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Sample records for catalytically active trp

  1. Opportunistic activation of TRP receptors by endogenous lipids: exploiting lipidomics to understand TRP receptor cellular communication.

    Science.gov (United States)

    Bradshaw, Heather B; Raboune, Siham; Hollis, Jennifer L

    2013-03-19

    Transient receptor potential channels (TRPs) form a large family of ubiquitous non-selective cation channels that function as cellular sensors and in many cases regulate intracellular calcium. Identification of the endogenous ligands that activate these TRP receptors is still under intense investigation with the majority of these channels still remaining "orphans." That these channels respond to a variety of external stimuli (e.g. plant-derived lipids, changes in temperature, and changes in pH) provides a framework for their abilities as cellular sensors, however, the mechanism of direct activation is still under much debate and research. In the cases where endogenous ligands (predominately lipids) have shown direct activation of a channel, multiple ligands have been shown to activate the same channel suggesting that these receptors are "promiscuous" in nature. Lipidomics of a growing class of endogenous lipids, N-acyl amides, the most famous of which is N-arachidonoyl ethanolamine (the endogenous cannabinoid, Anandamide) is providing a novel set of ligands that have been shown to activate some members of the TRP family and have the potential to deorphanize many more. Here it is argued that activation of TRPV receptors, a subset of the larger family of TRPs, by multiple endogenous lipids that are structurally analogous is a model system to drive our understanding that many TRP receptors are not promiscuous, but are more characteristically "opportunistic" in nature; exploiting the structural similarity and biosynthesis of a narrow range of analogous endogenous lipids. In addition, this manuscript will compare the activation properties of TRPC5 to the activity profile of an "orphan" lipid, N-palmitoyl glycine; further demonstrating that lipidomics aimed at expanding our knowledge of the family of N-acyl amides has the potential to provide novel avenues of research for TRP receptors. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. Mutational analysis of amino acid residues involved in catalytic activity of a family 18 chitinase from tulip bulbs.

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    Suzukawa, Keisuke; Yamagami, Takeshi; Ohnuma, Takayuki; Hirakawa, Hideki; Kuhara, Satoru; Aso, Yoichi; Ishiguro, Masatsune

    2003-02-01

    We expressed chitinase-1 (TBC-1) from tulip bulbs (Tulipa bakeri) in E. coli cells and used site-directed mutagenesis to identify amino acid residues essential for catalytic activity. Mutations at Glu-125 and Trp-251 completely abolished enzyme activity, and activity decreased with mutations at Asp-123 and Trp-172 when glycolchitin was the substrate. Activity changed with the mutations of Trp-251 to one of several amino acids with side-chains of little hydrophobicity, suggesting that hydrophobic interaction of Trp-251 is important for the activity. Molecular dynamics (MD) simulation analysis with hevamine as the model compound showed that the distance between Asp-123 and Glu-125 was extended by mutation of Trp-251. Kinetic studies of Trp-251-mutated chitinases confirmed these various phenomena. The results suggested that Glu-125 and Trp-251 are essential for enzyme activity and that Trp-251 had a direct role in ligand binding.

  3. Structure-activity relationship of Trp-containing analogs of the antimicrobial peptide gomesin.

    Science.gov (United States)

    Domingues, Tatiana M; Buri, Marcus V; Daffre, Sirlei; Campana, Patricia T; Riske, Karin A; Miranda, Antonio

    2014-06-01

    Gomesin (Gm) has a broad antimicrobial activity making it of great interest for development of drugs. In this study, we analyzed three Gm analogs, [Trp(1) ]-Gm, [Trp(7) ]-Gm, and [Trp(9) ]-Gm, in an attempt to gain insight into the contributions of different regions of the peptide sequence to its activity. The incorporation of the tryptophan residue in different positions has no effect on the antimicrobial and hemolytic activities of the Gm analogs in relation to Gm. Spectroscopic studies (circular dichroism, fluorescence and absorbance) of Gm and its analogs were performed in the presence of SDS, below and above its critical micelle concentration (CMC) (~8 mM), in order to monitor structural changes induced by the interaction with this anionic surfactant (0-15 mM). Interestingly, we found that the analogs interact more strongly with SDS at low concentrations (0.3-6.0 mM) than close to or above its CMC. This suggests that SDS monomers are able to cover the whole peptide, forming large detergent-peptide aggregates. On the other hand, the peptides interact differently with SDS micelles, inserting partially into the micelle core. Among the peptides, Trp in position 1 becomes more motionally-restricted in the presence of SDS, probably because this residue is located at the N-terminal region, which presents higher conformational freedom to interact stronger with SDS molecules. Trp residues in positions 7 and 9, close to and in the region of the turn of the molecule, respectively, induced a more constrained structure and the compounds cannot insert deeper into the micelle core or be completely buried by SDS monomers. Copyright © 2014 European Peptide Society and John Wiley & Sons, Ltd.

  4. Histidine 352 (His352 and tryptophan 355 (Trp355 are essential for flax UGT74S1 glucosylation activity toward secoisolariciresinol.

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    Kaushik Ghose

    Full Text Available Flax secoisolariciresinol diglucoside (SDG lignan is a natural phytoestrogen for which a positive role in metabolic diseases is emerging. Until recently however, much less was known about SDG and its monoglucoside (SMG biosynthesis. Lately, flax UGT74S1 was identified and characterized as an enzyme sequentially glucosylating secoisolariciresinol (SECO into SMG and SDG when expressed in yeast. However, the amino acids critical for UGT74S1 glucosyltransferase activity were unknown. A 3D structural modeling and docking, site-directed mutagenesis of five amino acids in the plant secondary product glycosyltransferase (PSPG motif, and enzyme assays were conducted. UGT74S1 appeared to be structurally similar to the Arabidopsis thaliana UGT72B1 model. The ligand docking predicted Ser357 and Trp355 as binding to the phosphate and hydroxyl groups of UDP-glucose, whereas Cys335, Gln337 and Trp355 were predicted to bind the 7-OH, 2-OCH3 and 17-OCH3 of SECO. Site-directed mutagenesis of Cys335, Gln337, His352, Trp355 and Ser357, and enzyme assays revealed an alteration of these binding sites and a significant reduction of UGT74S1 glucosyltransferase catalytic activity towards SECO and UDP-glucose in all mutants. A complete abolition of UGT74S1 activity was observed when Trp355 was substituted to Ala355 and Gly355 or when changing His352 to Asp352, and an altered metabolite profile was observed in Cys335Ala, Gln337Ala, and Ser357Ala mutants. This study provided for the first time evidence that Trp355 and His352 are critical for UGT74S1's glucosylation activity toward SECO and suggested the possibility for SMG production in vitro.

  5. 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...

  6. Thioredoxin Txnl1/TRP32 Is a Redox-active Cofactor of the 26 S Proteasome

    DEFF Research Database (Denmark)

    Andersen, Katrine M; Klausen, Louise Kjær; Prag, Søren

    2009-01-01

    The 26S proteasome is a large proteolytic machine, which degrades most intracellular proteins. We found that thioredoxin, Txnl1/TRP32, binds to Rpn11, a subunit of the regulatory complex of the human 26S proteasome. Txnl1 is abundant, metabolically stable and widely expressed and is present...... in the cytoplasm and nucleus. Txnl1 has thioredoxin activity with a redox potential of about -250 mV. Mutant Txnl1 with one active site cysteine replaced by serine formed disulfide bonds to eEF1A1, a substrate-recruiting factor of the 26S proteasome. eEF1A1 is therefore a likely physiological substrate...

  7. Ni2+ binds to active site of hen egg-white lysozyme and quenches fluorescence of Trp62 and Trp108

    International Nuclear Information System (INIS)

    Li Shujie; Nakagawa, Atsushi; Tsukihara, Tomitake

    2004-01-01

    We found that the maximum emission of the tryptophyl fluorescence of hen egg-white lysozyme is shifted from 337 to 323 nm and quenched to the extent of 55% with an increase in concentrations of NiCl 2 from 0 to 2 M in 50 mM Na acetate buffer (pH 4.7). In contrast, NaCl does not influence the fluorescence of lysozyme up to 2 M. To elucidate the particular effects of Ni 2+ on the tryptophyl fluorescence of lysozyme, we have measured the assembly behavior and secondary structure of lysozyme in various concentrations of NiCl 2 , and determined the structures of lysozyme crystals grown in 0.3, 0.5, and 1.0 M NiCl 2 , respectively. The results of analytical centrifugation and circular dichroism experiments show that lysozyme keeps a monomer state and has an identical secondary structure, irrespective of NiCl 2 concentrations. The crystal structures show that all crystals grown in different concentrations of NiCl 2 have an identical main chain and side chain conformation. And one Ni 2+ binding with Oδ atom of Asp52 in the active site and coordinating with five water molecules to form hexagonal coordination has been determined for each crystal structure. Based on these results, we have proposed that Ni 2+ quenches the fluorescence of Trp62 and Trp108 due to the binding of Ni 2+ to the active site of lysozyme

  8. Ehrlichia chaffeensis TRP120 Activates Canonical Notch Signaling To Downregulate TLR2/4 Expression and Promote Intracellular Survival

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    Taslima T. Lina

    2016-07-01

    Full Text Available Ehrlichia chaffeensis preferentially targets mononuclear phagocytes and survives through a strategy of subverting innate immune defenses, but the mechanisms are unknown. We have shown E. chaffeensis type 1 secreted tandem repeat protein (TRP effectors are involved in diverse molecular pathogen-host interactions, such as the TRP120 interaction with the Notch receptor-cleaving metalloprotease ADAM17. In the present study, we demonstrate E. chaffeensis, via the TRP120 effector, activates the canonical Notch signaling pathway to promote intracellular survival. We found that nuclear translocation of the transcriptionally active Notch intracellular domain (NICD occurs in response to E. chaffeensis or recombinant TRP120, resulting in upregulation of Notch signaling pathway components and target genes notch1, adam17, hes, and hey. Significant differences in canonical Notch signaling gene expression levels (>40% were observed during early and late stages of infection, indicating activation of the Notch pathway. We linked Notch pathway activation specifically to the TRP120 effector, which directly interacts with the Notch metalloprotease ADAM17. Using pharmacological inhibitors and small interfering RNAs (siRNAs against γ-secretase enzyme, Notch transcription factor complex, Notch1, and ADAM17, we demonstrated that Notch signaling is required for ehrlichial survival. We studied the downstream effects and found that E. chaffeensis TRP120-mediated activation of the Notch pathway causes inhibition of the extracellular signal-regulated kinase 1/2 (ERK1/2 and p38 mitogen-activated protein kinase (MAPK pathways required for PU.1 and subsequent Toll-like receptor 2/4 (TLR2/4 expression. This investigation reveals a novel mechanism whereby E. chaffeensis exploits the Notch pathway to evade the host innate immune response for intracellular survival.

  9. A polycystin-type transient receptor potential (Trp channel that is activated by ATP

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    David Traynor

    2017-02-01

    Full Text Available ATP and ADP are ancient extra-cellular signalling molecules that in Dictyostelium amoebae cause rapid, transient increases in cytosolic calcium due to an influx through the plasma membrane. This response is independent of hetero-trimeric G-proteins, the putative IP3 receptor IplA and all P2X channels. We show, unexpectedly, that it is abolished in mutants of the polycystin-type transient receptor potential channel, TrpP. Responses to the chemoattractants cyclic-AMP and folic acid are unaffected in TrpP mutants. We report that the DIF morphogens, cyclic-di-GMP, GABA, glutamate and adenosine all induce strong cytoplasmic calcium responses, likewise independently of TrpP. Thus, TrpP is dedicated to purinergic signalling. ATP treatment causes cell blebbing within seconds but this does not require TrpP, implicating a separate purinergic receptor. We could detect no effect of ATP on chemotaxis and TrpP mutants grow, chemotax and develop almost normally in standard conditions. No gating ligand is known for the human homologue of TrpP, polycystin-2, which causes polycystic kidney disease. Our results now show that TrpP mediates purinergic signalling in Dictyostelium and is directly or indirectly gated by ATP.

  10. Extracts and compounds active on TRP ion channels from Waldheimia glabra, a ritual medicinal plant from Himalaya.

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    Giorgi, Annamaria; Bassoli, Angela; Borgonovo, Gigliola; Panseri, Sara; Manzo, Alessandra; Pentimalli, Daniela; Schiano Moriello, Aniello; De Petrocellis, Luciano

    2017-08-15

    Waldheimia glabra (Decne.) Regel is a wild plant from the Himalayan Mountains, commonly known as Smooth Ground Daisy. This plant is traditionally used by local populations in religious rituals (incense) or in traditional herbal medicine to treat skin diseases, headache, joint pain and fever. In literature few data are available on the investigation of this aromatic plant. The present work aims at deepening knowledge about the chemical composition of W. glabra extracts and incense, as well as its activity on TRP ion channels. Extracts and incense of W. glabra were analyzed by using HS-SPME GC/MS, GC/MS and NMR analysis. Tests on the activity of W. glabra extracts and isolated compounds (+)-ludartin 1 and B-ring-homo-tonghaosu 2 on TRP channels were also performed. Some extracts and pure compounds from W. glabra showed an interesting activity in terms of efficacy and potency on rat TRPA1, an ion channel involved in several sensory mechanisms, including pungency, environmental irritation and pain perception. Activity is discussed and compared with that of other known TRPA1 natural agonists with different chemical structures. All compounds showed only a negligible inhibition activity on rat TRPM8 ion channel. Our findings demonstrate that W. glabra is involved in the receptor activation mechanism and therefore represents a new natural product potentially useful in pharmaceutical and agrifood research. Copyright © 2017 Elsevier GmbH. All rights reserved.

  11. Structure-activity relationship studies on a Trp dendrimer with dual activities against HIV and enterovirus A71. Modifications on the amino acid.

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    Martínez-Gualda, Belén; Sun, Liang; Rivero-Buceta, Eva; Flores, Aida; Quesada, Ernesto; Balzarini, Jan; Noppen, Sam; Liekens, Sandra; Schols, Dominique; Neyts, Johan; Leyssen, Pieter; Mirabelli, Carmen; Camarasa, María-José; San-Félix, Ana

    2017-03-01

    We have recently described a new class of dendrimers with tryptophan (Trp) on the surface that show dual antiviral activities against HIV and EV71 enterovirus. The prototype compound of this family is a pentaerythritol derivative with 12 Trps on the periphery. Here we complete the structure-activity relationship studies of this family to identify key features that might be significant for the antiviral activity. With this aim, novel dendrimers containing different amino acids (aromatic and non-aromatic), tryptamine (a "decarboxylated" analogue of Trp) and N-methyl Trp on the periphery have been prepared. Dendrimer with N-Methyl Trp was the most active against HIV-1 and HIV-2 while dendrimer with tyrosine was endowed with the most potent antiviral activity against EV71. This tyrosine dendrimer proved to inhibit a large panel of EV71 clinical isolates (belonging to different clusters) in the low nanomolar/high picomolar range. In addition, a new synthetic procedure (convergent approach) has been developed for the synthesis of the prototype and some other dendrimers. This convergent approach proved more efficient (higher yields, easier purification) than the divergent approach previously reported. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  12. Phytochemicals from Ruta graveolens Activate TAS2R Bitter Taste Receptors and TRP Channels Involved in Gustation and Nociception.

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    Mancuso, Giuseppe; Borgonovo, Gigliola; Scaglioni, Leonardo; Bassoli, Angela

    2015-10-16

    Ruta graveolens (rue) is a spontaneous plant in the Mediterranean area with a strong aroma and a very intense bitter taste, used in gastronomy and in folk medicine. From the leaves, stems and fruits of rue, we isolated rutin, rutamarin, three furanocoumarins, two quinolinic alkaloids, a dicoumarin and two long chain ketones. Bitter taste and chemesthetic properties have been evaluated by in vitro assays with twenty receptors of the TAS2R family and four TRP ion channels involved in gustation and nociception. Among the alkaloids, skimmianine was active as a specific agonist of T2R14, whereas kokusaginin did not activate any of the tested receptors. The furanocoumarins activates TAS2R10, 14, and 49 with different degrees of selectivity, as well as the TRPA1 somatosensory ion channel. Rutamarin is an agonist of TRPM5 and TRPV1 and a strong antagonist of TRPM8 ion channels.

  13. Phytochemicals from Ruta graveolens Activate TAS2R Bitter Taste Receptors and TRP Channels Involved in Gustation and Nociception

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    Giuseppe Mancuso

    2015-10-01

    Full Text Available Ruta graveolens (rue is a spontaneous plant in the Mediterranean area with a strong aroma and a very intense bitter taste, used in gastronomy and in folk medicine. From the leaves, stems and fruits of rue, we isolated rutin, rutamarin, three furanocoumarins, two quinolinic alkaloids, a dicoumarin and two long chain ketones. Bitter taste and chemesthetic properties have been evaluated by in vitro assays with twenty receptors of the TAS2R family and four TRP ion channels involved in gustation and nociception. Among the alkaloids, skimmianine was active as a specific agonist of T2R14, whereas kokusaginin did not activate any of the tested receptors. The furanocoumarins activates TAS2R10, 14, and 49 with different degrees of selectivity, as well as the TRPA1 somatosensory ion channel. Rutamarin is an agonist of TRPM5 and TRPV1 and a strong antagonist of TRPM8 ion channels.

  14. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2017-12-19

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  15. Method to produce catalytically active nanocomposite coatings

    Science.gov (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2016-02-09

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  16. Catalytic

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    S.A. Hanafi

    2014-03-01

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

  17. Impaired 8-Hydroxyguanine Repair Activity of MUTYH Variant p.Arg109Trp Found in a Japanese Patient with Early-Onset Colorectal Cancer

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    Kazuya Shinmura

    2014-01-01

    Full Text Available Purpose. The biallelic inactivation of the 8-hydroxyguanine repair gene MUTYH leads to MUTYH-associated polyposis (MAP, which is characterized by colorectal multiple polyps and carcinoma(s. However, only limited information regarding MAP in the Japanese population is presently available. Since early-onset colorectal cancer (CRC is a characteristic of MAP and might be caused by the inactivation of another 8-hydroxyguanine repair gene, OGG1, we investigated whether germline MUTYH and OGG1 mutations are involved in early-onset CRC in Japanese patients. Methods. Thirty-four Japanese patients with early-onset CRC were examined for germline MUTYH and OGG1 mutations using sequencing. Results. Biallelic pathogenic mutations were not found in any of the patients; however, a heterozygous p.Arg19*  MUTYH variant and a heterozygous p.Arg109Trp MUTYH variant were detected in one patient each. The p.Arg19* and p.Arg109Trp corresponded to p.Arg5* and p.Arg81Trp, respectively, in the type 2 nuclear-form protein. The defective DNA repair activity of p.Arg5* is apparent, while that of p.Arg81Trp has been demonstrated using DNA cleavage and supF forward mutation assays. Conclusion. These results suggest that biallelic MUTYH or OGG1 pathogenic mutations are rare in Japanese patients with early-onset CRC; however, the p.Arg19* and p.Arg109Trp MUTYH variants are associated with functional impairments.

  18. Additive Manufacturing of Catalytically Active Living Materials.

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    Saha, Abhijit; Johnston, Trevor G; Shafranek, Ryan T; Goodman, Cassandra J; Zalatan, Jesse G; Storti, Duane W; Ganter, Mark A; Nelson, Alshakim

    2018-04-10

    Living materials, which are composites of living cells residing in a polymeric matrix, are designed to utilize the innate functionalities of the cells to address a broad range of applications such as fermentation and biosensing. Herein, we demonstrate the additive manufacturing of catalytically active living materials (AMCALM) for continuous fermentation. A multi-stimuli-responsive yeast-laden hydrogel ink, based on F127-dimethacrylate, was developed and printed using a direct-write 3D printer. The reversible stimuli-responsive behaviors of the polymer hydrogel inks to temperature and pressure are critical, as they enabled the facile incorporation of yeast cells and subsequent fabrication of 3D lattice constructs. Subsequent photo-cross-linking of the printed polymer hydrogel afforded a robust elastic material. These yeast-laden living materials were metabolically active in the fermentation of glucose into ethanol for 2 weeks in a continuous batch process without significant reduction in efficiency (∼90% yield of ethanol). This cell immobilization platform may potentially be applicable toward other genetically modified yeast strains to produce other high-value chemicals in a continuous biofermentation process.

  19. Transient receptor potential (TRP) A1 activated currents in TRPV1 and cholecystokinin-sensitive cranial visceral afferent neurons.

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    Choi, Myung-Jin; Jin, Zhenhua; Park, Yong Seek; Rhee, Young Kyoung; Jin, Young-Ho

    2011-04-06

    Culinary use of the pungent spices has potential health benefits including a reduction in food intake. Pungent spices often contain ingredients that activate members of the transient receptor potential (TRP) family A1 and evoke pain from capsaicin-sensitive somatosensory neurons. TRPA1 channel have also been identified on cranial visceral afferent neurons but their distribution and functional contributions are poorly understood. Visceral vagal neurons transduce mechanical and chemical signals from peripheral organs to the nucleus tractus solitarii. Many capsaicin-sensitive vagal afferents participate in peripheral satiety signaling that includes cholecystokinin (CCK) sensitive neurons. To assess signaling, the TRPA1 selective agonist allyl isothiocyanate (AITC) was tested together with CCK and capsaicin (200nM), a TRPV1 specific agonist. In isolated nodose neurons, AITC (0.05-0.2mM) evoked concentration-dependent inward currents in 38% of the tested neurons. The TRPA1 specific antagonist HC-030031 (10μM) blocked AITC responses. TRPA1 responses were mixed across neurons that were capsaicin-sensitive and -insensitive. However CCK evoked inward currents only on capsaicin-sensitive neurons and 28% of the CCK-sensitive neurons expressed TRPA1. Our results indicate that TRPA1 is co-expressed with TRPV1 in CCK-sensitive nodose neurons. The findings indicate a potential mechanism by which spices can act within cranial visceral afferent pathways mediating satiety and contribute to the reduction of the food intake associated with spiced diets. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Surface composition of carburized tungsten trioxide and its catalytic activity

    International Nuclear Information System (INIS)

    Nakazawa, M.; Okamoto, H.

    1985-01-01

    The surface composition and electronic structure of carburized tungsten trioxide are investigated using x-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The tungsten carbide concentration in the surface layer increases with the carburization time. The formation of tungsten carbide enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity

  1. Active Component Migration and Catalytic Properties of Nitrogen Modified Composite Catalytic Materials

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    Miaomiao Li

    2018-03-01

    Full Text Available During the catalytic combustion reaction of methane, the migration of the active species on surface facilitates the catalytic reaction, and the element doping can improve the redox performance of the catalyst. Nitrogen-modified perovskite type composite catalysts were prepared by hydrothermal method and then characterized by X-ray diffractometer (XRD, scanning electron microscopy (SEM, Brunauer-Emmett-Teller (BET, temperature-programmed reductions (TPR, and X-ray photoelectron spectra (XPS. The results revealed that nitrogen sources (urea, biuret, melamine, carbohydrazide, and semicarbazide hydrochloride and nitrogen source addition changed the catalytic performance in physical and chemical properties, the migration of reactive species and the catalytic performance. When the addition amount of semicarbazide hydrochloride was three times that of LaCoO3, the composite catalysts had high Co3+/Co2+ (1.39 and Oads/Olat (15.18 and showed the best catalytic performance: the temperatures that are required for achieving methane conversion of 50% and 90% were 277 and 360 °C, which are more effective than noble metal oxides. Moreover, the in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS were applied to elucidate the efficient for CH4 removal and also can further explain the surface reaction mechanism of the composite catalyst during the methane catalytic combustion.

  2. Synthesis and Catalytic Activity of Two New Cyclic Tetraaza Ligands

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    Burkhard König

    2003-05-01

    Full Text Available Two new chiral cyclic tetraaza ligands were synthesized and characterized. Their catalytic activity was tested in the asymmetric addition of diethylzinc to benzaldehyde. The expected secondary alcohol was obtained in moderate yields, but with very low enantioselectivity.

  3. Resolving the Structure of Active Sites on Platinum Catalytic Nanoparticles

    DEFF Research Database (Denmark)

    Chang, Lan Yun; Barnard, Amanda S.; Gontard, Lionel Cervera

    2010-01-01

    Accurate understanding of the structure of active sites is fundamentally important in predicting catalytic properties of heterogeneous nanocatalysts. We present an accurate determination of both experimental and theoretical atomic structures of surface monatomic steps on industrial platinum nanop...

  4. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

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    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  5. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pozan, Gulin Selda, E-mail: gpozan@istanbul.edu.tr [Istanbul University, Faculty of Engineering, Chemical Engineering Department, Avcilar 34320, Istanbul (Turkey)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer {alpha}-Al{sub 2}O{sub 3}, obtained from Bohmite, as a support for enhancing of the activity. Black-Right-Pointing-Pointer The support material for catalytic oxidation. Black-Right-Pointing-Pointer The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO{sub 2} modified with different supports. {alpha}-Al{sub 2}O{sub 3} and {gamma}-Al{sub 2}O{sub 3} obtained from Boehmite, {gamma}-Al{sub 2}O{sub 3} (commercial), SiO{sub 2}, TiO{sub 2} and ZrO{sub 2} were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO{sub 2} was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO{sub 2}/{alpha}-Al{sub 2}O{sub 3}(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 Degree-Sign C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  6. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    International Nuclear Information System (INIS)

    Pozan, Gulin Selda

    2012-01-01

    Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  7. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms...

  8. Post-Translational Modifications of TRP Channels

    Directory of Open Access Journals (Sweden)

    Olaf Voolstra

    2014-04-01

    Full Text Available Transient receptor potential (TRP channels constitute an ancient family of cation channels that have been found in many eukaryotic organisms from yeast to human. TRP channels exert a multitude of physiological functions ranging from Ca2+ homeostasis in the kidney to pain reception and vision. These channels are activated by a wide range of stimuli and undergo covalent post-translational modifications that affect and modulate their subcellular targeting, their biophysical properties, or channel gating. These modifications include N-linked glycosylation, protein phosphorylation, and covalent attachment of chemicals that reversibly bind to specific cysteine residues. The latter modification represents an unusual activation mechanism of ligand-gated ion channels that is in contrast to the lock-and-key paradigm of receptor activation by its agonists. In this review, we summarize the post-translational modifications identified on TRP channels and, when available, explain their physiological role.

  9. ADP-Induced Ca2+Signaling and Proliferation of Rat Ventricular Myofibroblasts Depend on Phospholipase C-Linked TRP Channels Activation Within Lipid Rafts.

    Science.gov (United States)

    Certal, Mariana; Vinhas, Adriana; Barros-Barbosa, Aurora; Ferreirinha, Fátima; Costa, Maria Adelina; Correia-de-Sá, Paulo

    2017-06-01

    Nucleotides released during heart injury affect myocardium electrophysiology and remodeling through P2 purinoceptors activation in cardiac myofibroblasts. ATP and UTP endorse [Ca 2+ ] i accumulation and growth of DDR-2/α-SMA-expressing myofibroblasts from adult rat ventricles via P2Y 4 and P2Y 2 receptors activation, respectively. Ventricular myofibroblasts also express ADP-sensitive P2Y 1 , P2Y 12 , and P2Y 13 receptors as demonstrated by immunofluorescence confocal microscopy and western blot analysis, but little information exists on ADP effects in these cells. ADP (0.003-3 mM) and its stable analogue, ADPßS (100 μM), caused fast [Ca 2+ ] i transients originated from thapsigargin-sensitive internal stores, which partially declined to a plateau sustained by capacitative Ca 2+ entry through transient receptor potential (TRP) channels inhibited by 2-APB (50 μM) and flufenamic acid (100 μM). Hydrophobic interactions between G q/11 -coupled P2Y purinoceptors and TRP channels were suggested by prevention of the ADP-induced [Ca 2+ ] i plateau following PIP 2 depletion with LiCl (10 mM) and cholesterol removal from lipid rafts with methyl-ß-cyclodextrin (2 mM). ADP [Ca 2+ ] i transients were insensitive to P2Y 1 , P2Y 12 , and P2Y 13 receptor antagonists, MRS2179 (10μM), AR-C66096 (0.1 μM), and MRS2211 (10μM), respectively, but were attenuated by suramin and reactive blue-2 (100 μM) which also blocked P2Y 4 receptors activation by UTP. Cardiac myofibroblasts growth and type I collagen production were favored upon activation of MRS2179-sensitive P2Y 1 receptors with ADP or ADPßS (30 μM). In conclusion, ADP exerts a dual role on ventricular myofibroblasts: [Ca 2+ ] i transients are mediated by fast-desensitizing P2Y 4 receptors, whereas the pro-fibrotic effect of ADP involves the P2Y 1 receptor activation. Data also show that ADP-induced capacitative Ca 2+ influx depends on phospholipase C-linked TRP channels opening in lipid raft

  10. Peroxidase-like catalytic activities of ionic metalloporphyrins ...

    Indian Academy of Sciences (India)

    The efficiency order for the various PS-MTPPS was seen to be Co>Mn>Fe, with CoTPPS showing efficiency comparable to that of horseradish peroxidase. The catalytic efficiency was found to be increasing with temperature for all the catalysts. The re-usability of these PS-MTPPS systems for peroxidase-like activity was also ...

  11. Synthesis, characterization and investigation of catalytic activity of ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 124, No. 4, July 2012, pp. 827–834. c Indian Academy of Sciences. Synthesis, characterization and investigation of catalytic activity ..... 2004 J. Catal. 222 107. 8. Rajgopal R, Vetrivel R and Rao B S 2000 Catal. Lett. 65 99. 9. Rao B S, Sreekumar K and Jyothi T M 1998 Indian. Patent 2707/98. 10.

  12. Interplay of PTEN subcellular localization and catalytic activities in vivo

    NARCIS (Netherlands)

    Stumpf, Miriam

    2016-01-01

    This thesis describes the use of mammalian cells, S. cerevisiae and D. rerio to unravel the complex interplay of PTEN subcellular localization and catalytic activities. In Chapter 1 we provide a general introduction to the PI3K/Akt(PKB)/PTEN axis, PTEN phosphatase-dependent and –independent

  13. Functional and catalytic active sites prediction and docking analysis ...

    African Journals Online (AJOL)

    Bioinformatics

    2015-07-01

    Jul 1, 2015 ... African Journal of Biotechnology. Full Length Research Paper. Functional and catalytic active sites prediction and docking analysis of azoreductase enzyme in. Pseudomonas putida with a variety of commercially available azodyes. Bikash Thakuria, Chandra J Singha, Premchand Maisnam and Samrat ...

  14. Role of TRP channels in the cardiovascular system.

    Science.gov (United States)

    Yue, Zhichao; Xie, Jia; Yu, Albert S; Stock, Jonathan; Du, Jianyang; Yue, Lixia

    2015-02-01

    The transient receptor potential (TRP) superfamily consists of a large number of nonselective cation channels with variable degree of Ca(2+)-permeability. The 28 mammalian TRP channel proteins can be grouped into six subfamilies: canonical, vanilloid, melastatin, ankyrin, polycystic, and mucolipin TRPs. The majority of these TRP channels are expressed in different cell types including both excitable and nonexcitable cells of the cardiovascular system. Unlike voltage-gated ion channels, TRP channels do not have a typical voltage sensor, but instead can sense a variety of other stimuli including pressure, shear stress, mechanical stretch, oxidative stress, lipid environment alterations, hypertrophic signals, and inflammation products. By integrating multiple stimuli and transducing their activity to downstream cellular signal pathways via Ca(2+) entry and/or membrane depolarization, TRP channels play an essential role in regulating fundamental cell functions such as contraction, relaxation, proliferation, differentiation, and cell death. With the use of targeted deletion and transgenic mouse models, recent studies have revealed that TRP channels are involved in numerous cellular functions and play an important role in the pathophysiology of many diseases in the cardiovascular system. Moreover, several TRP channels are involved in inherited diseases of the cardiovascular system. This review presents an overview of current knowledge concerning the physiological functions of TRP channels in the cardiovascular system and their contributions to cardiovascular diseases. Ultimately, TRP channels may become potential therapeutic targets for cardiovascular diseases. Copyright © 2015 the American Physiological Society.

  15. Catalytic Activity Control via Crossover between Two Different Microstructures

    KAUST Repository

    Zhou, Yuheng

    2017-09-08

    Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

  16. Engineering Clostridia Neurotoxins with elevated catalytic activity.

    Science.gov (United States)

    Guo, Jiubiao; Pan, Xuehua; Zhao, Yanxiang; Chen, Sheng

    2013-11-01

    BoNT/B and TeNT cleave substrate VAMP2 at the same scissile bond, yet these two toxins showed different efficiency on substrate hydrolysis and had different requirements for the recognition of P2' site of VAMP2, E(78). These differences may be due to their different composition of their substrate recognition pockets in the active site. Swapping of LC/T S1' pocket residue, L(230), with the corresponding isoleucine in LC/B increased LC/T activity by ∼25 fold, while swapping of LC/B S1' pocket residue, S(201), with the corresponding proline in LC/T increased LC/B activity by ∼10 fold. Optimization of both S1 and S1' pocket residues of LC/T, LC/T (K(168)E, L(230)I) elevated LC/T activity by more than 100-fold. The highly active LC/T derivative engineered in this study has the potential to be used as a more effective tool to study mechanisms of exocytosis in central neuron. The LC/B derivative with elevated activity has the potential to be developed into novel therapy to minimize the impact of immunoresistance during BoNT/B therapy. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. TRP channels in kidney disease.

    NARCIS (Netherlands)

    Hsu, Y.J.; Hoenderop, J.G.J.; Bindels, R.J.M.

    2007-01-01

    Mammalian TRP channel proteins form six-transmembrane cation-permeable channels that may be grouped into six subfamilies on the basis of amino acid sequence homology (TRPC, TRPV, TRPM, TRPA, TRPP, and TRPML). Recent studies of TRP channels indicate that they are involved in numerous fundamental cell

  18. How absorbed hydrogen affects the catalytic activity of transition metals.

    Science.gov (United States)

    Aleksandrov, Hristiyan A; Kozlov, Sergey M; Schauermann, Swetlana; Vayssilov, Georgi N; Neyman, Konstantin M

    2014-12-01

    Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H(sub) , may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H(ad) , depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H(sub) , especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Study of the catalytic activity of supported technetium catalysts

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Mikhailenko, I.E.; Pokorovskaya, O.V.

    1985-01-01

    The radioactive d metal 43 Tc 99 has catalytic properties in the synthesis of ammonia. For the purpose of reducing the quantity of the radioactive metal and of increasing the specific surface, the active component was applied to BaTiO 3 and gamma-Al 2 O 3 supports. This paper uses charcoal as a support and a table presents the catalytic activity of the samples during the synthesis of ammonia. X-ray diffractometric investigation of the catalysts was carried out with the use of Cu K /SUB alpha/ radiation. It is shown that the catalysts. The values of the specific rate constants of technetium in the catalysts. The values of the specific rate constants remain practically constant for all the catalyst samples studied, attesting to the absence of a specific metal-support interaction during the synthesis of ammonia

  20. "TRP inflammation" relationship in cardiovascular system.

    Science.gov (United States)

    Numata, Tomohiro; Takahashi, Kiriko; Inoue, Ryuji

    2016-05-01

    Despite considerable advances in the research and treatment, the precise relationship between inflammation and cardiovascular (CV) disease remains incompletely understood. Therefore, understanding the immunoinflammatory processes underlying the initiation, progression, and exacerbation of many cardiovascular diseases is of prime importance. The innate immune system has an ancient origin and is well conserved across species. Its activation occurs in response to pathogens or tissue injury. Recent studies suggest that altered ionic balance, and production of noxious gaseous mediators link to immune and inflammatory responses with altered ion channel expression and function. Among plausible candidates for this are transient receptor potential (TRP) channels that function as polymodal sensors and scaffolding proteins involved in many physiological and pathological processes. In this review, we will first focus on the relevance of TRP channel to both exogenous and endogenous factors related to innate immune response and transcription factors related to sustained inflammatory status. The emerging role of inflammasome to regulate innate immunity and its possible connection to TRP channels will also be discussed. Secondly, we will discuss about the linkage of TRP channels to inflammatory CV diseases, from a viewpoint of inflammation in a general sense which is not restricted to the innate immunity. These knowledge may serve to provide new insights into the pathogenesis of various inflammatory CV diseases and their novel therapeutic strategies.

  1. Enhanced catalytic activity of lipase encapsulated in PCL nanofibers.

    Science.gov (United States)

    Song, Jie; Kahveci, Derya; Chen, Menglin; Guo, Zheng; Xie, Erqing; Xu, Xuebing; Besenbacher, Flemming; Dong, Mingdong

    2012-04-10

    Use of biocatalysis for industrial synthetic chemistry is on the verge of significant growth. Enzyme immobilization as an effective strategy for improving the enzyme activity has emerged from developments especially in nanoscience and nanotechnology. Here, lipase from Burkholderia cepacia (LBC), as an example of the luxuriant enzymes, was successfully encapsulated in polycaprolactone (PCL) nanofibers, proven by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Evaluated in both organic and aqueous medium, the activation factor of the encapsulated enzymes in the hydrolysis reaction was generally higher than that in the transesterification reaction. Enhanced catalytic activities were found when 5-20 w/w % of LBC was loaded. The effect of different solvents pretreatment on the activity of immobilized LBC was also investigated. The highest activation factor was found up to 14 for the sample containing acetone-treated LBC/PCL (10 w/w %). The encapsulated lipase reserved 50% of its original activity after the 10th run in the transesterification reaction in hexane medium. The mechanism of activation of lipase catalytic ability based on active PCL nanofiberous matrix is proposed. © 2012 American Chemical Society

  2. Finely tunable fabrication and catalytic activity of gold multipod nanoparticles.

    Science.gov (United States)

    Choi, Soon; Moon, Youngseo; Yoo, Hyojong

    2016-05-01

    Gold multipod nanoparticles (Au Multipod NPs) containing multi-branches with sharp edges and tips were synthesized in high yield through a facile seed-mediated method using cetyltrimethylammonium bromide (CTAB), Brij35, Au seed nanoparticles, Ag(+) ions, ascorbic acid, and sodium salicylate. The branch lengths of Au Multipod NPs were finely controlled by adjusting the molar ratio of mixed surfactants, and in particular by changing the amount of sodium salicylate. A formation mechanism for the star-shaped topologies was proposed and experimentally proved. The catalytic activity of the synthesized Au Multipod NPs was evaluated in ethanol electrooxidation reaction. The dependence of the catalytic performances on the nanostructural morphology was investigated. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    DEFF Research Database (Denmark)

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

    2006-01-01

    Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward...... the catalytic surface through the annulus between the tubes, and the gas is sampled close to the surface by the capillary. The influence of various design parameters on the lateral resolution and sensitivity of the measurements is investigated. It is found that the cuter diameter of the annulus sets the upper......, the limits of the range in reaction rate, which can be Studied are estimated. (c) 2005 Elsevier B.V. All rights reserved....

  4. Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y.; Grass, M.E.; Kuhn, J.N.; Tao, F.; Habas, S.E.; Huang, W.; Yang, P.; Somorjai, G.A.

    2009-02-21

    Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, horns and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl

  5. Copper-induced activation of TRP channels promotes extracellular calcium entry and activation of CaMs and CDPKs leading to copper entry and membrane depolarization in Ulva compressa

    Directory of Open Access Journals (Sweden)

    Melissa eGómez

    2015-03-01

    Full Text Available In order to identify channels involved in membrane depolarization, Ulva compressa was incubated with agonists of TRP channels C5, A1 and V1 and the level of intracellular calcium was detected. Agonists of TRPC5, A1 and V1 induced increases in intracellular calcium at 4, 9 and 12 min of exposure, respectively, and antagonists of TRPC5, A1 and V1 corresponding to SKF-96365 (SKF, HC-030031 (HC and capsazepin (CPZ, respectively, inhibited calcium increases indicating that functional TRPs exist in U. compressa. In addition, copper excess induced increases in intracellular calcium at 4, 9 and 12 min which were inhibited by SKF, HC and CPZ, respectively, indicating that copper activate TRPC5, A1 and V1 channels. Moreover, copper-induced calcium increases were inhibited by EGTA, a non-permeable calcium chelating agent, but not by thapsigargin, an inhibitor of endoplasmic reticulum (ER calcium ATPase, indicating that activation of TRPs leads to extracellular calcium entry. Furthermore, copper-induced calcium increases were not inhibited by W-7, an inhibitor of CaMs, and staurosporine, an inhibitor of CDPKs, indicating that extracellular calcium entry did not require CaMs and CDPKs activation. In addition, copper induced membrane depolarization events at 4, 8 and 11 min and these events were inhibited by SKF, HC, CPZ and bathocuproine, a specific copper chelating agent, indicating copper entry through TRP channels leading to membrane depolarization. Moreover, membrane depolarization events were inhibited by W-7 and staurosporine, indicating that CaMs and CDPKs are required in order to activate TRPs to allow copper entry. Thus, light-dependent copper-induced activation TRPC5, A1 and V1 promotes extracellular calcium entry leading to activation of CaMs and CDPKs which, in turn, promotes copper entry through these TRP channels leading to membrane depolarization.

  6. Catalytically and biologically active silver nanoparticles synthesized using essential oil

    Science.gov (United States)

    Vilas, Vidya; Philip, Daizy; Mathew, Joseph

    2014-11-01

    There are numerous reports on phytosynthesis of silver nanoparticles and various phytochemicals are involved in the reduction and stabilization. Pure explicit phytosynthetic protocol for catalytically and biologically active silver nanoparticles is of importance as it is an environmentally benign green method. This paper reports the use of essential oil of Myristica fragrans enriched in terpenes and phenyl propenes in the reduction and stabilization. FTIR spectra of the essential oil and the synthesized biogenic silver nanoparticles are in accordance with the GC-MS spectral analysis reports. Nanosilver is initially characterized by an intense SPR band around 420 nm, followed by XRD and TEM analysis revealing the formation of 12-26 nm sized, highly pure, crystalline silver nanoparticles. Excellent catalytic and bioactive potential of the silver nanoparticles is due to the surface modification. The chemocatalytic potential of nanosilver is exhibited by the rapid reduction of the organic pollutant, para nitro phenol and by the degradation of the thiazine dye, methylene blue. Significant antibacterial activity of the silver colloid against Gram positive, Staphylococcus aureus (inhibition zone - 12 mm) and Gram negative, Escherichia coli (inhibition zone - 14 mm) is demonstrated by Agar-well diffusion method. Strong antioxidant activity of the biogenic silver nanoparticles is depicted through NO scavenging, hydrogen peroxide scavenging, reducing power, DPPH and total antioxidant activity assays.

  7. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe

    2018-01-22

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  8. Mechanisms of Thermosensation in TRP Channels

    Science.gov (United States)

    Talavera, Karel; Voets, Thomas; Nilius, Bernd

    The transient receptor potential (TRP) superfamily encompasses a large number of cationic channels that are modulated by a wide variety of physical and chemical stimuli. A notorious subgroup of TRP channels, dubbed thermoTRPs, shows a dramatic dependence on temperature, which can be up to tenfold higher than that of classical ionic channels. Consequently, some thermoTRPs are thought to have a prominent role in the mechanisms of thermosensation and thermoregulation. However, the mechanisms underlying the high temperature sensitivity of thermoTRP activation are, for the most part, obscure. Only four out of the nine thermoTRPs known so far are sufficiently well characterised to allow a comprehensive model to be put forward. Temperature modulates the gating of TRPM8, TRPV1, TRPM4 and TRPM5 by shifting the voltage dependence of channel activation towards more negative potentials, which can be accounted for by a model in which voltage-dependent gating is directly affected by temperature. Heat activation of TRPV3 seems to be consistent with this mechanism, although a modification of the pore may also take place. For TRPV4, it has been proposed that an, as yet unidentified, diffusible ligand mediates activation by heat. The mechanisms for TRPV2, TRPA1 and TRPM2 are still unknown.

  9. TRP channel-associated factors are a novel protein family that regulates TRPM8 trafficking and activity.

    NARCIS (Netherlands)

    Gkika, D.; Lemonnier, L.; Shapovalov, G.; Gordienko, D.; Poux, C.; Bernardini, M.; Bokhobza, A.; Bidaux, G.; Degerny, C.; Verreman, K.; Guarmit, B.; Benahmed, M.; Launoit, Y. de; Bindels, R.J.M.; Fiorio Pla, A.; Prevarskaya, N.

    2015-01-01

    TRPM8 is a cold sensor that is highly expressed in the prostate as well as in other non-temperature-sensing organs, and is regulated by downstream receptor-activated signaling pathways. However, little is known about the intracellular proteins necessary for channel function. Here, we identify two

  10. Triggering activity of catalytic rod-like supramolecular polymers.

    Science.gov (United States)

    Huerta, Elisa; van Genabeek, Bas; Lamers, Brigitte A G; Koenigs, Marcel M E; Meijer, E W; Palmans, Anja R A

    2015-02-23

    Supramolecular polymers based on benzene-1,3,5-tricarboxamides (BTAs) functionalized with an L- or D-proline moiety display high catalytic activity towards aldol reactions in water. High turnover frequencies (TOF) of up to 27×10(-4) s(-1) and excellent stereoselectivities (up to 96% de, up to 99% ee) were observed. In addition, the catalyst could be reused and remained active at catalyst loadings and substrate concentrations as low as 0.1 mol % and 50 mM, respectively. A temperature-induced conformational change in the supramolecular polymer triggers the high activity of the catalyst. The supramolecular polymer's helical sense in combination with the configuration of the proline (L- or D-) is responsible for the observed selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Direct instrumental identification of catalytically active surface sites

    Science.gov (United States)

    Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

    2017-09-01

    The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

  12. Trp-999 of beta-galactosidase (Escherichia coli) is a key residue for binding, catalysis, and synthesis of allolactose, the natural lac operon inducer.

    Science.gov (United States)

    Huber, Reuben E; Hakda, Shamina; Cheng, Calvino; Cupples, Claire G; Edwards, Robert A

    2003-02-18

    Trp-999 is a key residue for the action of beta-galactosidases (Escherichia coli). Several site specific substitutions (Phe, Gly, Tyr, Leu) for Trp-999 were made. Each substitution caused greatly decreased affinities for substrates and inhibitors that bind in the "shallow" mode, while the affinities of inhibitors that bind in the "deep" mode were not decreased nearly as much. This shows that Trp-999 is important for binding in the shallow mode. The residue is also very important for binding glucose to galactosyl-beta-galactosidase (as a transgalactosidic acceptor). Substitution greatly diminished the affinity for glucose. Substitutions also changed the activation thermodynamics and, subsequently, the rates of the catalytic reactions. The enthalpies of activation of the glycolytic bond cleavage step (galactosylation, k(2)) became less favorable while the entropies of activation of that step became more favorable as a result of the substitutions. Differing magnitudes of these enthalpic and entropic effects with ONPG as compared to PNPG caused the k(2) values for ONPG to decrease but to increase for PNPG. The enthalpies of activation for the common hydrolytic step (degalactosylation, k(3)) increased while the entropies of activation for this step did not change much. As a result, k(3) became small and rate determining for each substituted enzyme. The substitutions caused the rate constant (k(4)) of the transgalactosidic acceptor reactions with glucose (for the formation of allolactose) to become much larger and of the same order of magnitude as the normally large rate constants for transgalactosidic acceptor reactions with small alcohols. This is probably because glucose can approach with less restriction in the absence of Trp-999. However, since glucose binds very poorly to the galactosyl-beta-galactosidases with substitutions for Trp-999, the proportion of lactose molecules converted to allolactose is small. Thus, Trp-999 is also important for ensuring that an

  13. Catalytic activity of nuclease P1: Experiment and theory

    International Nuclear Information System (INIS)

    Miller, J.H.; Falcone, J.M.; Shibata, M.; Box, H.C.

    1994-10-01

    Nuclease P1 from Penicillium citrinum is a zinc dependent glyco-enzyme that recognizes single stranded DNA and RNA as substrates and hydrolyzes the phosphate ester bond. Nuclease Pl seems to recognize particular conformations of the phosphodiester backbone and shows significant variation in the rate of hydrolytic activity depending upon which nucleosides are coupled by the phosphodiester bond. The efficiency of nuclease Pl in hydrolyzing the phosphodiester bonds of a substrate can be altered by modifications to one of the substrate bases induced by ionizing radiation or oxidative stress. Measurements have been made of the effect of several radiation induced lesions on the catalytic rate of nuclease Pl. A model of the structure of the enzyme has been constructed in order to better understand the binding and activity of this enzyme on various ssDNA substrates

  14. Studies Relevent to Catalytic Activation Co & other small Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Peter C

    2005-02-22

    Detailed annual and triannual reports describing the progress accomplished during the tenure of this grant were filed with the Program Manager for Catalysis at the Office of Basic Energy Sciences. To avoid unnecessary duplication, the present report will provide a brief overview of the research areas that were sponsored by this grant and list the resulting publications and theses based on this DOE supported research. The scientific personnel participating in (and trained by) this grant's research are also listed. Research carried out under this DOE grant was largely concerned with the mechanisms of the homogeneous catalytic and photocatalytic activation of small molecules such as carbon monoxide, dihydrogen and various hydrocarbons. Much of the more recent effort has focused on the dynamics and mechanisms of reactions relevant to substrate carbonylations by homogeneous organometallic catalysts. A wide range of modern investigative techniques were employed, including quantitative fast reaction methodologies such as time-resolved optical (TRO) and time-resolved infrared (TRIR) spectroscopy and stopped flow kinetics. Although somewhat diverse, this research falls within the scope of the long-term objective of applying quantitative techniques to elucidate the dynamics and understand the principles of mechanisms relevant to the selective and efficient catalytic conversions of fundamental feedstocks to higher value materials.

  15. Environmental Toxin Acrolein Alters Levels of Endogenous Lipids, Including TRP Agonists: A Potential Mechanism for Headache Driven by TRPA1 Activation.

    Science.gov (United States)

    Leishman, Emma; Kunkler, Phillip E; Manchanda, Meera; Sangani, Kishan; Stuart, Jordyn M; Oxford, Gerry S; Hurley, Joyce H; Bradshaw, Heather B

    2017-01-01

    Exposure to airborne toxins can trigger headaches, but the mechanisms are not well understood. Some environmental toxins, such as acrolein, activate transient receptor potential ankyrin 1 (TRPA1), a receptor involved in pain sensation that is highly expressed in the trigeminovascular system. It has been shown in rat models that repeated exposure to acrolein induces trigeminovascular sensitization to both TRPA1 and TRP vanilloid 1 (TRPV1) agonists, a phenomenon linked to headache. In this study, we test the hypothesis that the sensitization of trigeminovascular responses in rats after acrolein exposure via inhalation is associated with changes in levels of endogenous lipids, including TRPV1 agonists, in the trigeminal ganglia, trigeminal nucleus, and cerebellum. Lipidomics analysis of 80 lipids was performed on each tissue after acute acrolein, chronic acrolein, or room air control. Both acute and chronic acrolein exposure drove widespread alterations in lipid levels. After chronic acrolein exposure, levels of all 6 N -acyl ethanolamines in the screening library, including the endogenous cannabinoid and TRPV1 agonist, N -arachidonoyl ethanolamine, were elevated in trigeminal tissue and in the cerebellum. This increase in TRPV1 ligands by acrolein exposure may indicate further downstream signaling, in that we also show here that a combination of these TRPV1 endogenous agonists increases the potency of the individual ligands in TRPV1-HEK cells. In addition to these TRPV1 agonists, 3 TRPV3 antagonists, 4 TRPV4 agonists, and 25 orphan lipids were up and down regulated after acrolein exposure. These data support the hypothesis that lipid signaling may represent a mechanism by which repeated exposure to the TRPA1 agonist and environmental toxin, acrolein, drives trigeminovascular sensitization.

  16. Environmental toxin acrolein alters levels of endogenous lipids, including TRP agonists: A potential mechanism for headache driven by TRPA1 activation

    Directory of Open Access Journals (Sweden)

    Emma Leishman

    2017-01-01

    Full Text Available Exposure to airborne toxins can trigger headaches, but the mechanisms are not well understood. Some environmental toxins, such as acrolein, activate transient receptor potential ankyrin 1 (TRPA1, a receptor involved in pain sensation that is highly expressed in the trigeminovascular system. It has been shown in rat models that repeated exposure to acrolein induces trigeminovascular sensitization to both TRPA1 and TRP vanilloid 1 (TRPV1 agonists, a phenomenon linked to headache. In this study, we test the hypothesis that the sensitization of trigeminovascular responses in rats after acrolein exposure via inhalation is associated with changes in levels of endogenous lipids, including TRPV1 agonists, in the trigeminal ganglia, trigeminal nucleus, and cerebellum. Lipidomics analysis of 80 lipids was performed on each tissue after acute acrolein, chronic acrolein, or room air control. Both acute and chronic acrolein exposure drove widespread alterations in lipid levels. After chronic acrolein exposure, levels of all 6 N-acyl ethanolamines in the screening library, including the endogenous cannabinoid and TRPV1 agonist, N-arachidonoyl ethanolamine, were elevated in trigeminal tissue and in the cerebellum. This increase in TRPV1 ligands by acrolein exposure may indicate further downstream signaling, in that we also show here that a combination of these TRPV1 endogenous agonists increases the potency of the individual ligands in TRPV1-HEK cells. In addition to these TRPV1 agonists, 3 TRPV3 antagonists, 4 TRPV4 agonists, and 25 orphan lipids were up and down regulated after acrolein exposure. These data support the hypothesis that lipid signaling may represent a mechanism by which repeated exposure to the TRPA1 agonist and environmental toxin, acrolein, drives trigeminovascular sensitization. Keywords: Lipidomics, Endogenous cannabinoid, TRPA1, TRPV1, Lipoamine, Acrolein, Migraine

  17. ACh-induced depolarization in inner ear artery is generated by activation of a TRP-like non-selective cation conductance and inactivation of a potassium conductance.

    Science.gov (United States)

    Ma, Ke-Tao; Guan, Bing-Cai; Yang, Yu-Qin; Zhao, Hui; Jiang, Zhi-Gen

    2008-05-01

    Adequate cochlear blood supply by the spiral modiolar artery (SMA) is critical for normal hearing. ACh may play a role in neuroregulation of the SMA but several key issues including its membrane action mechanisms remain poorly understood. Besides its well-known endothelium-dependent hyperpolarizing action, ACh can induce a depolarization in vascular cells. Using intracellular and whole-cell recording techniques on cells in guinea pig in vitro SMA, we studied the ionic mechanism underlying the ACh-depolarization and found that: (1) ACh induced a DAMP-sensitive depolarization when intermediate conductance KCa channels were blocked by charybdotoxin or nitrendipine. The ACh-depolarization was associated with a decrease in input resistance (R(input)) in high membrane potential (V(m)) ( approximately -40 mV) cells but with no change or an increase in R input in low Vm ( approximately -75 mV) cells. ACh-depolarization was attenuated by background membrane depolarization from approximately -70 mV in the majority of cells; (2) ACh-induced inward current in smooth muscle cells embedded in a SMA segment often showed a U-shaped I/V curve, the reversal potential of its two arms being near EK and 0 mV, respectively; (3) ACh-depolarization was reduced by low Na+, zero K+ or 20mM K+ bath solutions; (4) ACh-depolarization was inhibited by La3+ in all cells tested, by 4-AP and flufenamic acid in low Vm cells, but was not sensitive to Cd2+, Ni2+, nifedipine, niflumic acid, DIDS, IAA94, linopirdine or amiloride. We conclude that ACh-induced vascular depolarization was generated mainly by activation of a TRP-like non-selective cation channel and by inactivation of an inward rectifier K+ channel.

  18. TRP channels: sensors and transducers of gasotransmitter signals

    Directory of Open Access Journals (Sweden)

    Nobuaki eTakahashi

    2012-08-01

    Full Text Available The transient receptor potential (trp gene superfamily encodes cation channels that act as multimodal sensors for a wide variety of stimuli from outside and inside the cell. Upon sensing, they transduce electrical and Ca2+ signals via their cation channel activities. These functional features of TRP channels allow the body to react and adapt to different forms of environmental changes. Indeed, members of one class of TRP channels have emerged as sensors of gaseous messenger molecules that control various cellular processes. Nitric oxide (NO, a vasoactive gaseous molecule, regulates TRP channels directly via cysteine S-nitrosylation or indirectly via cGMP/PKG-dependent phosphorylation. Recent studies have revealed that changes in the availability of molecular oxygen (O2 also control the activation of TRP channels. Anoxia induced by O2-glucose deprivation and severe hypoxia (1% O2 activates TRPM7 and TRPC6, respectively, whereas TRPA1 has recently been identified as a novel sensor of hyperoxia and mild hypoxia (15% O2 in vagal and sensory neurons. TRPA1 also detects other gaseous molecules such as hydrogen sulfide (H2S and carbon dioxide (CO2. In this review, we focus on how signaling by gaseous molecules is sensed and integrated by TRP channels.

  19. N-terminal Ile-Orn- and Trp-Orn-motif repeats enhance membrane interaction and increase the antimicrobial activity of apidaecins against Pseudomonas aeruginosa

    Directory of Open Access Journals (Sweden)

    Martina E. C. Bluhm

    2016-05-01

    Full Text Available The Gram-negative bacterium Pseudomonas aeruginosa is a life-threatening nosocomial pathogen due to its generally low susceptibility towards antibiotics. Furthermore, many strains have acquired resistance mechanisms requiring new antimicrobials with novel mechanisms to enhance treatment options. Proline-rich antimicrobial peptides, such as the apidaecin analog Api137, are highly efficient against various Enterobacteriaceae infections in mice, but less active against P. aeruginosa in vitro. Here, we extended our recent work by optimizing lead peptides Api755 (gu-OIORPVYOPRPRPPHPRL-OH; gu = N,N,N’,N’-tetramethylguanidino, O = L-ornithine and Api760 (gu-OWORPVYOPRPRPPHPRL-OH by incorporation of Ile-Orn- and Trp-Orn-motifs, respectively. Api795 (gu-O(IO2RPVYOPRPRPPHPRL-OH and Api794 (gu O(WO3RPVYOPRPRPPHPRL-OHwere highly active against P. aeruginosa with minimal inhibitory concentrations of 8-16 µg/mL and 8-32 µg/mL against E. coli and K. pneumoniae. Assessed using a quartz crystal microbalance, these peptides inserted into a membrane layer and the surface activity increased gradually from Api137, over Api795, to Api794. This mode of action was confirmed by transmission electron microscopy indicating some membrane damage only at the high peptide concentrations. Api794 and Api795 were highly stable against serum proteases (half-life times > 5 h and non-hemolytic to human erythrocytes at peptide concentrations of 0.6 g/L. At this concentration, Api795 reduced the cell viability of HeLa cells only slightly, whereas the IC50 of Api794 was 0.23 ± 0.09 g/L. Confocal fluorescence microscopy revealed no colocalization of 5(6-carboxyfluorescein-labeled Api794 or Api795 with the mitochondria, excluding interactions with the mitochondrial membrane. Interestingly, Api795 was localized in endosomes, whereas Api794 was present in endosomes and the cytosol. This was verified using flow cytometry showing a 50 % higher uptake of Api794 in HeLa cells compared

  20. Catalytic oxidation of NO to NO2 on activated carbon

    International Nuclear Information System (INIS)

    Zhancheng Guo; Yusheng Xie

    2001-01-01

    Catalytic oxidation of NO to NO 2 over activated carbons PAN-ACF, pitch-ACF and coconut-AC at room temperature (30 o C) were studied to develop a method based on oxidative removal of NO from flue gases. For a dry gas, under the conditions of a gas space flow rate 1500 h -1 in the presence of oxygen of 2-20% in volume concentration, the activated coconut carbon with a surface area 1200 m 2 /g converted about 81-94% of NO with increasing oxygen concentration, the pitch based activated carbon fiber with a surface area 1000 m 2 /g about 44-75%, and the polyacrylonitrile-based activated carbon fiber with a surface area 1810 m 2 /g about 25-68%. The order of activity of the activated carbons was PAN-ACF c P NO P O2 β (F/W), where β is 0.042, 0.16, 0.31 for the coconut-AC, the pitch-ACF and the PAN-ACF respectively, and k c is 0.94 at 30 o C. (author)

  1. [Effect Of Polyelectrolytes on Catalytic Activity of Alcohol Dehydrogenase].

