typical SCOR enzyme. This is the first observation of a SCOR protein with this alternate catalytic center that includes threonine replacing the catalytic tyrosine and an ion replacing the hydroxyl moiety of the catalytic tyrosine.

  3. Generalized Resolution and NC—Resolution

    Institute of Scientific and Technical Information of China (English)

    刘叙华; 孙吉贵

    1994-01-01

    The relation between generalized resolution and NC-resolution is discussed.The proof of the completeness of NC linear resolution is then given.The incompleteness of NC lock resolution is also presented,thus the conclusion in [3] of “a simple completeness-preserving restriction” is shown to be wrong.

  4. Computational design of chemically propelled catalytic nanorotors.

    Science.gov (United States)

    Chen, Yanping; Shi, Yunfeng

    2013-08-14

    We designed catalytic nanorotors and investigated the rotational motion and energy conversion efficiency using reactive molecular dynamics in two dimensions. First, a two-arm nanorotor was constructed by decorating a slender beam with catalysts asymmetrically on its two long edges, while fixing the beam center as the rotational axis. Autonomous rotation was observed for the two-arm nanorotor immersing in a fuel environment. Here fuel molecules undergo exothermic combination reaction facilitated by the catalysts. It was found that the angular velocity increases with the catalyst coverage parabolically, while the rotary nanomotor efficiency stays roughly constant. These observations are consistent with a single-collision-momentum-transfer-based propulsion model. Furthermore, multi-arm nanorotors (up to eight arms) were constructed by carving radially distributed arms followed by decorating catalysts. For multi-arm nanorotors, both the angular velocity and the efficiency decrease as the number of arms increases. These behaviors contradict the aforementioned model, which are likely due to the deceleration from secondary collisions between products and the nanorotor arms. Our simulation results show that the optimal design for a nanorotor that maximizes its angular velocity and the motor efficiency is a two-arm nanorotor with nearly full coverage of catalysts.

  5. Measuring Hg and MeHg fluxes from dynamic systems using high resolution in situ monitoring - case study: the Sacramento-San Joaquin Delta

    Science.gov (United States)

    Fleck, J. A.; Bergamaschi, B. A.; Downing, B. D.; Lionberger, M. A.; Schoellhamer, D.; Boss, E.; Heim, W.; Stephenson, M.

    2006-12-01

    Quantifying net loads in tidal systems is difficult, time consuming, and often very expensive. Owing to the relatively rapid nature of tidal exchange, numerous measurements are required in a brief amount of time to accurately quantify constituent fluxes between a tidal wetland and its surrounding waters. Further complicating matters, the differences in chemical concentrations of a constituent between the flood and ebb tides are often small, so that the net export of the constituent is orders of magnitude smaller than the bulk exchange in either direction over the tidal cycle. Thus, high-resolution sampling coupled with high-sensitivity instruments over an adequate amount of time is required to accurately determine a net flux. These complications are exacerbated for mercury species because of the difficulties related to clean sampling and trace-level analysis. The USGS currently is collecting data to determine the fluxes of total mercury (Hg) and methyl-Hg (MeHg) in dissolved and particulate phases at Browns Island in the San Francisco Bay-Delta, a tidally influenced estuarine system. Our field deployment package consists of an upward-looking current profiler to quantify water flux, and an array of other instruments measuring the following parameters: UV absorption, DO, pH, salinity, temperature, water depth, optical backscatter, fluorescence, and spectral attenuation. Measurements are collected at 30-minute intervals for seasonal, month-long deployments in the main slough of Brown's Island. We infer Hg and MeHg concentrations by using multivariate analysis of spectral absorbance and fluorescence properties of the continuous measurements, and comparing them to those of discrete samples taken hourly over a 25-hour tidal cycle for each deployment. Preliminary results indicate that in situ measurements can be used to predict MeHg concentrations in a tidal wetland slough in both the filtered (r2=0.96) and unfiltered (r2=0.95) fractions. Despite seasonal differences in

  6. Ultrafast supercontinuum fiber-laser based pump-probe scanning MOKE microscope for the investigation of electron spin dynamics in semiconductors at cryogenic temperatures with picosecond time and micrometer spatial resolution

    CERN Document Server

    Henn, T; Ossau, W; Molenkamp, L W; Biermann, K; Santos, P V

    2013-01-01

    We describe a two-color pump-probe scanning magneto-optical Kerr effect (MOKE) microscope which we have developed to investigate electron spin phenomena in semiconductors at cryogenic temperatures with picosecond time and micrometer spatial resolution. The key innovation of our microscope is the usage of an ultrafast `white light' supercontinuum fiber-laser source which provides access to the whole visible and near-infrared spectral range. Our Kerr microscope allows for the independent selection of the excitation and detection energy while avoiding the necessity to synchronize the pulse trains of two separate picosecond laser systems. The ability to independently tune the pump and probe wavelength enables the investigation of the influence of excitation energy on the optically induced electron spin dynamics in semiconductors. We demonstrate picosecond real-space imaging of the diffusive expansion of optically excited electron spin packets in a (110) GaAs quantum well sample to illustrate the capabilities of t...

  7. PKS 1502+106: A high-redshift Fermi blazar at extreme angular resolution. Structural dynamics with VLBI imaging up to 86 GHz

    CERN Document Server

    Karamanavis, V; Krichbaum, T P; Angelakis, E; Hodgson, J; Nestoras, I; Myserlis, I; Zensus, J A; Sievers, A; Ciprini, S

    2016-01-01

    Context. Blazars are among the most energetic objects in the Universe. In 2008 August, Fermi/LAT detected the blazar PKS 1502+106 showing a rapid and strong gamma-ray outburst followed by high and variable flux over the next months. This activity at high energies triggered an intensive multi-wavelength campaign covering also the radio, optical, UV, and X-ray bands indicating that the flare was accompanied by a simultaneous outburst at optical/UV/X-rays and a delayed outburst at radio bands. Aims: In the current work we explore the phenomenology and physical conditions within the ultra-relativistic jet of the gamma-ray blazar PKS 1502+106. Additionally, we address the question of the spatial localization of the MeV/GeV-emitting region of the source. Methods: We utilize ultra-high angular resolution mm-VLBI observations at 43 and 86 GHz complemented by VLBI observations at 15 GHz. We also employ single-dish radio data from the F-GAMMA program at frequencies matching the VLBI monitoring. Results: PKS 1502+106 sh...

  8. Holocene Amazon rainforest-savanna dynamics and climatic implications: high-resolution pollen record from Laguna Loma Linda in eastern Colombia

    Science.gov (United States)

    Behling, Hermann; Hooghiemstra, Henry

    2000-10-01

    We present a high-resolution pollen record of a 695-cm-long sediment core from Laguna Loma Linda, located at an altitude of 310 m in the transitional zone between the savannas of the Llanos Orientales and the Amazonian rainforest, about 100 km from the Eastern Cordillera. Based on eight AMS 14C ages, the record represents the last 8700 14C yr BP. During the period from 8700 to 6000 14C yr BP the vegetation was dominated by grass savanna with only a few woody taxa, such as Curatella and Byrsonima, present in low abundance. Gallery forest along the drainage system apparently was poorly developed. Compared with today, precipitation must have been significantly lower and seasonality stronger. During the period from 6000 to 3600 14C yr BP, rainforest taxa increased markedly, reflecting an increase in precipitation. Rainforest and gallery forest taxa such as Moraceae/Urticaceae, Melastomataceae, Alchornea, Cecropia and Acalypha, were abundant, whereas Poaceae were reduced in frequency. From 3600 to 2300 14C yr BP rainforest taxa continued to increase; Moraceae/Urticaceae became very frequent, and Myrtaceae and Myrsine became common. Savanna vegetation decreased continuously. We infer that precipitation was still increasing, and that the length of the annual dry period possibly shortened. From 2300 14C yr BP onwards, grass savanna (mainly represented by Poaceae) expanded and Mauritia palms became frequent. This reflects increased human impact on the vegetation.

  9. High-temporospatial-resolution dynamic contrast-enhanced (DCE) wrist MRI with variable-density pseudo-random circular Cartesian undersampling (CIRCUS) acquisition: evaluation of perfusion in rheumatoid arthritis patients.

    Science.gov (United States)

    Liu, Jing; Pedoia, Valentina; Heilmeier, Ursula; Ku, Eric; Su, Favian; Khanna, Sameer; Imboden, John; Graf, Jonathan; Link, Thomas; Li, Xiaojuan

    2016-01-01

    This study is to evaluate highly accelerated three-dimensional (3D) dynamic contrast-enhanced (DCE) wrist MRI for assessment of perfusion in rheumatoid arthritis (RA) patients. A pseudo-random variable-density undersampling strategy, circular Cartesian undersampling (CIRCUS), was combined with k-t SPARSE-SENSE reconstruction to achieve a highly accelerated 3D DCE wrist MRI. Two healthy volunteers and 10 RA patients were studied. Two patients were on methotrexate (MTX) only (Group I) and the other eight were treated with a combination therapy of MTX and anti-tumor necrosis factor (TNF) therapy (Group II). Patients were scanned at baseline and 3 month follow-up. DCE MR images were used to evaluate perfusion in synovitis and bone marrow edema pattern in the RA wrist joints. A series of perfusion parameters was derived and compared with clinical disease activity scores of 28 joints (DAS28). 3D DCE wrist MR images were obtained with a spatial resolution of 0.3 × 0.3 × 1.5 mm(3) and temporal resolution of 5 s (with an acceleration factor of 20). The derived perfusion parameters, most notably transition time (dT) of synovitis, showed significant negative correlations with DAS28-ESR (r = -0.80, p perfusion in RA joints, showing promise as a potential tool for evaluating treatment responses.

  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. 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.

  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. 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.

  14. Dynamic gauge adjustment of high-resolution X-band radar data for convective rain storms: Model-based evaluation against measured combined sewer overflow

    DEFF Research Database (Denmark)

    Borup, Morten; Grum, Morten; Linde, Jens Jørgen

    2016-01-01

    , well defined, 64 ha urban catchment, for nine overflow generating rain events. The dynamically adjusted radar data perform best when the aggregation period is as small as 10–20 min, in which case it performs much better than static adjusted radar data and data from rain gauges situated 2–3 km away.......Numerous studies have shown that radar rainfall estimates need to be adjusted against rain gauge measurements in order to be useful for hydrological modelling. In the current study we investigate if adjustment can improve radar rainfall estimates to the point where they can be used for modelling...... overflows from urban drainage systems, and we furthermore investigate the importance of the aggregation period of the adjustment scheme. This is done by continuously adjusting X-band radar data based on the previous 5–30 min of rain data recorded by multiple rain gauges and propagating the rainfall...

  15. Tracking Land Use/Land Cover Dynamics in Cloud Prone Areas Using Moderate Resolution Satellite Data: A Case Study in Central Africa

    Directory of Open Access Journals (Sweden)

    Bikash Basnet

    2015-05-01

    Full Text Available Tracking land surface dynamics over cloud prone areas with complex mountainous terrain is an important challenge facing the Earth Science community. One such region is the Lake Kivu region in Central Africa. We developed a processing chain to systematically monitor the spatio-temporal land use/land cover dynamics of this region over the years 1988, 2001, and 2011 using Landsat data, complemented by ancillary data. Topographic compensation was performed on Landsat reflectances to avoid the strong illumination angle impacts and image compositing was used to compensate for frequent cloud cover and thus incomplete annual data availability in the archive. A systematic supervised classification was applied to the composite Landsat imagery to obtain land cover thematic maps with overall accuracies of 90% and higher. Subsequent change analysis between these years found extensive conversions of the natural environment as a result of human related activities. The gross forest cover loss for 1988–2001 and 2001–2011 period was 216.4 and 130.5 thousand hectares, respectively, signifying significant deforestation in the period of civil war and a relatively stable and lower deforestation rate later, possibly due to conservation and reforestation efforts in the region. The other dominant land cover changes in the region were aggressive subsistence farming and urban expansion displacing natural vegetation and arable lands. Despite limited data availability, this study fills the gap of much needed detailed and updated land cover change information for this biologically important region of Central Africa. These multi-temporal datasets will be a valuable baseline for land use managers in the region interested in developing ecologically sustainable land management strategies and measuring the impacts of biodiversity conservation efforts.

  16. Low temperature catalytic combustion of natural gas - hydrogen - air mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Newson, E.; Roth, F. von; Hottinger, P.; Truong, T.B. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The low temperature catalytic combustion of natural gas - air mixtures would allow the development of no-NO{sub x} burners for heating and power applications. Using commercially available catalysts, the room temperature ignition of methane-propane-air mixtures has been shown in laboratory reactors with combustion efficiencies over 95% and maximum temperatures less than 700{sup o}C. After a 500 hour stability test, severe deactivation of both methane and propane oxidation functions was observed. In cooperation with industrial partners, scaleup to 3 kW is being investigated together with startup dynamics and catalyst stability. (author) 3 figs., 3 refs.

