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Sample records for b-c bond cleavage

  1. Substituent Directed Phototransformations of BN-Heterocycles: Elimination vs Isomerization via Selective B-C Bond Cleavage.

    PubMed

    Yang, Deng-Tao; Mellerup, Soren K; Peng, Jin-Bao; Wang, Xiang; Li, Quan-Song; Wang, Suning

    2016-09-14

    Electron-rich and -poor BN-heterocycles with benzyl-pyridyl backbones and two bulky aryls on the boron (Ar = tipp, BN-1, Ar = MesF, BN-2) have been found to display distinct molecular transformations upon irradiation by UV light. BN-1 undergoes an efficient photoelimination reaction forming a BN-phenanthrene with ΦPE = 0.25, whereas BN-2 undergoes a thermally reversible, stereoselective, and quantitative isomerization to a dark colored BN-1,3,5-cyclooctatriene (BN-1,3,5-COT, BN-2a). This unusual photoisomerization persists for other BN-heterocycles with electron-deficient aryls such as BN-3 with a benzyl-benzothiazolyl backbone and Mes(F) substituents or BN-4 with a benzyl-pyridyl backbone and two C6F5 groups on the boron. The photoisomerization of BN-4 goes beyond BN-1,3,5-COT (BN-4a), forming a new species (BN-1,3,6-COT, BN-4b) via C-F bond cleavage and [1,3]-F atom sigmatropic migration. Computational studies support that BN-4a is an intermediate in the formation of BN-4b. This work establishes that steric and electronic factors can effectively control the transformations of BN-heterocycles, allowing access to important and previously unknown BN-embedded species.

  2. Simple Bond Cleavage

    SciTech Connect

    Gary S. Groenewold

    2005-08-01

    Simple bond cleavage is a class of fragmentation reactions in which a single bond is broken, without formation of new bonds between previously unconnected atoms. Because no bond making is involved, simple bond cleavages are endothermic, and activation energies are generally higher than for rearrangement eliminations. The rate of simple bond cleavage reactions is a strong function of the internal energy of the molecular ion, which reflects a loose transition state that resembles reaction products, and has a high density of accessible states. For this reason, simple bond cleavages tend to dominate fragmentation reactions for highly energized molecular ions. Simple bond cleavages have negligible reverse activation energy, and hence they are used as valuable probes of ion thermochemistry, since the energy dependence of the reactions can be related to the bond energy. In organic mass spectrometry, simple bond cleavages of odd electron ions can be either homolytic or heterolytic, depending on whether the fragmentation is driven by the radical site or the charge site. Simple bond cleavages of even electron ions tend to be heterolytic, producing even electron product ions and neutrals.

  3. 31 CFR 315.32 - Series A, B, C, D, F, G, J, and K bonds.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 31 Money and Finance:Treasury 2 2013-07-01 2013-07-01 false Series A, B, C, D, F, G, J, and K.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.32 Series A, B, C, D, F, G, J, and K bonds. All bonds of these series have matured and no longer earn interest....

  4. 31 CFR 315.32 - Series A, B, C, D, F, G, J, and K bonds.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false Series A, B, C, D, F, G, J, and K.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.32 Series A, B, C, D, F, G, J, and K bonds. All bonds of these series have matured and no longer earn interest....

  5. 31 CFR 315.32 - Series A, B, C, D, F, G, J, and K bonds.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 31 Money and Finance: Treasury 2 2014-07-01 2014-07-01 false Series A, B, C, D, F, G, J, and K.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.32 Series A, B, C, D, F, G, J, and K bonds. All bonds of these series have matured and no longer earn interest....

  6. 31 CFR 315.32 - Series A, B, C, D, F, G, J, and K bonds.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 31 Money and Finance:Treasury 2 2012-07-01 2012-07-01 false Series A, B, C, D, F, G, J, and K.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.32 Series A, B, C, D, F, G, J, and K bonds. All bonds of these series have matured and no longer earn interest....

  7. 31 CFR 315.32 - Series A, B, C, D, F, G, J, and K bonds.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false Series A, B, C, D, F, G, J, and K.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.32 Series A, B, C, D, F, G, J, and K bonds. All bonds of these series have matured and no longer earn interest....

  8. Microbial cleavage of organic C-S bonds

    DOEpatents

    Kilbane, II, John J.

    1994-01-01

    A microbial process for selective cleavage of organic C--S bonds which may be used for reducing the sulfur content of sulfur-containing organic carbonaceous materials, Microorganisms of Rhodococcus rhodochrous and Bacillus sphaericus have been found which have the ability of selective cleavage of organic C--S bonds. Particularly preferred microorganisms are Rhodococcus rhodochrous strain ATCC 53968 and Bacillus sphaericus strain ATCC 53969 and their derivatives.

  9. Microbial cleavage of organic C-S bonds

    DOEpatents

    Kilbane, J.J. II.

    1994-10-25

    A microbial process is described for selective cleavage of organic C-S bonds which may be used for reducing the sulfur content of sulfur-containing organic carbonaceous materials. Microorganisms of Rhodococcus rhodochrous and Bacillus sphaericus have been found which have the ability of selective cleavage of organic C-S bonds. Particularly preferred microorganisms are Rhodococcus rhodochrous strain ATCC 53968 and Bacillus sphaericus strain ATCC 53969 and their derivatives.

  10. Glutamic Acid Selective Chemical Cleavage of Peptide Bonds.

    PubMed

    Nalbone, Joseph M; Lahankar, Neelam; Buissereth, Lyssa; Raj, Monika

    2016-03-04

    Site-specific hydrolysis of peptide bonds at glutamic acid under neutral aqueous conditions is reported. The method relies on the activation of the backbone amide chain at glutamic acid by the formation of a pyroglutamyl (pGlu) imide moiety. This activation increases the susceptibility of a peptide bond toward hydrolysis. The method is highly specific and demonstrates broad substrate scope including cleavage of various bioactive peptides with unnatural amino acid residues, which are unsuitable substrates for enzymatic hydrolysis.

  11. Site-selective chemical cleavage of peptide bonds.

    PubMed

    Elashal, Hader E; Raj, Monika

    2016-05-07

    Site-selective cleavage of extremely unreactive peptide bonds is a very important chemical modification that provides invaluable information regarding protein sequence, and it acts as a modulator of protein structure and function for therapeutic applications. For controlled and selective cleavage, a daunting task, chemical reagents must selectively recognize or bind to one or more amino acid residues in the peptide chain and selectively cleave a peptide bond. Building on this principle, we have developed an approach that utilizes a chemical reagent to selectively modify the serine residue in a peptide chain and leads to the cleavage of a peptide backbone at the N-terminus of the serine residue. After cleavage, modified residues can be converted back to the original fragments. This method exhibits broad substrate scope and selectively cleaves various bioactive peptides with post-translational modifications (e.g. N-acetylation and -methylation) and mutations (d- and β-amino acids), which are a known cause of age related diseases.

  12. Stille coupling via C–N bond cleavage

    PubMed Central

    Wang, Dong-Yu; Kawahata, Masatoshi; Yang, Ze-Kun; Miyamoto, Kazunori; Komagawa, Shinsuke; Yamaguchi, Kentaro; Wang, Chao; Uchiyama, Masanobu

    2016-01-01

    Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C–N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R–NMe3]+ react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod)2 and imidazole ligand together with 3.0 equivalents of CsF, affording the corresponding biaryl with broad functional group compatibility. The reaction pathway, including C–N bond cleavage step, is proposed based on the experimental and computational findings, as well as isolation and single-crystal X-ray diffraction analysis of Ni-containing intermediates. This reaction should be widely applicable for transformation of amines/quaternary ammonium salts into multi-aromatics. PMID:27686744

  13. Stille coupling via C-N bond cleavage

    NASA Astrophysics Data System (ADS)

    Wang, Dong-Yu; Kawahata, Masatoshi; Yang, Ze-Kun; Miyamoto, Kazunori; Komagawa, Shinsuke; Yamaguchi, Kentaro; Wang, Chao; Uchiyama, Masanobu

    2016-09-01

    Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C-N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R-NMe3]+ react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod)2 and imidazole ligand together with 3.0 equivalents of CsF, affording the corresponding biaryl with broad functional group compatibility. The reaction pathway, including C-N bond cleavage step, is proposed based on the experimental and computational findings, as well as isolation and single-crystal X-ray diffraction analysis of Ni-containing intermediates. This reaction should be widely applicable for transformation of amines/quaternary ammonium salts into multi-aromatics.

  14. Biotic and abiotic carbon to sulfur bond cleavage

    SciTech Connect

    Frost, J.W.

    1991-01-01

    Cleavage of aliphatic organosulfonate carbon to sulfur (C-S) bonds, a critical link in the global biogeochemical sulfur cycle, has been identified in Escherichia coli K-12. Enormous quantities of inorganic sulfate are continuously converted (Scheme I) into methanesulfonic acid 1 and acylated 3-(6-sulfo-{alpha}-D-quinovopyranosyl)-L-glycerol 2. Biocatalytic desulfurization (Scheme I) of 1 and 2, which share the structural feature of an aliphatic carbon bonded to a sulfonic acid sulfur, completes the cycle, Discovery of this desulfurization in E. coli provides an invaluable paradigm for study of a biotic process which, via the biogeochemical cycle, significantly influences the atmospheric concentration of sulfur-containing molecules.

  15. Catalyzed hydrolytic cleavage reaction of carbon-carbon bond

    SciTech Connect

    Ioffe, I.I.; Rubinskaya, E.V.

    1986-12-01

    The authors split the carbon-carbon bond for a series of simple and complex organic compounds in neutral aqueous solutions on a heterogeneous metal-containing catalyst, palladium on carbon. The experimental results are given. In each case, the catalytic effect was controlled by a blank experiment, without a catalyst, where there was no decomposition of the substrate. The occurrence of the heterogeneous-catalytic cleavage reaction of the carbon-carbon bonds in the molecules is indicated not only by their extensive conversion, but also by the almost complete depletion of the content of organic carbon, confirmed by a similar decrease in the chemical consumption of oxygen coefficient in the system, which is possible only in the complete decomposition of the organic compounds to gaseous products or with the formation of inappreciable amounts of low-molecular-weight water-soluble compounds.

  16. Cleavage of an amide bond by a ribozyme

    NASA Technical Reports Server (NTRS)

    Dai, X.; De Mesmaeker, A.; Joyce, G. F.; Miller, S. L. (Principal Investigator)

    1995-01-01

    A variant form of a group I ribozyme, optimized by in vitro evolution for its ability to catalyze magnesium-dependent phosphoester transfer reactions involving DNA substrates, also catalyzes the cleavage of an unactivated alkyl amide when that linkage is presented in the context of an oligodeoxynucleotide analog. Substrates containing an amide bond that joins either two DNA oligos, or a DNA oligo and a short peptide, are cleaved in a magnesium-dependent fashion to generate the expected products. The first-order rate constant, kcat, is 0.1 x 10(-5) min-1 to 1 x 10(-5) min-1 for the DNA-flanked substrates, which corresponds to a rate acceleration of more than 10(3) as compared with the uncatalyzed reaction.

  17. Bond cleavage of lignin model compounds into aromatic monomers using supported metal catalysts in supercritical water

    PubMed Central

    Yamaguchi, Aritomo; Mimura, Naoki; Shirai, Masayuki; Sato, Osamu

    2017-01-01

    More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units. The catalytic cleavage of C–O bonds is still challenging, and cleavage of C–C bonds is even more difficult. Here, we report cleavage of the aromatic C–O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C–C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds. PMID:28387304

  18. C-S bond cleavage by a polyketide synthase domain

    PubMed Central

    Ma, Ming; Lohman, Jeremy R.; Liu, Tao; Shen, Ben

    2015-01-01

    Leinamycin (LNM) is a sulfur-containing antitumor antibiotic featuring an unusual 1,3-dioxo-1,2-dithiolane moiety that is spiro-fused to a thiazole-containing 18-membered lactam ring. The 1,3-dioxo-1,2-dithiolane moiety is essential for LNM’s antitumor activity, by virtue of its ability to generate an episulfonium ion intermediate capable of alkylating DNA. We have previously cloned and sequenced the lnm gene cluster from Streptomyces atroolivaceus S-140. In vivo and in vitro characterizations of the LNM biosynthetic machinery have since established that: (i) the 18-membered macrolactam backbone is synthesized by LnmP, LnmQ, LnmJ, LnmI, and LnmG, (ii) the alkyl branch at C-3 of LNM is installed by LnmK, LnmL, LnmM, and LnmF, and (iii) leinamycin E1 (LNM E1), bearing a thiol moiety at C-3, is the nascent product of the LNM hybrid nonribosomal peptide synthetase (NRPS)-acyltransferase (AT)-less type I polyketide synthase (PKS). Sulfur incorporation at C-3 of LNM E1, however, has not been addressed. Here we report that: (i) the bioinformatics analysis reveals a pyridoxal phosphate (PLP)-dependent domain, we termed cysteine lyase (SH) domain (LnmJ-SH), within PKS module-8 of LnmJ; (ii) the LnmJ-SH domain catalyzes C-S bond cleavage by using l-cysteine and l-cysteine S-modified analogs as substrates through a PLP-dependent β-elimination reaction, establishing l-cysteine as the origin of sulfur at C-3 of LNM; and (iii) the LnmJ-SH domain, sharing no sequence homology with any other enzymes catalyzing C-S bond cleavage, represents a new family of PKS domains that expands the chemistry and enzymology of PKSs and might be exploited to incorporate sulfur into polyketide natural products by PKS engineering. PMID:26240335

  19. Radical induced disulfide bond cleavage within peptides via ultraviolet irradiation of an electrospray plume.

    PubMed

    Stinson, Craig A; Xia, Yu

    2013-05-21

    Radical induced disulfide bond cleavage in peptides was demonstrated by ultraviolet (UV) radiation of the electrospray ionization (ESI) plume using a low pressure mercury (LP-Hg) lamp. Tandem mass spectrometry and accurate mass measurements confirmed that the primary reaction products were due to disulfide bond cleavage to form thiol (-SH) and sulfinyl radical (-SO˙). Mechanistic studies showed that the 185 nm emission from a LP-Hg lamp was responsible for UV photolysis of atmospheric O2, which further initiated secondary radical formation and subsequent disulfide bond cleavage by radical attack. The radical induced disulfide bond cleavage was found to be analytically useful in providing rich sequence information for naturally occurring peptides containing intrachain disulfide bonds. The utility of this method was also demonstrated for facile disulfide peptide identification and characterization from protein digests.

  20. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes.

    PubMed

    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M; Hall, Michael B; Bullock, R Morris

    2016-07-04

    Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode. The structures of both the heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P-C/C-H bond cleavage, which involves C-H bond cleavage, hydride rotation, Ni-C/P-H bond formation, and P-C bond cleavage.

  1. Deficiency of Aph1B/C-γ-secretase disturbs Nrg1 cleavage and sensorimotor gating that can be reversed with antipsychotic treatment

    PubMed Central

    Dejaegere, T.; Serneels, L.; Schäfer, M. K.; Van Biervliet, J.; Horré, K.; Depboylu, C.; Alvarez-Fischer, D.; Herreman, A.; Willem, M.; Haass, C.; Höglinger, G. U.; D'Hooge, R.; De Strooper, B.

    2008-01-01

    Regulated intramembrane proteolysis by γ-secretase cleaves proteins in their transmembrane domain and is involved in important signaling pathways. At least four different γ-secretase complexes have been identified, but little is known about their biological role and specificity. Previous work has demonstrated the involvement of the Aph1A-γ-secretase complex in Notch signaling, but no specific function could be assigned to Aph1B/C-γ-secretase. We demonstrate here that the Aph1B/C-γ-secretase complex is expressed in brain areas relevant to schizophrenia pathogenesis and that Aph1B/C deficiency causes pharmacological and behavioral abnormalities that can be reversed by antipsychotic drugs. At the molecular level we find accumulation of Nrg1 fragments in the brain of Aph1BC−/− mice. Our observations gain clinical relevance by the demonstration that a Val-to-Leu mutation in the Nrg1 transmembrane domain, associated with increased risk for schizophrenia, affects γ-secretase cleavage of Nrg1. This finding suggests that dysregulation of intramembrane proteolysis of Nrg1 could increase risk for schizophrenia and related disorders. PMID:18626010

  2. Deficiency of Aph1B/C-gamma-secretase disturbs Nrg1 cleavage and sensorimotor gating that can be reversed with antipsychotic treatment.

    PubMed

    Dejaegere, T; Serneels, L; Schäfer, M K; Van Biervliet, J; Horré, K; Depboylu, C; Alvarez-Fischer, D; Herreman, A; Willem, M; Haass, C; Höglinger, G U; D'Hooge, R; De Strooper, B

    2008-07-15

    Regulated intramembrane proteolysis by gamma-secretase cleaves proteins in their transmembrane domain and is involved in important signaling pathways. At least four different gamma-secretase complexes have been identified, but little is known about their biological role and specificity. Previous work has demonstrated the involvement of the Aph1A-gamma-secretase complex in Notch signaling, but no specific function could be assigned to Aph1B/C-gamma-secretase. We demonstrate here that the Aph1B/C-gamma-secretase complex is expressed in brain areas relevant to schizophrenia pathogenesis and that Aph1B/C deficiency causes pharmacological and behavioral abnormalities that can be reversed by antipsychotic drugs. At the molecular level we find accumulation of Nrg1 fragments in the brain of Aph1BC(-/-) mice. Our observations gain clinical relevance by the demonstration that a Val-to-Leu mutation in the Nrg1 transmembrane domain, associated with increased risk for schizophrenia, affects gamma-secretase cleavage of Nrg1. This finding suggests that dysregulation of intramembrane proteolysis of Nrg1 could increase risk for schizophrenia and related disorders.

  3. Cleavage of a specific bond in troponin C by thrombin.

    PubMed

    Leavis, P C; Rosenfeld, S; Lu, R C

    1978-08-21

    Limited proteolysis of rabbit skeletal troponin C with bovine thrombin yielded two fragments, TH1 (Mr = 11000) containing Ca2+ binding regions I--III and TH2 (Mr = 6000) containing region IV. Determination of the partial sequences of the fragments established the site of cleavage at Arg120-Ala121. Secondary cleavage by thrombin at other arginyl or lysyl residues in troponin C was ruled out by the sequence data and by the amino acid compositions of the two fragments.

  4. Photocatalytic C-C Bond Cleavage and Amination of Cycloalkanols by Cerium(III) Chloride Complex.

    PubMed

    Guo, Jing-Jing; Hu, Anhua; Chen, Yilin; Sun, Jianfeng; Tang, Haoming; Zuo, Zhiwei

    2016-12-05

    A general strategy for the cleavage and amination of C-C bonds of cycloalkanols has been achieved through visible-light-induced photoredox catalysis utilizing a cerium(III) chloride complex. This operationally simple methodology has been successfully applied to a wide array of unstrained cyclic alcohols, and represents the first example of catalytic C-C bond cleavage and functionalization of unstrained secondary cycloalkanols.

  5. Microphase separation through competitive hydrogen bonding in self-assembled A-b-B/C diblock copolymer/homopolymer complexes

    NASA Astrophysics Data System (ADS)

    Hameed, Nishar; Salim, Nisa V.; Guo, Qipeng

    2009-12-01

    We present a study of microphase separation induced by competitive hydrogen bonding in A-b-B/C diblock copolymer/homopolymer complexes where the diblock copolymer A-b-B is immiscible and the homopolymer C can interact unequally with both A and B blocks through hydrogen bonding. A model system containing poly(2-vinyl pyridine)-block-poly(methyl methacrylate) (P2VP-b-PMMA) and poly(4-vinyl phenol) (PVPh) in tetrahydrofuran was investigated. In these self-assembled complexes, microphase separation takes place due to the disparity in intermolecular interactions. Specifically, PVPh and P2VP blocks interact strongly to form complex, whereas PVPh and PMMA blocks interact weakly. The hydrogen bonding interactions were revealed by infrared spectroscopy and analyzed in terms of the difference in interassociation constants (K), i.e., interaction parameters of each blocks of the block copolymer to the homopolymer and according to the random phase approximation. The phase behavior of the complexes was investigated with small-angle x-ray scattering and transmission electron microscopy. A series of morphologies including lamellae, hexagonal cylinders, wormlike microdomains, and hierarchical structures was documented as a function of the copolymer concentration. Moreover, we outlined how hydrogen bonding determines the self-assembly and causes morphological transitions in different A-b-B/C diblock copolymer/homopolymer systems with respect to the K values.

  6. Catalytic cleavage of ether C-O bonds by pincer iridium complexes.

    PubMed

    Haibach, Michael C; Lease, Nicholas; Goldman, Alan S

    2014-09-15

    The development of efficient catalytic methods to cleave the relatively unreactive C-O bonds of ethers remains an important challenge in catalysis. Building on our group's recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom-economical method for ether C-O bond cleavage.

  7. Cleavage enhancement of specific chemical bonds in DNA-Cisplatin complexes induced by X-rays

    NASA Astrophysics Data System (ADS)

    Zheng, Yi; Yao, Xiaobin; Luo, Xinglan; Fu, Xianzhi

    2014-04-01

    The chemical bond transformation of cisplatin-DNA complexes can be probed efficiently by XPS which provides a concomitant X-ray irradiation source as well. The presence to Pt could considerably increase formation of the SE induced by X-ray and that the further interaction of these LEE with DNA leads to the enhancement of bond cleavages.

  8. Carbon-Carbon Bond Cleavage in Activation of the Prodrug Nabumetone

    PubMed Central

    Varfaj, Fatbardha; Zulkifli, Siti N. A.; Park, Hyoung-Goo; Challinor, Victoria L.; De Voss, James J.

    2014-01-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbon bond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbon bond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbon bond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs. PMID:24584631

  9. Carbon-carbon bond cleavage in activation of the prodrug nabumetone.

    PubMed

    Varfaj, Fatbardha; Zulkifli, Siti N A; Park, Hyoung-Goo; Challinor, Victoria L; De Voss, James J; Ortiz de Montellano, Paul R

    2014-05-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbon bond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbon bond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbon bond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs.

  10. How the glycosyltransferase OGT catalyzes amide bond cleavage

    PubMed Central

    Janetzko, John; Trauger, Sunia A.; Lazarus, Michael B.; Walker, Suzanne

    2016-01-01

    The essential human enzyme O-GlcNAc transferase (OGT), known for modulating the functions of nuclear and cytoplasmic proteins through Ser/Thr glycosylation, was unexpectedly implicated in the proteolytic maturation of the cell cycle regulator host cell factor-1 (HCF-1). Here we show that HCF-1 cleavage occurs via glycosylation of a glutamate side chain followed by on-enzyme formation of an internal pyroglutamate, which undergoes spontaneous backbone hydrolysis. PMID:27618188

  11. Room temperature ring expansion of N-heterocyclic carbenes and B-B bond cleavage of diboron(4) compounds.

    PubMed

    Pietsch, Sabrina; Paul, Ursula; Cade, Ian A; Ingleson, Michael J; Radius, Udo; Marder, Todd B

    2015-06-15

    We report the isolation and detailed structural characterization, by solid-state and solution NMR spectroscopy, of the neutral mono- and bis-NHC adducts of bis(catecholato)diboron (B2 cat2 ). The bis-NHC adduct undergoes thermally induced rearrangement, forming a six-membered -B-C=N-C=C-N-heterocyclic ring via C-N bond cleavage and ring expansion of the NHC, whereas the mono-NHC adduct is stable. Bis(neopentylglycolato)diboron (B2 neop2 ) is much more reactive than B2 cat2 giving a ring expanded product at room temperature, demonstrating that ring expansion of NHCs can be a very facile process with significant implications for their use in catalysis.

  12. Potential of Metal-Catalyzed C-C Single Bond Cleavage for Organic Synthesis.

    PubMed

    Murakami, Masahiro; Ishida, Naoki

    2016-10-11

    Conventional organic synthesis has been mainly based upon the reactivities of π-bonds and polar σ-bonds. Carbon-carbon single bonds are nonpolar and generally far less reactive. Although they remain intact under most reaction conditions, it is possible to activate and cleave them if suitable organometallic compounds or metal catalysts are applied. Such C-C single bond cleavage reactions are attracting increasing attention in the context of synthetic chemistry because they provide a unique and more straightforward route from readily available substances to targets, while requiring significantly fewer steps. The present Perspective aims to exemplify the potential of metal-catalyzed C-C single bond cleavage for organic synthesis.

  13. Methods to produce B-C, B-P, B-N and B-S bonds in boron clusters.

    PubMed

    Olid, David; Núñez, Rosario; Viñas, Clara; Teixidor, Francesc

    2013-04-21

    Boranes, heteroboranes and metallacarboranes, all named as boron clusters, offer an alternative to typical organic molecules or organic molecular materials. Carbon and boron share the important property of self-catenation thus these elements can produce individually large and sophisticated molecules. Boron clusters and organic molecules display electronic, physical, chemical and geometrical characteristics manifestly different. These differences highlight the complementarity of organic molecules and boron clusters, and therefore the feasibility or necessity to produce hybrid molecules incorporating both types of fragments. To join these two types of fragments, or alternatively these two types of molecular compounds, tools are needed. In this review the current methods of producing boron clusters with carbon, B-C, nitrogen, B-N, phosphorus, B-P and sulphur bonds, B-S, are indicated. As there are many existing borane clusters of different sizes, heteroboranes and metallacarboranes, the revision of methods to generate the B-C, B-P, B-S, and B-N bonds has been restricted to the most widely used boron clusters; [B12H12](2-), dianionic and an example of a borane, 1,2-C2B10H12, neutral and an example of a heteroborane, and [Co(C2B9H11)2](-), monoanionic and an example of a metallacarborane.

  14. Metabolic Engineering to Develop a Pathway for the Selective Cleavage of Carbon-Nitrogen Bonds

    SciTech Connect

    John J. Kilbane II

    2005-10-01

    The objective of the project is to develop a biochemical pathway for the selective cleavage of C-N bonds in molecules found in petroleum. Specifically a novel biochemical pathway will be developed for the selective cleavage of C-N bonds in carbazole. The cleavage of the first C-N bond in carbazole is accomplished by the enzyme carbazole dioxygenase, that catalyzes the conversion of carbazole to 2-aminobiphenyl-2,3-diol. The genes encoding carbazole dioxygenase were cloned from Sphingomonas sp. GTIN11 and from Pseudomonas resinovorans CA10. The selective cleavage of the second C-N bond has been challenging, and efforts to overcome that challenge have been the focus of recent research in this project. Enrichment culture experiments succeeded in isolating bacterial cultures that can metabolize 2-aminobiphenyl, but no enzyme capable of selectively cleaving the C-N bond in 2-aminobiphenyl has been identified. Aniline is very similar to the structure of 2-aminobiphenyl and aniline dioxygenase catalyzes the conversion of aniline to catechol and ammonia. For the remainder of the project the emphasis of research will be to simultaneously express the genes for carbazole dioxygenase and for aniline dioxygenase in the same bacterial host and then to select for derivative cultures capable of using carbazole as the sole source of nitrogen.

  15. Scandium(iii) triflate-promoted serine/threonine-selective peptide bond cleavage.

    PubMed

    Ni, Jizhi; Sohma, Youhei; Kanai, Motomu

    2017-02-01

    The site-selective cleavage of peptide bonds is an important chemical modification that is useful not only for the structural determination of peptides, but also as an artificial modulator of peptide/protein function and properties. Here we report site-selective hydrolysis of peptide bonds at the Ser and Thr positions with a high conversion yield. This chemical cleavage relies on Sc(iii)-promoted N,O-acyl rearrangement and subsequent hydrolysis. The method is applicable to a broad scope of polypeptides with various functional groups, including a post-translationally modified peptide that is unsuitable for enzymatic hydrolysis. The system was further extended to site-selective cleavage of a native protein, Aβ1-42, which is closely related to the onset of Alzheimer's disease.

  16. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

    SciTech Connect

    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M.; Hall, Michael B.; Bullock, R. Morris

    2016-06-07

    Unusual cleavage of P-C and C-H bonds of the P2N2 ligand in heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode.

  17. Carbon-Carbon Bond Cleavage Reaction: Synthesis of Multisubstituted Pyrazolo[1,5-a]pyrimidines.

    PubMed

    Saikia, Pallabi; Gogoi, Sanjib; Boruah, Romesh C

    2015-07-02

    A new carbon-carbon bond cleavage reaction was developed for the efficient synthesis of multisubstituted pyrazolo[1,5-a]pyrimidines. This base induced reaction of 1,3,5-trisubstituted pentane-1,5-diones and substituted pyrazoles afforded good yields of the pyrazolo[1,5-a]pyrimidines.

  18. Biotic and abiotic carbon to sulfur bond cleavage. Final report

    SciTech Connect

    Frost, J.W.

    1994-05-01

    The microbial desulfurization of organosulfur compounds occurs by unprecedented and largely unexplored biochemical processes. A study of such biotic desulfurizations can be expected to give rise to new and useful chemistry and enzymology. The potential value of understanding and harnessing these processes is seen in relation to the need for methods for the removal of organically bound sulfur from coal and the degradation of organic sulfur-containing pollutants. This research effort has been directed towards an examination of desulfurization ability in well characterized microorganisms, the isolation of bacteria with desulfurization ability from natural sources, the characterization and mechanistic evaluation of the observed biocatalytic processes, the development of biomimetic synthetic organic chemistry based on biotic desulfurization mechanisms and the design and preparation of improved coal model compounds for use in microbial selection processes. A systematic approach to studying biodesulfurizations was undertaken in which organosulfur compounds have been broken down into classes based on the oxidation state of the sulfur atom and the structure of the rest of the organic material. Microbes have been evaluated in terms of ability to degrade organosulfur compounds with sulfur in its sulfonic acid oxidation state. These compounds are likely intermediates in coal desulfurization and are present in the environment as persistent pollutants in the form of detergents. It is known that oxygen bonded to sulfur lowers the carbon-sulfur bond energy, providing a thermodynamic basis for starting with this class of compounds.

  19. Carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride

    NASA Astrophysics Data System (ADS)

    Hu, Shaowei; Shima, Takanori; Hou, Zhaomin

    2014-08-01

    The cleavage of carbon-carbon (C-C) bonds by transition metals is of great interest, especially as this transformation can be used to produce fuels and other industrially important chemicals from natural resources such as petroleum and biomass. Carbon-carbon bonds are quite stable and are consequently unreactive under many reaction conditions. In the industrial naphtha hydrocracking process, the aromatic carbon skeleton of benzene can be transformed to methylcyclopentane and acyclic saturated hydrocarbons through C-C bond cleavage and rearrangement on the surfaces of solid catalysts. However, these chemical transformations usually require high temperatures and are fairly non-selective. Microorganisms can degrade aromatic compounds under ambient conditions, but the mechanistic details are not known and are difficult to mimic. Several transition metal complexes have been reported to cleave C-C bonds in a selective fashion in special circumstances, such as relief of ring strain, formation of an aromatic system, chelation-assisted cyclometallation and β-carbon elimination. However, the cleavage of benzene by a transition metal complex has not been reported. Here we report the C-C bond cleavage and rearrangement of benzene by a trinuclear titanium polyhydride complex. The benzene ring is transformed sequentially to a methylcyclopentenyl and a 2-methylpentenyl species through the cleavage of the aromatic carbon skeleton at the multi-titanium sites. Our results suggest that multinuclear titanium hydrides could serve as a unique platform for the activation of aromatic molecules, and may facilitate the design of new catalysts for the transformation of inactive aromatics.

  20. EGFR induces DNA decomposition via phosphodiester bond cleavage

    PubMed Central

    Tong, Yongpeng; Li, Shuiming; Huang, Chunliu

    2017-01-01

    EGFR may induce DNA degradation. This activity had not been previously described as an EGRF function. To confirm this unexpected activity, testing of EGFR in the presence of ATP and either 5A, 5C, 5G, 5T, or 5U oligonucleotides was performed. HPLC-MS analysis demonstrated that 5A and 5U levels significantly decreased in the presence of EGFR. Furthermore, fragments 4A and 4U were produced in 5A+EGFR+ATP and in 5U+EGFR+ATP reaction mixtures, respectively, but not in EGFR-negative controls. Degradation of Poly(A), Poly(C), Poly(G), Poly(I), Poly(T), and Poly(U) oligomers in the presence of EGFR and ATP correlated with the lower ability of reaction products to pair with complementary oligonucleotides. Gel electrophoresis showed that breakdown products migrated more quickly than controls, especially after addition of paired (complementary) oligomers, Poly(A) and Poly(U). Furthermore, λ DNA reaction products also migrated more quickly after incubation with EGFR. The results suggest that EGFR can induce breakage of certain types of nucleotide phosphodiester bonds, especially within the A residues of DNA or U residues of RNA, to induce DNA or RNA decomposition, respectively. This activity may be important in EGRF signaling, DNA degradation, or repair in normal or cancer cell activities. PMID:28272528

  1. Achieving C-N bond cleavage in dinuclear metal cyanide complexes.

    PubMed

    Cavigliasso, Germán; Christian, Gemma J; Stranger, Robert; Yates, Brian F

    2011-07-28

    Cleavage of cyanide is more difficult to achieve compared to dinitrogen and carbon monoxide, even though these species contain triple bonds of greater strength. In this work, we have used computational methods to investigate thermodynamic and mechanistic aspects of the C-N bond cleavage process in [L(3)M-CN-M'L(3)] systems consisting of a central cyanide unit bound in an end-on fashion to two terminal metal tris-amide complexes. In these systems, [M] is a d(3) transition metal from the 3d, 4d, 5d, or 6d series and groups 4 through 7, and [L] is either [NH(2)], [NMe(2)], [N(i)PrPh], or [N(t)BuAr]. A comparison of various models for the experimentally relevant [L(3)Mo-CN-MoL(3)] system has shown that while the C-N cleavage step appears to be an energetically favourable process, a large barrier exists for the dissociation of [L(3)Mo-CN-MoL(3)]((-)) into [L(3)Mo-C]((-)) and [N-MoL(3)], which possibly explains why C-N bond scission is not observed experimentally. The general structural, bonding, and thermochemical trends across the transition metal series investigated, indicate that the systems exhibiting the greatest degree of C-N activation, and most favourable energetics for C-N cleavage, also possess the most favourable electronic properties, namely, a close match between the relevant π-like orbitals on the metal-based and cyanide fragments. The negative charge on the cyanide fragment leads to significant destabilization of the π* level which needs to be populated through back-donation from the metal centres in order for C-N bond scission to be achieved. Therefore, metal-based systems with high-lying d(π) orbitals are best suited to C-N cleavage. In terms of chemical periodicity, these systems can be identified as the heavier members within a group and the earlier members within a period. As a consequence, Mo complexes are not well suited to cleaving the C-N bond, whereas the Ta analogues are the most favourable systems and should, in principle, be capable of

  2. Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation.

    PubMed

    Kunishita, Atsushi; Ishimaru, Hirohito; Nakashima, Satoru; Ogura, Takashi; Itoh, Shinobu

    2008-04-02

    A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

  3. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    NASA Astrophysics Data System (ADS)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  4. Yeast ribonuclease III uses a network of multiple hydrogen bonds for RNA binding and cleavage.

    PubMed

    Lavoie, Mathieu; Abou Elela, Sherif

    2008-08-19

    Members of the bacterial RNase III family recognize a variety of short structured RNAs with few common features. It is not clear how this group of enzymes supports high cleavage fidelity while maintaining a broad base of substrates. Here we show that the yeast orthologue of RNase III (Rnt1p) uses a network of 2'-OH-dependent interactions to recognize substrates with different structures. We designed a series of bipartite substrates permitting the distinction between binding and cleavage defects. Each substrate was engineered to carry a single or multiple 2'- O-methyl or 2'-fluoro ribonucleotide substitutions to prevent the formation of hydrogen bonds with a specific nucleotide or group of nucleotides. Interestingly, introduction of 2'- O-methyl ribonucleotides near the cleavage site increased the rate of catalysis, indicating that 2'-OH are not required for cleavage. Substitution of nucleotides in known Rnt1p binding site with 2'- O-methyl ribonucleotides inhibited cleavage while single 2'-fluoro ribonucleotide substitutions did not. This indicates that while no single 2'-OH is essential for Rnt1p cleavage, small changes in the substrate structure are not tolerated. Strikingly, several nucleotide substitutions greatly increased the substrate dissociation constant with little or no effect on the Michaelis-Menten constant or rate of catalysis. Together, the results indicate that Rnt1p uses a network of nucleotide interactions to identify its substrate and support two distinct modes of binding. One mode is primarily mediated by the dsRNA binding domain and leads to the formation of stable RNA/protein complex, while the other requires the presence of the nuclease and N-terminal domains and leads to RNA cleavage.