    Science.gov (United States)

    Dubrovsky, A V; Musina, E V; Kim, A L; Tikhonenko, S A

    2016-01-01

    Fluorescent and optical spectroscopy were used to study the interaction of alcohol dehydrogenase (ADH) with negatively charged polystyrene sulfonate (PSS) and dextran sulfate (DS), as well as positively charged poly(diallyldimethylammonium) (PDADMA). As found, DS and PDADMA did not affect the structural and catalytic enzyme properties. In contrast, PSS slightly decreased the protein self-fluorescence over 1 h of incubation, which is associated with partial destruction of its quaternary (globular) structure. Investigation of the ADH activity with and without PSS showed its dependency on the incubation time and the PSS presence. Sodium chloride (2.0 M and 0.2 M) or ammonium sulfate (0.1 M) added to the reaction mixture did not completely protect the enzyme quaternary structure from the PSS action. However ammonium sulfate or 0.2 M sodium chloride stabilized the enzyme and partially inhibited the negative PSS effect.

  2. Synthesis, characterization and catalytic activity of CdO nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Singh, G., E-mail: gsingh4us@yahoo.com [Department of Chemistry, D.D.U. Gorakhpur University, Gorakhpur 273009 (India); Kapoor, I.P.S.; Dubey, Reena; Srivastava, Pratibha [Department of Chemistry, D.D.U. Gorakhpur University, Gorakhpur 273009 (India)

    2011-02-15

    In this paper, we report the synthesis of nanocrystalline cadmium oxide (CdO) and its characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Its catalytic activity was investigated on the thermal decomposition of 1,2,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), ammonium perchlorate (AP), hydroxyl terminated polybutadiene (HTPB) and composite solid propellants (CSPs) using thermogravimetric analysis (TG), simultaneous thermogravimerty and differential scanning calorimetry (TG-DSC) and ignition delay measurements. Kinetics of thermal decomposition of AP + CdO has also been investigated using model free (isoconversional) and model-fitting approaches which have been applied to data for isothermal TG decomposition. All these studies show enhancement in the rate of decomposition of AP, HTPB and CSPs but no effect on HMX. The burning rate of CSPs has also been found to be increased with CdO nanocrystals.

  3. Role of Zinc in Catalytic Activity of Carbonic Anhydrase IX

    Science.gov (United States)

    Tu, Chingkuang; Foster, Lauren; Alvarado, Andrea; McKenna, Robert; Silverman, David N.; Frost, Susan C.

    2012-01-01

    The carbonic anhydrases (CAs) in the α class are zinc-dependent metalloenzymes. Previous studies have reported that recombinant forms of carbonic anhydrase IX (CAIX), a membrane-bound form of CA expressed in solid tumors, appear to be activated by low levels of zinc independent of its well-studied role at the catalytic site. In this study, we sought to determine if CAIX is stimulated by zinc in its native environment. MDA-MB-231 breast cancer cells express CAIX in response to hypoxia. We compared CAIX activity associated with membrane ghosts isolated from hypoxic cells with that in intact hypoxic cells. We measured CA activity directly using 18O exchange from 13CO2 into water determined by membrane inlet mass spectrometry. In membrane ghosts, there was little effect of zinc at low concentrations on CAIX activity, although at high concentration zinc was inhibitory. In intact cells, zinc had no significant effect on CAIX activity. This suggests that there is an appreciable decrease in sensitivity to zinc when CAIX is in its natural membrane milieu compared to the purified forms. PMID:22465027

  4. Bacillus Pumilus Cyanide Dihydratase Mutants with Higher Catalytic Activity

    Directory of Open Access Journals (Sweden)

    Mary A Crum

    2016-08-01

    Full Text Available Cyanide degrading nitrilases are noted for their potential to detoxify industrial wastewater contaminated with cyanide. However, such application would benefit from an improvement to characteristics such as their catalytic activity and stability. Following error-prone PCR for random mutagenesis, several cyanide dihydratases mutants from Bacillus pumilus were isolated based on improved catalysis. Four point mutations, K93R, D172N, A202T and E327K were characterized and their effects on kinetics, thermostability and pH tolerance were studied. K93R and D172N increased the enzyme’s thermostability whereas E327K mutation had a less pronounced effect on stability. The D172N mutation also increased the affinity of the enzyme for its substrate at pH 7.7 but lowered its kcat. However, the A202T mutation, located in the dimerization or the A surface, destabilized the protein and abolished its activity. No significant effect on activity at alkaline pH was observed for any of the purified mutants. These mutations help confirm the model of CynD and are discussed in the context of the protein-protein interfaces leading to the protein quaternary structure.

  5. Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed.

    Science.gov (United States)

    Paul, Indrajit; Goswami, Abir; Mittal, Nikita; Schmittel, Michael

    2018-01-02

    Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N pyr →ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider-on-deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

    Science.gov (United States)

    Sherly, K. B.; Rakesh, K.

    2014-01-01

    Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl2ṡ8H2O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

  7. Pair Interaction of Catalytical Sphere Dimers in Chemically Active Media

    Directory of Open Access Journals (Sweden)

    Jing-Min Shi

    2018-01-01

    Full Text Available We study the pair dynamics of two self-propelled sphere dimers in the chemically active medium in which a cubic autocatalytic chemical reaction takes place. Concentration gradient around the dimer, created by reactions occurring on the catalytic sphere surface and responsible for the self-propulsion, is greatly influenced by the chemical activities of the environment. Consequently, the pair dynamics of two dimers mediated by the concentration field are affected. In the particle-based mesoscopic simulation, we combine molecular dynamics (MD for potential interactions and reactive multiparticle collision dynamics (RMPC for solvent flow and bulk reactions. Our results indicate three different configurations between a pair of dimers after the collision, i.e., two possible scenarios of bound dimer pairs and one unbound dimer pair. A phase diagram is sketched as a function of the rate coefficients of the environment reactions. Since the pair interactions are the basic elements of larger scale systems, we believe the results may shed light on the understanding of the collective dynamics.

  8. Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Sherly, K. B.; Rakesh, K. [Mahatma Gandhi University Regional Research Center in Chemistry, Department of Chemistry, Mar Athanasius College, Kothamangalam-686666, Kerala (India)

    2014-01-28

    Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl{sub 2}⋅8H{sub 2}O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

  9. Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

    Science.gov (United States)

    Ranchani, A. Amala Jeya; Parthasarathy, V.; Devi, A. Anitha; Meenarathi, B.; Anbarasan, R.

    2017-11-01

    A novel Ni complexed aminoclay (AC) catalyst was prepared by complexation method followed by reduction reaction. Various analytical techniques such as FTIR spectroscopy, UV-visible spectroscopy, DSC, TGA, SEM, HRTEM, EDX, XPS and WCA measurement are used to characterize the synthesized material. The AC-Ni catalyst system exhibited improved thermal stability and fiber-like morphology. The XPS results declared the formation of Ni nanoparticles. Thus, synthesized catalyst was tested towards the Schiff base formation reaction between various bio-medical polymers and aniline under air atmosphere at 85 °C for 24 h. The catalytic activity of the catalyst was studied by varying the % weight loading of the AC-Ni system towards the Schiff base formation. The Schiff base formation was quantitatively calculated by the 1H-NMR spectroscopy. While increasing the % weight loading of the AC-Ni catalyst, the % yield of Schiff base was also increased. The k app and Ti values were determined for the reduction of indole and α-terpineol in the presence of AC-Ni catalyst system. The experimental results were compared with the literature report.

  10. Catalytic activity of catalysts for steam reforming reaction. Contract research

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Hirofumi; Inagaki, Yoshiyuki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment

    2003-05-01

    Japan Atomic Energy Research Institute has been developing a hydrogen production system by means of steam reforming of methane (chemical reation: CH{sub 4} + H{sub 2}O = CO + 3H{sub 2}) coupling with High Temperature Engineering Test Reactor (HTTR) to demonstrate effectiveness of high-temperature nuclear heat utilization. Prior to construction of HTTR hydrogen production system, a mock-up test facility with a full-scale reaction tube was constructed to investigate transient behavior of the hydrogen production system an establish system controllability. In order to predict transient behavior and hydrogen productivity of the hydrogen production system, it is important to estimate the reaction characteristics under the same temperature and pressure conditions as those of HTTR hydrogen production system. For the purpose of investigate an apparent activation energy of catalysts, catalytic activity test using small apparatus was carried out under the condition of methane flow rate from 1.18 x 10{sup -3} to 3.19 x 10{sup -3} mol/s, temperature from 500 to 900degC, pressure from 1.1 to 4.1MPa, and mol ratio of steam to methane from 2.5 to 3.5. It was confirmed that apparent activation energies of two kinds of Ni catalysts which are to be used in the mock-up test were 51.7 and 57.4kJ/mol, respectively, and reaction rate constants were propositional to the value from P{sup -0.15} to P{sup -0.33}. (author)

  11. TrpA1 activation in peripheral sensory neurons underlies the ionic basis of pain hypersensitivity in response to vinca alkaloids.

    Directory of Open Access Journals (Sweden)

    Nina Boiko

    Full Text Available Chemotherapy induced peripheral neuropathy (CIPN, a side effect of many anti-cancer drugs including the vinca alkaloids, is characterized by a severe pain syndrome that compromises treatment in many patients. Currently there are no effective treatments for this pain syndrome except for the reduction of anti-cancer drug dose. Existing data supports the model that the pain associated with CIPN is the result of anti-cancer drugs augmenting the function of the peripheral sensory nociceptors but the cellular mechanisms underlying the effects of anti-cancer drugs on sensory neuron function are not well described. Studies from animal models have suggested a number of disease etiologies including mitotoxicity, axonal degeneration, immune signaling, and reduced sensory innervations but these outcomes are the result of prolonged treatment paradigms and do not necessarily represent the early formative events associated with CIPN. Here we show that acute exposure to vinca alkaloids results in an immediate pain syndrome in both flies and mice. Furthermore, we demonstrate that exposure of isolated sensory neurons to vinca alkaloids results in the generation of an inward sodium current capable of depolarizing these neurons to threshold resulting in neuronal firing. These neuronal effects of vinca alkaloids require the transient receptor potential ankyrin-1 (TrpA1 channel, and the hypersensitization to painful stimuli in response to the acute exposure to vinca alkaloids is reduced in TrpA1 mutant flies and mice. These findings demonstrate the direct excitation of sensory neurons by CIPN-causing chemotherapy drugs, and identify TrpA1 as an important target during the pathogenesis of CIPN.

  12. The catalytic domain of acanthamoeba myosin I heavy chain kinase. II. Expression of active catalytic domain and sequence homology to p21-activated kinase (PAK).

    Science.gov (United States)

    Brzeska, H; Szczepanowska, J; Hoey, J; Korn, E D

    1996-10-25

    Acanthamoeba myosin I heavy chain (MIHC) kinase is a monomeric 97-kDa protein that is activated by binding to acidic phospholipids or by autophosphorylation. Activation by phospholipids is inhibited by Ca2+-calmodulin. In the accompanying paper (Brzeska, H., Martin, B., and Korn, E. D. (1996) J. Biol. Chem. 271, 27049-27055), we identified the catalytic domain as the COOH-terminal 35 kDa produced by trypsin digestion of phosphorylated MIHC kinase. In this paper, we report the cloning and sequencing of the corresponding cDNA and expression of fully active catalytic domain. The expressed catalytic domain has substrate specificity similar to that of native kinase and resistance to trypsin similar to that of fully phosphorylated MIHC kinase. MIHC kinase catalytic domain has only 25% sequence identity to the catalytic domain of protein kinase A and similarly low sequence identity to the catalytic domains of protein kinase C- and calmodulin-dependent kinases, but 50% sequence identity and 70% similarity to the p21-activated kinase (PAK) and STE20 family of kinases. This suggests that MIHC kinase is (at least) evolutionarily related to the PAK family, whose activities are regulated by small GTP-binding proteins. The homology includes the presence of a potential MIHC kinase autophosphorylation site as well as conserved Tyr and Ser/Thr residues in the region corresponding to the P+1 loop of protein kinase A. A synthetic peptide corresponding to this region of MIHC kinase is phosphorylated by both the expressed catalytic domain and native MIHC kinase.

  13. Catalytic Promiscuity of the Radical S-adenosyl-L-methionine Enzyme NosL.

    Science.gov (United States)

    Ding, Wei; Ji, Xinjian; Li, Yongzhen; Zhang, Qi

    2016-01-01

    Catalytic promiscuity plays a key role in enzyme evolution and the acquisition of novel biological functions. Because of the high reactivity of radical species, in our view enzymes involving radical-mediated mechanisms could intrinsically be more prone to catalytic promiscuity. This mini-review summarizes the recent advances in the study of NosL, a radical S-adenosyl-L-methionine (SAM)-dependent L-tryptophan (L-Trp) lyase. We demonstrate here the interesting chemistry and remarkable catalytic promiscuity of NosL, and attempt to highlight the high evolvability of radical SAM enzymes and the potential to engineer these enzymes for novel and improved activities.

  14. The effect of catalyst preparation on catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, J.A.

    1992-01-01

    Three intrinsically connected phenomena occur during adsorption/impregnation of aqueous electrolytes onto oxide carriers. They are: pH-dependent development of surface carriers on the oxide; pH-dependent aqueous speciation of catalytic precursors; surface adsorption by complexation and coordination. Modeling of these processes yields basic thermodynamic properties of the adsorbed phase, which could provide useful information of the catalytic properties of the metal, support, and reveal metal-support interactions, thus contributing to design criteria for supported-metal catalysts. The spectrum of catalytic systems that can be studied using the above approach is greatly extended when both pure and composite oxide carriers are considered. This presentation will focus on three metal/support systems, each of which provides results of both practical and fundamental importance.

  15. Evolutionary conservation and changes in insect TRP channels

    Directory of Open Access Journals (Sweden)

    Tominaga Makoto

    2009-09-01

    Full Text Available Abstract Background TRP (Transient Receptor Potential channels respond to diverse stimuli and thus function as the primary integrators of varied sensory information. They are also activated by various compounds and secondary messengers to mediate cell-cell interactions as well as to detect changes in the local environment. Their physiological roles have been primarily characterized only in mice and fruit flies, and evolutionary studies are limited. To understand the evolution of insect TRP channels and the mechanisms of integrating sensory inputs in insects, we have identified and compared TRP channel genes in Drosophila melanogaster, Bombyx mori, Tribolium castaneum, Apis mellifera, Nasonia vitripennis, and Pediculus humanus genomes as part of genome sequencing efforts. Results All the insects examined have 2 TRPV, 1 TRPN, 1 TRPM, 3 TRPC, and 1 TRPML subfamily members, demonstrating that these channels have the ancient origins in insects. The common pattern also suggests that the mechanisms for detecting mechanical and visual stimuli and maintaining lysosomal functions may be evolutionarily well conserved in insects. However, a TRPP channel, the most ancient TRP channel, is missing in B. mori, A. mellifera, and N. vitripennis. Although P. humanus and D. melanogaster contain 4 TRPA subfamily members, the other insects have 5 TRPA subfamily members. T. castaneum, A. mellifera, and N. vitripennis contain TRPA5 channels, which have been specifically retained or gained in Coleoptera and Hymenoptera. Furthermore, TRPA1, which functions for thermotaxis in Drosophila, is missing in A. mellifera and N. vitripennis; however, they have other Hymenoptera-specific TRPA channels (AmHsTRPA and NvHsTRPA. NvHsTRPA expressed in HEK293 cells is activated by temperature increase, demonstrating that HsTRPAs function as novel thermal sensors in Hymenoptera. Conclusion The total number of insect TRP family members is 13-14, approximately half that of mammalian TRP

  16. DEVELOPMENT OF HIGH ACTIVITY, CATALYTIC SYSTEMS FOR NOx REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Unknown

    2001-12-01

    This project was directed at an investigation of catalytic NO{sub x} reduction on carbonaceous supports at low temperatures. The experimental work was conducted primarily in a packed bed reactor/gas flow system that was constructed for this work. The analytical techniques employed were mass spectrometry, NO{sub x} chemiluminescence, and gas chromatography. The experimental plan was focused on steady-state reactivity experiments, followed by temperature programmed desorption (TPD) of surface intermediates, and also selected temperature-programmed reaction (TPR) experiments. Both uncatalyzed and catalyzed (potassium-promoted) phenolic resin char, were investigated as well as the catalytic effect of additional CO in the gas phase.

  17. Sub-cellular distribution and translocation of TRP channels.

    Science.gov (United States)

    Toro, Carlos A; Arias, Luis A; Brauchi, Sebastian

    2011-01-01

    Cellular electrical activity is the result of a highly complex processes that involve the activation of ion channel proteins. Ion channels make pores on cell membranes that rapidly transit between conductive and non-conductive states, allowing different ions to flow down their electrochemical gradients across cell membranes. In the case of neuronal cells, ion channel activity orchestrates action potentials traveling through axons, enabling electrical communication between cells in distant parts of the body. Somatic sensation -our ability to feel touch, temperature and noxious stimuli- require ion channels able to sense and respond to our peripheral environment. Sensory integration involves the summing of various environmental cues and their conversion into electrical signals. Members of the Transient Receptor Potential (TRP) family of ion channels have emerged as important mediators of both cellular sensing and sensory integration. The regulation of the spatial and temporal distribution of membrane receptors is recognized as an important mechanism for controlling the magnitude of the cellular response and the time scale on which cellular signaling occurs. Several studies have shown that this mechanism is also used by TRP channels to modulate cellular response and ultimately fulfill their physiological function as sensors. However, the inner-working of this mode of control for TRP channels remains poorly understood. The question of whether TRPs intrinsically regulate their own vesicular trafficking or weather the dynamic regulation of TRP channel residence on the cell surface is caused by extrinsic changes in the rates of vesicle insertion or retrieval remain open. This review will examine the evidence that sub-cellular redistribution of TRP channels plays an important role in regulating their activity and explore the mechanisms that control the trafficking of vesicles containing TRP channels.

  18. Correction: 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)

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

    2016-01-28

    Correction for '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' by Jorge Ignacio Martínez-Araya et al., Phys. Chem. Chem. Phys., 2015, DOI: 10.1039/c5cp03822g.

  19. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U.J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A.M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  20. Synthesis, characterization and study of catalytic activity of Silver ...

    Indian Academy of Sciences (India)

    tophenone are precursors for some pharmaceuticals, drugs, vitamins, fragrances alcohols, esters and useful in the food processing or cosmetics industry and are important intermediates in many complex syntheses.2. Today, heterogeneous catalytic systems are available for the selective oxidation of different alcohols to the.

  1. Catalytic activity of noble metals promoting hydrogen uptake

    NARCIS (Netherlands)

    Borgschulte, A.; Westerwaal, R.J.; Rector, J.H.; Schreuders, H.; Dam, B.; Griessen, R.P.

    2006-01-01

    The engineering of pure and metal alloy catalysts for hydrogen absorption is needed to improve the kinetics of hydrogen-related devices. We introduce a new route to search for alloys that can yield superior catalytic behavior for hydrogen absorption, using an optical technique to measure the

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

    Directory of Open Access Journals (Sweden)

    Jerome M Karp

    2017-02-01

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

  3. Very Low Rate Constants of Bimolecular CO Adsorption on Anionic Gold Clusters: Implications for Catalytic Activity

    Czech Academy of Sciences Publication Activity Database

    Balteanu, I.; Balaj, O. P.; Fox, B. S.; Beyer, M. K.; Bastl, Zdeněk; Bondybey, V. E.

    2003-01-01

    Roč. 5, - (2003), s. 1213-1218 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z4040901 Keywords : bimolecular * adsorption * catalytic activity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.959, year: 2003

  4. Peroxidase-like catalytic activities of ionic metalloporphyrins ...

    Indian Academy of Sciences (India)

    Unknown

    The ideal pH was seen to be in the 8⋅0–8⋅5 range, with maximum effect at 8⋅2. The efficiency order for the various PS-MTPPS was seen to be Co>Mn>Fe, with CoTPPS showing efficiency comparable to that of horseradish peroxidase. The catalytic efficiency was found to be increasing with temperature for all the catalysts.

  5. Catalytic activity of metal borides in the reaction of decomposition

    International Nuclear Information System (INIS)

    Labodi, I.; Korablev, L.I.; Tavadyan, L.A.; Blyumberg, Eh.A.

    1982-01-01

    Catalytic effect of CoB, MoB 2 , ZrB 2 and NbB 2 , prepared by the method of self-propagating high-temperature synthesis, on decomposition of tertiary butyl hydroperoxide has been studied. A technigue of determination of action mechanism of heterogeneous catalysts in liquid-phase process is suggested. It is established that CoB in contrast to other metal borides catalyzes only hydroperoxide decomposition into radicals

  6. Glu-Trp-ONa or its acylated analogue (R-Glu-Trp-ONa) administration enhances the wound healing in the model of chronic skin wounds in rabbits

    Science.gov (United States)

    Shevtsov, Maxim A; Smagina, Larisa V; Kudriavtceva, Tatiana A; Petlenko, Sergey V; Voronkina, Irina V

    2015-01-01

    The management of chronic skin wounds represents a major therapeutic challenge. The synthesized dipeptide (Glu-Trp-ONa) and its acylated analogue (R-Glu-Trp-ONa) were assessed in the model of nonhealing dermal wounds in rabbits in relation to their healing properties in wound closure. Following wound modeling, the rabbits received a course of intraperitoneal injections of Glu-Trp-ONa or R-Glu-Trp-ONa. Phosphate-buffered saline and Solcoseryl® were applied as negative and positive control agents, respectively. An injection of Glu-Trp-ONa and R-Glu-Trp-ONa decreased the period of wound healing in animals in comparison to the control and Solcoseryl-treated groups. Acylation of Glu-Trp-ONa proved to be beneficial as related to the healing properties of the dipeptide. Subsequent zymography analyses showed that the applied peptides decreased the proteolytic activity of matrix metalloproteinases MMP-9, MMP-8, and MMP-2 in the early inflammatory phase and reversely increased the activity of MMP-9, MMP-8, and MMP-1 in the remodeling phase. Histological analyses of the wound sections (hematoxylin–eosin, Mallory’s staining) confirmed the enhanced formation of granulation tissue and re-epithelialization in the experimental groups. By administering the peptides, wound closures increased significantly through the modulation of the MMPs’ activity, indicating their role in wound healing. PMID:25848208

  7. Transient receptor potential (TRP gene superfamily encoding cation channels

    Directory of Open Access Journals (Sweden)

    Pan Zan

    2011-01-01

    Full Text Available Abstract Transient receptor potential (TRP non-selective cation channels constitute a superfamily, which contains 28 different genes. In mammals, this superfamily is divided into six subfamilies based on differences in amino acid sequence homology between the different gene products. Proteins within a subfamily aggregate to form heteromeric or homomeric tetrameric configurations. These different groupings have very variable permeability ratios for calcium versus sodium ions. TRP expression is widely distributed in neuronal tissues, as well as a host of other tissues, including epithelial and endothelial cells. They are activated by environmental stresses that include tissue injury, changes in temperature, pH and osmolarity, as well as volatile chemicals, cytokines and plant compounds. Their activation induces, via intracellular calcium signalling, a host of responses, including stimulation of cell proliferation, migration, regulatory volume behaviour and the release of a host of cytokines. Their activation is greatly potentiated by phospholipase C (PLC activation mediated by coupled GTP-binding proteins and tyrosine receptors. In addition to their importance in maintaining tissue homeostasis, some of these responses may involve various underlying diseases. Given the wealth of literature describing the multiple roles of TRP in physiology in a very wide range of different mammalian tissues, this review limits itself to the literature describing the multiple roles of TRP channels in different ocular tissues. Accordingly, their importance to the corneal, trabecular meshwork, lens, ciliary muscle, retinal, microglial and retinal pigment epithelial physiology and pathology is reviewed.

  8. Structural Insights into the Catalytic Active Site and Activity of Human Nit2/ω-Amidase

    Science.gov (United States)

    Chien, Chin-Hsiang; Gao, Quan-Ze; Cooper, Arthur J. L.; Lyu, Jyun-Hong; Sheu, Sheh-Yi

    2012-01-01

    Human nitrilase-like protein 2 (hNit2) is a putative tumor suppressor, recently identified as ω-amidase. hNit2/ω-amidase plays a crucial metabolic role by catalyzing the hydrolysis of α-ketoglutaramate (the α-keto analog of glutamine) and α-ketosuccinamate (the α-keto analog of asparagine), yielding α-ketoglutarate and oxaloacetate, respectively. Transamination between glutamine and α-keto-γ-methiolbutyrate closes the methionine salvage pathway. Thus, hNit2/ω-amidase links sulfur metabolism to the tricarboxylic acid cycle. To elucidate the catalytic specificity of hNit2/ω-amidase, we performed molecular dynamics simulations on the wild type enzyme and its mutants to investigate enzyme-substrate interactions. Binding free energies were computed to characterize factors contributing to the substrate specificity. The predictions resulting from these computations were verified by kinetic analyses and mutational studies. The activity of hNit2/ω-amidase was determined with α-ketoglutaramate and succinamate as substrates. We constructed three catalytic triad mutants (E43A, K112A, and C153A) and a mutant with a loop 116–128 deletion to validate the role of key residues and the 116–128 loop region in substrate binding and turnover. The molecular dynamics simulations successfully verified the experimental trends in the binding specificity of hNit2/ω-amidase toward various substrates. Our findings have revealed novel structural insights into the binding of substrates to hNit2/ω-amidase. A catalytic triad and the loop residues 116–128 of hNit2 play an essential role in supporting the stability of the enzyme-substrate complex, resulting in the generation of the catalytic products. These observations are predicted to be of benefit in the design of new inhibitors or activators for research involving cancer and hyperammonemic diseases. PMID:22674578

  9. Nociceptive TRP Channels: Sensory Detectors and Transducers in Multiple Pain Pathologies

    Directory of Open Access Journals (Sweden)

    Aaron D. Mickle

    2016-11-01

    Full Text Available Specialized receptors belonging to the transient receptor potential (TRP family of ligand-gated ion channels constitute the critical detectors and transducers of pain-causing stimuli. Nociceptive TRP channels are predominantly expressed by distinct subsets of sensory neurons of the peripheral nervous system. Several of these TRP channels are also expressed in neurons of the central nervous system, and in non-neuronal cells that communicate with sensory nerves. Nociceptive TRPs are activated by specific physico-chemical stimuli to provide the excitatory trigger in neurons. In addition, decades of research has identified a large number of immune and neuromodulators as mediators of nociceptive TRP channel activation during injury, inflammatory and other pathological conditions. These findings have led to aggressive targeting of TRP channels for the development of new-generation analgesics. This review summarizes the complex activation and/or modulation of nociceptive TRP channels under pathophysiological conditions, and how these changes underlie acute and chronic pain conditions. Furthermore, development of small-molecule antagonists for several TRP channels as analgesics, and the positive and negative outcomes of these drugs in clinical trials are discussed. Understanding the diverse functional and modulatory properties of nociceptive TRP channels is critical to function-based drug targeting for the development of evidence-based and efficacious new generation analgesics.

  10. Different Mechanisms of Catalytic Complex Formation in Two L-Tryptophan Processing Dioxygenases

    Directory of Open Access Journals (Sweden)

    Karin Nienhaus

    2018-01-01

    Full Text Available The human heme enzymes tryptophan 2,3-dioxygenase (hTDO and indoleamine 2,3 dioxygenase (hIDO catalyze the initial step in L-tryptophan (L-Trp catabolism, the insertion of dioxygen into L-Trp. Overexpression of these enzymes causes depletion of L-Trp and accumulation of metabolic products, and thereby contributes to tumor immune tolerance and immune dysregulation in a variety of disease pathologies. Understanding the assembly of the catalytically active, ternary enzyme-substrate-ligand complexes is not yet fully resolved, but an essential prerequisite for designing efficient and selective de novo inhibitors. Evidence is mounting that the ternary complex forms by sequential binding of ligand and substrate in a specific order. In hTDO, the apolar L-Trp binds first, decreasing active-site solvation and, as a result, reducing non-productive oxidation of the heme iron by the dioxygen ligand, which may leave the substrate bound to a ferric heme iron. In hIDO, by contrast, dioxygen must first coordinate to the heme iron because a bound substrate would occlude ligand access to the heme iron, so the ternary complex can no longer form. Consequently, faster association of L-Trp at high concentrations results in substrate inhibition. Here, we summarize our present knowledge of ternary complex formation in hTDO and hIDO and relate these findings to structural peculiarities of their active sites.

  11. Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

    Science.gov (United States)

    Manzoor, Dar; Pal, Sourav

    2015-06-18

    Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

  12. The Catalytic Activity of Modified Zeolite Lanthanum on the Catalytic Cracking of Al-Duara Atmospheric Distillation Residue

    Directory of Open Access Journals (Sweden)

    Karim Khalifa Esgair

    2016-03-01

    Full Text Available Atmospheric residue fluid catalytic cracking was selected as a probe reaction to test the catalytic performance of modified NaY zeolites and prepared NaY zeolites. Modified NaY zeolites have been synthesized by simple ion exchange methods. Three samples of modified zeolite Y have been obtained by replacing the sodium ions in the original sample with lanthanum and the weight percent added are 0.28, 0.53, and 1.02 respectively. The effects of addition of lanthanum to zeolite Y in different weight percent on the cracking catalysts were investigated using an experimental laboratory plant scale of fluidized bed reactor. The experiments have been performed with weight hourly space velocity (WHSV range of 6 to 24 h-1, and the range of temperature from 450 to 510 oC. The activity of the catalyst with 1.02 wt% lanthanum has been shown to be much greater than that of the sample parent NaY. Also it was observed that the addition of the lanthanum causes an increase in the thermal stability of the zeolite.

  13. Greatly Enhancing Catalytic Activity of Graphene by Doping the Underlying Metal Substrate.

    Science.gov (United States)

    Guo, Na; Xi, Yongjie; Liu, Shuanglong; Zhang, Chun

    2015-07-09

    Graphene-based solid-state catalysis represents a new direction in applications of graphene and has attracted a lot of interests recently. However, the difficulty in fine control and large-scale production of previously proposed graphene catalysts greatly limits their industrial applications. Here we present a novel way to enhance the catalytic activity of graphene, which is highly efficient yet easy to fabricate and control. By first-principles calculations, we show that when the underlying metal substrate is doped with impurities, the catalytic activity of the supported graphene can be drastically enhanced. Graphene supported on a Fe/Ni(111) surface is chosen as a model catalyst, and the chemical reaction of CO oxidation is used to probe the catalytic activity of graphene. When the underlying Fe/Ni(111) substrate is impurity free, the graphene is catalytically inactive. When a Zn atom is doped into the substrate, the catalytic activity of the supported graphene is greatly enhanced, and the reaction barrier of the catalyzed CO oxidation is reduced to less than 0.5 eV. Intriguing reaction mechanism of catalyzed CO oxidation is revealed. These studies suggest a new class of graphene-based catalysts and pave the way for future applications of graphene in solid-state catalysis.

  14. Fluorescence kinetics of Trp-Trp dipeptide and its derivatives in water via ultrafast fluorescence spectroscopy.

    Science.gov (United States)

    Jia, Menghui; Yi, Hua; Chang, Mengfang; Cao, Xiaodan; Li, Lei; Zhou, Zhongneng; Pan, Haifeng; Chen, Yan; Zhang, Sanjun; Xu, Jianhua

    2015-08-01

    Ultrafast fluorescence dynamics of Tryptophan-Tryptophan (Trp-Trp/Trp2) dipeptide and its derivatives in water have been investigated using a picosecond resolved time correlated single photon counting (TCSPC) apparatus together with a femtosecond resolved upconversion spectrophotofluorometer. The fluorescence decay profiles at multiple wavelengths were fitted by a global analysis technique. Nanosecond fluorescence kinetics of Trp2, N-tert-butyl carbonyl oxygen-N'-aldehyde group-l-tryptophan-l-tryptophan (NBTrp2), l-tryptophan-l-tryptophan methyl ester (Trp2Me), and N-acetyl-l-tryptophan-l-tryptophan methyl ester (NATrp2Me) exhibit multi-exponential decays with the average lifetimes of 1.99, 3.04, 0.72 and 1.22ns, respectively. Due to the intramolecular interaction between two Trp residues, the "water relaxation" lifetime was observed around 4ps, and it is noticed that Trp2 and its derivatives also exhibit a new decay with a lifetime of ∼100ps, while single-Trp fluorescence decay in dipeptides/proteins shows 20-30ps. The intramolecular interaction lifetime constants of Trp2, NBTrp2, Trp2Me and NATrp2Me were then calculated to be 3.64, 0.93, 11.52 and 2.40ns, respectively. Candidate mechanisms (including heterogeneity, solvent relaxation, quasi static self-quenching or ET/PT quenching) have been discussed. Copyright © 2015. Published by Elsevier B.V.

  15. Bimetallic Cu-Ni nanoparticles supported on activated carbon for catalytic oxidation of benzyl alcohol

    Science.gov (United States)

    Kimi, Melody; Jaidie, Mohd Muazmil Hadi; Pang, Suh Cem

    2018-01-01

    A series of bimetallic copper-nickel (CuNix, x = 0.1, 0.2, 0.5 and 1) nanoparticles supported on activated carbon (AC) were prepared by deposition-precipitation method for the oxidation of benzyl alcohol to benzaldehyde using hydrogen peroxide as oxidising agent. Analyses by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) confirmed that Cu and Ni was successfully added on the surface of activated carbon. CuNi1/AC showed the best catalytic activity for the oxidation of benzyl alcohols to the corresponding aldehyde within a short reaction period at 80 °C. The catalytic performance is significantly enhanced by the addition of equal amount of Ni as compared to the monometallic counterpart. This result indicates the synergistic effect between Ni and Cu particles in the catalytic oxidation reaction.

  16. The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation

    Science.gov (United States)

    Hou, Jingtao; Li, Yuanzhi; Mao, Mingyang; Zhao, Xiujian; Yue, Yuanzheng

    2014-11-01

    The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel and facile strategy of synthesizing these unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework by hydrothermal redox reaction between Ce(NO3)3 and KMnO4 with KMnO4/Ce(NO3)3 at a molar ratio of 3 : 1 at 120 °C. Compared to pure OMS-2, the produced catalyst of Ce ion substituted OMS-2 ultrathin nanorods exhibits an enormous enhancement in the catalytic activity for benzene oxidation, which is evidenced by a significant decrease (ΔT50 = 100 °C, ΔT90 = 129 °C) in the reaction temperature of T50 and T90 (corresponding to the benzene conversion = 50% and 90%), which is considerably more efficient than the expensive supported noble metal catalyst (Pt/Al2O3). We combine both theoretical and experimental evidence to provide a new physical insight into the significant effect due to the defects induced by the Ce ion substitution on the catalytic activity of OMS-2. The formation of unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework leads to a significant enhancement of the lattice oxygen activity, thus tremendously increasing the catalytic activity.The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel

  17. Catalytic activity of metallic nanoisland coatings. The influence of size effects on the recombination properties

    International Nuclear Information System (INIS)

    Tomilina, O A; Berzhansky, V N; Shaposhnikov, A N; Tomilin, S V

    2016-01-01

    The results of investigations of the quantum-size effects influence on selective properties of heterogeneous nanocatalysts are presents. As etalon exothermic reaction was used the reaction of atomic hydrogen recombination. The nanostructured Pd and Pt films on Teflon substrate were used as a samples of heterogeneous nanocatalysts. It was shown that for nanoparticles with various sizes the catalytic activity has the periodic dependence. It has been found that for certain sizes of nanoparticles their catalytic activity is less than that of Teflon substrate. (paper)

  18. cDNA cloning of human DNA topoisomerase I. Catalytic activity of a 67.7-kDa carboxyl-terminal fragment

    International Nuclear Information System (INIS)

    D'Arpa, P.; Machlin, P.S.; Ratrie, H. III; Rothfield, N.F.; Cleveland, D.W.; Earnshaw, W.C.

    1988-01-01

    cDNA clones encoding human topoisomerase I were isolated from an expression vector library (λgt11) screened with autoimmune anti-topoisomerase I serum. One of these clones has been expressed as a fusion protein comprised of a 32-kDa fragment of the bacterial TrpE protein linked to 67.7 kDa of protein encoded by the cDNA. Three lines of evidence indicate that the cloned cDNA encodes topoisomerase I. (i) Proteolysis maps of the fusion protein and human nuclear topoisomerase I are essentially identical. (ii) The fusion protein relaxes supercoiled DNA, an activity that can be immunoprecipitated by anti-topoisomerase I serum. (iii) Sequence analysis has revealed that the longest cDNA clone (3645 base pairs) encodes a protein of 765 amino acids that shares 42% identity with Saccharomyces cerevisiae topoisomerase I. The sequence data also show that the catalytically active 67.7-kDa fragment is comprised of the carboxyl terminus

  19. PREPARATION, CHARACTERIZATION, AND CATALYTIC ACTIVITY TEST OF Ni-Mo/NATURAL ZEOLITE ON PYRIDINE HYDRODENITROGENATION

    Directory of Open Access Journals (Sweden)

    Sri Kadarwati

    2010-12-01

    Full Text Available Preparation, characterization, and catalytic activity test of Ni-Mo/natural zeolite on pyridine hydrodenitrogenation were carried out. Preparation of catalyst was conducted by impregnation method using nickel nitrate hexahydrate and ammonium heptamolibdate precursor as Ni and Mo source respectively. Characterization of catalyst was conducted by using gravimetry, atomic absorption spectrophotometry, and X-ray diffraction method. Catalytic activity test on pyridine hydrodenitrogenation was carried out by using flow system reactor with hydrogen flow rate variable. The research results showed that the catalyst's total acidity and crystallinity are increased with level of impregnation success of 96.71% and 90.08% respectively. Ni-Mo/natural zeolites able to increase the catalytic conversion up to 71.78% at 350 °C and hydrogen flow rate of 10 mL/min with more highly varied product distribution. Assuming that the pyridine hydrodenitrogenation follows the pseudo first order kinetics.

  20. One-pot environmentally friendly approach toward highly catalytically active bimetal-nanoparticle-graphene hybrids.

    Science.gov (United States)

    Liu, Chang-Hai; Chen, Xiao-Qi; Hu, Yong-Feng; Sham, Tsun-Kong; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Sun, Xu-Hui; Wang, Sui-Dong

    2013-06-12

    A one-pot universal approach with simple metal sputtering onto room temperature ionic liquids has been developed to prepare bimetal-nanoparticle (NP)-graphene hybrids, and the process is environmentally friendly and completely free of additives and byproducts. The graphene-supported bimetallic NPs have an Ag-based core and an Au/Pd-rich shell, demonstrated by the scanning transmission electron microscopy. The X-ray absorption near-edge spectroscopy using synchrotron radiation reveals the occurrence of charge redistribution at both the Ag@Au and Ag@Pd core-shell interfaces. The as-prepared Ag@Au and Ag@Pd bimetal-NP-graphene hybrids are highly catalytically active for reduction of 4-nitrophenol, whose catalytic activity is superior to the corresponding monometallic hybrids. The catalytic superiority is ascribed to the electronic structure modification and morphological irregularity of the graphene-supported bimetallic NPs.

  1. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  2. 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.

  3. Baicalin and scutellarin are proteasome inhibitors that specifically target chymotrypsin-like catalytic activity.

    Science.gov (United States)

    Wu, Yi-Xin; Sato, Eiji; Kimura, Wataru; Miura, Naoyuki

    2013-09-01

    Baicalin and scutellarin are the major active principal flavonoids extracted from the Chinese herbal medicines Scutellaria baicalensis and Erigeron breviscapus (Vant.) Hand-Mazz. It has recently been reported that baicalin and scutellarin have antitumor activity. However, the mechanisms of action are unknown. We previously reported that some flavonoids have a specific role in the inhibition of the activity of proteasome subunits and induced apoptosis in tumor cells. To further investigate these pharmacological effects, we examined the inhibitory activity of baicalin and scutellarin on the extracted proteasomes from mice and cancer cells. Using fluorogenic substrates for proteasome catalytic subunits, we found that baicalin and scutellarin specifically inhibited chymotrypsin-like activity but did not inhibit trypsin-like and peptidyl-glutamyl peptide hydrolyzing activities. These data suggested that baicalin and scutellarin specifically inhibit chymotrypsin-like catalytic activity in the proteasome. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Listeriosis in p47(phox-/-) and TRp55-/- mice: protection despite absence of ROI and susceptibility despite presence of RNI.

    Science.gov (United States)

    Endres, R; Luz, A; Schulze, H; Neubauer, H; Fütterer, A; Holland, S M; Wagner, H; Pfeffer, K

    1997-09-01

    The significance of host defense mechanisms in primary listeriosis in vivo is incompletely understood. Here, we show that tumor necrosis factor receptor p55-/- (TRp55-/-) mice are susceptible to Listeria monocytogenes infection in the presence of leukocyte recruitment, inflammatory cytokine production (including IFNgamma), nitric oxide synthesis, and oxidative burst formation. Mice deficient for oxidative burst (p47[phox-/-] mice) are relatively resistant to listeriosis. Despite activation of these antibacterial effector systems, TRp55-/- phagocytes in vivo are incapable of confining and eradicating L. monocytogenes inside phagolysosomes. Bone marrow chimeras reveal that for eradication of L. monocytogenes, TRp55 is crucially required only on cells from hematopoietic origin. Unexpectedly, prior to death, exocrine pancreatic cells undergo apoptosis in TRp55-/- mice. Collectively, these data demonstrate that in vivo, TRp55 initiates a protective, listericidal mechanism in phagocytes that differs from nitric oxide production and oxidative burst formation and that uncontrolled listeriosis results in necrotizing pancreatitis in TRp55-/- mice.

  5. Identification and characterization of hydrophobic gate residues in TRP channels.

    Science.gov (United States)

    Zheng, Wang; Hu, Ruikun; Cai, Ruiqi; Hofmann, Laura; Hu, Qiaolin; Fatehi, Mohammad; Long, Wentong; Kong, Tim; Tang, Jingfeng; Light, Peter; Flockerzi, Veit; Cao, Ying; Chen, Xing-Zhen

    2018-02-01

    Transient receptor potential (TRP) channels, subdivided into 6 subfamilies in mammals, have essential roles in sensory physiology. They respond to remarkably diverse stimuli, comprising thermal, chemical, and mechanical modalities, through opening or closing of channel gates. In this study, we systematically substituted the hydrophobic residues within the distal fragment of pore-lining helix S6 with hydrophilic residues and, based on Xenopus oocyte and mammalian cell electrophysiology and a hydrophobic gate theory, identified hydrophobic gates in TRPV6/V5/V4/C4/M8. We found that channel activity drastically increased when TRPV6 Ala616 or Met617 or TRPV5 Ala576 or Met577 , but not any of their adjacent residues, was substituted with hydrophilic residues. Channel activity strongly correlated with the hydrophilicity of the residues at those sites, suggesting that consecutive hydrophobic residues TRPV6 Ala616-Met617 and TRPV5 Ala576-Met577 form a double-residue gate in each channel. By the same strategy, we identified a hydrophobic single-residue gate in TRPV4 Iso715 , TRPC4 Iso617 , and TRPM8 Val976 . In support of the hydrophobic gate theory, hydrophilic substitution at the gate site, which removes the hydrophobic gate seal, substantially increased the activity of TRP channels in low-activity states but had little effect on the function of activated channels. The double-residue gate channels were more sensitive to small changes in the gate's hydrophobicity or size than single-residue gate channels. The unconventional double-reside gating mechanism in TRP channels may have been evolved to respond especially to physiologic stimuli that trigger relatively small gate conformational changes.-Zheng, W., Hu, R., Cai, R., Hofmann, L., Hu, Q., Fatehi, M., Long, W., Kong, T., Tang, J., Light, P., Flockerzi, V., Cao, Y., Chen, X.-Z. Identification and characterization of hydrophobic gate residues in TRP channels.

  6. Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

    Science.gov (United States)

    Shi, Hui; Eckstein, Sebastian; Vjunov, Aleksei; Camaioni, Donald M.; Lercher, Johannes A.

    2017-05-01

    Acid catalysis by hydronium ions is ubiquitous in aqueous-phase organic reactions. Here we show that hydronium ion catalysis, exemplified by intramolecular dehydration of cyclohexanol, is markedly influenced by steric constraints, yielding turnover rates that increase by up to two orders of magnitude in tight confines relative to an aqueous solution of a Brønsted acid. The higher activities in zeolites BEA and FAU than in water are caused by more positive activation entropies that more than offset higher activation enthalpies. The higher activity in zeolite MFI with pores smaller than BEA and FAU is caused by a lower activation enthalpy in the tighter confines that more than offsets a less positive activation entropy. Molecularly sized pores significantly enhance the association between hydronium ions and alcohols in a steric environment resembling the constraints in pockets of enzymes stabilizing active sites.

  7. Synthesis and bio-catalytic activity of isostructural cobalt(III ...

    Indian Academy of Sciences (India)

    which revealed that the cationic complex efficiently inhibits catalytic activity with kcat value 9.65×102 h−1. [1]+ cleaved pBR 322 DNA without .... 2.2 Physical measurements. Infrared spectra (KBr) were recorded .... Mean OD of untreated cells (control) - Mean OD of treated cells(treat) × 100. Mean absorbance of untreated ...

  8. Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

    KAUST Repository

    Li, Wenjun

    2017-02-15

    An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

  9. Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

    Science.gov (United States)

    Bandini, Marco; Tragni, Michele

    2009-04-21

    The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

  10. Natural clinoptilolite exchanged with iron: characterization and catalytic activity in nitrogen monoxide reduction

    Directory of Open Access Journals (Sweden)

    Daria Tito-Ferro

    2016-12-01

    Full Text Available The aim of this work was to characterize the natural clinoptilolite from Tasajeras deposit, Cuba, modified by hydrothermal ion-exchange with solutions of iron (II sulfate and iron (III nitrate in acid medium. Besides this, its catalytic activity to reduce nitrogen monoxide with carbon monoxide/propene in the presence of oxygen was evaluated. The characterization was performed by Mössbauer and UV-Vis diffuse reflectance spectroscopies and adsorption measurements. The obtained results lead to conclude that in exchanged samples, incorporated divalent and trivalent irons are found in octahedral coordination. Both irons should be mainly in cationic extra-framework positions inside clinoptilolite channels as charge compensating cations, and also as iron oxy-hydroxides resulting from limited hydrolysis of these cations. The iron (III exchanged samples has a larger amount of iron oxy-hydroxides agglomerates. The iron (II exchanged samples have additionally iron (II sulfate adsorbed. The catalytic activity in the nitrogen monoxide reduction is higher in the exchanged zeolites than starting. Among all samples, those exchanged of iron (II has the higher catalytic activity. This lead to outline that, main catalytically active centers are associated with divalent iron.

  11. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  12. Catalytic promiscuity of a proline-based tautomerase : Aldolase activities and enzyme redesign

    NARCIS (Netherlands)

    Rahimi, Mehran

    2016-01-01

    Numerous enzymes have been found to catalyze additional and completely different types of reactions relative to the natural activity they evolved for. This interesting phenomenon, called catalytic promiscuity, has proven to be a fruitful guide for the development of novel biocatalysts for organic

  13. Enantioselective Synthesis of a PKC Inhibitor via Catalytic C-HBond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Rebecca M.; Thalji, Reema K.; Bergman, Robert G.; Ellman,Jonathan A.

    2006-02-26

    The syntheses of two biologically active molecules possessing dihydropyrroloindole cores (1 and 2) were completed using rhodium-catalyzed imine-directed C-H bond functionalization, with the second of these molecules containing a stereocenter that can be set with 90% ee during cyclization using chiral nonracemic phosphoramidite ligands. Catalytic decarbonylation and direct indole/maleimide coupling provide efficient access to 2.

  14. A highly sensitive technique for detecting catalytically active nanoparticles against a background of general workplace aerosols

    International Nuclear Information System (INIS)

    Neubauer, N; Weis, F; Seipenbusch, M; Kasper, G; Binder, A

    2011-01-01

    A new measurement technique was studied using catalysis to specifically detect airborne nanoparticles in presence of background particles in the workplace air. Catalytically active nanoparticles produced by spark discharge were used as aerosol catalysts. According to these particles suitable catalytic test reactions were chosen and investigated by two different approaches: catalysis on airborne nanoparticles and catalysis on deposited nanoparticles. The results indicate that catalysis is applicable for the specific measurement of nanoparticles in the workplace air. Catalysis on airborne particles is suitable for the specific detection of very active nanoparticles, e.g. platinum or nickel, at high concentrations of about 10 7 /cm 3 . The approach of catalysis on deposited particles is better suited for nanoparticle aerosols at low concentrations, for slow catalytic reactions or less active nanoparticles like iron oxide (Fe 2 O 3 ). On the basis of the experimental results detection limits in the range of μg or even ng were calculated which assure the good potential of catalysis for the specific detection of nanoparticles in the workplace air based on their catalytic activity.

  15. Direct Hysteresis Heating of Catalytically Active Ni–Co Nanoparticles as Steam Reforming Catalyst

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Engbæk, Jakob Soland; Vendelbo, Søren Bastholm

    2017-01-01

    We demonstrated a proof-of-concept catalytic steam reforming flow reactor system heated only by supported magnetic nickel–cobalt nanoparticles in an oscillating magnetic field. The heat transfer was facilitated by the hysteresis heating in the nickel–cobalt nanoparticles alone. This produced...... a sufficient power input to equilibrate the reaction at above 780 °C with more than 98% conversion of methane. The high conversion of methane indicated that Co-rich nanoparticles with a high Curie temperature provide sufficient heat to enable the endothermic reaction, with the catalytic activity facilitated...... by the Ni content in the nanoparticles. The magnetic hysteresis losses obtained from temperature-dependent hysteresis measurements were found to correlate well with the heat generation in the system. The direct heating of the catalytic system provides a fast heat transfer and thereby overcomes the heat...

  16. Modulation of catalytic activity in multi-domain protein tyrosine phosphatases.

    Directory of Open Access Journals (Sweden)

    Lalima L Madan

    Full Text Available Signaling mechanisms involving protein tyrosine phosphatases govern several cellular and developmental processes. These enzymes are regulated by several mechanisms which include variation in the catalytic turnover rate based on redox stimuli, subcellular localization or protein-protein interactions. In the case of Receptor Protein Tyrosine Phosphatases (RPTPs containing two PTP domains, phosphatase activity is localized in their membrane-proximal (D1 domains, while the membrane-distal (D2 domain is believed to play a modulatory role. Here we report our analysis of the influence of the D2 domain on the catalytic activity and substrate specificity of the D1 domain using two Drosophila melanogaster RPTPs as a model system. Biochemical studies reveal contrasting roles for the D2 domain of Drosophila Leukocyte antigen Related (DLAR and Protein Tyrosine Phosphatase on Drosophila chromosome band 99A (PTP99A. While D2 lowers the catalytic activity of the D1 domain in DLAR, the D2 domain of PTP99A leads to an increase in the catalytic activity of its D1 domain. Substrate specificity, on the other hand, is cumulative, whereby the individual specificities of the D1 and D2 domains contribute to the substrate specificity of these two-domain enzymes. Molecular dynamics simulations on structural models of DLAR and PTP99A reveal a conformational rationale for the experimental observations. These studies reveal that concerted structural changes mediate inter-domain communication resulting in either inhibitory or activating effects of the membrane distal PTP domain on the catalytic activity of the membrane proximal PTP domain.

  17. Mn-Ce-V-WOx/TiO2 SCR Catalysts: Catalytic Activity, Stability and Interaction among Catalytic Oxides

    Directory of Open Access Journals (Sweden)

    Xuteng Zhao

    2018-02-01

    Full Text Available A series of Mn-Ce-V-WOx/TiO2 composite oxide catalysts with different molar ratios (active components/TiO2 = 0.1, 0.2, 0.3, 0.6 have been prepared by wet impregnation method and tested in selective catalytic reduction (SCR of NO by NH3 in a wide temperature range. These catalysts were also characterized by X-ray diffraction (XRD, Transmission Electron Microscope (TEM, in situ Fourier Transform infrared spectroscopy (in situ FTIR, H2-Temperature programmed reduction (H2-TPR and X-ray photoelectron spectroscopy (XPS. The results show the catalyst with a molar ratio of active components/TiO2 = 0.2 exhibits highest NO conversion value between 150 °C to 400 °C and good resistance to H2O and SO2 at 250 °C with a gas hourly space velocity (GHSV value of 40,000 h−1. Different oxides are well dispersed and interact with each other. NH3 and NO are strongly adsorbed on the catalyst surface and the adsorption of the reactant gas leads to a redox cycle with the valence state change among the surface oxides. The adsorption of SO2 on Mn4+ and Ce4+ results in good H2O and SO2 resistance of the catalyst, but the effect of Mn and Ce are more than superior water and sulfur resistance. The diversity of valence states of the four active components and their high oxidation-reduction performance are the main reasons for the high NO conversion in this system.

  18. Effects of Mn- and K-addition on catalytic activity of calcium oxide for methane activation

    International Nuclear Information System (INIS)

    Park, Jong Sik; Kong, Jang Il; Lee, Sung Han; Jun, Jong Ho

    1998-01-01

    Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800 .deg. C to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction (XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally p(CH 4 )/p(O 2 )=250 Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best C 2 yield of 8.0% with a selectivity of 43.2% at 775 .deg. C. The C 2 selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO((Mn)>6.3 mol%)catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the C 2 selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000 .deg. C at Po2's of 10 -3 to 10 -1 atm. The electrical conductivity was decreased with Mn-doping and increased with increasing Po 2 in the range of 10 -3 to 10 -1 atm, indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry

  19. Antibacterial & Catalytic Activities of 2,2\\'-Dithio (2-Hydroxyphenyl ...

    African Journals Online (AJOL)

    This paper describes the in vitro evaluation of antibacterial activity of DNBH and its ruthenium complexes. All the synthesized compounds exhibited antibacterial activity against the Gram-positive bacteria namely Staphylococcus aureus at a conc of 100-25 mg/ml and Gram-negative bacteria such as Escherichia coli, ...

  20. Designer Ligands. Part 13. Synthesis and Catalytic Activity of ...

    African Journals Online (AJOL)

    Copper(I), copper(II), cobalt(II) and zinc(II) complexes of a macrocyclic, multidentate Schiff-base ligand have been prepared and, with the exception of the zinc(II) complex, have been shown to exhibit biomimetic catecholase activity. Keywords: Copper(II);Cobalt(II); Zinc(II); Biomimetic complexes; Catecholase activity

  1. Catalytic role of transition metals supported on niobium oxide in O2 activation

    Science.gov (United States)

    Omidvar, Akbar

    2018-03-01

    Metal particles supported on metal oxides (MMO) are promising materials with versatile applications such as catalyst in fuel cell technologies. As one of the transition metal oxides, niobium oxide (NbO) demonstrates a wide interesting properties that make it a potentially applicable in MMO materials. Here, the catalytic activity for the O2 activation of transition metals (Fe, Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) supported on the NbO has been studied theoretically using density functional theory (DFT). The activation of O2 molecule and yielding two separated O atoms is an essential step for the oxygen reduction reaction. Our study demonstrates that the transition metals supported on the NbO can act as driving force for O2 dissociation. Consistent with the prediction of reactivity descriptors, the maximum catalytic activity toward O2 activation is related to the Pt-supported on the NbO metal oxide.

  2. Catalytic Activities of Ribozymes and DNAzymes in Water and Mixed Aqueous Media

    Directory of Open Access Journals (Sweden)

    Shu-ichi Nakano

    2017-11-01

    Full Text Available Catalytic nucleic acids are regarded as potential therapeutic agents and biosensors. The catalytic activities of nucleic acid enzymes are usually investigated in dilute aqueous solutions, although the physical properties of the reaction environment inside living cells and that in the area proximal to the surface of biosensors in which they operate are quite different from those of pure water. The effect of the molecular environment is also an important focus of research aimed at improving and expanding nucleic acid function by addition of organic solvents to aqueous solutions. In this study, the catalytic activities of RNA and DNA enzymes (hammerhead ribozyme, 17E DNAzyme, R3C ribozyme, and 9DB1 DNAzyme were investigated using 21 different mixed aqueous solutions comprising organic compounds. Kinetic measurements indicated that these enzymes can display enhanced catalytic activity in mixed solutions with respect to the solution containing no organic additives. Correlation analyses revealed that the turnover rate of the reaction catalyzed by hammerhead ribozyme increased in a medium with a lower dielectric constant than water, and the turnover rate of the reaction catalyzed by 17E DNAzyme increased in conditions that increased the strength of DNA interactions. On the other hand, R3C ribozyme and 9DB1 DNAzyme displayed no significant turnover activity, but their single-turnover rates increased in many mixed solutions. Our data provide insight into the activity of catalytic nucleic acids under various conditions that are applicable to the medical and technology fields, such as in living cells and in biosensors.

  3. Lipase immobilized catalytically active membrane for synthesis of lauryl stearate in a pervaporation membrane reactor.

    Science.gov (United States)

    Zhang, Weidong; Qing, Weihua; Ren, Zhongqi; Li, Wei; Chen, Jiangrong

    2014-11-01

    A composite catalytically active membrane immobilized with Candida rugosa lipase has been prepared by immersion phase inversion technique for enzymatic synthesis of lauryl stearate in a pervaporation membrane reactor. SEM images showed that a "sandwich-like" membrane structure with a porous lipase-PVA catalytic layer uniformly coated on a polyvinyl alcohol (PVA)/polyethersulfone (PES) bilayer was obtained. Optimum conditions for lipase immobilization in the catalytic layer were determined. The membrane was proved to exhibit superior thermal stability, pH stability and reusability than free lipase under similar conditions. In the case of pervaporation coupled synthesis of lauryl stearate, benefited from in-situ water removal by the membrane, a conversion enhancement of approximately 40% was achieved in comparison to the equilibrium conversion obtained in batch reactors. In addition to conversion enhancement, it was also found that excess water removal by the catalytically active membrane appears to improve activity of the lipase immobilized. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Catalytic Synthesis and Antifungal Activity of New Polychlorinated Natural Terpenes

    Directory of Open Access Journals (Sweden)

    Hana Ighachane

    2017-01-01

    Full Text Available Various unsaturated natural terpenes were selectively converted to the corresponding polychlorinated products in good yields using iron acetylacetonate in combination with nucleophilic cocatalyst. The synthesized compounds were evaluated for their in vitro antifungal activity. The antifungal bioassays showed that 2c and 2d possessed significant antifungal activity against Fusarium oxysporum f. sp. albedinis (Foa, Fusarium oxysporum f. sp. canariensis (Foc, and Verticillium dahliae (Vd.