  17. Sediment Dynamics and the Burial and Exhumation of Bedrock Reefs as Elucidated by High-resolution Repetitive Sonar Surveys: Northern Monterey Bay, CA

    Science.gov (United States)

    Storlazzi, C. D.; Fregoso, T. A.; Golden, N. E.; Finlayson, D. P.

    2011-12-01

    Two high-resolution bathymetric and acoustic backscatter sonar surveys were conducted along the energetic emergent inner shelf of northern Monterey Bay, CA, USA, in the fall of 2005 and the spring of 2006 to determine the impact of winter storm waves, beach erosion, and river floods on biologically-important bedrock reef habitats. The surveys extended from water depths of 4 m to 22 m and covered an area of 3.14 km2, of which 45.8% was bedrock, gravel, and coarse-grained sand and 54.2% was fine-grained sand. Our analysis of the bathymetric and acoustic backscatter data demonstrates that during the 6 months between surveys, 11.4% of the study area was buried by fine-grained sand while erosion exposed of bedrock or coarse-grained sand over 26.5% of the study area. The probability of burial decreased with increasing water depth and rugosity; the probability of exhumation increased with increasing seabed slope and rugosity. Much of the detected change was at the boundary between bedrock and unconsolidated sediment due to burial or exhumation of bedrock. In a number of cases, however, the change in seabed character was apparently due to fluctuations in sediment grain size, where scour exposed what appeared to be an underlying coarser-grained lag or fine-grained sand buried coarser-grained sand. These findings suggest that, in some places, (a) single acoustic surveys typically employed for geologic characterization and/or habitat mapping may not adequately characterize the geomorphology and sedimentologic nature of rocky, energetic inner shelves, and (b) burial and exhumation likely play a role in the life history of the numerous organisms that inhabit these reefs and thus information on the frequency and magnitude of such processes may better constrain our understanding of physical controls on benthic species' distribution patterns.

  18. Actively heated high-resolution fiber-optic-distributed temperature sensing to quantify streambed flow dynamics in zones of strong groundwater upwelling

    Science.gov (United States)

    Briggs, Martin A.; Buckley, Sean F.; Bagtzoglou, Amvrossios C.; Werkema, Dale D.; Lane, John W.

    2016-07-01

    Zones of strong groundwater upwelling to streams enhance thermal stability and moderate thermal extremes, which is particularly important to aquatic ecosystems in a warming climate. Passive thermal tracer methods used to quantify vertical upwelling rates rely on downward conduction of surface temperature signals. However, moderate to high groundwater flux rates (>-1.5 m d-1) restrict downward propagation of diurnal temperature signals, and therefore the applicability of several passive thermal methods. Active streambed heating from within high-resolution fiber-optic temperature sensors (A-HRTS) has the potential to define multidimensional fluid-flux patterns below the extinction depth of surface thermal signals, allowing better quantification and separation of local and regional groundwater discharge. To demonstrate this concept, nine A-HRTS were emplaced vertically into the streambed in a grid with ˜0.40 m lateral spacing at a stream with strong upward vertical flux in Mashpee, Massachusetts, USA. Long-term (8-9 h) heating events were performed to confirm the dominance of vertical flow to the 0.6 m depth, well below the extinction of ambient diurnal signals. To quantify vertical flux, short-term heating events (28 min) were performed at each A-HRTS, and heat-pulse decay over vertical profiles was numerically modeled in radial two dimension (2-D) using SUTRA. Modeled flux values are similar to those obtained with seepage meters, Darcy methods, and analytical modeling of shallow diurnal signals. We also observed repeatable differential heating patterns along the length of vertically oriented sensors that may indicate sediment layering and hyporheic exchange superimposed on regional groundwater discharge.

  19. 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

  20. Deterministic methods for the relativistic Vlasov-Maxwell equations and the Van Allen belts dynamics; Methodes deterministes de resolution des equations de Vlasov-Maxwell relativistes en vue du calcul de la dynamique des ceintures de Van Allen

    Energy Technology Data Exchange (ETDEWEB)

    Le Bourdiec, S

    2007-03-15

    Artificial satellites operate in an hostile radiation environment, the Van Allen radiation belts, which partly condition their reliability and their lifespan. In order to protect them, it is necessary to characterize the dynamics of the energetic electrons trapped in these radiation belts. This dynamics is essentially determined by the interactions between the energetic electrons and the existing electromagnetic waves. This work consisted in designing a numerical scheme to solve the equations modelling these interactions: the relativistic Vlasov-Maxwell system of equations. Our choice was directed towards methods of direct integration. We propose three new spectral methods for the momentum discretization: a Galerkin method and two collocation methods. All of them are based on scaled Hermite functions. The scaling factor is chosen in order to obtain the proper velocity resolution. We present in this thesis the discretization of the one-dimensional Vlasov-Poisson system and the numerical results obtained. Then we study the possible extensions of the methods to the complete relativistic problem. In order to reduce the computing time, parallelization and optimization of the algorithms were carried out. Finally, we present 1Dx-3Dv (mono-dimensional for x and three-dimensional for velocity) computations of Weibel and whistler instabilities with one or two electrons species. (author)

  1. Quantum-state resolved reactive scattering at the gas-liquid interface: F +squalane (C30H62) dynamics via high-resolution infrared absorption of nascent HF(v,J)

    Science.gov (United States)

    Zolot, Alexander M.; Dagdigian, Paul J.; Nesbitt, David J.

    2008-11-01

    Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic beam of F atoms [Ecom=0.7(3)kcal/mol] with a continuously refreshed liquid hydrocarbon (squalane) surface under high vacuum conditions. Absolute HF(v,J) product densities are determined by infrared laser absorption spectroscopy, with velocity distributions along the probe axis derived from high resolution Dopplerimetry. Nascent HF(v ⩽3) products are formed in a highly nonequilibrium (inverted) vibrational distribution [⟨Evib⟩=13.2(2)kcal/mol], reflecting insufficient time for complete thermal accommodation with the surface prior to desorption. Colder, but still non-Boltzmann, rotational state populations [⟨Erot⟩=1.0(1)kcal/mol] indicate that some fraction of molecules directly scatter into the gas phase without rotationally equilibrating with the surface. Nascent HF also recoils from the liquid surface with excess translational energy, resulting in Doppler broadened linewidths that increase systematically with internal HF excitation. The data are consistent with microscopic branching in HF-surface dynamics following the reactive event, with (i) a direct reactive scattering fraction of newly formed product molecules leaving the surface promptly and (ii) a trapping desorption fraction that accommodates rotationally (though still not vibrationally) with the bulk liquid. Comparison with analogous gas phase F +hydrocarbon processes reveals that the liquid acts as a partial "heat sink" for vibrational energy flow on the time scale of the chemical reaction event.

  2. Dynamic gauge adjustment of high-resolution X-band radar data for convective rain storms: Model-based evaluation against measured combined sewer overflow

    Science.gov (United States)

    Borup, Morten; Grum, Morten; Linde, Jens Jørgen; Mikkelsen, Peter Steen

    2016-08-01

    Numerous studies have shown that radar rainfall estimates need to be adjusted against rain gauge measurements in order to be useful for hydrological modelling. In the current study we investigate if adjustment can improve radar rainfall estimates to the point where they can be used for modelling overflows from urban drainage systems, and we furthermore investigate the importance of the aggregation period of the adjustment scheme. This is done by continuously adjusting X-band radar data based on the previous 5-30 min of rain data recorded by multiple rain gauges and propagating the rainfall estimates through a hydraulic urban drainage model. The model is built entirely from physical data, without any calibration, to avoid bias towards any specific type of rainfall estimate. The performance is assessed by comparing measured and modelled water levels at a weir downstream of a highly impermeable, well defined, 64 ha urban catchment, for nine overflow generating rain events. The dynamically adjusted radar data perform best when the aggregation period is as small as 10-20 min, in which case it performs much better than static adjusted radar data and data from rain gauges situated 2-3 km away.

  3. Dimerization interface of 3-hydroxyacyl-CoA dehydrogenase tunes the formation of its catalytic intermediate.

    Directory of Open Access Journals (Sweden)

    Yingzhi Xu

    Full Text Available 3-Hydroxyacyl-CoA dehydrogenase (HAD, EC 1.1.1.35 is a homodimeric enzyme localized in the mitochondrial matrix, which catalyzes the third step in fatty acid β-oxidation. The crystal structures of human HAD and subsequent complexes with cofactor/substrate enabled better understanding of HAD catalytic mechanism. However, numerous human diseases were found related to mutations at HAD dimerization interface that is away from the catalytic pocket. The role of HAD dimerization in its catalytic activity needs to be elucidated. Here, we solved the crystal structure of Caenorhabditis elegans HAD (cHAD that is highly conserved to human HAD. Even though the cHAD mutants (R204A, Y209A and R204A/Y209A with attenuated interactions on the dimerization interface still maintain a dimerization form, their enzymatic activities significantly decrease compared to that of the wild type. Such reduced activities are in consistency with the reduced ratios of the catalytic intermediate formation. Further molecular dynamics simulations results reveal that the alteration of the dimerization interface will increase the fluctuation of a distal region (a.a. 60-80 that plays an important role in the substrate binding. The increased fluctuation decreases the stability of the catalytic intermediate formation, and therefore the enzymatic activity is attenuated. Our study reveals the molecular mechanism about the essential role of the HAD dimerization interface in its catalytic activity via allosteric effects.

  4. Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

    Directory of Open Access Journals (Sweden)

    Xiaonan Leng

    2015-01-01

    Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

  5. Homology modeling, docking studies and molecular dynamic simulations using graphical processing unit architecture to probe the type-11 phosphodiesterase catalytic site: a computational approach for the rational design of selective inhibitors.

    Science.gov (United States)

    Cichero, Elena; D'Ursi, Pasqualina; Moscatelli, Marco; Bruno, Olga; Orro, Alessandro; Rotolo, Chiara; Milanesi, Luciano; Fossa, Paola

    2013-12-01

    Phosphodiesterase 11 (PDE11) is the latest isoform of the PDEs family to be identified, acting on both cyclic adenosine monophosphate and cyclic guanosine monophosphate. The initial reports of PDE11 found evidence for PDE11 expression in skeletal muscle, prostate, testis, and salivary glands; however, the tissue distribution of PDE11 still remains a topic of active study and some controversy. Given the sequence similarity between PDE11 and PDE5, several PDE5 inhibitors have been shown to cross-react with PDE11. Accordingly, many non-selective inhibitors, such as IBMX, zaprinast, sildenafil, and dipyridamole, have been documented to inhibit PDE11. Only recently, a series of dihydrothieno[3,2-d]pyrimidin-4(3H)-one derivatives proved to be selective toward the PDE11 isoform. In the absence of experimental data about PDE11 X-ray structures, we found interesting to gain a better understanding of the enzyme-inhibitor interactions using in silico simulations. In this work, we describe a computational approach based on homology modeling, docking, and molecular dynamics simulation to derive a predictive 3D model of PDE11. Using a Graphical Processing Unit architecture, it is possible to perform long simulations, find stable interactions involved in the complex, and finally to suggest guideline for the identification and synthesis of potent and selective inhibitors.

  6. In-Situ High-Resolution Transmission Electron Microscopy Investigation of Overheating of Cu Nanoparticles

    Science.gov (United States)

    Chen, Chunlin; Hu, Ziyu; Li, Yanfen; Liu, Limin; Mori, Hirotaro; Wang, Zhangchang

    2016-01-01

    Synthesizing and functionalizing metal nanoparticles supported on substrates is currently the subject of intensive study owing to their outstanding catalytic performances for heterogeneous catalysis. Revealing the fundamental effect of the substrates on metal nanoparticles represents a key step in clarifying mechanisms of stability and catalytic properties of these heterogeneous systems. However, direct identification of these effects still poses a significant challenge due to the complicacy of interactions between substrates and nanoparticles and also for the technical difficulty, restraining our understanding of these heterogeneous systems. Here, we combine in situ high-resolution transmission electron microscopy with molecular dynamics simulations to investigate Cu nanoparticles supported on graphite and Cu2O substrates, and demonstrate that melting behavior and thermal stability of Cu nanoparticles can be markedly influenced by substrates. The graphite-supported Cu nanoparticles do not melt during annealing at 1073 K until they vanish completely, i.e. only the sublimation occurs, while the Cu2O-supported Cu nanoparticles suffer melting during annealing at 973 K. Such selective superheating of the Cu nanoparticles can be attributed to the adsorption of a thin carbon layer on the surface of the Cu nanoparticles, which helps guide further stability enhancement of functional nanoparticles for realistic applications.

