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Sample records for catalytically active trp

  1. Spectroscopic evidence for an engineered, catalytically active Trp radical that creates the unique reactivity of lignin peroxidase.

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    Smith, Andrew T; Doyle, Wendy A; Dorlet, Pierre; Ivancich, Anabella

    2009-09-22

    The surface oxidation site (Trp-171) in lignin peroxidase (LiP) required for the reaction with veratryl alcohol a high-redox-potential (1.4 V) substrate, was engineered into Coprinus cinereus peroxidase (CiP) by introducing a Trp residue into a heme peroxidase that has similar protein fold but lacks this activity. To create the catalytic activity toward veratryl alcohol in CiP, it was necessary to reproduce the Trp site and its negatively charged microenvironment by means of a triple mutation. The resulting D179W+R258E+R272D variant was characterized by multifrequency EPR spectroscopy. The spectra unequivocally showed that a new Trp radical [g values of g(x) = 2.0035(5), g(y) = 2.0027(5), and g(z) = 2.0022(1)] was formed after the [Fe(IV)=O Por(*+)] intermediate, as a result of intramolecular electron transfer between Trp-179 and the porphyrin. Also, the EPR characterization crucially showed that [Fe(IV)=O Trp-179(*)] was the reactive intermediate with veratryl alcohol. Accordingly, our work shows that it is necessary to take into account the physicochemical properties of the radical, fine-tuned by the microenvironment, as well as those of the preceding [Fe(IV)=O Por(*+)] intermediate to engineer a catalytically competent Trp site for a given substrate. Manipulation of the microenvironment of the Trp-171 site in LiP allowed the detection by EPR spectroscopy of the Trp-171(*), for which direct evidence has been missing so far. Our work also highlights the role of Trp residues as tunable redox-active cofactors for enzyme catalysis in the context of peroxidases with a unique reactivity toward recalcitrant substrates that require oxidation potentials not realized at the heme site.

  2. Time-resolved EPR studies with DNA photolyase: excited-state FADH0 abstracts an electron from Trp-306 to generate FADH-, the catalytically active form of the cofactor.

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    Kim, S T; Sancar, A; Essenmacher, C; Babcock, G T

    1993-09-01

    Photolyase repairs UV-induced cyclobutane-pyrimidine dimers in DNA by photoinduced electron transfer. The enzyme isolated from Escherichia coli contains 5,10-methenyltetrahydrofolate, which functions as the light-harvesting chromophore, and fully reduced flavin adenine dinucleotide (FAD), which functions as the redox catalyst. During enzyme preparation, the flavin is oxidized to FADH0, which is catalytically inert. Illumination of the enzyme with 300- to 600-nm light converts the flavin to the fully reduced form in a reaction that involves photooxidation of an amino acid in the apoenzyme. The results of earlier optical studies had indicated that the redox-active amino acid in this photoactivation process was tryptophan. We have now used time-resolved electron paramagnetic resonance (EPR) spectroscopy to investigate the photoactivation reaction. Excitation of the flavin-radical-containing inactive enzyme produces a spin-polarized radical that we identify by 2H and 15N labeling as originating from a tryptophan residue, confirming the inferences from the optical work. These results and Trp-->Phe replacement by site-directed mutagenesis reveal that flavin radical photoreduction is achieved by electron abstraction from Trp-306 by the excited-state FADH0. Analysis of the hyperfine couplings and spin density distribution deduced from the isotopic-labeling results shows that the product of the light-driven redox chemistry is the Trp-306 cation radical. The results strongly suggest that the active form of photolyase contains FADH- and not FADH2.

  3. Human salivary alpha-amylase Trp58 situated at subsite -2 is critical for enzyme activity.

    Science.gov (United States)

    Ramasubbu, Narayanan; Ragunath, Chandran; Mishra, Prasunkumar J; Thomas, Leonard M; Gyémánt, Gyöngyi; Kandra, Lili

    2004-06-01

    The nonreducing end of the substrate-binding site of human salivary alpha-amylase contains two residues Trp58 and Trp59, which belong to beta2-alpha2 loop of the catalytic (beta/alpha)(8) barrel. While Trp59 stacks onto the substrate, the exact role of Trp58 is unknown. To investigate its role in enzyme activity the residue Trp58 was mutated to Ala, Leu or Tyr. Kinetic analysis of the wild-type and mutant enzymes was carried out with starch and oligosaccharides as substrates. All three mutants exhibited a reduction in specific activity (150-180-fold lower than the wild type) with starch as substrate. With oligosaccharides as substrates, a reduction in k(cat), an increase in K(m) and distinct differences in the cleavage pattern were observed for the mutants W58A and W58L compared with the wild type. Glucose was the smallest product generated by these two mutants in the hydrolysis oligosaccharides; in contrast, wild-type enzyme generated maltose as the smallest product. The production of glucose by W58L was confirmed from both reducing and nonreducing ends of CNP-labeled oligosaccharide substrates. The mutant W58L exhibited lower binding affinity at subsites -2, -3 and +2 and showed an increase in transglycosylation activity compared with the wild type. The lowered affinity at subsites -2 and -3 due to the mutation was also inferred from the electron density at these subsites in the structure of W58A in complex with acarbose-derived pseudooligosaccharide. Collectively, these results suggest that the residue Trp58 plays a critical role in substrate binding and hydrolytic activity of human salivary alpha-amylase.

  4. Time-resolved EPR studies with DNA photolyase: excited-state FADH0 abstracts an electron from Trp-306 to generate FADH-, the catalytically active form of the cofactor.

    OpenAIRE

    1993-01-01

    Photolyase repairs UV-induced cyclobutane-pyrimidine dimers in DNA by photoinduced electron transfer. The enzyme isolated from Escherichia coli contains 5,10-methenyltetrahydrofolate, which functions as the light-harvesting chromophore, and fully reduced flavin adenine dinucleotide (FAD), which functions as the redox catalyst. During enzyme preparation, the flavin is oxidized to FADH0, which is catalytically inert. Illumination of the enzyme with 300- to 600-nm light converts the flavin to th...

  5. Role of Non-Active-Site Residue Trp-93 in the Function and Stability of New Delhi Metallo-β-Lactamase 1

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    Rehman, M. Tabish

    2015-01-01

    New Delhi metallo-β-lactamase-1 (NDM-1) is expressed by various members of Enterobacteriaceae as a defense mechanism to hydrolyze β-lactam antibiotics. Despite various studies showing the significance of active-site residues in the catalytic mechanism, there is a paucity of reports addressing the role of non-active-site residues in the structure and function of NDM-1. In this study, we investigated the significance of non-active-site residue Trp-93 in the structure and function of NDM-1. We cloned blaNDM-1 from an Enterobacter cloacae clinical strain (EC-15) and introduced the mutation of Trp-93 to Ala (yielding the Trp93Ala mutant) by PCR-based site-directed mutagenesis. Proteins were expressed and purified to homogeneity by affinity chromatography. The MICs of the Trp93Ala mutant were reduced 4- to 8-fold for ampicillin, cefotaxime, ceftazidime, cefoxitin, imipenem, and meropenem. The poor hydrolytic activity of the Trp93Ala mutant was also reflected by its reduced catalytic efficiency. The overall catalytic efficiency of the Trp93Ala mutant was reduced by 40 to 55% (the Km was reduced, while the kcat was similar to that of wild-type NDM-1 [wtNDM-1]). Heat-induced denaturation showed that the ΔGDo and Tm of Trp93Ala mutant were reduced by 1.8 kcal/mol and 4.8°C, respectively. Far-UV circular dichroism (CD) analysis showed that the α-helical content of the Trp93Ala mutant was reduced by 2.9%. The decrease in stability and catalytic efficiency of the Trp93Ala mutant was due to the loss of two hydrogen bonds with Ser-63 and Val-73 and hydrophobic interactions with Leu-65, Val-73, Gln-123, and Asp-124. The study provided insight into the role of non-active-site amino acid residues in the hydrolytic mechanism of NDM-1. PMID:26525789

  6. Caffeine and other methylxanthines as interceptors of food-borne aromatic mutagens: inhibition of Trp-P-1 and Trp-P-2 mutagenic activity.

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    Woziwodzka, Anna; Gołuński, Grzegorz; Wyrzykowski, Dariusz; Kaźmierkiewicz, Rajmund; Piosik, Jacek

    2013-11-18

    Caffeine is one of the most important biologically active food components. In this article, we demonstrate that caffeine and other methylxanthines significantly reduce the mutagenic activity of two food-derived heterocyclic aromatic amines, Trp-P-1 and Trp-P-2 in the Salmonella typhimurium TA98 strain. Moreover, protection against Trp-P-1-induced mutagenicity was independent of liver S9 enzymatic fraction, suggesting that mechanisms other than modulation of mutagen bioactivation can contribute to the observed protective effects. UV-vis spectroscopy and computational studies revealed that methylxanthines intercept Trp-P-1 and Trp-P-2 in noncovalent molecular complexes, with association constants (KAC) in the 10(2) M(-1) range. Enthalpy values (ΔH about -30 kJ·mol(-1)) of mutagen-methylxanthine heterocomplexation obtained microcalorimetrically correspond to stacking (π-π) interactions. Finally, we demonstrated that the biological activity of Trp-P-1 and Trp-P-2 is strictly dependent on the presence of the mutagen in a free (unbound with methylxanthine) form, suggesting that mutagen sequestration in stacking heterocomplexes with methylxanthines can decrease its bioavailability and diminish its biological effects.

  7. A structural view of ligand-dependent activation in thermoTRP channels

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    Ximena eSteinberg

    2014-05-01

    Full Text Available Transient Receptor Potential (TRP proteins are a large family of ion channels, grouped intoseven sub-families. Although great advances have been made regarding the activation andmodulation of TRP channel activity, detailed molecular mechanisms governing TRPchannel gating are still needed. Sensitive to electric, chemical, mechanical, and thermalcues, TRP channels are tightly associated with the detection and integration of sensoryinput, emerging as a model to study the polymodal activation of ion channel proteins.Among TRP channels, the temperature-activated kind constitute a subgroup by itself,formed by Vanilloid receptors 1-4, Melastatin receptors 2, 4, 5 and 8, TRPC5, and TRPA1.Some of the so-called thermoTRP channels participate in the detection of noxious stimulimaking them an interesting pharmacological target for the treatment of pain. However, thepoor specificity of the compounds available in the market represents an important obstacleto overcome. Understanding the molecular mechanics underlying ligand-dependentmodulation of TRP channels may help with the rational design of novel syntheticanalgesics. The present review focuses on the structural basis of ligand-dependentactivation of TRPV1 and TRPM8 channels. Special attention is drawn to the dissection ofligand-binding sites within TRPV1, PIP 2 -dependent modulation of TRP channels, and thestructure of natural and synthetic ligands.

  8. Metabolic activation of 2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine and DNA adduct formation depends on p53: Studies in Trp53(+/+),Trp53(+/-) and Trp53(-/-) mice.

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    Krais, Annette M; Speksnijder, Ewoud N; Melis, Joost P M; Singh, Rajinder; Caldwell, Anna; Gamboa da Costa, Gonçalo; Luijten, Mirjam; Phillips, David H; Arlt, Volker M

    2016-02-15

    The expression of the tumor suppressor p53 can influence the bioactivation of, and DNA damage induced by, the environmental carcinogen benzo[a]pyrene, indicating a role for p53 in its cytochrome P450 (CYP)-mediated biotransformation. The carcinogen 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), which is formed during the cooking of food, is also metabolically activated by CYP enzymes, particularly CYP1A2. We investigated the potential role of p53 in PhIP metabolism in vivo by treating Trp53(+/+), Trp53(+/-) and Trp53(-/-) mice with a single oral dose of 50 mg/kg body weight PhIP. N-(Deoxyguanosin-8-yl)-2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP-C8-dG) levels in DNA, measured by liquid chromatography-tandem mass spectrometry, were significantly lower in liver, colon, forestomach and glandular stomach of Trp53(-/-) mice compared to Trp53(+/+) mice. Lower PhIP-DNA adduct levels in the livers of Trp53(-/-) mice correlated with lower Cyp1a2 enzyme activity (measured by methoxyresorufin-O-demethylase activity) in these animals. Interestingly, PhIP-DNA adduct levels were significantly higher in kidney and bladder of Trp53(-/-) mice compared to Trp53(+/+) mice, which was accompanied by higher sulfotransferase (Sult) 1a1 protein levels and increased Sult1a1 enzyme activity (measured by 2-naphthylsulfate formation from 2-naphthol) in kidneys of these animals. Our study demonstrates a role for p53 in the metabolism of PhIP in vivo, extending previous results on a novel role for p53 in xenobiotic metabolism. Our results also indicate that the impact of p53 on PhIP biotransformation is tissue-dependent and that in addition to Cyp1a enzymes, Sult1a1 can contribute to PhIP-DNA adduct formation.

  9. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  10. Position-Dependent Influence of the Three Trp Residues on the Membrane Activity of the Antimicrobial Peptide, Tritrpticin

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    Mauricio Arias

    2014-11-01

    Full Text Available Antimicrobial peptides (AMPs constitute promising candidates for the development of new antibiotics. Among the ever-expanding family of AMPs, tritrpticin has strong antimicrobial activity against a broad range of pathogens. This 13-residue peptide has an unusual amino acid sequence that is almost symmetrical and features three central Trp residues with two Arg residues near each end of the peptide. In this work, the role of the three sequential Trp residues in tritrpticin was studied in a systematic fashion by making a series of synthetic peptides with single-, double- and triple-Trp substitutions to Tyr or Ala. 1H NMR and fluorescence spectroscopy demonstrated the ability of all of the tritrpticin-analog peptides to interact with negatively-charged membranes. Consequently, most tritrpticin analogs exhibited the ability to permeabilize synthetic ePC:ePG (egg-yolk phosphatidylcholine (ePC, egg-yolk phosphatidylglycerol (ePG vesicles and live Escherichia coli bacteria. The membrane perturbation characteristics were highly dependent on the location of the Trp residue substitution, with Trp6 being the most important residue and Trp8 the least. The membrane permeabilization activity of the peptides in synthetic and biological membranes was directly correlated with the antimicrobial potency of the peptides against E. coli. These results contribute to the understanding of the role of each of the three Trp residues to the antimicrobial activity of tritrpticin.

  11. 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.

  12. Structural analysis of a penicillin V acylase from Pectobacterium atrosepticum confirms the importance of two Trp residues for activity and specificity.

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    Avinash, Vellore Sunder; Panigrahi, Priyabrata; Chand, Deepak; Pundle, Archana; Suresh, Cheravakattu Gopalan; Ramasamy, Sureshkumar

    2016-02-01

    Penicillin V acylases (PVA) catalyze the deacylation of the beta-lactam antibiotic phenoxymethylpenicillin (Pen V). They are members of the Ntn hydrolase family and possess an N-terminal cysteine as the main catalytic nucleophile residue. They form the evolutionarily related cholylglycine hydrolase (CGH) group which includes bile salt hydrolases (BSH) responsible for bile deconjugation. Even though a few PVA and BSH structures have been reported, no structure of a functional PVA from Gram-negative bacteria is available. Here, we report the crystal structure of a highly active PVA from Gram-negative Pectobacterium atrosepticum (PaPVA) at 2.5Å resolution. Structural comparison with PVAs from Gram-positive bacteria revealed that PaPVA had a distinctive tetrameric structure and active site organization. In addition, mutagenesis of key active site residues and biochemical characterization of the resultant variants elucidated the role of these residues in substrate binding and catalysis. The importance of residue Trp23 and Trp87 side chains in binding and correct positioning of Pen V by PVAs was confirmed using mutagenesis and substrate docking with a 15ns molecular dynamics simulation. These results establish the unique nature of Gram-negative CGHs and necessitate further research about their substrate spectrum.

  13. TRP channels in schistosomes

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    Swarna Bais

    2016-12-01

    Full Text Available Praziquantel (PZQ is effectively the only drug currently available for treatment and control of schistosomiasis, a disease affecting hundreds of millions of people worldwide. Many anthelmintics, likely including PZQ, target ion channels, membrane protein complexes essential for normal functioning of the neuromusculature and other tissues. Despite this fact, only a few classes of parasitic helminth ion channels have been assessed for their pharmacological properties or for their roles in parasite physiology. One such overlooked group of ion channels is the transient receptor potential (TRP channel superfamily. TRP channels share a common core structure, but are widely diverse in their activation mechanisms and ion selectivity. They are critical to transducing sensory signals, responding to a wide range of external stimuli. They are also involved in other functions, such as regulating intracellular calcium and organellar ion homeostasis and trafficking. Here, we review current literature on parasitic helminth TRP channels, focusing on those in schistosomes. We discuss the likely roles of these channels in sensory and locomotor activity, including the possible significance of a class of TRP channels (TRPV that is absent in schistosomes. We also focus on evidence indicating that at least one schistosome TRP channel (SmTRPA has atypical, TRPV1-like pharmacological sensitivities that could potentially be exploited for future therapeutic targeting.

  14. Thioredoxin-related protein 32 (TRP32) specifically reduces oxidized phosphatase of regenerating liver (PRL).

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    Ishii, Tasuku; Funato, Yosuke; Miki, Hiroaki

    2013-03-08

    PRL family constitutes a unique class of phosphatases associated with metastasis. The phosphatase activity of PRL has been reported to be important for promoting metastasis, and it is inactivated by reversible oxidation of its catalytic cysteine. Here, we show that TRP32 specifically reduces PRL. Reduction of oxidized PRL in cells is inhibited by 2,4-dinitro-1-chlorobenzene, an inhibitor of TRX reductase. In vitro assays for the reduction of PRL show that only TRP32 can potently reduce oxidized PRL, whereas other TRX-related proteins linked to TRX reductase show little or no reducing activity. Indeed, TRP32 knockdown significantly prolongs the H2O2-induced oxidation of PRL. Binding analyses reveal that the unique C-terminal domain of TRP32 is required and sufficient for its direct interaction with PRL. These results suggest that TRP32 maintains the reduced state of PRL and thus regulates the biological function of PRL.

  15. Food Compounds Activating Thermosensitive TRP Channels in Asian Herbal and Medicinal Foods.

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    Watanabe, Tatsuo; Terada, Yuko

    2015-01-01

    There are several thermosensitive transient receptor potential (TRP) ion channels including capsaicin receptor, TRPV1. Food components activating TRPV1 inhibit body fat deposition through sympathetic nerve stimulation. TRPA1 is another pungency sensor for pungent compounds and is mainly coexpressed with TRPV1 in sensory nerve endings. Therefore, TRPA1 activation is expected to have an anti-obesity effect similar to TRPV1 activation. We have searched for agonists for TRPV1 and TRPA1 in vitro from Asian spices by the use of TRPV1- and TRPA1-expressing cells. Further, we performed food component addition tests to high-fat and high-sucrose diets in mice. We found capsiate, capsiconiate, capsainol from hot and sweet peppers, several piperine analogs from black pepper, gingeriols and shogaols from ginger, and sanshools and hydroxysanshools from sansho (Japanese pepper) to be TRPV1 agonists. We also identified several sulfides from garlic and durian, hydroxy fatty acids from royal jelly, miogadial and miogatrial from mioga (Zingiber mioga), piperine analogs from black pepper, and acetoxychavicol acetate (ACA) from galangal (Alpinia galanga) as TRPA1 agonists. Piperine addition to diets diminished visceral fats and increased the uncoupling protein 1 (UCP1) in interscapular brown adipose tissue (IBAT), and black pepper extract showed stronger effects than piperine. Cinnamaldehyde and ACA as TRPA1 agonists inhibited fat deposition and increased UCP1. We found that several agonists of TRPV1 and TRPA1 and some agonists of TRPV1 and TRPA1 inhibit visceral fat deposition in mice. The effects of such compounds on humans remain to be clarified, but we expect that they will be helpful in the prevention of obesity.

  16. Alphavirus replicon particles expressing TRP-2 provide potent therapeutic effect on melanoma through activation of humoral and cellular immunity.

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    Francesca Avogadri

    Full Text Available BACKGROUND: Malignant melanoma is the deadliest form of skin cancer and is refractory to conventional chemotherapy and radiotherapy. Therefore alternative approaches to treat this disease, such as immunotherapy, are needed. Melanoma vaccine design has mainly focused on targeting CD8+ T cells. Activation of effector CD8+ T cells has been achieved in patients, but provided limited clinical benefit, due to immune-escape mechanisms established by advanced tumors. We have previously shown that alphavirus-based virus-like replicon particles (VRP simultaneously activate strong cellular and humoral immunity against the weakly immunogenic melanoma differentiation antigen (MDA tyrosinase. Here we further investigate the antitumor effect and the immune mechanisms of VRP encoding different MDAs. METHODOLOGY/PRINCIPAL FINDINGS: VRP encoding different MDAs were screened for their ability to prevent the growth of the B16 mouse transplantable melanoma. The immunologic mechanisms of efficacy were investigated for the most effective vaccine identified, focusing on CD8+ T cells and humoral responses. To this end, ex vivo immune assays and transgenic mice lacking specific immune effector functions were used. The studies identified a potent therapeutic VRP vaccine, encoding tyrosinase related protein 2 (TRP-2, which provided a durable anti-tumor effect. The efficacy of VRP-TRP2 relies on a novel immune mechanism of action requiring the activation of both IgG and CD8+ T cell effector responses, and depends on signaling through activating Fcγ receptors. CONCLUSIONS/SIGNIFICANCE: This study identifies a VRP-based vaccine able to elicit humoral immunity against TRP-2, which plays a role in melanoma immunotherapy and synergizes with tumor-specific CD8+ T cell responses. These findings will aid in the rational design of future immunotherapy clinical trials.

  17. TRP channels and pain.

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    Julius, David

    2013-01-01

    Nociception is the process whereby primary afferent nerve fibers of the somatosensory system detect noxious stimuli. Pungent irritants from pepper, mint, and mustard plants have served as powerful pharmacological tools for identifying molecules and mechanisms underlying this initial step of pain sensation. These natural products have revealed three members of the transient receptor potential (TRP) ion channel family--TRPV1, TRPM8, and TRPA1--as molecular detectors of thermal and chemical stimuli that activate sensory neurons to produce acute or persistent pain. Analysis of TRP channel function and expression has validated the existence of nociceptors as a specialized group of somatosensory neurons devoted to the detection of noxious stimuli. These studies are also providing insight into the coding logic of nociception and how specification of nociceptor subtypes underlies behavioral discrimination of noxious thermal, chemical, and mechanical stimuli. Biophysical and pharmacological characterization of these channels has provided the intellectual and technical foundation for developing new classes of analgesic drugs.

  18. 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.

  19. 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.

  20. PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

    Institute of Scientific and Technical Information of China (English)

    Yu-yuan Yao; Wen-xing Chen; Bao-yan Zhao; Shen-shui Lü

    2006-01-01

    Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives (Mt2Pc2) were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center ofbioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.

  1. 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.

  2. TRP Channels in Skin Biology and Pathophysiology

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    Caterina, Michael J.; Pang, Zixuan

    2016-01-01

    Ion channels of the Transient Receptor Potential (TRP) family mediate the influx of monovalent and/or divalent cations into cells in response to a host of chemical or physical stimuli. In the skin, TRP channels are expressed in many cell types, including keratinocytes, sensory neurons, melanocytes, and immune/inflammatory cells. Within these diverse cell types, TRP channels participate in physiological processes ranging from sensation to skin homeostasis. In addition, there is a growing body of evidence implicating abnormal TRP channel function, as a product of excessive or deficient channel activity, in pathological skin conditions such as chronic pain and itch, dermatitis, vitiligo, alopecia, wound healing, skin carcinogenesis, and skin barrier compromise. These diverse functions, coupled with the fact that many TRP channels possess pharmacologically accessible sites, make this family of proteins appealing therapeutic targets for skin disorders. PMID:27983625

  3. TRP Channels in Skin Biology and Pathophysiology

    Directory of Open Access Journals (Sweden)

    Michael J. Caterina

    2016-12-01

    Full Text Available Ion channels of the Transient Receptor Potential (TRP family mediate the influx of monovalent and/or divalent cations into cells in response to a host of chemical or physical stimuli. In the skin, TRP channels are expressed in many cell types, including keratinocytes, sensory neurons, melanocytes, and immune/inflammatory cells. Within these diverse cell types, TRP channels participate in physiological processes ranging from sensation to skin homeostasis. In addition, there is a growing body of evidence implicating abnormal TRP channel function, as a product of excessive or deficient channel activity, in pathological skin conditions such as chronic pain and itch, dermatitis, vitiligo, alopecia, wound healing, skin carcinogenesis, and skin barrier compromise. These diverse functions, coupled with the fact that many TRP channels possess pharmacologically accessible sites, make this family of proteins appealing therapeutic targets for skin disorders.

  4. REPLACEMENT OF TRYPTOPHAN RESIDUES IN HALOALKANE DEHALOGENASE REDUCES HALIDE BINDING AND CATALYTIC ACTIVITY

    NARCIS (Netherlands)

    KENNES, C; PRIES, F; KROOSHOF, GH; BOKMA, E; Kingma, Jacob; JANSSEN, DB

    1995-01-01

    Haloalkane dehalogenase catalyzes the hydrolytic cleavage of carbon-halogen bonds in short-chain haloalkanes. Two tryptophan residues of the enzyme (Trp125 and Trp175) form a halide-binding site in the active-site cavity, and were proposed to play a role in catalysis. The function of these residues

  5. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

    2005-05-15

    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  6. TRP channels and psychiatric disorders.

    Science.gov (United States)

    Chahl, Loris A

    2011-01-01

    Depression and schizophrenia are major psychiatric disorders that cause much human suffering. Current treatments have major limitations and new drug targets are eagerly sought. Study of transient receptor potential (TRP) channels in these disorders is at an early stage and the potential of agents that activate or inhibit these channels remains speculative. The findings that TRPC6 channels promote dendritic growth and are selectively activated by hyperforin, the key constitutent of St John's wort, suggest that TRPC6 channels might prove to be a new target for antidepressant drug development. There is now considerable evidence that TRPV1 antagonists have anxiolytic activity but there is no direct evidence that they have antidepressant activity. There is also no direct evidence that TRP channels play a role in schizophrenia. However, the findings that TRPC channels are involved in neuronal development and fundamental synaptic mechanisms, and that TRPV1 channels play a role in central dopaminergic and cannabinoid mechanisms is suggestive of potential roles of these channels in schizophrenia. Investigation of TRP channels in psychiatric disorders holds the promise of yielding further understanding of the aetiology of psychiatric disorders and the development of new drug treatments.

  7. 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...

  8. Protein composition of catalytically active human telomerase from immortal cells

    DEFF Research Database (Denmark)

    Cohen, Scott B; Graham, Mark E; Lovrecz, George O;

    2007-01-01

    on the enzyme's ability to catalyze nucleotide addition onto a DNA oligonucleotide of telomeric sequence, thereby providing specificity for catalytically active telomerase. Mass spectrometric sequencing of the protein components and molecular size determination indicated an enzyme composition of two molecules...

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

    Directory of Open Access Journals (Sweden)

    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.

  10. Augmented activity of the pelvic nerve afferent mediated by TRP channels in dextran sulfate sodium (DSS)-induced colitis of rats.

    Science.gov (United States)

    Makimura, Yukitoshi; Ito, Koichi; Kuwahara, Masayoshi; Tsubone, Hirokazu

    2012-08-01

    Enteritis has been recognized as a major symptom in domestic animals and human patients suffering from feed and food poisonings. The aim of the present study was to clarify the excitatory mechanism of the pelvic nerve afferent which may influence the occurrence of enteritis in response to nociceptive chemical stimuli of the colon in normal and abnormal rats with colitis induced by dextran sulfate sodium (DSS). The pelvic nerve afferent activity was markedly increased by colonic instillation of solution (0.5 ml) of acetic acid (5-25%) and capsaicin (100 μg/ml). The nerve activity was augmented by colonic instillation of capsaicin to a greater extent in rats with DSS-induced colitis than in normal control rats. This augmented activity by capsaicin was more prominent at one day (DSS-1) than at 8 day (DSS-8) after the administration of DSS. The increased nerve activity caused by capsaicin in DSS-1 and DSS-8 was significantly inhibited by pretreatment with ruthenium red, which is a nonselective inhibitor of TRP channels of unmyelinated C-fibers (nociceptors). In conclusion, it was elucidated that the nociceptive function of the pelvic nerve was largely elevated at one day after DSS-induced colitis and such increased function was mostly mediated by TRP channels.

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

    Science.gov (United States)

    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.

  12. Functional diversity and evolutionary dynamics of thermoTRP channels.

    Science.gov (United States)

    Saito, Shigeru; Tominaga, Makoto

    2015-03-01

    Animals have evolved sophisticated physiological systems for sensing ambient temperature since changes in environmental temperatures affect various biological processes. Thermosensitive transient receptor potential (thermoTRP) channels serve as thermal sensors in diverse animal species. They are multimodal receptors that are activated by temperature as well as other physical and chemical stimuli. Since thermoTRP channels are calcium permeable non-selective cation channels, their activation leads to an influx of calcium and sodium ions into the cell and triggers downstream signal transduction. ThermoTRP channels have been characterized in diverse animal species over the past several years, illuminating the diversification of thermoTRP channels in the course of evolution. The gene repertoires of thermoTRP channels differ among animal species. Additionally, in some cases, the temperature and chemical sensitivities among orthologous thermoTRP channels vary among species. The evolutionary flexibility of thermoTRP channels enabled them to contribute to unique physiological systems such as infrared sensation in snakes and bats and seasonal adaptation in silk moth. On the other hand, the functional differences of thermoTRP channels among species have been utilized for understanding the molecular basis for their activation (or inhibition) mechanisms, and amino acid residues (or domains) responsible for the respective channel properties have been identified in various thermoTRP channels. Here we summarize the current understanding of the functional diversity and evolutionary dynamics of thermoTRP channels.

  13. TRP channels: an overview

    DEFF Research Database (Denmark)

    Pedersen, Stine Falsig; Owsianik, Grzegorz; Nilius, Bernd

    2005-01-01

    to a plethora of data on the roles of TRPs in a variety of tissues and species, including mammals, insects, and yeast. The present review summarizes the most pertinent recent evidence regarding the structural and functional properties of TRP channels, focusing on the regulation and physiology of mammalian TRPs....

  14. Anti-tumor Immunity Elicited by Adenovirus Encoding AdhTrp2 or AdmTrp2 without Vitiligo

    Institute of Scientific and Technical Information of China (English)

    Hongju LIU; Xianzhi XIONG; Zuoya LI; Jianbao XIN; Xiaonan TAO; Yu HU

    2008-01-01

    To compare the difference in tumor immunity and autoimmunity elicited by adenovirus (Ad) encoding human or murine tyrosinase-related protein 2 (AdhTRP2 or AdmTRP2), and to find the most effective way to induce immunity by AdhTRP2 or AdmTRP2, C57BL/6 mice were im-munized with AdhTRP2 or AdmTRP2 intramuscularly at different doses of 105, 106, 107 and 108 separately (10 mice for each dose). Two weeks after the immunization, in vivo CTL assay and in- tracellular staining (ICS) of IFN-γ were carried out to analyze the dose-effect relationship. Tumor growth and vitiligo (as an sign of autoimmunity) were observed until 3 months after challenge with 105 B I6F10 tumor cells. The results showed that Ad encoding AdmTrp2 induced weak tumor im- mune response. Similar immunization with AdhTrp-2 elicited stronger protective immunity. CTL activity and IFN-γ-produced CD8+T cells were directly proportional to dose of AdhTrp2 or AdmTrp2. Moreover, AdhTrp2 group showed tumor rejection in 100% of challenged mice till the end of 3rd month while 60% of mice immunized with AdmTrp2 were protected against tumor. In the whole process of this experiment, no vitiligo was observed in mice immunized either with AdhTrp2 or AdmTrp2. It is concluded that anti-melanoma responses induced by genetic vaccina- tion expressing xenoantigens breaks immune tolerance effectively and is able to elicit strong anti-gen-specific cytotoxic T cell response without vitiligo.

  15. Targeting TRP channels for novel migraine therapeutics.

    Science.gov (United States)

    Dussor, Gregory; Yan, J; Xie, Jennifer Y; Ossipov, Michael H; Dodick, David W; Porreca, Frank

    2014-11-19

    Migraine is increasingly understood to be a disorder of the brain. In susceptible individuals, a variety of "triggers" may influence altered central excitability, resulting in the activation and sensitization of trigeminal nociceptive afferents surrounding blood vessels (i.e., the trigeminovascular system), leading to migraine pain. Transient receptor potential (TRP) channels are expressed in a subset of dural afferents, including those containing calcitonin gene related peptide (CGRP). Activation of TRP channels promotes excitation of nociceptive afferent fibers and potentially lead to pain. In addition to pain, allodynia to mechanical and cold stimuli can result from sensitization of both peripheral afferents and of central pain pathways. TRP channels respond to a variety of endogenous conditions including chemical mediators and low pH. These channels can be activated by exogenous stimuli including a wide range of chemical and environmental irritants, some of which have been demonstrated to trigger migraine in humans. Activation of TRP channels can elicit CGRP release, and blocking the effects of CGRP through receptor antagonism or antibody strategies has been demonstrated to be effective in the treatment of migraine. Identification of approaches that can prevent activation of TRP channels provides an additional novel strategy for discovery of migraine therapeutics.

  16. Catalytically highly active top gold atom on palladium nanocluster.

    Science.gov (United States)

    Zhang, Haijun; Watanabe, Tatsuya; Okumura, Mitsutaka; Haruta, Masatake; Toshima, Naoki

    2011-10-23

    Catalysis using gold is emerging as an important field of research in connection with 'green' chemistry. Several hypotheses have been presented to explain the markedly high activities of Au catalysts. So far, the origin of the catalytic activities of supported Au catalysts can be assigned to the perimeter interfaces between Au nanoclusters and the support. However, the genesis of the catalytic activities of colloidal Au-based bimetallic nanoclusters is unclear. Moreover, it is still a challenge to synthesize Au-based colloidal catalysts with high activity. Here we now present the 'crown-jewel' concept (Supplementary Fig. S1) for preparation of catalytically highly Au-based colloidal catalysts. Au-Pd colloidal catalysts containing an abundance of top (vertex or corner) Au atoms were synthesized according to the strategy on a large scale. Our results indicate that the genesis of the high activity of the catalysts could be ascribed to the presence of negatively charged top Au atoms.

  17. 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.

  18. 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 to a...

  19. Activation of a TRP-like channel and intracellular Ca2+ dynamics during phospholipase-C-mediated cell death.

    Science.gov (United States)

    Gonçalves, A Pedro; Cordeiro, J Miguel; Monteiro, João; Muñoz, Alberto; Correia-de-Sá, Paulo; Read, Nick D; Videira, Arnaldo

    2014-09-01

    The model organism Neurospora crassa undergoes programmed cell death when exposed to staurosporine. Here, we show that staurosporine causes defined changes in cytosolic free Ca(2+) ([Ca(2+)]c) dynamics and a distinct Ca(2+) signature that involves Ca(2+) influx from the external medium and internal Ca(2+) stores. We investigated the molecular basis of this Ca(2+) response by using [Ca(2+)]c measurements combined with pharmacological and genetic approaches. Phospholipase C was identified as a pivotal player during cell death, because modulation of the phospholipase C signaling pathway and deletion of PLC-2, which we show to be involved in hyphal development, results in an inability to trigger the characteristic staurosporine-induced Ca(2+) signature. Using Δcch-1, Δfig-1 and Δyvc-1 mutants and a range of inhibitors, we show that extracellular Ca(2+) entry does not occur through the hitherto described high- and low-affinity Ca(2+) uptake systems, but through the opening of plasma membrane channels with properties resembling the transient receptor potential (TRP) family. Partial blockage of the response to staurosporine after inhibition of a putative inositol-1,4,5-trisphosphate (IP3) receptor suggests that Ca(2+) release from internal stores following IP3 formation combines with the extracellular Ca(2+) influx.

  20. Catalytically active nanomaterials: a promising candidate for artificial enzymes.

    Science.gov (United States)

    Lin, Youhui; Ren, Jinsong; Qu, Xiaogang

    2014-04-15

    Natural enzymes, exquisite biocatalysts mediating every biological process in living organisms, are able to accelerate the rate of chemical reactions up to 10(19) times for specific substrates and reactions. However, the practical application of enzymes is often hampered by their intrinsic drawbacks, such as low operational stability, sensitivity of catalytic activity to environmental conditions, and high costs in preparation and purification. Therefore, the discovery and development of artificial enzymes is highly desired. Recently, the merging of nanotechnology with biology has ignited extensive research efforts for designing functional nanomaterials that exhibit various properties intrinsic to enzymes. As a promising candidate for artificial enzymes, catalytically active nanomaterials (nanozymes) show several advantages over natural enzymes, such as controlled synthesis in low cost, tunability in catalytic activities, as well as high stability against stringent conditions. In this Account, we focus on our recent progress in exploring and constructing such nanoparticulate artificial enzymes, including graphene oxide, graphene-hemin nanocomposites, carbon nanotubes, carbon nanodots, mesoporous silica-encapsulated gold nanoparticles, gold nanoclusters, and nanoceria. According to their structural characteristics, these enzyme mimics are categorized into three classes: carbon-, metal-, and metal-oxide-based nanomaterials. We aim to highlight the important role of catalytic nanomaterials in the fields of biomimetics. First, we provide a practical introduction to the identification of these nanozymes, the source of the enzyme-like activities, and the enhancement of activities via rational design and engineering. Then we briefly describe new or enhanced applications of certain nanozymes in biomedical diagnosis, environmental monitoring, and therapeutics. For instance, we have successfully used these biomimetic catalysts as colorimetric probes for the detection of

  1. Indoleamine 2,3-dioxygenases with very low catalytic activity are well conserved across kingdoms: IDOs of Basidiomycota.

    Science.gov (United States)

    Yuasa, Hajime J; Ball, Helen J

    2013-07-01

    Indoleamine 2,3-dioxygenase (IDO) is a tryptophan-degrading enzyme and is found in animals, fungi and bacteria. In fungi, its primary role is to supply nicotinamide adenine dinucleotide (NAD(+)) via the kynurenine pathway. A number of organisms possess more than one IDO gene, for example, mammals have IDO1 and IDO2 genes. We previously reported that the Pezizomycotina fungi commonly possess three types of IDO genes, IDOα, IDOβ and IDOγ. In this study, we surveyed the nature of IDO genes from Basidiomycota fungi, which are categorized into three subphyla (Agaricomycotina, Pucciniomycotina and Ustilaginomycotina). The Agaricomycotina fungi generally have three types of IDO genes (IDOa, IDOb and IDOc), which are distinct from Pezizomycotina three isozymes. Pucciniomycotina and Ustilaginomycotina species possess two types of IDO; one forms a monophyletic clade with Agaricomycotina IDOs in the phylogenetic tree, these IDOs are referred to as "typical Basidiomycota IDOs". The other is IDOγ, which showed more than 40% identity with Pezizomycotina and ciliate IDOγ. We previously demonstrated that IDO2 in mammals and IDOγ in Perzizomycotina fungi have much lower catalytic efficiencies in an in vitro assay, compared with the other IDO isoforms found in the respective species. We have developed a functional assay to determine whether particular IDO enzymes have sufficient enzymatic activity to rescue a yeast strain where IDO-deletion has rendered it auxotrophic for nicotinic acid. IDOα and IDOβ showed comparable catalytic efficiency, both of them could function in the Pezizomycotina fungal L-Trp metabolism. The catalytic efficiency and functional capacity of the Basidiomycota IDOa and IDOb were similar to Pezizomycotina IDOα/IDOβ. We found that Basidiomycota IDOc could not rescue the nicotinic acid auxotroph, similar to other IDO enzymes with low catalytic efficiency (mammalian IDO2 and most fungal IDOγ). Our study suggests that some fungal IDO enzymes function in

  2. 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...

  3. Catalytic Ethanol Dehydration over Different Acid-activated Montmorillonite Clays.

    Science.gov (United States)

    Krutpijit, Chadaporn; Jongsomjit, Bunjerd

    2016-01-01

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

  4. Activity of catalytic silver nanoparticles modulated by capping agent hydrophobicity.

    Science.gov (United States)

    Janani, Seralathan; Stevenson, Priscilla; Veerappan, Anbazhagan

    2014-05-01

    In this paper, a facile in situ method is reported for the preparation of catalytic silver nanoparticles (AgNPs) using N-acyl tyramine (NATA) with variable hydrophobic acyl length. Scanning electron microscopic analysis shows that NATA exists initially as larger aggregates in alkaline aqueous solution. The addition of AgNO3 dissociates these larger aggregate and subsequently promotes the formation of self-assembled NATA and AgNPs. Characterization of AgNPs using UV-vis spectroscopy, scanning electron microscope and transmission electron microscope revealed that the hydrophobic acyl chain length of NATA does not influence the particle size, shape and morphology. All NATA-AgNPs yielded relatively identical values in full width at half-maximum (FWHM) analysis, indicating that the AgNPs prepared with NATA are relatively polydispersed at all tested acyl chain lengths. These nanoparticles are able to efficiently catalyze the reduction of 4-nitro phenol to 4-amino phenol, 2-nitro aniline to 1,2-diamino benzene, 2,4,6-trinitro phenol to 2,4,6-triamino phenol by NaBH4 in an aqueous environment. The reduction reaction rate is determined to be pseudo-first order and the apparent rate constant is linearly dependent on the hydrophobic acyl chain length of the NATA. All reaction kinetics presented an induction period, which is dependent on the N-acyl chain length, indicating that the hydrophobic effects play a critical role in bringing the substrate to the metal nanoparticle surface to induce the catalytic reaction. In this study, however, the five catalytic systems have similar size and polydispersity, differing only in terms of capping agent hydrophobicity, and shows different catalytic activity with respect to the alkyl chain length of the capping agent. As discussed, the ability to modulate the metal nanoparticles catalytic property, by modifying the capping agent hydrophobicity represents a promising future for developing an efficient nanocatalyst without altering the size

  5. Guiding catalytically active particles with chemically patterned surfaces

    CERN Document Server

    Uspal, W E; Dietrich, S; Tasinkevych, M

    2016-01-01

    Catalytically active Janus particles suspended in solution create gradients in the chemical composition of the solution along their surfaces, as well as along any nearby container walls. The former leads to self-phoresis, while the latter gives rise to chemi-osmosis, providing an additional contribution to self-motility. Chemi-osmosis strongly depends on the molecular interactions between the diffusing chemical species and the wall. We show analytically, using an approximate "point-particle" approach, that by chemically patterning a planar substrate one can direct the motion of Janus particles: the induced chemi-osmotic flows can cause particles to either "dock" at the chemical step between the two materials, or to follow a chemical stripe. These theoretical predictions are confirmed by full numerical calculations. Generically, docking occurs for particles which tend to move away from their catalytic caps, while stripe-following occurs in the opposite case. Our analysis reveals the physical mechanisms governi...

  6. TRP Channels in Human Prostate

    Directory of Open Access Journals (Sweden)

    Carl Van Haute

    2010-01-01

    Full Text Available This review gives an overview of morphological and functional characteristics in the human prostate. It will focus on the current knowledge about transient receptor potential (TRP channels expressed in the human prostate, and their putative role in normal physiology and prostate carcinogenesis. Controversial data regarding the expression pattern and the potential impact of TRP channels in prostate function, and their involvement in prostate cancer and other prostate diseases, will be discussed.

  7. Calmodulin modulates the delay period between release of calcium from internal stores and activation of calcium influx via endogenous TRP1 channels.

    Science.gov (United States)

    Vaca, Luis; Sampieri, Alicia

    2002-11-01

    In the present study we have explored the role of calmodulin (CaM) and inositol 1,4,5-trisphosphate receptor (IP(3)R) in the communication process activated after the release of calcium from the endoplasmic reticulum (ER) and the activation of calcium influx via endogenous TRP1 channels from Chinese hamster ovary cells. Experiments using combined rapid confocal calcium and electrophysiology measurements uncovered a consistent delay of around 900 ms between the first detectable calcium released from the ER and the activation of the calcium current. This delay was evident with two different methods used to release calcium from the ER: either the blockade of the microsomal calcium ATPase with thapsigargin or activation of bradykinin receptors linked to the IP(3) cascade. Direct application of IP(3) or a peptide from the NH(2)-terminal region of the IP(3)R activated store operated calcium, reducing the delay period. Introduction of CaM into the cell via the patch pipette increased the delay period from 900 +/- 100 ms to 10 +/- 2.1 s (n = 18). Furthermore, the use of selective CaM antagonists W7 and trifluoperazine maleate resulted in a substantial reduction of the delay period to 200 +/- 100 ms with 5 microm trifluoperazine maleate (n = 16) and 150 +/- 50 ms with 500 nm W7 (n = 22). CaM reduced also the current density activated by thapsigargin or brandykinin to about 60% from control. The CaM antagonists did not affect significantly the current density. The results presented here are consistent with an antagonistic effect of IP(3)R and CaM for the activation of store operated calcium after depletion of the ER. The functional competition between the activating effect of IP(3)R and the inhibiting effect of CaM may modulate the delay period between the release of calcium from the ER and the activation of calcium influx observed in different cells, as well as the amount of current activated after depletion of the ER.

  8. 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.

  9. Copper on activated carbon for catalytic wet air oxidation

    Directory of Open Access Journals (Sweden)

    Nora Dolores Martínez

    2009-03-01

    Full Text Available Textile industry is an important source of water contamination. Some of the organic contaminants cannot be eliminated by nature in a reasonable period. Heterogeneous catalytic wet air oxidation is one of the most effective methods to purify wastewater with organic contaminants. In this work, catalysts based on copper supported on activated carbon were synthesized. The activated carbons were obtained from industrial wastes (apricot core and grape stalk of San Juan, Argentina. These were impregnated with a copper salt and thermically treated in an inert atmosphere. Analysis of specific surface, pore volume, p zc, acidity, basicity and XRD patterns were made in order to characterize the catalysts. The catalytic activity was tested in the oxidation of methylene blue (MB and polyvinyl alcohol (PVA in aqueous phase with pure oxygen. Reaction tests were carried out in a Parr batch reactor at different temperatures, with a 0.2 MPa partial pressure of oxygen. The amount of unconverted organics was measured by spectrophotometry. Higher temperatures were necessary for the degradation of PVA compared to those for methylene blue.

  10. Trafficking of ThermoTRP Channels

    Directory of Open Access Journals (Sweden)

    Clotilde Ferrandiz-Huertas

    2014-08-01

    Full Text Available ThermoTRP channels (thermoTRPs define a subfamily of the transient receptor potential (TRP channels that are activated by changes in the environmental temperature, from noxious cold to injurious heat. Acting as integrators of several stimuli and signalling pathways, dysfunction of these channels contributes to several pathological states. The surface expression of thermoTRPs is controlled by both, the constitutive and regulated vesicular trafficking. Modulation of receptor surface density during pathological processes is nowadays considered as an interesting therapeutic approach for management of diseases, such as chronic pain, in which an increased trafficking is associated with the pathological state. This review will focus on the recent advances trafficking of the thermoTRP channels, TRPV1, TRPV2, TRPV4, TRPM3, TRPM8 and TRPA1, into/from the plasma membrane. Particularly, regulated membrane insertion of thermoTRPs channels contributes to a fine tuning of final channel activity, and indeed, it has resulted in the development of novel therapeutic approaches with successful clinical results such as disruption of SNARE-dependent exocytosis by botulinum toxin or botulinomimetic peptides.

  11. 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

  12. TRP channels in microglia: role in physiology and disease

    OpenAIRE

    2015-01-01

    Microglia are responsible for modulating the cellular environment in the nervous system, where they have neuroprotective effects. In these cells has been reported the expression of different ion channels, including those belonging to the transient receptor potential (TRP) family. TRP are nonselective cation channels that have six transmembrane domains and both N-terminus and C-terminus domain located in the cytoplasm. These proteins can be activated by mechanical, thermal and chemical stimuli...

  13. 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.

  14. Guiding catalytically active particles with chemically patterned surfaces

    Science.gov (United States)

    Uspal, William; Popescu, Mihail; Dietrich, Siegfried; Tasinkevych, Mykola

    Catalytically active Janus particles in solution create gradients in the chemical composition of the solution along their surfaces, as well as along any nearby container walls. The former leads to self-phoresis, while the latter gives rise to chemi-osmosis, providing an additional contribution to self-motility. Chemi-osmosis strongly depends on the molecular interactions between the diffusing chemical species and the wall. We show analytically, using an approximate ``point-particle'' approach, that by chemically patterning a planar substrate (e.g., by adsorbing two different materials) one can direct the motion of Janus particles: the induced chemi-osmotic flows can cause particles to either ``dock'' at a chemical step between the two materials, or to follow a chemical stripe. These theoretical predictions are confirmed by full numerical calculations. Generically, docking occurs for particles which tend to move away from their catalytic caps, while stripe-following occurs in the opposite case. Our analysis reveals the physical mechanisms governing this behavior.

  15. Size Effect of Gold Sol/γ-Alumina on the Catalytic Activities of CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    WANG Wei-Hua; GAO Geng-Yu

    2006-01-01

    The relationship between particle size and catalytic activity of gold nanoparticle catalysts with γ-Al2O3 as support has been investigated. The catalysts were prepared via the gold sol with different particle sizes by micelle method, and their structures were characterized by HRTEM and XRD, respectively. Furthermore, the catalytic activities were tested by CO oxidation. Experimental results showed that the catalytic activity became much weaker when gold particles were increased from 3.2 to 6.6 nm. Additionally, the particle size was also a key factor to govern catalytic activity with regard to gold supported on TiO2 prepared by the methods of deposition-precipitation.

  16. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pourmortazavi, Seied Mahdi, E-mail: pourmortazavi@yahoo.com [Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran (Iran, Islamic Republic of); Rahimi-Nasrabadi, Mehdi, E-mail: rahiminasrabadi@gmail.com [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Khalilian-Shalamzari, Morteza [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh [Islamic Azad University, Varamin Pishva Branch, Varamin (Iran, Islamic Republic of); Omrani, Ismail [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of)

    2012-12-15

    Graphical abstract: NiWO{sub 4} nanoparticles were prepared via precipitation technique. Experimental parameters of procedure were optimized statistically. Highlights: Black-Right-Pointing-Pointer NiWO{sub 4} spherical nanoparticles were synthesized via direct precipitation method. Black-Right-Pointing-Pointer Taguchi robust design was used for optimization of synthesis reaction parameters. Black-Right-Pointing-Pointer Composition and structural properties of NiWO{sub 4} nanoparticles were characterized. Black-Right-Pointing-Pointer EDAX, XRD, SEM, FT-IR, UV-vis and photoluminescence techniques were employed. Black-Right-Pointing-Pointer Catalytic activity of the product in a cyclo-addition reaction was investigated. - Abstract: Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO{sub 4} nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO{sub 4} particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO{sub 4} were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV

  17. Psychiatric Disorders and TRP Channels: Focus on Psychotropic Drugs.

    Science.gov (United States)

    Nazıroğlu, Mustafa; Demirdaş, Arif

    2015-01-01

    Psychiatric and neurological disorders are mostly associated with the changes in neural calcium ion signaling pathways required for activity-triggered cellular events. One calcium channel family is the TRP cation channel family, which contains seven subfamilies. Results of recent papers have discovered that calcium ion influx through TRP channels is important. We discuss the latest advances in calcium ion influx through TRP channels in the etiology of psychiatric disorders. Activation of TRPC4, TRPC5, and TRPV1 cation channels in the etiology of psychiatric disorders such as anxiety, fear-associated responses, and depression modulate calcium ion influx. Evidence substantiates that anandamide and its analog (methanandamide) induce an anxiolytic-like effect via CB1 receptors and TRPV1 channels. Intracellular calcium influx induced by oxidative stress has an significant role in the etiology of bipolar disorders (BDs), and studies recently reported the important role of TRP channels such as TRPC3, TRPM2, and TRPV1 in converting oxidant or nitrogen radical signaling to cytosolic calcium ion homeostasis in BDs. The TRPV1 channel also plays a function in morphine tolerance and hyperalgesia. Among psychotropic drugs, amitriptyline and capsazepine seem to have protective effects on psychiatric disorders via the TRP channels. Some drugs such as cocaine and methamphetamine also seem to have an important role in alcohol addiction and substance abuse via activation of the TRPV1 channel. Thus, we explore the relationships between the etiology of psychiatric disorders and TRP channel-regulated mechanisms. Investigation of the TRP channels in psychiatric disorders holds the promise of the development of new drug treatments.