  5. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium

    Directory of Open Access Journals (Sweden)

    Sayed M. Badawy

    2015-07-01

    Full Text Available Copper/Copper oxide (Cu/Cu2O nanoparticles were synthesized by modified chemical reduction method in an aqueous medium using hydrazine as reducing agent and copper sulfate pentahydrate as precursor. The Cu/Cu2O nanoparticles were characterized by X-ray Diffraction (XRD, Energy Dispersive X-ray Fluorescence (EDXRF, Scanning Electron Microscope (SEM, and Transmission Electron Microscope (TEM. The analysis revealed the pattern of face-centered cubic (fcc crystal structure of copper Cu metal and cubic cuprites structure for Cu2O. The SEM result showed monodispersed and agglomerated particles with two micron sizes of about 180 nm and 800 nm, respectively. The TEM result showed few single crystal particles of face-centered cubic structures with average particle size about 11-14 nm. The catalytic activity of Cu/Cu2O nanoparticles for the decomposition of hydrogen peroxide was investigated and compared with manganese oxide MnO2. The results showed that the second-order equation provides the best correlation for the catalytic decomposition of H2O2 on Cu/Cu2O. The catalytic activity of hydrogen peroxide by Cu/Cu2O is less than the catalytic activity of MnO2 due to the presence of copper metal Cu with cuprous oxide Cu2O. © 2015 BCREC UNDIP. All rights reservedReceived: 6th January 2015; Revised: 14th March 2015; Accepted: 15th March 2015How to Cite: Badawy, S.M., El-Khashab, R.A., Nayl, A.A. (2015. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 169-174. (doi:10.9767/bcrec.10.2.7984.169-174 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7984.169-174  

  6. 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.

  7. Thermo-sensitive TRP channels in peripheral nerve injury: a review of their role in cold intolerance.

    Science.gov (United States)

    Kambiz, S; Duraku, L S; Holstege, J C; Hovius, S E R; Ruigrok, T J H; Walbeehm, E T

    2014-05-01

    One of the sensory complications of traumatic peripheral nerve injury is thermal intolerance, which manifests in humans mainly as cold intolerance. It has a major effect on the quality of life, and adequate therapy is not yet available. In order to better understand the pathophysiological background of thermal intolerance, we focus first on the various transient receptor potential (TRP) channels that are involved in temperature sensation, including their presence in peripheral nerves and in keratinocytes. Second, the role of thermo-sensitive TRP channels in cold and heat intolerance is described showing three different mechanisms that contribute to thermal intolerance in the skin: (a) an increased expression of TRP channels on nerve fibres and on keratinocytes, (b) a lower activation threshold of TRP channels and (c) the sprouting of non-injured nerve fibres. Finally, the data that are available on the effects of TRP channel agonists and antagonists and their clinical use are discussed. In conclusion, TRP channels play a major role in temperature sensation and in cold and heat intolerance. Unfortunately, the available pharmaceutical agents that successfully target TRP channels and counteract thermal intolerance are still very limited. Yet, our focus should remain on TRP channels since it is difficult to imagine a reliable treatment for thermal intolerance that will not involve TRP channels. Copyright © 2013 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

  8. Reactive oxygen species inhibit catalytic activity of peptidylarginine deiminase

    DEFF Research Database (Denmark)

    Damgaard, Dres; Bjørn, Mads Emil; Jensen, Peter Østrup

    2017-01-01

    on calcium and reducing conditions. However, reactive oxygen species (ROS) have been shown to induce citrullination of histones in granulocytes. Here we examine the ability of H2O2 and leukocyte-derived ROS to regulate PAD activity using citrullination of fibrinogen as read-out. H2O2 at concentrations above...... from stimulated leukocytes was unaffected by exogenously added H2O2 at concentrations up to 1000 µM. The role of ROS in regulating PAD activity may play an important part in preventing hypercitrullination of proteins....

  9. The role of Ala231 and Trp227 in the substrate specificities of fungal 17β-hydroxysteroid dehydrogenase and trihydroxynaphthalene reductase: Steroids versus smaller substrates.

    Science.gov (United States)

    Svegelj, Mojca Brunskole; Stojan, Jure; Rižner, Tea Lanišnik

    2012-03-01

    17β-Hydroxysteroid dehydrogenase and trihydroxynaphthalene reductase from the fungus Curvularia lunata (teleomorph: Cochliobolus lunatus; 17β-HSDcl and 3HNR, respectively) are two homologous short-chain dehydrogenase/reductase proteins that are 58% identical and have 86% similar amino acids. The minor differences in their substrate-binding regions are believed to be crucial for their substrate specificities. 3HNR shows high affinity for substrates with two rings, like trihydroxynaphthalene and 2,3-dihydro-2,5-dihydroxy-4H-benzopyran-4-one (DDBO), while 17β-HSDcl can accommodate ligands with four rings, like steroids. In the present study, we examined the role of Ala231 in 17β-HSDcl and Trp227 in 3HNR, as the potential key amino acids in the determination of substrate recognition based on size. We constructed Ala231Trp 17β-HSDcl and Trp227Ala 3HNR mutant proteins and used spectrophotometric analyses to compare their catalytic activities with those of the wild-type enzymes, for oxidation of 4-estrene-17β-ol-3-one and DDBO and for reduction of 4-estrene-3,17-dione and 9,10-phenanthrenequinone (PQ). The Ala231Trp side-chain substitution in 17β-HSDcl abolished and decreased (by 14.6-fold) the initial rates for steroid oxidation and reduction, respectively, while the initial rate for PQ reduction was increased 5.6-fold. The bulky Trp227Ala side-chain substitution in 3HNR enabled oxidation of 4-estrene-17β-ol-3-one, increased the initial rates for reduction of 4-estrene-3,17-dione and PQ by 4.5-fold and 1.5-fold, respectively, while the initial rate for DDBO oxidation was decreased 4.1-fold. Our TLC analysis and docking simulations also support these findings. Our study thus confirms the important roles of Ala231 in 17β-HSDcl and Trp227 in 3HNR, for the selection between larger and smaller substrates. Article from a special issue on steroids and microorganisms. Copyright © 2011 Elsevier Ltd. All rights reserved.

  10. Catalytic Activation of Nitrogen Dioxide for Selective Synthesis of Nitroorganics

    Science.gov (United States)

    2015-01-15

    reactivity from electrophilic nitration to ipso nitro-deboronation. Catalysis ; nitrogen dioxide; oxidative addition; reductive elimination; nitroarenes. U U...Brown, University of Notre Dame FINAL PERFORMANCE REPORT 1 Reductive Elimination to Form Carbon-NO2 Bonds. Contemporary methods in homogeneous ...Activation. One of the most significant recent developments in organometallic catalysis is the successful functionalization of hydrocarbons under

  11. Flexible macrocycles as versatile supports for catalytically active metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, JD; Gagnon, KJ; Teat, SJ; McIntosh, RD

    2016-02-12

    Here we present three structurally diverse clusters stabilised by the same macrocyclic polyphenol; t-butylcalix[8]arene. This work demonstrates the range of conformations the flexible ligand is capable of adopting, highlighting its versatility in metal coordination. In addition, a Ti complex displays activity for the ring-opening polymerisation of lactide

  12. Synthesis, characterization and study of catalytic activity of Silver ...

    Indian Academy of Sciences (India)

    activity was tested using liquid-phase selective oxidation of benzylic alcohols to aldehydes. The influence of some parameters such as optimum weight of Ag, catalyst dosage, ... Ag/ZnO nanocomposite; selective oxidation; benzyl alcohol; heterogeneous catalysis. ..... Rodríguez-Reyes J C F, Friend C M and Madix R J 2012.

  13. Glu-Trp-ONa or its acylated analogue (R-Glu-Trp-ONa administration enhances the wound healing in the model of chronic skin wounds in rabbits

    Directory of Open Access Journals (Sweden)

    Shevtsov MA

    2015-03-01

    Full Text Available Maxim A Shevtsov,1,2 Larisa V Smagina,1 Tatiana A Kudriavtceva,3 Sergey V Petlenko,4 Irina V Voronkina1 1Institute of Cytology of the Russian Academy of Sciences (RAS, St Petersburg, Russia; 2IP Pavlov State Medical University of St Petersburg, St Petersburg, Russia; 3Institute of Experimental Medicine of the North-West Branch of the Russian Academy of Medical Sciences (IEM NWB RAMS, St Petersburg, Russia; 4Military Medical Academy, St Petersburg, Russia Abstract: The management of chronic skin wounds represents a major therapeutic challenge. The synthesized dipeptide (Glu-Trp-ONa and its acylated analogue (R-Glu-Trp-ONa were assessed in the model of nonhealing dermal wounds in rabbits in relation to their healing properties in wound closure. Following wound modeling, the rabbits received a course of intraperitoneal injections of Glu-Trp-ONa or R-Glu-Trp-ONa. Phosphate-buffered saline and Solcoseryl® were applied as negative and positive control agents, respectively. An injection of Glu-Trp-ONa and R-Glu-Trp-ONa decreased the period of wound healing in animals in comparison to the control and Solcoseryl-treated groups. Acylation of Glu-Trp-ONa proved to be beneficial as related to the healing properties of the dipeptide. Subsequent zymography analyses showed that the applied peptides decreased the proteolytic activity of matrix metalloproteinases MMP-9, MMP-8, and MMP-2 in the early inflammatory phase and reversely increased the activity of MMP-9, MMP-8, and MMP-1 in the remodeling phase. Histological analyses of the wound sections (hematoxylin–eosin, Mallory’s staining confirmed the enhanced formation of granulation tissue and re-epithelialization in the experimental groups. By administering the peptides, wound closures increased significantly through the modulation of the MMPs’ activity, indicating their role in wound healing. Keywords: chronic wound, matrix metalloproteinases, small peptides

  14. Trends in Catalytic Activity for SOFC Anode materials

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Bessler, W. G.

    2008-01-01

    Quantum mechanical calculations on the level of density-functional theory are used to calculate the stability of surface-adsorbed hydrogen atoms, oxygen atoms, and hydroxyl radicals for a variety of metals (Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Pt, Au) that may be used as electrode materials...... for solid oxide fuel cell (SOFC) anodes. The reaction energies along the hydrogen oxidation pathway were quantified for both, oxygen spillover and hydrogen spillover mechanisms at the three-phase boundary. The ab initio results are compared to previously-obtained experimental anode activities measured...... for nine different metal/stabilized zirconia anodes. The experimentally-observed variation of electrode activity with anode material is well-correlated with the calculated stability of surface-adsorbed atomic oxygen, but uncorrelated with the stability of surface-adsorbed hydrogen. This finding indicates...

  15. Catalytic activity of bovine glutamate dehydrogenase requires a hexamer structure.

    OpenAIRE

    Bell, E T; Bell, J E

    1984-01-01

    Previous workers have shown that the hexamers of glutamate dehydrogenase are dissociated first into trimers and subsequently into monomers by increasing guanidinium chloride concentrations. In renaturation experiments it is shown that trimers of glutamate dehydrogenase can be reassociated to give the hexamer form of the enzyme, with full regain of activity. Monomeric subunits produced at high guanidinium chloride concentrations cannot be renatured. The trimer form of the enzyme is shown to ha...

  16. Stability and phase transfer of catalytically active platinum nanoparticle suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Sriram, Indira; Curtin, Alexandra E.; Chiaramonti, Ann N.; Cuchiaro, J. Hunter; Weidner, Andrew R.; Tingley, Tegan M.; Greenlee, Lauren F.; Jeerage, Kavita M., E-mail: jeerage@boulder.nist.gov [National Instrument of Standards and Technology, Applied Chemicals and Materials Division (United States)

    2015-05-15

    In this work, we present a robust synthesis protocol for platinum nanoparticles that yields a monomodal dispersion of particles that are approximately 100 nm in diameter. We determine that these particles are actually agglomerates of much smaller particles, creating a “raspberry” morphology. We demonstrate that these agglomerates are stable at room temperature for at least 8 weeks by dynamic light scattering. Furthermore, we demonstrate consistent electrocatalytic activity for methanol oxidation. Finally, we quantitatively explore the relationship between dispersion solvent and particle agglomeration; specifically, particles are found to agglomerate abruptly as solvent polarity decreases.

  17. Stability and phase transfer of catalytically active platinum nanoparticle suspensions

    International Nuclear Information System (INIS)

    Sriram, Indira; Curtin, Alexandra E.; Chiaramonti, Ann N.; Cuchiaro, J. Hunter; Weidner, Andrew R.; Tingley, Tegan M.; Greenlee, Lauren F.; Jeerage, Kavita M.

    2015-01-01

    In this work, we present a robust synthesis protocol for platinum nanoparticles that yields a monomodal dispersion of particles that are approximately 100 nm in diameter. We determine that these particles are actually agglomerates of much smaller particles, creating a “raspberry” morphology. We demonstrate that these agglomerates are stable at room temperature for at least 8 weeks by dynamic light scattering. Furthermore, we demonstrate consistent electrocatalytic activity for methanol oxidation. Finally, we quantitatively explore the relationship between dispersion solvent and particle agglomeration; specifically, particles are found to agglomerate abruptly as solvent polarity decreases

  18. Carbon Nanotube Materials for Substrate Enhanced Control of Catalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Heben, M.; Dillon, A. C.; Engtrakul, C.; Lee, S.-H.; Kelley, R. D.; Kini, A. M.

    2007-05-01

    Carbon SWNTs are attractive materials for supporting electrocatalysts. The properties of SWNTs are highly tunable and controlled by the nanotube's circumferential periodicity and their surface chemistry. These unique characteristics suggest that architectures constructed from these types of carbon support materials would exhibit interesting and useful properties. Here, we expect that the structure of the carbon nanotube support will play a major role in stabilizing metal electrocatalysts under extreme operating conditions and suppress both catalyst and support degradation. Furthermore, the chemical modification of the carbon nanotube surfaces can be expected to alter the interface between the catalyst and support, thus, enhancing the activity and utilization of the electrocatalysts. We plan to incorporate discrete reaction sites into the carbon nanotube lattice to create intimate electrical contacts with the catalyst particles to increase the metal catalyst activity and utilization. The work involves materials synthesis, design of electrode architectures on the nanoscale, control of the electronic, ionic, and mass fluxes, and use of advanced optical spectroscopy techniques.

  19. Small-Pore Molecular Sieves SAPO-34 with Chabazite Structure: Theoretical Study of Silicon Incorporation and Interrelated Catalytic Activity

    Science.gov (United States)

    Wang, Hong; Lewis, James; Liu, Zhongmin

    2011-03-01

    The catalytic conversion of methonal to olefin (MTO) has attracted attention both in industrial and academic fields. Strong evidence shows that small-pore molecular sieves with certain amount silicon incorporated (SAPO) present promising high catalytic activity in MTO conversion. Using DFT, we study the structural and electronic properties of chabazite SAPO-34. Although there are extensively experimental results show that silicon incorporation does not change the overall structure as the original AlPO structure, local structural changes are still created by silicon substitution, which probably accounted for the high catalytic activity. It is noted that the catalytic activity of SAPO-34 presents increasing trend along with the silicon incorporation amount increasing and maintain a flat peak even with more silicon incorporated. Hence, there is an optimal silicon incorporation amount which possibly yields the highest catalytic MTO conversion.

  20. Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity.

    Science.gov (United States)

    Potsi, Georgia; Ladavos, Athanasios K; Petrakis, Dimitrios; Douvalis, Alexios P; Sanakis, Yiannis; Katsiotis, Marios S; Papavassiliou, Georgios; Alhassan, Saeed; Gournis, Dimitrios; Rudolf, Petra

    2018-01-15

    Novel pillared structures were developed from the intercalation of iron-substituted cubic silsesquioxanes in a sodium and an acid-activated montmorillonite nanoclay and evaluated as acid catalysts. Octameric cubic oligosiloxanes were formed upon controlled hydrolytic polycondensation of the corresponding monomer (a diamino-alkoxysilane) and reacted with iron cations to form complexes that were intercalated within the layered nanoclay matrices. Upon calcination iron oxide nanoparticles are formed which are located on the silica cubes (pillars) and on the surfaces of the clay platelets. Acid activation of the nanoclay was performed in order to increase the number of acid active sites in the pristine clay and thus increase its catalytic activity. A plethora of analytical techniques including X-ray diffraction, thermal analyses, Fourier transform infrared, electron paramagnetic resonance, Raman, Mössbauer and X-ray photoelectron spectroscopies and porosimetry measurements were used in order to follow the synthesis steps and to fully characterize the final catalysts. The resulting pillared clays exhibit a high specific area and show significant acid catalytic activity that was verified using the catalytic dehydration of isopropanol asa probe reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Nanodiamond-Gold Nanocomposites with the Peroxidase-Like Oxidative Catalytic Activity.

    Science.gov (United States)

    Kim, Min-Chul; Lee, Dukhee; Jeong, Seong Hoon; Lee, Sang-Yup; Kang, Eunah

    2016-12-21

    Novel nanodiamond-gold nanocomposites (NDAus) are prepared, and their oxidative catalytic activity is examined. Gold nanoparticles are deposited on carboxylated nanodiamonds (NDs) by in situ chemical reduction of gold precursor ions to produce NDAus, which exhibit catalytic activity for the oxidation of o-phenylenediamine in the presence of hydrogen peroxide similarly to a peroxidase. This remarkable catalytic activity is exhibited only by the gold nanoparticle-decorated NDs and is not observed for either Au nanoparticles or NDs separately. Kinetic oxidative catalysis studies show that NDAus exhibit a ping-pong mechanism with an activation energy of 93.3 kJ mol -1 , with the oxidation reaction rate being proportional to the substrate concentration. NDAus retain considerable activity even after several instances of reuse and are compatible with a natural enzyme, allowing the detection of xanthine using cascade catalysis. Association with gold nanoparticles makes NDs a good carbonic catalyst due to charge transfer at the metal-carbon interface and facilitated substrate adsorption. The results of this study suggest that diverse carbonic catalysts can be obtained by interfacial incorporation of various metal/inorganic substances.

  2. Comprehensive Characterization of AMP-Activated Protein Kinase Catalytic Domain by Top-Down Mass Spectrometry

    Science.gov (United States)

    Yu, Deyang; Peng, Ying; Ayaz-Guner, Serife; Gregorich, Zachery R.; Ge, Ying

    2016-02-01

    AMP-activated protein kinase (AMPK) is a serine/threonine protein kinase that is essential in regulating energy metabolism in all eukaryotic cells. It is a heterotrimeric protein complex composed of a catalytic subunit (α) and two regulatory subunits (β and γ). C-terminal truncation of AMPKα at residue 312 yielded a protein that is active upon phosphorylation of Thr172 in the absence of β and γ subunits, which is refered to as the AMPK catalytic domain and commonly used to substitute for the AMPK heterotrimeric complex in in vitro kinase assays. However, a comprehensive characterization of the AMPK catalytic domain is lacking. Herein, we expressed a His-tagged human AMPK catalytic domin (denoted as AMPKΔ) in E. coli, comprehensively characterized AMPKΔ in its basal state and after in vitro phosphorylation using top-down mass spectrometry (MS), and assessed how phosphorylation of AMPKΔ affects its activity. Unexpectedly, we found that bacterially-expressed AMPKΔ was basally phosphorylated and localized the phosphorylation site to the His-tag. We found that AMPKΔ had noticeable basal activity and was capable of phosphorylating itself and its substrates without activating phosphorylation at Thr172. Moreover, our data suggested that Thr172 is the only site phosphorylated by its upstream kinase, liver kinase B1, and that this phosphorylation dramatically increases the kinase activity of AMPKΔ. Importantly, we demonstrated that top-down MS in conjunction with in vitro phosphorylation assay is a powerful approach for monitoring phosphorylation reaction and determining sequential order of phosphorylation events in kinase-substrate systems.

  3. Highly Oriented Growth of Catalytically Active Zeolite ZSM-5 Films with a Broad Range of Si/Al Ratios

    NARCIS (Netherlands)

    Fu, Donglong|info:eu-repo/dai/nl/412516918; Schmidt, Joel E.|info:eu-repo/dai/nl/413333736; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Chowdhury, Abhishek Dutta|info:eu-repo/dai/nl/412438003; Meirer, Florian; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2017-01-01

    Highly b-oriented zeolite ZSM-5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films.

  4. Rational design of ornithine decarboxylase with high catalytic activity for the production of putrescine.

    Science.gov (United States)

    Choi, Hyang; Kyeong, Hyun-Ho; Choi, Jung Min; Kim, Hak-Sung

    2014-09-01

    Putrescine finds wide industrial applications in the synthesis of polymers, pharmaceuticals, agrochemicals, and surfactants. Owing to economic and environmental concerns, the microbial production of putrescine has attracted a great deal of attention, and ornithine decarboxylase (ODC) is known to be a key enzyme in the biosynthetic pathway. Herein, we present the design of ODC from Escherichia coli with high catalytic efficiency using a structure-based rational approach. Through a substrate docking into the model structure of the enzyme, we first selected residues that might lead to an increase in catalytic activity. Of the selected residues that are located in the α-helix and the loops constituting the substrate entry site, a mutational analysis of the single mutants identified two key residues, I163 and E165. A combination of two single mutations resulted in a 62.5-fold increase in the catalytic efficiency when compared with the wild-type enzyme. Molecular dynamics simulations of the best mutant revealed that the substrate entry site becomes more flexible through mutations, while stabilizing the formation of the dimeric interface of the enzyme. Our approach can be applied to the design of other decarboxylases with high catalytic efficiency for the production of various chemicals through bio-based processes.

  5. Preparation of amino-functionalized regenerated cellulose membranes with high catalytic activity.

    Science.gov (United States)

    Wang, Wei; Bai, Qian; Liang, Tao; Bai, Huiyu; Liu, Xiaoya

    2017-09-01

    The modification of regenerated cellulose (RC) membranes was carried out by using silane coupling agents presenting primary and secondary amino-groups. The grafting of the amino groups onto the modified cellulose molecule was confirmed by X-ray photoelectron spectroscopies and 13 C nuclear magnetic resonance spectroscopic analyses. The crystallinity of the cellulose membranes (CM) decreased after chemical modification as indicated by the X-ray diffraction results. Moreover, a denser structure was observed at the surface and cross section of the modified membranes by SEM images. The contact angle measurements showed that the silane coupling treatment enhanced the hydrophobicity of the obtained materials. Then the catalytic properties of two types of modified membranes were studied in a batch process by evaluating their catalytic performance in a Knoevenagel condensation. The results indicated that the cellulose membrane grafted with many secondary amines exhibited a better catalytic activity compared to the one grafted only by primary amines. In addition, the compact structure of the modified membranes permitted their application in a pervaporation catalytic membrane reactor. Therefore, functional CM that prepared in this paper represented a promising material in the field of industrial catalysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Expression of the benign HEXA mutations, Arg247Trp and Arg249Trp, associated with beta-hexosaminidase A pseudodeficiency

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Z.; Petroulakis, E.; Salo, T. [Univ. of Manitoba (Canada)] [and others

    1994-09-01

    {beta}-Hexosaminidase (Hex A) is a heterodimer of {alpha} and {beta} subunits encoded by the HEXA and HEXB genes, respectively. Mutations in the HEXA gene typically cause Tay-Sachs disease or less severe forms of G{sub M2} gangliosidosis. However, two benign mutations (Arg247Trp and Arg249Trp) in the {alpha}-subunit of Hex A account for Hex A deficiency in {approximately}36% of non-Jewish enzyme-defined Tay-Sachs disease carriers. These mutations do not result in any apparent clinical phenotype in individuals who are genetic compounds with a second disease-causing mutation. We expressed the {alpha}-subunit harboring each of the benign mutations separately to study activity toward the synthetic substrate, 4-MUGS, for comparison to activity from enzymes containing mutations associated with other forms of G{sub M2} gangliosidosis. The C739T (Arg247Trp;benign), C745T (Arg 249Trp; benign), G805A (Gly269Ser; adult-onset), G749A (Gly250Asp; juvenile), and C508T (Arg170Trp; infantile) mutations were introduced into the {alpha}-subunit cDNA. These were transfected alone, or with the {beta}-subunit cDNA, to generate Hex S ({alpha}{alpha}) or Hex A ({alpha}{beta}), respectively. The activities were monitored using 4-MUGS, and the levels of {alpha}-subunit protein were assessed by Western blotting. Repeated experiments show that the benign mutations produce approximately 35% of normal Hex S and 40% of normal Hex A activity. This level is much higher than that of Hex A harbouring the Gly169Ser adult-onset mutation (12%). A sequential decrease in expressed Hex A activity is observed as mutations associated with more severe phenotypes are expressed. The benign mutations also result in lower levels of mature {alpha}-subunit protein compared to normal, and slightly reduced levels of {alpha}-subunit precursor protein. The Hex A deficiency resulting from benign mutations is not as great as that associated with disease-causing mutations.

  7. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  8. ALD Functionalized Nanoporous Gold: Thermal Stability, Mechanical Properties, and Catalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Biener, M M; Biener, J; Wichmann, A; Wittstock, A; Baumann, T F; Baeumer, M; Hamza, A V

    2011-03-24

    Nanoporous metals have many technologically promising applications but their tendency to coarsen limits their long-term stability and excludes high temperature applications. Here, we demonstrate that atomic layer deposition (ALD) can be used to stabilize and functionalize nanoporous metals. Specifically, we studied the effect of nanometer-thick alumina and titania ALD films on thermal stability, mechanical properties, and catalytic activity of nanoporous gold (np-Au). Our results demonstrate that even only one-nm-thick oxide films can stabilize the nanoscale morphology of np-Au up to 1000 C, while simultaneously making the material stronger and stiffer. The catalytic activity of np-Au can be drastically increased by TiO{sub 2} ALD coatings. Our results open the door to high temperature sensor, actuator, and catalysis applications and functionalized electrodes for energy storage and harvesting applications.

  9. Gold Incorporated Mesoporous Silica Thin Film Model Surface as a Robust SERS and Catalytically Active Substrate

    Directory of Open Access Journals (Sweden)

    Anandakumari Chandrasekharan Sunil Sekhar

    2016-05-01

    Full Text Available Ultra-small gold nanoparticles incorporated in mesoporous silica thin films with accessible pore channels perpendicular to the substrate are prepared by a modified sol-gel method. The simple and easy spin coating technique is applied here to make homogeneous thin films. The surface characterization using FESEM shows crack-free films with a perpendicular pore arrangement. The applicability of these thin films as catalysts as well as a robust SERS active substrate for model catalysis study is tested. Compared to bare silica film our gold incorporated silica, GSM-23F gave an enhancement factor of 103 for RhB with a laser source 633 nm. The reduction reaction of p-nitrophenol with sodium borohydride from our thin films shows a decrease in peak intensity corresponding to –NO2 group as time proceeds, confirming the catalytic activity. Such model surfaces can potentially bridge the material gap between a real catalytic system and surface science studies.

  10. Integrating nanotubes into microsystems with electron beam lithography and in situ catalytically activated growth

    DEFF Research Database (Denmark)

    Gjerde, Kjetil; Fornés-Mora, Marc; Kjelstrup-Hansen, Jakob

    2006-01-01

    Integration of freestanding wire-like structures such as multi walled carbon nanotubes (MWCNT) into microsystems has many potential applications. Devices such as AFM tips or improved electrodes for conductivity measurements are obvious candidates. Catalytically activated growth opens up the possi......Integration of freestanding wire-like structures such as multi walled carbon nanotubes (MWCNT) into microsystems has many potential applications. Devices such as AFM tips or improved electrodes for conductivity measurements are obvious candidates. Catalytically activated growth opens up...... the possibility of waferscale fabrication of such devices. We combine conventional microfabrication techniques with state of the art electron beam lithography (EBL) to precisely position catalyst nanoparticles with sub 100 nm diameter into the microsystems. In particular, we have explored two main approaches...

  11. Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins

    Directory of Open Access Journals (Sweden)

    Maria Rosaria Acocella

    2017-04-01

    Full Text Available This article compares the catalytic activities of oxidized carbon black (oCB and graphene oxide (eGO samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC. Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m2/g, as oxidized by the Hummers’ method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.

  12. Plasma-catalytic reforming of ethanol: influence of air activation rate and reforming temperature

    International Nuclear Information System (INIS)

    Nedybaliuk, O.A.; Chernyak, V.Ya.; Fedirchuk, I.I.; Demchina, V.P.; Bortyshevsky, V.A.; Korzh, R.V.

    2016-01-01

    This paper presents the study of the influence that air activation rate and reforming temperature have on the gaseous products composition and conversion efficiency during the plasma-catalytic reforming of ethanol. The analysis of product composition showed that the conversion efficiency of ethanol has a maximum in the studied range of reforming temperatures. Researched system provided high reforming efficiency and high hydrogen energy yield at the lower temperatures than traditional conversion technologies

  13. Enantioselective synthesis of a PKC inhibitor via catalytic C-H bond activation.

    Science.gov (United States)

    Wilson, Rebecca M; Thalji, Reema K; Bergman, Robert G; Ellman, Jonathan A

    2006-04-13

    [reaction: see text] The syntheses of two biologically active molecules possessing dihydropyrroloindole cores (1 and 2) were completed using rhodium-catalyzed imine-directed C-H bond functionalization, with the second of these molecules containing a stereocenter that can be set with 90% ee during cyclization using chiral nonracemic phosphoramidite ligands. Catalytic decarbonylation and direct indole/maleimide coupling provide efficient access to 2.

  14. Fabricating highly catalytically active block copolymer/metal nanoparticle microstructures at the liquid/liquid interface.

    Science.gov (United States)

    Diao, Qi; Li, Xiaoyang; Diao, Mengxiao; Lee, Yong-Ill; Liu, Hong-Guo

    2018-03-22

    Our previous studies have shown that the metal nanoparticle/polymer composite structures fabricated at the liquid/liquid interface have good reusability but lower catalytic activity for heterogeneous reactions in aqueous solutions. This should be attributed to the poor water wettability and more compact structure of the polymer matrices. Therefore, it should be possible to improve the catalytic activity through designing and fabricating a porous composite structure with good water wettability. A modified liquid/liquid interface adsorption and fabrication method was used. An aqueous solution of copper acetate and a chloroform/DMF mixed solution of PS-b-PAA acted as the two phases. Through spontaneous emulsification, self-assembly of the polymer molecules with Cu 2+ ions in the droplets, and adsorption of the formed spherical micelles and nanofibers to the planar liquid/liquid interface, a porous composite microstructure was formed. This structure consisted of nanofiber-connected nanospheres which have a PS core and a PAA corona. Tiny and well-dispersed Cu nanoparticles were embedded in the hydrophilic corona and were adsorbed on the nanofibers surface as well. After physical cross-linking with 1,6-diaminohexane, the composite material exhibited high catalytic activity and good reusability for the reactions in aqueous solutions. For example, the rate constant for the reduction of p-nitroaniline reached 1965 s -1  g -1 . Copyright © 2018 Elsevier Inc. All rights reserved.

  15. Regulating Water-Reduction Kinetics in Cobalt Phosphide for Enhancing HER Catalytic Activity in Alkaline Solution.

    Science.gov (United States)

    Xu, Kun; Ding, Hui; Zhang, Mengxing; Chen, Min; Hao, Zikai; Zhang, Lidong; Wu, Changzheng; Xie, Yi

    2017-07-01

    Electrochemical water splitting to produce hydrogen renders a promising pathway for renewable energy storage. Considering limited electrocatalysts have good oxygen-evolution reaction (OER) catalytic activity in acid solution while numerous economical materials show excellent OER catalytic performance in alkaline solution, developing new strategies that enhance the alkaline hydrogen-evolution reaction (HER) catalytic activity of cost-effective catalysts is highly desirable for achieving highly efficient overall water splitting. Herein, it is demonstrated that synergistic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts can significantly promote alkaline HER catalysis. Using oxygen-incorporated Co 2 P as an example, the synergistic effect brings about 15-fold enhancement of alkaline HER activity. Theory calculations confirm that the water dissociation free energy of Co 2 P decreases significantly after oxygen incorporation, and the hydrogen adsorption free energy can also be optimized simultaneously. The finding suggests the powerful effectiveness of synergetic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts for alkaline HER catalysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Effect of the synthetic method on the catalytic activity of alumina: Epoxidation of cyclohexene

    Energy Technology Data Exchange (ETDEWEB)

    Valderruten, N.E., E-mail: nevalderruten@icesi.edu.co [Departamento de Ciencias Químicas, Universidad Icesi, Cali (Colombia); Peña, W.F.; Ramírez, A.E. [Departamento de Química, Universidad del Cauca, Popayán (Colombia); Rodríguez-Páez, J.E. [Departamento de Física, Universidad del Cauca, Popayán (Colombia)

    2015-02-15

    Graphical abstract: Temperature influence on percent conversion and selectivity in the epoxidation of cyclohexene using commercial alumina as a catalyst. - Highlights: • Aluminum oxide was synthesized using Pechini method. • The alumina obtained showed a mix of boehmite and γ-alumina phases. • We research an economically feasible method to obtain alumina for use as a catalyst. • Alumina obtained by Pechini showed high percent conversion and/or selectivity. • The best results were 78% conversion and 78% selectivity to epoxidation reactions. - Abstract: Al{sub 2}O{sub 3} was prepared from different inorganic precursors via the Pechini method and compared with Al{sub 2}O{sub 3} prepared by the sol–gel method. Structural characterization of these materials was carried out by FTIR, X-ray diffraction (XRD), N{sub 2} adsorption at −196 °C and transmission electron microscopy (TEM). The solids were tested in the epoxidation of cyclohexene and a difference in their catalytic activities was observed. The characterization results indicate that the samples prepared by Pechini have a mixture of γ-alumina and boehmite, a condition favoring catalytic activity, whereas the sol–gel sample is less crystalline due to higher boehmite content. These results indicate that both the nature of the precursor and the method of synthesis strongly affect the catalytic activity of Al{sub 2}O{sub 3}.

  17. Computational study of retro Trp-cage

    Czech Academy of Sciences Publication Activity Database

    Vymětal, Jiří; Bathula, S. R.; Žídek, L.; Černý, Jiří; Sklenář, V.; Vondrášek, Jiří

    2012-01-01

    Roč. 12, č. 1 (2012), s. 54-55 ISSN 1210-8529. [10th Discussions in Structural Molecular Biology . 22.03.2012-24.03.2012, Nové Hrady] Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : TRP-cage Subject RIV: CF - Physical ; Theoretical Chemistry

  18. Regulation of xanthine oxidase activity by substrates at active sites via cooperative interactions between catalytic subunits: implication to drug pharmacokinetics.

    Science.gov (United States)

    Tai, L A; Hwang, K C

    2011-01-01

    Three xanthine oxidase substrates (i.e., xanthine, adenine, and 2-amino-4-hydroxypterin) show a "substrate inhibition" pattern (i.e., slower turnover rates at higher substrate concentrations), whereas another two substrates (i.e., xanthopterin and lumazine) show a "substrate activation" pattern (i.e., higher turnover rates at higher substrate concentrations). Binding of a 6-formylpterin at one of the two xanthine oxidase active sites slows down the turnover rate of xanthine at the adjacent active site from 17.0 s(-1) to 10.5 s(-1), and converts the V-[S] plot from "substrate inhibition" pattern to a classical Michaelis-Menten hyperbolic saturation pattern. In contrast, binding of xanthine at an active site accelerates the turnover rate of 6-formylpterin at the neighboring active site. The experimental results demonstrate that a substrate can regulate the activity of xanthine oxidase via binding at the active sites; or a xanthine oxidase catalytic subunit can simultaneously serve as a regulatory unit. Theoretical simulation based on the velocity equation derived from the extended Michaelis-Menten model shows that the substrate inhibition and the substrate activation behavior in the V-[S] plots could be obtained by introducing cooperative interactions between two catalytic subunits in homodimeric enzymes. The current work confirms that there exist very strong cooperative interactions between the two catalytic subunits of xanthine oxidase.

  19. 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

  20. Rapid glucocorticoid-induced activation of TRP and CB1 receptors causes biphasic modulation of glutamate release in gastric-related hypothalamic preautonomic neurons

    Directory of Open Access Journals (Sweden)

    Carie R. Boychuk

    2013-01-01

    Full Text Available Glucocorticoids rapidly regulate synaptic input to neuroendocrine cells in the hypothalamic paraventricular nucleus (PVN by inducing the retrograde release of endogenous messengers. Here we investigated the rapid effects of dexamethasone (DEX on excitatory synaptic input to feeding-related, preautonomic PVN neurons using whole-cell patch-clamp recordings. In ~50% of identified gastric-related preautonomic PVN neurons, DEX elicited a biphasic synaptic response characterized by an initial rapid and transient increase in the frequency of miniature excitatory postsynaptic currents (mEPSCs, followed by a decrease in mEPSC frequency within 9 min; remaining cells displayed only a decrease in mEPSC frequency. The late-phase decrease in mEPSC frequency was mimicked by the cannabinoid receptor agonists anandamide and WIN 55,212-2, and it was blocked by the CB1 receptor antagonist AM251. The biphasic DEX effect was mimicked by anandamide (AEA. The early increase in mEPSCs was mimicked by activation of transient receptor potential vanilloid type 1 (TRPV1 receptors with capsaicin and by activation of TRPV4 receptors with 4-α-PDD. The increase was reduced, but not blocked, by selective TRPV1 antagonists and in TRPV1-knockout mice; it was blocked completely by the broad-spectrum TRPV antagonist ruthenium red and by combined application of selective TRPV1 and TRPV4 antagonists. The DEX effects were prevented entirely by intracellular infusion of the G-protein inhibitor, GDPβS. Thus, DEX biphasically modulates synaptic glutamate onto a subset of gastric-related PVN neurons, which is likely mediated by induction of a retrograde messenger. The effect includes a TRPV1/4 receptor-mediated transient increase and subsequent CB1 receptor-mediated suppression of glutamate release. Multiphasic modulation of glutamate input to PVN neurons represents a previously unappreciated complexity of control of autonomic output by glucocorticoids and eCBs.

  1. Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

    Directory of Open Access Journals (Sweden)

    Azzedine Bouleghlimat

    2017-09-01

    Full Text Available In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 °C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

  2. Facile and green synthesis of cellulose nanocrystal-supported gold nanoparticles with superior catalytic activity.

    Science.gov (United States)

    Yan, Wei; Chen, Chang; Wang, Ling; Zhang, Dan; Li, Ai-Jun; Yao, Zheng; Shi, Li-Yi

    2016-04-20

    The emphasis of science and technology shifts toward environmentally friendly and sustainable resources and processes. Herein, we report a facile, one-pot and green synthesis of biomaterial-supported gold nanoparticles (AuNPs) with superior catalytic activity. Cellulose nanocrystal (CNC)-supported AuNPs were prepared by heating the aqueous mixture of HAuCl4, CNCs and polyethylene glycol, avoiding toxic chemicals, extreme condition and complicated procedure. The resultant CNC-supported AuNPs exhibited catalytic activities for the reduction of 4-nitrophenol by sodium borohydride. The maximum apparent rate constant reached 1.47×10(-2)s(-1), and the turnover frequency reached 641h(-1). The superior catalytic performance can be ascribed to the large amount of highly dispersed AuNPs with few nanometers in size which are loaded on CNCs. About 90% of the AuNPs are smaller than 10nm, and nearly 60% of the AuNPs are smaller than 5nm. The synthesis is eco-friendly, facile and low-cost, thus has great potential for industrial and medical applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. The non-catalytic domains of Drosophila katanin regulate its abundance and microtubule-disassembly activity.

    Directory of Open Access Journals (Sweden)

    Kyle D Grode

    Full Text Available Microtubule severing is a biochemical reaction that generates an internal break in a microtubule and regulation of microtubule severing is critical for cellular processes such as ciliogenesis, morphogenesis, and meiosis and mitosis. Katanin is a conserved heterodimeric ATPase that severs and disassembles microtubules, but the molecular determinants for regulation of microtubule severing by katanin remain poorly defined. Here we show that the non-catalytic domains of Drosophila katanin regulate its abundance and activity in living cells. Our data indicate that the microtubule-interacting and trafficking (MIT domain and adjacent linker region of the Drosophila katanin catalytic subunit Kat60 cooperate to regulate microtubule severing in two distinct ways. First, the MIT domain and linker region of Kat60 decrease its abundance by enhancing its proteasome-dependent degradation. The Drosophila katanin regulatory subunit Kat80, which is required to stabilize Kat60 in cells, conversely reduces the proteasome-dependent degradation of Kat60. Second, the MIT domain and linker region of Kat60 augment its microtubule-disassembly activity by enhancing its association with microtubules. On the basis of our data, we propose that the non-catalytic domains of Drosophila katanin serve as the principal sites of integration of regulatory inputs, thereby controlling its ability to sever and disassemble microtubules.

  4. Lanthanide(III) ion - luminescent and catalytically active center of aniline condensation with butyric aldehyde

    International Nuclear Information System (INIS)

    Bulgakov, R.G.; Kuleshov, S.P.; Makhmutov, A.R.

    2007-01-01

    New type of chemiluminescent-catalytic transformation, where lanthanide(III) ion performs as luminescent and high effective catalytic active center, is observed. The chemiluminescent (CL) is generated in the reaction of aniline condensation with butyric aldehyde in DMFA with the formation of 2-propyl-3-ethyl quinoline that is catalyzed by LnCl 3 ·6H 2 O (Ln=Eu, Tb and Ho). Excited ions Eu* 3+ and Tb* 3+ are served as emitters of CL when using salts EuCl 3 ·6H 2 O and TbCl 3 ·6H 2 O by way of catalysts, and in the case of HoCl 3 ·6H 2 O triplet-excited state of 2-propyl-3-ethyl quinoline ( 3 C 14 H 17 N*) is an emitter of CL [ru

  5. Catalytic Activity of Silicon Nanowires Decorated with Gold and Copper Nanoparticles Deposited by Pulsed Laser Ablation

    Directory of Open Access Journals (Sweden)

    Michele Casiello

    2018-01-01

    Full Text Available Silicon nanowires (SiNWs decorated by pulsed laser ablation with gold or copper nanoparticles (labeled as AuNPs@SiNWs and CuNPs@SiNWs were investigated for their catalytic properties. Results demonstrated high catalytic performances in the Caryl–N couplings and subsequent carbonylations for gold and copper catalysts, respectively, that have no precedents in the literature. The excellent activity, attested by the very high turn over number (TON values, was due both to the uniform coverage along the NW length and to the absence of the chemical shell surrounding the metal nanoparticles (MeNPs. A high recyclability was also observed and can be ascribed to the strong covalent interaction at the Me–Si interface by virtue of metal “silicides” formation.

  6. Preparation, Characterization and Catalytic Activity of Nickel Molybdate (NiMoO4 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hicham Oudghiri-Hassani

    2018-01-01

    Full Text Available Nickel molybdate (NiMoO4 nanoparticles were synthesized via calcination of an oxalate complex in static air at 500 °C. The oxalate complex was analyzed by thermal gravimetric analysis (TGA and Fourier transform infrared spectroscopy (FTIR. The as-synthesized nickel molybdate was characterized by Brunauer–Emmett–Teller technique (BET, X-ray diffraction (XRD, and transmission electron microscopy (TEM and its catalytic efficiency was tested in the reduction reaction of the three-nitrophenol isomers. The nickel molybdate displays a very high activity in the catalytic reduction of the nitro functional group to an amino. The reduction progress was controlled using Ultraviolet-Visible (UV-Vis absorption.

  7. Preparation, photo-catalytic activity of cuprous oxide nano-crystallites with different sizes

    International Nuclear Information System (INIS)

    Tang Aidong; Xiao Yu; Ouyang Jing; Nie Sha

    2008-01-01

    Cuprous oxide (Cu 2 O) nano-crystallites with different sizes were prepared via electrolysis method and characterized by X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Its photo-catalytic activities in the degradation of methyl orange as the model pollutant using UV light as an energy source were investigated. The XRD patterns showed that the sizes of Cu 2 O nano-crystallite decreased with the increasement of cetyltrimethyl ammonium bromide (CTAB) being added into the electrolyte, which were ranging from 27 nm to 48 nm. The progress of photo-catalytic degradation of the methyl orange was observed by monitoring the concentration change of the methyl orange solution. The highest decolorization ratio of 90% was observed for the sample prepared by addition of 0.05 g/L CTAB after photo-degradating 50 mg/L of methyl orange solution for 70 min. The mechanism of photo-degradation was discussed

  8. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland

    2013-08-14

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  9. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  10. Effects of Acid Treatment on the Acidic Properties and Catalytic Activity of MCM-41 for the Oxidative Dehydrogenation of Isobutane

    OpenAIRE

    Ehiro, Takuya; Itagaki, Ai; Misu, Hisanobu; Nakagawa, Keizo; Katoh, Masahiro; Katou, Yuuki; Ninomiya, Wataru; Sugiyama, Shigeru

    2016-01-01

    Mesoporous silicas have shown promise as materials for solid catalysts or catalyst supports due to their unique characteristics. Metal-doped mesoporous silicas are known to be catalytically active in the oxidative dehydrogenation (ODH) of isobutane. However, heavy-metal-free mesoporous silicas have not been studied closely for their use as catalysts. In the present study, MCM-41 (#41 Mobil composition of matter) was acid-treated to enhance its catalytic activity, although pure MCM-41 was conf...

  11. Catalytic Y-tailed amphiphilic homopolymers - aqueous nanoreactors for high activity, low loading SCS pincer catalysts.

    Science.gov (United States)

    Patterson, Joseph P; Cotanda, Pepa; Kelley, Elizabeth G; Moughton, Adam O; Lu, Annhelen; Epps, Thomas H; O'Reilly, Rachel K

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity.

  12. Catalytically active and hierarchically porous SAPO-11 zeolite synthesized in the presence of polyhexamethylene biguanidine

    KAUST Repository

    Liu, Yan

    2014-03-01

    Hierarchically porous SAPO-11 zeolite (H-SAPO-11) is rationally synthesized from a starting silicoaluminophosphate gel in the presence of polyhexamethylene biguanidine as a mesoscale template. The sample is well characterized by XRD, N2 sorption, SEM, TEM, NMR, XPS, NH3-TPD, and TG techniques. The results show that the sample obtained has good crystallinity, hierarchical porosity (mesopores at ca. 10nm and macropores at ca. 50-200nm), high BET surface area (226m2/g), large pore volume (0.25cm3/g), and abundant medium and strong acidic sites (0.36mmol/g). After loading Pt (0.5wt.%) on H-SAPO-11 by using wet impregnation method, catalytic hydroisomerization tests of n-dodecane show that the hierarchical Pt/SAPO-11 zeolite exhibits high conversion of n-dodecane and enhanced selectivity for branched products as well as reduced selectivity for cracking products, compared with conventional Pt/SAPO-11 zeolite. This phenomenon is reasonably attributed to the presence of hierarchical porosity, which is favorable for access of reactants on catalytically active sites. The improvement in catalytic performance in long-chain paraffin hydroisomerization over Pt/SAPO-11-based catalyst is of great importance for its industrial applications in the future. © 2013 Elsevier Inc.

  13. New insights into the active site structure and catalytic mechanism of tyrosinase and its related proteins.

    Science.gov (United States)

    Olivares, Concepcion; Solano, Francisco

    2009-12-01

    Tyrosinases are widely distributed in nature. They are copper-containing oxidases belonging to the type 3 copper protein family, together with catechol oxidases and haemocyanins. Tyrosinases are essential enzymes in melanin biosynthesis and therefore responsible for pigmentation of skin and hair in mammals, where two more enzymes, the tyrosinase-related proteins (Tyrps), participate in the pathway. The structure and catalytic mechanism of mammalian tyrosinases have been extensively studied but they are not completely understood because of the lack of information on the tertiary structure. The availability of crystallographic data of one plant catechol oxidase and one bacterial tyrosinase has improved the model of the three-dimensional structure of the active site of the enzyme. Furthermore, sequence comparison of tyrosinase and the Tyrps reveals that the three orthologue proteins share many key structural features, because of their common origin from an ancestral gene, although the specific residues responsible for their different catalytic capabilities have not been identified yet. This review summarizes our current knowledge of tyrosinase and Tyrps structure and function and describes the catalytic mechanism of tyrosinase and Dct/Tyrp2, which are better characterized.

  14. The Contribution of Non-catalytic Carbohydrate Binding Modules to the Activity of Lytic Polysaccharide Monooxygenases*

    Science.gov (United States)

    Crouch, Lucy I.; Labourel, Aurore; Walton, Paul H.; Davies, Gideon J.; Gilbert, Harry J.

    2016-01-01

    Lignocellulosic biomass is a sustainable industrial substrate. Copper-dependent lytic polysaccharide monooxygenases (LPMOs) contribute to the degradation of lignocellulose and increase the efficiency of biofuel production. LPMOs can contain non-catalytic carbohydrate binding modules (CBMs), but their role in the activity of these enzymes is poorly understood. Here we explored the importance of CBMs in LPMO function. The family 2a CBMs of two monooxygenases, CfLPMO10 and TbLPMO10 from Cellulomonas fimi and Thermobispora bispora, respectively, were deleted and/or replaced with CBMs from other proteins. The data showed that the CBMs could potentiate and, surprisingly, inhibit LPMO activity, and that these effects were both enzyme-specific and substrate-specific. Removing the natural CBM or introducing CtCBM3a, from the Clostridium thermocellum cellulosome scaffoldin CipA, almost abolished the catalytic activity of the LPMOs against the cellulosic substrates. The deleterious effect of CBM removal likely reflects the importance of prolonged presentation of the enzyme on the surface of the substrate for efficient catalytic activity, as only LPMOs appended to CBMs bound tightly to cellulose. The negative impact of CtCBM3a is in sharp contrast with the capacity of this binding module to potentiate the activity of a range of glycoside hydrolases including cellulases. The deletion of the endogenous CBM from CfLPMO10 or the introduction of a family 10 CBM from Cellvibrio japonicus LPMO10B into TbLPMO10 influenced the quantity of non-oxidized products generated, demonstrating that CBMs can modulate the mode of action of LPMOs. This study demonstrates that engineered LPMO-CBM hybrids can display enhanced industrially relevant oxygenations. PMID:26801613

  15. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

    International Nuclear Information System (INIS)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-01

    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO x . • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO 2 species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO 2 and H 2 O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO 2 /MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO x conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO 2 species responsible for fast SCR reactions.

  16. Enhanced catalytic activity without the use of an external light source using microwave-synthesized CuO nanopetals

    Directory of Open Access Journals (Sweden)

    Govinda Lakhotiya

    2017-05-01

    Full Text Available We report enhanced catalytic activity of CuO nanopetals synthesized by microwave-assisted wet chemical synthesis. The catalytic reaction of CuO nanopetals and H2O2 was studied with the application of external light source and also under dark conditions for the degradation of the hazardous dye methylene blue. The CuO nanopetals showed significant catalytic activity for the fast degradation of methylene blue and rhodamine B (RhB under dark conditions, without the application of an external light source. This increased catalytic activity was attributed to the co-operative role of H2O2 and the large specific surface area (≈40 m2·g−1 of the nanopetals. We propose a detail mechanism for this fast degradation. A separate study of the effect of different H2O2 concentrations for the degradation of methylene blue under dark conditions is also illustrated.

  17. Modulation of TRP channels by resveratrol and other stilbenoids

    Directory of Open Access Journals (Sweden)

    Yu Lina

    2013-02-01

    Full Text Available Abstract Background Resveratrol (3,5,4’ - trihydroxy-trans-stilbene, a widely distributed natural stilbenoid, was proposed to account for the unique effects of red wine on life span and health. It has been reported to possess various biological and pharmacological activities, such as anti-oxidant, anti-inflammatory, and anti-carcinogenic effects. Here, using whole-cell patch-clamp techniques and behavioral analyses, we investigated whether resveratrol and other stilbenoids can modulate TRP channels in sensory neurons in vitro, and have analgesic effects in vivo. Results We found that resveratrol dose-dependently suppressed the allyl isothiocyanate (AITC-induced currents (IAITC in HEK293 cells that express TRPA1, as well as in rat dorsal root ganglion (DRG neurons. Instead, pinosylvin methyl ether (PME, another derivate of stilbene which has a similar structure to resveratrol, dose-dependently blocked the capsaicin-induced currents (ICAP in HEK293 cells that express TRPV1 as well as in DRG neurons. Interestingly, resveratrol had no inhibitory effect on the ICAP, and PME had no effect on the IAITC. Otherwise, trans-stilbene showed no any effect on IAITC or ICAP. The concentration response curve of AITC showed that resveratrol inhibited the action of TRPA1 not by changing the EC50, but by suppressing the AITC-induced maximum response. By contrast, the inhibition of TRPV1 by PME did not change the capsaicin-induced maximum response but did cause a right shift of the EC50. Moreover, pre-administration of resveratrol suppressed intraplantar injections of AITC-evoked nocifensive behaviors, as well as that PME suppressed capsaicin-evoked one. Conclusions These data suggest that resveratrol and other stilbenoids may have an inhibitory effect on TRP channels. In addition, these stilbenoids modulate TRP channel activity in different ways.

  18. Effect of dose and dose rate of gamma radiation on catalytic activity of catalase

    International Nuclear Information System (INIS)

    Vaclav Cuba; Tereza Pavelkova; Viliam Mucka

    2010-01-01

    Catalytic activity of gamma irradiated catalase from bovine liver was studied for hydrogen peroxide decomposition at constant temperature and pressure. The measurement was performed at temperatures 27, 32, 37, 42 and 47 deg C. Solutions containing 1 and 0.01 g dm -3 of catalase in phosphate buffer were used for the study. Repeatability of both sample preparation and kinetics measurement was experimentally verified. Rate constants of the reaction were determined for all temperatures and the activation energy was evaluated from Arrhenius plot. Gamma irradiation was performed using 60 Co radionuclide source Gammacell 220 at two different dose rates 5.5 and 70 Gy h -1 , with doses ranging from 10 to 1000 Gy. The observed reaction of irradiated and non-irradiated catalase with hydrogen peroxide is of the first order. Irradiation significantly decreases catalytic activity of catalase, but the activation energy does not depend markedly on the dose. The effect of irradiation is more significant at higher dose rate. (author)

  19. Catalytic performance of activated carbon supported cobalt catalyst for CO2 reforming of CH4.

    Science.gov (United States)

    Zhang, Guojie; Su, Aiting; Du, Yannian; Qu, Jiangwen; Xu, Ying

    2014-11-01

    Syngas production by CO2 reforming of CH4 in a fixed bed reactor was investigated over a series of activated carbon (AC) supported Co catalysts as a function of Co loading (between 15 and 30wt.%) and calcination temperature (Tc=300, 400 or 500°C). The catalytic performance was assessed through CH4 and CO2 conversions and long-term stability. XRD and SEM were used to characterize the catalysts. It was found that the stability of Co/AC catalysts was strongly dependent on the Co loading and calcination temperature. For the loadings (25wt.% for Tc=300°C), stable activities have been achieved. The loading of excess Co (>wt.% 25) causes negative effects not only on the performance of the catalysts but also on the support surface properties. In addition, the experiment showed that ultrasound can enhance and promote dispersion of the active metal on the carrier, thus improving the catalytic performance of the catalyst. The catalyst activity can be long-term stably maintained, and no obvious deactivation has been observed in the first 2700min. After analyzing the characteristics, a reaction mechanism for CO2 reforming of CH4 over Co/AC catalyst was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. 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.

  1. Green Synthesis and Catalytic Activity of Gold Nanoparticles Synthesized by Artemisia capillaris Water Extract

    Science.gov (United States)

    Lim, Soo Hyeon; Ahn, Eun-Young; Park, Youmie

    2016-10-01

    Gold nanoparticles were synthesized using a water extract of Artemisia capillaris (AC-AuNPs) under different extract concentrations, and their catalytic activity was evaluated in a 4-nitrophenol reduction reaction in the presence of sodium borohydride. The AC-AuNPs showed violet or wine colors with characteristic surface plasmon resonance bands at 534 543 nm that were dependent on the extract concentration. Spherical nanoparticles with an average size of 16.88 ± 5.47 29.93 ± 9.80 nm were observed by transmission electron microscopy. A blue shift in the maximum surface plasmon resonance was observed with increasing extract concentration. The face-centered cubic structure of AC-AuNPs was confirmed by high-resolution X-ray diffraction analysis. Based on phytochemical screening and Fourier transform infrared spectra, flavonoids, phenolic compounds, and amino acids present in the extract contributed to the reduction of Au ions to AC-AuNPs. The average size of the AC-AuNPs decreased as the extract concentration during the synthesis was increased. Higher 4-nitrophenol reduction reaction rate constants were observed for smaller sizes. The extract in the AC-AuNPs was removed by centrifugation to investigate the effect of the extract in the reduction reaction. Interestingly, the removal of extracts greatly enhanced their catalytic activity by up to 50.4 %. The proposed experimental method, which uses simple centrifugation, can be applied to other metallic nanoparticles that are green synthesized with plant extracts to enhance their catalytic activity.

  2. A new experimental setup for high-pressure catalytic activity measurements on surface deposited mass-selected Pt clusters

    International Nuclear Information System (INIS)

    Watanabe, Yoshihide; Isomura, Noritake

    2009-01-01

    A new experimental setup to study catalytic and electronic properties of size-selected clusters on metal oxide substrates from the viewpoint of cluster-support interaction and to formulate a method for the development of heterogeneous catalysts such as automotive exhaust catalysts has been developed. The apparatus consists of a size-selected cluster source, a photoemission spectrometer, a scanning tunneling microscope (STM), and a high-pressure reaction cell. The high-pressure reaction cell measurements provided information on catalytic properties in conditions close to practical use. The authors investigated size-selected platinum clusters deposited on a TiO 2 (110) surface using a reaction cell and STM. Catalytic activity measurements showed that the catalytic activities have a cluster-size dependency.

  3. Improved Acylation of Phytosterols Catalyzed by Candida Antarctica Lipase a with Superior Catalytic Activity

    DEFF Research Database (Denmark)

    Panpipat, Worawan; Xu, Xuebing; Guo, Zheng

    approach to synthesize phytosterol ( -sitosterol as a model) fatty acid esters by employing immobilized CAL A which shows a superior catalytic activity to other immobilized lipases including CAL B, Lipozyme NS-40044 TLL and Lipozyme TL IM. CAL A achieves 6-14 times faster esterification of -sitosterol...... be achieved with hexane as solvent, fatty acid (C8-C18)/-sitosterol (1:1, mol:mol), 5-10% CALA load at 40- 50°C for 24h. This work demonstrated the promising potential of CAL A in bioprocess of phytosterols for value-added application....

  4. Cage-like Fe,Na-Germsesquioxanes: Structure, Magnetism, and Catalytic Activity.

    Science.gov (United States)

    Bilyachenko, Alexey N; Levitsky, Mikhail M; Yalymov, Alexey I; Korlyukov, Alexander A; Khrustalev, Viktor N; Vologzhanina, Anna V; Shul'pina, Lidia S; Ikonnikov, Nikolay S; Trigub, Alexander E; Dorovatovskii, Pavel V; Bantreil, Xavier; Lamaty, Frédéric; Long, Jérôme; Larionova, Joulia; Golub, Igor E; Shubina, Elena S; Shul'pin, Georgiy B

    2016-12-05

    A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe 6 O 19 } core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O] 5 . This structural organization induces antiferromagnetic interactions between the Fe III ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis, characterization and catalytic activity of oxovanadium (IV) complexes of heterocyclic acid hydrazones

    International Nuclear Information System (INIS)

    Pandey, Manju; Sunaja Devi, K.R.; Sreeja, P.B.