  7. 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

  8. Requirements on high resolution detectors

    Energy Technology Data Exchange (ETDEWEB)

    Koch, A. [European Synchrotron Radiation Facility, Grenoble (France)

    1997-02-01

    For a number of microtomography applications X-ray detectors with a spatial resolution of 1 {mu}m are required. This high spatial resolution will influence and degrade other parameters of secondary importance like detective quantum efficiency (DQE), dynamic range, linearity and frame rate. This note summarizes the most important arguments, for and against those detector systems which could be considered. This article discusses the mutual dependencies between the various figures which characterize a detector, and tries to give some ideas on how to proceed in order to improve present technology.

  9. 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.

  10. High-resolution studies of tropolone in the S0 and S1 electronic states: isotope driven dynamics in the zero-point energy levels.

    Science.gov (United States)

    Keske, John C; Lin, Wei; Pringle, Wallace C; Novick, Stewart E; Blake, Thomas A; Plusquellic, David F

    2006-02-21

    Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S(0) and S(1) electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one (18)O and four (13)C isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except (18)O have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric (13)C structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance between the heavy atom and the tunneling proton. In the limit of closest approach, the 0(+) state of (18)O was well fitted to an asymmetric rotor Hamiltonian, reflecting significant changes in the tautomerization dynamics. Comparisons of the substituted atom coordinates with theoretical predictions at the MP2/aug-cc-pVTZ level of theory suggest the localized 0(+) and 0(-) wave functions of the heavier isotopes favor the C-OH and C=O forms of tropolone, respectively. The only exception occurs for the (13)C-OH and (13)C[Double Bond]O structures which correlate to the 0(-) and 0(+) states, respectively. These preferences reflect kinetic isotope effects as quantitatively verified by the calculated zero-point energy differences between members of the asymmetric atom pairs. From rotationally resolved data of the 0(+) <--0(+) and 0(-) <--0(-) bands in S(1), line-shape fits have yielded Lorentzian linewidths that differ by 12.2(16) MHz over the 19.88(4) cm(-1) interval in S(1). The fluorescence decay rates together with previously reported quantum yield data give nonradiative decay rates of 7.7(5) x 10(8) and 8.5(5) x 10(8) s(-1) for the 0(+) and 0(-) levels of the S(1) state of tropolone.

  11. 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.

  12. Crystal Structure of the Catalytic Domain of a Serine Threonine Protein Phosphatase

    Science.gov (United States)

    Swinglel, Mark; Honkanel, Richard; Ciszak, Ewa

    2003-01-01

    Reversible phosphorylation of serine and threonine residues is a well-recognized mechanism in eukaryotic cells for the regulation of cell-cycle progression, cell growth and metabolism. Human serine/threonine phosphatases can be placed into two major families, PPP and PPM. To date the structure on one PPP family member (PPl) has been determined. Here we present the structure of a 323-residue catalytic domain of a second phosphatase belonging to the PPP family of enzyme. catalytic domain of the enzyme has been determined to 1.60Angstrom resolution and refined to R=17.5 and Rfree = 20.8%. The catalytic domain possesses a unique fold consisting of a largely monolithic structure, divisible into closely-associated helical and sheet regions. The catalytic site contains two manganese ions that are involved in substrate binding and catalysis. The enzyme crystallizes as a dimer that completely buries catalytic surfaces of both monomers, Also, the structure shows evidence of some flexibility around the active site cleft that may be related to substrate specificity of this enzyme.

  13. Catalytic removal of carbon monoxide over carbon supported palladium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Avanish Kumar [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Saxena, Amit [Centre for Fire Explosive and Environmental Safety, Timarpur, Delhi-110054 (India); Shah, Dilip; Mahato, T.H. [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Singh, Beer, E-mail: beerbs5@rediffmail.com [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Shrivastava, A.R.; Gutch, P.K. [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Shinde, C.P. [School of Studies in Chemistry, Jiwaji University, Gwalior-474002 (MP) (India)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer Carbon supported palladium (Pd/C) catalyst was prepared. Black-Right-Pointing-Pointer Catalytic removal of CO over Pd/C catalyst was studied under dynamic conditions. Black-Right-Pointing-Pointer Effects of Pd %, CO conc., humidity, GHSV and reaction environment were studied. - Abstract: Carbon supported palladium (Pd/C) catalyst was prepared by impregnation of palladium chloride using incipient wetness technique, which was followed by liquid phase reduction with formaldehyde. Thereafter, Pd/C catalyst was characterized using X-ray diffractometery, scanning electron microscopy, atomic absorption spectroscopy, thermo gravimetry, differential scanning calorimetry and surface characterization techniques. Catalytic removal of carbon monoxide (CO) over Pd/C catalyst was studied under dynamic conditions. Pd/C catalyst was found to be continuously converting CO to CO{sub 2} through the catalyzed reaction, i.e., CO + 1/2O{sub 2} {yields} CO{sub 2}. Pd/C catalyst provided excellent protection against CO. Effects of palladium wt%, CO concentration, humidity, space velocity and reaction environment were also studied on the breakthrough behavior of CO.

  14. 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....

  15. 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.

  16. 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

  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. 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.

  19. 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...

  20. High Resolution Formaldehyde Photochemistry

    Science.gov (United States)

    Ernest, C. T.; Bauer, D.; Hynes, A. J.

    2010-12-01

    Formaldehyde (HCHO) is the most abundant and most important organic carbonyl compound in the atmosphere. The sources of formaldehyde are the oxidation of methane, isoprene, acetone, and other volatile organic compounds (VOCs); fossil fuel combustion; and biomass burning. The dominant loss mechanism for formaldehyde is photolysis which occurs via two pathways: (R1) HCHO + hv → HCO + H (R2) HCHO + hv → H2 + CO The first pathway (R1) is referred to as the radical channel, while the second pathway (R2) is referred to as the molecular channel. The products of both pathways play a significant role in atmospheric chemistry. The CO that is produced in the molecular channel undergoes further oxidation to produce CO2. Under atmospheric conditions, the H atom and formyl radical that are produced in the radical channel undergo rapid reactions with O2 to produce the hydroperoxyl radical (HO2) via (R3) and (R4). (R3) HCO + O2 → HO2 + CO (R4) H + O2 → HO2 Thus, for every photon absorbed, the photolysis of formaldehyde can contribute one CO2 molecule to the global greenhouse budget or two HO2 radicals to the tropospheric HOx (OH + HO2) cycle. The HO2 radicals produced during formaldehyde photolysis have also been implicated in the formation of photochemical smog. The HO2 radicals act as radical chain carriers and convert NO to NO2, which ultimately results in the catalytic production of O3. Constraining the yield of HO2 produced via HCHO photolysis is essential for improving tropospheric chemistry models. In this study, both the absorption cross section and the quantum yield of the radical channel (R1) were measured at high resolution over the tropospherically relevant wavelength range 304-330 nm. For the cross section measurements a narrow linewidth Nd:YAG pumped dye laser was used with a multi-pass cell. Partial pressures of HCHO were kept below 0.3 torr. Simultaneous measurement of OH LIF in a flame allowed absolute calibration of the wavelength scale. Pressure

  1. Crystal structure of the bacteriophage P2 integrase catalytic domain.

    Science.gov (United States)

    Skaar, Karin; Claesson, Magnus; Odegrip, Richard; Högbom, Martin; Haggård-Ljungquist, Elisabeth; Stenmark, Pål

    2015-11-30

    Bacteriophage P2 is a temperate phage capable of integrating its DNA into the host genome by site-specific recombination upon lysogenization. Integration and excision of the phage genome requires P2 integrase, which performs recognition, cleavage and joining of DNA during these processes. This work presents the high-resolution crystal structure of the catalytic domain of P2 integrase, and analysis of the structure-function relationship of several previously identified non-functional P2 integrase mutants. The DNA binding area is characterized by a large positively charged patch, harboring key residues. The structure reveals potential for large dimer flexibility, likely essential for rearrangement of DNA strands upon integration and excision of the phage DNA.

  2. Adsorbent catalytic nanoparticles and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-01-31

    The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

  3. Challenges and Development Opportunities for Catalytic Technologies in Petrochemical Industry in the 21st Century

    Institute of Scientific and Technical Information of China (English)

    CHEN Qing-ling

    2004-01-01

    The propellent drive and development opportunities for future catalytic technologies in petrochemical industry in the 21st century are reviewed in this paper. It focuses on the following five aspects:(1) The environmentally-friendly catalytic technologies, such as new technologies for the production of organic chemicals changing the raw material and synthetic process, the chemicals production replacing phosgene and hydrogen cyanide toxicant, and the conversion and utilization of organic wastes etc.(2) Utilization and development of cheaper light alkanes, for example, the chemical use of natural gas and the development technologies of methane chain, the production of acetic acid, ethylene and vinyl chloride from selective oxidation of ethane, as well as the manufacture of acrolein and acrylonitrile from the oxidation and ammoxidation of propane.(3) The new propylene-plus technologies of the low value higher olefins, such as catalytic cracking of C4,C5 olefins and metathesis of C4 olefin.(4) The technologies of high selective oxidation, e.g. production of propylene oxide with TS-1 molecular sieve, oxidation process by lattice oxygen and direct oxidation of benzene to phenol etc.(5) Development and application of novel catalytic materials, especially, mesopore molecular sieve materials for a larger molecule reaction, zeolite catalyst with MWW structure for alkylation of benzene and propylene, ionic liquid, and membrane reactor catalyst etc.Meanwhile,the challenging research subjects for future industrial catalysis and the several viewpoints for development strategy of new catalytic technologies are proposed. These viewpoints are as follows:(1) Catalysis discipline must be integrated with many other disciplines and should be multidisciplinary and transdisciplinary.(2) New preparation methods of catalytic materials must be originally developed.(3) The instrumentation having better time resolution and spatial resolution and applying under reaction conditions must be

  4. Observing lysozyme's closing and opening motions by high-resolution single-molecule enzymology.

    Science.gov (United States)

    Akhterov, Maxim V; Choi, Yongki; Olsen, Tivoli J; Sims, Patrick C; Iftikhar, Mariam; Gul, O Tolga; Corso, Brad L; Weiss, Gregory A; Collins, Philip G

    2015-06-19

    Single-molecule techniques can monitor the kinetics of transitions between enzyme open and closed conformations, but such methods usually lack the resolution to observe the underlying transition pathway or intermediate conformational dynamics. We have used a 1 MHz bandwidth carbon nanotube transistor to electronically monitor single molecules of the enzyme T4 lysozyme as it processes substrate. An experimental resolution of 2 μs allowed the direct recording of lysozyme's opening and closing transitions. Unexpectedly, both motions required 37 μs, on average. The distribution of transition durations was also independent of the enzyme's state: either catalytic or nonproductive. The observation of smooth, continuous transitions suggests a concerted mechanism for glycoside hydrolysis with lysozyme's two domains closing upon the polysaccharide substrate in its active site. We distinguish these smooth motions from a nonconcerted mechanism, observed in approximately 10% of lysozyme openings and closings, in which the enzyme pauses for an additional 40-140 μs in an intermediate, partially closed conformation. During intermediate forming events, the number of rate-limiting steps observed increases to four, consistent with four steps required in the stepwise, arrow-pushing mechanism. The formation of such intermediate conformations was again independent of the enzyme's state. Taken together, the results suggest lysozyme operates as a Brownian motor. In this model, the enzyme traces a single pathway for closing and the reverse pathway for enzyme opening, regardless of its instantaneous catalytic productivity. The observed symmetry in enzyme opening and closing thus suggests that substrate translocation occurs while the enzyme is closed.

  5. The catalytic mechanism of an aspartic proteinase explored with neutron and X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Kovalevsky, Andrey [Los Alamos National Laboratory (LANL); Erskine, Peter T. [University of Southampton, England; Cooper, Jon [University of Southampton, England

    2008-01-01

    Hydrogen atoms play key roles in enzyme mechanism, but as this study shows, even high-quality X-ray data to a resolution of 1 {angstrom} cannot directly visualize them. Neutron diffraction, however, can locate deuterium atoms even at resolutions around 2 {angstrom}. Both neutron and X-ray diffraction data have been used to investigate the transition state of the aspartic proteinase endothiapepsin. The different techniques reveal a different part of the story, revealing the clearest picture yet of the catalytic mechanism by which the enzyme operates. Room temperature neutron and X-ray diffraction data were used in a newly developed joint refinement software package to visualize deuterium atoms within the active site of the enzyme when a gem-diol transition state analogue inhibitor is bound at the active site. These data were also used to estimate their individual occupancy, while analysis of the differences between the bond lengths of the catalytic aspartates was performed using atomic resolution X-ray data. The two methods are in agreement on the protonation state of the active site with a transition state analogue inhibitor bound confirming the catalytic mechanism at which the enzyme operates.

