Significance of the enzymatic properties of yeast S39A enolase to the catalytic mechanism.

Science.gov (United States)

Brewer, J M; Glover, C V; Holland, M J; Lebioda, L

1998-04-02

The S39A mutant of yeast enolase (isozyme 1), prepared by site-directed mutagenesis, has a relative Vmax of 0.01% and an activation constant for Mg2+ ca. 10-fold higher, compared with native enzyme. It is correctly folded. There is little effect of solvent viscosity on activity. We think that the loop Ser36-His43 fails to move to the 'closed' position upon catalytic Mg2+ binding, weakening several electrostatic interactions involved in the mechanism.

230Th/234U age of a Mousterian site in France

International Nuclear Information System (INIS)

Schwarcz, H.P.; Blackwell, B.

1983-01-01

The 230 Th/ 234 U dating method has been used to determine the age of a travertine layer in the Pech 1 cave of Sarlat, South-West France. The reported age of 123 +- 15 kyr is consistent with deposition of this travertine during isotope state 5e, the warmest substage of the last inter-glacial. It is shown that this result is consistent with geological and paleontological estimates of the age of sediments filling the cave. (U.K.)

Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study

Science.gov (United States)

Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J.; Martínez, Angel T.

2014-01-01

Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H2O2-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (kcat> 200 s−1) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 kcat ~20 s−1) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant. PMID:25495127

On the mechanism of sulfite activation of chloroplast thylakoid ATPase and the relation of ADP tightly bound at a catalytic site to the binding change mechanism

International Nuclear Information System (INIS)

Du, Z.; Boyer, P.D.

1990-01-01

Washed chloroplast thylakoid membranes upon exposure to [ 3 H]ADP retain in tightly bound [ 3 H]ADP on a catalytic site of the ATP synthase. The presence of sufficient endogenous or added Mg 2+ results in an enzyme with essentially no ATPase activity. Sulfite activates the ATPase, and many molecules of ATP per synthase can be hydrolyzed before most of the bound [ 3 H]ADP is released, a result interpreted as indicating that the ADP is not bound at a site participating in catalysis by the sulfite-activated enzyme. The authors present evidence that this is not the case. The Mg 2+ - and ADP-inhibited enzyme when exposed to MgATP and 20-100 mM sulfite shows a lag of about 1 min at 22 degree C and of about 15 s at 37 degree C before reaching the same steady-state rate as attained with light-activated ATPase that has not been inhibited by Mg 2+ and ADP. The lag is not eliminated if the enzyme is exposed to sulfite prior to MgATP addition, indicating that ATPase turnover is necessary for the activation. The release of most of the bound [ 3 H]ADP parallels the onset of ATPase activity, although some [ 3 H]ADP is not released even with prolonged catalytic turnover and may be on poorly active or inactive enzyme or at noncatalytic sites. The results are consistent with most of the tightly bound [ 3 H]ADP being at a catalytic site and being replaced as this Mg 2+ - and ADP-inhibited site regains equivalent participation with other catalytic sites on the activated enzyme. The sulfite activation can be explained by sulfite combination at a P i binding site of the enzyme-ADP-Mg 2+ complex to give a form more readily activated by ATP binding at an alternative site

A conserved mechanism of autoinhibition for the AMPK kinase domain: ATP-binding site and catalytic loop refolding as a means of regulation

International Nuclear Information System (INIS)

Littler, Dene R.; Walker, John R.; Davis, Tara; Wybenga-Groot, Leanne E.; Finerty, Patrick J. Jr; Newman, Elena; Mackenzie, Farell; Dhe-Paganon, Sirano

2010-01-01

A 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. The AMP-activated protein kinase (AMPK) is a highly conserved trimeric protein complex that is responsible for energy homeostasis in eukaryotic cells. Here, a 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. This human form adopts a catalytically inactive state with distorted ATP-binding and substrate-binding sites. The ATP site is affected by changes in the base of the activation loop, which has moved into an inhibited DFG-out conformation. The substrate-binding site is disturbed by changes within the AMPKα2 catalytic loop that further distort the enzyme from a catalytically active form. Similar structural rearrangements have been observed in a yeast AMPK homologue in response to the binding of its auto-inhibitory domain; restructuring of the kinase catalytic loop is therefore a conserved feature of the AMPK protein family and is likely to represent an inhibitory mechanism that is utilized during function

Measurement of 233U/234U ratios in contaminated groundwater using alpha spectrometry

International Nuclear Information System (INIS)

Harrison, Jennifer J.; Payne, Timothy E.; Wilsher, Kerry L.; Thiruvoth, Sangeeth; Child, David P.; Johansen, Mathew P.; Hotchkis, Michael A.C.

2016-01-01

The uranium isotope 233 U is not usually observed in alpha spectra from environmental samples due to its low natural and fallout abundance. It may be present in samples from sites in the vicinity of nuclear operations such as reactors or fuel reprocessing facilities, radioactive waste disposal sites or sites affected by clandestine nuclear operations. On an alpha spectrum, the two most abundant alpha emissions of 233 U (4.784 MeV, 13.2%; and 4.824 MeV, 84.3%) will overlap with the 234 U doublet peak (4.722 MeV, 28.4%; and 4.775 MeV, 71.4%), if present, resulting in a combined 233+234 U multiplet. A technique for quantifying both 233 U and 234 U from alpha spectra was investigated. A series of groundwater samples were measured both by accelerator mass spectrometry (AMS) to determine 233 U/ 234 U atom and activity ratios and by alpha spectrometry in order to establish a reliable 233 U estimation technique using alpha spectra. The Genie™ 2000 Alpha Analysis and Interactive Peak Fitting (IPF) software packages were used and it was found that IPF with identification of three peaks ( 234 U minor, combined 234 U major and 233 U minor, and 233 U major) followed by interference correction on the combined peak and a weighted average activity calculation gave satisfactory agreement with the AMS data across the 233 U/ 234 U activity ratio range (0.1–20) and 233 U activity range (2–300 mBq) investigated. Correlation between the AMS 233 U and alpha spectrometry 233 U was r 2  = 0.996 (n = 10). - Highlights: • Describes a technique for deconvoluting the combined 233 U and 234 U multiplet in alpha spectra. • Enables 233 U and 234 U activities and 233 U/ 234 U ratios to be quantified without requiring additional analysis and measurement. • Applicable to an environmental matrix (groundwater) using standard alpha spectrometry counting equipment, operation and set-up.

Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

Energy Technology Data Exchange (ETDEWEB)

Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua; (OSU); (FIU)

2009-05-12

S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a {beta}-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

Piv site-specific invertase requires a DEDD motif analogous to the catalytic center of the RuvC Holliday junction resolvases.

Science.gov (United States)

Buchner, John M; Robertson, Anne E; Poynter, David J; Denniston, Shelby S; Karls, Anna C

2005-05-01

Piv, a unique prokaryotic site-specific DNA invertase, is related to transposases of the insertion elements from the IS110/IS492 family and shows no similarity to the site-specific recombinases of the tyrosine- or serine-recombinase families. Piv tertiary structure is predicted to include the RNase H-like fold that typically encompasses the catalytic site of the recombinases or nucleases of the retroviral integrase superfamily, including transposases and RuvC-like Holliday junction resolvases. Analogous to the DDE and DEDD catalytic motifs of transposases and RuvC, respectively, four Piv acidic residues D9, E59, D101, and D104 appear to be positioned appropriately within the RNase H fold to coordinate two divalent metal cations. This suggests mechanistic similarity between site-specific inversion mediated by Piv and transposition or endonucleolytic reactions catalyzed by enzymes of the retroviral integrase superfamily. The role of the DEDD motif in Piv catalytic activity was addressed using Piv variants that are substituted individually or multiply at these acidic residues and assaying for in vivo inversion, intermolecular recombination, and DNA binding activities. The results indicate that all four residues of the DEDD motif are required for Piv catalytic activity. The DEDD residues are not essential for inv recombination site recognition and binding, but this acidic tetrad does appear to contribute to the stability of Piv-inv interactions. On the basis of these results, a working model for Piv-mediated inversion that includes resolution of a Holliday junction is presented.

Direct comparison of {sup 210}Po, {sup 234}Th and POC particle-size distributions and export fluxes at the Bermuda Atlantic Time-series Study (BATS) site

Energy Technology Data Exchange (ETDEWEB)

Stewart, Gillian, E-mail: gstewart@qc.cuny.ed [Queens College, CUNY Flushing, NY 11367 (United States); Moran, S. Bradley, E-mail: moran@gso.uri.ed [Graduate School of Oceanography, URI Narragansett, RI 02882 (United States); Lomas, Michael W., E-mail: Michael.Lomas@bios.ed [Bermuda Institute for Ocean Sciences, St. George' s, GE01 (Bermuda); Kelly, Roger P., E-mail: rokelly@gso.uri.ed [Graduate School of Oceanography, URI Narragansett, RI 02882 (United States)

2011-05-15

Particle-reactive, naturally occurring radionuclides are useful tracers of the sinking flux of organic matter from the surface to the deep ocean. Since the Joint Global Ocean Flux Study (JGOFS) began in 1987, the disequilibrium between {sup 234}Th and its parent {sup 238}U has become widely used as a technique to measure particle export fluxes from surface ocean waters. Another radionuclide pair, {sup 210}Po and {sup 210}Pb, can be used for the same purpose but has not been as widely adopted due to difficulty with accurately constraining the {sup 210}Po/{sup 210}Pb radiochemical balance in the ocean and because of the more time-consuming radiochemical procedures. Direct comparison of particle flux estimated in different ocean regions using these short-lived radionuclides is important in evaluating their utility and accuracy as tracers of particle flux. In this paper, we present paired {sup 234}Th/{sup 238}U and {sup 210}Po/{sup 210}Pb data from oligotrophic surface waters of the subtropical Northwest Atlantic and discuss their advantages and limitations. Vertical profiles of total and particle size-fractionated {sup 210}Po and {sup 234}Th activities, together with particulate organic carbon (POC) concentrations, were measured during three seasons at the Bermuda Atlantic Time-series Study (BATS) site. Both {sup 210}Po and {sup 234}Th reasonably predict sinking POC flux caught in sediment traps, and each tracer provides unique information about the magnitude and efficiency of the ocean's biological pump.

On the mechanism of sulfite activation of chloroplast thylakoid ATPase and the relation of ADP tightly bound at a catalytic site to the binding change mechanism

Energy Technology Data Exchange (ETDEWEB)

Du, Z.; Boyer, P.D. (Univ. of California, Los Angeles (USA))

1990-01-16

Washed chloroplast thylakoid membranes upon exposure to ({sup 3}H)ADP retain in tightly bound ({sup 3}H)ADP on a catalytic site of the ATP synthase. The presence of sufficient endogenous or added Mg{sup 2+} results in an enzyme with essentially no ATPase activity. Sulfite activates the ATPase, and many molecules of ATP per synthase can be hydrolyzed before most of the bound ({sup 3}H)ADP is released, a result interpreted as indicating that the ADP is not bound at a site participating in catalysis by the sulfite-activated enzyme. The authors present evidence that this is not the case. The Mg{sup 2+}- and ADP-inhibited enzyme when exposed to MgATP and 20-100 mM sulfite shows a lag of about 1 min at 22{degree}C and of about 15 s at 37{degree}C before reaching the same steady-state rate as attained with light-activated ATPase that has not been inhibited by Mg{sup 2+} and ADP. The lag is not eliminated if the enzyme is exposed to sulfite prior to MgATP addition, indicating that ATPase turnover is necessary for the activation. The release of most of the bound ({sup 3}H)ADP parallels the onset of ATPase activity, although some ({sup 3}H)ADP is not released even with prolonged catalytic turnover and may be on poorly active or inactive enzyme or at noncatalytic sites. The results are consistent with most of the tightly bound ({sup 3}H)ADP being at a catalytic site and being replaced as this Mg{sup 2+}- and ADP-inhibited site regains equivalent participation with other catalytic sites on the activated enzyme. The sulfite activation can be explained by sulfite combination at a P{sub i} binding site of the enzyme-ADP-Mg{sup 2+} complex to give a form more readily activated by ATP binding at an alternative site.

Some studies on extractive liquid scintillation counting for Th-234/P-234m

International Nuclear Information System (INIS)

Grudpan, K.; Singjanusong, P.; Punyodom, W.

1990-01-01

A study on solvent extraction for Th-234/Pa-234m by liquid scintillation counting has not been reported. This paper will report an application of the technique on such a study. In a hydrochloric acid solution of an uranyl salt, Pa-234m which is one of the daughters of U-238 can be separated by extraction into isobutyl methyl ketone (IBMK). Cerenkov counting was applied for the extraction investigation. Solvent extraction of Th-234/Pa-234m from an aqueous nitric acid solution by TOPO/PPO in toluene by using liquid scintillation counting will be described

Comparison of FeS, FeS + S and solid superacid catalytic properties for coal hydro-liquefaction

Energy Technology Data Exchange (ETDEWEB)

Zhicai Wang; Hengfu Shui; Dexiang Zhang; Jinsheng Gao [East China University of Science and Technology, Shanghai (China). College of Resource and Environment Engineering

2007-03-15

Catalyst plays an important role in direct coal liquefaction. This paper focuses on the catalytic behavior of a novel SO{sub 4}{sup 2-}/ZrO{sub 2} superacid catalyst in coal hydro-liquefaction. A series of hydro-liquefaction experiments were conducted under mild conditions - 400{sup o}C, 30 min and H{sub 2} initial pressure 4 MPa in a batch autoclave with a volume of 100 ml. The catalytic property of SO{sub 4}{sup 2-}/ZrO{sub 2} was compared with FeS and FeS + S by Shenhua coal. The liquefaction products catalyzed by different catalysts were analyzed by FTIR spectrum, {sup 1}H NMR spectrum and element analysis. In addition, the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid was characterized. The results indicated that the SO{sub 4}{sup 2-}/ZrO{sub 2} solid superacid shows outstanding catalytic property for direct liquefaction of coal and gives the highest coal conversion and gas + oil yield compared to other two catalysts. The THF conversion and the extraction yield of CS{sub 2}/NMP mixed solvent of liquefied coal catalyzed with SO{sub 4}{sup 2-}/ZrO{sub 2} are 76.3%, daf and 81.2%, daf respectively, and the yield of gas + oil is 62.5%, daf under the condition used in this study. The pyrolysis of coal macromolecular clusters can be promoted by catalysts such as FeS, FeS + S and SO{sub 4}{sup 2-}/ZrO{sub 2}. There may be only the pyrolysis of volatile matter and the relaxation of the structure of coal macromolecular clusters in non-catalytic liquefaction at 400{sup o}C. Added sulfur in FeS can improve the catalytic activity of hydrogenation. SO{sub 4}{sup 2-}/ZrO{sub 2} is a notable catalyst in the study of coal direct liquefaction because it shows excellent catalytic activities for the pyrolysis and the hydrogenation. In addition, it has been found that the C-O bond is the most stable group in coal liquefaction reaction except for the covalent bond between carbon and carbon. 34 refs., 6 figs., 6 tabs.

Catalytic water co-existing with a product peptide in the active site of HIV-1 protease revealed by X-ray structure analysis.

Science.gov (United States)

Prashar, Vishal; Bihani, Subhash; Das, Amit; Ferrer, Jean-Luc; Hosur, Madhusoodan

2009-11-17

It is known that HIV-1 protease is an important target for design of antiviral compounds in the treatment of Acquired Immuno Deficiency Syndrome (AIDS). In this context, understanding the catalytic mechanism of the enzyme is of crucial importance as transition state structure directs inhibitor design. Most mechanistic proposals invoke nucleophilic attack on the scissile peptide bond by a water molecule. But such a water molecule coexisting with any ligand in the active site has not been found so far in the crystal structures. We report here the first observation of the coexistence in the active site, of a water molecule WAT1, along with the carboxyl terminal product (Q product) peptide. The product peptide has been generated in situ through cleavage of the full-length substrate. The N-terminal product (P product) has diffused out and is replaced by a set of water molecules while the Q product is still held in the active site through hydrogen bonds. The position of WAT1, which hydrogen bonds to both the catalytic aspartates, is different from when there is no substrate bound in the active site. We propose WAT1 to be the position from where catalytic water attacks the scissile peptide bond. Comparison of structures of HIV-1 protease complexed with the same oligopeptide substrate, but at pH 2.0 and at pH 7.0 shows interesting changes in the conformation and hydrogen bonding interactions from the catalytic aspartates. The structure is suggestive of the repositioning, during substrate binding, of the catalytic water for activation and subsequent nucleophilic attack. The structure could be a snap shot of the enzyme active site primed for the next round of catalysis. This structure further suggests that to achieve the goal of designing inhibitors mimicking the transition-state, the hydrogen-bonding pattern between WAT1 and the enzyme should be replicated.

Carbon nanotube aerogel-CoS2 hybrid catalytic counter electrodes for enhanced photovoltaic performance dye-sensitized solar cells.

Science.gov (United States)

Liu, Tao; Mai, Xianmin; Chen, Haijun; Ren, Jing; Liu, Zheting; Li, Yingxiang; Gao, Lina; Wang, Ning; Zhang, Jiaoxia; He, Hongcai; Guo, Zhanhu

2018-03-01

The carbon nanotube aerogel (CNA) with an ultra-low density, three-dimensional network nanostructure, superior electronic conductivity and large surface area is being widely employed as a catalytic electrode and catalytic support. Impressively, dye-sensitized solar cells (DSSCs) assembled with a CNA counter electrode (CE) achieved a maximum power conversion efficiency (PCE) of 8.28%, which exceeded that of the conventional platinum (Pt)-based DSSC (7.20%) under the same conditions. Furthermore, highly dispersed CoS 2 nanoparticles endowed with excellent intrinsic catalytic activity were hydrothermally incorporated to form a CNA-supported CoS 2 (CNA-CoS 2 ) CE, which was due to the large number of catalytically active sites and sufficient connections between CoS 2 and the CNA. The electrocatalytic ability and stability were systematically evaluated by cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and Tafel polarization, which confirmed that the resultant CNA-CoS 2 hybrid CE exhibited a remarkably higher electrocatalytic activity toward I 3 - reduction, and faster ion diffusion and electron transfer than the pure CNA CE. Such cost-effective DSSCs assembled with an optimized CNA-CoS 2 CE yielded an enhanced PCE of 8.92%, comparable to that of the cell fabricated with the CNA-Pt hybrid CE reported in our published literature (9.04%). These results indicate that the CNA-CoS 2 CE can be considered as a promising candidate for Pt-free CEs used in low-cost and high-performance DSSCs.

Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

Energy Technology Data Exchange (ETDEWEB)

Krajčí, Marian [Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84511 Bratislava (Slovakia); Kameoka, Satoshi; Tsai, An-Pang [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

2016-08-28

We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al{sub 2}Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped (211) surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir–Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO–OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.

Seawater 234U/238U recorded by modern and fossil corals

Science.gov (United States)

Chutcharavan, Peter M.; Dutton, Andrea; Ellwood, Michael J.

2018-03-01

U-series dating of corals is a crucial tool for generating absolute chronologies of Late Quaternary sea-level change and calibrating the radiocarbon timescale. Unfortunately, coralline aragonite is susceptible to post-depositional alteration of its primary geochemistry. One screening technique used to identify unaltered corals relies on the back-calculation of initial 234U/238U activity (δ234Ui) at the time of coral growth and implicitly assumes that seawater δ234U has remained constant during the Late Quaternary. Here, we test this assumption using the most comprehensive compilation to date of coral U-series measurements. Unlike previous compilations, this study normalizes U-series measurements to the same decay constants and corrects for offsets in interlaboratory calibrations, thus reducing systematic biases between reported δ234U values. Using this approach, we reassess (a) the value of modern seawater δ234U, and (b) the evolution of seawater δ234U over the last deglaciation. Modern coral δ234U values (145.0 ± 1.5‰) agree with previous measurements of seawater and modern corals only once the data have been normalized. Additionally, fossil corals in the surface ocean display δ234Ui values that are ∼5-7‰ lower during the last glacial maximum regardless of site, taxon, or diagenetic setting. We conclude that physical weathering of U-bearing minerals exposed during ice sheet retreat drives the increase in δ234U observed in the oceans, a mechanism that is consistent with the interpretation of the seawater Pb-isotope signal over the same timescale.

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

Science.gov (United States)

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

Processivity and Subcellular Localization of Glycogen Synthase Depend on a Non-catalytic High Affinity Glycogen-binding Site*

OpenAIRE

Díaz, Adelaida; Martínez-Pons, Carlos; Fita, Ignacio; Ferrer, Juan C.; Guinovart, Joan J.

2011-01-01

Glycogen synthase, a central enzyme in glucose metabolism, catalyzes the successive addition of α-1,4-linked glucose residues to the non-reducing end of a growing glycogen molecule. A non-catalytic glycogen-binding site, identified by x-ray crystallography on the surface of the glycogen synthase from the archaeon Pyrococcus abyssi, has been found to be functionally conserved in the eukaryotic enzymes. The disruption of this binding site in both the archaeal and the human muscle glycogen synth...

Catalytic water co-existing with a product peptide in the active site of HIV-1 protease revealed by X-ray structure analysis.

Directory of Open Access Journals (Sweden)

Vishal Prashar

Full Text Available BACKGROUND: It is known that HIV-1 protease is an important target for design of antiviral compounds in the treatment of Acquired Immuno Deficiency Syndrome (AIDS. In this context, understanding the catalytic mechanism of the enzyme is of crucial importance as transition state structure directs inhibitor design. Most mechanistic proposals invoke nucleophilic attack on the scissile peptide bond by a water molecule. But such a water molecule coexisting with any ligand in the active site has not been found so far in the crystal structures. PRINCIPAL FINDINGS: We report here the first observation of the coexistence in the active site, of a water molecule WAT1, along with the carboxyl terminal product (Q product peptide. The product peptide has been generated in situ through cleavage of the full-length substrate. The N-terminal product (P product has diffused out and is replaced by a set of water molecules while the Q product is still held in the active site through hydrogen bonds. The position of WAT1, which hydrogen bonds to both the catalytic aspartates, is different from when there is no substrate bound in the active site. We propose WAT1 to be the position from where catalytic water attacks the scissile peptide bond. Comparison of structures of HIV-1 protease complexed with the same oligopeptide substrate, but at pH 2.0 and at pH 7.0 shows interesting changes in the conformation and hydrogen bonding interactions from the catalytic aspartates. CONCLUSIONS/SIGNIFICANCE: The structure is suggestive of the repositioning, during substrate binding, of the catalytic water for activation and subsequent nucleophilic attack. The structure could be a snap shot of the enzyme active site primed for the next round of catalysis. This structure further suggests that to achieve the goal of designing inhibitors mimicking the transition-state, the hydrogen-bonding pattern between WAT1 and the enzyme should be replicated.

Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

Science.gov (United States)

Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

2015-04-07

The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing the electrostatics of active site microenvironments along the catalytic cycle for Escherichia coli dihydrofolate reductase.

Science.gov (United States)

Liu, C Tony; Layfield, Joshua P; Stewart, Robert J; French, Jarrod B; Hanoian, Philip; Asbury, John B; Hammes-Schiffer, Sharon; Benkovic, Stephen J

2014-07-23

Electrostatic interactions play an important role in enzyme catalysis by guiding ligand binding and facilitating chemical reactions. These electrostatic interactions are modulated by conformational changes occurring over the catalytic cycle. Herein, the changes in active site electrostatic microenvironments are examined for all enzyme complexes along the catalytic cycle of Escherichia coli dihydrofolate reductase (ecDHFR) by incorporation of thiocyanate probes at two site-specific locations in the active site. The electrostatics and degree of hydration of the microenvironments surrounding the probes are investigated with spectroscopic techniques and mixed quantum mechanical/molecular mechanical (QM/MM) calculations. Changes in the electrostatic microenvironments along the catalytic environment lead to different nitrile (CN) vibrational stretching frequencies and (13)C NMR chemical shifts. These environmental changes arise from protein conformational rearrangements during catalysis. The QM/MM calculations reproduce the experimentally measured vibrational frequency shifts of the thiocyanate probes across the catalyzed hydride transfer step, which spans the closed and occluded conformations of the enzyme. Analysis of the molecular dynamics trajectories provides insight into the conformational changes occurring between these two states and the resulting changes in classical electrostatics and specific hydrogen-bonding interactions. The electric fields along the CN axes of the probes are decomposed into contributions from specific residues, ligands, and solvent molecules that make up the microenvironments around the probes. Moreover, calculation of the electric field along the hydride donor-acceptor axis, along with decomposition of this field into specific contributions, indicates that the cofactor and substrate, as well as the enzyme, impose a substantial electric field that facilitates hydride transfer. Overall, experimental and theoretical data provide evidence for

Networks of High Mutual Information Define the Structural Proximity of Catalytic Sites: Implications for Catalytic Residue Identification

DEFF Research Database (Denmark)

Buslje, Cristina Marino; Teppa, Elin; Di Doménico, Tomas

2010-01-01

other non-functional conserved residues. Using a data set of 434 Pfam families included in the catalytic site atlas (CSA) database, we tested this hypothesis and demonstrated that MI can complement amino acid conservation scores to detect CR. The Kullback-Leibler (KL) conservation measurement was shown.......90, the Cls method was found to have a sensitivity of 0.816. In summary, we demonstrate that networks of residues with high MI provide a distinct signature on CR and propose that such a signature should be present in other classes of functional residues where the requirement to maintain a particular function...

Effect of A-site deficiency in LaMn_0_._9Co_0_._1O_3 perovskites on their catalytic performance for soot combustion

International Nuclear Information System (INIS)

Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel; Fierro, J.L.G.; Pecchi, Gina

2016-01-01

Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La_1_-_xAg_xMn_0_._9Co_0_._1O_3) and A-site deficient (La_1_-_xMn_0_._9Co_0_._1O_3_-_δ) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O_2-TPD and TPR. The formation of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag_2O segregated phases and the redox pair Mn"4"+/Mn"3"+. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn"4"+/Mn"3"+, which is attributed to the cubic crystalline structure.

Residual β activity of particulate 234Th as a novel proxy for tracking sediment resuspension in the ocean

Science.gov (United States)

Lin, Wuhui; Chen, Liqi; Zeng, Shi; Li, Tao; Wang, Yinghui; Yu, Kefu

2016-01-01

Sediment resuspension occurs in the global ocean, which greatly affects material exchange between the sediment and the overlying seawater. The behaviours of carbon, nutrients, heavy metals, and other pollutants at the sediment-seawater boundary will further link to climate change, eutrophication, and marine pollution. Residual β activity of particulate 234Th (RAP234) is used as a novel proxy to track sediment resuspension in different marine environments, including the western Arctic Ocean, the South China Sea, and the Southern Ocean. Sediment resuspension identified by high activity of RAP234 is supported by different lines of evidence including seawater turbidity, residence time of total 234Th, Goldschmidt’s classification, and ratio of RAP234 to particulate organic carbon. A conceptual model is proposed to elucidate the mechanism for RAP234 with dominant contributions from 234Th-238U and 212Bi-228Th. The ‘slope assumption’ for RAP234 indicated increasing intensity of sediment resuspension from spring to autumn under the influence of the East Asian monsoon system. RAP234 can shed new light on 234Th-based particle dynamics and should benefit the interpretation of historical 234Th-238U database. RAP234 resembles lithophile elements and has broad implications for investigating particle dynamics in the estuary-shelf-slope-ocean continuum and linkage of the atmosphere-ocean-sediment system. PMID:27252085

Dissecting the Catalytic Mechanism of Betaine-Homocysteine S-Methyltransferase Using Intrinsic Tryptophan Fluorescence and Site-Directed Mutagenesis

Energy Technology Data Exchange (ETDEWEB)

Castro, C.; Gratson, A.A.; Evans, J.C.; Jiracek, J.; Collinsova, M.; Ludwig, M.L.; Garrow, T.A. (ASCR); (UIUC); (Michigan)

2010-03-05

Betaine-homocysteine S-methyltransferase (BHMT) is a zinc-dependent enzyme that catalyzes the transfer of a methyl group from glycine betaine (Bet) to homocysteine (Hcy) to form dimethylglycine (DMG) and methionine (Met). Previous studies in other laboratories have indicated that catalysis proceeds through the formation of a ternary complex, with a transition state mimicked by the inhibitor S-({delta}-carboxybutyl)-l-homocysteine (CBHcy). Using changes in intrinsic tryptophan fluorescence to determine the affinity of human BHMT for substrates, products, or CBHcy, we now demonstrate that the enzyme-substrate complex reaches its transition state through an ordered bi-bi mechanism in which Hcy is the first substrate to bind and Met is the last product released. Hcy, Met, and CBHcy bind to the enzyme to form binary complexes with K{sub d} values of 7.9, 6.9, and 0.28 {micro}M, respectively. Binary complexes with Bet and DMG cannot be detected with fluorescence as a probe, but Bet and DMG bind tightly to BHMT-Hcy to form ternary complexes with K{sub d} values of 1.1 and 0.73 {micro}M, respectively. Mutation of each of the seven tryptophan residues in human BHMT provides evidence that the enzyme undergoes two distinct conformational changes that are reflected in the fluorescence of the enzyme. The first is induced when Hcy binds, and the second, when Bet binds. As predicted by the crystal structure of BHMT, the amino acids Trp44 and Tyr160 are involved in binding Bet, and Glu159 in binding Hcy. Replacing these residues by site-directed mutagenesis significantly reduces the catalytic efficiency (V{sub max}/K{sub m}) of the enzyme. Replacing Tyr77 with Phe abolishes enzyme activity.

Kinetic catalytic studies of scorpion's hemocyanin

International Nuclear Information System (INIS)

Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.

1991-01-01

Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr

Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

Science.gov (United States)

Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

2018-06-01

A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

Energy-dependent dissociation of ATP from high affinity catalytic sites of beef heart mitochondrial adenosine triphosphatase

International Nuclear Information System (INIS)

Penefsky, H.S.

1985-01-01

Incubation of [gamma- 32 P]ATP with a molar excess of the membrane-bound form of mitochondrial ATPase (F1) results in binding of the bulk of the radioactive nucleotide in high affinity catalytic sites (Ka = 10(12) M-1). Subsequent initiation of respiration by addition of succinate or NADH is accompanied by a profound decrease in the affinity for ATP. About one-third of the bound radioactive ATP appears to dissociate, that is, the [gamma- 32 P]ATP becomes accessible to hexokinase. The NADH-stimulated dissociation of [gamma- 32 P]ATP is energy-dependent since the stimulation is inhibited by uncouplers of oxidative phosphorylation and is prevented by respiratory chain inhibitors. The rate of the energy-dependent dissociation of ATP that occurs in the presence of NADH, ADP, and Pi is commensurate with the measured initial rate of ATP synthesis in NADH-supported oxidative phosphorylation catalyzed by the same submitochondrial particles. Thus, the rate of dissociation of ATP from the high affinity catalytic site of submitochondrial particles meets the criterion of kinetic competency under the conditions of oxidative phosphorylation. These experiments provide evidence in support of the argument that energy conserved during the oxidation of substrates by the respiratory chain can be utilized to reduce the very tight binding of product ATP in high affinity catalytic sites and to promote dissociation of the nucleotide

49 CFR 234.105 - Activation failure.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Activation failure. 234.105 Section 234.105... of Warning System Malfunction § 234.105 Activation failure. Upon receipt of a credible report of warning system malfunction involving an activation failure, a railroad having maintenance responsibility...

32 CFR 234.16 - Gambling.

Science.gov (United States)

2010-07-01

... 32 National Defense 2 2010-07-01 2010-07-01 false Gambling. 234.16 Section 234.16 National Defense Department of Defense (Continued) OFFICE OF THE SECRETARY OF DEFENSE (CONTINUED) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.16 Gambling. Gambling in any form, or the operation of gambling devices, is...

Engineered disulfide bonds increase active-site local stability and reduce catalytic activity of a cold-adapted alkaline phosphatase.

Science.gov (United States)

Asgeirsson, Bjarni; Adalbjörnsson, Björn Vidar; Gylfason, Gudjón Andri

2007-06-01

Alkaline phosphatase is an extracellular enzyme that is membrane-bound in eukaryotes but resides in the periplasmic space of bacteria. It normally carries four cysteine residues that form two disulfide bonds, for instance in the APs of Escherichia coli and vertebrates. An AP variant from a Vibrio sp. has only one cysteine residue. This cysteine is second next to the nucleophilic serine in the active site. We have individually modified seven residues to cysteine that are on two loops predicted to be within a 5 A radius. Four of them formed a disulfide bond to the endogenous cysteine. Thermal stability was monitored by circular dichroism and activity measurements. Global stability was similar to the wild-type enzyme. However, a significant increase in heat-stability was observed for the disulfide-containing variants using activity as a measure, together with a large reduction in catalytic rates (k(cat)) and a general decrease in Km values. The results suggest that a high degree of mobility near the active site and in the helix carrying the endogenous cysteine is essential for full catalytic efficiency in the cold-adapted AP.

Catalytic Ozonation of Toluene Using Chilean Natural Zeolite: The Key Role of Brønsted and Lewis Acid Sites

Directory of Open Access Journals (Sweden)

Serguei Alejandro-Martín

2018-05-01

Full Text Available The influence of surface physical-chemical characteristics of Chilean natural zeolite on the catalytic ozonation of toluene is presented in this article. Surface characteristics of natural zeolite were modified by acid treatment with hydrochloric acid and ion-exchange with ammonium sulphate. Prior to catalytic ozonation assays, natural and chemically modified zeolite samples were thermally treated at 623 and 823 K in order to enhance Brønsted and Lewis acid sites formation, respectively. Natural and modified zeolite samples were characterised by N2 adsorption at 77 K, elemental analysis, X-ray fluorescence, and Fourier transform infrared (FTIR spectroscopy, using pyridine as a probe molecule. The highest values of the reaction rate of toluene oxidation were observed when NH4Z1 and 2NH4Z1 zeolite samples were used. Those samples registered the highest density values of Lewis acid sites compared to other samples used here. Results indicate that the presence of strong Lewis acid sites at the 2NH4Z1 zeolite surface causes an increase in the reaction rate of toluene oxidation, confirming the role of Lewis acid sites during the catalytic ozonation of toluene at room temperature. Lewis acid sites decompose gaseous ozone into atomic oxygen, which reacts with the adsorbed toluene at Brønsted acid sites. On the other hand, no significant contribution of Brønsted acid sites on the reaction rate was registered when NH4Z1 and 2NH4Z1 zeolite samples were used.

The ab initio study of the catalytic hydrogenation of the oxirene

Directory of Open Access Journals (Sweden)

J.B. Mensah

2008-04-01

Full Text Available The oxirene is an unsaturated heterocyclic molecule with one oxygen atom and two carbon atoms. Its hydrogenation has been performed on two catalytic site based on molybdenum disulfide (MoS2 and tungsten disulfide (WS2 of MoS3H3+ and WS3H3+ type, respectively. The calculations were carried out using the SCF and MP2 methods and B3LYP functional calculations. The results obtained showed that the hydrogenation of the oxirene is possible on these two kinds of catalytic sites on the one hand, and the reaction product is the acetaldehyde molecule, on the other hand. The reaction process study that led to the results showed that the catalytic hydrogenation of the oxirene is a dissociative process. On the basis of the variation of some parameters during the process, a mechanism of the reaction has been proposed.

49 CFR 234.251 - Standby power.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Standby power. 234.251 Section 234.251 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION..., Inspection, and Testing Inspections and Tests § 234.251 Standby power. Standby power shall be tested at least...

49 CFR 234.221 - Lamp voltage.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Lamp voltage. 234.221 Section 234.221 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION..., Inspection, and Testing Maintenance Standards § 234.221 Lamp voltage. The voltage at each lamp shall be...

20 CFR 234.33 - Survivor annuities.

Science.gov (United States)

2010-04-01

... 20 Employees' Benefits 1 2010-04-01 2010-04-01 false Survivor annuities. 234.33 Section 234.33 Employees' Benefits RAILROAD RETIREMENT BOARD REGULATIONS UNDER THE RAILROAD RETIREMENT ACT LUMP-SUM PAYMENTS Annuities Due but Unpaid at Death § 234.33 Survivor annuities. Any survivor annuity which is...

222Rn content and 234U/238U activity ratio in groundwaters

International Nuclear Information System (INIS)

Olguin, M.T.; Segovia, N.; Ordonez, E.; Iturbe, J.L.; Bulbulian, S.; Carrillo, J.

1990-01-01

Geochemical radioanalytical studies of ground water were perfomed in the valleys of Villa de Reyes and San Luis Potosi, Mexico. The experiments were designed to measure radon and uranium content and 234 U/ 238 U activity ratio in ground water samples taken from wells in these sites and at the Nuclear Center of Salazar, Mexico. 222 Rn content varied depending on the sample source, reaching a maximum value of 235 pCi/l; uranium concentration results were less than 1 μg/l and 234 U/ 238 U activity ratios were close to equilibrium. (author) 9 refs.; 1 fig.; 1 tab

14 CFR 234.11 - Disclosure to consumers.

Science.gov (United States)

2010-01-01

... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Disclosure to consumers. 234.11 Section 234...) ECONOMIC REGULATIONS AIRLINE SERVICE QUALITY PERFORMANCE REPORTS § 234.11 Disclosure to consumers. Link to..., § 234.11 was revised, effective Apr. 29, 2010. For the convenience of the user, the revised text is set...

Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

KAUST Repository

Huang, Jianfeng

2013-06-12

Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. © 2013 American Chemical Society.

Statistical Profiling of One Promiscuous Protein Binding Site: Illustrated by Urokinase Catalytic Domain.

Science.gov (United States)

Cerisier, Natacha; Regad, Leslie; Triki, Dhoha; Petitjean, Michel; Flatters, Delphine; Camproux, Anne-Claude

2017-10-01

While recent literature focuses on drug promiscuity, the characterization of promiscuous binding sites (ability to bind several ligands) remains to be explored. Here, we present a proteochemometric modeling approach to analyze diverse ligands and corresponding multiple binding sub-pockets associated with one promiscuous binding site to characterize protein-ligand recognition. We analyze both geometrical and physicochemical profile correspondences. This approach was applied to examine the well-studied druggable urokinase catalytic domain inhibitor binding site, which results in a large number of complex structures bound to various ligands. This approach emphasizes the importance of jointly characterizing pocket and ligand spaces to explore the impact of ligand diversity on sub-pocket properties and to establish their main profile correspondences. This work supports an interest in mining available 3D holo structures associated with a promiscuous binding site to explore its main protein-ligand recognition tendency. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

49 CFR 234.259 - Warning time.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Warning time. 234.259 Section 234.259..., Inspection, and Testing Inspections and Tests § 234.259 Warning time. Each crossing warning system shall be tested for the prescribed warning time at least once every 12 months and when the warning system is...

24 CFR 234.65 - Nature of title.

Science.gov (United States)

2010-04-01

... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Nature of title. 234.65 Section 234.65 Housing and Urban Development Regulations Relating to Housing and Urban Development (Continued... OWNERSHIP MORTGAGE INSURANCE Eligibility Requirements-Individually Owned Units § 234.65 Nature of title. A...

Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

Science.gov (United States)

Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

2014-01-09

Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

Extended Impact of Pin1 Catalytic Loop Phosphorylation Revealed by S71E Phosphomimetic.

Science.gov (United States)

Mahoney, Brendan J; Zhang, Meiling; Zintsmaster, John S; Peng, Jeffrey W

2018-03-02

Pin1 is a two-domain human protein that catalyzes the cis-trans isomerization of phospho-Ser/Thr-Pro (pS/T-P) motifs in numerous cell-cycle regulatory proteins. These pS/T-P motifs bind to Pin1's peptidyl-prolyl isomerase (PPIase) domain in a catalytic pocket, between an extended catalytic loop and the PPIase domain core. Previous studies showed that post-translational phosphorylation of S71 in the catalytic loop decreases substrate binding affinity and isomerase activity. To define the origins for these effects, we investigated a phosphomimetic Pin1 mutant, S71E-Pin1, using solution NMR. We find that S71E perturbs not only its host loop but also the nearby PPIase core. The perturbations identify a local network of hydrogen bonds and salt bridges that is more extended than previously thought, and includes interactions between the catalytic loop and the α2/α3 turn in the PPIase core. Explicit-solvent molecular dynamics simulations and phylogenetic analysis suggest that these interactions act as conserved "latches" between the loop and PPIase core that enhance binding of phosphorylated substrates, as they are absent in PPIases lacking pS/T-P specificity. Our results suggest that S71 is a hub residue within an electrostatic network primed for phosphorylation, and may illustrate a common mechanism of phosphorylation-mediated allostery. Copyright © 2018 Elsevier Ltd. All rights reserved.