    2014-01-01

    Two acid hydrazones, Furan-2-carbaldehyde nicotinic hydrazone (L 1 ) and Furan-2-carbaldehyde benzhydrazone (L 2 ) have been synthesised and they are characterized by elemental analysis, IR, NMR and UV spectral analysis. Oxovanadium (IV) complexes of these two hydrazones were synthesised and characterised by elemental analysis, IR, UV, EPR, molar conductivity and magnetic susceptibility measurements. Conductivity measurements reveal that the complexes are nonelectrolytes. Spectral data indicates the square pyramidal geometry for the monomeric give coordinated oxovanadium (IV) complexes with the general formula (VO(L)(OCH 3 )). The complex was studied for its catalytic activity and was found to be a good catalyst in quinoxaline synthesis. (author)

  6. Synthesis of monodisperse palladium nanocubes and their catalytic activity for methanol electrooxidation

    International Nuclear Information System (INIS)

    Hao, Ding; Xue-Zhao, Shi; Cheng-Min, Shen; Chao, Hui; Zhi-Chuan, Xu; Chen, Li; Yuan, Tian; Deng-Ke, Wang; Hong-Jun, Gao

    2010-01-01

    The single crystalline palladium nanocubes with an average size of 7 nm were prepared in the presence of poly (vinyl pyrrolidone) (PVP) and KBr using the polyol method. The as-prepared Pd nanocubes were highly uniform in both size and shape. The ordered packing structures including monolayer and multilayer can be fabricated via the rate-controlled evaporation of solution solvent. The electrochemical catalytic activity of these Pd nanocubes towards methanol oxidation was found to be higher than that of spherical Pd nanoparticles of similar size. (condensed matter: structure, thermal and mechanical properties)

  7. Synthesis of monodisperse palladium nanocubes and their catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Ding, Hao; Shi, Xue-Zhao; Shen, Cheng-Min; Hui, Chao; Xu, Zhi-Chuan; Li, Chen; Tian, Yuan; Wang, Deng-Ke; Gao, Hong-Jun

    2010-10-01

    The single crystalline palladium nanocubes with an average size of 7 nm were prepared in the presence of poly (vinyl pyrrolidone) (PVP) and KBr using the polyol method. The as-prepared Pd nanocubes were highly uniform in both size and shape. The ordered packing structures including monolayer and multilayer can be fabricated via the rate-controlled evaporation of solution solvent. The electrochemical catalytic activity of these Pd nanocubes towards methanol oxidation was found to be higher than that of spherical Pd nanoparticles of similar size.

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

    Science.gov (United States)

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

    2016-01-01

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

  9. 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.

  10. Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

    Science.gov (United States)

    Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

    2018-02-01

    Understanding the nature and effect of the multitude of plasma–surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

  11. Active site structure and catalytic mechanism of phosphodiesterase for degradation of intracellular second messengers

    Science.gov (United States)

    Zhan, Chang-Guo

    2002-03-01

    Phosphodiesterases are clinical targets for a variety of biological disorders, because this superfamily of enzymes regulate intracellular concentration of cyclic nucleotides that serve as the second messengers playing a critical role in a variety of physiological processes. Understanding structure and mechanism of a phosphodiesterase will provide a solid basis for rational design of the more efficient therapeutics. Although a three-dimensional X-ray crystal structure of the catalytic domain of human phosphodiesterase 4B2B was recently reported, it was uncertain whether a critical bridging ligand in the active site is a water molecule or a hydroxide ion. The identity of this bridging ligand has been determined by performing first-principles quantum chemical calculations on models of the active site. All the results obtained indicate that this critical bridging ligand in the active site of the reported X-ray crystal structure is a hydroxide ion, rather than a water molecule, expected to serve as the nucleophile to initialize the catalytic degradation of the intracellular second messengers.

  12. The Botrytis cinerea xylanase Xyn11A contributes to virulence with its necrotizing activity, not with its catalytic activity

    Directory of Open Access Journals (Sweden)

    González Celedonio

    2010-02-01

    Full Text Available Abstract Background The Botrytis cinerea xylanase Xyn11A has been previously shown to be required for full virulence of this organism despite its poor contribution to the secreted xylanase activity and the low xylan content of B. cinerea hosts. Intriguingly, xylanases from other fungi have been shown to have the property, independent of the xylan degrading activity, to induce necrosis when applied to plant tissues, so we decided to test the hypothesis that secreted Xyn11A contributes to virulence by promoting the necrosis of the plant tissue surrounding the infection, therefore facilitating the growth of this necrotroph. Results We show here that Xyn11A has necrotizing activity on plants and that this capacity is conserved in site-directed mutants of the protein lacking the catalytic activity. Besides, Xyn11A contributes to the infection process with the necrotizing and not with the xylan hydrolyzing activity, as the catalytically-impaired Xyn11A variants were able to complement the lower virulence of the xyn11A mutant. The necrotizing activity was mapped to a 30-amino acids peptide in the protein surface, and this region was also shown to mediate binding to tobacco spheroplasts by itself. Conclusions The main contribution of the xylanase Xyn11A to the infection process of B. cinerea is to induce necrosis of the infected plant tissue. A conserved 30-amino acids region on the enzyme surface, away from the xylanase active site, is responsible for this effect and mediates binding to plant cells.

  13. Effect of ageing atmosphere on the deactivation of Pd/Rh automotive exhaust gas catalysts. Catalytic activity and XPS studies

    Energy Technology Data Exchange (ETDEWEB)

    Lassi, U.; Keiski, R.L. [Department of Process and Environmental Engineering, University of Oulu, P.O. Box 4300, FIN-90014 Oulu (Finland); Polvinen, R.; Suhonen, S.; Valden, M. [Surface Science Laboratory, Institute of Physics, Tampere University of Technology, P.O. Box 692, FIN-33101 Tampere (Finland); Kallinen, K.; Savimaki, A.; Harkonen, M. [Kemira Metalkat Oy, Catalyst Research, P.O. Box 171, FIN-90101 Oulu (Finland)

    2004-06-10

    In the present work, the catalytic activity and thermal stability of metallic Pd and Rh catalysts have been examined under different ageing atmospheres. It was shown that thermal treatment under the reducing and oxidising ageing atmospheres strongly affected catalyst stability in terms of surface areas and the changes observed in the chemical states of active metals. This was also related to catalytic activities that remained higher if laboratory scale ageing was carried out in the reducing ageing atmosphere. It was also found that engine bench and vehicle ageings correlated with the reducing laboratory scale ageing. Thermal deactivation of the aged catalysts is due to the collapse in surface area and the sintering of the Rh metal particles. Active metal particles may also be encapsulated in the sintered washcoat that is observed as a decrease in catalytic activity.

  14. Preparation of gold nanoparticles using Salicornia brachiata plant extract and evaluation of catalytic and antibacterial activity

    Science.gov (United States)

    Ayaz Ahmed, Khan Behlol; Subramanian, Swetha; Sivasubramanian, Aravind; Veerappan, Ganapathy; Veerappan, Anbazhagan

    2014-09-01

    The current study deals with the synthesis of gold nanoparticles (AuNPs) using Salicornia brachiata (Sb) and evaluation of their antibacterial and catalytic activity. The SbAuNPs showed purple color with a characteristic surface plasmon resonance peak at 532 nm. Scanning electron microscopy and transmission electron microscopy revealed polydispersed AuNPs with the size range from 22 to 35 nm. Energy dispersive X-ray and thin layer X-ray diffraction analysis clearly shows that SbAuNPs was pure and crystalline in nature. As prepared gold nanoparticles was used as a catalyst for the sodium borohydride reduction of 4-nitro phenol to 4-amino phenol and methylene blue to leucomethylene blue. The green synthesized nanoparticles exhibited potent antibacterial activity against the pathogenic bacteria, as evidenced by their zone of inhibition. In addition, we showed that the SbAuNPs in combination with the regular antibiotic, ofloxacin, exhibit superior antibacterial activity than the individual.

  15. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.

    2007-01-01

    Full Text Available Zirconium-hydroxide precursor samples are synthesized from Zr-hydroxide, Zr-nitrate, and Zr-alkoxide, by precipitation/impregnation, as well as by a modified sol-gel method. Precursor samples are further sulphated for the intended SO4 2- content of 4 wt.%, and calcined at 500-700oC. Differences in precursors’ origin and calcination temperature induce the incorporation of SO4 2- groups into ZrO2 matrices by various mechanisms. As a result, different amounts of residual sulphates are coupled with other structural, as well as surface properties, resulting in various catalytic activities of sulphated zirconia samples. Catalyst activity and selectivity are a complex synergistic function of tetragonal phase fraction, sulphates contents, textural and surface characteristics. Superior activity of SZ of alkoxide origin can be explained by a beneficial effect of meso-pores owing to a better accommodation of coke deposits.

  16. Promoting effect of vanadium on catalytic activity of Pt/Ce-Zr-O diesel oxidation catalysts.

    Science.gov (United States)

    Huang, Haifeng; Jiang, Bo; Gu, Lei; Qi, Zhonghua; Lu, Hanfeng

    2015-07-01

    A series of Pt-V/Ce-Zr-O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt-V/Ce-Zr-O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer-Emmett-Teller method, X-ray diffraction, H2 temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce-Zr-O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation. Copyright © 2015. Published by Elsevier B.V.

  17. Effect of citrate on Aspergillus niger phytase adsorption and catalytic activity in soil

    Science.gov (United States)

    Mezeli, Malika; Menezes-Blackburn, Daniel; Zhang, Hao; Giles, Courtney; George, Timothy; Shand, Charlie; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Stutter, Marc; Blackwell, Martin; Darch, Tegan; Wearing, Catherine; Haygarth, Philip

    2015-04-01

    Current developments in cropping systems that promote mobilisation of phytate in agricultural soils, by exploiting plant-root exudation of phytase and organic acids, offer potential for developments in sustainable phosphorus use. However, phytase adsorption to soil particles and phytate complexion has been shown to inhibit phytate dephosphorylation, thereby inhibiting plant P uptake, increasing the risk of this pool contributing to diffuse pollution and reducing the potential benefits of biotechnologies and management strategies aimed to utilise this abundant reserve of 'legacy' phosphorus. Citrate has been seen to increase phytase catalytic efficiency towards complexed forms of phytate, but the mechanisms by which citrate promotes phytase remains poorly understood. In this study, we evaluated phytase (from Aspergillus niger) inactivation, and change in catalytic properties upon addition to soil and the effect citrate had on adsorption of phytase and hydrolysis towards free, precipitated and adsorbed phytate. A Langmuir model was fitted to phytase adsorption isotherms showing a maximum adsorption of 0.23 nKat g-1 (19 mg protein g-1) and affinity constant of 435 nKat gˉ1 (8.5 mg protein g-1 ), demonstrating that phytase from A.niger showed a relatively low affinity for our test soil (Tayport). Phytases were partially inhibited upon adsorption and the specific activity was of 40.44 nKat mgˉ1 protein for the free enzyme and 25.35 nKat mgˉ1 protein when immobilised. The kinetics of adsorption detailed that most of the adsorption occurred within the first 20 min upon addition to soil. Citrate had no effect on the rate or total amount of phytase adsorption or loss of activity, within the studied citrate concentrations (0-4mM). Free phytases in soil solution and phytase immobilised on soil particles showed optimum activity (>80%) at pH 4.5-5.5. Immobilised phytase showed greater loss of activity at pH levels over 5.5 and lower activities at the secondary peak at pH 2

  18. Direct observation of enhanced plasmon-driven catalytic reaction activity of Au nanoparticles supported on reduced graphene oxides by SERS.

    Science.gov (United States)

    Liang, Xiu; You, Tingting; Liu, Dapeng; Lang, Xiufeng; Tan, Enzhong; Shi, Jihua; Yin, Penggang; Guo, Lin

    2015-04-21

    Graphene-based nanocomposites have recently attracted tremendous research interest in the field of catalysis due to their unique optical and electronic properties. However, direct observation of enhanced plasmon-driven catalytic activity of Au nanoparticles (NPs) supported on reduced graphene oxides (Au/rGO) has rarely been reported. Herein, based on the reduction from 4-nitrobenzenethiol (4-NBT) to p,p'-dimercaptoazobenzene (DMAB), the catalytic property of Au/rGO nanocomposites was investigated and compared with corresponding Au NP samples with similar size distribution. Our results show that Au/rGO nanocomposites could serve as a good catalytic and analytic platform for plasmon-driven chemical reactions. In addition, systematic comparisons were conducted during power- and time-dependent surface-enhanced Raman scattering (SERS) experiments, which exhibited a lower power threshold and higher catalytic efficiency for Au/rGO as compared to Au NPs toward the reaction.

  19. μ-reactor measurements of catalytic activity of mass selected nano-particles

    DEFF Research Database (Denmark)

    Riedel, Jakob Nordheim

    The work of this thesis revolves around catalytic activity measurements of nano-particles tested using a μ-reactor platform, developed and produced at DTU, in a collaboration between CINF and Nanotech. The thesis contains the results from two separate research projects; both utilising μ-reactors ......The work of this thesis revolves around catalytic activity measurements of nano-particles tested using a μ-reactor platform, developed and produced at DTU, in a collaboration between CINF and Nanotech. The thesis contains the results from two separate research projects; both utilising μ......-reactors in combination with surface science techniques and computer simulations. The first project described is a study of hydrogen dissociation on mono-disperse platinum clusters. The second project studies methanation from carbon monoxide and hydrogen on nano-particles of nickel-iron alloys. The second study is a work...... in progress, and the corresponding chapter aims to summarise the results so far. Other projects are not included in the thesis because they are inconclusive or dead ends. Hydrogen dissociation was studied by the H2/D2 exchange reaction on SiO2-supported mono-disperse platinum clusters in a -reactor...

  20. Reactivity and catalytic activity of tert-butoxy-aluminium hydride reagents.

    Science.gov (United States)

    Less, Robert J; Simmonds, Hayley R; Wright, Dominic S

    2014-04-21

    The reactivity and catalytic activities of the tert-butoxy aluminium hydride reagents [((t)BuO)xAlH3-x] [x = 1 (1), 2 (2)] and (L)Li[((t)BuO)2AlH2] [L = THF (3), 1,4-dioxane (4)] are investigated. The structural characterisation of the novel compounds 3 and 4 shows that the nature of the hydridic species present is affected dramatically by the donor ligand coordinating the Li(+) cation. Stoichiometric reaction of 1 with pyridine gives [(1,4-H-pyrid-1-yl)4Al](-)[(pyridine)4AlH2](+) (5) while reaction with the amine-borane Me2NHBH3 in the presence of PMDETA [(Me2NCH2CH2)2NMe] affords [(PMDETA)AlH2](+)[(BH3)2NMe2](-) (6). The reagents 1-4 catalyse the dehydrocoupling reaction of the amine-borane Me2NHBH3 into the ring compound [Me2NBH2]2, with the activity decreasing in the order 1≫2∼3 > 4. The greater reactivity of the neutral dihydride 1 provides the potential basis for future catalytic optimisation.

  1. Process for forming a homogeneous oxide solid phase of catalytically active material

    Science.gov (United States)

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  2. An approach to establish the uncertainty budget of catalytic activity concentration measurements in a reference laboratory.

    Science.gov (United States)

    Rami, Laura; Canalias, Francesca

    2015-04-01

    Reference laboratories providing reference services recognized by the Joint Committee for Traceability in Laboratory Medicine (JCTLM) must be accredited as calibration laboratories according to ISO 17025 and ISO 15195. These standards require laboratories to establish an uncertainty budget, in which the uncertainty contributions of the relevant uncertainty components are specified. We present a model to estimate the measurement uncertainty of creatine kinase catalytic activity concentration results obtained by IFCC primary reference measurement procedure. The measurement uncertainty has been estimated by following the next steps: 1) specification of the measurand; 2) identification of the most relevant uncertainty sources; 3) estimation of standard uncertainties by either type A or type B evaluation; 4) estimation of combined uncertainty while taking into account sensitivity coefficients, as well as existence of correlated uncertainty sources; and 5) estimation of expanded uncertainty with a defined coverage probability. The estimated expanded uncertainty was 2.2% (k=2). Uncertainty sources with a significant contribution to the measurement uncertainty were the following: pH adjustment (0.68%), absorbance accuracy (0.48%), wavelength adjustment (0.20%), reaction temperature (0.19%), volume fraction of sample (0.15%) and absorbance linearity (0.06%). The present model is an approach to establish the uncertainty budget of primary reference procedures for the measurement of the catalytic activity concentration of enzymes, and aims at being an example to be followed by other reference laboratories, as well as by laboratories that carry out primary reference measurement procedures.

  3. Support-shape Dependent Catalytic Activity in Pt/alumina Systems Using USANS/SANS

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sang Hoon; Han, Sugyeong; Ha, Heonphil; Byun, Jiyoung; Kim, Man-ho [KIST, Seoul (Korea, Republic of)

    2015-10-15

    Pt nanoparticles dispersed on ceramic powder such as alumina and ceria powder are used as catalyst materials to reduce pollution from automobile exhaust, power plant exhaust, etc. Much effort has been put to investigate the relationship between types of catalyst support materials and reactivity of the supported metallic particles. The surface shape of support materials can also be expected to control the catalysts size with the surface shape of support materials. In this presentation, we show our SANS (small angle neutron scattering) -USANS (ultra small angle neutron scattering) analysis on the structural differences of different shapes of the same γ alumina powder with different loadings of Pt nanoparticles. Then, the reactivity of the prepared catalyst materials are presented and discussed based on the investigation of the structure of the support materials by SANS. The shapes of gamma alumina, rod-like or plate-like shape, were determined from nanometer to micrometer with USANS and SANS analysis. We found that the platelet-like alumina consists of an aggregate of 2 - 3 layers, which further reduce specific surface area and catalytic activity compared to rod-like shape. Rod-like shape shows more than 100% enhancement in the catalytic activities in model three-way-catalyst (TWC) reactions of CO, NO, and C{sub 3}H{sub 6} at low temperature around 200 .deg. C.

  4. Support-shape Dependent Catalytic Activity in Pt/alumina Systems Using USANS/SANS

    International Nuclear Information System (INIS)

    Kim, Sang Hoon; Han, Sugyeong; Ha, Heonphil; Byun, Jiyoung; Kim, Man-ho

    2015-01-01

    Pt nanoparticles dispersed on ceramic powder such as alumina and ceria powder are used as catalyst materials to reduce pollution from automobile exhaust, power plant exhaust, etc. Much effort has been put to investigate the relationship between types of catalyst support materials and reactivity of the supported metallic particles. The surface shape of support materials can also be expected to control the catalysts size with the surface shape of support materials. In this presentation, we show our SANS (small angle neutron scattering) -USANS (ultra small angle neutron scattering) analysis on the structural differences of different shapes of the same γ alumina powder with different loadings of Pt nanoparticles. Then, the reactivity of the prepared catalyst materials are presented and discussed based on the investigation of the structure of the support materials by SANS. The shapes of gamma alumina, rod-like or plate-like shape, were determined from nanometer to micrometer with USANS and SANS analysis. We found that the platelet-like alumina consists of an aggregate of 2 - 3 layers, which further reduce specific surface area and catalytic activity compared to rod-like shape. Rod-like shape shows more than 100% enhancement in the catalytic activities in model three-way-catalyst (TWC) reactions of CO, NO, and C 3 H 6 at low temperature around 200 .deg. C

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

    KAUST Repository

    Abdel-Azeim, Safwat

    2014-11-11

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

  6. PEEM microscopy and DFT calculations of catalytically active platinum surfaces and interfaces

    International Nuclear Information System (INIS)

    Spiel, C.

    2012-01-01

    The aim of this thesis was to investigate the properties of catalytically active platinum surfaces and interfaces both with experimental and theoretical methods. Using experimental methods, catalytic CO oxidation on individual grains of a polycrystalline platinum foil was studied in situ under high vacuum (HV) conditions. A polycrystalline platinum foil consists of individual µm-sized crystal grains that are mainly [100]-, [110]- and [111]-oriented and differ significantly in their catalytic activity. In order to elucidate the differences existing between the reactivity of the individual grains, a combination of photoemission electron microscopy (PEEM) and quadrupole mass spectrometry (QMS) was used in this work. The working principle of PEEM is based on the photoelectric effect where illumination of the sample with (UV-)light causes emission of photoelectrons. The emitted photoelectrons are used to visualize the sample surface (with typical resolution in the low micrometer range). The PEEM image contrast originates from differences in the local work function that may arise due to different crystallographic orientations and/or changes in the adsorbate coverage. With a combination of PEEM and QMS, it was possible to study the kinetics of catalytic CO oxidation on polycrystalline platinum foil both in a global and a laterally-resolved way simultaneously. If catalytic CO oxidation on surfaces of platinum is followed at constant temperature and oxygen partial pressure under cyclic variation of the CO pressure, a hysteresis in the CO2 production rate is observed in the bistability region with two noticeable kinetic transitions (called tA and tB) taking place at different CO pressures when the catalyst surface switches back-and-forth between two steady states of high and low reactivity while the Pt-surface is, correspondingly, either oxygen- or CO-covered. In the bistability region between τ A and τ B , the system stays (at the same values of the external parameters p

  7. Thermodynamic implications of high Q 10 of thermo-TRP channels in living cells

    OpenAIRE

    Ito, Etsuro; Ikemoto, Yusuke; Yoshioka, Tohru

    2015-01-01

    The activity of thermo-transient receptor potential (TRP) channels is highly dependent on temperature, and thus thermo-TRP reactions have a high temperature coefficient Q 10. In thermodynamics, a high value of Q 10 indicates the existence of a large activation energy (i.e., a large enthalpy) over a short period during the transition process between the closed and open states of the channels. The Gibbs free energy equation shows that a large entropy is required to compensate for this large ent...

  8. Highly effective catalytic peroxymonosulfate activation on N-doped mesoporous carbon for o-phenylphenol degradation.

    Science.gov (United States)

    Hou, Jifei; Yang, Shasha; Wan, Haiqin; Fu, Heyun; Qu, Xiaolei; Xu, Zhaoyi; Zheng, Shourong

    2018-04-01

    As a broad-spectrum preservative, toxic o-phenylphenol (OPP) was frequently detected in aquatic environments. In this study, N-doped mesoporous carbon was prepared by a hard template method using different nitrogen precursors and carbonization temperatures (i.e., 700, 850 and 1000 °C), and was used to activate peroxymonosulfate (PMS) for OPP degradation. For comparison, mesoporous carbon (CMK-3) was also prepared. Characterization results showed that the N-doped mesoporous carbon samples prepared under different conditions were perfect replica of their template. In comparison with ethylenediamine (EDA) and dicyandiamide (DCDA) as the precursors, N-doped mesoporous carbon prepared using EDA and carbon tetrachloride as the precursors displayed a higher catalytic activity for OPP degradation. Increasing carbonization temperature of N-doped mesoporous carbon led to decreased N content and increased graphitic N content at the expense of pyridinic and pyrrolic N. Electron paramagnetic resonance (EPR) analysis showed that PMS activation on N-doped mesoporous carbon resulted in highly active species and singlet oxygen, and catalytic PMS activation for OPP degradation followed a combined radical and nonradical reaction mechanism. Increasing PMS concentration enhanced OPP degradation, while OPP degradation rate was independent on initial OPP concentration. Furthermore, the dependency of OPP degradation on PMS concentration followed the Langmuir-Hinshelwood model, reflecting that the activation of adsorbed PMS was the rate controlling step. Based on the analysis by time-of-flight mass spectrometry, the degradation pathway of OPP was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Enhancing catalytic activity of a hybrid xylanase through single substitution of Leu to Pro near the active site.

    Science.gov (United States)

    Wang, Qian; Zhao, Li-Li; Sun, Jian-Yi; Liu, Jian-Xin; Weng, Xiao-Yan

    2012-03-01

    A modified error-prone PCR and high-throughout screening system based on 96-well plate were employed to improve catalytic activity of a hybrid xylanase (ATx). The mutant (FSI-A124) with enhanced activity was further heterologously expressed in Pichia pastoris under the control of GAP promoter. The recombinant xylanase driven by the Saccharomyces cerevisiae α-mating factor was secreted into culture medium. After growth in YPD medium for 96 h, xylanase activity in the culture supernatant reached 66.1 U ml(-1), which was 2.92 times as that of its parent. 6 × His-tagged purification increased the specific activity to 1557.61 U mg(-1). The optimum temperature and pH of recombinant xylanase were 55°C and 6.0, respectively. A single amino acid substitution (L49P) was observed within sequence of the mutant. Insight of the three dimensional structure revealed that proline possibly produced weaker hydrogen bond, van der Waals force and hydrophobic interaction with other residues nearby than leucine, especially for V174, contributing to the flexibility of catalytic residue E177. In this study, FSI-A124 exhibited higher xylanase activity but poorer thermostability than its parent, indicating that activity and stability might be negatively correlated.

  10. The active site of a carbohydrate esterase displays divergent catalytic and noncatalytic binding functions.

    Directory of Open Access Journals (Sweden)

    Cedric Montanier

    2009-03-01

    Full Text Available Multifunctional proteins, which play a critical role in many biological processes, have typically evolved through the recruitment of different domains that have the required functional diversity. Thus the different activities displayed by these proteins are mediated by spatially distinct domains, consistent with the specific chemical requirements of each activity. Indeed, current evolutionary theory argues that the colocalization of diverse activities within an enzyme is likely to be a rare event, because it would compromise the existing activity of the protein. In contrast to this view, a potential example of multifunctional recruitment into a single protein domain is provided by CtCel5C-CE2, which contains an N-terminal module that displays cellulase activity and a C-terminal module, CtCE2, which exhibits a noncatalytic cellulose-binding function but also shares sequence identity with the CE2 family of esterases. Here we show that, unlike other CE2 members, the CtCE2 domain displays divergent catalytic esterase and noncatalytic carbohydrate binding functions. Intriguingly, these diverse activities are housed within the same site on the protein. Thus, a critical component of the active site of CtCE2, the catalytic Ser-His dyad, in harness with inserted aromatic residues, confers noncatalytic binding to cellulose whilst the active site of the domain retains its esterase activity. CtCE2 catalyses deacetylation of noncellulosic plant structural polysaccharides to deprotect these substrates for attack by other enzymes. Yet it also acts as a cellulose-binding domain, which promotes the activity of the appended cellulase on recalcitrant substrates. The CE2 family encapsulates the requirement for multiple activities by biocatalysts that attack challenging macromolecular substrates, including the grafting of a second, powerful and discrete noncatalytic binding functionality into the active site of an enzyme. This article provides a rare example of

  11. Sensory TRP Channel Interactions with Endogenous Lipids and Their Biological Outcomes

    Directory of Open Access Journals (Sweden)

    Sungjae Yoo

    2014-04-01

    Full Text Available Lipids have long been studied as constituents of the cellular architecture and energy stores in the body. Evidence is now rapidly growing that particular lipid species are also important for molecular and cellular signaling. Here we review the current information on interactions between lipids and transient receptor potential (TRP ion channels in nociceptive sensory afferents that mediate pain signaling. Sensory neuronal TRP channels play a crucial role in the detection of a variety of external and internal changes, particularly with damaging or pain-eliciting potentials that include noxiously high or low temperatures, stretching, and harmful substances. In addition, recent findings suggest that TRPs also contribute to altering synaptic plasticity that deteriorates chronic pain states. In both of these processes, specific lipids are often generated and have been found to strongly modulate TRP activities, resulting primarily in pain exacerbation. This review summarizes three standpoints viewing those lipid functions for TRP modulations as second messengers, intercellular transmitters, or bilayer building blocks. Based on these hypotheses, we discuss perspectives that account for how the TRP-lipid interaction contributes to the peripheral pain mechanism. Still a number of blurred aspects remain to be examined, which will be answered by future efforts and may help to better control pain states.

  12. Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

    Directory of Open Access Journals (Sweden)

    Arshid M. Ali

    2015-01-01

    Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

  13. Non-cell autonomous and non-catalytic activities of ATX in the developing brain

    Directory of Open Access Journals (Sweden)

    Raanan eGreenman

    2015-03-01

    Full Text Available The intricate formation of the cerebral cortex requires a well-coordinated series of events, which are regulated at the level of cell-autonomous and non-cell autonomous mechanisms. Whereas cell-autonomous mechanisms that regulate cortical development are well-studied, the non cell-autonomous mechanisms remain poorly understood. A non-biased screen allowed us to identify Autotaxin (ATX as a non cell-autonomous regulator of neural stem cell proliferation. ATX (also known as ENPP2 is best known to catalyze lysophosphatidic acid (LPA production. Our results demonstrate that ATX affects the localization and adhesion of neuronal progenitors in a cell autonomous and non-cell autonomous manner, and strikingly, this activity is independent from its catalytic activity in producing LPA.

  14. Non-cell autonomous and non-catalytic activities of ATX in the developing brain.

    Science.gov (United States)

    Greenman, Raanan; Gorelik, Anna; Sapir, Tamar; Baumgart, Jan; Zamor, Vanessa; Segal-Salto, Michal; Levin-Zaidman, Smadar; Aidinis, Vassilis; Aoki, Junken; Nitsch, Robert; Vogt, Johannes; Reiner, Orly

    2015-01-01

    The intricate formation of the cerebral cortex requires a well-coordinated series of events, which are regulated at the level of cell-autonomous and non-cell autonomous mechanisms. Whereas cell-autonomous mechanisms that regulate cortical development are well-studied, the non-cell autonomous mechanisms remain poorly understood. A non-biased screen allowed us to identify Autotaxin (ATX) as a non-cell autonomous regulator of neural stem cells. ATX (also known as ENPP2) is best known to catalyze lysophosphatidic acid (LPA) production. Our results demonstrate that ATX affects the localization and adhesion of neuronal progenitors in a cell autonomous and non-cell autonomous manner, and strikingly, this activity is independent from its catalytic activity in producing LPA.

  15. Photodynamic Effect of Hypericin on the Conformation and Catalytic Activity of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Genxi Li

    2008-02-01

    Full Text Available Hypericin, extracted from H. perforatum, can induce the generation of reactive oxygen species by visible light irradiation, which may consequently induce the conformational change of hemoglobin. We have not only employed UV-vis spectroscopy to observe the changes of UV-vis spectra of the protein, which reveals the conformational changes of the protein, but also employed electrochemical method to obtain its enhanced peroxidase activity. The photodynamic effect of hypericin on the conformation and catalytic activity of the protein has also been proven to be strongly dependent on the irradiation time, the hypericin concentration and the presence of oxygen. This work is beneficial not only to the fabrication of more sensitive hydrogen peroxide biosensor, but also to the guidance of the usage of this medicinal herb molecule, since the conformational change of the protein and the enhanced peroxidase can be easily obtained only by visible light irradiation on hypericin, the process of which is so common to happen.

  16. Synthesis of 1-dodecanethiol-capped Ag nanoparticles and their high catalytic activity

    Science.gov (United States)

    Zhang, Danhui; Yang, Youbo

    2017-01-01

    Silver nanoparticles, which were produced by the borohydride reduction of silver nitrate, were stabilized by means of 1-dodecanethiol providing sulfur atom in two-phase system involving water and organic solvent (such as toluene, chloroform and hexane). Different organic solvent played a major role in the particle size of silver nanoparticles. These silver nanoparticles synthesized in the three different organic solvent were characterized by X-ray Diffraction, transmission electron microscopy and ultraviolet-visible absorption spectroscopy. The results indicate that the particles size of silver nanoparticles formed in three organic solvents was different. Furthermore, 1-dodecanethiol-capped silver nanoparticles were found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH4, where the size of silver nanoparticles played the determining role in catalytic activity.

  17. LASER INDUCED SELECTIVE ACTIVATION UTILIZING AUTO-CATALYTIC ELECTROLESS PLATING ON POLYMER SURFACE

    DEFF Research Database (Denmark)

    Zhang, Yang; Nielsen, Jakob Skov; Tang, Peter Torben

    2009-01-01

    . Characterization of the deposited copper layer was used to select and improve laser parameters. Several types of polymers with different melting points were used as substrate. Using the above mentioned laser treatment, standard grades of thermoplastic materials such as ABS, SAN, PE, PC and others have been......This paper presents a new method for selective micro metallization of polymers induced by laser. An Nd: YAG laser was employed to draw patterns on polymer surfaces using a special set-up. After subsequent activation and auto-catalytic electroless plating, copper only deposited on the laser tracks....... Induced by the laser, porous and rough structures are formed on the surface, which favours the palladium attachment during the activation step prior to the metallization. Laser focus detection, scanning electron microscopy (SEM) and other instruments were used to analyze the topography of the laser track...

  18. Protein-directed gold nanoparticles with excellent catalytic activity for 4-nitrophenol reduction.

    Science.gov (United States)

    Liu, Kewei; Han, Lei; Zhuang, Junyang; Yang, Da-Peng

    2017-09-01

    To explore high-performance noble metal nanomaterials for the reduction of the biotoxin 4-nitrophenol (4-NP) in medicine, we developed a green synthesis strategy of bovine serum albumin-stabilized Au nanoparticles (Au@BSA NPs). The as-synthesized Au@BSA NPs were characterized by ultraviolet-visible absorption spectrum, fourier transformed infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The functional bio-nanocomposites showed Au-protein core-shell structure and uniform distribution, and their sizes were dependent on the additive amount of HAuCl 4 . Interestingly, Au@BSA NPs showed remarkable catalytic activity for the reduction of 4-NP into 4-aminophenol in the presence of sodium borohydride. Due to the introduction of Au@BSA NPs, the reduction reaction could be conducted at ambient temperature and pressure without any additional conditions. Moreover, the reduction rate was closely related to the sizes of NPs and reaction temperature, and the catalytic mechanism was verified to follow the pseudo-first-order kinetics. Due to the environmentally friendly synthesis process and green reduction strategy of 4-NP, Au@BSA NPs would show great potential in governance of the biotoxin in medicine. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress*♦

    Science.gov (United States)

    Benoit, Stéphane L.; Maier, Robert J.

    2016-01-01

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H2O2). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains (katAH56A and katAY339A) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H2O2-dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. PMID:27605666

  20. Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

    International Nuclear Information System (INIS)

    Dzhordano, N.; Bart, D.; Madzhori, R.

    1984-01-01

    A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

  1. Green Synthesis of Smart Metal/Polymer Nanocomposite Particles and Their Tuneable Catalytic Activities

    Directory of Open Access Journals (Sweden)

    Noel Peter Bengzon Tan

    2016-03-01

    Full Text Available Herein we report a simple and green synthesis of smart Au and Ag@Au nanocomposite particles using poly(N-isopropylacrylamide/polyethyleneimine (PNIPAm/PEI core-shell microgels as dual reductant and templates in an aqueous system. The nanocomposite particles were synthesized through a spontaneous reduction of tetrachloroauric (III acid to gold nanoparticles at room temperature, and in situ encapsulation and stabilization of the resultant gold nanoparticles (AuNPs with amine-rich PEI shells. The preformed gold nanoparticles then acted as seed nanoparticles for further generation of Ag@Au bimetallic nanoparticles within the microgel templates at 60 °C. These nanocomposite particles were characterized by TEM, AFM, XPS, UV-vis spectroscopy, zeta-potential, and particle size analysis. The synergistic effects of the smart nanocomposite particles were studied via the reduction of p-nitrophenol to p-aminophenol. The catalytic performance of the bimetallic Ag@Au nanocomposite particles was 25-fold higher than that of the monometallic Au nanoparticles. Finally, the controllable catalytic activities of the Au@PNIPAm/PEI nanocomposite particles were demonstrated via tuning the solution pH and temperature.

  2. Multiple functionalities of Ni nanoparticles embedded in carboxymethyl guar gum polymer: catalytic activity and superparamagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Sardar, Debasmita [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Sengupta, Manideepa; Bordoloi, Ankur [Nano Catalysis, Catalytic Conversion and Process Division, CSIR—Indian Institute of Petroleum (IIP), Mohkampur, Dehradun 248005 (India); Ahmed, Md. A.; Neogi, S.K.; Bandyopadhyay, Sudipta [Department of Physics, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Jain, Ruchi; Gopinath, Chinnakonda S. [Catalysis Division and Center of Excellence on Surface Science, CSIR—National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008 (India); Bala, Tanushree, E-mail: tanushreebala@gmail.com [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India)

    2017-05-31

    Highlights: • Ni nanoparticles were synthesized in polymer to form Ni-Polymer composite. • Ni nanoparticles retain their superparamagnetism in the composite. • Ni-Polymer composites showed catalytic activity. - Abstract: Composites comprising of metallic nanoparticles in polymer matrices have allured significant importance due to multifunctionalities. Here a simple protocol has been described to embed Ni nanoparticles in carboxymethyl guar gum (CMGG) polymer. The composite formation helps in the stabilization of Ni nanoparticles which are otherwise prone towards aerial oxidation. Further the nanoparticles retain their superparamagnetic nature and catalytic capacity. Ni-Polymer composite catalyses the reduction of 4-Nitrophenol to 4-Aminophenol very efficiently in presence of NaBH{sub 4}, attaining a complete conversion under some experimental conditions. Ni-Polymer composite is well characterized using UV–vis spectroscopy, FTIR, XPS, powder XRD, TGA, SEM and TEM. A detailed magnetic measurement using superconducting quantum interference device-vibrating sample magnetometer (SQUID-VSM) reveals superparamagnetic behaviour of the composite.

  3. Green synthesis, characterization and catalytic activity of silver nanoparticles using Cassia auriculata flower extract separated fraction

    Science.gov (United States)

    Muthu, Karuppiah; Priya, Sethuraman

    2017-05-01

    Cassia auriculata L., the flower aqueous extract was fractionated by separating funnel using n-hexane (A1), chloroform (A2), ethyl acetate (A3) and triple distilled water (A4). The A4 fraction was concentrated and determined the presence of preliminary phytochemicals such as tannins, flavonoids, glycosides, carbohydrates and polyphenolic compounds. These phytochemical compounds acted as reducing as well as a stabilizing agent in the green synthesis of Ag NPs from aqueous silver ions. Initially, the colour change and UV-vis absorbance surface Plasmon resonance strong, wide band located at 435 nm has confirmed the synthesis of Ag NPs. The X-ray diffraction (XRD) pattern of Ag NPs shows a face-centered cubic crystal structure. The observed values were calculated by Debye-Scherrer equation to theoretical confirms the particle size of 18 nm. The surface morphology of Ag NPs was viewed by HRTEM, the particles are spherical and triangle shapes with sizes from 10 to 35 nm. Further, the Ag NPs was effective catalytic activity in the reduction of highly environmental polluted organic compounds of 4-nitrophenol and methyl orange. The green synthesis of Ag NPs seems to eco-friendly, cost-effective, conventional one spot synthesis and greater performance of catalytic degradation of environmentally polluted organic dyes.

  4. Polyelectrolyte Brush-Grafted Polydopamine-Based Catalysts with Enhanced Catalytic Activity and Stability.

    Science.gov (United States)

    Kaang, Byung Kwon; Han, Nara; Lee, Ha-Jin; Choi, Won San

    2018-01-10

    Three types of surface treatments, namely, polyethyleneimine (PEI) coating, short PEI (S-PEI) grafting, and long PEI (L-PEI) grafting, were performed on polydopamine (Pdop)-based catalysts to enhance their catalytic activity and stability. Brush-grafted catalysts were prepared by the stepwise synthesis of Au and short (or long) PEI brushes on Pdop particles (PdopP/Au/S- or L-PEI grafting). PEI-coated Pdop-based catalysts (PdopP/Au/PEI coating) were also prepared as non-brush-grafted catalysts. Among the surface-treated PdopP/Au catalysts, the brush-grafted catalysts (S-PEI and L-PEI grafting) exhibited excellent and stable catalytic performance because the brush grafting enabled the protection of the catalysts against harsh conditions, effective transfer of reactants to the catalysts, and confinement of reactants around the catalysts. The brush-grafted catalysts could also more effectively decompose larger dyes than the non-brush-grafted catalysts. The process-to-effectiveness of PEI coating is the best because the release of Pdop from PdopP/Au was moderately inhibited by the presence of only one layer of PEI coating on the PdopP/Au. Thus, this approach could be an alternative method to enhance the stability of PdopP/Au catalysts.

  5. Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity.

    Science.gov (United States)

    Arafa, Wael A A; Kärkäs, Markus D; Lee, Bao-Lin; Åkermark, Torbjörn; Liao, Rong-Zhen; Berends, Hans-Martin; Messinger, Johannes; Siegbahn, Per E M; Åkermark, Björn

    2014-06-28

    During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2(II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.

  6. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  7. Mutations in the catalytic loop HRD motif alter the activity and function of Drosophila Src64.

    Directory of Open Access Journals (Sweden)

    Taylor C Strong

    Full Text Available The catalytic loop HRD motif is found in most protein kinases and these amino acids are predicted to perform functions in catalysis, transition to, and stabilization of the active conformation of the kinase domain. We have identified mutations in a Drosophila src gene, src64, that alter the three HRD amino acids. We have analyzed the mutants for both biochemical activity and biological function during development. Mutation of the aspartate to asparagine eliminates biological function in cytoskeletal processes and severely reduces fertility, supporting the amino acid's critical role in enzymatic activity. The arginine to cysteine mutation has little to no effect on kinase activity or cytoskeletal reorganization, suggesting that the HRD arginine may not be critical for coordinating phosphotyrosine in the active conformation. The histidine to leucine mutant retains some kinase activity and biological function, suggesting that this amino acid may have a biochemical function in the active kinase that is independent of its side chain hydrogen bonding interactions in the active site. We also describe the phenotypic effects of other mutations in the SH2 and tyrosine kinase domains of src64, and we compare them to the phenotypic effects of the src64 null allele.

  8. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    International Nuclear Information System (INIS)

    Lu, Shixiang; Yu, Jianying; Cheng, Yuanyuan; Wang, Qian; Barras, Alexandre; Xu, Wenguo; Szunerits, Sabine; Cornu, David; Boukherroub, Rabah

    2017-01-01

    Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH 4 ) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  9. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

    Science.gov (United States)

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-05

    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

  10. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Shixiang, E-mail: shixianglu@bit.edu.cn [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Yu, Jianying; Cheng, Yuanyuan [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Qian; Barras, Alexandre [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Xu, Wenguo [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Szunerits, Sabine [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Cornu, David [Institut Européen des Membranes, UMR 5635, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), CNRS, Université Montpellier 2, 276 rue de la Galéra, Montpellier 34000 (France); Boukherroub, Rabah, E-mail: rabah.boukherroub@iemn.univ-lille1.fr [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France)

    2017-07-31

    Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH{sub 4}) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  11. Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

    2017-04-01

    Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

  12. TRP, TRPL and cacophony channels mediate Ca2+ influx and exocytosis in photoreceptors axons in Drosophila.

    Directory of Open Access Journals (Sweden)

    Guadalupe Astorga

    Full Text Available In Drosophila photoreceptors Ca(2+-permeable channels TRP and TRPL are the targets of phototransduction, occurring in photosensitive microvilli and mediated by a phospholipase C (PLC pathway. Using a novel Drosophila brain slice preparation, we studied the distribution and physiological properties of TRP and TRPL in the lamina of the visual system. Immunohistochemical images revealed considerable expression in photoreceptors axons at the lamina. Other phototransduction proteins are also present, mainly PLC and protein kinase C, while rhodopsin is absent. The voltage-dependent Ca(2+ channel cacophony is also present there. Measurements in the lamina with the Ca(2+ fluorescent protein G-CaMP ectopically expressed in photoreceptors, revealed depolarization-induced Ca(2+ increments mediated by cacophony. Additional Ca(2+ influx depends on TRP and TRPL, apparently functioning as store-operated channels. Single synaptic boutons resolved in the lamina by FM4-64 fluorescence revealed that vesicle exocytosis depends on cacophony, TRP and TRPL. In the PLC mutant norpA bouton labeling was also impaired, implicating an additional modulation by this enzyme. Internal Ca(2+ also contributes to exocytosis, since this process was reduced after Ca(2+-store depletion. Therefore, several Ca(2+ pathways participate in photoreceptor neurotransmitter release: one is activated by depolarization and involves cacophony; this is complemented by internal Ca(2+ release and the activation of TRP and TRPL coupled to Ca(2+ depletion of internal reservoirs. PLC may regulate the last two processes. TRP and TRPL would participate in two different functions in distant cellular regions, where they are opened by different mechanisms. This work sheds new light on the mechanism of neurotransmitter release in tonic synapses of non-spiking neurons.

  13. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Science.gov (United States)

    You, Fu-Tian; Yu, Guang-Wei; Wang, Yin; Xing, Zhen-Jiao; Liu, Xue-Jiao; Li, Jie

    2017-08-01

    Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnOx)-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnOx and the test conditions on the reaction. MLAC with 7.5 wt.% MnOx (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O2, room temperature and GHSV ca. 16000 h-1. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O2 concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnOx loading is assumed to be related to Mn4+/Mn3+ ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnOx lattice O transfer is proposed.

  14. Improved acylation of phytosterols catalyzed by Candida antarctica lipase A with superior catalytic activity

    DEFF Research Database (Denmark)

    Panpipat, Worawan; Xu, Xuebing; Guo, Zheng

    2013-01-01

    This work reported a novel approach to synthesize phytosterol (ˇ-sitosterol as a model) fatty acid esters by employing Candida antarctica lipase A (CAL A) which shows a superior catalytic activity to other lipases. A series of ˇ-sitosteryl fatty acid esters (C2–C18) have been successfully prepared...... spectrum of log P values, was observed. 93–98% yield of ˇ-sitosteryl esters could be achieved with hexane as solvent, fatty acid (C8–C18)/ˇ-sitosterol (1:1, mol:mol), 5–10% CAL A load at 40–50 ◦C for 24 h. This work demonstrated the promising potential of CAL A in bioprocess of phytosterols for value...

  15. Study of the catalytic activity of ceramic nano fibers in the methane combustion

    International Nuclear Information System (INIS)

    Reolon, R.P.; Berutti, F.A.; Alves, A.K.; Bergmann, C.P.

    2009-01-01

    In this work titanium oxide fibers, doped with cerium and copper, were synthesized using the electro spinning process. Titanium propoxide was used as a precursor in the electro spinning synthesis. The obtained fibers were heat treated after receive a spray with an alcoholic solution of cerium acetate and copper nitrate. The non-tissue material obtained was characterized by X-ray diffraction to determine the phase and crystallite size, X-ray photoelectron spectroscopy (XPS), BET method to determine the surface and SEM to analyze the microstructure of the fibers. The catalytic activity was evaluated by methane and air combustion under different temperatures. The amount of combustion gases such as NO x , C x H y , CO e CO 2 , were analyzed. (author)

  16. Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D-Printed Mesoreactors.

    Science.gov (United States)

    Rossi, Sergio; Porta, Riccardo; Brenna, Davide; Puglisi, Alessandra; Benaglia, Maurizio

    2017-04-03

    3D-printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D-printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best-performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous-flow synthesis of biologically active chiral 1,2-amino alcohols (norephedrine, metaraminol, and methoxamine) through a two-step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    Science.gov (United States)

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  18. Phoenix dactylifera L. leaf extract phytosynthesized gold nanoparticles; controlled synthesis and catalytic activity

    Science.gov (United States)

    Zayed, Mervat F.; Eisa, Wael H.

    2014-03-01

    A green synthesis route was reported to explore the reducing and capping potential of Phoenix dactylifera extract for the synthesis of gold nanoparticles. The processes of nucleation and growth of gold nanoparticles were followed by monitoring the absorption spectra during the reaction. The size and morphology of these nanoparticles was typically imaged using transmission electron microscopy (TEM). The particle size ranged between 32 and 45 nm and are spherical in shape. Fourier transform infrared (FTIR) analysis suggests that the synthesized gold nanoparticles might be stabilized through the interactions of hydroxyl and carbonyl groups in the carbohydrates, flavonoids, tannins and phenolic acids present in P. dactylifera. The as-synthesized Au colloids exhibited good catalytic activity for the degradation of 4-nitrophenol.

  19. Microbially supported synthesis of catalytically active bimetallic Pd-Au nanoparticles

    DEFF Research Database (Denmark)

    Hosseinkhani, Baharak; Søbjerg, Lina Sveidal; Rotaru, Amelia-Elena

    2012-01-01

    Bimetallic nanoparticles are considered the next generation of nanocatalysts with increased stability and catalytic activity. Bio-supported synthesis of monometallic nanoparticles has been proposed as an environmentally friendly alternative to the conventional chemical and physical protocols....... In this study we synthesize bimetallic bio-supported Pd-Au nanoparticles for the first time using microorganisms as support material. The synthesis involved two steps: (1) Formation of monometallic bio-supported Pd(0) and Au(0) nanoparticles on the surface of Cupriavidus necator cells, and (2) formation...... of bimetallic bio-supported nanoparticles by reduction of either Au(III) or Pd(II) on to the nanoparticles prepared in step one. Bio-supported monometallic Pd(0) or Au(0) nanoparticles were formed on the surface of C. necator by reduction of Pd(II) or Au(III) with formate. Addition of Au(III) or Pd...

  20. Synthesis of gold nanoparticles using renewable Punica granatum juice and study of its catalytic activity

    Science.gov (United States)

    Dash, Shib Shankar; Bag, Braja Gopal

    2014-01-01

    Punica granatum juice, a delicious multivitamin drink of great medicinal significance, is rich in different types of phytochemicals, such as terpenoids, alkaloids, sterols, polyphenols, sugars, fatty acids, aromatic compounds, amino acids, tocopherols, etc. We have demonstrated the use of the juice for the synthesis of gold nanoparticles (AuNPs) at room temperature under very mild conditions. The synthesis of the AuNPs was complete in few minutes and no extra stabilizing or capping agents were necessary. The size of the nanoparticles could be controlled by varying the concentration of the fruit extract. The AuNPs were characterized by surface plasmon resonance spectroscopy, high resolution transmission electron microscopy, fourier transform infrared spectroscopy and X-ray diffraction studies. Catalytic activity of the synthesized colloidal AuNPs has also been demonstrated.

  1. Synthesis, characterization and catalytic activity of carbon-silica hybrid catalyst from rice straw

    Science.gov (United States)

    Janaun, J.; Safie, N. N.; Siambun, N. J.

    2016-07-01

    The hybrid-carbon catalyst has been studied because of its promising potential to have high porosity and surface area to be used in biodiesel production. Silica has been used as the support to produce hybrid carbon catalyst due to its mesoporous structure and high surface area properties. The chemical synthesis of silica-carbon hybrid is expensive and involves more complicated preparation steps. The presence of natural silica in rice plants especially rice husk has received much attention in research because of the potential as a source for solid acid catalyst synthesis. But study on rice straw, which is available abundantly as agricultural waste is limited. In this study, rice straw undergone pyrolysis and functionalized using fuming sulphuric acid to anchor -SO3H groups. The presence of silica and the physiochemical properties of the catalyst produced were studied before and after sulphonation. The catalytic activity of hybrid carbon silica acid catalyst, (H-CSAC) in esterification of oleic acid with methanol was also studied. The results showed the presence of silica-carbon which had amorphous structure and highly porous. The carbon surface consisted of higher silica composition, had lower S element detected as compared to the surface that had high carbon content but lower silica composition. This was likely due to the fact that Si element which was bonded to oxygen was highly stable and unlikely to break the bond and react with -SO3H ions. H-CSAC conversions were 23.04 %, 35.52 % and 34.2 7% at 333.15 K, 343.15 K and 353.15 K, respectively. From this research, rice straw can be used as carbon precursor to produce hybrid carbon-silica catalyst and has shown catalytic activity in biodiesel production. Rate equation obtained is also presented.

  2. Catalytic Activity of Sulfated and Phosphated Catalysts towards the Synthesis of Substituted Coumarin

    Directory of Open Access Journals (Sweden)

    Nagi R. E. Radwan

    2018-01-01

    Full Text Available New modified acidic catalysts were prepared from the treatment of silica, titania and silica prepared from hydrolyzed tetraethyl orthosilicate (TEOS with sulfuric and phosphoric acid. The sulfated and phosphated silica synthesized from TEOS were calcined at 450 and 650 °C. These catalysts were characterized by X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR, transmission electron microscope (TEM, and scanning electron microscope (SEM. The surface areas, total pore volume, and mean pore radius of the acidic catalysts were investigated, while the pore size distribution was determined by the Barrett, Joyner and Halenda (BJH method. The catalytic activity of the sulfated and phosphated silica and/or titania were examined with the Pechmann condensation reaction, in which different phenols reacted with ethyl acetoacetate as a neat reaction to obtain the corresponding coumarin derivatives. The results indicated that the treatment of the catalysts with sulfuric or phosphoric acid led to a decrease in the phases’ crystallinity to a certain degree. The morphology and the structure of the acidified catalysts were examined and their particle size was calculated. Furthermore, the amount of the used catalysts played a vital role in controlling the formation of the products as well as their performance was manipulated by the number and nature of the active acidic sites on their surfaces. The obtained results suggested that the highest catalytic conversion of the reaction was attained at 20 wt % of the catalyst and no further increase in the product yield was detected when the amount of catalyst exceeded this value. Meanwhile the phenol molecules were a key feature in obtaining the final product.

  3. Catalytic diesel particulate filters reduce the in vitro estrogenic activity of diesel exhaust

    Energy Technology Data Exchange (ETDEWEB)

    Wenger, Daniela; Gerecke, Andreas C.; Heeb, Norbert V. [Laboratory for Analytical Chemistry, Empa, Swiss Federal Laboratories for Materials Testing and Research, Duebendorf (Switzerland); Naegeli, Hanspeter [University of Zurich-Vetsuisse, Institute of Pharmacology and Toxicology, Zurich (Switzerland); Zenobi, Renato [ETH Zurich, Department of Chemistry and Applied Biosciences, Zurich (Switzerland)

    2008-04-15

    An in vitro reporter gene assay based on human breast cancer T47D cells (ER-CALUX {sup registered}) was applied to examine the ability of diesel exhaust to induce or inhibit estrogen receptor (ER)-mediated gene expression. Exhaust from a heavy-duty diesel engine was either treated by iron- or copper/iron-catalyzed diesel particulate filters (DPFs) or studied as unfiltered exhaust. Collected samples included particle-bound and semivolatile constituents of diesel exhaust. Our findings show that all of the samples contained compounds that were able to induce ER-mediated gene expression as well as compounds that suppressed the activity of the endogenous hormone 17{beta}-estradiol (E2). Estrogenic activity prevailed over antiestrogenic activity. We found an overall ER-mediated activity of 1.63 {+-} 0.31 ng E2 CALUX equivalents (E2-CEQs) per m{sup 3} of unfiltered exhaust. In filtered exhaust, we measured 0.74 {+-} 0.07 (iron-catalyzed DPF) and 0.55 {+-} 0.09 ng E2-CEQ m{sup -3} (copper/iron-catalyzed DPF), corresponding to reductions in estrogenic activity of 55 and 66%, respectively. Our study demonstrates that both catalytic DPFs lowered the ER-mediated endocrine-disrupting potential of diesel exhaust. (orig.)

  4. COMPARISON OF CATALYTIC ACTIVITIES BOTH FOR SELECTIVE OXIDATION AND DECOMPOSITION OF AMMONIA OVER Fe/HZβ CATALYST

    Directory of Open Access Journals (Sweden)

    YELİZ ÇETİN

    2016-11-01

    Full Text Available Ammonia is one of the syngas contaminants that must be removed before using the syngas downstream applications. The most promising hot-gas clean-up techniques of ammonia are selective catalytic oxidation (SCO and catalytic decomposition. In this study, the catalytic activities over Zeolite Hβ supported iron catalyst (Fe/HZβ were compared both for the two catalytic routes. For SCO experiments; temperature (300-550 °C, O2 (2000-6000 ppmv and (0-10% H2 concentrations were investigated with the presence of 800 ppm NH3 in each of the final gas mixture. In the second route, catalytic ammonia decomposition experiments were carried out with H2 in balance N2 (0-30% containing 800 ppm NH3 at 700°C and 800°C. In the SCO, NH3 conversions were increased with increasing reaction temperatures with the absence of H2 in the reaction mixture. With 10% H2, it was shown that NH3 conversions increased with decreasing the reaction temperature. This was interpreted as the competing H2 and NH3 oxidations over the catalyst. On the other hand, in the catalytic decomposition, thermodynamic equilibrium conversion of almost 100% was attained at both 700 and 800 °C. Upon H2 addition, all conversions decreased. The decrease in conversion seemed to be linear with inlet hydrogen concentration. Hydrogen was seen to inhibit ammonia decomposition reaction. It was shown that Fe/HZβ catalyst is better to use for catalytic decomposition of NH3 in syngas rather than SCO of NH3 in spite of higher reaction temperatures needed in the decomposition reaction.

  5. Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation

    Science.gov (United States)

    Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Dok Kim, Young

    2018-04-01

    NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (˜20 m2 g-1) than expected for a flat-surface structure (present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

  6. A new generation approach in enzyme immobilization: Organic-inorganic hybrid nanoflowers with enhanced catalytic activity and stability.

    Science.gov (United States)

    Altinkaynak, Cevahir; Tavlasoglu, Sureyya; Özdemir, Nalan; Ocsoy, Ismail

    2016-11-01

    Many different micro and nano sized materials have been used for enzymes immobilization in order to increase their catalytic activity and stability. Generally, immobilized enzymes with conventional immobilization techniques exhibit improved stability while their activity is lowered compared to free enzymes. Recently, an elegant immobilization approach was discovered in synthesis of flower-like organic-inorganic hybrid nanostructures with extraordinary catalytic activity and stability. In this novel immobilization strategy, proteins (enzymes) and metal ions acted as organic and inorganic components, respectively to form hybrid nanoflowers (hNFs). It is demonstrated that the hNFs highly enhanced catalytic activities and stability in a wide range of experimental conditions (pHs, temperatures and salt concentration, etc.) compared to free and conventionally immobilized enzymes. This review mainly discussed the synthesis, characterization, development and applications of organic-inorganic hybrid nanoflowers formed of various enzymes and metal ions and explained potential mechanism underlying enhanced catalytic activity and stability. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Inter-domain synergism is required for efficient feeding of cellulose chain into active site of cellobiohydrolase Cel7A

    DEFF Research Database (Denmark)

    Kont, Riin; Kari, Jeppe; Borch, Kim

    2016-01-01

    systems. TrCel7A consists of catalytic domain (CD) and a smaller carbohydrate binding module (CBM) connected through the glycosylated linker peptide. A tunnel shaped active site rests in the CD and contains 10 glucose unit binding sites. The active site of TrCel7A is lined with four Trp residues with two...... to Ala substitution on on-rates was strongly dependent on the presence of the CBM-linker. This compensation between CBM-linker and Trp-38 indicates synergism between CBM-linker and CD in feeding the cellulose chain into the active site. The inter-domain synergism was pre-requisite for the efficient...