  5. Mercury Detoxification by Bacteria: Simulations of Transcription Activation and Mercury-Carbon Bond Cleavage

    SciTech Connect

    Guo, Hao-Bo; Parks, Jerry M; Johs, Alexander; Smith, Jeremy C

    2011-01-01

    In this chapter, we summarize recent work from our laboratory and provide new perspective on two important aspects of bacterial mercury resistance: the molecular mechanism of transcriptional regulation by MerR, and the enzymatic cleavage of the Hg-C bond in methylmercury by the organomercurial lyase, MerB. Molecular dynamics (MD) simulations of MerR reveal an opening-and-closing dynamics, which may be involved in initiating transcription of mercury resistance genes upon Hg(II) binding. Density functional theory (DFT) calculations on an active-site model of the enzyme reveal how MerB catalyzes the Hg-C bond cleavage using cysteine coordination and acid-base chemistry. These studies provide insight into the detailed mechanisms of microbial gene regulation and defense against mercury toxicity.

  6. Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

    PubMed Central

    Sugiishi, Tsuyuka; Aikawa, Kohsuke

    2015-01-01

    Summary This short review highlights the copper-mediated fluoroalkylation using perfluoroalkylated carboxylic acid derivatives. Carbon–carbon bond cleavage of perfluoroalkylated carboxylic acid derivatives takes place in fluoroalkylation reactions at high temperature (150–200 °C) or under basic conditions to generate fluoroalkyl anion sources for the formation of fluoroalkylcopper species. The fluoroalkylation reactions, which proceed through decarboxylation or tetrahedral intermediates, are useful protocols for the synthesis of fluoroalkylated aromatics. PMID:26734112

  7. Biodehalogenation: The kinetics and rates of the microbial cleavage of carbon-halogen bonds

    SciTech Connect

    Castro, C.E. . Nematology Dept.)

    1993-09-01

    Specific rate constants associated with defined molecular paths of carbon-halogen bond cleavage from a variety of alkyl halide substrates by six soil organisms are presented. Five aerobes (three pseudomonads, one methylotroph, and one flavobacterium) and one anaerobe (a methanogen) are compared. The rate constants were obtained with resting cells in phosphate buffer at pH 7.4 in the absence of nutrients or other substances. The observed general rate law is d(X[sup [minus

  8. D-β-aspartyl residue exhibiting uncommon high resistance to spontaneous peptide bond cleavage

    NASA Astrophysics Data System (ADS)

    Aki, Kenzo; Okamura, Emiko

    2016-02-01

    Although L-amino acids were selected as main constituents of peptides and proteins during chemical evolution, D-aspartyl (Asp) residue is found in a variety of living tissues. In particular, D-β-Asp is thought to be stable than any other Asp isomers, and this could be a reason for gradual accumulation in abnormal proteins and peptides to modify their structures and functions. It is predicted that D-β-Asp shows high resistance to biomolecular reactions. For instance, less reactivity of D-β-Asp is expected to bond cleavage, although such information has not been provided yet. In this work, the spontaneous peptide bond cleavage was compared between Asp isomers, by applying real-time solution-state NMR to eye lens αΑ-crystallin 51–60 fragment, S51LFRTVLD58SG60 and αΒ-crystallin 61–67 analog, F61D62TGLSG67 consisting of L-α- and D-β-Asp 58 and 62, respectively. Kinetic analysis showed how tough the uncommon D-β-Asp residue was against the peptide bond cleavage as compared to natural L-α-Asp. Differences in pKa and conformation between L-α- and D-β-Asp side chains were plausible factors to determine reactivity of Asp isomers. The present study, for the first time, provides a rationale to explain less reactivity of D-β-Asp to allow abnormal accumulation.

  9. Biotic and abiotic carbon to sulfur bond cleavage. Technical report, July 1, 1991--September 30, 1991

    SciTech Connect

    Frost, J.W.

    1991-12-31

    Cleavage of aliphatic organosulfonate carbon to sulfur (C-S) bonds, a critical link in the global biogeochemical sulfur cycle, has been identified in Escherichia coli K-12. Enormous quantities of inorganic sulfate are continuously converted (Scheme I) into methanesulfonic acid 1 and acylated 3-(6-sulfo-{alpha}-D-quinovopyranosyl)-L-glycerol 2. Biocatalytic desulfurization (Scheme I) of 1 and 2, which share the structural feature of an aliphatic carbon bonded to a sulfonic acid sulfur, completes the cycle, Discovery of this desulfurization in E. coli provides an invaluable paradigm for study of a biotic process which, via the biogeochemical cycle, significantly influences the atmospheric concentration of sulfur-containing molecules.

  10. Entropic origin of cobalt-carbon bond cleavage catalysis in adenosylcobalamin-dependent ethanolamine ammonia-lyase.

    PubMed

    Wang, Miao; Warncke, Kurt

    2013-10-09

    Adenosylcobalamin-dependent enzymes accelerate the cleavage of the cobalt-carbon (Co-C) bond of the bound coenzyme by >10(10)-fold. The cleavage-generated 5'-deoxyadenosyl radical initiates the catalytic cycle by abstracting a hydrogen atom from substrate. Kinetic coupling of the Co-C bond cleavage and hydrogen-atom-transfer steps at ambient temperatures has interfered with past experimental attempts to directly address the factors that govern Co-C bond cleavage catalysis. Here, we use time-resolved, full-spectrum electron paramagnetic resonance spectroscopy, with temperature-step reaction initiation, starting from the enzyme-coenzyme-substrate ternary complex and (2)H-labeled substrate, to study radical pair generation in ethanolamine ammonia-lyase from Salmonella typhimurium at 234-248 K in a dimethylsulfoxide/water cryosolvent system. The monoexponential kinetics of formation of the (2)H- and (1)H-substituted substrate radicals are the same, indicating that Co-C bond cleavage rate-limits radical pair formation. Analysis of the kinetics by using a linear, three-state model allows extraction of the microscopic rate constant for Co-C bond cleavage. Eyring analysis reveals that the activation enthalpy for Co-C bond cleavage is 32 ± 1 kcal/mol, which is the same as for the cleavage reaction in solution. The origin of Co-C bond cleavage catalysis in the enzyme is, therefore, the large, favorable activation entropy of 61 ± 6 cal/(mol·K) (relative to 7 ± 1 cal/(mol·K) in solution). This represents a paradigm shift from traditional, enthalpy-based mechanisms that have been proposed for Co-C bond-breaking in B12 enzymes. The catalysis is proposed to arise from an increase in protein configurational entropy along the reaction coordinate.

  11. Disulfide bond cleavage in TEMPO-free radical initiated peptide sequencing mass spectrometry.

    PubMed

    Lee, Minhee; Lee, Younjin; Kang, Minhyuk; Park, Hyeyeon; Seong, Yeonmi; Sung, Bong June; Moon, Bongjin; Oh, Han Bin

    2011-08-01

    The gas-phase free radical initiated peptide sequencing (FRIPS) fragmentation behavior of o-TEMPO-Bz-conjugated peptides with an intra- and intermolecular disulfide bond was investigated using MS(n) tandem mass spectrometry experiments. Investigated peptides included four peptides with an intramolecular cyclic disulfide bond, Bactenecin (RLCRIVVIRVCR), TGF-α (CHSGYVGVRC), MCH (DFDMLRCMLGRVFRPCWQY) and Adrenomedullin (16-31) (CRFGTCTVQKLAHQIY), and two peptides with an intermolecular disulfide bond. Collisional activation of the benzyl radical conjugated peptide cation, which was generated through the release of a TEMPO radical from o-TEMPO-Bz-conjugated peptides upon initial collisional activation, produced a large number of peptide backbone fragments in which the S-S or C-S bond was readily cleaved. The observed peptide backbone fragments included a-, c-, x- or z-types, which indicates that the radical-driven peptide fragmentation mechanism plays an important role in TEMPO-FRIPS mass spectrometry. FRIPS application of the linearly linked disulfide peptides further showed that the S-S or C-S bond was selectively and preferentially cleaved, followed by peptide backbone dissociations. In the FRIPS mass spectra, the loss of •SH or •SSH was also abundantly found. On the basis of these findings, FRIPS fragmentation pathways for peptides with a disulfide bond are proposed. For the cleavage of the S-S bond, the abstraction of a hydrogen atom at C(β) by the benzyl radical is proposed to be the initial radical abstraction/transfer reaction. On the other hand, H-abstraction at C(α) is suggested to lead to C-S bond cleavage, which yields [ion ± S] fragments or the loss of •SH or •SSH.

  12. Study on Expression Modes and Cleavage Role of miR156b/c/d and its Target Gene Vv-SPL9 During the Whole Growth Stage of Grapevine.

    PubMed

    Wang, Baoju; Wang, Jian; Wang, Chen; Shen, Wenbiao; Jia, Haifeng; Zhu, Xudong; Li, Xiaopeng

    2016-01-01

    miR156 regulates the expression of its target SPL (PROMOTER BINDING-LIKE) genes during flower and fruit development, diverse developmental stage transitions, especially from vegetative to reproductive growth phases, by cleaving the target mRNA SPL of one plant-specific transcription factor. However, systematic reports on grapevine have yet to be presented. Here, the precise sequence of miR156 (vvi-miR156b/c/d) in grapevine "Takatsuma" was cloned with a previously cloned grapevine SPL (Vv-SPL9). Expression profiles in 18 grapevine tissues were identified through stem-loop RT-PCR. The interaction mode between vvi-miR156b/c/d and Vv-SPL9 was further validated by detecting the cleavage site and cleavage products of 3'- and 5'-ends via an integrated approach of 5'-RLM-RACE (RNA ligase-mediated 5'-rapid amplification of cDNA ends), 3'-PPM-RACE (poly(A) polymerase-mediated 3'-rapid amplification of cDNA ends), and qRT-PCR (real time reverse transcriptase-polymerase chain reaction). The variation in their cleavage roles in the whole growth stage of grapevine was also systematically investigated. Results showed that vvi-miR156b/c/d exhibited typical temporal-spatial-specific expression levels. The expression levels were higher in vegetative organs, such as leaf, than in reproductive organs, such as tendrils, flowers, and berries. A significant variation was observed during vegetative-to-reproductive transition. The expression patterns of Vv-SPL9 showed the opposite trends with those of vvi-miR156b. We confirmed that the cleavage site was at the 10th site of vvi-miR156b/c/d complementary to Vv-SPL9 in "Takatsuma" grapevine. We also identified the temporal-spatial variation of the cleavage products. This variation can indicate the regulatory function of miR156 on SPL in grapevines. Our findings provide further insights into the functions of vvi-miR156b/c/d and its target Vv-SPL9, and also help enrich our knowledge of small RNA-mediated regulation in grapevine.

  13. A density functional theory study on peptide bond cleavage at aspartic residues: direct vs cyclic intermediate hydrolysis.

    PubMed

    Sang-aroon, Wichien; Amornkitbamrung, Vittaya; Ruangpornvisuti, Vithaya

    2013-12-01

    In this work, peptide bond cleavages at carboxy- and amino-sides of the aspartic residue in a peptide model via direct (concerted and step-wise) and cyclic intermediate hydrolysis reaction pathways were explored computationally. The energetics, thermodynamic properties, rate constants, and equilibrium constants of all hydrolysis reactions, as well as their energy profiles were computed at the B3LYP/6-311++G(d,p) level of theory. The result indicated that peptide bond cleavage of the Asp residue occurred most preferentially via the cyclic intermediate hydrolysis pathway. In all reaction pathways, cleavage of the peptide bond at the amino-side occurred less preferentially than at the carboxy-side. The overall reaction rate constants of peptide bond cleavage of the Asp residue at the carboxy-side for the assisted system were, in increasing order: concerted < step-wise < cyclic intermediate.

  14. High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

    DOE PAGES

    Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung; ...

    2016-09-30

    The addition of Lewis or Brönsted acids (LA = Zn(OTf)2, B(C6F5)3, HBArF, TFA) to the high-valent manganese–oxo complex MnV(O)(TBP8Cz) results in the stabilization of a valence tautomer MnIV(O-LA)(TBP8Cz•+). The ZnII and B(C6F5)3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn–Nave = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminalmore » oxo ligand. This Mn–O bond length is elongated compared to the MnV(O) starting material (Mn–O = 1.55 Å). The reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H substrates was examined, and it was found that H• abstraction from C–H bonds occurs in a 1:1 stoichiometry, giving a MnIV complex and the dehydrogenated organic product. The rates of C–H cleavage are accelerated for the MnIV(O-LA)(TBP8Cz•+) valence tautomer as compared to the MnV(O) valence tautomer when LA = ZnII, B(C6F5)3, and HBArF, whereas for LA = TFA, the C–H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of kH/kD = 25–27 was observed for LA = B(C6F5)3 and HBArF, indicating that H-atom transfer (HAT) is the rate-limiting step in the C–H cleavage reaction and implicating a potential tunneling mechanism for HAT. Furthermore, the reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H bonds depends on the strength of the Lewis acid. The HAT reactivity is compared with the analogous corrole complex MnIV(O–H)(tpfc•+) recently reported.« less

  15. [Polycationic catalysts for phosphodiester bond cleavage on the basis of 1,4-diazabicyclo[2.2.2]octane].

    PubMed

    Burakova, E A; Kovalev, N A; Kuznetsova, I L; Zenkova, M A; Vlasov, V V; Sil'nikov, V N

    2007-01-01

    A number of tetracationic compounds capable of phosphodiester bond cleavage within a 21 -membered ribooligonucleotide were designed and synthesized. The artificial ribonucleases represent two residues of quaternized 1,4-diazabicyclo[2.2.2]octane bearing alkyl substituents of various lengths and connected with a rigid linker. The efficiency of cleavage of phosphodiester bonds in an RNA target depends on the linker structure and the length of alkyl substituent.

  16. New chemical insights using weakly supported voltammetry: the reductive cleavage of Aryl-Br bonds is reversible.

    PubMed

    Wang, Yijun; Barnes, Edward O; Compton, Richard G

    2012-10-22

    Cyclic voltammetry carried out at a wide range of supporting electrolyte concentrations and compositions can elucidate additional kinetic and mechanistic details of the electrochemical reduction of aryl halides. The cleavage of the C-Br bond is reversible, driven by H abstraction and the second electron transfer. This is a new chemical insight, as the cleavage of such bonds has usually been regarded as irreversible.

  17. A pH-responsive cleavage route based on a metal-organic coordination bond.

    PubMed

    Xing, Lei; Zheng, Haoquan; Che, Shunai

    2011-06-20

    The physical or chemical event that generally causes stimuli responses is limited to the formation or destruction of secondary forces, such as hydrogen bonding, hydrophobic effects, electrostatic interactions, and simple reactions. Here, pH-responsive behavior of metal-organic coordination bonding, which is intrinsic to natural systems (e.g., transferrin recycling in cells), is becoming a strong candidate for a new stimulus-responsive route. We have designed a simple pH-responsive release system by integrating a metal ion and ligand or self-assembling these species with biodegradable host molecules to form nanoparticles with "metal-ligand" or "host-metal-ligand" architectures. The cleavage of either or both the "metal-ligand" or the "host-metal" coordination bond in response to pH variations causes significant damage to the nanoparticles and the subsequent release of ligand molecules under designated pH conditions.

  18. Ruthenium-Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon-Heteroatom Bonds with Unconventional Chemoselectivity.

    PubMed

    Kondo, Hikaru; Akiba, Nana; Kochi, Takuya; Kakiuchi, Fumitoshi

    2015-08-03

    Ruthenium-catalyzed selective monoalkenylation of ortho C-O or C-N bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon-heteroatom bonds, thus suggesting an unconventional chemoselectivity, where smaller, more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C-O bonds in the presence of ortho C-H bonds was also achieved.

  19. Te-Te and Te-C bond cleavage reactions using a monovalent gallanediyl.

    PubMed

    Ganesamoorthy, Chelladurai; Bendt, Georg; Bläser, Dieter; Wölper, Christoph; Schulz, Stephan

    2015-03-21

    LGa (L = [(2,6-i-Pr2-C6H3)NC(Me)]2CH) reacts with elemental tellurium with formation of the Te-bridged compound [LGa-μ-Te]2 1, whereas the reactions with Ph2Te2 and i-Pr2Te occurred with cleavage of the Te-Te and Te-C bond, respectively, and subsequent formation of LGa(TePh)2 2 and LGa(i-Pr)Tei-Pr 3. 1-3 were characterized by heteronuclear NMR ((1)H, (13)C, (125)Te) and IR spectroscopy and their solid state structures were determined by single crystal X-ray analyses.

  20. Bond cleavages of adenosine 5'-triphosphate induced by monochromatic soft X-rays

    NASA Astrophysics Data System (ADS)

    Fujii, K.; Narita, A.; Yokoya, A.

    2014-04-01

    To investigate which type of bond is likely to be cleaved by soft X-ray exposure to an adenosine 5'-triphosphate (ATP), we observed spectral changes in X-ray absorption near edge structure (XANES) around nitrogen and oxygen K-edge of an ATP film by soft X-ray irradiation. Experiments were performed at a synchrotron soft X-ray beamline at SPring-8, Japan. The XANES spectra around the nitrogen and oxygen .K-edge slightly varied by exposure to 560 eV soft X-rays. These changes are originated from the cleavage of C-N bonds between a sugar and a nucleobase site and of C-O, P-O or O-H bond of sugar and phosphate site. From the comparison between the change in XANES intensity of σ* peak at nitrogen and that at oxygen K-edges, it is inferred that the C-O, P-O or O-H bond of sugar and phosphate is much efficiently cleaved than the C-N of N-glycoside bond by the exposure of 560 eV soft X-ray to ATP film.

  1. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    SciTech Connect

    John J. Kilbane II

    2004-10-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project was focused on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate deaminase. The objective of the final phase of the project will be to develop derivative C-N bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments resulted in the isolation of microbial cultures that utilize aromatic amides as sole nitrogen sources, several amidase genes were cloned and were included in directed evolution experiments to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. During the second year of the project (October, 2003-September, 2004) enrichment culture experiments succeeded in isolating a mixed bacterial culture that can utilize 2-aminobiphenyl as a sole nitrogen source, directed evolution experiments were focused on the aniline dioxygenase enzyme that is capable of deaminating aniline, and expression vectors were constructed to enable the expression of genes encoding C-N bond cleaving enzymes in Rhodococcus hosts. The construction of a new metabolic pathway to selectively remove nitrogen from carbazole and other molecules typically found in petroleum should lead to the development of a process to improve oil refinery efficiency by reducing the

  2. Aromatic thiol-mediated cleavage of N–O bonds enables chemical ubiquitylation of folded proteins

    PubMed Central

    Weller, Caroline E.; Dhall, Abhinav; Ding, Feizhi; Linares, Edlaine; Whedon, Samuel D.; Senger, Nicholas A.; Tyson, Elizabeth L.; Bagert, John D.; Li, Xiaosong; Augusto, Ohara; Chatterjee, Champak

    2016-01-01

    Access to protein substrates homogenously modified by ubiquitin (Ub) is critical for biophysical and biochemical investigations aimed at deconvoluting the myriad biological roles for Ub. Current chemical strategies for protein ubiquitylation, however, employ temporary ligation auxiliaries that are removed under harsh denaturing conditions and have limited applicability. We report an unprecedented aromatic thiol-mediated N–O bond cleavage and its application towards native chemical ubiquitylation with the ligation auxiliary 2-aminooxyethanethiol. Our interrogation of the reaction mechanism suggests a disulfide radical anion as the active species capable of cleaving the N–O bond. The successful semisynthesis of full-length histone H2B modified by the small ubiquitin-like modifier-3 (SUMO-3) protein further demonstrates the generalizability and compatibility of our strategy with folded proteins. PMID:27680493

  3. Aromatic thiol-mediated cleavage of N-O bonds enables chemical ubiquitylation of folded proteins

    NASA Astrophysics Data System (ADS)

    Weller, Caroline E.; Dhall, Abhinav; Ding, Feizhi; Linares, Edlaine; Whedon, Samuel D.; Senger, Nicholas A.; Tyson, Elizabeth L.; Bagert, John D.; Li, Xiaosong; Augusto, Ohara; Chatterjee, Champak

    2016-09-01

    Access to protein substrates homogenously modified by ubiquitin (Ub) is critical for biophysical and biochemical investigations aimed at deconvoluting the myriad biological roles for Ub. Current chemical strategies for protein ubiquitylation, however, employ temporary ligation auxiliaries that are removed under harsh denaturing conditions and have limited applicability. We report an unprecedented aromatic thiol-mediated N-O bond cleavage and its application towards native chemical ubiquitylation with the ligation auxiliary 2-aminooxyethanethiol. Our interrogation of the reaction mechanism suggests a disulfide radical anion as the active species capable of cleaving the N-O bond. The successful semisynthesis of full-length histone H2B modified by the small ubiquitin-like modifier-3 (SUMO-3) protein further demonstrates the generalizability and compatibility of our strategy with folded proteins.

  4. NHC-Organocatalyzed CAr -O Bond Cleavage: Mild Access to 2-Hydroxybenzophenones.

    PubMed

    Janssen-Müller, Daniel; Singha, Santanu; Lied, Fabian; Gottschalk, Karin; Glorius, Frank

    2017-01-27

    A Truce-Smiles rearrangement of acyl-anion equivalents generated by N-heterocyclic carbene (NHC) catalysis has been achieved. The developed method includes CAr -O, CAr -S, or CAr -N bond cleavage for the formation of a CAr -C bond and enables access to 2-hydroxybenzophenones, an important structural motif that is present in several bioactive natural products. By utilizing this procedure, the alkaloid taxilamine was synthesized in three steps. DFT calculations and control experiments support a classical SN Ar mechanism with a catalyst-bound Meisenheimer-type intermediate. The method features mild reaction conditions, excellent functional-group tolerance, and a broad substrate scope, including various classes of (hetero)arenes.

  5. Rh-Catalyzed C–C Bond Cleavage by Transfer Hydroformylation

    PubMed Central

    Murphy, Stephen K.; Park, Jung-Woo; Cruz, Faben A.; Dong, Vy M.

    2015-01-01

    The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rh(Xantphos)(benzoate) catalyst activates aldehyde C–H bonds with high chemoselectivity to trigger C–C bond cleavage and generate olefins at low loadings (0.3 to 2 mol%) and temperatures (22 to 80 °C). This mild protocol can be applied to various natural products and was used to achieve a three step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton-shuttle to enable transfer hydroformylation. PMID:25554782

  6. Reversible extrusion and uptake of HCl molecules by crystalline solids involving coordination bond cleavage and formation.

    PubMed

    Mínguez Espallargas, Guillermo; Brammer, Lee; van de Streek, Jacco; Shankland, Kenneth; Florence, Alastair J; Adams, Harry

    2006-08-02

    Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.

  7. Aromatic thiol-mediated cleavage of N-O bonds enables chemical ubiquitylation of folded proteins.

    PubMed

    Weller, Caroline E; Dhall, Abhinav; Ding, Feizhi; Linares, Edlaine; Whedon, Samuel D; Senger, Nicholas A; Tyson, Elizabeth L; Bagert, John D; Li, Xiaosong; Augusto, Ohara; Chatterjee, Champak

    2016-09-29

    Access to protein substrates homogenously modified by ubiquitin (Ub) is critical for biophysical and biochemical investigations aimed at deconvoluting the myriad biological roles for Ub. Current chemical strategies for protein ubiquitylation, however, employ temporary ligation auxiliaries that are removed under harsh denaturing conditions and have limited applicability. We report an unprecedented aromatic thiol-mediated N-O bond cleavage and its application towards native chemical ubiquitylation with the ligation auxiliary 2-aminooxyethanethiol. Our interrogation of the reaction mechanism suggests a disulfide radical anion as the active species capable of cleaving the N-O bond. The successful semisynthesis of full-length histone H2B modified by the small ubiquitin-like modifier-3 (SUMO-3) protein further demonstrates the generalizability and compatibility of our strategy with folded proteins.

  8. Molecular features in complex environment: Cooperative team players during excited state bond cleavage

    PubMed Central

    Thallmair, Sebastian; Roos, Matthias K.; de Vivie-Riedle, Regina

    2016-01-01

    Photoinduced bond cleavage is often employed for the generation of highly reactive carbocations in solution and to study their reactivity. Diphenylmethyl derivatives are prominent precursors in polar and moderately polar solvents like acetonitrile or dichloromethane. Depending on the leaving group, the photoinduced bond cleavage occurs on a femtosecond to picosecond time scale and typically leads to two distinguishable products, the desired diphenylmethyl cations (Ph2CH+) and as competing by-product the diphenylmethyl radicals (Ph2CH•). Conical intersections are the chief suspects for such ultrafast branching processes. We show for two typical examples, the neutral diphenylmethylchloride (Ph2CH–Cl) and the charged diphenylmethyltriphenylphosphonium ions (Ph2CH−PPh3+) that the role of the conical intersections depends not only on the molecular features but also on the interplay with the environment. It turns out to differ significantly for both precursors. Our analysis is based on quantum chemical and quantum dynamical calculations. For comparison, we use ultrafast transient absorption measurements. In case of Ph2CH–Cl, we can directly connect the observed signals to two early three-state and two-state conical intersections, both close to the Franck-Condon region. In case of the Ph2CH−PPh3+, dynamic solvent effects are needed to activate a two-state conical intersection at larger distances along the reaction coordinate. PMID:26958588

  9. NMR-spectroscopic characterization of phosphodiester bond cleavage catalyzed by the minimal hammerhead ribozyme.

    PubMed

    Fürtig, Boris; Richter, Christian; Schell, Peter; Wenter, Philipp; Pitsch, Stefan; Schwalbe, Harald

    2008-01-01

    In order to relate the conformational dynamics of the hammerhead ribozyme to its biological function the cleavage reaction catalyzed by the hammerhead ribozyme was monitored by time-resolved nuclear magnetic resonance (NMR) spectroscopy. For this purpose, the two nucleosides around the scissile phosphodiester bond were selectively (13)C labelled in multi-step organic syntheses starting from uniformly (13)C-labelled glucose. The phosphoamidites were incorporated using phosphoamidite chemistry in the hammerhead substrate strand. In addition, the 2'-OH group on the 5'-side of the hammerhead substrate strand was labelled with a photolabile protecting group. This labelling strategy enabled a detailed characterisation of the nucleotides around the scissile phosphodiester bond in the ground state conformation of the hammerhead ribozyme in the absence and presence of Mg(2+) ions as well as of the product state. Photochemical induction of the reaction in situ was further characterized by time-resolved NMR spectroscopy. The detailed structural and dynamic investigations revealed that the conformation of the hammerhead ribozyme is significantly affected by addition of Mg(2+) leading to an ensemble of conformations where dynamic transitions between energetically similar conformations occur on the ms-timescale in the presence of Mg(2+). The dynamic transitions are localized around the catalytic core. Cleavage from this ensemble cannot be described by mono-exponential kinetics but follows bi-exponential kinetics. A model is described to take into account these experimental data.

  10. Ab initio study of carbon-chlorine bond cleavage in carbon tetrachloride.

    PubMed

    Zhang, Nianliu; Blowers, Paul; Farrell, James

    2005-01-15

    Chlorinated solvents in groundwater are known to undergo reductive dechlorination reactions with Fe(ll)-containing minerals and with corroding metals in permeable-barrier treatment systems. This research investigated the effect of the reaction energy on the reaction pathway for C-Cl bond cleavage in carbon tetrachloride (CCl4). Hartree-Fock, density functional theory, and modified complete basis set ab initio methods were used to study adiabatic electron transfer to aqueous-phase CCl4. The potential energies associated with fragmentation of the carbon tetrachloride anion radical (CCl4-) into a trichloromethyl radical (CCl3) and a chloride ion (Cl-) were explored as a function of the carbon-chlorine bond distance during cleavage. The effect of aqueous solvation was investigated using a continuum conductor-like screening model. Solvation significantly lowered the energies of the reaction products, suggesting that dissociative electron transfer was enhanced by solvation. The potential energy curves in an aqueous medium indicate that reductive cleavage undergoes a change from an inner-sphere to an outer-sphere mechanism as the overall energy change for the reaction is increased. The activation energy for the reaction was found to be a linear function of the overall energy change, and the Marcus-Hush model was used to relate experimentally measured activation energies for CCl4 reduction to overall reaction energies. Experimentally measured activation energies for CCl4 reduction by corroding iron correspond to reaction energies that are insufficiently exergonic for promoting the outer-sphere mechanism. This suggests that the different reaction pathways that have been observed for CCl4 reduction by corroding iron arise from different catalytic interactions with the surface, and not from differences in energy of the transferred electrons.

  11. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    SciTech Connect

    John J. Kilbane III

    2003-12-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project will focus on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate amidase. The objective of the final phase of the project will be to develop derivative CN bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. The project is on schedule and no major difficulties have been encountered. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments have resulted in the isolation of promising cultures that may be capable of cleaving C-N bonds in aromatic amides, several amidase genes have been cloned and are currently undergoing directed evolution to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. Future research will address expression of these genes in Rhodococcus erythropolis. Enrichment culture experiments and directed evolution experiments continue to be a main focus of research activity and further work is required to obtain an appropriate amidase that will selectively cleave C-N bonds in aromatic substrates. Once an appropriate amidase gene is obtained it must be combined with genes encoding an enzyme capable of converting carbazole to 2'aminobiphenyl-2,3-diol: specifically carA genes. The carA genes from two sources have been cloned and are ready for construction of C-N bond cleavage pathway

  12. Heterolytic OO bond cleavage: Functional role of Glu113 during bis-Fe(IV) formation in MauG.

    PubMed

    Geng, Jiafeng; Huo, Lu; Liu, Aimin

    2017-02-01

    The diheme enzyme MauG utilizes H2O2 to perform oxidative posttranslational modification on a protein substrate. A bis-Fe(IV) species of MauG was previously identified as a key intermediate in this reaction. Heterolytic cleavage of the OO bond of H2O2 drives the formation of the bis-Fe(IV) intermediate. In this work, we tested a hypothesis that a glutamate residue, Glu113 in the distal pocket of the pentacoordinate heme of MauG, facilitates heterolytic OO bond cleavage, thereby leading to bis-Fe(IV) formation. This hypothesis was proposed based on sequence alignment and structural comparison with other H2O2-utilizing hemoenzymes, especially those from the diheme enzyme superfamily that MauG belongs to. Electron paramagnetic resonance (EPR) characterization of the reaction between MauG and H2O2 revealed that mutation of Glu113 inhibited heterolytic OO bond cleavage, in agreement with our hypothesis. This result was further confirmed by the HPLC study in which an analog of H2O2, cumene hydroperoxide, was used to probe the pattern of OO bond cleavage. Together, our data suggest that Glu113 functions as an acid-base catalyst to assist heterolytic OO bond cleavage during the early stage of the catalytic reaction. This work advances our mechanistic understanding of the H2O2-activation process during bis-Fe(IV) formation in MauG.

  13. Computational study of the effects of steric hindrance on amide bond cleavage.

    PubMed

    Matsubara, Toshiaki; Ueta, Chikako

    2014-09-25

    The reaction mechanism of amide bond cleavages of the 2,2,6,6-tetramethylpiperidine derivatives, which proceeds in methanol solvent under mild conditions, is examined by the density functional method (B3LYP) using a model substrate. We performed the calculations to clarify the reason why the amide bond is readily broken in the present system, on the basis of an experimentally proposed "proton switching pathway" that is different from the generally known mechanisms. As a result, it was found that the stepwise decomposition of the amide bond by the "proton switching pathway" significantly lowers the energy barrier. The delocalization of the π electron in the -C(═O)-N< part is hindered by the steric effect of the four Me groups of the piperidine so that the acetyl group can easily rotate around the C-N axis and then the α-H migrates to the amide N. The subsequent amide bond dissociation, which is thought to be a rate-determining step in the experiment, was very facile. The reaction is completed by the addition of methanol to the formed ketene. Both the energy barriers of the α-H migration to the amide N and the methanol addition to ketene are largely decreased by the mediation of methanol solvent molecules. The rate-determining step of the entire reaction was found to be the α-H migration.

  14. Lewis Acid Accelerated Aryl Ether Bond Cleavage with Nickel: Orders of Magnitude Rate Enhancement Using AlMe3.

    PubMed

    Kelley, Paul; Edouard, Guy A; Lin, Sibo; Agapie, Theodor

    2016-11-21

    Study of the kinetics of intramolecular aryl ether C-O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 was studied in detail, and showed an increase in rate by several orders of magnitude. Low temperature NMR spectroscopy studies demonstrate quantitative coordination of ether to Al. From the Lewis acid-bound precursor, the activation parameters for ether cleavage are significantly lower. These findings provide a mechanistic basis for milder catalyst design for the activation of strong bonds.

  15. Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

    PubMed

    Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

    2016-11-16

    Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH(-) or (•)OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

  16. The role of alkane coordination in CH bond cleavage at a Pt(II) center

    PubMed Central

    Chen, George S.; Labinger, Jay A.; Bercaw, John E.

    2007-01-01

    The rates of CH bond activation for various alkanes by [(N–N)Pt(Me)(TFEd3)]+ (N N = ArNC(Me)C(Me)NAr; Ar = 3,5-di-tert-butylphenyl; TFE-d3 = CF3CD2OD) were studied. Both linear and cyclic alkanes give the corresponding alkene-hydride cation [(N–N)Pt(H)(alkene)]+ via (i) rate determining alkane coordination to form a CH σ complex, (ii) oxidative cleavage of the coordinated CH bond to give a platinum(IV) alkyl-methyl-hydride intermediate, (iii) reductive coupling to generate a methane σ complex, (iv) dissociation of methane, and (v) β-H elimination to form the observed product. Second-order rate constants for cycloalkane activation (CnH2n), are proportional to the size of the ring (k ∼ n). For cyclohexane, the deuterium kinetic isotope effect (kH/kD) of 1.28 (5) is consistent with the proposed rate determining alkane coordination to form a CH σ complex. Statistical scrambling of the five hydrogens of the Pt-methyl and the coordinated methylene unit, via rapid, reversible steps ii and iii, and interchange of geminal CH bonds of the methane and cyclohexane CH σ adducts, is observed before loss of methane. PMID:17416678

  17. A mechanistic study of Trichoderma reesei Cel7B catalyzed glycosidic bond cleavage.

    PubMed

    Zhang, Yu; Yan, Shihai; Yao, Lishan

    2013-07-25

    An ONIOM study is performed to illustrate the mechanism of Trichoderma reesei Cel7B catalyzed p-nitrophenyl lactoside hydrolysis. In both the glycosylation and deglycosylation steps, the reaction proceeds in a concerted way, meaning the nucleophilic attack and the glycosidic bond cleavage occur simultaneously. The glycosylation step is rate limiting with a barrier of 18.9 kcal/mol, comparable to the experimental value derived from the kcat measured in this work. The function of four residues R108, Y146, Y170, and D172, which form a hydrogen-bond network involving the substrate, is studied by conservative mutations. The mutants, including R108K, Y146F, Y170F, and D172N, decrease the enzyme activity by about 150-8000-fold. Molecular dynamics simulations show that the mutations disrupt the hydrogen-bond network, cause the substrate to deviate from active binding and hinder either the proton transfer from E201 to O4(+1) or the nucleophilic attack from E196 to C1(-1).

  18. Cleavage enhancement of specific chemical bonds in DNA by cisplatin radiosensitization.

    PubMed

    Xiao, Fangxing; Luo, Xinglan; Fu, Xianzhi; Zheng, Yi

    2013-05-02

    X-ray photoelectron spectroscopy (XPS) is harnessed as an in situ efficient characterization technique for monitoring chemical bond transformation in DNA and cisplatin-DNA complexes under synergic X-ray irradiation. By analyzing the variation of relative peak area of core elements of DNA as a function of irradiation time, we find that the most vulnerable scission sites in DNA are those containing phosphate and glycosidic bonds. Compared to DNA, the effective rate constants of the corresponding phosphodiester and glycosidic bond cleavages for cisplatin-DNA complexes are 1.8 and 1.9 folds larger. These damages and their enhancements are similar to those induced by low energy electrons (LEE). Consistently, the magnitude of the secondary electron distribution produced by the X-rays on the cisplatin-DNA complexes is considerably increased compared to that of pristine DNA. The data suggest that DNA radiosensization by cisplatin results not only from the sensitization of DNA to the action of LEE, but also from an increase the production of LEE at the site of binding of the cisplatin. The results provide new insights into the mechanisms of cisplatin-induced sensitization of DNA under X-ray irradiation, which could be helpful in the design of new cisplatin-based antitumor drugs.