CMASA: an accurate algorithm for detecting local protein structural similarity and its application to enzyme catalytic site annotation

Directory of Open Access Journals (Sweden)

Li Gong-Hua

2010-08-01

Full Text Available Abstract Background The rapid development of structural genomics has resulted in many "unknown function" proteins being deposited in Protein Data Bank (PDB, thus, the functional prediction of these proteins has become a challenge for structural bioinformatics. Several sequence-based and structure-based methods have been developed to predict protein function, but these methods need to be improved further, such as, enhancing the accuracy, sensitivity, and the computational speed. Here, an accurate algorithm, the CMASA (Contact MAtrix based local Structural Alignment algorithm, has been developed to predict unknown functions of proteins based on the local protein structural similarity. This algorithm has been evaluated by building a test set including 164 enzyme families, and also been compared to other methods. Results The evaluation of CMASA shows that the CMASA is highly accurate (0.96, sensitive (0.86, and fast enough to be used in the large-scale functional annotation. Comparing to both sequence-based and global structure-based methods, not only the CMASA can find remote homologous proteins, but also can find the active site convergence. Comparing to other local structure comparison-based methods, the CMASA can obtain the better performance than both FFF (a method using geometry to predict protein function and SPASM (a local structure alignment method; and the CMASA is more sensitive than PINTS and is more accurate than JESS (both are local structure alignment methods. The CMASA was applied to annotate the enzyme catalytic sites of the non-redundant PDB, and at least 166 putative catalytic sites have been suggested, these sites can not be observed by the Catalytic Site Atlas (CSA. Conclusions The CMASA is an accurate algorithm for detecting local protein structural similarity, and it holds several advantages in predicting enzyme active sites. The CMASA can be used in large-scale enzyme active site annotation. The CMASA can be available by the

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.

Structural/surface characterization and catalytic evaluation of rare-earth (Y, Sm and La) doped ceria composite oxides for CH{sub 3}SH catalytic decomposition

Energy Technology Data Exchange (ETDEWEB)

He, Dedong; Chen, Dingkai; Hao, Husheng; Yu, Jie; Liu, Jiangping; Lu, Jichang; Liu, Feng [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Wan, Gengping [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Research Center for Analysis and Measurement, Hainan University, Haikou, 570228 (China); He, Sufang [Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming, 650093 (China); Luo, Yongming, E-mail: environcatalysis222@yahoo.com [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China)

2016-12-30

Highlights: • Ce{sub 0.75}RE{sub 0.25}O{sub 2-δ} (RE = Y, Sm and La) were synthesized by citrate complexation method. • Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ} exhibited the best stability for the decomposition of CH{sub 3}SH. • Cation radius played a key role in determining structure and surface characteristics. • Catalytic behavior depended on synergistic role of oxygen vacancies and basic sites. • Ce{sub 2}S{sub 3} accumulation on the surface was responsible for the deactivation of catalyst. - Abstract: A series of rare earth (Y, Sm and La) doped ceria composite oxides and pure CeO{sub 2} were synthesized and evaluated by conducting CH{sub 3}SH catalytic decomposition test. Several characterization studies, including XRD, BET, Raman, H{sub 2}-TPR, XPS, FT-IR, CO{sub 2}-TPD and CH{sub 3}SH-TPD, were undertaken to correlate structural and surface properties of the obtained ceria-based catalysts with their catalytic performance for CH{sub 3}SH decomposition. More oxygen vacancies and increased basic sites exhibited in the rare earth doped ceria catalysts. Y doped ceria sample (Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ}), with a moderate increase in basic sites, contained more oxygen vacancies. More structural defects and active sites could be provided, and a relatively small amount of sulfur would accumulate, which resulted in better catalytic performance. The developed catalyst presented good catalytic behavior with stability very similar to that of typical zeolite-based catalysts reported previously. However, La doped ceria catalyst (Ce{sub 0.75}La{sub 0.25}O{sub 2-δ}) with the highest alkalinity was not the most active one. More sulfur species would be adsorbed and a large amount of cerium sulfide species (Ce{sub 2}S{sub 3}) would accumulate, which caused deactivation of the catalysts. The combined effect of increased oxygen vacancies and alkalinity led to the catalytic stability of Ce{sub 0.75}Sm{sub 0.25}O{sub 2-δ} sample was comparable to that of pure Ce

Key Feature of the Catalytic Cycle of TNF-α Converting Enzyme Involves Communication Between Distal Protein Sites and the Enzyme Catalytic Core

International Nuclear Information System (INIS)

Solomon, A.; Akabayov, B.; Frenkel, A.; Millas, M.; Sagi, I.

2007-01-01

Despite their key roles in many normal and pathological processes, the molecular details by which zinc-dependent proteases hydrolyze their physiological substrates remain elusive. Advanced theoretical analyses have suggested reaction models for which there is limited and controversial experimental evidence. Here we report the structure, chemistry and lifetime of transient metal-protein reaction intermediates evolving during the substrate turnover reaction of a metalloproteinase, the tumor necrosis factor-α converting enzyme (TACE). TACE controls multiple signal transduction pathways through the proteolytic release of the extracellular domain of a host of membrane-bound factors and receptors. Using stopped-flow x-ray spectroscopy methods together with transient kinetic analyses, we demonstrate that TACE's catalytic zinc ion undergoes dynamic charge transitions before substrate binding to the metal ion. This indicates previously undescribed communication pathways taking place between distal protein sites and the enzyme catalytic core. The observed charge transitions are synchronized with distinct phases in the reaction kinetics and changes in metal coordination chemistry mediated by the binding of the peptide substrate to the catalytic metal ion and product release. Here we report key local charge transitions critical for proteolysis as well as long sought evidence for the proposed reaction model of peptide hydrolysis. This study provides a general approach for gaining critical insights into the molecular basis of substrate recognition and turnover by zinc metalloproteinases that may be used for drug design

Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

KAUST Repository

Al-Khattaf, S.

2012-01-10

Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

Effect of A-site deficiency in LaMn{sub 0.9}Co{sub 0.1}O{sub 3} perovskites on their catalytic performance for soot combustion

Energy Technology Data Exchange (ETDEWEB)

Dinamarca, Robinson [Department of Physical Chemistry, Faculty of Chemical Sciences, University of Concepción, Concepción (Chile); Garcia, Ximena; Jimenez, Romel [Department of Chemical Engineering, Faculty of Engineering, University of Concepción, Concepción (Chile); Fierro, J.L.G. [Instituto de Catálisis y Petroleoquímica, CSIC, Cantoblanco, 28049 Madrid (Spain); Pecchi, Gina, E-mail: gpecchi@udec.cl [Department of Physical Chemistry, Faculty of Chemical Sciences, University of Concepción, Concepción (Chile)

2016-09-15

Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La{sub 1-x}Ag{sub x}Mn{sub 0.9}Co{sub 0.1}O{sub 3}) and A-site deficient (La{sub 1-x}Mn{sub 0.9}Co{sub 0.1}O{sub 3-δ}) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O{sub 2}-TPD and TPR. The formation of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag{sub 2}O segregated phases and the redox pair Mn{sup 4+}/Mn{sup 3+}. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn{sup 4+}/Mn{sup 3+}, which is attributed to the cubic crystalline structure.

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.

The roles of the catalytic and noncatalytic activities of Rpd3L and Rpd3S in the regulation of gene transcription in yeast.

Directory of Open Access Journals (Sweden)

Daniella Yeheskely-Hayon

Full Text Available In budding yeasts, the histone deacetylase Rpd3 resides in two different complexes called Rpd3L (large and Rpd3S (small that exert opposing effects on the transcription of meiosis-specific genes. By introducing mutations that disrupt the integrity and function of either Rpd3L or Rpd3S, we show here that Rpd3 function is determined by its association with either of these complexes. Specifically, the catalytic activity of Rpd3S activates the transcription of the two major positive regulators of meiosis, IME1 and IME2, under all growth conditions and activates the transcription of NDT80 only during vegetative growth. In contrast, the effects of Rpd3L depends on nutrients; it represses or activates transcription in the presence or absence of a nitrogen source, respectively. Further, we show that transcriptional activation does not correlate with histone H4 deacetylation, suggesting an effect on a nonhistone protein. Comparison of rpd3-null and catalytic-site point mutants revealed an inhibitory activity that is independent of either the catalytic activity of Rpd3 or the integrity of Rpd3L and Rpd3S.

The Roles of the Catalytic and Noncatalytic Activities of Rpd3L and Rpd3S in the Regulation of Gene Transcription in Yeast

Science.gov (United States)

Yeheskely-Hayon, Daniella; Kotler, Anat; Stark, Michal; Hashimshony, Tamar; Sagee, Shira; Kassir, Yona

2013-01-01

In budding yeasts, the histone deacetylase Rpd3 resides in two different complexes called Rpd3L (large) and Rpd3S (small) that exert opposing effects on the transcription of meiosis-specific genes. By introducing mutations that disrupt the integrity and function of either Rpd3L or Rpd3S, we show here that Rpd3 function is determined by its association with either of these complexes. Specifically, the catalytic activity of Rpd3S activates the transcription of the two major positive regulators of meiosis, IME1 and IME2, under all growth conditions and activates the transcription of NDT80 only during vegetative growth. In contrast, the effects of Rpd3L depends on nutrients; it represses or activates transcription in the presence or absence of a nitrogen source, respectively. Further, we show that transcriptional activation does not correlate with histone H4 deacetylation, suggesting an effect on a nonhistone protein. Comparison of rpd3-null and catalytic-site point mutants revealed an inhibitory activity that is independent of either the catalytic activity of Rpd3 or the integrity of Rpd3L and Rpd3S. PMID:24358376

32 CFR 234.12 - Restriction on animals.

Science.gov (United States)

2010-07-01

... 32 National Defense 2 2010-07-01 2010-07-01 false Restriction on animals. 234.12 Section 234.12 National Defense Department of Defense (Continued) OFFICE OF THE SECRETARY OF DEFENSE (CONTINUED) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.12 Restriction on animals. Animals, except guide dogs...

49 CFR 234.201 - Location of plans.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Location of plans. 234.201 Section 234.201..., Inspection, and Testing Maintenance Standards § 234.201 Location of plans. Plans required for proper maintenance and testing shall be kept at each highway-rail grade crossing warning system location. Plans shall...

32 CFR 234.17 - Vehicles and traffic safety.

Science.gov (United States)

2010-07-01

... 32 National Defense 2 2010-07-01 2010-07-01 false Vehicles and traffic safety. 234.17 Section 234...) MISCELLANEOUS CONDUCT ON THE PENTAGON RESERVATION § 234.17 Vehicles and traffic safety. (a) In general. Unless... an alcoholic beverage. (1) Each person within a vehicle is responsible for complying with the...

Tracking particle-associated processes in nearshore environments by use of 234Th/238U disequilibrium

International Nuclear Information System (INIS)

Aller, R.C.; Benninger, L.K.; Cochran, J.K.

1980-01-01

Measurement of excess 234 Th (t 1 sub(/) 2 = 24.1 days) in surface sediment from 12 stations throughout Long Island Sound, U.S.A., demonstrates: (1) a mean (summer) sediment inventory of 3.6 dpm/cm 2 consistent with complete, nearly instantaneous removal of 234 Th from the overlying water and capture within the estuary, and (2) preferential association of excess 234 Th with small particles and inventory build-ups in muddy bottom areas. There may also be a tendency for higher inventories in areas of high physical or biogenic reworking of surface sediments. A range of particle reworking rates (0-5 cm) from -6 to 1.6 x 10 -6 cm 2 /s is found in the Sound with most values approx. 0.2-0.5 x 10 -6 cm 2 /s. The inventory and reworking patterns demonstrate the high mobility, both horizontal and vertical, of particles in the estuary on 234 Th decay time scales and are unequivocal evidence for control of reactive element distribution in the water column by the muddy regions of the basin. (orig.)

Biosphere reserves – learning sites of sustainable development?

Czech Academy of Sciences Publication Activity Database

Kušová, Drahomíra; Těšitel, Jan; Bartoš, Michael

2008-01-01

Roč. 14, č. 3 (2008), s. 221-234 ISSN 1211-7420 Institutional research plan: CEZ:AV0Z60870520 Keywords : nature protection * learning sites * biosphere reserves * sustainable development Subject RIV: DO - Wilderness Conservation

22 CFR 23.4 - Representative value in exchange.

Science.gov (United States)

2010-04-01

... 22 Foreign Relations 1 2010-04-01 2010-04-01 false Representative value in exchange. 23.4 Section 23.4 Foreign Relations DEPARTMENT OF STATE FEES AND FUNDS FINANCE AND ACCOUNTING § 23.4 Representative value in exchange. Representative value in exchange for the collection of a fee means foreign...

Determination of the positions of aluminum atoms introduced into SSZ-35 and the catalytic properties of the generated Brønsted acid sites.

Science.gov (United States)

Miyaji, Akimitsu; Kimura, Nobuhiro; Shiga, Akinobu; Hayashi, Yoshihiro; Nishitoba, Toshiki; Motokura, Ken; Baba, Toshihide

2017-03-01

The positions of aluminum (Al) atoms in SSZ-35 together with the characteristics of the generated protons were investigated by 27 Al multiple quantum magic-angle spinning (MQ-MAS), 29 Si MAS, and 1 H MAS NMR data analyses accompanied by a variable temperature 1 H MAS NMR analysis. The origin of the acidic -OH groups (Brønsted acid sites) generated by introducing Al atoms into the T sites was investigated and the T sites introduced into the Al atoms were revealed. To further determine the catalytic properties of the acidic protons generated in SSZ-35, the influence of the concentration of the Al atoms on the catalytic activity and selectivity during the transformation of toluene was examined.

Solution structure of the parvulin-type PPIase domain of Staphylococcus aureus PrsA – Implications for the catalytic mechanism of parvulins

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Koskela Harri

2009-03-01

Full Text Available Abstract Background Staphylococcus aureus is a Gram-positive pathogenic bacterium causing many kinds of infections from mild respiratory tract infections to life-threatening states as sepsis. Recent emergence of S. aureus strains resistant to numerous antibiotics has created a need for new antimicrobial agents and novel drug targets. S. aureus PrsA is a membrane associated extra-cytoplasmic lipoprotein which contains a parvulin-type peptidyl-prolyl cis-trans isomerase domain. PrsA is known to act as an essential folding factor for secreted proteins in Gram-positive bacteria and thus it is a potential target for antimicrobial drugs against S. aureus. Results We have solved a high-resolution solution structure of the parvulin-type peptidyl-prolyl cis-trans isomerase domain of S. aureus PrsA (PrsA-PPIase. The results of substrate peptide titrations pinpoint the active site and demonstrate the substrate preference of the enzyme. With detailed NMR spectroscopic investigation of the orientation and tautomeric state of the active site histidines we are able to give further insight into the structure of the catalytic site. NMR relaxation analysis gives information on the dynamic behaviour of PrsA-PPIase. Conclusion Detailed structural description of the S. aureus PrsA-PPIase lays the foundation for structure-based design of enzyme inhibitors. The structure resembles hPin1-type parvulins both structurally and regarding substrate preference. Even though a wealth of structural data is available on parvulins, the catalytic mechanism has yet to be resolved. The structure of S. aureus PrsA-PPIase and our findings on the role of the conserved active site histidines help in designing further experiments to solve the detailed catalytic mechanism.

Effect of protein S-nitrosylation on autolysis and catalytic ability of μ-calpain.

Science.gov (United States)

Liu, Rui; Li, Yupin; Wang, Mengqin; Zhou, Guanghong; Zhang, Wangang

2016-12-15

The effect of S-nitrosylation on the autolysis and catalytic ability of μ-calpain in vitro in the presence of 50μM Ca(2 +) was investigated. μ-Calpain was incubated with different concentrations of nitric oxide donor S-nitrosoglutathione (GSNO) and subsequently reacted with purified myofibrils. Results showed that the amount of 80kDa μ-calpain subunit significantly decreased as GSNO increased from 0 to 300μM, but increases of GSNO to 300, 500 and 1000μM did not result in further inhibition. The catalytic ability of nitrosylated μ-calpain to degrade titin, nebulin, troponin-T and desmin was significantly reduced when the GSNO concentration was higher than 300μM. The cysteine residues of μ-calpain at positions 49, 351, 384, and 592 in the catalytic subunit and at 142 in small subunit were S-nitrosylated, which could be responsible for decreased μ-calpain activity. Thus, S-nitrosylation can negatively regulate the activation of μ-calpain resulting in decreased proteolytic ability on myofibrils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

Energy Technology Data Exchange (ETDEWEB)

Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

2015-01-01

ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

48 CFR 234.004 - Acquisition strategy.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false Acquisition strategy. 234..., DEPARTMENT OF DEFENSE SPECIAL CATEGORIES OF CONTRACTING MAJOR SYSTEM ACQUISITION 234.004 Acquisition strategy. (1) See 209.570 for policy applicable to acquisition strategies that consider the use of lead system...

Investigation of the Origin of Catalytic Activity in Oxide-Supported Nanoparticle Gold

Energy Technology Data Exchange (ETDEWEB)

Harrison, Ian [Univ. of Virginia, Charlottesville, VA (United States)

2017-05-26

Since Haruta’s discovery in 1987 of the surprising catalytic activity of supported Au nanoparticles, we have seen a very large number of experimental and theoretical efforts to explain this activity and to fully understand the nature of the behavior of the responsible active sites. In 2011, we discovered that a dual catalytic site at the perimeter of ~3nm diameter Au particles supported on TiO₂ is responsible for oxidative catalytic activity. O₂ molecules bind with Au atoms and Ti4+ ions in the TiO₂ support and the weakened O-O bond dissociates at low temperatures, proceeding to produce O atoms which act as oxidizing agents for the test molecule, CO. The papers supported by DOE have built on this finding and have been concerned with two aspects of the behavior of Au/TiO₂ catalysts: (1). Mechanistic behavior of dual catalytic sites in the oxidation of organic molecules such as ethylene and acetic acid; (2). Studies of the electronic properties of the TiO₂ (110) single crystal in relation to its participation in charge transfer at the occupied dual catalytic site. A total of 20 papers have been produced through DOE support of this work. The papers combine IR spectroscopic investigations of Au/TiO₂ catalysts with surface science on the TiO₂(110) and TiO₂ nanoparticle surfaces with modern density functional modeling. The primary goals of the work were to investigate the behavior of the dual Au/Ti⁴⁺ site for the partial oxidation of alcohols to acids, the hydrogenation of aldehydes and ketones to alcohols, and the condensation of oxygenate intermediates- all processes related to the utilization of biomass in the production of useful chemical energy sources.

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Energy Technology Data Exchange (ETDEWEB)

Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

49 CFR 195.234 - Welds: Nondestructive testing.

Science.gov (United States)

2010-10-01

... 49 Transportation 3 2010-10-01 2010-10-01 false Welds: Nondestructive testing. 195.234 Section 195... HAZARDOUS LIQUIDS BY PIPELINE Construction § 195.234 Welds: Nondestructive testing. (a) A weld may be... weld. (b) Any nondestructive testing of welds must be performed— (1) In accordance with a written set...

14 CFR 234.6 - Baggage-handling statistics.

Science.gov (United States)

2010-01-01

... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Baggage-handling statistics. 234.6 Section 234.6 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION... statistics. Each reporting carrier shall report monthly to the Department on a domestic system basis...

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...

46 CFR 153.234 - Fore and aft location.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Fore and aft location. 153.234 Section 153.234 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING... Containment Systems § 153.234 Fore and aft location. Except as allowed in § 153.7, each ship must meet the...

Structural and Catalytic Properties of S1 Nuclease from Aspergillus oryzae Responsible for Substrate Recognition, Cleavage, Non-Specificity, and Inhibition.

Directory of Open Access Journals (Sweden)

Tomáš Kovaľ

Full Text Available The single-strand-specific S1 nuclease from Aspergillus oryzae is an archetypal enzyme of the S1-P1 family of nucleases with a widespread use for biochemical analyses of nucleic acids. We present the first X-ray structure of this nuclease along with a thorough analysis of the reaction and inhibition mechanisms and of its properties responsible for identification and binding of ligands. Seven structures of S1 nuclease, six of which are complexes with products and inhibitors, and characterization of catalytic properties of a wild type and mutants reveal unknown attributes of the S1-P1 family. The active site can bind phosphate, nucleosides, and nucleotides in several distinguished ways. The nucleoside binding site accepts bases in two binding modes-shallow and deep. It can also undergo remodeling and so adapt to different ligands. The amino acid residue Asp65 is critical for activity while Asn154 secures interaction with the sugar moiety, and Lys68 is involved in interactions with the phosphate and sugar moieties of ligands. An additional nucleobase binding site was identified on the surface, which explains the absence of the Tyr site known from P1 nuclease. For the first time ternary complexes with ligands enable modeling of ssDNA binding in the active site cleft. Interpretation of the results in the context of the whole S1-P1 nuclease family significantly broadens our knowledge regarding ligand interaction modes and the strategies of adjustment of the enzyme surface and binding sites to achieve particular specificity.

Chemically-modified cellulose paper as a microstructured catalytic reactor.

Science.gov (United States)

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

Directory of Open Access Journals (Sweden)

Hirotaka Koga

2015-01-01

Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

Dependence of crystal size on the catalytic performance of a porous coordination polymer.

Science.gov (United States)

Kiyonaga, Tomokazu; Higuchi, Masakazu; Kajiwara, Takashi; Takashima, Yohei; Duan, Jingui; Nagashima, Kazuro; Kitagawa, Susumu

2015-02-14

Submicrosized MOF-76(Yb) exhibits a higher catalytic performance for esterification than microsized MOF-76(Yb). Control of the crystal size of porous heterogeneous catalysts, such as PCP/MOFs, offers a promising approach to fabricating high-performance catalysts based on accessibility to the internal catalytic sites.

Switch in Site of Inhibition: A Strategy for Structure-Based Discovery of Human Topoisomerase IIα Catalytic Inhibitors

Science.gov (United States)

2015-01-01

A study of structure-based modulation of known ligands of hTopoIIα, an important enzyme involved in DNA processes, coupled with synthesis and in vitro assays led to the establishment of a strategy of rational switch in mode of inhibition of the enzyme’s catalytic cycle. 6-Arylated derivatives of known imidazopyridine ligands were found to be selective inhibitors of hTopoIIα, while not showing TopoI inhibition and DNA binding. Interestingly, while the parent imidazopyridines acted as ATP-competitive inhibitors, arylated derivatives inhibited DNA cleavage similar to merbarone, indicating a switch in mode of inhibition from ATP-hydrolysis to the DNA-cleavage stage of catalytic cycle of the enzyme. The 6-aryl-imidazopyridines were relatively more cytotoxic than etoposide in cancer cells and less toxic to normal cells. Such unprecedented strategy will encourage research on “choice-based change” in target-specific mode of action for rapid drug discovery. PMID:25941559

Upper ocean carbon flux determined by the 234Th approach and sediment traps using size-fractionated POC and 234Th data from the Golf of Mexico

International Nuclear Information System (INIS)

Hung, Chin-Chang; Roberts, Kimberly A.; Santschi, Peter H.; Guo, Laodong

2004-01-01

Size-fractionated particulate 234 Th and particulate organic carbon (POC) fluxes were measured in the Gulf of Mexico during 2000 and 2001 in order to obtain a better estimation of upper ocean organic carbon export out of the euphotic zone within cold core and warm core rings, and to assess the relative merit of sediment trap and POC/ 234 Th methods. In 2000, the flux of POC measured by sediment traps at 120 m ranged from 60 to 148 mg C m -2 d -1 , while 234 Th-derived POC fluxes in large particles (>53 μm) varied from 18 to 61 mg C m -2 d -1 using the ratio of POC/ 234 Th at 120 m, and from 51 to 163 mg C m -2 d -1 using an average ratio of POC/ 234 Th for the upper 120 m water column. In 2001, the fluxes of POC measured by traps deployed at 120 m water depth ranged from 39 to 48 mg C m -2 d -1 , while the 234 Th-derived POC fluxes in large particles (>53 μm) varied from 7 to 37 mg C m -2 d -1 using a ratio of POC/ 234 Th at 120 m, and from 37 to 45 mg C m -2 d -1 using an average ratio of POC/ 234 Th within the 0-120 m interval. The results show that POC fluxes estimated by the 234 Th method using the average ratio of POC/ 234 Th within the euphotic zone are similar to those measured by sediment traps. Furthermore, the results demonstrate that the variability in POC export fluxes estimated by the 234 Th/ 238 U disequilibrium approach is strongly related to the ratio of POC/ 234 Th that is taken, and for which we have independent evidence that it may be controlled by the chemical composition of the suspended particles. The results also reveal that using POC/ 234 Th ratios in small particles may result in an estimate of the POC export flux that is considerably higher than when using POC/ 234 Th ratios in large particles (>53 μm). The POC flux calculated from ratios in large particles is, however, more comparable to the POC flux determined directly by sediment traps, but both of these estimates are much lower than that determined by using the POC/ 234 Th ratios in

48 CFR 352.234-4 - Partial earned value management system.

Science.gov (United States)

2010-10-01

... management system. 352.234-4 Section 352.234-4 Federal Acquisition Regulations System HEALTH AND HUMAN....234-4 Partial earned value management system. As prescribed in 334.203-70(d), the Contracting Officer shall insert the following clause: Partial Earned Value Management System (October 2008) (a) The...

48 CFR 352.234-3 - Full earned value management system.

Science.gov (United States)

2010-10-01

... management system. 352.234-3 Section 352.234-3 Federal Acquisition Regulations System HEALTH AND HUMAN....234-3 Full earned value management system. As prescribed in 334.203-70(c), the Contracting Officer shall insert the following clause: Full Earned Value Management System (October 2008) (a) The Contractor...

Cys-X scanning for expansion of active-site residues and modulation of catalytic functions in a glutathione transferase.

Science.gov (United States)

Norrgård, Malena A; Hellman, Ulf; Mannervik, Bengt

2011-05-13

We propose Cys-X scanning as a semisynthetic approach to engineer the functional properties of recombinant proteins. As in the case of Ala scanning, key residues in the primary structure are identified, and one of them is replaced by Cys via site-directed mutagenesis. The thiol of the residue introduced is subsequently modified by alternative chemical reagents to yield diverse Cys-X mutants of the protein. This chemical approach is orthogonal to Ala or Cys scanning and allows the expansion of the repertoire of amino acid side chains far beyond those present in natural proteins. In its present application, we have introduced Cys-X residues in human glutathione transferase (GST) M2-2, replacing Met-212 in the substrate-binding site. To achieve selectivity of the modifications, the Cys residues in the wild-type enzyme were replaced by Ala. A suite of simple substitutions resulted in a set of homologous Met derivatives ranging from normethionine to S-heptyl-cysteine. The chemical modifications were validated by HPLC and mass spectrometry. The derivatized mutant enzymes were assayed with alternative GST substrates representing diverse chemical reactions: aromatic substitution, epoxide opening, transnitrosylation, and addition to an ortho-quinone. The Cys substitutions had different effects on the alternative substrates and differentially enhanced or suppressed catalytic activities depending on both the Cys-X substitution and the substrate assayed. As a consequence, the enzyme specificity profile could be changed among the alternative substrates. The procedure lends itself to large-scale production of Cys-X modified protein variants.

Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst

Directory of Open Access Journals (Sweden)

Luqman Buchori

2017-05-01

Full Text Available Biodiesel synthesis through transesterification of soybean oil with methanol on hybrid catalytic-plasma reactor over sulphated zinc oxide (SO42-/ZnO active acid catalyst was investigated. This research was aimed to study effects of Weight Hourly Space Velocity (WHSV and the catalyst diameter on performance of the hybrid catalytic-plasma reactor for biodiesel synthesis. The amount (20.2 g of active sulphated zinc oxide solid acid catalysts was loaded into discharge zone of the reactor. The WHSV and the catalyst diameter were varied between 0.89 to 1.55 min-1 and 3, 5, and 7 mm, respectively. The molar ratio of methanol to oil as reactants of 15:1 is fed to the reactor, while operating condition of the reactor was kept at reaction temperature of 65 oC and ambient pressure. The fatty acid methyl ester (FAME component in biodiesel product was identified by Gas Chromatography - Mass Spectrometry (GC-MS. The results showed that the FAME yield decreases with increasing WHSV. It was found that the optimum FAME yield was achieved of 56.91 % at WHSV of 0.89 min-1 and catalyst diameter of 5 mm and reaction time of 1.25 min. It can be concluded that the biodiesel synthesis using the hybrid catalytic-plasma reactor system exhibited promising the FAME yield. Copyright © 2017 BCREC Group. All rights reserved Received: 15th November 2016; Revised: 24th December 2016; Accepted: 16th February 2017 How to Cite: Buchori, L., Istadi, I., Purwanto, P. (2017. Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 227-234 (doi:10.9767/bcrec.12.2.775.227-234 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.775.227-234

Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma

KAUST Repository

Cheng, Chia-Chin

2016-09-10

Two-dimensional layered transition metal dichalcogenide (TMD) materials such as Molybdenum disufide (MoS2) have been recognized as one of the low-cost and efficient electrocatalysts for hydrogen evolution reaction (HER). The crystal edges that account for a small percentage of the surface area, rather than the basal planes, of MoS2 monolayer have been confirmed as their active catalytic sites. As a result, extensive efforts have been developing in activating the basal planes of MoS2 for enhancing their HER activity. Here, we report a simple and efficient approach-using a remote hydrogen-plasma process-to creating S-vacancies on the basal plane of monolayer crystalline MoS2; this process can generate high density of S-vacancies while mainly maintaining the morphology and structure of MoS2 monolayer. The density of S-vacancies (defects) on MoS2 monolayers resulted from the remote hydrogen-plasma process can be tuned and play a critical role in HER, as evidenced in the results of our spectroscopic and electrical measurements. The H2-plasma treated MoS2 also provides an excellent platform for systematic and fundamental study of defect-property relationships in TMDs, which provides insights for future applications including electrical, optical and magnetic devices. © 2016 Elsevier Ltd.

Essential histidyl residues at the active site(s) of sucrose-phosphate synthase from Prosopis juliflora.

Science.gov (United States)

Sinha, A K; Pathre, U V; Sane, P V

1998-11-10

Chemical modification of sucrose-phosphate synthase (EC 2.4.1.14) from Prosopis juliflora by diethyl pyrocarbonate (DEP) and photo-oxidation in the presence of rose bengal (RB) which modify the histidyl residues of the protein resulted in the inactivation of the enzyme activity. This inactivation was dependent on the concentration of the modifying reagent and the time of incubation and followed pseudo-first order kinetics. For both the reagents, the inactivation was maximum at pH 7.5, which is consistent with the involvement and presence of histidine residues at the active site of the enzyme. Substrates, UDPG and F6P protected the enzyme against the inactivation by the modifying reagents suggesting that the histidine residues may be involved in the binding of these substrates and are essential for the catalytic activity. Specificity of DEP was indicated by an increase in absorbance at 240 nm along with concomitant inactivation of the enzyme and reactivation of the modified enzyme by hydroxylamine. These results strongly suggest the presence of histidine residue(s) at or near the active site of the enzyme.

40 CFR 86.233-94-86.234-94 - [Reserved

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 18 2010-07-01 2010-07-01 false [Reserved] 86.233-94-86.234-94 Section 86.233-94-86.234-94 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... New Medium-Duty Passenger Vehicles; Cold Temperature Test Procedures §§ 86.233-94—86.234-94 [Reserved] ...

Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

Science.gov (United States)

Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C

2018-03-14

Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.

Residual β activity of particulate (234)Th as a novel proxy for tracking sediment resuspension in the ocean.

Science.gov (United States)

Lin, Wuhui; Chen, Liqi; Zeng, Shi; Li, Tao; Wang, Yinghui; Yu, Kefu

2016-06-02

Sediment resuspension occurs in the global ocean, which greatly affects material exchange between the sediment and the overlying seawater. The behaviours of carbon, nutrients, heavy metals, and other pollutants at the sediment-seawater boundary will further link to climate change, eutrophication, and marine pollution. Residual β activity of particulate (234)Th (RAP234) is used as a novel proxy to track sediment resuspension in different marine environments, including the western Arctic Ocean, the South China Sea, and the Southern Ocean. Sediment resuspension identified by high activity of RAP234 is supported by different lines of evidence including seawater turbidity, residence time of total (234)Th, Goldschmidt's classification, and ratio of RAP234 to particulate organic carbon. A conceptual model is proposed to elucidate the mechanism for RAP234 with dominant contributions from (234)Th-(238)U and (212)Bi-(228)Th. The 'slope assumption' for RAP234 indicated increasing intensity of sediment resuspension from spring to autumn under the influence of the East Asian monsoon system. RAP234 can shed new light on (234)Th-based particle dynamics and should benefit the interpretation of historical (234)Th-(238)U database. RAP234 resembles lithophile elements and has broad implications for investigating particle dynamics in the estuary-shelf-slope-ocean continuum and linkage of the atmosphere-ocean-sediment system.

Catalytic properties of ADAM12 and its domain deletion mutants

DEFF Research Database (Denmark)

Jacobsen, Jonas; Visse, Robert; Sørensen, Hans Peter

2008-01-01

of pro, catalytic, disintegrin, cysteine-rich, and EGF domains. Here we present a novel activity of recombinant ADAM12-S and its domain deletion mutants on S-carboxymethylated transferrin (Cm-Tf). Cleavage of Cm-Tf occurred at multiple sites, and N-terminal sequencing showed that the enzyme exhibits...... restricted specificity but a consensus sequence could not be defined as its subsite requirements are promiscuous. Kinetic analysis revealed that the noncatalytic C-terminal domains are important regulators of Cm-Tf activity and that ADAM12-PC consisting of the pro domain and catalytic domain is the most...... active on this substrate. It was also observed that NaCl inhibits ADAM12. Among the tissue inhibitors of metalloproteinases (TIMP) examined, the N-terminal domain of TIMP-3 (N-TIMP-3) inhibits ADAM12-S and ADAM12-PC with low nanomolar Ki(app) values while TIMP-2 inhibits them with a slightly lower...

Early hominid stone tool production and technical skill 2.34 Myr ago in West Turkana, Kenya.

Science.gov (United States)

Roche, H; Delagnes, A; Brugal, J P; Feibel, C; Kibunjia, M; Mourre, V; Texier, P J

1999-05-06

Well-documented Pliocene archaeological sites are exceptional. At present they are known only in East Africa, in the Hadar and Shungura formations of Ethiopia and in the Nachukui formation of Kenya. Intensive archeological survey and a series of test excavations conducted in the Nachukui formation since 1987 have led to the discovery of more than 25 archaeological sites whose ages range from 2.34 to 0.7 million years before present (Myr), and to the extensive excavation of two 2.34-Myr sites, Lokalalei 1 in 1991 and Lokalalei 2C in 1997. Lokalalei 2C yielded nearly 3,000 archaeological finds from a context of such good preservation that it was possible to reconstitute more than 60 sets of complementary matching stone artefacts. These refits, predating the Koobi Fora refits by 500 Kyr, are the oldest ever studied. Here we describe a technological analysis of the core reduction sequences, based on these refits, which allows unprecedented accuracy in the understanding of flake production processes. We can thus demonstrate greater cognitive capacity and motor skill than previously assumed for early hominids, and highlight the diversity of Pliocene technical behaviour.

238U, 234U and 232Th in seawater

International Nuclear Information System (INIS)

Chen, J.H.; Edwards, R.L.; Wasserburg, G.J.

1986-01-01

We have developed techniques to determine 238 U, 234 U and 232 Th concentrations in seawater by isotope dilution mass spectrometry. Using these techniques, we have measured 238 U, 234 U and 232 Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and 238 U and 234 U in vertical profiles from the Pacific. Determinations of 234 U/ 238 U at depths ranging from 0 to 4900 m in the Atlantic (7 0 44'N, 40 0 43'W) and the Pacific (14 0 41'N, 160 0 01'W) Oceans are the same within experimental error (±5per mille, 2σ). The average of these 234 U/ 238 U measurements is 144±2per mille (2σ) higher than the equilibrium ratio of 5.472 x 10 -5 . U concentrations, normalized to 35per mille salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31 0 4'N, 159 0 1'W) is ∝1% higher than that of the Atlantic (7 0 44'N, 40 0 43'W and 31 0 49'N, 64 0 6'W). 232 Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the 234 U/ 238 U ratio is consistent with the predicted range of 234 U/ 238 U using a simple two-box model and the residence time of deep water in the ocean determined from 14 C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought. (orig./WB)

Progrès apportés par l'utilisation des zéolithes en cracking catalytique Advances Resulting from Using Zeolites in Catalytic Cracking

Directory of Open Access Journals (Sweden)

Marcilly Ch.

2006-11-01

Full Text Available Cet article a pour but d'exposer les progrès intervenus dans le cracking catalytique depuis l'utilisation des tamis moléculaires. II présente les nouveaux catalyseurs, compare leurs propriétés et leurs performances à celles des catalyseurs traditionnels et décrit les modifications et les progrès technologiques qu'ont entraînés l'utilisation des zéolithes. II se limite au cracking catalytique en lit fluide (FCC qui est le type de mise en oeuvre de loin le plus exploité. The aim of this article is to describe advances made in catalytic cracking since molecular sieves began being used. New catalyts are described, their properties and performances are compared with those of traditional catalysts, and the changes and technological advances resulting from the use of zeolites are explained. The article is limited to fluid catalytic cracking IFCCI which is by far the most widely used procedure.

Oxidation of a [Cu2S] complex by N2O and CO2: insights into a role of tetranuclearity in the CuZ site of nitrous oxide reductase.

Science.gov (United States)

Bagherzadeh, Sharareh; Mankad, Neal P

2018-01-25

Oxidation of a [Cu 2 (μ-S)] complex by N 2 O or CO 2 generated a [Cu 2 (μ-SO 4 )] product. In the presence of a sulfur trap, a [Cu 2 (μ-O)] species also formed from N 2 O. A [Cu 2 (μ-CS 3 )] species derived from CS 2 modeled initial reaction intermediates. These observations indicate that one role of tetranuclearity in the Cu Z catalytic site of nitrous oxide reductase is to protect the crucial S 2- ligand from oxidation.

Predicting the catalytic sites of isopenicillin N synthase (IPNS ...

African Journals Online (AJOL)

Isopenicillin N synthase (IPNS) related Non-haem iron-dependent oxygenases and oxidases (NHIDOX) demonstrated a striking structural conservativeness, even with low protein sequence homology. It is evident that these enzymes have an architecturally similar catalytic centre with active ligands lining the reactive pocket.

8 CFR 234.4 - International airports for entry of aliens.

Science.gov (United States)

2010-01-01

... 8 Aliens and Nationality 1 2010-01-01 2010-01-01 false International airports for entry of aliens. 234.4 Section 234.4 Aliens and Nationality DEPARTMENT OF HOMELAND SECURITY IMMIGRATION REGULATIONS DESIGNATION OF PORTS OF ENTRY FOR ALIENS ARRIVING BY CIVIL AIRCRAFT § 234.4 International airports for entry...

A catalytic approach to estimate the redox potential of heme-peroxidases

International Nuclear Information System (INIS)

Ayala, Marcela; Roman, Rosa; Vazquez-Duhalt, Rafael

2007-01-01

The redox potential of heme-peroxidases varies according to a combination of structural components within the active site and its vicinities. For each peroxidase, this redox potential imposes a thermodynamic threshold to the range of oxidizable substrates. However, the instability of enzymatic intermediates during the catalytic cycle precludes the use of direct voltammetry to measure the redox potential of most peroxidases. Here we describe a novel approach to estimate the redox potential of peroxidases, which directly depends on the catalytic performance of the activated enzyme. Selected p-substituted phenols are used as substrates for the estimations. The results obtained with this catalytic approach correlate well with the oxidative capacity predicted by the redox potential of the Fe(III)/Fe(II) couple

Catalysis on singly dispersed bimetallic sites

Science.gov (United States)

Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia; Shan, Junjun; Liu, Jingyue; Frenkel, Anatoly I.; Patlolla, Anitha; Huang, Weixin; Li, Jun; Tao, Franklin

2015-08-01

A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh1Co3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh1Co3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.

Janus droplet as a catalytic micromotor

Science.gov (United States)

Shklyaev, Sergey

2015-06-01

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 μ \\text{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 the Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers.