  18. TRP channels in microglia: role in physiology and disease

    Directory of Open Access Journals (Sweden)

    Yolima P Torres

    2015-02-01

    Full Text Available Microglia are responsible for modulating the cellular environment in the nervous system, where they have neuroprotective effects. In these cells has been reported the expression of different ion channels, including those belonging to the transient receptor potential (TRP family. TRP are nonselective cation channels that have six transmembrane domains and both N-terminus and C-terminus domain located in the cytoplasm. These proteins can be activated by mechanical, thermal and chemical stimuli as well as pH changes. Their activation can induce calcium influx contributing to regulate the intracellular calcium concentration. Different studies describe the effect of TRP channels in cellular processes such as osmotic regulation, cytokine production, proliferation, activation, cell death and responses to oxidative stress. As a result, these channels have an important role in neurodegenerative diseases, ischemia, inflammatory responses and pain perception. Modulating the activity of the TRP channels can be a therapeutic target for various diseases associated with the central nervous system. In this review the most relevant aspects about the role of the TRP channels in the physiology of microglia and their potential use as a therapeutic target in central nervous system diseases will be described.

  19. 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.

  20. 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.

  1. Role of TRP channels in the induction of heat shock proteins (Hsps) by heating skin.

    Science.gov (United States)

    Hsu, Wen-Li; Yoshioka, Tohru

    2015-01-01

    Transient receptor potential (TRP) channels in skin are crucial for achieving temperature sensitivity to maintain internal temperature balance and thermal homeostasis, as well as to protect skin cells from environmental stresses such as infrared (IR) or near-infrared (NIR) radiation via heat shock protein (Hsp) production. However, the mechanisms by which IR and NIR activate TRP channels and produce Hsps intracellularly have been independently reported. In this review, we discuss the relationship between TRP channel activation and Hsp production, and introduce the roles of several skin TRP channels in the regulation of HSP production by IR and NIR exposure.

  2. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    Science.gov (United States)

    Pourmortazavi, Seied Mahdi; Rahimi-Nasrabadi, Mehdi; Khalilian-Shalamzari, Morteza; Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh; Omrani, Ismail

    2012-12-01

    Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO4 nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO4 particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO4 were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV-vis spectroscopy, and photoluminescence. Finally, catalytic activity of the nanoparticles in a cycloaddition reaction was examined.

  3. [Role of thermo TRP channels in cutaneous neurogenic inflammation and itch].

    Science.gov (United States)

    XIE, Zhi-qiang

    2009-07-01

    The temperature-sensitive transient receptor potential (TRP) channels, is also called thermo TRP, including TRPV1, TRPV2, TRPV3, TRPV4, TRPM8 and TRPA1, which are expressed in sensory neurons and non-neuronal cells (e.g.keratinocyte, mast cell) of the skin. Thermo TRP channels are activated/sensitized by physical and chemical mediators, which participate in thermosensation and thermoregulation, so that they are key players in pruritus or pain pathogenesis. Thermo TRP channels are also involved in cutaneous neurogenic inflammation, thus they are regarded as molecular targets for future therapy in skin inflammation, pruritus and pain. In addition, following a basic syntax and molecular substrate of nociception and pruriception established by TRP channels-centered concept, the sensory categories can be distinguished and re-defined. Thermo TRP channels should be taken into account when analyzing the pathogenesis and management of itch or pruritic dermatosis.

  4. Tailoring micro-mesoporosity in activated carbon fibers to enhance SO₂ catalytic oxidation.

    Science.gov (United States)

    Diez, Noel; Alvarez, Patricia; Granda, Marcos; Blanco, Clara; Gryglewicz, Grażyna; Wróbel-Iwaniec, Iwona; Sliwak, Agata; Machnikowski, Jacek; Menendez, Rosa

    2014-08-15

    Enhanced SO2 adsorption of activated carbon fibers is obtained by tailoring a specific micro-mesoporous structure in the fibers. This architecture is obtained via metal catalytic activation of the fibers with a novel precursor, cobalt naphthenate, which contrary to other precursors, also enhances spinnability and carbon fiber yield. In the SO2 oxidation, it is demonstrated that the combination of micropores and large mesopores is the main factor for an enhanced catalytic activity which is superior to that observed in other similar microporous activated carbon fibers. This provides an alternative way for the development of a new generation of catalytic material.

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

    Science.gov (United States)

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

    2015-04-28

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

  6. A novel strategy to analyze L-tryptophan through allosteric Trp repressor based on rolling circle amplification.

    Science.gov (United States)

    Zhao, Guojie; Hu, Tianyu; Li, Jun; Wei, Hua; Shang, Hong; Guan, Yifu

    2015-09-15

    Rolling circle amplification (RCA) has been considered as a powerful tool for nucleic acids detection. Here, a novel repressor-RCA-based method for L-tryptophan (L-Trp) detection was developed. This method utilizes the specific interaction between the RCA circular template and the Trp repressor protein (TrpR) involved in trp operon of Escherichia coli (E. coli). In the absence of L-Trp, the TrpR protein could not bind to the RCA template, and the RCA process can be continued. When L-Trp is present, the activated TrpR will bind to the operon sequence on the RCA template and inhibit the RCA reaction. Thus, the concentration of L-Trp is correlated directly with the fluorescent RCA signals. We succeeded in detecting L-Trp in a single step in simple homogeneous reaction system. The detection limit was estimated to be 0.77 μM (S/N=3) with good linearity. The method can unambiguously distinguish L-Trp from other 19 standard amino acids and L-Trp analogs. This strategy is also promising for detecting many small molecules such as other amino acids and carbohydrates.

  7. Graphene incorporated, N doped activated carbon as catalytic electrode in redox active electrolyte mediated supercapacitor

    Science.gov (United States)

    Gao, Zhiyong; Liu, Xiao; Chang, Jiuli; Wu, Dapeng; Xu, Fang; Zhang, Lingcui; Du, Weimin; Jiang, Kai

    2017-01-01

    Graphene incorporated, N doped activated carbons (GNACs) are synthesized by alkali activation of graphene-polypyrrole composite (G-PPy) at different temperatures for application as electrode materials of supercapacitors. Under optimal activation temperature of 700 °C, the resultant samples, labeled as GNAC700, owns hierarchically porous texture with high specific surface area and efficient ions diffusion channels, N, O functionalized surface with apparent pseudocapacitance contribution and high wettability, thus can deliver a moderate capacitance, a high rate capability and a good cycleability when used as supercapacitor electrode. Additionally, the GNAC700 electrode demonstrates high catalytic activity for the redox reaction of pyrocatechol/o-quinone pair in H2SO4 electrolyte, thus enables a high pseudocapacitance from electrolyte. Under optimal pyrocatechol concentration in H2SO4 electrolyte, the electrode capacitance of GNAC700 increases by over 4 folds to 512 F g-1 at 1 A g-1, an excellent cycleability is also achieved simultaneously. Pyridinic- N is deemed to be responsible for the high catalytic activity. This work provides a promising strategy to ameliorate the capacitive performances of supercapacitors via the synergistic interaction between redox-active electrolyte and catalytic electrodes.

  8. 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

  9. Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Susana [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela); Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); D' Ornelas, Lindora [Centro de Quimica Organometalica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778 (Venezuela); Betancourt, Paulino [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679 (Venezuela)], E-mail: pbetanco@strix.ciens.ucv.ve

    2008-06-30

    Vanadium nanoparticles ({approx}7 nm) stabilized on activated carbon were synthesized by the reduction of VCl{sub 3}.3THF with K[BEt{sub 3}H]. This material was characterized by inductive coupled plasma-atomic emission spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 deg. C and P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the synthesis of such a catalyst led to an excellent performance of the HDS process.

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

    Science.gov (United States)

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

    2017-02-01

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

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

    Science.gov (United States)

    2017-01-01

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

  12. CHARACTERIZATION OF IRON COMPLEXES SUPPORTED ON POLYMER AND THEIR CATALYTIC ACTIVITY IN BUTADIENE POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    YU Guangqian; LI Yuliang; YANG Zhifan; WANG Hong

    1990-01-01

    Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C) and the Fe-O bond is higher in covalency. R-C-O-Fe-O-Fe(C) The complex SAAC Fe with the structure of(C) showed a higher catalytic activity in butadiene polymerization. When Fe/- COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.

  13. TRP Channels in Skin Biology and Pathophysiology

    OpenAIRE

    2016-01-01

    Ion channels of the Transient Receptor Potential (TRP) family mediate the influx of monovalent and/or divalent cations into cells in response to a host of chemical or physical stimuli. In the skin, TRP channels are expressed in many cell types, including keratinocytes, sensory neurons, melanocytes, and immune/inflammatory cells. Within these diverse cell types, TRP channels participate in physiological processes ranging from sensation to skin homeostasis. In addition, there is a growing body ...

  14. 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.

  15. Size-dependent peroxidase-like catalytic activity of Fe3O4 nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Fang Fang Peng; Yu Zhang; Ning Gu

    2008-01-01

    Peroxidase-like catalytic properties of Fe3O4 nanoparticles (NPs) with three different sizes, synthesized by chemical coprecipitation and sol-gel methods, were investigated by UV-vis spectrum analysis. By comparing Fe3O4 NPs with average diameters of 11,20, and 150 nm, we found that the catalytic activity increases with the reduced nanoparticle size. The electrochemical method to characterize the catalytic activity of Fe3O4 NPs using the response currents of the reaction product and substrate was also developed.

  16. Design, synthesis, insecticidal activity, and structure-activity relationship (SAR): studies of novel triazone derivatives containing a urea bridge group based on transient receptor potential (TRP) channels.

    Science.gov (United States)

    Yang, Yan; Liu, Yuxiu; Song, Hongjian; Li, Yongqiang; Wang, Qingmin

    2016-11-01

    Numerous compounds containing urea bridge and biurea moieties are used in a variety of fields, especially as drugs and pesticides. To search for novel, environmentally benign and ecologically safe pesticides with unique modes of action, four series of novel triazone analogues containing urea, thiourea, biurea, and thiobiurea bridge, respectively, were designed and synthesized, according to various calcium ion channel inhibitors which act on transient receptor potential protein. Their structures were characterized by [Formula: see text] NMR, [Formula: see text] NMR, and HRMS. The insecticidal activities of the new compounds were obtained. The bioassay results indicated that compounds containing a thiourea bridge and a thiobiurea bridge exhibited excellent insecticidal activities against bean aphid. Specifically, compounds [Formula: see text], [Formula: see text], and [Formula: see text] exhibited 85, 90, and 95 % activities, respectively, at 10 mg/kg. Compounds [Formula: see text] (30 %), [Formula: see text] (35 %), [Formula: see text] (30 %), and [Formula: see text] (40 %) exhibited the approximate aphicidal activity of pymetrozine (30 %) at 5 mg/kg. In addition, some target compounds exhibited insecticidal activities against lepidopteran pests. From a molecular design standpoint, the information obtained in this study could help in the further design of new derivatives with improved insecticidal activities.

  17. Functional interaction between TRP4 and CFTR in mouse aorta endothelial cells

    Directory of Open Access Journals (Sweden)

    Droogmans Guy

    2001-05-01

    Full Text Available Abstract Background This study describes the functional interaction between the putative Ca2+ channel TRP4 and the cystic fibrosis transmembrane conductance regulator, CFTR, in mouse aorta endothelium (MAEC. Results MAEC cells express CFTR transcripts as shown by RT-PCR analysis. Application of a phosphorylating cocktail activated a Cl- current with characteristics similar to those of CFTR mediated currents in other cells types (slow activation by cAMP, absence of rectification, block by glibenclamide. The current is present in trp4 +/+ MAEC, but not in trp4 -/- cells, although the expression of CFTR seems unchanged in the trp4 deficient cells as judged from RT-PCR analysis. Conclusions It is concluded that TRP4 is necessary for CFTR activation in endothelium, possibly by providing a scaffold for the formation of functional CFTR channels.

  18. 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.

  19. 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

  20. 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.

  1. 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.

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

    Science.gov (United States)

    Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H

    2012-06-30

    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.

  3. A C. elegans sperm TRP protein required for sperm-egg interactions during fertilization.

    Science.gov (United States)

    Xu, X-Z Shawn; Sternberg, Paul W

    2003-08-08

    Fertilization, a critical step in animal reproduction, is triggered by a series of specialized sperm-egg interactions. However, the molecular mechanisms underlying fertilization are not well understood. Here, we identify a sperm-enriched C. elegans TRPC homolog, TRP-3. Mutations in trp-3 lead to sterility in both hermaphrodites and males due to a defect in their sperm. trp-3 mutant sperm are motile, but fail to fertilize oocytes after gamete contact. TRP-3 is initially localized in intracellular vesicles, and then translocates to the plasma membrane during sperm activation. This translocation coincides with a marked increase in store-operated calcium entry, providing an in vivo mechanism for the regulation of TRP-3 activity. As C. elegans oocytes lack egg coats, our data suggest that some TRPC family channels might function to mediate calcium influx during sperm-egg plasma membrane interactions leading to fertilization.

  4. Solubility of cerium in LaCoO3-influence on catalytic activity.

    Science.gov (United States)

    French, S A; Catlow, C R A; Oldman, R J; Rogers, S C; Axon, S A

    2002-11-21

    The recent interest in the catalytic properties of lanthanum perovskites for methane combustion and three way catalysis has led to considerable debate as to their structure and defect chemistry. We have investigated the doping of LaCoO3 with the tetravalent cerium cation using atomistic simulation techniques. We have compared three routes for cerium insertion and identified the favoured doping mechanism, which explain experimental observations relating to the effect of cerium on catalytic activity.

  5. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Watzke, Anja; Wilson, Rebecca; O' Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  6. The preparation, characterisation and catalytic activity of tungsten bronzes

    OpenAIRE

    Stevenson, Sheena

    1987-01-01

    This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University. The structure and catalytic aspects of tungsten bronzes have been considered. A series of potassium tungsten bronzes, KxW03, 0.05 =< x =< 0.8, and the corresponding series of sodium tungsten bronzes, NaxW03, 0.05 =< x =< 0.8 were prepared by a thermal method. The thermal stability of the prepared samples was studied in the presence of both an oxidising and a reducing gas. The number and...

  7. Immunologically driven chemical engineering of antibodies for catalytic activity.

    Science.gov (United States)

    Dias, Sonia; Jovic, Florence; Renard, Pierre-Yves; Taran, Fréderic; Créminon, Christophe; Mioskowski, Charles; Grassi, Jacques

    2002-11-01

    We describe a new strategy for the preparation of catalytic antibodies based on a two-step procedure. Firstly, monoclonal antibodies are selected only if displaying the following binding features: binding both the substrate and a reactive group in such a way that the two groups are in a reactive position towards each other. Secondly, the selected monoclonal antibodies (mAbs) are chemically engineered by covalently binding the reactive group into the binding pocket of the antibody. Using previously isolated monoclonal antibodies, we have focused our studies on the control of this second step.

  8. Expression of transient receptor potential (TRP) channel mRNAs in the mouse olfactory bulb.

    Science.gov (United States)

    Dong, Hong-Wei; Davis, James C; Ding, ShengYuan; Nai, Qiang; Zhou, Fu-Ming; Ennis, Matthew

    2012-08-22

    Transient receptor potential (TRP) channels are a large family of cation channels. The 28 TRP channel subtypes in rodent are divided into 6 subfamilies: TRPC1-7, TRPV1-6, TRPM1-8, TRPP2/3/5, TRPML1-3 and TRPA1. TRP channels are involved in peripheral olfactory transduction. Several TRPC channels are expressed in unidentified neurons in the main olfactory bulb (OB), but the expression of most TRP channels in the OB has not been investigated. The present study employed RT-PCR as an initial survey of the expression of TRP channel mRNAs in the mouse OB and in 3 cell types: external tufted, mitral and granule cells. All TRP channel mRNAs except TRPV5 were detected in OB tissue. Single cell RT-PCR revealed that external tufted, mitral and granule cell populations expressed in aggregate 14 TRP channel mRNAs encompassing members of all 6 subfamilies. These different OB neuron populations expressed 7-12 channel mRNAs. Common channel expression was more similar among external tufted and mitral cells than among these cells and granule cells. These results indicate that a large number of TRP channel subtypes are expressed in OB neurons, providing the molecular bases for these channels to regulate OB neuron activity and central olfactory processing.

  9. Isolated Cu2+ ions: active sites for selective catalytic reduction of NO

    NARCIS (Netherlands)

    Korhonen, S.T.; Fickel, D.W.; Lobo, R.F.; Weckhuysen, B.M.; Beale, A.M.

    2011-01-01

    Cu chabazite catalysts show remarkable low temperature activity in selective catalytic reduction (SCR) of NO. This high activity is due to the unique character of the zeolite framework that allows only the presence of one type of isolated mononuclear Cu2+ species. These Cu2+ species are the active s

  10. High activity in catalytic cracking of large molecules over micro-mesoporous silicoaluminophosphate with controlled morphology

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel micro-mesoporous silicoaluminophosphate(MUS-5) with controlled morphology has been first synthesized in a two-step route.The physical properties of the silicoaluminophosphate were characterized using XRD,SEM,TEM,nitrogen adsorption-desorption and NH3-TPD techniques.When the pH value of the solution system was varied in the range from 2.0 to 5.0,three different morphologies of silicoaluminophosphate including chain-like,flower-like and barrel-like morphology were obtained.Catalytic tests showed that the silicoaluminophosphate exhibited higher catalytic activity compared with the conventional microporous SAPO-5 under the same conditions for catalytic cracking of 1,3,5-triisopropylbenzene heavy aromatics.The remarkable catalytic reactivity was mainly attributed to the presence of the hierarchical porosity in the silicoaluminophosphate catalyst.

  11. Structural models of vanadate-dependent haloperoxidases, their reactivity, immobilization on polymer support and catalytic activities

    Indian Academy of Sciences (India)

    Mannar R Maurya

    2011-03-01

    The design of structural and functional models of enzymes vanadate-dependent haloperoxidases (VHPO) and the isolation and/or generation of species having {VO(H2O)}, {VO2}, {VO(OH)} and {VO(O2)} cores, proposed as intermediate(s) during catalytic action, in solution have been studied. Catalytic potential of these complexes have been tested for oxo-transfer as well as oxidative bromination and sulfide oxidation reactions. Some of the oxidovanadium(IV) and dioxidovanadium(V) complexes have been immobilized on polymer support in order to improve their recycle ability during catalytic activities and turn over number. The formulations of the polymer-anchored complexes are based on the respective neat complexes and conclusions drawn from the various characterization studies. These catalysts have successfully been used for all catalytic reactions mentioned above. These catalysts are stable and recyclable.

  12. Study on the correlation between the surface active species of Pd/cordierite monolithic catalyst and its catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Hengcheng, E-mail: hengchengliao@seu.edu.cn; Zuo, Peiyuan; Liu, Miaomiao

    2016-09-15

    Two Pd-loading routes and three Pd-precursor matters were adopted to prepare Pd/(Ce,Y)O{sub 2}/γ-Al{sub 2}O{sub 3}/cordierite monolithic catalyst. The surface active species on the catalyst were characterized by XPS, and its catalytic activity for methane combustion was tested, and the dynamics of the catalytic combustion reaction was also discussed. Pd-loading route and Pd-precursor mass have a significant influence on the catalytic activity and surface active species. The sol dipping method is more advanced than the aqueous solution impregnating method. PN-sol catalyst, by sol dipping combined with Pd(NO{sub 3}){sub 2}-precursor, has the best catalytic activity. The physical reason is the unique active Pd phase coexisting with active PdO phase on the surface, and thus the Pd3d{sub 5/2} binding energy of surface species and apparent activation energy of combustion reaction are considerably decreased. The catalytic activity index, Pd3d{sub 5/2} binding energy and apparent activation energy are highly tied each other with exponential relations.

  13. Removal performance and mechanism of ibuprofen from water by catalytic ozonation using sludge-corncob activated carbon as catalyst.

    Science.gov (United States)

    Wang, Hongjuan; Zhang, Liqiu; Qi, Fei; Wang, Xue; Li, Lu; Feng, Li

    2014-09-01

    To discover the catalytic activity of sludge-corncob activated carbon in catalytic ozonation of Ibuprofen, the performance of sludge-corncob activated carbon and three selected commercial activated carbons as catalysts in catalytic ozonation was investigated. The observation indicates the degradation rate of Ibuprofen increases significantly in the presence of sludge-corncob activated carbon and the catalytic activity of sludge-corncob activated carbon is much higher than that of the other three commercial activated carbons. Ibuprofen's removal rate follows pseudo-first order kinetics model well. It is also found that the adsorption removal of Ibuprofen by sludge-corncob activated carbon is less than 30% after 40 min. And the removal efficiency of Ibuprofen in the hybrid ozone/sludge-corncob activated carbon system is higher than the sum of sludge-corncob activated carbon adsorption and ozonation alone, which is a supportive evidence for catalytic reaction. In addition, the results of radical scavenger experiments demonstrate that catalytic ozonation of Ibuprofen by sludge-corncob activated carbon follows a hydroxyl radical reaction pathway. During ozonation of Ibuprofen in the presence of activated carbon, ozone could be catalytically decomposed to form hydrogen peroxide, which can promote the formation of hydroxyl radical. The maximum amount of hydrogen peroxide occurs in the presence of sludge-corncob activated carbon, which can explain why sludge-corncob activated carbon has the best catalytic activity among four different activated carbons.

  14. Catalytic activity of cerium-doped Ru/Al2O3 during ozonation of dimethyl phthalate

    Institute of Scientific and Technical Information of China (English)

    Yunrui ZHOU; Wanpeng ZHU; Xun CHEN

    2008-01-01

    In this paper, factors influencing the mineraliza-tion of dimethyl phthalate (DMP) during catalytic ozona-tion with a cerium-doped Ru/Al2O3 catalyst were studied. The catalytic contribution was calculated through the results of a companrison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 rain reached 75.1%, 61.3% using Ru/Al2O3 catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium'were simultaneously loaded onto Al2O3 support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion's and heterogeneous catalytic ozonation confirmed that the contribution of het-erogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru-Ce/Al2O3 on catalytic activity.

  15. Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones.

    Science.gov (United States)

    Zhang, Junmin; Xing, Chong; Tiwari, Bhoopendra; Chi, Yonggui Robin

    2013-06-05

    We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.

  16. Catalytic activity of titania zirconia mixed oxide catalyst for dimerization eugenol

    Science.gov (United States)

    Tursiloadi, S.; Kristiani, A.; Jenie, S. N. Aisyiyah; Laksmono, J. A.

    2017-01-01

    Clove oil has been found to possess antibacterial, antifungal, antiviral, antitumor, antioxidant and insecticidal properties. The major compound of clove oil is eugenol about 49-87%. Eugenol as phenolic compounds exhibits antioxidant and antimicrobial activities. The derivative compound of eugenol, dieugenol, show antioxidant potency better than parent eugenol. A series of TiO2-ZrO2 mixed oxides (TZ) with various titanium contents from 0 to 100wt%, prepared by using sol gel method were tested their catalytic activity for dimerization eugenol, Their catalytic activity show that these catalysts resulted a low yield of dimer eugenol, dieugenol, about 2-9 % and the purity is more than 50%.

  17. 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.

  18. [Catalytic ozonation of nitrobenzene in water by acidification-activated red mud].

    Science.gov (United States)

    Kang, Ya-ning; Li, Hua-nan; Xu, Bing-bing; Qi, Fei; Zhao, Lun

    2013-05-01

    Red mud as one kind of aluminum industrial wastes was used as raw material for catalyst preparation. It was activated by acidification in order to enhance its catalytic activity in the system of catalytic ozonation. Furthermore, removal performance and reaction mechanism in degradation of organic pollutants were discussed. Results showed that acid modified red mud had more significant catalytic activity than the raw red mud. The removal efficiency of nitrobenzene by catalytic ozonation with acidified red mud (RM6.0) increased with the increasing ozone concentration. When the ozone concentration was increased from 0.4 mg x L(-1) to 1.7 mg x L(-1), the removal efficiency of nitrobenzene increased from 45% to 92%. There was a consistent effect of water pH on the removal efficiency and the ozone concentration variation. The variation of the removal efficiency depended on the initial water pH. This was because the concentration of OH(-) led to ozone decomposition to generate hydroxyl radicals. The higher water pH value led to the quenching of hydroxyl radicals, resulting in the reduction of catalytic activity of RM6.0. The experimental results of aqueous ozone concentration variation in the presence of RM6.0 and inhibition by hydroxyl radicals indicated that the main reaction mechanism was catalytic ozonation of NB. Firstly, aqueous ozone was absorbed onto the surface of RM6.0, and then the concentrated ozone oxidized NB in water which was with a combination of direct and indirect oxidation. In catalytic reaction, hydroxyl radicals were present, which were generated during the oxidation of NB on the surface of RM6.0.

  19. Effect of BaO on Catalytic Activity of Pt-Rh TWC

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The effects of BaO doping on the three-way catalytic activity of Pt-Rh catalyst and on water-gas shift were investigated. The results show that the light-off temperatures of hydrocarbon and carbon monoxide and nitrogen oxides of the fresh catalysts slightly differ from those of the aged catalysts, and the catalysts containing CeO2-ZrO2-BaO have lower lightoff temperature and better catalytic activity than these containing BaO and CeO2-ZrO2 after hydrothermal aging for 5 h at 1000 C. The catalysts were characterized by means of the temperature-programmed reduction (TPR) in hydrogen and the temperature-programmed desorption (TPD) in oxygen. It is confirmed that the suggested route of CeO2-ZrO2-BaO by coprecipitation can improve the catalytic activity of catalysts.

  20. 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

  1. A Model of Irregular Impurity at the Surface of Nanoparticle and Catalytic Activity

    Institute of Scientific and Technical Information of China (English)

    I.V.Blinova; V.V.Gusarov; I.Yu.Popov

    2012-01-01

    A problem of nanocatalyst improvement is considered. The existence of irregularities at the surface of nanoparticle leads to the increasing of the surface/volume ratio and, correspondingly, to the improvement of the catalytic activity. But this impurity gives one an additional effect due to the change of the electronic density at the surface. We suggest simple model for the description of this effect. The model allows one to find the discrete spectrum of the Schrdinger operator for nanoparticle. Due to this impurity induced bound states the electron density increases near the surface. It leads to the increase of the catalytic activity of nanoparticles with surface impurities.

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

    Science.gov (United States)

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

    2016-08-01

    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.

  3. Influence of Al content on textural properties and catalytic activity of hierarchical porous aluminosilicate materials

    Indian Academy of Sciences (India)

    Ling Xu; Limei Duan; Zongrui Liu; Jingqi Guan; Qiubin Kan

    2013-12-01

    A series of hierarchical porous aluminosilicate materials were prepared using hydrothermal treatment of the composite formed by polystyrene colloidal spheres and aluminosilicate gel. Influence of Al content on the textural properties, acidic properties and catalytic activity of the hierarchical porous aluminosilicate materials was studied. The results showed that textural and acidic properties of the hierarchical porous aluminosilicate materials were strongly related to Al content. As Al content is increased (Si/Al = 25), the hierarchical porous catalysts exhibited higher catalytic activity and major product selectivity for alkylation of phenol with tert-butanol than the catalysts with a lower Al content (Si/Al = 50).

  4. Catalytic decomposition of low level ozone with gold nanoparticles supported on activated carbon

    Institute of Scientific and Technical Information of China (English)

    Pengyi ZHANG; Bo ZHANG; Rui SHI

    2009-01-01

    Highly dispersed gold nanoparticles were supported on coal-based activated carbon (AC) by a sol immobilization method and were used to investigate their catalytic activity for low-level ozone decomposition at ambient temperature. Nitrogen adsorption-desorption,scanning electron microscope (SEM), and X-ray photo-electron spectroscopy (XPS) were used to characterize the catalysts before and after ozone decomposition. The results showed that the supported gold nanoparticles prepared with microwave heating were much smaller and more uniformly dispersed on the activated carbon than those prepared with traditional conduction heating, exhibiting higher catalytic activity for ozone decomposition. The pH values of gold precursor solution significantly influenced the catalytic activity of supported gold for ozone decomposition, and the best pH value was 8. In the case of space velocity of 120000 h-1, inlet ozone concentration of 50mg/m3, and relative humidity of 45%, the Au/AC catalyst maintained the ozone removal ratio at 90.7% after 2500 min. After being used for ozone decomposition, the surface carbon of the catalyst was partly oxidized and the oxygen content increased accordingly, while its specific surface area and pore volume only decreased a little.Ozone was mainly catalytically decomposed by the gold nanoparticles supported on the activated carbon.

  5. CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung

    2009-12-15

    This paper presents an original approach to the removal of phenol in synthetic wastewater by catalytic wet peroxide oxidation with copper binding activated carbon (CuAC) catalysts. The characteristics and oxidation performance of CuAC in the wet hydrogen peroxide catalytic oxidation of phenol were studied in a batch reactor at 80 degrees C. Complete conversion of the oxidant, hydrogen peroxide, was observed with CuAC catalyst in 20 min oxidation, and a highly efficient phenol removal and chemical oxygen demand (COD) abatement were achieved in the first 30 min. The good oxidation performance of CuAC catalyst was contributed to the activity enhancement of copper oxide, which was binding in the carbon matrix. It can be concluded that the efficiency of oxidation dominated by the residual H2O2 in this study. An over 90% COD removal was achieved by using the multiple-step addition in this catalytic oxidation.

  6. The Impact of Enzyme Orientation and Electrode Topology on the Catalytic Activity of Adsorbed Redox Enzymes

    Science.gov (United States)

    McMillan, Duncan G. G.; Marritt, Sophie J.; Kemp, Gemma L.; Gordon-Brown, Piers; Butt, Julea N.; Jeuken, Lars J. C.

    2014-01-01

    It is well established that the structural details of electrodes and their interaction with adsorbed enzyme influences the interfacial electron transfer rate. However, for nanostructured electrodes, it is likely that the structure also impacts on substrate flux near the adsorbed enzymes and thus catalytic activity. Furthermore, for enzymes converting macro-molecular substrates it is possible that the enzyme orientation determines the nature of interactions between the adsorbed enzyme and substrate and therefore catalytic rates. In essence the electrode may impede substrate access to the active site of the enzyme. We have tested these possibilities through studies of the catalytic performance of two enzymes adsorbed on topologically distinct electrode materials. Escherichia coli NrfA, a nitrite reductase, was adsorbed on mesoporous, nanocrystalline SnO2 electrodes. CymA from Shewanella oneidensis MR-1 reduces menaquinone-7 within 200 nm sized liposomes and this reaction was studied with the enzyme adsorbed on SAM modified ultra-flat gold electrodes. PMID:24634538

  7. The Impact of Enzyme Orientation and Electrode Topology on the Catalytic Activity of Adsorbed Redox Enzymes.

    Science.gov (United States)

    McMillan, Duncan G G; Marritt, Sophie J; Kemp, Gemma L; Gordon-Brown, Piers; Butt, Julea N; Jeuken, Lars J C

    2013-11-01

    It is well established that the structural details of electrodes and their interaction with adsorbed enzyme influences the interfacial electron transfer rate. However, for nanostructured electrodes, it is likely that the structure also impacts on substrate flux near the adsorbed enzymes and thus catalytic activity. Furthermore, for enzymes converting macro-molecular substrates it is possible that the enzyme orientation determines the nature of interactions between the adsorbed enzyme and substrate and therefore catalytic rates. In essence the electrode may impede substrate access to the active site of the enzyme. We have tested these possibilities through studies of the catalytic performance of two enzymes adsorbed on topologically distinct electrode materials. Escherichia coli NrfA, a nitrite reductase, was adsorbed on mesoporous, nanocrystalline SnO2 electrodes. CymA from Shewanella oneidensis MR-1 reduces menaquinone-7 within 200 nm sized liposomes and this reaction was studied with the enzyme adsorbed on SAM modified ultra-flat gold electrodes.

  8. Role of Phe-99 and Trp-196 of sepiapterin reductase from Chlorobium tepidum in the production of L-threo-tetrahydrobiopterin

    Institute of Scientific and Technical Information of China (English)

    Supangat; Sun Ok Park; Kyung Hye Seo; Sang Yeol Lee; Young Shik Park; Kon Ho Lee

    2008-01-01

    Sepiapterin reductase from Chlorobium tepidum (cSR) catalyzes the synthesis of a distinct tetrahydrobiopterin (BH4), L-threo-BH4, different from the mammalian enzyme product. The 3-D crystal structure of cSR has revealed that the product configuration is determined solely by the substrate binding mode within the well-conserved catalytic triads. In cSR, the sepiapterin is stacked between two aromatic side chains of Phe-99 and Trp-196 and rotated approximately 180o around the active site from the position in mouse sepiapterin reductase. To confirm their roles in substrate binding, we mutated Phe-99 and/or Trp-196 to alanine (F99A, W196A) by site-directed mutagenesis and comparatively examined substrate binding of the purified proteins by kinetics analysis and differential scanning calorimetry. These mutants had higher Km values than the wild type. Remarkably, the W196A mutation resulted in a higher Km increase compared with the F99A mutation. Consistent with the results, the melting temperature (Tm) in the presence of sepiapterin was lower in the mutant proteins and the worst was W196A. These findings indicate that the two residues are indispensable for substrate binding in cSR, and Trp-196 is more important than Phe-99 for different stereoisomer production.

  9. Study on the Carbon-Methanation and Catalytic Activity of Ru/AC for Ammonia Synthesis

    Institute of Scientific and Technical Information of China (English)

    祝一锋; 李小年; 季德春; 刘化章

    2004-01-01

    The effects of promoters K, Ba, Sm on the resistance to carbon-methanation and catalytic activity of ruthenium supported on active carbon (Ru/AC) for ammonia synthesis have been studied by means of TG-DTG (thermalgravity-differential thermalgravity), temperature-programmed desorption, and activity test. Promoters Ba,K, and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly. Much higher activity can be reached for Ru/AC catalyst with bi- or tri-promoters. Indeed, the triply promoted catalyst showed the highest activity, coupled to a surprisingly high resistance to methanation. The ability of resistance of promoter to methanation of Ru/AC catalyst is dependent on the adsorption intensity of hydrogen. The strong adsorption of hydrogen would enhance methanation and impact the adsorption of nitrogen, which results in the decrease of catalytic activity.

  10. Studies relevant to the catalytic activation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Ford, P.C.

    1992-06-04

    Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.

  11. CATALYTIC ACTIVITIES OF RARE-EARTH CALIXARENE COMPLEXES IN POLYMER SYNTHESES

    Institute of Scientific and Technical Information of China (English)

    Zhi-quan Shen

    2005-01-01

    The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene,styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

  12. HIGH-THROUGHPUT IDENTIFICATION OF CATALYTIC REDOX-ACTIVE CYSTEINE RESIDUES

    Science.gov (United States)

    Cysteine (Cys) residues often play critical roles in proteins; however, identification of their specific functions has been limited to case-by-case experimental approaches. We developed a procedure for high-throughput identification of catalytic redox-active Cys in proteins by se...

  13. 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.

  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...

  15. 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.

  16. SYNTHESIS AND CATALYTIC ACTIVITY OF PLATINUM COMPLEX OF ACRYLATE TERPOLYMER WITH Se,N BIDENTATE LIGAND

    Institute of Scientific and Technical Information of China (English)

    MengLingzhi; QiLiangwei; 等

    1998-01-01

    Acrylate terpolymer-bound Se,N bidentate ligand was synthesized from the side chain chlorine of copolymer and β-dimethylamino-β′-hydroxyl-diethyl selenoether.The polymer-supported platinum complex exhibited high catalytic activity in the hydrosilylation of olefins with triethoxysilane.

  17. Activity prediction of substrates in NADH-dependent carbonyl reductase by docking requires catalytic constraints and charge parameterization of catalytic zinc environment.

    Science.gov (United States)

    Dhoke, Gaurao V; Loderer, Christoph; Davari, Mehdi D; Ansorge-Schumacher, Marion; Schwaneberg, Ulrich; Bocola, Marco

    2015-11-01

    Molecular docking of substrates is more challenging compared to inhibitors as the reaction mechanism has to be considered. This becomes more pronounced for zinc-dependent enzymes since the coordination state of the catalytic zinc ion is of greater importance. In order to develop a predictive substrate docking protocol, we have performed molecular docking studies of diketone substrates using the catalytic state of carbonyl reductase 2 from Candida parapsilosis (CPCR2). Different docking protocols using two docking methods (AutoDock Vina and AutoDock4.2) with two different sets of atomic charges (AM1-BCC and HF-RESP) for catalytic zinc environment and substrates as well as two sets of vdW parameters for zinc ion were examined. We have selected the catalytic binding pose of each substrate by applying mechanism based distance criteria. To compare the performance of the docking protocols, the correlation plots for the binding energies of these catalytic poses were obtained against experimental Vmax values of the 11 diketone substrates for CPCR2. The best correlation of 0.73 was achieved with AutoDock4.2 while treating catalytic zinc ion in optimized non-bonded (NBopt) state with +1.01 charge on the zinc ion, compared to 0.36 in non-bonded (+2.00 charge on the zinc ion) state. These results indicate the importance of catalytic constraints and charge parameterization of catalytic zinc environment for the prediction of substrate activity in zinc-dependent enzymes by molecular docking. The developed predictive docking protocol described here is in principle generally applicable for the efficient in silico substrate spectra characterization of zinc-dependent ADH.

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

    Science.gov (United States)

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

    2004-01-01

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

  19. Positions of Trp codons in the leader peptide-coding region of the at operon influence anti-trap synthesis and trp operon expression in Bacillus licheniformis.

    Science.gov (United States)

    Levitin, Anastasia; Yanofsky, Charles

    2010-03-01

    Tryptophan, phenylalanine, tyrosine, and several other metabolites are all synthesized from a common precursor, chorismic acid. Since tryptophan is a product of an energetically expensive biosynthetic pathway, bacteria have developed sensing mechanisms to downregulate synthesis of the enzymes of tryptophan formation when synthesis of the amino acid is not needed. In Bacillus subtilis and some other Gram-positive bacteria, trp operon expression is regulated by two proteins, TRAP (the tryptophan-activated RNA binding protein) and AT (the anti-TRAP protein). TRAP is activated by bound tryptophan, and AT synthesis is increased upon accumulation of uncharged tRNA(Trp). Tryptophan-activated TRAP binds to trp operon leader RNA, generating a terminator structure that promotes transcription termination. AT binds to tryptophan-activated TRAP, inhibiting its RNA binding ability. In B. subtilis, AT synthesis is upregulated both transcriptionally and translationally in response to the accumulation of uncharged tRNA(Trp). In this paper, we focus on explaining the differences in organization and regulatory functions of the at operon's leader peptide-coding region, rtpLP, of B. subtilis and Bacillus licheniformis. Our objective was to correlate the greater growth sensitivity of B. licheniformis to tryptophan starvation with the spacing of the three Trp codons in its at operon leader peptide-coding region. Our findings suggest that the Trp codon location in rtpLP of B. licheniformis is designed to allow a mild charged-tRNA(Trp) deficiency to expose the Shine-Dalgarno sequence and start codon for the AT protein, leading to increased AT synthesis.

  20. New insights into TRP channels: Interaction with pattern recognition receptors.

    Science.gov (United States)

    Han, Huirong; Yi, Fan

    2014-01-01

    An increasing number of studies have implicated that the activation of innate immune system and inflammatory mechanisms are of importance in the pathogenesis of numerous diseases. The innate immune system is present in almost all multicellular organisms in response to pathogens or tissue injury, which is performed via germ-line encoded pattern-recognition receptors (PRRs) to recognize pathogen-associated molecular patterns (PAMPs) or dangers-associated molecular patterns (DAMPs). Intracellular pathways linking immune and inflammatory response to ion channel expression and function have been recently identified. Among ion channels, transient receptor potential (TRP) channels are a major family of non-selective cation-permeable channels that function as polymodal cellular sensors involved in many physiological and pathological processes. In this review, we summarize current knowledge about classifications, functions, and interactions of TRP channels and PRRs, which may provide new insights into their roles in the pathogenesis of inflammatory diseases.

  1. A Polyphenylene Support for Pd Catalysts with Exceptional Catalytic Activity

    DEFF Research Database (Denmark)

    Wang, Feng; Mielby, Jerrik Jørgen; Richter, Felix Herrmann

    2014-01-01

    We describe a solid polyphenylene support that serves as an excellent platform for metal-catalyzed reactions that are normally carried out under homogeneous conditions. The catalyst is synthesized by palladium-catalyzed Suzuki coupling which directly results in formation of palladium nanoparticles...... confined to a porous polyphenylene network. The composite solid is in turn highly active for further Suzuki coupling reactions, including non-activated substrates that are challenging even for molecular catalysts....

  2. Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction

    Science.gov (United States)

    Cherkezova-Zheleva, Z.; Paneva, D.; Todorova, S.; Kolev, H.; Shopska, M.; Yordanova, I.; Mitov, I.

    2014-04-01

    Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H2 oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.

  3. 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

  4. 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  

  5. Anacardic acid inhibits the catalytic activity of matrix metalloproteinase-2 and matrix metalloproteinase-9.

    Science.gov (United States)

    Omanakuttan, Athira; Nambiar, Jyotsna; Harris, Rodney M; Bose, Chinchu; Pandurangan, Nanjan; Varghese, Rebu K; Kumar, Geetha B; Tainer, John A; Banerji, Asoke; Perry, J Jefferson P; Nair, Bipin G

    2012-10-01

    Cashew nut shell liquid (CNSL) has been used in traditional medicine for the treatment of a wide variety of pathophysiological conditions. To further define the mechanism of CNSL action, we investigated the effect of cashew nut shell extract (CNSE) on two matrix metalloproteinases, MMP-2/gelatinase A and MMP-9/gelatinase B, which are known to have critical roles in several disease states. We observed that the major constituent of CNSE, anacardic acid, markedly inhibited the gelatinase activity of 3T3-L1 cells. Our gelatin zymography studies on these two secreted gelatinases, present in the conditioned media from 3T3-L1 cells, established that anacardic acid directly inhibited the catalytic activities of both MMP-2 and MMP-9. Our docking studies suggested that anacardic acid binds into the MMP-2/9 active site, with the carboxylate group of anacardic acid chelating the catalytic zinc ion and forming a hydrogen bond to a key catalytic glutamate side chain and the C15 aliphatic group being accommodated within the relatively large S1' pocket of these gelatinases. In agreement with the docking results, our fluorescence-based studies on the recombinant MMP-2 catalytic core domain demonstrated that anacardic acid directly inhibits substrate peptide cleavage in a dose-dependent manner, with an IC₅₀ of 11.11 μM. In addition, our gelatinase zymography and fluorescence data confirmed that the cardol-cardanol mixture, salicylic acid, and aspirin, all of which lack key functional groups present in anacardic acid, are much weaker MMP-2/MMP-9 inhibitors. Our results provide the first evidence for inhibition of gelatinase catalytic activity by anacardic acid, providing a novel template for drug discovery and a molecular mechanism potentially involved in CNSL therapeutic action.

  6. Trends in Catalytic Activity for SOFC Anode materials

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Bessler, W. G.

    2008-01-01

    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...

  7. Chelating ruthenium phenolate complexes: synthesis, general catalytic activity, and applications in olefin metathesis polymerization.

    Science.gov (United States)

    Kozłowska, Anna; Dranka, Maciej; Zachara, Janusz; Pump, Eva; Slugovc, Christian; Skowerski, Krzysztof; Grela, Karol

    2014-10-20

    Cyclic Ru-phenolates were synthesized, and these compounds were used as olefin metathesis catalysts. Investigation of their catalytic activity pointed out that, after activation with chemical agents, these catalysts promote ring-closing metathesis (RCM), enyne and cross-metathesis (CM) reactions, including butenolysis, with good results. Importantly, these latent catalysts are soluble in neat dicyclopentadiene (DCPD) and show good applicability in ring-opening metathesis polymeriyation (ROMP) of this monomer.

  8. Study on the active sites of Cu-ZSM-5 in trichloroethylene catalytic combustion with air

    Institute of Scientific and Technical Information of China (English)

    Cheng Hua Xu; Chuan Qi Liu; Yan Zhong; Xiu Zhou Yang; Jian Ying Liu; Ying Chun Yang; Zhi Xiang Ye

    2008-01-01

    The catalytic activity of Cu-ZSM-5 in trichloroethylene (TCE) combustion increases with the increasing skeletal Cu amount and however decreases with the increase of surface amorphous CuO,which is detected by infrared spectroscopy (IR) and diffuse reflectance ultraviolet-visible spectroscopy (DRS-UV-vis),therefore the skeletal Cu species are concluded to be the active sites for the TCE combustion.

  9. Aged nano-structured platinum based catalyst: effect of chemical treatment on adsorption and catalytic activity.

    Science.gov (United States)

    Shim, Wang Geun; Nahm, Seung Won; Park, Hyuk Ryeol; Yun, Hyung Sun; Seo, Seong Gyu; Kim, Sang Chai

    2011-02-01

    To examine the effect of chemical treatment on the adsorption and catalytic activity of nanostructured platinum based catalyst, the aged commercial Pt/AC catalyst was pretreated with sulfuric acid (H2SO4) and a cleaning agent (Hexane). Several reliable methods such as nitrogen adsorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) were employed to characterize the aged Pt/AC catalyst and its chemically pretreated Pt/AC catalysts. The catalytic and adsorption activities of nano-structured heterogeneous Pt/AC catalyst were investigated on the basis of toluene oxidation and adsorption isotherm data. In addition, the adsorption isotherms of toluene were used to calculate the adsorption energy distribution functions for the parent catalyst and its pre-treated nano-structured Pt/AC catalysts. It was found that sulfuric acid aqueous treatment can enhance the catalytic performance of aged Pt/AC catalyst toward catalytic oxidation of toluene. It was also shown that a comparative analysis of the energy distribution functions for nano-structured Pt/AC catalysts as well as the pore size distribution provides valuable information about their structural and energetic heterogeneity.

  10. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Abdou, Safaa N.

    2015-01-01

    The 3D-supramolecular coordination polymer (SCP) 3∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3ṡMe3Pbṡqox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.

  11. Ehrlichia chaffeensis TRP32 is a Nucleomodulin that Directly Regulates Expression of Host Genes Governing Differentiation and Proliferation.

    Science.gov (United States)

    Farris, Tierra R; Dunphy, Paige S; Zhu, Bing; Kibler, Clayton E; McBride, Jere W

    2016-08-29

    Ehrlichia chaffeensis is an obligately intracellular bacterium that reprograms the mononuclear phagocyte through diverse effector-host interactions to modulate numerous host cell processes, including transcription. In a previous study, we reported that E. chaffeensis TRP32, a type 1 secreted effector, interacts with multiple host nucleus-associated proteins and also auto-activates reporter gene expression in yeast. In this study, we demonstrate that TRP32 is a nucleomodulin that binds host DNA and alters host gene transcription. TRP32 enters the host cell nucleus via a noncanonical translocation mechanism that involves phosphorylation of Y179 located in a C-terminal tri-tyrosine motif. Both genistein and mutation of Y179 inhibited TRP32 nuclear entry. An electromobility shift assay (EMSA) demonstrated TRP32 host DNA binding via its tandem repeat domain. TRP32 DNA binding and motif preference were further confirmed by supershift assays, as well as competition and mutant probe analyses. Using ChIP-Seq, we determined that TRP32 binds a G-rich motif primarily within ±500 bp of the gene transcription start site. An ontology analysis identified genes involved in processes such as immune cell differentiation, chromatin remodeling, and RNA transcription and processing, as primary TRP32 targets. TRP32 bound genes (n=1223) were distributed on all chromosomes and included several global regulators of proliferation and inflammation such as FOS and JUN, AKT3 and NRAS, and non-coding RNA genes, miRNA 21 and miRNA 142. TRP32 target genes were differentially regulated during infection, the majority of which were repressed, and direct repression/activation of these genes by TRP32 was confirmed in vitro with a cellular luciferase reporter assay.

  12. Comparative catalytic activity of PET track-etched membranes with embedded silver and gold nanotubes

    Science.gov (United States)

    Mashentseva, Anastassiya; Borgekov, Daryn; Kislitsin, Sergey; Zdorovets, Maxim; Migunova, Anastassiya

    2015-12-01

    Irradiated by heavy ions nanoporous polyethylene terephthalate track-etched membranes (PET TeMs) after +15Kr84 ions bombardment (1.75 MeV/nucl with the ion fluency of 1 × 109 cm-2) and sequential etching was applied in this research as a template for development of composites with catalytically enriched properties. A highly ordered silver and gold nanotubes arrays were embedded in 100 nm pores of PET TeMs via electroless deposition technique at 4 °C during 1 h. All "as-prepared" composites were examined for catalytic activity using reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride as a common reaction to test metallic nanostructures catalysts. The effect of temperature on the catalytic activity was investigated in range of 292-313 K and activation energy were calculated. Kapp of Ag/PET composites linearly increase with an increase of the temperature thus normal Arrhenius behavior have been seen and the activation energy was calculated to be 42.13 kJ/mol. Au/PET composites exhibit not only more powerful catalytic activity but also non-linear dependence of rate constant from temperature. Kapp increased with increasing temperature throughout the 292-308 K temperature range; the reaction had an activation energy 65.32 kJ/mol. In range 311-313 K rate constant dramatically decreased and the apparent activation energy at this temperature rang was -91.44 kJ/mol due some structural changes, i.e. agglomeration of Au nanoparticles on the surface of composite.

  13. Comparative catalytic activity of PET track-etched membranes with embedded silver and gold nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Mashentseva, Anastassiya, E-mail: mashentseva.a@gmail.com [Institute of Nuclear Physics, Ibragimov St. 1, 050032 Almaty (Kazakhstan); The L.N. Gumilyov Eurasian National University, Satpayev Str., 2, 010008 Astana (Kazakhstan); Borgekov, Daryn [Institute of Nuclear Physics, Ibragimov St. 1, 050032 Almaty (Kazakhstan); The L.N. Gumilyov Eurasian National University, Satpayev Str., 2, 010008 Astana (Kazakhstan); Kislitsin, Sergey [Institute of Nuclear Physics, Ibragimov St. 1, 050032 Almaty (Kazakhstan); Zdorovets, Maxim [Institute of Nuclear Physics, Ibragimov St. 1, 050032 Almaty (Kazakhstan); The L.N. Gumilyov Eurasian National University, Satpayev Str., 2, 010008 Astana (Kazakhstan); Migunova, Anastassiya [Institute of Nuclear Physics, Ibragimov St. 1, 050032 Almaty (Kazakhstan)

    2015-12-15

    Irradiated by heavy ions nanoporous polyethylene terephthalate track-etched membranes (PET TeMs) after {sup +15}Kr{sup 84} ions bombardment (1.75 MeV/nucl with the ion fluency of 1 × 10{sup 9} cm{sup −2}) and sequential etching was applied in this research as a template for development of composites with catalytically enriched properties. A highly ordered silver and gold nanotubes arrays were embedded in 100 nm pores of PET TeMs via electroless deposition technique at 4 °C during 1 h. All “as-prepared” composites were examined for catalytic activity using reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride as a common reaction to test metallic nanostructures catalysts. The effect of temperature on the catalytic activity was investigated in range of 292–313 K and activation energy were calculated. K{sub app} of Ag/PET composites linearly increase with an increase of the temperature thus normal Arrhenius behavior have been seen and the activation energy was calculated to be 42.13 kJ/mol. Au/PET composites exhibit not only more powerful catalytic activity but also non-linear dependence of rate constant from temperature. K{sub app} increased with increasing temperature throughout the 292–308 K temperature range; the reaction had an activation energy 65.32 kJ/mol. In range 311–313 K rate constant dramatically decreased and the apparent activation energy at this temperature rang was −91.44 kJ/mol due some structural changes, i.e. agglomeration of Au nanoparticles on the surface of composite.

  14. 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.