  19. A study on Zr-Ir multiple bonding active for C-H bond cleavage.

    PubMed

    Oishi, Masataka; Oshima, Masato; Suzuki, Hiroharu

    2014-07-07

    Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)(amide) as the supporting ligand in the zirconium fragment, e.g., (L(1)ZrR)(Cp*Ir)(μ-H)3 [L(1) = Me2Si(η(5)-C5Me4)(N(t)Bu), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early-late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 Å] were slightly longer than the sum of the element radii of Zr and Ir [2.719 Å]. These hydrocarbyl complexes displayed the thermolytic C-H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr-Ir system were studied. The regiochemical outcomes during the C-H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., (L(1)Zr)(Cp*IrH2) (III). The existence of III and relevant σ-complex intermediates {L(1)Zr(η(2)-R-H)}(Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIPh, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M' interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.

  20. ATP-Dependent C–F Bond Cleavage Allows the Complete Degradation of 4-Fluoroaromatics without Oxygen

    PubMed Central

    Tiedt, Oliver; Mergelsberg, Mario; Boll, Kerstin; Müller, Michael; Adrian, Lorenz; Jehmlich, Nico; von Bergen, Martin

    2016-01-01

    ABSTRACT Complete biodegradation of the abundant and persistent fluoroaromatics requires enzymatic cleavage of an arylic C–F bond, probably the most stable single bond of a biodegradable organic molecule. While in aerobic microorganisms defluorination of fluoroaromatics is initiated by oxygenases, arylic C–F bond cleavage has never been observed in the absence of oxygen. Here, an oxygen-independent enzymatic aryl fluoride bond cleavage is described during the complete degradation of 4-fluorobenzoate or 4-fluorotoluene to CO2 and HF in the denitrifying Thauera aromatica: the ATP-dependent defluorination of 4-fluorobenzoyl-coenzyme A (4-F-BzCoA) to benzoyl-coenzyme A (BzCoA) and HF, catalyzed by class I BzCoA reductase (BCR). Adaptation to growth with the fluoroaromatics was accomplished by the downregulation of a promiscuous benzoate-CoA ligase and the concomitant upregulation of 4-F-BzCoA-defluorinating/dearomatizing BCR on the transcriptional level. We propose an unprecedented mechanism for reductive arylic C–F bond cleavage via a Birch reduction-like mechanism resulting in a formal nucleophilic aromatic substitution. In the proposed anionic 4-fluorodienoyl-CoA transition state, fluoride elimination to BzCoA is favored over protonation to a fluorinated cyclic dienoyl-CoA. PMID:27507824

  1. An SRLLR motif downstream of the scissile bond enhances enterokinase cleavage efficiency.

    PubMed

    Liew, Oi Wah; Jenny Chong, Pek Ching; Lim, Yok Zuan; Ang, Cui Xia; Amy Lau, Yong Chen; Yandle, Tim G; Brennan, Stephen O

    2007-01-01

    In a previous paper, we reported more efficient enterokinase cleavage at a C-terminal non-target LKGDR(201) site compared with an internally sited canonical recognition site, DDDDK(156). When this non-target site was placed internally to replace DDDDK(156) between the thioredoxin moiety and mouse NT-proCNP(1-50), this site was poorly processed leading us to conclude that efficient processing at LKGDR(201) in the first instance was due to its accessibility at the C-terminus of the fusion protein. Subsequently, we reasoned that treatment of thioredoxin-fused NT-proCNP(1-81) would allow us to retrieve full-length NT-proCNP(1-81) without undue processing at the LKGDR(201) site since this non-target site would now be located internally about 36 residues away from the C-terminus and hence not be hydrolyzed efficiently. Surprisingly, ESI-MS data showed that the LKGDR site in thioredoxin-fused human NT-proCNP(1-81) was still very efficiently cleaved and revealed a new but slow hydrolysis site with the sequence RVDTK/SRAAW to yield a peptide consistent with NT-proCNP(58-81). The evidence obtained from these experiments led us to postulate that efficient cleavage at the non-target LKGDR(201) site was not merely influenced by steric constraints but also by the sequence context downstream of the scissile bond. Hence, we constructed variants of thioredoxin-mouse NT-proCNP(1-50) where SRLLR residues (i.e. those immediately downstream from the LKGDR(201) site in NT-proCNP(1-50)) were systematically added one at a time downstream of the internal DDDDK(156) site. To evaluate the relative effects of site accessibility and downstream sequence context on the efficiency of enterokinase cleavage, we have also replaced the native LKGDR(201) sequence with DDDDK(201). Our results showed that incremental addition of SRLLR residues led to a steady increase in the rate of hydrolysis at DDDDK(156). Further variants comprising DDDDK(156)SS, DDDDK(156)SD and DDDDK(156)RR showed that the minimal

  2. Controllable synthesis of silver and silver sulfide nanocrystals via selective cleavage of chemical bonds

    NASA Astrophysics Data System (ADS)

    Tang, Aiwei; Wang, Yu; Ye, Haihang; Zhou, Chao; Yang, Chunhe; Li, Xu; Peng, Hongshang; Zhang, Fujun; Hou, Yanbing; Teng, Feng

    2013-09-01

    A one-step colloidal process has been adopted to prepare silver (Ag) and silver sulfide (Ag2S) nanocrystals, thus avoiding presynthesis of an organometallic precursor and the injection of a toxic phosphine agent. During the reaction, a layered intermediate compound is first formed, which then acts as a precursor, decomposing into the nanocrystals. The composition of the as-obtained products can be controlled by selective cleavage of S-C bonds or Ag-S bonds. Pure Ag2S nanocrystals can be obtained by directly heating silver acetate (Ag(OAc)) and n-dodecanethiol (DDT) at 200 ° C without any surfactant, and pure Ag nanocrystals can be synthesized successfully if the reaction temperature is reduced to 190 ° C and the amount of DDT is decreased to 1 ml in the presence of a non-coordinating organic solvent (1-octadecene, ODE). Otherwise, the mixture of Ag and Ag2S is obtained by directly heating Ag(OAc) in DDT by increasing the reaction temperature or in a mixture of DDT and ODE at 200 ° C. The formation mechanism has been discussed in detail in terms of selective S-C and Ag-S bond dissociation due to the nucleophilic attack of DDT and the lower bonding energy of Ag-S. Interestingly, some products can easily self-assemble into two- or three-dimensional (2D or 3D) highly ordered superlattice structures on a copper grid without any additional steps. The excess DDT plays a key role in the superlattice structure due to the bundling and interdigitation of the thiolate molecules adsorbed on the as-obtained nanocrystals.

  3. Controllable synthesis of silver and silver sulfide nanocrystals via selective cleavage of chemical bonds.

    PubMed

    Tang, Aiwei; Wang, Yu; Ye, Haihang; Zhou, Chao; Yang, Chunhe; Li, Xu; Peng, Hongshang; Zhang, Fujun; Hou, Yanbing; Teng, Feng

    2013-09-06

    A one-step colloidal process has been adopted to prepare silver (Ag) and silver sulfide (Ag₂S) nanocrystals, thus avoiding presynthesis of an organometallic precursor and the injection of a toxic phosphine agent. During the reaction, a layered intermediate compound is first formed, which then acts as a precursor, decomposing into the nanocrystals. The composition of the as-obtained products can be controlled by selective cleavage of S-C bonds or Ag-S bonds. Pure Ag₂S nanocrystals can be obtained by directly heating silver acetate (Ag(OAc)) and n-dodecanethiol (DDT) at 200 ° C without any surfactant, and pure Ag nanocrystals can be synthesized successfully if the reaction temperature is reduced to 190 ° C and the amount of DDT is decreased to 1 ml in the presence of a non-coordinating organic solvent (1-octadecene, ODE). Otherwise, the mixture of Ag and Ag₂S is obtained by directly heating Ag(OAc) in DDT by increasing the reaction temperature or in a mixture of DDT and ODE at 200 ° C. The formation mechanism has been discussed in detail in terms of selective S-C and Ag-S bond dissociation due to the nucleophilic attack of DDT and the lower bonding energy of Ag-S. Interestingly, some products can easily self-assemble into two- or three-dimensional (2D or 3D) highly ordered superlattice structures on a copper grid without any additional steps. The excess DDT plays a key role in the superlattice structure due to the bundling and interdigitation of the thiolate molecules adsorbed on the as-obtained nanocrystals.

  4. Photo-assisted cyanation of transition metal nitrates coupled with room temperature C-C bond cleavage of acetonitrile.

    PubMed

    Zou, Shihui; Li, Renhong; Kobayashi, Hisayoshi; Liu, Juanjuan; Fan, Jie

    2013-03-07

    It is a challenge to use acetonitrile as a cyanating agent because of the difficulty in cleaving its C-CN bond. Herein, we report a mild photo-assisted route to conduct the cyanation of transition metal nitrates using acetonitrile as the cyanating agent coupled with room-temperature C-C bond cleavage. DFT calculations and experimental observations suggest a radical-involved reaction mechanism, which excludes toxicity from free cyanide ions.

  5. An unusual carbon-carbon bond cleavage reaction during phosphinothricin biosynthesis

    SciTech Connect

    Cicchillo, Robert M; Zhang, Houjin; Blodgett, Joshua A.V.; Whitteck, John T; Li, Gongyong; Nair, Satish K; van derDonk, Wilfred A; Metcalf, William W

    2010-01-12

    Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture. One such compound, phosphinothricin tripeptide, contains the unusual amino acid phosphinothricin attached to two alanine residues. Synthetic phosphinothricin (glufosinate) is a component of two top-selling herbicides (Basta and Liberty), and is widely used with resistant transgenic crops including corn, cotton and canola. Recent genetic and biochemical studies showed that during phosphinothricin tripeptide biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP). Here we report the in vitro reconstitution of this unprecedented C(sp{sup 3})-C(sp{sup 3}) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-haem iron(II)-dependent dioxygenase that converts HEP to HMP and formate. In contrast to most other members of this family, the oxidative consumption of HEP does not require additional cofactors or the input of exogenous electrons. The current study expands the scope of reactions catalysed by the 2-His-1-carboxylate mononuclear non-haem iron family of enzymes.

  6. Palladium-catalyzed oxidative arylalkylation of activated alkenes: dual C-H bond cleavage of an arene and acetonitrile.

    PubMed

    Wu, Tao; Mu, Xin; Liu, Guosheng

    2011-12-23

    Not one but two: The title reaction proceeds through the dual C-H bond cleavage of both aniline and acetonitrile. The reaction affords a variety of cyano-bearing indolinones in excellent yield. Mechanistic studies demonstrate that this reaction involves a fast arylation of the olefin and a rate-determining C-H activation of the acetonitrile.

  7. An efficient cleavage of the aryl ether C-O bond in supercritical carbon dioxide-water.

    PubMed

    Chatterjee, Maya; Ishizaka, Takayuki; Suzuki, Akira; Kawanami, Hajime

    2013-05-18

    A simple and highly efficient Rh/C catalyzed route for the cleavage of the C-O bond of aromatic ether at 80 °C in the presence of 0.5 MPa of H2 in the scCO2-water medium is reported; CO2 pressure and water play a key role under the tested conditions.

  8. Iron-mediated cleavage of C-C bonds in vicinal tricarbonyl compounds in water.

    PubMed

    Mecinović, Jasmin; Hamed, Refaat B; Schofield, Christopher J

    2009-01-01

    Three of a kind: Vicinal tricarbonyl compounds undergo C-C cleavage mediated by ferric ions (see scheme). The observed cleavage of ninhydrin and dehydroascorbic acid has relevance for amino acid detection and the metabolism of vitamin C.

  9. Coupling of the guanosine glycosidic bond conformation and the ribonucleotide cleavage reaction: implications for barnase catalysis.

    PubMed

    Roca, Maite; De Maria, Leonardo; Wodak, Shoshana J; Moliner, Vicente; Tuñón, Iñaki; Giraldo, Jesús

    2008-02-01

    To examine the possible relationship of guanine-dependent GpA conformations with ribonucleotide cleavage, two potential of mean force (PMF) calculations were performed in aqueous solution. In the first calculation, the guanosine glycosidic (Gchi) angle was used as the reaction coordinate, and computations were performed on two GpA ionic species: protonated (neutral) or deprotonated (negatively charged) guanosine ribose O2 '. Similar energetic profiles featuring two minima corresponding to the anti and syn Gchi regions were obtained for both ionic forms. For both forms the anti conformation was more stable than the syn, and barriers of approximately 4 kcal/mol were obtained for the anti --> syn transition. Structural analysis showed a remarkable sensitivity of the phosphate moiety to the conformation of the Gchi angle, suggesting a possible connection between this conformation and the mechanism of ribonucleotide cleavage. This hypothesis was confirmed by the second PMF calculations, for which the O2 '--P distance for the deprotonated GpA was used as reaction coordinate. The computations were performed from two selected starting points: the anti and syn minima determined in the first PMF study of the deprotonated guanosine ribose O2'. The simulations revealed that the O2 ' attack along the syn Gchi was more favorable than that along the anti Gchi: energetically, significantly lower barriers were obtained in the syn than in the anti conformation for the O--P bond formation; structurally, a lesser O2 '--P initial distance, and a better suited orientation for an in-line attack was observed in the syn relative to the anti conformation. These results are consistent with the catalytically competent conformation of barnase-ribonucleotide complex, which requires a guanine syn conformation of the substrate to enable abstraction of the ribose H2 ' proton by the general base Glu73, thereby suggesting a coupling between the reactive substrate conformation and enzyme structure

  10. Mechanistic examination of Cβ-Cγ bond cleavages of tryptophan residues during dissociations of molecular peptide radical cations.

    PubMed

    Song, Tao; Ma, Ching-Yung; Chu, Ivan K; Siu, Chi-Kit; Laskin, Julia

    2013-02-14

    In this study, we used collision-induced dissociation (CID) to examine the gas-phase fragmentations of [G(n)W](•+) (n = 2-4) and [GXW](•+) (X = C, S, L, F, Y, Q) species. The C(β)-C(γ) bond cleavage of a C-terminal decarboxylated tryptophan residue ([M - CO(2)](•+)) can generate [M - CO(2) - 116](+), [M - CO(2) - 117](•+), and [1H-indole](•+) (m/z 117) species as possible product ions. Competition between the formation of [M - CO(2) - 116](+) and [1H-indole](•+) systems implies the existence of a proton-bound dimer formed between the indole ring and peptide backbone. Formation of such a proton-bound dimer is facile via a protonation of the tryptophan γ-carbon atom as suggested by density functional theory (DFT) calculations. DFT calculations also suggested the initially formed ion 2, the decarboxylated species that is active against C(β)-C(γ) bond cleavage, can efficiently isomerize to form a more stable π-radical isomer (ion 9) as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. The C(β)-C(γ) bond cleavage of a tryptophan residue also can occur directly from peptide radical cations containing a basic residue. CID of [WG(n)R](•+) (n = 1-3) radical cations consistently resulted in predominant formation of [M - 116](+) product ions. It appears that the basic arginine residue tightly sequesters the proton and allows the charge-remote C(β)-C(γ) bond cleavage to prevail over the charge-directed one. DFT calculations predicted that the barrier for the former is 6.2 kcal mol(-1) lower than that of the latter. Furthermore, the pathway involving a salt-bridge intermediate also was accessible during such a bond cleavage event.

  11. Mechanistic Examination of Cβ–Cγ Bond Cleavages of Tryptophan Residues during Dissociations of Molecular Peptide Radical Cations

    SciTech Connect

    Song, Tao; Ma, Ching-Yung; Chu, Ivan K.; Siu, Chi-Kit; Laskin, Julia

    2013-02-14

    In this study, we used collision-induced dissociation (CID) to examine the gas-phase fragmentations of [GnW]•+ (n = 2-4) and [GXW]•+ (X = C, S, L, F, Y, Q) species. The Cβ–Cγ bond cleavage of a C-terminal decarboxylated tryptophan residue ([M - CO2]•+) can generate [M - CO2 - 116]+, [M - CO2 - 117]•+, and [1H-indole]•+ (m/z 117) species as possible product ions. Competition between the formation of [M - CO2 - 116]+ and [1H-indole]•+ systems implies the existence of a proton-bound dimer formed between the indole ring and peptide backbone. Formation of such a proton-bound dimer is facile via a protonation of the tryptophan γ-carbon atom as suggested by density functional theory (DFT) calculations. DFT calculations also suggested the initially formed ion 2--the decarboxylated species that is active against Cβ–Cγ bond cleavage -can efficiently isomerize to form a more-stable -radical isomer (ion 9) as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. The Cβ–Cγ bond cleavage of a tryptophan residue also can occur directly from peptide radical cations containing a basic residue. CID of [WGnR]•+ (n = 1-3) radical cations consistently resulted in predominant formation of [M-116]+ product ions. It appears that the basic arginine residue tightly sequesters the proton and allows the charge-remote Cβ–Cγ bond cleavage to prevail over the charge-directed one. DFT calculations predicted the barrier for the former is 6.2 kcal mol -1 lower than that of the latter. Furthermore, the pathway involving a salt-bridge intermediate also was accessible during such a bond cleavage event.

  12. High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

    SciTech Connect

    Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung; Leeladee, Pannee; Goldberg, David P.

    2016-09-30

    The addition of Lewis or Brönsted acids (LA = Zn(OTf)2, B(C6F5)3, HBArF, TFA) to the high-valent manganese–oxo complex MnV(O)(TBP8Cz) results in the stabilization of a valence tautomer MnIV(O-LA)(TBP8Cz•+). The ZnII and B(C6F5)3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn–Nave = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal oxo ligand. This Mn–O bond length is elongated compared to the MnV(O) starting material (Mn–O = 1.55 Å). The reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H substrates was examined, and it was found that H abstraction from C–H bonds occurs in a 1:1 stoichiometry, giving a MnIV complex and the dehydrogenated organic product. The rates of C–H cleavage are accelerated for the MnIV(O-LA)(TBP8Cz•+) valence tautomer as compared to the MnV(O) valence tautomer when LA = ZnII, B(C6F5)3, and HBArF, whereas for LA = TFA, the C–H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of kH/kD = 25–27 was observed for LA = B(C6F5)3 and HBArF, indicating that H-atom transfer (HAT) is the rate-limiting step in the C–H cleavage reaction and implicating a potential tunneling mechanism for HAT. Furthermore, the reactivity of MnIV(O-LA)(TBP8Cz•+) toward C–H bonds

  13. Implications of protonation and substituent effects for C-O and O-P bond cleavage in phosphate monoesters.

    PubMed

    Loncke, Paul G; Berti, Paul J

    2006-05-10

    A recent study of phosphate monoesters that broke down exclusively through C-O bond cleavage and whose reactivity was unaffected by protonation of the nonbridging oxygens (Byczynski et al. J. Am. Chem. Soc. 2003, 125, 12541) raised several questions about the reactivity of phosphate monoesters, R-O-P(i). Potential catalytic strategies, particularly with regard to selectively promoting C-O or O-P bond cleavage, were investigated computationally through simple alkyl and aryl phosphate monoesters. Both C-O and O-P bonds lengthened upon protonating the bridging oxygen, R-O(H(+))-P(i), and heterolytic bond dissociation energies, DeltaH(C)(-)(O) and DeltaH(O)(-)(P), decreased. Which bond will break depends on the protonation state of the phosphoryl moiety, P(i), and the identity of the organosubstituent, R. Protonating the bridging oxygen when the nonbridging oxygens were already protonated favored C-O cleavage, while protonating the bridging oxygen of the dianion form, R-O-PO(3)(2)(-), favored O-P cleavage. Alkyl R groups capable of forming stable cations were more prone to C-O bond cleavage, with tBu > iPr > F(2)iPr > Me. The lack of effect on the C-O cleavage rate from protonating nonbridging oxygens could arise from two precisely offsetting effects: Protonating nonbridging oxygens lengthens the C-O bond, making it more reactive, but also decreases the bridging oxygen proton affinity, making it less likely to be protonated and, therefore, less reactive. The lack of effect could also arise without bridging oxygen protonation if the ratio of rate constants with different protonation states precisely matched the ratio of acidity constants, K(a). Calculations used hybrid density functional theory (B3PW91/6-31++G) methods with a conductor-like polarizable continuum model (CPCM) of solvation. Calculations on Me-phosphate using MP2/aug-cc-pVDZ and PBE0/aug-cc-pVDZ levels of theory, and variations on the solvation model, confirmed the reproducibility with different

  14. Bond cleavage reactions in the tripeptide trialanine upon free electron capture

    NASA Astrophysics Data System (ADS)

    Puschnigg, Benjamin; Huber, Stefan E.; Scheier, Paul; Probst, Michael; Denifl, Stephan

    2014-05-01

    In the present study we performed dissociative electron attachment (DEA) measurements with the tripeptide trialanine, C9H17N3O4, utilizing a crossed electron-molecular beam experiment with high electron energy resolution (~100 meV). Anion efficiency yields as a function of the incident electron energy are obtained for the most abundant anions up to electron energies of ~4 eV. Quantum chemical calculations are performed to determine the thermochemical thresholds for the anions observed in the measurements. There is no evidence of a molecular anion with lifetime of mass spectrometric timescales. The dehydrogenated closed shell anion (M-H)- is one of the fragment anions observed for which the calculations show that H-loss is energetically possible from carboxyl, as well as amide groups. In contrast to the dipeptide dialanine and monomer alanine the cleavage of the N-Cα bond in the peptide chain is already possible by attachment of electrons at ~0 eV. Contribution to the Topical Issue "Nano-scale Insights into Ion-beam Cancer Therapy", edited by Andrey V. Solov'yov, Nigel Mason, Paulo Limão-Vieira and Malgorzata Smialek-Telega.

  15. Mechanisms for enzymatic cleavage of the N-glycosidic bond in DNA

    PubMed Central

    Drohat, Alexander C.; Maiti, Atanu

    2014-01-01

    DNA glycosylases remove damaged or enzymatically modified nucleobases from DNA, thereby initiating the base excision repair (BER) pathway, which is found in all forms of life. These ubiquitous enzymes promote genomic integrity by initiating repair of mutagenic and/or cytotoxic lesions that arise continuously due to alkylation, deamination, or oxidation of the normal bases in DNA. Glycosylases also perform essential roles in epigenetic regulation of gene expression, by targeting enzymatically-modified forms of the canonical DNA bases. Monofunctional DNA glycosylases hydrolyze the N-glycosidic bond to liberate the target base, while bifunctional glycosylases mediate glycosyl transfer using an amine group of the enzyme, generating a Schiff base intermediate that facilitates their second activity, cleavage of the DNA backbone. Here we review recent advances in understanding the chemical mechanism of monofunctional DNA glycosylases, with an emphasis on how the reactions are influenced by properties of the nucleobase leaving-group, the moiety that varies across the vast range of substrates targeted by these enzymes. PMID:25181003

  16. Proton-driven amide bond-cleavage pathways of gas-phase peptide ions lacking mobile protons.

    PubMed

    Bythell, Benjamin J; Suhai, Sándor; Somogyi, Arpád; Paizs, Béla

    2009-10-07

    The mobile proton model (Dongre, A. R., Jones, J. L., Somogyi, A. and Wysocki, V. H. J. Am. Chem. Soc. 1996, 118 , 8365-8374) of peptide fragmentation states that the ionizing protons play a critical role in the gas-phase fragmentation of protonated peptides upon collision-induced dissociation (CID). The model distinguishes two classes of peptide ions, those with or without easily mobilizable protons. For the former class mild excitation leads to proton transfer reactions which populate amide nitrogen protonation sites. This enables facile amide bond cleavage and thus the formation of b and y sequence ions. In contrast, the latter class of peptide ions contains strongly basic functionalities which sequester the ionizing protons, thereby often hindering formation of sequence ions. Here we describe the proton-driven amide bond cleavages necessary to produce b and y ions from peptide ions lacking easily mobilizable protons. We show that this important class of peptide ions fragments by different means from those with easily mobilizable protons. We present three new amide bond cleavage mechanisms which involve salt-bridge, anhydride, and imine enol intermediates, respectively. All three new mechanisms are less energetically demanding than the classical oxazolone b(n)-y(m) pathway. These mechanisms offer an explanation for the formation of b and y ions from peptide ions with sequestered ionizing protons which are routinely fragmented in large-scale proteomics experiments.

  17. Characterization of heme environment and mechanism of peroxide bond cleavage in human prostacyclin synthase

    PubMed Central

    Yeh, Hui-Chun; Hsu, Pei-Yung; Wang, Jinn-Shyan; Tsai, Ah-Lim; Wang, Lee-Ho

    2010-01-01

    Prostacyclin is a potent mediator of vasodilation and anti-platelet aggregation. It is synthesized from prostaglandin H2 by prostacyclin synthase (PGIS), a member of Family 8 in the cytochrome P450 superfamily. Unlike most P450s, which require exogenous reducing equivalents and an oxygen molecule for mono-oxygenation, PGIS catalyzes an isomerization with an initial step of endoperoxide bond cleavage of prostaglandin H2 (PGH2). The low abundance of PGIS in natural tissues necessitates heterologous expression for studies of structure/function relationships and reaction mechanism. We report here a high-yield prokaryotic system for expression of enzymatically active human PGIS. The PGIS cDNA is modified by replacing the hydrophobic amino-terminal sequence with the more hydrophilic amino-terminal sequence from P450 2C5 and by adding a four-histidine tag at the carboxyl terminus. The resulting recombinant PGIS associates with host cell membranes and was purified to electrophoretic homogeneity by nickel affinity, hydroxyapatite and CM Sepharose column chromatography. The recombinant PGIS, with a heme:protein ratio of 0.9:1, catalyzes prostacyclin formation at a Km of 13.3 µM PGH2 and a Vmax of 980 per min. The dithionite-reduced PGIS binds CO with an on-rate of 5.6 × 105 M−1 s−1 and an off-rate of 15 s−1. The ferrous–CO complex of PGIS is very short-lived and decays at a rate of 0.7 s−1. Spectral binding assays showed that imidazole binds weakly to PGIS (Kd ~0.5 mM,) but clotrimazole, a bulky and rigid imidazole derivative, binds strongly (Kd ~1 µM). The transient nature of the CO complex and the weak imidazole binding seem to support an earlier proposal that PGIS active site has a limited space, but the tight binding of clotrimazole argues against this view. It appears that the heme distal pocket of PGIS is fairly adaptable to ligands of various structures. UV-visible absorption, magnetic circular dichroism and electron paramagnetic resonance spectra

  18. Presolvated Low Energy Electron Attachment to Peptide Methyl esters in Aqueous Solution: C-O Bond Cleavage at 77K

    PubMed Central

    Kheir, Jeanette; Chomicz, Lidia; Engle, Alyson; Rak, Janusz; Sevilla, Michael D.

    2013-01-01

    In this study, the reactions of presolvated electrons with glycine methyl ester and N-acetylalanylalanine methyl ester (N-aAAMe) are investigated by electron spin resonance (ESR) spectroscopy and DFT calculations. Electrons were produced by gamma irradiation in neutral 7.5 M LiCl-D2O aqueous glasses at low temperatures. For glycine methyl ester electron addition at 77K results in both N-terminal deamination to form a glycyl radical and C-O ester bond cleavage to form methyl radicals. For samples of N-acetylalanylalanine methyl ester electrons are found to add to the peptide bonds at 77K and cleave the carboxyl ester groups to produce methyl radicals. On annealing to 160K electron adducts at the peptide links undergo chain scission to produce alanyl radicals and further annealing to 170K α-carbon peptide backbone radicals are produced by hydrogen abstraction. DFT calculations for electron addition to the methyl ester portion of N-aAAMe show the cleavage reaction is highly favorable (free energy equals to −30.7 kcal/mol) with the kinetic barrier of only 9.9 kcal/mol. A substantial electron affinity of the ester link (38.0 kcal/mol) provides more than sufficient energy to overcome this small barrier. Protonated peptide bond electron adducts, also show favorable N-C chain cleavage reactions of −12.7 to −15.5 kcal/mol with a barrier from 7.4 to 10.0 kcal/mol. The substantial adiabatic electron affinity (AEA) of the peptide bond and ester groups provides sufficient energy for the bond dissociation. PMID:23406302

  19. Presolvated low energy electron attachment to peptide methyl esters in aqueous solution: C-O bond cleavage at 77 K.

    PubMed

    Kheir, Jeanette; Chomicz, Lidia; Engle, Alyson; Rak, Janusz; Sevilla, Michael D

    2013-03-14

    In this study, the reactions of presolvated electrons with glycine methyl ester and N-acetylalanylalanine methyl ester (N-aAAMe) are investigated by electron spin resonance (ESR) spectroscopy and DFT calculations. Electrons were produced by γ-irradiation in neutral 7.5 M LiCl-D2O aqueous glasses at low temperatures. For glycine methyl ester, electron addition at 77 K results in both N-terminal deamination to form a glycyl radical and C-O ester bond cleavage to form methyl radicals. For samples of N-acetylalanylalanine methyl ester, electrons are found to add to the peptide bonds at 77 K and cleave the carboxyl ester groups to produce methyl radicals. On annealing to 160 K, electron adducts at the peptide links undergo chain scission to produce alanyl radicals and on further annealing to 170 K α-carbon peptide backbone radicals are produced by hydrogen abstraction. DFT calculations for electron addition to the methyl ester portion of N-aAAMe show the cleavage reaction is highly favorable (free energy equals to -30.7 kcal/mol) with the kinetic barrier of only 9.9 kcal/mol. A substantial electron affinity of the ester link (38.0 kcal/mol) provides more than sufficient energy to overcome this small barrier. Protonated peptide bond electron adducts also show favorable N-C chain cleavage reactions of -12.7 to -15.5 kcal/mol with a barrier from 7.4 to 10.0 kcal/mol. The substantial adiabatic electron affinity (AEA) of the peptide bond and ester groups provides sufficient energy for the bond dissociation.

  20. Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

    SciTech Connect

    Hanson, Susan K; Gordon, John C; Thorn, David L; Scott, Brian L; Baker, R Tom

    2009-01-01

    The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A

  1. Facile C-S, S-H, and S-S bond cleavage using a nickel(0) NHC complex.

    PubMed

    Schaub, Thomas; Backes, Marc; Plietzsch, Oliver; Radius, Udo

    2009-09-21

    [Ni2(iPr2Im)4(COD)] 1 (iPr2Im = 1,3-di(isopropyl)-imidazol-2-ylidene) reacts at room temperature with the thioethers methyl para-tolyl sulfide, ethyl phenyl sulfide, benzothiophene and dibenzothiophene to afford the C-S bond cleavage products [Ni(iPr2Im)2(4-CH3-C6H4)(SMe)] 2, [Ni(iPr2Im)2(C6H5)(SEt)] 3, [Ni(iPr2Im)2(1,8-benzothiophenylato)] 4 and [Ni(iPr2Im)2(C,S-dibenzothiophenylato)] 5. In contrast to the reaction of thioethers or sulfoxides (reported earlier), no C-S bond cleavage was observed for the reaction of 1 with the sulfones bezothiophene-1,1-dioxide and methyl phenyl sulfone. In those cases the stable compounds [Ni(iPr2Im)2(eta2-2,3-benzothiophene-1,1-dioxide)] 6 and [Ni(iPr2Im)2(eta2-MeSO2C6H5)] 7 with a eta2-coordinated sulfone ligand have been isolated. Compound 6 has been structurally characterized. S-H bond cleavage was observed using 2-methyl-2-propanthiol to afford [Ni(iPr2Im)2(H)(StBu)] 8. The reaction of 1 with disulfides led to the dithiolato complexes [Ni(iPr2Im)2(SR)2] (R = tBu 9, Me 10, Ph 11) by S-S bond scission.

  2. Effect of trastuzumab interchain disulfide bond cleavage on Fcγ receptor binding and antibody-dependent tumour cell phagocytosis.

    PubMed

    Suzuki, Mami; Yamanoi, Ayaka; Machino, Yusuke; Ootsubo, Michiko; Izawa, Ken-ichi; Kohroki, Junya; Masuho, Yasuhiko

    2016-01-01

    The Fc domain of human IgG1 binds to Fcγ receptors (FcγRs) to induce effector functions such as phagocytosis. There are four interchain disulfide bonds between the H and L chains. In this study, the disulfide bonds within the IgG1 trastuzumab (TRA), which is specific for HER2, were cleaved by mild S-sulfonation or by mild reduction followed by S-alkylation with three different reagents. The cleavage did not change the binding activities of TRA to HER2-bearing SK-BR-3 cells. The binding activities of TRA to FcγRIIA and FcγRIIB were greatly enhanced by modification with mild reduction and S-alkylation with ICH2CONH2 or N-(4-aminophenyl) maleimide, while the binding activities of TRA to FcγRI and FcγRIIIA were decreased by any of the four modifications. However, the interchain disulfide bond cleavage by the different modifications did not change the antibody-dependent cell-mediated phagocytosis (ADCP) of SK-BR-3 cells by activated THP-1 cells. The order of FcγR expression levels on the THP-1 cells was FcγRII > FcγRI > FcγRIII and ADCP was inhibited by blocking antibodies against FcγRI and FcγRII. These results imply that the effect of the interchain disulfide bond cleavage on FcγRs binding and ADCP is dependent on modifications of the cysteine residues and the FcγR isotypes.

  3. Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: from C-C bond cleavage to C-C bond ligation.

    PubMed

    Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael

    2014-12-22

    ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant.

  4. Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

    PubMed

    Wang, Teng; Jiao, Ning

    2014-04-15

    Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

  5. Aromatic Cations from Oxidative Carbon–Hydrogen Bond Cleavage in Bimolecular Carbon–Carbon Bond Forming Reactions

    PubMed Central

    Clausen, Dane J.

    2012-01-01

    Chromenes and isochromenes react quickly with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form persistent aromatic oxocarbenium ions through oxidative carbon–hydrogen cleavage. This process is tolerant of electron-donating and electron-withdrawing groups on the benzene ring and additional substitution on the pyran ring. A variety of nucleophiles can be added to these cations to generate a diverse set of structures. PMID:22780559

  6. Reaction of five-membered zirconacycloallenoids with the strong Lewis acid B(C6F5)3.

    PubMed

    Bender, Georg; Daniliuc, Constantin G; Wibbeling, Birgit; Kehr, Gerald; Erker, Gerhard

    2014-08-28

    Two alkyl and aryl substituted five-membered zirconacycloallenoids underwent a typical σ-alkyl metallocene reaction with B(C6F5)3, namely cleavage of the Zr-C(sp(3)) bond with formation of zwitterionic (η(2)-allenyl)zirconium/alkylborate products. Both products were characterized by X-ray crystal structural analyses.

  7. Facile C(sp(2))-C(sp(2)) bond cleavage in oxalic acid-derived radicals.

    PubMed

    Molt, Robert W; Lecher, Alison M; Clark, Timothy; Bartlett, Rodney J; Richards, Nigel G J

    2015-03-11

    Oxalate decarboxylase (OxDC) catalyzes the Mn-dependent conversion of the oxalate monoanion into CO2 and formate. Many questions remain about the catalytic mechanism of OxDC although it has been proposed that the reaction proceeds via substrate-based radical intermediates. Using coupled cluster theory combined with implicit solvation models we have examined the effects of radical formation on the structure and reactivity of oxalic acid-derived radicals in aqueous solution. Our results show that the calculated solution-phase free-energy barrier for C-C bond cleavage to form CO2 is decreased from 34.2 kcal/mol for oxalic acid to only 9.3 kcal/mol and a maximum of 3.5 kcal/mol for the cationic and neutral oxalic acid-derived radicals, respectively. These studies also show that the C-C σ bonding orbital of the radical cation contains only a single electron, giving rise to an elongated C-C bond distance of 1.7 Å; a similar lengthening of the C-C bond is not observed for the neutral radical. This study provides new chemical insights into the structure and stability of plausible intermediates in the catalytic mechanism of OxDC, and suggests that removal of an electron to form a radical (with or without the concomitant loss of a proton) may be a general strategy for cleaving the unreactive C-C bonds between adjacent sp(2)-hybridized carbon atoms.

  8. Titanium alkoxyimido (Ti=N-OR) complexes: reductive N-O bond cleavage at the boundary between hydrazide and peroxide ligands.

    PubMed

    Schwarz, Andrew D; Nova, Ainara; Clot, Eric; Mountford, Philip

    2011-05-07

    The first Group 4 alkoxyimido compounds are reported. The Ti=N-O(t)Bu group in Ti(N(2)N(Me))(NO(t)Bu)(py) undergoes facile 2-electron N-O bond cleavage with PhCCMe as the reductant to form a 1,2-diamidoalkene group via two highly selective N-C bond forming events.