A Novel Regulator of Activation-Induced Cytidine Deaminase/APOBECs in Immunity and Cancer: Schrödinger’s CATalytic Pocket

Directory of Open Access Journals (Sweden)

Mani Larijani

2017-04-01

Full Text Available Activation-induced cytidine deaminase (AID and its relative APOBEC3 cytidine deaminases boost immune response by mutating immune or viral genes. Because of their genome-mutating activities, AID/APOBECs are also drivers of tumorigenesis. Due to highly charged surfaces, extensive non-specific protein–protein/nucleic acid interactions, formation of polydisperse oligomers, and general insolubility, structure elucidation of these proteins by X-ray crystallography and NMR has been challenging. Hence, almost all available AID/APOBEC structures are of mutated and/or truncated versions. In 2015, we reported a functional structure for AID using a combined computational–biochemical approach. In so doing, we described a new regulatory mechanism that is a first for human DNA/RNA-editing enzymes. This mechanism involves dynamic closure of the catalytic pocket. Subsequent X-ray and NMR studies confirmed our discovery by showing that other APOBEC3s also close their catalytic pockets. Here, we highlight catalytic pocket closure as an emerging and important regulatory mechanism of AID/APOBEC3s. We focus on three sub-topics: first, we propose that variable pocket closure rates across AID/APOBEC3s underlie differential activity in immunity and cancer and review supporting evidence. Second, we discuss dynamic pocket closure as an ever-present internal regulator, in contrast to other proposed regulatory mechanisms that involve extrinsic binding partners. Third, we compare the merits of classical approaches of X-ray and NMR, with that of emerging computational–biochemical approaches, for structural elucidation specifically for AID/APOBEC3s.

A facile strategy for the preparation of ZnS nanoparticles deposited on montmorillonite and their higher catalytic activity for rapidly colorimetric detection of H{sub 2}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Ding, Yanyuan; Sun, Lifang; Jiang, Yanling; Liu, Shunxiang; Chen, Mingxing; Chen, Miaomiao; Ding, Yanan; Liu, Qingyun, E-mail: qyliu@sdust.edu.cn

2016-10-01

In this paper, ZnS nanoparticles deposited on montmorillonite (ZnS-MMT) were prepared by a facile method at room temperature and characterized by powder X-ray diffraction (XRD), Energy-dispersive X-ray Detector (EDX) and transmission electron microscope (TEM), respectively. Significantly, the as-prepared ZnS-MMT nanocomposites have been proven to possess intrinsic peroxidase-like activity that can rapidly catalyze the reaction of peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H{sub 2}O{sub 2} and produce a blue color product in less than 30 seconds, which provides a sensitive colorimetric sensor to detect H{sub 2}O{sub 2}. Due to the synergistic effects between montmorillonite and ZnS nanoparticles, the obtained ZnS-MMT nanocomposites exhibit higher catalytic activity than that of MMT or ZnS alone. The catalytic behaviors of the ZnS-MMT nanocomposites showed a typical Michaelis–Menten kinetics. The catalytic activity and the catalytic mechanism were investigated using the procedures of steady-state kinetics and hydroxyl radical detection. ESR data revealed that the peroxidase-like activity of ZnS-MMT originated from the generation of ·OH radicals. - Highlights: • ZnS nanocomposites deposited on MMT was synthesized by a facile one step method. • MMT-ZnS nanocomposites possess excellent intrinsic peroxidase-like activity and show highly catalytic activity. • A sensitive colorimetric sensor for H{sub 2}O{sub 2} is provided based on MMT-ZnS nanocomposites. • The catalytic mechanism is from the generation of hydroxyl radical (·OH) decomposed from H{sub 2}O{sub 2}.

Influence of glacial meltwater on global seawater δ234U

Science.gov (United States)

Arendt, Carli A.; Aciego, Sarah M.; Sims, Kenneth W. W.; Das, Sarah B.; Sheik, Cody; Stevenson, Emily I.

2018-03-01

We present the first published uranium-series measurements from modern Greenland Ice Sheet (GrIS) runoff and proximal seawater, and investigate the influence of glacial melt on global seawater δ234U over glacial-interglacial (g-ig) timescales. Climate reconstructions based on closed-system uranium-thorium (U/Th) dating of fossil corals assume U chemistry of seawater has remained stable over time despite notable fluctuations in major elemental compositions, concentrations, and isotopic compositions of global seawater on g-ig timescales. Deglacial processes increase weathering, significantly increasing U-series concentrations and changing the δ234U of glacial meltwater. Analyses of glacial discharge from GrIS outlet glaciers indicate that meltwater runoff has elevated U concentrations and differing 222Rn concentrations and δ234U compositions, likely due to variations in subglacial residence time. Locations with high δ234U have the potential to increase proximal seawater δ234U. To better understand the impact of bulk glacial melt on global seawater δ234U over time, we use a simple box model to scale these processes to periods of extreme deglaciation. We account for U fluxes from the GrIS, Antarctica, and large Northern Hemisphere Continental Ice Sheets, and assess sensitivity by varying melt volumes, duration and U flux input rates based on modern subglacial water U concentrations and compositions. All scenarios support the hypothesis that global seawater δ234U has varied by more than 1‰ through time as a function of predictable perturbations in continental U fluxes during g-ig periods.

Towards the rationalization of catalytic activity values by means of local hyper-softness on the catalytic site: a criticism about the use of net electric charges.

Science.gov (United States)

Ignacio Martínez-Araya, Jorge; Grand, André; Glossman-Mitnik, Daniel

2015-11-28

By means of the Spin-Polarized Conceptual Density Functional Theory (SP-CDFT), three 2,6-bis(imino)pyridine catalysts based on iron(II), used for polymerization of ethylene, were studied. The catalysts differed by the substituent group, bearing either -H, -NO2 or -OCH3. To date, catalytic activity, a purely experimental parameter measuring the mass of polyethylene produced per millimole of iron per time and pressure unit at a fixed temperature, has not been explained in terms of local hyper-softness. The latter is a purely theoretical parameter designed for quantifying electronic effects; it is measured using the metal atom responsible for the coordination process with the monomer (ethylene). Because steric effects are not relevant in these kinds of catalysts and only electronic effects drive the catalytic process, an interesting link is found between catalytic activity and the local hyper-softness condensed on the iron atom by means of four functionals (B3LYP, BP86, B97D, and VSXC). This work demonstrates that the use of local hyper-softness, predicted by the SP-CDFT, is a suitable parameter for explaining order relationships among catalytic activity values, thus quantifying the electronic influence of the substituent group inducing this difference; the use of only net electric charges does not lead to clear conclusions. This finding can aid in estimating catalytic activities leading to a more rational design of new catalysts via computational chemistry.

Combining Ru, Ni and Ni(OH){sub 2} active sites for improving catalytic performance in benzene hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Lihua, E-mail: lihuazhu@stu.xmu.edu.cn [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Sun, Hanlei; Zheng, Jinbao [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Yu, Changlin, E-mail: yuchanglinjx@163.com [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Zhang, Nuowei [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Shu, Qing [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiang Xi (China); Chen, Bing H., E-mail: chenbh@xmu.edu.cn [Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

2017-05-01

In this study, the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were successfully prepared by the simple methods of hydrazine-reduction and galvanic replacement, where 0.04/0.96 and T represented the Ru/Ni atomic ratio and reducing temperature of the catalyst in N{sub 2}+10%H{sub 2}, respectively. The nanostructures of the Ru{sub 0.04}Ni{sub 0.96} nanoparticles in the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts were controlled by modulating their annealing temperature in N{sub 2}+10%H{sub 2} and characterized by an array of techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) mapping and high-sensitivity low-energy ion scattering (HS-LEIS). The Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, which was composed of Ru clusters or single atoms supported on Ni/Ni(OH){sub 2} nanoparticles, exhibited much better catalytic performance for benzene hydrogenation than the Ru{sub 0.04}Ni{sub 0.96}/C(T) catalysts reduced at above 30 °C, such as Ru{sub 0.04}Ni{sub 0.96}/C(160) with the nanostructure of partial Ru{sub 0.04}Ni{sub 0.9} alloy and Ru{sub 0.04}Ni{sub 0.96}/C(280) with the nanostructure of complete Ru{sub 0.04}Ni{sub 0.9} alloy. The reason was that the synergistic effect of multiple active sites – Ru, Ni and Ni(OH){sub 2} sites was present in the Ru{sub 0.04}Ni{sub 0.96}/C(30) catalyst, where hydrogen was preferentially activated at Ru sites, benzene was probably activated at Ni(OH){sub 2} surface and Ni acted as a “bridge” for transferring activated H{sup ∗} species to activated benzene by hydrogen spillover effect, hydrogenating and forming product – cyclohexane. This study also provided a typical example to illustrate that the synergy effect of multiple active sites can largely improve the catalytic hydrogenation performance. - Highlights: • The Ru

COMPARISON OF WEST GERMAN AND U.S. FLUE GAS DESULFURIZATION AND SELECTIVE CATALYTIC REDUCTION COSTS

Science.gov (United States)

The report documents a comparison of the actual cost retrofitting flue gas desulfurization (FGD) and selective catalytic reduction (SCR) on Federal Republic of German (FRG) boilers to cost estimating procedures used in the U.S. to estimate the retrofit of these controls on U.S. b...

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

Science.gov (United States)

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

48 CFR 252.234-7002 - Earned Value Management System.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false Earned Value Management... of Provisions And Clauses 252.234-7002 Earned Value Management System. As prescribed in 234.203(2), use the following clause: Earned Value Management System (APR 2008) (a) In the performance of this...

N- versus C-domain selectivity of catalytic inactivation of human angiotensin converting enzyme by lisinopril-coupled transition metal chelates.

Science.gov (United States)

Hocharoen, Lalintip; Joyner, Jeff C; Cowan, J A

2013-12-27

The N- and C-terminal domains of human somatic angiotensin I converting enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates was tested for both reversible binding and irreversible catalytic inactivation of each domain of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and catalytic factors (double-filter effect).

Simultaneous pore enlargement and introduction of highly dispersed Fe active sites in MSNs for enhanced catalytic activity

International Nuclear Information System (INIS)

Gu Jinlou; Dong Xu; Elangovan, S.P.; Li Yongsheng; Zhao Wenru; Iijima, Toshio; Yamazaki, Yasuo; Shi Jianlin

2012-01-01

An effective post-hydrothermal treatment strategy has been developed to dope highly dispersed iron catalytical centers into the framework of mesoporous silica, to keep the particle size in nanometric scale, and in the meanwhile, to expand the pore size of the synthesized mesoporous silica nanoparticles (MSNs). Characterization techniques such as XRD, BET, SEM and TEM support that the synthesized samples are long period ordered with particles size about 100 nm and a relatively large pore size of ca. 3.5 nm. UV–vis, XPS and EPR measurements demonstrate that the introduced iron active centers are highly dispersed in a coordinatively unsaturated status. NH 3 -TPD verifies that the acid amount of iron-doped MSNs is quite high. The synthesized nanocatalysts show an excellent catalytic performance for benzylation of benzene by benzyl chloride, and they present relatively higher yield and selectivity to diphenylmethane with a lower iron content and much shorter reaction time. - Graphical abstract: Uniform MSNs with iron active centers and large pore size have been prepared by a newly developed strategy, which demonstrates enhanced catalytic performance for benzylation of benzene by benzyl chloride. Highlights: ► Iron species were introduced into the framework of mesoporous silica nanoparticles with uniform dispersion. ► The pore sizes of the synthesized nanocatalysts were expanded. ► The acidic site quantities were quite high and the acidic centers were accessible. ► The nanocatalysts presented higher yield and selectivity to diphenylmethane with significantly lower Fe content.

A QM/MM study of the catalytic mechanism of nicotinamidase.

Science.gov (United States)

Sheng, Xiang; Liu, Yongjun

2014-02-28

Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications.

Implication of POC/234Th ratios in oceanic particulate matter. An approach to particle aggregation

International Nuclear Information System (INIS)

Hirose, Katumi

2003-01-01

234 Th has been widely applied as a tracer of particulate organic carbon (POC) fluxes in the upper ocean. Fundamental to this approach is the determination of 234 Th fluxes from water column measurements of the 234 Th- 238 U disequilibria, and the conversion of 234 Th flux to POC export, using the measured POC/ 234 Th ratio on particles. As such, POC/ 234 Th ratios are one of the most critical factors in quantifying the carbon export flux in ocean interior when using this approach. However, the POC/ 234 Th ratios show significant temporal and spatial variations, but cannot be predicted at this time. therefore, it is important to elucidate factors controlling the variations of the POC/ 234 Th ratios. To achieve this purpose, we should understand the chemical interactions between POC and 234 Th. In the open ocean, POC/ 234 Th ratios have been determined together with other oceanographic parameters. We examined here the relationship between POC/ 234 Th and primary production. The POC/ 234 Th ratios were linearly related to logarithmic values of primary production. Taken into account the complexation between surface ligand on particulate organic matter (POM) and 234 Th, a complexation model suggests that the size of particles adsorbing 234 Th is related to primary production; in the equatorial Pacific, the size of particles adsorbing 234 Th apparently decreases with increasing primary production, whereas opposite phenomenon occurs in the North Atlantic. Since the POC/ 234 Th ratios were determined in filtered particulate matter, this finding suggests that aggregation of small particles would be dominant in the equatorial Pacific, which can be explained by a chemical aggregation model. (author)

Catalytic Pyrolysis of Chilean Oak: Influence of Brønsted Acid Sites of Chilean Natural Zeolite

Directory of Open Access Journals (Sweden)

Serguei Alejandro Martín

2017-11-01

Full Text Available This paper proposes the Chilean natural zeolite as catalyst on bio-oil upgrade processes. The aim of this study was to analyze chemical composition of bio-oil samples obtained from catalytic pyrolysis of Chilean native oak in order to increase bio-oil stability during storage. In order to identify chemical compounds before and after storage, biomass pyrolysis was carried out in a fixed bed reactor at 623 K and bio-oil samples were characterized by gas chromatography/mass spectrophotometry (GC/MS. A bio-oil fractionation method was successfully applied here. Results indicate that bio-oil viscosity decreases due to active sites on the zeolite framework. Active acids sites were associated with an increment of alcohols, aldehydes, and hydrocarbon content during storage. Higher composition on aldehydes and alcohols after storage could be attributed to the occurrence of carbonyl reduction reactions that promotes them. These reactions are influenced by zeolite surface characteristics and could be achieved via the direct contribution of Brønsted acid sites to Chilean natural zeolite.

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.

Including lateral interactions into microkinetic models of catalytic reactions

DEFF Research Database (Denmark)

Hellman, Anders; Honkala, Johanna Karoliina

2007-01-01

In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

Rice Cellulose SynthaseA8 Plant-Conserved Region Is a Coiled-Coil at the Catalytic Core Entrance

Energy Technology Data Exchange (ETDEWEB)

Rushton, Phillip S.; Olek, Anna T.; Makowski, Lee; Badger, John; Steussy, C. Nicklaus; Carpita, Nicholas C.; Stauffacher, Cynthia V. (NEU); (Purdue)

2016-11-22

The crystallographic structure of a rice (Oryza sativa) cellulose synthase, OsCesA8, plant-conserved region (P-CR), one of two unique domains in the catalytic domain of plant CesAs, was solved to 2.4 Å resolution. Two antiparallel α-helices form a coiled-coil domain linked by a large extended connector loop containing a conserved trio of aromatic residues. The P-CR structure was fit into a molecular envelope for the P-CR domain derived from small-angle X-ray scattering data. The P-CR structure and molecular envelope, combined with a homology-based chain trace of the CesA8 catalytic core, were modeled into a previously determined CesA8 small-angle X-ray scattering molecular envelope to produce a detailed topological model of the CesA8 catalytic domain. The predicted position for the P-CR domain from the molecular docking models places the P-CR connector loop into a hydrophobic pocket of the catalytic core, with the coiled-coil aligned near the entrance of the substrate UDP-glucose into the active site. In this configuration, the P-CR coiled-coil alone is unlikely to regulate substrate access to the active site, but it could interact with other domains of CesA, accessory proteins, or other CesA catalytic domains to control substrate delivery.

XPS-UPS, ISS characterization studies and the effect of Pt and K addition on the catalytic properties of MoO2-x(OH)y deposited on TiO2

International Nuclear Information System (INIS)

Al-Kandari, H.; Mohamed, A.M.; Al-Kharafi, F.; Katrib, A.

2011-01-01

Highlights: → Surface electronic structure-catalytic activity correlation is presented in this research work. → In situ characterization by XPS-UPS and ISS techniques were employed at the same experimental conditions applied for catalytic reactions. → Catalytic reactions of Mo deposited on titanium oxide for the isomerization and hydrogenation reactions using 1-hexene and n-hexane were studied. → The bifunctional properties of the molybdenum dioxide phase were modified by the addition of potassium. - Abstract: Characterization by XPS-UPS, ISS surface techniques of MoO 3 /TiO 2 catalysts before and after addition of Pt (PtMo) 2.5% by weight of MoO 3 and potassium (KMo) enabled to identify different chemical species present on the outermost surface layer at different reduction temperatures. Catalytic activities of these systems using 1-hexene and n-hexane reactants were studied. Correlation between catalytic activity and surface electronic structure enabled us to identify the chemical species, active site(s), responsible for specific catalytic reaction(s).

20 CFR 234.32 - Spouse or divorced spouse annuities.

Science.gov (United States)

2010-04-01

... 20 Employees' Benefits 1 2010-04-01 2010-04-01 false Spouse or divorced spouse annuities. 234.32... LUMP-SUM PAYMENTS Annuities Due but Unpaid at Death § 234.32 Spouse or divorced spouse annuities. A spouse annuity or divorced spouse annuity which is unpaid at the death of the spouse or divorced spouse...

Roles of s3 site residues of nattokinase on its activity and substrate specificity.

Science.gov (United States)

Wu, Shuming; Feng, Chi; Zhong, Jin; Huan, Liandong

2007-09-01

Nattokinase (Subtilisin NAT, NK) is a bacterial serine protease with high fibrinolytic activity. To probe their roles on protease activity and substrate specificity, three residues of S3 site (Gly(100), Ser(101) and Leu(126)) were mutated by site-directed mutagenesis. Kinetics parameters of 20 mutants were measured using tetrapeptides as substrates, and their fibrinolytic activities were determined by fibrin plate method. Results of mutation analysis showed that Gly(100) and Ser(101) had reverse steric and electrostatic effects. Residues with bulky or positively charged side chains at position 100 decreased the substrate binding and catalytic activity drastically, while residues with the same characters at position 101 could obviously enhance protease and fibrinolytic activity of NK. Mutation of Leu(126) might impair the structure of the active cleft and drastically decreased the activity of NK. Kinetics studies of the mutants showed that S3 residues were crucial to keep protease activity while they moderately affected substrate specificity of NK. The present study provided some original insight into the P3-S3 interaction in NK and other subtilisins, as well as showed successful protein engineering cases to improve NK as a potential therapeutic agent.

Biochemical similarities and differences between the catalytic [4Fe-4S] cluster containing fumarases FumA and FumB from Escherichia coli.

Directory of Open Access Journals (Sweden)

Barbara M A van Vugt-Lussenburg

Full Text Available BACKGROUND: The highly homologous [4Fe-4S] containing fumarases FumA and FumB, sharing 90% amino acid sequence identity, from Escherichia coli are differentially regulated, which suggests a difference in their physiological function. The ratio of FumB over FumA expression levels increases by one to two orders of magnitude upon change from aerobic to anaerobic growth conditions. METHODOLOGY/PRINCIPAL FINDINGS: To understand this difference in terms of structure-function relations, catalytic and thermodynamic properties were determined for the two enzymes obtained from homologous overexpression systems. FumA and FumB are essentially identical in their Michaelis-Menten kinetics of the reversible fumarate to L-malate conversion; however, FumB has a significantly greater catalytic efficiency for the conversion of D-tartrate to oxaloacetate consistent with the requirement of the fumB gene for growth on D-tartrate. Reduction potentials of the [4Fe-4S](2+ Lewis acid active centre were determined in mediated bulk titrations in the presence of added substrate and were found to be approximately -290 mV for both FumA and FumB. CONCLUSIONS/SIGNIFICANCE: This study contradicts previously published claims that FumA and FumB exhibit different catalytic preferences for the natural substrates L-malate and fumarate. FumA and FumB differ significantly only in the catalytic efficiency for the conversion of D-tartrate, a supposedly non-natural substrate. The reduction potential of the substrate-bound [4Fe-4S] active centre is, contrary to previously reported values, close to the cellular redox potential.

Specificity and versatility of substrate binding sites in four catalytic domains of human N-terminal acetyltransferases.

Directory of Open Access Journals (Sweden)

Cédric Grauffel

Full Text Available Nt-acetylation is among the most common protein modifications in eukaryotes. Although thought for a long time to protect proteins from degradation, the role of Nt-acetylation is still debated. It is catalyzed by enzymes called N-terminal acetyltransferases (NATs. In eukaryotes, several NATs, composed of at least one catalytic domain, target different substrates based on their N-terminal sequences. In order to better understand the substrate specificity of human NATs, we investigated in silico the enzyme-substrate interactions in four catalytic subunits of human NATs (Naa10p, Naa20p, Naa30p and Naa50p. To date hNaa50p is the only human subunit for which X-ray structures are available. We used the structure of the ternary hNaa50p/AcCoA/MLG complex and a structural model of hNaa10p as a starting point for multiple molecular dynamics simulations of hNaa50p/AcCoA/substrate (substrate=MLG, EEE, MKG, hNaa10p/AcCoA/substrate (substrate=MLG, EEE. Nine alanine point-mutants of the hNaa50p/AcCoA/MLG complex were also simulated. Homology models of hNaa20p and hNaa30p were built and compared to hNaa50p and hNaa10p. The simulations of hNaa50p/AcCoA/MLG reproduce the interactions revealed by the X-ray data. We observed strong hydrogen bonds between MLG and tyrosines 31, 138 and 139. Yet the tyrosines interacting with the substrate's backbone suggest that their role in specificity is limited. This is confirmed by the simulations of hNaa50p/AcCoA/EEE and hNaa10p/AcCoA/MLG, where these hydrogen bonds are still observed. Moreover these tyrosines are all conserved in hNaa20p and hNaa30p. Other amino acids tune the specificity of the S1' sites that is different for hNaa10p (acidic, hNaa20p (hydrophobic/basic, hNaa30p (basic and hNaa50p (hydrophobic. We also observe dynamic correlation between the ligand binding site and helix [Formula: see text] that tightens under substrate binding. Finally, by comparing the four structures we propose maps of the peptide

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

Energy Technology Data Exchange (ETDEWEB)

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

2003-03-31

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

Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic ...

Indian Academy of Sciences (India)

The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail. ... in the presence of a weak acid.4 This prompted us to investigate whether .... shifted to lower magnetic field strengths than those in parent ...

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

OpenAIRE

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-01-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of M...

49 CFR 234.211 - Security of warning system apparatus.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Security of warning system apparatus. 234.211... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION GRADE CROSSING SIGNAL SYSTEM SAFETY AND STATE ACTION PLANS Maintenance, Inspection, and Testing Maintenance Standards § 234.211 Security of warning system apparatus...

SABER: a computational method for identifying active sites for new reactions.

Science.gov (United States)

Nosrati, Geoffrey R; Houk, K N

2012-05-01

A software suite, SABER (Selection of Active/Binding sites for Enzyme Redesign), has been developed for the analysis of atomic geometries in protein structures, using a geometric hashing algorithm (Barker and Thornton, Bioinformatics 2003;19:1644-1649). SABER is used to explore the Protein Data Bank (PDB) to locate proteins with a specific 3D arrangement of catalytic groups to identify active sites that might be redesigned to catalyze new reactions. As a proof-of-principle test, SABER was used to identify enzymes that have the same catalytic group arrangement present in o-succinyl benzoate synthase (OSBS). Among the highest-scoring scaffolds identified by the SABER search for enzymes with the same catalytic group arrangement as OSBS were L-Ala D/L-Glu epimerase (AEE) and muconate lactonizing enzyme II (MLE), both of which have been redesigned to become effective OSBS catalysts, demonstrated by experiments. Next, we used SABER to search for naturally existing active sites in the PDB with catalytic groups similar to those present in the designed Kemp elimination enzyme KE07. From over 2000 geometric matches to the KE07 active site, SABER identified 23 matches that corresponded to residues from known active sites. The best of these matches, with a 0.28 Å catalytic atom RMSD to KE07, was then redesigned to be compatible with the Kemp elimination using RosettaDesign. We also used SABER to search for potential Kemp eliminases using a theozyme predicted to provide a greater rate acceleration than the active site of KE07, and used Rosetta to create a design based on the proteins identified. Copyright © 2012 The Protein Society.

An ab initio study of hydrotreating of thiirene and thiirane on MoS 3 ...

African Journals Online (AJOL)

The catalytic site used is based on molybdenum disulfide (MoS2), which is considered ... Two steps characterise the desulfurization process: the adsorption and the ... catalytic site and molecules obtained in previous works in the EHT method.

49 CFR 234.213 - Grounds.

Science.gov (United States)

2010-10-01

... Maintenance Standards § 234.213 Grounds. Each circuit that affects the proper functioning of a highway-rail... in the circuit. This requirement does not apply to: circuits that include track rail; alternating current power distribution circuits that are grounded in the interest of safety; and common return wires...

Catalytic extraction processing of contaminated scrap metal

Energy Technology Data Exchange (ETDEWEB)

Griffin, T.P.; Johnston, J.E.; Payea, B.M. [Molten Metal Technology, Inc., Waltham, MA (United States)] [and others

1995-10-01

The U.S. Department of Energy issued a Planned Research and Development Announcement (PRDA) in 1993, with the objective of identifying unique technologies which could be applied to the most hazardous waste streams at DOE sites. The combination of radioactive contamination with additional contamination by hazardous constituents such as those identified by the Resource Conservation and Recovery Act (RCRA) pose an especially challenging problem. Traditional remediation technologies are increasingly becoming less acceptable to stakeholders and regulators because of the risks they pose to public health and safety. Desirable recycling technologies were described by the DOE as: (1) easily installed, operated, and maintained; (2) exhibiting superior environmental performance; (3) protective of worker and public health and safety; (4) readily acceptable to a wide spectrum of evaluators; and (5) economically feasible. Molten Metal Technology, Inc. (MMT) was awarded a contract as a result of the PRDA initiative to demonstrate the applicability of Catalytic Extraction Processing (CEP), MMT`s proprietary elemental recycling technology, to DOE`s inventory of low level mixed waste. This includes DOE`s inventory of radioactively- and RCRA-contaminated scrap metal and other waste forms expected to be generated by the decontamination and decommissioning (D&D) of DOE sites.

Metal Oxide Nanoparticles Supported on Macro-Mesoporous Aluminosilicates for Catalytic Steam Gasification of Heavy Oil Fractions for On-Site Upgrading

Directory of Open Access Journals (Sweden)

Daniel López

2017-10-01

Full Text Available Catalytic steam gasification of extra-heavy oil (EHO fractions was studied using functionalized aluminosilicates, with NiO, MoO3, and/or CoO nanoparticles with the aim of evaluating the synergistic effect between active phase and the support in heavy oil on-site upgrading. Catalysts were characterized by chemical composition through X-ray Fluorescence, surface area, and pore size distribution through N2 adsorption/desorption, catalyst acidity by temperature programmed desorption (TPD, and metal dispersion by pulse H2 chemisorption. Batch adsorption experiments and catalytic steam gasification of adsorbed heavy fractions was carried out by thermogravimetric analysis and were performed with heavy oil model solutions of asphaltenes and resins (R–A in toluene. Effective activation energy estimation was used to determine the catalytic effect of the catalyst in steam gasification of Colombian EHO. Additionally, R–A decomposition under inert atmosphere was conducted for the evaluation of oil components reactions with active phases and steam atmosphere. The presence of a bimetallic active phase Inc.reases the decomposition of the heavy compounds at low temperature by an increase in the aliphatic chains decomposition and the dissociation of heteroatoms bonds. Also, coke formation after steam gasification process is reduced by the application of the bimetallic catalyst yielding a conversion greater than 93%.

Effectiveness of intragastric administration of 8102 for removal of thorium-234 in rats

International Nuclear Information System (INIS)

Luo Meichu; Li Landi; Sun Meizhen; Ye Qian; Liu Yi

1992-01-01

8102, a 1,2-dihydroxy-3,6-bismethylamino diacetic derivative, is a new chelating agent for decorporation of radionuclides. The effectiveness of intragastric administration of this drug at different doses (50-1000 mg/kg of body) and at different times before or after giving thorium-234 in rats was reported. The results show that for rats given intragastricly 1000 mg/kg of 8102, the excretion of thorium-234 in urine for first two days is 4.5 times more than that for control rats and accumulations of thorium-234 in liver, skeleton and kidney for these rats were 30%, 62% and 68% as those for control rats, respectively. The effectiveness was reduced with decrease in dosage of 8102. Administration of 8102 at 1 or 2 h before injection of thorium-234 can improve the effectiveness for decorporation of thorium-234: accumulation of thorium-234 in liver was markedly less than that for rats given 8102 immediately after injection of thorium-234. Delayed administration of 9102 resulted in reduction of the effectiveness. The practicality of oral administration of 8102 in clinic for decorporation of radionuclides was discussed

Two oxidation sites for low redox potential substrates: a directed mutagenesis, kinetic, and crystallographic study on Pleurotus eryngii versatile peroxidase.

Science.gov (United States)

Morales, María; Mate, María J; Romero, Antonio; Martínez, María Jesús; Martínez, Ángel T; Ruiz-Dueñas, Francisco J

2012-11-30

Versatile peroxidase shares with manganese peroxidase and lignin peroxidase the ability to oxidize Mn(2+) and high redox potential aromatic compounds, respectively. Moreover, it is also able to oxidize phenols (and low redox potential dyes) at two catalytic sites, as shown by biphasic kinetics. A high efficiency site (with 2,6-dimethoxyphenol and p-hydroquinone catalytic efficiencies of ∼70 and ∼700 s(-1) mM(-1), respectively) was localized at the same exposed Trp-164 responsible for high redox potential substrate oxidation (as shown by activity loss in the W164S variant). The second site, characterized by low catalytic efficiency (∼3 and ∼50 s(-1) mM(-1) for 2,6-dimethoxyphenol and p-hydroquinone, respectively) was localized at the main heme access channel. Steady-state and transient-state kinetics for oxidation of phenols and dyes at the latter site were improved when side chains of residues forming the heme channel edge were removed in single and multiple variants. Among them, the E140G/K176G, E140G/P141G/K176G, and E140G/W164S/K176G variants attained catalytic efficiencies for oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) at the heme channel similar to those of the exposed tryptophan site. The heme channel enlargement shown by x-ray diffraction of the E140G, P141G, K176G, and E140G/K176G variants would allow a better substrate accommodation near the heme, as revealed by the up to 26-fold lower K(m) values (compared with native VP). The resulting interactions were shown by the x-ray structure of the E140G-guaiacol complex, which includes two H-bonds of the substrate with Arg-43 and Pro-139 in the distal heme pocket (at the end of the heme channel) and several hydrophobic interactions with other residues and the heme cofactor.

MgATP-concentration dependence of protection of yeast vacuolar V-ATPase from inactivation by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole supports a bi-site catalytic mechanism of ATP hydrolysis

International Nuclear Information System (INIS)

Milgrom, Elena M.; Milgrom, Yakov M.

2012-01-01

Highlights: ► MgATP protects V-ATPase from inactivation by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole. ► V-ATPase activity saturation with MgATP is not sufficient for complete protection. ► The results support a bi-site catalytic mechanism for V-ATPase. -- Abstract: Catalytic site occupancy of the yeast vacuolar V-ATPase during ATP hydrolysis in the presence of an ATP-regenerating system was probed using sensitivity of the enzyme to inhibition by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl). The results show that, regardless of the presence or absence of the proton-motive force across the vacuolar membrane, saturation of V-ATPase activity at increasing MgATP concentrations is accompanied by only partial protection of the enzyme from inhibition by NBD-Cl. Both in the presence and absence of an uncoupler, complete protection of V-ATPase from inhibition by NBD-Cl requires MgATP concentrations that are significantly higher than those expected from the K m values for MgATP. The results are inconsistent with a tri-site model and support a bi-site model for a mechanism of ATP hydrolysis by V-ATPase.

XPS-UPS, ISS characterization studies and the effect of Pt and K addition on the catalytic properties of MoO{sub 2-x}(OH){sub y} deposited on TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Al-Kandari, H. [Public Authority of Applied Education and Training (Kuwait); Mohamed, A.M.; Al-Kharafi, F. [Kuwait University, Department of Chemistry, P.O. Box 5969, Safat 13060 (Kuwait); Katrib, A., E-mail: ali.katrib@ku.edu.kw [Kuwait University, Department of Chemistry, P.O. Box 5969, Safat 13060 (Kuwait)

2011-11-15

Highlights: {yields} Surface electronic structure-catalytic activity correlation is presented in this research work. {yields} In situ characterization by XPS-UPS and ISS techniques were employed at the same experimental conditions applied for catalytic reactions. {yields} Catalytic reactions of Mo deposited on titanium oxide for the isomerization and hydrogenation reactions using 1-hexene and n-hexane were studied. {yields} The bifunctional properties of the molybdenum dioxide phase were modified by the addition of potassium. - Abstract: Characterization by XPS-UPS, ISS surface techniques of MoO{sub 3}/TiO{sub 2} catalysts before and after addition of Pt (PtMo) 2.5% by weight of MoO{sub 3} and potassium (KMo) enabled to identify different chemical species present on the outermost surface layer at different reduction temperatures. Catalytic activities of these systems using 1-hexene and n-hexane reactants were studied. Correlation between catalytic activity and surface electronic structure enabled us to identify the chemical species, active site(s), responsible for specific catalytic reaction(s).

Preparation of microcuries of 234-thorium

International Nuclear Information System (INIS)

Suner, A.; La Gamma de Batistoni, A.M.; Botbol, J.

1974-11-01

A procedure for the preparation of microcuries of 234 Th from hydrochloric acid solutions of uranium (VI) is described. A solution of uranyl chloride in radioactive equilibrium with 234 Th (older than 6 months) and having 232 Th as carrier, is percoled through a Dowex 50 Wx8 (H + ) resin bed, wherein is absorbed 85% of Th and some uranium, which is then desorbed with 10 N HCl. The thorium remains in the column and is extracted later with a 0,025 M SO 4 H 2 plus 1 M SO 4 (NH 4 ) 2 solution. The thorium solution is freed from sulfate by precipitation with ammonia, dissolving the precipitate with 10 N HCl, whose solution is treated with Dowex 2x8 resin. The ion exchanger absorbs the anionic impurities and the thorium obtained is of high chemical and radiochemical purity. (author)

Relation between 234Th scavenging and zooplankton biomass in Mediterranean surface waters

International Nuclear Information System (INIS)

Schmidt, S.; Reyss, J.L.; Buat-Menard, P.; Nival, P.; Baker, M.

1992-01-01

Dissolved and particulate 234 Th activities were determined and phyto-and zooplankton biomass were periodically measured 8 miles off Nice (Mediterranean Sea) during spring 1987. The results show a strong variability of 234 Th distribution on short time scales in northwestern Mediterranean surface waters. The good correlation observed the zooplankton biomass and the rate of 234 Th export to deep water in particulate form is agreement with the assumption that the residence time of particulate 234 Th in oceanic surface waters is controlled by zooplankton grazing. Moreover, our results indicate the importance of salps in particular as efficient removers of small suspended particles in surface waters

Testing the FOODBANCS hypothesis: Seasonal variations in near-bottom particle flux, bioturbation intensity, and deposit feeding based on 234Th measurements

Science.gov (United States)

McClintic, Mark A.; DeMaster, David J.; Thomas, Carrie J.; Smith, Craig R.

2008-11-01

Naturally occurring 234Th (24-d half-life) was used on the West Antarctic continental shelf to evaluate temporal variations in the flux of particulate material reaching the seabed, bioturbation intensity, the seasonal continuity of feeding by benthic fauna, and trends in particle selection during ingestion for six common detritivores (four surface deposit feeders and two subsurface deposit feeders). These measurements were made at three stations during the five FOODBANCS cruises (December 1999, March, June, and October 2000, and March 2001) to assess the nature of pelagic-benthic coupling on the shelf and to evaluate the seabed as a potential food bank for deposit feeders when surface primary production is minimal. Two summer regimes were sampled (March 2000 and March 2001) with the latter exhibiting a distinct 1-2-cm-thick phytodetritus layer in nearly all sediment core samples. At site B, the 234Th fluxes into the near-bottom (150/170 mab) sediment traps were indistinguishable for the December-March 2000, March-June 2000, and June-October 2000 sampling intervals (fluxes ranging from 170 to 280 dpm m -2 d -1). However, the sediment-trap 234Th flux measured for the October 2000-March 2001 interval (1000 dpm m -2 d -1) was ˜5-fold greater than during the other three sampling periods, consistent with the deposition of a phytodetritus layer. The steady-state 234Th fluxes derived from seabed inventories at site B were 2.4-2.7 times greater than the sediment-trap 234Th fluxes, indicating substantial scavenging of this particle-reactive radiotracer in the bottom 150 m of the water column and/or lateral transport near the seabed. The seabed 234Th inventories at the three stations showed no variation during the first four cruises, but were significantly greater during cruise FB-V (March 2001), when the phytodetritus layer occurred. Based on 234Th distributions in the seabed, bioturbation intensities (quantified using the diffusive mixing coefficient, Db) varied from 0

49 CFR 234.253 - Flashing light units and lamp voltage.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Flashing light units and lamp voltage. 234.253... Maintenance, Inspection, and Testing Inspections and Tests § 234.253 Flashing light units and lamp voltage. (a... voltage shall be tested when installed and at least once every 12 months thereafter. (c) Each flashing...

N- vs. C-Domain Selectivity of Catalytic Inactivation of Human Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

Science.gov (United States)

Hocharoen, Lalintip; Joyner, Jeff C.; Cowan, J. A.

2014-01-01

The N- and C-terminal domains of human somatic Angiotensin I Converting Enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates were tested for both reversible binding and irreversible catalytic inactivation of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of the M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and orientation factors (double-filter effect). PMID:24228790

Quantum mechanical design of enzyme active sites.

Science.gov (United States)

Zhang, Xiyun; DeChancie, Jason; Gunaydin, Hakan; Chowdry, Arnab B; Clemente, Fernando R; Smith, Adam J T; Handel, T M; Houk, K N

2008-02-01

The design of active sites has been carried out using quantum mechanical calculations to predict the rate-determining transition state of a desired reaction in presence of the optimal arrangement of catalytic functional groups (theozyme). Eleven versatile reaction targets were chosen, including hydrolysis, dehydration, isomerization, aldol, and Diels-Alder reactions. For each of the targets, the predicted mechanism and the rate-determining transition state (TS) of the uncatalyzed reaction in water is presented. For the rate-determining TS, a catalytic site was designed using naturalistic catalytic units followed by an estimation of the rate acceleration provided by a reoptimization of the catalytic site. Finally, the geometries of the sites were compared to the X-ray structures of related natural enzymes. Recent advances in computational algorithms and power, coupled with successes in computational protein design, have provided a powerful context for undertaking such an endeavor. We propose that theozymes are excellent candidates to serve as the active site models for design processes.

Determination of 234U and 238U activity concentrations in groundwaters from three deep wells drilled in Itu Intrusive Suite (SP)

International Nuclear Information System (INIS)

Souza, Francisca de

2006-01-01

Activity concentrations of ( 234 U) and ( 238 U) were determined in groundwaters drawn from three deep wells drilled in rocks from Itu Intrusive Suite (SP), two located in Salto town (S and SY wells) and the other one in Itu (I well). Sampling was done from September, 2004 to December, 2005, and twelve samples of each well were collected monthly. For those determinations alpha spectrometry technique was used, providing high precision results, as shown by the very good agreement of the data obtained in the analyses of 23 duplicates. The waters from the three wells presented a considerable enrichment of 234 U in relation to 238 U, indicating an important radioactive disequilibrium of these isotopes. In well I, the activity concentrations of ( 238 U) varied from (1,06 +- 0,03) to (2,1+- 0,2) mBq/L and those of ( 234 U) spanned from (3,1 +- 0,2) to (6,0 +- 0,4) mBq/L, whereas ( 234 U/ 238 U) activity ratios did not present significant variation, during the sampling time interval, presenting an average of 2,8 +- 0,1. The S waters showed the lowest uranium concentrations and the largest diversity of ( 238 U) and ( 234 U) activity concentrations, which varied from (0,26 +- 0,02) to (1,07+- 0,08) mBq/L and from (1,8 +- 0,1) to (7,0 +- 0,5) mBq/L, respectively, and also presented variable ( 234 U/ 238 U) activity ratios, spanning from (2,79 +- 0,07) to (8,1+- 0,3). In SY well, ( 238 U) activities varied between (0,8 +- 0,1) and (4,2 +- 0,3) mBq/L and those ones of ( 234 U) from (14 +- 1) to (53 +- 4) mBq/L, whereas ( 234 U/ 238 U) ratios fell in the interval from 12,6 +- 0,3 to 18,3 +- 0,4, with the highest activities of both radioisotopes registered during the dry season and the lowest ones in the rainy time period. The ( 234 U/ 238 U) activity ratios, which were invariable during sampling period of well I, indicated the contribution of rainfall to recharge the aquifer. The observed correlation between those ratios and uranium concentrations, for S and SY wells, showed

Co-Aromatization of Methane with Olefins: The Role of Inner Pore and External Surface Catalytic Sites

Energy Technology Data Exchange (ETDEWEB)

Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); He, Peng [University of Calgary; Jarvis, Jack [University of Calgary; Meng, Shijun [University of Calgary; Wang, Aiguo [University of Calgary; Kou, Shiyu [University of Calgary; Gatip, Richard [University of Calgary; Liu, Lijia [Soochow University; Song, Hua [University of Calgary

2018-04-22

The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, which might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B.