  8. Effect of Support Materials on Catalytic Activity of Nano Ruthenium Catalyst in Hydrogenolysis of Glycerol

    International Nuclear Information System (INIS)

    Noraini Hamzah; Mohd Ambar Yarmo

    2016-01-01

    A series of heterogenous catalysts based on supported ruthenium were prepared from RuCl 3 precursor by impregnation method. The effect of support materials (bentonite, TiO 2 , Al 2 O 3 and SiO 2 ) on catalytic activity of Ru catalyst for hydrogenolysis of glycerol were investigated under mild reaction condition of 150 degree Celsius and 20 bar initial hydrogen pressure for 7 hours reaction time and glycerol concentration was 20 % (wt). It was found that the type of support material have significant effects on the activity and selectivity of glycerol hydrogenolysis. The order of Ru catalyst activity was Ru/ bentonite > Ru /Al 2 O 3 ≅ Ru/ TiO 2 > Ru/ SiO 2 . This study showed that bentonite supported Ru catalyst was the most active with glycerol conversion reaching 62.5 % compared to other supports. All the tested catalyst exhibited high selectivity to 1,2-propanediol with more than 80 %. Characterization of the catalysts was carried out using BET, XPS, FESEM-EDX and TEM to obtain the physicochemical properties of the catalysts. (author)

  9. Cytochrome c oxidase loses catalytic activity and structural integrity during the aging process in Drosophila melanogaster

    International Nuclear Information System (INIS)

    Ren, Jian-Ching; Rebrin, Igor; Klichko, Vladimir; Orr, William C.; Sohal, Rajindar S.

    2010-01-01

    Research highlights: → Cytochrome c oxidase loses catalytic activity during the aging process. → Abundance of seven nuclear-encoded subunits of cytochrome c oxidase decreased with age in Drosophila. → Cytochrome c oxidase is specific intra-mitochondrial site of age-related deterioration. -- Abstract: The hypothesis, that structural deterioration of cytochrome c oxidase (CcO) is a causal factor in the age-related decline in mitochondrial respiratory activity and an increase in H 2 O 2 generation, was tested in Drosophila melanogaster. CcO activity and the levels of seven different nuclear DNA-encoded CcO subunits were determined at three different stages of adult life, namely, young-, middle-, and old-age. CcO activity declined progressively with age by 33%. Western blot analysis, using antibodies specific to Drosophila CcO subunits IV, Va, Vb, VIb, VIc, VIIc, and VIII, indicated that the abundance these polypeptides decreased, ranging from 11% to 40%, during aging. These and previous results suggest that CcO is a specific intra-mitochondrial site of age-related deterioration, which may have a broad impact on mitochondrial physiology.

  10. Cytochrome c oxidase loses catalytic activity and structural integrity during the aging process in Drosophila melanogaster

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Jian-Ching; Rebrin, Igor [Department of Pharmacology and Pharmaceutical Sciences, University of Southern California, Los Angeles, CA 90033 (United States); Klichko, Vladimir; Orr, William C. [Department of Biological Sciences, Southern Methodist University, Dallas, TX 75275 (United States); Sohal, Rajindar S., E-mail: sohal@usc.edu [Department of Pharmacology and Pharmaceutical Sciences, University of Southern California, Los Angeles, CA 90033 (United States)

    2010-10-08

    Research highlights: {yields} Cytochrome c oxidase loses catalytic activity during the aging process. {yields} Abundance of seven nuclear-encoded subunits of cytochrome c oxidase decreased with age in Drosophila. {yields} Cytochrome c oxidase is specific intra-mitochondrial site of age-related deterioration. -- Abstract: The hypothesis, that structural deterioration of cytochrome c oxidase (CcO) is a causal factor in the age-related decline in mitochondrial respiratory activity and an increase in H{sub 2}O{sub 2} generation, was tested in Drosophila melanogaster. CcO activity and the levels of seven different nuclear DNA-encoded CcO subunits were determined at three different stages of adult life, namely, young-, middle-, and old-age. CcO activity declined progressively with age by 33%. Western blot analysis, using antibodies specific to Drosophila CcO subunits IV, Va, Vb, VIb, VIc, VIIc, and VIII, indicated that the abundance these polypeptides decreased, ranging from 11% to 40%, during aging. These and previous results suggest that CcO is a specific intra-mitochondrial site of age-related deterioration, which may have a broad impact on mitochondrial physiology.

  11. Mutation of tryptophan residues in lipoprotein lipase. Effects on stability, immunoreactivity, and catalytic properties

    NARCIS (Netherlands)

    Lookene, A.; Groot, N. B.; Kastelein, J. J.; Olivecrona, G.; Bruin, T.

    1997-01-01

    Previous studies had pointed to an important function of a putative exposed loop in the C-terminal domain of lipoprotein lipase for activity against emulsified lipid substrates. This loop contains 3 tryptophan residues (Trp390, Trp393, and Trp394). We have expressed and characterized lipase mutants

  12. Synthesis, characterization and catalytic activity of highly ordered hexagonal and cubic composite monoliths.

    Science.gov (United States)

    El-Safty, Sherif A

    2008-03-15

    Design of nanocatalysts for efficient heterogeneous catalytic systems is needed to high ingredients for environmental cleanup of organic pollutant species. Here, well-defined order NiO-silica monolithic catalysts with hexagonal P6mm and cubic Pm3n mesostructures were successfully fabricated by using an instant direct-templating method of lyotropic and microemulsion phases of Brij 76 (C18H37(OCH2CH2)10 OH, C18EO 10). Ordered hexagonal P6mm NiO/HOM-2 monoliths could be fabricated in lyotropic system of Brij 76 at phase composition domains of TMOS/Brij 76 (50 wt%). However, periodically ordered cubic Pm3n NiO-supported monoliths were synthesized in microemulsion system formed by addition of C12-alkane to the hexagonal phase domains. This synthetic strategy also revealed that the NiO particles were well-dispersed into the silicate pore surface matrices of mesostructures. Monolithic NiO-silica composites with 2D hexagonal and 3D cubic geometries and with large particle morphologies show promise to act as catalysts. The current study revealed evidence of the advantages of nanoscale pore geometry and shape, and particle morphology of the supported silica monoliths in the design of nanocatalysts that can efficiently enhance the catalytic functionality in terms of stability, reversibility and reactivity. Furthermore, a key finding in our study was that 2D hexagonal and 3D cubic mesostructured NiO-silica catalysts retained the specific activity towards the oxidation reaction even after several regeneration/reuse cycles. Significant study of the mechanistic cyclization of the organic reactant using the density functional (DFT) calculations provided evidence of the key components of conformations of the functional model during the formation of the oxidation product.

  13. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress.

    Science.gov (United States)

    Benoit, Stéphane L; Maier, Robert J

    2016-11-04

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H 2 O 2 ). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains ( katA H56A and katA Y339A ) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H 2 O 2 -dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  14. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  15. Immobilized Cu (II)—Amino Acid Complexes as Prospective Highly Efficient Catalytic Materials: Synthesis, Structural Characterization and Catalytic Activities

    Science.gov (United States)

    Pálinkó, István; Ordasi, Adrien; Kiss, János T.; Labádi, Imre

    2008-11-01

    In this work the covalent anchoring of N-or C-protected Cu(II)—L-tyrosine complexes onto a swellable resin or surface-modified silica gel is described. Experimental conditions (solvents, the availability of ligands) of the synthesis were varied; the structures (by IR spectroscopy) and the superoxide dismutase activities of the anchored complexes were studied.

  16. Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

    Science.gov (United States)

    Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

    2018-04-01

    In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

  17. Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

    OpenAIRE

    Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

    2017-01-01

    Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

  18. Treatment of organic pollutants in coke plant wastewater by the method of ultrasonic irradiation, catalytic oxidation and activated sludge

    NARCIS (Netherlands)

    Ning, Ping; Bart, Hans-Jörg; Jiang, Yijiao; de Haan, A.B.; Tien, C.

    2005-01-01

    The paper deals with the degradation of the organic pollutants in coke plant wastewater by the combination process of ultrasonic irradiation, catalytic oxidation and activated sludge. The effect factors of ultrasonic irradiation on the degradation of the organic pollutants such as saturating gas,

  19. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong, E-mail: zdnan@yzu.edu.cn

    2016-11-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H{sub 2} gas by hydrolysis of NaBH{sub 4} solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH{sub 4} was calculated to be about 15.42 kJ mol{sup −1}. The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H{sub 2} gas.

  20. Synthesis of Co/N-HNTs composites and investigation on its catalytic activity for H2 generation

    International Nuclear Information System (INIS)

    Zhao, Dongcui; Cheng, Zhilin; Nan, Zhaodong

    2016-01-01

    Co/N-HNTs composites were synthesized via a one-pot solvothermal method, where amine functional halloysite nanotubes (N-HNTs) were used as support materials. Effects of sulfosuccinate sodium salt (AOT), an anionic surfactant, on morphology and dispersibility of Co particles anchored at the N-HNTs were studied. The dispersibility of the Co particles was promoted with the increase of the AOT concentration. The as-obtained composite was used as a catalyst to generate H 2 gas by hydrolysis of NaBH 4 solution. The catalytic activity of the composite was significantly enhanced than the pure Co and Co/graphene composite at the same experimental conditions reported by our laboratory, and the catalyst was conveniently separated from the solution by a magnet. The catalytic activity was enhanced when the dispersibility of the Co particles was improved at the surface of the N-HNTs and the Co content contained in the composite was lowed. At the same time, the Co particles anchored at the inner surface of the N-HNTs resulted in higher catalytic activity, where the Co particles may bond with nitrogen atoms. The activation energy for the hydrolysis of NaBH 4 was calculated to be about 15.42 kJ mol −1 . The catalyst can be continuously used for four times with about the same catalytic activity. - Highlights: • Co/N-HNTs composites are synthesized. • The dispersibility and morphology of the Co particles anchored at the N-HNTs are modified by AOT. • The composite shows higher catalytic activity for production H 2 gas.

  1. Antitumour, antimicrobial and catalytic activity of gold nanoparticles synthesized by different pH propolis extracts

    Science.gov (United States)

    Gatea, Florentina; Teodor, Eugenia Dumitra; Seciu, Ana-Maria; Covaci, Ovidiu Ilie; Mănoiu, Sorin; Lazăr, Veronica; Radu, Gabriel Lucian

    2015-07-01

    The Romanian propolis was extracted in five different media, respectively, in water (pH 6.8), glycine buffer (pH 2.5), acetate buffer (pH 5), phosphate buffer (pH 7.4) and carbonate buffer (pH 9.2). The extracts presented different amounts of flavonoids and phenolic acids, increasing pH leading to higher concentrations of active compounds. Five variants of gold nanoparticles suspensions based on different pH Romanian propolis aqueous extracts were successfully synthesized. The obtained nanoparticles presented dimensions between 20 and 60 nm in dispersion form and around 18 nm in dried form, and different morphologies (spherical, hexagonal, triangular). Fourier transform infrared spectroscopy proved the attachment of organic compounds from propolis extracts to the colloidal gold suspensions and X-ray diffraction certified that the suspensions contain metallic gold. The obtained propolis gold nanoparticles do not exhibit any antibacterial or antifungal activity, but presented different catalytic activities and toxicity on tumour cells.

  2. Antitumour, antimicrobial and catalytic activity of gold nanoparticles synthesized by different pH propolis extracts

    Energy Technology Data Exchange (ETDEWEB)

    Gatea, Florentina; Teodor, Eugenia Dumitra, E-mail: eu-teodor@yahoo.com [National Institute for Biological Sciences, Centre of Bioanalysis (Romania); Seciu, Ana-Maria [National Institute for Biological Sciences, Cellular and Molecular Biology Department (Romania); Covaci, Ovidiu Ilie [SARA Pharm Solutions (Romania); Mănoiu, Sorin [National Institute for Biological Sciences, Cellular and Molecular Biology Department (Romania); Lazăr, Veronica [University of Bucharest, Faculty of Biology (Romania); Radu, Gabriel Lucian [University “Politehnica” Bucharest, Faculty of Applied Chemistry and Materials Science (Romania)

    2015-07-15

    The Romanian propolis was extracted in five different media, respectively, in water (pH 6.8), glycine buffer (pH 2.5), acetate buffer (pH 5), phosphate buffer (pH 7.4) and carbonate buffer (pH 9.2). The extracts presented different amounts of flavonoids and phenolic acids, increasing pH leading to higher concentrations of active compounds. Five variants of gold nanoparticles suspensions based on different pH Romanian propolis aqueous extracts were successfully synthesized. The obtained nanoparticles presented dimensions between 20 and 60 nm in dispersion form and around 18 nm in dried form, and different morphologies (spherical, hexagonal, triangular). Fourier transform infrared spectroscopy proved the attachment of organic compounds from propolis extracts to the colloidal gold suspensions and X-ray diffraction certified that the suspensions contain metallic gold. The obtained propolis gold nanoparticles do not exhibit any antibacterial or antifungal activity, but presented different catalytic activities and toxicity on tumour cells.

  3. Balancing Catalytic Activity and Interface Energetics of Electrocatalyst-Coated Photoanodes for Photoelectrochemical Water Splitting.

    Science.gov (United States)

    Xu, Zhe; Wang, Haoyu; Wen, Yunzhou; Li, Wenchao; Sun, Chuyu; He, Yuting; Shi, Zhan; Pei, Lang; Chen, Yongda; Yan, Shicheng; Zou, Zhigang

    2018-01-31

    For photoelectrochemical (PEC) water splitting, the interface interactions among semiconductors, electrocatalysts, and electrolytes affect the charge separation and catalysis in turn. Here, through the changing of the bath temperature, Co-based oxygen evolution catalysts (OEC) with different crystallinities were electrochemically deposited on Ti-doped Fe 2 O 3 (Ti-Fe 2 O 3 ) photoanodes. We found: (1) the OEC with low crystallinity is highly ion-permeable, decreasing the interactions between OEC and photoanode due to the intimate interaction between semiconductor and electrolyte; (2) the OEC with high crystallinity is nearly ion-impermeable, is beneficial to form a constant buried junction with semiconductor, and exhibits the low OEC catalytic activity; and (3) the OEC with moderate crystallinity is partially electrolyte-screened, thus contributing to the formation of ideal band bending underneath surface of semiconductor for charge separation and the highly electrocatalytic activity of OEC for lowering over-potentials of water oxidation. Our results demonstrate that to balance the water oxidation activity of OEC and OEC-semiconductor interface energetics is crucial for highly efficient solar energy conversion; in particular, the energy transducer is a semiconductor with a shallow or moderate valence-band level.

  4. The contrasting catalytic efficiency and cancer cell antiproliferative activity of stereoselective organoruthenium transfer hydrogenation catalysts.

    Science.gov (United States)

    Fu, Ying; Sanchez-Cano, Carlos; Soni, Rina; Romero-Canelon, Isolda; Hearn, Jessica M; Liu, Zhe; Wills, Martin; Sadler, Peter J

    2016-05-28

    The rapidly growing area of catalytic ruthenium chemistry has provided new complexes with potential as organometallic anticancer agents with novel mechanisms of action. Here we report the anticancer activity of four neutral organometallic Ru(II) arene N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) tethered transfer hydrogenation catalysts. The enantiomers (R,R)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8) and (S,S)-[Ru(η(6)-C6H5(CH2)3-TsDPEN-N-Me)Cl] (8a) exhibited higher potency than cisplatin against A2780 human ovarian cancer cells. When the N-methyl was replaced by N-H, i.e. to give (R,R)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7) and (S,S)-[Ru(η(6)-Ph(CH2)3-TsDPEN-NH)Cl] (7a), respectively, anticancer activity decreased >5-fold. Their antiproliferative activity appears to be linked to their ability to accumulate in cells, and their mechanism of action might involve inhibition of tubulin polymerisation. This appears to be the first report of the potent anticancer activity of tethered Ru(II) arene complexes, and the structure-activity relationship suggests that the N-methyl substituents are important for potency. In the National Cancer Institute 60-cancer-cell-line screen, complexes 8 and 8a exhibited higher activity than cisplatin towards a broad range of cancer cell lines. Intriguingly, in contrast to their potent anticancer properties, complexes 8/8a are poor catalysts for asymmetric transfer hydrogenation, whereas complexes 7/7a are effective asymmetric hydrogenation catalysts.

  5. Prostaglandin H synthase-mediated bioactivation of the amino acid pyrolysate product Trp P-2

    Energy Technology Data Exchange (ETDEWEB)

    Petry, T.W.; Krauss, R.S.; Eling, T.E.

    1986-08-01

    We report evidence that the mutagen and carcinogen 3-amino-1-methyl-5H pyrido(4,3b)indole (Trp P-2) is a substrate for co-oxidation by prostaglandin H synthase (PHS) in ram seminal vesicle (RSV) microsomes. Trp P-2 serves as a reducing cofactor for the hydroperoxidase activity of PHS as shown by the concentration-dependent inhibition of the hydroperoxidase catalyzed incorporation of molecular oxygen into phenylbutazone. Spectral data suggest that this metabolism results in disruption of the double bond conjugation within the nucleus of the molecule. A single metabolite peak which was dependent upon arachidonic acid and substrate concentration was separated from the parent compound by h.p.l.c. following incubation with RSV microsomes. Co-oxidation of Trp P-2 produced reactive intermediates which bound covalently to microsomal protein (9 nmol/mg) and to calf thymus DNA (475 pmol/mg). Binding was inhibited by indomethacin, and supported by substitution of hydrogen peroxide for arachidonic acid. These data suggest a possible role for PHS in the in situ activation of Trp P-2 to its ultimate carcinogenic form in tissues which contain PHS.

  6. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

    Science.gov (United States)

    Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao

    2014-10-01

    In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  7. Green synthesis of Silver and Gold Nanoparticles for Enhanced catalytic and bactericidal activity

    Science.gov (United States)

    Naraginti, S.; Tiwari, N.; Sivakumar, A.

    2017-11-01

    A rapid one step green synthetic method using kiwi fruit extract was employed for preparation of silver and gold nanoparticles. The synthesized nanoparticles were successfully used as green catalysts for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB). They also exhibited excellent antimicrobial activity against clinically isolated Pseudomonas aeruginosa (P.aeruginosa) and Staphylococcus aureus (S.aureus). It was noticed that with increase in concentration of the aqueous silver and gold solutions, particle size of the Ag and Au NPS showed increase as evidenced from UV-Visible spectroscopy and TEM micrograph. The method employed for the synthesis required only a few minutes for more than 90% formation of nanoparticles when the temperature was raised to 80°C. It was also noticed that the catalytic activity of nanoparticles depends upon the size of the particles. These nanoparticles were observed to be crystalline from the clear lattice fringes in the transmission electron microscopic (TEM) images, bright circular spots in the selected area electron diffraction (SAED) pattern and peaks in the X-ray diffraction (XRD) pattern. The Fourier-transform infrared (FTIR) spectrum indicated the presence of different functional groups in the biomolecule capping the nanoparticles.

  8. Studies on bis(halogeno) dioxomolybdenum(VI)-bipyridine complexes: synthesis and catalytic activity.

    Science.gov (United States)

    Günyar, Alev; Zhou, Ming-Dong; Drees, Markus; Baxter, Paul N W; Bassioni, Ghada; Herdtweck, Eberhardt; Kühn, Fritz E

    2009-10-28

    Dioxomolybdenum(VI) complexes with the general formula [MoO2Cl2L2] (L2=3,3'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-dibromo-2,2'-bipyridine, 5,5'-dibromo-2,2'-bipyridine, 5,5'-diamino-2,2'-bipyridine; 5,5'-dinitro-2,2'-bipyridine; 5,5'-di-ethoxycarbonyl-2,2'-bipyridine; 6-phenyl-2,2'-bipyridine; 2,2':6',2''-terpyridine) have been prepared and characterised. [MoO2Cl2(5,5'-di-ethoxycarbonyl-2,2'-bipyridine)] has been examined by single crystal X-ray analysis. The complexes were applied as homogenous catalysts for the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as oxidising agent. The new compounds show an overall high activity and are highly selective catalysts in the epoxidation of cyclooctene. The stability of the complexes and differences in the catalytic activity can be clearly attributed to electronic contributions of the functional groups on bipyridine ligands and to steric restrictions. DFT calculations have assisted in a better understanding of the stability of the complexes and are in agreement with experiment. The influence of the terminal oxo ligands and the Lewis base ligands on the Mo center keep the compounds on quite a stable level of electron density.

  9. Rapid biological synthesis of silver nanoparticles using Leucas martinicensis leaf extract for catalytic and antibacterial activity.

    Science.gov (United States)

    Ashokkumar, S; Ravi, S; Kathiravan, V; Velmurugan, S

    2014-10-01

    A novel green approach for the synthesis and stabilization of silver nanoparticles (AgNPs) using water extract of Leucas martinicensis leaf has been developed. As obtained, the nanoparticles are characterized by UV-visible (UV-Vis), transmission electron microscope (TEM), and X-ray diffraction (XRD). The crystalline nature of the AgNPs is confirmed by the prominent peaks in the XRD pattern. FTIR spectra suggest that the possible biomolecules are responsible for the efficient stabilization of the sample. The effects of leaf quantity on the biosynthesis of AgNPs are investigated by UV-Vis spectrophotometer. The synthesized AgNPs are observed to have a good catalytic activity on the reduction of methylene blue by L. martinicensis leaf. This is confirmed by the decrease in absorbance maximum values of methylene blue with respect to time through UV-Vis spectrophotometer. Moreover, the antibacterial activity of synthesized AgNPs against Staphylococcus aureus, Bacillus subtilis, Salmonella typhi, and Escherichia coli are screened.

  10. A Bio-Inspired, Catalytic E → Z Isomerization of Activated Olefins.

    Science.gov (United States)

    Metternich, Jan B; Gilmour, Ryan

    2015-09-09

    Herein, Nature's flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-riboflavin (up to 99:1 Z/E). In contrast to the prominent Z → E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E → Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.

  11. Hierarchical nano-on-micro copper with enhanced catalytic activity towards electro-oxidation of hydrazine

    Science.gov (United States)

    Yan, Xiaodong; Liu, Yuan; Scheel, Kyle R.; Li, Yong; Yu, Yunhua; Yang, Xiaoping; Peng, Zhonghua

    2018-01-01

    The electrochemical properties of catalyst materials are highly dependent on the materials structure and architecture. Herein, nano-on-micro Cu electrodes are fabricated by growing Cu microcrystals on Ni foam substrate, followed by introducing Cu nanocrystals onto the surface of the Cu microcrystals. The introduction of Cu nanocrystals onto the surface of Cu microcrystals is shown to dramatically increase the electrochemically active surface area and thus significantly enhances the catalytic activity of the catalyst electrode towards electro-oxidation of hydrazine. The onset potential (-1.04 V vs. Ag/AgCl) of the nano-on-micro Cu electrode is lower than those of the reported Cu-based catalysts under similar testing conditions, and a current density of 16 mA·cm-2, which is 2 times that of the microsized Cu electrode, is achieved at a potential of -0.95 V vs. Ag/AgCl. Moreover, the nano-on-micro Cu electrode demonstrates good long-term stability.

  12. Polymeric heterogeneous catalysts of transition-metal oxides: surface characterization, physicomechanical properties, and catalytic activity.

    Science.gov (United States)

    Nhi, Bui Dinh; Akhmadullin, Renat Maratovich; Akhmadullina, Alfiya Garipovna; Samuilov, Yakov Dmitrievich; Aghajanian, Svetlana Ivanova

    2013-12-16

    We investigate the physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, specifically, the specific surface area, elongation at break, breaking strength, specific electrical resistance, and volume resistivity. Digital microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. The experimental results show that polymeric heterogeneous catalysts of transition-metal oxides exhibit high stability and can maintain their catalytic activity under extreme reaction conditions for long-term use. The oxidation mechanism of sulfur-containing compounds in the presence of polymeric heterogeneous catalysts of transition-metal oxides is confirmed. Microstructural characterization of the catalysts is performed by using X-ray computed tomography. The activity of various catalysts in the oxidation of sulfur-containing compounds is determined. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Facile and green synthesis of palladium nanoparticles-graphene-carbon nanotube material with high catalytic activity.

    Science.gov (United States)

    Sun, Tai; Zhang, Zheye; Xiao, Junwu; Chen, Chen; Xiao, Fei; Wang, Shuai; Liu, Yunqi

    2013-01-01

    We report a facile and green method to synthesize a new type of catalyst by coating Pd nanoparticles (NPs) on reduced graphene oxide (rGO)-carbon nanotube (CNT) nanocomposite. An rGO-CNT nanocomposite with three-dimensional microstructures was obtained by hydrothermal treatment of an aqueous dispersion of graphene oxide (GO) and CNTs. After the rGO-CNT composites have been dipped in K₂PdCl₄ solution, the spontaneous redox reaction between the GO-CNT and PdCl₄(2-) led to the formation of nanohybrid materials consisting rGO-CNT decorated with 4 nm Pd NPs, which exhibited excellent and stable catalytic activity: the reduction of 4-nitrophenol to 4-aminophenol using NaBH4 as a catalyst was completed in only 20 s at room temperature, even when the Pd content of the catalyst was 1.12 wt%. This method does not require rigorous conditions or toxic agents and thus is a rapid, efficient, and green approach to the fabrication of highly active catalysts.

  14. Controlling catalytic activity of gold cluster on MgO thin film for water splitting

    Science.gov (United States)

    Ding, Zijing; Yan, Lei; Li, Zi; Ma, Wei; Lu, Gang; Meng, Sheng

    2017-09-01

    We propose that supported gold clusters on MgO thin film can potentially serve as an efficient photocatalyst for water splitting. The catalytic activity of the gold cluster is enhanced by excess electrons occupying its quantum well states (QWSs) and can be controlled by varying the oxide thickness, introducing defects/doping in the substrate, and modulating the plasmonic response of the Au cluster. We find that the bonding between the water molecule and certain QWSs can significantly reduce the water splitting energy barrier in its ground state. More importantly, the water splitting is nearly spontaneous when the QWS is photoexcited. First-principles real-time electron dynamics simulations reveal that the excited QWS in the supported gold cluster has a long lifetime on the scale of picoseconds. Generation of activated hydrogen atoms is predicted to occur spontaneously following photoexcitation, and the yield of H2 gas is maintained by enriching hydrogen concentration without poisoning the catalyst. These results illustrate promising routes for promoting photocatalysis via engineering the energy levels of supported metal clusters.

  15. Nanostructured Samarium Doped Fluorapatites and Their Catalytic Activity towards Synthesis of 1,2,4-Triazoles

    Directory of Open Access Journals (Sweden)

    Kranthi Kumar Gangu

    2016-09-01

    Full Text Available An investigation was conducted into the influence of the amino acids as organic modifiers in the facile synthesis of metal incorporated fluorapatites (FAp and their properties. The nanostructured Sm doped fluorapatites (Sm-FAp were prepared by a co-precipitation method using four different amino acids, namely glutamic acid, aspartic acid, glycine and histidine. The materials were characterized by various techniques including X-ray diffraction (XRD, Fourier transform infra-red spectroscopy (FT-IR, field emission scanning electron microscopy (FE-SEM, energy-dispersive X-ray spectroscopy (EDX, high resolution transmission electron microscopy (HR-TEM, N2-adsorption/desorption isotherm, temperature programmed desorption (TPD and fluorescence spectrophotometry. Under similar conditions, Sm-FAp prepared using different amino acids exhibited distinctly different morphological structures, surface area and pore properties. Their activity as catalysts was assessed and Sm-FAp/Glycine displayed excellent efficiency in the synthesis of 1,2,4-triazole catalyzing the reaction between 2-nitrobenzaldehyde and thiosemicarbazide with exceptional selectivity and 98% yield in a short time interval (10 min. The study provides an insight into the role of organic modifiers as controllers of nucleation, growth and aggregation which significantly influence the nature and activity of the catalytic sites on Sm-FAp. Sm-FAp could also have potential as photoactive material.

  16. Catalytic reaction pathway for the mitogen-activated protein kinase ERK2.

    Science.gov (United States)

    Prowse, C N; Hagopian, J C; Cobb, M H; Ahn, N G; Lew, J

    2000-05-23

    The structural, functional, and regulatory properties of the mitogen-activated protein kinases (MAP kinases) have long attracted considerable attention owing to the critical role that these enzymes play in signal transduction. While several MAP kinase X-ray crystal structures currently exist, there is by comparison little mechanistic information available to correlate the structural data with the known biochemical properties of these molecules. We have employed steady-state kinetic and solvent viscosometric techniques to characterize the catalytic reaction pathway of the MAP kinase ERK2 with respect to the phosphorylation of a protein substrate, myelin basic protein (MBP), and a synthetic peptide substrate, ERKtide. A minor viscosity effect on k(cat) with respect to the phosphorylation of MBP was observed (k(cat) = 10 +/- 2 s(-1), k(cat)(eta) = 0.18 +/- 0.05), indicating that substrate processing occurs via slow phosphoryl group transfer (12 +/- 4 s(-1)) followed by the faster release of products (56 +/- 4 s(-1)). At an MBP concentration extrapolated to infinity, no significant viscosity effect on k(cat)/K(m(ATP)) was observed (k(cat)/K(m(ATP)) = 0.2 +/- 0.1 microM(-1) s(-1), k(cat)/K(m(ATP))(eta) = -0.08 +/- 0.04), consistent with rapid-equilibrium binding of the nucleotide. In contrast, at saturating ATP, a full viscosity effect on k(cat)/K(m) for MBP was apparent (k(cat)/K(m(MBP)) = 2.4 +/- 1 microM(-1) s(-1), k(cat)/K(m(MBP))(eta) = 1.0 +/- 0.1), while no viscosity effect was observed on k(cat)/K(m) for the phosphorylation of ERKtide (k(cat)/K(m(ERKtide)) = (4 +/- 2) x 10(-3) microM(-1) s(-1), k(cat)/K(m(ERKtide))(eta) = -0.02 +/- 0.02). This is consistent with the diffusion-limited binding of MBP, in contrast to the rapid-equilibrium binding of ERKtide, to form the ternary Michaelis complex. Calculated values for binding constants show that the estimated value for K(d(MBP)) (/= 1.5 mM). The dramatically higher catalytic efficiency of MBP in comparison to that

  17. Catalysis by Glomerella cingulata cutinase requires conformational cycling between the active and inactive states of its catalytic triad.

    Science.gov (United States)

    Nyon, Mun Peak; Rice, David W; Berrisford, John M; Hounslow, Andrea M; Moir, Arthur J G; Huang, Huazhang; Nathan, Sheila; Mahadi, Nor Muhammad; Bakar, Farah Diba Abu; Craven, C Jeremy

    2009-01-09

    Cutinase belongs to a group of enzymes that catalyze the hydrolysis of esters and triglycerides. Structural studies on the enzyme from Fusarium solani have revealed the presence of a classic catalytic triad that has been implicated in the enzyme's mechanism. We have solved the crystal structure of Glomerella cingulata cutinase in the absence and in the presence of the inhibitors E600 (diethyl p-nitrophenyl phosphate) and PETFP (3-phenethylthio-1,1,1-trifluoropropan-2-one) to resolutions between 2.6 and 1.9 A. Analysis of these structures reveals that the catalytic triad (Ser136, Asp191, and His204) adopts an unusual configuration with the putative essential histidine His204 swung out of the active site into a position where it is unable to participate in catalysis, with the imidazole ring 11 A away from its expected position. Solution-state NMR experiments are consistent with the disrupted configuration of the triad observed crystallographically. H204N, a site-directed mutant, was shown to be catalytically inactive, confirming the importance of this residue in the enzyme mechanism. These findings suggest that, during its catalytic cycle, cutinase undergoes a significant conformational rearrangement converting the loop bearing the histidine from an inactive conformation, in which the histidine of the triad is solvent exposed, to an active conformation, in which the triad assumes a classic configuration.

  18. Synthesis of Rh/Macro-Porous Alumina Over Micro-Channel Plate and Its Catalytic Activity Tests for Diesel Reforming.

    Science.gov (United States)

    Seong, Yeon Baek; Kim, Yong Sul; Park, No-Kuk; Lee, Tae Jin

    2015-11-01

    Macro-porous Al2O3 as the catalytic support material was synthesized using colloidal polystyrene spheres over a micro-channel plate. The colloidal polystyrene spheres were used as a template for the production of an ordered macro porous material using an alumina nitrate solution as the precursor for Al2O3. The close-packed colloidal crystal array template method was applied to the formulation of ordered macro-porous Al2O3 used as a catalytic support material over a micro-channel plate. The solvent in the mixture solution, which also contained the colloidal polystyrene solution, aluminum nitrate solution and the precursor of the catalytic active materials (Rh), was evaporated in a vacuum oven at 50 degrees C. The ordered polystyrene spheres and aluminum salt of the solid state were deposited over a micro channel plate, and macro-porous Al2O3 was formed after calcination at 600 degrees C to remove the polystyrene spheres. The catalytic activity of the Rh/macro-porous alumina supported over the micro-channel plate was tested for diesel reforming.

  19. Enhanced catalytic activity of Ag nanoparticles supported on polyacrylamide/polypyrrole/graphene oxide nanosheets for the reduction of 4-nitrophenol

    Science.gov (United States)

    Mao, Hui; Ji, Chunguang; Liu, Meihong; Cao, Zhenqian; Sun, Dayin; Xing, Zhiqiang; Chen, Xia; Zhang, Yu; Song, Xi-Ming

    2018-03-01

    High-density and well-dispersed Ag nanoparticles (Ag NPs) with a mean size of 20 nm have been successfully supported on the surface of polyacrylamide functionalized polypyrrole/graphene oxide (PAM/PPy/GO) nanosheets. The obtained Ag/PAM/PPy/GO composite nanosheets exhibited an excellent catalytic activity for reduction of 4-nitrophenol by NaBH4 with the kinetic reaction rate constant of 3.38 × 10-2 s-1 due to the synergistic effect of all the components of the composite nanosheets. The corresponding catalytic mechanism has been revealed by investigating the effect of different components of Ag/PAM/PPy/GO composite nanosheets on the catalytic performance: GO with the excellent two-dimensional structures offered large surface area for the immobilization of more Ag NPs; PPy with a high electric conductivity promoted the electron transport in the reduction of 4-NP; PAM did not only act as a good linker between Ag NPs and PPy/GO nanosheets for the synthesis of Ag/PAM/PPy/GO composite nanosheets, but also could facilitate the efficient contact between 4-NP and Ag NPs; Ag NPs were the catalytic active site for the reduction of 4-NP, respectively.

  20. Green Adeptness in the Synthesis and Stabilization of Copper Nanoparticles: Catalytic, Antibacterial, Cytotoxicity, and Antioxidant Activities.

    Science.gov (United States)

    Din, Muhammad Imran; Arshad, Farhan; Hussain, Zaib; Mukhtar, Maria

    2017-12-28

    Copper nanoparticles (CuNPs) are of great interest due to their extraordinary properties such as high surface-to-volume ratio, high yield strength, ductility, hardness, flexibility, and rigidity. CuNPs show catalytic, antibacterial, antioxidant, and antifungal activities along with cytotoxicity and anticancer properties in many different applications. Many physical and chemical methods have been used to synthesize nanoparticles including laser ablation, microwave-assisted process, sol-gel, co-precipitation, pulsed wire discharge, vacuum vapor deposition, high-energy irradiation, lithography, mechanical milling, photochemical reduction, electrochemistry, electrospray synthesis, hydrothermal reaction, microemulsion, and chemical reduction. Phytosynthesis of nanoparticles has been suggested as a valuable alternative to physical and chemical methods due to low cytotoxicity, economic prospects, environment-friendly, enhanced biocompatibility, and high antioxidant and antimicrobial activities. The review explains characterization techniques, their main role, limitations, and sensitivity used in the preparation of CuNPs. An overview of techniques used in the synthesis of CuNPs, synthesis procedure, reaction parameters which affect the properties of synthesized CuNPs, and a screening analysis which is used to identify phytochemicals in different plants is presented from the recent published literature which has been reviewed and summarized. Hypothetical mechanisms of reduction of the copper ion by quercetin, stabilization of copper nanoparticles by santin, antimicrobial activity, and reduction of 4-nitrophenol with diagrammatic illustrations are given. The main purpose of this review was to summarize the data of plants used for the synthesis of CuNPs and open a new pathway for researchers to investigate those plants which have not been used in the past. Graphical abstract Proposed Mechanism for Antibacterial activity of copper nanoparticles.

  1. Oxygen-containing compounds as activators of cyclopentene polymerization under the effect of catalytic system WCl/sub 6/-tetraallylsilane

    Energy Technology Data Exchange (ETDEWEB)

    Pakuro, N.I.; Makovetskij, K.L.; Uantmakher, A.R.; Dolgoplosk, B.A. (Nauchno-Issledovatel' skij Fiziko-Khimicheskij Inst., Moscow (USSR))

    1982-03-01

    Kinetics of cyclopentene polymerization in toluene medium at -30 deg under the effect of certain tungsten halides in the presence of tetraallylsilane is studied. Catalytic system WCl/sub 6/-tetra-allylsilane under conditions of thorough purification from traces of moisture and oxygen is not active in cyclopentene polymerization with the cycle opening. Compounds resulting in the appearance of oxoligand near W atom (water, oxygen, epichlorohydrin) produce activating effect on the above mentioned system.

  2. A fungal P450 (CYP5136A3 capable of oxidizing polycyclic aromatic hydrocarbons and endocrine disrupting alkylphenols: role of Trp(129 and Leu(324.

    Directory of Open Access Journals (Sweden)

    Khajamohiddin Syed

    Full Text Available The model white rot fungus Phanerochaete chrysosporium, which is known for its versatile pollutant-biodegradation ability, possesses an extraordinarily large repertoire of P450 monooxygenases in its genome. However, the majority of these P450s have hitherto unknown function. Our initial studies using a genome-wide gene induction strategy revealed multiple P450s responsive to individual classes of xenobiotics. Here we report functional characterization of a cytochrome P450 monooxygenase, CYP5136A3 that showed common responsiveness and catalytic versatility towards endocrine-disrupting alkylphenols (APs and mutagenic/carcinogenic polycyclic aromatic hydrocarbons (PAHs. Using recombinant CYP5136A3, we demonstrated its oxidation activity towards APs with varying alkyl side-chain length (C3-C9, in addition to PAHs (3-4 ring size. AP oxidation involves hydroxylation at the terminal carbon of the alkyl side-chain (ω-oxidation. Structure-activity analysis based on a 3D model indicated a potential role of Trp(129 and Leu(324 in the oxidation mechanism of CYP5136A3. Replacing Trp(129 with Leu (W129L and Phe (W129F significantly diminished oxidation of both PAHs and APs. The W129L mutation caused greater reduction in phenanthrene oxidation (80% as compared to W129F which caused greater reduction in pyrene oxidation (88%. Almost complete loss of oxidation of C3-C8 APs (83-90% was observed for the W129L mutation as compared to W129F (28-41%. However, the two mutations showed a comparable loss (60-67% in C9-AP oxidation. Replacement of Leu(324 with Gly (L324G caused 42% and 54% decrease in oxidation activity towards phenanthrene and pyrene, respectively. This mutation also caused loss of activity towards C3-C8 APs (20-58%, and complete loss of activity toward nonylphenol (C9-AP. Collectively, the results suggest that Trp(129 and Leu(324 are critical in substrate recognition and/or regio-selective oxidation of PAHs and APs. To our knowledge, this is the first

  3. A Fungal P450 (CYP5136A3) Capable of Oxidizing Polycyclic Aromatic Hydrocarbons and Endocrine Disrupting Alkylphenols: Role of Trp129 and Leu324

    Science.gov (United States)

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Yadav, Jagjit S.

    2011-01-01

    The model white rot fungus Phanerochaete chrysosporium, which is known for its versatile pollutant-biodegradation ability, possesses an extraordinarily large repertoire of P450 monooxygenases in its genome. However, the majority of these P450s have hitherto unknown function. Our initial studies using a genome-wide gene induction strategy revealed multiple P450s responsive to individual classes of xenobiotics. Here we report functional characterization of a cytochrome P450 monooxygenase, CYP5136A3 that showed common responsiveness and catalytic versatility towards endocrine-disrupting alkylphenols (APs) and mutagenic/carcinogenic polycyclic aromatic hydrocarbons (PAHs). Using recombinant CYP5136A3, we demonstrated its oxidation activity towards APs with varying alkyl side-chain length (C3-C9), in addition to PAHs (3–4 ring size). AP oxidation involves hydroxylation at the terminal carbon of the alkyl side-chain (ω-oxidation). Structure-activity analysis based on a 3D model indicated a potential role of Trp129 and Leu324 in the oxidation mechanism of CYP5136A3. Replacing Trp129 with Leu (W129L) and Phe (W129F) significantly diminished oxidation of both PAHs and APs. The W129L mutation caused greater reduction in phenanthrene oxidation (80%) as compared to W129F which caused greater reduction in pyrene oxidation (88%). Almost complete loss of oxidation of C3-C8 APs (83–90%) was observed for the W129L mutation as compared to W129F (28–41%). However, the two mutations showed a comparable loss (60–67%) in C9-AP oxidation. Replacement of Leu324 with Gly (L324G) caused 42% and 54% decrease in oxidation activity towards phenanthrene and pyrene, respectively. This mutation also caused loss of activity towards C3-C8 APs (20–58%), and complete loss of activity toward nonylphenol (C9-AP). Collectively, the results suggest that Trp129 and Leu324 are critical in substrate recognition and/or regio-selective oxidation of PAHs and APs. To our knowledge, this is the first

  4. Transient receptor potential (TRP) channels as drug targets for diseases of the digestive system

    Science.gov (United States)

    Holzer, Peter

    2011-01-01

    Approximately 20 of the 30 mammalian transient receptor potential (TRP) channel subunits are expressed by specific neurons and cells within the alimentary canal. They subserve important roles in taste, chemesthesis, mechanosensation, pain and hyperalgesia and contribute to the regulation of gastrointestinal motility, absorptive and secretory processes, blood flow, and mucosal homeostasis. In a cellular perspective, TRP channels operate either as primary detectors of chemical and physical stimuli, as secondary transducers of ionotropic or metabotropic receptors, or as ion transport channels. The polymodal sensory function of TRPA1, TRPM5, TRPM8, TRPP2, TRPV1, TRPV3 and TRPV4 enables the digestive system to survey its physical and chemical environment, which is relevant to all processes of digestion. TRPV5 and TRPV6 as well as TRPM6 and TRPM7 contribute to the absorption of Ca2+ and Mg2+, respectively. TRPM7 participates in intestinal pacemaker activity, and TRPC4 transduces muscarinic acetylcholine receptor activation to smooth muscle contraction. Changes in TRP channel expression or function are associated with a variety of diseases/disorders of the digestive system, notably gastro-esophageal reflux disease, inflammatory bowel disease, pain and hyperalgesia in heartburn, functional dyspepsia and irritable bowel syndrome, cholera, hypomagnesemia with secondary hypocalcemia, infantile hypertrophic pyloric stenosis, esophageal, gastrointestinal and pancreatic cancer, and polycystic liver disease. These implications identify TRP channels as promising drug targets for the management of a number of gastrointestinal pathologies. As a result, major efforts are put into the development of selective TRP channel agonists and antagonists and the assessment of their therapeutic potential. PMID:21420431

  5. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    Science.gov (United States)

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

  6. Maternal high fat diet alters skeletal muscle mitochondrial catalytic activity in adult male rat offspring.

    Directory of Open Access Journals (Sweden)

    Chantal Anne Pileggi

    2016-11-01

    Full Text Available A maternal high-fat (HF diet during pregnancy can lead to metabolic compromise such as insulin resistance in adult offspring. Skeletal muscle mitochondrial dysfunction is one mechanism contributing to metabolic impairments in insulin resistant states. Therefore, the present study aimed to investigate whether mitochondrial dysfunction is evident in metabolically compromised offspring born to HF-fed dams. Sprague-Dawley dams were randomly assigned to receive a purified control diet (CD; 10% kcal from fat or a high fat diet (HFD; 45% kcal from fat for 10 days prior to mating, throughout pregnancy and during lactation. From weaning, all male offspring received a standard chow diet and soleus muscle was collected at day 150. Expression of the mitochondrial transcription factors nuclear respiratory factor-1 (NRF1 and mitochondrial transcription factor A (mtTFA were downregulated in HF offspring. Furthermore, genes encoding the mitochondrial electron transport system (ETS respiratory complex subunits were supressed in HF offspring. Moreover, protein expression of the complex I subunit, NDUFB8, was downregulated in HF offspring (36%, which was paralleled by decreased maximal catalytic linked activity of complex I and III (40%. Together, these results indicate that exposure to a maternal HF diet during development may elicit lifelong mitochondrial alterations in offspring skeletal muscle.

  7. DNA/RNA hybrid substrates modulate the catalytic activity of purified AID.

    Science.gov (United States)

    Abdouni, Hala S; King, Justin J; Ghorbani, Atefeh; Fifield, Heather; Berghuis, Lesley; Larijani, Mani

    2018-01-01

    Activation-induced cytidine deaminase (AID) converts cytidine to uridine at Immunoglobulin (Ig) loci, initiating somatic hypermutation and class switching of antibodies. In vitro, AID acts on single stranded DNA (ssDNA), but neither double-stranded DNA (dsDNA) oligonucleotides nor RNA, and it is believed that transcription is the in vivo generator of ssDNA targeted by AID. It is also known that the Ig loci, particularly the switch (S) regions targeted by AID are rich in transcription-generated DNA/RNA hybrids. Here, we examined the binding and catalytic behavior of purified AID on DNA/RNA hybrid substrates bearing either random sequences or GC-rich sequences simulating Ig S regions. If substrates were made up of a random sequence, AID preferred substrates composed entirely of DNA over DNA/RNA hybrids. In contrast, if substrates were composed of S region sequences, AID preferred to mutate DNA/RNA hybrids over substrates composed entirely of DNA. Accordingly, AID exhibited a significantly higher affinity for binding DNA/RNA hybrid substrates composed specifically of S region sequences, than any other substrates composed of DNA. Thus, in the absence of any other cellular processes or factors, AID itself favors binding and mutating DNA/RNA hybrids composed of S region sequences. AID:DNA/RNA complex formation and supporting mutational analyses suggest that recognition of DNA/RNA hybrids is an inherent structural property of AID. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Effective treatment of oily scum via catalytic wet persulfate oxidation process activated by Fe2.

    Science.gov (United States)

    Yuan, Xingzhong; Guan, Renpeng; Wu, Zhibin; Jiang, Longbo; Li, Yifu; Chen, Xiaohong; Zeng, Guangming

    2018-04-05

    Oily scum, a hazardous by-product of petroleum industry, need to be deposed urgently to reduce environmental risks. This paper introduces catalytic wet persulfate oxidation (CWPO) process in the treatment of oily scum to realize risk relief. Under the activation of heat and Fe 2+ , persulfate (PS) was decomposed into sulfate radicals and hydroxyl radicals, which played a major role on the degradation of petroleum hydrocarbons. The effects of wet air oxidation (WAO) and CWPO process on the degradation of oily scum were compared. In CWPO process, the total petroleum hydrocarbons (TPHs) content of oily scum was decreased from 92.63% to 16.75%, which was still up to 70.19% in WAO process. The degradation rate of TPHs in CWPO process was about 3.38 times higher than that in WAO process. The great performance of CWPO process was also confirmed by elemental analysis, which indicated that the C and H contents of oily scum were reduced significantly by CWPO process. These results indicated that CWPO process has high potential on the degradation of oily scum for environmental protection. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Evolution behavior of catalytically activated replication—decline in a coagulation process

    International Nuclear Information System (INIS)

    Gao Yan; Wang Hai-Feng; Zhang Ji-Dong; Yang Xia; Sun Mao-Zhu; Lin Zhen-Quan

    2013-01-01

    We propose a catalytically activated replication—decline model of three species, in which two aggregates of the same species can coagulate themselves, an A aggregate of any size can replicate itself with the help of B aggregates, and the decline of A aggregate occurs under the catalysis of C aggregates. By means of mean-field rate equations, we derive the asymptotic solutions of the aggregate size distribution a k (t) of species A, which is found to depend strongly on the competition among three mechanisms: the self-coagulation of species A, the replication of species A catalyzed by species B, and the decline of species A catalyzed by species C. When the self-coagulation of species A dominates the system, the aggregate size distribution a k (t) satisfies the conventional scaling form. When the catalyzed replication process dominates the system, a k (t) takes the generalized scaling form. When the catalyzed decline process dominates the system, a k (t) approaches the modified scaling form. (condensed matter: structural, mechanical, and thermal properties)

  10. Microfluidic system for enzymeless electrochemical determination of inulin using catalytically active metal nanowires

    International Nuclear Information System (INIS)

    García, Miguel; García -Carmona, Laura; Escarpa, Alberto

    2015-01-01

    We report on a microfluidic system for the electrochemical determination of inulin. It is making use of electro-synthesized catalytically active nanowires (NWs; made from nickel or copper; 6 μm long and 300 nm wide) capable of detecting inulin at a working voltage of +0.70 V (vs. Ag/AgCl) and a pH value of 12.0 with a sensitivity that is 40 times better than that for fructose (its monomer). The copper nanoelectrodes were characterized by field emission scanning electron microscopy and photoelectron spectroscopy which revealed a random distribution of copper NWs. Their core is found to be metallic while the outer few atomic layers (<2 nm) are oxidized (CuO). Both the intra-electrode repeatability (with RSDs of <8 % for 5 samples) and the inter-electrode reproducibility (RSDs <9 %; n =4) are very good. The approach presented here allows for a direct determination of both inulin and free fructose within <300 s with a LOD of 3 μM for inulin. Inulin was determined with recoveries ranging from 97 to 103 % (with RSDs of <4 %). This approach is perceived to represent an alternative to enzymatic assays or HPLC based approaches. It has the additional advantages of rapidity and low sample and reagent consumption. Given the electrochemical behavior of inulin, the results also suggest that this method will pave novel avenues towards the detection of complex carbohydrates. (author)

  11. Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons.

    Science.gov (United States)

    Bu, Quan; Lei, Hanwu; Wang, Lu; Wei, Yi; Zhu, Lei; Zhang, Xuesong; Liu, Yupeng; Yadavalli, Gayatri; Tang, Juming

    2014-06-01

    The aim of this study is to explore catalytic microwave pyrolysis of lignin for renewable phenols and fuels using activated carbon (AC) as a catalyst. A central composite experimental design (CCD) was used to optimize the reaction condition. The effects of reaction temperature and weight hourly space velocity (WHSV, h(-1)) on product yields were investigated. GC/MS analysis showed that the main chemical compounds of bio-oils were phenols, guaiacols, hydrocarbons and esters, most of which were ranged from 71% to 87% of the bio-oils depending on different reaction conditions. Bio-oils with high concentrations of phenol (45% in the bio-oil) were obtained. The calorific value analysis revealed that the high heating values (HHV) of the lignin-derived biochars were from 20.4 to 24.5 MJ/kg in comparison with raw lignin (19 MJ/kg). The reaction mechanism of this process was analyzed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Biosynthesis of gold nanoparticles using Capsicum annuum var. grossum pulp extract and its catalytic activity

    Science.gov (United States)

    Yuan, Chun-Gang; Huo, Can; Yu, Shuixin; Gui, Bing

    2017-01-01

    Biological synthesis approach has been regarded as a green, eco-friendly and cost effective method for nanoparticles preparation without any toxic solvents and hazardous bi-products during the process. This present study reported a facile and rapid biosynthesis method for gold nanoparticles (GNPs) from Capsicum annuum var. grossum pulp extract in a single-pot process. The aqueous pulp extract was used as biotic reducing agent for gold nanoparticle growing. Various shapes (triangle, hexagonal, and quasi-spherical shapes) were observed within range of 6-37 nm. The UV-Vis spectra showed surface plasmon resonance (SPR) peak for the formed GNPs at 560 nm after 10 min incubation at room temperature. The possible influences of extract amount, gold ion concentration, incubation time, reaction temperature and solution pH were evaluated to obtain the optimized synthesis conditions. The effects of the experimental factors on NPs synthesis process were also discussed. The produced gold nanoparticles were characterized by transform electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrated that the as-obtained GNPs were well dispersed and stable with good catalytic activity. Biomolecules in the aqueous extract were responsible for the capping and stabilization of GNPs.

  13. Protection of tobacco cells from oxidative copper toxicity by catalytically active metal-binding DNA oligomers.

    Science.gov (United States)

    Iwase, Junichiro; Furukawa, Hiroka; Hiramatsu, Takuya; Bouteau, François; Mancuso, Stefano; Tanaka, Kenichiro; Okazaki, Toshihiko; Kawano, Tomonori

    2014-03-01

    The impact of copper ions on the oxidative and calcium signal transductions, leading to cell death in plant cells, have been documented. Copper induces a series of biological and chemical reactions in plant cells including the oxidative burst reflecting the production of reactive oxygen species and the stimulation of calcium channel opening allowing a transient increase in cytosolic calcium concentrations. These early events, completed within a few minutes after the contact with copper, are known to trigger the development of cell death. The effects of DNA fragments with copper-binding motifs as novel plant cell-protecting agents were assessed using cell suspension cultures of transgenic tobacco (Nicotiana tabacum L., cell line BY-2) expressing the aequorin gene. The addition of GC-rich double-stranded DNA fragments, prior to the addition of copper ions, effectively blocked both the copper-induced calcium influx and cell death. In addition, the DNA-Cu complex examined was shown to possess superoxide-scavenging catalytic activity, suggesting that DNA-mediated protection of the cells from copper toxicity is due to the removal of superoxide. Lastly, a possible mechanism of DNA-Cu interaction and future applications of these DNA fragments in the protection of plant roots from metal toxicity or in aid of phyto-remediation processes are discussed.

  14. Synthesis and catalytic activity of Birnessite-Type Manganese Oxide synthesized by solvent-free method

    Science.gov (United States)

    Siregar, S. S.; Awaluddin, A.

    2018-04-01

    Redox reaction between KMnO4 and glucose usingsolvent-free method produces the octahedral layer birnessite-type manganese oxide. The effects of mole ratios, temperatures, and calcinations time on the structures and crystallinity of the oxides were studied throughthe X-ray powder diffraction analysis. The mole ratio of KMnO4/glucose (1:3) produces the purebirnessite with low crystallinity, whereas the mole ratio of KMnO4/glucose (3:1) yields high crystalline birnessite with minor components of hausmannite-type manganese oxide.The increasing of the temperature and calcinations times (300-700 °C and 3-7 h, respectively) willimprove the crystallinity and the purity of the as-synthesized oxide. Further experiments also showed that the as-syntesized octahedral layer birnessite-type manganese oxides have catalytic activity on the degradation of methylene blue (MB) dye with H2O2 as oxidant. The results revealed that the effective degradation could be achieved only in the presence of both the birnessite and H2O2, whereas without the addition of catalyst (H2O2only) or addition of H2O2 (catalyst only), the 3.5% and 15.5% of MB removal were obtained, respectively.

  15. Biomimetic synthesis of silver nanoparticles and evaluation of their catalytic activity towards degradation of methyl orange

    Science.gov (United States)

    Manjari Mishra, Pravat; Bihari Pani, Khirod

    2017-11-01

    This paper described the significant effect of process variables like reductant concentrations, substrate concentration, reaction pH and reaction temperature on the size, morphology and yield of the silver nanoparticles (AgNPs) synthesized using aqueous leaf extract of a medicinal plant Momordica charantia (Bitter guard). By means of UV-vis spectroscopy, XRD analysis, TEM analysis and Fluorescence analysis, it is observed that the reaction solution containing 10-3 M of AgNO3 of pH 5.3  +  10 ml of aqueous leaf extract at normal room temperature, was optimum for synthesis of stable, polydisperse, predominantly spherical AgNPs with average size of 12.15 nm. FT-IR and TEM studies confirmed the stability of AgNPs was due to the capping of phytoconstituents present in the leaf extract. The aqueous solution of leaf extract containing AgNPs showed remarkable catalytic activity towards degradation of methyl orange (MO) in aqueous medium.

  16. In Situ Synthesis of Catalytic Active Au Nanoparticles onto Gibbsite-Polydopamine Core-Shell Nanoplates.

    Science.gov (United States)

    Cao, Jie; Mei, Shilin; Jia, He; Ott, Andreas; Ballauff, Matthias; Lu, Yan

    2015-09-01

    We report a facile method to synthesize anisotropic platelike gibbsite-polymer core-shell particles. Dopamine is self-polymerized on the surface of gibbsite nanoplates and forms a homogeneous layer on it. Transmission electron microscopy characterization of the resulting latexes demonstrates the formation of well-defined platelike core-shell particles. Reaction time and ultrasonification are found to be important factors to control the thickness of the polymer shell and avoid aggregation. Good control over the platelike morphology and 100% encapsulation efficiency have been achieved via this novel route. The resulting well-defined gibbsite-polydamine (G-PDA) core-shell nanoplates show excellent colloidal stability and can form opal-like columnar crystal with iridescent Bragg reflection after modest centrifugation. In addition, G-PDA core-shell nanoplates can serve both as reductant and stabilizer for the generation of Au nanoparticles (NPs) in situ. Au NPs with tunable size have been formed on the G-PDA particle surface, which show efficient catalytic activity for the reduction of 4-nitrophenol and Rhodamine B (RhB) in the presence of borohydride. Such nanocatalysts can be easily deposited on silicon substrate by spin-coating due to the large contact area of platelike G-PDA particles and the strong adhesive behavior of the PDA layer. The substrate-deposited nanocatalyst can be easily recycled which show excellent reusability for the reduction of RhB.

  17. Green Adeptness in the Synthesis and Stabilization of Copper Nanoparticles: Catalytic, Antibacterial, Cytotoxicity, and Antioxidant Activities

    Science.gov (United States)

    Din, Muhammad Imran; Arshad, Farhan; Hussain, Zaib; Mukhtar, Maria

    2017-12-01

    Copper nanoparticles (CuNPs) are of great interest due to their extraordinary properties such as high surface-to-volume ratio, high yield strength, ductility, hardness, flexibility, and rigidity. CuNPs show catalytic, antibacterial, antioxidant, and antifungal activities along with cytotoxicity and anticancer properties in many different applications. Many physical and chemical methods have been used to synthesize nanoparticles including laser ablation, microwave-assisted process, sol-gel, co-precipitation, pulsed wire discharge, vacuum vapor deposition, high-energy irradiation, lithography, mechanical milling, photochemical reduction, electrochemistry, electrospray synthesis, hydrothermal reaction, microemulsion, and chemical reduction. Phytosynthesis of nanoparticles has been suggested as a valuable alternative to physical and chemical methods due to low cytotoxicity, economic prospects, environment-friendly, enhanced biocompatibility, and high antioxidant and antimicrobial activities. The review explains characterization techniques, their main role, limitations, and sensitivity used in the preparation of CuNPs. An overview of techniques used in the synthesis of CuNPs, synthesis procedure, reaction parameters which affect the properties of synthesized CuNPs, and a screening analysis which is used to identify phytochemicals in different plants is presented from the recent published literature which has been reviewed and summarized. Hypothetical mechanisms of reduction of the copper ion by quercetin, stabilization of copper nanoparticles by santin, antimicrobial activity, and reduction of 4-nitrophenol with diagrammatic illustrations are given. The main purpose of this review was to summarize the data of plants used for the synthesis of CuNPs and open a new pathway for researchers to investigate those plants which have not been used in the past.