  6. Measuring hepatic functional reserve using low temporal resolution Gd-EOB-DTPA dynamic contrast-enhanced MRI: a preliminary study comparing galactosyl human serum albumin scintigraphy with indocyanine green retention

    Energy Technology Data Exchange (ETDEWEB)

    Saito, Kazuhiro; Hashimoto, Tsuyoshi; Araki, Yoichi; Akata, Soichi; Tokuuye, Koichi [Tokyo Medical University, Department of Radiology, Tokyo (Japan); Ledsam, Joseph; Sourbron, Steven [University of Leeds, Division of Medical Physics, Leeds (United Kingdom)

    2014-01-15

    To investigate if tracer kinetic modelling of low temporal resolution dynamic contrast-enhanced (DCE) MRI with Gd-EOB-DTPA could replace technetium-99 m galactosyl human serum albumin (GSA) single positron emission computed tomography (SPECT) and indocyanine green (ICG) retention for the measurement of liver functional reserve. Twenty eight patients awaiting liver resection for various cancers were included in this retrospective study that was approved by the institutional review board. The Gd-EOB-DTPA MRI sequence acquired five images: unenhanced, double arterial phase, portal phase, and 4 min after injection. Intracellular contrast uptake rate (UR) and extracellular volume (Ve) were calculated from DCE-MRI, along with the ratio of GSA radioactivity of liver to heart-plus-liver and per cent of cumulative uptake from 15-16 min (LHL15 and LU15, respectively) from GSA-scintigraphy. ICG retention at 15 min, Child-Pugh cirrhosis score (CPS) and postoperative Inuyama fibrosis criteria were also recorded. Statistical analysis was with Spearman rank correlation analysis. Comparing MRI parameters with the reference methods, significant correlations were obtained for UR and LHL15, LU15, ICG15 (all 0.4-0.6, P < 0.05); UR and CPS (-0.64, P < 0.001); Ve and Inuyama (0.44, P < 0.05). Measures of liver function obtained by routine Gd-EOB-DTPA DCE-MRI with tracer kinetic modelling may provide a suitable method for the evaluation of liver functional reserve. (orig.)

  7. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Science.gov (United States)

    de Smit, Emiel; Creemer, J. Fredrik; Zandbergen, Henny W.; Weckhuysen, Bert M.; de Groot, Frank M. F.

    2009-11-01

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  8. In-situ Scanning Transmission X-ray Microscopy of catalytic materials under reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Smit, Emiel de; Weckhuysen, Bert M; Groot, Frank M F de [Inorganic Chemistry and Catalysis group, Debye Institute for Nanomaterials Science, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (Netherlands); Creemer, J Fredrik [DIMES-ECTM, Delft University of Technology, 2600 GB Delft (Netherlands); Zandbergen, Henny W, E-mail: e.desmit@uu.n [Kavli Institute of NanoScience, National Centre for High Resolution Electron Microscopy, Delft University of Technology, 2600 GA Delft (Netherlands)

    2009-11-15

    In-situ Scanning X-ray Transmission Microscopy (STXM) allows the measurement of the soft X-ray absorption spectra with 10 to 30 nm spatial resolution under realistic reaction conditions. We show that STXM-XAS in combination with a micromachined nanoreactor can image a catalytic system under relevant reaction conditions, and provide detailed information on the morphology and composition of the catalyst material. The nanometer resolution combined with powerful chemical speciation by XAS and the ability to image materials under realistic conditions opens up new opportunities to study many chemical processes.

  9. SOFC system with integrated catalytic fuel processing

    Science.gov (United States)

    Finnerty, Caine; Tompsett, Geoff. A.; Kendall, Kevin; Ormerod, R. Mark

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm -2 at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H 2/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack.

  10. SOFC system with integrated catalytic fuel processing

    Energy Technology Data Exchange (ETDEWEB)

    Finnerty, C.; Tompsett, G.A.; Kendall, K.; Ormerod, R.M. [Birchall Centre for Inorganic Chemistry and Materials Science, Keele Univ. (United Kingdom)

    2000-03-01

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm{sup -2} at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H{sub 2}/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack. (orig.)

  11. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    ) surface. Furthermore, STM investigations indicate that the minimum required temperature for CO dissociation on ruthenium is 500 K. The Cu/ZnO model system is created via oxidation and subsequent reduction of size selected CuZn alloy nanoparticles deposited on a rutile TiO2(110) single crystal. Dynamics...... as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....... is investigated. Second the development of a complex Cu/ZnO nanoparticle model system is described and gas-induced dynamical changes in the model system is investigated. The ruthenium crystal serves as an extremely simple model for studying CO dissociation which is the rate limiting step of the methanation...

  12. Catalytic coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Weller, S W

    1981-01-01

    Monolith catalysts of MoO/sub 3/-CoO-Al/sub 2/O/sub 3/ were prepared and tested for coal liquefaction in a stirred autoclave. In general, the monolith catalysts were not as good as particulate catalysts prepared on Corning alumina supports. Measurement of O/sub 2/ chemisorption and BET surface area has been made on a series of Co/Mo/Al/sub 2/O/sub 3/ catalysts obtained from PETC. The catalysts were derived from Cyanamid 1442A and had been tested for coal liquefaction in batch autoclaves and continuous flow units. MoO/sub 3/-Al/sub 2/O/sub 3/ catalysts over the loading range 3.9 to 14.9 wt % MoO/sub 3/ have been studied with respect to BET surface (before and after reduction), O/sub 2/ chemisorption at -78/sup 0/C, redox behavior at 500/sup 0/C, and activity for cyclohexane dehydrogenation at 500/sup 0/C. In connection with the fate of tin catalysts during coal liquefaction, calculations have been made of the relative thermodynamic stability of SnCl/sub 2/, Sn, SnO/sub 2/, and SnS in the presence of H/sub 2/, HCl, H/sub 2/S and H/sub 2/O. Ferrous sulfate dispersed in methylnaphthalene has been shown to be reduced to ferrous sulfide under typical coal hydroliquefaction conditions (1 hour, 450/sup 0/C, 1000 psi initial p/sub H/sub 2//). This suggests that ferrous sulfide may be the common catalytic ingredient when either (a) ferrous sulfate impregnated on powdered coal, or (b) finely divided iron pyrite is used as the catalyst. Old research on impregnated ferrous sulfate, impregnated ferrous halides, and pyrite is consistent with this assumption. Eight Co/Mo/Al/sub 2/O/sub 3/ catalysts from commercial suppliers, along with SnCl/sub 2/, have been studied for the hydrotreating of 1-methylnaphthalene (1-MN) in a stirred autoclave at 450 and 500/sup 0/C.

  13. Structure of the human protein kinase CK2 catalytic subunit CK2α' and interaction thermodynamics with the regulatory subunit CK2β

    DEFF Research Database (Denmark)

    Bischoff, Nils; Olsen, Birgitte; Raaf, Jennifer;

    2011-01-01

    the limited biochemical knowledge about the second paralog (CK2α'), we developed a well-soluble catalytically active full-length mutant of human CK2α', characterized it by Michaelis-Menten kinetics and isothermal titration calorimetry, and determined its crystal structure to a resolution of 2 Å. The affinity......Protein kinase CK2 (formerly "casein kinase 2") is composed of a central dimer of noncatalytic subunits (CK2β) binding two catalytic subunits. In humans, there are two isoforms of the catalytic subunit (and an additional splicing variant), one of which (CK2α) is well characterized. To supplement...

  14. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu Chieh; Otten, Edwin; Couzijn, Erik P A; Lutz, Martin; Minnaard, Adriaan J.

    2014-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides. © 2014 The Royal Society o

  15. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  16. Limit of Spectral Resolution in Terahertz Time-Domain Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Jingzhou Xu; Tao Yuan; Samuel Mickan; X.-C.Zhang

    2003-01-01

    The pulsed nature of terahertz time-domain spectroscopy (THz-TDS) sets a fundamental limit on its spectral resolution. The spectral resolution of THz-TDS can be improved by increasing the duration of the temporal measurement, but is limited by the dynamic range of the system in the time domain. This paper presents calculations and experimental results relating the temporal dynamic range of a THz-TDS system to its spectral resolution. We discuss three typical terahertz sources in terms of their dynamic range and hence achievable spectral resolution.

  17. A novel liquid system of catalytic hydrogenation

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    On the basis that endothermic aqueous-phase reforming of oxygenated hydrocarbons for H2 production and exothermic liquid phase hydrogenation of organic compounds are carried out under extremely close conditions of temperature and pressure over the same type of catalyst, a novel liquid system of catalytic hydrogenation has been proposed, in which hydrogen produced from aqueous-phase reforming of oxygenated hydrocarbons is in situ used for liquid phase hydrogenation of organic compounds. The usage of active hydrogen generated from aqueous-phase reforming of oxygenated hydrocarbons for liquid catalytic hydrogenation of organic compounds could lead to increasing the selectivity to H2 in the aqueous-phase reforming due to the prompt removal of hydrogen on the active centers of the catalyst. Meanwhile, this novel liquid system of catalytic hydrogenation might be a potential method to improve the selectivity to the desired product in liquid phase catalytic hydrogenation of organic compounds. On the other hand, for this novel liquid system of catalytic hydrogenation, some special facilities for H2 generation, storage and transportation in traditional liquid phase hydrogenation industry process are yet not needed. Thus, it would simplify the working process of liquid phase hydrogenation and increase the energy usage and hydrogen productivity.

  18. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    Laster, W. R.; Anoshkina, E.

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy’s National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1- Implementation Plan, Phase 2- Validation Testing and Phase 3 – Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  19. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    W. R. Laster; E. Anoshkina

    2008-01-31

    Under the sponsorship of the U. S. Department of Energy's National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1 - Implementation Plan, Phase 2 - Validation Testing and Phase 3 - Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  20. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  1. Catalytic microreactors for portable power generation

    Energy Technology Data Exchange (ETDEWEB)

    Karagiannidis, Symeon [Paul Scherer Institute, Villigen (Switzerland)

    2011-07-01

    ''Catalytic Microreactors for Portable Power Generation'' addresses a problem of high relevance and increased complexity in energy technology. This thesis outlines an investigation into catalytic and gas-phase combustion characteristics in channel-flow, platinum-coated microreactors. The emphasis of the study is on microreactor/microturbine concepts for portable power generation and the fuels of interest are methane and propane. The author carefully describes numerical and experimental techniques, providing a new insight into the complex interactions between chemical kinetics and molecular transport processes, as well as giving the first detailed report of hetero-/homogeneous chemical reaction mechanisms for catalytic propane combustion. The outcome of this work will be widely applied to the industrial design of micro- and mesoscale combustors. (orig.)

  2. Catalytic nanoarchitectonics for environmentally compatible energy generation

    Directory of Open Access Journals (Sweden)

    Hideki Abe

    2016-01-01

    Full Text Available Environmentally compatible energy management is one of the biggest challenges of the 21st century. Low-temperature conversion of chemical to electrical energy is of particular importance to minimize the impact to the environment while sustaining the consumptive economy. In this review, we shed light on one of the most versatile energy-conversion technologies: heterogeneous catalysts. We establish the integrity of structural tailoring in heterogeneous catalysts at different scales in the context of an emerging paradigm in materials science: catalytic nanoarchitectonics. Fundamental backgrounds of energy-conversion catalysis are first provided together with a perspective through state-of-the-art energy-conversion catalysis including catalytic exhaust remediation, fuel-cell electrocatalysis and photosynthesis of solar fuels. Finally, the future evolution of catalytic nanoarchitectonics is overviewed: possible combinations of heterogeneous catalysts, organic molecules and even enzymes to realize reaction-selective, highly efficient and long-life energy conversion technologies which will meet the challenge we face.

  3. Gene targeting of CK2 catalytic subunits

    Science.gov (United States)

    Lou, David Y.; Toselli, Paul; Landesman-Bollag, Esther; Dominguez, Isabel

    2013-01-01

    Protein kinase CK2 is a highly conserved and ubiquitous serine–threonine kinase. It is a tetrameric enzyme that is made up of two regulatory CK2β subunits and two catalytic subunits, either CK2α/CK2α, CK2α/ CK2α′, or CK2α′/CK2α′. Although the two catalytic subunits diverge in their C termini, their enzymatic activities are similar. To identify the specific function of the two catalytic subunits in development, we have deleted them individually from the mouse genome by homologous recombination. We have previously reported that CK2α′is essential for male germ cell development, and we now demonstrate that CK2α has an essential role in embryogenesis, as mice lacking CK2α die in mid-embryogenesis, with cardiac and neural tube defects. PMID:18594950

  4. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh.M.; Bragin, O.V.