  15. Killing of Staphylococcus aureus and Salmonella enteritidis and neutralization of lipopolysaccharide by 17-residue bovine lactoferricins: improved activity of Trp/Ala-containing molecules

    Science.gov (United States)

    Hao, Ya; Yang, Na; Wang, Xiumin; Teng, Da; Mao, Ruoyu; Wang, Xiao; Li, Zhanzhan; Wang, Jianhua

    2017-01-01

    Bovine lactoferricin (LfcinB) has potent antibacterial, antifungal and antiparasitic activities but is also hemolytic. Our objective was to identify LfcinB17-31 derivatives with reduced hemolysis and improved antimicrobial activity via substituting Cys3, Arg4, Gln7, Met10, and Gly14 with more hydrophobic residues. Two peptides, Lfcin4 and Lfcin5, showed higher activity against Staphylococcus aureus and Salmonella enteritidis and lower hemolytic activity than the parent peptide LfcinB17-31. These peptides permeabilized the outer and inner membranes of S. enteritidis; however, Lfcin5 did not permeabilize the inner membrane of S. aureus. Gel retardation and circular dichroism spectra showed that Lfcin4 and Lfcin5 bound to bacterial genomic DNA. Lfcin4 inhibited DNA, RNA and protein synthesis. Both peptides induced the peeling of membranes and the lysis of S. enteritidis. At doses of 10 and 15 mg/kg, Lfcin4 and Lfcin5 reduced the bacterial counts in infected thigh muscles by 0.03‒0.10 and 0.05‒0.63 log10 CFU/g of tissue, respectively, within 10 h. Lfcin4 and Lfcin5 enhanced the survival rate of endotoxemic mice; reduced serum IL-6, IL-1β and TNF-α levels; and protected mice from lipopolysaccharide-induced lung injury. These data suggest that Lfcin4 and Lfcin5 may be antimicrobial and anti-endotoxin peptides that could serve as the basis for the development of dual-function agents. PMID:28287172

  16. 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.

  17. Structural properties of cyanase. Denaturation, renaturation, and role of sulfhydryls and oligomeric structure in catalytic activity.

    Science.gov (United States)

    Little, R M; Anderson, P M

    1987-07-25

    Cyanase is an inducible enzyme in Escherichia coli that catalyzes bicarbonate-dependent decomposition of cyanate to give ammonia and bicarbonate. The enzyme is composed of 8-10 identical subunits (Mr = 17,008). The objective of this study was to clarify some of the structural properties of cyanase for the purpose of understanding the relationship between oligomeric structure and catalytic activity. Circular dichroism studies showed that cyanase has a significant amount of alpha-helix and beta-sheet structure. The one sulfhydryl group per subunit does not react with 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB) unless cyanase is denatured. Denaturation is apparently complete in 10 M urea or 6 M guanidine hydrochloride, but is significantly reduced in 10 M urea by the presence of azide (analog of cyanate) and is incomplete in 8 M urea. Denatured cyanase could be renatured and reactivated (greater than 85%) by removal of denaturants. Reactivation was greatly facilitated by the presence of certain anions, particularly bicarbonate, and by high ionic strength and protein concentration. The catalytic activity of renatured cyanase was associated only with oligomer. Cyanase that had been denatured in the presence of DTNB to give a cyanase-DTNB derivative could also be renatured at 26 degrees C to give active cyanase-DTNB oligomer. The active oligomeric form of the cyanase-DTNB derivative could be converted reversibly to inactive dimer by lowering the temperature to 4 degrees C or by reduction of the ionic strength and removal of monoanions. These results provide evidence that free sulfhydryl groups are not required for catalytic activity and that catalytic activity may be dependent upon oligomeric structure.

  18. Analysis list: Trp53 [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Trp53 Embryo,Embryonic fibroblast + mm9 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/target/Trp53....1.tsv http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/target/Trp53.5.tsv http://dbarchive.bi...osciencedbc.jp/kyushu-u/mm9/target/Trp53.10.tsv http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/colo/Trp53.Em...bryo.tsv,http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/colo/Trp53.Embryonic_fibr

  19. 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.

  20. Chaperones are necessary for the expression of catalytically active potato apyrases in prokaryotic cells.

    Science.gov (United States)

    Porowińska, Dorota; Czarnecka, Joanna; Komoszyński, Michał

    2014-07-01

    NTPDases (nucleoside triphosphate diphosphohydrolases) (also called in plants apyrases) hydrolyze nucleoside 5'-tri- and/or diphosphate bonds producing nucleosides di or monophosphate and inorganic phosphate. For years, studies have been carried out to use both plant and animal enzymes for medicine. Therefore, there is a need to develop an efficient method for the quick production of large amounts of homogeneous proteins with high catalytic activity. Expression of proteins in prokaryotic cells is the most common way for the protein production. The aim of our study was to develop a method of expression of potato apyrase (StAPY4, 5, and 6) genes in bacterial cells under conditions that allowed the production of catalytically active form of these enzymes. Apyrase 4 and 6 were overexpressed in BL21-CodonPlus (DE3) bacteria strain but they were accumulated in inclusion bodies, regardless of the culture conditions and induction method. Co-expression of potato apyrases with molecular chaperones allowed the expression of catalytically active apyrase 5. However, its high nucleotidase activity could be toxic for bacteria and is therefore synthesized in small amounts in cells. Our studies show that each protein requires other conditions for maturation and even small differences in amino acid sequence can essentially affect protein folding regardless of presence of chaperones.

  1. [Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon].

    Science.gov (United States)

    Wang, Jia-Yu; Dai, Qi-Zhou; Yu, Jie; Yan, Yi-Zhou; Chen, Jian-Meng

    2013-04-01

    The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon (AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55.11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20.22%) and activated carbon alone (27.39%), showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction), indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values: the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.

  2. 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.

  3. An improved d-band model of the catalytic activity of magnetic transition metal surfaces

    CERN Document Server

    Bhattacharjee, Satadeep; Lee, S C

    2016-01-01

    The d-band center model of Hammer and N{\\o}rskov is widely used in understanding and predicting catalytic activity on transition metal (TM) surfaces. Here, we demonstrate that this model is inadequate for capturing the complete catalytic activity of the magnetically polarized TM surfaces and propose its generalization. We validate the generalized model through comparison of adsorption energies of the NH$_3$ molecule on the surfaces of 3d TMs (V, Cr, Mn, Fe, Co, Ni, Cu and Zn) determined with spin-polarized density functional theory (DFT)-based methods with the predictions of our model. Compared to the conventional d-band model, where the nature of the metal-adsorbate interaction is entirely determined through the energy and the occupation of the d-band center, we emphasize that for the surfaces with high spin polarization, the metal-adsorbate system can be stabilized through a competition of the spin-dependent metal-adsorbate interactions.

  4. 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.

  5. Characterization and catalytic activity of gold nanoparticles synthesized using ayurvedic arishtams.

    Science.gov (United States)

    Aromal, S Aswathy; Babu, K V Dinesh; Philip, Daizy

    2012-10-01

    The development of new synthesis methods for monodispersed nanocrystals using cheap and nontoxic chemicals, environmentally benign solvents and renewable materials remains a challenge to the scientific community. The present work reports a new green method for the synthesis of gold nanoparticles. Four different ayurvedic arishtams are used for the reduction of Au(3+) to Au nanoparticles. This method is simple, efficient, economic and nontoxic. Gold nanoparticles having different sizes in the range from 15 to 23 nm could be obtained. The nanoparticles have been characterized by UV-Visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. The high crystallinity of nanoparticles is evident from bright circular spots in the SAED pattern and peaks in the XRD pattern. The synthesized gold nanoparticles show good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol by excess NaBH(4). The synthesized nanoparticles are found to exhibit size dependent catalytic property, the smaller nanoparticles showing faster activity.

  6. Synthesis and Catalytic Activity of Copper(Ⅱ) Resorcylic Acid Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Copper(Ⅱ) resorcylic acid(CuRes) nanoparticles were synthesized by using reactive precipitation method with resorcylic acid and blue copperas as the raw material in a rotating packed bed. The sample obtained was characterized by using X-ray diffraction( XRD), transmission electron microscopy( TEM ), Fourier transform infrared spectroscopy (FTIR), thermo-gravimetric analyses (TG), and element analysis. In addition, the catalytic activity of CuRes nanoparticles on the thermal decomposition of nitrocellulose-nitroglycerine (NC-NG) was also determined via DSC.The results show that the spherical nanoparticles with a diameter of 20 nm were obtained in ethanol solution. The peak temperature of the thermal decomposition of NC-NG-CuRes decreases by 3 ℃ compared with that of normal CuRes,and the decomposition enthalpy is increased by 735 J/g, and therefore, it is reasonable to assume that CuRes nanoparticles have a better catalytic activity.

  7. Peroxidase-like catalytic activity of Ag3PO4 nanocrystals prepared by a colloidal route.

    Directory of Open Access Journals (Sweden)

    Yuanjun Liu

    Full Text Available Nearly monodispersed Ag3PO4 nanocrystals with size of 10 nm were prepared through a colloidal chemical route. It was proven that the synthesized Ag3PO4 nanoparticles have intrinsic peroxidase-like catalytic activity. They can quickly catalyze oxidation of the peroxidase substrate 3, 3, 5, 5-tetramethylbenzidine (TMB in the presence of H2O2, producing a blue color. The catalysis reaction follows Michaelis-Menten kinetics. The calculated kinetic parameters indicate a high catalytic activity and the strong affinity of Ag3PO4 nanocrystals to the substrate (TMB. These results suggest the potential applications of Ag3PO4 nanocrystals in fields such as biotechnology, environmental chemistry, and medicine.

  8. 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...... stable. DFT simulations demonstrated that even a single oxygen atom binds strongly to SiO2-supported Pt8 clusters and changes the morphology and chemical properties of the cluster. Catalytic methanation reaction from CO and H2 was studied on Ni75Fe25 nano-particles with sizes 3.5nm, 5nm, 7nm and 9nm...... reproducing activity measurements on all sample sizes and more consistent characterisation with ISS and XPS. An ambitious plan is to do a similar size study on pure nickel nano-particles, to examine differences and similarities between the catalysts under reaction conditions....

  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. High catalytic activity of anatase titanium dioxide for decomposition of electrolyte solution in lithium ion battery

    Science.gov (United States)

    Liu, Ming; He, Yan-Bing; Lv, Wei; Zhang, Chen; Du, Hongda; Li, Baohua; Yang, Quan-Hong; Kang, Feiyu

    2014-12-01

    It has been indicated that anatase TiO2 is a promising anode material for lithium ion power battery from many previous researches. Whereas, in this work, we find that the anatase TiO2, when used as an anode for lithium ion battery, has high catalytic activity to initiate the decarboxylation reaction of electrolyte solution, resulting in the large generation of sole gaseous component, CO2. The ROLi species and the new phase of flake-like Li2TiF6 material are the main reaction products between anatase TiO2 and LiPF6 based electrolyte solution. This work provides important and urgent information that the surface chemistry of anatase TiO2 used as the anode material of lithium ion battery must be modified to suppress its catalytic activity for the decomposition of solvents.

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

    Science.gov (United States)

    Krajčí, Marian; Kameoka, Satoshi; Tsai, An-Pang

    2016-08-28

    We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al2Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped {211} surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir-Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO-OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.

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

    Science.gov (United States)

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

    2017-03-01

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

  13. 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 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...

  14. Catalytic layer for oxygen activation on ionic solid electrolytes at high temperature

    OpenAIRE

    Serra Alfaro, José Manuel; Vert Belenguer, Vicente Bernard; Escolástico Rozalén, Sonia

    2008-01-01

    The present invention relates to a catalytic porous layer for oxygen activation which may be utilised in solid oxide fuel cells (SOFCs) and in dense ceramic membranes for oxygen separation at high temperature. Said porous layer is principally formed by a mixed electron and oxygen ion conductive material possessing a structure selected from among structures of the simple perovskite or double perovskite type or structures related to perovskite, that is to say: structures of the Ruddlesden-Poppe...

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

    Science.gov (United States)

    Honarparvar, Bahareh; Skelton, Adam A

    2015-04-01

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

  16. A simple red-ox titrimetric method for the evaluation of photo-catalytic activity of titania based catalysts

    Indian Academy of Sciences (India)

    Y S Satpute; S A Borkar; S R Dharwadkar

    2003-12-01

    A simple red-ox titrimetry method has been developed for rapid evaluation of the photo catalytic activity of TiO2 based photo-catalysts. The analytical procedure employs monitoring the kinetics of a simple one electron transfer reduction reaction of conversion of Ce4+ to Ce3+ in dilute aqueous solution in presence of sunlight. The photo-catalytic activity of TiO2 synthesized by two different routes was evaluated by the above technique. The effect of surface area, crystallite size and polymorphic contents on the photo-catalytic activity of TiO2 was also studied employing this method.

  17. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface.

    Science.gov (United States)

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, Lindsay R; Lammich, Lutz; Besenbacher, Flemming; Mavrikakis, Manos; Wendt, Stefan

    2015-08-25

    Within the area of surface science, one of the "holy grails" is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFT+U calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  18. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface

    Energy Technology Data Exchange (ETDEWEB)

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, L. R.; Lammich, Lutz; Besenbacher, Fleming; Mavrikakis, Manos; Wendt, Stefen

    2015-08-25

    Within the area of surface science, one of the “holy grails” is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFTþU calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  19. A microreactor array for spatially resolved measurement of catalytic activity for high-throughput catalysis science

    Energy Technology Data Exchange (ETDEWEB)

    Kondratyuk, Petro; Gumuslu, Gamze; Shukla, Shantanu; Miller, James B; Morreale, Bryan D; Gellman, Andrew J

    2013-04-01

    We describe a 100 channel microreactor array capable of spatially resolved measurement of catalytic activity across the surface of a flat substrate. When used in conjunction with a composition spread alloy film (CSAF, e.g. Pd{sub x}Cu{sub y}Au{sub 1-x-y}) across which component concentrations vary smoothly, such measurements permit high-throughput analysis of catalytic activity and selectivity as a function of catalyst composition. In the reported implementation, the system achieves spatial resolution of 1 mm{sup 2} over a 10×10 mm{sup 2} area. During operation, the reactant gases are delivered at constant flow rate to 100 points of differing composition on the CSAF surface by means of a 100-channel microfluidic device. After coming into contact with the CSAF catalyst surface, the product gas mixture from each of the 100 points is withdrawn separately through a set of 100 isolated channels for analysis using a mass spectrometer. We demonstrate the operation of the device on a Pd{sub x}Cu{sub y}Au{sub 1-x-y} CSAF catalyzing the H{sub 2}-D{sub 2} exchange reaction at 333 K. In essentially a single experiment, we measured the catalytic activity over a broad swathe of concentrations from the ternary composition space of the Pd{sub x}Cu{sub y}Au{sub 1-x-y} alloy.

  20. Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

    2015-11-15

    Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

  1. 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

  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.

  3. Tough and catalytically active hybrid biofibers wet-spun from nanochitin hydrogels.

    Science.gov (United States)

    Das, Paramita; Heuser, Thomas; Wolf, Andrea; Zhu, Baolei; Demco, Dan Eugen; Ifuku, Shinsuke; Walther, Andreas

    2012-12-10

    Sustainable alternatives for high-performance and functional materials based on renewable resources are intensely needed as future alternatives for present-day, fossil-based materials. Nanochitin represents an emerging class of highly crystalline bionanoparticles with high intrinsic mechanical properties and the ability for conjugation into functional materials owing to reactive amine and hydroxyl groups. Herein we demonstrate that hydrogels containing surface-deacetylated chitin nanofibrils of micrometer length and average diameters of 9 nm, as imaged by cryogenic transmission electron microscopy, can be wet-spun into macrofibers via extrusion in a coagulation bath, a simple low energy and large-scale processing route. The resulting biofibers display attractive mechanical properties with a large plastic region of about 12% in strain, in which frictional sliding of nanofibrils allows dissipation of fracture energy and enables a high work-of-fracture of near 10 MJ/m3. We further show how to add functionality to these macrofibers by exploiting the amine functions of the surface chitosan groups to host catalytically active noble metal nanoparticles, furnishing biobased, renewable catalytic hybrids. These inorganic/organic macrofibers can be used repeatedly for fast catalytic reductions of model compounds without loss of activity, rendering the concept of hybridized chitin materials interesting as novel bioderived supports for nanoparticle catalysts.

  4. 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.

  5. Catalytic activity of copper (II) oxide prepared via ultrasound assisted Fenton-like reaction.

    Science.gov (United States)

    Angı, Arzu; Sanlı, Deniz; Erkey, Can; Birer, Özgür

    2014-03-01

    Copper (II) oxide nanoparticles were synthesized in an ultrasound assisted Fenton-like aqueous reaction between copper (II) cations and hydrogen peroxide. The reactions were initiated with the degradation of hydrogen peroxide by ultrasound induced cavitations at 0 °C or 5 °C and subsequent generation of the OH radical. The radical was converted into hydroxide anion in Fenton-like reactions and copper hydroxides were readily converted to oxides without the need of post annealing or aging of the samples. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis. Catalytic activity of the nanoparticles for the hydrogen peroxide assisted degradation of polycyclic aromatic hydrocarbons in the dark was tested by UV-visible spectroscopy with methylene blue as the model compound. The rate of the reaction was first order, however the rate constants changed after the initial hour. Initial rate constants as high as 0.030 min(-1) were associated with the high values of surface area, i.e. 70 m(2)/g. Annealing of the products at 150 °C under vacuum resulted in the decrease of the catalytic activity, underlying the significance of the cavitation induced surface defects in the catalytic process.

  6. Co-Cu Nanoparticles: Synthesis by Galvanic Replacement and Phase Rearrangement during Catalytic Activation.

    Science.gov (United States)

    Nafria, Raquel; Genç, Aziz; Ibáñez, Maria; Arbiol, Jordi; de la Piscina, Pilar Ramírez; Homs, Narcís; Cabot, Andreu

    2016-03-08

    The control of the phase distribution in multicomponent nanomaterials is critical to optimize their catalytic performance. In this direction, while impressive advances have been achieved in the past decade in the synthesis of multicomponent nanoparticles and nanocomposites, element rearrangement during catalyst activation has been frequently overseen. Here, we present a facile galvanic replacement-based procedure to synthesize Co@Cu nanoparticles with narrow size and composition distributions. We further characterize their phase arrangement before and after catalytic activation. When oxidized at 350 °C in air to remove organics, Co@Cu core-shell nanostructures oxidize to polycrystalline CuO-Co3O4 nanoparticles with randomly distributed CuO and Co3O4 crystallites. During a posterior reduction treatment in H2 atmosphere, Cu precipitates in a metallic core and Co migrates to the nanoparticle surface to form Cu@Co core-shell nanostructures. The catalytic behavior of such Cu@Co nanoparticles supported on mesoporous silica was further analyzed toward CO2 hydrogenation in real working conditions.

  7. Nickel-doped ceria nanoparticles for promoting catalytic activity of Pt/C for ethanol electrooxidation

    Science.gov (United States)

    Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

    2014-10-01

    This paper reports the facile synthesis of monodispersed nickel-doped ceria nanoparticles by a thermal decomposition method, which is used to promote catalytic properties of Pt/C. The Pt/Ni-doped CeO2/C catalyst obtained exhibits remarkably high activity and stability towards the ethanol electrooxidation in acidic media. This is attributed to higher oxygen releasing capacity and stronger interaction of Ni-doped CeO2 with Pt than pure CeO2 nanoparticles that contribute positively to the removal of poisoning intermediates. We believe that the design concept and synthetic strategy of metal doped oxides used for fuel cell catalysts can be potentially extended to other catalytic fields.

  8. Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

    Science.gov (United States)

    Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

    2016-05-24

    Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

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

    Science.gov (United States)

    Hilke, Roland; Pradeep, Neelakanda; Madhavan, Poornima; Vainio, Ulla; Behzad, Ali Reza; Sougrat, Rachid; Nunes, Suzana P; Peinemann, Klaus-Viktor

    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.

  10. Green synthesis of silver nanoparticles, decorated on graphene oxide nanosheets and their catalytic activity

    Science.gov (United States)

    Sreekanth, T. V. M.; Jung, Min-Ji; Eom, In-Yong

    2016-01-01

    In this study, we develop an inexpensive and green route for the synthesis of silver nanoparticles (AgNPs) using Picrasma quassioides bark aqueous extract as reducing and capping agent and also eco-friendly decorate graphene oxide (GO) nanosheets with AgNPs (GO-AgNPs). Green synthesized AgNPs and GO-AgNPs composites were characterized by UV-Visible spectroscopy, SEM-EDX, and TEM-SAED techniques. The resulting GO-AgNPs contained about 41.35% of Ag and the AgNPs size ranges 17.5-66.5 nm, and GO-AgNPs size ranges 10-49.5 nm. Moreover, the GO-AgNPs exhibited excellent catalytic activity towards the methylene blue (MB) in the presence of sodium borohydride (NaBH4) at room temperature. This catalytic reaction completed within 15 min.

  11. Graphdiyne oxides as excellent substrate for electroless deposition of Pd clusters with high catalytic activity.

    Science.gov (United States)

    Qi, Hetong; Yu, Ping; Wang, Yuexiang; Han, Guangchao; Liu, Huibiao; Yi, Yuanping; Li, Yuliang; Mao, Lanqun

    2015-04-29

    Graphdiyne (GDY), a novel kind of two-dimensional carbon allotrope consisting of sp- and sp(2)-hybridized carbon atoms, is found to be able to serve as the reducing agent and stabilizer for electroless deposition of highly dispersed Pd nanoparticles owing to its low reduction potential and highly conjugated electronic structure. Furthermore, we observe that graphdiyne oxide (GDYO), the oxidation form of GDY, can be used as an even excellent substrate for electroless deposition of ultrafine Pd clusters to form Pd/GDYO nanocomposite that exhibits a high catalytic performance toward the reduction of 4-nitrophenol. The high catalytic performance is considered to benefit from the rational design and electroless deposition of active metal catalysts with GDYO as the support.

  12. 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.

  13. Species-specific identity elements of tRNA Trp

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Through the comparisons among 91 tRNA Trp sequences from prokaryotes, archea and eukaryotes, the potential species-specific identity elements of tRNA Trp are found to be located within acceptor stem, dihydrouridine (D) stem, anticodon(AC) stem and discriminator base. Mutagenesis of B. subtilis tRNA Trp to the eukaryotic consensus se quence, in vitro transcription and enzymatic assay of tRNA Trp toward different tryptophanyl-tRNA synthetases (TrpRS) were employed to shed light on these species-specific identity elements and demonstrate the accurate recognition and the coevolution between tRNA and TrpRS. B. subtilis tRNA Trp with its acceptor stem and discriminator base transplanted by eukaryotic counterparts exhibited diminished reactivity toward B. subtilis enzyme but could be efficiently aminoacylated by rat liver crude enzyme. In contrast, B. subtilis tRNA Trp analog with the eukaryotic anticodon stem and D stem retains its recognition by B. subtilis enzyme. The results provide a strong evidence that the species-specific identity elements of tRNA Trp are orientated within the acceptor stem and discriminator base of tRNA Trp, and the anticodon stem and D stem are of little importance to the interaction between tRNA Trp and its cognate synthetase (TrpRS).

  14. Saccharomyces cerevisiae DNA ligase IV supports imprecise end joining independently of its catalytic activity.

    Directory of Open Access Journals (Sweden)

    Kishore K Chiruvella

    2013-06-01

    Full Text Available DNA ligase IV (Dnl4 in budding yeast is a specialized ligase used in non-homologous end joining (NHEJ of DNA double-strand breaks (DSBs. Although point and truncation mutations arise in the human ligase IV syndrome, the roles of Dnl4 in DSB repair have mainly been examined using gene deletions. Here, Dnl4 catalytic point mutants were generated that were severely defective in auto-adenylation in vitro and NHEJ activity in vivo, despite being hyper-recruited to DSBs and supporting wild-type levels of Lif1 interaction and assembly of a Ku- and Lif1-containing complex at DSBs. Interestingly, residual levels of especially imprecise NHEJ were markedly higher in a deletion-based assay with Dnl4 catalytic mutants than with a gene deletion strain, suggesting a role of DSB-bound Dnl4 in supporting a mode of NHEJ catalyzed by a different ligase. Similarly, next generation sequencing of repair joints in a distinct single-DSB assay showed that dnl4-K466A mutation conferred a significantly different imprecise joining profile than wild-type Dnl4 and that such repair was rarely observed in the absence of Dnl4. Enrichment of DNA ligase I (Cdc9 in yeast at DSBs was observed in wild-type as well as dnl4 point mutant strains, with both Dnl4 and Cdc9 disappearing from DSBs upon 5' resection that was unimpeded by the presence of catalytically inactive Dnl4. These findings indicate that Dnl4 can promote mutagenic end joining independently of its catalytic activity, likely by a mechanism that involves Cdc9.

  15. Saccharomyces cerevisiae DNA ligase IV supports imprecise end joining independently of its catalytic activity.

    Science.gov (United States)

    Chiruvella, Kishore K; Liang, Zhuobin; Birkeland, Shanda R; Basrur, Venkatesha; Wilson, Thomas E

    2013-06-01

    DNA ligase IV (Dnl4 in budding yeast) is a specialized ligase used in non-homologous end joining (NHEJ) of DNA double-strand breaks (DSBs). Although point and truncation mutations arise in the human ligase IV syndrome, the roles of Dnl4 in DSB repair have mainly been examined using gene deletions. Here, Dnl4 catalytic point mutants were generated that were severely defective in auto-adenylation in vitro and NHEJ activity in vivo, despite being hyper-recruited to DSBs and supporting wild-type levels of Lif1 interaction and assembly of a Ku- and Lif1-containing complex at DSBs. Interestingly, residual levels of especially imprecise NHEJ were markedly higher in a deletion-based assay with Dnl4 catalytic mutants than with a gene deletion strain, suggesting a role of DSB-bound Dnl4 in supporting a mode of NHEJ catalyzed by a different ligase. Similarly, next generation sequencing of repair joints in a distinct single-DSB assay showed that dnl4-K466A mutation conferred a significantly different imprecise joining profile than wild-type Dnl4 and that such repair was rarely observed in the absence of Dnl4. Enrichment of DNA ligase I (Cdc9 in yeast) at DSBs was observed in wild-type as well as dnl4 point mutant strains, with both Dnl4 and Cdc9 disappearing from DSBs upon 5' resection that was unimpeded by the presence of catalytically inactive Dnl4. These findings indicate that Dnl4 can promote mutagenic end joining independently of its catalytic activity, likely by a mechanism that involves Cdc9.

  16. Brevicompanine C, cyclo-(D-Ile-L-Trp), and cyclo-(D-Leu-L-Trp), plant growth regulators from Penicillium brevi-compactum.

    Science.gov (United States)

    Kimura, Yasuo; Sawada, Aya; Kuramata, Masato; Kusano, Miyako; Fujioka, Shozo; Kawano, Tsuyoshi; Shimada, Atsumi

    2005-02-01

    New plant growth regulators, named brevicompanine C (1), cyclo-(D-Ile-L-Trp) (2), and cyclo-(D-Leu-L-Trp) (3), have been isolated from Penicillium brevi-compactum Dierckx, and their structures have been established by spectroscopic methods including 2D NMR and chiral TLC analysis. Plant growth activities of 1, 2, and 3 have been examined using lettuce seedling bioassay methods. All compounds accelerated the root growth of the seedlings in proportion to their concentration from 1 to 100 mg/L.

  17. Electrosynthesis and catalytic activity of polymer-nickel particles composite electrode materials

    Energy Technology Data Exchange (ETDEWEB)

    Melki, Tahar; Zouaoui, Ahmed; Bendemagh, Barkahoum [Universite Ferhat Abbas, Setif (Algeria). Faculte des Sciences de l' Ingenieur. Dept. du Tronc Commun; Oliveira, Ione M.F. de; Oliveira, Gilver F. de [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica; Lepretre, Jean-Claude [UMR-5631 CNRS-INPG-UJF, St. Martin d' Heres Cedex (France). Lab. d' Electrochimie et de Physicochimie des Materiaux et Interfaces; Bucher, Christophe; Mou tet, Jean-Claude [Universite Joseph Fourier Grenoble 1 (France). Dept. de Chimie Moleculaire], e-mail: Jean-Claude.Moutet@ujf-grenoble.fr

    2009-07-01

    Nickel-polymer composite electrode materials have been synthesized using various strategies, all comprising the electrochemical reduction of nickel(II) cations or complexes, incorporated by either ion-exchange or complexation into various poly(pyrrole-carboxylate) thin films coated by oxidative electropolymerization onto carbon electrodes. The electrocatalytic activity and the stability of the different composites have been then evaluated in the course of the electrocatalytic hydrogenation of ketones and enones in aqueous electrolytes. The best results were obtained using nickel-polymer composites synthesized by electroreduction of nickel(II) ions complexed into polycarboxylate films, which are characterized by a high catalytic activity and a good operational stability. (author)

  18. Identification and characterization of TRP14, a thioredoxin-related protein of 14 kDa from orange-spotted grouper, Epinephelus coioides.

    Science.gov (United States)

    Wei, Jingguang; Ji, Huasong; Guo, Minglan; Yan, Yang; Qin, Qiwei

    2013-11-01

    Thioredoxin (abbreviated as Trx) is an important ubiquitous disulfide reductase, which can protect organisms against various oxidative stresses. In the present study, a thioredoxin-related protein of 14 kDa (named as Ec-TRP14) was identified from the marine fish grouper, Epinephelus coioides by RACE PCR. The full-length cDNA of Ec-TRP14 was comprised of 1066 bp with a 372 bp open reading frame that encodes a putative protein of 123 amino acids. Similar to most TRP14s, Ec-TRP14 contained the conserved motif C-P-D-C. Ec-TRP14 mRNA is predominately expressed in liver, brain and muscle. The expression of Ec-TRP14 was up-regulated in the liver of grouper challenged with SGIV. Ec-TRP14 was recombined and expressed in Escherichia coli BL21 (DE3), and the rEc-Ec-TRP14 fusion protein was demonstrated to possess the antioxidant activity. The grouper spleen (GS) cells were treated with a high concentration of rEc-TRP14 (8.3 μg/ml), which significantly enhanced cells viability under damage caused by viral infection. These results together indicated that Ec-TRP14 could function as an important antioxidant in a physiological context, and might be involved in the responses to viral challenge.

  19. Influence of hydrophobic mismatch on the catalytic activity of Escherichia coli GlpG rhomboid protease.

    Science.gov (United States)

    Foo, Alexander C Y; Harvey, Brandon G R; Metz, Jeff J; Goto, Natalie K

    2015-04-01

    Rhomboids comprise a broad family of intramembrane serine proteases that are found in a wide range of organisms and participate in a diverse array of biological processes. High-resolution structures of the catalytic transmembrane domain of the Escherichia coli GlpG rhomboid have provided numerous insights that help explain how hydrolytic cleavage can be achieved below the membrane surface. Key to this are observations that GlpG hydrophobic domain dimensions may not be sufficient to completely span the native lipid bilayer. This formed the basis for a model where hydrophobic mismatch Induces thinning of the local membrane environment to promote access to transmembrane substrates. However, hydrophobic mismatch also has the potential to alter the functional properties of the rhomboid, a possibility we explore in the current work. For this purpose, we purified the catalytic transmembrane domain of GlpG into phosphocholine or maltoside detergent micelles of varying alkyl chain lengths, and assessed proteolytic function with a model water-soluble substrate. Catalytic turnover numbers were found to depend on detergent alkyl chain length, with saturated chains containing 10-12 carbon atoms supporting maximal activity. Similar results were obtained in phospholipid bicelles, with no proteolytic activity being detected in longer-chain lipids. Although differences in thermal stability and GlpG oligomerization could not explain these activity differences, circular dichroism spectra suggest that mismatch gives rise to a small change in structure. Overall, these results demonstrate that hydrophobic mismatch can exert an inhibitory effect on rhomboid activity, with the potential for changes in local membrane environment to regulate activity in vivo.

  20. Catalytic oxidation of pulping effluent by activated carbon-supported heterogeneous catalysts.

    Science.gov (United States)

    Yadav, Bholu Ram; Garg, Anurag

    2016-01-01

    The present study deals with the non-catalytic and catalytic wet oxidation (CWO) for the removal of persistent organic compounds from the pulping effluent. Two activated carbon-supported heterogeneous catalysts (Cu/Ce/AC and Cu/Mn/AC) were used for CWO after characterization by the following techniques: temperature-programmed reduction, Fourier transform infrared spectroscopy and thermo-gravimetric analysis. The oxidation reaction was performed in a batch high-pressure reactor (capacity = 0.7  L) at moderate oxidation conditions (temperature = 190°C and oxygen pressure = 0.9 MPa). With Cu/Ce/AC catalyst, the maximum chemical oxygen demand (COD), total organic carbon (TOC) and lignin removals of 79%, 77% and 88% were achieved compared to only 50% removal during the non-catalytic process. The 5-day biochemical oxygen demand (BOD5) to COD ratio (a measure for biodegradability) of the pulping effluent was improved to 0.52 from an initial value of 0.16. The mass balance calculations for solid recovered after CWO reaction showed 8% and 10% deduction in catalyst mass primarily attributed to the loss of carbon and metal leaching. After the CWO process, carbon deposition was also observed on the recovered catalyst which was responsible for around 3-4% TOC reduction.

  1. Synthesis, characterization and catalytic activity of birnessite type potassium manganese oxide nanotubes and nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Khalid Abdelazez Mohamed, E-mail: khalidgnad@hotmail.com [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Department of Chemistry, School of Chemistry and Chemical Technology, Faculty of Science and Technology, Al-Neelain University, P.O. Box 12702, Khartoum (Sudan); Huang Kaixun, E-mail: hxxzrf@mail.hust.edu.cn [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2012-04-16

    Highlights: Black-Right-Pointing-Pointer Birnessite type manganese oxides nanotubes and nanorods were prepared by calcination route. Black-Right-Pointing-Pointer The transition from tube to rod structure is described by an oriented attachment-thermodynamical (OA-TD) process. Black-Right-Pointing-Pointer The catalytic degradation efficiency of safranin O by as-prepared products was compared. - Abstract: Birnessite-type manganese oxide nanotubes and nanorods were synthesized via a calcination process using manganese acetate and potassium hydroxide as precursors in presence of polyethylene glycol-melamine-formaldehyde. As-prepared products were characterized by XRD, FT-IR, FE-SEM, TEM, SA-ED, HR-TEM, Brunauer-Emmett-Teller (BET) and TGA analyses. The influences of reaction temperature and time on the morphology of manganese oxide nanocrystals were investigated. The oriented attachment-thermodynamical (OA-TD) process is suggested to describe the transition from tube to rod structure. Their capability of catalytic degradation of safranin O was compared. The results indicate that birnessite-type manganese oxide nanotube has higher catalytic activity for than nanorod crystal in aqueous solution, because it has a larger surface area. The decomposition of safranin O follows pseudo-first order kinetics and is markedly affected by pH.

  2. 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.

  3. 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.

  4. Physics-based enzyme design: predicting binding affinity and catalytic activity.

    Science.gov (United States)

    Sirin, Sarah; Pearlman, David A; Sherman, Woody

    2014-12-01

    Computational enzyme design is an emerging field that has yielded promising success stories, but where numerous challenges remain. Accurate methods to rapidly evaluate possible enzyme design variants could provide significant value when combined with experimental efforts by reducing the number of variants needed to be synthesized and speeding the time to reach the desired endpoint of the design. To that end, extending our computational methods to model the fundamental physical-chemical principles that regulate activity in a protocol that is automated and accessible to a broad population of enzyme design researchers is essential. Here, we apply a physics-based implicit solvent MM-GBSA scoring approach to enzyme design and benchmark the computational predictions against experimentally determined activities. Specifically, we evaluate the ability of MM-GBSA to predict changes in affinity for a steroid binder protein, catalytic turnover for a Kemp eliminase, and catalytic activity for α-Gliadin peptidase variants. Using the enzyme design framework developed here, we accurately rank the most experimentally active enzyme variants, suggesting that this approach could provide enrichment of active variants in real-world enzyme design applications.

  5. A thermodynamic framework for understanding temperature sensing by transient receptor potential (TRP) channels.

    Science.gov (United States)

    Clapham, David E; Miller, Christopher

    2011-12-06

    The exceptionally high temperature sensitivity of certain transient receptor potential (TRP) family ion channels is the molecular basis of hot and cold sensation in sensory neurons. The laws of thermodynamics dictate that opening of these specialized TRP channels must involve an unusually large conformational standard-state enthalpy, ΔH(o): positive ΔH(o) for heat-activated and negative ΔH(o) for cold-activated TRPs. However, the molecular source of such high-enthalpy changes has eluded neurobiologists and biophysicists. Here we offer a general, unifying mechanism for both hot and cold activation that recalls long-appreciated principles of protein folding. We suggest that TRP channel gating is accompanied by large changes in molar heat capacity, ΔC(P). This postulate, along with the laws of thermodynamics and independent of mechanistic detail, leads to the conclusion that hot- and cold-sensing TRPs operate by identical conformational changes.

  6. A Redox 2-Cys Mechanism Regulates the Catalytic Activity of Divergent Cyclophilins1[W

    Science.gov (United States)

    Campos, Bruna Medéia; Sforça, Mauricio Luis; Ambrosio, Andre Luis Berteli; Domingues, Mariane Noronha; Brasil de Souza, Tatiana de Arruda Campos; Barbosa, João Alexandre Ribeiro Gonçalvez; Leme, Adriana Franco Paes; Perez, Carlos Alberto; Whittaker, Sara Britt-Marie; Murakami, Mario Tyago; Zeri, Ana Carolina de Matos; Benedetti, Celso Eduardo

    2013-01-01

    The citrus (Citrus sinensis) cyclophilin CsCyp is a target of the Xanthomonas citri transcription activator-like effector PthA, required to elicit cankers on citrus. CsCyp binds the citrus thioredoxin CsTdx and the carboxyl-terminal domain of RNA polymerase II and is a divergent cyclophilin that carries the additional loop KSGKPLH, invariable cysteine (Cys) residues Cys-40 and Cys-168, and the conserved glutamate (Glu) Glu-83. Despite the suggested roles in ATP and metal binding, the functions of these unique structural elements remain unknown. Here, we show that the conserved Cys residues form a disulfide bond that inactivates the enzyme, whereas Glu-83, which belongs to the catalytic loop and is also critical for enzyme activity, is anchored to the divergent loop to maintain the active site open. In addition, we demonstrate that Cys-40 and Cys-168 are required for the interaction with CsTdx and that CsCyp binds the citrus carboxyl-terminal domain of RNA polymerase II YSPSAP repeat. Our data support a model where formation of the Cys-40-Cys-168 disulfide bond induces a conformational change that disrupts the interaction of the divergent and catalytic loops, via Glu-83, causing the active site to close. This suggests a new type of allosteric regulation in divergent cyclophilins, involving disulfide bond formation and a loop-displacement mechanism. PMID:23709667

  7. Biorecovery of gold as nanoparticles and its catalytic activities for p-nitrophenol degradation.

    Science.gov (United States)

    Zhu, Nengwu; Cao, Yanlan; Shi, Chaohong; Wu, Pingxiao; Ma, Haiqin

    2016-04-01

    Recovery of gold from aqueous solution using simple and economical methodologies is highly desirable. In this work, recovery of gold as gold nanoparticles (AuNPs) by Shewanella haliotis with sodium lactate as electron donor was explored. The results showed that the process was affected by the concentration of biomass, sodium lactate, and initial gold ions as well as pH value. Specifically, the presence of sodium lactate determines the formation of nanoparticles, biomass, and AuCl4 (-) concentration mainly affected the size and dispersity of the products, reaction pH greatly affected the recovery efficiency, and morphology of the products in the recovery process. Under appropriate conditions (5.25 g/L biomass, 40 mM sodium lactate, 0.5 mM AuCl4 (-), and pH of 5), the recovery efficiency was almost 99 %, and the recovered AuNPs were mainly spherical with size range of 10-30 nm (~85 %). Meanwhile, Fourier transforms infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated that carboxyl and amine groups might play an important role in the process. In addition, the catalytic activity of the AuNPs recovered under various conditions was testified by analyzing the reduction rate of p-nitrophenol by borohydride. The biorecovered AuNPs exhibited interesting size and shape-dependent catalytic activity, of which the spherical particle with smaller size showed the highest catalytic reduction activity with rate constant of 0.665 min(-1).

  8. The roles of active site residues in the catalytic mechanism of methylaspartate ammonia-lyase.

    Science.gov (United States)

    Raj, Hans; Poelarends, Gerrit J

    2013-01-01

    Methylaspartate ammonia-lyase (MAL; EC 4.3.1.2) catalyzes the reversible addition of ammonia to mesaconate to yield l-threo-(2S,3S)-3-methylaspartate and l-erythro-(2S,3R)-3-methylaspartate as products. In the proposed minimal mechanism for MAL of Clostridium tetanomorphum, Lys-331 acts as the (S)-specific base catalyst and abstracts the 3S-proton from l-threo-3-methylaspartate, resulting in an enolate anion intermediate. This enolic intermediate is stabilized by coordination to the essential active site Mg(2+) ion and hydrogen bonding to the Gln-329 residue. Collapse of this intermediate results in the release of ammonia and the formation of mesaconate. His-194 likely acts as the (R)-specific base catalyst and abstracts the 3R-proton from the l-erythro isomer of 3-methylaspartate, yielding the enolic intermediate. In the present study, we have investigated the importance of the residues Gln-73, Phe-170, Gln-172, Tyr-356, Thr-360, Cys-361 and Leu-384 for the catalytic activity of C. tetanomorphum MAL. These residues, which are part of the enzyme surface lining the substrate binding pocket, were subjected to site-directed mutagenesis and the mutant enzymes were characterized for their structural integrity, ability to catalyze the amination of mesaconate, and regio- and diastereoselectivity. Based on the observed properties of the mutant enzymes, combined with previous structural studies and protein engineering work, we propose a detailed catalytic mechanism for the MAL-catalyzed reaction, in which the side chains of Gln-73, Gln-172, Tyr-356, Thr-360, and Leu-384 provide favorable interactions with the substrate, which are important for substrate binding and activation. This detailed knowledge of the catalytic mechanism of MAL can serve as a guide for future protein engineering experiments.

  9. 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.

  10. BAX and tumor suppressor TRP53 are important in regulating mutagenesis in spermatogenic cells in mice.

    Science.gov (United States)

    Xu, Guogang; Vogel, Kristine S; McMahan, C Alex; Herbert, Damon C; Walter, Christi A

    2010-12-01

    During the first wave of spermatogenesis, and in response to ionizing radiation, elevated mutant frequencies are reduced to a low level by unidentified mechanisms. Apoptosis is occurring in the same time frame that the mutant frequency declines. We examined the role of apoptosis in regulating mutant frequency during spermatogenesis. Apoptosis and mutant frequencies were determined in spermatogenic cells obtained from Bax-null or Trp53-null mice. The results showed that spermatogenic lineage apoptosis was markedly decreased in Bax-null mice and was accompanied by a significantly increased spontaneous mutant frequency in seminiferous tubule cells compared to that of wild-type mice. Apoptosis profiles in the seminiferous tubules for Trp53-null were similar to control mice. Spontaneous mutant frequencies in pachytene spermatocytes and in round spermatids from Trp53-null mice were not significantly different from those of wild-type mice. However, epididymal spermatozoa from Trp53-null mice displayed a greater spontaneous mutant frequency compared to that from wild-type mice. A greater proportion of spontaneous transversions and a greater proportion of insertions/deletions 15 days after ionizing radiation were observed in Trp53-null mice compared to wild-type mice. Base excision repair activity in mixed germ cell nuclear extracts prepared from Trp53-null mice was significantly lower than that for wild-type controls. These data indicate that BAX-mediated apoptosis plays a significant role in regulating spontaneous mutagenesis in seminiferous tubule cells obtained from neonatal mice, whereas tumor suppressor TRP53 plays a significant role in regulating spontaneous mutagenesis between postmeiotic round spermatid and epididymal spermatozoon stages of spermiogenesis.

  11. Polyvinylpyrrolidone adsorption effects on the morphologies of synthesized platinum particles and its catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Ooi, Mahayatun Dayana Johan [Nano - Optoelectronic Research and Technology Laboratory, School of Physics, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia); Aziz, Azlan Abdul [Nano - Optoelectronic Research and Technology Laboratory, School of Physics, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia); Nanobiotechnology Research and Innovation (NanoBRI), INFORMM, Universiti Sains Malaysia, 11800, Minden, Pulau Pinang (Malaysia)

    2015-04-24

    Flower-like Platinum micro-structures were synthesized from different concentration of the PVP using solvothermal method. At 5.0×10{sup −3} mmol of PVP, well-defined flower-like pattern consists of triangular petals radiating from the centre were produced whereas larger flower network developed at higher PVP concentration. High degree of crystallinity was obtained upon each increment of PVP. The well defined flower like pattern synthesized using 5.0×10{sup −3} mmol PVP exhibit the highest catalytic activity and stability towards electro-oxidation of formic acid.

  12. Structure of the catalytic domain of Plasmodium falciparum ARF GTPase-activating protein (ARFGAP)

    Energy Technology Data Exchange (ETDEWEB)

    Cook, William J.; Senkovich, Olga; Chattopadhyay, Debasish (UAB)

    2012-03-26

    The crystal structure of the catalytic domain of the ADP ribosylation factor GTPase-activating protein (ARFGAP) from Plasmodium falciparum has been determined and refined to 2.4 {angstrom} resolution. Multiwavelength anomalous diffraction (MAD) data were collected utilizing the Zn{sup 2+} ion bound at the zinc-finger domain and were used to solve the structure. The overall structure of the domain is similar to those of mammalian ARFGAPs. However, several amino-acid residues in the area where GAP interacts with ARF1 differ in P. falciparum ARFGAP. Moreover, a number of residues that form the dimer interface in the crystal structure are unique in P. falciparum ARFGAP.

  13. Catalytic Activity and Photophysical Properties of Biomolecules Immobilized on Mesoporous Silica

    DEFF Research Database (Denmark)

    Ikemoto, Hideki

    hybrid materials used for further study. One metalloenzyme, horseradish peroxidase(HRP), was immobilized on rod-shaped SBA-15 by physical adsorption. The catalytic activity of free and immobilized enzyme was first compared at room temperature. Details of the enzyme kinetics including the apparent...... and increased hydration strength of the protein inside the nanopores. A copper-containing enzyme, galactose oxidase (GAOX), was immobilized on SBA-15 with a hexagonally ordered pore structure, or on mesocellular foam (MCF)-type mesoporous silica with a cage-like pore structure. Physical adsorption...

  14. Facile synthesis and excellent catalytic activity of gold nanoparticles on graphene oxide

    Institute of Scientific and Technical Information of China (English)

    Yong Qiang He; Na Na Zhang; Yu Liu; Jian Ping Gao; Mao Cong Yi; Qiao Juan Gong; Hai Xia Qiu

    2012-01-01

    For the first time,Au nanoparticles on graphene oxide (GO-AuNPs) were successfully fabricated without applying any additional reductants,just by the redox reaction between AuCl4-1 and GO.Their structure was characterized by transmission electron microscopy and X-ray powder diffraction.The results show that flower-like AuNPs were successfully dispersed on GO surface.Importantly,they showed a high catalytic activity for the Suzuki-Miyaura coupling reaction in an aqueous medium.

  15. Structure prediction of the EcoRV DNA methyltransferase based on mutant profiling, secondary structure analysis, comparison with known structures of methyltransferases and isolation of catalytically inactive single mutants.

    Science.gov (United States)

    Jeltsch, A; Sobotta, T; Pingoud, A

    1996-05-01

    The EcoRV DNA methyltransferase (M.EcoRV) is an alpha-adenine methyltransferase. We have used two different programs to predict the secondary structure of M.EcoRV. The resulting consensus prediction was tested by a mutant profiling analysis. 29 neutral mutations of M.EcoRV were generated by five cycles of random mutagenesis and selection for active variants to increase the reliability of the prediction and to get a secondary structure prediction for some ambiguously predicted regions. The predicted consensus secondary structure elements could be aligned to the common topology of the structures of the catalytic domains of M.HhaI and M.TaqI. In a complementary approach we have isolated nine catalytically inactive single mutants. Five of these mutants contain an amino acid exchange within the catalytic domain of M.EcoRV (Val2-Ala, Lys81Arg, Cys192Arg, Asp193Gly, Trp231Arg). The Trp231Arg mutant binds DNA similarly to wild-type M.EcoRV, but is catalytically inactive. Hence this mutant behaves like a bona fide active site mutant. According to the structure prediction, Trp231 is located in a loop at the putative active site of M.EcoRV. The other inactive mutants were insoluble. They contain amino acid exchanges within the conserved amino acid motifs X, III or IV in M.EcoRV confirming the importance of these regions.

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

    Science.gov (United States)

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

    2016-02-10

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

  17. 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.

  18. Relation between the structure and catalytic activity for automotive emissions. Use of x-ray anomalous dispersion effect

    CERN Document Server

    Mizuki, J; Tanaka, H

    2003-01-01

    The employment of the X-ray anomalous dispersion effect allows us to detect the change in structure of catalytic converters with the environment exposed. Here we show that palladium atoms in a perovskite crystal move into and out of the crystal by anomalous X-ray diffraction and absorption techniques. This movement of the precious metal plays an important role to keep the catalytic activity long-lived. (author)

  19. CO oxidation over ruthenium: identification of the catalytically active phases at near-atmospheric pressures

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Goodman, Wayne D.

    2012-05-21

    CO oxidation was carried out over Ru(0001) and RuO2(110) thin film grown on Ru(0001) at various O2/CO ratios near atmospheric pressures. Reaction kinetics, coupled with in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and post-reaction Auger electron spectroscopy (AES) measurements were used to identify the catalytically relevant phases at different reaction conditions. Under stoichiometric and reducing conditions at all reaction temperatures, as well as net-oxidizing reaction conditions below {approx}475 K, a reduced metallic phase with chemisorbed oxygen is the thermodynamically stable and catalytically active phase. On this surface CO oxidation occurs at surface defect sites, for example step edges. Only at net-oxidizing reaction conditions and above {approx}475 K is the RuO2 thin film grown on metallic Ru stable and active. However, RuO2 is not active itself without the existence of the metal substrate, suggesting the importance of a strong metal-substrate interaction (SMSI).

  20. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism

    Institute of Scientific and Technical Information of China (English)

    Xinde Zheng; Tony Hunter

    2013-01-01

    Pink1,a mitochondrial kinase,and Parkin,an E3 ubiquitin ligase,function in mitochondrial maintenance.Pink1 accumulates on depolarized mitochondria,where it recruits Parkin to mainly induce K63-1inked chain ubiquitination of outer membrane proteins and eventually mitophagy.Parkin belongs to the RBR E3 iigase family.Recently,it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine-ubiquitin enzyme intermediate,in a manner similar to HECT domain E3 ligases.However,direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing.Here,we report that Parkin E3 activity relies on cysteinemediated ubiquitin transfer during mitophagy.Mutating the putative catalytic cysteine to serine (Parkin C431S)traps ubiquitin,and surprisingly,also abrogates Parkin mitochondrial translocation,indicating that E3 activity is essential for Parkin translocation.We found that Parkin can bind to K63-1inked ubiquitin chains,and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization.We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism.

  1. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism

    Science.gov (United States)

    Zheng, Xinde; Hunter, Tony

    2013-01-01

    Pink1, a mitochondrial kinase, and Parkin, an E3 ubiquitin ligase, function in mitochondrial maintenance. Pink1 accumulates on depolarized mitochondria, where it recruits Parkin to mainly induce K63-linked chain ubiquitination of outer membrane proteins and eventually mitophagy. Parkin belongs to the RBR E3 ligase family. Recently, it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine∼ubiquitin enzyme intermediate, in a manner similar to HECT domain E3 ligases. However, direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing. Here, we report that Parkin E3 activity relies on cysteine-mediated ubiquitin transfer during mitophagy. Mutating the putative catalytic cysteine to serine (Parkin C431S) traps ubiquitin, and surprisingly, also abrogates Parkin mitochondrial translocation, indicating that E3 activity is essential for Parkin translocation. We found that Parkin can bind to K63-linked ubiquitin chains, and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization. We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism. PMID:23670163

  2. 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.