  18. Role of the NC-loop in catalytic activity and stability in lipase from Fervidobacterium changbaicum.

    Directory of Open Access Journals (Sweden)

    Binchun Li

    Full Text Available Flexible NC-loops between the catalytic domain and the cap domain of the α/β hydrolase fold enzymes show remarkable diversity in length, sequence, and configuration. Recent investigations have suggested that the NC-loop might be involved in catalysis and substrate recognition in many enzymes from the α/β hydrolase fold superfamily. To foster a deep understanding of its role in catalysis, stability, and divergent evolution, we here systemically investigated the function of the NC-loop (residues 131-151 in a lipase (FClip1 from thermophilic bacterium Fervidobacterium changbaicum by loop deletion, alanine-scanning mutagenesis and site-directed mutagenesis. We found that the upper part of the NC-loop (residues 131-138 was of great importance to enzyme catalysis. Single substitutions in this region could fine-tune the activity of FClip1 as much as 41-fold, and any deletions from this region rendered the enzyme completely inactive. The lower part of the NC-loop (residues 139-151 was capable of enduring extensive deletions without loss of activity. The shortened mutants in this region were found to show both improved activity and increased stability simultaneously. We therefore speculated that the NC-loop, especially the lower part, would be a perfect target for enzyme engineering to optimize the enzymatic properties, and might present a hot zone for the divergent evolution of α/β hydrolases. Our findings may provide an opportunity for better understanding of the mechanism of divergent evolution in the α/β hydrolase fold superfamily, and may also guide the design of novel biocatalysts for industrial applications.

  19. Forecasting the zeolite-containing catalyst activity in catalytic cracking technology taking into account the feedstock composition

    Science.gov (United States)

    Ivashkina, Elena; Nazarova, Galina; Shafran, Tatyana; Stebeneva, Valeriya

    2017-08-01

    The effect of the feedstock composition and the process conditions on the current catalyst activity in catalytic cracking technology using a mathematical model is performed in this research. The mathematical model takes into account the catalyst deactivation by coke for primary and secondary cracking reactions. The investigation results have shown that the feedstock has significant effect on the yield and the content of coke on the catalyst. Thus, the relative catalyst activity is significantly reduced by 7.5-10.7 %. With increasing the catalytic cracking temperature due to the catalyst flow temperature rising, the coke content and the yield per feedstock increase and the catalyst activity decreases by 5.3-7.7%. Rising the process temperature together with the catalyst circulation ratio contributes to increase of the coke yield per feedstock in the catalytic cracking and decrease of the coke content on the catalyst. It is connected with the catalyst flow rising to the riser and the contact time decreasing in the reaction zone. Also, the catalyst activity decreases in the range of 3.8-5.5% relatively to the regenerated catalyst activity (83 %).

  20. Structure of a novel class II phospholipase D: catalytic cleft is modified by a disulphide bridge.

    Science.gov (United States)

    de Giuseppe, Priscila Oliveira; Ullah, Anwar; Silva, Dilza Trevisan; Gremski, Luiza Helena; Wille, Ana Carolina Martins; Chaves Moreira, Daniele; Ribeiro, Andrea Senff; Chaim, Olga Meiri; Murakami, Mario Tyago; Veiga, Silvio Sanches; Arni, Raghuvir Krishnaswamy

    2011-06-17

    Phospholipases D (PLDs) are principally responsible for the local and systemic effects of Loxosceles envenomation including dermonecrosis and hemolysis. Despite their clinical relevance in loxoscelism, to date, only the SMase I from Loxosceles laeta, a class I member, has been structurally characterized. The crystal structure of a class II member from Loxosceles intermedia venom has been determined at 1.7Å resolution. Structural comparison to the class I member showed that the presence of an additional disulphide bridge which links the catalytic loop to the flexible loop significantly changes the volume and shape of the catalytic cleft. An examination of the crystal structures of PLD homologues in the presence of low molecular weight compounds at their active sites suggests the existence of a ligand-dependent rotamer conformation of the highly conserved residue Trp230 (equivalent to Trp192 in the glycerophosphodiester phosphodiesterase from Thermus thermophofilus, PDB code: 1VD6) indicating its role in substrate binding in both enzymes. Sequence and structural analyses suggest that the reduced sphingomyelinase activity observed in some class IIb PLDs is probably due to point mutations which lead to a different substrate preference. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. Nicotinamide adenine dinucleotide assisted shape-controlled synthesis of catalytically active raspberry-like gold nanostructures

    International Nuclear Information System (INIS)

    Das, Ashok Kumar; Layek, Rama K.; Kim, Nam Hoon; Samdani, Jitendra; Kang, Myung Chul; Lee, Joong Hee

    2015-01-01

    Graphical abstract: A facile method was developed for the synthesis of raspberry-like Au nanostructure and it was used as an electrocatalyst for the oxidation of methanol and reduction of oxygen. - Highlights: • Raspberry-like gold nanostructures have been synthesized. • Nicotinamide adenine dinucleotide plays an important role in the synthesis. • Raspberry-like Au nanostructure has an excellent electrocatalytic activity in methanol oxidation and oxygen reduction. - Abstract: We describe the shape-controlled growth of raspberry-like gold (Au) nanostructures and their application in the electrochemical oxidation of methanol and reduction of oxygen. Nicotinamide adenine dinucleotide (NAD + ) plays a vital role in the growth of raspberry-like Au nanostructures. The preferential adsorption of NAD + onto the (011) facets of Au favors the growth of raspberry-like morphology. In the absence of NAD + , icosahedral Au nanostructures were obtained. The raspberry-like Au nanostructures have been characterized by UV-visible spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and electrochemical measurements. The FESEM image shows that the raspberry-like morphology has an average size of 170 nm. The spectral profile shows a broad band between 650 and 795 nm. Compared to Au nanoseeds and icosahedral Au nanostructures that were grown in the absence of NAD + , the raspberry-like morphology has excellent catalytic activity towards the electrochemical oxidation of methanol and reduction of oxygen. On the raspberry-like nanoparticle-based electrode, the oxidation of methanol was observed at 0.35 V in alkaline pH, and the reduction of oxygen was observed at -0.06 and -0.4 V in 0.1 M PBS. The electrochemical reduction of oxygen occurs in two steps: (i) reduction of oxygen to H 2 O 2 and (ii) further reduction of electrogenerated H 2 O 2 to water. The electrochemical performance of the raspberry-like nanostructure-based electrode is highly

  2. Catalytic activity, duplication and evolution of the CYP98 cytochrome P450 family in wheat.

    Science.gov (United States)

    Morant, Marc; Schoch, Guillaume A; Ullmann, Pascaline; Ertunç, Tanya; Little, Dawn; Olsen, Carl Erik; Petersen, Maike; Negrel, Jonathan; Werck-Reichhart, Danièle

    2007-01-01

    A burst of evolutionary duplication upon land colonization seems to have led to the large superfamily of cytochromes P450 in higher plants. Within this superfamily some clans and families are heavily duplicated. Others, such as genes involved in the phenylpropanoid pathway have led to fewer duplication events. Eight coding sequences belonging to the CYP98 family reported to catalyze the 3-hydroxylation step in this pathway were isolated from Triticum aestivum (wheat) and expressed in yeast. Comparison of the catalytic properties of the recombinant enzymes with those of CYP98s from other plant taxa was coupled to phylogenetic analyses. Our results indicate that the unusually high frequency of gene duplication in the wheat CYP98 family is a direct or indirect result from ploidization. While ancient duplication led to evolution of enzymes with different substrate preferences, most of recent duplicates underwent silencing via degenerative mutations. Three of the eight tested CYP98s from wheat have phenol meta-hydroxylase activity, with p-coumaroylshikimate being the primary substrate for all of these, as it is the case for CYP98s from sweet basil and Arabidopsis thaliana. However, CYP98s from divergent taxa have acquired different additional subsidiary activities. Some of them might be significant in the metabolism of various free or conjugated phenolics in different plant species. One of the most significant is meta-hydroxylation of p-coumaroyltyramine, predominantly by the wheat enzymes, for the synthesis of suberin phenolic monomers. Homology modeling, confirmed by directed mutagenesis, provides information on the protein regions and structural features important for some observed changes in substrate selectivity. They indicate that the metabolism of quinate ester and tyramine amide of p-coumaric acid rely on the same recognition site in the protein.

  3. Catalytically-etched hexagonal boron nitride flakes and their surface activity

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Do-Hyun, E-mail: nanotube@korea.ac.kr [School of Electrical Engineering, Korea University, 5-ga, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of); Lee, Minwoo; Ye, Bora [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of); Jang, Ho-Kyun; Kim, Gyu Tae [School of Electrical Engineering, Korea University, 5-ga, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of); Lee, Dong-Jin [New Functional Components Research Team, Korea Institute of Footware & Leather Technology, 152 Danggamseo-ro, Busanjin-gu, Busan 614-100 (Korea, Republic of); Kim, Eok-Soo [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of); Kim, Hong Dae, E-mail: hdkim@kitech.re.kr [Green Manufacturing 3Rs R& D Group, Korea Institute of Industrial Technology, Ulsan 681-310 (Korea, Republic of)

    2017-04-30

    Highlights: • Hexagonal boron nitride flakes are etched at low temperature in air by catalysts. • The presence of transition metal oxides produces an etched structure in the flakes. • Etched surfaces become highly active due to vacancy defects formed in the flakes. - Abstract: Hexagonal boron nitride (h-BN) is a ceramic compound which is thermally stable up to 1000 °C in air. Due to this, it is a very challenging task to etch h-BN under air atmosphere at low temperature. In this study, we report that h-BN flakes can be easily etched by oxidation at 350 °C under air atmosphere in the presence of transition metal (TM) oxide. After selecting Co, Cu, and Zn elements as TM precursors, we simply oxidized h-BN sheets impregnated with the TM precursors at 350 °C in air. As a result, microscopic analysis revealed that an etched structure was created on the surface of h-BN flakes regardless of catalyst type. And, X-ray diffraction patterns indicated that the air oxidation led to the formation of Co{sub 3}O{sub 4}, CuO, and ZnO from each precursor. Thermogravimetric analysis showed a gradual weight loss in the temperature range where the weight of h-BN flakes increased by air oxidation. As a result of etching, pore volume and pore area of h-BN flakes were increased after catalytic oxidation in all cases. In addition, the surface of h-BN flakes became highly active when the h-BN samples were etched by Co{sub 3}O{sub 4} and CuO catalysts. Based on these results, we report that h-BN flakes can be easily oxidized in the presence of a catalyst, resulting in an etched structure in the layered structure.

  4. Catalytic properties of inositol trisphosphate kinase: activation by Ca2+ and calmodulin

    International Nuclear Information System (INIS)

    Ryu, S.H.; Lee, S.Y.; Lee, K.Y.; Rhee, S.G.

    1987-01-01

    Inositol 1,4,5-triphosphate (Ins-1,4,5-P 3 ) is an important second-messenger molecule that mobilizes Ca 2+ from intracellular stores in response to the occupancy of receptor by various Ca 2+ -mobilizing agonists. The fate of Ins-1,4,5-P 3 is determined by two enzymes, a 3-kinase and a 5-phosphomonoesterase. The first enzyme converts Ins-1,4,5-P 3 to Ins-1,3,4,5-P 4 , whereas the latter forms Ins-1,4-P 2 . Recent studies suggest that Ins-1,3,4,5-P 4 might modulate the entry of Ca 2+ from an extracellular source. In the current report, the authors describe the partial purification of the 3-kinase from the cytosolic fraction of bovine brain and studies of its catalytic properties. They found that the 3-kinase activity is significantly activated by the Ca 2+ /calmodulin complex. Therefore, they propose that Ca 2+ mobilized from endoplasmic reticulum by the action of Ins-1,4,5-P 3 forms a complex with calmodulin, and that the Ca 2+ /calmodulin complex stimulates the conversion of Ins-1,4,5-P 3 , and intracellular Ca 2+ mobilizer, to Ins-1,3,4,5-P 4 , an extracellular Ca 2+ mobilizer. A rapid assay method for the 3-kinase was developed that is based on the separation of [3- 32 P]Ins-1,3,4,5-P 4 and [γ- 32 P]ATP by thin-layer chromatography. Using this new assay method, they evaluated kinetic parameters (K/sub m/ for ATP = 40 μM, K/sub m/ for Ins-1,4,5-P 3 = 0.7 μM, K/sub i/ for ADP = 12 μM) and divalent cation specificity (Mg 2+ > > Mn 2+ > Ca 2+ ) for the 3-kinase

  5. Conformational dynamics of free and catalytically active thermolysin are indistinguishable by hydrogen/deuterium exchange mass spectrometry.

    Science.gov (United States)

    Liu, Yu-Hong; Konermann, Lars

    2008-06-17

    Conformational dynamics are thought to be a prerequisite for the catalytic activity of enzymes. However, the exact relationship between structural fluctuations and function is not well understood. In this work hydrogen/deuterium exchange (HDX) and electrospray ionization mass spectrometry (ESI-MS) are used for exploring the conformational dynamics of thermolysin. Amide HDX reflects the internal mobility of proteins; regions that undergo frequent unfolding-refolding show faster exchange than segments that are highly stable. Thermolysin is a zinc protease with an active site that is located between two lobes. Substrate turnover is associated with hinge bending that leads to a closed conformation. Product release regenerates the open form, such that steady-state catalysis involves a continuous closing/opening cycle. HDX/ESI-MS with proteolytic peptide mapping in the absence of substrate shows that elements in the periphery of the two lobes are most mobile. A comparison with previous X-ray data suggests that these peripheral regions undergo quite pronounced structural changes during the catalytic cycle. In contrast, active site residues exhibit only a moderate degree of backbone flexibility, and the central zinc appears to be in a fairly rigid environment. The presence of both rigid and moderately flexible elements in the active site may reflect a carefully tuned balance that is required for function. Interestingly, the HDX behavior of catalytically active thermolysin is indistinguishable from that of the free enzyme. This result is consistent with the view that catalytically relevant motions preexist in the resting state and that enzyme function can only be performed within the limitations given by the intrinsic dynamics of the protein. The data presented in this work indicate the prevalence of stochastic elements in the function of thermolysin, rather than supporting a deterministic mechanism.

  6. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  7. Enhancement in the Catalytic Activity of Pd/USY in the Heck Reaction Induced by H2 Bubbling

    Directory of Open Access Journals (Sweden)

    Miki Niwa

    2010-12-01

    Full Text Available Pd was loaded on ultra stable Y (USY zeolites prepared by steaming NH4-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h−1, which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OHstrong generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  8. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    Science.gov (United States)

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. Optimisation of the antifungal potency of the amidated peptide H-Orn-Orn-Trp-Trp-NH2 against food contaminants.

    Science.gov (United States)

    Thery, Thibaut; O'Callaghan, Yvonne; O'Brien, Nora; Arendt, Elke K

    2018-01-16

    The design of novel efficient antimicrobial peptides (AMPs) faces several issues, such as cost of synthesis, proteolytic stability or cytotoxicity. The identification of key determinants involved in the activity of AMPs, such as cationicity and amphipathicity, allowed the synthesis of short peptides with optimized properties. An ultrashort peptide made of the sequence H-Orn-Orn-Trp-Trp-NH2 (O3TR) showed antifungal activity against several contaminants from food products. This peptide inhibited the growth of the filamentous fungi Fusarium culmorum, Penicillium expansum and Aspergillus niger within a range of concentration of 12.5-50μg/ml. In addition, O3TR inhibited the growth of the yeast Saccharomyces cerevisiae, Zygosaccharomyces bailii, Zygosaccharomyces rouxii, Debaryomyces hansenii and Kluyveromyces lactis within the range 12.5-50μg/ml. A derivative peptide, called C12O3TR, made by the addition of lauric acid at the N-terminus of O3TR was 2- to 8-fold more active than O3TR against every species. In addition to the inhibition of conidial germination, O3TR and C12O3TR killed F. culmorum hyphae at 100 and 50μg/ml respectively. The MIC of the two peptides against F. culmorum and Z. bailii after heat treatment at 100°C for 60 min and within the pH range 3-10, were not changed. However, the activity of O3TR against F.culmorum and Z. bailii was strongly reduced in salt solutions, whereas the lauric acid peptide kept its antifungal activity and resistance to proteolytic digestion. The conjugation with lauric acid reduced the random coiled structure and increased the α-helical content of O3TR. After conjugation with the dye tetramethylrhodamine (TMR), both peptides entered F. culmorum spores. They also both induced permeabilization of F. culmorum hyphae but only C12O3TR permeabilized Z. bailii membrane. In contrast to the lipopeptide, O3TR did not show haemolytic or cytotoxic activity when applied at the concentrations that exhibited antifungal potency. The two

  11. Transit safety retrofit package development : TRP concept of operations.

    Science.gov (United States)

    2014-05-01

    This document describes the Concept of Operations (ConOps) for the Transit Safety Retrofit Package (TRP). The : ConOps describes the current state of operations with respect to the integration of Connected Vehicle technology in : transit buses, estab...

  12. The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

    Science.gov (United States)

    Fortea-Pérez, Francisco R.; Mon, Marta; Ferrando-Soria, Jesús; Boronat, Mercedes; Leyva-Pérez, Antonio; Corma, Avelino; Herrera, Juan Manuel; Osadchii, Dmitrii; Gascon, Jorge; Armentano, Donatella; Pardo, Emilio

    2017-07-01

    The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes.

  13. Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

    Science.gov (United States)

    Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

    2018-03-01

    Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

  14. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    OpenAIRE

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. Thi...

  15. Mononuclear Nickel(II Complexes with Schiff Base Ligands: Synthesis, Characterization, and Catalytic Activity in Norbornene Polymerization

    Directory of Open Access Journals (Sweden)

    Yi-Mei Xu

    2017-03-01

    Full Text Available The nickel(II catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and the steric hindrance influence polymerization. The molecular structures of 2, 4 and 5 were further confirmed by single-crystal X-ray diffraction.

  16. Light Chain of Botulinum A Neurotoxin Expressed as an Inclusion Body from a Synthetic Gene is Catalytically and Functionally Active

    Science.gov (United States)

    2000-01-01

    catalytically and biologically active, stable, gram quantities of the purified LC of a BoNT. Like a new class of zinc-endopeptidases (Monte- cucco and Schiavo...Monte- cucco , C. (1997). FEBSLett. 418, 1-5. Winkler, H. H. and Wood, D. O. (1988). Biochimie 70, 977-986. Zhou, L., de Paiva, A., Liu, D., Aoki, R., and Dolly, J. O. (1995). Bio- chemistry 34, 15175-15181.

  17. Improved surface-enhanced Raman and catalytic activities of reduced graphene oxide–osmium hybrid nano thin films

    OpenAIRE

    Kavitha, C.; Bramhaiah, K.; John, Neena S.; Aggarwal, Shantanu

    2017-01-01

    Reduced graphene oxide–osmium (rGO-Os) hybrid nano dendtrites have been prepared by simple liquid/liquid interface method for the first time. The method involves the introduction of phase-transfered metal organic precursor in toluene phase and GO dispersion in the aqueous phase along with hydrazine hydrate as the reducing agent. Dendritic networks of Os nanoparticles and their aggregates decorating rGO layers are obtained. The substrate shows improved catalytic and surface-enhanced activities...

  18. Improved surface-enhanced Raman and catalytic activities of reduced graphene oxide-osmium hybrid nano thin films

    Science.gov (United States)

    Kavitha, C.; Bramhaiah, K.; John, Neena S.; Aggarwal, Shantanu

    2017-09-01

    Reduced graphene oxide-osmium (rGO-Os) hybrid nano dendtrites have been prepared by simple liquid/liquid interface method for the first time. The method involves the introduction of phase-transfered metal organic precursor in toluene phase and GO dispersion in the aqueous phase along with hydrazine hydrate as the reducing agent. Dendritic networks of Os nanoparticles and their aggregates decorating rGO layers are obtained. The substrate shows improved catalytic and surface-enhanced activities comparable with previous reports. The catalytic activity was tested for the reduction of p-nitroaniline into p-phenyldiamine with an excess amount of NaBH4. The catalytic activity factors of these hybrid films are 2.3 s-1 g-1 (Os film) and 4.4 s-1 g-1 (rGO-Os hybrid film), which are comparable with other noble metal nanoparticles such as Au, Ag, but lower than Pd-based catalysts. Surface-enhanced Raman spectroscopy (SERS) measurements have been done on rhodamine 6G (R6G) and methylene blue dyes. The enhancement factor for the R6G adsorbed on rGO-Os thin film is 1.0 × 105 and for Os thin film is 7 × 103. There is a 14-fold enhancement observed for Os hybrids with rGO. The enhanced catalytic and SERS activities of rGO-Os hybrid thin film prepared by simple liquid/liquid interface method open up new challenges in electrocatalytic application and SERS-based detection of biomolecules.

  19. Novel Co(II) phthalocyanines of extended periphery and their water-soluble derivatives. Synthesis, spectral properties and catalytic activity

    Science.gov (United States)

    Filippova, Anna; Vashurin, Artur; Znoyko, Serafima; Kuzmin, Ilya; Razumov, Mikhail; Chernova, Alena; Shaposhnikov, Gennady; Koifman, Oscar

    2017-12-01

    Novel complexes of cobalt and copper with substituted phthalocyanines were synthesized and characterized. Their water-soluble derivatives were obtained by sulfonation under mild conditions and structurally proved. Aggregation equilibrium in water mediums was shown and influence of geometrical and electron parameters of macroheterocycle peripheral substituents on these processes was established. Catalytic activity upon liquid-phase oxidation of N,N-diethylcarbamodithiolate to thiuram E was studied. Kinetic parameters of substrate oxidation in presence of cobalt phthalocyanines were considered.

  20. Cell foundry with high product specificity and catalytic activity for 21-deoxycortisol biotransformation.

    Science.gov (United States)

    Xiong, Shuting; Wang, Ying; Yao, Mingdong; Liu, Hong; Zhou, Xiao; Xiao, Wenhai; Yuan, Yingjin

    2017-06-13

    21-deoxycortisol (21-DF) is the key intermediate to manufacture pharmaceutical glucocorticoids. Recently, a Japan patent has realized 21-DF production via biotransformation of 17-hydroxyprogesterone (17-OHP) by purified steroid 11β-hydroxylase CYP11B1. Due to the less costs on enzyme isolation, purification and stabilization as well as cofactors supply, whole-cell should be preferentially employed as the biocatalyst over purified enzymes. No reports as so far have demonstrated a whole-cell system to produce 21-DF. Therefore, this study aimed to establish a whole-cell biocatalyst to achieve 21-DF transformation with high catalytic activity and product specificity. In this study, Escherichia coli MG1655(DE3), which exhibited the highest substrate transportation rate among other tested chassises, was employed as the host cell to construct our biocatalyst by co-expressing heterologous CYP11B1 together with bovine adrenodoxin and adrenodoxin reductase. Through screening CYP11B1s (with mutagenesis at N-terminus) from nine sources, Homo sapiens CYP11B1 mutant (G25R/G46R/L52 M) achieved the highest 21-DF transformation rate at 10.6 mg/L/h. Furthermore, an optimal substrate concentration of 2.4 g/L and a corresponding transformation rate of 16.2 mg/L/h were obtained by screening substrate concentrations. To be noted, based on structural analysis of the enzyme-substrate complex, two types of site-directed mutations were designed to adjust the relative position between the catalytic active site heme and the substrate. Accordingly, 1.96-fold enhancement on 21-DF transformation rate (to 47.9 mg/L/h) and 2.78-fold improvement on product/by-product ratio (from 0.36 to 1.36) were achieved by the combined mutagenesis of F381A/L382S/I488L. Eventually, after 38-h biotransformation in shake-flask, the production of 21-DF reached to 1.42 g/L with a yield of 52.7%, which is the highest 21-DF production as known. Heterologous CYP11B1 was manipulated to construct E. coli

  1. The effect of catalyst preparation on catalytic activity. Final report, December 1, 1988--June 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, J.A.

    1992-12-01

    Three intrinsically connected phenomena occur during adsorption/impregnation of aqueous electrolytes onto oxide carriers. They are: pH-dependent development of surface carriers on the oxide; pH-dependent aqueous speciation of catalytic precursors; surface adsorption by complexation and coordination. Modeling of these processes yields basic thermodynamic properties of the adsorbed phase, which could provide useful information of the catalytic properties of the metal, support, and reveal metal-support interactions, thus contributing to design criteria for supported-metal catalysts. The spectrum of catalytic systems that can be studied using the above approach is greatly extended when both pure and composite oxide carriers are considered. This presentation will focus on three metal/support systems, each of which provides results of both practical and fundamental importance.

  2. Spatial decoupling of light absorption and catalytic activity of Ni-Mo-loaded high-aspect-ratio silicon microwire photocathodes

    Science.gov (United States)

    Vijselaar, Wouter; Westerik, Pieter; Veerbeek, Janneke; Tiggelaar, Roald M.; Berenschot, Erwin; Tas, Niels R.; Gardeniers, Han; Huskens, Jurriaan

    2018-01-01

    A solar-driven photoelectrochemical cell provides a promising approach to enable the large-scale conversion and storage of solar energy, but requires the use of Earth-abundant materials. Earth-abundant catalysts for the hydrogen evolution reaction, for example nickel-molybdenum (Ni-Mo), are generally opaque and require high mass loading to obtain high catalytic activity, which in turn leads to parasitic light absorption for the underlying photoabsorber (for example silicon), thus limiting production of hydrogen. Here, we show the fabrication of a highly efficient photocathode by spatially and functionally decoupling light absorption and catalytic activity. Varying the fraction of catalyst coverage over the microwires, and the pitch between the microwires, makes it possible to deconvolute the contributions of catalytic activity and light absorption to the overall device performance. This approach provided a silicon microwire photocathode that exhibited a near-ideal short-circuit photocurrent density of 35.5 mA cm-2, a photovoltage of 495 mV and a fill factor of 62% under AM 1.5G illumination, resulting in an ideal regenerative cell efficiency of 10.8%.

  3. Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [Key Laboratory of Integrated Exploitation of Bayan Obo Multi-Metal Resources, Inner Mongolia University of Science and Technology, Baotou 014010 (China); The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China); Deng, Xiangong; Jiao, Chengpeng; Lu, Lilin; Zhang, Shaowei [The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China)

    2016-07-15

    Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.

  4. Theoretical explanation for the enhanced water-splitting catalytic activity in delithiated LiCoO2

    Science.gov (United States)

    Bajdich, Michal; Lu, Zhiyi; Norskov, Jens K.; Cui, Yi

    Layered LiCoO2 (LCO) is important battery material not well know for its electrochemical catalytic activity. On the other hand, layered 3 d -metal-oxyhydroxides, including CoOOH, are very active water-splitting (oxygen-evolution reaction, OER) catalysts in alkaline media with structure very similar to LCO. In this work, we use DFT+U calculations to explain the enhancement effect in OER catalytic activity in the electrochemically delithiated LCO (De-LCO). We analyze the surface stability and OER activity of the 5 most stable surface facets of LCO and the De-LCO, with 50% Li removed. Using standard thermodynamic approach of the theoretical OER overpotential, we show that all surface facets have more active sites under Li removal. Particularly, the non-polar facets are identified to be highly active and are further activated by the delithiation process, while the dominant (0001) surface has negligible activity. These findings are in very good agreement with our experimental investigation of LCO and De-LCO nanosheets and nanoparticles with well defined surface morphology.

  5. Ultrasonic Preparation of Nitrogen-doped TiO2 Nan crystalline Photo catalysts and Evaluation of Photo catalytic Activity

    Science.gov (United States)

    Zhang, Huifang; Lu, Zixin; Tang, Mengyao; Cao, Wenping; Cai, Kangni; Liu, Hanhu

    2017-12-01

    Pure TiO2 and N-doped nano-TiO2 photo catalysts were individually prepared following the sol-gel method under ultrasonic conditions. The photo catalytic decomposition of methyl orange (MO) solution under ultraviolet and visible light irradiation was used as a probe reaction to estimate their photo catalytic activities. The particle size, crystal structure, and optical properties of the prepared TiO2 were performed by X-ray diffraction, transmission electron microscopy and UV-vis diffuse reflectance spectroscopy. The results suggest that ultrasound significantly reduced the size of the TiO2 particles, improved particle dispersion, which in turn improve the photo catalytic activity of TiO2 under ultraviolet light. Ultrasound also promoted the doping of non-metal nitrogen and markedly enhanced the visible light absorption capacity of the N-doped nano-TiO2. Compared with pure TiO2, the degradation rate for MO under visible light of U-N-TiO2 was increased by 70%.

  6. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    Science.gov (United States)

    Lu, Shixiang; Yu, Jianying; Cheng, Yuanyuan; Wang, Qian; Barras, Alexandre; Xu, Wenguo; Szunerits, Sabine; Cornu, David; Boukherroub, Rabah

    2017-07-01

    The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH4) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  7. Activation of Al–Cu–Fe quasicrystalline surface: fabrication of a fine nanocomposite layer with high catalytic performance

    Directory of Open Access Journals (Sweden)

    Satoshi Kameoka

    2014-01-01

    Full Text Available A fine layered nanocomposite with a total thickness of about 200 nm was formed on the surface of an Al63Cu25Fe12 quasicrystal (QC. The nanocomposite was found to exhibit high catalytic performance for steam reforming of methanol. The nanocomposite was formed by a self-assembly process, by leaching the Al–Cu–Fe QC using a 5 wt% Na2CO3 aqueous solution followed by calcination in air at 873 K. The quasiperiodic nature of the QC played an important role in the formation of such a structure. Its high catalytic activity originated from the presence of highly dispersed copper and iron species, which also suppressed the sintering of nanoparticles.

  8. Sulfur-Functionalized N-Heterocyclic Carbene Complexes of Pd(II: Syntheses, Structures and Catalytic Activities

    Directory of Open Access Journals (Sweden)

    Dan Yuan

    2012-03-01

    Full Text Available N-heterocyclic carbenes (NHCs can be easily modified by introducing functional groups at the nitrogen atoms, which leads to versatile coordination chemistry as well as diverse catalytic applications of the resulting complexes. This article summarizes our contributions to the field of NHCs bearing different types of sulfur functions, i.e., thioether, sulfoxide, thiophene, and thiolato. The experimental evidence for the truly hemilabile coordination behavior of a Pd(II thioether-NHC complex has been reported as well. In addition, complexes bearing rigid CSC-pincer ligands have been synthesized and the reasons for pincer versus pseudo-pincer formation investigated. Incorporation of the electron-rich thiolato function resulted in the isolation of structurally diverse complexes. The catalytic activities of selected complexes have been tested in Suzuki-Miyaura, Mizoroki-Heck and hydroamination reactions.

  9. Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride)

    Energy Technology Data Exchange (ETDEWEB)

    You, Jyun-Guo; Shanmugam, Chandirasekar [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); Liu, Yao-Wen; Yu, Cheng-Ju [Department of Applied Physics and Chemistry, University of Taipei, Taiwan (China); Tseng, Wei-Lung, E-mail: tsengwl@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Taiwan (China)

    2017-02-15

    Highlights: • The choice of capping ligand determines catalytic activity of metal nanocatalysts. • PDDA-capped metal nanoparticles electrostatically interact with 4-NP and BH4{sup −}. • PDDA-capped metal nanoparticles have good recyclability and large scalability. • PDDA-capped Pd nanoparticles show the highest rate constant and activity parameter. - Abstract: Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195 s{sup −1} g{sup −1}) and provided excellent scalability and reusability.

  10. Energy Efficient Catalytic Activation of Hydrogen peroxide for Green Chemical Processes: Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Collins, Terrence J.; Horwitz, Colin

    2004-11-12

    A new, highly energy efficient approach for using catalytic oxidation chemistry in multiple fields of technology has been pursued. The new catalysts, called TAML® activators, catalyze the reactions of hydrogen peroxide and other oxidants for the exceptionally rapid decontamination of noninfectious simulants (B. atrophaeus) of anthrax spores, for the energy efficient decontamination of thiophosphate pesticides, for the facile, low temperature removal of color and organochlorines from pulp and paper mill effluent, for the bleaching of dyes from textile mill effluents, and for the removal of recalcitrant dibenzothiophene compounds from diesel and gasoline fuels. Highlights include the following: 1) A 7-log kill of Bacillus atrophaeus spores has been achieved unambiguously in water under ambient conditions within 15 minutes. 2) The rapid total degradation under ambient conditions of four thiophosphate pesticides and phosphonate degradation intermediates has been achieved on treatment with TAML/peroxide, opening up potential applications of the decontamination system for phosphonate structured chemical warfare agents, for inexpensive, easy to perform degradation of stored and aged pesticide stocks (especially in Africa and Asia), for remediation of polluted sites and water bodies, and for the destruction of chemical warfare agent stockpiles. 3) A mill trial conducted in a Pennsylvanian bleached kraft pulp mill has established that TAML catalyst injected into an alkaline peroxide bleach tower can significantly lower color from the effluent stream promising a new, more cost effective, energy-saving approach for color remediation adding further evidence of the value and diverse engineering capacity of the approach to other field trials conducted on effluent streams as they exit the bleach plant. 4) Dibenzothiophenes (DBTs), including 4,6-dimethyldibenzothiophene, the most recalcitrant sulfur compounds in diesel and gasoline, can be completely removed from model gasoline

  11. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions

    KAUST Repository

    Feng, Zhenxing

    2016-05-05

    δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1–ySry)2CoO4±δ/La1–xSrxCo0.2Fe0.8O3−δ. Sr enrichment in many electrocatalysts, such as La1–xSrxMO3−δ (M = Cr, Co, Mn, or Co and Fe) and Sm1–xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst’s activity while maintaining stability to design efficient, cost-effective electrocatalysts.

  12. Activation loop dynamics determine the different catalytic efficiencies of B cell- and T cell-specific tec kinases.

    Science.gov (United States)

    Joseph, Raji E; Kleino, Iivari; Wales, Thomas E; Xie, Qian; Fulton, D Bruce; Engen, John R; Berg, Leslie J; Andreotti, Amy H

    2013-08-27

    Itk (interleukin-2-inducible T cell kinase) and Btk (Bruton's tyrosine kinase) are nonreceptor tyrosine kinases of the Tec family that signal downstream of the T cell receptor (TCR) and B cell receptor (BCR), respectively. Despite their high sequence similarity and related signaling roles, Btk is a substantially more active kinase than Itk. We showed that substitution of 6 of the 619 amino acid residues of Itk with the corresponding residues of Btk (and vice versa) was sufficient to completely switch the activities of Itk and Btk. The substitutions responsible for the swap in activity are all localized to the activation segment of the kinase domain. Nuclear magnetic resonance and hydrogen-deuterium exchange mass spectrometry analyses revealed that Itk and Btk had distinct protein dynamics in this region, which could explain the differences in catalytic efficiency between these kinases. Introducing Itk with enhanced activity into T cells led to enhanced and prolonged TCR signaling compared to that in cells with wild-type Itk. These findings imply that evolutionary pressures have led to Tec kinases having distinct enzymatic properties, depending on the cellular context. We suggest that the weaker catalytic activities of T cell-specific kinases serve to regulate cellular activation and prevent aberrant immune responses.

  13. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    Science.gov (United States)

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity. PMID:23539324

  14. Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Nørskov, Jens Kehlet

    2010-01-01

    Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced...... and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbate-adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small...... influence on the position of the top of the volcano, that is, on which metal is the best catalyst....

  15. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    Science.gov (United States)

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1). 2010 Elsevier B.V. All rights reserved.

  16. New potential nonsteroidal anti-inflammatory drugs with antileukotrienic effects: influence on model proteins with catalytic activity.

    Science.gov (United States)

    Netopilová, Miloslava; Drsata, Jaroslav; Beránek, Martin; Palicka, Vladimír

    2002-01-01

    Unspecific and side effects caused by interaction with proteins belong to common problems of many structures synthesized as potential medicaments. Possible in vitro interactions with proteins of a group of phenylsulfonyl benzoic acid derivatives (VUFB 19363, 19369, 19370, 19371, and 19760) as new potential anti-inflammatory compounds with anti-leukotrienic activities were studied in the present work. Three purified enzymes were used as model proteins with catalytic activities: Pig heart aspartate aminotransferase (AST, EC 2.6.1.1), alanine aminotransferase (ALT, EC 2.6.1.2), and glutamate decarboxylase (GAD, EC 4.1.1.15) from E. coli. Catalytic activities during incubation of individual compounds (6 x 10(-5) M solution to 5 x 10(-2) M suspension) at 37 degrees C with enzymes served as criteria of stability and function of the proteins. No immediate influence of any compound studied on enzyme activities was found. Aminotransferase activities were not affected even during incubation up to 20 d. In the case of GAD, the compounds VUFB 19369, 19370, 19371, and 19760 had stabilizing influence on GAD activity during incubation at enzyme concentrations of 11.25 and 5.62 mg prot/l. The lack of an immediate effect of compounds and the stability of enzymes during incubation them are favorable and support the prospective of the compounds as potential drugs.

  17. Catalytic activity of hydrophobic Pt/C/PTFE catalysts of different PTFE content for hydrogen-water liquid exchange reaction

    International Nuclear Information System (INIS)

    Hu Sheng; Xiao Chengjian; Zhu Zuliang; Luo Shunzhong; Wang Heyi; Luo Yangming; Wang Changbin

    2007-01-01

    10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their activity decreases when the mass ratio is 1:1. (authors)

  18. Synthesis, characterization and catalytic activity of indium substituted nanocrystalline Mobil Five (MFI) zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Kishor Kr. [Department of Chemistry, ADP College, Nagaon, Assam 782002 (India); Nandi, Mithun [Department of Chemistry, Gauhati University, Guwahati, Assam 781014 (India); Talukdar, Anup K., E-mail: anup_t@sify.com [Department of Chemistry, Gauhati University, Guwahati, Assam 781014 (India)

    2015-06-15

    Highlights: • In situ modification of the MFI zeolite by incorporation of indium. • The samples were characterized by XRD, FTIR, TGA, UV–vis (DRS), SAA, EDX and SEM. • The incorporation of indium was confirmed by XRD, FT-IR, UV–vis (DRS), EDX and TGA. • Hydroxylation of phenol reaction was studied on the synthesized catalysts. - Abstract: A series of indium doped Mobil Five (MFI) zeolite were synthesized hydrothermally with silicon to aluminium and indium molar ratio of 100 and with aluminium to indium molar ratios of 1:1, 2:1 and 3:1. The MFI zeolite phase was identified by XRD and FT-IR analysis. In XRD analysis the prominent peaks were observed at 2θ values of around 6.5° and 23° with a few additional shoulder peaks in case of all the indium incorporated samples suggesting formation of pure phase of the MFI zeolite. All the samples under the present investigation were found to exhibit high crystallinity (∼92%). The crystallite sizes of the samples were found to vary from about 49 to 55 nm. IR results confirmed the formation of MFI zeolite in all cases showing distinct absorbance bands near 1080, 790, 540, 450 and 990 cm{sup −1}. TG analysis of In-MFI zeolites showed mass losses in three different steps which are attributed to the loss due to adsorbed water molecules and the two types TPA{sup +} cations. Further, the UV–vis (DRS) studies reflected the position of the indium metal in the zeolite framework. Surface area analysis of the synthesized samples was carried out to characterize the synthesized samples The analysis showed that the specific surface area ranged from ∼357 to ∼361 m{sup 2} g{sup −1} and the pore volume of the synthesized samples ranged from 0.177 to 0.182 cm{sup 3} g{sup −1}. The scanning electron microscopy studies showed the structure of the samples to be rectangular and twinned rectangular shaped. The EDX analysis was carried out for confirmation of Si, Al and In in zeolite frame work. The catalytic activities of

  19. Relationship between the catalytic activity of Pt/alumina and the relaxation process of the photoexcited electrons

    International Nuclear Information System (INIS)

    Ito, Junji; Hanaki, Yasunari; Shen, Qing; Toyoda, Taro

    2012-01-01

    Highlights: ► We determined the decay time of photoexcited electrons of Pt/Al 2 O 3 . ► Faster decay of excited electrons in Pt/Al 2 O 3 leads to its faster oxidation rate. ► Decreasing excited electron lifetime in Pt/Al 2 O 3 may decrease Pt consumption in catalytic convertors. - Abstract: In order to decrease the consumption of precious metals used in the catalytic converters used in automobiles, we studied the relationship between the catalytic activity of Pt/alumina (Pt/Al 2 O 3 ) and the relaxation process of photoexcited electrons. Firstly, we studied the relationship between the size of the Pt particles in Pt/Al 2 O 3 and catalytic performance. Secondly, the relationship between the size of the Pt particles in Pt/Al 2 O 3 and the decay time of the excited electrons was studied using an improved transient grating (TG) technique. The results showed that faster decay of the excited electrons leads to greater oxidation rates. The decay time obtained with the improved TG technique gives an indication of the time that the exited electrons take to return to the ground state. According to studies utilizing FT-IR, one of the processes necessary for quickly generating CO 2 with Pt is that the electron in the Pt-O bond moves to the Pt side and that the Pt + becomes Pt metal. Thus, the decay time obtained with the improved TG technique corresponds to the process whereby Pt + returns to Pt metal. Thus, we found that the consumption of precious metals can be reduced by increasing the speed of the decay of the excited electrons.

  20. Computational Design of Enone-Binding Proteins with Catalytic Activity for the Morita-Baylis-Hillman Reaction

    Science.gov (United States)

    Bjelic, Sinisa; Nivon, Lucas G.; Çelebi-Ölçüm, Nihan; Kiss, Gert; Rosewall, Carolyn F.; Lovick, Helena M.; Ingalls, Erica L.; Gallaher, Jasmine Lynn; Seetharaman, Jayaraman; Lew, Scott; Montelione, Gaetano Thomas; Hunt, John Francis; Michael, Forrest Edwin; Houk, K. N.; Baker, David

    2013-01-01

    The Morita-Baylis-Hillman reaction forms a carbon-carbon bond between the alpha carbon of a conjugated carbonyl compound and a carbon electrophile. The reaction mechanism involves Michael addition of a nucleophile catalyst at the carbonyl beta carbon, followed by bond formation with the electrophile and catalyst disassociation to release the product. We used Rosetta to design 48 proteins containing active sites predicted to carry out this mechanism, of which two show catalytic activity by mass spectrometry (MS). Substrate labeling measured by MS and site-directed mutagenesis experiments show that the designed active-site residues are responsible for activity, although rate acceleration over background is modest. To characterize the designed proteins, we developed a fluorescence-based screen for intermediate formation in cell lysates, carried out microsecond molecular dynamics simulations, and solved X-ray crystal structures. These data indicate a partially formed active site, and suggest several clear avenues for designing more active catalysts. PMID:23330600

  1. The catalytic activity of several tungsten oxides for the oxidation of propene

    International Nuclear Information System (INIS)

    De Rossi, S.; Schiavello, M.; Rome Univ.; Iguchi, E.; Tilley, R.J.D.

    1976-01-01

    A study has been made of the catalytic oxidation of propene over the oxides WO 3 , WOsub(2,95), WOsub(2,90), WOsub(2,72) and Wo 2 , which were selected because they possess specific features of chemical and structural interest rather than for their catalytic ability. It was found that the oxides WOsub(2,95), WOsub(2,90) and WOsub(2,72) all selectively produce acrolein in small amounts. The oxides WO 3 and WO 2 were non-selective and rather inactive. The results are discussed in terms of a mechanism involving both variable valence in the crystal and the specific structural geometry of these compounds. (orig.) [de

  2. Iron impurities as the active sites for peroxidase-like catalytic reaction on graphene and its derivatives.

    Science.gov (United States)

    Dong, Ying; Li, Jing; Shi, Lei; Guo, Zhiguang

    2015-07-22

    We established four kinds of good dispersing systems of graphene and its derivatives with different structural characteristics to estimate their peroxidase-like activity. Besides graphene oxide (GO), it is demonstrated that defect-free graphene, low-oxygen graphene, and iron(III)-doped graphene oxide (GO-Fe) are all capable of H2O2 activation to oxidize peroxidase substrates. As for defect-free graphene, the dispersibility in reaction medium exerts great impact on its catalytic activity and our further judgements concerning the nature of active sites. Improved stability and further exfoliation of defect-free graphene in reaction medium are beneficial to the access of reactants to active sites on the basal planes and enhance its peroxidase-like activity, which is superior to that of low-oxygen graphene and much higher than that of GO. In addition, their peroxidase-like activity can be greatly inhibited by the addition of iron chelators. Interestingly, the introduction of trace ferric ions into GO does not lead to an apparent change except for remarkable increase of its peroxidase-like activity. Therefore, we propose that the observed iron impurities rather than the doped nonmetallic heteroatoms play an important role in the peroxidase-like activity of graphene and its derivatives. In this light, saturated iron(III) was immobilized onto the oxygen-donor coordination of GO to immensely promote its activity. The peroxidase-like activity of the prepared GO-Fe was systematically evaluated by using 3,3',5,5'-tetramethylbenzidine and pyrogallol as peroxidase substrates and was compared to that of horseradish peroxidase and hemin. As a result, GO-Fe shows excellent peroxidase-like catalytic activity, which is comparable to that of hemin. Furthermore, GO-Fe was used for the quantitative detection of H2O2 and glucose.

  3. Catalytic Performance of Co3O4 on Different Activated Carbon Supports in the Benzyl Alcohol Oxidation

    Directory of Open Access Journals (Sweden)

    Misael Cordoba

    2017-12-01

    Full Text Available Co3O4 particles were supported on a series of activated carbons (G60, CNR, RX3, and RB3. Incipient wetness method was used to prepare these catalysts. The effect of the structural and surface properties of the carbonaceous supports during oxidation of benzyl alcohol was evaluated. The synthetized catalysts were characterized via IR, TEM, TGA/MS, XRD, TPR, AAS, XPS, and N2 adsorption/desorption isotherm techniques. Co3O4/G60 and Co3O4/RX3 catalysts have high activity and selectivity on the oxidation reaction reaching conversions above 90% after 6 h, without the presence of promoters. Catalytic performances show that differences in chemistry of support surface play an important role in activity and suggest that the presence of different ratios of species of cobalt and oxygenated groups on surface in Co3O4/G60 and Co3O4/RX3 catalysts, offered a larger effect synergic between both active phase and support increasing their catalytic activity when compared to the other tested catalysts.

  4. The proteolytic system of pineapple stems revisited: Purification and characterization of multiple catalytically active forms.

    Science.gov (United States)

    Matagne, André; Bolle, Laetitia; El Mahyaoui, Rachida; Baeyens-Volant, Danielle; Azarkan, Mohamed

    2017-06-01

    Crude pineapple proteases extract (aka stem bromelain; EC 3.4.22.4) is an important proteolytic mixture that contains enzymes belonging to the cysteine proteases of the papain family. Numerous studies have been reported aiming at the fractionation and characterization of the many molecular species present in the extract, but more efforts are still required to obtain sufficient quantities of the various purified protease forms for detailed physicochemical, enzymatic and structural characterization. In this work, we describe an efficient strategy towards the purification of at least eight enzymatic forms. Thus, following rapid fractionation on a SP-Sepharose FF column, two sub-populations with proteolytic activity were obtained: the unbound (termed acidic) and bound (termed basic) bromelain fractions. Following reversible modification with monomethoxypolyethylene glycol (mPEG), both fractions were further separated on Q-Sepharose FF and SP-Sepharose FF, respectively. This procedure yielded highly purified molecular species, all titrating ca. 1 mol of thiol group per mole of enzyme, with distinct biochemical properties. N-terminal sequencing allowed identifying at least eight forms with proteolytic activity. The basic fraction contained previously identified species, i.e. basic bromelain forms 1 and 2, ananain forms 1 and 2, and comosain (MEROPS identifier: C01.027). Furthermore, a new proteolytic species, showing similarities with basic bomelain forms 1 and 2, was discovered and termed bromelain form 3. The two remaining species were found in the acidic bromelain fraction and were arbitrarily named acidic bromelain forms 1 and 2. Both, acidic bromelain forms 1, 2 and basic bromelain forms 1, 2 and 3 are glycosylated, while ananain forms 1 and 2, and comosain are not. The eight protease forms display different amidase activities against the various substrates tested, namely small synthetic chromogenic compounds (DL-BAPNA and Boc-Ala-Ala-Gly-pNA), fluorogenic compounds

  5. Cycloaddition of CO 2 to challenging N -tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights

    KAUST Repository

    Arayachukiat, Sunatda

    2017-11-06

    An efficient and facile approach to the regioselective synthesis of N-tosyloxazolidinones from the corresponding N-tosylaziridines and CO2 was developed using dual catalytic systems involving an early transition metal coordination compound as a Lewis acid and a nucleophilic cocatalyst. Among the screened Lewis acids, halogen-free niobium pentaethoxide (Nb(OEt)5) displayed the best catalytic activity when used in the presence of tetrabutylammonium iodide (TBAI). Systematic DFT calculations, supported by catalytic experiments, demonstrate that CO2 insertion is the rate determining step for this process and it is highly dependent on the steric hindrance at the niobium center.

  6. Effect of alteration of translation error rate on enzyme microheterogeneity as assessed by variation in single molecule electrophoretic mobility and catalytic activity.

    Science.gov (United States)

    Nichols, Ellert R; Shadabi, Elnaz; Craig, Douglas B

    2009-06-01

    The role of translation error for Escherichia coli individual beta-galactosidase molecule catalytic and electrophoretic heterogeneity was investigated using CE-LIF. An E. coli rpsL mutant with a hyperaccurate translation phenotype produced enzyme molecules that exhibited significantly less catalytic heterogeneity but no reduction of electrophoretic heterogeneity. Enzyme expressed with streptomycin-induced translation error had increased thermolability, lower activity, and no significant change to catalytic or electrophoretic heterogeneity. Modeling of the electrophoretic behaviour of beta-galactosidase suggested that variation of the hydrodynamic radius may be the most significant contributor to electrophoretic heterogeneity.

  7. TRP ion channels in thermosensation, thermoregulation and metabolism

    Science.gov (United States)

    Wang, Hong; Siemens, Jan

    2015-01-01

    In humans, the TRP superfamily of cation channels includes 27 related molecules that respond to a remarkable variety of chemical and physical stimuli. While physiological roles for many TRP channels remain unknown, over the past years several have been shown to function as molecular sensors in organisms ranging from yeast to humans. In particular, TRP channels are now known to constitute important components of sensory systems, where they participate in the detection or transduction of osmotic, mechanical, thermal, or chemosensory stimuli. We here summarize our current understanding of the role individual members of this versatile receptor family play in thermosensation and thermoregulation, and also touch upon their immerging role in metabolic control. PMID:27227022

  8. Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Barroso-Quiroga, Maria Martha; Castro-Luna, Adolfo Eduardo [Facultad de Ingenieria y Ciencias Economico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384 (5730) Villa Mercedes (S.L.) (Argentina)

    2010-06-15

    Ni catalysts supported on different ceramic oxides (Al{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, ZrO{sub 2}) were prepared by wet impregnation. The catalytic behavior toward hydrogen production through the dry reforming of methane using a fixed-bed reactor was evaluated under certain experimental conditions, and the catalyst supported on ZrO{sub 2} showed the highest stable activity during the period of time studied. The catalyst supported on CeO{sub 2} has a relatively good activity, but shows signs of deactivation after a certain time during the reaction. This catalyst was chosen to be studied after the addition of 0.5 wt% Li and K as activity modifiers. The introduction of the alkaline metals produces a reduction of the catalytic activity but a better stability over the reactant conversion time. The reverse water-gas shift reaction influences the global system of reactions, and as the results indicate, should be considered near equilibrium. (author)

  9. On the catalytic role of the active site residue E121 of E. coli L-aspartate oxidase.

    Science.gov (United States)

    Tedeschi, Gabriella; Nonnis, Simona; Strumbo, Bice; Cruciani, Gabriele; Carosati, Emanuele; Negri, Armando

    2010-10-01

    L-aspartate oxidase (LASPO) is a flavoenzyme catalyzing the first step in the de novo biosynthesis of NAD+. The enzyme oxidizes L-aspartate both under aerobic and anaerobic conditions using oxygen as well as fumarate as electron acceptor. In accordance with its catalytic activities, LASPO displays strong primary and tertiary structure similarity with the flavin containing subunit of the proteins belonging to the succinate dehydrogenase/fumarate reductase family. The similarity extends to the active site residues, with LASPO differing from the other enzymes of the family only for the presence of a conserved glutamate (E121), which is substituted by apolar amino acids in the other enzymes. Three complementary approaches have been used to define the role of E121 in LASPO: characterization of mutants (E121A, E121Q, E121D and E121K), investigation of the catalytic activities of WT and mutants towards substrates and substrate analogues and molecular docking studies. All mutants retain fumarate reductase activity. On the contrary, all mutants lack L-aspartate oxidase activity, although retaining the ability to bind L-aspartate (except for E121K). These results and investigations on the oxidase activity towards substrate analogues suggest that the roles of E121 in catalysis include orienting L-aspartate in a productive binding mode and favouring proton abstraction from C2 by an active site base. Molecular docking studies of the substrate (L-aspartate), inhibitor (D-aspartate) and product (imino aspartate) in the active site of LASPO confirm that (a) the substrate/product energetically favoured orientation in the active site supports the conclusions reported above, (b) E121 interacts favourably with the charged amino group of the substrate and (c) different ligands might assume different orientations in the active site of the enzyme. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  10. Development of Chemically Defined Media to Express Trp-Analog-Labeled Proteins in a Lactococcus lactis Trp Auxotroph.

    Science.gov (United States)

    Shao, Jinfeng; Marcondes, Marcelo F M; Oliveira, Vitor; Broos, Jaap

    2016-01-01

    Chemically defined media for growth of Lactococcus lactis strains contain about 50 components, making them laborious and expensive growth media. However, they are crucial for metabolism studies as well as for expression of heterologous proteins labeled with unnatural amino acids. In particular, the L. lactis Trp auxotroph PA1002, overexpressing the tryptophanyl tRNA synthetase enzyme of L. lactis, is very suitable for the biosynthetic incorporation of Trp analogs in proteins because of its most relaxed substrate specificity reported towards Trp analogs. Here we present two much simpler defined media for L. lactis, which consist of only 24 or 31 components, respectively, and with which the L. lactis Trp auxotroph shows similar growth characteristics as with a 50-component chemically defined medium. Importantly, the expression levels of two recombinant proteins used for evaluation were up to 2-3 times higher in these new media than in the 50-component medium, without affecting the Trp analog incorporation efficiency. Taken together, the simplest chemically defined media reported so far for L. lactis are presented. Since L. lactis also shows auxotrophy for Arg, His, Ile, Leu Val, and Met, our simplified media may also be useful for the biosynthetic incorporation of analogs of these five amino acids. © 2016 The Author(s) Published by S. Karger AG, Basel.

  11. Increased biomass yield of Lactococcus lactis by reduced overconsumption of amino acids and increased catalytic activities of enzymes.

    Directory of Open Access Journals (Sweden)

    Kaarel Adamberg

    Full Text Available Steady state cultivation and multidimensional data analysis (metabolic fluxes, absolute proteome, and transcriptome are used to identify parameters that control the increase in biomass yield of Lactococcus lactis from 0.10 to 0.12 C-mol C-mol(-1 with an increase in specific growth rate by 5 times from 0.1 to 0.5 h(-1. Reorganization of amino acid consumption was expressed by the inactivation of the arginine deiminase pathway at a specific growth rate of 0.35 h(-1 followed by reduced over-consumption of pyruvate directed amino acids (asparagine, serine, threonine, alanine and cysteine until almost all consumed amino acids were used only for protein synthesis at maximal specific growth rate. This balanced growth was characterized by a high glycolytic flux carrying up to 87% of the carbon flow and only amino acids that relate to nucleotide synthesis (glutamine, serine and asparagine were consumed in higher amounts than required for cellular protein synthesis. Changes in the proteome were minor (mainly increase in the translation apparatus. Instead, the apparent catalytic activities of enzymes and ribosomes increased by 3.5 times (0.1 vs 0.5 h(-1. The apparent catalytic activities of glycolytic enzymes and ribosomal proteins were seen to follow this regulation pattern while those of enzymes involved in nucleotide metabolism increased more than the specific growth rate (over 5.5 times. Nucleotide synthesis formed the most abundant biomonomer synthetic pathway in the cells with an expenditure of 6% from the total ATP required for biosynthesis. Due to the increase in apparent catalytic activity, ribosome translation was more efficient at higher growth rates as evidenced by a decrease of protein to mRNA ratios. All these effects resulted in a 30% decrease of calculated ATP spilling (0.1 vs 0.5 h(-1. Our results show that bioprocesses can be made more efficient (using a balanced metabolism by varying the growth conditions.

  12. Catalytic Activities of Fe3+- and Zn2+-Natural Zeolite on the Direct Cyclisation-Acetylation of (R-(+-Citronellal

    Directory of Open Access Journals (Sweden)

    Edy Cahyono

    2014-07-01

    Full Text Available Characterisation and catalytic ativities investigation of modified natural zeolite on cyclisation acetylation reaction of (R-(+-citronellal was performed. The experimental work involved isolation of (R-(+-citronellal from Java Citronella oil (Cymbopogon winterianus by vacuum fractional distillation, determination of its enantiomer, preparation and characterisation of different catalysts i.e. H-natural zeolite (H-Za, Fe3+-natural zeolite (Fe3+-Za, and Zn2+-natural zeolite (Zn2+-Za, followed by examination of catalytic activity and selectivity. Isolated citronellal contained 88.21% ee of (R-(+-citronellal. The main products of cyclisation-acetylation of (R-(+-citronellal was IPA (isopulegyl acetate and NIPA (neo-isopulegyl acetate. Although the highest yield of IPA and NIPA was obtained by Fe3+-Za catalyst (78.69% at 80oC and 120 min, the stereoselectivity of Fe3+-Za slightly lower than that of Zn2+-Za. Structure elucidation of citronellal and products was carried out by means of GC and GC-MS. Lewis acidity plays the role of acetyl ionic formation from acetic anhydride. The Activity and stereoselectivity of catalysts depended on Lewis acidity and cation distribution on the catalyst surface. © 2014 BCREC UNDIP. All rights reservedReceived: 18th December 2013; Revised: 9th April 2014; Accepted: 17th April 2014[ How to Cite: Cahyono, E., Muchalal, M., Triyono, T., Pranowo, H.D. (2014. Catalytic Activities of Fe3+- and Zn2+-Natural Zeolite on the Direct Cyclisation-Acetylation of (R-(+-Citronellal. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 128-135. (doi:10.9767/bcrec.9.2.5936.128-135 ][ Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.5936.128-135 ] 

  13. PREPARATION, CHARACTERIZATION AND CATALYTIC ACTIVITY TEST OF CoMo/ZnO CATALYST ON ETHANOL CONVERSION USING STEAM REFORMING METHOD

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available Preparation, characterization and catalytic activity test of CoMo/ZnO catalyst for steam reforming of ethanol have been investigated. The catalysts preparation was carried out by impregnation of Co and/or Mo onto ZnO sample. Water excess was used in ethanol feed for steam reforming process under mol ratio of ethanol:water (1:10. Characterizations of catalysts were conducted by analysis of metal content using Atomic Absorption Spectroscopy (AAS. Determination of catalysts acidity was conducted by gravimetric method of adsorption of pyridine base. Catalytic activity test on ethanol conversion using steam reforming method was conducted in a semi-flow reactor system, at a temperature of 400 oC, for 1.5 h under N2 flow rate of 10 mL/min. Gas product was analyzed by gas chromatograph with TCD system. The results of catalysts characterizations showed that the impregnation of Co and/or Mo metals on ZnO sample increased its acidity and specific surface area. The content of Co in Co/ZnO and CoMo/ZnO catalysts was 1.14 and 0.49 wt%. The Mo content in CoMo/ZnO catalyst was 0.36 wt%. The catalytic activity test result on ethanol conversion showed that the ZnO, Co/ZnO, and CoMo/ZnO catalysts produced gas fraction of 16.73, 28.53, and 35.53 wt%, respectively. The coke production of ZnO, Co/ZnO, and CoMo/ZnO catalysts was 0.86, 0.24, and 0.08 wt%, respectively. The gas products consisted mainly of hydrogen.   Keywords: CoMo/ZnO catalyst, steam reforming, ethanol

  14. Ensemble perspective for catalytic promiscuity: calorimetric analysis of the active site conformational landscape of a detoxification enzyme.