    1978-01-01

    A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

  5. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  6. Gene targeting of CK2 catalytic subunits.

    Science.gov (United States)

    Seldin, David C; Lou, David Y; Toselli, Paul; Landesman-Bollag, Esther; Dominguez, Isabel

    2008-09-01

    Protein kinase CK2 is a highly conserved and ubiquitous serine-threonine kinase. It is a tetrameric enzyme that is made up of two regulatory CK2beta subunits and two catalytic subunits, either CK2alpha/CK2alpha, CK2alpha/CK2alpha', or CK2alpha'/CK2alpha'. Although the two catalytic subunits diverge in their C termini, their enzymatic activities are similar. To identify the specific function of the two catalytic subunits in development, we have deleted them individually from the mouse genome by homologous recombination. We have previously reported that CK2alpha' is essential for male germ cell development, and we now demonstrate that CK2alpha has an essential role in embryogenesis, as mice lacking CK2alpha die in mid-embryogenesis, with cardiac and neural tube defects.

  7. Temperature modulation of a catalytic gas sensor.

    Science.gov (United States)

    Brauns, Eike; Morsbach, Eva; Kunz, Sebastian; Baeumer, Marcus; Lang, Walter

    2014-10-29

    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, additional information about the gas characteristics can be measured and drift effects caused by material shifting or environmental temperature changes can be avoided. In this work a miniaturized catalytic gas sensor which offers a very short response time (electronic device was developed, since theory shows that harmonics induced by the electronics must be avoided to generate a comprehensible signal.

  8. Enumerating pathways of proton abstraction based on a spatial and electrostatic analysis of residues in the catalytic site.

    Directory of Open Access Journals (Sweden)

    Sandeep Chakraborty

    Full Text Available The pathways of proton abstraction (PA, a key aspect of most catalytic reactions, is often controversial and highly debated. Ultrahigh-resolution diffraction studies, molecular dynamics, quantum mechanics and molecular mechanic simulations are often adopted to gain insights in the PA mechanisms in enzymes. These methods require expertise and effort to setup and can be computationally intensive. We present a push button methodology--Proton abstraction Simulation (PRISM--to enumerate the possible pathways of PA in a protein with known 3D structure based on the spatial and electrostatic properties of residues in the proximity of a given nucleophilic residue. Proton movements are evaluated in the vicinity of this nucleophilic residue based on distances, potential differences, spatial channels and characteristics of the individual residues (polarity, acidic, basic, etc. Modulating these parameters eliminates their empirical nature and also might reveal pathways that originate from conformational changes. We have validated our method using serine proteases and concurred with the dichotomy in PA in Class A β-lactamases, both of which are hydrolases. The PA mechanism in a transferase has also been corroborated. The source code is made available at www.sanchak.com/prism.

  9. Green synthesis of silver nanoparticles using Terminalia cuneata and its catalytic action in reduction of direct yellow-12 dye

    Science.gov (United States)

    Edison, Thomas Nesakumar Jebakumar Immanuel; Lee, Yong Rok; Sethuraman, Mathur Gopalakrishnan

    2016-05-01

    Facile green synthesis of silver nanoparticles (AgNPs) using aqueous bark extract of Terminalia cuneata has been reported in this article. The effects of concentration of the extract, reaction time and pH were studied by UV-Vis spectroscopy. Appearance of yellow color with λmax around ~ 420 nm suggested the formation of AgNPs. The stable AgNPs were further characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) with zeta potential and high resolution transmission electron microscopy (HR-TEM) with energy dispersive X-ray spectroscopy (EDS) analysis. The synthesized AgNPs were in the size range of 25-50 nm with a distorted spherical shape identified from HR-TEM analysis. The catalytic activity of AgNPs on the reduction of direct yellow-12 using NaBH4 was analyzed using a UV-Vis spectrophotometer. This study showed the efficacy of biogenic AgNPs in catalyzing the reduction of direct yellow-12.

  10. The use of Phoenics in the design of catalytic converters

    Energy Technology Data Exchange (ETDEWEB)

    Luoma, M. [Kemira Metalkat Oy, Oulu (Finland); Smith, A.G. [S and C Thermofluids Ltd, Bath (United Kingdom)

    1996-12-31

    Manufacturers of automotive catalytic converters are constrained to design a system which is mechanically reliable, puts low back pressure on the engine, has adequate conversion performance, is low cost and of minimum size. In recent years, computational fluid dynamics (CFD) has been widely examined as a means of predicting the performance of catalytic converters to aid with the design process. Kemira Metalkat and S and C Thermofluids have put together and developed a number of existing CFD techniques in order to create a tool which is integrated within the design process. PHOENICS is used in the heart of the system in order to produce predictions of transient (light-off) and steady state catalyst performance. Grid generation tools have been provided to allow simplified and rapid geometry definition with suitable integration (via FEMGEN) within other parts of the catalyst design process. Simplified input techniques have been provided along with associated translators to create specification of the model for PHOENICS. Post-processing software has been provided through FEMVIEW to allow visualisation of catalyst monolith variables and transient performance animation. The whole system is controlled via a menu. The system have been use to study the effects of the catalyst design parameters on the converter performance. The results obtained using the system have so far been more qualitative than quantitative. However, validation studies have been carried out to check pressure drop prediction. A new model for the pressure drop over a metallic monolith has been developed. (author)

  11. Porous media for catalytic renewable energy conversion

    Science.gov (United States)

    Hotz, Nico

    2012-05-01

    A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

  12. Thermal and catalytic pyrolysis of plastic waste

    Directory of Open Access Journals (Sweden)

    Débora Almeida

    2016-02-01

    Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

  13. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  14. Heterogeneous Catalytic Ozonization of Sulfosalicylic Acid

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    This paper describes the potential of heterogeneous catalytic ozonization of sulfo-salicylic acid (SSal). It was found that catalytic ozonization in the presence of Mn-Zr-O (a modified manganese dioxide supported on silica gel) had significantly enhanced the removal rate (72%) of total organic carbon (TOC) compared with that of ozonization alone (19%). The efficient removal rate of TOC was probably due to increasing the adsorption ability of catalyst and accelerating decomposition of ozone to produce more powerful oxidants than ozone.

  15. Lake topography and wind waves determining seasonal-spatial dynamics of total suspended matter in turbid Lake Taihu, China: assessment using long-term high-resolution MERIS data.

    Science.gov (United States)

    Zhang, Yunlin; Shi, Kun; Liu, Xiaohan; Zhou, Yongqiang; Qin, Boqiang

    2014-01-01

    Multiple comprehensive in situ bio-optical investigations were conducted from 2005 to 2010 and covered a large variability of total suspended matter (TSM) in Lake Taihu to calibrate and validate a TSM concentration estimation model based on Medium Resolution Imaging Spectrometer (MERIS) data. The estimation model of the TSM concentration in Lake Taihu was developed using top-of-atmosphere (TOA) radiance of MERIS image data at band 9 in combination with a regional empirical atmospheric correction model, which was strongly correlated with the in situ TSM concentration (r(2) = 0.720, pmean square error (RRMSE) and mean relative error (MRE) were 36.9% and 31.6%, respectively, based on an independent validation dataset that produced reliable estimations of the TSM concentration. The developed algorithm was applied to 50 MERIS images from 2003 to 2011 to obtain a high spatial and temporal heterogeneity of TSM concentrations in Lake Taihu. Seasonally, the highest and lowest TSM concentrations were found in spring and autumn, respectively. Spatially, TSM concentrations were high in the southern part and center of the lake and low in Xukou Bay, East Lake Taihu. The lake topography, including the water depth and distance from the shore, had a significant effect on the TSM spatial distribution. A significant correlation was found between the daily average wind speed and TSM concentration (r(2)= 0.685, p<0.001, and n = 50), suggesting a critical role of wind speed in the TSM variations in Lake Taihu. In addition, a low TSM concentration was linked to the appearance of submerged aquatic vegetation (SAV). Therefore, TSM dynamics were controlled by the lake topography, wind-driven sediment resuspension and SAV distribution.

  16. Assessment of Acute Antivascular Effects of Vandetanib with High-Resolution Dynamic Contrast-Enhanced Computed Tomographic Imaging in a Human Colon Tumor Xenograft Model in the Nude Rat

    Directory of Open Access Journals (Sweden)

    Joo Ho Tai

    2010-09-01

    Full Text Available Tumor size is not a reliable marker for the assessment of early antivascular effects of antiangiogenics. In the present study, we used 200-µm in-plane high-resolution dynamic contrast-enhanced computed tomography (DCE-CT to noninvasively assess the immediate antivascular effects of vandetanib in a subcutaneous human colon cancer (LoVo xenograft model in nude rats and to investigate correlation between changes in CT perfusion parameters and tumor volume or immunohistochemical end points. At 3 to 4 weeks after LoVo cell implantation, the animal was gavaged with either vandetanib (50 mg/kg or vehicle twice (22 hours apart and scanned with a preclinical DCE-CT scanner before (0 hour and after treatment (24 hours. Quantitative maps of blood flow (BF and volume (BV of the tumor were calculated from the acquired DCE-CT images. The rats were divided into nonhypovascular, hypovascular, and combined (regardless of vascularity groups. In the nonhypovascular group, significant decreases in both tumor BF and BV were observed in the vandetanib-treated rats compared with increases in the vehicle-treated rats. A significant decrease in BV was detected in the vandetanib-treated rats in the combined group as well. No differences in tumor growth, vascular endothelial growth factor expression, microvessel density, or apoptosis were observed between vandetanib- and vehicle-treated rats in all three groups. These results demonstrate that BF and BV imaging biomarkers from DCE-CT imaging can be used for rapid monitoring of immediate (24 hours after antimicrovascular effects of vandetanib on tumors, even in the absence of significant changes of tumor volume or clinically relevant immunohistochemical end points.

  17. Warm absorbers in X-rays (WAX), a comprehensive high-resolution grating spectral study of a sample of Seyfert Galaxies - II. Warm absorber dynamics and feedback to galaxies

    Science.gov (United States)

    Laha, Sibasish; Guainazzi, Matteo; Chakravorty, Susmita; Dewangan, Gulab C.; Kembhavi, Ajit K.

    2016-04-01

    This paper is a sequel to the extensive study of warm absorber (WA) in X-rays carried out using high-resolution grating spectral data from XMM-Newton satellite (WAX-I). Here we discuss the global dynamical properties as well as the energetics of the WA components detected in the WAX sample. The slope of WA density profile (n ∝ r-α) estimated from the linear regression slope of ionization parameter ξ and column density NH in the WAX sample is α = 1.236 ± 0.034. We find that the WA clouds possibly originate as a result of photoionized evaporation from the inner edge of the torus (torus wind). They can also originate in the cooling front of the shock generated by faster accretion disc outflows, the ultrafast outflows, impinging on to the interstellar medium or the torus. The acceleration mechanism for the WA is complex and neither radiatively driven wind nor MHD-driven wind scenario alone can describe the outflow acceleration. However, we find that radiative forces play a significant role in accelerating the WA through the soft X-ray absorption lines, and also with dust opacity. Given the large uncertainties in the distance and volume filling factor estimates of the WA, we conclude that the kinetic luminosity ĖK of WA may sometimes be large enough to yield significant feedback to the host galaxy. We find that the lowest ionization states carry the maximum mass outflow, and the sources with higher Fe M UTA absorption (15-17 Å) have more mass outflow rates.

  18. Index Conditions of Resolution

    Institute of Scientific and Technical Information of China (English)

    Xiao-Chun Cheng

    2005-01-01

    In this paper, the following results are proved: (1) Using both deletion strategy and lock strategy, resolution is complete for a clause set where literals with the same predicate or proposition symbol have the same index. (2) Using deletion strategy, both positive unit lock resolution and input lock resolution are complete for a Horn set where the indexes of positive literals are greater than those of negative literals. (3) Using deletion strategy, input half-lock resolution is complete for a Horn set.

  19. 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.

  20. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...... understanding of the nature of the electrochemical promotion is also presented....

  1. Shungite carbon catalytic effect on coal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Grigorieva, E.N.; Rozhkova, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). Institute for High Temperature

    1999-07-01

    The catalytic ability of shungite carbon in reactions of coal organic matter models appeared to be due to its fullerene structure only. Transition metal sulphides present in shungite carbon are not active in the conditions of coal treatment. Shungite carbon was shown to exhibit an acceleration of thermolysis of coal and organic matter models, mainly dehydrogenation. 5 refs., 1 tabs.