  9. Single-site N-N bond cleavage by Mo(IV): possible mechanisms of hydrazido(1-) to nitrido conversion.

    PubMed

    DiFranco, Stephen A; Staples, Richard J; Odom, Aaron L

    2013-02-21

    Mo(NMe(2))(4) and the tridentate, dipyrrolyl ligand H(2)dpma(mes) were found to form 5-coordinate Mo(NMe(2))(2)(dpma(mes)) (1), which exhibits spin-crossover behaviour in solution. The complex is a ground state singlet with a barrier of 1150 cm(-1) for production of the triplet in d(8)-toluene. The complex reacts with 1,1-disubstituted hydrazines or O-benzylhydroxylamine to produce nitrido MoN(NMe(2))(dpma(mes)). The mechanism of the 1,1-dimethylhydrazine reaction with 1 was examined along with the mechanism of substitution of NMe(2) with H(2)NNMe(2) in a diamagnetic zirconium analogue. The proposed mechanism involves production of a hydrazido(1-) intermediate, Mo(NMe(2))(NHNMe(2))(dpma(mes)), which undergoes an α,β-proton shift and N-N bond cleavage with metal oxidation to form the nitrido. The rate law for the reaction was found to be -d[1]/dt = k(obs)[1][hydrazine] by initial rate experiments and examination of the full reaction profile. This conversion from hydrazido(1-) to nitrido is somewhat analogous to the proposed mechanism for O-O bond cleavage in some peroxidases.

  10. Use of a Novel Fluorinated Organosulfur Compound To Isolate Bacteria Capable of Carbon-Sulfur Bond Cleavage

    PubMed Central

    Van Hamme, Jonathan D.; Fedorak, Phillip M.; Foght, Julia M.; Gray, Murray R.; Dettman, Heather D.

    2004-01-01

    The vacuum residue fraction of heavy crudes contributes to the viscosity of these oils. Specific microbial cleavage of C—S bonds in alkylsulfide bridges that form linkages in this fraction may result in dramatic viscosity reduction. To date, no bacterial strains have been shown conclusively to cleave C—S bonds within alkyl chains. Screening for microbes that can perform this activity was greatly facilitated by the use of a newly synthesized compound, bis-(3-pentafluorophenylpropyl)-sulfide (PFPS), as a novel sulfur source. The terminal pentafluorinated aromatic rings of PFPS preclude growth of aromatic ring-degrading bacteria but allow for selective enrichment of strains capable of cleaving C—S bonds. A unique bacterial strain, Rhodococcus sp. strain JVH1, that used PFPS as a sole sulfur source was isolated from an oil-contaminated environment. Gas chromatography-mass spectrometry analysis revealed that JVH1 oxidized PFPS to a sulfoxide and then a sulfone prior to cleaving the C—S bond to form an alcohol and, presumably, a sulfinate from which sulfur could be extracted for growth. Four known dibenzothiophene-desulfurizing strains, including Rhodococcus sp. strain IGTS8, were all unable to cleave the C—S bond in PFPS but could oxidize PFPS to the sulfone via the sulfoxide. Conversely, JVH1 was unable to oxidize dibenzothiophene but was able to use a variety of alkyl sulfides, in addition to PFPS, as sole sulfur sources. Overall, PFPS is an excellent tool for isolating bacteria capable of cleaving subterminal C—S bonds within alkyl chains. The type of desulfurization displayed by JVH1 differs significantly from previously described reaction results. PMID:15006770

  11. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

    PubMed

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

    2017-03-17

    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1).

  12. Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin*

    PubMed Central

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; Heins, Richard A.; McAndrew, Ryan P.; Bingman, Craig; Deng, Kai; Holland, Keefe C.; Noguera, Daniel R.; Simmons, Blake A.; Sale, Kenneth L.; Ralph, John; Donohue, Timothy J.; Adams, Paul D.; Phillips, George N.

    2016-01-01

    Lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin. PMID:26637355

  13. Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin.

    PubMed

    Helmich, Kate E; Pereira, Jose Henrique; Gall, Daniel L; Heins, Richard A; McAndrew, Ryan P; Bingman, Craig; Deng, Kai; Holland, Keefe C; Noguera, Daniel R; Simmons, Blake A; Sale, Kenneth L; Ralph, John; Donohue, Timothy J; Adams, Paul D; Phillips, George N

    2016-03-04

    Lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50-70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.

  14. Structural basis of stereospecificity in the bacterial enzymatic cleavage of β-aryl ether bonds in lignin

    DOE PAGES

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; ...

    2015-12-04

    Here, lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, wemore » present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.« less

  15. Structural basis of stereospecificity in the bacterial enzymatic cleavage of β-aryl ether bonds in lignin

    SciTech Connect

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; Heins, Richard A.; McAndrew, Ryan P.; Bingman, Craig; Deng, Kai; Holland, Keefe C.; Noguera, Daniel R.; Simmons, Blake A.; Sale, Kenneth L.; Ralph, John; Donohue, Timothy J.; Adams, Paul D.; Phillips, George N.

    2015-12-04

    Here, lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.

  16. Quantum Dynamics in an Explicit Solvent Environment: A Photochemical Bond Cleavage Treated with a Combined QD/MD Approach.

    PubMed

    Thallmair, Sebastian; Zauleck, Julius P P; de Vivie-Riedle, Regina

    2015-05-12

    In quantum chemistry methods to describe environmental effects on different levels of complexity are available in the common program packages. Electrostatic effects of a solvent for example can be included in an implicit or explicit way. For chemical reactions with large structural changes additional mechanical effects come into play. Their treatment within a quantum dynamical context is a major challenge, especially when excited states are involved. Recently, we introduced a method that realizes an implicit description. Here, we present an approach combining quantum dynamics and molecular dynamics. It explicitly incorporates the solvent environment, whereby the electrostatic as well as the dynamic effects are captured. This new method is demonstrated for the ultrafast photoinduced bond cleavage of diphenylmethylphosphonium ions (Ph2CH-PPh3(+)), a common precursor to generate reactive carbocations in solution.

  17. Cα-C bond cleavage of the peptide backbone in MALDI in-source decay using salicylic acid derivative matrices.

    PubMed

    Asakawa, Daiki; Takayama, Mitsuo

    2011-07-01

    The use of 5-formylsalicylic acid (5-FSA) and 5-nitrosalicylic acid (5-NSA) as novel matrices for in-source decay (ISD) of peptides in matrix-assisted laser desorption/ionization (MALDI) is described. The use of 5-FSA and 5-NSA generated a- and x-series ions accompanied by oxidized peptides [M - 2 H + H](+). The preferential formation of a- and x-series ions was found to be dependent on the hydrogen-accepting ability of matrix. The hydrogen-accepting ability estimated from the ratio of signal intensity of oxidized product [M - 2 H + H](+) to that of non-oxidized protonated molecule [M + H](+) of peptide was of the order 5-NSA > 5-FSA > 5-aminosalicylic acid (5-ASA) ≒ 2,5-dihydroxyl benzoic acid (2,5-DHB) ≒ 0. The results suggest that the hydrogen transfer reaction from peptide to 5-FSA and 5-NSA occurs during the MALDI-ISD processes. The hydrogen abstraction from peptides results in the formation of oxidized peptides containing a radical site on the amide nitrogen with subsequent radical-induced cleavage at the Cα-C bond, leading to the formation of a- and x-series ions. The most significant feature of MALDI-ISD with 5-FSA and 5-NSA is the specific cleavage of the Cα-C bond of the peptide backbone without degradation of side-chain and post-translational modifications (PTM). The matrix provides a useful complementary method to conventional MALDI-ISD for amino acid sequencing and site localization of PTMs in peptides.

  18. Photodecomposition profiles of beta-bond cleavage of phenylphenacyl derivatives in the higher triplet excited states during stepwise two-color two-laser flash photolysis.

    PubMed

    Yamaji, Minoru; Cai, Xichen; Sakamoto, Masanori; Fujitsuka, Mamoru; Majima, Tetsuro

    2008-11-13

    Photochemical properties of p-phenylphenacyl derivatives (PP-X) having C-halide, C-S, and C-O bonds in the lowest (T 1) and higher (T n ) triplet excited states were investigated in solution by using single-color and stepwise two-color two-laser flash photolysis techniques. PP-Xs (X = Br, SH, and SPh) undergo beta-bond dissociation in the lowest singlet excited states (S 1) while the C-X bonds of other PP-Xs are stable upon 266-nm laser photolysis. The T 1(pi,pi*) states of PP-X were efficiently produced during 355-nm laser photolysis of benzophenone as a triplet sensitizer. Triplet PP-Xs deactivate to the ground state without photochemical reactions. Upon 430-nm laser photolysis of the T 1 states of PP-X (X = Br, Cl, SH, SPh, OH, OMe, and OPh), decomposition of PP-X in the T n states was found. On the basis of the changes in the transient absorption, quantum yields (Phi dec) of the decomposition of PP-X in the T n states were determined, while bond dissociation energies (BDE) of the C-X bonds were calculated by computations. According to the relationship between the Phi dec and BDE values, it was shown that the decomposition of PP-X in the T n state is due to beta-cleavage of the corresponding C-X bond, and that the state energy of the reactive T n for the C-O bond cleavage differs from that for the C-halide and C-S bond cleavage. The reaction profiles of the C-X bond cleavage of PP-X in the T n states were discussed.

  19. Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C-O Bonds.

    PubMed

    Wang, Meng; Shi, Hui; Camaioni, Donald M; Lercher, Johannes A

    2017-02-13

    Metallic palladium surfaces are highly selective in promoting the reductive hydrolysis of aromatic ethers in aqueous phase at relatively mild temperatures and pressures of H2 . At quantitative conversions, the selectivity to hydrolysis products of PhOR ethers was observed to range from 50 % (R=Ph) to greater than 90 % (R=n-C4 H9 , cyclohexyl, and PhCH2 CH2 ). By analysis of the evolution of products with and without incorporation of H2(18) O, the pathway was concluded to be initiated by palladium metal catalyzed partial hydrogenation of the phenyl group to an enol ether. Water then rapidly adds to the enol ether to form a hemiacetal, which then undergoes elimination to cyclohexanone and phenol/alkanol products. A remarkable feature of the reaction is that the stronger Ph-O bond is cleaved rather than the weaker aliphatic O-R bond.

  20. Characterization of carbon-sulfur bond cleavage by axenic and mixed cultures of Rhodococcus rhodochrous IGTS8

    SciTech Connect

    Kayser, K.J.; Bielaga, B.A.; Jackowski, K.; Oduson, O.; Kilbane, J. II

    1992-12-31

    Growth assays reveal that Rhodococcus rhodochrous IGTS8 can utilize a wide range of organosulfur compounds as the sole source of sulfur. Compounds that are utilized include thiophenes, sulfides, disulfides, mercaptans, sulfoxides, and sulfones. None of the organosulfur compounds tested can serve as a carbon source. A convenient spectrophotometric assay (Gibbs assay) based on the chromogenic reaction of 2,6-dichloroquinone-4-chloroimide with aromatic hydroxyl groups was developed and used in conjunction with GC/MS analysis to examine the kinetics of carbon-sulfur bond cleavage by axenic and mixed cell cultures of Rhodococcus rhodochrous IGTS8. The desulfurization trait is expressed at uniform levels during the mid-exponential phase, reaches a maximum during idiophase, and then declines in stationary-phase cells. Desulfurization rates for dibenzothiophene (DBT) range from 8 to 15 {mu}M of DBT/10{sup 12} cells/hour. Mixtures of genetically marked Rhodococcus rhodochrous IGTS8 and an organisms incapable of cleaning carbon-sulfur bonds in relevant test compounds, Enterobacter cloacae, were prepared in ratios that varied over six orders of magnitude. Growth studies revealed that Enterobacter cloacae was able to gain access to sulfur liberated from organosulfur compounds by IGTS8; however, cell-to-cell contact was required. These data also indicate that the desulfurization activity of IGTS8 cells in mixed cultures may be as much as 200-fold higher than in axenic cultures.

  1. Metal-catalyzed C-C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability.

    PubMed

    Flaherty, David W; Hibbitts, David D; Iglesia, Enrique

    2014-07-09

    Methyl substituents at C-C bonds influence hydrogenolysis rates and selectivities of acyclic and cyclic C2-C8 alkanes on Ir, Rh, Ru, and Pt catalysts. C-C cleavage transition states form via equilibrated dehydrogenation steps that replace several C-H bonds with C-metal bonds, desorb H atoms (H*) from saturated surfaces, and form λ H2(g) molecules. Activation enthalpies (ΔH(‡)) and entropies (ΔS(‡)) and λ values for (3)C-(x)C cleavage are larger than for (2)C-(2)C or (2)C-(1)C bonds, irrespective of the composition of metal clusters or the cyclic/acyclic structure of the reactants. (3)C-(x)C bonds cleave through α,β,γ- or α,β,γ,δ-bound transition states, as indicated by the agreement between measured activation entropies and those estimated for such structures using statistical mechanics. In contrast, less substituted C-C bonds involve α,β-bound species with each C atom bound to several surface atoms. These α,β configurations weaken C-C bonds through back-donation to antibonding orbitals, but such configurations cannot form with (3)C atoms, which have one C-H bond and thus can form only one C-M bond. (3)C-(x)C cleavage involves attachment of other C atoms, which requires endothermic C-H activation and H* desorption steps that lead to larger ΔH(‡) values but also larger ΔS(‡) values (by forming more H2(g)) than for (2)C-(2)C and (2)C-(1)C bonds, irrespective of alkane size (C2-C8) or cyclic/acyclic structure. These data and their mechanistic interpretation indicate that low temperatures and high H2 pressures favor cleavage of less substituted C-C bonds and form more highly branched products from cyclic and acyclic alkanes. Such interpretations and catalytic consequences of substitution seem also relevant to C-X cleavage (X = S, N, O) in desulfurization, denitrogenation, and deoxygenation reactions.

  2. Mechanism of SN2 disulfide bond cleavage by phosphorus nucleophiles. Implications for biochemical disulfide reducing agents.

    PubMed

    Dmitrenko, Olga; Thorpe, Colin; Bach, Robert D

    2007-10-26

    The B3LYP variant of DFT has been used to study the mechanism of S-S bond scission in dimethyl disulfide by a phosphorus nucleophile, trimethylphospine (TMP). The reaction is highly endothermic in the gas phase and requires significant external stabilization of the charged products. DFT calculations (B3LYP) were performed with explicit (water molecules added) and implicit solvent corrections (COSMO model). The transition structures for this SN2 displacement reaction in a number of model systems have been located and fully characterized. The reaction barriers calculated with different approaches for different systems are quite close (around 11 kcal/mol). Remarkably, the calculations suggest that the reaction is almost barrierless with respect to the preorganized reaction complex and that most of the activation energy is required to rearrange the disulfide and TMP to its most effective orientation for the SMe group transfer way. Different reactivities of different phosphorus nucleophiles were suggested to be the result of steric effects, as manifested largely by varying amounts of hindrance to solvation of the initial product phosphonium ion. These data indicate that the gas-phase addition of a phosphine to the disulfide moiety will most likely form a phosphonium cation-thiolate anion salt, in the presence of four or more water molecules, that provide sufficient H-bonding stabilization to allow displacement of the thiolate anion, a normal uncomplicated SN2 transition state is to be expected.

  3. Promotion of exocyclic bond cleavages in the decomposition of 1,3-disilacyclobutane in the presence of a metal filament.

    PubMed

    Badran, I; Shi, Y J

    2015-01-29

    The primary decomposition of 1,3-disilacyclobutane (DSCB) on a tungsten filament and its secondary gas-phase reactions in a hot-wire chemical vapor deposition (CVD) reactor have been studied using laser ionization mass spectrometry. Under the collision-free conditions, DSCB decomposes on the W filament to produce H2 molecules with an activation energy of 43.6 ± 4.1 kJ·mol(-1). With the help of the isotope labeling and chemical trapping methods, the mechanistic details in the secondary gas-phase reactions important in the hot-wire CVD reactor setup have been examined. The dominant pathway has been demonstrated to be the insertion of the cyclic 1,3-disilacyclobut-1-ylidene, generated by exocyclic Si-H bond rupture, into the Si-H bond in DSCB to form 1,1'-bis(1,3-disilacyclobutane) (174 amu). The successful trapping of 1,3-disilacyclobut-1-ylidene by both 1,3-butadiene and trimethylsilane provides compelling evidence for the existence of this cyclic silylene species in the hot-wire CVD reactor with DSCB. Other reactions operating in the reactor include the DSCB cycloreversion to form silene and the ring opening of DSCB via 1,2-H shift to produce silene/methylsilylene and 1-methylsilene/silylene. The introduction of an additional Si atom in the four-membered ring monosilacyclobutane molecule has caused two major changes in the reaction chemistry assumed by DSCB: (1) The endocyclic cycloreversion reactions that dominate in the decomposition of monosilacyclobutane molecules only play a much less important role in the dissociation of DSCB; and (2) the exocyclic bond cleavages are promoted in DSCB due to the ring stabilization caused by the introduction of one additional Si atom.

  4. Mass Spectrometry and Theoretical Studies on N-C Bond Cleavages in the N-Sulfonylamidino Thymine Derivatives

    NASA Astrophysics Data System (ADS)

    Kobetić, Renata; Kazazić, Snježana; Kovačević, Borislav; Glasovac, Zoran; Krstulović, Luka; Bajić, Miroslav; Žinić, Biserka

    2015-05-01

    The reactivity of new biologically active thymine derivatives substituted with 2-(arylsulfonamidino)ethyl group at N1 and N3 position was investigated in the gas phase using CID experiments (ESI-MS/MS) and by density functional theory (DFT) calculations. Both derivatives show similar chemistry in the negative mode with a retro-Michael addition (Path A-) being the most abundant reaction channel, which correlate well with the fluoride induced retro-Michael addition observed in solution. The difference in the fragmentation of N-3 substituted thymine 5 and N-1 substituted thymine 1 in the positive mode relates to the preferred cleavage of the sulfonyl group ( m/z 155, Path B) in N-3 isomer and the formation of the acryl sulfonamidine 3 ( m/z 309) via Path A in N-1 isomer. Mechanistic studies of the cleavage reaction conducted by DFT calculations give the trend of the calculated activation energies that agree well with the experimental observations. A mechanism of the retro-Michael reaction was interpreted as a McLafferty type of fragmentation, which includes Hβ proton shift to one of the neighboring oxygen atoms in a 1,5-fashion inducing N1(N3)-Cα bond scission. This mechanism was found to be kinetically favorable over other tested mechanisms. Significant difference in the observed fragmentation pattern of N-1 and N-3 isomers proves the ESI-MS/MS technique as an excellent method for tracking the fate of similar sulfonamidine drugs. Also, the observed N-1 and/or N-3 thymine alkylation with in situ formed reactive acryl sulfonamidine 3 as a Michael acceptor may open interesting possibilities for the preparation of other N-3 substituted pyrimidines.

  5. CH stretching excitation in the early barrier F + CHD3 reaction inhibits CH bond cleavage.

    PubMed

    Zhang, Weiqing; Kawamata, Hiroshi; Liu, Kopin

    2009-07-17

    Most studies of the impact of vibrational excitation on molecular reactivity have focused on reactions with a late barrier (that is, a transition state resembling the products). For an early barrier reaction, conventional wisdom predicts that a reactant's vibration should not couple efficiently to the reaction coordinate and thus should have little impact on the outcome. We report here an in-depth experimental study of the reactivity effects exerted by reactant C-H stretching excitation in a prototypical early-barrier reaction, F + CHD3. Rather counterintuitively, we find that the vibration hinders the overall reaction rate, inhibits scission of the excited bond itself (favoring the DF + CHD2 product channel), and influences the coproduct vibrational distribution despite being conserved in the CHD2 product. The results highlight substantial gaps in our predictive framework for state-selective polyatomic reactivity.

  6. An ab initio Study of Decay Mechanism of Adenine: the Facile Path of the Amino NH Bond Cleavage

    SciTech Connect

    Conti, Irene; Garavelli, Marco; Orlandi, Giorgio

    2007-12-26

    A comprehensive study of the radiationless decay processes of the lowest excited singlet states in the isolated 9H-Adenine has been performed at the CASPT2//CASSCF level. The minimum energy paths of the L{sub a}, L{sub b} and n{pi}* singlet states along different skeletal distortions have been computed and the Conical Intersections (CIs) involving these states have been determined. The fast deactivation path of L{sub a} along a skeletal deformation, which leads to a S{sub 0}/L{sub a} CI, as previously discussed, is confirmed. Moreover, low-lying CIs between S{sub 0} and {pi}{sigma}* singlet states have been characterized, where {sigma}* is the antibonding orbital localized on a N-H bond of the amino ({pi}{sigma}{sub NH2*}) or of the azine group ({pi}{sigma}{sub N9H*}). We have found that the repulsive {pi}{sigma}{sub NH2*} state associated with an amino N-H bond can be populated through a barrierless way. Therefore, the decay path shows a bifurcation leading to two possible ways of radiationless deactivation: on one hand a non-photochemical decay through the S{sub 0}/L{sub a} or S{sub 0}/n{pi}* CIs and on the other hand a photochemical process via the possible access to the S{sub 0}/{pi}{sigma}{sub NH2*} CI that produces N-H cleavage. In this way, we can explain the H atom loss found upon UV excitation. We have considered also the decay of higher energy bright states. We have found that these states can decay also by converting to the repulsive {pi}{sigma}{sub N9H*} state associated with the azine NH bond. This new channel suggests an increase of H-atom photoproduction yield by excitating Adenine with lower wavelength radiations. The study of the decay processes of an Adenine molecule in the double strand d(A)10{center_dot}d(T)10 in water solvent is currently underway: Adenine is treated by the Quantum Mechanical (QM) approach and the remaining molecules are described at the Molecular Mechanics (MM) level. We use the COBRAMM program that is a tunable QM/MM approach

  7. Processive degradation of unstructured protein by Escherichia coli Lon occurs via the slow, sequential delivery of multiple scissile sites followed by rapid and synchronized peptide bond cleavage events.

    PubMed

    Mikita, Natalie; Cheng, Iteen; Fishovitz, Jennifer; Huang, Jonathan; Lee, Irene

    2013-08-20

    Processive protein degradation is a common feature found in ATP-dependent proteases. This study utilized a physiological substrate of Escherichia coli Lon protease known as the lambda N protein (λN) to initiate the first kinetic analysis of the proteolytic mechanism of this enzyme. To this end, experiments were designed to determine the timing of three selected scissile sites in λN approaching the proteolytic site of ELon and their subsequent cleavages to gain insight into the mechanism by which ATP-dependent proteases attain processivity in protein degradation. The kinetic profile of peptide bond cleavage at different regions of λN was first detected by the iTRAQ/mass spectrometry technique. Fluorogenic λN constructs were then generated as reporter substrates for transient kinetic characterization of the ATP- versus AMPPNP-dependent peptide bond cleavage and the delivery of the scissile sites near the amino- versus carboxyl-terminal of the λN protein to the proteolytic site of ELon. Collectively, our results support a mechanism by which the cleavage of multiple peptide bonds awaits the "almost complete" delivery of all the scissile sites in λN to the proteolytic site in an ATP-dependent manner. Comparing the time courses of delivery to the active site of the selected scissile sites further implicates the existence of a preferred directionality in the final stage of substrate delivery, which begins at the carboxyl-terminal. The subsequent cleavage of the scissile sites in λN, however, appears to lack a specific directionality and occurs at a much faster rate than the substrate delivery step.

  8. Reactions in 1,1,1-trifluoroacetone triggered by low energy electrons (0-10 eV): from simple bond cleavages to complex unimolecular reactions.

    PubMed

    Illenberger, Eugen; Meinke, Martina C

    2014-08-21

    The impact of low energy electrons (0-10 eV) to 1,1,1-trifluoroacetone yields a variety of fragment anions which are formed via dissociative electron attachment (DEA) through three pronounced resonances located at 0.8 eV, near 4 eV, and in the energy range 8-9 eV. The fragment ions arise from different reactions ranging from the direct cleavage of one single or double bond (formation of F(-), CF3(-), O(-), (M-H)(-), and M-F)(-)) to remarkably complex unimolecular reactions associated with substantial geometric and electronic rearrangement in the transitory intermediate (formation of OH(-), FHF(-), (M-HF)(-), CCH(-), and HCCO(-). The ion CCH(-), for example, is formed by an excision of unit from the target molecule through the concerted cleavage of four bonds and recombination to H2O within the neutral component of the reaction.

  9. Three-Component Coupling of Triflyloxy-Substituted Benzocyclobutenones, Organolithium Reagents, and Arynophiles Promoted by Generation of Aryne via Carbon-Carbon Bond Cleavage.

    PubMed

    Uchida, Keisuke; Yoshida, Suguru; Hosoya, Takamitsu

    2017-02-23

    Treatment of benzocyclobutenones bearing a triflyloxy group adjacent to the four-membered ring with organolithium reagents in the presence of arynophiles efficiently affords three-component coupled α-arylketones. Mechanistic studies indicate that the reaction is promoted by generation of the aryne via carbon-carbon bond cleavage of a benzocyclobutenoxide intermediate, which led us to find a fluoride-mediated aryne generation method from triflyloxy-substituted benzocyclobutenone silyl acetal precursors.

  10. Visible Light Copper Photoredox-Catalyzed Aerobic Oxidative Coupling of Phenols and Terminal Alkynes: Regioselective Synthesis of Functionalized Ketones via C≡C Triple Bond Cleavage.

    PubMed

    Sagadevan, Arunachalam; Charpe, Vaibhav Pramod; Ragupathi, Ayyakkannu; Hwang, Kuo Chu

    2017-03-01

    Direct oxidative coupling of phenols and terminal alkynes was achieved at room temperature by a visible-light-mediated copper-catalyzed photoredox process. This method allows regioselective synthesis of hydroxyl-functionalized aryl and alkyl ketones from simple phenols and phenylacetylene via C≡C triple bond cleavage. 47 examples were presented. From a synthetic perspective, this protocol offers an efficient synthetic route for the preparation of pharmaceutical drugs, such as pitofenone and fenofibrate.

  11. Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO.

    PubMed

    Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng

    2012-08-04

    With atmospheric oxygen as the oxidant, a novel copper(I)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation.

  12. Reaction of SO2 with pure and metal-doped MgO: Basic principles for the cleavage of S-O bonds

    NASA Astrophysics Data System (ADS)

    Rodriguez, J. A.; Jirsak, T.; González, L.; Evans, J.; Pérez, M.; Maiti, A.

    2001-12-01

    Synchrotron-based high-resolution photoemission, x-ray absorption near-edge spectroscopy, and first-principles density-functional calculations are used to examine the interaction of SO2 with pure and modified surfaces of magnesium oxide. On a MgO(100) single crystal, SO2 reacts with O centers to form SO3 and SO4 species. The bonding interactions with the Mg cations are weak and do not lead to cleavage of S-O bonds. An identical result is found after adsorbing SO2 on pure stoichiometric powders of MgO and other oxides (TiO2, Cr2O3, Fe2O3, NiO, CuO, ZnO, V2O5, CeO2, BaO). In these systems, the occupied cations bands are too stable for effective bonding interactions with the LUMO of SO2. To activate an oxide for S-O bond cleavage, one has to create occupied metal states above the valence band of the oxide. DF calculations predict that in the presence of these "extra" electronic states the adsorption energy of SO2 should increase, and there should be a significant oxide→SO2(LUMO) charge transfer that facilitates the cleavage of the S-O bonds. In this article, we explore three different approaches (formation of O vacancies, promotion with alkali metals, and doping with transition metals) that lead to the activation of SO2 and S-O bond breaking on MgO and oxides in general. Basic principles for a rational design of catalysts with a high efficiency for the destruction of SO2 are presented.

  13. Demonstration of the heterolytic O-O bond cleavage of putative nonheme iron(II)-OOH(R) complexes for Fenton and enzymatic reactions.

    PubMed

    Bang, Suhee; Park, Sora; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nam, Wonwoo

    2014-07-21

    One-electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe(III)-OOH) and iron(III) alkylperoxo (Fe(III)-OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one-electron reduced iron(II) (hydro/alkyl)peroxo species is the rate-determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O-O bond-cleavage mechanism. The present results provide the first example showing the one-electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O-O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions.

  14. Cobryketone derived from vitamin B12 via palladium-catalyzed cleavage of the sp3-sp3 carbon-carbon bond.

    PubMed

    Kurcoń, Sylwester; Proinsias, Keith ó; Gryko, Dorota

    2013-04-19

    Heptamethyl cobyrinate was transformed into hexamethyl 8-nor-cobyrinate. The crucial step involved the synthesis of new, vitamin B12 derived cobryketone via palladium-catalyzed cleavage of the sp(3)-sp(3) carbon-carbon bond with the liberation of the ketone. The replacement of sp(3) carbon atom with sp(2) (C═O) at the 8-position produces a bathochromic shift of all absorption bands and makes α and β bands equal as a consequence of the expansion of the existing conjugated system of double bonds.

  15. Selective Gas-Phase Ion/Ion Reactions: Enabling Disulfide Mapping via Oxidation and Cleavage of Disulfide Bonds in Intermolecularly-Linked Polypeptide Ions.

    PubMed

    Pilo, Alice L; McLuckey, Scott A

    2016-09-20

    The selective gas-phase oxidation of disulfide bonds to their thiosulfinate form using ion/ion reactions and subsequent cleavage is demonstrated here. Oxidizing reagent anions are observed to attach to all polypeptides, regardless of amino acid composition. Direct proton transfer yielding a charge-reduced peptide is also frequently observed. Activation of the ion/ion complex between an oxidizing reagent anion and a disulfide-containing peptide cation results in oxygen transfer from the reagent anion to the peptide cation to form the [M+H+O](+) species. This thiosulfinate derivative can undergo one of several rearrangements that result in cleavage of the disulfide bond. Species containing an intermolecular disulfide bond undergo separation of the two chains upon activation. Further activation can be used to generate more sequence information from each chain. These oxidation ion/ion reactions have been used to illustrate the identification of S-glutathionylated and S-cysteinylated peptides, in which low molecular weight thiols are attached to cysteine residues in peptides via disulfide bonds. The oxidation chemistry effectively labels peptide ions with readily oxidized groups, such as disulfide bonds. This enables a screening approach for the identification of disulfide-linked peptides in a disulfide mapping application involving enzymatic digestion. The mixtures of ions generated by tryptic and peptic digestions of lysozyme and insulin, respectively, without prior separation or isolation were subjected both to oxidation and proton transfer ion/ion chemistry to illustrate the identification of peptides in the mixtures with readily oxidized groups.

  16. Mechanism of the Glycosidic Bond Cleavage of Mismatched Thymine in Human Thymine DNA Glycosylase Revealed by Classical Molecular Dynamics and Quantum Mechanical/Molecular Mechanical Calculations.

    PubMed

    Kanaan, Natalia; Crehuet, Ramon; Imhof, Petra

    2015-09-24

    Base excision of mismatched or damaged nucleotides catalyzed by glycosylase enzymes is the first step of the base excision repair system, a machinery preserving the integrity of DNA. Thymine DNA glycosylase recognizes and removes mismatched thymine by cleaving the C1'-N1 bond between the base and the sugar ring. Our quantum mechanical/molecular mechanical calculations of this reaction in human thymine DNA glycosylase reveal a requirement for a positive charge in the active site to facilitate C1'-N1 bond scission: protonation of His151 significantly lowers the free energy barrier for C1'-N1 bond dissociation compared to the situation with neutral His151. Shuttling a proton from His151 to the thymine base further reduces the activation free energy for glycosidic bond cleavage. Classical molecular dynamics simulations of the H151A mutant suggest that the mutation to the smaller, neutral, residue increases the water accessibility of the thymine base, rendering direct proton transfer from the bulk feasible. Quantum mechanical/molecular mechanical calculations of the glycosidic bond cleavage reaction in the H151A mutant show that the activation free energy is slightly lower than in the wild-type enzyme, explaining the experimentally observed higher reaction rates in this mutant.

  17. Oxidative Cleavage of C=S and P=S Bonds at an Al(I) Center: Preparation of Terminally Bound Aluminum Sulfides.

    PubMed

    Chu, Terry; Vyboishchikov, Sergei F; Gabidullin, Bulat; Nikonov, Georgii I

    2016-10-10

    The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl (1; NacNac=[ArNC(Me)CHC(Me)NAr](-) , Ar=2,6-Pr(i)2 C6 H3 ) resulted in oxidative cleavage of the C=S bond and the formation of 3 and 5, the first monomeric aluminum complexes with an Al=S double bond stabilized by N-heterocyclic carbenes. Compound 1 also reacted with triphenylphosphine sulfide in a similar manner, which resulted in cleavage of the P=S bond and production of the adduct [NacNacAl=S(S=PPh3 )] (8). The Al=S double bond in 3 can react with phenyl isothiocyanate to furnish the cycloaddition product 9 and zwitterion 10 as a result of coupling between the liberated carbene and PhN=C=S. All novel complexes were characterized by multinuclear NMR spectroscopy, and the structures of 5, 9, and 10 were confirmed by X-ray diffraction analysis. The nature of the Al=S bond in 5 was also probed by DFT calculations.

  18. Effect of immunoglobulin G (IgG) interchain disulfide bond cleavage on efficacy of intravenous immunoglobulin for immune thrombocytopenic purpura (ITP).

    PubMed

    Machino, Y; Ohta, H; Suzuki, E; Higurashi, S; Tezuka, T; Nagashima, H; Kohroki, J; Masuho, Y

    2010-12-01

    Intravenous immunoglobulin (IVIG) has been used widely to treat immune thrombocytopenic purpura (ITP), but the mechanisms of its action remain unclear. We investigated the affinity for Fcγ receptors (FcγRs) and the thrombocytopenia-ameliorating effect of S-sulfonated gammaglobulin (SGG) and S-alkylated gammaglobulin (AGG), in comparison with unmodified gammaglobulin (GG), in a mouse ITP model. Cleavage of immunoglobulin (Ig)G interchain disulfide bonds by either S-sulfonation or S-alkylation did not decrease the affinity for FcγRIIA (CD32A) and FcγRIIB (CD32B), but did decrease the affinity for FcγRIA (CD64A) and FcγRIIIA (CD16A), presumably because of changes in H-chain configuration. The interchain disulfide bond cleavage decreased the affinity much more for mouse FcγRIV than for mouse FcγRIIB. The ability of AGG to ameliorate ITP was greatly diminished, while SGG, whose disulfide bonds are reconstituted in vivo, was as effective as GG. These results suggest that the interchain disulfide bonds are important for therapeutic effect. It is also suggested that the interaction of IVIG with the inhibitory receptor FcγRIIB is insufficient for effective amelioration of ITP and that, at least in this model, direct binding of IVIG to FcγRIIIA is also required.

  19. Selective Cleavage of the Aryl Ether Bonds in Lignin for Depolymerization by Acidic Lithium Bromide Molten Salt Hydrate under Mild Conditions.

    PubMed

    Yang, Xiaohui; Li, Ning; Lin, Xuliang; Pan, Xuejun; Zhou, Yonghong

    2016-11-09

    The present study demonstrates that the concentrated lithium bromide (LiBr) solution with acid as catalyst was able to selectively cleave the β-O-4 aryl ether bond and lead to lignin depolymerization under mild conditions (e.g., in 60% LiBr with 0.3 M HCl at 110 °C for 2 h). Four industrial lignins from different pulping and biorefining processes, including softwood kraft lignin (SKL), hardwood kraft lignin (HKL), softwood ethanol organosolv lignin (EOL), and acid corncob lignin (ACL), were treated in the LiBr solution. The molecular weight, functional group, and interunit linkages of the lignins were characterized using GPC, FTIR, and NMR. The results indicated that the β-O-4 aryl ether bonds of the lignins were selectively cleaved, and both LiBr and HCl played crucial roles in catalyzing the cleavage of the ether bonds.

  20. Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Quarterly report No. 13, October 1-December 31, 1981

    SciTech Connect

    Hirschon, A.S.; Zevely, J.; Mayo, F.R.

    1982-02-26

    Bituminous coal is assumed to consist mostly of aggregates of condensed aromatic and aliphatic rings which are connected and made soluble by crosslinks containing single bonds. The objective of this project is to determine the structure of bituminous coal with emphasis on the crosslinks and breakable single bonds. During this past quarter the following studies were conducted on Illinois No. 6 coal: extraction with benzylamine (BnH/sub 2/), ethanolamine, ethylenediamine (EDA), pyridine; saponification of some toluene-insoluble, pyridine-soluble (TIPS) fraction; cleavages by amines; oxidation with aqueous NaOCl of butylated and methylated pyridine-extracted coal; decarboxylation on black acids. The investigations dealt with two kinds of connecting links in coal, which are designated as ester and ether groups. The ester groups are cleaved by strongly basic amines (to give amides) at 25/sup 0/C and by alcoholic KOH at 100/sup 0/C (to give salts and alcohols or phenols). Both esters and ethers are cleaved by HI or ZnCL/sub 2/ in pyridine at or below 50/sup 0/C. The ethers are also cleaved by BnNH/sub 2/, EDA, and EDA/DMSO to nearly the same extent on several days heating at 100/sup 0/C. Although a cleavage of model ethers by amines were not established, the parallel easy reactions of HI and ZnCl/sub 2/ and the slow 100/sup 0/C reactions of amines on coal lead the authors to designate the non-ester cleavages as ether cleavages. (ATT)

  1. Heterolytic cleavage of hydrogen by an iron hydrogenase model: an Fe-H⋅⋅⋅H-N dihydrogen bond characterized by neutron diffraction.