  3. Comparing ion conductance recordings of synthetic lipid bilayers with cell membranes containing TRP channels

    CERN Document Server

    Laub, Katrine R; Blicher, Andreas; Madsen, Soren B; Luckhoff, Andreas; Heimburg, Thomas

    2011-01-01

    In this article we compare electrical conductance events from single channel recordings of three TRP channel proteins (TRPA1, TRPM2 and TRPM8) expressed in human embryonic kidney cells with channel events recorded on synthetic lipid membranes close to melting transitions. Ion channels from the TRP family are involved in a variety of sensory processes including thermo- and mechano-reception. Synthetic lipid membranes close to phase transitions display channel-like events that respond to stimuli related to changes in intensive thermodynamic variables such as pressure and temperature. TRP channel activity is characterized by typical patterns of current events dependent on the type of protein expressed. Synthetic lipid bilayers show a wide spectrum of electrical phenomena that are considered typical for the activity of protein ion channels. We find unitary currents, burst behavior, flickering, multistep-conductances, and spikes behavior in both preparations. Moreover, we report conductances and lifetimes for lipi...

  4. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

    2015-08-01

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

  5. Catalytic activity of phosphoric acid impregnated as a thin layer on quartz

    Energy Technology Data Exchange (ETDEWEB)

    Obraztosv, P.A. (Inst. Chem. Phys. Acad. Sci., USSR); Vinnik, M.I.; Batalin, O.E.

    1978-05-01

    The catalytic activity of phosphoric acid impregnated as a thin layer on quartz was studied in tert.-butanol dehydration at 100/sup 0/C by a pulse chromatographic method, and it was shown that the activity of the catalyst was due only to the free H/sub 3/PO/sub 4/, and that the observed gradual deactivation of the catalyst was caused by loss of the acid due to its interaction with quartz, with the formation of an SiO/sub 2/-P/sub 2/O/sub 5/ complex. Catalyst samples thermally pretreated for 5-7 hr at 330/sup 0/C conserved high activity for over 205 hr, and contained only ortho- but no meta- or pyrophosphoric acid.

  6. 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.

  7. 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

  8. Activities of human RRP6 and structure of the human RRP6 catalytic domain

    Energy Technology Data Exchange (ETDEWEB)

    Januszyk, Kurt; Liu, Quansheng; Lima, Christopher D. (SKI)

    2011-08-29

    The eukaryotic RNA exosome is a highly conserved multi-subunit complex that catalyzes degradation and processing of coding and noncoding RNA. A noncatalytic nine-subunit exosome core interacts with Rrp44 and Rrp6, two subunits that possess processive and distributive 3'-to-5' exoribonuclease activity, respectively. While both Rrp6 and Rrp44 are responsible for RNA processing in budding yeast, Rrp6 may play a more prominent role in processing, as it has been demonstrated to be inhibited by stable RNA secondary structure in vitro and because the null allele in budding yeast leads to the buildup of specific structured RNA substrates. Human RRP6, otherwise known as PM/SCL-100 or EXOSC10, shares sequence similarity to budding yeast Rrp6 and is proposed to catalyze 3'-to-5' exoribonuclease activity on a variety of nuclear transcripts including ribosomal RNA subunits, RNA that has been poly-adenylated by TRAMP, as well as other nuclear RNA transcripts destined for processing and/or destruction. To characterize human RRP6, we expressed the full-length enzyme as well as truncation mutants that retain catalytic activity, compared their activities to analogous constructs for Saccharomyces cerevisiae Rrp6, and determined the X-ray structure of a human construct containing the exoribonuclease and HRDC domains that retains catalytic activity. Structural data show that the human active site is more exposed when compared to the yeast structure, and biochemical data suggest that this feature may play a role in the ability of human RRP6 to productively engage and degrade structured RNA substrates more effectively than the analogous budding yeast enzyme.

  9. Controllable preparation of CeO2 nanostructure materials and their catalytic activity

    Institute of Scientific and Technical Information of China (English)

    Shan Wenjuan; Guo Hongjuan; Liu Chang; Wang Xiaonan

    2012-01-01

    Well-crystalline CeO2 nanostructures with the morphology ofnanorods and nanocubes were synthesized by a template-free hydrothermal method.X-ray diffraction (XRD),transmission electron microscopy (TEM),Brunauer-Emmett-Teller (BET) nitrogen adsorption-desorption measurements were employed to characterize the synthesized materials.The reducibility and catalytic activity of nanostructured CeO2 were examined by hydrogen temperature-programmed reduction (H2-TPR) and CO oxidation.The results showed that CeO2 nanorods could be converted into CeO2 nanocubes with the increasing of the reaction time and the hydrothermal temperature,CeO2 nanorods became longer gradually with the increasing of the concentrations of NaOH.H2-TPR characterization demonstrated that the intense low-temperature reduction peak in the CeO2 nanorods indicated the amount of hydrogen consumed is larger than CeO2 nanocubes.Meantime the CeO2 nanorods enhanced catalytic activity for CO oxidation,the total conversion temperature was 340 ℃.The reasons were that CeO2 nanorods have much smaller crystalline sizes and higher surface areas than CeO2 nanocubes.

  10. Generation 9 polyamidoamine dendrimer encapsulated platinum nanoparticle mimics catalase size, shape, and catalytic activity.

    Science.gov (United States)

    Wang, Xinyu; Zhang, Yincong; Li, Tianfu; Tian, Wende; Zhang, Qiang; Cheng, Yiyun

    2013-04-30

    Poly(amidoamine) (PAMAM) encapsulated platinum nanoparticles were synthesized and used as catalase mimics. Acetylated generation 9 (Ac-G9) PAMAM dendrimer with a molecular size around 10 nm was used as a template to synthesize platinum nanoparticles. The feeding molar ratio of Pt(4+) and Ac-G9 is 2048, and the synthesized platinum nanoparticle (Ac-G9/Pt NP) has an average size of 3.3 nm. Ac-G9/Pt NP has a similar molecular size and globular shape with catalase (~11 nm). The catalytic activity of Ac-G9/Pt NP on the decomposition of H2O2 is approaching that of catalase at 37 °C. Ac-G9/Pt NP shows differential response to the changes of pH and temperature compared with catalase, which can be explained by different catalytic mechanisms of Ac-G9/Pt NP and catalase. Ac-G9/Pt NP also shows horseradish peroxidase activity and is able to scavenge free radicals such as di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH). Furthermore, Ac-G9/Pt NP shows excellent biocompatibility on different cell lines and can down-regulate H2O2-induced intracellular reactive oxygen species (ROS) in these cells. These results suggest that dendrimers are promising mimics of proteins with different sizes and Ac-G9/Pt NP can be used as an alternative candidate of catalase to decrease oxidation stress in cells.

  11. Prominent catalytic activity of mesoporous molecular sieves in the vapor phase dehydration of cyclohexanol to cyclohexene

    Institute of Scientific and Technical Information of China (English)

    Azhagapillai Prabhu; Ahmed Al Shoaibi; Chandrasekar Srinivasakannan; Muthaiahpillai Palanichamy; Velayutham Murugesan

    2013-01-01

    Cerium incorporated KIT-6 mesoporous materials were synthesized through direct hydrothermal method and characterized by using X-ray diffraction (XRD),nitrogen sorption isotherm (BET),Fourier transform infrared spectroscopy (FT-IR),inductively coupled plasma-atomic emission spectroscopy (ICP-AES),diffuse reflectance ultraviolet visible spectroscopy (DRS-UV-Vis),thermogravimetric analysis (TGA),scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods.It appeared that stable cerium ions were inserted into the silica framework of KIT-6,thus generating acid properties in their host materials.The catalytic activity of Ce-KIT-6 materials was evaluated in the vapor phase dehydration of cyclohexanol to cyclohexene and dicyclohexyl ether at different temperatures with various Si/Ce molar ratios.Ce-KIT-6 (25) showed higher activity with 54% cyclohexanol conversion and 64% selectivity to cyclohexene.The catalytic results indicated that Ce-KIT-6 mesoporous materials could be used as versatile and stable acid catalysts.

  12. Peroxidase-like catalytic activities of ionic metalloporphyrins supported on functionalised polystyrene surface

    Indian Academy of Sciences (India)

    Mikki V Vinodu; M Padmanabhan

    2001-02-01

    Metalloderivatives of anionic tetrasulphonated tetraphenylporphyrin (MTPPS, M = Mn(III), Fe(III) and Co(III)) were synthesized and immobilized on cationically functionalised divinylbenzene(DVB)-crosslinked polystyrene(PS). These supported catalysts (PS-MTPPS) were found to exhibit peroxidase-like activity. The co-oxidation of 4-aminoantipyrine and phenol by H2O2 was attempted with these catalysts to mimic this enzyme function. The catalytic efficiency of all these immobilized MTPPS was found to be superior to the corresponding unsupported MTPPS in solution. The effect of the central metal ion of the porphyrin, H of the reaction medium and also the temperature effect are investigated. The ideal H 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. The re-usability of these PS-MTPPS systems for peroxidase-like activity was also studied and it was found that they exhibited a very high degree of recyclability without much poisoning.

  13. Emergence of a catalytic tetrad during evolution of a highly active artificial aldolase

    Science.gov (United States)

    Obexer, Richard; Godina, Alexei; Garrabou, Xavier; Mittl, Peer R. E.; Baker, David; Griffiths, Andrew D.; Hilvert, Donald

    2017-01-01

    Designing catalysts that achieve the rates and selectivities of natural enzymes is a long-standing goal in protein chemistry. Here, we show that an ultrahigh-throughput droplet-based microfluidic screening platform can be used to improve a previously optimized artificial aldolase by an additional factor of 30 to give a >109 rate enhancement that rivals the efficiency of class I aldolases. The resulting enzyme catalyses a reversible aldol reaction with high stereoselectivity and tolerates a broad range of substrates. Biochemical and structural studies show that catalysis depends on a Lys-Tyr-Asn-Tyr tetrad that emerged adjacent to a computationally designed hydrophobic pocket during directed evolution. This constellation of residues is poised to activate the substrate by Schiff base formation, promote mechanistically important proton transfers and stabilize multiple transition states along a complex reaction coordinate. The emergence of such a sophisticated catalytic centre shows that there is nothing magical about the catalytic activities or mechanisms of naturally occurring enzymes, or the evolutionary process that gave rise to them.

  14. 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.

  15. 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.

  16. Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

    Science.gov (United States)

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

    2015-03-01

    Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

  17. Photo-catalytic activities of plant hormones on semiconductor nanoparticles by laser-activated electron tunneling and emitting.

    Science.gov (United States)

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

    2015-01-01

    Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO₂), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi₂O₃)₀.₀₇(CoO)₀.₀₃(ZnO)₀.₉ semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

  18. Mutation in aspartic acid residues modifies catalytic and haemolytic activities of Bacillus cereus sphingomyelinase.

    Science.gov (United States)

    Tamura, H; Tameishi, K; Yamada, A; Tomita, M; Matsuo, Y; Nishikawa, K; Ikezawa, H

    1995-01-01

    Four aspartic acid residues (Asp126, Asp156, Asp233 and Asp295) of Bacillus cereus sphingomyelinase (SMase) in the conservative regions were changed to glycine by in vitro mutagenesis, and the mutant SMases [D126G (Asp126-->Gly etc.), D156G, D233G and D295G] were produced in Bacillus brevis 47, a protein-producing strain. The sphingomyelin (SM)-hydrolysing activity of D295G was completely abolished and those of D126G and D156G were reduced by more than 80%, whereas that of D233G was not so profoundly affected. Two mutant enzymes (D126G and D156G) were purified and characterized further. The hydrolytic activities of D126G and D156G toward four phosphocholine-containing substrates with different hydrophobicities, SM, 2-hexadecanoylamino-4-nitrophenylphosphocholine(HNP), lysophosphatidylcholine (lysoPC) and p-nitro-phenylphosphocholine (p-NPPC), were compared with those of the wild-type. The activity of D126G toward water-soluble p-NPPC was comparable with that of the wild-type. On the other hand, D156G catalysed the hydrolysis of hydrophilic substrates such as HNP and p-NPPC more efficiently (> 4-fold) than the wild-type. These results suggested that Asp126 and Asp156, located in the highly conserved region, may well be involved in a substrate recognition process rather than catalytic action. Haemolytic activities of the mutant enzymes were found to be parallel with their SM-hydrolysing activities. Two regions, including the C-terminal region containing Asp295, were found to show considerable sequence identity with the corresponding regions of bovine pancreatic DNase I. Structural predictions indicated structural similarity between SMase and DNase I. An evolutionary relationship based on the catalytic function was suggested between the structures of these two phosphodiesterases. Images Figure 2 Figure 3 Figure 4 Figure 6 PMID:7639690

  19. Molecular basis of reduced pyridoxine 5'-phosphate oxidase catalytic activity in neonatal epileptic encephalopathy disorder.

    Science.gov (United States)

    Musayev, Faik N; Di Salvo, Martino L; Saavedra, Mario A; Contestabile, Roberto; Ghatge, Mohini S; Haynes, Alexina; Schirch, Verne; Safo, Martin K

    2009-11-06

    Mutations in pyridoxine 5'-phosphate oxidase are known to cause neonatal epileptic encephalopathy. This disorder has no cure or effective treatment and is often fatal. Pyridoxine 5'-phosphate oxidase catalyzes the oxidation of pyridoxine 5'-phosphate to pyridoxal 5'-phosphate, the active cofactor form of vitamin B(6) required by more than 140 different catalytic activities, including enzymes involved in amino acid metabolism and biosynthesis of neurotransmitters. Our aim is to elucidate the mechanism by which a homozygous missense mutation (R229W) in the oxidase, linked to neonatal epileptic encephalopathy, leads to reduced oxidase activity. The R229W variant is approximately 850-fold less efficient than the wild-type enzyme due to an approximately 192-fold decrease in pyridoxine 5'-phosphate affinity and an approximately 4.5-fold decrease in catalytic activity. There is also an approximately 50-fold reduction in the affinity of the R229W variant for the FMN cofactor. A 2.5 A crystal structure of the R229W variant shows that the substitution of Arg-229 at the FMN binding site has led to a loss of hydrogen-bond and/or salt-bridge interactions between FMN and Arg-229 and Ser-175. Additionally, the mutation has led to an alteration of the configuration of a beta-strand-loop-beta-strand structure at the active site, resulting in loss of two critical hydrogen-bond interactions involving residues His-227 and Arg-225, which are important for substrate binding and orientation for catalysis. These results provide a molecular basis for the phenotype associated with the R229W mutation, as well as providing a foundation for understanding the pathophysiological consequences of pyridoxine 5'-phosphate oxidase mutations.

  20. Remediation of actual groundwater polluted with nitrate by the catalytic reduction over copper-palladium supported on active carbon

    OpenAIRE

    Wang, Yi; Sakamoto, Yoshinori; Kamiya, Yuichi

    2009-01-01

    Catalytic reduction of nitrate (NO3-) in groundwater over a Cu-Pd catalyst supported on active carbon was investigated in a gas-liquid co-current flow system at 298 K. Although Cu-Pd/active carbon, in which the Cu/Pd molar ratio was more than 0.66, showed high activity, high selectivity for the formation of N2 and N2O (98%), and high durability for the reduction of 100 ppm NO3- in distilled water, the catalytic performance decreased during the reduction of NO3- in groundwater. The catalyst al...

  1. 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.

  2. Inhibition effect of graphene oxide on the catalytic activity of acetylcholinesterase enzyme.

    Science.gov (United States)

    Wang, Yong; Gu, Yao; Ni, Yongnian; Kokot, Serge

    2015-11-01

    Variations in the enzyme activity of acetylcholinesterase (AChE) in the presence of the nano-material, graphene oxide (GO), were investigated with the use of molecular spectroscopy UV-visible and fluorescence methods. From these studies, important kinetic parameters of the enzyme were extracted; these were the maximum reaction rate, Vm , and the Michaelis constant, Km . A comparison of these parameters indicated that GO inhibited the catalytic activity of the AChE because of the presence of the AChE-GO complex. The formation of this complex was confirmed with the use of fluorescence data, which was resolved with the use of the MCR-ALS chemometrics method. Furthermore, it was found that the resonance light-scattering (RLS) intensity of AChE changed in the presence of GO. On this basis, it was demonstrated that the relationship between AChE and GO was linear and such models were used for quantitative analyses of GO.

  3. 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...

  4. Strong and coverage-independent promotion of catalytic activity of a noble metal by subsurface vanadium

    Science.gov (United States)

    Reichl, Wolfgang; Hayek, Konrad

    2003-07-01

    While common bimetallic surfaces have a variable composition, the stable subsurface alloys of V/Rh and V/Pd are characterised by a purely noble metal-terminated surface and the second metal positioned in near-surface layers. The uniform composition of the topmost surface layer excludes conventional ensemble effects in catalysis, and the activity of the surface can be controlled by the metal loading and by the temperature of annealing. For example, the activity of a polycrystalline Rh surface in CO hydrogenation is significantly increased by promotion with subsurface vanadium. The modification of the subsurface layer with a different metal must be considered a promising approach to improve the catalytic properties of a metal surface.

  5. 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.

  6. Catalytic activity in individual cracking catalyst particles imaged throughout different life stages by selective staining

    Science.gov (United States)

    Buurmans, Inge L. C.; Ruiz-Martínez, Javier; Knowles, William V.; van der Beek, David; Bergwerff, Jaap A.; Vogt, Eelco T. C.; Weckhuysen, Bert M.

    2011-11-01

    Fluid catalytic cracking (FCC) is the major conversion process used in oil refineries to produce valuable hydrocarbons from crude oil fractions. Because the demand for oil-based products is ever increasing, research has been ongoing to improve the performance of FCC catalyst particles, which are complex mixtures of zeolite and binder materials. Unfortunately, there is limited insight into the distribution and activity of individual zeolitic domains at different life stages. Here we introduce a staining method to visualize the structure of zeolite particulates and other FCC components. Brønsted acidity maps have been constructed at the single particle level from fluorescence microscopy images. By applying a statistical methodology to a series of catalysts deactivated via industrial protocols, a correlation is established between Brønsted acidity and cracking activity. The generally applicable method has clear potential for catalyst diagnostics, as it determines intra- and interparticle Brønsted acidity distributions for industrial FCC materials.

  7. Gold-Loaded Polymeric Micelles with Temperature-Modulated Catalytic Activity

    Institute of Scientific and Technical Information of China (English)

    HU Na; SHI Dongjian; LI Jihang; LI Junfeng; CHEN Mingqing

    2015-01-01

    Four-armed amphiphilic block copolymers, polystyrene-b-poly(N-isopropylacrylamide) (PS-b-PNIPAM)4, were synthesized by atom transfer radical polymerization (ATRP). (PS-b-PNIPAM)4 self-assembled into micelles with PS block as core and thermoresponsive PNIPAM block as corona. The gold nanoparticles (Au NPs) with average diameter about 5.8 nm were immobilized on the surfaces of the micelles by the reduction of the corresponding ions. The micelle-supported gold nanoparticles (Au-micelles) were applied to catalyze the reduction ofp-nitrophenol. Moreover, the activity of the Au-micelle catalyst could be modulated by the temperature and the Au-micelles could be easily recovered by changing the temperature and recycled four times with high catalytic activity.

  8. 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.

  9. The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

    Science.gov (United States)

    Kato, Shunsuke; Matam, Santhosh Kumar; Kerger, Philipp; Bernard, Laetitia; Battaglia, Corsin; Vogel, Dirk; Rohwerder, Michael; Züttel, Andreas

    2016-05-10

    Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites.

  10. Side chain flexibility and coupling between the S4-S5 linker and the TRP domain in thermo-sensitive TRP channels: Insights from protein modeling.

    Science.gov (United States)

    Romero-Romero, Sergio; Gomez Lagunas, Froylan; Balleza, Daniel

    2017-04-01

    The transient receptor potential (TRP) superfamily is subdivided into several subfamilies on the basis of sequence similarity, which is highly heterogeneous but shows a molecular architecture that resembles the one present in members of the Kv channel superfamily. Because of this diversity, they produce a large variety of channels with different gating and permeability properties. Elucidation of these particular features necessarily requires comparative studies based on structural and functional data. The present study aims to compilate, analyze, and determine, in a coherent way, the relationship between intrinsic side-chain flexibility and the allosteric coupling in members of the TRPV, TRPM, and TRPC families. Based on the recently determined structures of TRPV1 and TRPV2, we have generated protein models for single subunits of TRPV5, TRPM8, and TRPC5 channels. With these models, we focused our attention on the apparently crucial role of the GP dipeptide at the center of the S4-S5 linker and discussed its role in the interaction with the TRP domain, specifically with the highly-conserved Trp during this coupling. Our analysis suggests an important role of the S4-S5L flexibility in the thermosensitivity, where heat-activated channels possess rigid S4-S5 linkers, whereas cold-activated channels have flexible ones. Finally, we also present evidence of the key interaction between the conserved Trp residue of the TRP box and of several residues in the S4-S5L, importantly the central Pro. Proteins 2017; 85:630-646. © 2016 Wiley Periodicals, Inc.

  11. Catalytic activity of Mn-substituted barium hexaaluminates for methane combustion

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The catalysts of hexaaluminate (BaMnxAl12-xO19-δ , x = 1.0, 2.0, 3.0, 4.0) to be used in methane combustion have been successfully synthesized by co-precipitation method and supercritical drying. The crystalline structure and surface area of catalyst were characterized by X-ray diffraction (XRD) and nitrogen adsorption analysis of BET method. BET analysis revealed that the preparing and drying method proposed here provides stable materials with higher surface area of 51.4 m2/g in comparison to materials prepared using conventional ambient drying method for BaMnxAl12?xO19-δ calcined at 1200℃ under oxygen. XRD analysis indicated that formation of a pure single phase BaMnxAl12-xO19-δ occurred up to x = 3 in the case of Mn-substituted barium hexaaluminates. Incorporation of Mn in excess leads to BaAl2O4 phase formation. As far as the valence state of Manganese ions was concerned, the introduced Mn ions were either divalent or trivalent. The first Mn ions were introduced in the matrix essentially as Mn2+ and only for BaMn3Al9O19-δ does manganese exist exclusively as Mn3+; the higher the Mn concen- tration, the higher the proportion of Mn3+. Catalytic activity for methane combustion has been measured for Mn-substituted barium hexaaluminates, light-off temperature was observed in the 512-624℃ range. The highest activity was obtained for catalysts containing 3 Mn ions per unit cell, which reveals that the BaMnxAl12-xO19-δ catalyst was a promising methane combustion catalyst with high activity and good thermal stability. Temperature programmed reduction (TPR) under hydrogen has been used to correlate the catalytic activity with the amount of easily reducible species.

  12. The stability and catalytic activity of W13@Pt42 core-shell structure.

    Science.gov (United States)

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-10-19

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application.

  13. Improving the catalytic activity of semiconductor nanocrystals through selective domain etching.

    Science.gov (United States)

    Khon, Elena; Lambright, Kelly; Khnayzer, Rony S; Moroz, Pavel; Perera, Dimuthu; Butaeva, Evgeniia; Lambright, Scott; Castellano, Felix N; Zamkov, Mikhail

    2013-05-01

    Colloidal chemistry offers an assortment of synthetic tools for tuning the shape of semiconductor nanocrystals. While many nanocrystal architectures can be obtained directly via colloidal growth, other nanoparticle morphologies require alternative processing strategies. Here, we show that chemical etching of colloidal nanoparticles can facilitate the realization of nanocrystal shapes that are topologically inaccessible by hot-injection techniques alone. The present methodology is demonstrated by synthesizing a two-component CdSe/CdS nanoparticle dimer, constructed in a way that both CdSe and CdS semiconductor domains are exposed to the external environment. This structural morphology is highly desirable for catalytic applications as it enables both reductive and oxidative reactions to occur simultaneously on dissimilar nanoparticle surfaces. Hydrogen production tests confirmed the improved catalytic activity of CdSe/CdS dimers, which was enhanced 3-4 times upon etching treatment. We expect that the demonstrated application of etching to shaping of colloidal heteronanocrystals can become a common methodology in the synthesis of charge-separating nanocrystals, leading to advanced nanoparticles architectures for applications in areas of photocatalysis, photovoltaics, and light detection.

  14. Synthesis, structural properties and catalytic activity of MgO-SnO2 nanocatalysts

    Science.gov (United States)

    Perveen, Hina; Farrukh, Muhammad Akhyar; Khaleeq-ur-Rahman, Muhammad; Munir, Badar; Tahir, Muhammad Ashraf

    2015-01-01

    Surfactant controlled synthesis of magnesium oxide-tin oxide (MgO-SnO2) nanocatalysts was carried out via the hydrothermal method. Concentration of sodium dodecyl sulfate (SDS) was varied while all other reaction conditions were kept constant same for this purpose. Furthermore, MgO-SnO2 nanocatalysts were also prepared by changing the precursor's concentration. These precursors are magnesium nitrate Mg(NO3)2 · 6H2O and tin chloride (SnCl4 · 5H2O). The influence of these reaction parameters on the sizes and morphology of the nanocatalysts were studied by using Fourier transform infrared (FTIR) spectroscopy, Scanning electron microscopy-Energy dispersive X-ray (SEM-EDX), Powder X-ray diffraction (XRD), Transmission electron microscopy and Thermo gravimetric analysis (TGA). The catalytic efficiency of MgO-SnO2 was checked against 2,4-dinitrophenylhydrazine (DNPH), which is an explosive compound. The nanocatalysts were found as a good catalyst to degrade the DNPH. Catalytic activity of nanocatalysts was observed up to 19.13% for the degradation DNPH by using UV-spectrophotometer.

  15. Catalytic ozonation of pentachlorophenol in aqueous solutions using granular activated carbon

    Science.gov (United States)

    Asgari, Ghorban; Samiee, Fateme; Ahmadian, Mohammad; Poormohammadi, Ali; solimanzadeh, Bahman

    2014-11-01

    The efficiency of granular activated carbon (GAC) was investigated in this study as a catalyst for the elimination of pentachlorophenol (PCP) from contaminated streams in a laboratory-scale semi-batch reactor. The influence of important parameters including solution pH (2-10), radical scavenger (tert-butanol, 0.04 mol/L), catalyst dosage (0.416-8.33 g/L), initial PCP concentration (100-1000 mg/L) and ozone flow rate (2.3-12 mg/min) was examined on the efficiency of the catalytic ozonation process (COP) in degradation and mineralization of PCP in aqueous solution. The experimental results showed that catalytic ozonation with GAC was most effective at pH of 8 with ozone flow rate of 12 mg/min and a GAC dosage of 2 g. Compared to the sole ozonation process (SOP), the removal levels of PCP and COP were, 98, and 79 %, respectively. The degradation rate of kinetics was also investigated. The results showed that using a GAC catalyst in the ozonation of PCP produced an 8.33-fold increase in rate kinetic compared to the SOP under optimum conditions. Tert-butanol alcohol (TBA) was used as a radical scavenger. The results demonstrated that COP was affected less by TBA than by SOP. These findings suggested that GAC acts as a suitable catalyst in COP to remove refractory pollutants from aqueous solution.

  16. Antibiotic Binding Drives Catalytic Activation of Aminoglycoside Kinase APH(2″)-Ia.

    Science.gov (United States)

    Caldwell, Shane J; Huang, Yue; Berghuis, Albert M

    2016-06-01

    APH(2″)-Ia is a widely disseminated resistance factor frequently found in clinical isolates of Staphylococcus aureus and pathogenic enterococci, where it is constitutively expressed. APH(2″)-Ia confers high-level resistance to gentamicin and related aminoglycosides through phosphorylation of the antibiotic using guanosine triphosphate (GTP) as phosphate donor. We have determined crystal structures of the APH(2″)-Ia in complex with GTP analogs, guanosine diphosphate, and aminoglycosides. These structures collectively demonstrate that aminoglycoside binding to the GTP-bound kinase drives conformational changes that bring distant regions of the protein into contact. These changes in turn drive a switch of the triphosphate cofactor from an inactive, stabilized conformation to a catalytically competent active conformation. This switch has not been previously reported for antibiotic kinases or for the structurally related eukaryotic protein kinases. This catalytic triphosphate switch presents a means by which the enzyme can curtail wasteful hydrolysis of GTP in the absence of aminoglycosides, providing an evolutionary advantage to this enzyme.

  17. Effect of substrate (ZnO) morphology on enzyme immobilization and its catalytic activity

    Science.gov (United States)

    Zhang, Yan; Wu, Haixia; Huang, Xuelei; Zhang, Jingyan; Guo, Shouwu

    2011-07-01

    In this study, zinc oxide (ZnO) nanocrystals with different morphologies were synthesized and used as substrates for enzyme immobilization. The effects of morphology of ZnO nanocrystals on enzyme immobilization and their catalytic activities were investigated. The ZnO nanocrystals were prepared through a hydrothermal procedure using tetramethylammonium hydroxide as a mineralizing agent. The control on the morphology of ZnO nanocrystals was achieved by varying the ratio of CH3OH to H2O, which were used as solvents in the hydrothermal reaction system. The surface of as-prepared ZnO nanoparticles was functionalized with amino groups using 3-aminopropyltriethoxysilane and tetraethyl orthosilicate, and the amino groups on the surface were identified and calculated by FT-IR and the Kaiser assay. Horseradish peroxidase was immobilized on as-modified ZnO nanostructures with glutaraldehyde as a crosslinker. The results showed that three-dimensional nanomultipod is more appropriate for the immobilization of enzyme used further in catalytic reaction.

  18. The stability and catalytic activity of W13@Pt42 core-shell structure

    Science.gov (United States)

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-01-01

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application. PMID:27759038

  19. The stability and catalytic activity of W13@Pt42 core-shell structure

    Science.gov (United States)

    Huo, Jin-Rong; Wang, Xiao-Xu; Li, Lu; Cheng, Hai-Xia; Su, Yan-Jing; Qian, Ping

    2016-10-01

    This paper reports a study of the electronic properties, structural stability and catalytic activity of the W13@Pt42 core-shell structure using the First-principles calculations. The degree of corrosion of W13@Pt42 core-shell structure is simulated in acid solutions and through molecular absorption. The absorption energy of OH for this structure is lower than that for Pt55, which inhibits the poison effect of O containing intermediate. Furthermore we present the optimal path of oxygen reduction reaction catalyzed by W13@Pt42. Corresponding to the process of O molecular decomposition, the rate-limiting step of oxygen reduction reaction catalyzed by W13@Pt42 is 0.386 eV, which is lower than that for Pt55 of 0.5 eV. In addition by alloying with W, the core-shell structure reduces the consumption of Pt and enhances the catalytic efficiency, so W13@Pt42 has a promising perspective of industrial application.

  20. Synthesis and catalytic activity of metallo-organic complexes bearing 5-amino 2-ethylpyridine -2-carboximidate

    Indian Academy of Sciences (India)

    LUO MEI; XU JIA; ZHANG JING CHENG

    2016-06-01

    A series of copper, cobalt, nickel and manganese complexes were synthesized and characterized. Reaction of 5-amino-2-cyanopyridine with $ MCl_{2}$·x$H_{2}O$ (M: $Cu^{2+}$, $Co^{2+}$, $Ni^{2+}$, $Mn^{2+})$ in anhydrous ethanol resulted in the formation of four complexes $[NH_{2}EtPyCuCl_{2}(CH_{3}OH)].H_{2}O 1$, $[(NH_{2}EtPyHCl)_{3}Co]$$(Cl)_{3}.3H_{2}O 2$, $[(NH_{2}EtPy)_{2}$ 2$(H_{2}O)Ni]$ $(Cl_{2})$ 3, and $[(NH_{2}EtPy)_{2}$ 2$(H_{2}O)$ Mn]$(Cl_{2})$ 4 $[NH_{2} EtPy=5-amino-oethylpyridine-2-carboximidate], respectively. The structures of these compounds were determined by X-raydiffraction, NMR and IR spectroscopy, and elemental analysis. Each complex was then used as a catalyst in the Henry reaction, and its catalytic activity was determined by 1H NMR. Good catalytic effects were achieved (69–87%).

  1. Effect of substrate (ZnO morphology on enzyme immobilization and its catalytic activity

    Directory of Open Access Journals (Sweden)

    Huang Xuelei

    2011-01-01

    Full Text Available Abstract In this study, zinc oxide (ZnO nanocrystals with different morphologies were synthesized and used as substrates for enzyme immobilization. The effects of morphology of ZnO nanocrystals on enzyme immobilization and their catalytic activities were investigated. The ZnO nanocrystals were prepared through a hydrothermal procedure using tetramethylammonium hydroxide as a mineralizing agent. The control on the morphology of ZnO nanocrystals was achieved by varying the ratio of CH3OH to H2O, which were used as solvents in the hydrothermal reaction system. The surface of as-prepared ZnO nanoparticles was functionalized with amino groups using 3-aminopropyltriethoxysilane and tetraethyl orthosilicate, and the amino groups on the surface were identified and calculated by FT-IR and the Kaiser assay. Horseradish peroxidase was immobilized on as-modified ZnO nanostructures with glutaraldehyde as a crosslinker. The results showed that three-dimensional nanomultipod is more appropriate for the immobilization of enzyme used further in catalytic reaction.

  2. Synthesis of Water Dispersible and Catalytically Active Gold-Decorated Cobalt Ferrite Nanoparticles.

    Science.gov (United States)

    Silvestri, Alessandro; Mondini, Sara; Marelli, Marcello; Pifferi, Valentina; Falciola, Luigi; Ponti, Alessandro; Ferretti, Anna Maria; Polito, Laura

    2016-07-19

    Hetero-nanoparticles represent an important family of composite nanomaterials that in the past years are attracting ever-growing interest. Here, we report a new strategy for the synthesis of water dispersible cobalt ferrite nanoparticles (CoxFe3-xO4 NPs) decorated with ultrasmall (2-3 nm) gold nanoparticles (Au NPs). The synthetic procedure is based on the use of 2,3-meso-dimercaptosuccinic acid (DMSA), which plays a double role. First, it transfers cobalt ferrite NPs from the organic phase to aqueous media. Second, the DMSA reductive power promotes the in situ nucleation of gold NPs in proximity of the magnetic NP surface. Following this procedure, we achieved a water dispersible nanosystem (CoxFe3-xO4-DMSA-Au NPs) which combines the cobalt ferrite magnetic properties with the catalytic features of ultrasmall Au NPs. We showed that CoxFe3-xO4-DMSA-Au NPs act as an efficient nanocatalyst to reduce 4-nitrophenol to 4-aminophenol and that they can be magnetically recovered and recycled. It is noteworthy that such nanosystem is more catalytically active than Au NPs with equal size. Finally, a complete structural and chemical characterization of the hetero-NPs is provided.

  3. Evidence for Novel Pharmacological Sensitivities of Transient Receptor Potential (TRP Channels in Schistosoma mansoni.

    Directory of Open Access Journals (Sweden)

    Swarna Bais

    2015-12-01

    Full Text Available Schistosomiasis, caused by parasitic flatworms of the genus Schistosoma, is a neglected tropical disease affecting hundreds of millions globally. Praziquantel (PZQ, the only drug currently available for treatment and control, is largely ineffective against juvenile worms, and reports of PZQ resistance lend added urgency to the need for development of new therapeutics. Ion channels, which underlie electrical excitability in cells, are validated targets for many current anthelmintics. Transient receptor potential (TRP channels are a large family of non-selective cation channels. TRP channels play key roles in sensory transduction and other critical functions, yet the properties of these channels have remained essentially unexplored in parasitic helminths. TRP channels fall into several (7-8 subfamilies, including TRPA and TRPV. Though schistosomes contain genes predicted to encode representatives of most of the TRP channel subfamilies, they do not appear to have genes for any TRPV channels. Nonetheless, we find that the TRPV1-selective activators capsaicin and resiniferatoxin (RTX induce dramatic hyperactivity in adult worms; capsaicin also increases motility in schistosomula. SB 366719, a highly-selective TRPV1 antagonist, blocks the capsaicin-induced hyperactivity in adults. Mammalian TRPA1 is not activated by capsaicin, yet knockdown of the single predicted TRPA1-like gene (SmTRPA in S. mansoni effectively abolishes capsaicin-induced responses in adult worms, suggesting that SmTRPA is required for capsaicin sensitivity in these parasites. Based on these results, we hypothesize that some schistosome TRP channels have novel pharmacological sensitivities that can be targeted to disrupt normal parasite neuromuscular function. These results also have implications for understanding the phylogeny of metazoan TRP channels and may help identify novel targets for new or repurposed therapeutics.

  4. Catalytic activity of oil soluble molybdenum compounds for heavy oil hydrotreatment

    Energy Technology Data Exchange (ETDEWEB)

    Kushiyama, Satoshi; Aizawa, Reiji; Kobayashi, Satoru; Koinuma, Yutaka; Uemasu, Isamu; Shimizu, Yoshikazu (National Research Institute for Pollution and Resources, Tsukuba (Japan))

    1989-04-20

    Catalytic activity of oil-soluble molybdenum compounds in the hydrotreatment of heavy oil, with high content of the catalyst-poison compounds such as vanadium compounds and asphaltene, was studied. Reactions were performed using Venezuela Morichal crude and catalysts: molybdenum-dithiophoshpates, -dithiocarbamates and -naphthenates; and cobalt-cotylates, -dioctylphosphates. Catalyst systems containing Mo, Co, P and S (or mixtures of compounds containing each element) were found to show high activity for sulfur and vanadium removal. It was revealed that the addition of P compounds is essential for vanadium removal and the effect of Co compounds on the activity enhancement is shown in the only case of coexistence of P and S. No Mo, Co, P were found in the oil products. Recycle use of the Mo-Co-P-S catalyst resulted in a gradual decline of activity. However, the activity seems to be constant after three to four recycle uses, its activity was still higher than the initial activity of conventional Co-Mo-Al{sub 2}O{sub 3} catalyst. 13 refs., 5 tabs.

  5. Catalytic effect of activated carbon on bioleaching of low-grade primary copper sulfide ores

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The catalytic effect of activated carbon on the bioleaching of low-grade primary copper sulfide ores using mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans was investigated. The results show that the addition of activated carbon can greatly accelerate the rate and efficiency of copper dissolution from low-grade primary copper sulfide ores. The solution with the concentration of 3.0 g/L activated carbon is most beneficial to the dissolution of copper. The resting time of the mixture of activated carbon and ores has an impact on the bioleaching of low-grade primary copper sulfide ores. The 2 d resting time is most favorable to the dissolution of copper. The enhanced dissolution rate and efficiency of copper can be attributed to the galvanic interaction between activated carbon and chalcopyrite. The addition of activated carbon obviously depresses the dissolution of iron and the bacterial oxidation of ferrous ions in solution. The lower redox potentials are more favorable to the copper dissolution than the higher potentials for low-grade primary copper sulfide ores in the presence of activated carbon.

  6. Water-gas shift reaction on CuO-ZnO catalysts: I. Structure and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Kalchev, M.G.; Andreev, A.A. [Institute of Catalysis, Sofia (Bulgaria); Zotov, N.S. [Institute of Applied Mineralogy, Sofia (Bulgaria)

    1995-11-01

    The physicochemical properties of CuO-ZnO samples with different CuO contents were investgated by a complex of physical methods: DSC, XPS, EPR, TPR, and XRD. The samples containing {approximately}25 wt % CuO exhibited a maximum catalytic activity in the water-gas shift reaction. The catalytic activity was attributed to copper ions aggregated on the highly dispersed and defective CuO surface and to an anion-modified ZnO surface. Aggregates of copper ions, formed on metal species and probably modified with hydroxyl and carbonate groups, were shown to play a decisive role in the catalytic activity of the samples containing more than 15 wt % CuO.

  7. Optical Absorption Property and Photo-catalytic Activity of Tin Dioxide-doped Titanium Dioxides

    Institute of Scientific and Technical Information of China (English)

    LI,Huai-Xiang; XIA,Rong-Hua; JIANG,Zheng-Wei; CHEN,Shan-Shan; CHEN,De-Zhan

    2008-01-01

    SnO2-doped TiO2 films and composite oxide powders have been prepared by a sol-gel method. Ti(OC4H9)4 and SnCl4·5H2O were used as precursors and C2H5OH was used as solvent. The optical absorption measurements indicate that the composite oxide SnO2-TiO2 thin films exhibit smaller optical energy band gaps than pure TiO2 thin films and the optical energy band gap decreases as calcining temperature increases. X-ray diffraction was used to characterize the phase transition for the composite oxide powders at different calcining temperatures. Aanatase phase is the main crystal structure in both pure TiO2 and Sn0.05Ti0.95O2 samples if calcining temperature is below 500℃. The rutile phase has appeared and coexisted with the anatase crystal phase for both pure TiO2 and Sn0.05Ti0.95O2 composite oxides when calcining was at 600℃ . Transmission electron microscopy analysis shows a smaller grain size in Sn0.05Ti0.95O2 powders than TiO2 powders calcined at 600℃. When calcining temperature is 700℃ , there is only rutile phase in Sn0.05Ti0.95O2 samples, but there are still two crystal phases, anatase and rutile, coexisting in the pure TiO2 samples. Assuming the grain growth obeys the first order kinetics, Arrhenius empirical relation has been used to estimate the activation energy of 47.486 and 33.103 kJ·mol-1 for the grain growth of TiO2 and Sn0.05Ti0.95O2, respectively. The photo-catalytic activity of the powder samples has been examined by measuring the degradation of methylene blue solution under ultra-violet irradiation. Two effective factors of photo-catalytic activity namely, the content of SnO2 in the TiO2 samples and the calcining temperature, have been optimized based on the photo-catalytic degradation of methylene blue solution.

  8. Extending Thymidine Kinase Activity to the Catalytic Repertoire of Human Deoxycytidine Kinase

    Energy Technology Data Exchange (ETDEWEB)

    Hazra, Saugata; Sabini, Eliszbetta; Ort, Stephan; Konrad, Manfred; Lavie, Arnon; (UIC); (MXPL-G)

    2009-03-04

    Salvage of nucleosides in the cytosol of human cells is carried out by deoxycytidine kinase (dCK) and thymidine kinase 1 (TK1). Whereas TK1 is only responsible for thymidine phosphorylation, dCK is capable of converting dC, dA, and dG into their monophosphate forms. Using structural data on dCK, we predicted that select mutations at the active site would, in addition to making the enzyme faster, expand the catalytic repertoire of dCK to include thymidine. Specifically, we hypothesized that steric repulsion between the methyl group of the thymine base and Arg104 is the main factor preventing the phosphorylation of thymidine by wild-type dCK. Here we present kinetic data on several dCK variants where Arg104 has been replaced by select residues, all performed in combination with the mutation of Asp133 to an alanine. We show that several hydrophobic residues at position 104 endow dCK with thymidine kinase activity. Depending on the exact nature of the mutations, the enzyme's substrate preference is modified. The R104M-D133A double mutant is a pyrimidine-specific enzyme due to large K{sub m} values with purines. The crystal structure of the double mutant R104M-D133A in complex with the L-form of thymidine supplies a structural explanation for the ability of this variant to phosphorylate thymidine and thymidine analogs. The replacement of Arg104 by a smaller residue allows L-dT to bind deeper into the active site, making space for the C5-methyl group of the thymine base. The unique catalytic properties of several of the mutants make them good candidates for suicide-gene/protein-therapy applications.

  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. Synthesis of novel carbon/silica composites based strong acid catalyst and its catalytic activities for acetalization

    Indian Academy of Sciences (India)

    Yueqing Lu; Xuezheng Liang; Chenze Qi

    2012-06-01

    Novel solid acid based on carbon/silica composites are synthesized through one-pot hydrothermal carbonization of hydroxyethylsulfonic acid, sucrose and tetraethyl orthosilicate (TEOS). The novel solid acid owned the acidity of 2.0 mmol/g, much higher than that of the traditional solid acids such as Nafion and Amberlyst-15 (0.8 mmol/g). The catalytic activities of the solid acid are investigated through acetalization. The results showed that the novel solid acid was very efficient for the reactions. The high acidity and catalytic activities made the novel carbon/silica composites based solid acid hold great potential for the green chemical processes.

  11. Nanocasted synthesis of the mesostructured LaCoO3 perovskite and its catalytic activity in methane combustion.

    Science.gov (United States)

    Wang, Yangang; Wang, Yanqin; Liu, Xiaohui; Guo, Yun; Guo, Yanglong; Lu, Guanzhong

    2009-02-01

    Extremely high surface area, mesostructured LaCoO3 perovskite has been synthesized by nanocasting from mesoporous cubic (Ia3d) vinyl silica. Thus-prepared material was characterized by XRD, TEM, and N2-sorption, and its catalytic property was also tested in methane combustion. The catalytic results demonstrated that thus-prepared mesostructured LaCoO3 perovskite had higher activity than the conventional bulk LaCoO3 perovskite prepared by citrate method. Further analysis showed that both the high surface area and the existence of high valent cobalt ions (Co4+, XPS analysis) were contributed to the high activity.

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

    Institute of Scientific and Technical Information of China (English)

    Anaswara RAVINDRAN; Rajendra SRIVASTAVA

    2011-01-01

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

  13. Catalytic Pyrolyses of Rayon and the Effect on Activated Carbon Fiber

    Institute of Scientific and Technical Information of China (English)

    曾凡龙; 潘鼎

    2004-01-01

    The catalytic pyrolyses of rayon have been studied respectively by thermo-gravimetric analysis (TGA) when rayon was treated with phosphoric acid (PA), three ammonium phosphate salts and ammonium sulfate (AS). The air is favorable to the catalysis of dibasic ammonium phosphate (DAP), but not to those of ADP, PA, AP, and AS obviously. It is put forward that a peak's shape character can be described with the ratio of height to half-height-width (H/W/2) of the peak on a differential thermo-gravimetric (DTG) curve. A flat cracking peak, presenting a more moderate dehydration reaction, has a smaller ratio and could lead to higher carbonization and activation yields. The experimental results prove this view. According to expectation, the order of catalysis is: DAP≥ADP>PA>AP(>>)AS(>>) no catalyst.

  14. Palladium nanoparticle anchored polyphosphazene nanotubes: preparation and catalytic activity on aryl coupling reactions

    Indian Academy of Sciences (India)

    V Devi; A Ashok Kumar; S Sankar; K Dinakaran

    2015-06-01

    Highly accessible-supported palladium (Pd) nanoparticles anchored polyphosphazene (PPZ) nanotubes (NTs) having average diameter of 120 nm were synthesized rapidly at room temperature and homogeneously decorated with Pd nanoparticles. The resultant PPZ–Pd nanocomposites were morphologically and structurally characterized by means of transmission electron microscope equipped with energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PPZ NTs. The PPZ–Pd NTs show enhanced catalytic activity for the Suzuki coupling of aryl bromides with arylboronic acid. In addition, these PPZ–Pd NTs show excellent behaviour as reusable catalysts of the Suzuki and Heck coupling reactions.

  15. 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...

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

    Science.gov (United States)

    Zayed, Mervat F; Eisa, Wael H

    2014-01-01

    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.

  17. 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.

  18. Catalytic activity of polymer-bound Ru(III)–EDTA complex

    Indian Academy of Sciences (India)

    Mahesh K Dalal; R N Ram

    2001-04-01

    Chloromethylated styrene–divinylbenzene copolymer was chemically modified with ethylenediaminetetraacetic acid ligand. Catalytically active polymer containing Ru(III) moieties were synthesized from this polymeric ligand. They were characterized using FTIR, UV-vis, SEM, ESR and TGA. Other physico-chemical properties such as bulk density, surface area, moisture content and swelling behaviour in different solvents were also studied. The polymer bound complex was used to study hydrogenation of 1-hexene to -hexane under mild conditions. Influence of [1-hexene], [catalyst], temperature and nature of the solvent on the rate of the reaction was investigated. A rate expression is proposed based on the observed initial rate data. Recycling efficiency of the catalyst has also been studied.

  19. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

    Science.gov (United States)

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-05-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

  20. Carbon supported trimetallic nickel-palladium-gold hollow nanoparticles with superior catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Shang, Changshuai; Hong, Wei; Wang, Jin; Wang, Erkang

    2015-07-01

    In this paper, Ni nanoparticles (NPs) are prepared in an aqueous solution by using sodium borohydride as reducing agent. With Ni NPs as the sacrificial template, hollow NiPdAu NPs are successfully prepared via partly galvanic displacement reaction between suitable metal precursors and Ni NPs. The as-synthesized hollow NiPdAu NPs can well dispersed on the carbon substrate. Transmission electron microscopy, X-ray diffraction and inductively coupled plasma mass spectrometry are taken to analyze the morphology, structure and composition of the as-synthesized catalysts. The prepared catalysts show superior catalytic activity and stability for methanol electrooxidation in alkaline media compared with commercial Pd/C and Pt/C. Catalysts prepared in this work show great potential to be anode catalysts in direct methanol fuel cells.

  1. Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions.

    Science.gov (United States)

    Aguirre-Díaz, Lina María; Gándara, Felipe; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2015-05-20

    The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOFs with general formula [InxGa1-x(O2C2H4)0.5(hfipbb)] were prepared by the combination of Ga and In. They are isostructural with their monometal counterparts, synthesized with Al, Ga, and In. Differences in their behavior as heterogeneous catalysts in the three-component, one pot Strecker reaction illustrate the potential of solid solution MOFs to provide the ability to address the various stages involved in the reaction mechanism.

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

    Science.gov (United States)

    Wenger, Daniela; Gerecke, Andreas C; Heeb, Norbert V; Naegeli, Hanspeter; Zenobi, Renato

    2008-04-01

    An in vitro reporter gene assay based on human breast cancer T47D cells (ER-CALUX) 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 17beta-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(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(-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.

  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. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    Science.gov (United States)

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  5. 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.

  6. Correlation between the extent of catalytic activity and charge density of montmorillonites.

    Science.gov (United States)

    Ertem, Gözen; Steudel, Annett; Emmerich, Katja; Lagaly, Gerhard; Schuhmann, Rainer

    2010-09-01

    The clay mineral montmorillonite is a member of the phyllosilicate group of minerals, which has been detected on martian soil. Montmorillonite catalyzes the condensation of activated monomers to form RNA-like oligomers. Extent of catalysis, that is, the yield of oligomers, and the length of the longest oligomer formed in these reactions widely varies with the source of montmorillonite (i.e., the locality where the mineral is mined). This study was undertaken to establish whether there exists a correlation between the extent of catalytic property and the charge density of montmorillonites. Charge density was determined by saturating the montmorillonites with alkyl ammonium cations that contained increasing lengths of alkyl chains, [CH₃-(CH₂)(n)-NH₃](+), where n = 3-16 and 18, and then measuring d(₀₀₁), interlayer spacing of the resulting montmorillonite-alkyl ammonium-montmorillonite complex by X-ray diffractometry (XRD). Results demonstrate that catalytic activity of montmorillonites with lower charge density is superior to that of higher charge density montmorillonite. They produce longer oligomers that contain 9 to 10 monomer units, while montmorillonite with high charge density catalyzes the formation of oligomers that contain only 4 monomer units. The charge density of montmorillonites can also be calculated from the chemical composition if elemental analysis data of the pure mineral are available. In the next mission to Mars, CheMin (Chemistry and Mineralogy), a combined X-ray diffraction/X-ray fluorescence instrument, will provide information on the mineralogical and elemental analysis of the samples. Possible significance of these results for planning the future missions to Mars for the search of organic compounds and extinct or extant life is discussed.

  7. Monoclonal Antibodies Targeting the Alpha-Exosite of Botulinum Neurotoxin Serotype/A Inhibit Catalytic Activity.

    Directory of Open Access Journals (Sweden)

    Yongfeng Fan

    Full Text Available The paralytic disease botulism is caused by botulinum neurotoxins (BoNT, multi-domain proteins containing a zinc endopeptidase that cleaves the cognate SNARE protein, thereby blocking acetylcholine neurotransmitter release. Antitoxins currently used to treat botulism neutralize circulating BoNT but cannot enter, bind to or neutralize BoNT that has already entered the neuron. The light chain endopeptidase domain (LC of BoNT serotype A (BoNT/A was targeted for generation of monoclonal antibodies (mAbs that could reverse paralysis resulting from intoxication by BoNT/A. Single-chain variable fragment (scFv libraries from immunized humans and mice were displayed on the surface of yeast, and 19 BoNT/A LC-specific mAbs were isolated by using fluorescence-activated cell sorting (FACS. Affinities of the mAbs for BoNT/A LC ranged from a KD value of 9.0×10-11 M to 3.53×10-8 M (mean KD 5.38×10-9 M and median KD 1.53×10-9 M, as determined by flow cytometry analysis. Eleven mAbs inhibited BoNT/A LC catalytic activity with IC50 values ranging from 8.3 ~73×10-9 M. The fine epitopes of selected mAbs were also mapped by alanine-scanning mutagenesis, revealing that the inhibitory mAbs bound the α-exosite region remote from the BoNT/A LC catalytic center. The results provide mAbs that could prove useful for intracellular reversal of paralysis post-intoxication and further define epitopes that could be targeted by small molecule inhibitors.