Directory of Open Access Journals (Sweden)

Zhu Li

Full Text Available The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase.

Improving the reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase through stabilizing a long loop in domain B.

Science.gov (United States)

Li, Zhu; Duan, Xuguo; Chen, Sheng; Wu, Jing

2017-01-01

The reversibility of thermal denaturation and catalytic efficiency of Bacillus licheniformis α-amylase were improved through site-directed mutagenesis. By using multiple sequence alignment and PoPMuSiC algorithm, Ser187 and Asn188, which located within a long loop in Domain B of Bacillus licheniformis α-amylase, were selected for mutation. In addition, Ala269, which is adjacent to Ser187 and Asn188, was also investigated. Seven mutants carrying the mutations S187D, N188T, N188S, A269K, A269K/S187D, S187D/N188T, and A269K/S187D/N188T were generated and characterized. The most thermostable mutant, A269K/S187D/N188T, exhibited a 9-fold improvement in half-life at 95°C and pH 5.5, compared with that of the wild-type enzyme. Mutant A269K/S187D/N188T also exhibited improved catalytic efficiency. The catalytic efficiency of mutant A269K/S187D/N188T reached 5.87×103±0.17 g·L-1·s-1 at pH 5.5, which is 1.84-fold larger than the corresponding value determined for the wild-type enzyme. Furthermore, the structure analysis showed that immobilization of the loop containing Ser187 and Asn188 plays a significant role in developing the properties of Bacillus licheniformis α-amylase.

Uranium concentrations and 234U/238U activity ratios in fault-associated groundwater as possible earthquake precursors

International Nuclear Information System (INIS)

Finkel, R.C.

1981-01-01

In order to assess the utility of uranium isotopes as fluid phase earthquake precursors, uranium concentrations and 234 U/ 238 U activity ratios have been monitored on a monthly or bimonthly basis in water from 24 wells and springs associated with Southern California fault zones. Uranium concentrations vary from 0.002 ppb at Indian Canyon Springs on the San Jacinto fault to 8.3 ppb at Lake Hughes well on the San Andreas fault in the Palmdale area. 234 U/ 238 U activity ratios vary from 0.88 at Agua Caliente Springs on the Elsinore fault to 5.4 at Niland Slab well on the San Andreas fault in the Imperial Valley. There was one large earthquake in the study area during 1979, the 15 October 1979 M = 6.6 Imperial Valley earthquake. Correlated with this event, uranium concentrations varied by a factor of more than 60 and activity ratios by a factor of 3 at the Niland Slab site, about 70 km from the epicenter. At the other sites monitored, uranium concentrations varied in time, but with no apparent pattern, while uranium activity ratios remained essentially constant throughout the monitoring period

Hydrogen bonds between the alpha and beta subunits of the F1-ATPase allow communication between the catalytic site and the interface of the beta catch loop and the gamma subunit.

Science.gov (United States)

Boltz, Kathryn W; Frasch, Wayne D

2006-09-19

F(1)-ATPase mutations in Escherichia coli that changed the strength of hydrogen bonds between the alpha and beta subunits in a location that links the catalytic site to the interface between the beta catch loop and the gamma subunit were examined. Loss of the ability to form the hydrogen bonds involving alphaS337, betaD301, and alphaD335 lowered the k(cat) of ATPase and decreased its susceptibility to Mg(2+)-ADP-AlF(n) inhibition, while mutations that maintain or strengthen these bonds increased the susceptibility to Mg(2+)-ADP-AlF(n) inhibition and lowered the k(cat) of ATPase. These data suggest that hydrogen bonds connecting alphaS337 to betaD301 and betaR323 and connecting alphaD335 to alphaS337 are important to transition state stabilization and catalytic function that may result from the proper alignment of catalytic site residues betaR182 and alphaR376 through the VISIT sequence (alpha344-348). Mutations betaD301E, betaR323K, and alphaR282Q changed the rate-limiting step of the reaction as determined by an isokinetic plot. Hydrophobic mutations of betaR323 decreased the susceptibility to Mg(2+)-ADP-AlF(n)() inhibition and lowered the number of interactions required in the rate-limiting step yet did not affect the k(cat) of ATPase, suggesting that betaR323 is important to transition state formation. The decreased rate of ATP synthase-dependent growth and decreased level of lactate-dependent quenching observed with alphaD335, betaD301, and alphaE283 mutations suggest that these residues may be important to the formation of an alternative set of hydrogen bonds at the interface of the alpha and beta subunits that permits the release of intersubunit bonds upon the binding of ATP, allowing gamma rotation in the escapement mechanism.

Amine binding and oxidation at the catalytic site for photosynthetic water oxidation

Science.gov (United States)

Ouellette, Anthony J. A.; Anderson, Lorraine B.; Barry, Bridgette A.

1998-01-01

Photosynthetic water oxidation occurs at the Mn-containing catalytic site of photosystem II (PSII). By the use of 14C-labeled amines and SDS-denaturing PAGE, covalent adducts derived from primary amines and the PSII subunits, CP47, D2/D1, and the Mn-stabilizing protein, can be observed. When PSII contains the 18- and 24-kDa extrinsic proteins, which restrict access to the active site, no 14C labeling is obtained. NaCl, but not Na2SO4, competes with 14C labeling in Mn-containing PSII preparations, and the concentration dependence of this competition parallels the activation of oxygen evolution. Formation of 14C-labeled adducts is observed in the presence or in the absence of a functional manganese cluster. However, no significant Cl− effect on 14C labeling is observed in the absence of the Mn cluster. Isolation and quantitation of the 14C-labeled aldehyde product, produced from [14C]benzylamine, gives yields of 1.8 ± 0.3 mol/mol PSII and 2.9 ± 0.2 mol/mol in Mn-containing and Mn-depleted PSII, respectively. The corresponding specific activities are 0.40 ± 0.07 μmol(μmol PSII-hr)−1 and 0.64 ± 0.04 μmol(μmol PSII-hr)−1. Cl− suppresses the production of [14C]benzaldehyde in Mn-containing PSII, but does not suppress the production in Mn-depleted preparations. Control experiments show that these oxidation reactions do not involve the redox-active tyrosines, D and Z. Our results suggest the presence of one or more activated carbonyl groups in protein subunits that form the active site of PSII. PMID:9482863

Spectroscopic study of 228-234Th nuclei using multi-nucleon transfer reactions

International Nuclear Information System (INIS)

Amzal, N.; Butler, P.A.; Cann, K.J.; Greenlees, P.T.; Jones, G.D.; Cocks, J.F.C.; Asztalos, S.; Clark, R.M.; Deleplanque, M.A.; Diamond, R.M.; Fallon, P.; Lees, I.Y.; Machiavelli, A.O.; MacLeod, R.W.; Stephens, F.S.; Jones, P.M.; Julin, R.; Broda, R.; Fornal, B.; Smith, J.F.; Lauritsen, T.; Bhattacharyya, P.; Zhang, C.T.

1999-01-01

Light-actinide nuclei in the octupole deformed region have been populated using multi-nucleon transfer from 232 Th. The energy level schemes of several thorium isotopes with A=228-234 have been extended up to I∼24ℎ and negative parity states have been observed for the first time in 234 Th. A systematic study of the difference in alignment between the positive- and negative-parity bands in thorium nuclei in this mass region shows that 228,230,234 Th behave like octupole vibrators, in contrast with 224,226 Th, which are octupole-deformed in character. An intrinsic electric dipole moment has been measured for the first time in 234 Th. The small value obtained is consistent with the vibrational description of this nucleus. (author)

Impact of A cation size of double perovskite A2AlTaO6 (A = Ca, Sr, Ba) on dielectric and catalytic properties

International Nuclear Information System (INIS)

Gorodea, I.; Goanta, M.; Toma, M.

2015-01-01

Highlights: • Synthesis by solid state reaction of the double perovskite A 2 AlTaO 6 , where A = Ca, Sr and Ba. • The role of different A-site cations on their synthesis and structures was investigated. • The influence of the divalent A-site cations on the dielectric properties was evaluated by resistivity measurements. • Catalytic properties were evaluated in water splitting process, under gamma-rays irradiation emitted by a 60 Co source, for the first time. - Abstract: Double perovskite-type oxide A 2 AlTaO 6 materials, where A = Ca, Sr and Ba, were prepared using conventional solid state reaction. The role of different A-site cations on their synthesis, structures, dielectric and catalytic properties was investigated. Double perovskite oxide structures were evaluated using X-ray diffraction (XRD). As the average cation size decreases, the crystallographic structure at room temperature evolves from cubic to monoclinic. The influence of the nature of the divalent A-site cations on the dielectric properties was evaluated by resistivity measurements in the frequency range of 10–10 6 Hz. It can be found that relative permittivity and dielectric loss regularly changed with A cation size. Catalytic properties of the obtained compounds were evaluated in water splitting process, under gamma-rays irradiation emitted by a 60 Co source for the first time. From experimental data it was noticed that the double perovskite Ca 2 AlTaO 6 had a higher catalytic effect

Extreme fractionation of 234U 238U and 230Th 234U in spring waters, sediments, and fossils at the Pomme de Terre Valley, southwestern Missouri

Science.gov (United States)

Szabo, B. J.

1982-01-01

Isotopic fractionation as great as 1600% exists between 234U and 238U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of 234U 238U in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in 234U 238U ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in 230Th relative to their parent 234U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment. ?? 1982.

Method of fabricating a catalytic structure

Science.gov (United States)

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

2009-09-22

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

The estuarine chemistry and isotope systematics of 234,238U in the Amazon and Fly Rivers

Science.gov (United States)

Swarzenski, P.; Campbell, P.; Porcelli, D.; McKee, B.

2004-01-01

Natural concentrations of 238U and ??234U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land-sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates. On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0-16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (???1 m) zones of Fe(III) - and, to a lesser degree, Mn(IV) - reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved 238U profile co-varied closely with Mn(II). Isotopic variations as evidenced in ??234U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the ??234U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched ??234U values represent a riverine surface complexation product that is actively involved in Mn-Fe diagenetic cycles and surface

The estuarine chemistry and isotope systematics of 234,238U in the Amazon and Fly Rivers

Science.gov (United States)

Swarzenski, Peter; Campbell, Pamela; Porcelli, Don; McKee, Brent

2004-12-01

Natural concentrations of 238U and δ234U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land-sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates. On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0-16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (˜1 m) zones of Fe(III)—and, to a lesser degree, Mn(IV)—reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved 238U profile co-varied closely with Mn(II). Isotopic variations as evidenced in δ234U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the δ234U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched δ234U values represent a riverine surface complexation product that is actively involved in Mn-Fe diagenetic cycles and surface

The catalytic destruction of antibiotic tetracycline by sulfur-doped manganese oxide (S-MgO) nanoparticles.

Science.gov (United States)

Moussavi, Gholamreza; Mashayekh-Salehi, Ali; Yaghmaeian, Kamyar; Mohseni-Bandpei, Anoshiravan

2018-03-15

The present study evaluates the efficacy of S-doped MgO (S-MgO) as compared with the plain MgO as a catalyst for destructive removal of tetracycline (TTC) in aqueous solutions. The S-MgO had around 6% S in its structure. Doping MgO with S caused increase in surface oxygen vacancy defects. Adding S-MgO (12 g/L) to a TTC aqueous solution (50 mg/L) caused removal of around 99% TTC at the neutral pH (ca. 5.1) and a short reaction time of 10 min. In comparison, plain MgO could remove only around 15% of TTC under similar experimental conditions. Diffusing O 2 into the TTC solution under the reaction with S-MgO resulted in a considerable improvement of TTC removal as compared to diffusing N 2 . Complete removal of TTC and 86.4% removal of its TOC could be obtained using 2 g/L S-MgO nanoparticles. The removal of TTC increased with the increase in solution temperature. The presence of nitrate, sulfate and chloride did not considerably affect the removal of TTC using S-MgO while TTC removal significantly decreased at the presence of bicarbonate and phosphate. The S-MgO was a stable and reusable catalyst exhibiting much higher catalytic activity than plain MgO for the TTC destruction. Accordingly, S-MgO is an emerging and efficient catalyst for catalytic decomposition and mineralization of such pharmaceutical compounds as TTC under atmospheric temperature and pressure. Copyright © 2018 Elsevier Ltd. All rights reserved.

Relief of autoinhibition by conformational switch explains enzyme activation by a catalytically dead paralog

Energy Technology Data Exchange (ETDEWEB)

Volkov, Oleg A.; Kinch, Lisa; Ariagno, Carson; Deng, Xiaoyi; Zhong, Shihua; Grishin, Nick; Tomchick, Diana R.; Chen, Zhe; Phillips, Margaret A.

2016-12-15

Catalytically inactive enzyme paralogs occur in many genomes. Some regulate their active counterparts but the structural principles of this regulation remain largely unknown. We report X-ray structures ofTrypanosoma brucei S-adenosylmethionine decarboxylase alone and in functional complex with its catalytically dead paralogous partner, prozyme. We show monomericTbAdoMetDC is inactive because of autoinhibition by its N-terminal sequence. Heterodimerization with prozyme displaces this sequence from the active site through a complex mechanism involving acis-to-transproline isomerization, reorganization of a β-sheet, and insertion of the N-terminal α-helix into the heterodimer interface, leading to enzyme activation. We propose that the evolution of this intricate regulatory mechanism was facilitated by the acquisition of the dimerization domain, a single step that can in principle account for the divergence of regulatory schemes in the AdoMetDC enzyme family. These studies elucidate an allosteric mechanism in an enzyme and a plausible scheme by which such complex cooperativity evolved.

Enhancement of the catalytic activity of ferulic acid decarboxylase from Enterobacter sp. Px6-4 through random and site-directed mutagenesis.

Science.gov (United States)

Lee, Hyunji; Park, Jiyoung; Jung, Chaewon; Han, Dongfei; Seo, Jiyoung; Ahn, Joong-Hoon; Chong, Youhoon; Hur, Hor-Gil

2015-11-01

The enzyme ferulic acid decarboxylase (FADase) from Enterobacter sp. Px6-4 catalyzes the decarboxylation reaction of lignin monomers and phenolic compounds such as p-coumaric acid, caffeic acid, and ferulic acid into their corresponding 4-vinyl derivatives, that is, 4-vinylphenol, 4-vinylcatechol, and 4-vinylguaiacol, respectively. Among various ferulic acid decarboxylase enzymes, we chose the FADase from Enterobacter sp. Px6-4, whose crystal structure is known, and produced mutants to enhance its catalytic activity by random and site-directed mutagenesis. After three rounds of sequential mutations, FADase(F95L/D112N/V151I) showed approximately 34-fold higher catalytic activity than wild-type for the production of 4-vinylguaiacol from ferulic acid. Docking analyses suggested that the increased activity of FADase(F95L/D112N/V151I) could be due to formation of compact active site compared with that of the wild-type FADase. Considering the amount of phenolic compounds such as lignin monomers in the biomass components, successfully bioengineered FADase(F95L/D112N/V151I) from Enterobacter sp. Px6-4 could provide an ecofriendly biocatalytic tool for producing diverse styrene derivatives from biomass.

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....

Unmasking tandem site interaction in human acetylcholinesterase. Substrate activation with a cationic acetanilide substrate.

Science.gov (United States)

Johnson, Joseph L; Cusack, Bernadette; Davies, Matthew P; Fauq, Abdul; Rosenberry, Terrone L

2003-05-13

Acetylcholinesterase (AChE) contains a narrow and deep active site gorge with two sites of ligand binding, an acylation site (or A-site) at the base of the gorge, and a peripheral site (or P-site) near the gorge entrance. The P-site contributes to catalytic efficiency by transiently binding substrates on their way to the acylation site, where a short-lived acyl enzyme intermediate is produced. A conformational interaction between the A- and P-sites has recently been found to modulate ligand affinities. We now demonstrate that this interaction is of functional importance by showing that the acetylation rate constant of a substrate bound to the A-site is increased by a factor a when a second molecule of substrate binds to the P-site. This demonstration became feasible through the introduction of a new acetanilide substrate analogue of acetylcholine, 3-(acetamido)-N,N,N-trimethylanilinium (ATMA), for which a = 4. This substrate has a low acetylation rate constant and equilibrates with the catalytic site, allowing a tractable algebraic solution to the rate equation for substrate hydrolysis. ATMA affinities for the A- and P-sites deduced from the kinetic analysis were confirmed by fluorescence titration with thioflavin T as a reporter ligand. Values of a >1 give rise to a hydrolysis profile called substrate activation, and the AChE site-specific mutant W86F, and to a lesser extent wild-type human AChE itself, showed substrate activation with acetylthiocholine as the substrate. Substrate activation was incorporated into a previous catalytic scheme for AChE in which a bound P-site ligand can also block product dissociation from the A-site, and two additional features of the AChE catalytic pathway were revealed. First, the ability of a bound P-site ligand to increase the substrate acetylation rate constant varied with the structure of the ligand: thioflavin T accelerated ATMA acetylation by a factor a(2) of 1.3, while propidium failed to accelerate. Second, catalytic rate

Effect of Number of Various-Type Acid Sites Located on 20 % Co/ZrO2 • SiO2 Sample Surface on Parameters of Catalytic Process in Synthesis of High-Octane Motor Fuel Components

Directory of Open Access Journals (Sweden)

A. P. Nesenchouk

2011-01-01

Full Text Available The paper considers an effect of ZrO2 content in 20%Co/xZrO2∙(100 – xSiO2 (x = 0, 10, 15, 25, 30, 40 and 100 mass percent catalyst carriers on their catalytic properties. Temperature programmed desorption of NH3 has made it possible to determine relations between their acid and catalytic properties. The paper reveals the TPD spectrum is the result of 4 overlapping peaks originating during NH3 desorption from the respective groups of acid sites. Total acidity of samples and contribution of separate acid site groups into the given acidity have been have been determined in the paper. The paper contains graphical dependences of a various-type acid site number on  content of zirconium oxide in the carrier. Correlations between change in various-type acid site number and catalytic process parameters (CO conversion, C5+ hydrocarbon output and  C5+ isoparaffin output have been found in the paper. The paper shows that the highest values of CO conversion and C5+ hydrocarbon output correspond to maximum number of acid sites, and that number accounts for a peak of desorbed ammonia at Tmax = 122 °C, while the lowest isoparaffin output corresponds to minimum number of acid sites, which characterizes a peak of desorbed ammonia at Tmax = 224–257 °C. 

Internal tides and sediment dynamics in the deep sea-Evidence from radioactive Th-234/U-238 disequilibria

International Nuclear Information System (INIS)

Turnewitsch, R.; Turnewitsch, R.; Waniek, J.J.; Reyss, J.L.; Nycander, J.; Lampitt, R.S.

2008-01-01

Residual flow, baro-tropic tides and internal (baro-clinic) tides interact in a number of ways with kilometer-scale sea floor topography such as abyssal hills and sea mounts. Because of their likely impact on vertical mixing such interactions are potentially important for ocean circulation and the mechanisms and the geometry of these interactions are a matter of ongoing studies. In addition, very little is known about how these interactions are reflected in the sedimentary record. This multi-year study investigates if flow/topography interactions are reflected in distributional patterns of the natural short-lived (half-life: 24.1 d) particulate-matter tracer 234 Th relative to its conservative (non-particle-reactive) and very long-lived parent nuclide 238 U. The sampling sites were downstream of, or surrounded by, fields of short sea mounts and, therefore, very likely to be influenced by nearby flow/topography interactions. At the sampling sites between about 200 and 1000 m above the sea floor recurrent 'fossil' disequilibria were detected. 'Fossil' disequilibria are defined by clearly detectable 234 Th/ 238 U disequilibria (total 234 Th radioactivity ≤ 238 U radioactivity, indicating a history of intense particulate 234 Th scavenging and particulate-matter settling from the sampled parcel of water) and conspicuously low particle-associated 234 Th activities. 'Fossil' disequilibria were centered at levels in the water column that correspond to the average height of the short sea mounts near the sampling sites. This suggests the 'fossil' disequilibria are formed on the sea mount slopes. Moreover, the magnitude of the 'fossil' disequilibria suggests that the slopes of the short sea mounts in the study region are characterized by particularly vigorous fluid dynamics. Since 'fossil' disequilibria already occurred at ∼ O (1-10 km) away from the sea mount slopes it is likely that these vigorous fluid dynamics rapidly decay away from the slopes on scales of O (1-10 km

The catalytic activity of Ag{sub 2}S-montmorillonites as peroxidase mimetic toward colorimetric detection of H{sub 2}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Liu, Qingyun, E-mail: qyliu@sdust.edu.cn [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China); Jiang, Yanling; Zhang, Leyou; Zhou, Xinpei [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China); Lv, Xintian [School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000 (China); Ding, Yanyuan; Sun, Lifang; Chen, Pengpeng [School of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China); Yin, Hailiang [Academy of Science & Technology, China University of Petroleum, Dongying 257061 (China)

2016-08-01

Nanocomposites based on silver sulfide (Ag{sub 2}S) and Ca-montmorillonite (Ca{sup 2+}-MMT) were synthesized by a simple hydrothermal method. The nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectra (FTIR). The as-prepared Ag{sub 2}S-MMT nanocomposites were firstly demonstrated to possess intrinsic peroxidase-like activity and could rapidly catalytically oxidize the substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H{sub 2}O{sub 2} to produce a blue product which can be seen by the naked eye in only one minute. The experimental results revealed that the Ag{sub 2}S-MMT nanocomposites exhibit higher thermal durance. Based on the TMB–H{sub 2}O{sub 2} catalyzed color reaction, the Ag{sub 2}S-MMT nanocomposites were exploited as a new type of biosensor for detection and estimation of H{sub 2}O{sub 2} through a simple, cheap and selective colorimetric method. - Highlights: • Ag{sub 2}S – montmorillonites (MMT) was synthesized by a facile one step method. • The as-prepared Ag{sub 2}S-MMT nanocomposites firstly demonstrate to possess intrinsic peroxidase-like activity. • Ag{sub 2}S-MMT nanocomposites showed highly catalytic activity. • Ag{sub 2}S-MMT could rapidly catalytically oxidize substrates TMB in the presence of H{sub 2}O{sub 2} in 1 min. • The catalytic mechanism is from the generation of hydroxyl radical (·OH) decomposed from H{sub 2}O{sub 2}.

49 CFR 234.5 - Definitions.

Science.gov (United States)

2010-10-01

... TRANSPORTATION GRADE CROSSING SIGNAL SYSTEM SAFETY AND STATE ACTION PLANS General § 234.5 Definitions. As used in... meaning of this paragraph if—more than 50% of the flashing lights (not gate arm lights) on any approach.... For nighttime flagging, similar outside garments shall be retro reflective. Acceptable hand signal...

14 CFR 13.234 - Petition to reconsider or modify a final decision and order of the FAA decisionmaker on appeal.

Science.gov (United States)

2010-01-01

... decision and order of the FAA decisionmaker on appeal. 13.234 Section 13.234 Aeronautics and Space FEDERAL... PROCEDURES Rules of Practice in FAA Civil Penalty Actions § 13.234 Petition to reconsider or modify a final decision and order of the FAA decisionmaker on appeal. (a) General. Any party may petition the FAA...

Synthesis and Evaluation of ABO3 Perovskites (A=La and B=Mn, Co with Stoichiometric and Over-stoichiometric Ratios of B/A for Catalytic Oxidation of Trichloroethylene

Directory of Open Access Journals (Sweden)

Razieh Alagheband

2018-01-01

Full Text Available In this contribution, perovskite catalysts (ABO3 were probed that site A and site B were occupied by lanthanum and transition metals of manganese or cobalt, respectively, with stoichiometric ratios as well as 20 % over-stoichiometric ratios of B/A. The perovskite samples were synthesized using a gel-combustion method and characterized by BET, XRD, SEM and O2-TPD analyses. After mounting in a fixed bed reactor, the catalysts were examined in atmospheric pressure conditions at different temperatures for oxidation of 1000 ppm trichloroethylene in the air. Evaluation of over-stoichiometric catalysts activity showed that the increased ratio of B/A in the catalysts compared to the stoichiometric one led to BET surface area, oxygen mobility, and consequently catalytic performance improvement. The lanthanum manganite perovskite with 20 % excess manganese yielded the best catalytic performance among the probed perovskites. Copyright © 2018 BCREC Group. All rights reserved Received: 28th April 2017; Revised: 31st July 2017; Accepted: 4th August 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Alagheband, R., Maghsoodi, S., Kootenaei, A.S., Kianmanesh, H. (2018. Synthesis and Evaluation of ABO3 Perovskites (A=La and B=Mn, Co with Stoichiometric and Over-stoichiometric Ratios of B/A for Catalytic Oxidation of Trichloroethylene. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 47-56 (doi:10.9767/bcrec.13.1.1188.47-56

Uranium Age Determination by Measuring the 230Th / 234U Ratio

International Nuclear Information System (INIS)

LAMONT, STEPHEN P.

2004-01-01

A radiochemical isotope dilution mass spectrometry method has been developed to determine the age of uranium materials. The amount of 230Th activity, the first progeny of 234U, that had grown into a small uranium metal sample was used to determine the elapsed time since the material was last radiochemically purified. To preserve the sample, only a small amount of oxidized uranium was removed from the surface of the sample and dissolved. Aliquots of the dissolved sample were spiked with 233U tracer and radiochemically purified by anion-exchange chromatography. The 234U isotopic concentration was then determined by thermal ionization mass spectrometry. Additional aliquots of the sample were spiked with 229Th tracer, and the thorium was purified using two sequential anion-exchange chromatography separations. The isotopic concentrations of 230Th and 232Th were determined by TIMS. The lack of any 232Th confirmed the assumption that all thorium was removed from the uranium sample at the time of purification. The 230Th and 234U mass concentrations were converted to activities and the 230Th/234U ratio for the sample was calculated. The experimental 230Th/234U ratio showed the uranium in this sample was radiochemically purified in about 1945. Isotope dilution thermal ionization mass spectrometry has sufficient sensitivity to determine the age of 100 samples of uranium. This method could certainly be employed as a nuclear forensic method to determine the age of small quantities of uranium metal or salts. Accurate determination of the ultra-trace 230Th radiochemically separated from the uranium is possible due to the use of 229Th as an isotope dilution tracer. The precision in the experimental age of the uranium could be improved by making additional replicate measurements of the 230Th/234U isotopic ratio or using a larger initial sample

45 CFR 234.11 - Assistance in the form of money payments.

Science.gov (United States)

2010-10-01

... 45 Public Welfare 2 2010-10-01 2010-10-01 false Assistance in the form of money payments. 234.11... FINANCIAL ASSISTANCE TO INDIVIDUALS § 234.11 Assistance in the form of money payments. (a) Federal financial participation is available in money payments made under a State plan under title I, IV-A, X, XIV, or XVI of the...

X-ray Absorption Spectroscopy of the Zinc-Binding Sites in the Class B2 Metallo-B-lactamsase ImiS from Aeromonas veronii bv. sobria

Energy Technology Data Exchange (ETDEWEB)

Costello,A.; Sharma, N.; Yang, K.; Crowder, M.; Tierney, D.

2006-01-01

X-ray absorption spectroscopy was used to investigate the metal-binding sites of ImiS from Aeromonas veronii bv. sobria in catalytically active (1-Zn), product-inhibited (1-Zn plus imipenem), and inactive (2-Zn) forms. The first equivalent of zinc(II) was found to bind to the consensus Zn{sub 2} site. The reaction of 1-Zn ImiS with imipenem leads to a product-bound species, coordinated to Zn via a carboxylate group. The inhibitory binding site of ImiS was examined by a comparison of wild-type ImiS with 1 and 2 equiv of bound zinc. 2-Zn ImiS extended X-ray absorption fine structure data support a binding site that is distant from the active site and contains both one sulfur donor and one histidine ligand. On the basis of the amino acid sequence of ImiS and the crystal structure of CphA [Garau et al. (2005) J. Mol. Biol. 345, 785-795], we propose that the inhibitory binding site is formed by M146, found on the B2-distinct {alpha}3 helix, and H118, a canonical Zn{sub 1} ligand, proposed to help activate the nucleophilic water. The mutation of M146 to isoleucine abolishes metal inhibition. This is the first characterization of ImiS with the native metal Zn and establishes, for the first time, the location of the inhibitory metal site.

Investigation on catalytic gasification of high-ash coal with mixing-gas in a small-scale fluidised bed

Energy Technology Data Exchange (ETDEWEB)

Chen, X.; Zhang, J.; Lin, J. [Fuzhou University, Fuzhou (China)

2005-10-15

The experimental study on the Yangquan high-ash coal catalytic gasification with mixing gas by using solid alkali or waste liquid of viscose fiber as the catalyst in a small-scale fluidized bed with 28 mm i.d. was carried out. The loading saturation levels of two catalysts in Yangquan high-ash coal are about 6%. Under the gasification temperature ranging from 830 to 900{sup o}C and from 900 to 920{sup o}C, the apparent reaction order of Yangquan high-ash coal with respect to the unreacted carbon fraction approximates to 2.3 and 1/3 for the non-catalyst case, respectively. Also, the different values of apparent reaction order in the two temperature ranges are presented for the case with 3% solid alkali catalyst loaded. At the low temperature ranging from 830 to 860{sup o}C, the apparent reaction order of catalytic gasification is 1 since enough active carbon sites on the coal surface are formed during the catalytic gasification by solid alkali. But at the high temperature ranging from 860 to 920{sup o}C, the sodium carbonate produced by the reaction of solid alkali with carbon dioxide can be easily fused, transferred and re-distributed, which affects the gasification reaction rate, and the apparent reaction order of catalytic gasification is reduced to 1.3. 10 refs., 9 figs., 4 tab s.

Detection of Intracellular Reduced (Catalytically Active) SHP-1 and Analyses of Catalytically Inactive SHP-1 after Oxidation by Pervanadate or H2O2.

Science.gov (United States)

Choi, Seeyoung; Love, Paul E

2018-01-05

Oxidative inactivation of cysteine-dependent Protein Tyrosine Phosphatases (PTPs) by cellular reactive oxygen species (ROS) plays a critical role in regulating signal transduction in multiple cell types. The phosphatase activity of most PTPs depends upon a 'signature' cysteine residue within the catalytic domain that is maintained in the de-protonated state at physiological pH rendering it susceptible to ROS-mediated oxidation. Direct and indirect techniques for detection of PTP oxidation have been developed (Karisch and Neel, 2013). To detect catalytically active PTPs, cell lysates are treated with iodoacetyl-polyethylene glycol-biotin (IAP-biotin), which irreversibly binds to reduced (S - ) cysteine thiols. Irreversible oxidation of SHP-1 after treatment of cells with pervanadate or H 2 O 2 is detected with antibodies specific for the sulfonic acid (SO 3 H) form of the conserved active site cysteine of PTPs. In this protocol, we describe a method for the detection of the reduced (S - ; active) or irreversibly oxidized (SO 3 H; inactive) form of the hematopoietic PTP SHP-1 in thymocytes, although this method is applicable to any cysteine-dependent PTP in any cell type.

COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER; FINAL

International Nuclear Information System (INIS)

Phillip E. Savage

1999-01-01

phenoxy radicals, which then react in the fluid phase by the same mechanism operative for non-catalytic SCWO of phenol. The rates of phenol disappearance and CO(sub 2) formation are sensitive to the phenol and O(sub 2) concentrations, but independent of the water density. Power-law rate expressions were developed to correlate the catalytic kinetics. The catalytic kinetics were also consistent with a Langmuir-Hinshelwood rate law derived from a dual-site mechanism comprising the following steps: reversible adsorption of phenol on one type of catalytic site, reversible dissociative adsorption of oxygen on a different type of site, and irreversible, rate-determining surface reaction between adsorbed phenol and adsorbed oxygen

Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution

Energy Technology Data Exchange (ETDEWEB)

Wang, Longlu; Duan, Xidong; Liu, Chengbin; Zhang, Shuqu; Zeng, Yunxiong [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha (China); Liu, Xia; Pei, Yong [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University (China); Luo, Jinming; Crittenden, John [Brook Byers Institute for Sustainable Systems and School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA (United States); Duan, Xiangfeng [Department of Chemistry and Biochemistry, University of California, Los Angeles, CA (United States)

2017-06-19

The metallic 1T-MoS{sub 2} has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS{sub 2} and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS{sub 2} by hydrothermal exfoliation of MoS{sub 2} nanosheets vertically rooted into rigid one-dimensional TiO{sub 2} nanofibers. The 1T-MoS{sub 2} can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a ''catalytic site self-optimization''. Hydrogen atom adsorption is the major driving force for this phase transition. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Thioredoxin binding site of phosphoribulokinase overlaps the catalytic site

International Nuclear Information System (INIS)

Porter, M.A.; Hartman, F.C.

1986-01-01

The ATP-regulatory binding site of phosphoribulokinase was studied using bromoacetylethanolamine phosphate (BrAcNHEtOP). BrAcNHEtOP binds to the active-regulatory binding site of the protein. Following trypsin degradation of the labeled protein, fragments were separated by HPLC and sequenced. (DT)

234Th/238U disequilibrium in near-shore sediment: particle reworking and diagenetic time scales

International Nuclear Information System (INIS)

Aller, R.C.; Cochran, J.K.

1976-01-01

The distribution of 234 Th (tsub(1.2)=24.1 days) in excess of its parent 238 U in the upper layers of near-shore sediment makes possible the evaluation of short-term sediment reworking and diagenetic rates. 234 Th has a maximum residence time in Long Island Sound water of 1.4 days. Seasonal measurement of 234 Th/ 238 U disequilibrium in sediment at a single station in central Long Island Sound demonstrates rapid particle reworking and high 234 Thsub(XS)(>1 dpm/g) in the upper 4 cm of sediment with slower, irregular reworking and low 234 Thsub(XS) to at least 12 cm. The rate of rapid particle reworking varies seasonally and is highest in the fall. The rapidly mixed zone is characterized by steep gradients in sediment chemistry implying fast reactions spanned by 234 Th decay time scales. 238 U is depleted in the upper mixed zone and shows addition in reducing sediment at depth. (Auth.)

14 CFR 234.5 - Form of reports.

Science.gov (United States)

2010-01-01

... REGULATIONS AIRLINE SERVICE QUALITY PERFORMANCE REPORTS § 234.5 Form of reports. Except where otherwise noted... in accounting and reporting directives issued by the Bureau of Transportation Statistics' Assistant...

45 CFR 234.70 - Protective payments for the aged, blind, or disabled.

Science.gov (United States)

2010-10-01

..., administrator or fiscal agent of a nursing home, or social care, medical or nonmedical institution, except for... disabled. 234.70 Section 234.70 Public Welfare Regulations Relating to Public Welfare OFFICE OF FAMILY ASSISTANCE (ASSISTANCE PROGRAMS), ADMINISTRATION FOR CHILDREN AND FAMILIES, DEPARTMENT OF HEALTH AND HUMAN...

The conserved Lysine69 residue plays a catalytic role in Mycobacterium tuberculosis shikimate dehydrogenase

Directory of Open Access Journals (Sweden)

Rodrigues Valnês

2009-01-01

Full Text Available Abstract Background The shikimate pathway is an attractive target for the development of antitubercular agents because it is essential in Mycobacterium tuberculosis, the causative agent of tuberculosis, but absent in humans. M. tuberculosis aroE-encoded shikimate dehydrogenase catalyzes the forth reaction in the shikimate pathway. Structural and functional studies indicate that Lysine69 may be involved in catalysis and/or substrate binding in M. tuberculosis shikimate dehydrogenase. Investigation of the kinetic properties of mutant enzymes can bring important insights about the role of amino acid residues for M. tuberculosis shikimate dehydrogenase. Findings We have performed site-directed mutagenesis, steady-state kinetics, equilibrium binding measurements and molecular modeling for both the wild-type M. tuberculosis shikimate dehydrogenase and the K69A mutant enzymes. The apparent steady-state kinetic parameters for the M. tuberculosis shikimate dehydrogenase were determined; the catalytic constant value for the wild-type enzyme (50 s-1 is 68-fold larger than that for the mutant K69A (0.73 s-1. There was a modest increase in the Michaelis-Menten constant for DHS (K69A = 76 μM; wild-type = 29 μM and NADPH (K69A = 30 μM; wild-type = 11 μM. The equilibrium dissociation constants for wild-type and K69A mutant enzymes are 32 (± 4 μM and 134 (± 21, respectively. Conclusion Our results show that the residue Lysine69 plays a catalytic role and is not involved in substrate binding for the M. tuberculosis shikimate dehydrogenase. These efforts on M. tuberculosis shikimate dehydrogenase catalytic mechanism determination should help the rational design of specific inhibitors, aiming at the development of antitubercular drugs.

Disk mini-adsorbers with radial flow for determination of 234Th concentration in seawater

International Nuclear Information System (INIS)

Gulin, S.B.; Gorelov, Yu.S.; Sidorov, I.G.; Proskurnin, V.Yu.

2013-01-01

A modified method has been developed for measuring the 234 Th concentration in seawater, which is based upon the use of MnO 2 -impregnated disk mini adsorbers with radial flow connected in-line and the direct beta counting of 234 Th and/or its daughter 234m Pa. This allows determining the 234 Th concentration in a relatively small volume of seawater (20-50 L) with the possibility to check the extraction efficiency in every individual sample. The field testing, which was carried out at different areas of Sevastopol Bay during different seasons, has shown applicability of the proposed method to evaluate particle fluxes in marine environments within a wide range of concentrations of suspended matter. (author)

Biological availability of 238U, 234U and 226Ra for wild berries and meadow grasses in natural ecosystems of Belarus

International Nuclear Information System (INIS)

Sokolik, G.A.; Ovsiannikova, S.V.; Voinikava, K.V.; Ivanova, T.G.; Papenia, M.V.

2014-01-01

with high-moor peat and sandy soils. The lowest CRs for grasses were common to loamy and peat-gley soils. The CRs for the same berry species in the sites with sandy soils exceeded the appropriate CR values in the sites with loamy soils by factors of 3–4 for uranium and 4–6 for radium. The data obtained on radionuclide accumulation by plants were used to estimate the average annual effective doses to the population from radionuclide intake through the “soil – wild berries – man” and “soil – meadow vegetation – animal – cow milk-beef – man” trophic chains. The effective doses resulting from 234 U, 238 U and 226 Ra intake with the wild berries for adults were estimated as 0.02–0.09 μSv y −1 (GM is 0.044, GSD is 1.6). It was established that only in the territory with 137 Cs deposition of ∼1.0–1.5 kBq m −2 the doses resulting from 234 U, 238 U and 226 Ra intake with wild berries can be comparable with corresponding doses from 137 Cs. In the territories with higher levels of 137 Cs deposition the doses resulting from its intake with the wild berries are usually over the summarized doses of uranium and 226 Ra. The total doses for adults resulting from uranium and 226 Ra intake with cow milk and beef ranged between 0.2 and 7.2 μSv y −1 (GM is 2.0; GSD is 2.9) and the doses from 226 Ra usually exceeded the appropriate doses of uranium with a factor of 3–37. In the sites with 137 Cs deposition less than 3.7 kBq m −2 , the doses from 234 U, 238 U and 226 Ra intake with cow milk and beef were assessing as 1.1–7.2 μSv y −1 and they were usually higher than the doses from 137 Cs, which were assessing as 0.4–3.2 μSv y −1 for its deposition 2 kBq m −2 . In the territory with 137 Cs deposition 10–20 kBq m −2 and higher, the internal doses resulting from 137 Cs intake with cow milk and beef (10–50 μSv y −1 ) exceeded the proper doses from natural 234 U, 238 U and 226 Ra

Defense In-Depth Accident Analysis Evaluation of Tritium Facility Bldgs. 232-H, 233-H, and 234-H

International Nuclear Information System (INIS)

Blanchard, A.

1999-01-01

'The primary purpose of this report is to document a Defense-in-Depth (DID) accident analysis evaluation for Department of Energy (DOE) Savannah River Site (SRS) Tritium Facility Buildings 232-H, 233-H, and 234-H. The purpose of a DID evaluation is to provide a more realistic view of facility radiological risks to the offsite public than the bounding deterministic analysis documented in the Safety Analysis Report, which credits only Safety Class items in the offsite dose evaluation.'