    Science.gov (United States)

    Honaker, Matthew T; Acchione, Mauro; Sumida, John P; Atkins, William M

    2011-12-09

    Enzymological paradigms have shifted recently to acknowledge the biological importance of catalytic promiscuity. However, catalytic promiscuity is a poorly understood property, and no thermodynamic treatment has described the conformational landscape of promiscuous versus substrate-specific enzymes. Here, two structurally similar glutathione transferase (GST, glutathione S-transferase) isoforms with high specificity or high promiscuity are compared. Differential scanning calorimetry (DSC) indicates a reversible low temperature transition for the promiscuous GSTA1-1 that is not observed with substrate-specific GSTA4-4. This transition is assigned to rearrangement of the C terminus at the active site of GSTA1-1 based on the effects of ligands and mutations. Near-UV and far-UV circular dichroism indicate that this transition is due to repacking of tertiary contacts with the remainder of the subunit, rather than "unfolding" of the C terminus per se. Analysis of the DSC data using a modified Landau theory indicates that the local conformational landscape of the active site of GSTA1-1 is smooth, with barrierless transitions between states. The partition function of the C-terminal states is a broad unimodal distribution at all temperatures within this DSC transition. In contrast, the remainder of the GSTA1-1 subunit and the GSTA4-4 protein exhibit folded and unfolded macrostates with a significant energy barrier separating them. Their partition function includes a sharp unimodal distribution of states only at temperatures that yield either folded or unfolded macrostates. At intermediate temperatures the partition function includes a bimodal distribution. The barrierless rearrangement of the GSTA1-1 active site within a local smooth energy landscape suggests a thermodynamic basis for catalytic promiscuity.

  15. Eco-friendly synthesis of silver nanoparticles using green algae (Caulerpa serrulata): reaction optimization, catalytic and antibacterial activities.

    Science.gov (United States)

    Aboelfetoh, Eman F; El-Shenody, Rania A; Ghobara, Mohamed M

    2017-07-01

    Stable colloidal silver nanoparticles (AgNPs) were synthesized using Caulerpa serrulata (green marine algae) aqueous extract as an efficient reducing and stabilizing agent. This method is considered to be a sustainable alternate to the more complicated chemical procedures. To achieve the optimization synthesis of AgNPs, several effects such as extract concentration, contact time, pH values, and temperature were examined. The synthesized AgNPs were characterized by UV-Vis spectroscopy, FT-IR, XRD, and HR-TEM. The synthesized AgNPs showed an intense surface plasmon resonance band at 412 nm at the optimal conditions (20% (v/v) extract and 95 °C). TEM reveal that higher extract concentration and higher temperature leading to the formation of spherical AgNPs with an average particle size of 10 ± 2 nm. The synthesized AgNPs showed excellent catalytic reduction activity of Congo red (CR) dye from aqueous solutions. The degradation percentage of CR with AgNPs accelerated by increasing either NaBH 4 concentration or catalytic dosage. The AgNPs synthesized at higher temperature (e.g., 10Ag-95) exhibited the highest catalytic activity. The reaction kinetics was found to be pseudo first order with respect to the dye concentration. Moreover, the AgNPs displayed antibacterial activity at lower concentration against Staphylococcus aureus, Pseudomonas aeruginosa, Shigella sp., Salmonella typhi, and Escherichia coli and may be a good alternative therapeutic approach. The outcomes of the current study confirmed that the synthesized AgNPs had an awesome guarantee for application in catalysis and wastewater treatment.

  16. Structural Changes of Highly Active Pd/MeOx (Me = Fe, Co, Ni during Catalytic Methane Combustion

    Directory of Open Access Journals (Sweden)

    Dominik Seeburg

    2018-01-01

    Full Text Available Fe2O3, Co3O4 and NiO nanoparticles were prepared via a citrate method and further functionalized with Pd by impregnation. The pure oxides as well as Pd/Fe2O3, Pd/Co3O4, and Pd/NiO (1, 5 and 10 wt % Pd were employed for catalytic methane combustion under methane lean (1 vol %/oxygen rich (18 vol %, balanced with nitrogen conditions. Already, the pure metal oxides showed a high catalytic activity leading to complete conversion temperature of T100 ≤ 500 °C. H2-TPR (Temperature-programmed reduction experiments revealed that Pd-functionalized metal oxides exhibited enhanced redox activity compared to the pure oxides leading to improved catalytic combustion activity at lower temperatures. At a loading of 1 wt % Pd, 1Pd/Co3O4 (T100 = 360 °C outperforms 1Pd/Fe2O3 (T100 = 410 °C as well as 1Pd/NiO (T100 = 380 °C. At a loading of 10 wt % Pd, T100 could only be slightly reduced in all cases. 1Pd/Co3O4 and 1Pd/NiO show reasonable stability over 70 h on stream at T100. XPS (X-ray photoelectron spectroscopy and STEM (Scanning transmission electron microscopy investigations revealed strong interactions between Pd and NiO as well as Co3O4, respectively, leading to dynamic transformations and reoxidation of Pd due to solid state reactions, which leads to the high long-term stability.

  17. New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity

    Directory of Open Access Journals (Sweden)

    Julia Fritsch

    2010-03-01

    Full Text Available We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry.

  18. Near-Monodisperse Ni-Cu Bimetallic Nanocrystals of Variable Composition: Controlled Synthesis and Catalytic Activity for H2 Generation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yawen; Huang, Wenyu; Habas, Susan E.; Kuhn, John N.; Grass, Michael E.; Yamada, Yusuke; Yang, Peidong; Somorjai, Gabor A.

    2008-07-22

    Near-monodisperse Ni{sub 1-x}Cu{sub x} (x = 0.2-0.8) bimetallic nanocrystals were synthesized by a one-pot thermolysis approach in oleylamine/1-octadecene, using metal acetylacetonates as precursors. The nanocrystals form large-area 2D superlattices, and display a catalytic synergistic effect in the hydrolysis of NaBH{sub 4} to generate H{sub 2} at x = 0.5 in a strongly basic medium. The Ni{sub 0.5}Cu{sub 0.5} nanocrystals show the lowest activation energy, and also exhibit the highest H{sub 2} generation rate at 298 K.

  19. The masked cysteine residues in methylmalonyl-CoA mutase from Propionibacterium shermanii are essential for catalytic activity.

    Science.gov (United States)

    Roy, I

    1996-09-30

    Two masked cysteine residues have been reported in methylmalonyl-CoA mutase from Propionibacterium shermanii, Cys-535 in the alpha-subunit and Cys-517 in the beta-subunit, which are revealed only after reduction of the denatured enzyme with dithiothreitol. It has been postulated that these residues are involved in disulphide linkages to unknown thiols of low M(r). These two masked cysteine residues have been changed to an alanine, individually. Both the mutants, C535alphaA and C517betaA, were inactive. This shows that both these residues are essential for catalytic activity.

  20. Syntheses, characterizations, and catalytic activities of mesostructured aluminophosphates with tailorable acidity assembled with various preformed zeolite nanoclusters

    KAUST Repository

    Suo, Hongri

    2015-02-25

    © 2015, Springer Science+Business Media New York. A series of ordered hexagonal mesoporous zeolites have been successfully synthesized by the assembly of various preformed aluminosilicates zeolite (MFI, FAU, BEA etc.) with surfactants (cetyltrimethylammonium chloride) under hydrothermal conditions. These unique samples were further characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption, infrared spectroscopy. Characterization results showed that these samples contain primary and secondary structural building units of various zeolites, which may be responsible for their distinguished acidic strength, suggesting that the acidic strength of these mesoporous silicoaluminophosphates could be tailored and controlled. Furthermore, the prepared samples were catalytically active in the cracking of cumene.

  1. Dawning of a new era in TRP channel structural biology by cryo-electron microscopy.

    Science.gov (United States)

    Madej, M Gregor; Ziegler, Christine M

    2018-02-01

    Cryo-electron microscopy (cryo-EM) permits the determination of atomic protein structures by averaging large numbers of individual projection images recorded at cryogenic temperatures-a method termed single-particle analysis. The cryo-preservation traps proteins within a thin glass-like ice layer, making literally a freeze image of proteins in solution. Projections of randomly adopted orientations are merged to reconstruct a 3D density map. While atomic resolution for highly symmetric viruses was achieved already in 2009, the development of new sensitive and fast electron detectors has enabled cryo-EM for smaller and asymmetrical proteins including fragile membrane proteins. As one of the most important structural biology methods at present, cryo-EM was awarded in October 2017 with the Nobel Prize in Chemistry. The molecular understanding of Transient-Receptor-Potential (TRP) channels has been boosted tremendously by cryo-EM single-particle analysis. Several near-atomic and atomic structures gave important mechanistic insights, e.g., into ion permeation and selectivity, gating, as well as into the activation of this enigmatic and medically important membrane protein family by various chemical and physical stimuli. Lastly, these structures have set the starting point for the rational design of TRP channel-targeted therapeutics to counteract life-threatening channelopathies. Here, we attempt a brief introduction to the method, review the latest advances in cryo-EM structure determination of TRP channels, and discuss molecular insights into the channel function based on the wealth of TRP channel cryo-EM structures.

  2. TrpC5 Mediates Acute Leptin and Serotonin Effects via Pomc Neurons

    Directory of Open Access Journals (Sweden)

    Yong Gao

    2017-01-01

    Full Text Available The molecular mechanisms underlying acute leptin and serotonin 2C receptor-induced hypophagia remain unclear. Here, we show that neuronal and pro-opiomelanocortin (Pomc-specific loss of transient receptor potential cation 5 (TrpC5 subunits is sufficient to decrease energy expenditure and increase food intake resulting in elevated body weight. Deficiency of Trpc5 subunits in Pomc neurons is also sufficient to block the anorexigenic effects of leptin and serotonin 2C receptor (Ht2Cr agonists. The loss of acute anorexigenic effects of these receptors is concomitant with a blunted electrophysiological response to both leptin and Ht2Cr agonists in arcuate Pomc neurons. We also demonstrate that the Ht2Cr agonist lorcaserin-induced improvements in glucose and insulin tolerance are blocked by TrpC5 deficiency in Pomc neurons. Together, our results link TrpC5 subunits in the brain with leptin- and serotonin 2C receptor-dependent changes in neuronal activity, as well as energy balance, feeding behavior, and glucose metabolism.

  3. Ferredoxin-thioredoxin reductase: a catalytically active dithiol group links photoreduced ferredoxin to thioredoxin functional in photosynthetic enzyme regulation

    International Nuclear Information System (INIS)

    Droux, M.; Miginiac-Maslow, M.; Jacquot, J.P.; Gadal, P.; Crawford, N.A.; Kosower, N.S.; Buchanan, B.B.

    1987-01-01

    The mechanism by which the ferredoxin-thioredoxin system activates the target enzyme, NADP-malate dehydrogenase, was investigated by analyzing the sulfhydryl status of individual protein components with [ 14 C]iodoacetate and monobromobimane. The data indicate that ferredoxin-thioredoxin reductase (FTR)--an iron-sulfur enzyme present in oxygenic photosynthetic organisms--is the first member of a thiol chain that links light to enzyme regulation. FTR possesses a catalytically active dithiol group localized on the 13 kDa (similar) subunit, that occurs in all species investigated and accepts reducing equivalents from photoreduced ferredoxin and transfers them stoichiometrically to the disulfide form of thioredoxin m. The reduced thioredoxin m, in turn, reduces NADP-malate dehydrogenase, thereby converting it from an inactive (S-S) to an active (SH) form. The means by which FTR is able to combine electrons (from photoreduced ferredoxin) with protons (from the medium) to reduce its active disulfide group remains to be determined

  4. Mechanistic Investigations of C-H Activations on Silica-Supported Co(ii) Sites in Catalytic Propane Dehydrogenation.

    Science.gov (United States)

    Estes, Deven P

    2017-04-26

    Catalytic reactions involving C-H bond activations are central to the chemical industry. One such example, alkane dehydrogenation, has recently become very important due to shortfalls in propene production and a large supply of cheap propane. However, current technologies are inefficient and have only moderate selectivity. In order to understand how to improve currently used catalysts, we must know more about the mechanism by which propane is dehydrogenated. We show here that Co(ii) sites on silica are good catalysts for the dehydrogenation of propane, having high activity and selectivity that is reasonably stable over the course of 10 h. Mechanistic investigations of this catalyst show that the main activation mechanism is most likely C-H activation by 1,2 addition.

  5. Evolutionary Divergence in the Catalytic Activity of the CAM-1, ROR1 and ROR2 Kinase Domains

    Science.gov (United States)

    Izrael-Tomasevic, Anita; Chalouni, Cécile; Pan, Borlan; Goldsmith, Joshua; Schoen, Alia P.; Quiñones, Gabriel A.; Kelly, Ryan; Lill, Jennie R.; Sandoval, Wendy; Costa, Mike; Polakis, Paul; Arnott, David; Rubinfeld, Bonnee; Ernst, James A.

    2014-01-01

    Receptor tyrosine kinase-like orphan receptors (ROR) 1 and 2 are atypical members of the receptor tyrosine kinase (RTK) family and have been associated with several human diseases. The vertebrate RORs contain an ATP binding domain that deviates from the consensus amino acid sequence, although the impact of this deviation on catalytic activity is not known and the kinase function of these receptors remains controversial. Recently, ROR2 was shown to signal through a Wnt responsive, β-catenin independent pathway and suppress a canonical Wnt/β-catenin signal. In this work we demonstrate that both ROR1 and ROR2 kinase domains are catalytically deficient while CAM-1, the C. elegans homolog of ROR, has an active tyrosine kinase domain, suggesting a divergence in the signaling processes of the ROR family during evolution. In addition, we show that substitution of the non-consensus residues from ROR1 or ROR2 into CAM-1 and MuSK markedly reduce kinase activity, while restoration of the consensus residues in ROR does not restore robust kinase function. We further demonstrate that the membrane-bound extracellular domain alone of either ROR1 or ROR2 is sufficient for suppression of canonical Wnt3a signaling, and that this domain can also enhance Wnt5a suppression of Wnt3a signaling. Based on these data, we conclude that human ROR1 and ROR2 are RTK-like pseudokinases. PMID:25029443

  6. Evolutionary divergence in the catalytic activity of the CAM-1, ROR1 and ROR2 kinase domains.

    Directory of Open Access Journals (Sweden)

    Travis W Bainbridge

    Full Text Available Receptor tyrosine kinase-like orphan receptors (ROR 1 and 2 are atypical members of the receptor tyrosine kinase (RTK family and have been associated with several human diseases. The vertebrate RORs contain an ATP binding domain that deviates from the consensus amino acid sequence, although the impact of this deviation on catalytic activity is not known and the kinase function of these receptors remains controversial. Recently, ROR2 was shown to signal through a Wnt responsive, β-catenin independent pathway and suppress a canonical Wnt/β-catenin signal. In this work we demonstrate that both ROR1 and ROR2 kinase domains are catalytically deficient while CAM-1, the C. elegans homolog of ROR, has an active tyrosine kinase domain, suggesting a divergence in the signaling processes of the ROR family during evolution. In addition, we show that substitution of the non-consensus residues from ROR1 or ROR2 into CAM-1 and MuSK markedly reduce kinase activity, while restoration of the consensus residues in ROR does not restore robust kinase function. We further demonstrate that the membrane-bound extracellular domain alone of either ROR1 or ROR2 is sufficient for suppression of canonical Wnt3a signaling, and that this domain can also enhance Wnt5a suppression of Wnt3a signaling. Based on these data, we conclude that human ROR1 and ROR2 are RTK-like pseudokinases.

  7. Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

    Science.gov (United States)

    Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

    2009-06-15

    Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

  8. New Ulvan-Degrading Polysaccharide Lyase Family: Structure and Catalytic Mechanism Suggests Convergent Evolution of Active Site Architecture.

    Science.gov (United States)

    Ulaganathan, ThirumalaiSelvi; Boniecki, Michal T; Foran, Elizabeth; Buravenkov, Vitaliy; Mizrachi, Naama; Banin, Ehud; Helbert, William; Cygler, Miroslaw

    2017-05-19

    Ulvan is a complex sulfated polysaccharide biosynthesized by green seaweed and contains predominantly rhamnose, xylose, and uronic acid sugars. Ulvan-degrading enzymes have only recently been identified and added to the CAZy ( www.cazy.org ) database as family PL24, but neither their structure nor catalytic mechanism(s) are yet known. Several homologous, new ulvan lyases, have been discovered in Pseudoalteromonas sp. strain PLSV, Alteromonas LOR, and Nonlabens ulvanivorans, defining a new family PL25, with the lyase encoded by the gene PLSV_3936 being one of them. This enzyme cleaves the glycosidic bond between 3-sulfated rhamnose (R3S) and glucuronic acid (GlcA) or iduronic acid (IdoA) via a β-elimination mechanism. We report the crystal structure of PLSV_3936 and its complex with a tetrasaccharide substrate. PLSV_3936 folds into a seven-bladed β-propeller, with each blade consisting of four antiparallel β-strands. Sequence conservation analysis identified a highly conserved region lining at one end of a deep crevice on the protein surface. The putative active site was identified by mutagenesis and activity measurements. Crystal structure of the enzyme with a bound tetrasaccharide substrate confirmed the identity of base and acid residues and allowed determination of the catalytic mechanism and also the identification of residues neutralizing the uronic acid carboxylic group. The PLSV_3936 structure provides an example of a convergent evolution among polysaccharide lyases toward a common active site architecture embedded in distinct folds.

  9. A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shujun; Peng, Qingpo [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Chen, Xuenian, E-mail: xnchen@htu.edu.cn [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Wang, Ruoya; Zhai, Jianxin; Hu, Weihua [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Ma, Fengji, E-mail: fengji.ma@yahoo.com [College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, Henan 453000 (China); Zhang, Jie, E-mail: jie.zhang@htu.edu.cn [School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Henan Normal University, Xinxiang, Henan 453007 (China); Liu, Shuxia [Key Laboratory of Polyoxometalates Science of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun City, Jilin 130024 (China)

    2016-11-15

    A new HPAs H{sub 20}[P{sub 8}W{sub 60}Ta{sub 12}(H{sub 2}O){sub 4}(OH){sub 8}O{sub 236}]·125H{sub 2}O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10{sup −3} S cm{sup −1} (25 °C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H{sub 0} of H-1 in CH{sub 3}CN is −2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction. - Highlights: • A Ta/W mixed addenda Heteropolyacid (H-1) was isolated. • Hammett acidity constant H{sub 0} of H-1 is the strongest among the present known HPAs. • H-1 exhibits excellent catalytic activities toward acetal reaction. • H-1 is a good solid state proton conducting material at room temperature.

  10. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    Science.gov (United States)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  11. Using scaling relations to understand trends in the catalytic activity of transition metals

    International Nuclear Information System (INIS)

    Jones, G; Bligaard, T; Abild-Pedersen, F; Noerskov, J K

    2008-01-01

    A method is developed to estimate the potential energy diagram for a full catalytic reaction for a range of late transition metals on the basis of a calculation (or an experimental determination) for a single metal. The method, which employs scaling relations between adsorption energies, is illustrated by calculating the potential energy diagram for the methanation reaction and ammonia synthesis for 11 different metals on the basis of results calculated for Ru. It is also shown that considering the free energy diagram for the reactions, under typical industrial conditions, provides additional insight into reactivity trends

  12. Synthesis and characterization of tantalum organometallic complexes. Catalytic activity for olefins

    International Nuclear Information System (INIS)

    Baley, A.S.

    1990-11-01

    Synthesis of monoaryloxy (alcoxy) neopentyl compounds is investigated. The tantalum-oxygen bond is formed by two parallel ways from TaCl 5 or TaR 2 Cl 3 with R = neopentyl and the tantalum carbon bond from a neopentyl derivative of the main series. Some compounds were isolated and characterized by NMR, elemental analysis and sometimes X-ray structure, some others are characterized in solution only. Catalytic effect is tested by ethylene dimerization and olefin polymerization. Reactivity of tantalum aryloxy neopentyl in respect to complexing and chelating ligands is studied for preparation of neopentylidene complexes

  13. Catalytic oxidation of dibromomethane over Ti-modified Co3O4 catalysts: Structure, activity and mechanism.

    Science.gov (United States)

    Mei, Jian; Huang, Wenjun; Qu, Zan; Hu, Xiaofang; Yan, Naiqiang

    2017-11-01

    Ti-modified Co 3 O 4 catalysts with various Co/Ti ratios were synthesized using the co-precipitation method and were used in catalytic oxidation of dibromomethane (CH 2 Br 2 ), which was selected as the model molecule for brominated volatile organic compounds (BVOCs). Addition of Ti distorted the crystal structure and led to the formation of a Co-O-Ti solid solution. Co 4 Ti 1 (Co/Ti molar ratio was 4) achieved higher catalytic activity with a T 90 (the temperature needed for 90% conversion) of approximately 245°C for CH 2 Br 2 oxidation and higher selectivity to CO 2 at a low temperature than the other investigated catalysts. In addition, Co 4 Ti 1 was stable for at least 30h at 500ppm CH 2 Br 2 , 0 or 2vol% H 2 O, 0 or 500ppm p-xylene (PX), and 10% O 2 at a gas hourly space velocity of 60,000h -1 . The final products were CO x , Br 2 , and HBr, without the formation of other Br-containing organic byproducts. The high catalytic activity was attributed to the high Co 3+ /Co 2+ ratio and high surface acidity. Additionally, the synergistic effect of Co and Ti made it superior for CH 2 Br 2 oxidation. Furthermore, based on the analysis of products and in situ DRIFTs studies, a receivable reaction mechanism for CH 2 Br 2 oxidation over Ti-modified Co 3 O 4 catalysts was proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. 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.

  15. Structural origins for the loss of catalytic activities of bifunctional human LTA4H revealed through molecular dynamics simulations.

    Directory of Open Access Journals (Sweden)

    Sundarapandian Thangapandian

    Full Text Available Human leukotriene A4 hydrolase (hLTA4H, which is the final and rate-limiting enzyme of arachidonic acid pathway, converts the unstable epoxide LTA4 to a proinflammatory lipid mediator LTB4 through its hydrolase function. The LTA4H is a bi-functional enzyme that also exhibits aminopeptidase activity with a preference over arginyl tripeptides. Various mutations including E271Q, R563A, and K565A have completely or partially abolished both the functions of this enzyme. The crystal structures with these mutations have not shown any structural changes to address the loss of functions. Molecular dynamics simulations of LTA4 and tripeptide complex structures with functional mutations were performed to investigate the structural and conformation changes that scripts the observed differences in catalytic functions. The observed protein-ligand hydrogen bonds and distances between the important catalytic components have correlated well with the experimental results. This study also confirms based on the structural observation that E271 is very important for both the functions as it holds the catalytic metal ion at its location for the catalysis and it also acts as N-terminal recognition residue during peptide binding. The comparison of binding modes of substrates revealed the structural changes explaining the importance of R563 and K565 residues and the required alignment of substrate at the active site. The results of this study provide valuable information to be utilized in designing potent hLTA4H inhibitors as anti-inflammatory agents.

  16. Evidence of the Participation of Remote Residues in the Catalytic Activity of Co-Type Nitrile Hydratase from Pseudomonas putida

    Energy Technology Data Exchange (ETDEWEB)

    Brodkin, Heather R.; Novak, Walter R.P.; Milne, Amy C.; D’Aquino, J. Alejandro; Karabacak, N.M.; Goldberg, Ilana G.; Agar, Jeffrey N.; Payne, Mark S.; Petsko, Gregory A.; Ondrechen, Mary Jo; Ringe, Dagmar (Brandeis); (E.I. DuPont); (NEU)

    2011-09-28

    Active sites may be regarded as layers of residues, whereby the residues that interact directly with substrate also interact with residues in a second shell and these in turn interact with residues in a third shell. These residues in the second and third layers may have distinct roles in maintaining the essential chemical properties of the first-shell catalytic residues, particularly their spatial arrangement relative to the substrate binding pocket, and their electrostatic and dynamic properties. The extent to which these remote residues participate in catalysis and precisely how they affect first-shell residues remains unexplored. To improve our understanding of the roles of second- and third-shell residues in catalysis, we used THEMATICS to identify residues in the second and third shells of the Co-type nitrile hydratase from Pseudomonas putida (ppNHase) that may be important for catalysis. Five of these predicted residues, and three additional, conserved residues that were not predicted, have been conservatively mutated, and their effects have been studied both kinetically and structurally. The eight residues have no direct contact with the active site metal ion or bound substrate. These results demonstrate that three of the predicted second-shell residues ({alpha}-Asp164, {beta}-Glu56, and {beta}-His147) and one predicted third-shell residue ({beta}-His71) have significant effects on the catalytic efficiency of the enzyme. One of the predicted residues ({alpha}-Glu168) and the three residues not predicted ({alpha}-Arg170, {alpha}-Tyr171, and {beta}-Tyr215) do not have any significant effects on the catalytic efficiency of the enzyme.

  17. Decreased catalytic activity and altered activation properties of PDE6C mutants associated with autosomal recessive achromatopsia

    DEFF Research Database (Denmark)

    Grau, Tanja; Artemyev, Nikolai O; Rosenberg, Thomas

    2011-01-01

    Mutations in the gene encoding the catalytic subunit of the cone photoreceptor phosphodiesterase (PDE6C) have been recently reported in patients with autosomal recessive inherited achromatopsia (ACHM) and early-onset cone photoreceptor dysfunction. Here we present the results of a comprehensive...

  18. Substrate-mediated enhanced activity of Ru nanoparticles in catalytic hydrogenation of benzene

    KAUST Repository

    Liu, Xin

    2012-01-01

    The impact of carbon substrate-Ru nanoparticle interactions on benzene and hydrogen adsorption that is directly related to the performance in catalytic hydrogenation of benzene has been investigated by first-principles based calculations. The stability of Ru 13 nanoparticles is enhanced by the defective graphene substrate due to the hybridization between the dsp states of the Ru 13 particle with the sp 2 dangling bonds at the defect sites. The local curvature formed at the interface will also raise the Ru atomic diffusion barrier, and prohibit the particle sintering. The strong interfacial interaction results in the shift of averaged d-band center of the deposited Ru nanoparticle, from -1.41 eV for a freestanding Ru 13 particle, to -1.17 eV for the Ru/Graphene composites, and to -1.54 eV on mesocellular foam carbon. Accordingly, the adsorption energies of benzene are increased from -2.53 eV for the Ru/mesocellular foam carbon composites, to -2.62 eV on freestanding Ru 13 particles, to -2.74 eV on Ru/graphene composites. A similar change in hydrogen adsorption is also observed, and all these can be correlated to the shift of the d-band center of the nanoparticle. Thus, Ru nanoparticles graphene composites are expected to exhibit both high stability and superior catalytic performance in hydrogenation of arenes. © 2012 The Royal Society of Chemistry.

  19. The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

    International Nuclear Information System (INIS)

    Song, Sang-Hoon; Son, Ju-Hee; Budiman, Anatta Wahyu; Choi, Myoung-Jae; Chang, Tae-Sun; Shin, Chae-Ho

    2014-01-01

    The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 .deg. C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 .deg. C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 .deg. C showed a higher and more stable catalytic activity without changing of support characteristics

  20. Catalytic activity of mono and bimetallic Zn/Cu/MWCNTs catalysts for the thermocatalyzed conversion of methane to hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Erdelyi, B. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Institute of Physics, Faculty of Science, P.J. Šafárik University, Park Angelium 9, 040 01 Košice (Slovakia); Oriňak, A., E-mail: andrej.orinak@upjs.sk [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Oriňaková, R. [Department of Physical Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, 041 54 Košice (Slovakia); Lorinčík, J. [Research Center Rez, Hlavní 130, 250 68 Husinec-Řež (Czech Republic); Jerigová, M. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); Velič, D. [Department of Physical Chemistry, Comenius University, Mlynská dolina 842 15 Bratislava 4 (Slovakia); International Laser Centre, Ilkovičová 3, 841 01 Bratislava (Slovakia); Mičušík, M. [Polymer institute, Slovak Academy of Sciences, Dubravská cesta 9, 84541 Bratislava (Slovakia); and others

    2017-02-28

    Highlights: • Zn/Cu/MWCNTs catalyst with good activity. • Methane conversion to hydrogen with high effectivity. • ZnO/Cu responsible for catalytic activity. - Abstract: Mono and bimetallic multiwalled carbon nanotubes (MWCNTs) fortified with Cu and Zn metal particles were studied to improve the efficiency of the thermocatalytic conversion of methane to hydrogen. The surface of the catalyst and the dispersion of the metal particles were studied by scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS) and with energy-dispersive X-ray spectroscopy (EDS). It was confirmed that the metal particles were successfully dispersed on the MWCNT surface and XPS analysis showed that the Zn was oxidised to ZnO at high temperatures. The conversion of methane to hydrogen during the catalytic pyrolysis was studied by pyrolysis gas chromatography using different amounts of catalyst. The best yields of hydrogen were obtained using pyrolysis conditions of 900 °C and 1.2 mg of Zn/Cu/MWCNT catalyst for 1.5 mL of methane.The initial conversion of methane to hydrogen obtained with Zn/Cu/MWCNTs was 49%, which represent a good conversion rate of methane to hydrogen for a non-noble metal catalyst.

  1. Actinomycetes mediated synthesis of gold nanoparticles from the culture supernatant ofStreptomyces griseoruberwith special reference to catalytic activity.

    Science.gov (United States)

    Ranjitha, V R; Rai, V Ravishankar

    2017-10-01

    Biogenic synthesis of nanoparticles has received a tremendous attention from the past few decades. The significant progress in the field of nanotechnology has resulted in a cost-effective and eco-friendly process for nanoparticle synthesis. In the present study, the extracellular synthesis of gold nanoparticles was carried out using culture supernatant of Streptomyces griseoruber , actinomycetes isolated from the soil. Bioreduction of gold nanoparticles was confirmed by UV-visible spectrophotometer that showed the peak between 520 and 550 nm. The crystalline nature and mean size of the GNPs were confirmed using XRD. FTIR revealed the possible functional group that could be useful in immobilisation and stabilisation of GNPs. Size and distribution of the biosynthesized GNPs were analysed by HR-TEM that showed the formation of GNPs in the range of 5-50 nm. The synthesised GNPs showed good catalytic activity for the degradation of methylene blue. The study shows the rapid and eco-friendly synthesis of GNPs from Streptomyces griseoruber , and this is the first report on the catalytic activity of GNPs from actinomycetes so far.

  2. Synthesis of bimetallic Au-Ag alloyed mesocomposites and their catalytic activity for the reduction of nitroaromatics

    Science.gov (United States)

    Sareen, Shweta; Mutreja, Vishal; Pal, Bonamali; Singh, Satnam

    2018-03-01

    Homogeneously dispersed Au-Ag alloyed nanostructures varying from spherical (6-8 nm) to rod shape (aspect ratio ∼15-20 nm) were synthesized within the channels of amine modified mesoporous SBA-15 using post modification. Formation of alloy nanostructures for varying Au-Ag loadings have been supported by XPS and elemental mapping studies. Furthermore, changes in the surface/electronic properties of mesocomposites as a function of increased bimetallic Au:Ag loading have been elucidated with the help of XRD, BET, TEM and XPS studies respectively. It was found that synergism owing to electronic interplay between Au and Ag species concurrently improved the catalytic activity of bimetallic nanocomposites. Among the various monometallic and bimetallic mesocomposites, Au-Ag (5:1)/m-SBA-15 nanocomposites exhibited the best catalytic activity (k = 2.12 × 10-2 min-1 and 3.99 × 10-2 min-1) for the selective reduction of nitrobenzene to aniline and p-nitroacetophenone to p-aminoacetophenone respectively.

  3. Modeling and Simulation of the Hydrogenation of α-Methylstyrene on Catalytically Active Metal Foams as Tubular Reactor Packing

    Directory of Open Access Journals (Sweden)

    Farzad Lali

    2016-01-01

    Full Text Available This work presents a one-dimensional reactor model for a tubular reactor packed with a catalytically active foam packing with a pore density of 30 PPI in cocurrent upward flow in the example of hydrogenation reaction of α-methylstyrene to cumene. This model includes material, enthalpy, and momentum balances as well as continuity equations. The model was solved within the parameter space applied for experimental studies under assumption of a bubbly flow. The method of orthogonal collocation on finite elements was applied. For isothermal and polytropic processes and steady state conditions, axial profiles for concentration, temperature, fluid velocities, pressure, and liquid holdup were computed and the conversions for various gas and liquid flow rates were validated with experimental results. The obtained results were also compared in terms of space time yield and catalytic activity with experimental results and stirred tank and also with random packed bed reactor. The comparison shows that the application of solid foams as reactor packing is advantageous compared to the monolithic honeycombs and random packed beds.

  4. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  5. High catalytic activity of monometallic Ag, Cu nanostructures in the degradation of acid blue 113 dye: an electron relay effect

    Science.gov (United States)

    Udayabhaskar, R.; Mangalaraja, R. V.; Pandiyarajan, T.; Karthikeyan, B.; Mansilla, Héctor D.

    2017-09-01

    This report discusses the observed faster decoloration of an azo dye with an enhanced degradation rate constant achieved using metal nanostructures as a catalyst. Silver and copper nanostructures were synthesized by reducing the corresponding nitrate salts using hydrazine and hexamethylenetetramine (HMTA) in sodium hydroxide (NaOH) solution. The influence of HMTA was clearly evident from the scanning electron microscopy (SEM) images; with increasing concentration it caused agglomeration and the formation of net-like nanostructures. An x-ray diffraction study confirmed the formation of monometallic Ag and Cu nanostructures. The prepared nanostructures exhibited dipole and multipole surface plasmon resonance-related optical absorption bands which were size and shape dependent. The degradation of the azo dye acid blue 113 (AB113) in the presence of sodium borohydride (NaBH4) was taken as model system for studying the catalytic activity of the metal nanostructures. From the optical absorption spectral studies of dye degradation it was observed that the rate constant (k) was of the order of k Cu   >  k Ag   >  k no catalyst. From the dye degradation studies a high catalytic activity was observed for Cu nanostructures with a rate constant of 20.93  ×  10-4 s-1.

  6. Effects of tryptophan starvation on levels of the trp RNA-binding attenuation protein (TRAP) and anti-TRAP regulatory protein and their influence on trp operon expression in Bacillus subtilis.

    Science.gov (United States)

    Yang, Wen-Jen; Yanofsky, Charles

    2005-03-01

    The anti-TRAP protein (AT), encoded by the rtpA gene of Bacillus subtilis, can bind to and inhibit the tryptophan-activated trp RNA-binding attenuation protein (TRAP). AT binding can prevent TRAP from promoting transcription termination in the leader region of the trp operon, thereby increasing trp operon expression. We show here that AT levels continue to increase as tryptophan starvation becomes more severe, whereas the TRAP level remains relatively constant and independent of tryptophan starvation. Assuming that the functional form of AT is a trimer, we estimate that the ratios of AT trimers per TRAP molecule are 0.39 when the cells are grown under mild tryptophan starvation conditions, 0.83 under more severe starvation conditions, and approximately 2.0 when AT is expressed maximally. As the AT level is increased, a corresponding increase is observed in the anthranilate synthase level. When AT is expressed maximally, the anthranilate synthase level is about 70% of the level observed in a strain lacking TRAP. In a nutritional shift experiment where excess phenylalanine and tyrosine could potentially starve cells of tryptophan, both the AT level and anthranilate synthase activity were observed to increase. Expression of the trp operon is clearly influenced by the level of AT.

  7. Observation of Different Catalytic Activity of Various 1-Olefins during Ethylene/1-Olefin Copolymerization with Homogeneous Metallocene Catalysts

    Directory of Open Access Journals (Sweden)

    Mingkwan Wannaborworn

    2011-01-01

    Full Text Available This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C6 up to 1-octadecene (1-C18 in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between Cp(centroid-M-Cp-(centroid, which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and 13C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  8. Observation of different catalytic activity of various 1-olefins during ethylene/1-olefin copolymerization with homogeneous metallocene catalysts.

    Science.gov (United States)

    Wannaborworn, Mingkwan; Praserthdam, Piyasan; Jongsomjit, Bunjerd

    2011-01-07

    This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C₆) up to 1-octadecene (1-C₁₈) in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between C(p)(centroid)-M-C(p)-(centroid), which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and ¹³C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  9. TRP Channels as Therapeutic Targets in Diabetes and Obesity

    Directory of Open Access Journals (Sweden)

    Andrea Zsombok

    2016-08-01

    Full Text Available During the last three to four decades the prevalence of obesity and diabetes mellitus has greatly increased worldwide, including in the United States. Both the short- and long-term forecasts predict serious consequences for the near future, and encourage the development of solutions for the prevention and management of obesity and diabetes mellitus. Transient receptor potential (TRP channels were identified in tissues and organs important for the control of whole body metabolism. A variety of TRP channels has been shown to play a role in the regulation of hormone release, energy expenditure, pancreatic function, and neurotransmitter release in control, obese and/or diabetic conditions. Moreover, dietary supplementation of natural ligands of TRP channels has been shown to have potential beneficial effects in obese and diabetic conditions. These findings raised the interest and likelihood for potential drug development. In this mini-review, we discuss possibilities for better management of obesity and diabetes mellitus based on TRP-dependent mechanisms.

  10. Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

    Science.gov (United States)

    Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

    2017-07-03

    Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

  11. Nanocrystalline Ferrihydrite-Based Catalysts for Fischer-Tropsch Synthesis: Part II. Effects of Activation Gases on the Catalytic Performance.

    Science.gov (United States)

    Rhim, Geun Bae; Hong, Seok Yong; Park, Ji Chan; Jung, Heon; Rhee, Young Woo; Chun, Dong Hyun

    2016-02-01

    Fischer-Tropsch synthesis (FTS) was carried out over nanocrystalline ferrihydrite-based (Fe9O2(OH)23) catalysts activated by different reducing agents: syngas (H2+CO), CO, and H2. The syngas activation successfully changed the ferrihydrite-based catalysts into an active and stable catalytic structure with chi-carbide (Fe2.5 C) and epsilon'-carbide (Fe2.2 C). The crystal structure of the catalysts obtained by syngas activation was similar to the structure obtained by CO activation; this similarity was probably due to the peculiar reduction behavior of the ferrihydrite-based catalysts, which exhibit much greater reducibility in CO atmosphere than in H2 atmosphere. The performance of the catalysts activated by syngas was much higher than the performance of the catalysts activated by H2 and was comparable to the performance of the catalysts activated by CO. This strongly demonstrates that the ferrihydrite-based catalysts are advantageous for industrial FTS processes because syngas can be commonly used for both activation pre-treatment and subsequent reaction.

  12. Endocannabinoids as regulators of transient receptor potential (TRP) channels: A further opportunity to develop new endocannabinoid-based therapeutic drugs.

    Science.gov (United States)

    Di Marzo, V; De Petrocellis, L

    2010-01-01

    In the late 1990's, a series of experiments carried out independently in two laboratories led to establish an important connection between the function of the endocannabinoids, which, as exemplified in this special issue, is per se very complex and ubiquitous in animals, and that of the transient receptor potential (TRP) channels, a large family of plasma membrane cation channels involved in several mammalian and non-mammalian physiological and pathological conditions, overlapping only in part with those in which the cannabinoid receptors participate. These experiments were initially based on the observation that the endocannabinoid anandamide and the xenobiotic ligand of TRP channels of V1 type (TRPV1), capsaicin, are somehow chemically similar, both compounds being fatty acid amides, as are also synthetic activators of these channels and inhibitors of anandamide cellular re-uptake. As discussed in this article, the same type of "chemical thoughts" led to the discovery of N-arachidonoyl-dopamine, an endogenous ligand of TRPV1 channels that behaves also an endocannabinoid. The overlap between the ligand recognition properties of some TRP channels and proteins of the endocannabinoid system, namely the cannabinoid receptors and the proteins and enzymes catalyzing anandamide cellular re-uptake and hydrolysis, is being actively explored through the rational design and synthesis of new endocannabinoid-based drugs with multiple mechanisms of action. These aspects are discussed in this review article, together with the possible functional and pharmacological consequences of endocannabinoid-TRP channel interactions.

  13. Surface Characteristics and Catalytic Activity of Copper Deposited Porous Silicon Powder

    Directory of Open Access Journals (Sweden)

    Muhammad Yusri Abdul Halim

    2014-12-01

    Full Text Available Porous structured silicon or porous silicon (PS powder was prepared by chemical etching of silicon powder in an etchant solution of HF: HNO3: H2O (1:3:5 v/v. An immersion time of 4 min was sufficient for depositing Cu metal from an aqueous solution of CuSO4 in the presence of HF. Scanning electron microscopy (SEM analysis revealed that the Cu particles aggregated upon an increase in metal content from 3.3 wt% to 9.8 wt%. H2-temperature programmed reduction (H2-TPR profiles reveal that re-oxidation of the Cu particles occurs after deposition. Furthermore, the profiles denote the existence of various sizes of Cu metal on the PS. The Cu-PS powders show excellent catalytic reduction on the p-nitrophenol regardless of the Cu loadings.

  14. Architecture engineering toward highly active palladium integrated titanium dioxide yolk-double-shell nanoreactor for catalytic applications.

    Science.gov (United States)

    Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun

    2014-10-21

    Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd(2+) ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus

  15. Functional TRP and ASIC-like channels in cultured urothelial cells from the rat.

    Science.gov (United States)

    Kullmann, F Aura; Shah, M A; Birder, L A; de Groat, W C

    2009-04-01

    Transient receptor potential (TRP) and acid-sensing ion channels (ASIC) are molecular detectors of chemical, mechanical, thermal, and nociceptive stimuli in sensory neurons. They have been identified in the urothelium, a tissue considered part of bladder sensory pathways, where they might play a role in bladder function. This study investigated functional properties of TRP and ASIC channels in cultured urothelial cells from the rat using patch-clamp and fura 2 Ca(2+) imaging techniques. The TRPV4 agonist 4alpha-phorbol-12,13 didecanoate (4alpha-PDD; 1-5 microM) and the TRPA1/TRPM8 agonist icilin (50-100 microM) elicited transient currents in a high percentage of cells (>70%). 4alpha-PDD responses were suppressed by the TRPV4 antagonist HC-010961 (10 microM). The TRPV1 agonist capsaicin (1-100 microM) and the TRPA1/TRPM8 agonist menthol (5-200 microM) elicited transient currents in a moderate percentage of cells ( approximately 25%). All of these agonists increased intracellular calcium concentration ([Ca(2+)](i)). Most cells responded to more than one TRP agonist (e.g., capsaicin and 4alpha-PDD), indicating coexpression of different TRP channels. In the presence of the TRPV1 antagonist capsazepine (10 microM), changes in pH induced by HCl elicited ionic currents (pH 5.5) and increased [Ca(2+)](i) (pH 6.5) in approximately 50% of cells. Changes in pH using acetic acid (pH 5.5) elicited biphasic-like currents. Responses induced by acid were sensitive to amiloride (10 microM). In summary, urothelial cells express multiple TRP and ASIC channels, whose activation elicits ionic currents and Ca(2+) influx. These "neuron-like" properties might be involved in transmitter release, such as ATP, that can act on afferent nerves or smooth muscle to modulate their responses to different stimuli.

  16. Architecture engineering toward highly active palladium integrated titanium dioxide yolk-double-shell nanoreactor for catalytic applications

    Science.gov (United States)

    Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun

    2014-09-01

    Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus

  17. A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property

    Science.gov (United States)

    Li, Shujun; Peng, Qingpo; Chen, Xuenian; Wang, Ruoya; Zhai, Jianxin; Hu, Weihua; Ma, Fengji; Zhang, Jie; Liu, Shuxia

    2016-11-01

    A new HPAs H20[P8W60Ta12(H2O)4(OH)8O236]·125H2O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10-3 S cm-1 (25 °C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H0 of H-1 in CH3CN is -2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction.

  18. Free-Standing Metal Oxide Nanoparticle Superlattices Constructed with Engineered Protein Containers Show in Crystallo Catalytic Activity.

    Science.gov (United States)

    Lach, Marcel; Künzle, Matthias; Beck, Tobias

    2017-12-11

    The construction of defined nanostructured catalysts is challenging. In previous work, we established a strategy to assemble binary nanoparticle superlattices with oppositely charged protein containers as building blocks. Here, we show that these free-standing nanoparticle superlattices are catalytically active. The metal oxide nanoparticles inside the protein scaffold are accessible for a range of substrates and show oxidase-like and peroxidase-like activity. The stable superlattices can be reused for several reaction cycles. In contrast to bulk nanoparticle-based catalysts, which are prone to aggregation and difficult to characterize, nanoparticle superlattices based on engineered protein containers provide an innovative synthetic route to structurally defined heterogeneous catalysts with control over nanoparticle size and composition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...... and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of the Sabatier analysis and a Sabatier–Gibbs-type analysis and obtain an activity trend in agreement with experimental results. We show specifically why the key...... problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen. We calculate adsorption and transition state energies for the full CO oxidation reaction pathway by the use of DFT for a number...

  20. Novel Cage-Like Hexanuclear Nickel(II Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

    Directory of Open Access Journals (Sweden)

    Alexey N. Bilyachenko

    2016-05-01

    Full Text Available New hexanuclear nickel(II silsesquioxane [(PhSiO1.512(NiO6(NaCl] (1 was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,512(NiO6(NaCl(C4H8O213(PhCN2(H2O2 and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

  1. Shape-Controlled Metal-Free Catalysts: Facet-Sensitive Catalytic Activity Induced by the Arrangement Pattern of Noncovalent Supramolecular Chains.

    Science.gov (United States)

    Geng, Guangwei; Chen, Penglei; Guan, Bo; Jiang, Lang; Xu, Zhongfei; Di, Dawei; Tu, Zeyi; Hao, Weichang; Yi, Yuanping; Chen, Chuncheng; Liu, Minghua; Hu, Wenping

    2017-05-23

    Metal-free catalytic materials have recently received broad attention as promising alternatives to metal-involved catalysts. This is owing to their inherent capability to overcome the inevitable limitations of metal-involved catalysts, such as high sensitivity to poisoning, the limited reserves, high cost and scarcity of metals (especially noble metals), etc. However, the lack of shape-controlled metal-free catalysts with well-defined facets is a formidable bottleneck limiting our understandings on the underlying structure-activity relationship at atomic/molecular level, which thereby restrains their rational design. Here, we report that catalytically active crystals of a porphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, could be shaped into well-defined cubes and sheet-like tetradecahedrons (TDHD), which are exclusively and predominantly enclosed by {101} and {001} facets, respectively. Fascinatingly, compared to the cubes, the TDHDs display substantially enhanced catalytic activity toward water decontamination under visible-light irradiation, although both the architectures have identical crystalline structure. We disclose that such interesting shape-sensitive catalytic activity is ascribed to the distinct spatial separation efficiency of photogenerated electrons and holes induced by single-channel and multichannel charge transport pathways along noncovalent supramolecular chains, which are arranged as parallel-aligned and 2D network patterns, respectively. Our findings provide an ideal scientific platform to guide the rational design of next-generation metal-free catalysts of desired catalytic performances.

  2. High activity of g-C3N4/multiwall carbon nanotube in catalytic ozonation promotes electro-peroxone process.

    Science.gov (United States)

    Guo, Zhuang; Cao, Hongbin; Wang, Yuxian; Xie, Yongbing; Xiao, Jiadong; Yang, Jin; Zhang, Yi

    2018-03-07

    Three kinds of graphitic carbon nitride materials (bulk, porous and nanosheet g-C 3 N 4 ) were composited with a multiwall carbon nanotube (MWCNT) by a hydrothermal method, and the obtained b-C 3 N 4 /CNT, p-C 3 N 4 /CNT and n-C 3 N 4 /CNT materials were used in the electrodes for electro-peroxone process. It was found that the n-C 3 N 4 /CNT composite exhibited the highest efficiency in oxalate degradation, though it performed the worst in the oxygen-reduction reaction for H 2 O 2 production. The n-C 3 N 4 /CNT composite exhibited higher activity than CNT and other composites in catalytic ozonation experiments, due to the higher pyrrolic-N content modified on the CNT surface and higher surface area. It also has higher electron transfer ability, which benefited to the electro-reduction of both O 2 and O 3 . The result confirmed that catalytic ozonation process was an important means to enhance the degradation efficiency in the electro-peroxone process, besides peroxone process and O 3 -electrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    Science.gov (United States)

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

  4. Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@N-doped activated carbon composite

    Science.gov (United States)

    Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein

    2018-03-01

    In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.

  5. Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

    Science.gov (United States)

    Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

    2018-03-07

    The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

  6. Bimetallic Rh-Fe catalysts for N2O decomposition: effects of surface structures on catalytic activity.

    Science.gov (United States)

    Chen, Hao; Lu, Qinghua; Yi, Chunhai; Yang, Bolun; Qi, Suitao

    2018-02-14

    Well-homogenized RhFe alloy nanoparticles and core-shell structured Fe@Rh nanoparticles were highly dispersed on SBA-15 and then applied to N 2 O catalytic conversion. Compared to RhFe/SBA-15, Fe@Rh/SBA-15 showed a higher catalytic activity for N 2 O decomposition. This is because the Rh layers covering the Fe core were able to protect against oxidization and so Fe@Rh/SBA-15 was prevented from deactivating. DFT calculations were performed to study the reaction mechanism of N 2 O decomposition. The rate-determining step, which was found to be the formation of O 2 from adsorbed oxygen atoms on the surfaces of RhFe and Fe@Rh, revealed that O atoms prefer to be adsorbed on exposed Fe atoms on the surface of RhFe rather than that of Fe@Rh. The calculation results indicate that the exposed Fe atoms tend to be oxidized on the surface of RhFe, resulting in the deactivation of RhFe/SBA-15 during the experiment.

  7. Selectivity of an Active Natural Zeolite in Catalytic Conversion Process of Bangkirai, Kruing and Kamper Woods Biofuel to Gasoline Fraction

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available The selectivity of an active natural zeolite (ZAAH in catalytic conversion process of Bangkirai, Kruing and Kamper woods biofuels has been studied. The ZAAH catalyst was prepared from a natural zeolite (ZA treated with acids solution (1% HF and 6M HCI and hydrothermal then calcined at 500 °C and oxidized at 400 °C under nitrogen and oxygen gas stream, respectively. Characterizations of the catalysts including Si/Al ratio and acidity were determined by atomic adsorption spectroscopy (AAS and ammonia gas adsorption method, respectively. The conversion process was carried out in a flow reactor system at 400 °C, under N2 stream (20 mL/min. The biofuel was vaporized from the pyrolysis zone to the catalytic reactor. A liquid product was covered and analyzed by gas chromatograph (GC and that connected with mass spectroscopy (GC-MS. The characterization results showed that the Si/AI ratio and acidity of the ZAAH were higher than that of the ZA catalyst. The GC-MS data showed that the highest product selectivity was 2,4-dimethyl heptane and 1,2-dimethyl benzene. The total product selectivity using the ZAAH catalyst (bangkirai = 68.10%; kruing = 54.76%; kamper = 50.72% was higher than that of the ZA catalyst (bangkirai = 39.24%; kruing = 44.38%; kamper = 46.11%.

  8. Study of the catalytic activity of mixed non-stoichiometric uranium-thorium oxides in carbon monoxide oxidation

    International Nuclear Information System (INIS)

    Brau, G.

    1969-06-01

    The aim of this work has been to study the catalytic properties of non-stoichiometric uranium-thorium oxides having the general formula U x Th 1-x O 2+y , for the oxidation of carbon monoxide. The preparation of pure, homogeneous, isotropic solids having good structural stability and a surface area as high as possible calls for a strict control of the conditions of preparation of these oxides right from the preparation of 'mother salts': the mixed oxalates U x Th 1-x (C 2 O 4 ) 2 , 2H 2 O. A study has been made of their physico-chemical properties (overall and surface chemical constitution, texture, structure, electrical conductivity), as well as of their adsorption properties with respect to gaseous species occurring in the catalytic reaction. This analysis has made it possible to put forward a reaction mechanism based on successive oxidations and reductions of the active surface by the reactants. A study of the reactions kinetics has confirmed the existence of this oxidation-reduction mechanism which only occurs for oxides having a uranium content of above 0.0014. The carbon dioxide produced by the reaction acts as an inhibitor by blocking the sites on which carbon monoxide can be adsorbed. These non-stoichiometric mixed oxides are a particularly clear example of catalysis by oxygen exchange between the solid and the gas phase. (author) [fr

  9. Chlorpromazine and dimethyl sulfoxide modulate the catalytic activity of the plasma membrane Ca2+-ATPase from human erythrocyte.

    Science.gov (United States)

    Plenge-Tellechea, Fernando; Domínguez-Solís, Carlos A; Díaz-Sánchez, Ángel G; Meléndez-Martínez, David; Vargas-Medrano, Javier; Sierra-Fonseca, Jorge A

    2018-02-01

    The plasma membrane Ca 2+ -ATPase (PMCA) removes Ca 2+ from the cytosol into the extracellular space. Its catalytic activity can be stimulated by calmodulin (CaM) or by limited proteolysis. We evaluated the effect of chlorpromazine (CPZ) and dimethyl sulfoxide (DMSO) over the hydrolytic activity of PMCA. Activity was monitored in three different forms: native, CaM-activated and proteolyzed by trypsin. CPZ appears to inhibit PMCA without directly interfering with the C-terminal site, since it is affected by CaM and proteolysis. Although the treatment of PMCA with trypsin and CaM produces an activation, it also produces an enzymatic form that is more sensitive to inhibition by CPZ. The same case was observed in the DMSO inhibition experiments. In the absence of CPZ, DMSO produces a progressive loss of activity, but in the presence of CPZ the profile of activity against DMSO changes and produces a recovery of activity, indicating a possible partition of CPZ by the solvent. Increasing Ca 2+ concentrations indicated that CPZ interacts with PMCA rather than with CaM. This observation is supported by docking analysis that suggests that the CPZ-PMCA interaction is non-competitive. We propose that CPZ interacts with the state of lower affinity for Ca 2 + .

  10. Preparation of CoFeO Nanocrystallites by Solvothermal Process and Its Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

    Directory of Open Access Journals (Sweden)

    Shusen Zhao

    2010-01-01

    Full Text Available Nanometer cobalt ferrite (CoFe2O4 was synthesized by polyol-medium solvothermal method and characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, and selected area electron diffraction (SAED. Further, the catalytic activity and kinetic parameters of CoFe2O4 nanocrystallites on the thermal decomposition behavior of ammonium perchlorate (AP have been investigated by thermogravimetry and differential scanning calorimetry analysis (TG-DSC. The results imply that the catalytic performance of CoFe2O4 nanocrystallites is significant and the decrease in the activation energy and the increase in the rate constant for AP further confirm the enhancement in catalytic activity of CoFe2O4 nanocrystallites. A mechanism based on an proton transfer process has also been proposed for AP in the presence of CoFe2O4 nanocrystallites.

  11. Modulation of PI3K/PTEN Pathway Does Not Affect Catalytic Activity of PDK1 in Jurkat Cells.

    Science.gov (United States)

    Yang, Keum-Jin; Piao, Longzhen; Shin, Sanghee; Shin, So-Yeon; Li, Yuwen; Lee, Hyunji; Tran, Quangdon; Park, Jisoo; Hong, Suntaek; Brazil, Derek P; Hemmings, Brian A; Kim, Seon-Hwan; Park, Jongsun

    2017-10-01

    Unopposed phosphoinositide 3-kinase (PI3K) activity and 3-phosphoinositide production in Jurkat cells, due to a mutation in the phosphatase and tensin homolog deleted on chromosome 10 (PTEN) tumor-suppressor protein, results in deregulation of PH domain-containing proteins including the serine/threonine kinase PKB. In Jurkat cells, PKB is constitutively active and phosphorylated at the activation-loop residue (Thr308). 3-Phosphoinositide-dependent protein kinase-1 (PDK1), an enzyme that also contains a PH domain, catalyses Thr308 phosphorylation of PKB in addition to other kinase families such as PKC isoforms. It is unknown, however, whether the loss of PTEN in Jurkat cells also results in unregulated PDK1 activity and whether such loss has an impact on activation-loop phosphorylation of other PDK1 substrates e.g. PKC. In this study, we addressed whether loss of PTEN in Jurkat cells affects PDK1 catalytic activity and intracellular localization. We demonstrated that reducing the level of 3-phosphoinositides in Jurkat cells with pharmacological inhibitors of PI3K or expression of PTEN does not affect PDK1 activity or its intracellular localization. We conclude, therefore, that although Jurkat cells lack PTEN expression, only a subset of pathways downstream of PDK1 are perturbed as a consequence of PTEN loss. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

  12. Highly active Ag clusters stabilized on TiO{sub 2} nanocrystals for catalytic reduction of p-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China); University of Chinese Academy of Sciences, Beijing, 100049 (China); Zhao, Zhe; Ou, Dingrong; Tu, Baofeng; Cui, Daan [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China); Wei, Xuming [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Cheng, Mojie, E-mail: mjcheng@dicp.ac.cn [Division of Fuel Cells, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (China)

    2016-11-01

    Graphical abstract: Ag/TiO{sub 2} nanocomposites have been synthesized through the reduction of silver-dodecylamine complexes by CH{sub 3}CHO in the presence of TiO{sub 2} nanocrystals and have shown excellent catalytic activity for the reduction of 4-NP into 4-AP by NaBH{sub 4}. Display Omitted - Highlights: • Ag/TiO{sub 2} nanocomposites with Ag clusters under 2 nm are synthesized through a silver mirror reaction in toluene. • The silver mirror reaction refers to the reduction of silver-dodecylamine complexes by acetaldehyde in toluene. • The Ag/TiO{sub 2} nanocomposites show a good ability of resistant against poisoning by the product in reduction of 4-NP. • TOFs of Ag/TiO{sub 2} nanocomposites obtained in this work are the highest among Ag based catalysts previously reported. - Abstract: Ag/TiO{sub 2} nanocomposites comprising of Ag clusters on TiO{sub 2} nanocrystal surfaces are of great significance in catalysts and advanced functional materials. Herein a novel method to synthesize Ag/TiO{sub 2} nanocomposites with Ag clusters under 2 nm on TiO{sub 2} nanocrystal surfaces have been developed. The success of this method relies on a silver mirror reaction in toluene, which refers to the reduction of silver-dodecylamine complexes by acetaldehyde in the presence of mono-dispersed TiO{sub 2} nanocrystals. The prepared Ag/TiO{sub 2} nanocomposites have been characterized by FT-IR spectra, UV–vis absorption spectra, X-ray diffraction (XRD) analysis, ultra high resolution scanning electron microscope (Ultra-HRSEM), high resolution transmission electron microscope (HRTEM) and X-ray photoelectron spectra (XPS). Catalytic activity of Ag/TiO{sub 2} nanocomposites is evaluated for the reduction of p-nitrophenol (4-NP) into p-aminophenol (4-AP) by NaBH{sub 4}. Results demonstrate that Ag/TiO{sub 2} nanocomposites have shown an outstanding catalytic activity as well as a good stability in successive reduction of 4-NP. Noticeably, TOF of Ag/TiO{sub 2

  13. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2017-04-01

    Full Text Available The modified coal char from low-rank coal by sulfonation, titanium impregnation and followed by alkyl silylation possesses high catalytic activity in styrene oxidation. The surface of coal char was undergone several steps as such: modification using concentrated sulfuric acid in the sulfonation process, impregnation of 500 mmol titanium(IV isopropoxide and followed by alkyl silylation of n-octadecyltriclorosilane (OTS. The catalysts were characterized by X-ray diffraction (XRD, IR spectroscopy, nitrogen adsorption, and hydrophobicity. The catalytic activity of the catalysts has been examined in the liquid phase styrene oxidation by using aqueous hydrogen peroxide as oxidant. The catalytic study showed the alkyl silylation could enhance the catalytic activity of Ti-SO3H/CC-600(2.0. High catalytic activity and reusability of the o-Ti-SO3H/CC-600(2.0 were related to the modification of local environment of titanium active sites and the enhancement the hydrophobicity of catalyst particle by alkyl silylation. Copyright © 2017 BCREC GROUP. All rights reserved Received: 24th May 2016; Revised: 11st October 2016; Accepted: 18th October 2016 How to Cite: Nurhadi, M. (2017. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 55-61 (doi:10.9767/bcrec.12.1.501.55-61 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.501.55-61

  14. Sustainability of the Catalytic Activity of a Silica-Titania Composite (STC) for Long-Term Indoor Air Quality Control

    Science.gov (United States)

    Coutts, Janelle L.; Levine, Lanfang H.; Richards, Jeffrey T.