  8. Construction of a Trp- commercial baker's yeast strain by using food-safe-grade dominant drug resistance cassettes.

    Science.gov (United States)

    Estruch, Francisco; Prieto, José Antonio

    2003-12-01

    We have designed a food-safe-grade module for gene disruptions in commercial baker's yeast strains, which contains the G418 resistance cassette, KanMX4, flanked by direct repeats from the MEL1 gene of Saccharomyces cerevisiae. This module was used to obtain a Trp(-) auxotrophic mutant of the polyploid HY strain by successive targeting to the TRP1 locus and later in vivo excision of the kan(r) marker. Southern blot analysis indicated that HY contains five copies of the TRP1 gene. However, after four disruption rounds, a strain named HYtrpM(4), unable to grow in the absence of tryptophan, was selected. Southern and Northern analysis of HYtrpM(4) cells showed that a remaining functional wild-type copy was still present, suggesting that the level of phosphoribosylanthranylate isomerase activity, resulting from a single copy of TRP1, is too low to sustain growth. Accordingly, a high reversion frequency of the Trp(-) phenotype, through gene conversion, was found in cells of the mutant strain. Nevertheless, this was not a drawback for its use as a recipient strain of heterologous genes. Indeed, YEpACT-X24 transformants were stable after 25 generations and expressed and secreted high levels of active recombinant xylanase. These data indicate that the new Trp(-) strain can be used to generate a stable recombinant yeast that fulfils all the requirements and market criteria for commercial utilisation.

  9. Environmental Topology and Water Availability Modulates the Catalytic Activity of β-Galactosidase Entrapped in a Nanosporous Silicate Matrix.

    Science.gov (United States)

    Burgos, M Ines; Velasco, Manuel I; Acosta, Rodolfo H; Perillo, María A

    2016-11-04

    In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (Eβ-Gal) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T2) of water protons through (1)H-NMR, and scanning electron microscopy analysis of the gel nanostructure, were performed. In conjunction, results provided evidence that water availability is crucial for the modulation observed in the catalytic activity of β-Gal as long as water participate in the rate limiting step of the reaction (only with ONPG). In this case, a biphasic rate vs. substrate concentration was obtained exhibiting one phase with catalytic rate constant (kcA), similar to that observed in solution, and another phase with a higher and aging-dependent catalytic rate constant (kcB). More structured water populations (lower T2) correlates with higher catalytic rate constants (kcB). The T2-kcB negative correlation observed along the aging of gels within the 15-days period assayed reinforces the coupling between water structure and the hydrolysis catalysis inside gels.

  10. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  11. 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.

  12. Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Bhagwati; Mandani, Sonam; Sarma, Tridib K., E-mail: tridib@iiti.ac.in [Indian Institute of Technology Indore, Discipline of Chemistry, School of Basic Sciences (India)

    2015-01-15

    Pepsin, a digestive protease enzyme, could function as a reducing as well as stabilizing agent for the synthesis of Au nanostructures of various size and shape under different reaction conditions. The simple tuning of the pH of the reaction medium led to the formation of spherical Au nanoparticles, anisotropic Au nanostructures such as triangles, hexagons, etc., as well as ultra small fluorescent Au nanoclusters. The activity of the enzyme was significantly inhibited after its participation in the formation of Au nanoparticles due to conformational changes in the native structure of the enzyme which was studied by fluorescence, circular dichroism (CD), and infra red spectroscopy. However, the Au nanoparticle-enzyme composites served as excellent catalyst for the reduction of p-nitrophenol and resazurin, with the catalytic activity varying with size and shape of the nanoparticles. The presence of pepsin as the surface stabilizer played a crucial role in the activity of the Au nanoparticles as reduction catalysts, as the approach of the reacting molecules to the nanoparticle surface was actively controlled by the stabilizing enzyme.

  13. Enhanced catalytic activity and inhibited biofouling of cathode in microbial fuel cells through controlling hydrophilic property

    Science.gov (United States)

    Li, Da; Liu, Jia; Wang, Haiman; Qu, Youpeng; Zhang, Jie; Feng, Yujie

    2016-11-01

    The hydrophilicity of activated carbon cathode directly determines the distribution of three-phase interfaces where oxygen reduction occurs. In this study, activated carbon cathodes are fabricated by using hydrophobic polytetrafluoroethylene (PTFE) and amphiphilic LA132 at various weight ratio to investigate the effect of hydrophilic property on cathode performance. Contact angle tests confirm the positive impact of LA132 content on hydrophilicity. Cathode with 67 wt% LA132 content shows the highest electrochemical activity as exchange current density increases by 71% and charge transfer resistance declines by 44.6% compared to that of PTFE cathode, probably due to the extended reaction interfaces by optimal hydrophilicity of cathode so that oxygen reduction is facilitated. As a result, the highest power density of 1171 ± 71 mW m-2 is obtained which is 14% higher than PTFE cathode. In addition to the hydrophilicity, this cathode had more negative charged surface of catalyst layer, therefore the protein content of cathodic biofilm decreased by 47.5%, indicating the effective bacterial inhibition when 67 wt% LA132 is used. This study shows that the catalytic activity of cathode is improved by controlling proper hydrophilicity of cathode, and that biofilm can be reduced by increasing hydrophilicity and lowering the surface potential.

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

    Science.gov (United States)

    Burda, Edyta; Rademann, Jörg

    2014-11-18

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

  15. Tumor endothelial expression of P-glycoprotein upon microvesicular transfer of TrpC5 derived from adriamycin-resistant breast cancer cells

    Energy Technology Data Exchange (ETDEWEB)

    Dong, YePing; Pan, QiongXi; Jiang, Li; Chen, Zhen; Zhang, FangFang; Liu, YanJun; Xing, Hui; Shi, Mei; Li, Jiao; Li, XiYuan; Zhu, YaoDan; Chen, Yun; Bruce, Iain C.; Jin, Jian, E-mail: jinjian31@126.com; Ma, Xin, E-mail: maxin@jiangnan.edu.cn

    2014-03-28

    Highlights: • TrpC5 was mainly accumulated in microvesicles of drug-resistant MCF-7/ADM cells. • Microvesicles from MCF-7/ADM transferred TrpC5 to endothelial cells. • TrpC5 inhibition reduced P-glycoprotein accumulation on tumor blood vessels in vivo. - Abstract: Treatment of carcinoma commonly fails due to chemoresistance. Studies have shown that endothelial cells acquire resistance via the tumor microenvironment. Microvesicle (MV) shedding from the cell membrane to the microenvironment plays an important role in communication between cells. The aim of the present study was to determine whether MCF-7 adriamycin-resistant cells (MCF-7/ADM) shed MVs that alter the characteristics of human microvessel endothelial cells (HMECs). MVs from tumor cells transferred a Ca{sup 2+}-permeable channel TrpC5 to HMECs, inducing the expression of P-glycoprotein (P-gp) by activation of the transcription factor NFATc3 (nuclear factor of activated T cells isoform c3). Expression of the mdr1 gene was blocked by the TrpC5-blocking antibody T5E3, and the production of P-gp in HMECs was reduced by blockade of TrpC5. Thus, we postulate that endothelial cells acquire the resistant protein upon exposure to TrpC5-containg MVs in the microenvironment, and express P-gp in the TrpC5–NFATc3 signal pathway.

  16. Catalytic stimulation by restrained active-site floppiness--the case of high density lipoprotein-bound serum paraoxonase-1.

    Science.gov (United States)

    Ben-David, Moshe; Sussman, Joel L; Maxwell, Christopher I; Szeler, Klaudia; Kamerlin, Shina C L; Tawfik, Dan S

    2015-03-27

    Despite the abundance of membrane-associated enzymes, the mechanism by which membrane binding stabilizes these enzymes and stimulates their catalysis remains largely unknown. Serum paraoxonase-1 (PON1) is a lipophilic lactonase whose stability and enzymatic activity are dramatically stimulated when associated with high-density lipoprotein (HDL) particles. Our mutational and structural analyses, combined with empirical valence bond simulations, reveal a network of hydrogen bonds that connect HDL binding residues with Asn168--a key catalytic residue residing >15Å from the HDL contacting interface. This network ensures precise alignment of N168, which, in turn, ligates PON1's catalytic calcium and aligns the lactone substrate for catalysis. HDL binding restrains the overall motion of the active site and particularly of N168, thus reducing the catalytic activation energy barrier. We demonstrate herein that disturbance of this network, even at its most far-reaching periphery, undermines PON1's activity. Membrane binding thus immobilizes long-range interactions via second- and third-shell residues that reduce the active site's floppiness and pre-organize the catalytic residues. Although this network is critical for efficient catalysis, as demonstrated here, unraveling these long-rage interaction networks is challenging, let alone their implementation in artificial enzyme design.

  17. Surface structure and catalytic activity of electrodeposited Ni-Fe-Co-Mo alloy electrode by partially leaching Mo and Fe

    Institute of Scientific and Technical Information of China (English)

    LUO Bei-ping; GONG Zhu-qing; REN Bi-ye; YANG Yu-fang; CHEN Meng-jun

    2006-01-01

    Ni-Fe-Mo-Co alloy electrode was prepared in a citrate solution by electrodeposition, and then Mo and Fe were partially leached out from the electrode in 30% KOH solution. The unique surface micromorphology of a hive-like structure was obtained with an average pore size of about 50 nm. The electrode has a very large real surface area and a stable structure. The effects of sodium molybdate concentration on the composition, surface morphology, and structure of electrodes were analyzed by EDS, SEM and XRD. The polarization curves of the different electrodes show that the catalytic activity of electrodes is strongly correlated with the mole fraction of alloy elements (Ni, Fe, Mo, Co), and the addition of cobalt element to Ni-Fe-Mo alloy improves the catalytic activity. The Ni35.63Fe24.67Mo23.52Co16.18 electrode has the best activity for hydrogen evolution reaction(HER), with an over-potential of 66.2 mV, in 30% KOH at 80 ℃ and 200 mA/cm2. The alloy maintains its good catalytic activity for HER during continuous or intermittent electrolysis. Its electrochemical activity and catalytic stability are much higher than the other iron-group with Mo alloy electrodes.

  18. Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

    Science.gov (United States)

    Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

    2016-12-01

    The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

  19. Identification of collagen binding domain residues that govern catalytic activities of matrix metalloproteinase-2 (MMP-2).

    Science.gov (United States)

    Mikhailova, Margarita; Xu, Xiaoping; Robichaud, Trista K; Pal, Sanjay; Fields, Gregg B; Steffensen, Bjorn

    2012-01-01

    An innovative approach to enhance the selectivity of matrix metalloproteinase (MMP) inhibitors comprises targeting these inhibitors to catalytically required substrate binding sites (exosites) that are located outside the catalytic cleft. In MMP-2, positioning of collagen substrate molecules occurs via a unique fibronectin-like domain (CBD) that contains three distinct modular collagen binding sites. To characterize the contributions of these exosites to gelatinolysis by MMP-2, seven MMP-2 variants were generated with single, or concurrent double and triple alanine substitutions in the three fibronectin type II modules of the CBD. Circular dichroism spectroscopy verified that recombinant MMP-2 wild-type (WT) and variants had the same fold. Moreover, the MMP-2 WT and variants had the same activity on a short FRET peptide substrate that is hydrolyzed independently of CBD binding. Among single-point variants, substitution in the module 3 binding site had greatest impact on the affinity of MMP-2 for gelatin. Simultaneous substitutions in two or three CBD modules further reduced gelatin binding. The rates of gelatinolysis of MMP-2 variants were reduced by 20-40% following single-point substitutions, by 60-75% after double-point modifications, and by >90% for triple-point variants. Intriguingly, the three CBD modules contributed differentially to cleavage of dissociated α-1(I) and α-2(I) collagen chains. Importantly, kinetic analyses (k(cat)/K(m)) revealed that catalysis of a triple-helical FRET peptide substrate by MMP-2 relied primarily on the module 3 binding site. Thus, we have identified three collagen binding site residues that are essential for gelatinolysis and constitute promising targets for selective inhibition of MMP-2.

  20. Evaluation of Performance Catalytic Ozonation Process with Activated Carbon in the Removal of Humic Acids from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Gh. Asgari

    2011-01-01

    Full Text Available Introduction & Objective: In recent years, the use of alternative disinfectants and the control of natural organic matters are two approaches that are typically applied in water treatment utilities to reduce the formation of chlorinated disinfection by-products. Catalytic ozonation is a new technology used to promote the efficiency of ozonation. The goal of this study was to survey the feasibility application of activated carbon as a catalyst in ozonation process for removal of humic acids from aqueous solution. Materials & Methods: This experimental study has been done in laboratory of water and wastewater chemistry, Tarbiat Modarres University. The solid structure and chemical composition of activated carbon were analyzed by X-ray fluorescence (XRF. Ozonation and catalytic ozonation experiments were performed in a semi-batch reactor and the mass of ozone produced was measured by iodometric titration methods. Concentration changes of humic acid in samples with a concentration of 15 mg/l were determined by using spectrophotometer at an absorbance wavelength of 254 nm. To evaluate the performance of catalytic ozonation in humic acid removal, total organic carbon and trihalomethane formation potential were evaluated and the results were analyzed by Excel software. Results: Catalytic ozone results showed that using activated carbon as a catalyst increased humic acid decomposition up to 11 times and removal efficiency increased with increasing pH (4-12 and catalyst dosage (0.25-1.5 g/250cc. The experimental results showed that catalytic ozonation was most effective in less time (10 min with considerable efficiency (95% compared to the sole ozonation process (SOP. Conclusion: The results indicated that the catalytic ozonation process, compared to SOP, was less affected by radical scavenger, and total organic carbon, and trihalomethane formation potential removal achieved were 30% and 83%, respectively. (Sci J Hamadan Univ Med Sci 2011;17(4:25-33

  1. Inhibition of the ATPase activity of the catalytic portion of ATP synthases by cationic amphiphiles.

    Science.gov (United States)

    Datiles, Manuel J; Johnson, Eric A; McCarty, Richard E

    2008-04-01

    Melittin, a cationic, amphiphilic polypeptide, has been reported to inhibit the ATPase activity of the catalytic portions of the mitochondrial (MF1) and chloroplast (CF1) ATP synthases. Gledhill and Walker [J.R. Gledhill, J.E. Walker. Inhibition sites in F1-ATPase from bovine heart mitochondria, Biochem. J. 386 (2005) 591-598.] suggested that melittin bound to the same site on MF1 as IF1, the endogenous inhibitor polypeptide. We have studied the inhibition of the ATPase activity of CF1 and of F1 from Escherichia coli (ECF1) by melittin and the cationic detergent, cetyltrimethylammonium bromide (CTAB). The Ca2+- and Mg2+-ATPase activities of CF1 deficient in its inhibitory epsilon subunit (CF1-epsilon) are sensitive to inhibition by melittin and by CTAB. The inhibition of Ca2+-ATPase activity by CTAB is irreversible. The Ca2+-ATPase activity of F1 from E. coli (ECF1) is inhibited by melittin and the detergent, but Mg2+-ATPase activity is much less sensitive to both reagents. The addition of CTAB or melittin to a solution of CF1-epsilon or ECF1 caused a large increase in the fluorescence of the hydrophobic probe, N-phenyl-1-naphthylamine, indicating that the detergent and melittin cause at least partial dissociation of the enzymes. ATP partially protects CF1-epsilon from inhibition by CTAB. We also show that ATP can cause the aggregation of melittin. This result complicates the interpretation of experiments in which ATP is shown to protect enzyme activity from inhibition by melittin. It is concluded that melittin and CTAB cause at least partial dissociation of the alpha/beta heterohexamer.

  2. A C. elegans stretch receptor neuron revealed by a mechanosensitive TRP channel homologue.

    Science.gov (United States)

    Li, Wei; Feng, Zhaoyang; Sternberg, Paul W; Xu, X Z Shawn

    2006-03-30

    The nematode Caenorhabditis elegans is commonly used as a genetic model organism for dissecting integration of the sensory and motor systems. Despite extensive genetic and behavioural analyses that have led to the identification of many genes and neural circuits involved in regulating C. elegans locomotion behaviour, it remains unclear whether and how somatosensory feedback modulates motor output during locomotion. In particular, no stretch receptors have been identified in C. elegans, raising the issue of whether stretch-receptor-mediated proprioception is used by C. elegans to regulate its locomotion behaviour. Here we have characterized TRP-4, the C. elegans homologue of the mechanosensitive TRPN channel. We show that trp-4 mutant worms bend their body abnormally, exhibiting a body posture distinct from that of wild-type worms during locomotion, suggesting that TRP-4 is involved in stretch-receptor-mediated proprioception. We show that TRP-4 acts in a single neuron, DVA, to mediate its function in proprioception, and that the activity of DVA can be stimulated by body stretch. DVA both positively and negatively modulates locomotion, providing a unique mechanism whereby a single neuron can fine-tune motor activity. Thus, DVA represents a stretch receptor neuron that regulates sensory-motor integration during C. elegans locomotion.

  3. 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.

  4. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    -relations between transition energies and adsorption energies. We establish a simple kinetic framework within the Sabatier analysis and obtain trends in catalytic activity based on the descriptors EO and ECO. We show that gold nanoparticles are optimal catalysts for low temperature CO oxidation and Pt closed packed...

  5. Confirmation of Isolated Cu2+ Ions in SSZ-13 Zeolite as Active Sites in NH3-Selective Catalytic Reduction

    NARCIS (Netherlands)

    Deka, U.; Juhin, A.F.; Eilertsen, E.A.; Emerich, H.; Green, M.A.; Korhonen, S.T.; Weckhuysen, B.M.; Beale, A.M.

    2012-01-01

    NH3-Selective Catalytic Reduction (NH3-SCR) is a widely used technology for NOx reduction in the emission control systems of heavy duty diesel vehicles. Copper-based ion exchanged zeolites and in particular Cu-SSZ-13 (CHA framework) catalysts show both exceptional activity and hydrothermal stability

  6. Preparation of Au-Pd bimetallic nanoparticles in porous germania nanospheres: A study of their morphology and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Regan, Maureen R. [Department of Chemistry, Fordham University, 441, East Fordham Road, Bronx, NY 10458 (United States); Banerjee, Ipsita A. [Department of Chemistry, Fordham University, 441, East Fordham Road, Bronx, NY 10458 (United States)]. E-mail: banerjee@fordham.edu

    2006-03-15

    Size controlled Au-Pd bimetallic nanoparticles with an average size of 7-10 nm were grown in porous germania nanospheres. The properties of the resulting nanocomposites were characterized by electron microscopy, energy dispersive spectroscopy, and ultraviolet-visible spectroscopy. The catalytic activity of the nanocomposites was also examined by studying the degradation of p-nitroaniline.

  7. Preparation and Acid Catalytic Activity of TiO2 Grafted Silica MCM-41 with Sulfate Treatment

    Institute of Scientific and Technical Information of China (English)

    Dai-shi Guo; Zi-feng Ma; Chun-sheng Yin; Qi-zhong Jiang

    2008-01-01

    TiO2 grafted silica MCM-41 catalyst with and without sulfate treatment were prepared.The structural and acid properties of these materials were investigated by XRD,N2 adsorption-desorption,element analysis,thermal analysis,Raman and FTIR measurements.Their acid-catalytic activities were evaluated using the cyclization reaction of pseudoionone.It was found that the obtained materials possess well-ordered mesostructure,and the grafted TiO2 components were in highly dispersed amorphous form.T/MCM41 without sulfation contained only Lewis acid sites,while Br(o)nsted and Lewis acidities were remarkably improved for the sulfated materials ST/MCM41 and d-ST/MCM41.T/MCM-41 was not active for the cyclization reaction of pseudoionone,but ST/MCM-41 and d-ST/MCM-41 possessed favorable catalytic activities.The catalytic performance of ST/MCM-41 was comparable with that of the commercial solid acid catalyst of Amberlyst-15,and better than that of d-ST/MCM-41,although the latter underwent a second TiO2 grafting process and accordingly had higher Ti and S content.The specific surface structure of Si-O-Ti-O-S=O in ST/MCM-41 and the bilateral induction effect of Si and S=O on Si-O-Ti bonds were speculated to account for its higher acid catalytic activity.

  8. 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.

  9. Synthesis and bio-catalytic activity of isostructural cobalt(III)-phenanthroline complexes

    Indian Academy of Sciences (India)

    Dhananjay Dey; Arnab Basu Roy; Anandan Ranjani; Loganathan Gayathri; Saravanan Chandraleka; Dharumadurai Dhanasekaran; Mohammad Abdulkader Akbarsha; Chung-Yu Shen; Hui-Lien Tsai; Milan Maji; Niranjan Kole; Bhaskar Biswas

    2015-04-01

    We have synthesized two isostructural mononuclear cobalt(III) complexes [1]NO3·3H2O and [1]NO3·CH3CO2H·H2O {[1]+ = [Co(1,10-phenanthroline)2Cl2]+} and characterized by single crystal X-ray structural analyses. Mass spectral studies of the complexes indicate both the compounds to produce identical cationic species viz., [Co(phen)2Cl2]+ in methanol solution. [1]+ has been evaluated as model system for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate in methanol medium, which revealed that the cationic complex efficiently inhibits catalytic activity with kcat value 9.65 × 102 h−1. [1]+ cleaved pBR 322 DNA without addition of an activating agent. Further, the anti-cancer activity of [1]+ on human hepatocarcinoma cell line (HepG2) has been examined. The induction of apoptosis induced in the cell line was assessed base on the changes in cell morphology, which showed the efficacy of [1]+ to induce apoptosis in 53% of cells during 24 h treatment. Interestingly, the observed IC50 values reveal that [1]+ brings about conformational change on DNA strongly and exhibits remarkable cytotoxicity.

  10. The role of transition metal sulfides in hydrotreatment. 3. Acidity, XPS and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    De Agudelo, M.M.; Reyes, L.G.; Do Campo, N.

    1987-05-15

    Although, recently, most of the research on catalysis has been devoted to hydrotreatment, attention has been paid to hydrodesulfurization (HDS) but very little has been done on hydrodemetallization (HDM). This article is part of a systematic study directed towards defining the role of transition metal sulfides in hydrotreatment reactions. Catalysts supported on silica or alumina have been considered. Acidity has been evaluated using pyridine as probe molecule. This property can be attributed to the sulfide phase of the catalysts. The alumina supported catalysts were more acid than the silica supported catalysts. Since the acidity might exclusively be of Lewis type, the pattern observed through the first row transition metal sulfides reflects the trend of the electron-acceptor character of these sulfides. The XPS results indicate that catalysts are partially sulfided (at 400 C). At the same time, the results corroborate a better Me-support interaction on alumina than on silica. The HDM and HDS intrinsic activities, using a desalphalted (DAO) Morichal as feed were evaluated normalizing conversion in terms of the surface metal sites per surface area. The intrinsic activity patterns obtained for the first row transition metal sulfides, were very similar to those mentioned of acidity, reaffirming the importance of the electronic structure of the sulfide phase on its catalytic activity. 21 refs.

  11. The activity and selectivity of catalytic peroxide oxidation of chlorophenols over Cu-Al hydrotalcite/clay composite.

    Science.gov (United States)

    Zhou, Shiwei; Gu, Chuantao; Qian, Zhenying; Xu, Jinguang; Xia, Chuanhai

    2011-05-15

    Liquid phase catalytic oxidation of chlorophenols (CPs) was carried out over Cu-Al hydrotalcite/clay composite at ambient temperature and pressure using hydrogen peroxide as oxidant. The results showed that the catalyst had high catalytic activity, with complete oxidation of 4-CP within 40 min at 40 °C. The content and position of chlorine on the aromatic ring had significantly different effects on the oxidation rate of CPs, with the rate sequence of phenol > monochlorophenol (MCP) > dichlorophenol (DCP) > trichlorophenol (TCP), 3-CP > 2-CP > 4-CP, and 3,5-DCP > 3,4-DCP > 2,5-DCP > 2,4-DCP > 2,6-DCP. This was ascribed to the interactions among σ-electron withdrawing conductive effect, π-electron donating conjugative effect, and steric hindrance effect of chlorine. It was evidenced that the catalytic peroxide oxidation of CPs in the first step was selective and rate-limiting, where chlorinated 1,4-benzoquinones formed.

  12. Trp63 is regulated by STAT5 in mammary tissue and subject to differentiation in cancer

    OpenAIRE

    Assefnia, Shahin; Kang, Keunsoo; Groeneveld, Svenja; Yamaji, Daisuke; Dabydeen, Sarah; Alamri, Ahmad; Liu, Xuefeng; Hennighausen, Lothar; Furth, Priscilla A

    2014-01-01

    Trp63, founding member of the Trp53 family, contributes to epithelial differentiation and is expressed in breast neoplasia. Trp63 features two distinct promoters yielding specific mRNAs encoding two major TRP63 isoforms, a transactivating transcription factor and a dominant negative isoform. Specific TRP63 isoforms are linked to cell cycle arrest, apoptosis, survival and epithelial mesenchymal transition. Although TRP63 overexpression in cultured cells is used to elucidate functions, little i...

  13. 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.

  14. Small molecule regulation of self-association and catalytic activity in a supramolecular coordination complex.

    Science.gov (United States)

    McGuirk, C Michael; Stern, Charlotte L; Mirkin, Chad A

    2014-03-26

    Herein, we report the synthesis and characterization of the first weak-link approach (WLA) supramolecular construct that employs the small molecule regulation of intermolecular hydrogen bonding interactions for the in situ control of catalytic activity. A biaryl urea group, prone to self-aggregation, was functionalized with a phosphinoalkyl thioether (P,S) hemilabile moiety and incorporated into a homoligated Pt(II) tweezer WLA complex. This urea-containing construct, which has been characterized by a single crystal X-ray diffraction study, can be switched in situ from a rigid fully closed state to a flexible semiopen state via Cl(-) induced changes in the coordination mode at the Pt(II) structural node. FT-IR and (1)H NMR spectroscopy studies were used to demonstrate that while extensive urea self-association persists in the flexible semiopen complex, these interactions are deterred in the rigid, fully closed complex because of geometric and steric restraints. Consequently, the urea moieties in the fully closed complex are able to catalyze a Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone to generate 2-acetyl-5-norbornene. The free urea ligand and the semiopen complex show no such activity. The successful incorporation and regulation of a hydrogen bond donating catalyst in a WLA construct open the doors to a vast and rapidly growing catalogue of allosteric catalysts for applications in the detection and amplification of organic analytes.

  15. Methodology to assay CYP2E1 mixed function oxidase catalytic activity and its induction

    Directory of Open Access Journals (Sweden)

    Arthur I. Cederbaum

    2014-01-01

    Full Text Available The cytochrome P450 mixed function oxidase enzymes are the major catalysts involved in drug metabolism. There are many forms of P450. CYP2E1 metabolizes many toxicologically important compounds including ethanol and is active in generating reactive oxygen species. Since several of the contributions in the common theme series “Role of CYP2E1 and Oxidative/Nitrosative Stress in the Hepatotoxic Actions of Alcohol” discuss CYP2E1, this methodology review describes assays on how CYP2E1 catalytic activity and its induction by ethanol and other inducers can be measured using substrate probes such as the oxidation of para-nitrophenol to para-nitrocatechol and the oxidation of ethanol to acetaldehyde. Approaches to validate that a particular reaction e.g. oxidation of a drug or toxin is catalyzed by CYP2E1 or that induction of that reaction is due to induction of CYP2E1 are important and specific examples using inhibitors of CYP2E1, anti-CYP2E1 IgG or CYP2E1 knockout and knockin mice will be discussed.

  16. Highly basic CaO nanoparticles in mesoporous carbon materials and their excellent catalytic activity.

    Science.gov (United States)

    Raja, Pradeep Kumar; Chokkalingam, Anand; Priya, Subramaniam V; Balasubramanian, Veerappan V; Benziger, Mercy R; Aldeyab, Salem S; Jayavell, Ramasamy; Ariga, Katsukiho; Vinu, Ajayan

    2012-06-01

    Highly basic CaO nanoparticles immobilized mesoporous carbon materials (CaO-CMK-3) with different pore diameters have been successfully prepared by using wet-impregnation method. The prepared materials were subjected to extensive characterization studies using sophisticated techniques such as XRD, nitrogen adsorption, HRSEM-EDX, HRTEM and temperature programmed desorption of CO2 (TPD of CO2). The physico-chemical characterization results revealed that these materials possess highly dispersed CaO nanoparticles, excellent nanopores with well-ordered structure, high specific surface area, large specific pore volume, pore diameter and very high basicity. We have also demonstrated that the basicity of the CaO-CMK-3 samples can be controlled by simply varying the amount of CaO loading and pore diameter of the carbon support. The basic catalytic performance of the samples was investigated in the base-catalyzed transesterification of ethylacetoacetate by aryl, aliphatic and cyclic primary alcohols. CMK-3 catalyst with higher CaO loading and larger pore diameter was found to be highly active with higher conversion within a very short reaction time. The activity of 30% CaO-CMK3-150 catalyst for transesterification of ethylacetoacetate using different alcohols increases in the following order: octanol > butanol > cyclohexanol > benzyl alcohol > furfuryl alcohol.

  17. Annealing crystallization and catalytic activity of ultrafine NiB amorphous alloy

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Annealing crystallization of ultrafine NiB amorphous alloy prepared by the chemical reduction method was studied by DTA,XRD and XAFS techniques. The XRD and XAFS results have revealed that the crystallization process of ultrafine NiB amorphous alloy proceeds in two steps. First,ultrafine NiB amorphous alloy is crystallized to form metastable nanocrystalline Ni3B at an annealing temperature of 325℃. Second,the nanocrystalline Ni3B is further decom-posed into crystalline Ni at 380℃ or higher tempera ture,the local structure around Ni atoms in resultant product is similar to that in Ni foil. It was found that the catalytic ac-tivity of nanocrystalline Ni3B for benzene hydrogenation is much higher than that of ultrafine NiB amorphous alloy or crystalline Ni. The result indicates that the active sites of nanocrystalline Ni3B for benzene hydrogenation are com-posed of both Ni and B with proper geometry configuration.

  18. Adenylate kinase from Streptococcus pneumoniae is essential for growth through its catalytic activity

    Directory of Open Access Journals (Sweden)

    Trung Thanh Thach

    2014-01-01

    Full Text Available Streptococcus pneumoniae (pneumococcus infection causes more than 1.6 million deaths worldwide. Pneumococcal growth is a prerequisite for its virulence and requires an appropriate supply of cellular energy. Adenylate kinases constitute a major family of enzymes that regulate cellular ATP levels. Some bacterial adenylate kinases (AdKs are known to be critical for growth, but the physiological effects of AdKs in pneumococci have been poorly understood at the molecular level. Here, by crystallographic and functional studies, we report that the catalytic activity of adenylate kinase from S. pneumoniae (SpAdK serotype 2 D39 is essential for growth. We determined the crystal structure of SpAdK in two conformations: ligand-free open form and closed in complex with a two-substrate mimic inhibitor adenosine pentaphosphate (Ap5A. Crystallographic analysis of SpAdK reveals Arg-89 as a key active site residue. We generated a conditional expression mutant of pneumococcus in which the expression of the adk gene is tightly regulated by fucose. The expression level of adk correlates with growth rate. Expression of the wild-type adk gene in fucose-inducible strains rescued a growth defect, but expression of the Arg-89 mutation did not. SpAdK increased total cellular ATP levels. Furthermore, lack of functional SpAdK caused a growth defect in vivo. Taken together, our results demonstrate that SpAdK is essential for pneumococcal growth in vitro and in vivo.

  19. Microwave-assisted facile green synthesis of silver nanoparticles and spectroscopic investigation of the catalytic activity

    Indian Academy of Sciences (India)

    Siby Joseph; Beena Mathew

    2015-06-01

    Silver nanoparticles have been successfully synthesized in aqueous medium by a green, rapid and costefficient synthetic approach based on microwave irradiation. In this study, iota-carrageenan (I-carrageenan) is used both as reducing and stabilizing agent. The formation of nanoparticles is determined using UV–vis, Fourier transform infrared (FTIR), X-ray diffraction (XRD), energy-dispersive X-ray (EDX) and high-resolution-transmission electron microscopic (HR-TEM) analysis. Transmission electron microscopic (TEM) images show that the nanoparticles are of spherical shape with an average diameter of 18.2 nm. I-carrageenan-stabilized silver nanoparticles show outstanding catalytic activity for the reduction of 4-nitrophenol in the presence of NaBH4 in aqueous medium. The reaction follows pseudo-first-order kinetics and the reaction rate increases with the increase in amount of the catalyst. The study of the temperature dependence of reaction rate gives activation energy of 42.81 kJ mol−1. The synthesized silver nanoparticles are anticipated to be a promising material for pollution abatement.

  20. Structure of the Photo-catalytically Active Surface of SrTiO 3

    Energy Technology Data Exchange (ETDEWEB)

    Plaza, Manuel; Huang, Xin; Ko, J. Y. Peter; Shen, Mei; Simpson, Burton H.; Rodríguez-López, Joaquín; Ritzert, Nicole L.; Letchworth-Weaver, Kendra; Gunceler, Deniz; Schlom, Darrell G.; Arias, Tomás A.; Brock, Joel D.; Abruña, Héctor D.

    2016-06-29

    A major goal of energy research is to use visible light to cleave water directly, without an applied voltage, into hydrogen and oxygen. Although SrTiO3 requires ultraviolet light, after four decades, it is still the "gold standard" for the photo-catalytic splitting of water. It is chemically robust and can carry out both hydrogen and oxygen evolution reactions without an applied bias. While ultrahigh vacuum surface science techniques have provided useful insights, we still know relatively little about the structure of these electrodes in contact with electrolytes under operating conditions. Here, we report the surface structure evolution of a n-SrTiO3 electrode during water splitting, before and after "training" with an applied positive bias. Operando high-energy X-ray reflectivity measurements demonstrate that training the electrode irreversibly reorders the surface. Scanning electrochemical microscopy at open circuit correlates this training with a 3-fold increase of the activity toward the photo-induced water splitting. A novel first-principles joint density functional theory simulation, constrained to the X-ray data via a generalized penalty function, identifies an anatase-like structure as the more active, trained surface.

  1. Restoration of catalytic activity beyond wild-type level in glucoamylase from Aspergillus awamori by oxidation of the Glu400-->Cys catalytic-base mutant to cysteinesulfinic acid.

    Science.gov (United States)

    Fierobe, H P; Mirgorodskaya, E; McGuire, K A; Roepstorff, P; Svensson, B; Clarke, A J

    1998-03-17

    Glucoamylase catalyzes the hydrolysis of glucosidic bonds with inversion of the anomeric configuration. Site-directed mutagenesis and three-dimensional structure determination of the glucoamylase from Aspergillus awamori previously identified Glu179 and Glu400 as the general acid and base catalyst, respectively. The average distance between the two carboxyl groups was measured to be 9.2 A, which is typical for inverting glycosyl hydrolases. In the present study, this distance was increased by replacing the catalytic base Glu400 with cysteine which was then oxidized to cysteinesulfinic acid. Initially, this oxidation occurred during attempts to carboxyalkylate the Cys400 residue with iodoacetic acid, 3-iodopropionic acid, or 4-bromobutyric acid. However, endoproteinase Lys-C digestion of modified glucoamylase followed by high-pressure liquid chromatography in combination with matrix-assisted laser desorption ionization/time-of-flight mass spectrometry on purified peptide fragments demonstrated that all enzyme derivatives contained the cysteinesulfinic acid oxidation product of Cys400. Subsequently, it was demonstrated that treatment of Glu400-->Cys glucoamylase with potassium iodide in the presence of bromine resulted in complete conversion to the cysteinesulfinic acid product. As expected, the catalytic base mutant Glu400-->Cys glucoamylase had very low activity, i.e., 0.2% compared to wild-type. The oxidation of Cys400 to cysteinesulfinic acid, however, restored activity (kcat) on alpha-1,4-linked substrates to levels up to 160% of the wild-type glucoamylase which corresponded to approximately a 700-fold increase in the kcat of the Glu400-->Cys mutant glucoamylase. Whereas Glu400-->Cys glucoamylase was much less thermostable and more sensitive to guanidinium chloride than the wild-type enzyme, the oxidation to cysteinesulfinic acid was accompanied by partial recovery of the stability.

  2. Catalytic activity of bimetallic catalysts highly sensitive to the atomic composition and phase structure at the nanoscale.

    Science.gov (United States)

    Shan, Shiyao; Petkov, Valeri; Prasai, Binay; Wu, Jinfang; Joseph, Pharrah; Skeete, Zakiya; Kim, Eunjoo; Mott, Derrick; Malis, Oana; Luo, Jin; Zhong, Chuan-Jian

    2015-12-07

    The ability to determine the atomic arrangement in nanoalloy catalysts and reveal the detailed structural features responsible for the catalytically active sites is essential for understanding the correlation between the atomic structure and catalytic properties, enabling the preparation of efficient nanoalloy catalysts by design. Herein we describe a study of CO oxidation over PdCu nanoalloy catalysts focusing on gaining insights into the correlation between the atomic structures and catalytic activity of nanoalloys. PdCu nanoalloys of different bimetallic compositions are synthesized as a model system and are activated by a controlled thermochemical treatment for assessing their catalytic activity. The results show that the catalytic synergy of Pd and Cu species evolves with both the bimetallic nanoalloy composition and temperature of the thermochemical treatment reaching a maximum at a Pd : Cu ratio close to 50 : 50. The nanoalloys are characterized structurally by ex situ and in situ synchrotron X-ray diffraction, including atomic pair distribution function analysis. The structural data show that, depending on the bimetallic composition and treatment temperature, PdCu nanoalloys adopt two different structure types. One features a chemically ordered, body centered cubic (B2) type alloy consisting of two interpenetrating simple cubic lattices, each occupied with Pd or Cu species alone, and the other structure type features a chemically disordered, face-centered cubic (fcc) type of alloy wherein Pd and Cu species are intermixed at random. The catalytic activity for CO oxidation is strongly influenced by the structural features. In particular, it is revealed that the prevalence of chemical disorder in nanoalloys with a Pd : Cu ratio close to 50 : 50 makes them superior catalysts for CO oxidation in comparison with the same nanoalloys of other bimetallic compositions. However, the catalytic synergy can be diminished if the Pd50Cu50 nanoalloys undergo

  3. Ru(0) and Ru(II) nitrosyl pincer complexes: structure, reactivity, and catalytic activity.

    Science.gov (United States)

    Fogler, Eran; Iron, Mark A; Zhang, Jing; Ben-David, Yehoshoa; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Milstein, David

    2013-10-07

    Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here we describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis((t)Bu2PCH2)pyridine) with RuCl3(NO)(PPh3)2 yielded the Ru(II) complex 3. Chloride displacement by BAr(F-) (BAr(F-) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallographicaly characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt3H yielded the Ru(0) complexes 5. The crystallographically characterized Ru(0) square planar complex 5·BF4 bears a linear NO ligand located trans to the pyridilic nitrogen. Further treatment of 5·BF4 with excess LiOH gave the crystallographicaly characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcohols to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-((t)Bu2PCH2)-6-(Et2NCH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equivalent of sodium isopropoxide gave the crystallographicaly characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl3(NO)(H2O)2 and Et3N in ethanol. Reaction of the "long arm" PN(2)N ligand (PN(2)N = 2-((t)Bu2PCH2-)-6-(Et2NCH2CH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN(2)N with RuCl3(NO)(H2O)2 and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidization state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in

  4. Surface Acidity as Descriptor of Catalytic Activity for Oxygen Evolution Reaction in Li-O2 Battery.

    Science.gov (United States)

    Zhu, Jinzhen; Wang, Fan; Wang, Beizhou; Wang, Youwei; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin

    2015-10-28

    Unraveling the descriptor of catalytic activity, which is related to physical properties of catalysts, is a major objective of catalysis research. In the present study, the first-principles calculations based on interfacial model were performed to study the oxygen evolution reaction mechanism of Li2O2 supported on active surfaces of transition-metal compounds (TMC: oxides, carbides, and nitrides). Our studies indicate that the O2 evolution and Li(+) desorption energies show linear and volcano relationships with surface acidity of catalysts, respectively. Therefore, the charging voltage and desorption energies of Li(+) and O2 over TMC could correlate with their corresponding surface acidity. It is found that certain materials with an appropriate surface acidity can achieve the high catalytic activity in reducing charging voltage and activation barrier of rate-determinant step. According to this correlation, CoO should have as active catalysis as Co3O4 in reducing charging overpotential, which is further confirmed by our comparative experimental studies. Co3O4, Mo2C, TiC, and TiN are predicted to have a relatively high catalytic activity, which is consistent with the previous experiments. The present study enables the rational design of catalysts with greater activity for charging reactions of Li-O2 battery.

  5. 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

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

    Science.gov (United States)

    Holzer, Peter

    2011-07-01

    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.

  7. Catalytically active bovine serum amine oxidase bound to fluorescent and magnetically drivable nanoparticles

    Directory of Open Access Journals (Sweden)

    Bidollari E

    2012-05-01

    Full Text Available Giulietta Sinigaglia1, Massimiliano Magro1, Giovanni Miotto1, Sara Cardillo1, Enzo Agostinelli2,3, Radek Zboril4, Eris Bidollari2,3, Fabio Vianello11Department of Biological Chemistry, University of Padua, Padua, Italy; 2Istituto Pasteur-Fondazione Cenci Bolognetti, Department of Biochemical Sciences "A. Rossi Fanelli", SAPIENZA University of Rome, Rome, Italy; 3CNR, Institute Biology and Molecular Pathology, Rome, Italy; 4Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Palacky University, Olomouc, Czech RepublicAbstract: Novel superparamagnetic surface-active maghemite nanoparticles (SAMNs characterized by a diameter of 10 ± 2 nm were modified with bovine serum amine oxidase, which used rhodamine B isothiocyanate (RITC adduct as a fluorescent spacer-arm. A fluorescent and magnetically drivable adduct comprised of bovine serum copper-containing amine oxidase (SAMN–RITC–BSAO that immobilized on the surface of specifically functionalized magnetic nanoparticles was developed. The multifunctional nanomaterial was characterized using transmission electron microscopy, infrared spectroscopy, mass spectrometry, and activity measurements. The results of this study demonstrated that bare magnetic nanoparticles form stable colloidal suspensions in aqueous solutions. The maximum binding capacity of bovine serum amine oxidase was approximately 6.4 mg g-1 nanoparticles. The immobilization procedure reduced the catalytic activity of the native enzyme to 30% ± 10% and the Michaelis constant was increased by a factor of 2. We suggest that the SAMN–RITC–BSAO complex, characterized by a specific activity of 0.81 IU g-1, could be used in the presence of polyamines to create a fluorescent magnetically drivable H2O2 and aldehydes-producing system. Selective tumor cell destruction is suggested as a potential future application of this system.Keywords: amine oxidase, hydrogen peroxide production, superparamagnetic

  8. Genetic factors affecting gene transcription and catalytic activity of UDP-glucuronosyltransferases in human liver.

    Science.gov (United States)

    Liu, Wanqing; Ramírez, Jacqueline; Gamazon, Eric R; Mirkov, Snezana; Chen, Peixian; Wu, Kehua; Sun, Chang; Cox, Nancy J; Cook, Edwin; Das, Soma; Ratain, Mark J

    2014-10-15

    The aim of this study was to discover cis- and trans-acting factors significantly affecting mRNA expression and catalytic activity of human hepatic UDP-glucuronosyltransferases (UGTs). Transcription levels of five major hepatic UGT1A (UGT1A1, UGT1A3, UGT1A4, UGT1A6 and UGT1A9) and five UGT2B (UGT2B4, UGT2B7, UGT2B10, UGT2B15 and UGT2B17) genes were quantified in human liver tissue samples (n = 125) using real-time PCR. Glucuronidation activities of 14 substrates were measured in 47 livers. We genotyped 167 tagSNPs (single-nucleotide polymorphisms) in UGT1A (n = 43) and UGT2B (n = 124), as well as the known functional UGT1A1*28 and UGT2B17 CNV (copy number variation) polymorphisms. Transcription levels of 15 transcription factors (TFs) known to regulate these UGTs were quantified. We found that UGT expression and activity were highly variable among the livers (median and range of coefficient of variations: 135%, 74-217% and 52%, 39-105%, respectively). CAR, PXR and ESR1 were found to be the most important trans-regulators of UGT transcription (median and range of correlation coefficients: 46%, 6-58%; 47%, 9-58%; and 52%, 24-75%, respectively). Hepatic UGT activities were mainly determined by UGT gene transcription levels. Twenty-one polymorphisms were significantly (FDR-adjusted P transcription and testosterone glucuronidation rate, in addition to that attributable to the UGT2B17 CNV. Our study discovered novel pharmacogenetic markers and provided detailed insight into the genetic network regulating hepatic UGTs.

  9. Molecular Basis of Reduced Pyridoxine 5′-Phosphate Oxidase Catalytic Activity in Neonatal Epileptic Encephalopathy Disorder*

    OpenAIRE

    2009-01-01

    Mutations in pyridoxine 5′-phosphate oxidase are known to cause neonatal epileptic encephalopathy. This disorder has no cure or effective treatment and is often fatal. Pyridoxine 5′-phosphate oxidase catalyzes the oxidation of pyridoxine 5′-phosphate to pyridoxal 5′-phosphate, the active cofactor form of vitamin B6 required by more than 140 different catalytic activities, including enzymes involved in amino acid metabolism and biosynthesis of neurotransmitters. Our aim is to elucidate the mec...

  10. IFCC primary reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 degrees C. International Federation of Clinical Chemistry and Laboratory Medicine. Part 4. Reference procedure for the measurement of catalytic concentration of alanine aminotransferase.

    Science.gov (United States)

    Schumann, Gerhard; Bonora, Roberto; Ceriotti, Ferruccio; Férard, Georges; Ferrero, Carlo A; Franck, Paul F H; Gella, F Javier; Hoelzel, Wieland; Jørgensen, Poul Jørgen; Kanno, Takashi; Kessner, Art; Klauke, Rainer; Kristiansen, Nina; Lessinger, Jean-Marc; Linsinger, Thomas P J; Misaki, Hideo; Panteghini, Mauro; Pauwels, Jean; Schiele, Françoise; Schimmel, Heinz G; Weidemann, Gerhard; Siekmann, Lothar

    2002-07-01

    This paper is the fourth in a series dealing with reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 degrees C and the certification of reference preparations. Other parts deal with: Part 1. The Concept of Reference Procedures for the Measurement of Catalytic Activity Concentrations of Enzymes; Part 2. Reference Procedure for the Measurement of Catalytic Concentration of Creatine Kinase; Part 3. Reference Procedure for the Measurement of Catalytic Concentration of Lactate Dehydrogenase; Part 5. Reference Procedure for the Measurement of Catalytic Concentration of Aspartate Aminotransferase; Part 6. Reference Procedure for the Measurement of Catalytic Concentration of Gamma-Glutamyltransferase; Part 7. Certification of Four Reference Materials for the Determination of Enzymatic Activity of Gamma-Glutamyltransferase, Lactate Dehydrogenase, Alanine Aminotransferase and Creatine Kinase at 37 degrees C. A document describing the determination of preliminary upper reference limits is also in preparation. The procedure described here is deduced from the previously described 30 degrees C IFCC reference method. Differences are tabulated and commented on in Appendix 2.

  11. IFCC primary reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 degrees C. International Federation of Clinical Chemistry and Laboratory Medicine. Part 6. Reference procedure for the measurement of catalytic concentration of gamma-glutamyltransferase.

    Science.gov (United States)

    Schumann, Gerhard; Bonora, Roberto; Ceriotti, Ferruccio; Férard, Georges; Ferrero, Carlo A; Franck, Paul F H; Gella, F Javier; Hoelzel, Wieland; Jørgensen, Poul Jørgen; Kanno, Takashi; Kessner, Art; Klauke, Rainer; Kristiansen, Nina; Lessinger, Jean-Marc; Linsinger, Thomas P J; Misaki, Hideo; Panteghini, Mauro; Pauwels, Jean; Schiele, Françoise; Schimmel, Heinz G; Weidemann, Gerhard; Siekmann, Lothar

    2002-07-01

    This paper is the sixth in a series dealing with reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 degrees C and the certification of reference preparations. Other parts deal with: Part 1. The Concept of Reference Procedures for the Measurement of Catalytic Activity Concentrations of Enzymes; Part 2. Reference Procedure for the Measurement of Catalytic Concentration of Creatine Kinase; Part 3. Reference Procedure for the Measurement of Catalytic Concentration of Lactate Dehydrogenase; Part 4. Reference Procedure for the Measurement of Catalytic Concentration of Alanine Aminotransferase; Part 5. Reference Procedure for the Measurement of Catalytic Concentration of Aspartate Aminotransferase; Part 7. Certification of Four Reference Materials for the Determination of Enzymatic Activity of Gamma-Glutamyltransferase, Lactate Dehydrogenase, Alanine Aminotransferase and Creatine Kinase at 37 degrees C A document describing the determination of preliminary upper reference limits is also in preparation. The procedure described here is deduced from the previously described 30 degrees C IFCC reference method. Differences are tabulated and commented on in Appendix 1.

  12. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    Science.gov (United States)

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-09-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h-1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

  13. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    Science.gov (United States)

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-01-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h−1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance. PMID:27666280

  14. 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.

  15. Heterogeneous catalytic ozonation of dibutyl phthalate in aqueous solution in the presence of iron-loaded activated carbon.

    Science.gov (United States)

    Huang, Yuanxing; Cui, Chenchen; Zhang, Daofang; Li, Liang; Pan, Ding

    2015-01-01

    Iron-loaded activated carbon was prepared and used as catalyst in heterogeneous catalytic ozonation of dibutyl phthalate (DBP). The catalytic activity of iron-loaded activated carbon was investigated under various conditions and the mechanisms of DBP removal were deduced. Characterization of catalyst indicated that the iron loaded on activated carbon was mainly in the form of goethite, which reduced its surface area, pore volume and pore diameter. The presence of metals on activated carbon positively contributed to its catalytic activity in ozonation of DBP. Iron loading content of 15% and initial water pH of 8 achieved highest DBP removal among all the tried conditions. Catalyst dosage of 10 mg L(-1) led to approximately 25% of increase in DBP (initial concentration 2 mg L(-1)) removal in 60 min as compared with ozone alone, and when catalyst dosage increased to 100 mg L(-1), the DBP removal was further improved by 46%. Based on a comparison of reaction rates for direct and indirect transformation of DBP, the increased removal of DBP in this study likely occurred via transformation of ozone into hydroxyl radicals on the catalyst surface.

  16. Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 7. Trp -> TyrO radical transformation in hen egg-white lysozyme. Effects of pH, temperature, Trp62 oxidation and inhibitor binding

    DEFF Research Database (Denmark)

    Bobrowski, K.; Holcman, J.; Poznanski, J.

    1997-01-01

    oxidation of Trp with N-3(.) radicals under low concentration of the reactants but at a high HEWL/N-3(.) molar ratio, so that more than 99% of the oxidized protein molecules contained only a single tryptophyl radical. Synchronous decay of Trp(.) and build-up of TyrO(.) conformed satisfactorily to first...... in shape, reflecting protonation of Glu35 (pK(a) approximate to 6) and pointing to involvement of conformational control of the kinetics of LRET, (ii) below pH5.2 a sharp increase in k(5) was observed due to the protonation of Trp(.) to form TrpH(.+), which is known to oxidize tyrosine faster than does Trp......(.). Arrhenius plots of the temperature-dependence of k(5) showed that the activation energy of LRET varies both with temperature and the protonation state of the enzyme. The activation energies are in the range 7.6-56.0 kJ mol(-1) and are similar to those for activation of amide hydrogen exchange in native HEWL...

  17. 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.