Fuel processor integrated H{sub 2}S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

Energy Technology Data Exchange (ETDEWEB)

Gardner, T.H.; Berry, D.A.; Lyons, K.D.; Beer, S.K.; Freed, A.D. [U.S. Department of Energy, Morgantown, WV (USA). National Energy Technology Laboratory

2002-12-01

H{sub 2}S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O{sub 2}-blown coal-derived synthesis gas. The H{sub 2}S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H{sub 2}S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H{sub 2}S and 0.3 order in O{sub 2}. 18 refs., 14 figs., 3 tabs.

Application of natural Ra isotopes and {sup 234}Th as tracers of organic carbon export in Bransfield Strait, Antarctica; Aplicacao dos isotopos naturais de Ra e do Th-234 como tracadores do carbono organico exportado para o Estreito de Bransfield, Antartica

Energy Technology Data Exchange (ETDEWEB)

Vieira, Lucia Helena

2011-07-01

The Southern Ocean is the largest of several high-nutrient, low-chlorophyll (HNLC) regions in the world's oceans. This region plays a major role in regulating the global net transfer of carbon dioxide between the ocean and the atmosphere, in part because the annual photosynthetic uptake of CO{sub 2} by phytoplankton and resulting export of particulate organic carbon (POC) to the deep ocean. The element thorium has multiple radioisotopes that have emerged collectively as a powerful set of tracers for particle associated processes in the oceans. Of all the Th isotopes, {sup 234}Th (half-life 24.1 d) has been the focus of increasing attention and application in the past years. The production of {sup 234}Th from {sup 238}U, coupled with the conservative behavior of {sup 238}U in seawater, makes the source of {sup 234}Th easy to characterize. Moreover, the half-life of {sup 234}Th is sufficiently short to make it sensitive to the short-term (e.g. seasonal) changes that occur in the upper water column of the open ocean or in sediments or water column in coastal areas. Because of its very particle reactive behavior, {sup 234}Th is removed from a parcel of water in only two ways, through decay and through particle flux. Therefore, a steady-state 1D activity balance can be used to calculate its flux. Natural Ra isotopes have been also widely used in marine studies to trace water masses and to quantify mixing processes. This work presents results of a collaborative research on organic carbon fluxes distribution in the Bransfield Strait in order to evaluate its influence in the CO{sub 2} drawdown. Macro-nutrients, micro-nutrients and chlorophyll-a distributions were used to examine the pathway sources. Natural radium isotopes were applied as tracers to study the movement of shelf water, while {sup 234}Th was used as a tracer of particle flux in the upper ocean, since POC export via sinking particles is the primary mechanism of carbon sequestration in the Southern Ocean

Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

Energy Technology Data Exchange (ETDEWEB)

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

2015-12-15

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

14 CFR 234.13 - Reports by air carriers on incidents involving animals during air transport.

Science.gov (United States)

2010-01-01

... involving animals during air transport. 234.13 Section 234.13 Aeronautics and Space OFFICE OF THE SECRETARY... REPORTS § 234.13 Reports by air carriers on incidents involving animals during air transport. (a) Any air... during air transport provided by the air carrier. (b) The report shall be made in the form and manner set...

New U.S. LHC Web site launched

CERN Multimedia

Katie Yurkewicz

2007-01-01

On September 12, the U.S. Department of Energy's Office of Science launched a new Web site, www.uslhc.us, to tell the story of the U.S. role in the LHC. The site provides general information for the public about the LHC and its six experiments, as well as detailed information about the participation of physicists, engineers and students from the United States. The U.S. site joins the UK's LHC site in providing information for a national audience, with sites from several more countries expected to launch within the next year. The US LHC site features news and information about the LHC, along with high-resolution images and resources for students and educators. The site also features blogs by four particle physicists, including ATLAS collaborators Monica Dunford from the University of Chicago and Peter Steinberg from Brookhaven National Laboratory. More than 1,300 scientists from over 90 U.S. institutions participate in the LHC and its experiments, representing universities and national laboratories from...

Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study

Directory of Open Access Journals (Sweden)

Nyoman Puspa Asri

2013-03-01

Full Text Available Non catalytic transesterification in sub and supercritical methanol have been used to produce biodiesel from palm oil and soybean oil. A kinetic study was done under reaction condition with temperature and time control. The experiments were carried out in a batch type reactor at reaction temperatures from 210 °C (subcritical condition to 290 °C (the supercritical state in the interval ranges of temperature of 20 °C and at various molar ratios of oil to methanol. The rate constants of the reaction were determined by employing a simple method, with the overall chemical reaction followed the pseudo-first–order reaction. Based on the results, the rate constants of vegetables oil were significantly influenced by reaction temperature, which were gradually increased at subcritical temperature, but sharply increased in the supercritical state. However, the rate constants of soybean oil were slightly higher than that of palm oil. The activation energy for transesterification of soybean oil was 89.32 and 79.05 kJ/mole for palm oil. Meanwhile, the frequency factor values of both oils were 72462892 and 391210 min-1, respectively. The rate reaction for both of oil were expressed as -rTG = 72462892 exp(-89.32/RTCTG for soybean oil and -rTG = 391210 exp(-79.05/RTCTG for palm oil. © 2013 BCREC UNDIP. All rights reservedReceived: 18th October 2012; Revised: 14th December 2012; Accepted: 16th December 2012[How to Cite: N.P. Asri, S. Machmudah, W. Wahyudiono, S. Suprapto, K. Budikarjono, A. Roesyadi, M. Goto, (2013. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 215-223. (doi:10.9767/bcrec.7.3.4060.215-223][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4060.215-223 ] View in  |

49 CFR 234.241 - Protection of insulated wire; splice in underground wire.

Science.gov (United States)

2010-10-01

... underground wire. 234.241 Section 234.241 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION, DEPARTMENT OF TRANSPORTATION GRADE CROSSING SIGNAL SYSTEM SAFETY... of insulated wire; splice in underground wire. Insulated wire shall be protected from mechanical...

Crystal Structure of a Monomeric Form of Severe Acute Respiratory Syndrome Coronavirus Endonuclease Nsp15 Suggests a Role for Hexamerization As An Allosteric Switch

Energy Technology Data Exchange (ETDEWEB)

Joseph, J.S.; Saikatendu, K.S.; Subramanian, V.; Neuman, B.W.; Buchmeier, M.J.; Stevens, R.C.; Kuhn, P.; /Scripps Res. Inst.

2007-07-09

Mature nonstructural protein-15 (nsp15) from the severe acute respiratory syndrome coronavirus (SARS-CoV) contains a novel uridylate-specific Mn{sup 2+}-dependent endoribonuclease (NendoU). Structure studies of the full-length form of the obligate hexameric enzyme from two CoVs, SARS-CoV and murine hepatitis virus, and its monomeric homologue, XendoU from Xenopus laevis, combined with mutagenesis studies have implicated several residues in enzymatic activity and the N-terminal domain as the major determinant of hexamerization. However, the tight link between hexamerization and enzyme activity in NendoUs has remained an enigma. Here, we report the structure of a trimmed, monomeric form of SARS-CoV nsp15 (residues 28 to 335) determined to a resolution of 2.9 Angstroms. The catalytic loop (residues 234 to 249) with its two reactive histidines (His 234 and His 249) is dramatically flipped by {approx}120 degrees into the active site cleft. Furthermore, the catalytic nucleophile Lys 289 points in a diametrically opposite direction, a consequence of an outward displacement of the supporting loop (residues 276 to 295). In the full-length hexameric forms, these two loops are packed against each other and are stabilized by intimate intersubunit interactions. Our results support the hypothesis that absence of an adjacent monomer due to deletion of the hexamerization domain is the most likely cause for disruption of the active site, offering a structural basis for why only the hexameric form of this enzyme is active.

Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

Energy Technology Data Exchange (ETDEWEB)

Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

2014-10-28

centers in the active site form another part of considerable interest of our grant because species with such sites [including methane monooxygenase (MMO) and more] are some of the most effective oxygenase catalysts known. Our team conducted the following research on γ-M2-Keggin complexes: (a) investigated stability of the trimer [{Fe3(OH)3(H2O)2}3(γ-SiW10O36)3]15-, 4, in water, and developed the chemistry and catalysis of the di-iron centered POM, [γ(1,2)-SiW10{Fe(OH)}2O38]6-, 5, in organic solvents (Figure 2). We also study the thermodynamic and structural stability of γ-M2-Keggin in aqueous media for different M’s (d-electron metals). We have defined two structural classes of POMs with proximally bound d-electron metal centers. We refer to these structural isomers of the {γ-M2SiW10} family of POMs as “in-pocket” and “out-of pocket”. We have elucidated the factors controlling the structure and stability of the V, Fe, Ru, Tc, Mo and Rh derivatives of [(SiO4)M2(OH)2W10O32]4- using a range of computational tools. We have: (a) demonstrated that heteroatom X in these polyanions may function as an “internal switch” for defining the ground electronic states and, consequently, the reactivity of the γ-M2-Keggin POM complexes; (b) elucidated reactivity of divacant lacunary species and polyperoxotungstates (PPTs), {Xn+O4[WO(O2)2]4}n-, which could be degradation products of γ-M2-Keggin complexes in aqueous media; (c) elucidated the role of the POM ligand in stabilization of {Ru2} and {(Ru-oxo)2} fragments in the reactant and product of the reaction of {γ-[(Xn+O4)Ru2(OH)2W10O32]}(8-n)- (where X = Si4+, P5+ and S6+) with O2, and (d) the mechanisms of olefin epoxidation catalyzed by these di-d-transition metal substituted and divacant lacunary γ-M2-Keggin complexes. III. Complementing the efforts presented above was the development of less time-consuming but reasonably accurate computational methods allowing one to explore more deeply large catalytic systems. We

Defense In-Depth Accident Analysis Evaluation of Tritium Facility Bldgs. 232-H, 233-H, and 234-H

Energy Technology Data Exchange (ETDEWEB)

Blanchard, A.

1999-05-10

'The primary purpose of this report is to document a Defense-in-Depth (DID) accident analysis evaluation for Department of Energy (DOE) Savannah River Site (SRS) Tritium Facility Buildings 232-H, 233-H, and 234-H. The purpose of a DID evaluation is to provide a more realistic view of facility radiological risks to the offsite public than the bounding deterministic analysis documented in the Safety Analysis Report, which credits only Safety Class items in the offsite dose evaluation.'

24 CFR 234.26 - Project requirements.

Science.gov (United States)

2010-04-01

... Commissioner for the purpose of constructing or converting the project in phases or stages, any special right..., the management company, the real estate broker, and the project developer, but the lender must ensure... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Project requirements. 234.26...

Bovine nucleus caudatus acetylcholinesterase: active site determination and investigation of a dimeric form obtained by selective proteolysis

Energy Technology Data Exchange (ETDEWEB)

Landauer, P.; Ruess, K.P.; Lieflaender, M.

1984-09-01

The number of catalytic subunits of purified bovine nucleus caudatus acetylcholinesterase (E.C. 3.1.1.7) has been determined by active site labelling with (3H)diisopropyl fluorophosphate ((3H)DFP). The 10.5 S, 16 S, and 20 S forms were estimated to contain two, four, and six active sites, respectively, per molecule. A 4.8 S form, which showed a weak amphiphile-dependent activity behavior, was obtained by selective proteolytic digestion with pronase. The inability of the purified 4.8 S form to aggregate after detergent removal, and the molecular mass in the range of 130-165 kD under nondenaturating conditions, indicate that this form is a dimeric form, lacking those hydrophobic regions responsible for aggregation.

234U and 238U in the Carrizo Sandstone aquifer of South Texas

International Nuclear Information System (INIS)

Cowart, J.B.; Osmond, J.K.

1974-01-01

The waters of the Carrizo Sand formation of South Texas, United States of America, exhibit a pattern of uranium isotopic disequilibrium, described in terms of 234 U/ 238 U activity ratio ('A.R.') and uranium concentration, which may be a function of geochemical factors and the hydrologic history of the area. In terms of uranium, two regimes seem to exist. The first, including outcrop and near outcrop sample locations, has waters with relatively high concentration and low A.R. Somewhat downdip, the uranium concentration decreases sharply at the downdip limit of the oxidation environment, a zone of uranium precipitation. Recoil of daughter products from the precipitated uranium causes an increase of A.R. of the water. Water of low uranium concentration and high A.R. is found throughout the downdip regime. If a constant input of 234 U through time is assumed, the downdip decrease in A.R. after the initial introduction of 234 U into the water may be ascribed to radioactive decay of 234 U. However, this assumption leads to the calculation of a water flow rate one twentieth that determined by other means. Alternatively, this pattern may be an artifact of a change of climate from 20,000 years to 10,000 years ago. In this case, the decrease in A.R. downdip is a function of a varying input of 234 U as well as decay. (author)

Phosphorylation of protein kinase A (PKA) regulatory subunit RIα by protein kinase G (PKG) primes PKA for catalytic activity in cells.

Science.gov (United States)

Haushalter, Kristofer J; Casteel, Darren E; Raffeiner, Andrea; Stefan, Eduard; Patel, Hemal H; Taylor, Susan S

2018-03-23

cAMP-dependent protein kinase (PKAc) is a pivotal signaling protein in eukaryotic cells. PKAc has two well-characterized regulatory subunit proteins, RI and RII (each having α and β isoforms), which keep the PKAc catalytic subunit in a catalytically inactive state until activation by cAMP. Previous reports showed that the RIα regulatory subunit is phosphorylated by cGMP-dependent protein kinase (PKG) in vitro , whereupon phosphorylated RIα no longer inhibits PKAc at normal (1:1) stoichiometric ratios. However, the significance of this phosphorylation as a mechanism for activating type I PKA holoenzymes has not been fully explored, especially in cellular systems. In this study, we further examined the potential of RIα phosphorylation to regulate physiologically relevant "desensitization" of PKAc activity. First, the serine 101 site of RIα was validated as a target of PKGIα phosphorylation both in vitro and in cells. Analysis of a phosphomimetic substitution in RIα (S101E) showed that modification of this site increases PKAc activity in vitro and in cells, even without cAMP stimulation. Numerous techniques were used to show that although Ser 101 variants of RIα can bind PKAc, the modified linker region of the S101E mutant has a significantly reduced affinity for the PKAc active site. These findings suggest that RIα phosphorylation may be a novel mechanism to circumvent the requirement of cAMP stimulus to activate type I PKA in cells. We have thus proposed a model to explain how PKG phosphorylation of RIα creates a "sensitized intermediate" state that is in effect primed to trigger PKAc activity.

Step sites in syngas catalysis

DEFF Research Database (Denmark)

Rostrup-Nielsen, J.; Nørskov, Jens Kehlet

2006-01-01

Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative explanat......Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative...... explanation of the impact of step sites on catalyst activity and side reactions such as carbon formation. This leads to a discussion of principles for catalyst promotion....

Tritium Facilities Modernization and Consolidation Project Process Waste Assessment (Project S-7726)

Energy Technology Data Exchange (ETDEWEB)

Hsu, R.H. [Westinghouse Savannah River Company, AIKEN, SC (United States); Oji, L.N.

1997-11-14

Under the Tritium Facility Modernization {ampersand} Consolidation (TFM{ampersand}C) Project (S-7726) at the Savannah River Site (SS), all tritium processing operations in Building 232-H, with the exception of extraction and obsolete/abandoned systems, will be reestablished in Building 233-H. These operations include hydrogen isotopic separation, loading and unloading of tritium shipping and storage containers, tritium recovery from zeolite beds, and stripping of nitrogen flush gas to remove tritium prior to stack discharge. The scope of the TFM{ampersand}C Project also provides for a new replacement R&D tritium test manifold in 233-H, upgrading of the 233- H Purge Stripper and 233-H/234-H building HVAC, a new 234-H motor control center equipment building and relocating 232-H Materials Test Facility metallurgical laboratories (met labs), flow tester and life storage program environment chambers to 234-H.

The influence of desilication on high-silica MFI and its catalytic performance for N2O decomposition

Science.gov (United States)

Shen, Qun; Wu, Minfang; Wang, Hui; Sun, Nannan; He, Chi; Wei, Wei

2018-05-01

A series of MFI zeolites with different Si/Al ratios were pretreated by a basic solution and their catalytic activity was evaluated in N2O decomposition after iron exchange. The performance of Fe-ZSM-5 catalysts could be improved by alkaline pretreatment. Among these samples, the activity curve of Fe-Z5-250-S sample could move to low temperature by >100 °C with a good preservation of hydrothermal stability. It is found that with the meso-microporous hybrid structure, the content of iron as active metal is significantly increased. Additionally, well preservation of the chemical environment around the tetrahedral aluminum and the site accessibility probably may be the other important factors to influence the catalytic activity.

Catalytic burners in larger boiler appliances

Energy Technology Data Exchange (ETDEWEB)

Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

2009-02-15

This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

Tailored synthesis of CuS nanodisks from a new macrocyclic precursor and their efficient catalytic properties on methylene blue dye degradation

International Nuclear Information System (INIS)

Islam, D. A.; Chakraborty, A.; Bhattacharya, B.; Sarkar, U.; Acharya, H.

2016-01-01

In this study, CuS nanodisks have been synthesized from a tetraaza (N_4) macrocyclic complex precursor by a facile wet chemical method. The crystallinity and morphology of the as-synthesized products were characterized by X-ray diffraction and transmission electron microscopy, which confirm a phase pure crystalline CuS nanostructures with ~15 to 20 nm in dimension with ~5 nm thickness. A possible formation mechanism and growth process of the CuS nanodisks are discussed using thiourea and tetraaza ligand as the sulfur donor and stabilizing agent, respectively. Cyclic N_4 ligand also acts as a binding agent to template-guide the oriented growth of CuS nanodisks. The optimized geometry of ligands and complexes was calculated using B3YLP functional, which indicates that the HOMO in the complex located on metal center and N atoms are weakly bonded to the metal center. The catalytic activity of CuS nanodisks toward MB degradation with light displays the higher MB degradation rate than under dark in the presence of H_2O_2. The C_t/C_0 plot as a function of time displays the higher MB degradation activity of CuS nanoparticles with H_2O_2. The recycle stability of CuS nanoparticles was even found to be >80 % after five cycles studied by repeating the MB degradation with same CuS nanoparticles sample.Graphical AbstractCuS nanostructures synthesized from a tetraaza macrocyclic complex precursor show the disk-like registry with average lateral dimension between 15 and 20 nm and thickness of 5 nm. The catalytic activity of CuS nanodisks toward MB degradation with light displays the higher MB degradation rate than in dark in the presence of H_2O_2.

Tailored synthesis of CuS nanodisks from a new macrocyclic precursor and their efficient catalytic properties on methylene blue dye degradation

Energy Technology Data Exchange (ETDEWEB)

Islam, D. A.; Chakraborty, A. [Assam University, Department of Chemistry, Centre for Soft Matters (India); Bhattacharya, B.; Sarkar, U. [Assam University, Department of Physics (India); Acharya, H., E-mail: himadriau@yahoo.co.in [Assam University, Department of Chemistry, Centre for Soft Matters (India)

2016-05-15

In this study, CuS nanodisks have been synthesized from a tetraaza (N{sub 4}) macrocyclic complex precursor by a facile wet chemical method. The crystallinity and morphology of the as-synthesized products were characterized by X-ray diffraction and transmission electron microscopy, which confirm a phase pure crystalline CuS nanostructures with ~15 to 20 nm in dimension with ~5 nm thickness. A possible formation mechanism and growth process of the CuS nanodisks are discussed using thiourea and tetraaza ligand as the sulfur donor and stabilizing agent, respectively. Cyclic N{sub 4} ligand also acts as a binding agent to template-guide the oriented growth of CuS nanodisks. The optimized geometry of ligands and complexes was calculated using B3YLP functional, which indicates that the HOMO in the complex located on metal center and N atoms are weakly bonded to the metal center. The catalytic activity of CuS nanodisks toward MB degradation with light displays the higher MB degradation rate than under dark in the presence of H{sub 2}O{sub 2}. The C{sub t}/C{sub 0} plot as a function of time displays the higher MB degradation activity of CuS nanoparticles with H{sub 2}O{sub 2}. The recycle stability of CuS nanoparticles was even found to be >80 % after five cycles studied by repeating the MB degradation with same CuS nanoparticles sample.Graphical AbstractCuS nanostructures synthesized from a tetraaza macrocyclic complex precursor show the disk-like registry with average lateral dimension between 15 and 20 nm and thickness of 5 nm. The catalytic activity of CuS nanodisks toward MB degradation with light displays the higher MB degradation rate than in dark in the presence of H{sub 2}O{sub 2}.

Carbon Domains on MoS2/TiO2 System via Catalytic Acetylene Oligomerization: Synthesis, Structure, and Surface Properties

Directory of Open Access Journals (Sweden)

Sara Cravanzola

2017-11-01

Full Text Available Carbon domains have been obtained at the surface of a MoS2/TiO2 (Evonik, P25 system via oligomerization and cyclotrimerization reactions involved in the interaction of the photoactive material with acetylene. Firstly, MoS2 nanosheets have been synthesized at the surface of TiO2, via sulfidation of a molybdenum oxide precursor with H2S (bottom-up method. Secondly, the morphology and the structure, the optical and the vibrational properties of the obtained materials, for each step of the synthesis procedure, have been investigated by microscopy and spectroscopy methods. In particular, transmission electron microscopy images provide a simple tool to highlight the effectiveness of the sulfidation process, thus showing 1L, 2L, and stacked MoS2 nanosheets anchored to the surface of TiO2 nanoparticles. Lastly, in-situ FTIR spectroscopy investigation gives insights into the nature of the oligomerized species, showing that the formation of both polyenic and aromatic systems can be taken into account, being their formation promoted by both Ti and Mo catalytic sites. This finding gives an opportunity for the assembly of extended polyenic, polyaromatic, or mixed domains firmly attached at the surface of photoactive materials. The presented approach, somehow different from the carbon adding or doping processes of TiO2, is of potential interest for the advanced green chemistry and energy conversion/transport applications.

Zymogen Activation and Subcellular Activity of Subtilisin Kexin Isozyme 1/Site 1 Protease*

Science.gov (United States)

da Palma, Joel Ramos; Burri, Dominique Julien; Oppliger, Joël; Salamina, Marco; Cendron, Laura; de Laureto, Patrizia Polverino; Seidah, Nabil Georges; Kunz, Stefan; Pasquato, Antonella

2014-01-01

The proprotein convertase subtilisin kexin isozyme 1 (SKI-1)/site 1 protease (S1P) plays crucial roles in cellular homeostatic functions and is hijacked by pathogenic viruses for the processing of their envelope glycoproteins. Zymogen activation of SKI-1/S1P involves sequential autocatalytic processing of its N-terminal prodomain at sites B′/B followed by the herein newly identified C′/C sites. We found that SKI-1/S1P autoprocessing results in intermediates whose catalytic domain remains associated with prodomain fragments of different lengths. In contrast to other zymogen proprotein convertases, all incompletely matured intermediates of SKI-1/S1P showed full catalytic activity toward cellular substrates, whereas optimal cleavage of viral glycoproteins depended on B′/B processing. Incompletely matured forms of SKI-1/S1P further process cellular and viral substrates in distinct subcellular compartments. Using a cell-based sensor for SKI-1/S1P activity, we found that 9 amino acid residues at the cleavage site (P1–P8) and P1′ are necessary and sufficient to define the subcellular location of processing and to determine to what extent processing of a substrate depends on SKI-1/S1P maturation. In sum, our study reveals novel and unexpected features of SKI-1/S1P zymogen activation and subcellular specificity of activity toward cellular and pathogen-derived substrates. PMID:25378398

24 CFR 234.285 - Waived title objections.

Science.gov (United States)

2010-04-01

... have not been violated to a material extent. (f) Federal tax liens and rights of redemption arising... Commissioner will not object to an outstanding right of redemption in IRS if: (1) The Federal tax lien was... CONDOMINIUM OWNERSHIP MORTGAGE INSURANCE Contract Rights and Obligations-Individually Owned Units § 234.285...

Calibration of a low background gas-flow proportional counter to estimate "2"3"4Th activity in coastal waters

International Nuclear Information System (INIS)

Cuesta, E.; Lozano, R.L.; Miguel, E.G. San; Casas-Ruiz, M.; Bolívar, J.P.

2016-01-01

This paper relates the calibration of a low background gas-flow proportional counter. This calibration has been used to determine low activity of "2"3"4Th in coastal water samples. Two methods were used to prepare calibration samples: Evaporation and Electrodeposition. First method was rejected due to the lack of reproducibility because the different geometry adopted by the drops of tracer once dried on the disk. On the contrary, through the second method, similar efficiencies were obtained in all detectors with an average of 0.401±0.004. In this paper, the whole procedure to obtain "2"3"4Th activity in dissolution as well as in particulate matter has been detailed, and all the algorithms needed to calculate activities and efficiencies are shown. Finally, two experiments have been designed in order to validate the calibration of the beta counter and the method to determine "2"3"4Th in coastal waters with high concentration of particulate matter. - Highlights: • This paper shows a Home-made calibration using two methods to prepare calibration samples. • The algorithms needed to obtain Th-234 activity concentrations are described in full detail. • This is the first time Th-234 has been determined in water samples from Huelva Estuary.

Synthesis and visible-light-induced catalytic activity of Ag{sub 2}S-coupled TiO{sub 2} nanoparticles and nanowires

Energy Technology Data Exchange (ETDEWEB)

Xie Yi; Heo, Sung Hwan; Kim, Yong Nam; Yoo, Seung Hwa; Cho, Sung Oh, E-mail: socho@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology (KAIST), 373-1 Guseong, Yuseong, Daejeon 305-701 (Korea, Republic of)

2010-01-08

We present the synthesis and visible-light-induced catalytic activity of Ag{sub 2}S-coupled TiO{sub 2} nanoparticles (NPs) and TiO{sub 2} nanowires (NWs). Through a simple wet chemical process from a mixture of peroxo titanic acid (PTA) solution, thiourea and AgAc, a composite of Ag{sub 2}S NPs and TiO{sub 2} NPs with sizes of less than 7 nm was formed. When the NP composite was further treated with NaOH solution followed by annealing at ambient conditions, a new nanocomposite material comprising Ag{sub 2}S NPs on TiO{sub 2} NWs was created. Due to the coupling with such a low bandgap material as Ag{sub 2}S, the TiO{sub 2} nanocomposites could have a visible-light absorption capability much higher than that of pure TiO{sub 2}. As a result, the synthesized Ag{sub 2}S/TiO{sub 2} nanocomposites exhibited much higher catalytic efficiency for the decomposition of methyl orange than commercial TiO{sub 2} (Degussa P25, Germany) under visible light.

Functional Sites Induce Long-Range Evolutionary Constraints in Enzymes.

Directory of Open Access Journals (Sweden)

Benjamin R Jack

2016-05-01

Full Text Available Functional residues in proteins tend to be highly conserved over evolutionary time. However, to what extent functional sites impose evolutionary constraints on nearby or even more distant residues is not known. Here, we report pervasive conservation gradients toward catalytic residues in a dataset of 524 distinct enzymes: evolutionary conservation decreases approximately linearly with increasing distance to the nearest catalytic residue in the protein structure. This trend encompasses, on average, 80% of the residues in any enzyme, and it is independent of known structural constraints on protein evolution such as residue packing or solvent accessibility. Further, the trend exists in both monomeric and multimeric enzymes and irrespective of enzyme size and/or location of the active site in the enzyme structure. By contrast, sites in protein-protein interfaces, unlike catalytic residues, are only weakly conserved and induce only minor rate gradients. In aggregate, these observations show that functional sites, and in particular catalytic residues, induce long-range evolutionary constraints in enzymes.

20 CFR 234.20 - Computation of the employee's 1937 Act LSDP basic amount.

Science.gov (United States)

2010-04-01

... compensation and section 209 of the Social Security Act for a definition of creditable wages.) Closing date... 20 Employees' Benefits 1 2010-04-01 2010-04-01 false Computation of the employee's 1937 Act LSDP basic amount. 234.20 Section 234.20 Employees' Benefits RAILROAD RETIREMENT BOARD REGULATIONS UNDER THE...

Conformational flexibility in the catalytic triad revealed by the high-resolution crystal structure of Streptomyces erythraeus trypsin in an unliganded state

Energy Technology Data Exchange (ETDEWEB)

Blankenship, Elise; Vukoti, Krishna [Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Miyagi, Masaru, E-mail: mxm356@cwru.edu [Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Lodowski, David T., E-mail: mxm356@cwru.edu [Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States); Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (United States)

2014-03-01

This work reports the first sub-angstrom resolution structure of S. erythraeus trypsin. The detailed model of a prototypical serine protease at a catalytically relevant pH with an unoccupied active site is presented and is compared with other high-resolution serine protease structures. With more than 500 crystal structures determined, serine proteases make up greater than one-third of all proteases structurally examined to date, making them among the best biochemically and structurally characterized enzymes. Despite the numerous crystallographic and biochemical studies of trypsin and related serine proteases, there are still considerable shortcomings in the understanding of their catalytic mechanism. Streptomyces erythraeus trypsin (SET) does not exhibit autolysis and crystallizes readily at physiological pH; hence, it is well suited for structural studies aimed at extending the understanding of the catalytic mechanism of serine proteases. While X-ray crystallographic structures of this enzyme have been reported, no coordinates have ever been made available in the Protein Data Bank. Based on this, and observations on the extreme stability and unique properties of this particular trypsin, it was decided to crystallize it and determine its structure. Here, the first sub-angstrom resolution structure of an unmodified, unliganded trypsin crystallized at physiological pH is reported. Detailed structural analysis reveals the geometry and structural rigidity of the catalytic triad in the unoccupied active site and comparison to related serine proteases provides a context for interpretation of biochemical studies of catalytic mechanism and activity.

Conformational flexibility in the catalytic triad revealed by the high-resolution crystal structure of Streptomyces erythraeus trypsin in an unliganded state

International Nuclear Information System (INIS)

Blankenship, Elise; Vukoti, Krishna; Miyagi, Masaru; Lodowski, David T.

2014-01-01

This work reports the first sub-angstrom resolution structure of S. erythraeus trypsin. The detailed model of a prototypical serine protease at a catalytically relevant pH with an unoccupied active site is presented and is compared with other high-resolution serine protease structures. With more than 500 crystal structures determined, serine proteases make up greater than one-third of all proteases structurally examined to date, making them among the best biochemically and structurally characterized enzymes. Despite the numerous crystallographic and biochemical studies of trypsin and related serine proteases, there are still considerable shortcomings in the understanding of their catalytic mechanism. Streptomyces erythraeus trypsin (SET) does not exhibit autolysis and crystallizes readily at physiological pH; hence, it is well suited for structural studies aimed at extending the understanding of the catalytic mechanism of serine proteases. While X-ray crystallographic structures of this enzyme have been reported, no coordinates have ever been made available in the Protein Data Bank. Based on this, and observations on the extreme stability and unique properties of this particular trypsin, it was decided to crystallize it and determine its structure. Here, the first sub-angstrom resolution structure of an unmodified, unliganded trypsin crystallized at physiological pH is reported. Detailed structural analysis reveals the geometry and structural rigidity of the catalytic triad in the unoccupied active site and comparison to related serine proteases provides a context for interpretation of biochemical studies of catalytic mechanism and activity

Changed membrane integration and catalytic site conformation are two mechanisms behind the increased Aβ42/Aβ40 ratio by presenilin 1 familial Alzheimer-linked mutations

Directory of Open Access Journals (Sweden)

Johanna Wanngren

2014-01-01

Full Text Available The enzyme complex γ-secretase generates amyloid β-peptide (Aβ, a 37–43-residue peptide associated with Alzheimer disease (AD. Mutations in presenilin 1 (PS1, the catalytical subunit of γ-secretase, result in familial AD (FAD. A unifying theme among FAD mutations is an alteration in the ratio Aβ species produced (the Aβ42/Aβ40 ratio, but the molecular mechanisms responsible remain elusive. In this report we have studied the impact of several different PS1 FAD mutations on the integration of selected PS1 transmembrane domains and on PS1 active site conformation, and whether any effects translate to a particular amyloid precursor protein (APP processing phenotype. Most mutations studied caused an increase in the Aβ42/Aβ40 ratio, but via different mechanisms. The mutations that caused a particular large increase in the Aβ42/Aβ40 ratio did also display an impaired APP intracellular domain (AICD formation and a lower total Aβ production. Interestingly, seven mutations close to the catalytic site caused a severely impaired integration of proximal transmembrane/hydrophobic sequences into the membrane. This structural defect did not correlate to a particular APP processing phenotype. Six selected FAD mutations, all of which exhibited different APP processing profiles and impact on PS1 transmembrane domain integration, were found to display an altered active site conformation. Combined, our data suggest that FAD mutations affect the PS1 structure and active site differently, resulting in several complex APP processing phenotypes, where the most aggressive mutations in terms of increased Aβ42/Aβ40 ratio are associated with a decrease in total γ-secretase activity.

Nature of active centers of catalytic system of VOCl/sub 3/ - Al(C/sub 2/H/sub 5/)/sub 2/Cl

Energy Technology Data Exchange (ETDEWEB)

Dubnikova, I L; Meshkova, I N [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1977-05-01

To investigate the nature of the active sites of the catalyst VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl during olefine polymerization, the following factors have been studied: composition and catalytic activity of homogeneous and heterogeneous components of the system, valent state of vanadium entering into the composition of the catalytic sites, effect of an organoaluminium component on the catalytic activity of the system, and the properties of the polymeric products being formed. It has been shown that the catalytic sites of the system VOCl/sub 3/-Al(C/sub 4/H/sub 5/)/sub 2/Cl are located, predominantly, in the heterogeneus phase of the catalyst. A conclusion has been made that heterogeneous catalytic sites are bimetal complexes of alkyl derivatives of vanadium trichloride and aluminuim alkylchlorides and that polycentral mechanism of catalysis of olefine polymerization in the presence of VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl is caused by two types of active vanadium-aluminium complexes differing in the nature of an organoaluminium component.

Interactions of a Pop5/Rpp1 heterodimer with the catalytic domain of RNase MRP.

Science.gov (United States)

Perederina, Anna; Khanova, Elena; Quan, Chao; Berezin, Igor; Esakova, Olga; Krasilnikov, Andrey S

2011-10-01

Ribonuclease (RNase) MRP is a multicomponent ribonucleoprotein complex closely related to RNase P. RNase MRP and eukaryotic RNase P share most of their protein components, as well as multiple features of their catalytic RNA moieties, but have distinct substrate specificities. While RNase P is practically universally found in all three domains of life, RNase MRP is essential in eukaryotes. The structural organizations of eukaryotic RNase P and RNase MRP are poorly understood. Here, we show that Pop5 and Rpp1, protein components found in both RNase P and RNase MRP, form a heterodimer that binds directly to the conserved area of the putative catalytic domain of RNase MRP RNA. The Pop5/Rpp1 binding site corresponds to the protein binding site in bacterial RNase P RNA. Structural and evolutionary roles of the Pop5/Rpp1 heterodimer in RNases P and MRP are discussed.

In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

Science.gov (United States)

Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

2014-04-01

Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

Characterization of a human coagulation factor Xa-binding site on Viperidae snake venom phospholipases A2 by affinity binding studies and molecular bioinformatics

Directory of Open Access Journals (Sweden)

Gowda Veerabasappa T

2007-12-01

Full Text Available Abstract Background The snake venom group IIA secreted phospholipases A2 (SVPLA2, present in the Viperidae snake family exhibit a wide range of toxic and pharmacological effects. They exert their different functions by catalyzing the hydrolysis of phospholipids (PL at the membrane/water interface and by highly specific direct binding to: (i presynaptic membrane-bound or intracellular receptors; (ii natural PLA2-inhibitors from snake serum; and (iii coagulation factors present in human blood. Results Using surface plasmon resonance (SPR protein-protein interaction measurements and an in vitro biological test of inhibition of prothrombinase activity, we identify a number of Viperidae venom SVPLA2s that inhibit blood coagulation through direct binding to human blood coagulation factor Xa (FXa via a non-catalytic, PL-independent mechanism. We classify the SVPLA2s in four groups, depending on the strength of their binding. Molecular electrostatic potentials calculated at the surface of 3D homology-modeling models show a correlation with inhibition of prothrombinase activity. In addition, molecular docking simulations between SVPLA2 and FXa guided by the experimental data identify the potential FXa binding site on the SVPLA2s. This site is composed of the following regions: helices A and B, the Ca2+ loop, the helix C-β-wing loop, and the C-terminal fragment. Some of the SVPLA2 binding site residues belong also to the interfacial binding site (IBS. The interface in FXa involves both, the light and heavy chains. Conclusion We have experimentally identified several strong FXa-binding SVPLA2s that disrupt the function of the coagulation cascade by interacting with FXa by the non-catalytic PL-independent mechanism. By theoretical methods we mapped the interaction sites on both, the SVPLA2s and FXa. Our findings may lead to the design of novel, non-competitive FXa inhibitors.

A radiological disadvantage for siting a repository at Yucca Mountain

International Nuclear Information System (INIS)

Spiegler, P.

1996-01-01

At Yucca mountain, the disposal of large amounts of U-238, U-234, and Pu-238 will result in a long term build-up of Rn-222. In time, because of erosion, the repository horizon will move closer to the surface and large amounts of Rn-222 gas will be able to leak into the atmosphere. The area surrounding Yucca Mountain will become a site of high radioactive background. Sullivan and Pescatore have brought the issue to the attention of the DOE

Application of Zeolitic Additives in the Fluid Catalytic Cracking (FCC

Directory of Open Access Journals (Sweden)

A. Nemati Kharat

2013-06-01

Full Text Available Current article describes application of zeolites in fluid catalytic cracking (FCC. The use of several zeolitic additives for the production light olefins and reduction of pollutants is described. Application of zeolites as fluid catalytic cracking (FCC catalysts and additives due to the presence of active acid sites in the zeolite framework  increase the formation of desired cracking products (i.e., olefin and branched products  in the FCC unit.

Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

KAUST Repository

Zhang, Tao

2014-01-01

Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

The role of short-range Cys171-Cys178 disulfide bond in maintaining cutinase active site integrity: A molecular dynamics simulation

International Nuclear Information System (INIS)

Matak, Mehdi Youssefi; Moghaddam, Majid Erfani

2009-01-01

Understanding structural determinants in enzyme active site integrity can provide a good knowledge to design efficient novel catalytic machineries. Fusarium solani pisi cutinase with classic triad Ser-His-Asp is a promising enzyme to scrutinize these structural determinants. We performed two MD simulations: one, with the native structure, and the other with the broken Cys171-Cys178 disulfide bond. This disulfide bond stabilizes a turn in active site on which catalytic Asp175 is located. Functionally important H-bonds and atomic fluctuations in catalytic pocket have been changed. We proposed that this disulfide bond within active site can be considered as an important determinant of cutinase active site structural integrity.

Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

Science.gov (United States)

Plaga, W; Frank, R; Knappe, J

1988-12-15

Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

NRC staff site characterization analysis of the Department of Energy`s Site Characterization Plan, Yucca Mountain Site, Nevada

Energy Technology Data Exchange (ETDEWEB)

NONE

1989-08-01

This Site Characterization Analysis (SCA) documents the NRC staff`s concerns resulting from its review of the US Department of Energy`s (DOE`s) Site Characterization Plan (SCP) for the Yucca Mountain site in southern Nevada, which is the candidate site selected for characterization as the nation`s first geologic repository for high-level radioactive waste. DOE`s SCP explains how DOE plans to obtain the information necessary to determine the suitability of the Yucca Mountain site for a repository. NRC`s specific objections related to the SCP, and major comments and recommendations on the various parts of DOE`s program, are presented in SCA Section 2, Director`s Comments and Recommendations. Section 3 contains summaries of the NRC staff`s concerns for each specific program, and Section 4 contains NRC staff point papers which set forth in greater detail particular staff concerns regarding DOE`s program. Appendix A presents NRC staff evaluations of those NRC staff Consultation Draft SCP concerns that NRC considers resolved on the basis of the SCP. This SCA fulfills NRC`s responsibilities with respect to DOE`s SCP as specified by the Nuclear Waste Policy Act (NWPA) and 10 CFR 60.18. 192 refs., 2 tabs.

Tritium Facilities Modernization and Consolidation Project Process Waste Assessment (Project S-7726)

International Nuclear Information System (INIS)

Hsu, R.H.; Oji, L.N.