    PubMed

    Liu, Tianbiao; Wang, Xiaoping; Hoffmann, Christina; DuBois, Daniel L; Bullock, R Morris

    2014-05-19

    Hydrogenase enzymes in nature use hydrogen as a fuel, but the heterolytic cleavage of H-H bonds cannot be readily observed in enzymes. Here we show that an iron complex with pendant amines in the diphosphine ligand cleaves hydrogen heterolytically. The product has a strong Fe-H⋅⋅⋅H-N dihydrogen bond. The structure was determined by single-crystal neutron diffraction, and has a remarkably short H⋅⋅⋅H distance of 1.489(10) Å between the protic N-H(δ+) and hydridic Fe-H(δ-) part. The structural data for [Cp(C5F4N)FeH(P(tBu)2N(tBu)2H)](+) provide a glimpse of how the H-H bond is oxidized or generated in hydrogenase enzymes. These results now provide a full picture for the first time, illustrating structures and reactivity of the dihydrogen complex and the product of the heterolytic cleavage of H2 in a functional model of the active site of the [FeFe] hydrogenase enzyme.

  2. Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

    SciTech Connect

    Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.; Garman, Elspeth F.; Owen, Robin L.; Snell, Edward H.; Bernhard, William A.

    2013-12-01

    Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage, to confirm a multi-track radiation-damage process and to develop a model of that process. Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.

  3. Kinetics of the competitive reactions of isomerization and peptide bond cleavage at l-α- and d-β-aspartyl residues in an αA-crystallin fragment.

    PubMed

    Aki, Kenzo; Okamura, Emiko

    2017-01-01

    d-β-aspartyl (Asp) residue has been found in a living body such as aged lens crystallin, although l-α-amino acids are constituents in natural proteins. Isomerization from l-α- to d-β-Asp probably modulates structures to affect biochemical reactions. At Asp residue, isomerization and peptide bond cleavage compete with each other. To gain insight into how fast each reaction proceeds, the analysis requires the consideration of both pathways simultaneously and independently. No information has been provided, however, about these competitive processes because each reaction has been studied separately. The contribution of Asp isomers to the respective pathways has still been veiled. In this work, the two competitive reactions, isomerization and spontaneous peptide bond cleavage at Asp residue, were simultaneously observed and compared in an αA-crystallin fragment, S(51) LFRTVLD(58) SG(60) containing l-α- and d-β-Asp58 isomers. The kinetics showed that the formation of l- and d-succinimide (Suc) intermediate, as a first step of isomerization, was comparable at l-α- and d-β-Asp. Although l-Suc was converted to l-β-Asp, d-Suc was liable to return to the original d-β-Asp, the reverse reaction marked enough to consider d-β-Asp as apparently stable. d-β-Asp was also resistant to the peptide bond cleavage. Such apparent less reactivity is probably the reason for gradual and abnormal accumulation of d-β-Asp in a living body under physiological conditions. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

  4. Synthesis and characterization of conformationally rigid chiral pyridine-N-heterocyclic carbene-based palladacycles with an unexpected Pd-N bond cleavage.

    PubMed

    Ng, Kim Hong; Li, Yongxin; Tan, Wei Xian; Chiang, Minyi; Pullarkat, Sumod A

    2013-03-01

    The versatility of a previously developed method for the synthesis of chiral carbene-based palladacycles is demonstrated through the synthesis of two new chiral pyridine-functionalized N-heterocyclic carbene palladacycles with different wingtip groups. The efficiency in their resolution with different counter anions and different chiral amino acid salt auxiliaries has been studied. The absolute stereochemistries of all the chiral compounds were confirmed by single crystal X-ray crystallography. An unexpected Pd-N bond cleavage that resulted in the racemization of the α-carbon center in these complexes has also been investigated.

  5. Organometallic Modeling of the Hydrodesulfurization (HDS) Process: Rhenium Carbonyl-promoted C-S Bond Cleavage and Hydrogenation of Thiophenes and Benozothiophenes

    SciTech Connect

    Reynolds, Michael A.

    2000-09-21

    Organometallic modeling of the HDS process at single or multiple metal centers is one approach to better understanding the mechanism that govern commercial HDS. Therefore, we have currently been investigating the use of Re2(CO)10 as a potential model system for catalytic HDS with respect to S-binding, ring-opening, and hydrogenation of thiophenes andbenzothiophenes. We have also been investigating the use of UV-light as a method for activating thiophenic molecules towards C-S and C-H bond cleavage.

  6. A copper complex supported by an N2S-tridentate ligand inducing efficient heterolytic O-O bond cleavage of alkylhydroperoxide.

    PubMed

    Tano, Tetsuro; Mieda, Kaoru; Sugimoto, Hideki; Ogura, Takashi; Itoh, Shinobu

    2014-03-28

    We have recently reported a copper(II)-superoxide complex supported by an N3-tridentate ligand (L(N3)), which exhibits a similar structure and reactivity to those of a putative reactive intermediate involved in the catalytic reactions of copper monooxygenases such as peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM). In this study, we have synthesised and characterised copper complexes supported by a related sulphur-containing ligand (L(N2S)) to get insight into the notable electronic effect of the sulphur donor atom in the reaction with cumene hydroperoxide, inducing efficient heterolytic O-O bond cleavage.

  7. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    PubMed

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  8. Selective cleavage of an azaGly peptide bond by copper(II). Long-range effect of histidine residue.

    PubMed

    Mhidia, Reda; Melnyk, Oleg

    2010-03-01

    Several reports have highlighted the interest of replacing Gly, a frequent amino acid within bioactive peptides, by azaGly (Agly) to improve their stability, activity or for the design of prodrugs. Because metal catalysis is increasingly used for tailoring peptide molecules, we have studied the stability of Agly peptides in the presence of metal ions. In this study, we show that Cu(II), unlike other metal ions such as Fe(II), Fe(III), Pd(II), or Pt(II), induces the cleavage of Agly peptides at room temperature and pH 7.3. The cleavage occurred in the absence of an anchoring His residue within the peptide but it was accelerated when this amino acid was present in the sequence. The influence of His residue on the cleavage rate was minimal when His and Agly were adjacent, whereas large effects were observed for distant His residues. The reaction between Cu(II) and Agly peptides induced the formation of Cu(I) species, which could be detected using bicinchoninic acid as a probe. The nature of products formed in this reaction allowed suggesting a mechanism for the Cu(II)-induced cleavage of Agly peptides.

  9. Selective disulfide bond cleavage in gold(I) cationized polypeptide ions formed via gas-phase ion/ion cation switching.

    PubMed

    Gunawardena, Harsha P; O'Hair, Richard A J; McLuckey, Scott A

    2006-09-01

    Gaseous multiply protonated disulfide-linked peptides have been subjected to reactions with AuCl2(-) ions to explore the possibility of effecting cation switching of Au+ for two protons and to determine whether cationization by Au+ ions affords selective dissociation of disulfide linkages. The incorporation of Au+ into several model disulfide-linked peptides proved to be straightforward. The primary ion/ion reaction channels were proton transfer, which does not lead to Au+ incorporation, and attachment of AuCl2(-) ions to the polypeptide cation, which does incorporate Au+. Fragmentation of the attachment product, the extent of which varied with peptide and charge state, led to losses of one or more molecules of HCl and, to some extent, cleavage of polypeptides at the disulfide linkage into its two constituent chains. Collisional activation of the intact metal-ion-incorporated peptides showed cleavage of the disulfide linkage to be a major, and in some cases exclusive, process. Cations with protons as the only cationizing agents showed only small contributions from cleavage of the disulfide linkage. These results indicate that Au+ incorporation into a disulfide-linked polypeptide ion is a promising way to effect selective dissociation of disulfide bonds. Cation switching via ion/ion reactions is a convenient means for incorporating gold and is attractive because it avoids the requirement of adding metal salts to the analyte solution.

  10. Tomato carotenoid cleavage dioxygenases 1A and 1B: Relaxed double bond specificity leads to a plenitude of dialdehydes, mono-apocarotenoids and isoprenoid volatiles

    PubMed Central

    Ilg, Andrea; Bruno, Mark; Beyer, Peter; Al-Babili, Salim

    2014-01-01

    The biosynthetic processes leading to many of the isoprenoid volatiles released by tomato fruits are still unknown, though previous reports suggested a clear correlation with the carotenoids contained within the fruit. In this study, we investigated the activity of the tomato (Solanum lycopersicum) carotenoid cleavage dioxygenase (SlCCD1B), which is highly expressed in fruits, and of its homolog SlCCD1A. Using in vitro assays performed with purified recombinant enzymes and by analyzing products formed by the two enzymes in carotene-accumulating Escherichia coli strains, we demonstrate that SlCCD1A and, to a larger extent, SlCCD1B, have a very relaxed specificity for both substrate and cleavage site, mediating the oxidative cleavage of cis- and all-trans-carotenoids as well as of different apocarotenoids at many more double bonds than previously reported. This activity gives rise to a plenitude of volatiles, mono-apocarotenoids and dialdehyde products, including cis-pseudoionone, neral, geranial, and farnesylacetone. Our results provide a direct evidence for a carotenoid origin of these compounds and point to CCD1s as the enzymes catalyzing the formation of the vast majority of tomato isoprenoid volatiles, many of which are aroma constituents. PMID:25057464

  11. Alcohol-Induced C-N Bond Cleavage of Cyclometalated N-Heterocyclic Carbene Ligands with a Methylene-Linked Pendant Imidazolium Ring.

    PubMed

    Zhong, Wei; Fei, Zhaofu; Scopelliti, Rosario; Dyson, Paul J

    2016-08-16

    Reaction of the pentamethylcyclopentadienyl rhodium iodide dimer [Cp*RhI2 ]2 with 1,1'-diphenyl-3,3'-methylenediimidazolium diiodide in non-alcohol solvents, in the presence of base, led to the formation of bis-carbene complex [Cp*Rh(bis-NHC)I]I (bis-NHC=1,1'-diphenyl-4,4'-methylenediimidazoline-5,5'-diylidene). In contrast, when employing alcohols as the solvent in the same reaction, cleavage of a methylene C-N bond is observed, affording ether-functionalized (cyclometalated) carbene ligands coordinated to the metal center and the concomitant formation of complexes with a coordinated imidazole ligand. Studies employing other 1,1'-diimidazolium salts indicate that the cyclometalation step is a prerequisite for the activation/scission of the C-N bond and, based on additional experimental data, a SN 2 mechanism for the reaction is tentatively proposed.

  12. Collision-activated cleavage of a peptide/antibiotic disulfide linkage: possible evidence for intramolecular disulfide bond rearrangement upon collisional activation.

    PubMed

    Fagerquist, Clifton K

    2004-01-01

    Ceftiofur is an important veterinary beta-lactam antibiotic whose bioactive metabolite, desfuroylceftiofur, has a free thiol group. Desfuroylceftiofur (DFC) was reacted with two peptides, [Arg8]-vasopressin and reduced glutathione, both of which have cysteine residues to form disulfide-linked peptide/antibiotic complexes. The products of the reaction, [vasopressin + (DFC-H) + (DFC-H) + H]+, [(vasopressin+H) + (DFC-H) + H]+ and [(glutathione-H) + (DFC-H) + H]+, were analyzed using collision-activated dissociation (CAD) with a quadrupole ion trap tandem mass spectrometer. MS/MS of [vasopressin + (DFC-H) + (DFC-H) + H]+ resulted in facile dissociative loss of one and two covalently bound DFC moieties. Loss of one DFC resulted from either homolytic or heterolytic dissociation of the peptide/antibiotic disulfide bond with equal or unequal partitioning of the two sulfur atoms between the fragment ion and neutral loss. Hydrogen migration preceded heterolytic dissociation. Loss of two DFC moieties from [vasopressin + (DFC-H) + (DFC-H) + H]+ appears to result from collision-activated intramolecular disulfide bond rearrangement (IDBR) to produce cyclic [vasopressin + H]+ (at m/z 1084) as well as other cyclic fragment ions at m/z 1084 +/- 32 and +64. The cyclic structure of these ions could only be inferred as MS/MS may result in rearrangement to non-cyclic structures prior to dissociative loss. IDBR was also detected from MS(3) experiments of [vasopressin + (DFC-H) + (DFC-H) + H]+ fragment ions. MS/MS of [(glutathione-H) + (DFC-H) + H]+ resulted in cleavage of the peptide backbone with retention of the DFC moiety as well as heterolytic cleavage of the peptide/antibiotic disulfide bond to produce the fragment ion: [(DFC-2H) + H]+. These results demonstrate the facile dissociative loss by CAD of DFC moieties covalently attached to peptides through disulfide bonds. Published in 2004 by John Wiley & Sons, Ltd.

  13. Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Annual report, October 1, 1980-September 30, 1981

    SciTech Connect

    Hirschon, A.S.; Zevely, J.; Mayo, F.R.

    1981-11-12

    The objective of this project is to determine the structure of bituminous coal by determining the proportions of the various kinds of connecting bonds and how they can best be broken. Results obtained during the past quarter are presented for the following tasks: (1) extractions and fractionations of coal products which covers pyridine extraction, fractionation of TIPS fractions, EDA extraction of Illinois No. 6 coal and swelling ratios of coal samples; (2) experiments on breakable single bonds which cover reactions of ethylenediamine and model ethers, reaction of pyridine-extracted coal with Me/sub 3/SiI, Baeyer-Villiger oxidations, reaction to diphenylmethane with 15% HNO/sub 3/, cleavage of TIPS with ZnI/sub 2/, and cleavage of black acids; and (3) oxygen oxidation No. 18. Some of the highlights of these studies are: (1) some model ethers are not cleaved by EDA under extraction conditions; (2) oxidation of diaryl ketones with m-chloroperbenzoic acid and saponification of the resulting esters in promising for identifying ketones, (3) treatment of a black acid with pyridine hydroiodide reduced the acid's molecular weight and increased its solubility in pyridine, but treatment with ZnI/sub 2/ was ineffective; (4) in comparison with 0.1 M K/sub 2/S/sub 2/O/sub 8/, 0.01 M persulfate is relatively ineffective in accelerating oxidation of BnNH/sub 2/-extracted coal in water suspension. 2 figures, 3 tables.

  14. Mechanism of ribonucleotide reductase from Herpes simplex virus type 1. Evidence for 3' carbon-hydrogen bond cleavage and inactivation by nucleotide analogs

    SciTech Connect

    Ator, M.A.; Stubbe, J.; Spector, T.

    1986-03-15

    Isotope effects of 2.5, 2.1, and 1.0 were measured on the conversion of (3'-3H)ADP, (3'-H)UDP, and (5-3H) UDP to the corresponding 2'-deoxynucleotides by herpes simplex virus type 1 ribonucleotide reductase. These results indicate that the reduction of either purine or pyrimidine nucleotides requires cleavage of the 3' carbon-hydrogen bond of the substrate. The substrate analogs 2'-chloro-2'-deoxyuridine 5'-diphosphate (ClUDP), 2'-deoxy-2'-fluorouridine 5'-diphosphate, and 2'-azido-2'-deoxyuridine 5'-diphosphate were time-dependent inactivators of the herpes simplex virus type 1 ribonucleotide reductase. Incubation of (3'-3H)ClUDP with the enzyme was accompanied by time-dependent release of 3H to the solvent. Reaction of (beta-32P)ClUDP with the reductase resulted in the production of inorganic pyrophosphate. These results are consistent with the enzyme-mediated cleavage of the 3' carbon-hydrogen bond of ClUDP and the subsequent conversion of the nucleotide to 2-methylene-3(2H)furanone, as previously reported with the Escherichia coli ribonucleotide reductase.

  15. Evidence of cytochrome P450-catalyzed cleavage of the ether bond of phenoxybutyrate herbicides in Rhodococcus erythropolis K2-3.

    PubMed

    Sträuber, Heike; Müller, Roland H; Babel, Wolfgang

    2003-01-01

    Bacterial strain Rhodococcus erythropolis K2-3 can cleave the ether bond of the phenoxybutyrate herbicides, i.e., 4-(2,4-dichlorophenoxy)butyrate (2,4-DB) and 4-(4-chloro-2-methylphenoxy)butyrate (MCPB), by an enzyme system that is constitutively expressed. The enzyme(s) involved were investigated in this study. The rate of disappearance of 2,4-DB determined in a whole cell assay amounted to 0.6 mmol/h x g(dry mass). Carbon monoxide difference spectra of dithionite-reduced whole cells and crude cell extracts suggested that strain K2-3 contains a soluble cytochrome P450 (P450), named P450(PB-1). The addition of various phenoxybutyrate substrates to crude cell extracts resulted in typical difference spectra following the type I pattern of substrate binding with P450. The rate of 2,4-DB cleavage was reduced by inhibitors of P450: 5 mM metyrapone and carbon monoxide at a CO/O2 ratio of 10 reduced the activity by about 20%, and 70%, respectively. The ether cleaving activity completely disappeared after disruption of the cells and could not be detected in crude extracts. To elucidate the enzymatic basis of this reaction, P450 was partially purified. With the resulting enzyme preparation, 2,4-DB cleavage activity was re-established, becoming measurable after the addition of either phenazine methosulfate or ferredoxin and ferredoxin/NADP oxidoreductase from spinach. We detected no activities attributable to alpha-ketoglutarate-dependent dioxygenase or NAD(P)H-dependent monooxygenase. These results collectively indicate that cleavage of the ether bond of phenoxybutyrate herbicides is catalyzed by P450-mediated activity in this strain. One of the products derived from this reaction is dichlorophenol, and comparative chromatographic analyses suggest that the other product is a C4-carbonic acid, most likely succinic semialdehyde/succinate.

  16. Me-Si bond cleavage of anionic bis(trimethylsilyl)amide in scorpionate-anchored rare earth metal complexes.

    PubMed

    Yi, Weiyin; Zhang, Jie; Chen, Zhenxia; Zhou, Xigeng

    2012-10-15

    A novel Tp(Me2)-supported (Tp(Me2) = tri(3,5-dimethylpyrazolyl)borate) rare earth metal complex promoted Me-Si cleavage of the bis(trimethylsilyl) amide ligand ([(Me(3)Si)(2)N](-)) was observed. Reaction of Tp(Me2)LnCl(2) with 2 equiv of K[(RN)(2)CN(SiMe(3))(2)] (KGua) gave the methylamidinate complexes Tp(Me2)Ln[(RN)(2)CMe][N(SiMe(3))(2)] (R = isopropyl, Ln = Y (1(Y)), Er (1(Er)); R = cyclohexyl, Ln = Y (2(Y))) in moderate yields. In contrast, Tp(Me2)YCl(2)(THF) reacted with 1 equiv of KGua to afford a C-N cleavage product Tp(Me2)Y(Cl)N(SiMe(3))(2)(THF) (4), indicating that this guanidinate ligand is not stable in the yttrium complex with the Tp(Me2) ligand, and a carbodiimide deinsertion takes place easily. The mechanism for the formation of complexes 1 and 2 was also studied by controlling the substrate stoichiometry and the reaction sequence and revealed that the bis(trimethylsilyl)amine anion N(SiMe(3))(2)(-) can undergo two routes of γ-methyl deprotonation and Si-Me cleavage for its functionalizations. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures were also confirmed by single-crystal X-ray diffraction.

  17. A thiophosphinidene complex as a vehicle in phosphinidene transmetalation: easy formation and cleavage of a P-S bond.

    PubMed

    Alvarez, Belén; Alvarez, M Angeles; Amor, Inmaculada; García, M Esther; Ruiz, Miguel A

    2011-11-07

    A method for the generation of transition metal-phosphorus multiple bonds has been developed using the reactions of a novel thiophosphinidene-bridged dimolybdenum complex with different metal carbonyls. The overall process could be considered as a transmetalation of the phosphinidene ligand involving the activation of P-S and P-Mo bonds.

  18. Resonance Raman spectroscopy reveals pH-dependent active site structural changes of lactoperoxidase compound 0 and its ferryl heme O-O bond cleavage products.

    PubMed

    Mak, Piotr J; Thammawichai, Warut; Wiedenhoeft, Dennis; Kincaid, James R

    2015-01-14

    The first step in the enzymatic cycle of mammalian peroxidases, including lactoperoxidase (LPO), is binding of hydrogen peroxide to the ferric resting state to form a ferric-hydroperoxo intermediate designated as Compound 0, the residual proton temporarily associating with the distal pocket His109 residue. Upon delivery of this "stored" proton to the hydroperoxo fragment, it rapidly undergoes O-O bond cleavage, thereby thwarting efforts to trap it using rapid mixing methods. Fortunately, as shown herein, both the peroxo and the hydroperoxo (Compound 0) forms of LPO can be trapped by cryoradiolysis, with acquisition of their resonance Raman (rR) spectra now permitting structural characterization of their key Fe-O-O fragments. Studies were conducted under both acidic and alkaline conditions, revealing pH-dependent differences in relative populations of these intermediates. Furthermore, upon annealing, the low pH samples convert to two forms of a ferryl heme O-O bond-cleavage product, whose ν(Fe═O) frequencies reflect substantially different Fe═O bond strengths. In the process of conducting these studies, rR structural characterization of the dioxygen adduct of LPO, commonly called Compound III, has also been completed, demonstrating a substantial difference in the strengths of the Fe-O linkage of the Fe-O-O fragment under acidic and alkaline conditions, an effect most reasonably attributed to a corresponding weakening of the trans-axial histidyl imidazole linkage at lower pH. Collectively, these new results provide important insight into the impact of pH on the disposition of the key Fe-O-O and Fe═O fragments of intermediates that arise in the enzymatic cycles of LPO, other mammalian peroxidases, and related proteins.

  19. Cleavage of the peptide bond of beta-alanyl-L-histidine (carnosine) induced by a Co(III)-amine complexes: reaction, structure and mechanism.

    PubMed

    Saha, Manas K; Mukhopadhyay, Uday; Bernal, Ivan

    2004-05-07

    Cleavage of the peptide bond occurs when beta]-alanyl-L-histidine (carnosine) reacts with [Co(tren)Cl2]+ (tren = tris(2-aminoethyl)amine) to give [Co(tren)(histidine)](2+) 1 and [Co(tren)(beta-alanine)](2+) 2. [Co(tren)(histidine)](2+) 1 crystallizes in the enantiomorphic space group P2(1)2(1)2(1) and 2 crystallizes in the P2(1)/c space group. The mechanism of the cleavage reactions were studied in detail for the precursor [Co(tren)Cl2]+ and [Co(trien)Cl2]+, which convert into [Co(tren)(OH)2]+/[Co(tren)(OH)(OH2)]2+ and [Co(trien)(OH)2]+/[Co(trien)(OH)(OH2)]2+ in water at basic pH (trien = 1,4,7,10-tetraazadecane). At a slightly basic pH, the initial coordination of the substrate (beta-alanyl-L-histidine) is by the carboxylate group for the reaction with [Co(tren)Cl2]+. This is followed by a rate-limiting nucleophilic attack of the hydroxide group at the beta-alanyl-L-histidine carbonyl group. In a strongly basic reaction medium substrate, binding of the metal was through carboxylate and amine terminals. On the other hand, for the reaction between [cis-beta-Co(trien)Cl2]+ and beta-alanyl-L-histidine, the initial coordination of the substrate takes place via an imidazole ring nitrogen, independently, and followed by a nucleophilic attack of the hydroxide group at the beta-alanyl-L-histidine carbonyl group. The circular dichroism spectrum for 1 suggests that a very small extent of racemization of the amino acid (L-histidine) takes place during the cleavage reaction between [Co(tren)Cl2]+ and beta-alanyl-L-histidine. Reaction between [cis-beta-Co(trien)Cl2]+ and beta-alanyl-L-histidine also causes cleavage of the peptide bond, producing a free beta-alanyl molecule and a cationic fragment [cis-alpha-Co(trien)(histidine)](2+) 3 that crystallizes in the optically active space group P2(1)2(1)2(1). Unlike the previous case an appreciable degree of racemization of the L-histidine takes place during the reaction between [cis-beta-Co(trien)Cl2]+ and beta

  20. Cleavage of the Nb=O bond of oxoniobium(V) porphyrins. Synthesis and characterization of novel niobium(V) porphyrins with two distinct catechols

    SciTech Connect

    Kurihara, Masato; Kotoh, Noriyuki; Kojima, Takahiko

    1995-09-13

    A novel catecholato complex, Nb{sup v}(tpp)(cat)(Hcat), where cat and Hcat are two distinct catechol ligands (a bidentate catecholate dianion and a monodentate catecholate monoanion, respectively) and tpp is 5, 10, 15, 20-tetaphenylporphyrin dianion, has been isolated in the reaction of Nb{sup v} (tpp)(O)(AcO) with catechol, where AcO is an acetatoligand. Its molecular structure has been determined by X-ray crystallography. Crystal data: monoclinic, space group P2{sub 1}/c, Z = 4, a = 14.592(3) {Angstrom}, b = 23.46(1) {Angstrom}, c = 14.415(4) {Angstrom}, {beta} = 100.95(2){degrees}, R = 0.079. The heptacoordinate niobium atom is displaced by 1.02 {Angstrom} from the mean plane of the four nitrogen atoms. The structure of the complex in solution and the mechanism of the Nb=O cleavage were investigated by means of {sup 1}H-NMR spectroscopy. The bidentate catechol is oriented in C{sub s} symmetry with respect to the porphyrin plane, and the monodentate catechol is located perpendicularly to both the bidentate catechol and the porphyrin plane. Two intermediates with the bidentate catechol were observed after addition of 2 equiv of catechol to Nb(tmp)(O)(AcO) at -30 {degrees}C, where tmp denotes the 5,10,15,20-tetramesitylporphyrin dianion. These intermediates were determined to be Nb(tmp)(cat)(OH) and Nb(tmp)(cat)(AcO). Thus, the Nb=O bond of Nb(tmp)(O)(AcO) was easily cleaved to create the two intermediates. The authors propose a unique route to the Nb=O cleavage that involves an intramolecular electron transfer from the catechol ligand coordinated at the first stage through a ligand exchange with AcO. Both protonation and electron transfer to the Nb=O moiety play important roles in the Nb=O cleavage.

  1. Protolytic cleavage of Hg-C bonds induced by 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone: synthesis and structural characterization of mercury complexes.

    PubMed

    Palmer, Joshua H; Parkin, Gerard

    2015-04-08

    Multinuclear ((1)H, (77)Se, and (199)Hg) NMR spectroscopy demonstrates that 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzim(Me)), a structural analogue of the selenoamino acid, selenoneine, binds rapidly and reversibly to the mercury centers of HgX2 (X = Cl, Br, I), while X-ray diffraction studies provide evidence for the existence of adducts of composition [H(sebenzim(Me))]xHgX2 (X = Cl, x = 2, 3, 4; X = I, x = 2) in the solid state. H(sebenzim(Me)) also reacts with methylmercury halides, but the reaction is accompanied by elimination of methane resulting from protolytic cleavage of the Hg-C bond, an observation that is of relevance to the report that selenoneine demethylates CysHgMe, thereby providing a mechanism for mercury detoxification. Interestingly, the structures of [H(sebenzim(Me))]xHgX2 exhibit a variety of different hydrogen bonding patterns resulting from the ability of the N-H groups to form hydrogen bonds with chlorine, iodine, and selenium.

  2. Catalysis and co-catalysis of bond cleavages in coal and coal analogs. Final report, August 1, 1990--January 31, 1994

    SciTech Connect

    Miller, B.

    1994-05-01

    In work prior to the inception of this project, the authors observed that mixtures of phenolic materials and polyalkoxyaromatic molecules were appreciably more effective in catalyzing the decompositions of di-2-naphthyl ether and of di-1-naphthyl sulfide in tetralin solutions at 450{degrees}C than were the phenols by themselves, even though the polyalkoxyaromatic molecules, in the absence of phenolic co- catalysts, show essentially no catalytic activity. This was of appreciable interest in coal research because dinapthyl ether and dinapthyl sulfide have been employed as model compounds for coals in studies aimed at cleaving ether and sulfide bonds similar to those in coals. The authors proposed (R. K. Sharma, K. P. Raman, and B. Miller) that the mixed catalysts used in these studies catalyze cleavages of ether and sulfide bonds by means of a mechanism involving electron transfer from the polyalkoxyaromatics to the substrates, which are activated as electron acceptors by hydrogen bonding to phenols. Since phenols themselves are electron donors, they also proposed that the well known effects of phenols in catalyzing the conversion of coals are due to similar electron transfer mechanisms.

  3. Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes

    PubMed Central

    2016-01-01

    Multinuclear (1H, 77Se, and 199Hg) NMR spectroscopy demonstrates that 1-methyl-1,3-dihydro-2H-benzimidazole-2-selone, H(sebenzimMe), a structural analogue of the selenoamino acid, selenoneine, binds rapidly and reversibly to the mercury centers of HgX2 (X = Cl, Br, I), while X-ray diffraction studies provide evidence for the existence of adducts of composition [H(sebenzimMe)]xHgX2 (X = Cl, x = 2, 3, 4; X = I, x = 2) in the solid state. H(sebenzimMe) also reacts with methylmercury halides, but the reaction is accompanied by elimination of methane resulting from protolytic cleavage of the Hg–C bond, an observation that is of relevance to the report that selenoneine demethylates CysHgMe, thereby providing a mechanism for mercury detoxification. Interestingly, the structures of [H(sebenzimMe)]xHgX2 exhibit a variety of different hydrogen bonding patterns resulting from the ability of the N–H groups to form hydrogen bonds with chlorine, iodine, and selenium. PMID:25822075

  4. The role of glandular kallikrein in the formation of a salivary proline-rich protein A by cleavage of a single bond in salivary protein C.

    PubMed Central

    Wong, R S; Madapallimattam, G; Bennick, A

    1983-01-01

    An enzyme was purified from human parotid saliva that can cleave a single arginine-glycine peptide bond between residues 106 and 107 in human salivary proline-rich protein C, hereby giving rise to another proline-rich protein A, which is also found in saliva. The enzyme was purified 2400-fold. It cleaved salivary protein C at the rate of 59 micrograms of protein/h per microgram of enzyme and had amino acid composition, molecular weight and inhibition characteristics similar to those reported for human salivary kallikrein. Confirmation that the enzyme was kallikrein was demonstrated by its kinin-generating ability. Histochemical evidence indicates that a post-synthetic cleavage of protein C by kallikrein would have to take place during passage of saliva through the secretory ducts. In secreted saliva, cleavage of salivary protein C can only be observed after 72 h incubation. In addition, there is no effect of salivary flow rate on the relative amounts of proteins A and C in saliva. On the basis of the experimental observations, it is proposed that in vivo it is unlikely that kallikrein secreted from ductal cells plays a significant role in converting protein C into protein A. PMID:6553499

  5. Cleavage of carbon-nitrogen bond in 1,3,5-tri-tert-butyl-1,3,5-triazacyclohexane by copper(I) bromide

    NASA Astrophysics Data System (ADS)

    Khatua, Suman; Majumdar, Amit

    2016-09-01

    Reactions of CuCl, CuCl2 and CuBr2 with 1,3,5-tri-tert-butyl-1,3,5-triazacyclohexane (tBu3tach) resulted in the formation of [(tBu3tach-H)+(CuCl2)] (1), [(tBu3tach)(CuCl2)] (2) and [(tBu3tach-H)+(CuBr2)] (3) respectively. Interestingly, CuBr was found to mediate the cleavage of the C-N bonds of tBu3tach in a vast range of solvents, namely, chloroform, dichloromethane, tetrahydrofuran, acetonitrile and methanol to yield [Cu4Br4(tBuNCH2)4] (4) and stands as an example of C-N bond cleavage of 1,3,5-triazacyclohexane rings by copper salts. Compounds 1 and 3 contains amidinium cations and are unstable in solution towards the release of copper. The release of copper from 3 in solution was confirmed by the isolation of the compound, [CuBr(MeCN)] (5). Formation of the amidinium cations [(tBu3tach-H)+] in 1 and 3 may be avoided by the use of PPh3 to yield [(tBu3tach)Cu(PPh3)](PF6) (6), while the coordinated N-tert-butylmethanimine (tBuNCH2) in 4 could be replaced by PPh3 to yield [Cu4Br4(PPh3)4] (7). Complexes 1-7 are characterized by a combination of single crystal X-ray structure determination and/or elemental analysis, NMR, IR, and UV-Vis spectroscopy, and Mass spectrometry.

  6. Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Quarterly report No. 12, June 1-September 30, 1981

    SciTech Connect

    Hirschon, A.S.; Zevely, J.; Mayo, F.R.

    1981-11-12

    We assume that bituminous coal consists mostly of an aggregate of condensed aromatic and aliphatic rings, connected and made insoluble (but swellable) by crosslinks containing single bonds. The objective of this project is to determine the proportions of the various kinds of connecting links and how they can best be broken - in other words, to determine the structure of bituminous coal, with emphasis on the crosslinks and breakable single bonds. The program began with an investigation of the structure of the TIPS fraction of Illinois No. 6 coal, that is, the two-thirds of the 16% extracted by pyridine that is toluene-insoluble, pyridine-soluble, mostly through changes in molecular weight during cleavage reactions in pyridine solution. The most promising of these cleavage reactions are now being applied to the 84% of coal that is insoluble in pyridine and presents the main problem in coal liquefaction, following the progress of the reactions by formation of soluble material and swelling of the insoluble portion. We found that benzylamine (BnNH/sub 2/) would extract an additional 14% (of the original weight of coal) of material from pyridine-extracted coal, and later that an ethylenediamine/dimethyl sulfoxide (EDA/DMSO) mixture would dissolve another 21% of the original coal. The BnNH/sub 2/ extract is soluble in pyridine. Our best present guess is that the BnNH/sub 2/ extract cleaves most of the ester groups in coal and that EDA/DMSO cleaves the remaining ester and most of the ether groups.

  7. The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study.

    PubMed

    Li, Yingzi; Liu, Song; Qi, Zisong; Qi, Xiaotian; Li, Xingwei; Lan, Yu

    2015-07-06

    Metal-catalyzed C-H activation not only offers important strategies to construct new bonds, it also allows the merge of important research areas. When quinoline N-oxide is used as an arene source in C-H activation studies, the N-O bond can act as a directing group as well as an O-atom donor. The newly reported density functional theory method, M11L, has been used to elucidate the mechanistic details of the coupling between quinoline N-O bond and alkynes, which results in C-H activation and O-atom transfer. The computational results indicated that the most favorable pathway involves an electrophilic deprotonation, an insertion of an acetylene group into a Rh-C bond, a reductive elimination to form an oxazinoquinolinium-coordinated Rh(I) intermediate, an oxidative addition to break the N-O bond, and a protonation reaction to regenerate the active catalyst. The regioselectivity of the reaction has also been studied by using prop-1-yn-1-ylbenzene as a model unsymmetrical substrate. Theoretical calculations suggested that 1-phenyl-2-quinolinylpropanone would be the major product because of better conjugation between the phenyl group and enolate moiety in the corresponding transition state of the regioselectivity-determining step. These calculated data are consistent with the experimental observations.

  8. Effects of alkoxy groups on arene rings of lignin β-O-4 model compounds on the efficiencies of single electron transfer-promoted photochemical and enzymatic C-C Bond Cleavage Reactions.

    PubMed

    Lim, Suk Hyun; Nahm, Keepyung; Ra, Choon Sup; Cho, Dae Won; Yoon, Ung Chan; Latham, John A; Dunaway-Mariano, Debra; Mariano, Patrick S

    2013-09-20

    To gain information about how alkoxy substitution in arene rings of β-O-4 structural units within lignin governs the efficiencies/rates of radical cation C1-C2 bond cleavage reactions, single electron transfer (SET) photochemical and lignin peroxidase-catalyzed oxidation reactions of dimeric/tetrameric model compounds have been explored. The results show that the radical cations derived from less alkoxy-substituted dimeric β-O-4 models undergo more rapid C1-C2 bond cleavage than those of more alkoxy-substituted analogues. These findings gained support from the results of DFT calculations, which demonstrate that C1-C2 bond dissociation energies of β-O-4 radical cations decrease as the degree of alkoxy substitution decreases. In SET reactions of tetrameric compounds consisting of two β-O-4 units, containing different degrees of alkoxy substitution, regioselective radical cation C-C bond cleavage was observed to occur in one case at the C1-C2 bond in the less alkoxy-substituted β-O-4 moiety. However, regioselective C1-C2 cleavage in the more alkoxy-substituted β-O-4 moiety was observed in another case, suggesting that other factors might participate in controlling this process. These observations show that lignins containing greater proportions of less rather than more alkoxylated rings as part of β-O-4 units would be more efficiently cleaved by SET mechanisms.