  18. Plasma Enhanced Chemical Vapor Deposition Nanocrystalline Tungsten Carbide Thin Film and Its Electro-catalytic Activity

    Institute of Scientific and Technical Information of China (English)

    Huajun ZHENG; Chunan MA; Jianguo HUANG; Guohua LI

    2005-01-01

    Nanocrystalline tungsten carbide thin films were fabricated on graphite substrates by plasma enhanced chemical vapor deposition (PECVD) at H2 and Ar atmosphere, using WF6 and CH4 as precursors. The crystal phase, structure and chemical components of the films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS), respectively. The results show that the film prepared at CH4/WF6concentration ratio of 20 and at 800℃ is composed of spherical particles with a diameter of 20~35 nm. Electrochemical investigations show that the electrochemical real surface area of electrode of the film is large, and the electrode of the film exhibits higher electro-catalytic activity in the reaction of methanol oxidation. The designated constant current of the film catalyst is 123.6 mA/cm2 in the mixture solution of H2SO4 and CH3OH at the concentration of 0.5 and 2.0 mol/L at 70℃, and the designated constant potential is only 0.306 V (vs SCE).

  19. Facile synthesis of porous Pd nanoflowers with excellent catalytic activity towards CO oxidation☆

    Institute of Scientific and Technical Information of China (English)

    Tareque Odoom-Wubah; Mingming Du; Williams Brown Osei; Daohua Sun; Jiale Huang; Qingbiao Li

    2015-01-01

    Microorganism-mediated, hexadecyltrimethylammonium chloride (CTAC)-directed (MCD) method was employed in this work to synthesize Pd nanoflowers (PdNFs). Proper Pichia pastoris cel s (PPCs) dosage, ascorbic acid (AA), Pd(NO3)2 and CTAC concentrations were essential for the growth of the PdNFs. The size of the as-synthesized PdNFs could be tuned by adjusting the amount of Pd(NO3)2 solution and dosage of PPCs used. Char-acterization techniques such as X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy were used to verify the nature of the PdNFs. Finally the PdNF/PPC nanocomposites were immobilized onto TiO2 supports to obtain bio-PdNF/TiO2 catalysts which showed excellent catalytic activity for CO oxidation, obtaining 100%conversion at 100 °C and remaining stable over a period of 52 h of reaction time.

  20. 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.

  1. Band gap calculation and photo catalytic activity of rare earths doped rutile TiO2

    Institute of Scientific and Technical Information of China (English)

    BIAN Liang; SONG Mianxin; ZHOU Tianliang; ZHAO Xiaoyong; DAI Qingqing

    2009-01-01

    The density of states (DOS) of 17 kinds of rare earths (RE) doped futile TiO2 was by using fast-principles density functional the-ory (DFF) calculation. The band gap widths of RE doped rutile TiO2 were important factors for altering their absorbing wavelengths. The results show that RE ions could obviously reduce the band gap widths and form of energy of rutile TiO2 except Lu, Y, Yb and Sc, and the order of absorbing wavelengths of RE doped rutile TiO2 were the same as that of the results of calculation. The ratio of RE dopant was an-other important factor for the photo catalytic activity of RE doped rutile TiO2, and there was an optimal ratio of dopant. There was a constant for predigesting the calculation difficulty, respectively, which were 0.5mol.% and 100 mol-1 under supposition. The band gap widths of RE doped rutile TiO2 by DFT calculation were much larger than that by experiment. Finally, by transferring the calculation values to experiment values, it could be found and predicted that RE enlarged obviously the absorbing wavelengh of futile TiO2. In addition, the degree of RE ions edging out the Ti atom using the parameters of RE elements was computed.

  2. 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.

  3. Maternal High Fat Diet Alters Skeletal Muscle Mitochondrial Catalytic Activity in Adult Male Rat Offspring

    Science.gov (United States)

    Pileggi, Chantal A.; Hedges, Christopher P.; Segovia, Stephanie A.; Markworth, James F.; Durainayagam, Brenan R.; Gray, Clint; Zhang, Xiaoyuan D.; Barnett, Matthew P. G.; Vickers, Mark H.; Hickey, Anthony J. R.; Reynolds, Clare M.; Cameron-Smith, David

    2016-01-01

    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 suppressed 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. PMID:27917127

  4. A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II

    Science.gov (United States)

    Schulze, Marcus; Kunz, Valentin; Frischmann, Peter D.; Würthner, Frank

    2016-06-01

    Mimicking the ingenuity of nature and exploiting the billions of years over which natural selection has developed numerous effective biochemical conversions is one of the most successful strategies in a chemist's toolbox. However, an inability to replicate the elegance and efficiency of the oxygen-evolving complex of photosystem II (OEC-PSII) in its oxidation of water into O2 is a significant bottleneck in the development of a closed-loop sustainable energy cycle. Here, we present an artificial metallosupramolecular macrocycle that gathers three Ru(bda) centres (bda = 2,2‧-bipyridine-6,6‧-dicarboxylic acid) that catalyses water oxidation. The macrocyclic architecture accelerates the rate of water oxidation via a water nucleophilic attack mechanism, similar to the mechanism exhibited by OEC-PSII, and reaches remarkable catalytic turnover frequencies >100 s-1. Photo-driven water oxidation yields outstanding activity, even in the nM concentration regime, with a turnover number of >1,255 and turnover frequency of >13.1 s-1.

  5. One pot synthesis of copper nanoparticles at room temperature and its catalytic activity

    Directory of Open Access Journals (Sweden)

    Nikhil V. Suramwar

    2016-11-01

    Full Text Available A facile reduction approach with sodium borohydride as a reducing agent and starch as a stabilizing agent leads to monodispersed Cu nanoparticles in aqueous medium at an ambient condition. The synthesized nanoparticles are highly pure with no traces of CuO found on surface. They are uniform in size in the range of 40–80 nm. The Cu nanoparticles have a FCC structure as characterized by powder X-ray diffraction (XRD. Transmission electron microscopy (TEM images show that they are arranged in a regular array which is separated by starch thin layer which controls the growth as well as stabilizes the Cu nanoparticles from air oxidation. The catalytic activity of prepared Cu nanomaterial was tested in Ullman reaction for the synthesis of biphenyl from iodobenzene. We have shown in this paper that the size as well as exposed surface area of the copper nanoparticles is responsible for the increase in yield of biphenyl up to 92%. This is higher compare to the 40% yield with the normal size copper powder under the same reaction condition.

  6. Characterization of systems active in selective catalytic reduction of NO{sub x}

    Energy Technology Data Exchange (ETDEWEB)

    Biglino, Daniele

    1998-06-01

    This thesis is in the field of gas emission control from automobile and stationary sources. Out of the possible approaches to the elimination of pollutant gases, such as nitrogen oxides (NO{sub x}), one consists in the selective catalytic reduction (SCR) of these NO{sub x} on a suitable heterogeneous catalyst. Ammonia or hydrocarbons are employed as reducing agents. The most important catalysts active in the SCR of NO{sub x} are based on ions of transition metal either supported on several oxides or dispersed in zeolites. The catalysts have been characterized by electron magnetic resonance techniques (EPR, ENDOR, ESEEM) and the interaction of catalysts with nitrogen oxides, with reducing and poisoned agents have been followed with the same techniques. Copper dispersed on alumina and its interaction with both NO and ammonia has been investigated. Also the interaction between both water and ammonia with copper dispersed in zeolite ZSM-5 has been investigated. The diffusion of NO{sub 2} in zeolites has been monitored 4 refs, 5 figs

  7. Annealed Crystallization and Catalytic activity of Ultrafine NiB Amorphous Alloy

    Institute of Scientific and Technical Information of China (English)

    WEIShiqing; HUTiandou; 等

    2001-01-01

    A Ultrafine amorphous NiB alloy was prepared via chemical reduction method;Its structures during the crystallizatioin precess was characterized by such techniques as Differential thermal analysis (DTA),X-ray absorption fine structure (XAFS) and X-ray diffraction(XRD),and correlated to the catalytic properties for benzene hydrogenation.It was found that the crystallization of amorphous NiB alloy was carried out in two steps,as indicated by two exothermic peaks centered at 598 and 652K respectively.During the first step.two metastable crystalline phases,i.e.,Ni3B and a noaocrstalline Ni phase(Ni-rich NiB alloy),were formed.Further annealing at higher temperature of 652 K may result in the decomposition of crystalline Ni3B and aggregation of nanocrystalline Ni,the benzene hydrogenation is optimized around the annealing temperature of 623K.It most probably results from the maximum amount of active site on nanocrystalline Ni formed by thermal treatment at appropriate annealing temperature.

  8. Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction.

    Science.gov (United States)

    Ye, Feng; Liu, Hui; Hu, Weiwei; Zhong, Junyu; Chen, Yingying; Cao, Hongbin; Yang, Jun

    2012-03-14

    Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.

  9. Catalytic Activation of Small Molecules. Development and Characterisation of Ruthenium Complexes for Application in Catalysis

    OpenAIRE

    Choi, Jong-Hoo

    2016-01-01

    In this work, the synthesis, characterisation and catalytic application of ruthenium pincer complexes is presented. In this context, new synthetic strategies are discussed to obtain novel ruthenium pincer dihydrogen complexes. Furthermore, the reactivity of the complexes towards small molecules (e.g. alcohols, boranes, ammonia, amines, nitriles and hydrogen) was observed, delivering fundamental insights into catalytic applications. With the reactivity testing, new borylated B-H-σ-complexes we...

  10. Promotion of catalytic activity for methanol electro-oxidation on CoPc-Pt/C co-catalysts

    Institute of Scientific and Technical Information of China (English)

    WU JingJie; XU YiMin; PAN Mu; MA WenTao; TANG HaoLin

    2009-01-01

    The catalytic activity for methanol electro-oxidation on CoPc-Pt/C co-catalysts, prepared by impregnation method, was studied in details through electrochemical methods. Cyclic voltammetry (CV) result demonstrates that CoPc has higher forward anodic peak current density and jf/jb value (forward anodic peak current density/backward anodic peak current density) than Pt/C. Chronoamperometry (CA) analysis indicates that CoPc-Pt/C exhibits both excellent transient current density and stable current density for methanol electro-oxidation compared with Pt/C. Two main mechanisms related to the promotion of catalytic activity are as follows: CoPc-Pt/C has the activity of tolerance to carbonaceous intermediates, thus inhibiting the self-poisoning of catalysts; CoPc-Pt/C owns prominent intrinsic catalytic activity indicated by the apparent activation energy for methanol oxidation on CoPc-Pt/C, which is 18 kJ/mol, less than that on Pt and PtRu catalysts as reported.

  11. 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.

  12. Down-regulation of tyrosinase, TRP-1, TRP-2 and MITF expressions by citrus press-cakes in murine B16 F10 melanoma

    Institute of Scientific and Technical Information of China (English)

    Sang Suk Kim; Min-Jin Kim; Young Hun Choi; Byung Kuk Kim; Kwang Sik Kim; Kyung Jin Park; Suk Man Park; Nam Ho Lee; Chang-Gu Hyun

    2013-01-01

    Objective: To investigate the suitability of citrus-press cakes, by-products of the juice industry as a source for the whitening agents for cosmetic industry. Methods:Ethylacetate extracts of citrus-press cakes (CCE) were examined for their anti-melanogenic potentials in terms of the inhibition of melanin production and mechanisim of melanogenesis by using Western Blot analysis with tyrosinese, tyrosinase-related protein-1 (TRP-1), TRP2, and microphthalmia-associated transcription factor (MITF) proteins. To apply the topical agents, citrus-press cakes was investigated the safety in human skin cell line. Finally flavonoid analysis of CCE was also determined by HPLC analysis. Results: Results indicated that CCE were shown to down-regulate melanin content in a dose-dependent pattern. The CCE inhibited tyrosinase, TRP-2, and MITF expressions in a dose-dependent manner. To test the applicability of CCE to human skin, we used MTT assay to assess the cytotoxic effects of CCE on human keratinocyte HaCaT cells. The CCE exhibited low cytotoxicity at 50 µg/mL. Characterization of the citrus-press cakes for flavonoid contents using HPLC showed varied quantity of rutin, narirutin, and hesperidin. Conclusions:Considering the anti-melanogenic activity and human safety, CCE is considered as a potential anti-melanogenic agent and may be effective for topical application for treating hyperpigmentation disorders.

  13. TRP Channels as Therapeutic Targets in Diabetes and Obesity

    Science.gov (United States)

    Zsombok, Andrea; Derbenev, Andrei V.

    2016-01-01

    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. PMID:27548188

  14. 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.

  15. Spectroscopic characterization of the catalytically competent ferrous site of the resting, activated, and substrate-bound forms of phenylalanine hydroxylase

    Energy Technology Data Exchange (ETDEWEB)

    Loeb, K.E.; Westre, T.E.; Hedman, B.; Hodgson, K.O.; Solomon, E.I. [Stanford Univ., CA (United States); Kappock, T.J.; Mitic, N.; Glasfeld, E.; Caradonna, J.P. [Yale Univ., New Haven, CT (United States)

    1997-02-26

    The geometric structure of the catalytically relevant ferrous active site of phenylalanine hydroxylase (PAH) has been investigated using magnetic circular dichroism (MCD) and X-ray absorption (XAS) spectroscopies. From the excited state ligand field transitions in the MCD spectrum, the temperature and field dependence of these transitions, and the XAS pre-edge shapes and intensities, the resting ferrous site of the `tense` from PAH is six-coordinate distorted octahedral. The low ligand field strength observed in the MCD spectrum results from significant oxygen ligation and longer Fe-O/N bond distances relative to model complexes as determined from an EXAFS analysis. Substrate-induced allosteric activation ({approx}34 kcal/mol) does not alter the structure of the iron site in the `relaxed` form of PAH compared to the substrate-bound `tense` state. Thus, while activation is necessary for the enzyme to achieve complete catalytic competence, it does not appear to affect the geometry of the catalytically relevent six-coordinate ferrous active site and only directly influences the surrounding protein conformation. In contrast, substrate addition results in a geometric and electronic structural change at the iron center which may help orient the substrate for completely coupled hydroxylation. 106 refs., 10 figs., 6 tabs.

  16. Synthesis and characterization of magnetically recyclable Ag nanoparticles immobilized on Fe3O4@C nanospheres with catalytic activity

    Science.gov (United States)

    Li, Wei-hong; Yue, Xiu-ping; Guo, Chang-sheng; Lv, Jia-pei; Liu, Si-si; Zhang, Yuan; Xu, Jian

    2015-04-01

    A novel approach for the synthesis of Ag-loaded Fe3O4@C nanospheres (Ag-Fe3O4@C) was successfully developed. The catalysts possessed a carbon-coated magnetic core and grew active silver nanoparticles on the outer shell using hydrazine monohydrate as the AgNO3 reductant in ethanol. The morphology, inner structure, and magnetic properties of the as-prepared composites were studied with transmission electron microscopy (TEM), X-ray powder diffraction (XRD), fourier translation infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. Catalytic activity was investigated by degrading rhodamine B (RhB) in the designed experiment. The obtained products were monodispersed and bifunctional with high magnetization, as well as exhibited excellent catalytic activity toward organic dye with 98% of RhB conversion within 20 min in the presence of NaBH4. The product also exhibited convenient magnetic separability and maintained high catalytic activity after six cycle runs.

  17. Identification of residues in the heme domain of soluble guanylyl cyclase that are important for basal and stimulated catalytic activity.

    Directory of Open Access Journals (Sweden)

    Padmamalini Baskaran

    Full Text Available Nitric oxide signals through activation of soluble guanylyl cyclase (sGC, a heme-containing heterodimer. NO binds to the heme domain located in the N-terminal part of the β subunit of sGC resulting in increased production of cGMP in the catalytic domain located at the C-terminal part of sGC. Little is known about the mechanism by which the NO signaling is propagated from the receptor domain (heme domain to the effector domain (catalytic domain, in particular events subsequent to the breakage of the bond between the heme iron and Histidine 105 (H105 of the β subunit. Our modeling of the heme-binding domain as well as previous homologous heme domain structures in different states point to two regions that could be critical for propagation of the NO activation signal. Structure-based mutational analysis of these regions revealed that residues T110 and R116 in the αF helix-β1 strand, and residues I41 and R40 in the αB-αC loop mediate propagation of activation between the heme domain and the catalytic domain. Biochemical analysis of these heme mutants allows refinement of the map of the residues that are critical for heme stability and propagation of the NO/YC-1 activation signal in sGC.

  18. Photo-catalytic activity of Zn1-x Mn x S nanocrystals synthesized by wet chemical technique

    Directory of Open Access Journals (Sweden)

    Singh Karamjit

    2011-01-01

    Full Text Available Abstract Polyvinyl pyrrolidone capped Zn1-x Mn x S (0 ≤ x ≤ 0.1 nanocrystals have been synthesized using wet chemical co-precipitation method. Crystallographic and morphological characterization of the synthesized materials have been done using X-ray diffraction and transmission electron microscope. Crystallographic studies show the zinc blende crystals having average crystallite size approx. 3 nm, which is almost similar to the average particle size calculated from electron micrographs. Atomic absorption spectrometer has been used for qualitative and quantitative analysis of synthesized nanomaterials. Photo-catalytic activity has been studied using methylene blue dye as a test contaminant. Energy resolved luminescence spectra have been recorded for the detailed description of radiative and non-radiative recombination mechanisms. Photo-catalytic activity dependence on dopant concentration and luminescence quantum yield has been studied in detail.

  19. 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.

  20. Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO.

    Science.gov (United States)

    Zhang, Jingxin; Zhang, Shule; Cai, Wei; Zhong, Qin

    2013-12-01

    This study introduced TiO2-pillared clays (TiO2-PILC) as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350 degrees C, the NO conversion was 61% under conditions of GHSV = 23600 hr(-1). The BET data showed that the support particles had a mesoporous structure. H2-TPR showed that Cr(10)TiP (10 wt.% Cr doping on TiO2-PILC) clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO + O2 adsorption, the intensity of evolution of superoxide ions (O2(-)) increased. The content of Cr3+ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr3+ increased to 50.28%. Additionally, O(alpha)/O(beta) increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4(2-).

  1. DNMT3B isoforms without catalytic activity stimulate gene body methylation as accessory proteins in somatic cells.

    Science.gov (United States)

    Duymich, Christopher E; Charlet, Jessica; Yang, Xiaojing; Jones, Peter A; Liang, Gangning

    2016-04-28

    Promoter DNA methylation is a key epigenetic mechanism for stable gene silencing, but is correlated with expression when located in gene bodies. Maintenance and de novo DNA methylation by catalytically active DNA methyltransferases (DNMT1 and DNMT3A/B) require accessory proteins such as UHRF1 and DNMT3L. DNMT3B isoforms are widely expressed, although some do not have active catalytic domains and their expression can be altered during cell development and tumourigenesis, questioning their biological roles. Here, we show that DNMT3B isoforms stimulate gene body methylation and re-methylation after methylation-inhibitor treatment. This occurs independently of the isoforms' catalytic activity, demonstrating a similar functional role to the accessory protein DNMT3L, which is only expressed in undifferentiated cells and recruits DNMT3A to initiate DNA methylation. This unexpected role for DNMT3B suggests that it might substitute for the absent accessory protein DNMT3L to recruit DNMT3A in somatic cells.

  2. Preparation of Ru Nanocatalysts Supported on SBA-15 and Their Excellent Catalytic Activity Towards Decolorization of Various Dyes.

    Science.gov (United States)

    Ghosh, Barun; Hazra, Subhenjit; Naik, Bhanudas; Ghosh, Narendra Nath

    2015-09-01

    In this paper, we report a simple aqueous solution based chemical method for preparation Ru nanocatalysts supported on mesoporous silica SBA-15 (Ru@SBA-15) catalysts. Synthesized catalysts were characterized by powder X-ray diffraction (XRD), Optical emission spectroscopy (ICP-OES), Fourier transform infrared spectroscopy (FTIR), high resolution transmission electron microscope (HRTEM) and N2 adsorption-desorption surface area and pore size analyzer, and particle size analyzer. Catalytic activity of the synthesized catalysts towards decolorization of various dyes, such as 4-nitrophenol, Methyl Orange, Congo Red, Rhodamine B, Methylene Blue and mixture of dyes was investigated in presence of excess NaBH4. Catalysis reactions were monitored by employing UV-vis spectroscopy. Catalysis reactions followed pseudo-first order rate equation. The catalyst with 2.5 wt% Ru nanoparticle exhibited excellent catalytic activity and convenient recycling. The high catalytic activity and simple preparation methodology make 2.5Ru@SBA-15 an attractive catalyst for decolorization of organic dyes.

  3. Ultrafine Au and Ag Nanoparticles Synthesized from Self-Assembled Peptide Fibers and Their Excellent Catalytic Activity.

    Science.gov (United States)

    Xu, Wenlong; Hong, Yue; Hu, Yuanyuan; Hao, Jingcheng; Song, Aixin

    2016-07-18

    The self-assembly of an amphiphilic peptide molecule to form nanofibers facilitated by Ag(+) ions was investigated. Ultrafine AgNPs (NPs=nanoparticles) with an average size of 1.67 nm were synthesized in situ along the fibers due to the weak reducibility of the -SH group on the peptide molecule. By adding NaBH4 to the peptide solution, ultrafine AgNPs and AuNPs were synthesized with an average size of 1.35 and 1.18 nm, respectively. The AuNPs, AgNPs, and AgNPs/nanofibers all exhibited excellent catalytic activity toward the reduction of 4-nitrophenol, with turnover frequency (TOF) values of 720, 188, and 96 h(-1) , respectively. Three dyes were selected for catalytic degradation by the prepared nanoparticles and the nanoparticles showed selective catalysis activity toward the different dyes. It was a surprising discovery that the ultrafine AuNPs in this work had an extremely high catalytic activity toward methylene blue, with a reaction rate constant of 0.21 s(-1) and a TOF value of 1899 h(-1) .

  4. Effect of structure and surface properties on the catalytic activity of nanodiamond in the conversion of 1,2-dichloroethane

    Science.gov (United States)

    Tveritinova, E. A.; Zhitnev, Yu. N.; Kulakova, I. I.; Maslakov, K. I.; Nesterova, E. A.; Kharlanov, A. N.; Ivanov, A. S.; Savilov, S. V.; Lunin, V. V.

    2015-04-01

    The catalytic activity of a detonation nanodiamond and its Ni-containing forms in the conversion of 1,2-dichloroethane is studied and compared with the activity of other carbon and nanocarbon materials: carbon nanotubes, "Dalan" synthetic diamond, and fluorinated graphite. The surface and structure of the carbon materials are characterized using XRD, diffuse reflectance IR spectroscopy, XPS, BET, and TPR. The catalytic properties of the materials are studied using the pulsed microcatalytic method. It is found that the synthetic diamond, the nanodiamond, and its Ni-containing forms are catalysts for dichloroethane conversion in a nitrogen atmosphere, where the main product is ethylene. It is noted that the catalytic activity of deactivated diamond catalysts is restored after hydrogen treatment. It is shown that the carbon structure of the nanodiamond and the "Dalan" synthetic diamond with hydrogen groups located on it plays a key role in the dichloroethane conversion. It is found that the nanodiamond acts simultaneously as a catalyst and an adsorbent of chlorine-containing products of dichloroethane conversion.

  5. Surface composition and catalytic activity of La-Fe mixed oxides for methane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fengxiang [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Li, Zhanping [Analysis Center, Tsinghua University, Beijing 100084 (China); Ma, Hongwei [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Gao, Zhiming, E-mail: zgao@bit.edu.cn [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The sample with La/Fe atomic ratio of 0.94 is single phase perovskite La{sub 0.94}FeO{sub 3−d}. • The excess ironic oxide exists on the surface of the perovskite crystallites. • La{sup 3+} ions are enriched on surface of the oxides even for the La{sub 0.68}Fe sample. - Abstract: Four La-Fe oxide samples with La/Fe atomic ratio y = 1.02 ∼ 0.68 (denoted as LayFe) were prepared by the citrate method. The samples had a decreased specific surface area with the La/Fe atomic ratio decreasing. XRD pattern proved that the sample La{sub 0.94}Fe is single phase perovskite La{sub 0.94}FeO{sub 3−d}. Phase composition of the samples was estimated by the Rietveld refinement method. XPS analyses indicate that La{sup 3+} ions are enriched on surface of crystallites for all the samples, and surface carbonate ions are relatively abundant on the samples La{sub 1.02}Fe and La{sub 0.94}Fe. Catalytic activity for methane oxidation per unit surface area of the samples is in the order of La{sub 0.68}Fe > La{sub 0.76}Fe > La{sub 0.94}Fe > La{sub 1.02}Fe both in the presence and in the absence of gaseous oxygen. A reason for this order would be the higher concentration of Fe{sup 3+} ion on the surface of the samples La{sub 0.68}Fe and La{sub 0.76}Fe.

  6. Wet hydrogen peroxide catalytic oxidation of phenol with FeAC (iron-embedded activated carbon) catalysts.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung; Huang, Cheng-Hsien; Hung, Mu-Ya; Chang, Jing-Song; Lai, Cheng-Lee

    2010-01-01

    This investigation aims at exploring the catalytic oxidation activity of iron-embedded activated carbon (FeAC) and the application for the degradation of phenol in the wet hydrogen peroxide catalytic oxidation (WHPCO). FeAC catalysts were prepared by pre-impregnating iron in coconut shell with various iron loadings in the range of 27.5 to 46.5% before they were activated. The FeAC catalysts were characterised by measuring their surface area, pore distribution, functional groups on the surface, and X-ray diffraction patterns. The effects of iron loading strongly inhibited the pore development of the catalyst but benefited the oxidation activity in WHPCO. It was found that the complete conversion of phenol was observed with all FeAC catalysts in oxidation. High level of chemical oxygen demand (COD) abatement can be achieved within the first 30 minutes of oxidation. The iron embedded in the activated carbon showed good performance in the degradation and mineralisation of phenol during the oxidation due to the active sites as iron oxides formed on the surface of the activated carbon. It was found that the embedding irons were presented in gamma-Fe(2)O(3), alpha-Fe(2)O(3), and alpha-FeCOOH forms on the activated carbon. The aging tests on FeAC catalysts showed less activity loss, and less iron leaching was found after four oxidation runs.

  7. VaSP1, catalytically active serine proteinase from Vipera ammodytes ammodytes venom with unconventional active site triad.

    Science.gov (United States)

    Kurtović, Tihana; Brgles, Marija; Leonardi, Adrijana; Lang Balija, Maja; Sajevic, Tamara; Križaj, Igor; Allmaier, Günter; Marchetti-Deschmann, Martina; Halassy, Beata

    2014-01-01

    VaSP1, a serine proteinase from Vipera ammodytes ammodytes venom, is a glycosylated monomer of 31.5 kDa, as determined by MALDI mass spectrometry, showing multiple isoelectric points between pH 6.5 and pH 8.5. Partial amino acid sequencing of VaSP1 by Edman degradation and MS/MS analysis identified sequences which allowed its classification among the so-called snake venom serine proteinase homologues, members of the peptidase S1 family, however being devoid of the canonical catalytic triad. Only few representatives of this group have been identified so far with just two of them characterised in detail at the protein level. Despite substitution of His57 with Arg, VaSP1 possesses proteolytic activity which can be inhibited by Pefabloc, benzamidine, Zn²⁺ ions, DTT and trypsin inhibitor II, a Kunitz/BPTI group member. It hydrolyses N(α)-benzoyl-Phe-Val-Arg-p-NA, exhibiting Michaelis-Menten behaviour with K(m) = 48.2 μM and V(m) = 0.019 nM s⁻¹. The pH for optimal activity on tested substrate is around 9.0. VaSP1 also cleaves insulin B-chain, digesting it at positions His¹⁰-Leu¹¹, Ala¹⁴-Leu¹⁵ and Tyr¹⁶-Leu¹⁷. Furthermore, the novel serine proteinase is active towards wide array of proteins involved in haemostasis where its degradation of fibrinogen, fibrin, prothrombin, factor X and plasminogen in vivo probably results in depletion of coagulation factors in blood circulation. The possibility that VaSP1 possesses anticoagulant properties has been further indicated by its ability to prolong prothrombin time and activated partial thromboplastin time.

  8. Determination of the catalytic activity of binuclear metallohydrolases using isothermal titration calorimetry.

    Science.gov (United States)

    Pedroso, Marcelo M; Ely, Fernanda; Lonhienne, Thierry; Gahan, Lawrence R; Ollis, David L; Guddat, Luke W; Schenk, Gerhard

    2014-03-01

    Binuclear metallohydrolases are a large and diverse family of enzymes that are involved in numerous metabolic functions. An increasing number of members find applications as drug targets or in processes such as bioremediation. It is thus essential to have an assay available that allows the rapid and reliable determination of relevant catalytic parameters (k cat, K m, and k cat/K m). Continuous spectroscopic assays are frequently only possible by using synthetic (i.e., nonbiological) substrates that possess a suitable chromophoric marker (e.g., nitrophenol). Isothermal titration calorimetry, in contrast, affords a rapid assay independent of the chromophoric properties of the substrate-the heat associated with the hydrolytic reaction can be directly related to catalytic properties. Here, we demonstrate the efficiency of the method on several selected examples of this family of enzymes and show that, in general, the catalytic parameters obtained by isothermal titration calorimetry are in good agreement with those obtained from spectroscopic assays.

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

    Science.gov (United States)

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

    2004-01-01

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

  10. Investigation on preparation of CuO-SnO2-CeO2/γ-Al2O3 catalysts for catalytic wet air oxidation process and their catalytic activity for degradation of phenol

    Institute of Scientific and Technical Information of China (English)

    SUN Xiao-jun; ZHANG Mi-lin; WAN Jia-feng; XIA Zhi; LIU Xiao-hui; LIU hui

    2008-01-01

    Catalytic Wet Air Oxidation process is an efficient measure for treatment of wastewater with great strength which is not biodegradable. Heterocatalysts now become the key investigation subject of catalytic wet air oxidation process due to their good stability and easy separation. In the paper, CuO-SnOE-CeO2/γ-Al2O3 catalysts are prepared by impregnation method, with SnO2 as a doping component, CuO as an active component, CeO2 as a structure stabilizer, γ-Al2O3 as a substrate. XPS test is carried out to investigate the effect of Sn on the chemical surrounding of Cu and O element on the catalyst surface and their catalytic activity. It is shown that the right do-ping of Sn can increase Cu+ content on the catalyst surface, as a result the quantity of adsorption oxygen is also increased. It is found that Cu + content on the catalyst surface is one of the primary factors that determin catalytic activity of catalyst through analyzing the catalytic wet air oxidation process of phenol.

  11. Catalytic modification of conventional SOFC anodes with a view to reducing their activity for direct internal reforming of natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Boder, M.; Dittmeyer, R. [Research Group Technical Chemistry, Karl-Winnacker-Institut, DECHEMA e.V., Theodor-Heuss-Allee 25, D-60486 Frankfurt (Germany)

    2006-04-18

    When using natural gas as fuel for the solid oxide fuel cell (SOFC), direct internal reforming lowers the requirement for cell cooling and, theoretically, offers advantages with respect to capital cost and efficiency. The high metal content of a nickel/zirconia anode and the high temperature, however, cause the endothermic reforming reaction to take place very fast. The resulting drop of temperature at the inlet produces thermal stresses, which may lower the system efficiency and limit the stack lifetime. To reduce the reforming rate without lowering the electrochemical activity of the cell, a wet impregnation procedure for modifying conventional cermets by coverage with a less active metal was developed. As the coating material copper was chosen. Copper is affordable, catalytically inert for the reforming reaction and exhibits excellent electronic conductivity. The current density-voltage characteristics of the modified units showed that it is possible to maintain a good electrochemical performance of the cells despite the catalytic modification. A copper to nickel ratio of 1:3 resulted in a strong diminution of the catalytic reaction rate. This indicates that the modification could be a promising method to improve the performance of solid oxide fuel cells with direct internal reforming of hydrocarbons. (author)

  12. 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.

  13. 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.

  14. 3D hierarchical walnut-like CuO nanostructures: Preparation, characterization and their efficient catalytic activity for CO oxidation

    Science.gov (United States)

    Yao, Weitang; Zhang, Yujuan; Duan, Tao; Zhu, Wenkun; Yi, Zao; Cui, Xudong

    2016-07-01

    In this work, 3D hierarchical walnut-shaped, 2D nanosheet and 3D microspheres single phase CuO nanostructures are functioning as catalysts and supporting materials, differing from the conventional ways. The novel nanostructures were synthesized via hydrothermal method under a stainless steel autoclave. The as-prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and H2 temperature-programmed reduction (H2-TPR). The walnut-shaped structures with high O/Cu atomic ratio (1.22) exhibit high oxygen adsorption capacity and greatly enhanced catalytic activity. These results will be enrich the techniques for tuning the morphologies of metal oxide micro/nanostructures and open a new field in catalytic applications.

  15. 3D hierarchical walnut-like CuO nanostructures: Preparation, characterization and their efficient catalytic activity for CO oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Weitang [Laboratory of Extreme Conditions Matter Properties, Southwest University of Science and Technology, Mianyang 621010 (China); Zhang, Yujuan [Laboratory of Extreme Conditions Matter Properties, Southwest University of Science and Technology, Mianyang 621010 (China); Science and Technology on Plasma Physics Laboratory, Research Center of Laser Fusion, CAEP, Mianyang, Sichuan 621900 (China); Duan, Tao, E-mail: duant@ustc.edu.cn [Laboratory of Extreme Conditions Matter Properties, Southwest University of Science and Technology, Mianyang 621010 (China); Zhu, Wenkun; Yi, Zao [Laboratory of Extreme Conditions Matter Properties, Southwest University of Science and Technology, Mianyang 621010 (China); Cui, Xudong, E-mail: xudcui@163.com [Science and Technology on Plasma Physics Laboratory, Research Center of Laser Fusion, CAEP, Mianyang, Sichuan 621900 (China)

    2016-07-15

    In this work, 3D hierarchical walnut-shaped, 2D nanosheet and 3D microspheres single phase CuO nanostructures are functioning as catalysts and supporting materials, differing from the conventional ways. The novel nanostructures were synthesized via hydrothermal method under a stainless steel autoclave. The as-prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and H{sub 2} temperature-programmed reduction (H{sub 2}-TPR). The walnut-shaped structures with high O/Cu atomic ratio (1.22) exhibit high oxygen adsorption capacity and greatly enhanced catalytic activity. These results will be enrich the techniques for tuning the morphologies of metal oxide micro/nanostructures and open a new field in catalytic applications.

  16. Adaptive organic nanoparticles of a teflon-coated iron (III) porphyrin catalytically activate dioxygen for cyclohexene oxidation.

    Science.gov (United States)

    Aggarwal, Amit; Singh, Sunaina; Samson, Jacopo; Drain, Charles Michael

    2012-07-26

    Self-organized organic nanoparticles (ONP) are adaptive to the environmental reaction conditions. ONP of fluorous alkyl iron(III) porphyrin catalytically oxidize cyclohexene to the allylic oxidation products. In contrast, the solvated metalloporphyrin yields both allylic oxidation and epoxidation products. The ONP system facilitates a greener reaction because about 89% reaction medium is water, molecular oxygen is used in place of synthetic oxidants, and the ambient reaction conditions used require less energy. The enhanced catalytic activity of these ONP is unexpected because the metalloporphyrins in the nanoaggregates are in the close proximity and the TON should diminish by self-oxidative degradation. The fluorous alkyl chain stabilizes the ONP toward self-oxidative degradation.

  17. DEVELOPMENT OF HIGH ACTIVITY, COAL DERIVED, PROMOTED CATALYTIC SYSTEMS FOR NOx REDUCTION AT LOW TEMPERATURES

    Energy Technology Data Exchange (ETDEWEB)

    Joseph M. Calo

    1998-12-31

    This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics. During the reporting period, the following has been accomplished: (1) A MS-TGA (mass spectrometric-thermogravimetric analysis) apparatus, which is one of the primary instruments that will be used in these studies, has been refurbished and modified to meet the requirements of this project. A NO{sub x} chemiluminescence analyzer (ThermoElectron, Model 10) has been added to the instrument to monitor NO{sub x} concentrations in the feed and product streams. Computer control and data acquisition system has been updated and modified to accommodate the requirements of the specific types of experiments planned. The diffusion pumps used to maintain vacuum for the mass spectrometer system have been replaced with turbomolecular pumps (Varian 300 HT). (2) A packed bed reactor/gas flow system has been assembled for performing reactivity studies. This system employs a Kin-Tek gas calibration/mixing system for varying NO and CO concentrations in the feed gas to the packed bed, a NO{sub x} chemiluminescence analyzer (ThermoElectron, Model 10), and a quadrupole mass spectrometer (Dycor). This system is required for steady-state reactivity studies, as well as mechanistic studies on the effects of NO and CO in the gas phase on intermediate oxygen surface complex populations on the carbon substrates. (3) Work has continued on the application of contrast matching, small angle neutron scattering to the characterization and development of char porosity. Contrast matching with perdeuterated toluene has

  18. 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

  19. Biologically active Phytophthora mating hormone prepared by catalytic asymmetric total synthesis

    NARCIS (Netherlands)

    Harutyunyan, S.R.; Zhao, Z.; Hartog, den T.; Bouwmeester, K.; Minnaard, A.J.; Feringa, B.L.; Govers, F.

    2008-01-01

    A Phytophthora mating hormone with an array of 1,5-stereogenic centers has been synthesized by using our recently developed methodology of catalytic enantioselective conjugate addition of Grignard reagents. We applied this methodology in a diastereo- and enantioselective iterative route and obtained

  20. Biologically active Phytophthora mating hormone prepared by catalytic asymmetric total synthesis

    NARCIS (Netherlands)

    Harutyunyan, Syuzanna R.; Zhao, Zhijian; den Hartog, Tim; Bouwmeester, Klaas; Minnaard, Adriaan J.; Feringa, Ben L.; Govers, Francine

    2008-01-01

    A Phytophthora mating hormone with an array of 11,5-stereogenic centers has been synthesized by using our recently developed methodology of catalytic enantioselective conjugate addition of Grignard reagents. We applied this methodology in a diastereo-and enantioselective iterative route and obtained

  1. Catalytic dioxygen activation by Co(II) complexes employing a coordinatively versatile ligand scaffold.

    Science.gov (United States)

    Sharma, Savita K; May, Philip S; Jones, Matthew B; Lense, Sheri; Hardcastle, Kenneth I; MacBeth, Cora E

    2011-02-14

    The ligand bis(2-isobutyrylamidophenyl)amine has been prepared and used to stabilize both mononuclear and dinuclear cobalt(II) complexes. The nuclearity of the cobalt product is regulated by the deprotonation state of the ligand. Both complexes catalytically oxidize triphenylphosphine to triphenylphosphine oxide in the presence of O(2).

  2. Catalytic activity of nuclear PLC-beta(1) is required for its signalling function during C2C12 differentiation.

    Science.gov (United States)

    Ramazzotti, Giulia; Faenza, Irene; Gaboardi, Gian Carlo; Piazzi, Manuela; Bavelloni, Alberto; Fiume, Roberta; Manzoli, Lucia; Martelli, Alberto M; Cocco, Lucio

    2008-11-01

    Here we report that PLC-beta(1) catalytic activity plays a role in the increase of cyclin D3 levels and induces the differentiation of C2C12 skeletal muscle cells. PLC-beta(1) mutational analysis revealed the importance of His(331) and His(378) for the catalysis. The expression of PLC-beta(1) and cyclin D3 proteins is highly induced during the process of skeletal myoblast differentiation. We have previously shown that PLC-beta(1) activates cyclin D3 promoter during the differentiation of myoblasts to myotubes, indicating that PLC-beta(1) is a crucial regulator of the mouse cyclin D3 gene. We show that after insulin treatment cyclin D3 mRNA levels are lower in cells overexpressing the PLC-beta(1) catalytically inactive form in comparison to wild type cells. We describe a novel signalling pathway elicited by PLC-beta(1) that modulates AP-1 activity. Gel mobility shift assay and supershift performed with specific antibodies indicate that the c-jun binding site is located in a cyclin D3 promoter region specifically regulated by PLC-beta(1) and that c-Jun binding activity is significantly increased by insulin and PLC-beta(1) overexpression. Mutation of AP-1 site decreased the basal cyclin D3 promoter activity and eliminated its induction by insulin and PLC-beta(1). These results hint at the fact that PLC-beta(1) catalytic activity signals a c-jun/AP-1 target gene, i.e. cyclin D3, during myogenic differentiation.

  3. Molecular basis of epithelial Ca2+ and Mg2+ transport: insights from the TRP channel family

    DEFF Research Database (Denmark)

    Dimke, Henrik Anthony; Hoenderop, Joost G J; Bindels, René J M

    2011-01-01

    active transcellular movement of divalent cations from the lumen into the enterocyte. Furthermore, in bone, TRPV channels play important roles by influencing the osteoclastic resorption process, thereby contributing importantly to overall bone mineral content. The divalent cation-permeable TRPV5 and TRPM......Maintenance of plasma Ca(2+) and Mg(2+) levels is of vital importance for many physiological functions. This is achieved via a coordinated interplay between the intestine, bone and kidney by amending the rate of absorption, storage and excretion, respectively. Discovery of the transient receptor...... potential (TRP) family identified several new ion channels acting as gatekeepers of Ca(2+) and Mg(2+) transport in these epithelia, greatly increasing our understanding of the molecular processes that facilitate the movement of these minerals. In the intestine, TRP channels contribute to the saturable...

  4. Inhibition by N'-nitrosonornicotine of the catalytic activity of glutamate dehydrogenase in alpha-ketoglutarate amination.

    Science.gov (United States)

    Mao, You-An; Zhong, Ke-Jun; Wei, Wan-Zhi; Wei, Xin-Liang; Lu, Hong-Bing

    2005-02-01

    The effect of N'-nitrosonornicotine (NNN), one of the tobacco-specific nitrosamines, on the catalytic activity of glutamate dehydrogenase (GLDH) in the alpha-ketoglutarate amination, using reduced nicotinamide adenine dinucleotide as coenzyme, was studied by a chronoamperometric method. The maximum reaction rate of the enzyme-catalyzed reaction and the Michaelis-Menten constant, or the apparent Michaelis-Menten constant, were determined in the absence and presence of NNN. NNN remarkably inhibited the bio-catalysis activity of GLDH, and was a reversible competitive inhibitior with K(i), estimated as 199 micromol l(-1) at 25 degrees C and pH 8.0.

  5. 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....

  6. Impact of Substituents Attached to N-Heterocyclic Carbenes on the Catalytic Activity of Copper Complexes in the Reduction of Carbonyl Compounds with Triethoxysilane

    Institute of Scientific and Technical Information of China (English)

    PENG, Jiajian; CHEN, Lingzhen; XU, Zheng; HU, Yingqian; LI, Jiayun; BAI, Ying; QIU, Huayu; LAI, Guoqiao

    2009-01-01

    By using functionalized imidazolium salts such as 1-allyl-3-alkylimidazolium or 1-alkyi-3-vinylimidazolium salts as carbene ligand precursors, the reduction of aryl ketones with triethoxysilane may be catalyzed by copper salt/imidazolium salt/KO~tBu systems. The functional substituents attached to the N-heterocyclic carbene (NHC) serve to enhance the catalytic activity. Different copper salts also have an effect on the catalytic activity, with copper(Ⅱ) acetate monohydrate being superior to copper(I) chloride.

  7. 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).

  8. 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.

  9. Synthesis and catalytic activity of Ln(III) complexes with an unsymmetrical Schiff base including multigroups

    Institute of Scientific and Technical Information of China (English)

    YAO; Kemin; (

    2003-01-01

    [1]Elder, R. C., Tridentate and unsymmetrical tetradentate Schiff base ligands from salicylaldehydes and dimeric nickel(II) complexes, Aust. J. Chem., 1978, 31:35-45.[2]Atkins, R., Brewer, G., Kokot, G. et al., Copper(II) and nickel(II) complexesof unsymmetrical tetradentate Schiff base ligand, Inorg. Chem., 1985, 24: 127-134.[3]Meng Qingjin, Wang Ruixue, Bu Xiuren et al., New Ni (II) complexes with mixedtrimeric double Schiff ligands, Chemical Journal of Chinese Universities (in Chinese), 1990, 10: 1126-1130.[4]Yao Kemin, Zhou Wen, Lu Gui et al., Synthesis, mechanism and NMR spectra of lanthanide complexes with a novel unsymmetrical Schiff base, Science in China, Series B, 1999, 42(2): 164-169.[5]Yao Kemin, Li Ning, Huang Qiaohong et al., Synthesis and catalytic activity of novel heteronuclear Ln(III)-Cu(II) complexes with noncyclic polyether-amino acid Schiff base, Science in China, Series B, 1999, 42 (1) : 54-81.[6]Li Ning, Yao Kemin, Lou Kaiyan, Synthesis of La(III), Y(III) complexes with polyglycol aldehyde-amino acid Schiff base and their high resolution solid state 13C NMR spectra, Science in China, Series B, 1999, 42(6): 599-604.[7]Lam Berf, J. B., Shurvell, H. F., Verbet, L. et al., Organic Structural Analysis, New York: Macmillan Publishing Co. Inc., 1975, 234-250.[8]Yao Kemin, Cai Lezhen, Shen Liangfang et al., Synthesis and characterization of lanthanide perchlorates with noncyclic polyethylene glycols and their 13C-NMRspectra, Polyhedron, 1992,11(7): 2245-2251.[9]Dewar, M. J. S., Zoebisch, E. G., Healy, E. F., AM1: A new general purpose quantum mechanical molecular model, J. Amer. Chem. Soc., 1985, 107: 3902-3909.[10]Feifer, P., Avnjr, D., Chemistry in noninteger dimensions between two and three, I. Fractal theory of heterogeneous surfaces, J. Chem. Phys., 1983, 79(7): 3558-3565.[11]Yang Haifeng, Wang Hui, Duan Jinxia et al., Ab initio research of organic ligand Schiff base 4-[(2-hydroxyphenyl) imine]-2

  10. 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

  11. Influence of heme-thiolate in shaping the catalytic properties of a bacterial nitric-oxide synthase.

    Science.gov (United States)

    Hannibal, Luciana; Somasundaram, Ramasamy; Tejero, Jesús; Wilson, Adjele; Stuehr, Dennis J

    2011-11-11

    Nitric-oxide synthases (NOS) are heme-thiolate enzymes that generate nitric oxide (NO) from L-arginine. Mammalian and bacterial NOSs contain a conserved tryptophan (Trp) that hydrogen bonds with the heme-thiolate ligand. We mutated Trp(66) to His and Phe (W66H, W66F) in B. subtilis NOS to investigate how heme-thiolate electronic properties control enzyme catalysis. The mutations had opposite effects on heme midpoint potential (-302, -361, and -427 mV for W66H, wild-type (WT), and W66F, respectively). These changes were associated with rank order (W66H < WT < W66F) changes in the rates of oxygen activation and product formation in Arg hydroxylation and N-hydroxyarginine (NOHA) oxidation single turnover reactions, and in the O(2) reactivity of the ferrous heme-NO product complex. However, enzyme ferrous heme-O(2) autoxidation showed an opposite rank order. Tetrahydrofolate supported NO synthesis by WT and the mutant NOS. All three proteins showed similar extents of product formation (L-Arg → NOHA or NOHA → citrulline) in single turnover studies, but the W66F mutant showed a 2.5 times lower activity when the reactions were supported by flavoproteins and NADPH. We conclude that Trp(66) controls several catalytic parameters by tuning the electron density of the heme-thiolate bond. A greater electron density (as in W66F) improves oxygen activation and reactivity toward substrate, but decreases heme-dioxy stability and lowers the driving force for heme reduction. In the WT enzyme the Trp(66) residue balances these opposing effects for optimal catalysis.

  12. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    Science.gov (United States)

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application.

  13. Oxygen reduction at carbon supported ruthenium-selenium catalysts: Selenium as promoter and stabilizer of catalytic activity

    Science.gov (United States)

    Schulenburg, Hendrik; Hilgendorff, Marcus; Dorbandt, Iris; Radnik, Jörg; Bogdanoff, Peter; Fiechter, Sebastian; Bron, Michael; Tributsch, Helmut

    Carbon supported ruthenium-based catalysts (Ru/C) for the oxygen reduction in acid electrolytes were investigated. A treatment of Ru/C catalysts with selenious acid had a beneficial effect on catalytic activity but no influence on intrinsic kinetic properties, like Tafel slope and hydrogen peroxide generation. Reasons for the increased activity of RuSe x/C catalysts are discussed. Potential step measurements suggest that at potentials around 0.8 V (NHE) a selenium or selenium-oxygen species protects the catalyst from formation of inactive RuO 2-films. This protective effect leads to an enhanced activity of RuSe x/C compared to Ru/C. No evidence was found for a catalytically active stoichiometric selenium compound. The active phase may be described as a ruthenium suboxide RuO x (x RuSe y phase or RuSe yO v (y < 2, v < 2) layer at the particle surface.

  14. Ni-, Pd-, or Pt-catalyzed ethylene dimerization: a mechanistic description of the catalytic cycle and the active species.

    Science.gov (United States)

    Roy, Dipankar; Sunoj, Raghavan B

    2010-03-07

    Two key mechanistic possibilities for group 10 transition metal [M(eta(3)-allyl)(PMe(3))](+) catalyzed (where M = Ni(II), Pd(II) and Pt(II)) ethylene dimerization are investigated using density functional theory methods. The nature of the potential active catalysts in these pathways is analyzed to gain improved insights into the mechanism of ethylene dimerization to butene. The catalytic cycle is identified as involving typical elementary steps in transition metal-catalyzed C-C bond formation reactions, such as oxidative insertion as well as beta-H elimination. The computed kinetic and thermodynamic features indicate that a commonly proposed metal hydride species (L(n)M-H) is less likely to act as the active species as compared to a metal-ethyl species (L(n)M-CH(2)CH(3)). Of the two key pathways considered, the active species is predicted to be a metal hydride in pathway-1, whereas a metal alkyl complex serves as the active catalyst in pathway-2. A metal-mediated hydride shift from a growing metal alkyl chain to the ethylene molecule, bound to the metal in an eta(2) fashion, is predicted to be the preferred route for the generation of the active species. Among the intermediates involved in the catalytic cycle, metal alkyls with a bound olefin are identified as thermodynamically stable for all three metal ions. In general, the Ni-catalyzed pathways are found to be energetically more favorable than those associated with Pd and Pt catalysts.

  15. Trp(56) of rac1 specifies interaction with a subset of guanine nucleotide exchange factors.

    Science.gov (United States)

    Gao, Y; Xing, J; Streuli, M; Leto, T L; Zheng, Y

    2001-12-14

    Signaling specificity of Rho GTPase pathways is achieved in part by selective interaction between members of the Dbl family guanine nucleotide exchange factors (GEFs) and their Rho GTPase substrates. For example, Trio, GEF-H1, and Tiam1 are a subset of GEFs that specifically activate Rac1 but not the closely related Cdc42. The Rac1 specificity of these GEFs appears to be governed by Rac1-GEF binding interaction. To understand the detailed mechanism underlying the GEF specificity issue, we have analyzed a panel of chimeras made between Rac1 and Cdc42 and examined a series of point mutants of Rac1 made at the switch I, switch II, and beta(2)/beta(3) regions for their ability to interact with and to be activated by the GEFs. The results reveal that Rac1 residues of both the switch I and switch II regions are involved in GEF docking and GEF-mediated nucleotide disruption, because mutation of Asp(38), Asn(39), Gln(61), Tyr(64), or Arg(66)/Leu(67) into Ala results in the loss of GEF binding, whereas mutation at Tyr(32), Asp(65), or Leu(70)/Ser(71) leads to the loss of GEF catalysis while retaining the binding capability. The region between amino acids 53-72 of Rac1 is required for specific recognition and activation by the GEFs, and Trp(56) in beta(3) appears to be the critical determinant. Introduction of Trp(56) to Cdc42 renders it fully responsive to the Rac-specific GEF in vitro and in cells. Further, a polypeptide derived from the beta(3) region of Rac1 including the Trp(56) residue serves as a specific inhibitor for Rac1 interaction with the GEFs. Taken together, these results indicate that Trp(56) is the necessary and sufficient determinant of Rac1 for discrimination by the subset of Rac1-specific GEFs and suggest that a compound mimicking Trp(56) action could be explored as an interfering reagent specifically targeting Rac1 activation.