1997-01-01

Under the Tritium Facility Modernization ampersand Consolidation (TFM ampersand C) Project (S-7726) at the Savannah River Site (SS), all tritium processing operations in Building 232-H, with the exception of extraction and obsolete/abandoned systems, will be reestablished in Building 233-H. These operations include hydrogen isotopic separation, loading and unloading of tritium shipping and storage containers, tritium recovery from zeolite beds, and stripping of nitrogen flush gas to remove tritium prior to stack discharge. The scope of the TFM ampersand C Project also provides for a new replacement R ampersand D tritium test manifold in 233-H, upgrading of the 233- H Purge Stripper and 233-H/234-H building HVAC, a new 234-H motor control center equipment building and relocating 232-H Materials Test Facility metallurgical laboratories (met labs), flow tester and life storage program environment chambers to 234-H

Sustainability as a Priority at Major U.S. Department of Energy’s Defense Sites: Surrounding Population Views

Directory of Open Access Journals (Sweden)

Michael R. Greenberg

2014-04-01

Full Text Available Sustainability is rapidly becoming a widely accepted and desired attitude, as well as a stimulus for both environmentally-conscious individuals and firm behavior. However, does the public interest in sustainability also extend to large U.S. federal agencies? Does the public care about on-site sustainability programs? To answer this question, we surveyed 922 people who live within 50 miles of one of four U.S. Department of Energy’s (DOE major facilities: Hanford, Idaho National Laboratory, Savannah River and the Waste Isolation Pilot Plant. Only 14% expressed no interest in DOE’s on-site sustainability efforts. Five percent said that they were interested enough to join a local community group to provide feedback to the DOE; 49% were interested and wanted more information, as well as interaction with the DOE’s site-specific advisory boards or local elected officials. Compared to other DOE on-site activities, respondents rated sustainability as “somewhat important”. Native Americans who live near a site, are familiar with it and self-identify as interested in environmental protection disproportionately belong to the “most interested” category. We conclude that public interest is sufficient to merit outreach by DOE to involve interested and knowledgeable local residents in on-site sustainability plans.

Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition

NARCIS (Netherlands)

Li, G.; Pidko, E.A.; Filot, I.A.W.; Santen, van R.A.; Li, Can; Hensen, E.J.M.

2013-01-01

The reactivity of mononuclear and binuclear iron-containing complexes in ZSM-5 zeolite for catalytic N2O decomposition has been investigated by periodic DFT calculations and microkinetic modeling. On mononuclear sites, the activation of a first N2O molecule is favorable. The rate of catalytic N2O

Uranium series disequilibrium studies at the Broubster analogue site

International Nuclear Information System (INIS)

Longworth, G.; Ivanovich, M.; Wilkins, M.A.

1989-09-01

Uranium series measurements at a natural analogue site at Broubster, Caithness have been used to investigate radionuclide migration over a period of several hundred to 10 6 years. The measured values for the uranium concentration and activity ratios 234 U/ 238 U and 230 Th/ 234 U indicate that the geochemical system is more complicated than that originally proposed of uranium dispersion and water transport into a peat bog. There appears to be little thorium mobility although there is evidence for an appreciable fraction of thorium on the colloidal phases. (author)

Catalytic growth of vertically aligned neutron sensitive 10Boron nitride nanotubes

International Nuclear Information System (INIS)

Ahmad, Pervaiz; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Khan, Ghulamullah; Ramay, Shahid M.; Mahmood, Asif; Amin, Muhammad; Muhammad, Nawshad

2016-01-01

10 Boron nitride nanotubes ( 10 BNNTs) are a potential neutron sensing element in a solid-state neutron detector. The aligned 10 BNNT can be used for its potential application without any further purification. Argon-supported thermal CVD is used to achieve vertically aligned 10 BNNT with the help of nucleation sites produced in a thin layer of magnesium–iron alloy deposited at the top of Si substrate. FESEM shows vertically aligned 10 BNNTs with ball-like catalytic tips at top. EDX reveals magnesium (Mg) contents in the tips that refer to catalytic growth of 10 BNNT. HR-TEM shows tubular morphology of the synthesized 10 BNNT with lattice fringes on its outer part having an interlayer spacing of ∼0.34 nm. XPS shows B 1 s and N 1 s peaks at 190.5 and 398 eV that correspond to hexagonal 10 Boron nitride ( 10 h-BN) nature of the synthesized 10 BNNT, whereas the Mg kll auger peaks at ∼301 and ∼311 eV represents Mg contents in the sample. Raman spectrum has a peak at 1390 (cm −1 ) that corresponds to E 2g mode of vibration in 10 h-BN

Multi-Institution Prospective Trial of Reduced-Dose Craniospinal Irradiation (23.4 Gy) Followed by Conformal Posterior Fossa (36 Gy) and Primary Site Irradiation (55.8 Gy) and Dose-Intensive Chemotherapy for Average-Risk Medulloblastoma

International Nuclear Information System (INIS)

Merchant, Thomas E.; Kun, Larry E.; Krasin, Matthew J.; Wallace, Dana; Chintagumpala, Murali M.; Woo, Shiao Y.; Ashley, David M.; Sexton, Maree; Kellie, Stewart J.; Ahern, Verity M.B.B.S.; Gajjar, Amar

2008-01-01

Purpose: Limiting the neurocognitive sequelae of radiotherapy (RT) has been an objective in the treatment of medulloblastoma. Conformal RT to less than the entire posterior fossa (PF) after craniospinal irradiation might reduce neurocognitive sequelae and requires evaluation. Methods and Materials: Between October 1996 and August 2003, 86 patients, 3-21 years of age, with newly diagnosed, average-risk medulloblastoma were treated in a prospective, institutional review board-approved, multi-institution trial of risk-adapted RT and dose-intensive chemotherapy. RT began within 28 days of definitive surgery and consisted of craniospinal irradiation (23.4 Gy), conformal PF RT (36.0 Gy), and primary site RT (55.8 Gy). The planning target volume for the primary site included the postoperative tumor bed surrounded by an anatomically confined margin of 2 cm that was then expanded with a geometric margin of 0.3-0.5 cm. Chemotherapy was initiated 6 weeks after RT and included four cycles of high-dose cyclophosphamide, cisplatin, and vincristine. Results: At a median follow-up of 61.2 months (range, 5.2-115.0 months), the estimated 5-year event-free survival and cumulative incidence of PF failure rate was 83.0% ± 5.3% and 4.9% ± 2.4% (± standard error), respectively. The targeting guidelines used in this study resulted in a mean reduction of 13% in the volume of the PF receiving doses >55 Gy compared with conventionally planned RT. The reductions in the dose to the temporal lobes, cochleae, and hypothalamus were statistically significant. Conclusion: This prospective trial has demonstrated that irradiation of less than the entire PF after 23.4 Gy craniospinal irradiation for average-risk medulloblastoma results in disease control comparable to that after treatment of the entire PF

Uranium series disequilibrium studies at the Broubster analogue site

International Nuclear Information System (INIS)

Longworth, G.; Ivanovich, M.; Wilkins, M.A.

1990-11-01

Uranium series measurements at a natural analogue site at Broubster, Caithness have been used to investigate radionuclide migration over periods ranging from several hundred to 10 6 years. The measured values for the uranium concentration and activity values 234 U/ 238 U and 230 Th/ 234 U indicate that the geochemical system is more complicated than that originally proposed of uranium dispersion and water transport into a peat bog. There appears to be little thorium mobility although there is evidence for an appreciable fraction of thorium on the colloidal phase. (author)

IGRINS NEAR-IR HIGH-RESOLUTION SPECTROSCOPY OF MULTIPLE JETS AROUND LkHα 234

Energy Technology Data Exchange (ETDEWEB)

Oh, Heeyoung; Yuk, In-Soo; Park, Byeong-Gon; Park, Chan; Chun, Moo-Young; Kim, Kang-Min; Oh, Jae Sok; Jeong, Ueejeong; Yu, Young Sam; Lee, Jae-Joon; Kim, Hwihyun; Hwang, Narae; Lee, Sungho [Korea Astronomy and Space Science Institute, 776 Daedeok-daero, Yuseong-gu, Daejeon 305-348 (Korea, Republic of); Pyo, Tae-Soo [Subaru Telescope, National Astronomical Observatory of Japan, 650 North A’ohoku Place, Hilo, HI 96720 (United States); Pak, Soojong; Lee, Hye-In; Le, Huynh Anh Nguyen [School of Space Research and Institute of Natural Sciences, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 17104 (Korea, Republic of); Kaplan, Kyle; Pavel, Michael; Mace, Gregory, E-mail: hyoh@kasi.re.kr [Department of Astronomy, University of Texas at Austin, Austin, TX (United States); and others

2016-02-01

We present the results of high-resolution near-IR spectroscopy toward the multiple outflows around the Herbig Be star LkHα 234 using the Immersion Grating Infrared Spectrograph. Previous studies indicate that the region around LkHα 234 is complex, with several embedded young stellar objects and the outflows associated with them. In simultaneous H- and K-band spectra from HH 167, we detected 5 [Fe ii] and 14 H{sub 2} emission lines. We revealed a new [Fe ii] jet driven by radio continuum source VLA 3B. Position–velocity diagrams of the H{sub 2} 1−0 S(1) λ2.122 μm line show multiple velocity peaks. The kinematics may be explained by a geometrical bow shock model. We detected a component of H{sub 2} emission at the systemic velocity (V{sub LSR} = −10.2 km s{sup −1}) along the whole slit in all slit positions, which may arise from the ambient photodissociation region. Low-velocity gas dominates the molecular hydrogen emission from knots A and B in HH 167, which is close to the systemic velocity; [Fe ii] emission lines are detected farther from the systemic velocity, at V{sub LSR} = −100–−130 km s{sup −1}. We infer that the H{sub 2} emission arises from shocked gas entrained by a high-velocity outflow. Population diagrams of H{sub 2} lines imply that the gas is thermalized at a temperature of 2500–3000 K and the emission results from shock excitation.

Surface electronic structure-catalytic activity correlation of partially reduced molybdenum oxide(s) for the isomerization of light alkenes and alkanes

International Nuclear Information System (INIS)

Al-Kandari, S; Al-Kandari, H; Al-Kharafi, F; Katrib, A

2008-01-01

Catalytic activity-surface electronic structure correlation was carried out using surface XPS-UPS techniques. In situ reduction by hydrogen, were carried out at similar experimental conditions to those employed for the catalytic reactions. In the case of MoO 3 deposited on TiO 2 , the reduction to MoO 2 state with the bifunctional MoO 2 (H x ) ac phase on its surface starts at 573 K and reaches a stable state at temperatures between 653-673 K. In the case of alumina support, a strong metal-support interaction takes place during the catalyst preparation, leading to Al 2 (MoO 4 ) 3 complex formation as characterized by XRD. The reduction process(s) of this complex by hydrogen as a function of temperature is different from what is observed in the case of titania support. The changes in the chemical structure of the sample surface in both systems were tested for the catalytic reactions of 1-pentene and n-pentane

Identification of the segment of the catalytic subunit of (Na+,K+)ATPase containing the digitalis binding site.

Science.gov (United States)

Rossi, B; Ponzio, G; Lazdunski, M

1982-01-01

Digitalis compounds that are extensively used in the treatment of cardiovascular disorders are known to bind specifically at the extracellular side of (Na+,K+)ATPase. We have recently reported the synthesis of [3H]p- nitrophenyltriazene -ouabain, a derivative of ouabain, which specifically alkylates the catalytic chain of the (Na+,K+)ATPase at a defined region of the sequence. The peptidic segment involved in the binding of digitalis to (Na+,K+)ATPase has been located after mild trypsin treatment of the labeled enzyme. In the presence of 100 mM KCl, tryptic fragmentation results in two peptide fragments of mol. wt. 58 000 and 41 000, respectively. The radioactive probe labeled only the 41 000 fragment indicating that the digitalis binding site is located on the 41 000 domain situated at the N-terminal part of the sequence of the alpha-subunit. Images Fig. 1. Fig. 3. PMID:6329711

The sediment budget of an urban coastal lagoon (Jamaica Bay, NY) determined using 234Th and 210Pb

Science.gov (United States)

Renfro, Alisha A.; Cochran, J. Kirk; Hirschberg, David J.; Bokuniewicz, Henry J.; Goodbred, Steven L.

2016-10-01

The sediment budget of Jamaica Bay (New York, USA) has been determined using the natural particle-reactive radionuclides 234Th and 210Pb. Inventories of excess thorium-234 (234Thxs, half-life = 24.1 d) were measured in bottom sediments of the Bay during four cruises from September 2004 to July 2006. The mean bay-wide inventory for the four sampling periods ranged from 3.5 to 5.0 dpm cm-2, four to six times that expected from 234Th production in the overlying water column. The presence of dissolved 234Th and a high specific activity of 234Thxs on particles at the bay inlet (∼30 dpm g-1) indicated that both dissolved and particulate 234Th could be imported into the bay from the ocean. Based on these observations, a mass balance of 234Th yields an annual input of ∼39 ± 14 × 1010 g sediment into the bay. Mass accumulation rates determined from profiles of excess 210Pb (half-life = 22.3 y) in sediment cores require annual sediment import of 7.4 ± 4.5 × 1010 g. Both radionuclides indicate that there is considerable marine-derived sediment import to Jamaica Bay, consistent with earlier work using 210Pb. Such sediment input may be important in sustaining longer-term accretion rates of salt marshes in the bay.

Membrane Guanylate Cyclase catalytic Subdomain: Structure and Linkage with Calcium Sensors and Bicarbonate

Directory of Open Access Journals (Sweden)

Sarangan Ravichandran

2017-06-01

Full Text Available Membrane guanylate cyclase (MGC is a ubiquitous multi-switching cyclic GMP generating signaling machine linked with countless physiological processes. In mammals it is encoded by seven distinct homologous genes. It is a single transmembrane spanning multi-modular protein; composed of integrated blocks and existing in homo-dimeric form. Its core catalytic domain (CCD module is a common transduction center where all incoming signals are translated into the production of cyclic GMP, a cellular signal second messenger. Crystal structure of the MGC’s CCD does not exist and its precise identity is ill-defined. Here, we define it at a sub-molecular level for the phototransduction-linked MGC, the rod outer segment guanylate cyclase type 1, ROS-GC1. (1 The CCD is a conserved 145-residue structural unit, represented by the segment V820-P964. (2 It exists as a homo-dimer and contains seven conserved catalytic elements (CEs wedged into seven conserved motifs. (3 It also contains a conserved 21-residue neurocalcin δ-modulated structural domain, V836-L857. (4 Site-directed mutagenesis documents that each of the seven CEs governs the cyclase’s catalytic activity. (5 In contrast to the soluble and the bacterium MGC which use Mn2+-GTP substrate for catalysis, MGC CCD uses the natural Mg2+-GTP substrate. (6 Strikingly, the MGC CCD requires anchoring by the Transmembrane Domain (TMD to exhibit its major (∼92% catalytic activity; in isolated form the activity is only marginal. This feature is not linked with any unique sequence of the TMD; there is minimal conservation in TMD. Finally, (7 the seven CEs control each of four phototransduction pathways- -two Ca2+-sensor GCAPs-, one Ca2+-sensor, S100B-, and one bicarbonate-modulated. The findings disclose that the CCD of ROS-GC1 has built-in regulatory elements that control its signal translational activity. Due to conservation of these regulatory elements, it is proposed that these elements also control the

Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites

Science.gov (United States)

2015-01-01

Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu–S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (HDA) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu–S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites. PMID:25310460

230Th/234U activity ratio in the products from Izu-Bonin island-arc volcanoes

International Nuclear Information System (INIS)

Kurihara, Y.; Takahashi, M.; Sato, J.

2006-01-01

Magma genesis at subduction zone is generally inferred to be induced by the partial melting of the mantle wedge by the addition of fluid derived from the subducting slab. Uranium-series disequilibria in the volcanic products are a useful tracer to understand various magma processes. Young island-arc volcanic rocks showed the characteristic feature of excess 234 U over 230 Th. Observation was carried out on the radioactive disequilibrium between 234 U and 230 Th in the volcanic products from Asama volcano and Izu-Mariana island-arc volcanoes. Thorium and Uranium in the volcanic rock samples were separated by anion-exchange resin and purified by TEVA·Spec. and UTEVA·Spec. resins, respectively. Purified Th and U were electrodeposited onto a stainless steel planchet for α-ray counting. U-234 and 230 Th in volcanic rock samples were determined by isotope dilution method coupled with α-ray spectrometry. 230 Th/ 234 U activity ratio in the volcanic products from Asama volcano and Izu-Bonin island-arc volcanoes were in radioactive disequilibrium, enriched in 234 U relative to 230 Th, which is often observed for volcanic products from young island-arc volcanic products. (author)

234Th distributions in coastal and open ocean waters by non-destructive β-counting

International Nuclear Information System (INIS)

Miller, L.A.; Svaeren, I.

2003-01-01

Non-destructive β-counting analyses of particulate and dissolved 234 Th activities in seawater are simpler but no less precise than traditional radioanalytical methods. The inherent accuracy limitations of the non-destructive β-counting method, particularly in samples likely to be contaminated with anthropogenic nuclides, are alleviated by recounting the samples over several half-lives and fitting the counting data to the 234 Th decay curve. Precision (including accuracy, estimated at an average of 3%) is better than 10% for particulate or 5% for dissolved samples. Thorium-234 distributions in the Skagerrak indicated a vigorous, presumably biological, particle export from the surface waters, and while bottom sediment resuspension was not an effective export mechanism, it did strip thorium from the dissolved phase. In the Greenland and Norwegian Seas, we saw clear evidence of particulate export from the surface waters, but at 75 m, total 234 Th activities were generally in equilibrium with 238 U. (author)

The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

Science.gov (United States)

Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

2017-12-01

The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.

Searching your site`s management information systems

Energy Technology Data Exchange (ETDEWEB)

Marquez, W.; Rollin, C. [S.M. Stoller Corp., Boulder, CO (United States)

1994-12-31

The Department of Energy`s guidelines for the Baseline Environmental Management Report (BEMR) encourage the use of existing data when compiling information. Specific systems mentioned include the Progress Tracking System, the Mixed-Waste Inventory Report, the Waste Management Information System, DOE 4700.1-related systems, Programmatic Environmental Impact Statement (PEIS) data, and existing Work Breakdown Structures. In addition to these DOE-Headquarters tracking and reporting systems, there are a number of site systems that will be relied upon to produce the BEMR, including: (1) site management control and cost tracking systems; (2) commitment/issues tracking systems; (3) program-specific internal tracking systems; (4) Site material/equipment inventory systems. New requirements have often prompted the creation of new, customized tracking systems. This is a very time and money consuming process. As the BEMR Management Plan emphasizes, an effort should be made to use the information in existing tracking systems. Because of the wealth of information currently available from in-place systems, development of a new tracking system should be a last resort.

Exploring functionally related enzymes using radially distributed properties of active sites around the reacting points of bound ligands

Directory of Open Access Journals (Sweden)

Ueno Keisuke

2012-04-01

Full Text Available Abstract Background Structural genomics approaches, particularly those solving the 3D structures of many proteins with unknown functions, have increased the desire for structure-based function predictions. However, prediction of enzyme function is difficult because one member of a superfamily may catalyze a different reaction than other members, whereas members of different superfamilies can catalyze the same reaction. In addition, conformational changes, mutations or the absence of a particular catalytic residue can prevent inference of the mechanism by which catalytic residues stabilize and promote the elementary reaction. A major hurdle for alignment-based methods for prediction of function is the absence (despite its importance of a measure of similarity of the physicochemical properties of catalytic sites. To solve this problem, the physicochemical features radially distributed around catalytic sites should be considered in addition to structural and sequence similarities. Results We showed that radial distribution functions (RDFs, which are associated with the local structural and physicochemical properties of catalytic active sites, are capable of clustering oxidoreductases and transferases by function. The catalytic sites of these enzymes were also characterized using the RDFs. The RDFs provided a measure of the similarity among the catalytic sites, detecting conformational changes caused by mutation of catalytic residues. Furthermore, the RDFs reinforced the classification of enzyme functions based on conventional sequence and structural alignments. Conclusions Our results demonstrate that the application of RDFs provides advantages in the functional classification of enzymes by providing information about catalytic sites.

New Catalytic DNA Biosensors for Radionuclides and Metal ions

International Nuclear Information System (INIS)

Lu, Yi

2003-01-01

The goals of the project are to develop new catalytic DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides and metal ions, and apply the sensors for on-site, real-time assessment of concentration, speciation and stability of the individual contaminants during and after bioremediation. A negative selection strategy was tested and validated. In vitro selection was shown to yield highly active and specific transition metal ion-dependent catalytic DNA/RNA. A fluorescence resonance energy transfer (FRET) study of in vitro selected DNA demonstrated that the trifluorophore labeled system is a simple and powerful tool in studying complex biomolecules structure and dynamics, and is capable of revealing new sophisticated structural changes. New fluorophore/quenchers in a single fluorosensor yielded improved signal to noise ratio in detection, identification and quantification of metal contaminants. Catalytic DNA fluorescent and colorimetric sensors were shown useful in sensing lead in lake water and in leaded paint. Project results were described in two papers and two patents, and won an international prize

Catalytic extraction processing of contaminated scrap metal

International Nuclear Information System (INIS)

Griffin, T.P.; Johnston, J.E.; Payea, B.M.

1995-01-01

The U.S. Department of Energy issued a Planned Research and Development Announcement (PRDA) in 1993, with the objective of identifying unique technologies which could be applied to the most hazardous waste streams at DOE sites. The combination of radioactive contamination with additional contamination by hazardous constituents such as those identified by the Resource Conservation and Recovery Act (RCRA) pose an especially challenging problem. Traditional remediation technologies are increasingly becoming less acceptable to stakeholders and regulators because of the risks they pose to public health and safety. Desirable recycling technologies were described by the DOE as: (1) easily installed, operated, and maintained; (2) exhibiting superior environmental performance; (3) protective of worker and public health and safety; (4) readily acceptable to a wide spectrum of evaluators; and (5) economically feasible. Molten Metal Technology, Inc. (MMT) was awarded a contract as a result of the PRDA initiative to demonstrate the applicability of Catalytic Extraction Processing (CEP), MMT's proprietary elemental recycling technology, to DOE's inventory of low level mixed waste. This includes DOE's inventory of radioactively- and RCRA-contaminated scrap metal and other waste forms expected to be generated by the decontamination and decommissioning (D ampersand D) of DOE sites

A Review on Catalytic Membranes Production and Applications

Directory of Open Access Journals (Sweden)

Heba Abdallah

2017-05-01

Full Text Available The development of the chemical industry regarding reducing the production cost and obtaining a high-quality product with low environmental impact became the essential requirements of the world in these days. The catalytic membrane is considered as one of the new alternative solutions of catalysts problems in the industries, where the reaction and separation can be amalgamated in one unit. The catalytic membrane has numerous advantages such as breaking the thermodynamic equilibrium limitation, increasing conversion rate, reducing the recycle and separation costs. But the limitation or most disadvantages of catalytic membranes related to the high capital costs for fabrication or the fact that manufacturing process is still under development. This review article summarizes the most recent advances and research activities related to preparation, characterization, and applications of catalytic membranes. In this article, various types of catalytic membranes are displayed with different applications and explained the positive impacts of using catalytic membranes in various reactions. Copyright © 2017 BCREC Group. All rights reserved. Received: 1st April 2016; Revised: 14th February 2017; Accepted: 22nd February 2017 How to Cite: Abdallah, H. (2017. A Review on Catalytic Membranes Production and Applications. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 136-156 (doi:10.9767/bcrec.12.2.462.136-156 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.462.136-156

Oriented Decoration in Metal-Functionalized Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds

Directory of Open Access Journals (Sweden)

Shijian Zhou

2018-02-01

Full Text Available Ordered mesoporous silicas (OMSs attract considerable attention due to their advanced structural properties. However, for the pristine silica materials, the inert property greatly inhibits their catalytic applications. Thus, to contribute to the versatile surface of OMSs, different metal active sites, including acidic/basic sites and redox sites, have been introduced into specific locations (mesoporous channels and framework of OMSs and the metal-functionalized ordered mesoporous silicas (MOMSs show great potential in the catalytic applications. In this review, we first present the categories of metal active sites. Then, the synthesized processes of MOMSs are thoroughly discussed, in which the metal active sites would be introduced with the assistance of organic groups into the specific locations of OMSs. In addition, the structural morphologies of OMSs are elaborated and the catalytic applications of MOMSs in the oxidation of aromatic compounds are illustrated in detail. Finally, the prospects for the future development in this field are proposed.

Double spike methodology for uranium determination by thermal ionisation mass spectrometry: separation and purification of 234U

International Nuclear Information System (INIS)

Shah, P.M.; Saxena, M.K.; Sanjai Kumar; Aggarwal, S.K.; Jain, H.C.

1995-01-01

With an objective to prepare double spike of 233 U+ 234 U for determination of uranium concentration by Isotopic Dilution Thermal Ionisation Mass Spectrometry (ID-TIMS), 234 U was separated and purified from aged 238 Pu sample (15 years old) using several ion exchange and solvent extraction procedures. Final product containing 95% and 5% alpha activities of 234 and 238 Pu, respectively, which translates into 99.998 atom% of 234 U and 0.002 atom% of 238 Pu was found suitable for double spike. (author). 1 ref

Control of ATP hydrolysis by ADP bound at the catalytic site of chloroplast ATP synthase as related to protonmotive force and Mg2+

International Nuclear Information System (INIS)

Du, Z.; Boyer, P.D.

1989-01-01

The activation of the ATP synthesis and hydrolysis capacity of isolated chloroplast membranes by protonmotive force is known to be associated with the release of tightly bound ADP from the ATP synthase. The data support the view that the activation requires only those structural changes occurring in the steady-state reaction mechanism. The trapping of ADP released during light activation or the chelation of Mg 2+ with EDTA effectively reduces the rate of decay of the ATPase activity. When the release of tightly bound ADP and Mg 2+ is promoted by light activation, followed by immediate dilution and washing to retard the rebinding of the ADP and Mg 2+ released, the ATPase activity remains high in the dark long after the protonmotive force has disappeared. After the addition of ADP and Mg 2+ the decay of the ATPase activity has the same characteristics as those of the unwashed chloroplast membrane. The results are interpreted as indicating that both Mg 2+ and ADP must be present prior to exposure to MgATP for the ATPase to be inhibited. However, in contrast to the isolated chloroplast ATPase, the steady-state activity of the membrane-bound ATPase is not inhibited by excess Mg 2+ . The replacement of [ 3 H]ADP from catalytic sites during hydrolysis of unlabeled ATP or during photophosphorylation with unlabeled ADP occurs as anticipated if Mg 2+ and ADP bound at one catalytic site without P i block catalysis by all three enzyme sites. The inhibited form induced by Mg 2+ and ADP may occur only under laboratory conditions and not have an in vivo role

Dissolution behaviour of 238U, 234U and 230Th deposited on filters from personal dosemeters

International Nuclear Information System (INIS)

Beckova, V.; Malatova, I.

2008-01-01

Kinetics of dissolution of 238 U, 234 U and 230 Th dust deposited on filters from personal alpha dosemeters was studied by means of a 26-d in vitro dissolution test with a serum ultra-filtrate simulant. Dosemeters had been used by miners at the uranium mine 'Dolni Rozinka' at Rozna, Czech Republic. The sampling flow-rate as declared by the producer is 4 l h -1 and the sampling period is typically 1 month. Studied filters contained 125 ± 6 mBq 238 U in equilibrium with 234 U and 230 Th; no 232 Th series nuclides were found. Half-time of rapid dissolution of 1.4 d for 238 U and 234 U and slow dissolution half-times of 173 and 116 d were found for 238 U and 234 U, respectively. No detectable dissolution of 230 Th was found. (authors)

Performance of a Novel Hydrophobic Mesoporous Material for High Temperature Catalytic Oxidation of Naphthalene

Directory of Open Access Journals (Sweden)

Guotao Zhao

2014-01-01

Full Text Available A high surface area, hydrophobic mesoporous material, MFS, has been successfully synthesized by a hydrothermal synthesis method using a perfluorinated surfactant, SURFLON S-386, as the single template. N2 adsorption and TEM were employed to characterize the pore structure and morphology of MFS. Static water adsorption test indicates that the hydrophobicity of MFS is significantly higher than that of MCM-41. XPS and Py-GC/MS analysis confirmed the existence of perfluoroalkyl groups in MFS which led to its high hydrophobicity. MFS was used as a support for CuO in experiments of catalytic combustion of naphthalene, where it showed a significant advantage over MCM-41 and ZSM-5. SEM was helpful in understanding why CuO-MFS performed so well in the catalytic combustion of naphthalene. Experimental results indicated that MFS was a suitable support for catalytic combustion of large molecular organic compounds, especially for some high temperature catalytic reactions when water vapor was present.

Emergence of traveling wave endothermic reaction in a catalytic fixed bed under microwave heating

International Nuclear Information System (INIS)

Gerasev, Alexander P.

2017-01-01

This paper presents a new phenomenon in a packed bed catalytic reactor under microwave heating - traveling wave (moving reaction zones) endothermic chemical reaction. A two-phase model is developed to simulate the nonlinear dynamic behavior of the packed bed catalytic reactor with an irreversible first-order chemical reaction. The absorbed microwave power was obtained from Lambert's law. The structure of traveling wave endothermic chemical reaction was explored. The effects of the gas velocity and microwave power on performance of the packed bed catalytic reactor were presented. Finally, the effects of the change in the location of the microwave source at the packed bed reactor was demonstrated. - Highlights: • A new phenomenon - traveling waves of endothermic reaction - is predicted. • The physical and mathematical model of a packed bed catalytic reactor under microwave heating is presented. • The structure of the traveling waves is explored. • The configuration of heating the packed bed reactor via microwave plays a key role.

Structural basis for the catalytic mechanism of a proficient enzyme: Orotidine 5'-Monophosphate Decarboxylase

DEFF Research Database (Denmark)

Harris, Pernille Hanne; Poulsen, Jens-Christian Navarro; Jensen, Kaj Frank

2000-01-01

/ß-barrels with two shared active sites. The orientation of the orotate moiety of the substrate is unambiguously deduced from the structure, and previously proposed catalytic mechanisms involving protonation of O2 or O4 can be ruled out. The proximity of the OMP carboxylate group with Asp71 appears to be instrumental...

Multiple nucleophilic elbows leading to multiple active sites in a single module esterase from Sorangium cellulosum

DEFF Research Database (Denmark)

Udatha, D.B.R.K. Gupta; Madsen, Karina Marie; Panagiotou, Gianni

2015-01-01

The catalytic residues in carbohydrate esterase enzyme families constitute a highly conserved triad: serine, histidine and aspartic acid. This catalytic triad is generally located in a very sharp turn of the protein backbone structure, called the nucleophilic elbow and identified by the consensus...... sequence GXSXG. An esterase from Sorangium cellulosum Soce56 that contains five nucleophilic elbows was cloned and expressed in Escherichia coli and the function of each nucleophilic elbowed site was characterized. In order to elucidate the function of each nucleophilic elbow, site directed mutagenesis....... To our knowledge, this is the first report presenting the role of multiple nucleophilic elbows in the catalytic promiscuity of an esterase. Further structural analysis at protein unit level indicates the new evolutionary trajectories in emerging promiscuous esterases....

Rational redesign of glucose oxidase for improved catalytic function and stability.

Directory of Open Access Journals (Sweden)

J Todd Holland

Full Text Available Glucose oxidase (GOx is an enzymatic workhorse used in the food and wine industries to combat microbial contamination, to produce wines with lowered alcohol content, as the recognition element in amperometric glucose sensors, and as an anodic catalyst in biofuel cells. It is naturally produced by several species of fungi, and genetic variants are known to differ considerably in both stability and activity. Two of the more widely studied glucose oxidases come from the species Aspergillus niger (A. niger and Penicillium amagasakiense (P. amag., which have both had their respective genes isolated and sequenced. GOx from A. niger is known to be more stable than GOx from P. amag., while GOx from P. amag. has a six-fold superior substrate affinity (K(M and nearly four-fold greater catalytic rate (k(cat. Here we sought to combine genetic elements from these two varieties to produce an enzyme displaying both superior catalytic capacity and stability. A comparison of the genes from the two organisms revealed 17 residues that differ between their active sites and cofactor binding regions. Fifteen of these residues in a parental A. niger GOx were altered to either mirror the corresponding residues in P. amag. GOx, or mutated into all possible amino acids via saturation mutagenesis. Ultimately, four mutants were identified with significantly improved catalytic activity. A single point mutation from threonine to serine at amino acid 132 (mutant T132S, numbering includes leader peptide led to a three-fold improvement in k(cat at the expense of a 3% loss of substrate affinity (increase in apparent K(M for glucose resulting in a specify constant (k(cat/K(M of 23.8 (mM(-1 · s(-1 compared to 8.39 for the parental (A. niger GOx and 170 for the P. amag. GOx. Three other mutant enzymes were also identified that had improvements in overall catalysis: V42Y, and the double mutants T132S/T56V and T132S/V42Y, with specificity constants of 31.5, 32.2, and 31.8 mM(-1 · s

The inflow of 234U and 238U from the River Odra drainage basin to the Baltic Sea

Directory of Open Access Journals (Sweden)

Bogdan Skwarzec

2010-12-01

Full Text Available In this study the activity of uranium isotopes 234U and 238U in Odra river water samples, collected from October 2003 to July2004, was measured using alpha spectrometry. The uranium concentrations were different in each of the seasons analysed; the lowest values were recorded in summer. In all seasons, uranium concentrations were the highest in Bystrzyca river waters (from 27.81 ± 0.29Bq m-3 of 234U and 17.82 ± 0.23 Bq m-3 of 238U in spring to 194.76 ± 3.43 Bq m-3 of 234U and 134.88 ± 2.85 Bq m-3 of 238U in summer. The lowest concentrations were noted in the Mała Panew (from 1.33 ± 0.02 Bq m-3 of 234U and 1.06 ± 0.02 Bq m-3 of 238U in spring to 3.52 ± 0.05 Bq m-3 of 234U and 2.59± 0.04 Bq m-3 of 238U in autumn. The uranium radionuclides 234U and 238U in the water samples were not in radioactive equilibrium. The 234U / 238U activity ratios were the highest in Odra water samples collected at Głogów (1.84 in autumn, and the lowest in water from the Noteć (1.03 in winter and spring. The 234U / 238U activity ratio decreases along the main stream of the Odra, owing to changes in the salinity of the river's waters. Annually, 8.19 tons of uranium (126.29 G Bq of 234U and 100.80 G Bq of 238U flow into the Szczecin Lagoon with Odra river waters.

Progress in catalytic naphtha reforming process: A review

International Nuclear Information System (INIS)

Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

2013-01-01

Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

Issues on a tritium measurement system's qualification on a dismantling site

Energy Technology Data Exchange (ETDEWEB)

Pigeon, Benoit; Met, Frederic [Waste Treatment and Nuclear Safety Service - SASN, Waste and Measurement Laboratory - LDM, CEA/SASN/LDM, DAM, DIF, Bruyeres Le Chatel, F-91297 Arpajon (France)

2015-07-01

In order to choose the suitable outlet, final disposal of radioactive package requires good knowledge of radiological characteristics of the waste. As part of a nuclear facility's dismantling within tritium proceeds, {sup 3}H contamination is evaluated by using wipe tests which are measured by liquid scintillation. The industrialist's choice is a triple coincidence to double coincidence ratio (TDCR) method with a dry counting protocol. The initial protocol had been defined to reduce the quantity of radioactive liquid waste and to perform an automatic quenching correction. A based on TDCR method liquid scintillation analyser was installed on the decommissioning site. It had had to be used by operator non specialized in metrology, This poster presents the laboratory's feedback on the use of the TDCR method on a site: - problems encountered about protocol on a decommissioning site - protocol adjustments and their consequences. (authors)

Dissolution behaviour of 238U, 234U and 230Th deposited on filters from personal dosemeters.

Science.gov (United States)

Becková, Vera; Malátová, Irena

2008-01-01

Kinetics of dissolution of (238)U, (234)U and (230)Th dust deposited on filters from personal alpha dosemeters was studied by means of a 26-d in vitro dissolution test with a serum ultrafiltrate simulant. Dosemeters had been used by miners at the uranium mine 'Dolní Rozínka' at Rozná, Czech Republic. The sampling flow-rate as declared by the producer is 4 l h(-1) and the sampling period is typically 1 month. Studied filters contained 125 +/- 6 mBq (238)U in equilibrium with (234)U and (230)Th; no (232)Th series nuclides were found. Half-time of rapid dissolution of 1.4 d for (238)U and (234)U and slow dissolution half-times of 173 and 116 d were found for (238)U and (234)U, respectively. No detectable dissolution of (230)Th was found.

Mechanisms of mono- and poly-ubiquitination: Ubiquitination specificity depends on compatibility between the E2 catalytic core and amino acid residues proximal to the lysine

Directory of Open Access Journals (Sweden)

Sadowski Martin

2010-08-01

Full Text Available Abstract Ubiquitination involves the attachment of ubiquitin to lysine residues on substrate proteins or itself, which can result in protein monoubiquitination or polyubiquitination. Ubiquitin attachment to different lysine residues can generate diverse substrate-ubiquitin structures, targeting proteins to different fates. The mechanisms of lysine selection are not well understood. Ubiquitination by the largest group of E3 ligases, the RING-family E3 s, is catalyzed through co-operation between the non-catalytic ubiquitin-ligase (E3 and the ubiquitin-conjugating enzyme (E2, where the RING E3 binds the substrate and the E2 catalyzes ubiquitin transfer. Previous studies suggest that ubiquitination sites are selected by E3-mediated positioning of the lysine toward the E2 active site. Ultimately, at a catalytic level, ubiquitination of lysine residues within the substrate or ubiquitin occurs by nucleophilic attack of the lysine residue on the thioester bond linking the E2 catalytic cysteine to ubiquitin. One of the best studied RING E3/E2 complexes is the Skp1/Cul1/F box protein complex, SCFCdc4, and its cognate E2, Cdc34, which target the CDK inhibitor Sic1 for K48-linked polyubiquitination, leading to its proteasomal degradation. Our recent studies of this model system demonstrated that residues surrounding Sic1 lysines or lysine 48 in ubiquitin are critical for ubiquitination. This sequence-dependence is linked to evolutionarily conserved key residues in the catalytic region of Cdc34 and can determine if Sic1 is mono- or poly-ubiquitinated. Our studies indicate that amino acid determinants in the Cdc34 catalytic region and their compatibility to those surrounding acceptor lysine residues play important roles in lysine selection. This may represent a general mechanism in directing the mode of ubiquitination in E2 s.

Environmental monitoring report for commercial low-level radioactive waste disposal sites (1960`s through 1990`s)

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-11-01

During the time period covered in this report (1960`s through early 1990`s), six commercial low-level radioactive waste (LLRW) disposal facilities have been operated in the US. This report provides environmental monitoring data collected at each site. The report summarizes: (1) each site`s general design, (2) each site`s inventory, (3) the environmental monitoring program for each site and the data obtained as the program has evolved, and (4) what the program has indicated about releases to off-site areas, if any, including a statement of the actual health and safety significance of any release. A summary with conclusions is provided at the end of each site`s chapter. The six commercial LLRW disposal sites discussed are located near: Sheffield, Illinois; Maxey Flats, Kentucky; Beatty, Nevada; West Valley, New York; Barnwell, South Carolina; Richland, Washington.

New explanation for extreme u-234 u-238 disequilibria in a dolomitic aquifer

CSIR Research Space (South Africa)

Kronfeld, J

1994-05-01

Full Text Available High U-234/U-238 activity ratios are found in the shallow groundwater of the phreatic Transvaal Dolomite Aquifer. The aquifer is uranium poor, while the waters are oxygen rich and young. Tritium and C-14 are used to show that the disequilibrium...