    2011-01-01

    TiO2-assisted photocatalytic oxidation (PCO) is an emerging technology for indoor air quality control and is also being evaluated as an alternative trace contaminant control technology for crew habitats in space exploration. Though there exists a vast range of literature on the development of photocatalysts and associated reactor systems, including catalyst performance and performance-influencing factors, the critical question of whether photocatalysts can sustain their initial catalytic activity over an extended period of operation has not been adequately addressed. For a catalyst to effectively serve as an air quality control product, it must be rugged enough to withstand exposure to a multitude of low concentration volatile organic compounds (VOCs) over long periods of time with minimal loss of activity. The objective of this study was to determine the functional lifetime of a promising photocatalyst - the silica-titania composite (STC) from Sol Gel Solutions, LLC in a real-world scenario. A bench-scale STC-packed annular reactor under continuous irradiation by a UV-A fluorescent black-light blue lamp ((lambda)max = 365 nm) was exposed to laboratory air continuously at an apparent contact time of 0.27 sand challenged with a known concentration of ethanol periodically to assess any changes in catalytic activity. Laboratory air was also episodically spiked with halocarbons (e.g., octafluoropropane), organosulfur compounds (e.g., sulfur hexafluoride), and organosilicons (e.g., siloxanes) to simulate accidental releases or leaks of such VOCs. Total organic carbon (TOC) loading and contaminant profiles of the laboratory air were also monitored. Changes in STC photocatalytic performance were evaluated using the ethanol mineralization rate, mineralization efficiency, and oxidation intermediate (acetaldehyde) formation. Results provide insights to any potential catalyst poisoning by trace halocarbons and organosulfur compounds.

  15. Catalytic activity of bimetallic Zn/TiO2 catalyst for degradation of herbicide paraquat: synthesis and characterization

    Science.gov (United States)

    Sakee, Uthai; Wanchanthuek, Ratchaneekorn

    2017-11-01

    The preparation and characterization of Zn/TiO2 catalysts were performed and the photocatalytic properties of the resulting catalysts were tested using the paraquat degradation reaction under UV and solar light irradiation. The effect of the preparation method, amount of Zn loading, the calcination temperature and the thermal annealing during the autoclave aging were studied as well as the light irradiation during the testing reaction. The initial concentration of paraquat was 400 ppm, the pH during the catalytic testing was seven and the reaction temperature was 30 °C. The characterization information were obtained from XRD, XPS, UV-vis diffuse reflectance, FTIR, TEM and BET techniques. They were used to explain the expressed catalytic activity of Zn/TiO2. The results showed that the Zn/TiO2 catalyst from the hydrothermal method could remove about 80% of the paraquat from the solution (using 4 g l-1 of catalyst). The characterization data showed that the surface area, porous structure and dispersion of Zn species could affect the ability of the paraquat removal rather than the crystallnity of the TiO2 in the catalyst. The XPS spectra suggested that the preparation method, between the sol gel and hydrothermal, could not affect the state of the Zn and Ti, which presented in the Zn2+ and Ti4+ forms. This primary result will lead us to further study to elucidate the main active site by the XPS technique. Moreover, it clearly showed that the lowering of the band gap energy in the Zn/TiO2 was achieved (compared to bare TiO2), and this phenomena was one of the factors that gave the higher photocatalytic activity of the Zn/TiO2 catalyst.

  16. Influence of different preparation conditions on catalytic activity of ag /gama-al/sub 2/o/sub 3/ for hydrogenation of coal slime pyrolysis

    International Nuclear Information System (INIS)

    Lei, Z.; Rong, C.

    2014-01-01

    This paper, introducing variable conditional factors with Ag/AL/sub 2/O/sub 3/ as catalyst, selects five variables to investigate the influences of experimental conditions on Ag/Al2O/sub 3/ catalytic activity and define the optimal process conditions. These variables include Ag loading amount, calcinations temperature, calcinations time, reduction temperature, reduction time. X ray diffraction (XRD), hydrogen temperature-programmed reduction (TPR), X ray photoelectron spectrum (XPS) and scanning electron microscopy (SEM) were utilized to characterize the catalytic activity of Ag/-Al/sub 2/O/sub 3/, active center structure and state and those of carrier were emphatically studied, In the meantime the effects of active center and carrier on catalytic activity are studied. The results showed that: (1) In the range of 600 degree C-900 degree C, the catalytic activity of Ag/-Al/sub 2/O/sub 3/ with different loading showed little difference when changing loading amount, in the range of 900 degree C-1100 degree C, when the loading was 5%, the catalytic activity was very high; From the XRD and SEM characterizations, when the loading was 5%, it showed strong intensity diffraction peak of Ag crystal, crystal Ag is the most important activity center to promote hydrogen yield. (2) the catalytic activity of Ag/-Al/sub 2/O/sub 3/ at 450 degree C was considerably higher than that at 400 degree C and 500 degree C. By BET, XRD and SEM characterization, it can be seen, the diffraction peaks intensity of Ag crystal at 450 degree C is higher and sharper than that at 400 degree C and 500 degree C and with the increase of calcinations temperature, the specific surface area of catalysts also increased. (3) In the range of 600 degree C - 1000 degree C, the effects of calcinations time can be negligible, while, with temperature higher than 1000 degree C, 4-hour-calcinations-time catalyst exhibits a more noticeable catalytic activity than 3-hour and 5-hour catalyst do; From the XRD

  17. 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.

  18. TrpA1 Regulates Defecation of Food-Borne Pathogens under the Control of the Duox Pathway.

    Directory of Open Access Journals (Sweden)

    Eun Jo Du

    2016-01-01

    Full Text Available Pathogen expulsion from the gut is an important defense strategy against infection, but little is known about how interaction between the intestinal microbiome and host immunity modulates defecation. In Drosophila melanogaster, dual oxidase (Duox kills pathogenic microbes by generating the microbicidal reactive oxygen species (ROS, hypochlorous acid (HOCl in response to bacterially excreted uracil. The physiological function of enzymatically generated HOCl in the gut is, however, unknown aside from its anti-microbial activity. Drosophila TRPA1 is an evolutionarily conserved receptor for reactive chemicals like HOCl, but a role for this molecule in mediating responses to gut microbial content has not been described. Here we identify a molecular mechanism through which bacteria-produced uracil facilitates pathogen-clearing defecation. Ingestion of uracil increases defecation frequency, requiring the Duox pathway and TrpA1. The TrpA1(A transcript spliced with exon10b (TrpA1(A10b that is present in a subset of midgut enteroendocrine cells (EECs is critical for uracil-dependent defecation. TRPA1(A10b heterologously expressed in Xenopus oocytes is an excellent HOCl receptor characterized with elevated sensitivity and fast activation kinetics of macroscopic HOCl-evoked currents compared to those of the alternative TRPA1(A10a isoform. Consistent with TrpA1's role in defecation, uracil-excreting Erwinia carotovora showed higher persistence in TrpA1-deficient guts. Taken together, our results propose that the uracil/Duox pathway promotes bacteria expulsion from the gut through the HOCl-sensitive receptor, TRPA1(A10b, thereby minimizing the chances that bacteria adapt to survive host defense systems.

  19. Iridium nanoparticles with high catalytic activity in degradation of acid red-26: an oxidative approach.

    Science.gov (United States)

    Goel, Anjali; Lasyal, Rajni

    2016-12-01

    Nanocatalysis using metal nanoparticles constitutes one of the emerging technologies for destructive oxidation of organics such as dyes. This paper deals with the degradation of acid red-26 (AR-26), an azo dye by hexacyanoferrate (abbreviated as HCF) (III) using iridium nanoparticles. UV-vis spectroscopy has been employed to obtain the details of the oxidative degradation of the selected dye. The effect of various operational parameters such as HCF(III) concentration, pH, initial dye concentration, catalyst and temperature was investigated systematically at the λ max , 507 nm, of the reaction mixture. Degradation kinetics follows the first order kinetic model with respect to AR-26 and Ir nano concentrations, while with respect to the HCF(III) concentration reaction it follows first order kinetics at lower concentrations, tending towards zero order at higher concentrations. Thermodynamic parameters have been calculated by studying the reaction rate at four different temperatures. The UV-vis, high performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS) analysis of degradation products showed the formation of carboxylic acid and substituted carboxylic acids as major degradation products, which are simple and less hazardous compounds. The big advantage of the present method is the recovery and reuse of iridium nanoparticles. Moreover, turnover frequencies for each catalytic cycle have been determined, indicating the long life span of Ir nanoparticles. Thus, the finding is a novel and highly economical alternative for environmental safety against pollution by dyes, and extendable for other contaminants as well.

  20. Gold nanostars: Benzyldimethylammonium chloride-assisted synthesis, plasmon tuning, SERS and catalytic activity.

    Science.gov (United States)

    Ndokoye, Pancras; Li, Xinyong; Zhao, Qidong; Li, Tingting; Tade, Moses O; Liu, Shaomin

    2016-01-15

    Fabrication of Au nanostars (AuNSs) can expand the application range of Au nanoparticles because of their high electron density and localized surface plasmon resonance (LSPR) on branches. Exploiting this potential requires further refinement of length of the branches and radius of their tips. To this end, we successfully synthesized AuNSs with uniform and sharply-pointed branches by combining benzyldimethylammonium chloride (BDAC) and cetyltrimethylammonium bromide (CTAB) at low BDAC/CTAB ratios. Once mixed with CTAB, BDAC lowers the critical micelle concentration (CMC) for quick formation of the micelles, which provides favorable growth templates for AuNSs formation. Besides, BDAC increases the concentration of Cl(-), which favors Ag(+) in adsorbing on Au facets. This feature is crucial for the yield boosting and synergic shape control of AuNSs regardless of types of Au seeds used. Use of less amounts of seeds as the center of nucleation benefited sharper and longer growth of the branches. AuNSs exhibited excellent enhancement of surface-enhanced Raman scattering (SERS) intensities as the result of high electron density localized at the tips; however, the enhancement degree varied in accordance with the size of branches. In addition, AuNSs showed high catalytic performance toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Efficient catalysis over AuNSs originates from their corners, stepped surfaces and high electron density at the tips. Copyright © 2015 Elsevier Inc. All rights reserved.

  1. Filtres à activité catalytique pour moteur Diesel Catalytic Activity Filters for Diesel Engines

    Directory of Open Access Journals (Sweden)

    Goldenberg E.

    2006-11-01

    Full Text Available A partir de l'examen des normes actuelles et envisagées dans le futur pour limiter les émissions de particules Diesel, et en considérant les propriétés physico-chimiques de ces particules, cet article expose les problèmes posés par la filtration des suies Diesel et leur élimination par combustion sur les différents types de filtres actuellement retenus. La régénération des filtres par combustion catalytique du dépôt est plus particulièrement discutée. From an examination of present regulations and ones being considered for the future to limit particle emissions by diesel engines, and considering the physicochemical properties of such particles, this article describes the problems raised by filtering soot from diesel engines and eliminating it by various types of filters now used. Filter regeneration by catalytic combustion of the deposit is considered in particular.

  2. A New Energy-Saving Catalytic System: Carbon Dioxide Activation by a Metal/Carbon Catalyst.

    Science.gov (United States)

    Yun, Danim; Park, Dae Sung; Lee, Kyung Rok; Yun, Yang Sik; Kim, Tae Yong; Park, Hongseok; Lee, Hyunjoo; Yi, Jongheop

    2017-09-22

    The conversion of CO 2 into useful chemicals is an attractive method to reduce greenhouse gas emissions and to produce sustainable chemicals. However, the thermodynamic stability of CO 2 means that a lot of energy is required for its conversion into chemicals. Here, we suggest a new catalytic system with an alternative heating system that allows minimal energy consumption during CO 2 conversion. In this system, electrical energy is transferred as heat energy to the carbon-supported metal catalyst. Fast ramping rates allow high operating temperatures (T app =250 °C) to be reached within 5 min, which leads to an 80-fold decrease of energy consumption in methane reforming using CO 2 (DRM). In addition, the consumed energy normalized by time during the DRM reaction in this current-assisted catalysis is sixfold lower (11.0 kJ min -1 ) than that in conventional heating systems (68.4 kJ min -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Enhancement in catalytic activity of Aspergillus niger XynB by selective site-directed mutagenesis of active site amino acids.

    Science.gov (United States)

    Wu, Xiuyun; Tian, Zhennan; Jiang, Xukai; Zhang, Qun; Wang, Lushan

    2018-01-01

    XynB from Aspergillus niger ATCC1015 (AnXynB) is a mesophilic glycoside hydrolase (GH) family 11 xylanase which holds great potentials in a wide variety of industrial applications. In the present study, the catalytic activity and stability of AnXynB were improved by a combination of computational and experimental approaches. Virtual mutation and molecular dynamics simulations indicated that the introduction of Glu and Asn altered the interaction network at the - 3 subsite. Interestingly, the double mutant S41N/T43E displayed 72% increase in catalytic activity when compared to the wild type (WT). In addition, it also showed a better thermostability than the WT enzyme. Kinetic determination of the T43E and S41N/T43E mutants suggested that the higher xylanase activity is probably due to the increasing binding affinity of enzyme and substrate. Consequently, the enzyme activity and thermostability of AnXynB was both increased by selective site-directed mutagenesis at the - 3 subsite of its active site architecture which provides a good example for a successfully engineered enzyme for potential industrial application. Moreover, the molecular evolution approach adopted in this study led to the design of a library of sequences that captures a meaningful functional diversity in a limited number of protein variants.

  4. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  5. Catalytic activity of Ni complexed aminoclay towards the reduction of Cr(V), p-nitrophenol and fluorescein dye

    Science.gov (United States)

    Ranchani, A. Amala Jeya; Parthasarathy, V.; Devi, A. Anitha; Meenarathi, B.; Anbarasan, R.

    2017-11-01

    A green-colored Ni-complexed aminoclay (AC) was synthesized and its size and crystalline nature were confirmed by HRTEM images and XRD, respectively. The AC-Ni system was used as a catalyst towards the reduction of environmental pollutants like Cr(VI), fluorescein (Fluor) and nitrophenol (NiP) individually and also their mixture. The catalytic reduction of Cr(VI) was elaborately studied under different experimental conditions. The thermodynamic parameters were determined. The AC-Ni system exhibited lower energy of activation ( E a) value. The apparent rate constant of individual components and their mixture was determined, analyzed and compared with the literature reports. The pollutants present in the mixture exhibited the lower k app value due to the complex formation.

  6. Promoting Effect of CeO2 Addition on Activity and Catalytic Stability in Steam Reforming of Methane over Ni/Al2O3

    International Nuclear Information System (INIS)

    Rakib, A.; Gennequin, C.; Ringot, S.; Aboukais, A.; Abi-Aad, E.; Dhainaut, T.

    2011-01-01

    Hydrogen production by steam reforming of methane was studied over Ni catalysts supported on CeO 2 , Al 2 O 3 and CeO 2 -Al 2 O 3 . These catalysts were prepared using the impregnation method and characterized by XRD. The effect of CeO2 promoter on the catalytic performance of Ni/Al 2 O 3 catalyst for methane steam reforming reaction was investigated. In fact, CeO 2 had a positive effect on the catalytic activity in this reaction. Experimental results demonstrated that Ni/CeO 2 -Al 2 O 3 catalyst showed excellent catalytic activity and high reaction performance. In addition, the effects of reaction temperature and metal content on the conversion of CH 4 and H 2 /CO ratio were also investigated. Results indicated that CH4 conversion increased significantly with the increase of the reaction temperature and metal content. (author)

  7. Photo-induced biosynthesis of silver nanoparticles using aqueous extract of Erigeron bonariensis and its catalytic activity against Acridine Orange.

    Science.gov (United States)

    Kumar, Vijay; Singh, Devendra K; Mohan, Sweta; Hasan, Syed Hadi

    2016-02-01

    The green synthesis of silver nanoparticles (AgNPs) has reduced the pollution load in the environment to a greater extent by avoiding the use of hazardous chemicals. In the present work we have developed an ecofriendly and zero cost approach for the green synthesis of more stable and spherical AgNPs using aqueous extract of Erigeron bonariensis (AEE) which act as both reducing and stabilizing agent. The reaction of AEE and AgNO3 was carried out in direct sunlight for the instant biosynthesis of AgNPs within minutes. The biosynthesis was monitored by UV-vis spectroscopy which exhibited a sharp SPR band at 442 nm and 435 nm after 5 and 35 min of sunlight exposure. The optimum conditions for biosynthesis of AgNPs were found to be 2.5mM AgNO3 concentration, 1.5% (v/v) of AEE inoculum dose and 35 min of sunlight exposure. Presence of spherical AgNPs with average size 13 nm was confirmed by SEM and TEM analysis. The XRD and SAED analysis confirmed the crystalline nature of the AgNPs where the Bragg's diffraction pattern at (111), (200), (220) and (311) corresponded to face centered cubic crystal lattice of metallic silver. The average roughness of the synthesized AgNPs was 3.21 nm which was confirmed by AFM analysis. FTIR analysis was recorded between 4000 and 400 cm(-1) which confirmed the involvement of various functional groups in the synthesis of AgNPs. The AgNPs thus obtained showed catalytic activity towards degradation of Acridine Orange (AO) without involvement of any hazardous reducing agent. The concentration dependent catalytic activity of the synthesized AgNPs was also monitored using 1, 2 and 3 mL of silver colloids and was found that the degradation of AO followed pseudo first-order kinetics. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

    KAUST Repository

    Baker, L. Robert

    2011-08-18

    The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

  9. TRP channels in prostate cancer: the good, the bad and the ugly?

    Science.gov (United States)

    Gkika, Dimitra; Prevarskaya, Natalia

    2011-01-01

    During the last decade, transient receptor potential (TRP) channels emerge as key proteins in central mechanisms of the carcinogenesis such as cell proliferation, apoptosis and migration. Initial studies showed that expression profile of some TRP channels, notably TRP melastatin 8 (TRPM8), TRP vanilloid 6 (TRPV6),TRP canonical (TRPC6) and TRPV2, is changing during the development and the progression of prostate cancer towards the hormone-refractory stages. The link between the change in expression levels and the functional role of these channels in prostate cancer is step by step being elucidated. These recent advances are here described and discussed. PMID:21623387

  10. Atomic-Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation.

    Science.gov (United States)

    Melzer, Daniel; Xu, Pinghong; Hartmann, Daniela; Zhu, Yuanyuan; Browning, Nigel D; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-07-25

    Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M6 O21 units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis of Ultra-Small Platinum, Palladium and Gold Nanoparticles by Shewanella loihica PV-4 Electrochemically Active Biofilm and Their Enhanced Catalytic Activities

    KAUST Repository

    Ahmed, Elaf

    2018-02-21

    Ultra-small nanoparticles (USNPs) of noble metals have a great potential in a variety of applications due to their high surface areas and high reactivity. This works employed electrochemically active biofilms (EABs) composed of a single bacterium strain of Shewanella loihica PV-4 and successfully synthesized USNPs of noble metal Au, Pd, and Pt. The synthesized USNPs had a size range between 2 and 7 nm and exhibited excellent catalytic performance in dye decomposition. The results of this work shine lights on the use of EABs in nanoparticle synthesis.

  12. 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

  13. Role of Hydrogen and Oxygen Activation over Pt and Pd-Doped Composites for Catalytic Hydrogen Combustion.

    Science.gov (United States)

    Singh, Satyapaul A; Vishwanath, Karan; Madras, Giridhar

    2017-06-14

    Removal of excess amount of hydrogen in a catalytic route is a safety measure to be implemented in fuel cell technologies and in nuclear power plants. Hydrogen and oxygen activation are crucial steps for hydrogen combustion that can be achieved by modifying supports with suitable noble metals. In the present study, Pt- and Pd-substituted Co 3 O 4 -ZrO 2 (CZ) were synthesized using PEG-assisted sonochemical synthesis. Ionic states of Pt and Pd in CZ supports were analyzed by X-ray photoelectron spectroscopy. Pd and Pt improved H 2 and O 2 activation extensively, which reduced the temperature of 50% conversion (T 50% ) to 33 °C compared with the support (CZ). The activation energy of PdCZ catalyst was decreased by more than 2 folds (13.4 ± 1.2 kJ mol -1 ) compared with CZ (34.3 ± 2.3 kJ mol -1 ). The effect of oxygen vacancies in the reaction mechanism is found to be insignificant with Pt- and Pd-substituted CZ supports. However, oxygen vacancies play an important role when CZ alone was used as catalyst. The importance of hydrogen and oxygen activation as well as the oxygen vacancies in mechanism was studied by H 2 -TPD, H 2 -TPR, and in situ FTIR spectroscopy.

  14. Ferredoxin-thioredoxin reductase: a catalytically active dithiol group links photoreduced ferredoxin to thioredoxin functional in photosynthetic enzyme regulation

    Energy Technology Data Exchange (ETDEWEB)

    Droux, M.; Miginiac-Maslow, M.; Jacquot, J.P.; Gadal, P.; Crawford, N.A.; Kosower, N.S.; Buchanan, B.B.

    1987-07-01

    The mechanism by which the ferredoxin-thioredoxin system activates the target enzyme, NADP-malate dehydrogenase, was investigated by analyzing the sulfhydryl status of individual protein components with (/sup 14/C)iodoacetate and monobromobimane. The data indicate that ferredoxin-thioredoxin reductase (FTR)--an iron-sulfur enzyme present in oxygenic photosynthetic organisms--is the first member of a thiol chain that links light to enzyme regulation. FTR possesses a catalytically active dithiol group localized on the 13 kDa (similar) subunit, that occurs in all species investigated and accepts reducing equivalents from photoreduced ferredoxin and transfers them stoichiometrically to the disulfide form of thioredoxin m. The reduced thioredoxin m, in turn, reduces NADP-malate dehydrogenase, thereby converting it from an inactive (S-S) to an active (SH) form. The means by which FTR is able to combine electrons (from photoreduced ferredoxin) with protons (from the medium) to reduce its active disulfide group remains to be determined.

  15. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

    Science.gov (United States)

    Wang, Liangbing; Zhang, Wenbo; Zheng, Xusheng; Chen, Yizhen; Wu, Wenlong; Qiu, Jianxiang; Zhao, Xiangchen; Zhao, Xiao; Dai, Yizhou; Zeng, Jie

    2017-11-01

    Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h-1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol-1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NHx, wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

  16. Support effects and catalytic trends for water gas shift activity of transition metals

    DEFF Research Database (Denmark)

    Boisen, Astrid; Janssens, T.V.W.; Schumacher, Nana Maria Pii

    2010-01-01

    Water gas shift activity measurements for 12 transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au) supported on inert MgAl2O4 and Ce0.75Zr0.25O2 are presented, to elucidate the influence of the active metal and the support. The activity is related to the adsorption energy of molecular...

  17. Catalytic activity of CuO-Gd0.1Ti0.1Zr0.1Ce0.7O2 in CO oxidation

    Indian Academy of Sciences (India)

    after accounting for instrumental broadening using ger- manium as reference. Quantitative phase analysis was ... with an X-ray microanalysis system INCA Energy 350. (Oxford Instruments). The catalytic activity of the synthesized samples in the oxidation of CO was determined by the flow method at atmospheric pressure.

  18. Enhanced catalytic performance of zeolite ZSM-5 for conversion of methanol to dimethyl ether by combining alkaline treatment and partial activation

    NARCIS (Netherlands)

    Wei, Ying; de Jongh, Petra E.|info:eu-repo/dai/nl/186125372; Bonati, Matteo L. M.; Law, David J.; Sunley, Glenn J.; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X

    2015-01-01

    Zeolite ZSM-5 (MFI) due to its excellent hydrothermal stability and high catalytic activity for methanol dehydration to dimethyl ether (MID) has been considered for use in combination with a methanol synthesis catalyst, such as Cu/ZnO/Al2O3, in the conversion of syngas to dimethyl ether. However,

  19. A new 3-D open-framework cadmium borovanadate with plane-shaped channels and high catalytic activity for the oxidation of cyclohexanol.

    Science.gov (United States)

    Feng, Yuquan; Qiu, Dongfang; Fan, Huitao; Li, Min; Huang, Qunzeng; Shi, Hengzhen

    2015-05-21

    A new 3-D open-framework cadmium borovanadate with 6-connected topology was hydrothermally obtained and structurally characterized. It not only features new cadmium(II) borovanadate which possesses an open-framework structure with unique plane-shaped channels, but also exhibits interesting absorption properties and high catalytic activities for the oxidation of cyclohexanol.

  20. Inflammatory events induced by Lys-49 and Asp-49 phospholipases A2 isolated from Bothrops asper snake venom: role of catalytic activity.

    Science.gov (United States)

    Zuliani, Juliana P; Fernandes, Cristina M; Zamuner, Stella R; Gutiérrez, José M; Teixeira, Catarina F P

    2005-03-01

    The inflammatory events induced in the peritoneal cavity of mice by two PLA2s isolated from Bothrops asper snake venom were investigated. MT-III, an Asp-49 catalytically active enzyme and MT-II, a catalytically inactive Lys-49 variant induced increase in vascular permeability. Inhibition of enzymatic activity of MT-III with p-bromophenacyl bromide reduced this effect. MT-III induced a larger neutrophil infiltrate than MT-II. This activity was significantly reduced after inhibition of catalytic activity. Reduction in the number of neutrophils was observed when antibodies against L-selectin, CD18 or LFA-1 were used, suggesting the involvement of these adhesion molecules in the effects of both PLA2s. There was no effect with antibodies against ICAM-1 and PECAM-1. Increase in the levels of LTB4 and TXA2, as well as of IL-1, IL-6 and TNF-alpha, were observed in the peritoneal exudates induced by MT-III. MT-II did not enhance levels of eicosanoids but increased those of cytokines. It is concluded that both PLA2s induce inflammatory events in this model. Since MT-III exerts a stronger proinflammatory effect, the enzymatic phospholipid hydrolysis may be relevant for these phenomena. However, the fact that MT-II induced inflammation suggests that molecular regions distinct from the catalytic site elicit inflammatory events perhaps by interacting with specific cell membrane acceptors.

  1. Synthesis, characterization and catalytic activity of stable [(NHC)H][ZnXY2] (NHC=N-Heterocyclic carbene, X, Y=Cl, Br) species

    KAUST Repository

    Santoro, Orlando

    2016-06-04

    The synthesis and characterization of imidazol(in)ium-based zinc(II) halide salts are reported. These compounds present interesting structural features and exhibit high stability. Their catalytic activity was explored in the methylation of amines with CO2 and PhSiH3.

  2. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

  3. Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

    Science.gov (United States)

    Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

    2007-01-01

    A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

  4. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    Directory of Open Access Journals (Sweden)

    Qiang Lu

    2018-02-01

    Full Text Available A new technique was proposed to co-produce phenol and activated carbon (AC from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g.

  5. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

    Science.gov (United States)

    Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

  6. Is TrpM5 a reliable marker for chemosensory cells? Multiple types of microvillous cells in the main olfactory epithelium of mice

    Directory of Open Access Journals (Sweden)

    Finger Thomas E

    2008-12-01

    Full Text Available Abstract Background In the past, ciliated receptor neurons, basal cells, and supporting cells were considered the principal components of the main olfactory epithelium. Several studies reported the presence of microvillous cells but their function is unknown. A recent report showed cells in the main olfactory epithelium that express the transient receptor potential channel TrpM5 claiming that these cells are chemosensory and that TrpM5 is an intrinsic signaling component of mammalian chemosensory organs. We asked whether the TrpM5-positive cells in the olfactory epithelium are microvillous and whether they belong to a chemosensory system, i.e. are olfactory neurons or trigeminally-innervated solitary chemosensory cells. Results We investigated the main olfactory epithelium of mice at the light and electron microscopic level and describe several subpopulations of microvillous cells. The ultrastructure of the microvillous cells reveals at least three morphologically different types two of which express the TrpM5 channel. None of these cells have an axon that projects to the olfactory bulb. Tests with a large panel of cell markers indicate that the TrpM5-positive cells are not sensory since they express neither neuronal markers nor are contacted by trigeminal nerve fibers. Conclusion We conclude that TrpM5 is not a reliable marker for chemosensory cells. The TrpM5-positive cells of the olfactory epithelium are microvillous and may be chemoresponsive albeit not part of the sensory apparatus. Activity of these microvillous cells may however influence functionality of local elements of the olfactory system.

  7. Is TrpM5 a reliable marker for chemosensory cells? Multiple types of microvillous cells in the main olfactory epithelium of mice.

    Science.gov (United States)

    Hansen, Anne; Finger, Thomas E

    2008-12-04

    In the past, ciliated receptor neurons, basal cells, and supporting cells were considered the principal components of the main olfactory epithelium. Several studies reported the presence of microvillous cells but their function is unknown. A recent report showed cells in the main olfactory epithelium that express the transient receptor potential channel TrpM5 claiming that these cells are chemosensory and that TrpM5 is an intrinsic signaling component of mammalian chemosensory organs. We asked whether the TrpM5-positive cells in the olfactory epithelium are microvillous and whether they belong to a chemosensory system, i.e. are olfactory neurons or trigeminally-innervated solitary chemosensory cells. We investigated the main olfactory epithelium of mice at the light and electron microscopic level and describe several subpopulations of microvillous cells. The ultrastructure of the microvillous cells reveals at least three morphologically different types two of which express the TrpM5 channel. None of these cells have an axon that projects to the olfactory bulb. Tests with a large panel of cell markers indicate that the TrpM5-positive cells are not sensory since they express neither neuronal markers nor are contacted by trigeminal nerve fibers. We conclude that TrpM5 is not a reliable marker for chemosensory cells. The TrpM5-positive cells of the olfactory epithelium are microvillous and may be chemoresponsive albeit not part of the sensory apparatus. Activity of these microvillous cells may however influence functionality of local elements of the olfactory system.

  8. Structural Insight into the Critical Role of the N-Terminal Region in the Catalytic Activity of Dual-Specificity Phosphatase 26.

    Directory of Open Access Journals (Sweden)

    Eun-Young Won

    Full Text Available Human dual-specificity phosphatase 26 (DUSP26 is a novel target for anticancer therapy because its dephosphorylation of the p53 tumor suppressor regulates the apoptosis of cancer cells. DUSP26 inhibition results in neuroblastoma cell cytotoxicity through p53-mediated apoptosis. Despite the previous structural studies of DUSP26 catalytic domain (residues 61-211, DUSP26-C, the high-resolution structure of its catalytically active form has not been resolved. In this study, we determined the crystal structure of a catalytically active form of DUSP26 (residues 39-211, DUSP26-N with an additional N-terminal region at 2.0 Å resolution. Unlike the C-terminal domain-swapped dimeric structure of DUSP26-C, the DUSP26-N (C152S monomer adopts a fold-back conformation of the C-terminal α8-helix and has an additional α1-helix in the N-terminal region. Consistent with the canonically active conformation of its protein tyrosine phosphate-binding loop (PTP loop observed in the structure, the phosphatase assay results demonstrated that DUSP26-N has significantly higher catalytic activity than DUSP26-C. Furthermore, size exclusion chromatography-multiangle laser scattering (SEC-MALS measurements showed that DUSP26-N (C152S exists as a monomer in solution. Notably, the crystal structure of DUSP26-N (C152S revealed that the N-terminal region of DUSP26-N (C152S serves a scaffolding role by positioning the surrounding α7-α8 loop for interaction with the PTP-loop through formation of an extensive hydrogen bond network, which seems to be critical in making the PTP-loop conformation competent for phosphatase activity. Our study provides the first high-resolution structure of a catalytically active form of DUSP26, which will contribute to the structure-based rational design of novel DUSP26-targeting anticancer therapeutics.

  9. 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.

  10. 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.

  11. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO2

    International Nuclear Information System (INIS)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik; Hong, Jongki; Lee, Won Woong; Ryu, Jung Bok

    2017-01-01

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li a X a+1 ] − are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl − are non-corrosive under the carboxylation condition

  12. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik [Dept. of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, Seoul (Korea, Republic of); Hong, Jongki; Lee, Won Woong [College of Pharmacy, Kyung Hee University, Seoul (Korea, Republic of); Ryu, Jung Bok [R and D Center, Chuncheon (Korea, Republic of)

    2017-02-15

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li{sub a} X{sub a+1}]{sup −} are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl{sup −} are non-corrosive under the carboxylation condition.

  13. Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

    Energy Technology Data Exchange (ETDEWEB)

    Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

    2016-05-30

    Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

  14. Ambient Temperature Hydrocarbon Selective Catalytic Reduction of NOx Using Atmospheric Pressure Nonthermal Plasma Activation of a Ag/Al2O3 Catalyst

    OpenAIRE

    Stere, Cristina E.; Adress, Wameedh; Burch, Robbie; Chansai, Sarayute; Goguet, Alexandre; Graham, William G.; De Rosa, Fabio; Palma, Vincenzo; Hardacre, Christopher

    2014-01-01

    Atmospheric pressure nonthermal-plasma-activated catalysis for the removal of NOx using hydrocarbon selective catalytic reduction has been studied utilizing toluene and n-octane as the hydrocarbon reductant. When the plasma was combined with a Ag/Al2O3 catalyst, a strong enhancement in activity was observed when compared with conventional thermal activation with high conversions of both. NOx and hydrocarbons obtained at temperature at temperature ≤250 °C, where the silver catalyst is normally...

  15. Effect of Val 73 --> Trp mutation on the reaction of "cambialistic" superoxide dismutase from Propionibacterium shermanii with hydrogen peroxide.

    Science.gov (United States)

    Gabbianelli, R; Battistoni, A; Capo, C; Polticelli, F; Rotilio, G; Meier, B; Desideri, A

    1997-09-01

    The H2O2 inactivation of the "cambialistic" superoxide dismutases from Propionibacterium shermanii, which is active with either iron or manganese at the active site, has been studied in the native and Val 73 --> Trp mutant enzymes. The wild-type iron-containing form of this enzyme is much more resistant to treatment with H2O2 with respect to the other metal-specific Fe superoxide dismutase isoenzymes. After incubation with high amounts of H2O2 the enzyme maintains more than 40% of the initial activity. The activity of the Val 73 --> Trp mutant drastically decreases to less than 5% of the initial activity after incubation with hydrogen peroxide. Amino acid analysis of the H2O2-treated mutant enzyme evidenced the loss of the Trp 73 residue which is shown to play a critical role in the stabilization of the monomer fold of the enzyme. On the other hand, the manganese-containing wild-type and mutant enzymes were completely resistant toward H2O2 demonstrating the specific role of iron in the inactivation process.

  16. Probing the nanoscale structure of the catalytically active overlayer on Pt alloys with rare earths

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Ulrikkeholm, Elisabeth Therese; Escribano, Maria Escudero

    2016-01-01

    PtxY and PtxGd exhibit exceptionally high activity for oxygen reduction, both in the polycrystalline form and the nanoparticulate form. In order to understand the origin of the enhanced activity of these alloys, we have investigated thin films of these alloys on bulk Pt(111) crystals, i.e. Y/Pt(111...

  17. Catalytic activity and stability of xanthine oxidase in aqueous-organic mixtures.

    Science.gov (United States)

    Rashidi, M R; Soruraddin, M H; Taherzadeh, F; Jouyban, A

    2009-01-01

    In the present study, bovine milk xanthine oxidase activity in various aqueous-organic mixtures and the effects of pH, temperature, and lyophilization on the enzyme activity have been investigated. The enzyme was incubated with xanthine as the substrate in Sorenson's phosphate buffer (pH 7.0) containing 0.1 mM EDTA, and the activity was determined spectrophotometrically in the absence and presence of different fractions of nine water-miscible organic solvents at 27-50 degrees C and at different pH values ranging from 6 to 9. The organic solvents reduced the enzyme activity to different extents. In spite of these inhibitory effects, the enzyme showed relatively good stability in the aqueous-organic mixtures compared with the aqueous medium. A significant increase in the activity of the lyophilized enzyme was observed in pure organic solvents.

  18. Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

    Science.gov (United States)

    Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

    2017-10-01

    Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

  19. Microwave-Assisted Synthesis of Fe3O4Nanocrystals with Predominantly Exposed Facets and Their Heterogeneous UVA/Fenton Catalytic Activity.

    Science.gov (United States)

    Zhong, Yuanhong; Yu, Lin; Chen, Zhi-Feng; He, Hongping; Ye, Fei; Cheng, Gao; Zhang, Qianxin

    2017-08-30

    Fe 3 O 4 nanocrystals with five different morphologies (i.e., nanospheres, nanorods, nanocubes, nano-octahedrons, and nanoplates) were acquired using a simple, efficient, and economic microwave-assisted oxidation technique. The microstructure, morphology, predominant exposed facets, and iron atom local environment of Fe 3 O 4 were revealed by powder X-ray diffraction (PXRD), scanning transmission electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometer (XPS), and Mössbauer spectrum. We demonstrated that the heterogeneous UVA/Fenton catalytic activities of Fe 3 O 4 nanocrystals are morphology/facets dependent. Under UVA irradiation, the catalytic activity of the as-prepared Fe 3 O 4 was in the sequence of nanospheres > nanoplates > nano-octahedrons ≈ nanocubes > nanorods > nano-octahedrons (by coprecipitation). The dominating factor for the catalytic performance was the particle size and BET specific surface area; moreover, the exposed {111} facets, which contained more Fe 2+ species, on the nanocrystal surface led to a stronger UVA/Fenton catalytic activity. Both • OH and O 2 •- radicals participated in the UVA/Fenton degradation process, and • OH played the dominant role. These morphology-controlled nanomagnetites showed great potential in applications as heterogeneous UVA/Fenton catalysts for effectively treating nonbiodegradable organic pollutants.

  20. Catalytic synthesis and antioxidant activity of sulfated polysaccharide from Momordica charantia L.

    Science.gov (United States)

    Liu, Xin; Chen, Tong; Hu, Yan; Li, Kexin; Yan, Liushui

    2014-03-01

    Sulfated derivatives of polysaccharide from Momordica charantia L. (MCPS) with different degree of sulfation (DS) were synthesized by chlorosulfonic acid method with ionic liquids as solvent. Fourier transform infrared spectra and 13C nuclear magnetic resonance spectra indicated that C-6 substitution was predominant in MCPS compared with the C-2 position. Compared with the native polysaccharide from Momordica charantia L. (MCP), MCPS exhibited more excellent antioxidant activities in vitro, which indicated that sulfated modification could enhance antioxidant activities of MCP. Furthermore, high DS and moderate molecular weight could improve the antioxidant activities of polysaccharide. Copyright © 2013 Wiley Periodicals, Inc.

  1. THE INFLUENCE OF Pd IMPREGNATION INTO Al-MCM-41 ON THE CHARACTERS AND ACTIVITY FOR BIOGASOLINE PRODUCTION BY CATALYTIC HYDROCRACKING OF FAMEs FROM NYAMPLUNG SEED OIL (Calophyllum Inophyllum)

    OpenAIRE

    Juwono, Hendro; Triyono, Triyono; Sutarno, Sutarno; Wahyuni, Endang Tri

    2013-01-01

    Biogasoline have been synthesized through catalytic hydrocracking reaction against FAMEs compounds (fatty acid methyl esters) obtained from the transesterification of Nyamplung seed oil. The performance of Al-MCM-41 and Pd/Al-MCM-41 as the catalytic hydrocracking was compared. In this research, the influence of Pd impregnation into Al-MCM-41 catalyst on the characters and catalytic activity has been evaluated. The characters determined were crystallinity by using X-Ray Diffractometer (XRD), S...

  2. Iron-substituted cubic silsesquioxane pillared clays : Synthesis, characterization and acid catalytic activity

    NARCIS (Netherlands)

    Potsi, Georgia; Ladavos, Athanasios K.; Petrakis, Dimitrios; Douvalis, Alexios P.; Sanakis, Yiannis; Katsiotis, Marios S.; Papavassiliou, Georgios; Alhassan, Saeed; Gournis, Dimitrios; Rudolf, Petra

    2018-01-01

    Novel pillared structures were developed from the intercalation of iron-substituted cubic silsesquioxanes in a sodium and an acid-activated montmorillonite nanoclay and evaluated as acid catalysts. Octameric cubic oligosiloxanes were formed upon controlled hydrolytic polycondensation of the

  3. 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

  4. Structural plasticity among glutathione transferase Phi members: natural combination of catalytic residues confers dual biochemical activities.

    Science.gov (United States)

    Pégeot, Henri; Mathiot, Sandrine; Perrot, Thomas; Gense, Frédéric; Hecker, Arnaud; Didierjean, Claude; Rouhier, Nicolas

    2017-08-01

    The glutathione transferase (GST) gene family is divided into 14 classes in photosynthetic organisms. Among them, the Phi class (GSTF) is composed of a large number of genes that are often induced in response to environmental constraints due to their ability to detoxify xenobiotics, to their peroxidase activity and to their involvement in the biosynthesis and/or transport of secondary metabolites. However, the exact functions of GSTFs from many plants including Populus trichocarpa are unknown. Here, following GSTF1 characterization, we have performed a comparative analysis of the seven other GSTFs found in poplar by systematically evaluating the biochemical and enzymatic properties of the corresponding recombinant proteins and of variants mutated for active site residues and by determining the three-dimensional structures of several representatives. Owing to the presence of a cysteine with a pK a value around 5 in their active site, GSTF3, F7, and F8 displayed a thiol transferase activity in addition to the usual glutathione transferase and peroxidase activities. From structural analyses, it appeared that these dual biochemical properties originate from the existence of a certain variability in the β1-α1 loop. This allows positioning of several active site residues at proximity of the glutathione molecule, which itself remains unchanged in GSTF three-dimensional structures. These results highlight the promiscuity of some GSTFs and that changes of active site residues in some isoforms during evolution generated functional diversity by modifying their activity profile. Structural data are available in the PDB under the accession numbers 5EY6, 5F05, 5F06, and 5F07. © 2017 Federation of European Biochemical Societies.

  5. Understanding the catalytic benefits of multi=metallic active sites in microporous aluminophosphates

    OpenAIRE

    Potter, Matthew

    2015-01-01

    Structure-property correlations, which direct the formation of specific active-acid sites, in nanoporous materials have been explored with the aim to further the notion of rational catalyst design. It is demonstrated that the influence of the specific zeotype framework extends beyond modulating Brønsted acidity, with the framework topology playing a fundamental role in reaction kinetics. The structural integrity and nature of the active site has been probed using a combined catalysis and mult...

  6. Catalytic activity control of restriction endonuclease--triplex forming oligonucleotide conjugates.

    Science.gov (United States)

    Silanskas, Arunas; Zaremba, Mindaugas; Sasnauskas, Giedrius; Siksnys, Virginijus

    2012-02-15

    Targeting of individual genes in complex genomes requires endonucleases of extremely high specificity. To direct cleavage at the unique site(s) in the genome, both naturally occurring and artificial enzymes have been developed. These include homing endonucleases, zinc-finger nucleases, transcription activator-like effector nucleases, and restriction or chemical nucleases coupled to a triple-helix forming oligonucleotide (TFO). The desired cleavage has been demonstrated both in vivo and in vitro for several model systems. However, to limit cleavage strictly to unique sites and avoid undesired reactions, endonucleases with controlled activity are highly desirable. In this study we present a proof-of-concept demonstration of two strategies to generate restriction endonuclease-TFO conjugates with controllable activity. First, we combined the restriction endonuclease caging and TFO coupling procedures to produce a caged MunI-TFO conjugate, which can be activated by UV-light upon formation of a triple helix. Second, we coupled TFO to a subunit interface mutant of restriction endonuclease Bse634I which shows no activity due to impaired dimerization but is assembled into an active dimer when two Bse634I monomers are brought into close proximity by triple helix formation at the targeted site. Our results push the restriction endonuclease-TFO conjugate technology one step closer to potential in vivo applications.

  7. Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

    Science.gov (United States)

    Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

    2017-12-01

    Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

  8. Biosynthesis of silver nanoparticles using Momordica charantia leaf broth: Evaluation of their innate antimicrobial and catalytic activities.

    Science.gov (United States)

    Ajitha, B; Reddy, Y Ashok Kumar; Reddy, P Sreedhara

    2015-05-01

    Silver nanoparticles (AgNPs) were prepared through green route with the aid of Momordica charantia leaf extract as both reductant and stabilizer. X-ray diffraction pattern (XRD) and selected area electron diffraction (SAED) fringes revealed the structure of AgNPs as face centered cubic (fcc). Morphological studies elucidate the nearly spherical AgNPs formation with particle size in nanoscale. Biosynthesized AgNPs were found to be photoluminescent and UV-Vis absorption spectra showed one surface plasmon resonance peak (SPR) at 424nm attesting the spherical nanoparticles formation. XPS study provides the surface chemical nature and oxidation state of the synthesized nanoparticles. FTIR spectra ascertain the reduction and capping nature of phytoconstituents of leaf extract in AgNPs synthesis. Further, these AgNPs showed effective antimicrobial activity against tested pathogens and thus applicable as potent antimicrobial agent. In addition, the synthesized AgNPs were observed to have an excellent catalytic activity on the reduction of methylene blue by M. charantia which was confirmed by the decrement in maximum absorbance values of methylene blue with respect to time and is ascribed to electron relay effect. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes

    Science.gov (United States)

    Yu, Renyuan Pony; Darmon, Jonathan M.; Milsmann, Carsten; Margulieux, Grant W.; E. Stieber, S. Chantal; DeBeer, Serena

    2013-01-01

    The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, (iPrCNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, (iPrCNC)CoCH3 is an effective pre-catalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, (iPrCNC)CoH was accomplished by hydrogenation of (iPrCNC)CoCH3. Over the course of 3 hours at 22 °C, migration of the metal-hydride to the 4-position of the pyridine ring yielded (4-H2-iPrCNC)CoN2. Similar alkyl migration was observed upon treatment of (iPrCNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redoxactive, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity and suggest a wide family of pyridine-based pincers may also be redox active. PMID:23968297

  10. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  11. Formation of carbon nanosheets via simultaneous activation and catalytic carbonization of macroporous anion-exchange resin for supercapacitors application.

    Science.gov (United States)

    Peng, Hui; Ma, Guofu; Sun, Kanjun; Mu, Jingjing; Zhang, Zhe; Lei, Ziqiang

    2014-12-10

    Two-dimensional mesoporous carbon nanosheets (CNSs) have been prepared via simultaneous activation and catalytic carbonization route using macroporous anion-exchange resin (AER) as carbon precursor and ZnCl2 and FeCl3 as activating agent and catalyst, respectively. The iron catalyst in the skeleton of the AER may lead to carburization to form a sheetlike structure during the carbonization process. The obtained CNSs have a large number of mesopores, a maximum specific surface area of 1764.9 m(2) g(-1), and large pore volume of 1.38 cm(3) g(-1). As an electrode material for supercapacitors application, the CNSs electrode possesses a large specific capacitance of 283 F g(-1) at 0.5 A g(-1) and excellent rate capability (64% retention ratio even at 50 A g(-1)) in 6 mol L(-1) KOH. Furthermore, CNSs symmetric supercapacitor exhibits specific energies of 17.2 W h kg(-1) at a power density of 224 W kg(-1) operated in the voltage range of 0-1.8 V in 0.5 mol L(-1) Na2SO4 aqueous electrolyte, and outstanding cyclability (retains about 96% initial capacitance after 5000 cycles).

  12. Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

    Science.gov (United States)

    Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

    2018-03-01

    Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

  13. Effect of L-arginine on the catalytic activity and stability of nickel nanoparticles for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2012-10-01

    Amorphous nickel catalysts were synthesized by reducing the nickel(II) species in an aqueous NaBH4/NH3BH3 solution with and without L-arginine. The nickel catalyst with L-arginine maintains relatively high activity for hydrolysis of NH3BH3 to generate a stoichiometric amount of hydrogen with the cycle number up to 11 (827 mL s-1 (mol-Ni)-1 at the 11th cycle with L-arginine = 35 mg), while the reaction rate in the presence of the bare nickel catalyst was relatively low through the cycle number up to 11 (232 mL s-1 (mol-Ni)-1 at the 11th cycle). After catalytic reaction, the nickel catalyst with L-arginine possesses the high dispersion (diameters of nickel nanoparticles L-arginine maintains the dispersion of nickel nanoparticles (diameters of nickel nanoparticles <10 nm), leading to higher activity against cycle tests than the bare nickel catalyst.

  14. Biosynthesis of Copper Oxide nanoparticles from Drypetes sepiaria Leaf extract and their catalytic activity to dye degradation

    Science.gov (United States)

    Narasaiah, Palajonna; Mandal, Badal Kumar; Sarada, N. C.

    2017-11-01

    The synthesis of metal nanoparticles through a green method is a rapid biogenic and offers few advantages over the common chemical and physical procedures, as it is an easy and fast, eco-friendly and does not involve any costly chemicals as well as hazardous chemicals. In this study, we report synthesis of CuO NPs by using Drypetes sepiaria Leaf extract (DSLE). The synthesized CuO NPs was characterization using different technique such as UV, IR, XRD, and TEM. The formation of CuO NPs was confirmed by Surface Plasmon Resonance (SRP) at 298 nm using UV-Vis spectroscopy. Crystallinity of CuO NPs was confirmed by powder XRD and the characteristic functional groups of synthesised CuO NPs were identified by FTIR spectroscopy. The size and shape of the synthesized CuO NPs was determined by transmission electron microscopy (TEM). In addition, we performed photocatalytic activity to examine the photocatalytic degradation efficiency of CuO NPs to Congo Red. The colloidal solutions of CuO NPs showed good catalytic activity.

  15. Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV–vis spectra: A comparative kinetic study

    International Nuclear Information System (INIS)

    Ankamwar, Balaprasad; Kamble, Vaishali; Sur, Ujjal Kumar; Santra, Chittaranjan

    2016-01-01

    Graphical abstract: - Highlights: • The biosynthesized silver nanoparticles were stable for 6 months and used as effective SERS active substrate. • They are effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. • Comparative catalytic efficiency of both silver and gold nanoparticles was studied spectrophotometrically. • Our results demonstrate surface morphology dependent catalytic activity of both nanoparticles. - Abstract: The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV–vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir–Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.

  16. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni{sub 2}P supported on active carbon

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yanli [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Sang, Huanxin [Tianjin Academy of Environmental Sciences, Tianjin 300191 (China); Wang, Kang [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wang, Xitao, E-mail: wangxt@tju.edu.cn [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Graphical abstract: - Highlights: • Ni{sub 2}P catalyst is tested in dehydrogenation of isobutane for the first time. • The effects of Cs promoter on catalytic performance of Ni2P/AC were investigated. • Cs-Ni2P/AC exhibits high activity and selectivity for isobutane dehydrogenation. - Abstract: In this article, an environmentally friendly non-noble-metal class of Cs-Ni{sub 2}P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H{sub 2}-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni{sub 2}P particles, which decreases the strength of Ni-C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni{sub 2}P/AC catalysts display much higher catalytic performance as compared to Ni{sub 2}P/AC catalyst. Cs-Ni{sub 2}P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni{sub 2}P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  17. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang

    2018-01-23

    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  18. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  19. Selective metal binding to Cys-78 within endonuclease V causes an inhibition of catalytic activities without altering nontarget and target DNA binding

    International Nuclear Information System (INIS)

    Prince, M.A.; Friedman, B.; Gruskin, E.A.; Schrock, R.D. III; Lloyd, R.S.

    1991-01-01

    T4 endonuclease V is a pyrimidine dimer-specific DNA repair enzyme which has been previously shown not to require metal ions for either of its two catalytic activities or its DNA binding function. However, we have investigated whether the single cysteine within the enzyme was able to bind metal salts and influence the various activities of this repair enzyme. A series of metals (Hg2+, Ag+, Cu+) were shown to inactivate both endonuclease Vs pyrimidine dimer-specific DNA glycosylase activity and the subsequent apurinic nicking activity. The binding of metal to endonuclease V did not interfere with nontarget DNA scanning or pyrimidine dimer-specific binding. The Cys-78 codon within the endonuclease V gene was changed by oligonucleotide site-directed mutagenesis to Thr-78 and Ser-78 in order to determine whether the native cysteine was directly involved in the enzyme's DNA catalytic activities and whether the cysteine was primarily responsible for the metal binding. The mutant enzymes were able to confer enhanced ultraviolet light (UV) resistance to DNA repair-deficient Escherichia coli at levels equal to that conferred by the wild type enzyme. The C78T mutant enzyme was purified to homogeneity and shown to be catalytically active on pyrimidine dimer-containing DNA. The catalytic activities of the C78T mutant enzyme were demonstrated to be unaffected by the addition of Hg2+ or Ag+ at concentrations 1000-fold greater than that required to inhibit the wild type enzyme. These data suggest that the cysteine is not required for enzyme activity but that the binding of certain metals to that amino acid block DNA incision by either preventing a conformational change in the enzyme after it has bound to a pyrimidine dimer or sterically interfering with the active site residue's accessibility to the pyrimidine dimer

  20. Structure and catalytic activation of the TRIM23 RING E3 ubiquitin ligase: DAWIDZIAK et al.

    Energy Technology Data Exchange (ETDEWEB)

    Dawidziak, Daria M. [Department of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville Virginia; Sanchez, Jacint G. [Department of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville Virginia; Wagner, Jonathan M. [Department of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville Virginia; Ganser-Pornillos, Barbie K. [Department of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville Virginia; Pornillos, Owen [Department of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville Virginia

    2017-07-24

    Tripartite motif (TRIM) proteins comprise a large family of RING-type ubiquitin E3 ligases that regulate important biological processes. An emerging general model is that TRIMs form elongated antiparallel coiled-coil dimers that prevent interaction of the two attendant RING domains. The RING domains themselves bind E2 conjugating enzymes as dimers, implying that an active TRIM ligase requires higher-order oligomerization of the basal coiled-coil dimers. Here, we report crystal structures of the TRIM23 RING domain in isolation and in complex with an E2–ubiquitin conjugate. Our results indicate that TRIM23 enzymatic activity requires RING dimerization, consistent with the general model of TRIM activation.

  1. Effects of the ratio of Cu/Co and metal precursors on the catalytic activity over Cu-Co/Al2O3 prepared using the polyol process

    International Nuclear Information System (INIS)

    Lu Chiyuan; Tseng, H.-H.; Wey Mingyen; Liu Lingyi; Chuang, K.-H.

    2009-01-01

    Cu-Co bimetallic catalysts were prepared using a simple polyol process. The effects of various metal precursors (nitrate, acetate, and chloride) and Cu/Co ratios on the activities of the catalysts were evaluated for toluene oxidation and NO reduction. The results indicated that the use of the metal precursor Cu-Co acetate in preparing the bimetallic catalysts resulted in good metal dispersion and high catalytic activity. When the atomic Cu/Co ratio was 0.21 in the Al 2 O 3 -supported catalyst, the dispersion of active sites was promoted by the Cu, and the catalytic activity was stable over the reaction time. CuO and Cu 0 species and large particle sizes (20 nm) formed when the Co loading weight in the catalyst increased, and conversion decreased. When the reaction temperature was 300 deg. C, NO and toluene were able to be simultaneously removed with high conversion rates (83% and 98%)

  2. 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.

  3. 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

  4. A Catalytically Active Membrane Reactor for Fast, Highly Exothermic, Heterogeneous Gas Reactions. A Pilot Plant Study

    NARCIS (Netherlands)

    Veldsink, Jan W.; Versteeg, Geert F.; Swaaij, Wim P.M. van

    1995-01-01

    Membrane reactors have been frequently studied because of their ability to combine chemical activity and separation properties into one device. Due to their thermal stability and mechanical strength, ceramic membranes are preferred over polymeric ones, but small transmembrane fluxes obstruct a

  5. Electrically active, doped monocrystalline silicon nanoparticles produced by hot wire thermal catalytic pyrolysis

    CSIR Research Space (South Africa)

    Scriba, MR

    2011-05-01

    Full Text Available particles have clean surfaces and are electrically active, with compacted powder having a resistivity of the order of 103 O m, phosphorus doped particles are covered by an oxide layer whose thickness increases from 0.3 nm to 0.6 nm with higher phosphine...

  6. Facile synthesis of catalytically active CeO 2-Gd 2 O 3 solid ...

    Indian Academy of Sciences (India)

    Raman studies further confirmed the presence of oxygen vacancies and lattice defects in the CG sample. TPR measurements indicated a facile reduction of ceria after Gd3+ addition. Activity studies revealed that incorporation of Gd3+ into the ceria matrix favoured the creation of more structural defects, which accelerates the ...

  7. Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

    Science.gov (United States)

    Li, Maoguo; Yu, Muping; Li, Xiang

    2018-05-01

    Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

  8. A structurally characterized Ni-Al methyl-bridged complex with catalytic ethylene oligomerization activity.

    Science.gov (United States)

    Weng, Zhiqiang; Teo, Shihui; Koh, Lip Lin; Hor, T S Andy

    2006-03-28

    A bimetallic Ni-Al (2.5087(15) A) complex with an agostic alpha-C-H, [eta-C5H4CH=N(C6F5)]Fe[eta-C5H4PPh2]Ni(AlMe3), has been isolated and crystallographically established. The complex is active towards ethylene oligomerization/polymerization under moderate conditions.

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

    Indian Academy of Sciences (India)

    dithiolate-bridged di-iron com- plexes have been investigated in modelling the active sites of [FeFe]-H2ases. However, the reports of elec- trochemical data on ene-1,2-dithiolate-bridged-{Fe2S2} complexes are scarce. In this study, compound [Fe2{µ-.

  10. Supported rhodium catalysts for ammonia-borane hydrolysis. Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Liangbing; Li, Hongliang; Zhang, Wenbo; Zhao, Xiao; Qiu, Jianxiang; Li, Aowen; Zheng, Xusheng; Zeng, Jie [Hefei National Lab. for Physical Sciences at the Microscale, Key Lab. of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences, Hefei, Anhui(China); Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui (China); Hu, Zhenpeng [School of Physics, Nankai University, Tianjin (China); Si, Rui [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Aca