  16. The importance of hinge sequence for loop function and catalytic activity in the reaction catalyzed by triosephosphate isomerase.

    Science.gov (United States)

    Xiang, J; Sun, J; Sampson, N S

    2001-04-01

    We have determined the sequence requirements for the N-terminal protein hinge of the active-site lid of triosephosphate isomerase. The codons for the hinge (PVW) were replaced with a genetic library of all possible 8000 amino acid combinations. The most active of these 8000 mutants were selected using in vivo complementation of a triosephosphate isomerase-deficient strain of Escherichia coli, DF502. Approximately 0.3 % of the mutants complement DF502 with an activity that is between 10 and 70 % of wild-type activity. They all contain Pro at the first position. Furthermore, the sequences of these hinge mutants reveal that hydrophobic packing is very important for efficient formation of the enediol intermediate. However, the reduced catalytic activities observed are not due to increased rates of loop opening. To explore the relationship between the N-terminal and C-terminal hinges, three semi-active mutants from the N-terminal hinge selection experiment (PLH, PHS and PTF), and six active C-terminal hinge mutants from previous work (NSS, LWA, YSL, KTK, NPN, KVA) were combined to form 18 "double-hinge" mutants. The activities of these mutants suggest that the N-terminal and C-terminal hinge structures affect one another. It appears that specific side-chain interactions are important for forming a catalytically active enzyme, but not for preventing release of the unstable enediol intermediate from the active site of the enzyme. The independence of intermediate release on amino acid sequence is consistent with the absence of a "universal" hinge sequence in structurally related enzymes.

  17. A computational analysis of the structural determinants of APOBEC3's catalytic activity and vulnerability to HIV-1 Vif.

    Science.gov (United States)

    Shandilya, Shivender M D; Bohn, Markus-Frederik; Schiffer, Celia A

    2014-12-01

    APOBEC3s (A3) are Zn(2+) dependent cytidine deaminases with diverse biological functions and implications for cancer and immunity. Four of the seven human A3s restrict HIV by 'hypermutating' the reverse-transcribed viral genomic DNA. HIV Virion Infectivity Factor (Vif) counters this restriction by targeting A3s to proteasomal degradation. However, there is no apparent correlation between catalytic activity, Vif binding, and sequence similarity between A3 domains. Our comparative structural analysis reveals features required for binding Vif and features influencing polynucleotide deaminase activity in A3 proteins. All Vif-binding A3s share a negatively charged surface region that includes residues previously implicated in binding the highly-positively charged Vif. Additionally, catalytically active A3s share a positively charged groove near the Zn(2+) coordinating active site, which may accommodate the negatively charged polynucleotide substrate. Our findings suggest surface electrostatics, as well as the spatial extent of substrate accommodating region, are critical determinants of substrate and Vif binding across A3 proteins with implications for anti-retroviral and anti-cancer therapeutic design.

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

    Science.gov (United States)

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

    2014-02-01

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

  19. Calpain-Mediated Processing of Adenylate Cyclase Toxin Generates a Cytosolic Soluble Catalytically Active N-Terminal Domain.

    Directory of Open Access Journals (Sweden)

    Kepa B Uribe

    Full Text Available Bordetella pertussis, the whooping cough pathogen, secretes several virulence factors among which adenylate cyclase toxin (ACT is essential for establishment of the disease in the respiratory tract. ACT weakens host defenses by suppressing important bactericidal activities of the phagocytic cells. Up to now, it was believed that cell intoxication by ACT was a consequence of the accumulation of abnormally high levels of cAMP, generated exclusively beneath the host plasma membrane by the toxin N-terminal catalytic adenylate cyclase (AC domain, upon its direct translocation across the lipid bilayer. Here we show that host calpain, a calcium-dependent Cys-protease, is activated into the phagocytes by a toxin-triggered calcium rise, resulting in the proteolytic cleavage of the toxin N-terminal domain that releases a catalytically active "soluble AC". The calpain-mediated ACT processing allows trafficking of the "soluble AC" domain into subcellular organella. At least two strategic advantages arise from this singular toxin cleavage, enhancing the specificity of action, and simultaneously preventing an indiscriminate activation of cAMP effectors throughout the cell. The present study provides novel insights into the toxin mechanism of action, as the calpain-mediated toxin processing would confer ACT the capacity for a space- and time-coordinated production of different cAMP "pools", which would play different roles in the cell pathophysiology.

  20. 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)

  1. 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.

  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. 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.

  4. Sensory TRP channels: the key transducers of nociception and pain.

    Science.gov (United States)

    Mickle, Aaron D; Shepherd, Andrew J; Mohapatra, Durga P

    2015-01-01

    Peripheral detection of nociceptive and painful stimuli by sensory neurons involves a complex repertoire of molecular detectors and/or transducers on distinct subsets of nerve fibers. The majority of such molecular detectors/transducers belong to the transient receptor potential (TRP) family of cation channels, which comprise both specific receptors for distinct nociceptive stimuli, as well as for multiple stimuli. This chapter discusses the classification, distribution, and functional properties of individual TRP channel types that have been implicated in various nociceptive and/or painful conditions.

  5. Methodological considerations to understand the sensory function of TRP channels.

    Science.gov (United States)

    Meseguer, Víctor M; Denlinger, Bristol L; Talavera, Karel

    2011-01-01

    Transient Receptor Potential channels are exquisite molecular transducers of multiple physical and chemical stimuli, hence the raising interest to study their relevance to Sensory Biology. Here we discuss a number of aspects of the biophysical and pharmacological properties of TRP channels, which we consider essential for a clear understanding of their sensory function in vivo. By examining concrete examples extracted from recent literature we illustrate that TRP channel research is a field in motion, and that many established dogmas on biophysical properties, drug specificity and physiological role are continuously reshaped, and sometimes even dismantled.

  6. Effect of preparation method on the catalytic activity of Au/CeO_2 for VOCs oxidation

    Institute of Scientific and Technical Information of China (English)

    李锦卫; 黎维彬

    2010-01-01

    The Au/CeO2 catalysts were synthesized by co-precipitation (CP), deposition-precipitation (DP) and metallic colloids deposition (MCD) method, and tested for oxidation of volatile organic compounds (VOCs). It was revealed that the Au/CeO2 catalyst prepared by DP method was the most efficient catalyst towards the total oxidation of toluene. The Au/CeO2 catalysts had obviously high catalytic activity, and the best results was obtained on 3 wt.% Au/CeO2 catalyst prepared by DP method. These catalysts were chara...

  7. 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.

  8. Environmental Topology and Water Availability Modulates the Catalytic Activity of β-Galactosidase Entrapped in a Nanosporous Silicate Matrix

    OpenAIRE

    M. Ines Burgos; Manuel I. Velasco; Acosta, Rodolfo H.; María A. Perillo

    2016-01-01

    In the present work we studied the catalytic activity of E. coli β-Gal confined in a nanoporous silicate matrix (Eβ-Gal) at different times after the beginning of the sol-gel polymerization process. Enzyme kinetic experiments with two substrates (ONPG and PNPG) that differed in the rate-limiting steps of the reaction mechanism for their β-Gal-catalyzed hydrolysis, measurements of transverse relaxation times (T 2 ) of water protons through 1H-NMR, and scanning electron microscopy analysis of t...

  9. 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.

  10. Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

    Directory of Open Access Journals (Sweden)

    Lucia M. Petkovic

    2014-01-01

    Full Text Available Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

  11. 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.

  12. High catalytic activity of heteropolynuclear cyanide complexes containing cobalt and platinum ions: visible-light driven water oxidation.

    Science.gov (United States)

    Yamada, Yusuke; Oyama, Kohei; Gates, Rachel; Fukuzumi, Shunichi

    2015-05-04

    A near-stoichiometric amount of O2 was evolved as observed in the visible-light irradiation of an aqueous buffer (pH 8) containing [Ru(II) (2,2'-bipyridine)3 ] as a photosensitizer, Na2 S2 O8 as a sacrificial electron acceptor, and a heteropolynuclear cyanide complex as a water-oxidation catalyst. The heteropolynuclear cyanide complexes exhibited higher catalytic activity than a polynuclear cyanide complex containing only Co(III) or Pt(IV) ions as C-bound metal ions. The origin of the synergistic effect between Co and Pt ions is discussed in relation to electronic and local atomic structures of the complexes.

  13. Copper sulfide nanoparticle-decorated graphene as a catalytic amplification platform for electrochemical detection of alkaline phosphatase activity.

    Science.gov (United States)

    Peng, Juan; Han, Xiao-Xia; Zhang, Qing-Chun; Yao, Hui-Qin; Gao, Zuo-Ning

    2015-06-01

    Copper sulfide nanoparticle-decorated graphene sheet (CuS/GR) was successfully synthesized and used as a signal amplification platform for electrochemical detection of alkaline phosphatase activity. First, CuS/GR was prepared through a microwave-assisted hydrothermal approach. The CuS/GR nanocomposites exhibited excellent electrocatalytic activity toward the oxidation of ALP hydrolyzed products such as 1-naphthol, which produced a current response. Thus, a catalytic amplification platform based on CuS/GR nanocomposite for electrochemical detection of ALP activity was designed using 1-naphthyl phosphate as a model substrate. The current response increased linearly with ALP concentration from 0.1 to 100 U L(-1) with a detection limit of 0.02 U L(-1). The assay was applied to estimate ALP activity in human serum samples with satisfactory results. This strategy may find widespread and promising applications in other sensing systems that involves ALP.

  14. Simultaneous realization of high catalytic activity and stability for catalytic cracking of n-heptane on highly exposed (010) crystal planes of nanosheet ZSM-5 zeolite.

    Science.gov (United States)

    Xiao, Xia; Zhang, Yaoyuan; Jiang, Guiyuan; Liu, Jia; Han, Shanlei; Zhao, Zhen; Wang, Ruipu; Li, Cong; Xu, Chunming; Duan, Aijun; Wang, Yajun; Liu, Jian; Wei, Yuechang

    2016-08-01

    Nanosheet ZSM-5 zeolite with highly exposed (010) crystal planes demonstrates high reactivity and good anti-coking stability for the catalytic cracking of n-heptane, which is attributed to the synergy of high external surface area and acid sites, fully accessible channel intersection acid sites, and hierarchical porosity caused by the unique morphology.

  15. Catalytic performance of symmetrical and unsymmetrical sulfur-containing pincer complexes: synthesis and tandem catalytic activity of the first PCS-pincer palladium complex

    NARCIS (Netherlands)

    Gagliardo, M.; Selander, N.; Mehendale, N.C.; van Koten, G.; Klein Gebbink, R.J.M.; Szabó, K.J.

    2008-01-01

    The synthesis and catalytic applications of a new aryl-based unsymmetrical PCS-pincer complex are reported. Preparation of the robust air- and moisture-stable PCS-pincer palladium complex 5[X] started from the symmetrical ,-dibromo-meta-xylene and involved the selective substitution of one bromide b

  16. The acidic domain of the endothelial membrane protein GPIHBP1 stabilizes lipoprotein lipase activity by preventing unfolding of its catalytic domain

    DEFF Research Database (Denmark)

    Mysling, Simon; Kristensen, Kristian Kølby; Larsson, Mikael

    2016-01-01

    and their lipolytic processing. The current work conceptualizes a model for the GPIHBP1•LPL interaction based on biophysical measurements with hydrogen-deuterium exchange/mass spectrometry, surface plasmon resonance, and zero-length cross-linking. According to this model, GPIHBP1 comprises two functionally distinct...... stabilizes LPL catalytic activity by mitigating the global unfolding of LPL's catalytic domain. This study provides a conceptual framework for understanding intravascular lipolysis and GPIHBP1 and LPL mutations causing familial chylomicronemia....

  17. Catalytic activity for nitrate electroreduction of nano-structured polypyrrole films electrochemically synthesized onto a copper electrode

    Science.gov (United States)

    Phuong Thoa Nguyen, Thi; Thinh Nguyen, Viet; Hai Le, Viet

    2010-03-01

    Polypyrrole film was synthesized electrochemically onto a copper electrode in oxalate, oxalic acid and salicylic acid solutions. The electrochemical oxidation of pyrrole to form polypyrrole film and the electroreduction of nitrate and nitrite ions at synthesized Ppy modified copper electrodes (Ppy/Cu) in potassium chloride aqueous solutions were studied by cyclic voltammetry. Polypyrrole nano-porous film formation and the activity of the modified Ppy/Cu electrode for nitrate reduction were found to be dependent on the synthesis medium and conditions: pH; content and concentrations of the electrolytes; pyrrole concentration; electrode potential; electrolysis duration; drying time and temperature for finishing the Ppy/Cu electrode and immersion time in water for storing the Ppy/Cu electrode before use. High catalytic activity for nitrate reduction was found for composite electrodes with nano-porous structured Ppy films. The Ppy/Cu electrodes prepared in oxalate buffer and salicylic acid solutions perform more stable catalytic activity for nitrate reduction; their service life is about ten times longer than for an electrode prepared in oxalic acid solution.

  18. Green synthesis of gold nanoparticles using Trigonella foenum-graecum and its size-dependent catalytic activity.

    Science.gov (United States)

    Aswathy Aromal, S; Philip, Daizy

    2012-11-01

    The development of new synthesis methods for monodispersed nanocrystals using cheap and nontoxic chemicals, environmentally benign solvents and renewable materials remains a challenge to the scientific community. Most of the current methods involve known protocols which may be potentially harmful to either environment or human health. Recent research has been focused on green synthesis methods to produce new nanomaterials, ecofriendly and safer with sustainable commercial viability. The present work reports the green synthesis of gold nanoparticles using the aqueous extract of fenugreek (Trigonella foenum-graecum) as reducing and protecting agent. The pathway is based on the reduction of AuCl(4)(-) by the extract of fenugreek. This method is simple, efficient, economic and nontoxic. Gold nanoparticles having different sizes in the range from 15 to 25 nm could be obtained by controlling the synthesis parameters. The nanoparticles have been characterized by UV-Visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. The high crystallinity of nanoparticles is evident from clear lattice fringes in the HRTEM images, bright circular spots in the SAED pattern and peaks in the XRD pattern. FTIR spectrum indicates the presence of different functional groups present in the biomolecule capping the nanoparticles. The synthesized gold nanoparticles show good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol by excess NaBH(4). The catalytic activity is found to be size-dependent, the smaller nanoparticles showing faster activity.

  19. Green synthesis of Au-rGO nanocomposite and its catalytic activity in nitro-reduction and degradation of dyes

    Science.gov (United States)

    Saikia, Indranirekha; Hazarika, Moushumi; Tamuly, Chandan

    2016-10-01

    An eco-friendly, very simple method for synthesis of gold-reduced graphene oxide nanocomposite was developed using leaf extract of Piper pedicellatum C.DC. Its characterization was done by UV-visible, FT-IR, XRD, XPS, Raman, TGA, EDX, TEM analysis. The nanocomposite was very efficiently utilized as catalyst for reduction reaction of 3-nitroaniline and 4-nitrophenol. The kinetic and rate constant of nitro-reduction also reported in this study. The nanocomposite showed excellent catalytic activity for reduction of nitro aromatic compound within very short period of time. The dye which are used in industries such as rhodamine B, methyl red, methyl orange, methylene blue and bromocresol green were degraded rapidly and efficiently in a photocatalytic pathway by the as-synthesized Au-rGO nanocomposite with only 6% activity loss in degradation after the 10th cycle. So, Au-rGO composite has significant catalytic activity in nitroreduction and photocatalytic degradation of dye molecules under sunlight.

  20. Catalytic activity vs. size correlation in platinum catalysts of PEM fuel cells prepared on carbon black by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Nores-Pondal, F.J.; Granada, M.; Corti, H.R. [Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica (CNEA), General Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Vilella, I.M.J.; de Miguel, S.R.; Scelza, O.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE), Facultad de Ingenieria Quimica (Universidad Nacional del Litoral) - CONICET, Santiago del Estero 2654, 3000 Santa Fe (Argentina); Troiani, H. [Departamento de Fisica, Centro Atomico Bariloche, Comision Nacional de Energia Atomica (CNEA), Av. Bustillo 9500, 8400 San Carlos de Bariloche (Argentina)

    2009-10-15

    In this work nanoparticulated platinum catalysts have been prepared on carbon Vulcan XC-72 using three methods starting with chloroplatinic acid as a precursor: (i) formic acid as a reductor agent; (ii) impregnation method followed by reduction in hydrogen atmosphere at moderated temperature; and (iii) microwave-assisted reduction in ethylene glycol. The catalytic and size studies were also performed on a commercial Pt catalyst (E-Tek, De Nora). The characterization of the particle size and distribution was performed by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD). The characterizations of the catalytic and electrocatalytic properties of the catalysts were determined by studying the cyclohexane dehydrogenation reaction (CHD) and the behavior under cyclic voltammetry (CV) in sulfuric acid solutions. The measured electrochemical activity, along with the hydrogen chemisorption of the catalysts allows the estimation of effective particle sizes, which are much larger than those measured by TEM and XRD. The catalysts prepared by reduction with formic acid and ethylene glycol (microwave-assisted) show electrochemical activities very close to those of the commercial catalyst, and are almost insensitive to the Pt dispersion or Pt particle size. The chemical activity in CHD correlates well with the metallic dispersion determined by hydrogen chemisorption, indicating similar accesibility of H{sub 2} and cyclohexane to the catalyst surface. (author)

  1. 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.

  2. Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

    Institute of Scientific and Technical Information of China (English)

    Xue Zhang; Yu-ping Li; Song-bai Qiu; Tie-jun Wang; Long-long Ma; Qi Zhang; Ming-yue Ding

    2013-01-01

    The effect of calcination temperature on the catalytic activity for the dimethyl ether (DME) carbonylation into methyl acetate (MA) was investigated over mordenite supported copper (Cu/HMOR) prepared by ion-exchange process.The results showed that the catalytic activity was obviously affected by the calcination temperature.The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃,1.5 MPa,and GSHV of 4883 h-1.The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction,N2 absorption,NH3 temperature program desorption,CO temperature program desorption,and Raman techniques.Proper calcination temperature was effective to promote copper ions migration and diffusion,and led the support HMOR to possess more acid activity sites,which exhibited the complete decomposing of copper nitrate,large surface area and optimum micropore structure,more amount of CO adsorption site and proper amount of weak acid centers.

  3. Triosephosphate isomerase of Taenia solium (TTPI): phage display and antibodies as tools for finding target regions to inhibit catalytic activity.

    Science.gov (United States)

    Sanabria-Ayala, Víctor; Belmont, Iaraset; Abraham, Landa

    2015-01-01

    Previous studies demonstrated that antibodies against triosephosphate isomerase of Taenia solium (TTPI) can alter its enzymatic catalysis. In the present study, we used antibodies produced against the NH2-terminal region of TTPI (1/3NH2TTPI) and the phage display technology to find target regions to inhibit TTPI activity. As a first step, we obtained polyclonal antibodies against non-conserved regions from the 1/3NH2TTPI, which had an inhibitory effect of about 74 % on catalytic activity. Afterward, they were used to screen a library of phage-displayed dodecapeptides; as a result, 41 phage mimotope clones were isolated and grouped according to their amino acid sequence, finding the consensus A1 (VPTXPI), A2 (VPTXXI), B (LTPGQ), and D (DPLPR). Antibodies against selected phage mimotope clones were obtained by rabbit's immunization; these ones clearly recognized TTPI by both Western blot and ELISA. However, only the mimotope PDTS16 (DSVTPTSVMAVA) clone, which belongs to the VPTXXI consensus, raised antibodies capable of inhibiting the TTPI catalytic activity in 45 %. Anti-PDTS16 antibodies were confronted to several synthetic peptides that encompass the 1/3NH2TTPI, and they only recognized three, which share the motif FDTLQK belonging to the helix-α1 in TTPI. This suggests that this motif is the main part of the epitope recognized by anti-PDTS16 antibodies and revealed its importance for TTPI catalysis.

  4. Highly stable and re-dispersible nano Cu hydrosols with sensitively size-dependent catalytic and antibacterial activities

    Science.gov (United States)

    Zhang, Yu; Zhu, Pengli; Li, Gang; Wang, Wenzhao; Chen, Liang; Lu, Daoqiang Daniel; Sun, Rong; Zhou, Feng; Wong, Chingping

    2015-08-01

    Highly stable monodispersed nano Cu hydrosols were facilely prepared by an aqueous chemical reduction method through selecting copper hydroxide (Cu(OH)2) as the copper precursor, poly(acrylic acid) (PAA) and ethanol amine (EA) as the complexing agents, and hydrazine hydrate as the reducing agent. The size of the obtained Cu colloidal nanoparticles was controlled from 0.96 to 26.26 nm by adjusting the dosage of the copper precursor. Moreover, the highly stable nano Cu hydrosols could be easily concentrated and re-dispersed in water meanwhile maintaining good dispersibility. A model catalytic reaction of reducing p-nitrophenol with NaBH4 in the presence of nano Cu hydrosols with different sizes was performed to set up the relationship between the apparent kinetic rate constant (kapp) and the particle size of Cu catalysts. The experimental results indicate that the corresponding kapp showed an obvious size-dependency. Calculations revealed that kapp was directly proportional to the surface area of Cu catalyst nanoparticles, and also proportional to the reciprocal of the particle size based on the same mass of Cu catalysts. This relationship might be a universal principle for predicting and assessing the catalytic efficiency of Cu nanoparticles. The activation energy (Ea) of this catalytic reaction when using 0.96 nm Cu hydrosol as a catalyst was calculated to be 9.37 kJ mol-1, which is considered an extremely low potential barrier. In addition, the synthesized nano Cu hydrosols showed size-dependent antibacterial activities against Pseudomonas aeruginosa (P. aeruginosa) and the minimal inhibitory concentration of the optimal sample was lower than 5.82 μg L-1.Highly stable monodispersed nano Cu hydrosols were facilely prepared by an aqueous chemical reduction method through selecting copper hydroxide (Cu(OH)2) as the copper precursor, poly(acrylic acid) (PAA) and ethanol amine (EA) as the complexing agents, and hydrazine hydrate as the reducing agent. The size of the

  5. 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.

  6. Synthesis and characterization of Nb2O5 supported Pd(II)@SBA15: Catalytic activity towards oxidation of benzhydrol and Rhodamine-B

    Science.gov (United States)

    Ramanjaneya Reddy, G.; Chennakesavulu, K.

    2014-10-01

    The mesoporous silica (SBA15) supported niobium pentoxide(Nb2O5) along with the palladium(II) nanocomposite catalysts was synthesised. The nanocomposites (PdSBA and NbPdSBA) impregnation and stability were studied by several spectroscopic, thermal analysis, sorption and microscopic techniques (FTIR, DRS/UV-Vis, XRD, XPS, BET - nitrogen adsorption isotherms, TGA, SEM and TEM). The catalytic activity of the nanocomposites was studied in liquid phase oxidation of benzhydrol/H2O2 and photo degradation of the Rhodamine-B (RhB) under UV light irradiation. The catalytic activity of the nanocomposite NbPdSBA was shows higher catalytic activity in the benzhydrol oxidation and RhB degradation. The oxidation ability of the nanocomposites was determined by the spectrophotometrically. Thus a reusable catalyst shows comparable activity with fresh catalyst without loss of it's activity.

  7. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Ja Hun; Tonkyn, Russell G.; Kim, Do Heui; Szanyi, Janos; Peden, Charles HF

    2010-10-21

    Superior activity and selectivity of a Cu ion-exchanged SSZ-13 zeolite in the selective catalytic reduction (SCR) of NOx with NH3 were observed, in comparison to Cu-beta and Cu-ZSM-5 zeolites. Cu-SSZ-13 was not only more active in the NOx SCR reaction over the entire temperature range studied (up to 550 °C), but also more selective toward nitrogen formation, resulting in significantly lower amounts of NOx by-products (i.e., NO2 and N2O) than the other two zeolites. In addition, Cu-SSZ-13 demonstrated the highest activity and N2 formation selectivity in the oxidation of NH3. The results of this study strongly suggest that Cu-SSZ-13 is a promising candidate as a catalyst for NOx SCR with great potential in after-treatment systems for either mobile or stationary sources.

  8. 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.

  9. FACILE GREEN SYNTHESIS OF GOLD NANOPARTICLES WITH GREAT CATALYTIC ACTIVITY USING ULVA FASCIATA

    Directory of Open Access Journals (Sweden)

    V. Sugantha Kumari

    2014-03-01

    Full Text Available We report a facile, green, and high yielding approache for the synthesis and stabilization of monodisperse gold nanoparticles (AuNPs using green seaweed Ulva fasciata extract. Characterization of the obtained AuNPs was performed using UV-visible, Fourier transform infrared (FTIR, X-ray diffraction (XRD and transmission electron microscopy (TEM. UV-visible absorption spectroscopy was used to determine the yield of the gold nanoparticles. The UV-visible absorption spectrum showed a characteristic optical peak of AuNPs at 541 nm. The X-ray diffraction pattern suggested the formation and crystallinity of AuNPs. Spherical AuNPs synthesized with an average particle size of 10 ± 3 nm were confirmed by TEM. FTIR analysis supported the role of phytochemicals of Ulva fasciata extract for bioreduction and stabilization of AuNPs. Moreover, the synthesized AuNPs exhibit remarkable catalytic efficiency by using the reduction of 4-nitroaniline by potassium borohydride in aqueous solution using UV-visible absorption spectroscopy. Catalytic reduction followed pseudo-first-order kinetics with respect to 4-Nitrophenol.

  10. Highly active metastable ruthenium nanoparticles for hydrogen production through the catalytic hydrolysis of ammonia borane.

    Science.gov (United States)

    Abo-Hamed, Enass K; Pennycook, Timothy; Vaynzof, Yana; Toprakcioglu, Chris; Koutsioubas, Alexandros; Scherman, Oren A

    2014-08-13

    Late transition metal nanoparticles (NPs) with a favorably high surface area to volume ratio have garnered much interest for catalytic applications. Yet, these NPs are prone to aggregation in solution, which has been mitigated through attachment of surface ligands, additives or supports; unfortunately, protective ligands can severely reduce the effective surface area on the NPs available for catalyzing chemical transformations. The preparation of 'metastable' NPs can readily address these challenges. We report herein the first synthesis of monodisperse metastable ruthenium nanoparticles (RuNPs), having sub 5 nm size and an fcc structure, in aqueous media at room temperature, which can be stored for a period of at least 8 months. The RuNPs can subsequently be used for the catalytic, quantitative hydrolysis of ammonia-borane (AB) yielding hydrogen gas with 21.8 turnovers per min at 25 °C. The high surface area available for hydrolysis of AB on the metastable RuNPs translated to an Ea of 27.5 kJ mol(-1) , which is notably lower than previously reported values for RuNP based catalysts.

  11. Preparation and photo-catalytic activities of FeOOH/ZnO/MMT composite

    Science.gov (United States)

    Zhou, Yao; Liu, Fusheng; Yu, Shitao

    2015-11-01

    Montmorillonite (MMT) was used as the carrier for synthesis of FeOOH and FeOOH/ZnO nano-material. FeOOH and FeOOH/ZnO were synthesized by the aqueous solutions of Fe(NO3)3-HNO3 and Zn(NO3)2-NaOH/Fe(NO3)3-HNO3 with the carrier of montmorillonite respectively. Transmission electron-microscopy (TEM) and X-ray diffraction (XRD) were used to study the morphology form and structure of the nano-materials. TEM was also used to demonstrate that FeOOH/ZnO can be formed with the appropriate interface. According to UV-vis absorption spectra, FeOOH/ZnO has a better response to visible light than FeOOH and ZnO, which indicates there is some coupling effect between FeOOH and ZnO. Pentachlorophenol (PCP) was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of the FeOOH/ZnO and FeOOH catalysts in visible light (λ > 400 nm). The photo-catalytic efficiency of FeOOH/ZnO/MMT is better than FeOOH/MMT. According to FTIR, changes of pH and TOC, the degradation mechanism was also discussed. PCP was degraded to aromatic ketone and chloro-hydrocarbon compounds and then to H2O, CO2 and HCl.

  12. The tumor suppressor gene Trp53 protects the mouse lens against posterior subcapsular cataracts and the BMP receptor Acvr1 acts as a tumor suppressor in the lens

    Directory of Open Access Journals (Sweden)

    Luke A. Wiley

    2011-07-01

    We previously found that lenses lacking the Acvr1 gene, which encodes a bone morphogenetic protein (BMP receptor, had abnormal proliferation and cell death in epithelial and cortical fiber cells. We tested whether the tumor suppressor protein p53 (encoded by Trp53 affected this phenotype. Acvr1 conditional knockout (Acvr1CKO mouse fiber cells had increased numbers of nuclei that stained for p53 phosphorylated on serine 15, an indicator of p53 stabilization and activation. Deletion of Trp53 rescued the Acvr1CKO cell death phenotype in embryos and reduced Acvr1-dependent apoptosis in postnatal lenses. However, deletion of Trp53 alone increased the number of fiber cells that failed to withdraw from the cell cycle. Trp53CKO and Acvr1;Trp53DCKO (double conditional knockout, but not Acvr1CKO, lenses developed abnormal collections of cells at the posterior of the lens that resembled posterior subcapsular cataracts. Cells from human posterior subcapsular cataracts had morphological and molecular characteristics similar to the cells at the posterior of mouse lenses lacking Trp53. In Trp53CKO lenses, cells in the posterior plaques did not proliferate but, in Acvr1;Trp53DCKO lenses, many cells in the posterior plaques continued to proliferate, eventually forming vascularized tumor-like masses at the posterior of the lens. We conclude that p53 protects the lens against posterior subcapsular cataract formation by suppressing the proliferation of fiber cells and promoting the death of any fiber cells that enter the cell cycle. Acvr1 acts as a tumor suppressor in the lens. Enhancing p53 function in the lens could contribute to the prevention of steroid- and radiation-induced posterior subcapsular cataracts.

  13. Conformational basis for substrate recognition and regulation of catalytic activity in Staphylococcus aureus nucleoside di-phosphate kinase.

    Science.gov (United States)

    Srivastava, Sandeep Kumar; Rajasree, Kalagiri; Gopal, B

    2011-10-01

    Nucleoside diphosphate kinases (NDK) are characterized by high catalytic turnover rates and diverse substrate specificity. These features make this enzyme an effective activator of a pro-drug-an application that has been actively pursued for a variety of therapeutic strategies. The catalytic mechanism of this enzyme is governed by a conserved histidine that coordinates a magnesium ion at the active site. Despite substantial structural and biochemical information on NDK, the mechanistic feature of the phospho-transfer that leads to auto-phosphorylation remains unclear. While the role of the histidine residue is well documented, the other active site residues, in particular the conserved serine remains poorly characterized. Studies on some homologues suggest no role for the serine residue at the active site, while others suggest a crucial role for this serine in the regulation and quaternary association of this enzyme in some species. Here we report the biochemical features of the Staphylococcus aureus NDK and the mutant enzymes. We also describe the crystal structures of the apo-NDK, as a transition state mimic with vanadate and in complex with different nucleotide substrates. These structures formed the basis for molecular dynamics simulations to understand the broad substrate specificity of this enzyme and the role of active site residues in the phospho-transfer mechanism and oligomerization. Put together, these data suggest that concerted changes in the conformation of specific residues facilitate the stabilization of nucleotide complexes thereby enabling the steps involved in the ping-pong reaction mechanism without large changes to the overall structure of this enzyme.

  14. Essential role of PSM/SH2-B variants in insulin receptor catalytic activation and the resulting cellular responses.

    Science.gov (United States)

    Zhang, Manchao; Deng, Youping; Tandon, Ruchi; Bai, Cheng; Riedel, Heimo

    2008-01-01

    The positive regulatory role of PSM/SH2-B downstream of various mitogenic receptor tyrosine kinases or gene disruption experiments in mice support a role of PSM in the regulation of insulin action. Here, four alternative PSM splice variants and individual functional domains were compared for their role in the regulation of specific metabolic insulin responses. We found that individual PSM variants in 3T3-L1 adipocytes potentiated insulin-mediated glucose and amino acid transport, glycogenesis, lipogenesis, and key components in the metabolic insulin response including p70 S6 kinase, glycogen synthase, glycogen synthase kinase 3 (GSK3), Akt, Cbl, and IRS-1. Highest activity was consistently observed for PSM alpha, followed by beta, delta, and gamma with decreasing activity. In contrast, dominant-negative peptide mimetics of the PSM Pro-rich, pleckstrin homology (PH), or src homology 2 (SH2) domains inhibited any tested insulin response. Potentiation of the insulin response originated at the insulin receptor (IR) kinase level by PSM variant-specific regulation of the Km (ATP) whereas the Vmax remained unaffected. IR catalytic activation was inhibited by peptide mimetics of the PSM SH2 or dimerization domain (DD). Either peptide should disrupt the complex of a PSM dimer linked to IR via SH2 domains as proposed for PSM activation of tyrosine kinase JAK2. Either peptide abolished downstream insulin responses indistinguishable from PSM siRNA knockdown. Our results implicate an essential role of the PSM variants in the activation of the IR kinase and the resulting metabolic insulin response. PSM variants act as internal IR ligands that in addition to potentiating the insulin response stimulate IR catalytic activation even in the absence of insulin.

  15. 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.

  16. 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.

  17. SIRT1 catalytic activity has little effect on tumor formation and metastases in a mouse model of breast cancer.

    Directory of Open Access Journals (Sweden)

    Katherine V Clark-Knowles

    Full Text Available The protein deacetylase SIRT1 has been implicated in the regulation of a large number of cellular processes that are thought to be required for cancer initiation and progression. There are conflicting data that make it unclear whether Sirt1 functions as an oncogene or tumor suppressor. To assess the effect of SIRT1 on the emergence and progression of mammary tumors, we crossed mice that harbor a point mutation that abolishes SIRT1 catalytic activity with mice carrying the polyoma middle T transgene driven by the murine mammary tumor virus promoter (MMTV-PyMT. The absence of SIRT1 catalytic activity neither accelerated nor blocked the formation of tumors and metastases in this model. There was a lag in tumor latency that modestly extended survival in Sirt1 mutant mice that we attribute to a delay in mammary gland development and not to a direct effect of SIRT1 on carcinogenesis. These results are consistent with previous evidence suggesting that Sirt1 is not a tumor promoter or a tumor suppressor.

  18. Understanding the enhanced catalytic activity of Cu1@Pd3(111) in formic acid dissociation, a theoretical perspective

    Science.gov (United States)

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-06-01

    The bimetallic Cu1@Pd3(111) catalyst has been synthesized recently and exhibits better catalytic activity and durability compared with pure Pd(111) as anode catalyst in direct formic acid fuel cells (DFAFCs). In this work, we studied the reaction mechanism of formic acid dissociation on both Pd(111) and Cu1@Pd3(111) by using the density functional method. Our calculations showed that the surface adsorption of the poisoning species CO on Cu1@Pd3(111) is weakened mainly by the strain effect rather than the Cusbnd Pd ligand effect. The Cu1@Pd3(111) can effectively promote the catalytic activity for formic acid dissociation by decreasing the barrier of CO2 formation from the preferential trans-COOH intermediate and increasing the barrier of CO formation from the reduction of CO2. We found that the H atom accumulation, electron accumulation and low electrode potential could accelerate the catalyst deactivation due to the contamination of the poisoning species CO. Furthermore, under low anode potential, the Cu1@Pd3(111) has better durability than pure Pd(111), which can be attributed to the unfavorable CO formation and the favorable CO desorption.

  19. Highly active Ag clusters stabilized on TiO2 nanocrystals for catalytic reduction of p-nitrophenol

    Science.gov (United States)

    Wang, Xin; Zhao, Zhe; Ou, Dingrong; Tu, Baofeng; Cui, Daan; Wei, Xuming; Cheng, Mojie

    2016-11-01

    Ag/TiO2 nanocomposites comprising of Ag clusters on TiO2 nanocrystal surfaces are of great significance in catalysts and advanced functional materials. Herein a novel method to synthesize Ag/TiO2 nanocomposites with Ag clusters under 2 nm on TiO2 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 TiO2 nanocrystals. The prepared Ag/TiO2 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/TiO2 nanocomposites is evaluated for the reduction of p-nitrophenol (4-NP) into p-aminophenol (4-AP) by NaBH4. Results demonstrate that Ag/TiO2 nanocomposites have shown an outstanding catalytic activity as well as a good stability in successive reduction of 4-NP. Noticeably, TOF of Ag/TiO2-0.75 nanocomposites obtained in this work is the highest among Ag based catalysts previously reported.

  20. Inhibition of SIRT1 Catalytic Activity Increases p53 Acetylation but Does Not Alter Cell Survival following DNA Damage

    Science.gov (United States)

    Solomon, Jonathan M.; Pasupuleti, Rao; Xu, Lei; McDonagh, Thomas; Curtis, Rory; DiStefano, Peter S.; Huber, L. Julie

    2006-01-01

    Human SIRT1 is an enzyme that deacetylates the p53 tumor suppressor protein and has been suggested to modulate p53-dependent functions including DNA damage-induced cell death. In this report, we used EX-527, a novel, potent, and specific small-molecule inhibitor of SIRT1 catalytic activity to examine the role of SIRT1 in p53 acetylation and cell survival after DNA damage. Treatment with EX-527 dramatically increased acetylation at lysine 382 of p53 after different types of DNA damage in primary human mammary epithelial cells and several cell lines. Significantly, inhibition of SIRT1 catalytic activity by EX-527 had no effect on cell growth, viability, or p53-controlled gene expression in cells treated with etoposide. Acetyl-p53 was also increased by the histone deacetylase (HDAC) class I/II inhibitor trichostatin A (TSA). EX-527 and TSA acted synergistically to increase acetyl-p53 levels, confirming that p53 acetylation is regulated by both SIRT1 and HDACs. While TSA alone reduced cell survival after DNA damage, the combination of EX-527 and TSA had no further effect on cell viability and growth. These results show that, although SIRT1 deacetylates p53, this does not play a role in cell survival following DNA damage in certain cell lines and primary human mammary epithelial cells. PMID:16354677

  1. Mild activation of CeO2-supported gold nanoclusters and insight into the catalytic behavior in CO oxidation.

    Science.gov (United States)

    Li, Weili; Ge, Qingjie; Ma, Xiangang; Chen, Yuxiang; Zhu, Manzhou; Xu, Hengyong; Jin, Rongchao

    2016-01-28

    We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 pretreatment (at 80 °C) can activate the catalyst, and the addition of reductive gases (CO or H2) can enhance the activation effects of O2 pretreatment via a redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies-which then adsorb and activate O2 to produce more active oxygen species. The CO/O2 pulse experiments confirm that CO is adsorbed on the cluster catalyst even with ligands on, and active oxygen species present on the surface of the pretreated catalyst reacts with CO pulses to generate CO2. The Au144(SR)60/CeO2 exhibits high CO oxidation activity at 80 °C without the removal of thiolate ligands. The surface lattice-oxygen of the support CeO2 possibly participates in the oxidation of CO over the Au144(SR)60/CeO2 catalyst.

  2. Catalytic hydrothermal treatment of pulping effluent using a mixture of Cu and Mn metals supported on activated carbon as catalyst.

    Science.gov (United States)

    Yadav, Bholu Ram; Garg, Anurag

    2016-10-01

    The present study was performed to investigate the performance of activated carbon-supported copper and manganese base catalyst for catalytic wet oxidation (CWO) of pulping effluent. CWO reaction was performed in a high pressure reactor (capacity = 0.7 l) at temperatures ranging from 120 to 190 °C and oxygen partial pressures of 0.5 to 0.9 MPa with the catalyst concentration of 3 g/l for 3 h duration. With Cu/Mn/AC catalyst at 190 °C temperature and 0.9 MPa oxygen partial pressures, the maximum chemical oxygen demand (COD), total organic carbon (TOC), lignin, and color removals of 73, 71, 86, and 85 %, respectively, were achieved compared to only 52, 51, 53, and 54 % removals during the non-catalytic process. Biodegradability (in terms of 5-day biochemical oxygen demand (BOD5) to COD ratio) of the pulping effluent was improved to 0.38 from an initial value of 0.16 after the catalytic reaction. The adsorbed carbonaceous fraction on the used catalyst was also determined which contributed meager TOC reduction of 3-4 %. The leaching test showed dissolution of the metals (i.e., Cu and Mn) from the catalysts in the wastewater during CWO reaction at 190 °C temperature and 0.9 MPa oxygen partial pressures. In the future, the investigations should focus on the catalyst reusability.

  3. mTOR Ser-2481 Autophosphorylation Monitors mTORC-specific Catalytic Activity and Clarifies Rapamycin Mechanism of Action*

    Science.gov (United States)

    Soliman, Ghada A.; Acosta-Jaquez, Hugo A.; Dunlop, Elaine A.; Ekim, Bilgen; Maj, Nicole E.; Tee, Andrew R.; Fingar, Diane C.

    2010-01-01

    The mammalian target of rapamycin (mTOR) Ser/Thr kinase signals in at least two multiprotein complexes distinguished by their different partners and sensitivities to rapamycin. Acute rapamycin inhibits signaling by mTOR complex 1 (mTORC1) but not mTOR complex 2 (mTORC2), which both promote cell growth, proliferation, and survival. Although mTORC2 regulation remains poorly defined, diverse cellular mitogens activate mTORC1 signaling in a manner that requires sufficient levels of amino acids and cellular energy. Before the identification of distinct mTOR complexes, mTOR was reported to autophosphorylate on Ser-2481 in vivo in a rapamycin- and amino acid-insensitive manner. These results suggested that modulation of mTOR intrinsic catalytic activity does not universally underlie mTOR regulation. Here we re-examine the regulation of mTOR Ser-2481 autophosphorylation (Ser(P)-2481) in vivo by studying mTORC-specific Ser(P)-2481 in mTORC1 and mTORC2, with a primary focus on mTORC1. In contrast to previous work, we find that acute rapamycin and amino acid withdrawal markedly attenuate mTORC1-associated mTOR Ser(P)-2481 in cycling cells. Although insulin stimulates both mTORC1- and mTORC2-associated mTOR Ser(P)-2481 in a phosphatidylinositol 3-kinase-dependent manner, rapamycin acutely inhibits insulin-stimulated mTOR Ser(P)-2481 in mTORC1 but not mTORC2. By interrogating diverse mTORC1 regulatory input, we find that without exception mTORC1-activating signals promote, whereas mTORC1-inhibitory signals decrease mTORC1-associated mTOR Ser(P)-2481. These data suggest that mTORC1- and likely mTORC2-associated mTOR Ser-2481 autophosphorylation directly monitors intrinsic mTORC-specific catalytic activity and reveal that rapamycin inhibits mTORC1 signaling in vivo by reducing mTORC1 catalytic activity. PMID:20022946

  4. pH dependent catalytic activities of platinum nanoparticles with respect to the decomposition of hydrogen peroxide and scavenging of superoxide and singlet oxygen

    Science.gov (United States)

    Liu, Yi; Wu, Haohao; Li, Meng; Yin, Jun-Jie; Nie, Zhihong

    2014-09-01

    Recently, platinum (Pt) nanoparticles (NPs) have received increasing attention in the field of catalysis and medicine due to their excellent catalytic activity. To rationally design Pt NPs for these applications, it is crucial to understand the mechanisms underlying their catalytic and biological activities. This article describes a systematic study on the Pt NP-catalyzed decomposition of hydrogen peroxide (H2O2) and scavenging of superoxide (O2&z.rad;-) and singlet oxygen (1O2) over a physiologically relevant pH range of 1.12-10.96. We demonstrated that the catalytic activities of Pt NPs can be modulated by the pH value of the environment. Our results suggest that Pt NPs possess peroxidase-like activity of decomposing H2O2 into &z.rad;OH under acidic conditions, but catalase-like activity of producing H2O and O2 under neutral and alkaline conditions. In addition, Pt NPs exhibit significant superoxide dismutase-like activity of scavenging O2&z.rad;- under neutral conditions, but not under acidic conditions. The 1O2 scavenging ability of Pt NPs increases with the increase in the pH of the environment. The study will provide useful guidance for designing Pt NPs with desired catalytic and biological properties.Recently, platinum (Pt) nanoparticles (NPs) have received increasing attention in the field of catalysis and medicine due to their excellent catalytic activity. To rationally design Pt NPs for these applications, it is crucial to understand the mechanisms underlying their catalytic and biological activities. This article describes a systematic study on the Pt NP-catalyzed decomposition of hydrogen peroxide (H2O2) and scavenging of superoxide (O2&z.rad;-) and singlet oxygen (1O2) over a physiologically relevant pH range of 1.12-10.96. We demonstrated that the catalytic activities of Pt NPs can be modulated by the pH value of the environment. Our results suggest that Pt NPs possess peroxidase-like activity of decomposing H2O2 into &z.rad;OH under acidic conditions

  5. Syntheses, Characterizations and Catalytic Activities of Rare Earth Derivatives of Molybdotungstovanado-Phosphoric Heteropoly Acid

    Institute of Scientific and Technical Information of China (English)

    周百斌; 韦永德; 马慧媛; 王玉和; 单永奎

    2002-01-01

    Seven new-type pentabasic heteropoly complexes with the general molecular formula K10H5[Ln(PMo5W4V2O39)2]*nH2O(Ln=La, Ce, Pr, Nd, Eu, Gd, Dy) were synthesized. The results of IR, UV, 31P, 51V NMR and X-ray powder diffraction pattern demonstrate that the product still maintains Keggin structure. The thermal stability studied by water solubility test, TG-DTA, XRD and IR at various temperature shows that the range of pyrolysis temperature is from 500~550 ℃. The catalytic action varies according to the contents of rare earths which are used to catalyze the decomposition of hydrogen peroxide.

  6. Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols

    Science.gov (United States)

    Zhitnev, Yu. N.; Tveritinova, E. A.; Chernyak, S. A.; Savilov, S. V.; Lunin, V. V.

    2016-06-01

    Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2-C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.

  7. A Sustainable Approach to Fabricating Ag Nanoparticles/PVA Hybrid Nanofiber and Its Catalytic Activity

    Directory of Open Access Journals (Sweden)

    Yongde Meng

    2015-06-01

    Full Text Available Ag nanoparticles were synthesized by using Ficus altissima Blume leaf extract as a reducing agent at room temperature. The resulting Ag nanoparticles/PVA mixture was employed to create Ag nanoparticles/PVA (polyvinyl alcohol hybrid nanofibers via an electrospinning technique. The obtained nanofibers were confirmed by means of UV-Vis spectroscopy, The X-ray diffraction (XRD, Fourier transform infrared (FTIR spectroscopy, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and then tested to catalyze KBH4 reduction of methylene blue (MB. The catalytic results demonstrate that the MB can be reduced completely within 15 min. In addition, the Ag nanoparticles/PVA hybrid nanofibers show reusability for three cycles with no obvious losses in degradation ratio of the MB.

  8. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Zhou, Yong [Eco-materials and Renewable Energy Research Center (ERERC), School of Physics, National Lab of Solid State Microstructure, ERERC, Nanjing University, Nanjing 210093 (China); Pei, Chonghua, E-mail: peichonghua@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China)

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  9. 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.

  10. Ligand-induced evolution of intrinsic fluorescence and catalytic activity from cobalt ferrite nanoparticles.

    Science.gov (United States)

    Pal, Monalisa; Kundu, Anirban; Rakshit, Rupali; Mandal, Kalyan

    2015-06-08

    To develop CoFe(2)O(4) as magneto-fluorescent nanoparticles (NPs) for biomedical applications, it would be advantageous to identify any intrinsic fluorescence of this important magnetic material by simply adjusting the surface chemistry of the NPs themselves. Herein, we demonstrate that intrinsic multicolor fluorescence, covering the whole visible region, can be induced by facile functionalization of CoFe(2)O(4) NPs with Na-tartrate. Moreover, the functionalized CoFe(2)O(4) NPs also show unprecedented catalytic efficiency in the degradation of both biologically and environmentally harmful dyes, pioneering the potential application of these NPs in therapeutics and wastewater treatment. Detailed investigation through various spectroscopic tools unveils the story behind the emergence of this unique optical property of CoFe(2)O(4) NPs upon functionalization with tartrate ligands. We believe our developed multifunctional CoFe(2)O(4) NPs hold great promise for advanced biomedical and technological applications.

  11. Incorporation of lanthanum into SBA-15 and its catalytic activity in trichloroethylene combustion

    Institute of Scientific and Technical Information of China (English)

    LI Dao; CHEN Guoping; WANG Xingyi

    2008-01-01

    s: The direct synthesis of La-SBA- 15 mesoporous material by two-step synthesis method was reported. The effect of pH value dur-ing the process on the incorporation of La into the framework of SBA-15 was investigated, and XRD, UV-vis, FT-IR, and ICP were used to characterize the obtained La-SBA-15. The experimental results showed that a large amount of La could enter SBA-15 framework under suitable pH value while a highly ordered mesostructure of samples containing La was retained. In addition, the obtained La-SBA-15 exhib-ited good catalytic performance in the combustion of trichioroethylene.

  12. A study on the morphology and catalytic activity of gold nanoparticles by the kinetic Monte Carlo simulation

    Science.gov (United States)

    He, Xiang; Chen, Zhao-Xu

    2016-05-01

    We studied the thermal-stability of supported Au nanoparticles on the substrates of different binding strength to gold by Monte Carlo simulations. It has been revealed that the stable Au morphology is determined by the temperature and the binding strength. When heated on the strongly-binding substrates, the Au nanoparticles would wet the substrate completely and form monolayer. The stable Au layered structure of few layers can be formed by the incomplete wetting of clusters on the intermediate-binding substrates. The simulation results are in good agreement with pertinent experimental and theoretical results. Based on the simulation results and experimental observations, we find the strong linkage between the top edge sites and the activity TOF of low-temperature CO oxidation. We conclude that the top edges sites of Au layered structures are possible reactive sites. This study may provide new perspective for controlling morphology and understanding catalytic activity of supported metallic clusters.

  13. A Short Review on the Catalytic Activity of Hydrotalcite-Derived Materials for Dry Reforming of Methane

    Directory of Open Access Journals (Sweden)

    Radosław Dębek

    2017-01-01

    Full Text Available Nickel-containing hydrotalcite-derived materials have been recently proposed as promising materials for methane dry reforming (DRM. Based on a literature review and on the experience of the authors, this review focuses on presenting past and recent achievements on increasing activity and stability of hydrotalcite-based materials for DRM. The use of different NiMgAl and NiAl hydrotalcite (HT precursors, various methods for nickel introduction into HT structure, calcination conditions and promoters are discussed. HT-derived materials containing nickel generally exhibit high activity in DRM; however, the problem of preventing catalyst deactivation by coking, especially below 700 °C, is still an open question. The proposed solutions in the literature include: catalyst regeneration either in oxygen atmosphere or via hydrogasification; or application of various promoters, such as Zr, Ce or La, which was proven to enhance catalytic stability.

  14. 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.

  15. 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

  16. Synthetically Tuned Atomic Ordering in PdCu Nanoparticles with Enhanced Catalytic Activity toward Solvent-Free Benzylamine Oxidation.

    Science.gov (United States)

    Marakatti, Vijaykumar S; Sarma, Saurav Ch; Joseph, Boby; Banerjee, Dipanjan; Peter, Sebastian C

    2017-02-01

    Synthesis of ordered compounds with nano size is of particular interest for tuning the surface properties with enhanced activity and selectivity toward various important industrial catalytic processes. In this work, we synthesized ordered PdCu nanoparticles as highly efficient catalyst for the solvent-free aerobic oxidation of benzylamine. The PdxCu1-x catalysts with different chemical compositions (x = 0, 0.25, 0.4, 0.5, 0.6, 0.75, 1) were prepared by polyol method using NaBH4 as a reducing agent and were well-characterized by X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM) energy-dispersive analysis of X-rays, and X-ray absorption fine structure. The effect of different metal concentrations of Pd and Cu on the formation of PdxCu1-x nanoparticles was investigated. The XRD and TEM confirmed the formation of ordered PdCu intermetallic phase with body-centered cubic (BCC) structure for the synthetic composition of Pd/Cu = 1:1. For compositions x = 0, 0.25, 0.75, and 1, PdxCu1-x alloy with face-centered cubic (FCC) structure was observed, whereas mixed phase of BCC and FCC was observed for x = 0.4 and 0.6. The use of strong reducing agent (NaBH4) was essential to synthesize PdCu ordered phase compared to weak reducing agents such as oleylamine and ascorbic acid. The PdCu nanocatalyst with ordered structure (BCC) showed excellent catalytic activity compared to PdxCu1-x alloy nanoparticles with FCC structure. The atomic ordering in the PdCu intermetallic was the driving force for the enhancement in the catalytic activity with high benzylamine conversion of 94.0% and dibenzylimine selectivity of 92.2% compared to its monometallic and alloy counterparts. Moreover, ordered PdCu alloy showed good recyclability and activity toward the oxidation of different amines.