Steam reformer with catalytic combustor

Science.gov (United States)

Voecks, Gerald E. (Inventor)

1990-01-01

A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

CREATING THE KULTUK POLYGON FOR EARTHQUAKE PREDICTION: VARIATIONS OF (234U/238U AND 87SR/86SR IN GROUNDWATER FROM ACTIVE FAULTS AT THE WESTERN SHORE OF LAKE BAIKAL

Directory of Open Access Journals (Sweden)

S. V. Rasskazov

2015-01-01

Full Text Available Introduction. Determinations of (234U/238U in groundwater samples are used for monitoring current deformations in active faults (parentheses denote activity ratio units. The cyclic equilibrium of activity ratio 234U/238U≈≈(234U/238U≈γ≈1 corresponds to the atomic ratio ≈5.47×10–5. This parameter may vary due to higher contents of 234U nuclide in groundwater as a result of rock deformation. This effect discovered by P.I. Chalov and V.V. Cherdyntsev was described in [Cherdyntsev, 1969, 1973; Chalov, 1975; Chalov et al., 1990; Faure, 1989]. In 1970s and 1980s, only quite laborious methods were available for measuring uranium isotopic ratios. Today it is possible to determine concentrations and isotopic ration of uranium by express analytical techniques using inductively coupled plasma mass spectrometry (ICP‐MS [Halicz et al., 2000; Shen et al., 2002; Cizdziel et al., 2005; Chebykin et al., 2007]. Sets of samples canbe efficiently analysed by ICP‐MS, and regularly collected uranium isotope values can be systematized at a new quality level for the purposes of earthquake prediction. In this study of (234U/238U in groundwater at the Kultuk polygon, we selected stations of the highest sensitivity, which can ensure proper monitoring of the tectonic activity of the Obruchev and Main Sayan faults. These two faults that limit the Sharyzhalgai block of the crystalline basement of the Siberian craton in the south are conjugated in the territory of the Kultuk polygon (Fig 1. Forty sets of samples taken from 27 June 2012 to 28 January 2014 were analysed, and data on 170 samples are discussed in this paper.Methods. Isotope compositions of uranium and strontium were determined by methods described in [Chebykin et al., 2007; Pin et al., 1992] with modifications. Analyses of uranium by ISP‐MS technique were performed using an Agilent 7500ce quadrapole mass spectrometer of the Ultramicroanalysis Collective Use Centre; analyses of

Derivation of uranium residual radioactive material guidelines for the Shpack site

International Nuclear Information System (INIS)

Cheng, J.J.; Yu, C.; Monette, F.; Jones, L.

1991-08-01

Residual radioactive material guidelines for uranium were derived for the Shpack site in Norton, Massachusetts. This site has been identified for remedial action under the Formerly Utilized Sites Remedial Action Program (FUSRAP) of the US Department of Energy (DOE). The uranium guidelines were derived on the basis of the requirement that the 50-year committed effective dose equivalent to a hypothetical individual who lives or works in the immediate vicinity of the Shpack site should not exceed a dose of 100 mrem/yr following decontamination. The DOE residual radioactive material guideline computer code, RESRAD, which implements the methodology described in the DOE manual for implementing residual radioactive material guidelines, was used in this evaluation. Three potential scenarios were considered for the site; the scenarios vary with regard to time spent at the site, sources of water used, and sources of food consumed. The results of the evaluation indicate that the basic dose limit of 100 mrem/yr will not be exceeded for uranium (including uranium-234, uranium-235, and uranium-238) within 1000 years, provided that the soil concentration of combined uranium (uranium-234 and uranium-238) at the Shpack site does not exceed the following levels: 2500 pCi/g for Scenario A (recreationist: the expected scenario); 1100 pCi/g for Scenario B (industrial worker: a plausible scenario); and 53 pCi/g for Scenario C (resident farmer using a well water as the only water source: a possible but unlikely scenario). The uranium guidelines derived in this report apply to the combined activity concentration of uranium-234 and uranium-238 and were calculated on the basis of a dose of 100 mrem/yr. In setting the actual uranium guidelines for the Shpack site, DOE will apply the as low as reasonably achievable (ALARA) policy to the decision-making process, along with other factors, such as whether a particular scenario is reasonable and appropriate. 8 refs., 2 figs., 8 tabs

Control of ATP hydrolysis by ADP bound at the catalytic site of chloroplast ATP synthase as related to protonmotive force and Mg sup 2+

Energy Technology Data Exchange (ETDEWEB)

Du, Z.; Boyer, P.D. (Univ. of California, Los Angeles (USA))

1989-01-24

The activation of the ATP synthesis and hydrolysis capacity of isolated chloroplast membranes by protonmotive force is known to be associated with the release of tightly bound ADP from the ATP synthase. The data support the view that the activation requires only those structural changes occurring in the steady-state reaction mechanism. The trapping of ADP released during light activation or the chelation of Mg{sup 2+} with EDTA effectively reduces the rate of decay of the ATPase activity. When the release of tightly bound ADP and Mg{sup 2+} is promoted by light activation, followed by immediate dilution and washing to retard the rebinding of the ADP and Mg{sup 2+} released, the ATPase activity remains high in the dark long after the protonmotive force has disappeared. After the addition of ADP and Mg{sup 2+} the decay of the ATPase activity has the same characteristics as those of the unwashed chloroplast membrane. The results are interpreted as indicating that both Mg{sup 2+} and ADP must be present prior to exposure to MgATP for the ATPase to be inhibited. However, in contrast to the isolated chloroplast ATPase, the steady-state activity of the membrane-bound ATPase is not inhibited by excess Mg{sup 2+}. The replacement of ({sup 3}H)ADP from catalytic sites during hydrolysis of unlabeled ATP or during photophosphorylation with unlabeled ADP occurs as anticipated if Mg{sup 2+} and ADP bound at one catalytic site without P{sub i} block catalysis by all three enzyme sites. The inhibited form induced by Mg{sup 2+} and ADP may occur only under laboratory conditions and not have an in vivo role.

Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

Science.gov (United States)

Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

2010-02-05

Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

48 CFR 52.234-4 - Earned Value Management System.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Earned Value Management....234-4 Earned Value Management System. As prescribed in 34.203(c), insert the following clause: Earned Value Management System (JUL 2006) (a) The Contractor shall use an earned value management system (EVMS...

The Savannah River site`s groundwater monitoring program: second quarter 1997

Energy Technology Data Exchange (ETDEWEB)

Rogers, C.D. [Westinghouse Savannah River Company, AIKEN, SC (United States)

1997-11-01

The Environmental Protection Department/Environmental Monitoring Section (EPD/EMS) administers the Savannah River Site`s (SRS) Groundwater Monitoring Program. During second quarter 1997, EPD/EMS conducted extensive sampling of monitoring wells. A detailed explanation of the flagging criteria is presented in the Flagging Criteria section of this document. Analytical results from second quarter 1997 are included in this report.

Normal and grazing incidence pulsed laser deposition of nanostructured MoSx hydrogen evolution catalysts from a MoS2 target

Science.gov (United States)

Fominski, V. Yu.; Romanov, R. I.; Fominski, D. V.; Dzhumaev, P. S.; Troyan, I. A.

2018-06-01

Pulsed laser ablation of a MoS2 target causes enhanced splashing of the material. So, for MoSx films obtained by pulsed laser deposition (PLD) in the conventional normal incidence (NI) configuration, their typical morphology is characterized by an underlying granular structure with an overlayer of widely dispersed spherical Mo and MoSx particles possessing micro-, sub-micro- and nanometer sizes. We investigated the possibility of using high surface roughness, which occurs due to particle deposition, as a support with a large exposed surface area for thin MoSx catalytic layers for the hydrogen evolution reaction (HER). For comparison, the HER performance of MoSx layers formed by grazing incidence (GI) PLD was studied. During GI-PLD, a substrate was placed along the direction of laser plume transport and few large particles loaded the substrate. The local structure and composition of thin MoSx layers formed by the deposition of the vapor component of the laser plume were varied by changing the pressure of the buffer gas (argon, Ar). In the case of NI-PLD, an increase in Ar pressure caused the formation of quasi-amorphous MoSx (x ≥ 2) films that possessed highly active catalytic sites on the edges of the layered MoS2 nanophase. At the same time, a decrease in the deposition rate of the MoSx film appeared due to the scattering of the vapor flux by Ar molecules during flux transport from the target to the substrate. This effect prevented uniform deposition of the MoSx catalytic film on the surface of most particles, whose deposition rate was independent of Ar pressure. The scattered vapor flux containing Mo and S atoms was a dominant source for MoSx film growth during GI-PLD. The thickness and composition distribution of the MoSx film on the substrate depended on both the pressure of the buffer gas and the distance from the target. For 1.0-2.5 cm from the target, the deposition rate was quite sufficient to form S-enriched quasi-amorphous MoSx (2.5 < x < 6) catalytic

27 CFR 24.234 - Other use of spirits.

Science.gov (United States)

2010-04-01

..., DEPARTMENT OF THE TREASURY LIQUORS WINE Spirits § 24.234 Other use of spirits. The proprietor producing sparkling wine, artificially carbonated wine, formula wine, or essences for which spirits are required may use tax-free wine spirits or brandy. For nonbeverage wine, tax-free spirits other than wine spirits or...

Structural Evidence of a Major Conformational Change Triggered by Substrate Binding in DapE Enzymes: Impact on the Catalytic Mechanism.

Science.gov (United States)

Nocek, Boguslaw; Reidl, Cory; Starus, Anna; Heath, Tahirah; Bienvenue, David; Osipiuk, Jerzy; Jedrzejczak, Robert; Joachimiak, Andrzej; Becker, Daniel P; Holz, Richard C

2018-02-06

The X-ray crystal structure of the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase from Haemophilus influenzae (HiDapE) bound by the products of hydrolysis, succinic acid and l,l-DAP, was determined at 1.95 Å. Surprisingly, the structure bound to the products revealed that HiDapE undergoes a significant conformational change in which the catalytic domain rotates ∼50° and shifts ∼10.1 Å (as measured at the position of the Zn atoms) relative to the dimerization domain. This heretofore unobserved closed conformation revealed significant movements within the catalytic domain compared to that of wild-type HiDapE, which results in effectively closing off access to the dinuclear Zn(II) active site with the succinate carboxylate moiety bridging the dinculear Zn(II) cluster in a μ-1,3 fashion forming a bis(μ-carboxylato)dizinc(II) core with a Zn-Zn distance of 3.8 Å. Surprisingly, His194.B, which is located on the dimerization domain of the opposing chain ∼10.1 Å from the dinuclear Zn(II) active site, forms a hydrogen bond (2.9 Å) with the oxygen atom of succinic acid bound to Zn2, forming an oxyanion hole. As the closed structure forms upon substrate binding, the movement of His194.B by more than ∼10 Å is critical, based on site-directed mutagenesis data, for activation of the scissile carbonyl carbon of the substrate for nucleophilic attack by a hydroxide nucleophile. Employing the HiDapE product-bound structure as the starting point, a reverse engineering approach called product-based transition-state modeling provided structural models for each major catalytic step. These data provide insight into the catalytic reaction mechanism and also the future design of new, potent inhibitors of DapE enzymes.

Preliminary X-ray crystallographic studies of BthTX-II, a myotoxic Asp49-phospholipase A2 with low catalytic activity from Bothrops jararacussu venom

International Nuclear Information System (INIS)

Corrêa, L. C.; Marchi-Salvador, D. P.; Cintra, A. C. O.; Soares, A. M.; Fontes, M. R. M.

2006-01-01

A myotoxic Asp49-PLA 2 with low catalytic activity from B. jararacussu (BthTX-II) was crystallized in the monoclinic crystal system; a complete X-ray diffraction data set was collected and a molecular-replacement solution was obtained. The oligomeric structure of BthTX-II resembles those of the Asp49-PLA 2 PrTX-III and all bothropic Lys49-PLA 2 s. For the first time, a complete X-ray diffraction data set has been collected from a myotoxic Asp49-phospholipase A 2 (Asp49-PLA 2 ) with low catalytic activity (BthTX-II from Bothrops jararacussu venom) and a molecular-replacement solution has been obtained with a dimer in the asymmetric unit. The quaternary structure of BthTX-II resembles the myotoxin Asp49-PLA 2 PrTX-III (piratoxin III from B. pirajai venom) and all non-catalytic and myotoxic dimeric Lys49-PLA 2 s. In contrast, the oligomeric structure of BthTX-II is different from the highly catalytic and non-myotoxic BthA-I (acidic PLA 2 from B. jararacussu). Thus, comparison between these structures should add insight into the catalytic and myotoxic activities of bothropic PLA 2 s

Catalytic nanoporous membranes

Science.gov (United States)

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Intake of 210Po, 234U and 238U radionuclides with beer in Poland

International Nuclear Information System (INIS)

Skwarzec, B.; Struminska, D.I.; Borylo, A.; Falandysz, J.

2004-01-01

238 U, 234 U and 210 Po activity concentrations were determined in beer in Poland by alpha-spectrometry with low-level activity silicon detectors. The results revealed that the mean concentrations of 238 U, 234 U and 210 Po in the analyzed beer samples were 4.63, 4.11 and 4.94 mBq x dm -3 , respectively, the highest in Tyskie (5.71 for 210 Po, 5.06 for 234 U and 6.11 for 238 U) and the lowest in Lech (2.49 for 210 Po). The effective radiation dose due to uranium and polonium ingestions by beer was calculated and were compared to the effective radiation dose from drinking water. (author)

Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

Science.gov (United States)

Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

2017-05-16

Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

Science.gov (United States)

Cao, Xinrui; Fu, Qiang; Luo, Yi

2014-05-14

The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

The Savannah River Site`s Groundwater Monitoring Program, third quarter 1991

Energy Technology Data Exchange (ETDEWEB)

1992-02-17

The Environmental Protection Department/Environmental Monitoring Section (EPD/EMS) administers the Savannah River Site`s (SRS) Groundwater Monitoring Program. During third quarter 1991, EPD/EMS conducted extensive sampling of monitoring wells. Analytical results from third quarter 1991 are listed in this report.

Oxidation of phosphine by sulfur or selenium involving a catalytic ...

Indian Academy of Sciences (India)

Administrator

P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

Stability for Function Trade-Offs in the Enolase Superfamily 'Catalytic Module'

Energy Technology Data Exchange (ETDEWEB)

Nagatani, R.A.; Gonzalez, A.; Shoichet, B.K.; Brinen, L.S.; Babbitt, P.C.; /UC, San Francisco /SLAC, SSRL

2007-07-12

Enzyme catalysis reflects a dynamic interplay between charged and polar active site residues that facilitate function, stabilize transition states, and maintain overall protein stability. Previous studies show that substituting neutral for charged residues in the active site often significantly stabilizes a protein, suggesting a stability trade-off for functionality. In the enolase superfamily, a set of conserved active site residues (the ''catalytic module'') has repeatedly been used in nature in the evolution of many different enzymes for the performance of unique overall reactions involving a chemically diverse set of substrates. This catalytic module provides a robust solution for catalysis that delivers the common underlying partial reaction that supports all of the different overall chemical reactions of the superfamily. As this module has been so broadly conserved in the evolution of new functions, we sought to investigate the extent to which it follows the stability-function trade-off. Alanine substitutions were made for individual residues, groups of residues, and the entire catalytic module of o-succinylbenzoate synthase (OSBS), a member of the enolase superfamily from Escherichia coli. Of six individual residue substitutions, four (K131A, D161A, E190A, and D213A) substantially increased protein stability (by 0.46-4.23 kcal/mol), broadly consistent with prediction of a stability-activity trade-off. The residue most conserved across the superfamily, E190, is by far the most destabilizing. When the individual substitutions were combined into groups (as they are structurally and functionally organized), nonadditive stability effects emerged, supporting previous observations that residues within the module interact as two functional groups within a larger catalytic system. Thus, whereas the multiple-mutant enzymes D161A/E190A/D213A and K131A/K133A/D161A/E190A/D213A/K235A (termed 3KDED) are stabilized relative to the wild-type enzyme (by 1

48 CFR 352.234-2 - Notice of earned value management system-post-award Integrated Baseline Review.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false Notice of earned value management system-post-award Integrated Baseline Review. 352.234-2 Section 352.234-2 Federal Acquisition... provision: Notice of Earned Value Management System—Post-Award Integrated Baseline Review (October 2008) (a...

Site-directed mutagenesis under the direction of in silico protein docking modeling reveals the active site residues of 3-ketosteroid-Δ1-dehydrogenase from Mycobacterium neoaurum.

Science.gov (United States)

Qin, Ning; Shen, Yanbing; Yang, Xu; Su, Liqiu; Tang, Rui; Li, Wei; Wang, Min

2017-07-01

3-Ketosteroid-Δ 1 -dehydrogenases (KsdD) from Mycobacterium neoaurum could transform androst-4-ene-3,17-dione (AD) to androst-1,4-diene-3,17-dione. This reaction has a significant effect on the product of pharmaceutical steroid. The crystal structure and active site residues information of KsdD from Mycobacterium is not yet available, which result in the engineering of KsdD is tedious. In this study, by the way of protein modeling and site-directed mutagenesis, we find that, Y122, Y125, S138, E140 and Y541 from the FAD-binding domain and Y365 from the catalytic domain play a key role in this transformation. Compared with the wild type, the decline in AD conversion for mutants illustrated that Y125, Y365, and Y541 were essential to the function of KsdD. Y122, S138 and E140 contributed to the catalysis of KsdD. The following analysis revealed the catalysis mechanism of these mutations in KsdD of Mycobacterium. These information presented here facilitate the manipulation of the catalytic properties of the enzyme to improve its application in the pharmaceutical steroid industry.

48 CFR 1852.234-2 - Earned Value Management System.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true Earned Value Management... and Clauses 1852.234-2 Earned Value Management System. As prescribed in 1834.203-70(b) insert the following clause: Earned Value Management System (NOV 2006) (a) In the performance of this contract, the...

Validation of the catalytic properties of Cu-Os/13X using single fixed bed reactor in selective catalytic reduction of NO

International Nuclear Information System (INIS)

Oh, Kwang Seok; Woo, Seong Ihl

2007-01-01

Catalytic decomposition of NO over Cu-Os/13X has been carried out in a tubular fixed bed reactor at atmospheric pressure and the results were compared with literature data performed by high-throughput screening (HTS). The activity and durability of Cu-Os/13X prepared by conventional ion-exchange method have been investigated in the presence of H 2 O and SO 2 . It was found that Cu-Os/13X prepared by ion-exchange shows a high activity in a wide temperature range in selective catalytic reduction (SCR) of NO with C 3 H 6 compared to Cu/13X, proving the existence of more NO adsorption site on Cu-Os/13X. However, Cu-Os/13X exhibited low activity in the presence of water, and was quite different from the result reported in literature. SO 2 resistance is also low and does not recover its original activity when the SO 2 was blocked in the feed gas stream. This result suggested that catalytic activity between combinatorial screening and conventional testing should be compared to confirm the validity of high-throughput screening

Outstanding catalytic activity of ultra-pure platinum nanoparticles.

Science.gov (United States)

Januszewska, Aneta; Dercz, Grzegorz; Piwowar, Justyna; Jurczakowski, Rafal; Lewera, Adam

2013-12-09

Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as-received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as-received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy-harvesting/data-storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

234U/238U activity ratio in groundwater - an indicator of past hydrogeological processes

International Nuclear Information System (INIS)

Rasilainen, K.; Suksi, J.; Marcos, N.; Nordman, H.

2005-01-01

In this report we describe the long-term behaviour of the uranium isotopes, U-234 and U-238 in groundwater systems. U is a redox sensitive element what for its behaviour is largely controlled by changes in the environmental conditions. A striking feature in U isotope geochemistry is seemingly different behaviour of U-238 and U-234. U isotopes fractionate at the rock-groundwater interface depending on chemical and radiological factors. Changes of the redox conditions in groundwater may thus affect the behaviour of U and its isotopes resulting in variable U concentration and U-234/U-238 activity ratios (AR). We examined the formation of ARs in different groundwater types from a geochemical and a physical/radiological point of view. It was envisaged that AR in groundwater is the consequence of radiological, chemical and hydrological processes. Groundwater condition (redox, flow, etc.) play a very important role in controlling the mass flow of U isotopes. Quantitative α-recoil modelling showed that α-recoil induced flux can be considered insignificant in cases of high-flow. This was an important finding because the exclusion of direct a-recoil means that it is groundwater chemistry and its variations which controls the U-234 mass flow and the formation of AR. Therefore, AR values could be used more confidently to indicate past redox changes and possibly flow paths. (orig.)

Catalytic growth of vertically aligned neutron sensitive {sup 10}Boron nitride nanotubes

Energy Technology Data Exchange (ETDEWEB)

Ahmad, Pervaiz, E-mail: pervaizahmad@siswa.um.edu.my, E-mail: Pervaiz-pas@yahoo.com; Khandaker, Mayeen Uddin, E-mail: mu-khandaker@yahoo.com, E-mail: mu-khandaker@um.edu.my; Amin, Yusoff Mohd [University of Malaya, Department of Physics, Faculty of Science (Malaysia); Khan, Ghulamullah [University of Malaya, Department of Mechanical Engineering (Malaysia); Ramay, Shahid M. [King Saud University, Department of Physics and Astronomy, College of Science (Saudi Arabia); Mahmood, Asif [King Saud University, Department of Chemical Engineering, College of Engineering (Saudi Arabia); Amin, Muhammad [University of the Punjab, Department of Physics (Pakistan); Muhammad, Nawshad [Interdisciplinary Research Centre in Biomedical Materials (IRCBM) COMSATS Institute of Information Technology (Pakistan)

2016-01-15

{sup 10}Boron nitride nanotubes ({sup 10}BNNTs) are a potential neutron sensing element in a solid-state neutron detector. The aligned {sup 10}BNNT can be used for its potential application without any further purification. Argon-supported thermal CVD is used to achieve vertically aligned {sup 10}BNNT with the help of nucleation sites produced in a thin layer of magnesium–iron alloy deposited at the top of Si substrate. FESEM shows vertically aligned {sup 10}BNNTs with ball-like catalytic tips at top. EDX reveals magnesium (Mg) contents in the tips that refer to catalytic growth of {sup 10}BNNT. HR-TEM shows tubular morphology of the synthesized {sup 10}BNNT with lattice fringes on its outer part having an interlayer spacing of ∼0.34 nm. XPS shows B 1 s and N 1 s peaks at 190.5 and 398 eV that correspond to hexagonal {sup 10}Boron nitride ({sup 10}h-BN) nature of the synthesized {sup 10}BNNT, whereas the Mg kll auger peaks at ∼301 and ∼311 eV represents Mg contents in the sample. Raman spectrum has a peak at 1390 (cm{sup −1}) that corresponds to E{sub 2g} mode of vibration in {sup 10}h-BN.

Catalytic Reforming of Oxygenates: State of the Art and Future Prospects.

Science.gov (United States)

Li, Di; Li, Xinyu; Gong, Jinlong

2016-10-12

This Review describes recent advances in the design, synthesis, reactivity, selectivity, structural, and electronic properties of the catalysts for reforming of a variety of oxygenates (e.g., from simple monoalcohols to higher polyols, then to sugars, phenols, and finally complicated mixtures like bio-oil). A comprehensive exploration of the structure-activity relationship in catalytic reforming of oxygenates is carried out, assisted by state-of-the-art characterization techniques and computational tools. Critical emphasis has been given on the mechanisms of these heterogeneous-catalyzed reactions and especially on the nature of the active catalytic sites and reaction pathways. Similarities and differences (reaction mechanisms, design and synthesis of catalysts, as well as catalytic systems) in the reforming process of these oxygenates will also be discussed. A critical overview is then provided regarding the challenges and opportunities for research in this area with a focus on the roles that systems of heterogeneous catalysis, reaction engineering, and materials science can play in the near future. This Review aims to present insights into the intrinsic mechanism involved in catalytic reforming and provides guidance to the development of novel catalysts and processes for the efficient utilization of oxygenates for energy and environmental purposes.

Black Bleeds and the Sites of a Trauma in GB Tran’s Vietnamerica

Directory of Open Access Journals (Sweden)

Jin Lee

2017-09-01

Full Text Available ‘The gutter’ is the space between panels where panel transitions happen—readers fill in the blank space by connecting panels to make sense of the story. In GB Tran’s 'Vietnamerica' (2010, however, black gutters become part of black ‘bleeds’ (pages congruent with single panels in them to portray the sites of a trauma. This article argues that if bleeds, as Scott McCloud claims, can depict timeless space, they could also represent the sites of a trauma where the memory of the past is intervened by the future interpretation of the memory. In 'Vietnamerica', the panels in black in a waffle-iron grid are simultaneously black gutters and a black bleed, where reinterpretation of trauma takes place as speech balloons are later imposed on the same recurrent waffle-iron grid. While Cathy Caruth’s trauma theory helps read Tran’s black bleeds as the sites of a trauma, the latter also extends Caruth’s notion of ‘traumatic awakenings’ since the black bleeds as the sites of a trauma turn into the places of reconciliation and healing.

Structural investigations of the active-site mutant Asn156Ala of outer membrane phospholipase A: Function of the Asn-His interaction in the catalytic triad

NARCIS (Netherlands)

Snijder, H.J.; van Eerde, J.H.; Kalk, K.H.; Dekker, N.; Egmond, M.R.; Dijkstra, B.W.

2010-01-01

Outer membrane phospholipase A (OMPLA) from Escherichia coli is an integral-membrane enzyme with a unique His-Ser-Asn catalytic triad. In serine proteases and serine esterases usually an Asp occurs in the catalytic triad; its role has been the subject of much debate. Here the role of the uncharged

Metal active site elasticity linked to activation of homocysteine in methionine synthases

Energy Technology Data Exchange (ETDEWEB)

Koutmos, Markos; Pejchal, Robert; Bomer, Theresa M.; Matthews, Rowena G.; Smith, Janet L.; Ludwig, Martha L. (Michigan)

2008-04-02

Enzymes possessing catalytic zinc centers perform a variety of fundamental processes in nature, including methyl transfer to thiols. Cobalamin-independent (MetE) and cobalamin-dependent (MetH) methionine synthases are two such enzyme families. Although they perform the same net reaction, transfer of a methyl group from methyltetrahydrofolate to homocysteine (Hcy) to form methionine, they display markedly different catalytic strategies, modular organization, and active site zinc centers. Here we report crystal structures of zinc-replete MetE and MetH, both in the presence and absence of Hcy. Structural investigation of the catalytic zinc sites of these two methyltransferases reveals an unexpected inversion of zinc geometry upon binding of Hcy and displacement of an endogenous ligand in both enzymes. In both cases a significant movement of the zinc relative to the protein scaffold accompanies inversion. These structures provide new information on the activation of thiols by zinc-containing enzymes and have led us to propose a paradigm for the mechanism of action of the catalytic zinc sites in these and related methyltransferases. Specifically, zinc is mobile in the active sites of MetE and MetH, and its dynamic nature helps facilitate the active site conformational changes necessary for thiol activation and methyl transfer.

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.

Relation Between Acid and Catalytic Properties of Chlorinated Gamma-Alumina. a 31p Mas Nmr and Ftir Investigation

Directory of Open Access Journals (Sweden)

Guillaume D.

1999-07-01

Full Text Available In this paper, we have studied the effect of chlorine on the surface properties of gamma-alumina, especially on their acid properties. The use of FTIR spectroscopy and 31P MAS NMR of adsorbed trimethylphosphine allows to propose a chlorination mechanism. To correlate the surface properties of these chlorinated gamma-alumina with their catalytic properties, we have used a model reaction, the cracking of n-heptane under reforming conditions. The analysis of the correlation between acid properties determined by 31P MAS NMR and the catalytic results (in terms of activities and selectivities allows to identify which sites are involved in the cracking reaction.

Tentative identification of the second substrate binding site in Arabidopsis phytochelatin synthase.

Directory of Open Access Journals (Sweden)

Ju-Chen Chia

Full Text Available Phytochelatin synthase (PCS uses the substrates glutathione (GSH, γGlu-Cys-Gly and a cadmium (Cd-bound GSH (Cd∙GS2 to produce the shortest phytochelatin product (PC2, (γGlu-Cys2-Gly through a ping-pong mechanism. The binding of the 2 substrates to the active site, particularly the second substrate binding site, is not well-understood. In this study, we generated a structural model of the catalytic domain of Arabidopsis AtPCS1 (residues 12-218 by using the crystal structure of the γGlu-Cys acyl-enzyme complex of the PCS of the cyanobacterium Nostoc (NsPCS as a template. The modeled AtPCS1 revealed a cavity in proximity to the first substrate binding site, consisting of 3 loops containing several conserved amino acids including Arg152, Lys185, and Tyr55. Substitutions of these amino acids (R152K, K185R, or double mutation resulted in the abrogation of enzyme activity, indicating that the arrangement of these 2 positive charges is crucial for the binding of the second substrate. Recombinant AtPCS1s with mutations at Tyr55 showed lower catalytic activities because of reduced affinity (3-fold for Y55W for the Cd∙GS2, further suggesting the role of the cation-π interaction in recognition of the second substrate. Our study results indicate the mechanism for second substrate recognition in PCS. The integrated catalytic mechanism of PCS is further discussed.

Crystal Structure of the Oxazolidinone Antibiotic Linezolid Bound to the 50S Ribosomal Subunit

Energy Technology Data Exchange (ETDEWEB)

Ippolito,J.; Kanyo, Z.; Wang, D.; Franceschi, F.; Moore, P.; Steitz, T.; Duffy, E.

2008-01-01

The oxazolidinone antibacterials target the 50S subunit of prokaryotic ribosomes. To gain insight into their mechanism of action, the crystal structure of the canonical oxazolidinone, linezolid, has been determined bound to the Haloarcula marismortui 50S subunit. Linezolid binds the 50S A-site, near the catalytic center, which suggests that inhibition involves competition with incoming A-site substrates. These results provide a structural basis for the discovery of improved oxazolidinones active against emerging drug-resistant clinical strains.

Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

Energy Technology Data Exchange (ETDEWEB)

Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

2008-01-15

Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

Directory of Open Access Journals (Sweden)

Rotcharin Sawisai

2017-01-01

Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

Catalytic ozonation of fenofibric acid over alumina-supported manganese oxide

Energy Technology Data Exchange (ETDEWEB)

Rosal, Roberto, E-mail: roberto.rosal@uah.es [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain); Gonzalo, Maria S.; Rodriguez, Antonio; Garcia-Calvo, Eloy [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain)

2010-11-15

The catalytic ozonation of fenofibric acid was studied using activated alumina and alumina-supported manganese oxide in a semicontinuous reactor. The rate constants at 20 deg. C for the non-catalytic reaction of fenofibric acid with ozone and hydroxyl radicals were 3.43 {+-} 0.20 M{sup -1} s{sup -1} and (6.55 {+-} 0.33) x 10{sup 9} M{sup -1} s{sup -1}, respectively. The kinetic constant for the catalytic reaction between fenofibric acid and hydroxyl radicals did not differ significantly from that of homogeneous ozonation, either using Al{sub 2}O{sub 3} or MnO{sub x}/Al{sub 2}O{sub 3}. The results showed a considerable increase in the generation of hydroxyl radicals due to the use of catalysts even in the case of catalytic runs performed using a real wastewater matrix. Both catalysts promoted the decomposition of ozone in homogeneous phase, but the higher production of hydroxyl radicals corresponded to the catalyst with more activity in terms of ozone decomposition. We did not find evidence of the catalysts having any effect on rate constants, which suggests that the reaction may not involve the adsorption of organics on catalyst surface.

Corotating Magnetic Reconnection Site in Saturn’s Magnetosphere

Energy Technology Data Exchange (ETDEWEB)

Yao, Z. H.; Coates, A. J.; Ray, L. C.; Rae, I. J.; Jones, G. H.; Owen, C. J.; Dunn, W. R.; Lewis, G. R. [UCL Mullard Space Science Laboratory, Dorking RH5 6NT (United Kingdom); Grodent, D.; Radioti, A.; Gérard, J.-C. [Laboratoire de Physique Atmosphérique et Planétaire, STAR institute, Université de Liège, B-4000 Liège (Belgium); Dougherty, M. K. [Imperial College of Science, Technology and Medicine, Space and Atmospheric Physics Group, Department of Physics, London SW7 2BW (United Kingdom); Guo, R. L. [Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing (China); Pu, Z. Y. [School of Earth and Space Sciences, Peking University, Beijing (China); Waite, J. H., E-mail: z.yao@ucl.ac.uk [Southwest Research Institute, San Antonio, TX (United States)

2017-09-10

Using measurements from the Cassini spacecraft in Saturn’s magnetosphere, we propose a 3D physical picture of a corotating reconnection site, which can only be driven by an internally generated source. Our results demonstrate that the corotating magnetic reconnection can drive an expansion of the current sheet in Saturn’s magnetosphere and, consequently, can produce Fermi acceleration of electrons. This reconnection site lasted for longer than one of Saturn’s rotation period. The long-lasting and corotating natures of the magnetic reconnection site at Saturn suggest fundamentally different roles of magnetic reconnection in driving magnetospheric dynamics (e.g., the auroral precipitation) from the Earth. Our corotating reconnection picture could also potentially shed light on the fast rotating magnetized plasma environments in the solar system and beyond.

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

Directory of Open Access Journals (Sweden)

Jianhui Luo

2018-03-01

Full Text Available Adipic acid is an important raw chemical for the commercial production of polyamides and polyesters. The traditional industrial adipic acid production utilizes nitric acid to oxidize KA oil (mixtures of cyclohexanone and cyclohexanol, leading to the emission of N2O and thus causing ozone depletion, global warming, and acid rain. Herein, we reported an organically functionalized β-isomer of Anderson polyoxometalates (POMs nanocluster with single-atom Mn, β-{[H3NC(CH2O3]2MnMo6O18}− (1, as a highly active catalyst to selectively catalyze the oxidation of cyclohexanone, cyclohexanol, or KA oil with atom economy use of 30% H2O2 for the eco-friendly synthesis of adipic acid. The catalyst has been characterized by single crystal and powder XRD, XPS, ESI-MS, FT-IR, and NMR. A cyclohexanone (cyclohexanol conversion of >99.9% with an adipic acid selectivity of ~97.1% (~85.3% could be achieved over catalyst 1 with high turnover frequency of 2427.5 h−1 (2132.5 h−1. It has been demonstrated that the existence of Mn3+ atom active site in catalyst 1 and the special butterfly-shaped topology of POMs both play vital roles in the enhancement of catalytic activity.

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.

Catalytic bioreactors and methods of using same

Science.gov (United States)

Worden, Robert Mark; Liu, Yangmu Chloe

2017-07-25

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

Measurement of the 234U/238U activity ratios in the organs and internal tissues of a domestic goat kid (Capra aegagrus hircus)

International Nuclear Information System (INIS)

Francesco De Santis; Massimo Esposito

2015-01-01

In this paper, we compare the 234 U/ 238 U activity ratios (ARs) in various internal tissues and organs of a goat kid with the ingested 234 U/ 238 U AR to assess isotopic fractionation. The results obtained from soft tissues (i.e., the kidneys, liver, lung, and bladder) that undergo indirect assimilation of uranium from the feed through the bloodstream suggest an increase in the 234 U/ 238 U AR. In contrast, the intestine, bones and feces had the same AR values as the feed. Finally, we broadly assess uranium transfer from the feed to the animal based on the concentration ratio and the feed transfer coefficient. (author)

Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite

Directory of Open Access Journals (Sweden)

Xuan Hoan Vu

2015-10-01

Full Text Available The catalytic cracking of triglyceride-rich biomass toward C2–C4 olefins was evaluated over a hierarchically textured nano-ZSM-5/SBA-15 analog composite (ZSC-24 under fluid catalytic cracking (FCC conditions. The experiments were performed on a fully automated Single-Receiver Short-Contact-Time Microactivity Test unit (SR-SCT-MAT, Grace Davison at 550 °C and different catalyst-to-oil mass ratios (0–1.2 g∙g−1. The ZSC-24 catalyst is very effective for transformation of triglycerides to valuable hydrocarbons, particularly lower olefins. The selectivity to C2–C4 olefins is remarkably high (>90% throughout the investigated catalyst-to-oil ratio range. The superior catalytic performance of the ZSC-24 catalyst can be attributed to the combination of its medium acid site amount and improved molecular transport provided by the bimodal pore system, which effectively suppresses the secondary reactions of primarily formed lower olefins.

Non-thermal plasmas for non-catalytic and catalytic VOC abatement

International Nuclear Information System (INIS)

Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

2011-01-01

Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

@u234@@Th scavenging and particle export fluxes from the upper 100 m of the Arabian Sea

Digital Repository Service at National Institute of Oceanography (India)

Sarin, M.M.; Rengarajan, R.; Ramaswamy, V.

for the upper 100 m yields a mean scavenging residence time of ~k30 days and a removal rate of ~k 3400 dpm m@u-2@@ d@u-1@@ for @u234@@Th, from dissolved to particulate phases. The deficiency of total @u234@@Th (dissolved + particulate) relative to @u238@@U...

Advances in computational modeling of catalytic systems used in Claus sulfur recovery

Energy Technology Data Exchange (ETDEWEB)

Clark, P.D.; Lo, J. [Alberta Sulphur Research Ltd., Calgary, AB (Canada). Center for Applied Catalysis and Industrial Sulfur Chemistry

2010-01-15

This poster session discussed advances in computation modeling of catalytic systems used in Claus sulfur recovery, focusing on the hydrogen sulphide (H{sub 2}S) and sulphur dioxide (S{sub O}2) absorption of non-alumina Claus active metal oxides, such as titanium oxide and vanadium oxide. These metal oxides were chosen because they promote carbon disulphide (CS{sub 2}) conversion and have a potential use in olefin chemistry. The redox process of H{sub 2}S dissociation on vanadium pentoxide (V{sub 2}O{sub 2}) can take place in single-site reaction or multiple site reactions. Both mechanisms lead to the production of V{sub 2}O{sub 4}S, water (H{sub 2}O) and other species. The overall process of forming VO{sub 4}S is neutral, but kinetics is a controlling factor. The surface sulfidation to form V{sub 2}O{sub 3}S{sub 2} requires a small energy cost but possesses a huge reaction barrier. The formation of H{sub 2}S{sub 2} is energetically favorable. The silica (SiO{sub 2})-supported V{sub 2}O{sub 2} catalyst was described. A proposed mechanism of H{sub 2}S conversion to H{sub 2}O and V=S group was presented along with another reaction route in which the dissociative absorption of H{sub 2}S takes place on O-bridges instead of V=O. Two vanadia catalysts were compared: V{sub 2}O{sub 5} and V{sub 2}O{sub 5}/SiO{sub 2}. 7 figs.

Coupled {sup 230}Th/{sup 234}U-ESR analyses for corals: A new method to assess sealevel change

Energy Technology Data Exchange (ETDEWEB)

Blackwell, Bonnie A.B. [Department of Chemistry, Williams College, Williamstown, MA 01267 (United States); RFK Science Research Institute, Glenwood Landing, NY 11547 (United States)], E-mail: bonnie.a.b.blackwell@williams.edu; Teng, Steve J.T. [RFK Science Research Institute, Glenwood Landing, NY 11547 (United States)], E-mail: mteng1584@gmail.com; Lundberg, Joyce A. [Department of Geography and Environmental Studies, Carleton University, Ottawa, ON, Canada K1S 5B6 (Canada)], E-mail: joyce_lundberg@carleton.ca; Blickstein, Joel I.B. [Department of Chemistry, Williams College, Williamstown, MA 01267 (United States); RFK Science Research Institute, Glenwood Landing, NY 11547 (United States); Skinner, Anne R. [Department of Chemistry, Williams College, Williamstown, MA 01267 (United States); RFK Science Research Institute, Glenwood Landing, NY 11547 (United States)], E-mail: anne.r.skinner@williams.edu

2007-07-15

Although coupled {sup 230}Th/{sup 234}U-ESR analyses have become routine for dating teeth, they have never been used for corals. While the ESR age depends on, and requires assumptions about, the time-averaged cosmic dose rate, D-bar{sub cos}(t), {sup 230}Th/{sup 234}U dates do not. Since D-bar{sub cos}(t) received by corals depends on the attenuation by any intervening material, D-bar{sub cos}(t) response reflects changing water depths and sediment cover. By coupling the two methods, one can determine the age and a unique D-bar{sub cos,coupled}(t) simultaneously. From a coral's water depth and sedimentary history as predicted by a given sealevel curve, one can predict D-bar{sub cos,sealevel}(t). If D-bar{sub cos,coupled}(t) agrees well with D-bar{sub cos,sealevel}(t), this provides independent validation for the curve used to build D-bar{sub cos,sealevel}(t). For six corals dated at 7-128 ka from Florida Platform reef crests, the sealevel curve by Waelbroeck et al. [2002. Sea-level and deep water temperature changes derived from benthonic foraminifera isotopic records. Quat. Sci. Rev. 21, 295-305] predicted their D-bar{sub cos,coupled}(t) values as well as, or better than, the SPECMAP sealevel curve. Where a whole reef can be sampled over a transect, a precise test for sealevel curves could be developed.