  2. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank;

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  3. Catalytic Amination of Alcohols, Aldehydes, and Ketones

    Science.gov (United States)

    Klyuev, M. V.; Khidekel', M. L.

    1980-01-01

    Data on the catalytic amination of alcohols and carbonyl compounds are examined, the catalysts for these processes are described, and the problems of their effectiveness, selectivity, and stability are discussed. The possible mechanisms of the reactions indicated are presented. The bibliography includes 266 references.

  4. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L

    2015-06-26

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.

  5. SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

    Science.gov (United States)

    A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

  6. Performance characterization of a hydrogen catalytic heater.

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry Alan; Kanouff, Michael P.

    2010-04-01

    This report describes the performance of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to the GM Hydrogen Storage Demonstration System. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to a circulating heat transfer fluid. The fluid then transfers the heat to one or more of the four hydrogen storage modules that make up the Demonstration System to drive off the chemically bound hydrogen. The heater consists of three main parts: (1) the reactor, (2) the gas heat recuperator, and (3) oil and gas flow distribution manifolds. The reactor and recuperator are integrated, compact, finned-plate heat exchangers to maximize heat transfer efficiency and minimize mass and volume. Detailed, three-dimensional, multi-physics computational models were used to design and optimize the system. At full power the heater was able to catalytically combust a 10% hydrogen/air mixture flowing at over 80 cubic feet per minute and transfer 30 kW of heat to a 30 gallon per minute flow of oil over a temperature range from 100 C to 220 C. The total efficiency of the catalytic heater, defined as the heat transferred to the oil divided by the inlet hydrogen chemical energy, was characterized and methods for improvement were investigated.

  7. The Catalytic Asymmetric Intramolecular Stetter Reaction.

    Science.gov (United States)

    de Alaniz, Javier Read; Rovis, Tomislav

    2009-05-01

    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  8. Selectivity of catalytic methods of determination.

    Science.gov (United States)

    Otto, M; Mueller, H; Werner, G

    1978-03-01

    By means of catalytic analytical methods, extremely low levels can be determined at low cost and with a high sensitivity that is equal to that of physical methods of trace analysis. The selectivity of the catalytic determinations, is, however, usually rather lower than that of other methods of trace analysis. The selectivity can sometimes be improved by modification of the indicator reaction through variation of the reagents and their concentrations, or by use of masking reagents or activators, or by combination with a separation method. Modification of the indicator reaction can be exemplified by the selective determination of osmium and ruthenium by their catalysis of the nitrate oxidation of 1-naphthylamine. By variation of the nitrate concentration and the use of 1,10-phenanthroline and 8-hydroxyquinoline as complexing agents it is possible to determine these two elements simultaneously. An especially significant increase in the selectivity is made possible by use of a preliminary separation step. If the ion to be determined is separated by solvent extraction and then catalytically determined directly in the extract, a very specific determination is possible; this technique has been called "extractive catalytic determination". This method has been used for determination of molybdenum (0.5 ng/ml) in sea-water, iron (5 ng/ml) in heavy metal salts, and copper (3 ng/ml) in the presence of numerous elements.

  9. Hamiltonian adaptive resolution simulation for molecular liquids.

    Science.gov (United States)

    Potestio, Raffaello; Fritsch, Sebastian; Español, Pep; Delgado-Buscalioni, Rafael; Kremer, Kurt; Everaers, Ralf; Donadio, Davide

    2013-03-08

    Adaptive resolution schemes allow the simulation of a molecular fluid treating simultaneously different subregions of the system at different levels of resolution. In this work we present a new scheme formulated in terms of a global Hamiltonian. Within this approach equilibrium states corresponding to well-defined statistical ensembles can be generated making use of all standard molecular dynamics or Monte Carlo methods. Models at different resolutions can thus be coupled, and thermodynamic equilibrium can be modulated keeping each region at desired pressure or density without disrupting the Hamiltonian framework.

  10. Adaptive resolution simulation of oligonucleotides

    Science.gov (United States)

    Netz, Paulo A.; Potestio, Raffaello; Kremer, Kurt

    2016-12-01

    Nucleic acids are characterized by a complex hierarchical structure and a variety of interaction mechanisms with other molecules. These features suggest the need of multiscale simulation methods in order to grasp the relevant physical properties of deoxyribonucleic acid (DNA) and RNA using in silico experiments. Here we report an implementation of a dual-resolution modeling of a DNA oligonucleotide in physiological conditions; in the presented setup only the nucleotide molecule and the solvent and ions in its proximity are described at the atomistic level; in contrast, the water molecules and ions far from the DNA are represented as computationally less expensive coarse-grained particles. Through the analysis of several structural and dynamical parameters, we show that this setup reliably reproduces the physical properties of the DNA molecule as observed in reference atomistic simulations. These results represent a first step towards a realistic multiscale modeling of nucleic acids and provide a quantitatively solid ground for their simulation using dual-resolution methods.

  11. Equivariant cohomology and resolution

    CERN Document Server

    Albin, Pierre

    2009-01-01

    The `Folk Theorem' that a smooth action by a compact Lie group can be (canonically) resolved, by iterated blow up, to have unique isotropy type is proved in the context of manifolds with corners. This procedure is shown to capture the simultaneous resolution of all isotropy types in a `resolution tower' which projects to a resolution, with iterated boundary fibration, of the quotient. Equivariant K-theory and the Cartan model for equivariant cohomology are tracked under the resolution procedure as is the delocalized equivariant cohomology of Baum, Brylinski and MacPherson. This leads to resolved models for each of these cohomology theories, in terms of relative objects over the resolution tower and hence to reduced models as flat-twisted relative objects over the resolution of the quotient. As a result an explicit equivariant Chern character is constructed, essentially as in the non-equivariant case, over the resolution of the quotient.

  12. Visualizing a Catalyst at Work during the Ignition of the Catalytic Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Kimmerle, Bertram; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2009-01-01

    We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which in comb...... in combination with temperature profiling by IR-thermography and catalytic activity measurements by online mass spectrometry gives insight into the first stages of the ignition of the reaction toward hydrogen and carbon monoxide....

  13. Modelling and parameter estimation in reactive continuous mixtures: the catalytic cracking of alkanes - part II

    Directory of Open Access Journals (Sweden)

    F. C. PEIXOTO

    1999-09-01

    Full Text Available Fragmentation kinetics is employed to model a continuous reactive mixture of alkanes under catalytic cracking conditions. Standard moment analysis techniques are employed, and a dynamic system for the time evolution of moments of the mixture's dimensionless concentration distribution function (DCDF is found. The time behavior of the DCDF is recovered with successive estimations of scaled gamma distributions using the moments time data.

  14. Second-Order Catalytic Quasispecies Yields First-Order Phase Transition

    OpenAIRE

    Wagner, Nathaniel; Tannenbaum, Emmanuel; Ashkenasy, Gonen

    2009-01-01

    The quasispecies model describes processes related to the origin of life and viral evolutionary dynamics. We discuss how the error catastrophe that reflects the transition from localized to delocalized quasispecies population is affected by catalytic replication of different reaction orders. Specifically, we find that 2nd order mechanisms lead to 1st order discontinuous phase transitions in the viable population fraction, and conclude that the "higher" the interaction the "lower" the transiti...

  15. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  16. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  17. Signal Propagation and Detection via Catalytically Immolative Biopolymer-Programmed Nanomaterials

    Science.gov (United States)

    2015-02-09

    Bioresponsive Nanomaterials Captured by Dynamic Transmission Electron Microscopy and High Resolution Optical Microscopy Source of Support: DOE...Galya Orr and Dr. Dehong Hu, in the development of STORM for the super high resolution reconstruction of fluorescence images of particles present in ex...for use by our laboratory with some training and professional assistance: STORM/PALM Super - resolution – 160 hrs. Fluorescence Single-Molecule – 100

  18. Structures of the human poly (ADP-ribose glycohydrolase catalytic domain confirm catalytic mechanism and explain inhibition by ADP-HPD derivatives.

    Directory of Open Access Journals (Sweden)

    Julie A Tucker

    Full Text Available Poly(ADP-ribose glycohydrolase (PARG is the only enzyme known to catalyse hydrolysis of the O-glycosidic linkages of ADP-ribose polymers, thereby reversing the effects of poly(ADP-ribose polymerases. PARG deficiency leads to cell death whilst PARG depletion causes sensitisation to certain DNA damaging agents, implicating PARG as a potential therapeutic target in several disease areas. Efforts to develop small molecule inhibitors of PARG activity have until recently been hampered by a lack of structural information on PARG. We have used a combination of bio-informatic and experimental approaches to engineer a crystallisable, catalytically active fragment of human PARG (hPARG. Here, we present high-resolution structures of the catalytic domain of hPARG in unliganded form and in complex with three inhibitors: ADP-ribose (ADPR, adenosine 5'-diphosphate (hydroxymethylpyrrolidinediol (ADP-HPD and 8-n-octyl-amino-ADP-HPD. Our structures confirm conservation of overall fold amongst mammalian PARG glycohydrolase domains, whilst revealing additional flexible regions in the catalytic site. These new structures rationalise a body of published mutational data and the reported structure-activity relationship for ADP-HPD based PARG inhibitors. In addition, we have developed and used biochemical, isothermal titration calorimetry and surface plasmon resonance assays to characterise the binding of inhibitors to our PARG protein, thus providing a starting point for the design of new inhibitors.

  19. Structural characterization of the catalytic site of a Nilaparvata lugens delta-class glutathione transferase.

    Science.gov (United States)

    Yamamoto, Kohji; Higashiura, Akifumi; Hossain, Md Tofazzal; Yamada, Naotaka; Shiotsuki, Takahiro; Nakagawa, Atsushi

    2015-01-15

    Glutathione transferases (GSTs) are a major class of detoxification enzymes that play a central role in the defense against environmental toxicants and oxidative stress. Here, we studied the crystal structure of a delta-class glutathione transferase from Nilaparvata lugens, nlGSTD, to gain insights into its catalytic mechanism. The structure of nlGSTD in complex with glutathione, determined at a resolution of 1.7Å, revealed that it exists as a dimer and its secondary and tertiary structures are similar to those of other delta-class GSTs. Analysis of a complex between nlGSTD and glutathione showed that the bound glutathione was localized to the glutathione-binding site. Site-directed mutagenesis of nlGSTD mutants indicated that amino acid residues Ser11, His52, Glu66, and Phe119 contribute to catalytic activity.

  20. Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Susana [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela); Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); D' Ornelas, Lindora [Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); Betancourt, Paulino [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela)], E-mail: pbetanco@strix.ciens.ucv.ve

    2008-06-30

    Vanadium nanoparticles ({approx}7 nm) stabilized on activated carbon were synthesized by the reduction of VCl{sub 3}.3THF with K[BEt{sub 3}H]. This material was characterized by inductive coupled plasma-atomic emission spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 deg. C and P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the synthesis of such a catalyst led to an excellent performance of the HDS process.

  1. Catalytic Chemical Vapor Deposition Synthesis of Carbon Aerogels of High-Surface Area and Porosity

    Directory of Open Access Journals (Sweden)

    Armando Peña

    2012-01-01

    Full Text Available In this work carbon aerogels were synthesized by catalytic chemical vapor deposition method (CCVD. Ferrocene were employed as a source both of catalytic material (Fe and of carbon. Gaseous hydrogen and argon were used as reductant and carrier gas, respectively. The products of reaction were collected over alumina. The morphology and textural properties of the soot produced in the reaction chamber were investigated using Scanning Electron Microscopy, High-Resolution Transmission Electron Microscopy, X-ray photoelectron spectroscopy, and N2 physisorption (BET and BHJ methods. After the evaluation of the porous structure of the synthesized products, 780 ± 20 m2/g of SBET and 0.55 ± 0.02 cm3/g of VBJH were found. The presence of iron carbide and the partial oxidation of carbon nanostructures were revealed by XPS.