  17. Compositions, structures, and catalytic activities of CeO₂@Cu₂O nanocomposites prepared by the template-assisted method.

    Science.gov (United States)

    Bao, Huizhi; Zhang, Zhenhua; Hua, Qing; Huang, Weixin

    2014-06-10

    CeO2@Cu2O nanocomposites were prepared from Cu2O cubes and octahedra by the template-assisted method involving the liquid (Ce(IV))-solid (Cu2O) interfacial reaction. Their compositions, structures, and catalytic activities in CO oxidation were studied in detail. Under the same reaction conditions, CeO2@Cu2O nanocomposites prepared from cubic and octahedral Cu2O templates exhibit different compositions and structures. With an increasing amount of Ce(IV) reactant, a smooth CeO2-CuOx shell develops on the surface of Cu2O cubes and eventually void cubic core/multishell Cu2O/CeO2-CuOx nanocomposites form; however, a rough CeO2-CuOx shell develops on the surface of Cu2O octahedra, and eventually hollow octahedral CeO2-CuOx nanocages form. The formation of different compositions and structures of CeO2@Cu2O nanocomposites was correlated with the different exposed crystal planes and surface reactivities of Cu2O cubes and octahedra. The catalytic activity of CeO2@Cu2O nanocomposites in CO oxidation depends on their compositions and structures. The most active CeO2@Cu2O nanocomposites become active at 70 °C and achieve a 100% CO conversion at 170 °C. These results broaden the versatility of Cu2O nanocrystals as the sacrificial template for the fabrication of novel nanocomposites with core/shell and hollow nanostructures and exemplify the morphology effect of Cu2O nanocrystals in liquid-solid interfacial reactions with respect to the composition, structure, and properties of nanocomposites prepared by the template-assisted method.

  18. Biogenic synthesis of palladium nanoparticles using Pulicaria glutinosa extract and their catalytic activity towards the Suzuki coupling reaction.

    Science.gov (United States)

    Khan, Mujeeb; Khan, Merajuddin; Kuniyil, Mufsir; Adil, Syed Farooq; Al-Warthan, Abdulrahman; Alkhathlan, Hamad Z; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2014-06-28

    Green synthesis of nanomaterials finds the edge over chemical methods due to its environmental compatibility. Herein, we report a facile and eco-friendly method for the synthesis of palladium (Pd) nanoparticles (NPs) using an aqueous solution of Pulicaria glutinosa, a plant widely found in a large region of Saudi Arabia, as a bioreductant. The as-prepared Pd NPs were characterized using ultraviolet-visible (UV-vis) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform-infrared spectroscopy (FT-IR). The hydroxyl groups of the plant extract (PE) molecules were found mainly responsible for the reduction and growth of Pd NPs. FT-IR analysis confirmed the dual role of the PE, both as a bioreductant as well as a capping ligand, which stabilizes the surface of Pd NPs. The crystalline nature of the Pd NPs was identified using XRD analysis which confirmed the formation of a face-centered cubic structure (JCPDS: 87-0641, space group: Fm3m (225)). Furthermore, the as-synthesized Pd NPs demonstrated excellent catalytic activity towards the Suzuki coupling reaction under aqueous and aerobic conditions. Kinetic studies of the catalytic reaction monitored using GC confirmed that the reaction completes in less than 5 minutes.

  19. Adsorption-Driven Catalytic and Photocatalytic Activity of Phase Tuned In2S3 Nanocrystals Synthesized via Ionic Liquids.

    Science.gov (United States)

    Sharma, Rahul Kumar; Chouryal, Yogendra Nath; Chaudhari, Sushmita; Saravanakumar, Jeganathan; Dey, Suhash Ranjan; Ghosh, Pushpal

    2017-03-14

    Phase tuned quantum confined In2S3 nanocrystals are accessible solvothermally using task-specific ionic liquids (ILs) as structure directing agents. Selective tuning of size, shape, morphology and, most importantly, crystal phase of In2S3 is achieved by changing the alkyl side chain length, the H-bonding and aromatic -stacking ability of the 1-alkyl-3- methylimidazolium bromide ILs, [Cnmim]Br (n=2,4,6,8 and 10). It is observed that crystallite size is significantly less when ILs are used compared to the synthesis without ILs keeping the other reaction parameters same. At 150oC, when no IL is used, pure tetragonal form of -In2S3 appears however in presence of [Cnmim]Br [n=2,4], at the same reaction condition, a pure cubic phase crystallizes. However in case of methylimidazolium bromides with longer pendant alkyl chains such as hexyl (C6), octyl (C8) or decyl (C10), nanoparticles of the tetragonal polymorph form. Likewise, judicious choice of reaction temperature and precursors has a profound effect to obtain phase pure and morphology controlled nanocrystals. Furthermore, the adsorption driven catalytic and photocatalytic activity of as-prepared nanosized indium sulphide is confirmed by studying the degradation of crystal violet (CV) dye in presence of dark and visible light. Maximum 94.8 % catalytic efficiency is obtained for the In2S3 nanocrystals using tetramethylammonium bromide (TMAB) ionic liquid.

  20. Catalytic activity of phosphorus and steam modified HZSM-5 and the theoretical selection of phosphorus grafting model

    Institute of Scientific and Technical Information of China (English)

    Renqing Lü; Zuogang Cao; Xinhai Liu

    2008-01-01

    The modification of HZSM-5 zeolite with phosphorus and steam has been studied. Results show that 1% phospho-rus and steam modified HZSM-5 has the highest catalytic activity for n-heptane. Physicochemical and catalytic properties of 1% phosphorus and steam modified HZSM-5 zeolites have been investigated. The X-ray diffraction (XRD) results exhibit that there is considerable variation in the relative intensity of the individual diffraction peaks. The acidity of the samples decreases with an increase in the steaming temperature, which is determined by the IR of adsorbed pyridine and temperature programmed desorption (TPD) of ammonia. The oxidation state of phosphorus shown by XPS is +5, and a model for surface structure modification is proposed. The nitrogen adsorption isotherm for all samples is a combination of type Ⅰ and type Ⅳ, all hysteresis loops resemble the H4-type. The density functional and cluster model methods have been invoked to select the phosphorus grafting model, and it was found that the phosphorus grafting model were more probable in the form of the terminal oxygen coordinating with aluminum.

  1. One-step preparation of Fe3O4/Pd@polypyrrole composites with enhanced catalytic activity and stability.

    Science.gov (United States)

    Zhang, Hui; Liu, Yang; Wu, Jie; Xin, Baifu

    2016-08-15

    Core/shell Fe3O4/Pd@polypyrrole (PPy) composites with a Fe3O4 core and a PPy shell embedding Pd nanoparticles were prepared in one-step. The diameter of highly dispersed Pd nanoparticles was as small as 2.9nm owing to coordination interaction generated between Pd(2+) ions and amino groups on PPy chains. The outer PPy shell was only 6.8nm: on one hand, the coverage was beneficial to improving the stability of resulting composites; on the other hand, the shell was thin enough to permit free contact between embedding Pd nanoparticles and reactants. Additionally, the as-prepared Fe3O4/Pd@PPy composites displayed good magnetic separation property due to incorporation of Fe3O4 nanospheres. Based on above merits, they served as suitable catalyst candidates. Their catalytic performance and reusability were evaluated by reduction of 4-nitrophenol with sodium borohydride as reducing agent. Compared with traditional Fe3O4/Pd composites, Fe3O4/Pd@PPy composites not only showed superior catalytic activity; but also exhibited much better stability in successive cycling tests.

  2. File list: Oth.EmF.05.Trp53.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

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  9. 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.

  10. Removal of aqueous oxalic acid by heterogeneous catalytic ozonation with MnOx/sewage sludge-derived activated carbon as catalysts.

    Science.gov (United States)

    Huang, Yuanxing; Sun, Yaru; Xu, Zhihua; Luo, Mengyu; Zhu, Chunlei; Li, Liang

    2017-01-01

    MnOx/sewage sludge-derived activated carbon (MnOx/SAC) was prepared as catalysts to improve the performance of aqueous oxalic acid degradation by ozonation. The results indicated that MnOx/SAC had excellent catalytic activity in mineralization of oxalic acid during heterogeneous catalytic ozonation process. MnOx/SAC with a manganese load of 30% exhibited the strongest catalytic activity under the condition of solution pH3.5, which enhanced the oxalic acid removal from 10.3% to 92.2% in 60min compared with that treated by ozone alone. Increase of catalyst dosage and aqueous ozone concentration was advantageous for oxalic acid removal from water. On the basis of catalyst characterization analysis and the observation of inhibitory effect induced by higher pH, less catalyst dosage as well as the presence of hydroxyl radical scavenger, it was deduced that the reaction mechanism involved both hydroxyl radicals attack and surface reactions.

  11. 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

  12. 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.

  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. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(Ⅱ)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    LI Chunxiang; YAN Yongsheng; XU Wanzhen

    2008-01-01

    Catalysts based on Co(Ⅱ) supported on active carbon were prepared and loaded in static bed.The hydroquinone wouid be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(Ⅱ)/active carbon catalyst.After activate treatment, the active carbon was immerged in cobaltoas nitrate solution, then put into a drying oven, Co(Ⅱ) could be loaded on the micro-surface of carbon.Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(Ⅱ) was used to reduce activation energy of hydroquinone.Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard.Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(Ⅱ).The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃, pH 5 and reaction time 2.5h.

  15. CATALYTIC WET PEROXIDE OXIDATION OF HYDROQUINONE WITH Co(II)/ACTIVE CARBON CATALYST LOADED IN STATIC BED

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Catalysts based on Co(II) supported on active carbon were prepared and loaded in static bed. The hydroquinone would be degraded completely after treated by Catalytic wet peroxide oxidation method with Co(II)/active carbon catalyst. After activate treatment, the active carbon was immerged in cobaltous nitrate solution, then put into a drying oven, Co(II) could be loaded on the micro-surface of carbon. Taking the static bed as the equipment, the absorption of active carbon and catalysis of Co(II) was used to reduce activation energy of hydroquinone. Thus hydroquinone could be drastically degraded and the effluent can be drained under the standard. Referring to Fenton reaction mechanism, experiment had been done to study the heterogeneous catalyzed oxidation mechanism of Co(II). The degradation rate of hydroquinone effluent could be achieved to 92% when treated in four columns at H2O2 concentration 10%, reaction temperature 40℃ , pH 5 and reaction time 2.5h.

  16. Phosphorylation of Ser-204 and Tyr-405 in human malonyl-CoA decarboxylase expressed in silkworm Bombyx mori regulates catalytic decarboxylase activity.

    Science.gov (United States)

    Hwang, In-Wook; Makishima, Yu; Suzuki, Tomohiro; Kato, Tatsuya; Park, Sungjo; Terzic, Andre; Chung, Shin-Kyo; Park, Enoch Y

    2015-11-01

    Decarboxylation of malonyl-CoA to acetyl-CoA by malonyl-CoA decarboxylase (MCD; EC 4.1.1.9) is a vital catalytic reaction of lipid metabolism. While it is established that phosphorylation of MCD modulates the enzymatic activity, the specific phosphorylation sites associated with the catalytic function have not been documented due to lack of sufficient production of MCD with proper post-translational modifications. Here, we used the silkworm-based Bombyx mori nucleopolyhedrovirus (BmNPV) bacmid system to express human MCD (hMCD) and mapped phosphorylation effects on enzymatic function. Purified MCD from silkworm displayed post-translational phosphorylation and demonstrated coherent enzymatic activity with high yield (-200 μg/silkworm). Point mutations in putative phosphorylation sites, Ser-204 or Tyr-405 of hMCD, identified by bioinformatics and proteomics analyses reduced the catalytic activity, underscoring the functional significance of phosphorylation in modulating decarboxylase-based catalysis. Identified phosphorylated residues are distinct from the decarboxylation catalytic site, implicating a phosphorylation-induced global conformational change of MCD as responsible in altering catalytic function. We conclude that phosphorylation of Ser-204 and Tyr-405 regulates the decarboxylase function of hMCD leveraging the silkworm-based BmNPV bacmid expression system that offers a fail-safe eukaryotic production platform implementing proper post-translational modification such as phosphorylation.

  17. Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes.

    Science.gov (United States)

    Liu, Yan; Sun, Dezhi

    2007-05-08

    In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.

  18. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.

    Science.gov (United States)

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K

    2010-09-07

    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

  19. Activity and leaching features of zinc-aluminum ferrites in catalytic wet oxidation of phenol.

    Science.gov (United States)

    Xu, Aihua; Yang, Min; Qiao, Ruiping; Du, Hongzhang; Sun, Chenglin

    2007-08-17

    A series of ZnFe(2-x)Al(x)O(4) spinel type catalysts prepared by sol-gel method have been characterized and tested for catalytic wet oxidation (CWO) of phenol with pure oxygen. The iron species existed in these materials as aggregated iron oxide clusters and Fe3+ species in octahedral sites. With a decrease in iron content the concentration of the first iron species decreased and the latter increased. Complete phenol conversions and high chemical oxygen demand (COD) removals were obtained for all catalysts during phenol degradation at mild reaction conditions (160 degrees C and 1.0 MPa of oxygen pressure). Increasing with the concentration of Fe3+ species in octahedral sites, induction period became significantly shortened. After phenol was completely degraded, the concomitant recycling of the leaching Fe3+ ions back to the catalyst surface was observed, and in this case it is possible to perform successful CWO reactions with some cycles. It is also suggested that during the reaction the Fe3+ cations coordinated in octahedral sites in the ZnFe(2-x)Al(x)O(4) catalysts are resistant to acid leaching, but the reduced Fe2+ cations become much more labile, leading to increased Fe leaching.

  20. Tuning size and catalytic activity of nano-clusters of cobalt oxide

    Indian Academy of Sciences (India)

    R Venkat Narayan; Vinod Kanniah; Aruna Dhathathreyan

    2006-03-01

    Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4-6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.

  1. 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.

  2. Detailed characterization of the cooperative mechanism of Ca(2+) binding and catalytic activation in the Ca(2+) transport (SERCA) ATPase.

    Science.gov (United States)

    Zhang, Z; Lewis, D; Strock, C; Inesi, G; Nakasako, M; Nomura, H; Toyoshima, C

    2000-08-01

    Expression of heterologous SERCA1a ATPase in Cos-1 cells was optimized to yield levels that account for 10-15% of the microsomal protein, as revealed by protein staining on electrophoretic gels. This high level of expression significantly improved our characterization of mutants, including direct measurements of Ca(2+) binding by the ATPase in the absence of ATP, and measurements of various enzyme functions in the presence of ATP or P(i). Mutational analysis distinguished two groups of amino acids within the transmembrane domain: The first group includes Glu771 (M5), Thr799 (M6), Asp800 (M6), and Glu908 (M8), whose individual mutations totally inhibit binding of the two Ca(2+) required for activation of one ATPase molecule. The second group includes Glu309 (M4) and Asn796 (M6), whose individual or combined mutations inhibit binding of only one and the same Ca(2+). The effects of mutations of these amino acids were interpreted in the light of recent information on the ATPase high-resolution structure, explaining the mechanism of Ca(2+) binding and catalytic activation in terms of two cooperative sites. The Glu771, Thr799, and Asp800 side chains contribute prominently to site 1, together with less prominent contributions by Asn768 and Glu908. The Glu309, Asn796, and Asp800 side chains, as well as the Ala305 (and possibly Val304 and Ile307) carbonyl oxygen, contribute to site 2. Sequential binding begins with Ca(2+) occupancy of site 1, followed by transition to a conformation (E') sensitive to Ca(2+) inhibition of enzyme phosphorylation by P(i), but still unable to utilize ATP. The E' conformation accepts the second Ca(2+) on site 2, producing then a conformation (E' ') which is able to utilize ATP. Mutations of residues (Asp813 and Asp818) in the M6/M7 loop reduce Ca(2+) affinity and catalytic turnover, suggesting a strong influence of this loop on the correct positioning of the M6 helix. Mutation of Asp351 (at the catalytic site within the cytosolic domain

  3. Facile synthesis of catalytically active CeO2-Gd2O3 solid solutions for soot oxidation

    Indian Academy of Sciences (India)

    D Naga Durgasri; T Vinodkumar; Benjaram M Reddy

    2014-03-01

    CeO2-Gd2O3 oxides were synthesized by a modified coprecipitation method and subjected to thermal treatments at different temperatures to understand their thermal behaviour. The obtained samples were characterized by XRD, BET, TEM, Raman and TPR techniques. Catalytic efficiencies for oxygen storage/release capacity (OSC) and soot oxidation were evaluated by a thermogravimetric (TG) method. XRD and Raman results indicated the formation of Ce0.8Gd0.2O2− (CG) solid solutions at lower calcination temperatures, and TEM studies confirmed nanosized nature of the particles. 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 oxidation rate of soot compared to pure ceria.

  4. Crystal structure of the DNA cytosine deaminase APOBEC3F: the catalytically active and HIV-1 Vif-binding domain.

    Science.gov (United States)

    Bohn, Markus-Frederik; Shandilya, Shivender M D; Albin, John S; Kouno, Takahide; Anderson, Brett D; McDougle, Rebecca M; Carpenter, Michael A; Rathore, Anurag; Evans, Leah; Davis, Ahkillah N; Zhang, Jingying; Lu, Yongjian; Somasundaran, Mohan; Matsuo, Hiroshi; Harris, Reuben S; Schiffer, Celia A

    2013-06-04

    Human APOBEC3F is an antiretroviral single-strand DNA cytosine deaminase, susceptible to degradation by the HIV-1 protein Vif. In this study the crystal structure of the HIV Vif binding, catalytically active, C-terminal domain of APOBEC3F (A3F-CTD) was determined. The A3F-CTD shares structural motifs with portions of APOBEC3G-CTD, APOBEC3C, and APOBEC2. Residues identified to be critical for Vif-dependent degradation of APOBEC3F all fit within a predominantly negatively charged contiguous region on the surface of A3F-CTD. Specific sequence motifs, previously shown to play a role in Vif susceptibility and virion encapsidation, are conserved across APOBEC3s and between APOBEC3s and HIV-1 Vif. In this structure these motifs pack against each other at intermolecular interfaces, providing potential insights both into APOBEC3 oligomerization and Vif interactions.

  5. Comparison of catalytic activity of bismuth substituted cobalt ferrite nanoparticles synthesized by combustion and co-precipitation method

    Science.gov (United States)

    Kiran, Venkat Savunthari; Sumathi, Shanmugam

    2017-01-01

    In this study, cobalt ferrite and bismuth substituted cobalt ferrite (CoFe2-xBixO4x=0, 0.1) nanoparticles were synthesized by two different methods viz combustion and co-precipitation. The nanoparticles were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance spectroscopy (DRS), scanning electron microscopy-energy dispersive X-ray analyzer (SEM-EDX) and vibrating sample magnetometer (VSM). The results of powder XRD pattern showed an increase in lattice parameter and decrease in particle size of cobalt ferrite by the substitution of bismuth. Catalytic activity of cobalt ferrite and bismuth substituted cobalt ferrite nanoparticles synthesized by two different methods were compared for the reduction of 4-nitrophenol to 4-aminophenol using NaBH4 as a reducing agent.

  6. 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.

  7. Postassembly Transformation of a Catalytically Active Composite Material, Pt@ZIF-8, via Solvent-Assisted Linker Exchange.

    Science.gov (United States)

    Stephenson, Casey J; Hupp, Joseph T; Farha, Omar K

    2016-02-15

    2-Methylimidazolate linkers of Pt@ZIF-8 are exchanged with imidazolate using solvent-assisted linker exchange (SALE) to expand the apertures of the parent material and create Pt@SALEM-2. Characterization of the material before and after SALE was performed. Both materials are active as catalysts for the hydrogenation of 1-octene, whereas the hydrogenation of cis-cyclohexene occurred only with Pt@SALEM-2, consistent with larger apertures for the daughter material. The largest substrate, β-pinene, proved to be unreactive with H2 when either material was employed as a candidate catalyst, supporting the contention that substrate molecules, for both composites, must traverse the metal-organic framework component in order to reach the catalytic nanoparticles.

  8. High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

    Science.gov (United States)

    Primo, Ana; Esteve-Adell, Ivan; Blandez, Juan F.; Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Candu, Natalia; Coman, Simona M.; Parvulescu, Vasile I.; García, Hermenegildo

    2015-10-01

    Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 °C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C-N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets.

  9. Increasing the catalytic activity of Bilirubin oxidase from Bacillus pumilus: Importance of host strain and chaperones proteins.

    Science.gov (United States)

    Gounel, Sébastien; Rouhana, Jad; Stines-Chaumeil, Claire; Cadet, Marine; Mano, Nicolas

    2016-07-20

    Aggregation of recombinant proteins into inclusion bodies (IBs) is the main problem of the expression of multicopper oxidase in Escherichia coli. It is usually attributed to inefficient folding of proteins due to the lack of copper and/or unavailability of chaperone proteins. The general strategies reported to overcome this issue have been focused on increasing the intracellular copper concentration. Here we report a complementary method to optimize the expression in E. coli of a promising Bilirubin oxidase (BOD) isolated from Bacillus pumilus. First, as this BOD has a disulfide bridge, we switched E.coli strain from BL21 (DE3) to Origami B (DE3), known to promote the formation of disulfide bridges in the bacterial cytoplasm. In a second step, we investigate the effect of co-expression of chaperone proteins on the protein production and specific activity. Our strategy allowed increasing the final amount of enzyme by 858% and its catalytic rate constant by 83%.

  10. Enhanced catalytic activity of gold nanoparticles doped in a mesoporous organic gel based on polymeric phloroglucinol carboxylic acid-formaldehyde.

    Science.gov (United States)

    Yang, Han; Nagai, Keiji; Abe, Toshiyuki; Homma, Hirofumi; Norimatsu, Takayoshi; Ramaraj, Ramasamy

    2009-09-01

    Gold nanoparticles were supported by a phloroglucinolcarboxylic acid-formaldehyde (PF) gel, a new organic gel with a 30 nm spheroid-like structure. The surface area of the PF gel with gold nanoparticles was 550 m(2)/g. Gold nanoparticles supported on a PF gel exhibited catalytic activity in the reduction of 4-nitrophenol with a reaction rate constant of 7.4 x 10(-3) s(-1), which is high in the reported heterogeneous reaction system. The adsorption behavior of 4-nitrophenol into the gel support was observed by ultraviolet-visible absorption spectroscopy. Gold nanoparticles in the PF network were characterized by scanning electron microscopy, atomic force microscopy, and transmission electron microscopy observation. The high reduction rate would be attributed to the extraction and diffusion of the reactant through the pores of a PF gel support to encounter the highly dispersed gold nanoparticles on the surface and inside the material.

  11. CoMn2O4 hierarchical microspheres with high catalytic activity towards p-nitrophenol reduction.

    Science.gov (United States)

    Shi, Xiaohui; Zheng, Fangcai; Yan, Nan; Chen, Qianwang

    2014-10-07

    The CoMn2O4 hierarchical microspheres assembled by nanosheets through thermal decomposition of the precursor at different temperatures were first used as catalysts in the reduction of p-nitrophenol to p-aminophenol. The sample prepared at 500 °C shows the highest catalytic activity (kapp 14.95 × 10(-3) s(-1)), which is even higher than some results reported for noble metal particles (Au, Ag and Pd). It is suggested that the presence of metal oxide with 'd(7)' (Co element) and 'd(5)' (Mn element) electronic configurations and the special morphology of CoMn2O4 hierarchical microspheres are beneficial to the reduction of p-nitrophenol to p-aminophenol.

  12. TRP channels in prostate cancer: the good,the bad and the ugly?

    Institute of Scientific and Technical Information of China (English)

    Dimitra Gkikal; Natalia Prevarskaya

    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.

  13. 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.

  14. Iridium ultrasmall nanoparticles, worm-like chain nanowires, and porous nanodendrites: One-pot solvothermal synthesis and catalytic CO oxidation activity

    Science.gov (United States)

    Zhang, Tao; Li, Shuai-Chen; Zhu, Wei; Ke, Jun; Yu, Jing-Wen; Zhang, Zhi-Ping; Dai, Lin-Xiu; Gu, Jun; Zhang, Ya-Wen

    2016-06-01

    We report a facile one-pot solvothermal synthesis of monodisperse iridium (Ir) ultrasmall (1.5-2.5 nm in diameter) nanoparticles (NPs), worm-like chain nanowires (NWs), and porous nanodendrites (NDs), for which CO oxidation reaction has been employed as a probe reaction to investigate the effects of nanoparticle size and surface-capping organics on the catalytic activities. Time-dependent experiments revealed that an oriented attachment mechanism induced by the strong adsorption of halide anions (Br- and I-) on specific facet of Ir nanoclusters or by decreasing the reduction rate of Ir precursors with changing their concentrations during the synthesis was responsible for the formation of Ir NWs and NDs. Annealing tests indicated that an O2-H2 atmosphere treatment turned out to be an effective measure to clean up the surface-capping organics of Ir NPs supported on commercial SiO2. Catalytic CO oxidation reaction illustrated that a significant improvement in the catalytic activity of CO oxidation reaction was achieved together with the changing of activation energies after such atmosphere treatment for the supported catalysts of the ultrasmall Ir NPs. It is noteworthy that this enhancement in catalytic activity could be ascribed to the changes in the surface status (including populations of Ir species in metallic and oxidized states, removal of surface capping organics, the variety of active sites, and total effective active site number) for the supported nanocatalysts during the atmosphere treatment.

  15. TRP channel gene expression in the mouse retina.

    Science.gov (United States)

    Gilliam, Jared C; Wensel, Theodore G

    2011-12-08

    In order to identify candidate cation channels important for retinal physiology, 28 TRP channel genes were surveyed for expression in the mouse retina. Transcripts for all TRP channels were detected by RT-PCR and sequencing. Northern blotting revealed that mRNAs for 12 TRP channel genes are enriched in the retina. The strongest signals were observed for TRPC1, TRPC3, TRPM1, TRPM3, and TRPML1, and clear signals were obtained for TRPC4, TRPM7, TRPP2, TRPV2, and TRPV4. In situ hybridization and immunofluorescence revealed widespread expression throughout multiple retinal layers for TRPC1, TRPC3, TRPC4, TRPML1, PKD1, and TRPP2. Striking localization of enhanced mRNA expression was observed for TRPC1 in the photoreceptor inner segment layer, for TRPM1 in the inner nuclear layer (INL), for TRPM3 in the INL, and for TRPML1 in the outer plexiform and nuclear layers. Strong immunofluorescence signal in cone outer segments was observed for TRPM7 and TRPP2. TRPC5 immunostaining was largely confined to INL cells immediately adjacent to the inner plexiform layer. TRPV2 antibodies stained photoreceptor axons in the outer plexiform layer. Expression of TRPM1 splice variants was strong in the ciliary body, whereas TRPM3 was strongly expressed in the retinal pigmented epithelium.

  16. Synthesis of PS/Ag nanocomposite spheres with catalytic and antibacterial activities.

    Science.gov (United States)

    Deng, Ziwei; Zhu, Haibao; Peng, Bo; Chen, Hong; Sun, Yuanfang; Gang, Xiaodong; Jin, Pujun; Wang, Juanli

    2012-10-24

    This paper describes a simple, mild, and environmentally friendly approach to synthesize polystyrene/Ag (PS/Ag) nanocomposite spheres, which makes use of both reducing and stabilizing functions of polyvinylpyrrolidone (PVP) in aqueous media. In this approach, monodisperse polystyrene (PS) spheres, which are used as templates for the synthesis of core-shell nanocomposite spheres, are sulfonated first. Then, [Ag(NH(3))(2)](+) ions are adsorbed onto the surface of the PS template spheres via electrostatic attraction between -SO(3)H groups (grafted on the surface of the PS template spheres) and [Ag(NH(3))(2)](+) ions. [Ag(NH(3))(2)](+) ions are then reduced by and simultaneously protected by PVP. In this way, the PS/Ag nanocomposite spheres in aqueous media are obtained through a so-called one-pot method. Neither additional reducing agents nor toxic organic solvents are utilized during the synthesis process. Furthermore, the coverage degree and the particle size of Ag nanoparticles on PS/Ag nanocomposite spheres is easily tuned by changing the concentration of [Ag(NH(3))(2)](+) ions in aqueous media. Moreover, these PS/Ag nanocomposite spheres can be used as catalyst for the reduction of organic dyes and as antibacterial agents against Salmonella and Escherichia coli. In the present study, these PS/Ag nanocomposite spheres exhibit excellent catalytic properties (both in efficiency and recyclability) for the reduction of organic dyes, and the preliminary antibacterial assays indicate that these PS/Ag nanocomposite spheres also possess extraordinary antibacterial abilities against Salmonella and Escherichia coli.

  17. E. coli histidine triad nucleotide binding protein 1 (ecHinT) is a catalytic regulator of D-alanine dehydrogenase (DadA) activity in vivo.

    Science.gov (United States)

    Bardaweel, Sanaa; Ghosh, Brahma; Chou, Tsui-Fen; Sadowsky, Michael J; Wagner, Carston R

    2011-01-01

    Histidine triad nucleotide binding proteins (Hints) are highly conserved members of the histidine triad (HIT) protein superfamily. Hints comprise the most ancient branch of this superfamily and can be found in Archaea, Bacteria, and Eukaryota. Prokaryotic genomes, including a wide diversity of both gram-negative and gram-positive bacteria, typically have one Hint gene encoded by hinT (ycfF in E. coli). Despite their ubiquity, the foundational reason for the wide-spread conservation of Hints across all kingdoms of life remains a mystery. In this study, we used a combination of phenotypic screening and complementation analyses with wild-type and hinT knock-out Escherichia coli strains to show that catalytically active ecHinT is required in E. coli for growth on D-alanine as a sole carbon source. We demonstrate that the expression of catalytically active ecHinT is essential for the activity of the enzyme D-alanine dehydrogenase (DadA) (equivalent to D-amino acid oxidase in eukaryotes), a necessary component of the D-alanine catabolic pathway. Site-directed mutagenesis studies revealed that catalytically active C-terminal mutants of ecHinT are unable to activate DadA activity. In addition, we have designed and synthesized the first cell-permeable inhibitor of ecHinT and demonstrated that the wild-type E. coli treated with the inhibitor exhibited the same phenotype observed for the hinT knock-out strain. These results reveal that the catalytic activity and structure of ecHinT is essential for DadA function and therefore alanine metabolism in E. coli. Moreover, they provide the first biochemical evidence linking the catalytic activity of this ubiquitous protein to the biological function of Hints in Escherichia coli.

  18. E. coli histidine triad nucleotide binding protein 1 (ecHinT is a catalytic regulator of D-alanine dehydrogenase (DadA activity in vivo.

    Directory of Open Access Journals (Sweden)

    Sanaa Bardaweel

    Full Text Available Histidine triad nucleotide binding proteins (Hints are highly conserved members of the histidine triad (HIT protein superfamily. Hints comprise the most ancient branch of this superfamily and can be found in Archaea, Bacteria, and Eukaryota. Prokaryotic genomes, including a wide diversity of both gram-negative and gram-positive bacteria, typically have one Hint gene encoded by hinT (ycfF in E. coli. Despite their ubiquity, the foundational reason for the wide-spread conservation of Hints across all kingdoms of life remains a mystery. In this study, we used a combination of phenotypic screening and complementation analyses with wild-type and hinT knock-out Escherichia coli strains to show that catalytically active ecHinT is required in E. coli for growth on D-alanine as a sole carbon source. We demonstrate that the expression of catalytically active ecHinT is essential for the activity of the enzyme D-alanine dehydrogenase (DadA (equivalent to D-amino acid oxidase in eukaryotes, a necessary component of the D-alanine catabolic pathway. Site-directed mutagenesis studies revealed that catalytically active C-terminal mutants of ecHinT are unable to activate DadA activity. In addition, we have designed and synthesized the first cell-permeable inhibitor of ecHinT and demonstrated that the wild-type E. coli treated with the inhibitor exhibited the same phenotype observed for the hinT knock-out strain. These results reveal that the catalytic activity and structure of ecHinT is essential for DadA function and therefore alanine metabolism in E. coli. Moreover, they provide the first biochemical evidence linking the catalytic activity of this ubiquitous protein to the biological function of Hints in Escherichia coli.

  19. Functional analyses for tRNase Z variants: an aspartate and a histidine in the active site are essential for the catalytic activity.

    Science.gov (United States)

    Elbarbary, Reyad A; Takaku, Hiroaki; Nashimoto, Masayuki

    2008-12-01

    We performed functional analyses for various single amino-acid substitution variants of Escherichia coli, Bacillus subtilis, and human tRNase Zs. The well-conserved six histidine, His(I)-His(VI), and two aspartate, Asp(I) and Asp(II), residues together with metal ions are thought to form the active site of tRNase Z. The Mn(2+)-rescue analysis for Thermotoga maritima tRNase Z(S) has suggested that Asp(I) and His(V) directly contribute the proton transfer for the catalysis, and a catalytic mechanism has been proposed. However, experimental evidence supporting the proposed mechanism was limited. Here we intensively examined E. coli and B. subtilis tRNase Z(S) variants and human tRNase Z(L) variants for cleavage activities on pre-tRNAs in the presence of Mg(2+) or Mn(2+) ions. We observed that the Mn(2+) ions cannot rescue the activities of Asp(I)Ala and His(V)Ala variants from each species, which are lost in the presence of Mg(2+). This observation may support the proposed catalytic mechanism.

  20. Simultaneous removal of NO x and SO2 by low-temperature selective catalytic reduction over modified activated carbon catalysts

    Science.gov (United States)

    Liu, Ye; Ning, Ping; Li, Kai; Tang, Lihong; Hao, Jiming; Song, Xin; Zhang, Guijian; Wang, Chi

    2017-03-01

    A series of modified porous activated carbon (AC) catalysts prepared by impregnation were investigated for the low-temperature (≤250°C) selective catalytic reduction (SCR) of NO x with NH3 with simultaneous removal of SO2. The effects of various preparation conditions and reaction conditions on NO and SO2 conversions were observed, such as support type, active components, copper loading, calcination temperature and presence of H2O and O2. The modified AC catalysts were characterized by BET, XRD, TG and TPX methods. The activity test results showed that the optimal catalyst is 15% Cu/WCSAC which can provide 52% NO conversion and 68% SO2 conversion simultaneously at 175°C with a space velocity of 30000 h‒1, and the optimal calcination temperature was 500°C. The presence of H2O could inhibit NO conversion and promote the SO2 conversion. The effect of O2 (0-5%) was evaluated, and the NO and SO2 conversions were best when the concentration of O2 was 3%. Research demonstrated that Cu/WCSAC catalyst was a kind of potential catalysts due to the amorphous phase, high specific areas and high active ability.

  1. Walker mutations reveal loose relationship between catalytic and channel-gating activities of purified CFTR (cystic fibrosis transmembrane conductance regulator).

    Science.gov (United States)

    Ramjeesingh, M; Li, C; Garami, E; Huan, L J; Galley, K; Wang, Y; Bear, C E

    1999-02-02

    The cystic fibrosis transmembrane conductance regulator (CFTR) functions as an ATPase and as a chloride channel. It has been hypothesized, on the basis of electrophysiological findings, that the catalytic activity of CFTR is tightly coupled to the opening and closing of the channel gate. In the present study, to determine the structural basis for the ATPase activity of CFTR, we assessed the effect of mutations within the "Walker A" consensus motifs on ATP hydrolysis by the purified, intact protein. Mutation of the lysine residue in the "Walker A" motif of either the first nucleotide binding fold (CFTRK464A) or the second nucleotide binding fold (CFTRK1250A) inhibited the ATPase activity of the purified intact CFTR protein significantly, by greater than 50%. This finding suggests that the two nucleotide binding folds of CFTR are functioning cooperatively in catalysis. However, the rate of channel gating was only significantly inhibited in one of these purified mutants, CFTRK1250A, suggesting that ATPase activity may not be tightly coupled to channel gating as previously hypothesized.

  2. Structural and mechanistic analysis of engineered trichodiene synthase enzymes from Trichoderma harzianum: towards higher catalytic activities empowering sustainable agriculture.

    Science.gov (United States)

    Kumari, Indu; Chaudhary, Nitika; Sandhu, Padmani; Ahmed, Mushtaq; Akhter, Yusuf

    2016-06-01

    Trichoderma spp. are well-known bioagents for the plant growth promotion and pathogen suppression. The beneficial activities of the fungus Trichoderma spp. are attributed to their ability to produce and secrete certain secondary metabolites such as trichodermin that belongs to trichothecene family of molecules. The initial steps of trichodermin biosynthetic pathway in Trichoderma are similar to the trichothecenes from Fusarium sporotrichioides. Trichodiene synthase (TS) encoded by tri5 gene in Trichoderma catalyses the conversion of farnesyl pyrophosphate to trichodiene as reported earlier. In this study, we have carried out a comprehensive comparative sequence and structural analysis of the TS, which revealed the conserved residues involved in catalytic activity of the protein. In silico, modelled tertiary structure of TS protein showed stable structural behaviour during simulations. Two single-substitution mutants, i.e. D109E, D248Y and one double-substitution mutant (D109E and D248Y) of TS with potentially higher activities are screened out. The mutant proteins showed more stability than the wild type, an increased number of electrostatic interactions and better binding energies with the ligand, which further elucidates the amino acid residues involved in the reaction mechanism. These results will lead to devise strategies for higher TS activity to ultimately enhance the trichodermin production by Trichoderma spp. for its better exploitation in the sustainable agricultural practices.

  3. Catalytically Active Guanylyl Cyclase B Requires Endoplasmic Reticulum-mediated Glycosylation, and Mutations That Inhibit This Process Cause Dwarfism.

    Science.gov (United States)

    Dickey, Deborah M; Edmund, Aaron B; Otto, Neil M; Chaffee, Thomas S; Robinson, Jerid W; Potter, Lincoln R

    2016-05-20

    C-type natriuretic peptide activation of guanylyl cyclase B (GC-B), also known as natriuretic peptide receptor B or NPR2, stimulates long bone growth, and missense mutations in GC-B cause dwarfism. Four such mutants (L658F, Y708C, R776W, and G959A) bound (125)I-C-type natriuretic peptide on the surface of cells but failed to synthesize cGMP in membrane GC assays. Immunofluorescence microscopy also indicated that the mutant receptors were on the cell surface. All mutant proteins were dephosphorylated and incompletely glycosylated, but dephosphorylation did not explain the inactivation because the mutations inactivated a "constitutively phosphorylated" enzyme. Tunicamycin inhibition of glycosylation in the endoplasmic reticulum or mutation of the Asn-24 glycosylation site decreased GC activity, but neither inhibition of glycosylation in the Golgi by N-acetylglucosaminyltransferase I gene inactivation nor PNGase F deglycosylation of fully processed GC-B reduced GC activity. We conclude that endoplasmic reticulum-mediated glycosylation is required for the formation of an active catalytic, but not ligand-binding domain, and that mutations that inhibit this process cause dwarfism.

  4. Synthesis, characterization, electronic structure and catalytic activity of new ruthenium carbonyl complexes of N-[(2-pyridyl)methylidene]-2-aminothiazole

    Science.gov (United States)

    Kundu, Subhankar; Sarkar, Deblina; Jana, Mahendra Sekhar; Pramanik, Ajoy Kumar; Jana, Subrata; Mondal, Tapan Kumar

    2013-03-01

    Reaction of ruthenium carbonyls, [Ru(CO)2Cl2]n/[Ru(CO)4I2] with bidentate Schiffs base ligands derived by the condensation of pyridine-2-carboxaldehyde with 2-aminothiazole in a 1:1 mole ratio in acetonitrile led to the formation of complexes having general formula [Ru(CO)2(L)X2] (X = Cl (1) and I (2)) (L = N-[(2-pyridyl)methylidene]-2-aminothiazole). The compounds have been characterized by various analytical and spectroscopic (IR, electronic and 1H NMR) studies. In acetonitrile solution the complexes exhibit a weak broad metal-ligand to ligand charge transfer (MLLCT) band along with ILCT transitions. The compounds are emissive in room temperature upon excitation in the ILCT band. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 1.44 V for 1 and 0.94 V for 2. Catalytic activity of these compounds is investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone, cyclohexanol to cyclohexanone, cycloheptanol to cycloheptanone and cycloctanol to cycloctanone using N-methylmorpholine-N-oxide (NMO) as oxidant. The catalytic efficiency of 2 is greater than complex 1 and well correlate with the metal oxidation potential of the complexes. DFT, NBO and TDDFT calculations are employed to explain the structural and electronic features and to support the spectroscopic assignments.

  5. Catalytic activity of Ni-YSZ anodes in a single-chamber solid oxide fuel cell reactor

    Science.gov (United States)

    Savoie, Sylvio; Napporn, Teko W.; Morel, Bertrand; Meunier, Michel; Roberge, Réal

    The importance of heterogeneous catalysis in single-chamber solid oxide fuel cells (SC-SOFC) is universally recognized, but little studied. This work presents a thorough investigation of the catalytic activity of three Ni-YSZ half-cells in a well-described single-chamber reactor. One in-house electrolyte-supported and two commercially available anode-supported half-cells composed of anodes with thicknesses ranging from 50 μm to 1.52 mm are investigated. They are exposed to methane and oxygen gas mixtures within CH 4:O 2 flow rate ratios (R in) of 0.8-2.0 and furnace temperatures of 600-800 °C. The conversion of methane always results in the formation of syngas species (H 2 and CO). However, their yields vary considerably based on the individual anode, the operating temperature, and R in. The SC-reactor design and the presence of hot-spots at the reactor entrance bring the methane and oxygen conversion rates well above the limit expected from experiments carried out with anode half-cells only. Major variations in the H 2/CO ratio are observed. In lowering the temperature from 800 °C to 600 °C, it spreads from well below to well above the stoichiometric value of 2.0 expected for the partial oxidation reaction. To optimize the SC-SOFC any further, the findings stress the need to undertake even more catalytic studies of its electrode materials under actual structure and morphology as well as final reactor configuration.

  6. Some physico-chemical properties and catalytic activity of sulfate ion supported on WO3/SnO2 catalyst

    Directory of Open Access Journals (Sweden)

    M.N. Alaya

    2017-02-01

    Full Text Available Solid acid catalyst 15 wt%WO3/SnO2 was synthesized and loaded with 15 wt%SO4. The obtained catalyst was calcined at 400, 500, 650 and 800 °C. The prepared catalysts were characterized by TG-DTA, XRD, FTIR and N2 adsorption at −196 °C. The surface acidity was measured by non aqueous potentiometric titration and FT-IR spectra of chemisorbed pyridine. The catalytic performance was evaluated on the esterification of propionic acid with n-butanol in liquid phase. The TG-DTA analysis shows that the decomposition of sulfate species occurred at >500 °C. XRD measurements showed that WO3 dispersed completely on the surface of SnO2 and that the sulfating of WO3/SnO2 tends to hinder the crystallization of SnO2. The specific surface area, total pore volume and micropore volume are increased with increasing thermal treatment up to 500 °C, and then decreased gradually with a further increase in calcination temperature. The prepared catalysts possess very strong acid sites and contain both Brønsted and Lewis acid sites. The total surface acidity decreased with raising of the calcination temperature. The highest conversion of propionic acid was for 400 °C product, and decreased with an increase in calcination temperature. The effect of the reaction parameters, i.e., time of reaction, reaction temperature, and reactant molar ratio and the weight of the catalyst were also studied. The reaction obeys the second order kinetic equation with respect to propionic acid concentration. Brønsted and Lewis acid sites appeared to be needed for catalytic activity in n-butyl propionate formation.

  7. Studies relevant to the catalytic activation of carbon monoxide. Technical progress report, September 1991

    Energy Technology Data Exchange (ETDEWEB)

    Ford, P.C.

    1992-06-04

    Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.

  8. Arginine kinase of the flagellate protozoa Trypanosoma cruzi. Regulation of its expression and catalytic activity.

    Science.gov (United States)

    Alonso, G D; Pereira, C A; Remedi, M S; Paveto, M C; Cochella, L; Ivaldi, M S; Gerez de Burgos, N M; Torres, H N; Flawiá, M M

    2001-06-01

    In epimastigotes of Trypanosoma cruzi, the etiological agent of Chagas' disease, arginine kinase activity increased continuously during the exponential phase of growth. A correlation between growth rate, enzyme-specific activity and enzyme protein was observed. Arginine kinase-specific activity, expressed as a function of enzyme protein, remains roughly constant up to 18 days of culture. In the whole range of the culture time mRNA levels showed minor changes indicating that the enzyme activity is post-transcriptionally regulated. Arginine kinase could be proposed as a modulator of energetic reserves under starvation stress condition.

  9. Use of Metallopeptide Based Mimics Demonstrates That the Metalloprotein Nitrile Hydratase Requires Two Oxidized Cysteinates for Catalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Shearer, J.; Callan, P; Amie, J

    2010-01-01

    Nitrile hydratases (NHases) are non-heme Fe{sup III} or non-corrin Co{sup III} containing metalloenzymes that possess an N{sub 2}S{sub 3} ligand environment with nitrogen donors derived from amidates and sulfur donors derived from cysteinates. A closely related enzyme is thiocyanate hydrolase (SCNase), which possesses a nearly identical active-site coordination environment as CoNHase. These enzymes are redox inactive and perform hydrolytic reactions; SCNase hydrolyzes thiocyanate anions while NHase converts nitriles into amides. Herein an active CoNHase metallopeptide mimic, [Co{sup III}NHase-m1] (NHase-m1 = AcNH-CCDLP-CGVYD-PA-COOH), that contains Co{sup III} in a similar N{sub 2}S{sub 3} coordination environment as CoNHase is reported. [Co{sup III}NHase-m1] was characterized by electrospray ionization-mass spectrometry (ESI-MS), gel-permeation chromatography (GPC), Co K-edge X-ray absorption spectroscopy (Co-S: 2.21 {angstrom}; Co-N: 1.93 {angstrom}), vibrational, and optical spectroscopies. We find that [Co{sup III}NHase-m1] will perform the catalytic conversion of acrylonitrile into acrylamide with up to 58 turnovers observed after 18 h at 25 C (pH 8.0). FTIR data used in concert with calculated vibrational data (mPWPW91/aug-cc-TZVPP) demonstrates that the active form of [Co{sup III}NHase-m1] has a ligated SO{sub 2} (? = 1091 cm{sup -1}) moiety and a ligated protonated SO(H) (? = 928 cm{sup -1}) moiety; when only one oxygenated cysteinate ligand (i.e., a mono-SO{sub 2} coordination motif) or the bis-SO{sub 2} coordination motif are found within [Co{sup III}NHase-m1] no catalytic activity is observed. Calculations of the thermodynamics of ligand exchange (B3LYP/aug-cc-TZVPP) suggest that the reason for this is that the SO{sub 2}/SO(H) equatorial ligand motif promotes both water dissociation from the Co{sup III}-center and nitrile coordination to the Co{sup III}-center. In contrast, the under- or overoxidized motifs will either strongly favor a five coordinate Co

  10. Understanding the effect of post-synthesis ammonium treatment on the catalytic activity of Au/Ti-SBA-15 catalysts for the oxidation of propene

    NARCIS (Netherlands)

    Sacaliuc-Parvulescu, E.; Friedrich, H.; Palkovits, R.; Weckhuysen, B.M.; Nijhuis, T.A.

    2008-01-01

    Postsynthesis ammonium treatment induces a substantial increase in the catalytic activity of Au/Ti- SBA-15 catalysts for the direct vapor-phase epoxidation of propylene using hydrogen and oxygen. The PO formation rate of a calcined Au/Ti-SBA-15 catalyst prepared by this method increased from 4.3 mgP

  11. 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…

  12. [Standardization of measurement of catalytic activity concentration of enzymes--current situation regarding the external quality assessment program provided by the Japan Medical Association].

    Science.gov (United States)

    Maekawa, Masato

    2010-01-01

    Measurement of the catalytic activity concentration of enzymes has been standardized using a traceability chain, consisting a reference measurement system for enzyme catalytic activity and reference standard-JSCC enzyme. The Japan Medical Association (JMA) has provided an external quality assessment (EQA) survey program for clinical laboratory testing. More than 3,100 clinical laboratories participated in 2008. The EQA program indicated that standardization of the measurement of the catalytic activity concentration of enzymes has been completed for AST, ALT, LD, ALP, gammaGT, and CK in more than 90% laboratories, and for Amy and ChE in nearly 80% of laboratories. Because such a large survey program must use artificial specimens, a matrix effect cannot be avoided, especially in dry chemistry. However, the bias produced by a matrix effect usually has a predictable tendency: it can be corrected. Next, after standardization of the measurement of the catalytic activity concentration of enzymes, we should develop and use common reference intervals. On completing the standardization, we can make standard medical decisions using reference measurement systems and rules.

  13. 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.; Bonati, Matteo L. M.; Law, David J.; Sunley, Glenn J.; de Jong, Krijn P.

    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, th

  14. Molecular cloning and catalytic activity of a membrane-bound prenyl diphosphate phosphatase from Croton stellatopilosus Ohba.

    Science.gov (United States)

    Nualkaew, Natsajee; Guennewich, Nils; Springob, Karin; Klamrak, Anuwatchakit; De-Eknamkul, Wanchai; Kutchan, Toni M

    2013-07-01

    Geranylgeraniol (GGOH), a bioactive acyclic diterpene with apoptotic induction activity, is the immediate precursor of the commercial anti-peptic, plaunotol (18-hydroxy geranylgeraniol), which is found in Croton stellatopilosus (Ohba). From this plant, a cDNA encoding a prenyl diphosphate phosphatase (CsPDP), which catalyses the dephosphorylation of geranylgeranyl diphosphate (GGPP) to GGOH, was isolated using a PCR approach. The full-length cDNA contained 888bp and encoded a 33.6 kDa protein (295 amino acids) that was phylogenetically grouped into the phosphatidic acid phosphatase (PAP) enzyme family. The deduced amino acid sequence showed 6 hydrophobic transmembrane regions with 57-85% homology to the sequences of other plant PAPs. The recombinant CsPDP and its 4 truncated constructs exhibited decreasing dephosphorylation activities relative to the lengths of the N-terminal deletions. While the full-length CsPDP successfully performed the two sequential monodephosphorylation steps on GGPP to form GGOH, the larger N-terminal deletion in the truncated enzymes appeared to specifically decrease the catalytic efficiency of the second monodephosphorylation step. The information presented here on the CsPDP cDNA and factors affecting the dephosphorylation activity of its recombinant protein may eventually lead to the discovery of the specific GGPP phosphatase gene and enzyme that are involved in the formation of GGOH in the biosynthetic pathway of plaunotol in C. stellatopilosus.

  15. 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.

  16. Effect of Sulfation on Zirconia-Pillared Montmorillonite to the Catalytic Activity in Microwave-Assisted Citronellal Conversion

    Directory of Open Access Journals (Sweden)

    Is Fatimah

    2014-01-01

    Full Text Available Preparation of sulfated zirconia-pillared montmorillonite was carried out in two steps; zirconia pillarization and sulfation to zirconia-pillared montmorillonite. The prepared materials were characterized by using X-ray diffraction (XRD, measurement of the specific surface area, total pore volume and pore size distribution by the N2 adsorption method, scanning electron microscopy-energy dispersive X-ray (SEM-EDX, and surface acidity determination by using pyridine adsorption-FTIR analysis. The activity of the materials as catalysts was evaluated for a microwave-assisted conversion of citronellal. The results showed that the prepared materials had a physicochemical character that promoted high catalytic activity to convert citronellal. From varied Zr content and study of the effect of sulfation on the activity, it was found that Zr content and sulfation increase the surface acidity of the materi