A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

DEFF Research Database (Denmark)

Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

2015-01-01

For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

GTP Binding and Oncogenic Mutations May Attenuate Hypervariable Region (HVR)-Catalytic Domain Interactions in Small GTPase K-Ras4B, Exposing the Effector Binding Site*

Science.gov (United States)

Lu, Shaoyong; Banerjee, Avik; Jang, Hyunbum; Zhang, Jian; Gaponenko, Vadim; Nussinov, Ruth

2015-01-01

K-Ras4B, a frequently mutated oncogene in cancer, plays an essential role in cell growth, differentiation, and survival. Its C-terminal membrane-associated hypervariable region (HVR) is required for full biological activity. In the active GTP-bound state, the HVR interacts with acidic plasma membrane (PM) headgroups, whereas the farnesyl anchors in the membrane; in the inactive GDP-bound state, the HVR may interact with both the PM and the catalytic domain at the effector binding region, obstructing signaling and nucleotide exchange. Here, using molecular dynamics simulations and NMR, we aim to figure out the effects of nucleotides (GTP and GDP) and frequent (G12C, G12D, G12V, G13D, and Q61H) and infrequent (E37K and R164Q) oncogenic mutations on full-length K-Ras4B. The mutations are away from or directly at the HVR switch I/effector binding site. Our results suggest that full-length wild-type GDP-bound K-Ras4B (K-Ras4BWT-GDP) is in an intrinsically autoinhibited state via tight HVR-catalytic domain interactions. The looser association in K-Ras4BWT-GTP may release the HVR. Some of the oncogenic mutations weaken the HVR-catalytic domain association in the K-Ras4B-GDP/-GTP bound states, which may facilitate the HVR disassociation in a nucleotide-independent manner, thereby up-regulating oncogenic Ras signaling. Thus, our results suggest that mutations can exert their effects in more than one way, abolishing GTP hydrolysis and facilitating effector binding. PMID:26453300

Crystal structures of wild-type Trichoderma reesei Cel7A catalytic domain in open and closed states

Energy Technology Data Exchange (ETDEWEB)

Bodenheimer, Annette M. [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA; Meilleur, Flora [Molecular and Structural Biochemistry Department, North Carolina State University, Raleigh NC USA; Neutron Sciences Directorate, Oak Ridge National Laboratory, TN USA

2016-11-07

Trichoderma reesei Cel7A efficiently hydrolyses cellulose. We report here the crystallographic structures of the wild-type TrCel7A catalytic domain (CD) in an open state and, for the first time, in a closed state. Molecular dynamics (MD) simulations indicate that the loops along the CD tunnel move in concerted motions. Together, the crystallographic and MD data suggest that the CD cycles between the tense and relaxed forms that are characteristic of work producing enzymes. Analysis of the interactions formed by R251 provides a structural rationale for the concurrent decrease in product inhibition and catalytic efficiency measured for product-binding site mutants.

Critical Role of Interdomain Interactions in the Conformational Change and Catalytic Mechanism of Endoplasmic Reticulum Aminopeptidase 1.

Science.gov (United States)

Stamogiannos, Athanasios; Maben, Zachary; Papakyriakou, Athanasios; Mpakali, Anastasia; Kokkala, Paraskevi; Georgiadis, Dimitris; Stern, Lawrence J; Stratikos, Efstratios

2017-03-14

Endoplasmic reticulum aminopeptidase 1 (ERAP1) is an intracellular enzyme that is important for the generation of antigenic epitopes and major histocompatibility class I-restricted adaptive immune responses. ERAP1 processes a vast variety of different peptides but still shows length and sequence selectivity, although the mechanism behind these properties is poorly understood. X-ray crystallographic analysis has revealed that ERAP1 can assume at least two distinct conformations in which C-terminal domain IV is either proximal or distal to active site domain II. To improve our understanding of the role of this conformational change in the catalytic mechanism of ERAP1, we used site-directed mutagenesis to perturb key salt bridges between domains II and IV. Enzymatic analysis revealed that these mutations, although located away from the catalytic site, greatly reduce the catalytic efficiency and change the allosteric kinetic behavior. The variants were more efficiently activated by small peptides and bound a competitive inhibitor with weaker affinity and faster dissociation kinetics. Molecular dynamics analysis suggested that the mutations affect the conformational distribution of ERAP1, reducing the population of closed states. Small-angle X-ray scattering indicated that both the wild type and the ERAP1 variants are predominantly in an open conformational state in solution. Overall, our findings suggest that electrostatic interactions between domains II and IV in ERAP1 are crucial for driving a conformational change that regulates the structural integrity of the catalytic site. The extent of domain opening in ERAP1 probably underlies its specialization for antigenic peptide precursors and should be taken into account in inhibitor development efforts.

A new 3DOM Ce-Fe-Ti material for simultaneously catalytic removal of PM and NOx from diesel engines.

Science.gov (United States)

Cheng, Ying; Liu, Jian; Zhao, Zhen; Song, Weiyu; Wei, Yuechang

2018-01-15

A new 3DOM material was designed and synthesized for the simultaneous removal of PM (soot particulates) and NOx from diesel engine exhausts. The catalytic purification taking place over the material with double efficacy is cost-efficient. The contact between solid PM and catalyst active site has been process intensified by 3DOM unique structure. 3DOM Ce 0.7 Fe 0.2 Ti 0.1 O 2 catalyst possess a high SCR activity and an excellent selectivity to N 2 , giving a maximum concentration of CO 2 at 385°C for PM combustion and 100% NO conversion in the temperature range of 281-425°C. The dual redox cycles (Fe 3+ +Ce 3+ ↔Fe 2+ +Ce 4+ ,Fe 3+ +Ti 3+ ↔Fe 2+ +Ti 4+ ) and the excellent reducibility and sufficient acid sites of catalysts play key roles for the highly catalytic performance. Copyright © 2017 Elsevier B.V. All rights reserved.

The use of 234Th/238U disequilibrium to examine the fate of particle-reactive species on the Yangtze continental shelf

International Nuclear Information System (INIS)

McKee, B.A.; DeMaster, D.J.; Nittrouer, C.A.

1984-01-01

Measurements of 234 Th (tsub(1/2)=24.1 d) in water column and seabed samples from an area near the mouth of the Yangtze River (People's Republic of China) provide the following information: Most of the 234 Th in waters near the mouth of the Yangtze River is in particulate form, and horizontal transport and sedimentation of 234 Th-bearing particles dominate the 234 Th budget in this area. A model incorporating processes in at least two dimensions is required to understand the fate of particle-reactive species on the Yangtze continental shelf. The residence times of particle-reactive species (with respect to scavenging) range from 0.3 days (nearshore) to 4.0 days (offshore). The residence times (with respect to removal to the seabed) range from 0.5 day (nearshore) to 11.0 days (offshore). Scavenging residence times for 234 Th decrease as the concentration of suspended particles increases. The time for removal of 234 Th to the seabed increases with distance from shore (a variable which integrates such factors as scavenging rate, bathymetry, and frequency of resuspension). (orig.)

Catalytic hydrodeoxygenation of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolites

International Nuclear Information System (INIS)

Lee, Hyung Won; Jun, Bo Ram; Kim, Hannah; Kim, Do Heui; Jeon, Jong-Ki; Park, Sung Hoon; Ko, Chang Hyun; Kim, Tae-Wan; Park, Young-Kwon

2015-01-01

The hydrodeoxygenation of 2-methoxy phenol and dibenzofuran, which are representative model compounds of bio-oil, was performed using two different Pt/mesoporous zeolite catalysts, Pt/mesoporous Y and Pt/mesoporous MFI. The reforming of 2-methoxy phenol and dibenzofuran via catalytic hydrodeoxygenation was investigated using a batch reactor at 40 bar and 250 °C. The characteristics of the catalysts were analyzed by N 2 adsorption-desorption, X-ray diffraction, and NH 3 temperature programmed desorption. Pt/mesoporous zeolite catalysts containing both strong acid sites and mesopores showed the higher conversion of 2-methoxy phenol than Pt/SiO 2 and Pt/Si-MCM-48 with no acid sites, Pt/γ-Al 2 O 3 , and a mixture of mesoporous Y and Pt/SiO 2 , indicating the importance of both Pt and strong acid sites for high catalytic activity. Among the two Pt/mesoporous zeolite catalysts tested, the conversion of 2-methoxy phenol to cyclohexane over Pt/mesoporous Y was much higher than that over the Pt/mesoporous MFI. This was attributed to the better textural properties, such as surface area, pore volume and micropore size, compared to those of Pt/mesoporous MFI. The catalytic conversions of dibenzofuran obtained using two Pt/mesoporous zeolite catalysts were similar and the main products were 1,1′-bicyclohexyl, cyclopentylmethyl-cyclohexane and cyclohexane. In addition, the reaction mechanisms of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolite were suggested. - Highlights: • HDO of 2-methoxy phenol and dibenzofuran was performed over Pt/mesoporous zeolites. • Pt/mesoporous zeolites have mesopores and strong acid sites. • Main product of HDO of 2-methoxy phenol was cyclohexane. • Main products of HDO of dibenzofuran were bicyclohexyl (BCH), i-BCH, and cyclohexane

238,234U contents on Lepomis Cyanellus from San Marcos dam located in a uraniferous area

Science.gov (United States)

Lares, Magaly Cabral; Luna-Porres, Mayra Y.; Montero-Cabrera, María E.; Renteria-Villalobos, Marusia

2014-07-01

Fish species are suitable biomonitors of radioisotopes in aquatic systems. In the present study, it was made the determination of uranium isotopic contents on fish fillet (Lepomis Cyanellus) from San Marcos dam which is located in uranium mineralized zone. Uranium activity concentrations (AC) in fish samples were obtained on wet weight (ww), using liquid scintillation. 238U and 234U AC in fish fillet ranged from 0.0004 to 0.0167 Bq kg-1, and from 0.0013 to 0.0394 Bq kg-1, respectively. The activity ratio (234U/overflow="scroll">238U) in fish fillet ranged from 2.2 to 8.8. Lepomis cyanellus from San Marcos dam shows bioaccumulation factor (FB) of 0.6 L kg-1. The results suggest that the Lepomis Cyanellus in environments with high U contents tends to have a greater bioaccumulation compared to others.

Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

KAUST Repository

Liu, He

2017-07-26

Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

KAUST Repository

Liu, He; Zhang, Haitao; Fei, Linfeng; Ma, Hongbin; Zhao, Guoying; Mak, CheeLeung; Zhang, Xixiang; Zhang, Suojiang

2017-01-01

Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

49 CFR 234.7 - Accidents involving grade crossing signal failure.

Science.gov (United States)

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Accidents involving grade crossing signal failure... PLANS Reports and Plans § 234.7 Accidents involving grade crossing signal failure. (a) Each railroad... (activation failure report) and 49 CFR 225.11 (accident/ incident report). (b) Each telephone report must...

Synthesis of [3]DIPPA: a potent irreversible antagonist selective for the κ opioid receptor

International Nuclear Information System (INIS)

Chang, Anchih; Portoghese, P.S.

1995-01-01

2-(3,4-Dichlorophenyl)-N-methyl-N-[(1S)-1-(3-isothiocyanatophe nyl)-2-(1-pyrrolidinyl)ethyl]acetamide (1,DIPPA) has been previously reported to be an opioid receptor affinity label that produces selective and long-lasting κ opioid receptor antagonism in mice. High specific activity [ 3 H]DIPPA (39.7 Ci/mmol) was prepared by bromination and catalytic tritiation of the amino precursor of DIPPA followed by conversion to the isothiocyanate with thiophosgene. (Author)

48 CFR 352.234-1 - Notice of earned value management system-pre-award Integrated Baseline Review.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false Notice of earned value management system-pre-award Integrated Baseline Review. 352.234-1 Section 352.234-1 Federal Acquisition... provision: Notice of Earned Value Management System—Pre-Award Integrated Baseline Review (October 2008) The...

Visualization of the Differential Transition State Stabilization within the Active Site Environment

Directory of Open Access Journals (Sweden)

Jerzy Leszczynski

2004-05-01

Full Text Available Abstract: Increasing interest in the enzymatic reaction mechanisms and in the nature of catalytic effects in enzymes causes the need of appropriate visualization methods. A new interactive method to investigate catalytic effects using differential transition state stabilization approach (DTSS [1, 2] is presented. The catalytic properties of the active site of cytidine deaminase (E.C. 3.5.4.5 is visualized in the form of differential electrostatic properties. The visualization was implemented using scripting interface of VMD [3]. Cumulative Atomic Multipole Moments (CAMM [4,5,6] were utilized for efficient yet accurate evaluation of the electrostatic properties. The implementation is efficient enough for interactive presentation of catalytic effects in the active site of the enzyme due to transition state or substrate movement. This system of visualization of DTTS approach can be potentially used to validate hypotheses regarding the catalytic mechanism or to study binding properties of transition state analogues.

Catalytic process for tritium exchange reaction

International Nuclear Information System (INIS)

Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

2001-01-01

The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

Probes of the catalytic site of cysteine dioxygenase.

Science.gov (United States)

Chai, Sergio C; Bruyere, John R; Maroney, Michael J

2006-06-09

The first major step of cysteine catabolism, the oxidation of cysteine to cysteine sulfinic acid, is catalyzed by cysteine dioxygenase (CDO). In the present work, we utilize recombinant rat liver CDO and cysteine derivatives to elucidate structural parameters involved in substrate recognition and x-ray absorption spectroscopy to probe the interaction of the active site iron center with cysteine. Kinetic studies using cysteine structural analogs show that most are inhibitors and that a terminal functional group bearing a negative charge (e.g. a carboxylate) is required for binding. The substrate-binding site has no stringent restrictions with respect to the size of the amino acid. Lack of the amino or carboxyl groups at the alpha-carbon does not prevent the molecules from interacting with the active site. In fact, cysteamine is shown to be a potent activator of the enzyme without being a substrate. CDO was also rendered inactive upon complexation with the metal-binding inhibitors azide and cyanide. Unlike many non-heme iron dioxygenases that employ alpha-keto acids as cofactors, CDO was shown to be the only dioxygenase known to be inhibited by alpha-ketoglutarate.

Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles.

Science.gov (United States)

Reske, Rulle; Mistry, Hemma; Behafarid, Farzad; Roldan Cuenya, Beatriz; Strasser, Peter

2014-05-14

A study of particle size effects during the catalytic CO2 electroreduction on size-controlled Cu nanoparticles (NPs) is presented. Cu NP catalysts in the 2-15 nm mean size range were prepared, and their catalytic activity and selectivity during CO2 electroreduction were analyzed and compared to a bulk Cu electrode. A dramatic increase in the catalytic activity and selectivity for H2 and CO was observed with decreasing Cu particle size, in particular, for NPs below 5 nm. Hydrocarbon (methane and ethylene) selectivity was increasingly suppressed for nanoscale Cu surfaces. The size dependence of the surface atomic coordination of model spherical Cu particles was used to rationalize the experimental results. Changes in the population of low-coordinated surface sites and their stronger chemisorption were linked to surging H2 and CO selectivities, higher catalytic activity, and smaller hydrocarbon selectivity. The presented activity-selectivity-size relations provide novel insights in the CO2 electroreduction reaction on nanoscale surfaces. Our smallest nanoparticles (~2 nm) enter the ab initio computationally accessible size regime, and therefore, the results obtained lend themselves well to density functional theory (DFT) evaluation and reaction mechanism verification.

Catalytic soman scavenging by Y337A/F338A acetylcholinesterase mutant assisted with novel site-directed aldoximes

Science.gov (United States)

Kovarik, Zrinka; Hrvat, Nikolina Maček; Katalinić, Maja; Sit, Rakesh K.; Paradyse, Alexander; Žunec, Suzana; Musilek, Kamil; Fokin, Valery V.; Taylor, Palmer; Radić, Zoran

2016-01-01

Exposure to the nerve agent soman is difficult to treat due to the rapid dealkylation of soman-acetylcholinesterase (AChE) conjugate known as aging. Oxime antidotes commonly used to reactivate organophosphate inhibited AChE are ineffective against soman, while the efficacy of the recommended nerve agent bioscavenger butyrylcholinesterase is limited by strictly stoichiometric scavenging. To overcome this limitation, we tested ex vivo, in human blood, and in vivo, in soman exposed mice, the capacity of aging-resistant human AChE mutant Y337A/F338A in combination with oxime HI-6 to act as a catalytic bioscavenger of soman. HI-6 was previously shown in vitro to efficiently reactivate this mutant upon soman, as well as VX, cyclosarin, sarin and paraoxon inhibition. We here demonstrate that ex vivo, in whole human blood, 1 μM soman was detoxified within 30 minutes when supplemented with 0.5 μM Y337A/F338A AChE and 100 μM HI-6. This combination was further tested in vivo. Catalytic scavenging of soman in mice improved the therapeutic outcome and resulted in the delayed onset of toxicity symptoms. Furthermore, in a preliminary in vitro screen we identified an even more efficacious oxime than HI-6, in a series of forty-two pyridinium aldoximes, and five imidazole 2-aldoxime N-propyl pyridinium derivatives. One of the later imidazole aldoximes, RS-170B, was a 2–3 –fold more effective reactivator of Y337A/F338A AChE than HI-6 due to the smaller imidazole ring, as indicated by computational molecular models, that affords a more productive angle of nucleophilic attack. PMID:25835984

Reduction and Methyl Transfer Kinetics of the Alpha Subunit from Acetyl-Coenzyme A Synthase

Energy Technology Data Exchange (ETDEWEB)

Xiangshi Tan; Christopher Sewell; Qingwu Yang; Paul A. Lindahl

2003-01-15

OAK-B135 Stopped-flow was used to evaluate the methylation and reduction kinetics of the isolated alpha subunit of acetyl-Coenzyme A synthase from Moorella thermoacetica. This catalytically active subunit contains a novel Ni-X-Fe4S4 cluster and a putative unidentified n =2 redox site called D. The D-site must be reduced for a methyl group to transfer from a corrinoid-iron-sulfur protein, a key step in the catalytic synthesis of acetyl-CoA. The Fe4S4 component of this cluster is also redox active, raising the possibility that it is the D-site or a portion thereof. Results presented demonstrate that the D-site reduces far faster than the Fe4S4 component, effectively eliminating this possibility. Rather, this component may alter catalytically important properties of the Ni center. The D-site is reduced through a pathway that probably does not involve the Fe4S4 component of this active-site cluster.

238U, 234U and 230Th in uranium miners' lungs

International Nuclear Information System (INIS)

Singh, M.P.; Wrenn, M.E.; Archer, V.E.; Saccomanno, G.

1981-01-01

Fourteen uranium miners' lungs from Colorado plateau were collected at autopsy and the concentrations of 238 U, 234 U and 230 Th were determined by radiochemical procedures utilizing solvent extraction - alpha spectrometric techniques. The uranium and thorium isotopes are in near equilibrium with average concentrations of 238 U, 234 U and 230 Th being 89.3, 95.2 and 91.1 pCi/kg respectively. The combined average radiation dose rate to lung from these three isotopes is about 24.2 mrad/year at death excluding the unmeasured contribution from the 226 Ra and daughters. The average concentration of 230 Th is about 65 times higher than the mean concentration of 230 Th in lungs of non-miners dying at comparable ages from the same region

A study on naphtha catalytic reforming reactor simulation and analysis.

Science.gov (United States)

Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

2005-06-01

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

A study on naphtha catalytic reforming reactor simulation and analysis

OpenAIRE

Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

2005-01-01

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation uni...

Catalytic Ethanol Dehydration over Different Acid-activated Montmorillonite Clays.

Science.gov (United States)

Krutpijit, Chadaporn; Jongsomjit, Bunjerd

2016-01-01

In the present study, the catalytic dehydration of ethanol to obtain ethylene over montmorillonite clays (MMT) with mineral acid activation including H2SO4 (SA-MMT), HCl (HA-MMT) and HNO3 (NA-MMT) was investigated at temperature range of 200 to 400°C. It revealed that HA-MMT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. At 400°C, the HA-MMT yielded 82% of ethanol conversion having 78% of ethylene yield. At lower temperature (i.e. 200 to 300°C), diethyl ether (DEE) was a major product. The highest activity obtained from HA-MMT can be attributed to an increase of weak acid sites and acid density by the activation of MMT with HCl. It can be also proven by various characterization techniques that in most case, the main structure of MMT did not alter by acid activation (excepted for NA-MMT). Upon the stability test for 72 h during the reaction, the MMT and HA-MMT showed only slight deactivation due to carbon deposition. Hence, the acid activation of MMT by HCl is promising to enhance the catalytic dehydration of ethanol.

The behavior of particle-reactive tracers in a high turbidity environment: 234Th and 210Pb on the Amazon continental shelf

International Nuclear Information System (INIS)

Smoak, J.M.; DeMaster, D.J.; Pope, R.H.; Kuehl, S.A.; McKee, B.A.

1996-01-01

Excess 234 Th and 210 Pb seabed inventories were measured in cores collected from the Amazon continental shelf to examine particle scavenging and seabed dynamics. Typical excess 210 Pb inventories range from 100 to 300 dpm cm -2 , and the total excess 210 Pb inventory for the Amazon shelf was determined to be 2.7 x 10 17 dpm. The 210 Pb measurements indicate that particle-reactive species are scavenged not only form the Amazon River but also from the lateral advection of offshore water. In order to sustain the 210 Pb inventories, the volume of water supplied by the lateral advection from offshore must be approximately five to ten times the water discharge of the Amazon River. This lateral advection supplies about 67% of the total excess 210 Pb to the Amazon continental shelf with relatively small contributions from riverine input (31%), atmospheric fallout (2.3%), and in-situ production (0.1%). The 234 Th inventories were measured on four cruises, which occurred during periods of differing river discharge, wind stress, and flow rates of the North Brazil Current. The 234 Th excess seabed inventories show large spatial and seasonal variability, with a range from 0 to 22 dpm cm -2 . This approach indicates that for most of the shelf, the inventories of the shorter-term tracer ( 234 Th) are less than predicted by the inventories of the longer-term tracer ( 210 Pb). There are two explanations for this trend. The first is that a larger portion of the 234 Th inventory occurs in the fluid muds or the water column relative to 210 Pb. The second is that the supply of offshore water, scavenging efficiency, and/or deposition have been lower over the two year study period relative to the last one hundred years. 38 refs., 7 figs

Application of natural Ra isotopes and 234Th as tracers of organic carbon export in Bransfield Strait, Antarctica

International Nuclear Information System (INIS)

Vieira, Lucia Helena

2011-01-01

The Southern Ocean is the largest of several high-nutrient, low-chlorophyll (HNLC) regions in the world's oceans. This region plays a major role in regulating the global net transfer of carbon dioxide between the ocean and the atmosphere, in part because the annual photosynthetic uptake of CO 2 by phytoplankton and resulting export of particulate organic carbon (POC) to the deep ocean. The element thorium has multiple radioisotopes that have emerged collectively as a powerful set of tracers for particle associated processes in the oceans. Of all the Th isotopes, 234 Th (half-life 24.1 d) has been the focus of increasing attention and application in the past years. The production of 234 Th from 238 U, coupled with the conservative behavior of 238 U in seawater, makes the source of 234 Th easy to characterize. Moreover, the half-life of 234 Th is sufficiently short to make it sensitive to the short-term (e.g. seasonal) changes that occur in the upper water column of the open ocean or in sediments or water column in coastal areas. Because of its very particle reactive behavior, 234 Th is removed from a parcel of water in only two ways, through decay and through particle flux. Therefore, a steady-state 1D activity balance can be used to calculate its flux. Natural Ra isotopes have been also widely used in marine studies to trace water masses and to quantify mixing processes. This work presents results of a collaborative research on organic carbon fluxes distribution in the Bransfield Strait in order to evaluate its influence in the CO 2 drawdown. Macro-nutrients, micro-nutrients and chlorophyll-a distributions were used to examine the pathway sources. Natural radium isotopes were applied as tracers to study the movement of shelf water, while 234 Th was used as a tracer of particle flux in the upper ocean, since POC export via sinking particles is the primary mechanism of carbon sequestration in the Southern Ocean. Sea water samples for total 234 Th and natural Ra

S1-sensitive sites in DNA after γ-irradiation

International Nuclear Information System (INIS)

Martin-Bertram, H.

1981-01-01

DNA from γ-irradiated T 1 bacteriophages was analyzed for 'single-stranded' sites by cleavage with S1 nuclease from Aspergillus oryzae as lesion probe. The ratio of 'S1-sensitive sites' to the amount of radiation-induced single-strand breaks was about one. Presumably these 'denatured' sites were associated with single-strand breaks. The subsequent check for the persistence of 'single-stranded' sites within the DNA molecule by thermokinetics demonstrated a strong affinity of the nuclease to its substrate, the single-stranded lesion, and a perfect excision. It is assumed that the direct absorption of radiation energy in the DNA gives rise to the formation of such bulky lesions. (Auth.)

sup(234) Th scavenging and particle export fluxes from the upper 100 m of the Arabian Sea

Digital Repository Service at National Institute of Oceanography (India)

Sarin, M.M.; Rengarajan, R.; Ramaswamy, V.

of column primary productivity. Using the sup(234) Th export fluxes and the measured specific activity of sup(234) Th in the sediment traps, we have computed th eparticle and carbon fluxes at 100 m. These results reveal that the particle fluxes determined...

HHM motif at the CuH-site of peptidylglycine monooxygenase is a pH-dependent conformational switch.

Science.gov (United States)

Kline, Chelsey D; Mayfield, Mary; Blackburn, Ninian J

2013-04-16

Peptidylglycine monooxygenase is a copper-containing enzyme that catalyzes the amidation of neuropeptides hormones, the first step of which is the conversion of a glycine-extended pro-peptide to its α-hydroxyglcine intermediate. The enzyme contains two mononuclear Cu centers termed CuM (ligated to imidazole nitrogens of H242, H244 and the thioether S of M314) and CuH (ligated to imidazole nitrogens of H107, H108, and H172) with a Cu-Cu separation of 11 Å. During catalysis, the M site binds oxygen and substrate, and the H site donates the second electron required for hydroxylation. The WT enzyme shows maximum catalytic activity at pH 5.8 and undergoes loss of activity at lower pHs due to a protonation event with a pKA of 4.6. Low pH also causes a unique structural transition in which a new S ligand coordinates to copper with an identical pKA, manifest by a large increase in Cu-S intensity in the X- ray absorption spectroscopy. In previous work (Bauman, A. T., Broers, B. A., Kline, C. D., and Blackburn, N. J. (2011) Biochemistry 50, 10819-10828), we tentatively assigned the new Cu-S interaction to binding of M109 to the H-site (part of an HHM conserved motif common to all but one member of the family). Here we follow up on these findings via studies on the catalytic activity, pH-activity profiles, and spectroscopic (electron paramagnetic resonance, XAS, and Fourier transform infrared) properties of a number of H-site variants, including H107A, H108A, H172A, and M109I. Our results establish that M109 is indeed the coordinating ligand and confirm the prediction that the low pH structural transition with associated loss of activity is abrogated when the M109 thioether is absent. The histidine mutants show more complex behavior, but the almost complete lack of activity in all three variants coupled with only minor differences in their spectroscopic properties suggests that unique structural elements at H are critical for functionality. The data suggest a more general

Catalytic transitions in the human MDR1 P-glycoprotein drug binding sites.

Science.gov (United States)

Wise, John G

2012-06-26

Multidrug resistance proteins that belong to the ATP-binding cassette family like the human P-glycoprotein (ABCB1 or Pgp) are responsible for many failed cancer and antiviral chemotherapies because these membrane transporters remove the chemotherapeutics from the targeted cells. Understanding the details of the catalytic mechanism of Pgp is therefore critical to the development of inhibitors that might overcome these resistances. In this work, targeted molecular dynamics techniques were used to elucidate catalytically relevant structures of Pgp. Crystal structures of homologues in four different conformations were used as intermediate targets in the dynamics simulations. Transitions from conformations that were wide open to the cytoplasm to transition state conformations that were wide open to the extracellular space were studied. Twenty-six nonredundant transitional protein structures were identified from these targeted molecular dynamics simulations using evolutionary structure analyses. Coupled movement of nucleotide binding domains (NBDs) and transmembrane domains (TMDs) that form the drug binding cavities were observed. Pronounced twisting of the NBDs as they approached each other as well as the quantification of a dramatic opening of the TMDs to the extracellular space as the ATP hydrolysis transition state was reached were observed. Docking interactions of 21 known transport ligands or inhibitors were analyzed with each of the 26 transitional structures. Many of the docking results obtained here were validated by previously published biochemical determinations. As the ATP hydrolysis transition state was approached, drug docking in the extracellular half of the transmembrane domains seemed to be destabilized as transport ligand exit gates opened to the extracellular space.

On the effect of atomic structure on the deactivation of catalytic gold nanoparticles

International Nuclear Information System (INIS)

Walsh, M J; Gai, P L; Boyes, E D

2012-01-01

Here we present atomic scale studies into the nature of both the internal structure and external surfaces of catalytic Au nanoparticles using aberration corrected in-situ electron microscopy. The activity of catalytic nanoparticles is thought to be highly sensitive to the particles' structure, meaning typical local atomic rearrangements are likely to significantly affect the overall performance of the catalyst. As-deposited Au nanoparticles are found to exhibit a variety of morphologies, with many being internally strained or highly stepped at the surface. Upon heating, surface atoms are observed to minimise the particles' surface energy by restructuring towards planar (111) facets, resulting in the removal of low co-ordinated sites thought to be crucial in catalysis by Au nanoparticles. These results suggest the process of surface energy minimisation made possible by heating may lead to a loss of active sites and consequently contribute to the deactivation of the catalyst.

A new surface catalytic model for silica-based thermal protection material for hypersonic vehicles

Directory of Open Access Journals (Sweden)

Li Kai

2015-10-01

Full Text Available Silica-based materials are widely employed in the thermal protection system for hypersonic vehicles, and the investigation of their catalytic characteristics is crucially important for accurate aerothermal heating prediction. By analyzing the disadvantages of Norman’s high and low temperature models, this paper combines the two models and proposes an eight-reaction combined surface catalytic model to describe the catalysis between oxygen and silica surface. Given proper evaluation of the parameters according to many references, the recombination coefficient obtained shows good agreement with experimental data. The catalytic mechanisms between oxygen and silica surface are then analyzed. Results show that with the increase of the wall temperature, the dominant reaction contributing to catalytic coefficient varies from Langmuir–Hinshelwood (LH recombination (TW  1350 K. The surface coverage of chemisorption areas varies evidently with the dominant reactions in the high temperature (HT range, while the surface coverage of physisorption areas varies within quite low temperature (LT range (TW < 250 K. Recommended evaluation of partial parameters is also given.

Carbon nanofibers: a versatile catalytic support

Directory of Open Access Journals (Sweden)

Nelize Maria de Almeida Coelho

2008-09-01

Full Text Available The aim of this article is present an overview of the promising results obtained while using carbon nanofibers based composites as catalyst support for different practical applications: hydrazine decomposition, styrene synthesis, direct oxidation of H2S into elementary sulfur and as fuel-cell electrodes. We have also discussed some prospects of the use of these new materials in total combustion of methane and in ammonia decomposition. The macroscopic carbon nanofibers based composites were prepared by the CVD method (Carbon Vapor Deposition employing a gaseous mixture of hydrogen and ethane. The results showed a high catalytic activity and selectivity in comparison to the traditional catalysts employed in these reactions. The fact was attributed, mainly, to the morphology and the high external surface of the catalyst support.

Catalytic Fast Pyrolysis: A Review

Directory of Open Access Journals (Sweden)

Theodore Dickerson

2013-01-01

Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

Science.gov (United States)

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

The Savannah River Site`s Groundwater Monitoring Program. Fourth quarter 1992

Energy Technology Data Exchange (ETDEWEB)

1993-05-17

This report summarizes the Savannah River Site (SRS) groundwater monitoring program conducted by the Environmental Protection Department`s Environmental Monitoring Section (EPD/EMS) during the fourth quarter of 1992. It includes the analytical data, field data, data review, quality control, and other documentation for this program, provides a record of the program`s activities; and serves as an official document of the analytical results.

The Savannah River Site`s Groundwater Monitoring Program. Fourth quarter, 1989

Energy Technology Data Exchange (ETDEWEB)

1989-12-31

The Environmental Monitoring Section of the Environmental and Health Protection (EHP) Department administers the Savannah River Site`s Groundwater Monitoring Program. During fourth quarter 1989 (October--December), EHP conducted routine sampling of monitoring wells and drinking water locations. EHP collected the drinking water samples from Savannah River Site (SRS) drinking water systems supplied by wells. EHP established two sets of flagging criteria in 1986 to assist in the management of sample results. The flagging criteria aid personnel in sample scheduling, interpretation of data, and trend identification. An explanation of flagging criteria for the fourth quarter is presented in the Flagging Criteria section of this document. All analytical results from fourth quarter 1989 are listed in this report, which is distributed to all waste-site custodians.

Uranium contents and 234U/238U activity ratios of modern and fossil marine bivalle molluscan shells

International Nuclear Information System (INIS)

Mitsuda, Hiroshi

1984-01-01

Uranium contents and 234 U/ 238 U activity ratios in modern and fossil marine bivalle molluscan shells were measured by alpha-spectrometry. Uranium contents and 234 U/ 238 U activity ratios in modern shells were averaged to be 0.266 (dpm/g), and 1.18, respectively and those in fossil shells were averaged to be 0.747 (dpm/g), and 1.19, respectivily. Uranium contents in fossil shells were obviously higher than those in modern shells. It can be explained by the addition of uranium to shell during the deposition. In fossil shells, 234 U/ 238 U activity ratio decreases as 238 U content increases the same tendency is not found in modern shells. The author proposed a mechanism of selective loss of 238 U from the fossil shells for the explanation of this tendency. The height activity ratio of 234 U/ 238 U measured on the fossil shells than that measured on the modern shells, also support the selective loss of 238 U from the fossil shells. (author)

Lamellar zirconium phosphates to host metals for catalytic purposes.

Science.gov (United States)

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

Thorium-230 dating of natural waters at the Nevada Test Site

International Nuclear Information System (INIS)

Bakhtiar, S.N.

1990-01-01

Radiocarbon determinations have been used in the past to estimate the ages of groundwater from the Paleozoic aquifer underlying the Nevada Test Site and adjacent areas. We measured the concentrations of 230 Th, 232 Th, 234 U and 238 U in several water samples taken from the wells and spring at the Nevada Test Site and calculated the 230 Th ages. 2 refs

Catalytic conversion reactions mediated by single-file diffusion in linear nanopores: hydrodynamic versus stochastic behavior.

Science.gov (United States)

Ackerman, David M; Wang, Jing; Wendel, Joseph H; Liu, Da-Jiang; Pruski, Marek; Evans, James W

2011-03-21

We analyze the spatiotemporal behavior of species concentrations in a diffusion-mediated conversion reaction which occurs at catalytic sites within linear pores of nanometer diameter. Diffusion within the pores is subject to a strict single-file (no passing) constraint. Both transient and steady-state behavior is precisely characterized by kinetic Monte Carlo simulations of a spatially discrete lattice-gas model for this reaction-diffusion process considering various distributions of catalytic sites. Exact hierarchical master equations can also be developed for this model. Their analysis, after application of mean-field type truncation approximations, produces discrete reaction-diffusion type equations (mf-RDE). For slowly varying concentrations, we further develop coarse-grained continuum hydrodynamic reaction-diffusion equations (h-RDE) incorporating a precise treatment of single-file diffusion in this multispecies system. The h-RDE successfully describe nontrivial aspects of transient behavior, in contrast to the mf-RDE, and also correctly capture unreactive steady-state behavior in the pore interior. However, steady-state reactivity, which is localized near the pore ends when those regions are catalytic, is controlled by fluctuations not incorporated into the hydrodynamic treatment. The mf-RDE partly capture these fluctuation effects, but cannot describe scaling behavior of the reactivity.

GTP Binding and Oncogenic Mutations May Attenuate Hypervariable Region (HVR)-Catalytic Domain Interactions in Small GTPase K-Ras4B, Exposing the Effector Binding Site.

Science.gov (United States)

Lu, Shaoyong; Banerjee, Avik; Jang, Hyunbum; Zhang, Jian; Gaponenko, Vadim; Nussinov, Ruth

2015-11-27

K-Ras4B, a frequently mutated oncogene in cancer, plays an essential role in cell growth, differentiation, and survival. Its C-terminal membrane-associated hypervariable region (HVR) is required for full biological activity. In the active GTP-bound state, the HVR interacts with acidic plasma membrane (PM) headgroups, whereas the farnesyl anchors in the membrane; in the inactive GDP-bound state, the HVR may interact with both the PM and the catalytic domain at the effector binding region, obstructing signaling and nucleotide exchange. Here, using molecular dynamics simulations and NMR, we aim to figure out the effects of nucleotides (GTP and GDP) and frequent (G12C, G12D, G12V, G13D, and Q61H) and infrequent (E37K and R164Q) oncogenic mutations on full-length K-Ras4B. The mutations are away from or directly at the HVR switch I/effector binding site. Our results suggest that full-length wild-type GDP-bound K-Ras4B (K-Ras4B(WT)-GDP) is in an intrinsically autoinhibited state via tight HVR-catalytic domain interactions. The looser association in K-Ras4B(WT)-GTP may release the HVR. Some of the oncogenic mutations weaken the HVR-catalytic domain association in the K-Ras4B-GDP/-GTP bound states, which may facilitate the HVR disassociation in a nucleotide-independent manner, thereby up-regulating oncogenic Ras signaling. Thus, our results suggest that mutations can exert their effects in more than one way, abolishing GTP hydrolysis and facilitating effector binding. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

238U, 234U and 230Th in uranium miners' lungs

International Nuclear Information System (INIS)

Singh, N.P.; Wrenn, M.E.; Bennett, D.B.; Archer, V.; Saccomanno, G.

1982-01-01

Fourteen uranium miners' lungs from the Colorado Plateau were collected at autopsy and the concentrations of 238 U, 234 U and 230 Th were determined by radiochemical procedures utilizing solvent extraction and alpha spectrometric techniques. The uranium and thorium isotopes are in near equilibrium with average concentrations of 238 U, 234 U and 230 Th being 89.3, 95.2, and 91.1 pCi/kg respectively. The combined average radiation dose rate to lung from these three isotopes is about 24.1 mrad/year at death excluding the unmeasured contribution from the 226 Ra and daughters. The average concentration of 230 Th is about 65 times higher than the mean concentration of 230 Th in lungs of non-miners from the same region dying at comparable ages

Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

Science.gov (United States)

Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

2007-07-01

Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

Development of a catalytically assisted combustor for a gas turbine

Energy Technology Data Exchange (ETDEWEB)

Ozawa, Yasushi; Fujii, Tomoharu; Sato, Mikio [Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka, Kanagawa 240-01 (Japan); Kanazawa, Takaaki; Inoue, Hitoshi [Kansai Electric Power Company, Inc., 3-11-20 Nakoji, Amagasaki, Hyoho 661 (Japan)

1999-01-01

A catalytically assisted low NO{sub x} combustor has been developed which has the advantage of catalyst durability. This combustor is composed of a burner section and a premixed combustion section behind the burner section. The burner system consists of six catalytic combustor segments and six premixing nozzles, which are arranged alternately and in parallel. Fuel flow rate for the catalysts and the premixing nozzles are controlled independently. The catalytic combustion temperature is maintained under 1000C, additional premixed gas is injected from the premixing nozzles into the catalytic combustion gas, and lean premixed combustion at 1300C is carried out in the premixed combustion section. This system was designed to avoid catalytic deactivation at high temperature and thermal or mechanical shock fracture of the honeycomb monolith. In order to maintain the catalyst temperature under 1000C, the combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected for the combustor test. A combustor for a 20MW class multi-can type gas turbine was designed and tested under high pressure conditions using LNG fuel. Measurements of NO{sub x}, CO and unburned hydrocarbon were made and other measurements were made to evaluate combustor performance under various combustion temperatures and pressures. As a result of the tests, it was proved that NO{sub x} emission was lower than 10ppm converted at 16% O{sub 2}, combustion efficiency was almost 100% at 1300C of combustor outlet temperature and 13.5ata of combustor inlet pressure

GASS-WEB: a web server for identifying enzyme active sites based on genetic algorithms.

Science.gov (United States)

Moraes, João P A; Pappa, Gisele L; Pires, Douglas E V; Izidoro, Sandro C

2017-07-03

Enzyme active sites are important and conserved functional regions of proteins whose identification can be an invaluable step toward protein function prediction. Most of the existing methods for this task are based on active site similarity and present limitations including performing only exact matches on template residues, template size restraints, despite not being capable of finding inter-domain active sites. To fill this gap, we proposed GASS-WEB, a user-friendly web server that uses GASS (Genetic Active Site Search), a method based on an evolutionary algorithm to search for similar active sites in proteins. GASS-WEB can be used under two different scenarios: (i) given a protein of interest, to match a set of specific active site templates; or (ii) given an active site template, looking for it in a database of protein structures. The method has shown to be very effective on a range of experiments and was able to correctly identify >90% of the catalogued active sites from the Catalytic Site Atlas. It also managed to achieve a Matthew correlation coefficient of 0.63 using the Critical Assessment of protein Structure Prediction (CASP 10) dataset. In our analysis, GASS was ranking fourth among 18 methods. GASS-WEB is freely available at http://gass.unifei.edu.br/. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.