  2. Estimation of Future PM2.5- and Ozone-related Mortality over the Continental United States in a Changing Climate: An application of High-resolution Dynamical Downscaling Technique

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Jian; Fu, Joshua S.; Huang, Kan; Gao, Yang

    2015-04-14

    This paper evaluates the PM2.5- and ozone-related mortality at present (2000s) and in the future (2050s) over the continental United States by using the Environmental Benefits Mapping and Analysis Program (BenMAP-CE). Atmospheric chemical fields are simulated by WRF/CMAQ (horizontal resolution: 12 × 12km), applying the dynamical downscaling technique from global climate-chemistry models under the Representative Concentration Pathways scenario (RCP 8.5). Future air quality results predict that the annual mean PM2.5 concentrations in continental US will decrease nationwide, especially in the eastern US and west coast. However, the ozone concentration is projected to decrease in the Eastern US but increase in the Western US. Future mortality is evaluated under two scenarios (1) holding future population and baseline incidence rate at the present level and (2) decreasing the future baseline incidence rate but increasing the future population. For PM2.5, the entire continental US presents a decreasing trend of PM2.5-related mortality by the 2050s in Scenario (1), primarily resulting from the emissions reduction. While in Scenario (2), almost half of the continental states show a rising tendency of PM2.5-related mortality, due to the dominant influence of population growth. In particular, the highest PM2.5-related deaths and the biggest discrepancy between present and future PM2.5-related deaths will both occur in California in 2050s. For the ozone-related premature mortality, the simulation shows nation-wide rising tendency in 2050s under both two scenarios, mainly due to the increase of ozone concentration and population in the future. Furthermore, the uncertainty analysis shows that the effect of the all causes mortality is much larger than for specific causes. This assessment is the result of the accumulated uncertainty of generating datasets. The uncertainty range of ozone-related all cause premature mortality is narrower than the PM2.5-related all cause mortality

  3. Metabolomics of Breast Cancer Using High-Resolution Magic Angle Spinning Magnetic Resonance Spectroscopy: Correlations with 18F-FDG Positron Emission Tomography-Computed Tomography, Dynamic Contrast-Enhanced and Diffusion-Weighted Imaging MRI.

    Directory of Open Access Journals (Sweden)

    Haesung Yoon

    Full Text Available Our goal in this study was to find correlations between breast cancer metabolites and conventional quantitative imaging parameters using high-resolution magic angle spinning (HR-MAS magnetic resonance spectroscopy (MRS and to find breast cancer subgroups that show high correlations between metabolites and imaging parameters.Between August 2010 and December 2013, we included 53 female patients (mean age 49.6 years; age range 32-75 years with a total of 53 breast lesions assessed by the Breast Imaging Reporting and Data System. They were enrolled under the following criteria: breast lesions larger than 1 cm in diameter which 1 were suspicious for malignancy on mammography or ultrasound (US, 2 were pathologically confirmed to be breast cancer with US-guided core-needle biopsy (CNB 3 underwent 3 Tesla MRI with dynamic contrast-enhanced (DCE and diffusion-weighted imaging (DWI and positron emission tomography-computed tomography (PET-CT, and 4 had an attainable immunohistochemistry profile from CNB. We acquired spectral data by HR-MAS MRS with CNB specimens and expressed the data as relative metabolite concentrations. We compared the metabolites with the signal enhancement ratio (SER, maximum standardized FDG uptake value (SUV max, apparent diffusion coefficient (ADC, and histopathologic prognostic factors for correlation. We calculated Spearman correlations and performed a partial least squares-discriminant analysis (PLS-DA to further classify patient groups into subgroups to find correlation differences between HR-MAS spectroscopic values and conventional imaging parameters.In a multivariate analysis, the PLS-DA models built with HR-MAS MRS metabolic profiles showed visible discrimination between high and low SER, SUV, and ADC. In luminal subtype breast cancer, compared to all cases, high SER, ADV, and SUV were more closely clustered by visual assessment. Multiple metabolites were correlated with SER and SUV in all cases. Multiple metabolites

  4. New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.

    Science.gov (United States)

    Zaera, Francisco

    2014-11-21

    Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are

  5. Spatially resolved characterization of catalyst-coated membranes by distance-controlled scanning mass spectrometry utilizing catalytic methanol oxidation as gas-solid probe reaction.

    Science.gov (United States)

    Li, Nan; Assmann, Jens; Schuhmann, Wolfgang; Muhler, Martin

    2007-08-01

    The spatially resolved catalytic activity of a catalyst-coated membrane (CCM), which is the essential part of PEM fuel cells, was visualized rapidly without any damage by a distance-controlled scanning mass spectrometer with an improved resolution of 250 microm. Methanol oxidation was identified as a suitable gas-solid probe reaction for the characterization of local catalytic activity. In addition, defects were manually generated in the CCM to simulate inhomogeneous coating and pinholes. The measurements successfully demonstrated that catalytically active and less active regions can be clearly distinguished. Simultaneously, the local topography was recorded, providing additional information on the location of the scratches and pinholes. The catalytic results were highly reproducible due to the constant-distance feedback loop rendering scanning mass spectrometry a promising tool for the quantitative quality control of CCMs.

  6. Rational design of ornithine decarboxylase with high catalytic activity for the production of putrescine.

    Science.gov (United States)

    Choi, Hyang; Kyeong, Hyun-Ho; Choi, Jung Min; Kim, Hak-Sung

    2014-09-01

    Putrescine finds wide industrial applications in the synthesis of polymers, pharmaceuticals, agrochemicals, and surfactants. Owing to economic and environmental concerns, the microbial production of putrescine has attracted a great deal of attention, and ornithine decarboxylase (ODC) is known to be a key enzyme in the biosynthetic pathway. Herein, we present the design of ODC from Escherichia coli with high catalytic efficiency using a structure-based rational approach. Through a substrate docking into the model structure of the enzyme, we first selected residues that might lead to an increase in catalytic activity. Of the selected residues that are located in the α-helix and the loops constituting the substrate entry site, a mutational analysis of the single mutants identified two key residues, I163 and E165. A combination of two single mutations resulted in a 62.5-fold increase in the catalytic efficiency when compared with the wild-type enzyme. Molecular dynamics simulations of the best mutant revealed that the substrate entry site becomes more flexible through mutations, while stabilizing the formation of the dimeric interface of the enzyme. Our approach can be applied to the design of other decarboxylases with high catalytic efficiency for the production of various chemicals through bio-based processes.

  7. Predicting CYP2C19 Catalytic Parameters for Enantioselective Oxidations Using Artificial Neural Networks and a Chirality Code

    Science.gov (United States)

    Hartman, Jessica H.; Cothren, Steven D.; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A.; Miller, Grover P.

    2013-01-01

    Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (kcat, Km, and kcat/Km), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (kcat and Km) were more consistent with experimental values than those for catalytic efficiency (kcat/Km). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds. PMID:23673224

  8. Predicting CYP2C19 catalytic parameters for enantioselective oxidations using artificial neural networks and a chirality code.

    Science.gov (United States)

    Hartman, Jessica H; Cothren, Steven D; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A; Miller, Grover P

    2013-07-01

    Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (k(cat), K(m), and k(cat)/K(m)), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (k(cat) and K(m)) were more consistent with experimental values than those for catalytic efficiency (k(cat)/K(m)). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds.

  9. PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

    Institute of Scientific and Technical Information of China (English)

    Yu-yuan Yao; Wen-xing Chen; Bao-yan Zhao; Shen-shui Lü

    2006-01-01

    Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives (Mt2Pc2) were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center ofbioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.

  10. Janus droplet as a catalytic micromotor

    CERN Document Server

    Shklyaev, Sergey

    2015-01-01

    Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, $60\\; {\\rm \\mu m/s}$ and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers. The paper was finalized and submitted by Denis S. Goldobin after Sergey Sklyaev had sadly passed away on June 2, 2014.

  11. Control of a catalytic fluid cracker

    Energy Technology Data Exchange (ETDEWEB)

    Arbel, A.; Huang, Z.; Rinard, I.; Shinnar, R.

    1993-12-13

    Control offers an important tool for savings in refineries, mainly by integration of process models into on-line control. This paper is part of a research effort to better understand problems of partial control; control of a Fluid Catalytic Cracker (FCC) is used as example. Goal is to understand better the control problems of an FCC in context of model based control of a refinery, and to understand the general problem of designing partial control systems.

  12. Materials for High-Temperature Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Ersson, Anders

    2003-04-01

    Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

  13. 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.

  14. Zeolitic catalytic conversion of alochols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2017-01-03

    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  15. Catalytic fast pyrolysis of lignocellulosic biomass

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.; Sun, Junming; Wang, Yong

    2014-11-21

    Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.

  16. Thermal and catalytic pyrolysis of plastic waste

    OpenAIRE

    Débora Almeida; Maria de Fátima Marques

    2016-01-01

    Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolit...

  17. Catalytic pyrolysis of olive mill wastewater sludge

    Science.gov (United States)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  18. Studies of catalytic coal gasification with steam

    Directory of Open Access Journals (Sweden)

    Porada Stanisław

    2016-09-01

    Full Text Available One of the promising processes, belonging to the so-called clean coal technologies, is catalytic coal gasification. The addition of a catalyst results in an increased process rate, in which synthesis gas is obtained. Therefore, the subject of this research was catalytic gasification of low-ranking coal which, due to a high reactivity, meets the requirements for fuels used in the gasification process. Potassium and calcium cations in an amount of 0.85, 1.7 and 3.4% by weight were used as catalytically active substances. Isothermal measurements were performed at 900°C under a pressure of 2 MPa using steam as a gasifying agent. On the basis of kinetic curves, the performance of main gasification products as well as carbon conversion degree were determined. The performed measurements allowed the determination of the type and amount of catalyst that ensure the most efficient gasification process of the coal ‘Piast’ in an atmosphere of steam.

  19. Highly sensitive catalytic spectrophotometric determination of ruthenium

    Science.gov (United States)

    Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

    2008-01-01

    A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

  20. A revolution in micropower : the catalytic nanodiode.

    Energy Technology Data Exchange (ETDEWEB)

    Cross, Karen Charlene; Heller, Edwin J.; Figiel, Jeffrey James; Coker, Eric Nicholas; Creighton, James Randall; Koleske, Daniel David; Bogart, Katherine Huderle Andersen; Coltrin, Michael Elliott; Pawlowski, Roger Patrick; Baucom, Kevin C.

    2010-11-01

    Our ability to field useful, nano-enabled microsystems that capitalize on recent advances in sensor technology is severely limited by the energy density of available power sources. The catalytic nanodiode (reported by Somorjai's group at Berkeley in 2005) was potentially an alternative revolutionary source of micropower. Their first reports claimed that a sizable fraction of the chemical energy may be harvested via hot electrons (a 'chemicurrent') that are created by the catalytic chemical reaction. We fabricated and tested Pt/GaN nanodiodes, which eventually produced currents up to several microamps. Our best reaction yields (electrons/CO{sub 2}) were on the order of 10{sup -3}; well below the 75% values first reported by Somorjai (we note they have also been unable to reproduce their early results). Over the course of this Project we have determined that the whole concept of 'chemicurrent', in fact, may be an illusion. Our results conclusively demonstrate that the current measured from our nanodiodes is derived from a thermoelectric voltage; we have found no credible evidence for true chemicurrent. Unfortunately this means that the catalytic nanodiode has no future as a micropower source.

  1. High-resolution intravital microscopy.

    Directory of Open Access Journals (Sweden)

    Volker Andresen

    Full Text Available Cellular communication constitutes a fundamental mechanism of life, for instance by permitting transfer of information through synapses in the nervous system and by leading to activation of cells during the course of immune responses. Monitoring cell-cell interactions within living adult organisms is crucial in order to draw conclusions on their behavior with respect to the fate of cells, tissues and organs. Until now, there is no technology available that enables dynamic imaging deep within the tissue of living adult organisms at sub-cellular resolution, i.e. detection at the level of few protein molecules. Here we present a novel approach called multi-beam striped-illumination which applies for the first time the principle and advantages of structured-illumination, spatial modulation of the excitation pattern, to laser-scanning-microscopy. We use this approach in two-photon-microscopy--the most adequate optical deep-tissue imaging-technique. As compared to standard two-photon-microscopy, it achieves significant contrast enhancement and up to 3-fold improved axial resolution (optical sectioning while photobleaching, photodamage and acquisition speed are similar. Its imaging depth is comparable to multifocal two-photon-microscopy and only slightly less than in standard single-beam two-photon-microscopy. Precisely, our studies within mouse lymph nodes demonstrated 216% improved axial and 23% improved lateral resolutions at a depth of 80 µm below the surface. Thus, we are for the first time able to visualize the dynamic interactions between B cells and immune complex deposits on follicular dendritic cells within germinal centers (GCs of live mice. These interactions play a decisive role in the process of clonal selection, leading to affinity maturation of the humoral immune response. This novel high-resolution intravital microscopy method has a huge potential for numerous applications in neurosciences, immunology, cancer research and

  2. Optical super-resolution microscopy in neurobiology.

    Science.gov (United States)

    Sigrist, Stephan J; Sabatini, Bernardo L

    2012-02-01

    Understanding the highly plastic nature of neurons requires the dynamic visualization of their molecular and cellular organization in a native context. However, due to the limited resolution of standard light microscopy, many of the structural specializations of neurons cannot be resolved. A recent revolution in light microscopy has given rise to several super-resolution light microscopy methods yielding 2-10-fold higher resolution than conventional microscopy. We here describe the principles behind these techniques as well as their application to the analysis of the molecular architecture of the synapse. Furthermore, we discuss the potential for continued development of super-resolution microscopy as necessary for live imaging of neuronal structure and function in the brain.