  9. Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed C¢X Bond Cleavage to Environmentally Benign Transition-Metal-Free C¢H Bond Activation.

    PubMed

    Xu, Zheng; Xu, Li-Wen

    2015-07-08

    The construction of carbon-silicon bonds is highlighted as an exciting achievement in the field of organosilicon chemistry and green chemistry. Recent developments in this area will enable the sustainable chemical conversion of silicon resources into synthetically useful compounds. Especially, the catalytic silylation through C¢H bond activation without directing groups and hydrogen acceptors is one of the most challenging topics in organic chemistry and green chemistry. These remarkable findings on catalytic silylation can pave the way to a more environmentally benign utilization of earth-abundant silicon-based resources in synthetic chemistry.

  10. Development of a Simple Adjustable Zinc Acid/Base Hybrid Catalyst for C-C and C-O Bond-Forming and C-C Bond-Cleavage Reactions.

    PubMed

    Yamashita, Yasuhiro; Minami, Kodai; Saito, Yuki; Kobayashi, Shū

    2016-09-06

    A newly designed zinc Lewis acid/base hybrid catalyst was developed. By adjusting the Lewis acidity of the zinc center, aldol-type additions of 2-picolylamine Schiff base to aldehydes proceeded smoothly to afford syn-aldol adduct equivalents, trans-N,O-acetal adducts, in high yields with high selectivities. NMR experiments, including microchanneled cell for synthesis monitoring (MICCS) NMR analysis, revealed that anti-aldol adducts were formed at the initial stage of the reactions under kinetic control, but the final products were the trans-(syn)-N,O-acetal adducts that were produced through a retro-aldol process under thermodynamic control. In the whole reaction process, the zinc catalyst played three important roles: i) promotion of the aldol process (C-C bond formation), ii) cyclization process to the N,O-acetal product (C-O bond formation), and iii) retro-aldol process from the anti-aldol adduct to the syn-aldol adduct (C-C bond cleavage and C-C bond formation).

  11. Peptide bond cleavage site determination of novel proteolytic enzymes found in ROS 17/2.8 cell lysates.

    PubMed

    Guidon, P T; Perrin, D; Harrison, P

    1996-02-01

    We have identified proteolytic activities in the rat osteoblastic osteosarcoma cell line ROS 17/2.8 which are capable of cleaving a peptide substrate for protein kinase C-mediated phosphorylation (PSPKC, Pro-Leu-Ser-Arg-Thr-Leu-Ser-Val-Ala-Ala-Lys). Using polyacrylamide gel electrophoresis conditions similar to those used to resolve small molecular weight proteins, the peptide bonds of PSPKC which are cleaved by the proteolytic activities present in ROS 17/2.8 cell lysates have been determined. These activities cleave the Ser-Arg, Thr-Leu, and Ser-Val peptide bonds. To date, no proteolytic activities present in osteoblast cell lysates have been described with the aforementioned peptide bond specificities, suggesting that these activities are novel. The PSPKC-cleaved peptide fragment pattern generated was similar for several different osteoblast cell lysates. Lysates generated from different rat tissues were also able to cleave PSPKC, but the peptide fragment pattern generated by ROS 17/2.8 cell lysates appeared to be unique amongst these tissues.

  12. Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies.

    PubMed

    Sutton, Kristin A; Black, Paul J; Mercer, Kermit R; Garman, Elspeth F; Owen, Robin L; Snell, Edward H; Bernhard, William A

    2013-12-01

    Electron paramagnetic resonance (EPR) and online UV-visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV-visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5-0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.

  13. Solvent dependent branching between C-I and C-Br bond cleavage following 266 nm excitation of CH{sub 2}BrI

    SciTech Connect

    Anderson, Christopher P.; Spears, Kenneth G.; Wilson, Kaitlynn R.; Sension, Roseanne J.

    2013-11-21

    It is well known that ultraviolet photoexcitation of halomethanes results in halogen-carbon bond cleavage. Each halogen-carbon bond has a dominant ultraviolet (UV) absorption that promotes an electron from a nonbonding halogen orbital (n{sub X}) to a carbon-halogen antibonding orbital (σ*{sub C-X}). UV absorption into specific transitions in the gas phase results primarily in selective cleavage of the corresponding carbon-halogen bond. In the present work, broadband ultrafast UV-visible transient absorption studies of CH{sub 2}BrI reveal a more complex photochemistry in solution. Transient absorption spectra are reported spanning the range from 275 nm to 750 nm and 300 fs to 3 ns following excitation of CH{sub 2}BrI at 266 nm in acetonitrile, 2-butanol, and cyclohexane. Channels involving formation of CH{sub 2}Br + I radical pairs, iso-CH{sub 2}Br-I, and iso-CH{sub 2}I-Br are identified. The solvent environment has a significant influence on the branching ratios, and on the formation and stability of iso-CH{sub 2}Br-I. Both iso-CH{sub 2}Br-I and iso-CH{sub 2}I-Br are observed in cyclohexane with a ratio of ∼2.8:1. In acetonitrile this ratio is 7:1 or larger. The observation of formation of iso-CH{sub 2}I-Br photoproduct as well as iso-CH{sub 2}Br-I following 266 nm excitation is a novel result that suggests complexity in the dissociation mechanism. We also report a solvent and concentration dependent lifetime of iso-CH{sub 2}Br-I. At low concentrations the lifetime is >4 ns in acetonitrile, 1.9 ns in 2-butanol and ∼1.4 ns in cyclohexane. These lifetimes decrease with higher initial concentrations of CH{sub 2}BrI. The concentration dependence highlights the role that intermolecular interactions can play in the quenching of unstable isomers of dihalomethanes.

  14. Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H - - - H-N Dihydorgen Bond Characterized by Neutron Diffraction

    SciTech Connect

    Liu, Tianbiao L.; Wang, Xiaoping; Hoffmann, Christina; DuBois, Daniel L.; Bullock, R. Morris

    2014-05-19

    Use of hydrogen as a fuel by [FeFe]-hydrogenase enzymes in nature requires heterolytic cleavage of the H-H bond into a proton (H+) and hydride (H-), a reaction that is also a critical step in homogeneous catalysts for hydrogenation of C=O and C=N bonds. An understanding of the catalytic oxidation of H2 by hydrogenases provides insights into the design of synthetic catalysts that are sought as cost-effective alternatives to the use of the precious metal platinum in fuel cells. Crystallographic studies on the [FeFe]-hydrogenase enzyme were critical to understanding of its reactivity, but the key H-H cleavage step is not readily observed experimentally in natural hydrogenases. Synthetic biomimics have provided evidence for H2 cleavage leading to hydride transfer to the metal and proton transfer to an amine. Limitations on the precise location of hydrogen atoms by x-ray diffraction can be overcome by use of neutron diffraction, though its use is severely limited by the difficulty of obtaining suitable crystals and by the scarcity of neutron sources. Here we show that an iron complex with a pendant amine in the diphosphine ligand cleaves hydrogen heterolytically under mild conditions, leading to [CpC5F4NFeH(PtBu2NtBu2H)]+BArF4-, [PtBu2NtBu2 = 1,5-di(tert-butyl)-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane; ArF = 3,5-bis(trifluoromethyl)phenyl]. The Fe-H- - - H-N moiety has a strong dihydrogen bond, with a remarkably short H • • • H distance of 1.489(10) Å between the protic N-Hδ+ and hydridic Fe-Hδ-. The structural data for [CpC5F4NFeH(PtBu2NtBu2H)]+ provide a glimpse of how the H-H bond is oxidized or generated in hydrogenase enzymes, with the pendant amine playing a key role as a proton relay. The iron complex [CpC5F4NFeH(PtBu2NtBu2H)]+BArF4- is an electrocatalyst for oxidation of H2 (1 atm) at 22 °C, so the structural data are obtained on a complex that is a functional model for catalysis by [FeFe]-hydrogenase enzymes. This research was supported

  15. Biomimetic oxidation with molecular oxygen. Selective carbon-carbon bond cleavage of 1,2-diols by molecular oxygen and dihydropyridine in the presence of iron-porphyrin catalysts

    SciTech Connect

    Okamoto, T.; Sasaki, K.; Oka, S.

    1988-02-17

    The selective carbon-carbon bond cleavage of 1,2-diols in the presence of an iron-porphyrin complex, molecular oxygen, and 1-benzyl-3-carbamoyl-1,4-dihydropyridine is reported. The C-C bonds of aryl-substituted ethane-1,2-diols were cleaved exclusively to aldehydes or ketones as the oxidation products at room temperature. The reaction rates were influenced by the steric hindrance of the substituents both in the catalysts and diols, but no differences in the reactivities were observed between the two stereo isomers (meso and dl) of diols. A kinetic analysis of this bond cleavage reaction is consistent with the reaction mechanism consisting of the initial binding of diol on the active catalyst forming an intermediate complex and its subsequent breakdown in the rate-determining step of the catalytic cycle. The initial binding step is favorable for electron-deficient diols and is influenced by steric hindrance, whereas the rate-determining bond cleavage step is accelerated by electron-rich diols and unaffected by the steric effect. The mechanism of this diol cleavage reaction is discussed on the basis of these observations.

  16. Electron-deficient ruthenium and osmium complexes: From 14-electron species to C-F bond cleavage reactions

    NASA Astrophysics Data System (ADS)

    Huang, Dejian

    1999-12-01

    Stepwise removal of the fluoride from RuRF(CO)L2 gives [RuR(CO)L 2]BAr'4 (L = PtBu 2Me, R = H, CH3, Ph, Ar' = 3,5- bis(trifluoromethyl)phenyl). This 14-electron cation has a saw-horse shape with two bulky L trans and CO and R cis. The two vacant sites are in fact occupied weakly by C-H bonds from the phosphines. [RuH(CO)L2] + has a strong Lewis acidic but weakened π- basic Ru center as it is illustrated by its reactivity pattern towards olefins and alkynes. While organic fluorocarbon is notorious for its inertness due to the strong C-F bond, the α-C-F bond of a transition metal fluorocarbyl complex is activated. The chemistry in Chapter 3 illustrates this argument. Attempts to replace fluoride of MHF(CO)L2 with CF3 using Me 3SiCF3 do not give MH(CF3)(CO)L2, instead, M[HF(CF2)(CO)L2 is isolated. Fast equilibrium exists between RuHF(CF2)(CO)L2 and RuH(CF3)(CO)L 2 but not for OsHF(CF2)(CO)L2, which is converted to OsF2(CFH)(CO)L2 upon heating. In contrast, isomerization of RuHF(CF2)(CO)L2 gives RUF(CF2H)(CO)L 2.

  17. The importance of the Lewis base in lithium mediated metallation and bond cleavage reaction of allyl amines and allyl phosphines.

    PubMed

    Blair, V L; Stevens, M A; Thompson, C D

    2016-06-21

    Metallation of two analogous N- and P-allyl molecules Ph2NCH2CHCH2 and Ph2PCH2CHCH2 with nBuLi have shown contrasting reactivities based on the choice of Lewis donor. With metallation of the alpha carbon atom was achieved regardless of the Lewis donor used while in comparison metallation of showed an unexpected donor denticity dependence with P-C bond clevage induced with the tri-dentate PMDETA. Complementary DFT and solution studies rationalise this outcome.

  18. Zirconocene-assisted remote cleavage of C-C and C-O bonds: application to acyclic stereodefined metalated hydrocarbons.

    PubMed

    Bruffaerts, J; Pierrot, D; Marek, I

    2016-11-08

    The molding of molecules through remote functionalisation has increasingly become popular as it provides original and flexible synthetic alternatives to classical retrosynthetic analysis. In this Perspective article, we summarise more than a decade of studies in the specific field of remote activation of inert C-C and C-O bonds using the unique abilities of organozirconocene species mainly from our own research group. By demonstrating that these reactions represent novel and powerful entries towards acyclic stereodefined reactive organometallic species, we aim to show the vast opportunities this concept-driven methodology discovery offers.

  19. Selective Monoarylation of Aromatic Ketones and Esters via Cleavage of Aromatic Carbon-Heteroatom Bonds by Trialkylphosphine Ruthenium Catalysts.

    PubMed

    Kondo, Hikaru; Kochi, Takuya; Kakiuchi, Fumitoshi

    2017-02-17

    We report here the ruthenium-catalyzed selective monoarylation of aromatic ketones bearing two ortho carbon-heteroatom (O or N) bonds. Under the newly developed catalyst system consisting of RuHCl(CO)(P(i)Pr3)2, CsF, and styrene, the C-O arylation of 2',6'-dimethoxyacetophenone with a phenylboronate gave the C-O monoarylation product selectively. The selective C-O monoarylation was applicable to a variety of arylboronates and aromatic ketones and proceeds with high regio- and chemoselectivities. A formal synthesis of altertenuol was also achieved using the C-O monoarylation of an aromatic ester as a key step.

  20. Synthesis of diorganoplatinum(IV) complexes by the Ssbnd S bond cleavage with platinum(II) complexes

    NASA Astrophysics Data System (ADS)

    Niroomand Hosseini, Fatemeh; Rashidi, Mehdi; Nabavizadeh, S. Masoud

    2016-12-01

    Reaction of [PtR2(NN)] (R = Me, p-MeC6H4 or p-MeOC6H4; NN = 2,2‧-bipyridine, 4,4‧-dimethyl-2,2‧-bipyridine, 1,10-phenanthroline or 2,9-dimethyl-1,10-phenanthroline) with MeSSMe gives the platinum(IV) complexes cis,trans-[PtR2(SMe)2(NN)]. They are characterized by NMR spectroscopy and elemental analysis. The geometries and the nature of the frontier molecular orbitals of Pt(IV) complexes containing Ptsbnd S bonds are studied by means of the density functional theory.

  1. Merging allylic C-H bond activation and C-C bond cleavage en route to the formation of a quaternary carbon stereocenter in acyclic systems.

    PubMed

    Vasseur, Alexandre; Marek, Ilan

    2017-01-01

    This protocol describes a diastereoselective approach for the synthesis of complex molecular architectures containing two stereogenic centers in a 1,4 relationship, one of which being an all-carbon quaternary stereogenic center. Such molecules could be intermediates in the synthesis of steroids, for example. Conceived as a single-flask synthetic sequence from ω-ene cyclopropanes, the protocol involves a concerted allylic C-H and C-C bond activation promoted by the Negishi reagent (Cp2Zr(η(2)-butene)). This zirconium-promenade-based procedure affords bifunctionalized products in high diastereomeric ratios after reaction of ω-ene cyclopropanes with the Negishi complex, followed by a thermal treatment and sequential addition of two different electrophiles. The method proves to be particularly efficient when carbonyl compounds are used as first electrophiles and hydrogen or elemental halides are used as second electrophiles. In addition, it offers the opportunity to create new C-C bonds via remote functionalization of a (sp(3))-C-H bond, a result of a copper or copper/palladium transmetalation step that extends the scope of the process to alkyl, acyl and aromatic halide compounds as second electrophiles. The typical described protocol allows the synthesis of the highly diastereo-enriched 2-((1R*,2S*)-2-butyl-2 propylcyclopropyl)ethanol and may provide a new entry to access complex molecular segments of natural products such as steroids or C30 botryococcene. It requires a simple reaction setup and takes ∼18.5 h to run the reaction and 2 h for isolation and purification.

  2. Molecular Basis of C–N Bond Cleavage by the Glycyl Radical Enzyme Choline Trimethylamine-Lyase

    SciTech Connect

    Bodea, Smaranda; Funk, Michael A.; Balskus, Emily P.; Drennan, Catherine L.

    2016-10-01

    We report that deamination of choline catalyzed by the glycyl radical enzyme choline trimethylamine-lyase (CutC) has emerged as an important route for the production of trimethylamine, a microbial metabolite associated with both human disease and biological methane production. Here, we have determined five high-resolution X-ray structures of wild-type CutC and mechanistically informative mutants in the presence of choline. Within an unexpectedly polar active site, CutC orients choline through hydrogen bonding with a putative general base, and through close interactions between phenolic and carboxylate oxygen atoms of the protein scaffold and the polarized methyl groups of the trimethylammonium moiety. These structural data, along with biochemical analysis of active site mutants, support a mechanism that involves direct elimination of trimethylamine. Lastly, this work broadens our understanding of radical-based enzyme catalysis and will aid in the rational design of inhibitors of bacterial trimethylamine production.

  3. OCO and NCO chelated derivatives of heavier group 15 elements. Study on possibility of cyclization reaction via intramolecular ether bond cleavage.

    PubMed

    Dostál, Libor; Jambor, Roman; Růžička, Aleš; Jirásko, Robert; Holeček, Jaroslav; De Proft, Frank

    2011-09-21

    A set of four pincer ligands, either the OCO type ligands L(1-3) [2,6-(ROCH(2))(2)C(6)H(3)](-), where R = Me (L(1)), mesityl (L(2)), t-Bu (L(3)) or novel NCO ligand [2-(Me(2)NCH(2))-6-(t-BuOCH(2))C(6)H(3)](-) was studied. The reaction of L(4)Li with PCl(3) resulted in isolation of [2-(OCH(2))-6-(Me(2)NCH(2))C(6)H(3)]PCl (1) as a result of intramolecular ether bond cleavage and elimination of t-BuCl. The conversion between the organolithium compounds L(1,2,4)Li and AsCl(3) led to the desired chlorides, i.e. (L(1))(2)AsCl (2), L(2)AsCl(2) (3), L(4)AsCl(2) (5), but an analogous reaction using the L(3)Li compound gave [2-(OCH(2))-6-(t-BuOCH(2))C(6)H(3)]AsCl (4) as a result of intramolecular cyclization. The organoantimony chloride L(3)SbCl(2) was shown to undergo very slow cyclization in CDCl(3) again via elimination of t-BuCl giving [2-(OCH(2))-6-(t-BuOCH(2))C(6)H(3)]SbCl (6) and it was demonstrated that this reaction may be accelerated by preparation of L(3)Sb(Cl)(OTf) (7) with more Lewis acidic central atom. On the contrary, both antimony derivatives of the NCO ligand L(4), not only the chloride L(4)SbCl(2) (8) but also the ionic pair containing highly Lewis acidic cation [L(4)SbCl](+)[CB(11)H(12)](-) (9), are stable without any indication for etheral bond cleavage. The situation is rather similar in the case of organobismuth derivatives of L(4), which allowed isolation of compounds L(4)BiCl(2) (10), L(4)Bi(Cl)(OTf) (11) and [L(4)BiCl](+)[CB(11)H(12)](-) (12). All studied compounds were characterized by the help of (1)H and (13)C NMR spectroscopy, ESI mass spectrometry, elemental analysis and (except 1) by single-crystal X-ray diffraction.

  4. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    PubMed

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase.

  5. Experimental and theoretical investigations of copper (I/II) complexes with triazine-pyrazole derivatives as ligands and their in situ C-N bond cleavage

    NASA Astrophysics Data System (ADS)

    Wang, Ji-Xiao; Wang, Che; Wang, Xuan; Wang, Xin-Yu; Xing, Yong-Heng; Sun, Qiao

    2015-05-01

    Two copper complexes, Cu(SCN)(Mpz∗T-(EtO)2) (1) (Mpz∗T-(EtO)2 = L3) and CuCl(H2O)(Mpz∗T-O2) (2) (Mpz∗T-O2 = L4) were synthesized by the reaction of 2,4,6-tri(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (L1) or 2,4,6-tri(1H-pyrazol-1-yl)-1,3,5-triazine (L2) with CuCl2·2H2O in anhydrous ethanol and methanol, respectively. The complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single crystal X-ray diffraction and X-ray powder diffraction. The structural characterizations and quantum mechanical calculations of the two complexes were analyzed in detail. It was found that an in site reaction occurred during the synthesis process of complexes 1 and 2, likely due to catalytic property of copper ions which leads to the C-N bond cleavage to generate new organic species, namely, Mpz∗T-(EtO)2 (L3) and Mpz∗T-O2 (L4).

  6. Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage.

    PubMed

    Kandasamy, Balamurugan; Vanhaecht, Stef; Nkala, Fiona Marylyn; Beelen, Tessa; Bassil, Bassem S; Parac-Vogt, Tatjana N; Kortz, Ulrich

    2016-09-19

    The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(β-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(β-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(β-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and β = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and β = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(β-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(β-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, β = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

  7. Hydrogenolysis and homologation of linear and branched pentenes on Ru/SiO/sub 2/ catalysts: implication in the mechanism of C-C bond formation and cleavage on metal surfaces

    SciTech Connect

    Rodriguez, E.; Leconte, M.; Basset, J.M.; Tanaka, K.; Tanaka, K.I.

    1988-01-06

    Hydrogenolysis and homologation of 1-pentene to butenes and hexenes take place simultaneously and at the same rate over a Ru/SiO/sub 2/ catalysts at 110/sup 0/C, suggesting that these two reactions are mechanistically related. /sup 13/C labeling experiments indicate that C-C cleavage occurs at the double bond of 1-pentene-1-/sup 13/C leading to unlabeled 1-butene and labeled hexenes. The product distribution in the hydrogenolysis of 1-pentene, 2-pentenes, 3-methyl-1-butene, 2-methyl-2-butene, and 2-methyl-1-butene is accounted for by a carbene-olefin mechanism, which can therefore be considered as a reasonable common path for the formation and cleavage of carbon-carbon bonds on metal surfaces.

  8. Transition-Metal-Free Deacylative Cleavage of Unstrained C(sp(3))-C(sp(2)) Bonds: Cyanide-Free Access to Aryl and Aliphatic Nitriles from Ketones and Aldehydes.

    PubMed

    Ge, Jing-Jie; Yao, Chuan-Zhi; Wang, Mei-Mei; Zheng, Hong-Xing; Kang, Yan-Biao; Li, Yadong

    2016-01-15

    A transition-metal-free deacylative C(sp(3))-C(sp(2)) bond cleavage for the synthetically practical oxidative amination of ketones and aldehydes to nitriles is first described, using cheap and commercially abundant NaNO2 as the oxidant and the nitrogen source. Various nitriles bearing aryl, heteroaryl, alkyl, and alkenyl groups could be smoothly obtained from ketones and aldehydes in high yields, avoiding highly toxic cyanides or transition metals.

  9. Spectroscopic and kinetic studies of perturbed trinuclear copper clusters: the role of protons in reductive cleavage of the O-O bond in the multicopper oxidase Fet3p.

    PubMed

    Augustine, Anthony J; Quintanar, Liliana; Stoj, Christopher S; Kosman, Daniel J; Solomon, Edward I

    2007-10-31

    The multicopper oxidase Fet3p couples four 1e(-) oxidations of substrate to the 4e(-) reduction of O2 to H2O. Fet3p uses four Cu atoms to accomplish this reaction: the type 1, type 2, and coupled binuclear type 3 sites. The type 2 and type 3 sites together form a trinuclear Cu cluster (TNC) which is the site of O2 reduction. This study focuses on mutants of two residues, E487 and D94, which lie in the second coordination sphere of the TNC and defines the role that each plays in the structural integrity of the TNC, its reactivity with O2, and in the directional movement of protons during reductive cleavage of the O-O bond. The E487D, E487A, and D94E mutants have been studied in the holo and type 1 depleted (T1D) forms. Residue E487, located near the T3 center, is found to be responsible for donation of a proton during the reductive cleavage of the O-O bond in the peroxide intermediate and an inverse kinetic solvent isotope effect, which indicates that this proton is already transferred when the O-O bond is cleaved. Residue D94, near the T2 site, plays a key role in the reaction of the reduced TNC with O2 and drives electron transfer from the T2 Cu to cleave the O-O bond by deprotonating the T2 Cu water ligand. A mechanism is developed where these second sphere residues participate in the proton assisted reductive cleavage of the O-O bond at the TNC.

  10. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    SciTech Connect

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-03

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

  11. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    NASA Astrophysics Data System (ADS)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-01

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-{3-(pyridin-2-yl)-pyrazolato} and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the CbenzoylN bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the {3-(pyridin-2-yl)-pyrazolato}{3-(pyridin-2-yl)-1H-pyrazole}Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ɛ = 116 dm3 mol-1 cm-1) supports the presence of Cu(II) centres.

  12. Irida-β-ketoimines Derived from Hydrazines To Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study.

    PubMed

    Zumeta, Itziar; Mendicute-Fierro, Claudio; Bustos, Itxaso; Huertos, Miguel A; Rodríguez-Diéguez, Antonio; Seco, José M; San Sebastian, Eider; Garralda, María A

    2016-10-17

    Unprecedented metallapyrazoles [IrH2{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (3) and [IrHCl{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (4) were obtained by the reaction of the irida-β-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNH2))H}] (2) in MeOH heated at reflux in the presence and absence of KOH, respectively. In solution, iridapyrazole 3 undergoes a dynamic process due to prototropic tautomerism with an experimental barrier for the exchange of ΔGcoal(⧧) = 53.7 kJ mol(-1). DFT calculations agreed with an intrapyrazole proton transfer process assisted by two water molecules (ΔG = 63.1 kJ mol(-1)). An X-ray diffraction study on 4 indicated electron delocalization in the iridapyrazole ring. The reaction of the irida-β-diketone [IrHCl{(PPh2(o-C6H4CO))2H}] (1) with H2NNRR' in aprotic solvents gave irida-β-ketoimines [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNRR'))H}] (R = R' = Me (5); R = H, R' = Ph (8)), which can undergo N-N bond cleavage to afford the acyl-amide complex [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4C(O)N(CH3)2))-κP,κO] (6) or [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP)(NH2NHPh-κNH2)] (9) containing o-(diphenylphosphine)benzonitrile and phenylhydrazine, respectively. From a CH2Cl2/CH3OH solution of 9 kept at -18 °C, single crystals of [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP))(HN═NPh-κNH)] (10) containing o-(diphenylphosphine)benzonitrile and phenyldiazene were formed, as shown by X-ray diffraction. The reaction of 1 with methylhydrazine in methanol gave the hydrazine complex [IrCl(PPh2(o-C6H4CO))2(NH2NH(CH3)-κNH2)] (7). Single-crystal X-ray diffraction analysis was performed on 6 and 7.

  13. Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by σ Bond C-C Cleavage.

    PubMed

    Eccleshare, Lee; Lozada-Rodríguez, Leticia; Cooper, Phillippa; Burroughs, Laurence; Ritchie, John; Lewis, William; Woodward, Simon

    2016-08-22

    Sequential treatment of 2-C6 H4 Br(CHO) with LiC≡CR(1) (R(1) =SiMe3 , tBu), nBuLi, CuBr⋅SMe2 and HC≡CCHClR(2) [R(2) =Ph, 4-CF3 Ph, 3-CNPh, 4-(MeO2 C)Ph] at -50 °C leads to formation of an intermediate carbanion (Z)-1,2-C6 H4 {CA (=O)C≡CB R(1) }{CH=CH(CH(-) )R(2) } (4). Low temperatures (-50 °C) favour attack at CB leading to kinetic formation of 6,8-bicycles containing non-classical C-carbanion enolates (5). Higher temperatures (-10 °C to ambient) and electron-deficient R(2) favour retro σ-bond C-C cleavage regenerating 4, which subsequently closes on CA providing 6,6-bicyclic alkoxides (6). Computational modelling (CBS-QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H(+) gave 1,2-dihydronaphthalen-1-ols, or under dehydrating conditions, 2-aryl-1-alkynylnaphthlenes. Enolates 5 react in situ with: H2 O, D2 O, I2 , allylbromide, S2 Me2 , CO2 and lead to the expected C-E derivatives (E=H, D, I, allyl, SMe, CO2 H) in 49-64 % yield directly from intermediate 5. The parents (E=H; R(1) =SiMe3 , tBu; R(2) =Ph) are versatile starting materials for NaBH4 and Grignard C=O additions, desilylation (when R(1) =SiMe) and oxime formation. The latter allows formation of 6,9-bicyclics via Beckmann rearrangement. The 6,8-ring iodides are suitable Suzuki precursors for Pd-catalysed C-C coupling (81-87 %), whereas the carboxylic acids readily form amides under T3P® conditions (71-95 %).

  14. [Cu30I16(mtpmt)12(μ(10-S4))]: an unusual 30-membered copper(I) cluster derived from the C-S bond cleavage and its use in heterogeneous catalysis.

    PubMed

    Li, Hong-Xi; Zhao, Wei; Li, Hai-Yan; Xu, Zhong-Lin; Wang, Wen-Xia; Lang, Jian-Ping

    2013-05-14

    The Cu(I)-mediated C-S bond cleavage of 5-methyl-4-(p-tolyl)pyrimidine-2-thiol (mtpmtH) gave one 30-nuclear cluster [Cu30I16(mtpmt)12(μ10-S4)], one polymeric complex [(bmtpms)Cu-(μ-I)]n and one tetranuclear complex [(bmptmds){Cu(μ-I)}2]2; the 30-nuclear cluster displayed excellent catalytic performances in the coupling reactions of N-heterocycles and arylboronic acids and could be recycled and reused.

  15. Comparison of the Effects of British Anti-Lewisite (BAL) and Beta Mercapto Ethanol on the Reduction and Cleavage of Disulfide Bonds in IgG and Human Keratinocyte Proteins

    DTIC Science & Technology

    1988-02-01

    34. Din1a.Z’atic representation of anticipated :-su ts I<•:;di.,’¢,i two-dimensionai e cto h rsswhen- sŕ,’ý" l s are trertet with a disulfide redu cer...Development Laboraliory A TTN: SGRD-UBG;-M l ;ort Detrick, Bldg 568 F~rederick, MD 21701-5010 2/88 S~WkWWW ~1W,$~/ b)AlEmm ...Cleavage of Disulfide Bonds in IgG and Human Keratinocyte Proteins Michael A . Deaton, PhD, CPT, MS Charles A . Barba, BS, SP4 Carlos R. Flores, BS, SP4

  16. Three-coordinate NiII: tracing the origin of an unusual, facile Si-C(sp3) bond cleavage in [(tBu2PCH2SiMe2)2N]Ni+.

    PubMed

    Fullmer, Benjamin C; Fan, Hongjun; Pink, Maren; Huffman, John C; Tsvetkov, Nikolay P; Caulton, Kenneth G

    2011-03-02

    All attempts to synthesize (PNP)Ni(OTf) form instead ((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)OTf)Ni(CH(2)P(t)Bu(2)). Abstraction of F(-) from (PNP)NiF by even a catalytic amount of BF(3) causes rearrangement of the (transient) (PNP)Ni(+) to analogous ring-opened [((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)F)]Ni(CH(2)P(t)Bu(2)). Abstraction of Cl(-) from (PNP)NiCl with NaB(C(6)H(3)(CF(3))(2))(4) in CH(2)Cl(2) or C(6)H(5)F gives (PNP)NiB(C(6)H(3)(CF(3))(2))(4), the key intermediate in these reactions is (PNP)Ni(+), [(PNP)Ni](+), in which one Si-C bond (together with N and two P) donates to Ni. This makes this Si-C bond subject to nucleophilic attack by F(-), triflate, and alkoxide/ether (from THF). This σ(Si-C) complex binds CO in the time of mixing and also binds chloride, both at nickel. Evidence is offered of a "self-healing" process, where the broken Si-C bond can be reformed in an equilibrium process. (PNP)Ni(+) reacts rapidly with H(2) to give (PN(H)P)NiH(+), which can be deprotonated to form (PNP)NiH. A variety of nucleophilic attacks (and THF polymerization) on the coordinated Si-C bond are envisioned to occur perpendicular to the Si-C bond, based on the character of the LUMO of (PNP)Ni(+).

  17. Dicationic ring opening reactions of trans-2-phenylcyclopropylamine•HCl: electrophilic cleavage of the distal (C2-C3) bond of cyclopropanes

    PubMed Central

    Lill, Sten O. Nilsson; Naredla, Rajasekhar Reddy; Zielinski, Matthew E.; Knoecer, Larecia; Klumpp, Douglas A.

    2013-01-01

    Electrophilic ring opening of trans-2-phenylcyclopropylamine•HCl occurs at the distal (C2-C3) bond. This is consistent with weakening of the distal bond by the σ-withdrawing ammonium group and charge-charge repulsive effects in the transition state. PMID:23941589

  18. A broken-symmetry density functional study of structures, energies, and protonation states along the catalytic O-O bond cleavage pathway in ba3 cytochrome c oxidase from Thermus thermophilus.

    PubMed

    Han Du, Wen-Ge; Götz, Andreas W; Yang, Longhua; Walker, Ross C; Noodleman, Louis

    2016-08-21

    Broken-symmetry density functional calculations have been performed on the [Fea3, CuB] dinuclear center (DNC) of ba3 cytochrome c oxidase from Thermus thermophilus in the states of [Fea3(3+)-(HO2)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], using both PW91-D3 and OLYP-D3 functionals. Tyr237 is a special tyrosine cross-linked to His233, a ligand of CuB. The calculations have shown that the DNC in these states strongly favors the protonation of His376, which is above propionate-A, but not of the carboxylate group of propionate-A. The energies of the structures obtained by constrained geometry optimizations along the O-O bond cleavage pathway between [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] have also been calculated. The transition of [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] → [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] shows a very small barrier, which is less than 3.0/2.0 kcal mol(-1) in PW91-D3/OLYP-D3 calculations. The protonation state of His376 does not affect this O-O cleavage barrier. The rate limiting step of the transition from state A (in which O2 binds to Fea3(2+)) to state PM ([Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], where the O-O bond is cleaved) in the catalytic cycle is, therefore, the proton transfer originating from Tyr237 to O-O to form the hydroperoxo [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] state. The importance of His376 in proton uptake and the function of propionate-A/neutral-Asp372 as a gate to prevent the proton from back-flowing to the DNC are also shown.

  19. Molecular approach to the mechanisms of C-C bond formation and cleavage on metal surfaces: Hydrogenolysis, homologation, and dimerization of ethylene over Ru/SiO sub 2 catalysts

    SciTech Connect

    Rodriguez, E.; Leconte, M.; Basset, J.M.; Tanaka, K. )

    1989-09-01

    At temperatures above ca. 50 C, over Ru/SiO{sub 2} catalysts and in the presence of hydrogen, ethylene undergoes hydrogenation, hydrogenolysis, homologation, and dimerization reactions. The influence of contact times and reaction temperatures on conversions and selectivities has been examined. At low temperatures (bond cleavage and formation; two mechanisms are proposed which involve either metallocarbene insertion-elimination reactions or formation and decomposition of dimetallacyclic intermediates. Several mechanisms are envisioned for dimerization of ethylene; experimental data seem to support a mechanism which involves formation and coupling of two ethylidene species.

  20. Palladium-catalyzed one-pot three- or four-component coupling of aryl iodides, alkynes, and amines through C-N bond cleavage: efficient synthesis of indole derivatives.

    PubMed

    Hao, Wei; Geng, Weizhi; Zhang, Wen-Xiong; Xi, Zhenfeng

    2014-02-24

    An efficient synthesis of N-substituted indole derivatives was realized by combining the Pd-catalyzed one-pot multicomponent coupling approach with cleavage of the C(sp(3))-N bonds. Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand showed high efficiency. A variety of aryl iodides, including cyclic and acyclic tertiary amino aryl iodides, and substituted 1-bromo-2-iodobenzene derivatives could be used. Both symmetric and unsymmetric alkynes substituted with alkyl, aryl, or trimethylsilyl groups could be applied. Cyclic secondary amines such as piperidine, morpholine, 4-methylpiperidine, 1-methylpiperazine, 2-methylpiperidine, and acyclic amines including secondary and primary amines all showed good reactivity. Further application of the resulting indole derivatives was demonstrated by the synthesis of benzosilolo[2,3-b]indole.

  1. Cleavage experiments with deoxythymidine 3',5'-bis-(p-nitrophenyl phosphate) suggest that the homing endonuclease I-PpoI follows the same mechanism of phosphodiester bond hydrolysis as the non-specific Serratia nuclease.

    PubMed

    Friedhoff, P; Franke, I; Krause, K L; Pingoud, A

    1999-01-25

    We show here that two nucleases, Serratia nuclease and I-PpoI, with contrasting specificities, i.e. non-specific vs. highly sequence specific, share a structurally similar active site region with conservation of the catalytically relevant histidine and asparagine residues. On the basis of a comparison of the available structures and biochemical data for wild type and mutant variants of Serratia nuclease and I-PpoI we propose that both enzymes have a common catalytic mechanism, a proposition that is supported by our finding that both enzymes accept deoxythymidine 3',5'-bis-(p-nitrophenyl phosphate) as a substrate and cleave it in an identical manner. According to this mechanism a histidine residue functions as a general base and Mg2+ bound to an asparagine residue as a Lewis acid in phosphodiester bond cleavage.