  3. Super-resolution

    DEFF Research Database (Denmark)

    Nasrollahi, Kamal; Moeslund, Thomas B.

    2014-01-01

    and aerial imaging to medical image processing, to facial image analysis, text image analysis, sign and number plates reading, and biometrics recognition, to name a few. This has resulted in many research papers, each developing a new super-resolution algorithm for a specific purpose. The current...... the contributions of different authors to the basic concepts of each group. Furthermore, common issues in super-resolution algorithms, such as imaging models and registration algorithms, optimization of the cost functions employed, dealing with color information, improvement factors, assessment of super......Super-resolution, the process of obtaining one or more high-resolution images from one or more low-resolution observations, has been a very attractive research topic over the last two decades. It has found practical applications in many real world problems in different fields, from satellite...

  4. Structure of the catalytic domain of Plasmodium falciparum ARF GTPase-activating protein (ARFGAP)

    Energy Technology Data Exchange (ETDEWEB)

    Cook, William J.; Senkovich, Olga; Chattopadhyay, Debasish (UAB)

    2012-03-26

    The crystal structure of the catalytic domain of the ADP ribosylation factor GTPase-activating protein (ARFGAP) from Plasmodium falciparum has been determined and refined to 2.4 {angstrom} resolution. Multiwavelength anomalous diffraction (MAD) data were collected utilizing the Zn{sup 2+} ion bound at the zinc-finger domain and were used to solve the structure. The overall structure of the domain is similar to those of mammalian ARFGAPs. However, several amino-acid residues in the area where GAP interacts with ARF1 differ in P. falciparum ARFGAP. Moreover, a number of residues that form the dimer interface in the crystal structure are unique in P. falciparum ARFGAP.

  5. A high-resolution time-to-digital converter using a three-level resolution

    Science.gov (United States)

    Dehghani, Asma; Saneei, Mohsen; Mahani, Ali

    2016-08-01

    In this article, a three-level resolution Vernier delay line time-to-digital converter (TDC) was proposed. The proposed TDC core was based on the pseudo-differential digital architecture that made it insensitive to nMOS and pMOS transistor mismatches. It also employed a Vernier delay line (VDL) in conjunction with an asynchronous read-out circuitry. The time interval resolution was equal to the difference of delay between buffers of upper and lower chains. Then, via the extra chain included in the lower delay line, resolution was controlled and power consumption was reduced. This method led to high resolution and low power consumption. The measurement results of TDC showed a resolution of 4.5 ps, 12-bit output dynamic range, and integral nonlinearity of 1.5 least significant bits. This TDC achieved the consumption of 68.43 µW from 1.1-V supply.

  6. Structure of the Tribolium castaneum Telomerase Catalytic Subunit TERT

    Energy Technology Data Exchange (ETDEWEB)

    Gillis,A.; Schuller, A.; Skordalakes, E.

    2008-01-01

    A common hallmark of human cancers is the overexpression of telomerase, a ribonucleoprotein complex that is responsible for maintaining the length and integrity of chromosome ends. Telomere length deregulation and telomerase activation is an early, and perhaps necessary, step in cancer cell evolution. Here we present the high-resolution structure of the Tribolium castaneum catalytic subunit of telomerase, TERT. The protein consists of three highly conserved domains, organized into a ring-like structure that shares common features with retroviral reverse transcriptases, viral RNA polymerases and B-family DNA polymerases. Domain organization places motifs implicated in substrate binding and catalysis in the interior of the ring, which can accommodate seven to eight bases of double-stranded nucleic acid. Modelling of an RNA-DNA heteroduplex in the interior of this ring demonstrates a perfect fit between the protein and the nucleic acid substrate, and positions the 3'-end of the DNA primer at the active site of the enzyme, providing evidence for the formation of an active telomerase elongation complex.

  7. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  8. High-resolution structure of the phosphorylated form of the histidine-containing phosphocarrier protein HPR from Escherichia coli determined by restrained molecular dynamics from NMR-NOE data

    NARCIS (Netherlands)

    van Nuland, Nicolaas; Boelens, R; Scheek, R.M.; Robillard, G.T.

    1995-01-01

    The solution structure of the phosphorylated form of the histidine-containing phosphocarrier protein, HPr, from Escherichia coli has been determined by NMR in combination with restrained molecular dynamics simulations. The structure of phospho-HPr (P-HPr) results from a molecular dynamics simulation

  9. Self-organized criticality of a catalytic reaction network under flow.

    Science.gov (United States)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-07-01

    Self-organized critical behavior in a catalytic reaction network system induced by smallness in the molecule number is reported. The system under a flow of chemicals is shown to undergo a transition from a stationary to an intermittent reaction phase when the flow rate is decreased. In the intermittent reaction phase, two temporal regimes with active and halted reactions alternate. The number frequency of reaction events at each active regime and its duration time are shown to obey a universal power law with the exponents 4/3 and 3/2, respectively, independently of the parameters and network structure. These power laws are explained by a one-dimensional random-walk representation of the number of catalytically active chemicals. Possible relevance of the result to reaction dynamics in artificial and biological cells is briefly discussed.

  10. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface.

    Science.gov (United States)

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, Lindsay R; Lammich, Lutz; Besenbacher, Flemming; Mavrikakis, Manos; Wendt, Stefan

    2015-08-25

    Within the area of surface science, one of the "holy grails" is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFT+U calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  11. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface

    Energy Technology Data Exchange (ETDEWEB)

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, L. R.; Lammich, Lutz; Besenbacher, Fleming; Mavrikakis, Manos; Wendt, Stefen

    2015-08-25

    Within the area of surface science, one of the “holy grails” is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFTþU calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  12. A microreactor array for spatially resolved measurement of catalytic activity for high-throughput catalysis science

    Energy Technology Data Exchange (ETDEWEB)

    Kondratyuk, Petro; Gumuslu, Gamze; Shukla, Shantanu; Miller, James B; Morreale, Bryan D; Gellman, Andrew J

    2013-04-01

    We describe a 100 channel microreactor array capable of spatially resolved measurement of catalytic activity across the surface of a flat substrate. When used in conjunction with a composition spread alloy film (CSAF, e.g. Pd{sub x}Cu{sub y}Au{sub 1-x-y}) across which component concentrations vary smoothly, such measurements permit high-throughput analysis of catalytic activity and selectivity as a function of catalyst composition. In the reported implementation, the system achieves spatial resolution of 1 mm{sup 2} over a 10×10 mm{sup 2} area. During operation, the reactant gases are delivered at constant flow rate to 100 points of differing composition on the CSAF surface by means of a 100-channel microfluidic device. After coming into contact with the CSAF catalyst surface, the product gas mixture from each of the 100 points is withdrawn separately through a set of 100 isolated channels for analysis using a mass spectrometer. We demonstrate the operation of the device on a Pd{sub x}Cu{sub y}Au{sub 1-x-y} CSAF catalyzing the H{sub 2}-D{sub 2} exchange reaction at 333 K. In essentially a single experiment, we measured the catalytic activity over a broad swathe of concentrations from the ternary composition space of the Pd{sub x}Cu{sub y}Au{sub 1-x-y} alloy.

  13. In situ structure of trypanosomal ATP synthase dimer reveals a unique arrangement of catalytic subunits

    Science.gov (United States)

    Mühleip, Alexander W.; Dewar, Caroline E.; Schnaufer, Achim; Kühlbrandt, Werner; Davies, Karen M.

    2017-01-01

    We used electron cryotomography and subtomogram averaging to determine the in situ structures of mitochondrial ATP synthase dimers from two organisms belonging to the phylum euglenozoa: Trypanosoma brucei, a lethal human parasite, and Euglena gracilis, a photosynthetic protist. At a resolution of 32.5 Å and 27.5 Å, respectively, the two structures clearly exhibit a noncanonical F1 head, in which the catalytic (αβ)3 assembly forms a triangular pyramid rather than the pseudo-sixfold ring arrangement typical of all other ATP synthases investigated so far. Fitting of known X-ray structures reveals that this unusual geometry results from a phylum-specific cleavage of the α subunit, in which the C-terminal αC fragments are displaced by ∼20 Å and rotated by ∼30° from their expected positions. In this location, the αC fragment is unable to form the conserved catalytic interface that was thought to be essential for ATP synthesis, and cannot convert γ-subunit rotation into the conformational changes implicit in rotary catalysis. The new arrangement of catalytic subunits suggests that the mechanism of ATP generation by rotary ATPases is less strictly conserved than has been generally assumed. The ATP synthases of these organisms present a unique model system for discerning the individual contributions of the α and β subunits to the fundamental process of ATP synthesis. PMID:28096380

  14. Catalytic bioscavengers in nerve agent poisoning: A promising approach?

    Science.gov (United States)

    Worek, Franz; Thiermann, Horst; Wille, Timo

    2016-02-26

    The repeated use of the nerve agent sarin against civilians in Syria in 2013 emphasizes the continuing threat by chemical warfare agents. Multiple studies demonstrated a limited efficacy of standard atropine-oxime treatment in nerve agent poisoning and called for the development of alternative and more effective treatment strategies. A novel approach is the use of stoichiometric or catalytic bioscavengers for detoxification of nerve agents in the systemic circulation prior to distribution into target tissues. Recent progress in the design of enzyme mutants with reversed stereo selectivity resulting in improved catalytic activity and their use in in vivo studies supports the concept of catalytic bioscavengers. Yet, further research is necessary to improve the catalytic activity, substrate spectrum and in vivo biological stability of enzyme mutants. The pros and cons of catalytic bioscavengers will be discussed in detail and future requirements for the development of catalytic bioscavengers will be proposed.

  15. Catalytic Synthesis Methods for Triazolopyrimidine Derivatives

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A new method for catalyzed synthesis of triazolopyrimidine derivatives is reported. Aikylamine reaction with dialkyl cyanodithioiminocarbonate was catalyzed by quaternary ammonium salts at room temperature to yield 3-alkylamine-5-amino-1,2,4-triazole in good quality and high yields. After imidization and reaction with an α,β-unsaturated acid derivative, the reaction intermediate was hydrolyzed in the presence of a Lewis acid to obtain the target product. This novel catalytic method for triazolopyrimidine derivatives can be carried out under inexpen-sive and mild conditions, and is safe and environmentally friendly. IH NMR results for all intermediates are re-ported.

  16. Thin film porous membranes for catalytic sensors

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, R.C.; Boyle, T.J.; Gardner, T.J. [and others

    1997-06-01

    This paper reports on new and surprising experimental data for catalytic film gas sensing resistors coated with nanoporous sol-gel films to impart selectivity and durability to the sensor structure. This work is the result of attempts to build selectivity and reactivity to the surface of a sensor by modifying it with a series of sol-gel layers. The initial sol-gel SiO{sub 2} layer applied to the sensor surprisingly showed enhanced O{sub 2} interaction with H{sub 2} and reduced susceptibility to poisons such as H{sub 2}S.

  17. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    , alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  18. Biomimetic, Catalytic Oxidation in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shun-lchi Murahashi

    2005-01-01

    @@ 1Introduction Oxidation is one of the most fundamental reactions in organic synthesis. Owing to the current need to develop forward-looking technology that is environmentally acceptable with respect many aspects. The most attractive approaches are biomimetic oxidation reactions that are closely related to the metabolism of living things. The metabolisms are governed by a variety of enzymes such as cytochrome P-450 and flavoenzyme.Simulation of the function of these enzymes with simple transition metal complex catalyst or organic catalysts led to the discovery of biomimetic, catalytic oxidations with peroxides[1]. We extended such biomimetic methods to the oxidation with molecular oxygen under mild conditions.

  19. Catalytic wet oxidation of black liquor

    OpenAIRE

    Viader Riera, Gerard

    2012-01-01

    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

  20. Catalytic enantioselective synthesis of quaternary carbon stereocentres

    Science.gov (United States)

    Quasdorf, Kyle W.; Overman, Larry E.

    2014-12-01

    Quaternary carbon stereocentres--carbon atoms to which four distinct carbon substituents are attached--are common features of molecules found in nature. However, before recent advances in chemical catalysis, there were few methods of constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for the synthesis of single stereoisomers of such organic molecules. This progress now makes it possible to incorporate quaternary stereocentres selectively in many organic molecules that are useful in medicine, agriculture and potentially other areas such as flavouring, fragrances and materials.