  2. Mechanisms of C-C bond formation and cleavage on metal surfaces: Formation of butenes and hexenes from linear and branched pentenes over Ru/SiO sub 2 catalysts

    SciTech Connect

    Rodriguez, E.; Leconte, M.; Basset, J. )

    1991-12-01

    Over Ru/SiO{sub 2} catalyst, at temperatures above 100-150C and in the presence of hydrogen, linear and branched pentenes (1-pentene, cis- and trans-2-pentene, 2-methyl-2-butene, 3-methyl-1-butene, and 2-methyl-1-butene) undergo isomerization, hydrogenation, hydrogenolysis, and homologation. The main primary products of these last two reactions of C-C bond cleavage and formation are methane, butenes, and hexanes. At low temperature (100-150C), the formation of methane is reduced and the major products are C{sub 4} and C{sub 6} olefinic hydrocarbons, which are obtained in roughly comparable amounts. The distribution of the butenes isomers and of the hexenes isomers strongly depends on the structure of the starting pentene (linear or branched, terminal or internal). The results confirm that hydrogenolysis and homologation of a C{sub 5} olefinic hydrocarbon occur at comparable rates and involve: (1) cleavage of mainly a terminal C-C bond of the pentene isomer leading to C{sup 4} and C{sup 1} fragments, (2) reaction of this C{sup 1} fragment with the starting C{sup 5} to give C{sup 6} hydrocarbons, and (or) (3) hydrogenation of the C{sup 1} fragment to methane. Two mechanisms, based on concepts of organometallic chemistry, can account for the results (especially for the distribution of the C{sup 4} and C{sup 6} olefinic isomers): (1) a methylene insertion-deinsertion mechanism or (2) a mechanism that involves formation and decomposition of dimetallacyclic intermediates. Several experimental results seem to be in favor of the last proposed mechanism.

  3. Ab initio molecular dynamics study of hydrogen cleavage by a Lewis base [tBu3P] and a Lewis acid [B(C6F5)3] at the mesoscopic level--dynamics in the solute-solvent molecular clusters.

    PubMed

    Pu, Maoping; Privalov, Timofei

    2014-12-01

    With the help of state-of-the-art ab initio molecular dynamics methods, we investigated the reaction pathway of the {tBu3 P + H2 + B(C6 F5 )3 } system at the mesoscopic level. It is shown that: i) the onset of H2 activation is at much larger boron⋅⋅⋅phosphorus distances than previously thought; ii) the system evolves to the product in a roaming-like fashion because of quasi-periodic nuclear motion along the asymmetric normal mode of P⋅⋅⋅HH⋅⋅⋅B fragment; iii) transient configurations of a certain type are present despite structural interference from the solvent; iv) transient-state configurations with sub-picosecond lifetime have potentially interesting infrared activity in the organic solvent (toluene) as well as in the gas phase. The presented results should be helpful for future experimental and theoretical studies of frustrated Lewis pair (FLP) activity.

  4. Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C-F Bond Cleavage.

    PubMed

    Zhou, Jing; Kuntze-Fechner, Maximilian W; Bertermann, Rüdiger; Paul, Ursula S D; Berthel, Johannes H J; Friedrich, Alexandra; Du, Zhenting; Marder, Todd B; Radius, Udo

    2016-04-27

    The [Ni(IMes)2]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C-F bond activation and transmetalation with bis(pinacolato)diboron (B2pin2) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.

  5. Is the 2,3-carbon-carbon bond of indole really inert to oxidative cleavage by Oxone?--synthesis of isatoic anhydrides from indoles.

    PubMed

    Nelson, Amber C; Kalinowski, Emily S; Czerniecki, Nikolas J; Jacobson, Taylor L; Grundt, Peter

    2013-11-21

    A recent report has indicated that the oxidizing agent Oxone does not possess the ability to cleave the 2,3-carbon-carbon bond of indole. Work in our laboratory shows that this is not the case. Indole and a variety of aryl ring substituted derivatives readily react to form synthetically important isatoic anhydrides.

  6. Immunolocalization of the cleavage of the aggrecan core protein at the Asn341-Phe342 bond, as an indicator of the location of the metalloproteinases active in the lysis of the rat growth plate.

    PubMed

    Lee, E R; Lamplugh, L; Leblond, C P; Mordier, S; Magny, M C; Mort, J S

    1998-09-01

    In view of the extensive lysis of hyaline cartilage known to take place during endochondral bone formation, the current study was designed to test the hypothesis that metalloproteinases are the agents that mediate this lysis. Since these enzymes have been shown in vitro to cleave the core protein of the major proteoglycan of cartilage, aggrecan, at the Asn341-Phe342 bond, an immunohistochemical method has been developed to find out whether or not there are sites in the growth plate of the rat tibia where cleavage of this bond takes place. The cleavage of aggrecan by metalloproteinases is followed by the retention of the fragment known as G1, for it includes the G1 domain. Since the G1 fragment terminates in the amino acid residues ...FVDIPEN, we prepared an antiserum against FVDIPEN, confirmed its specificity, then applied it to the growth plate of 21-day-old rat tibia in the hope of localizing the G1 fragments. The antiserum specificity was shown by its recognition of the ...FVDIPEN sequence at the C-terminus of peptides and of G1 fragments produced by aggrecan cleavage. When the antiserum was applied to Western blots of guanidinium chloride extracts prepared from epiphyseal growth plate, it recognized two species (56 and 52 kDa), which differed only in the degree of glycosylation. These fragments were comparable in size to the G1 fragments generated by the action of recombinant metalloproteinase in vitro, thus confirming antiserum specificity for these fragments. Applying the antiserum to cryosections of 21-day-old rat tibiae revealed immunostaining at two intensities within the growth plate matrix: a strong staining was observed in a 1-5 microm-wide layer designated "peripheral" matrix, which borders the epiphyseal and metaphyseal marrow spaces as well as the perichondrium, while a weak staining was found in the rest of the plate, designated "central" matrix. The abundance of G1 fragments terminating in ...FVDIPEN in the peripheral matrix indicates that this is

  7. Room-temperature activation of methane and dry re-forming with CO2 on Ni-CeO2 (111) surfaces: Effect of Ce3+ sites and metal–support interactions on C–H bond cleavage

    DOE PAGES

    Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan; ...

    2016-10-27

    The results of core-level photoemission indicate that Ni-CeO2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CHx and COx (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. The strong electronic perturbationsmore » in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.« less

  8. Selective and Nonselective Cleavages in Positive and Negative CID of the Fragments Generated from In-Source Decay of Intact Proteins in MALDI-MS

    NASA Astrophysics Data System (ADS)

    Takayama, Mitsuo; Sekiya, Sadanori; Iimuro, Ryunosuke; Iwamoto, Shinichi; Tanaka, Koichi

    2014-01-01

    Selective and nonselective cleavages in ion trap low-energy collision-induced dissociation (CID) experiments of the fragments generated from in-source decay (ISD) with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) of intact proteins are described in both positive and negative ion modes. The MALDI-ISD spectra of the proteins demonstrate common, discontinuous, abundant c- and z'-ions originating from cleavage at the N-Cα bond of Xxx-Asp/Asn and Gly-Xxx residues in both positive- and negative-ion modes. The positive ion CID of the c- and z'-ions resulted in product ions originating from selective cleavage at Asp-Xxx, Glu-Xxx and Cys-Xxx residues. Nonselective cleavage product ions rationalized by the mechanism of a "mobile proton" are also observed in positive ion CID spectra. Negative ion CID of the ISD fragments results in complex product ions accompanied by the loss of neutrals from b-, c-, and y-ions. The most characteristic feature of negative ion CID is selective cleavage of the peptide bonds of acidic residues, Xxx-Asp/Glu/Cys. A definite influence of α-helix on the CID product ions was not obtained. However, the results from positive ion and negative ion CID of the MALDI-ISD fragments that may have long α-helical domains suggest that acidic residues in helix-free regions tend to degrade more than those in helical regions.

  9. Cleavage of ether, ester, and tosylate C(sp3)-O bonds by an iridium complex, initiated by oxidative addition of C-H bonds. Experimental and computational studies.

    PubMed

    Kundu, Sabuj; Choi, Jongwook; Wang, David Y; Choliy, Yuriy; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

    2013-04-03

    A pincer-ligated iridium complex, (PCP)Ir (PCP = κ(3)-C6H3-2,6-[CH2P(t-Bu)2]2), is found to undergo oxidative addition of C(sp(3))-O bonds of methyl esters (CH3-O2CR'), methyl tosylate (CH3-OTs), and certain electron-poor methyl aryl ethers (CH3-OAr). DFT calculations and mechanistic studies indicate that the reactions proceed via oxidative addition of C-H bonds followed by oxygenate migration, rather than by direct C-O addition. Thus, methyl aryl ethers react via addition of the methoxy C-H bond, followed by α-aryloxide migration to give cis-(PCP)Ir(H)(CH2)(OAr), followed by iridium-to-methylidene hydride migration to give (PCP)Ir(CH3)(OAr). Methyl acetate undergoes C-H bond addition at the carbomethoxy group to give (PCP)Ir(H)[κ(2)-CH2OC(O)Me] which then affords (PCP-CH2)Ir(H)(κ(2)-O2CMe) (6-Me) in which the methoxy C-O bond has been cleaved, and the methylene derived from the methoxy group has migrated into the PCP Cipso-Ir bond. Thermolysis of 6-Me ultimately gives (PCP)Ir(CH3)(κ(2)-O2CR), the net product of methoxy group C-O oxidative addition. Reaction of (PCP)Ir with species of the type ROAr, RO2CMe or ROTs, where R possesses β-C-H bonds (e.g., R = ethyl or isopropyl), results in formation of (PCP)Ir(H)(OAr), (PCP)Ir(H)(O2CMe), or (PCP)Ir(H)(OTs), respectively, along with the corresponding olefin or (PCP)Ir(olefin) complex. Like the C-O bond oxidative additions, these reactions also proceed via initial activation of a C-H bond; in this case, C-H addition at the β-position is followed by β-migration of the aryloxide, carboxylate, or tosylate group. Calculations indicate that the β-migration of the carboxylate group proceeds via an unusual six-membered cyclic transition state in which the alkoxy C-O bond is cleaved with no direct participation by the iridium center.

  10. Structural insights into the role of iron–histidine bond cleavage in nitric oxide-induced activation of H-NOX gas sensor proteins

    PubMed Central

    Herzik, Mark A.; Jonnalagadda, Rohan; Kuriyan, John; Marletta, Michael A.

    2014-01-01

    Heme-nitric oxide/oxygen (H-NOX) binding domains are a recently discovered family of heme-based gas sensor proteins that are conserved across eukaryotes and bacteria. Nitric oxide (NO) binding to the heme cofactor of H-NOX proteins has been implicated as a regulatory mechanism for processes ranging from vasodilation in mammals to communal behavior in bacteria. A key molecular event during NO-dependent activation of H-NOX proteins is rupture of the heme–histidine bond and formation of a five-coordinate nitrosyl complex. Although extensive biochemical studies have provided insight into the NO activation mechanism, precise molecular-level details have remained elusive. In the present study, high-resolution crystal structures of the H-NOX protein from Shewanella oneidensis in the unligated, intermediate six-coordinate and activated five-coordinate, NO-bound states are reported. From these structures, it is evident that several structural features in the heme pocket of the unligated protein function to maintain the heme distorted from planarity. NO-induced scission of the iron–histidine bond triggers structural rearrangements in the heme pocket that permit the heme to relax toward planarity, yielding the signaling-competent NO-bound conformation. Here, we also provide characterization of a nonheme metal coordination site occupied by zinc in an H-NOX protein. PMID:25253889

  11. Ultrafast α -CC bond cleavage of acetone upon excitation to 3p and 3d Rydberg states by femtosecond time-resolved photoelectron imaging

    NASA Astrophysics Data System (ADS)

    Hüter, O.; Temps, F.

    2016-12-01

    The radiationless electronic relaxation and α -CC bond fission dynamics of jet-cooled acetone in the S1 (n π* ) state and in high-lying 3p and 3d Rydberg states have been investigated by femtosecond time-resolved mass spectrometry and photoelectron imaging. The S1 state was accessed by absorption of a UV pump photon at selected wavelengths between λ = 320 and 250 nm. The observed acetone mass signals and the S1 photoelectron band decayed on sub-picosecond time scales, consistent with a recently proposed ultrafast structural relaxation of the molecules in the S1 state away from the Franck-Condon probe window. No direct signatures could be observed by the experiments for CC dissociation on the S1 potential energy hypersurface in up to 1 ns. The observed acetyl mass signals at all pump wavelengths turned out to be associated with absorption by the molecules of one or more additional pump and/or probe photons. In particular, absorption of a second UV pump photon by the S1 (n π* ) state was found to populate a series of high-lying states belonging to the n = 3 Rydberg manifold. The respective transitions are favored by much larger cross sections compared to the S1 ← S0 transition. The characteristic energies revealed by the photoelectron images allowed for assignments to the 3p and 3dyz states. At two-photon excitation energies higher than 8.1 eV, an ultrafast reaction pathway for breaking the α -CC bond in 50-90 fs via the 3dyz Rydberg state and the elusive π π* state was observed, explaining the formation of acetyl radicals after femtosecond laser excitation of acetone at these wavelengths.

  12. Substrate and Lewis Acid Coordination Promote O-O Bond Cleavage of an Unreactive L2Cu(II)2(O2(2-)) Species to Form L2Cu(III)2(O)2 Cores with Enhanced Oxidative Reactivity.

    PubMed

    Garcia-Bosch, Isaac; Cowley, Ryan E; Díaz, Daniel E; Peterson, Ryan L; Solomon, Edward I; Karlin, Kenneth D

    2017-03-01

    Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O2-dependent enzymes. Landmark studies have shown that the conversion between dicopper(II)-peroxo species (L2Cu(II)2(O2(2-)) either side-on peroxo, (S)P, or end-on trans-peroxo, (T)P) and dicopper(III)-bis(μ-oxo) (L2Cu(III)2(O(2-))2: O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recently published ( J. Am. Chem. Soc. 2012 , 134 , 8513 , DOI: 10.1021/ja300674m ) the crystal structure of an unusual (S)P species [(MeAN)2Cu(II)2(O2(2-))](2+) ((S)P(MeAN), MeAN: N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that (S)P(MeAN) can be activated to generate O(MeAN) and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound O(MeAN)-RPhO(-) species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (1 or 2 equiv) of Lewis acids (LA's) to form an unprecedented series of O-type species (O(MeAN)-LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the (S)P(MeAN) core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes such as

  13. Spontaneous formation in the dark, and visible light-induced cleavage, of a Ru-S bond in water: a thermodynamic and kinetic study.

    PubMed

    Bahreman, Azadeh; Limburg, Bart; Siegler, Maxime A; Bouwman, Elisabeth; Bonnet, Sylvestre

    2013-08-19

    In this work the thermal and photochemical reactivity of a series of ruthenium complexes [Ru(terpy)(N-N)(L)](X)2 (terpy = 2,2';6',2″-terpyridine, L = 2-(methylthio)ethanol (Hmte) or water, and X is Cl(-) or PF6(-)) with four different bidentate chelates N-N = bpy (2,2'-bipyridine), biq (2,2'-biquinoline), dcbpy (6,6'-dichloro-2,2'-bipyridine), or dmbpy (6,6'-dimethyl-2,2'-bipyridine), is described. For each chelate N-N the thermodynamic constant of the dark equilibrium between the aqua- and Hmte- complexes, the Hmte photosubstitution quantum yield, and the rate constants of the thermal interconversion between the aqua and Hmte complexes were measured at room temperature. By changing the steric hindrance and electronic properties of the spectator N-N ligand along the series bpy, biq, dcbpy, dmbpy the dark reactivity clearly shifts from a nonlabile equilibrium with N-N = bpy to a very labile thermal equilibrium with N-N = dmbpy. According to variable-temperature rate constant measurements in the dark near pH = 7 the activation enthalpies for the thermal substitution of H2O by Hmte are comparable for all ruthenium complexes, whereas the activation entropies are negative for bpy and biq, and positive for dcbpy and dmbpy complexes. These data are indicative of a change in the substitution mechanism, being interchange associative with nonhindered or poorly hindered chelates (bpy, biq), and interchange dissociative for more bulky ligands (dcbpy, dmbpy). For the most labile dmbpy system, the thermal equilibrium is too fast to allow significant modification of the composition of the mixture using light, and for the nonhindered bpy complex the photosubstitution of Hmte by H2O is possible but thermal binding of Hmte to the aqua complex does not occur at room temperature. By contrast, with N-N = biq or dcbpy the thermodynamic and kinetic parameters describing the formation and breakage of the Ru-S bond lie in a range where the bond forms spontaneously in the dark, but is

  14. Substructure Main Bridge, Piers B & C Huey ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Substructure - Main Bridge, Piers B & C - Huey P. Long Bridge, Spanning Mississippi River approximately midway between nine & twelve mile points upstream from & west of New Orleans, Jefferson, Jefferson Parish, LA

  15. Cleavage of peptide bonds bearing ionizable amino acids at P{sub 1} by serine proteases with hydrophobic S{sub 1} pocket

    SciTech Connect

    Qasim, Mohammad A.; Song, Jikui; Markley, John L.; Laskowski, Michael

    2010-10-01

    Research highlights: {yields} Large pK shifts in ionizable groups when buried in the protein interior. {yields} Substrate dependent shifts in pH optimum for serine proteases. {yields} Lys side chain is a stronger acid in serine protease S{sub 1} pocket than Asp side chain. -- Abstract: Enzymatic hydrolysis of the synthetic substrate succinyl-Ala-Ala-Pro-Xxx-pNA (where Xxx = Leu, Asp or Lys) catalyzed by bovine chymotrypsin (CHYM) or Streptomyces griseus protease B (SGPB) has been studied at different pH values in the pH range 3-11. The pH optima for substrates having Leu, Asp, and Lys have been found to be 7.5-8.0, 5.5-6.0, and {approx}10, respectively. At the normally reported pH optimum (pH 7-8) of CHYM and SGPB, the substrate with Leu at the reactive site is more than 25,000-fold more reactive than that with Asp. However, when fully protonated, Asp is nearly as good a substrate as Leu. The pK values of the side chains of Asp and Lys in the hydrophobic S{sub 1} pocket of CHYM and SGPB have been calculated from pH-dependent hydrolysis data and have been found to be about 9 for Asp and 7.4 and 9.7 for Lys for CHYM and SGPB, respectively. The results presented in this communication suggest a possible application of CHYM like enzymes in cleaving peptide bonds contributed by acidic amino acids between pH 5 and 6.

  16. B-C-N compound synthesized under high temperature and high pressure

    NASA Astrophysics Data System (ADS)

    Tian, Y. J.; He, J. L.; Yu, D. L.; Li, D. C.; Zou, G. T.; Jia, X. R.; Chen, L. X.; Yanagisawa, O.

    2002-01-01

    Crystalline hexagonal B(N1-xCx) and cubic B-C-N compounds have been synthesized from a precursor produced from melamine and boric acid by application of high temperature and high pressure. The synthesized products were characterized by X-ray diffraction. The lattice parameters for the hexagonal crystal are a = 2.506 Angstrom, c = 6.657 Angstrom, and that for the cubic crystal is a = 3.596 Angstrom. The X-ray photoelectron spectra of the B-C-N compound indicate the presence of B-N, C-N, C-C, and B-C bonds, which suggests that boron, carbon, and nitrogen atoms all bond with one another and that the B-C-N crystal is a compound in which the three kinds of atoms are mixed atomically. The composition of the B-C-N compound is B0.47C0.23N0.30. A strong absorption band at 1000similar to1120cm(-1) attributable to the cubic B-C-N phase is observed in the infrared spectrum, The photoluminescence spectrum of hexagonal B-C-N powder measured at room temperature features a broad peak centered at 374 nin, corresponding to the band-edge emission of h-B-C-N, and is similar to that of w-GaN.

  17. Synthesis and reaction of monomeric germanium(II) and lead(II) dimethylamide and the synthesis of germanium(II) hydrazide by cleavage of one N-H bond of hydrazine.

    PubMed

    Jana, Anukul; Roesky, Herbert W; Schulzke, Carola; Samuel, Prinson P; Döring, Alexander

    2010-06-21

    The beta-diketiminate substituted germanium(II) and lead(II) dimethylamides, LGeNMe(2) (1) and LPbNMe(2) (2), [L = CH{(CMe)(2)(2,6-iPr(2)C(6)H(3)N)(2)}] have been synthesized by the reaction of LiNMe(2) with LGeCl and LPbCl respectively. Reaction of compound 1 with an equivalent amount of elemental sulfur leads to the germanium analogue of thioamide, LGe(S)NMe(2) (3). 2 reacts with 2-benzoyl pyridine (PhCOPy-2) to form the lead(II) alkoxide LPbOC(NMe(2))Ph(2-Py) (4) by nucleophilic addition of "NMe(2)" to the carbon oxygen double bond. The reaction of stable N-heterocyclic germylene L(1)Ge [L(1) = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}] with hydrazine yields the germanium(II) substituted hydrazide LGeNHNH(2) (5) by cleavage of one N-H bond of hydrazine. Finally, attempts to isolate lead(II) hydride LPbH from the reaction of 2 with phenylsilane (PhSiH(3)) failed, and instead LPbN(2,6-iPr(2)C(6)H(3)){C(CH(3))CHC(CH(3))=N(2,6-iPr(2)C(6)H(3))} (6) was obtained in very low yield. We are able to prove this only by single crystal X-ray structural analysis. Compounds 1, 2, 3, 4, and 5 were characterized by microanalysis, electron impact (EI) mass spectrometry, and multinuclear NMR spectroscopy. Furthermore compounds 1, 2, 5, and 6 were characterized by single crystal X-ray structural analysis, with the result that they are exhibiting monomeric structures in the solid state with trigonal-pyramidal environment at the metal center and a stereochemically active lone pair.

  18. In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds

    DOE PAGES

    Carrasco, Javier; Rodriguez, Jose A.; Lopez-Duran, David; ...

    2015-03-23

    Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Here, supported by experimental and density-functional theory results, we elucidate the effect of the support on O-H bond cleavage activity for nickel/ceria systems. Ambient-pressure O1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Our computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of thismore » support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.« less

  19. In-situ and theoretical studies for the dissociation of water on an active Ni/CeO₂ catalyst: Importance of strong metal-support interactions for the cleavage of O-H bonds

    SciTech Connect

    Carrasco, Javier; Rodriguez, Jose A.; Lopez-Duran, David; Liu, Zongyuan; Duchon, Tomas; Evans, Jaime; Senanayake, Sanjaya D.; Crumlin, Ethan J.; Matolin, Vladimir; Ganduglia-Pirovano, M. Veronica

    2015-03-23

    Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Here, supported by experimental and density-functional theory results, we elucidate the effect of the support on O-H bond cleavage activity for nickel/ceria systems. Ambient-pressure O1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Our computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f-states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water-gas shift and ethanol steam reforming reactions.

  20. Electron probe microanalysis in the ternary Gd B C system

    NASA Astrophysics Data System (ADS)

    Ruiz, Domingo; Garland, Maria Teresa; Saillard, Jean-Yves; Halet, Jean-François; Bohn, Marcel; Bauer, Josef

    2002-09-01

    EPMA exploration of the Gd-B-C system in the region "Gd-GdB 2-GdBC" and in the neighborhood of the recently described Gd 4B 3C 4 compound led to the identification of 9 new ternary phases, which allows to clear up the phase diagram of this ternary system. A structural description of the bonding between the non-metal atoms in most of the identified compounds is proposed, on the basis of simple electron counting rules and using the planar repeat units or the finite linear anions which have been shown to exist in the structurally characterized rare-earth borocarbide compounds.

  1. Ex vivo inhibition of Clostridium botulinum neurotoxin types B, C, E, and F by small molecular weight inhibitors.

    PubMed

    Montgomery, Vicki A; Ahmed, S Ashraf; Olson, Mark A; Mizanur, Rahman M; Stafford, Robert G; Roxas-Duncan, Virginia I; Smith, Leonard A

    2015-05-01

    Two small molecular weight inhibitors, compounds CB7969312 and CB7967495, that displayed inhibition of botulinum neurotoxin serotype A in a previous study, were evaluated for inhibition of botulinum neurotoxin serotypes B, C, E, and F. The small molecular weight inhibitors were assessed by molecular modeling, UPLC-based peptide cleavage assay; and an ex vivo assay, the mouse phrenic nerve - hemidiaphragm assay (MPNHDA). While both compounds were inhibitors of botulinum neurotoxin (BoNT) serotypes B, C, and F in the MPNHDA, compound CB7969312 was effective at lower molar concentrations than compound CB7967495. However, compound CB7967495 was significantly more effective at preventing BoNTE intoxication than compound CB7969312. In the UPLC-based peptide cleavage assay, CB7969312 was also more effective against LcC. Both compounds inhibited BoNTE, but not BoNTF, LcE, or LcF in the UPLC-based peptide cleavage assay. Molecular modeling studies predicted that both compounds would be effective inhibitors of BoNTs B, C, E, and F. But CB7967495 was predicted to be a more effective inhibitor of the four serotypes (B, C, E, and F) than CB7969312. This is the first report of a small molecular weight compound that inhibits serotypes B, C, E, and F in the ex vivo assay.

  2. Cleavage of nucleic acids

    DOEpatents

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow; Mary Ann D.; Dahlberg, James E.

    2010-11-09

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  3. Cleavage of nucleic acids

    DOEpatents

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor L.; Brow, Mary Ann D.; Dahlberg, James E.

    2007-12-11

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  4. Activation and cleavage of the N-N bond in side-on bound [L₂M-NN-ML₂] (L = NH₂, NMe₂, N(i)Pr₂, C₅H₅, C₅Me₄H) dinitrogen complexes of transition metals from groups 4 through 9.

    PubMed

    Cavigliasso, Germán; Wilson, Laurence; McAlpine, Sarlae; Attar, Mariam; Stranger, Robert; Yates, Brian F

    2010-05-21

    The activation and cleavage of the N-N bond in side-on bound [L₂M-NN-ML₂] (L = NH₂, NMe₂, N(i)Pr₂, C₅H₅, C₅Me₄H) dinitrogen complexes of transition metals in groups 4 through 9 have been investigated using density functional theory. Emphasis has been placed on Ti, Zr, and Hf (group 4) complexes due to their experimental relevance. Calculations on these species have shown that for cases when the structural configuration corresponds to the terminal [ML₂] fragments adopting a perpendicular orientation with respect to the central [N-N] unit, a considerably higher degree of N-N activation is predicted relative to that observed in the experimentally characterized cyclopentadienyl analogues and in related systems involving end-on dinitrogen coordination. An examination of the orbital interactions between the metal-based fragments and the dinitrogen unit shows that both σ and π bonding are important in the side-on binding mode, in contrast to the end-on mode where metal-nitrogen π interactions are dominant. This analysis also reveals that the model amide systems possess the orbital properties identified as necessary for successful N-N hydrogenation. A significant result obtained for the amide complexes containing metals from groups 5 (V, Nb, Ta), 6 (Cr, Mo, W), and 7 (Mn, Tc, Re), is the presence of metal-metal bonding in configurations that are considerably distorted from planarity. As a consequence, these complexes exhibit strongly enhanced stability relative to species where metal-metal bonding is absent. In contrast, the d² metal-based configurations in the group 4 complexes of Ti, Zr, and Hf are unable to provide the six electrons required for complete reductive cleavage of the dinitrogen unit which is necessary to allow the metal centres to approach one another sufficiently for metal-metal bond formation.

  5. Total Synthesis of Fellutamide B and Deoxy-Fellutamides B, C, and D

    PubMed Central

    Giltrap, Andrew M.; Cergol, Katie M.; Pang, Angel; Britton, Warwick J.; Payne, Richard J.

    2013-01-01

    The total syntheses of the marine-derived lipopeptide natural product fellutamide B and deoxy-fellutamides B, C, and D are reported. These compounds were accessed through a novel solid-phase synthetic strategy using Weinreb amide-derived resin. As part of the synthesis, a new enantioselective route to (3R)-hydroxy lauric acid was developed utilizing a Brown allylation reaction followed by an oxidative cleavage-oxidation sequence as the key steps. The activity of these natural products, and natural product analogues was also assessed against Mycobacterium tuberculosis in vitro. PMID:23880930

  6. Selective cleavage of pepsin by molybdenum metallopeptidase

    SciTech Connect

    Yenjai, Sudarat; Malaikaew, Pinpinat; Liwporncharoenvong, Teerayuth; Buranaprapuk, Apinya

    2012-03-02

    Graphical abstract: Molybdenum metallopeptidase: the Mo(VI) cluster with six molybdenum cations has the ability to cleave protein under mild conditions (37 Degree-Sign C, pH 7) without reducing agents. The reaction required only low concentration of ammonium heptamolybdatetetrahydrate ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) (0.125 mM). The reaction undergoes possibly via a hydrolytic mechanism. This is the first demonstration of protein cleavage by a molybdenum cluster. Highlights: Black-Right-Pointing-Pointer This is the first demonstration of protein cleavage by a Mo(VI) cluster with six molybdenum cations. Black-Right-Pointing-Pointer The cleavage reaction undergoes at mild conditions. Black-Right-Pointing-Pointer No need of reducing agents. Black-Right-Pointing-Pointer Only low concentration of Mo(VI) cluster and short time of incubation are needed. -- Abstract: In this study, the cleavage of protein by molybdenum cluster is reported for the first time. The protein target used is porcine pepsin. The data presented in this study show that pepsin is cleaved to at least three fragments with molecular weights of {approx}23, {approx}19 and {approx}16 kDa when the mixture of the protein and ammonium heptamolybdate tetrahydrate ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) was incubated at 37 Degree-Sign C for 24 h. No self cleavage of pepsin occurs at 37 Degree-Sign C, 24 h indicating that the reaction is mediated by the metal ions. N-terminal sequencing of the peptide fragments indicated three cleavage sites of pepsin between Leu 112-Tyr 113, Leu 166-Leu 167 and Leu 178-Asn 179. The cleavage reaction occurs after incubation of the mixture of pepsin and (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) only for 2 h. However, the specificity of the cleavage decreases when incubation time is longer than 48 h. The mechanism for cleavage of pepsin is expected to be hydrolytic chemistry of the amide bonds in the protein

  7. Tuning of the copper-thioether bond in tetradentate N₃S(thioether) ligands; O-O bond reductive cleavage via a [Cu(II)₂(μ-1,2-peroxo)]²⁺/[Cu(III)₂(μ-oxo)₂]²⁺ equilibrium.

    PubMed

    Kim, Sunghee; Ginsbach, Jake W; Billah, A Imtiaz; Siegler, Maxime A; Moore, Cathy D; Solomon, Edward I; Karlin, Kenneth D

    2014-06-04

    Current interest in copper/dioxygen reactivity includes the influence of thioether sulfur ligation, as it concerns the formation, structures, and properties of derived copper-dioxygen complexes. Here, we report on the chemistry of {L-Cu(I)}2-(O2) species L = (DMM)ESE, (DMM)ESP, and (DMM)ESDP, which are N3S(thioether)-based ligands varied in the nature of a substituent on the S atom, along with a related N3O(ether) (EOE) ligand. Cu(I) and Cu(II) complexes have been synthesized and crystallographically characterized. Copper(I) complexes are dimeric in the solid state, [{L-Cu(I)}2](B(C6F5)4)2, however are shown by diffusion-ordered NMR spectroscopy to be mononuclear in solution. Copper(II) complexes with a general formulation [L-Cu(II)(X)](n+) {X = ClO4(-), n = 1, or X = H2O, n = 2} exhibit distorted square pyramidal coordination geometries and progressively weaker axial thioether ligation across the series. Oxygenation (-130 °C) of {((DMM)ESE)Cu(I)}(+) results in the formation of a trans-μ-1,2-peroxodicopper(II) species [{((DMM)ESE)Cu(II)}2(μ-1,2-O2(2-))](2+) (1(P)). Weakening the Cu-S bond via a change to the thioether donor found in (DMM)ESP leads to the initial formation of [{((DMM)ESP)Cu(II)}2(μ-1,2-O2(2-))](2+) (2(P)) that subsequently isomerizes to a bis-μ-oxodicopper(III) complex, [{((DMM)ESP)Cu(III)}2(μ-O(2-))2](2+) (2(O)), with 2(P) and 2(O) in equilibrium (K(eq) = [2(O)]/[2(P)] = 2.6 at -130 °C). Formulations for these Cu/O2 adducts were confirmed by resonance Raman (rR) spectroscopy. This solution mixture is sensitive to the addition of methylsulfonate, which shifts the equilibrium toward the bis-μ-oxo isomer. Further weakening of the Cu-S bond in (DMM)ESDP or substitution with an ether donor in (DMM)EOE leads to only a bis-μ-oxo species (3(O) and 4(O), respectively). Reactivity studies indicate that the bis-μ-oxodicopper(III) species (2(O), 3(O)) and not the trans-peroxo isomers (1(P) and 2(P)) are responsible for the observed ligand

  8. Tyrosine Deprotonation Yields Abundant and Selective Backbone Cleavage in Peptide Anions upon Negative Electron transfer Dissociation and Ultraviolet Photodissociation

    PubMed Central

    Shaw, Jared B.; Ledvina, Aaron R.; Zhang, Xing; Julian, Ryan R.; Brodbelt, Jennifer S.

    2012-01-01

    Tyrosine deprotonation in peptides yields preferential electron detachment upon NETD or UVPD, resulting in prominent N – Cα bond cleavage N-terminal to the tyrosine residue. UVPD of iodo-tyrosine modified peptides was used to generate localized radicals on neutral tyrosine side chains by homolytic cleavage of the C – I bond. Subsequent collisional activation of the radical species yielded the same preferential cleavage of the adjacent N-terminal N – Cα bond. LC-MS/MS analysis of a tryptic digest of BSA demonstrated that these cleavages are regularly observed for peptides when using high pH mobile phases. PMID:22970927

  9. Tyrosine deprotonation yields abundant and selective backbone cleavage in peptide anions upon negative electron transfer dissociation and ultraviolet photodissociation.

    PubMed

    Shaw, Jared B; Ledvina, Aaron R; Zhang, Xing; Julian, Ryan R; Brodbelt, Jennifer S

    2012-09-26

    Tyrosine deprotonation in peptides yields preferential electron detachment upon NETD or UVPD, resulting in prominent N-Cα bond cleavage N-terminal to the tyrosine residue. UVPD of iodo-tyrosine-modified peptides was used to generate localized radicals on neutral tyrosine side chains by homolytic cleavage of the C-I bond. Subsequent collisional activation of the radical species yielded the same preferential cleavage of the adjacent N-terminal N-Cα bond. LC-MS/MS analysis of a tryptic digest of BSA demonstrated that these cleavages are regularly observed for peptides when using high-pH mobile phases.

  10. 100-B/C Target Analyte List Development for Soil

    SciTech Connect

    R.W. Ovink

    2010-03-18

    This report documents the process used to identify source area target analytes in support of the 100-B/C remedial investigation/feasibility study addendum to DOE/RL-2008-46. This report also establishes the analyte exclusion criteria applicable for 100-B/C use and the analytical methods needed to analyze the target analytes.

  11. 32 CFR Appendixes B-C to Part 636 - [Reserved

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 32 National Defense 4 2011-07-01 2011-07-01 false B Appendixes B-C to Part 636 National Defense Department of Defense (Continued) DEPARTMENT OF THE ARMY (CONTINUED) LAW ENFORCEMENT AND CRIMINAL INVESTIGATIONS MOTOR VEHICLE TRAFFIC SUPERVISION (SPECIFIC INSTALLATIONS) Appendixes B-C to Part 636...

  12. Efficient promotion of phosphate diester cleavage by a face-to-face cyclodextrin dimer without metal.

    PubMed

    Hu, Ping; Liu, Gao-Feng; Ji, Liang-Nian; Mao, Zong-Wan

    2012-06-04

    An organic face-to-face cyclodextrin dimer promotes the cleavage of bis(4-nitrophenyl) phosphate efficiently in neutral pH without the addition of metal. Both of the phosphate diester bonds can be cleaved.

  13. Homolytic, Heterolytic, Mesolytic - As You Like It: Steering the Cleavage of a HC(sp(3) )-C(sp(3) )H Bond in Bis(1H-2,1-benzazaborole) Derivatives.

    PubMed

    Hejda, Martin; Lyčka, Antonín; Mikysek, Tomáš; Jambor, Roman; Růžička, Aleš; Vinklárek, Jaromír; Wilfer, Claudia; Hoffmann, Alexander; Herres-Pawlis, Sonja; Dostál, Libor

    2016-10-17

    A set of (3,3')-bis(1-Ph-2-R-1H-2,1-benzazaborole) compounds, in which R=tBu (Bab-tBu)2 , R=Dipp (Bab-Dipp)2 or R=tBu and Dipp (Bab-Dipp)(Bab-tBu), was synthesized and fully characterized using (1) H, (11) B, (13) C, and (15) N NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The central HC(sp(3) )-C(sp(3) )H bond with restricted rotation at the junction of both 1H-2,1-benzazaborole rings displayed an intriguing reactivity. It was demonstrated that this bond is easily mesolytically cleaved using alkali metals to form the respective aromatic 1Ph-2R-1H-2,1-benzazaborolyl anions M(+) (THF)n (Bab-tBu)(-) (M=Li, Na, K) and K(+) (THF)n (Bab-Dipp)(-) . Furthermore, the central HC(sp(3) )-C(sp(3) )H bond of bis(1H-2,1-benzazaborole)s is also homolytically cleaved either by heating or photochemical means, giving corresponding 1Ph-2R-1H-2,1-benzazaborolyl radicals (Bab-tBu)(.) and (Bab-Dipp)(.) , which rapidly self-terminate. Nevertheless, their formation was unambiguously established by NMR analysis of the reaction mixtures containing products of the self-termination of the radicals after heating or irradiation. (Bab-Dipp)(.) radical was also characterized using EPR spectroscopy. Importantly, it turned out that the essentially non-polarized HC(sp(3) )-C(sp(3) )H bond in (Bab-tBu)2 is also cleaved heterolytically with 2 equiv of MeLi, giving the mixture of Li(+) (SOL)n (Bab-tBu)(-) (SOL=THF or Et2 O) and lithium methyl-substituted borate complex Li(+) (SOL)n (Bab-tBu-Me)(-) in a diastereoselective fashion.

  14. OH cleavage from tyrosine: debunking a myth

    PubMed Central

    Bury, Charles S.; Carmichael, Ian; Garman, Elspeth F

    2017-01-01

    During macromolecular X-ray crystallography experiments, protein crystals held at 100 K have been widely reported to exhibit reproducible bond scission events at doses on the order of several MGy. With the objective to mitigate the impact of radiation damage events on valid structure determination, it is essential to correctly understand the radiation chemistry mechanisms at play. OH-cleavage from tyrosine residues is regularly cited as amongst the most available damage pathways in protein crystals at 100 K, despite a lack of widespread reports of this phenomenon in protein crystal radiation damage studies. Furthermore, no clear mechanism for phenolic C—O bond cleavage in tyrosine has been reported, with the tyrosyl radical known to be relatively robust and long-lived in both aqueous solutions and the solid state. Here, the initial findings of Tyr –OH group damage in a myrosinase protein crystal have been reviewed. Consistent with that study, at increasing doses, clear electron density loss was detectable local to Tyr –OH groups. A systematic investigation performed on a range of protein crystal damage series deposited in the Protein Data Bank has established that Tyr –OH electron density loss is not generally a dominant damage pathway in protein crystals at 100 K. Full Tyr aromatic ring displacement is here proposed to account for instances of observable Tyr –OH electron density loss, with the original myrosinase data shown to be consistent with such a damage model. Systematic analysis of the effects of other environmental factors, including solvent accessibility and proximity to di­sulfide bonds or hydrogen bond interactions, is also presented. Residues in known active sites showed enhanced sensitivity to radiation-induced disordering, as has previously been reported. PMID:28009542

  15. Room-temperature activation of methane and dry re-forming with CO2 on Ni-CeO2 (111) surfaces: Effect of Ce3+ sites and metal–support interactions on C–H bond cleavage

    SciTech Connect

    Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan; Gutierrez, Ramon A.; Grinter, David G.; Carrasco, Javier; Senanayake, Sanjaya D.; Rodriguez, Jose A.; Ganduglia-Pirovano, M. Veronica

    2016-10-27

    The results of core-level photoemission indicate that Ni-CeO2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CHx and COx (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. The strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.

  16. Ring cleavage of sulfur heterocycles: how does it happen?

    PubMed

    Bressler, D C; Norman, J A; Fedorak, P M

    Sulfur heterocycles are common constituents of petroleum and liquids derived from coal, and they are found in some secondary metabolites of microorganisms and plants. They exist primarily as saturated rings and thiophenes. There are two major objectives driving investigations of the microbial metabolism of organosulfur compounds. One is the quest to develop a process for biodesulfurization of fossil fuels, and the other is to understand the fates of organosulfur compounds in petroleum- or creosote-contaminated environments which is important in assessing bioremediation processes. For these processes to be successful, cleavage of different types of sulfur heterocyclic rings is paramount. This paper reviews the evidence for microbial ring cleavage of a variety of organosulfur compounds and discusses the few well-studied cases which have shown that the C-S bond is most susceptible to breakage leading to disruption of the ring. In most cases, the introduction of one or more oxygen atom(s) onto the adjacent C atom and/or onto the S atom weakens the C-S bond, facilitating its cleavage. Although much is known about the thiophene ring cleavage in dibenzothiophene, there is still a great deal to be learned about the cleavage of other sulfur heterocycles.

  17. Thermodynamic and kinetic study of cleavage of the N-O bond of N-oxides by a vanadium(III) complex: enhanced oxygen atom transfer reaction rates for adducts of nitrous oxide and mesityl nitrile oxide.

    PubMed

    Palluccio, Taryn D; Rybak-Akimova, Elena V; Majumdar, Subhojit; Cai, Xiaochen; Chui, Megan; Temprado, Manuel; Silvia, Jared S; Cozzolino, Anthony F; Tofan, Daniel; Velian, Alexandra; Cummins, Christopher C; Captain, Burjor; Hoff, Carl D

    2013-07-31

    Thermodynamic, kinetic, and computational studies are reported for oxygen atom transfer (OAT) to the complex V(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2, 1) from compounds containing N-O bonds with a range of BDEs spanning nearly 100 kcal mol(-1): PhNO (108) > SIPr/MesCNO (75) > PyO (63) > IPr/N2O (62) > MesCNO (53) > N2O (40) > dbabhNO (10) (Mes = mesityl; SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene; Py = pyridine; IPr = 1,3-bis(diisopropyl)phenylimidazol-2-ylidene; dbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene). Stopped flow kinetic studies of the OAT reactions show a range of kinetic behavior influenced by both the mode and strength of coordination of the O donor and its ease of atom transfer. Four categories of kinetic behavior are observed depending upon the magnitudes of the rate constants involved: (I) dinuclear OAT following an overall third order rate law (N2O); (II) formation of stable oxidant-bound complexes followed by OAT in a separate step (PyO and PhNO); (III) transient formation and decay of metastable oxidant-bound intermediates on the same time scale as OAT (SIPr/MesCNO and IPr/N2O); (IV) steady-state kinetics in which no detectable intermediates are observed (dbabhNO and MesCNO). Thermochemical studies of OAT to 1 show that the V-O bond in O≡V(N[t-Bu]Ar)3 is strong (BDE = 154 ± 3 kcal mol(-1)) compared with all the N-O bonds cleaved. In contrast, measurement of the N-O bond in dbabhNO show it to be especially weak (BDE = 10 ± 3 kcal mol(-1)) and that dissociation of dbabhNO to anthracene, N2, and a (3)O atom is thermodynamically favorable at room temperature. Comparison of the OAT of adducts of N2O and MesCNO to the bulky complex 1 show a faster rate than in the case of free N2O or MesCNO despite increased steric hindrance of the adducts.

  18. Cleavage of an RNA model catalyzed by dinuclear Zn(II) complexes containing rate-accelerating pendants. Comparison of the catalytic benefits of H-bonding and hydrophobic substituents.

    PubMed

    Mohamed, Mark F; Brown, R Stan

    2010-12-17

    The transesterification of a simple RNA model, 2-hydroxypropyl p-nitrophenyl phosphate (2, HpNPP) promoted by seven dinuclear Zn(II) catalysts (3,4,5,6,7,8,9:Zn(II)2:(-OCH3)) based on the bis[bis(2-substituted-pyridinyl-6-methyl)]amine ligand system was investigated in methanol under sspH-controlled conditions at 25.0 ± 0.1 °C. The two metal complexing ligands were joined together via the amino N connected to a m-xylyl linker (3, 4, 5, 6, 7) where the 2-pyridinyl substituent = H, CH3, (CH)4, NH2, and NH(C═O)CH3, respectively, and a propyl linker (8, 9) where the ring substituent = H and CH3. All of the dinuclear complexes except 8:Zn(II)2 exhibit saturation kinetics for the kobs versus [catalyst] plots from which one can determine catalyst:substrate binding constants (KM), the catalytic rate constants for their decomposition (kcat), and the second order catalytic rate constants (k2cat = kcat/KM). In the case of 8:Zn(II)2, the plots of kobs versus [catalyst] as a function of sspH are linear, and the catalytic rate constants (k2cat) are defined as the gradients of the plots. Analysis of all of the data at the sspH optimum for each reaction indicates that the presence of the amino and acetamido H-bonding groups and the CH3 group provides similar increases of the kcat terms of 25−50 times that exhibited by the parent complex 3:Zn(II)2. However, in terms of substrate catalyst binding (KM), there is no clear trend that H-bonding groups or the CH3 group provides stronger binding than the parent complex. In terms of the overall second order catalytic rate constant, the CH3, amino, and NH(C═O)CH3 groups provide 20, 10, and 68 times the k2cat observed for the parent complex. In the case of 9:Zn(II)2, the presence of the methyl groups provides a 1000-fold increase in activity (judged by k2cat) over the parent complex 8:Zn(II)2. The results are interpreted to indicate that H-bonding effects may be important for catalysis and less so for substrate binding, but the

  19. Alpha and omega of carotenoid cleavage.

    PubMed

    Lakshman, M R

    2004-01-01

    molecular oxygen and is activated by ferrous ions. It is highly specific for 15:15' ethylenic bond of carotenoids although it has fairly broad specificity towards a number of carotenoids with at least one intact beta-ionone ring. The dioxygenase was recently cloned from Drosophila melanogaster and from the chicken intestine. The recombinant protein was found to form retinal as the sole cleavage product of beta-carotene. No apo-carotenoids were formed. Therefore, it is unequivocally proven that the major, if not the sole, pathway of beta-carotene cleavage to vitamin A is by oxidative cleavage of the central ethylenic bond of beta-carotene to yield two molecules of retinal. Most recently, human dioxygenase has also been cloned. Thus, the wisdom, vision and epoch-making mission of Jim Olson in the science of beta-carotene metabolism have been accomplished. I have no doubt that the impact of his original discovery of the dioxygenase and its importance in vitamin A nutriture should be forthcoming in the near future.

  20. The B(C6F5)3 boron Lewis acid route to arene-annulated pentalenes.

    PubMed

    Chen, Chao; Harhausen, Marcel; Fukazawa, Aiko; Yamaguchi, Shigehiro; Fröhlich, Roland; Daniliuc, Constantin G; Petersen, Jeffrey L; Kehr, Gerald; Erker, Gerhard

    2014-06-01

    4,5-Dimethyl-1,2-bis(1-naphthylethynyl)benzene (12) undergoes a rapid multiple ring-closure reaction upon treatment with the strong boron Lewis acid B(C6F5)3 to yield the multiply annulated, planar conjugated π-system 13 (50 % yield). In the course of this reaction, a C6F5 group was transferred from boron to carbon. Treatment of 12 with CH3B(C6F5)2 proceeded similarly, giving a mixture of 13 (C6F5-transfer) and the product 15, which was formed by CH3-group transfer. 1,2-Bis(phenylethynyl)benzene (8 a) reacts similarly with CH3B(C6F5)2 to yield a mixture of the respective C6F5- and CH3-substituted dibenzopentalenes 10 a and 16. The reaction is thought to proceed through zwitterionic intermediates that exhibit vinyl cation reactivities. Some B(C6F5)3-substituted species (26, 27) consequently formed by in situ deprotonation upon treatment of the respective 1,2-bis(alkynyl)benzene starting materials (24, 8) with the frustrated Lewis pair B(C6F5)3/P(o-tolyl)3. The overall formation of the C6F5-substituted products formally require HB(C6F5)2 cleavage in an intermediate dehydroboration step. This was confirmed in the reaction of a thienylethynyl-containing starting material 21 with B(C6F5)3, which gave the respective annulated pentalene product 23 that had the HB(C6F5)2 moiety 1,4-added to its thiophene ring. Compounds 12-14, 23, and 26 were characterized by X-ray diffraction.

  1. Measurements of B(c)+ production and mass with the B(c)+ → J/ψπ+ decay.

    PubMed

    Aaij, R; Abellan Beteta, C; Adametz, A; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves, A A; Amato, S; Amhis, Y; Anderlini, L; Anderson, J; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Bachmann, S; Back, J J; Baesso, C; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bates, A; Bauer, Th; Bay, A; Beddow, J; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Benayoun, M; Bencivenni, G; Benson, S; Benton, J; Berezhnoy, A; Bernet, R; Bettler, M-O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blanks, C; Blouw, J; Blusk, S; Bobrov, A; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Büchler-Germann, A; Burducea, I; Bursche, A; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carson, L; Carvalho Akiba, K; Casse, G; Cattaneo, M; Cauet, Ch; Charles, M; Charpentier, Ph; Chen, P; Chiapolini, N; Chrzaszcz, M; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Cogneras, E; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Corti, G; Couturier, B; Cowan, G A; Craik, D; Cunliffe, S; Currie, R; D'Ambrosio, C; David, P; David, P N Y; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Paula, L; De Simone, P; Decamp, D; Deckenhoff, M; Degaudenzi, H; Del Buono, L; Deplano, C; Derkach, D; Deschamps, O; Dettori, F; Di Canto, A; Dickens, J; Dijkstra, H; Diniz Batista, P; Domingo Bonal, F; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Dzhelyadin, R; Dziurda, A; Dzyuba, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisenhardt, S; Ekelhof, R; Eklund, L; El Rifai, I; Elsasser, Ch; Elsby, D; Esperante Pereira, D; Falabella, A; Färber, C; Fardell, G; Farinelli, C; Farry, S; Fave, V; Fernandez Albor, V; Ferreira Rodrigues, F; Ferro-Luzzi, M; Filippov, S; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furcas, S; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garnier, J-C; Garofoli, J; Garosi, P; Garra Tico, J; Garrido, L; Gaspar, C; Gauld, R; Gersabeck, E; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Grünberg, O; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hall, S; Hampson, T; Hansmann-Menzemer, S; Harnew, N; Harnew, S T; Harrison, J; Harrison, P F; Hartmann, T; He, J; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Hicks, E; Hill, D; Hoballah, M; Hopchev, P; Hulsbergen, W; Hunt, P; Huse, T; Hussain, N; Hutchcroft, D; Hynds, D; Iakovenko, V; Ilten, P; Imong, J; Jacobsson, R; Jaeger, A; Jahjah Hussein, M; Jans, E; Jansen, F; Jaton, P; Jean-Marie, B; Jing, F; John, M; Johnson, D; Jones, C R; Jost, B; Kaballo, M; Kandybei, S; Karacson, M; Karbach, T M; Keaveney, J; Kenyon, I R; Kerzel, U; Ketel, T; Keune, A; Khanji, B; Kim, Y M; Kochebina, O; Komarov, V; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kucharczyk, M; Kudryavtsev, V; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J-P; Lefèvre, R; Leflat, A; Lefrançois, J; Leroy, O; Lesiak, T; Li, Y; Li Gioi, L; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; von Loeben, J; Lopes, J H; Lopez Asamar, E; Lopez-March, N; Lu, H; Luisier, J; Mac Raighne, A; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Magnin, J; Maino, M; Malde, S; Manca, G; Mancinelli, G; Mangiafave, N; Marconi, U; Märki, R; Marks, J; Martellotti, G; Martens, A; Martin, L; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Massafferri, A; Mathe, Z; Matteuzzi, C; Matveev, M; Maurice, E; Mazurov, A; McCarthy, J; McGregor, G; McNulty, R; Meissner, M; Merk, M; Merkel, J; Milanes, D A; Minard, M-N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Mylroie-Smith, J; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neufeld, N; Nguyen, A D; Nguyen-Mau, C; Nicol, M; Niess, V; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Pal, B K; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perego, D L; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pessina, G; Petridis, K; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pie Valls, B; Pietrzyk, B; Pilař, T; Pinci, D; Playfer, S; Plo Casasus, M; Polci, F; Polok, G; Poluektov, A; Polycarpo, E; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pugatch, V; Puig Navarro, A; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Rauschmayr, N; Raven, G; Redford, S; Reid, M M; dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Rives Molina, V; Roa Romero, D A; Robbe, P; Rodrigues, E; Rodriguez Perez, P; Rogers, G J; Roiser, S; Romanovsky, V; Romero Vidal, A; Rouvinet, J; Ruf, T; Ruiz, H; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salzmann, C; Sanmartin Sedes, B; Sannino, M; Santacesaria, R; Santamarina Rios, C; Santinelli, R; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Schaack, P; Schiller, M; Schindler, H; Schleich, S; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M-H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Skwarnicki, T; Smith, N A; Smith, E; Smith, M; Sobczak, K; Soler, F J P; Soomro, F; Souza, D; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Swientek, S; Szczekowski, M; Szczypka, P; Szumlak, T; T'Jampens, S; Teklishyn, M; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Tonelli, D; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tsaregorodtsev, A; Tsopelas, P; Tuning, N; Ubeda Garcia, M; Ukleja, A; Urner, D; Uwer, U; Vagnoni, V; Valenti, G; Vazquez Gomez, R; Vazquez Regueiro, P; Vecchi, S; Velthuis, J J; Veltri, M; Veneziano, G; Vesterinen, M; Viaud, B; Videau, I; Vieira, D; Vilasis-Cardona, X; Visniakov, J; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voss, H; Voss, C; Waldi, R; Wallace, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wicht, J; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wishahi, J; Witek, M; Witzeling, W; Wotton, S A; Wright, S; Wu, S; Wyllie, K; Xie, Y; Xing, F; Xing, Z; Yang, Z; Young, R; Yuan, X; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhong, L; Zvyagin, A

    2012-12-07

    Measurements of B(c)(+) production and mass are performed with the decay mode B(c)(+)→J/ψπ(+) using 0.37 fb(-1) of data collected in pp collisions at √[s]=7 TeV by the LHCb experiment. The ratio of the production cross section times branching fraction between the B(c)(+)→J/ψπ(+) and the B(+)→J/ψK(+) decays is measured to be (0.68±0.10(stat)±0.03(syst)±0.05(lifetime))% for B(c)(+) and B(+) mesons with transverse momenta p(T)>4 GeV/c and pseudorapidities 2.5<η<4.5. The B(c)(+) mass is directly measured to be 6273.7±1.3(stat)±1.6(syst) MeV/c(2), and the measured mass difference with respect to the B(+) meson is M(B(c)(+))-M(B(+))=994.6±1.3(stat)±0.6(syst) MeV/c(2).

  2. Criticality of colloids with three distinct interaction patches: As simple as A ,B ,C ?

    NASA Astrophysics Data System (ADS)

    Tavares, J. M.; Teixeira, P. I. C.

    2017-01-01

    We systematically study the phase behavior of a simple model of associating fluids which consists of hard spherical particles with three short-ranged attractive sites on their surfaces (sticky spots or patches), of types A ,B , and C , that can form bonds with energy ɛi j (i ,j =A ,B ,C ). We consider realizations of the model with one, two, or three nonzero ɛi j. Using Wertheim's first order perturbation theory of association, we establish the minimum requirements on the bond energies for the model to exhibit a liquid-vapor critical point, and investigate the nature of criticality in each case. As a preliminary, we rigorously show that, within this theory, particles with M identical sites do not condense if M <3 , a result that was previously conjectured, but never proved.

  3. Molybdenum complexes of 1,2-bis(diphenylphosphino)benzene. Mononuclear molybdenum(II) species formed by facile metal-metal bond cleavage of the (Mo-/sup 4/Mo)/sup 4+/ core

    SciTech Connect

    Bakir, M.; Cotton, F.A.; Cudahy, M.M.; Simpson, C.Q.; Smith, T.J.; Vogel, E.F.; Walton, R.A.

    1988-07-27

    The quadruply bonded dimolybdenum(II) complexes K/sub 4/Mo/sub 2/Cl/sub 8/, (NH/sub 4/)/sub 5/MoCl/sub 9/ /times/ H/sub 2/O, and (NH/sub 4/)/sub 4/Mo/sub 2/Br/sub 8/ react with 1,2-C/sub 6/H/sub 4/(PPh/sub 2/)/sub 2/(dppbe) in methanol at room temperature to afford /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ complexes (X = Cl, Br), which do not isomerize to the /beta/ isomers. Under more forcing reactions conditions (refluxing 1-propanol), these same reactions give mononuclear trans-MoX/sub 2/(dppbe)/sub 2/ in good yield (ca. 50%) together with some (MoOX(dppbe)/sub 2/)X /times/ nH/sub 2/O. An alternative synthetic strategy for the preparation of /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ involves the reaction of Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ with dppbe and Me/sub 3/SiX in THF. The compound MoCl/sub 2/(dppbe)/sub 2/ forms crystals in space group P2/sub 1//n, with the following unit cell parameters: a = 10.884 (2) /angstrom/, b = 12.753 (2) /angstrom/, c = 18.141 (4) /angstrom/, /beta/ = 91.43 (2)/degree/, V = 2517 (2) /angstrom//sup 3/, and Z = 2. The centrosymmetric trans molecule has Mo-Cl = 2.410 (1) /angstrom/, Mo-P = 2.481 (1), 2.511 (1) /angstrom/, and P-Mo-P(intra-ring) = 78.68 (4)/degree/. 25 refs., 1 fig., 4 tabs.

  4. Structural and Biochemical Characterization of a Copper-Binding Mutant of the Organomercurial Lyase MerB: Insight into the Key Role of the Active Site Aspartic Acid in Hg-Carbon Bond Cleavage and Metal Binding Specificity.

    PubMed

    Wahba, Haytham M; Lecoq, Lauriane; Stevenson, Michael; Mansour, Ahmed; Cappadocia, Laurent; Lafrance-Vanasse, Julien; Wilkinson, Kevin J; Sygusch, Jurgen; Wilcox, Dean E; Omichinski, James G

    2016-02-23

    In bacterial resistance to mercury, the organomercurial lyase (MerB) plays a key role in the detoxification pathway through its ability to cleave Hg-carbon bonds. Two cysteines (C96 and C159; Escherichia coli MerB numbering) and an aspartic acid (D99) have been identified as the key catalytic residues, and these three residues are conserved in all but four known MerB variants, where the aspartic acid is replaced with a serine. To understand the role of the active site serine, we characterized the structure and metal binding properties of an E. coli MerB mutant with a serine substituted for D99 (MerB D99S) as well as one of the native MerB variants containing a serine residue in the active site (Bacillus megaterium MerB2). Surprisingly, the MerB D99S protein copurified with a bound metal that was determined to be Cu(II) from UV-vis absorption, inductively coupled plasma mass spectrometry, nuclear magnetic resonance, and electron paramagnetic resonance studies. X-ray structural studies revealed that the Cu(II) is bound to the active site cysteine residues of MerB D99S, but that it is displaced following the addition of either an organomercurial substrate or an ionic mercury product. In contrast, the B. megaterium MerB2 protein does not copurify with copper, but the structure of the B. megaterium MerB2-Hg complex is highly similar to the structure of the MerB D99S-Hg complexes. These results demonstrate that the active site aspartic acid is crucial for both the enzymatic activity and metal binding specificity of MerB proteins and suggest a possible functional relationship between MerB and its only known structural homologue, the copper-binding protein NosL.

  5. Rare radiative decays of the B c meson

    NASA Astrophysics Data System (ADS)

    Ju, Wan-Li; Wang, Tianhong; Jiang, Yue; Yuan, Han; Wang, Guo-Li

    2016-08-01

    In this paper, we study the rare radiative processes {B}c\\to {D}{sJ}(*)γ within the Standard Model, where {D}{sJ}(*) stands for the meson {D}s*, {D}s1(2460,2536) or {D}s2*(2573). During the investigations, we consider the contributions from the penguin, annihilation, color-suppressed and color-favored cascade diagrams. Our results show that: (1) the penguin and annihilation contributions are dominant in the branching fractions; (2) for the processes {B}c\\to {D}s*γ and {B}c\\to {D}s1(2460,2536)γ , the effects from the color-suppressed and color-favored cascade diagrams are un-negligible.

  6. Effects of extrinsic point defects in phosphorene: B, C, N, O, and F adatoms

    SciTech Connect

    Wang, Gaoxue E-mail: pandey@mtu.edu Pandey, Ravindra E-mail: pandey@mtu.edu; Karna, Shashi P. E-mail: pandey@mtu.edu

    2015-04-27

    Phosphorene is emerging as a promising 2D semiconducting material with a direct band gap and high carrier mobility. In this paper, we examine the role of the extrinsic point defects including surface adatoms in modifying the electronic properties of phosphorene using density functional theory. The surface adatoms considered are B, C, N, O, and F with a [He] core electronic configuration. Our calculations show that B and C, with electronegativity close to P, prefer to break the sp{sup 3} bonds of phosphorene and reside at the interstitial sites in the 2D lattice by forming sp{sup 2} like bonds with the native atoms. On the other hand, N, O, and F, which are more electronegative than P, prefer the surface sites by attracting the lone pairs of phosphorene. B, N, and F adsorption will also introduce local magnetic moment to the lattice. Moreover, B, C, N, and F adatoms will modify the band gap of phosphorene, yielding metallic transverse tunneling characters. Oxygen does not modify the band gap of phosphorene, and a diode like tunneling behavior is observed. Our results therefore offer a possible route to tailor the electronic and magnetic properties of phosphorene by the adatom functionalization and provide the physical insights of the environmental sensitivity of phosphorene, which will be helpful to experimentalists in evaluating the performance and aging effects of phosphorene-based electronic devices.

  7. Cp* as a removable protecting group: low valent Zn(I) compounds by reductive elimination, protolytic and oxidative cleavage of Zn-Cp*.

    PubMed

    Freitag, Kerstin; Banh, Hung; Ganesamoorthy, Chelladurai; Gemel, Christian; Seidel, Rüdiger W; Fischer, Roland A

    2013-08-07

    Zn-Cp* bond cleavage reactions leading to novel monovalent cationic zinc species are presented (Cp* = pentamethylcyclopentadienyl). The treatment of [Zn2Cp*2] with two equiv. of [H(Et2O)2][BAr4(F)] (BAr4(F) = B{C6H3(CF3)2}4) yields the triple-decker complex [Cp*3Zn4(Et2O)2][BAr4(F)] (1) via protolytic removal of a Cp* ligand as Cp*H, whereas the reaction with an equimolar amount of [FeCp2][BAr4(F)] (Cp = cyclopentadienyl) results in the formation of [Cp*Zn2(Et2O)3][BAr4(F)] (2) under oxidative cleavage of a Cp* ring giving decamethylfulvalene, (Cp*)2, and [FeCp2] as by-products. The molecular structures of compounds 1 and 2 are established by single-crystal X-ray diffraction studies. A new synthetic pathway for the formation of [Zn2Cp*2] based on the reductive elimination of Cp*H from in situ formed Cp*ZnH is presented.

  8. Taming B.C. Hydro: Site C and the implementation of the B.C. Utilities Commission Act

    NASA Astrophysics Data System (ADS)

    Smith, L. Graham

    1988-07-01

    Public policy making in resources management is greatly influenced by the institutional arrangements that arise out of the legal powers, administrative structures, and financial provisions of the decision system. In British Columbia, the institutional arrangements for energy planning in the province have been greatly altered by the passage of the Utilities Commission Act in 1980. This act redefines the policy implementation process for energy in British Columbia and provides for the regulation of the province's power utility, B.C. Hydro. This is the first time that the hitherto autonomous utility has been subject to regulation and the Utilities Commission Act represents a major reform in the institutional arrangements for energy planning in the province. The article evaluates the effectiveness of the 1980 B.C. Utilities Commission Act and assesses the impact of the legislation upon the institutional arrangements for energy planning in the province. Data for the article were derived from written sources and a series of personal interviews with key participants involved with energy planning in B.C. It is shown that the act represented a major departure in the management of energy resources in B.C. Moreover the implementation of the act's provisions, particularly in regard to B.C. Hydro, had a dramatic impact on the development of new energy projects in the province. It is suggested that while the political and economic climate during the period also favored restraint, the major influence on “taming” the utility was passage of the Utilities Commission Act. The article concludes by exploring the implications of policy changes that have occurred as a consequence of the act's impact on B.C. Hydro.

  9. B c -meson physics in the LHCb experiment

    NASA Astrophysics Data System (ADS)

    Egorychev, V. Yu.; Belyaev, I. M.

    2015-11-01

    Results obtained with the aid of the LHCb detector operating at the Large Hadron Collider (LHC, CERN, Geneva) are discussed. The accumulated data sample made it possible to study the production of B c mesons in proton-proton collisions. The inclusive production cross sections and lifetimes were measured for Bc mesons, and their new decay channels were studied.

  10. Copper Metal from Malachite Circa 4000 B.C.E.

    ERIC Educational Resources Information Center

    Yee, Gordon T.; Eddleton, Jeannine E.; Johnson, Cris E.

    2004-01-01

    The feasibility of the laboratory production of copper metal from a readily available, naturally occurring mineral malachite utilizing techniques that are consistent with the time period of around 4000 B.C.E. is presented. The starting materials are inexpensive and convenient and the procedure involves no hazardous reagents and produces no…

  11. Willingness of Medical Students for Hepatitis B & C Screening

    ERIC Educational Resources Information Center

    Ahmad, Iftikhar; Mahsud, Muhammad Amin Jan; Hussain, Javed; Khan, Muhammad Hussain; Khan, Habibullah; Noman, Nargis; Rabi, Fazle, Din, Siraj ud

    2010-01-01

    Background: Health care workers including medical students are vulnerable to hepatitis B & C virus infections. The objective of this study was to determine the level of willingness for screening among medical students. Methodology: This cross-sectional survey was carried out at Gomal Medical College, Dera Ismail Khan from 1st April 2010 to 15…

  12. ARCHITECTURAL SECTIONS A, B, C, D, OF HOT PILOT PLANT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    ARCHITECTURAL SECTIONS A, B, C, D, OF HOT PILOT PLANT (CPP-640). INL DRAWING NUMBER 200-0640-00-279-111681. ALTERNATE ID NUMBER 8952-CPP-640-A-5. - Idaho National Engineering Laboratory, Idaho Chemical Processing Plant, Fuel Reprocessing Complex, Scoville, Butte County, ID

  13. 24. VIEW EAST SHOWING BASCULE GIRDERS 'A', 'B', 'C', AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    24. VIEW EAST SHOWING BASCULE GIRDERS 'A', 'B', 'C', AND 'D'; DRIVE GEAR 'D' WITH GUARD IS LOCATED IN THE LOWER CENTER OF THE PHOTOGRAPH. REFER TO GEARING DIAGRAMS - STRAUSS SHEET #15 FOR POWER TRAIN RELATIONSHIPS - Tomlinson Bridge, Spanning Quinnipiac River at Forbes Street (U.S. Route 1), New Haven, New Haven County, CT

  14. 25. VIEW WEST SHOWING BASCULE GIRDERS 'A', 'B', 'C', AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    25. VIEW WEST SHOWING BASCULE GIRDERS 'A', 'B', 'C', AND 'D'; DRIVE GEAR 'D' WITH GUARD IS LOCATED IN THE LOWER CENTER OF THE PHOTOGRAPH. REFER TO GEARING DIAGRAMS - STRAUSS SHEET #15 FOR POWER TRAIN RELATIONSHIPS. - Tomlinson Bridge, Spanning Quinnipiac River at Forbes Street (U.S. Route 1), New Haven, New Haven County, CT

  15. Mechanism and specificity of RNA cleavage by chemical ribonucleases.

    PubMed

    Beloglazova, N; Vlassov, A; Konevetc, D; Sil'nikov, V; Zenkova, M; Giege, R; Vlassov, V

    1999-01-01

    Cleaving of model RNA substrates by chemical ribonucleases constructed by conjugation of 1,4 diazabicyclo[2,2,2]octane with histamine and histidine was investigated. Similarly to RNase A, the chemical RNases produce fragments with 5' hydroxy-group and 3'-cyclophosphate. The cleavage occurs as the catalytic reaction: more than 150 phosphodiester bonds in RNA can be cleaved by one molecule of RNase mimic.

  16. New insight into the cleavage reaction of Nostoc sp. strain PCC 7120 carotenoid cleavage dioxygenase in natural and nonnatural carotenoids.

    PubMed

    Heo, Jinsol; Kim, Se Hyeuk; Lee, Pyung Cheon

    2013-06-01

    Carotenoid cleavage dioxygenases (CCDs) are enzymes that catalyze the oxidative cleavage of carotenoids at a specific double bond to generate apocarotenoids. In this study, we investigated the activity and substrate preferences of NSC3, a CCD of Nostoc sp. strain PCC 7120, in vivo and in vitro using natural and nonnatural carotenoid structures. NSC3 cleaved β-apo-8'-carotenal at 3 positions, C-13 C-14, C-15 C-15', and C-13' C-14', revealing a unique cleavage pattern. NSC3 cleaves the natural structure of carotenoids 4,4'-diaponeurosporene, 4,4'-diaponeurosporen-4'-al, 4,4'-diaponeurosporen-4'-oic acid, 4,4'-diapotorulene, and 4,4'-diapotorulen-4'-al to generate novel cleavage products (apo-14'-diaponeurosporenal, apo-13'-diaponeurosporenal, apo-10'-diaponeurosporenal, apo-14'-diapotorulenal, and apo-10'-diapotorulenal, respectively). The study of carotenoids with natural or nonnatural structures produced by using synthetic modules could provide information valuable for understanding the cleavage reactions or substrate preferences of other CCDs in vivo and in vitro.

  17. New Insight into the Cleavage Reaction of Nostoc sp. Strain PCC 7120 Carotenoid Cleavage Dioxygenase in Natural and Nonnatural Carotenoids

    PubMed Central

    Heo, Jinsol; Kim, Se Hyeuk

    2013-01-01

    Carotenoid cleavage dioxygenases (CCDs) are enzymes that catalyze the oxidative cleavage of carotenoids at a specific double bond to generate apocarotenoids. In this study, we investigated the activity and substrate preferences of NSC3, a CCD of Nostoc sp. strain PCC 7120, in vivo and in vitro using natural and nonnatural carotenoid structures. NSC3 cleaved β-apo-8′-carotenal at 3 positions, C-13C-14, C-15C-15′, and C-13′C-14′, revealing a unique cleavage pattern. NSC3 cleaves the natural structure of carotenoids 4,4′-diaponeurosporene, 4,4′-diaponeurosporen-4′-al, 4,4′-diaponeurosporen-4′-oic acid, 4,4′-diapotorulene, and 4,4′-diapotorulen-4′-al to generate novel cleavage products (apo-14′-diaponeurosporenal, apo-13′-diaponeurosporenal, apo-10′-diaponeurosporenal, apo-14′-diapotorulenal, and apo-10′-diapotorulenal, respectively). The study of carotenoids with natural or nonnatural structures produced by using synthetic modules could provide information valuable for understanding the cleavage reactions or substrate preferences of other CCDs in vivo and in vitro. PMID:23524669

  18. Enhanced RNA cleavage within bulge-loops by an artificial ribonuclease

    PubMed Central

    Kuznetsova, Irina L.; Zenkova, Marina A.; Gross, Hans J.; Vlassov, Valentin V.

    2005-01-01

    Cleavage of phosphodiester bonds by small ribonuclease mimics within different bulge-loops of RNA was investigated. Bulge-loops of different size (1–7 nt) and sequence composition were formed in a 3′ terminal fragment of influenza virus M2 RNA (96 nt) by hybridization of complementary oligodeoxynucleotides. Small bulges (up to 4 nt) were readily formed upon oligonucleotide hybridization, whereas hybridization of the RNA to the oligonucleotides designed to produce larger bulges resulted in formation of several alternative structures. A synthetic ribonuclease mimic displaying Pyr–Pu cleavage specificity cleaved CpA motifs located within bulges faster than similar motifs within the rest of the RNA. In the presence of 10 mM MgCl2, 75% of the cleavage products resulted from the attack of this motif. Thus, selective RNA cleavage at a single target phosphodiester bond was achieved by using bulge forming oligonucleotides and a small ribonuclease A mimic. PMID:15731340

  19. Preparation of bulk superhard B-C-N nanocomposite compact

    DOEpatents

    Zhao, Yusheng; He, Duanwei

    2011-05-10

    Bulk, superhard, B--C--N nanocomposite compacts were prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture at a pressure in a range of from about 15 GPa to about 25 GPa, and sintering the pressurized encapsulated ball-milled mixture at a temperature in a range of from about 1800-2500 K. The product bulk, superhard, nanocomposite compacts were well sintered compacts with nanocrystalline grains of at least one high-pressure phase of B--C--N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compacts had a measured Vicker's hardness in a range of from about 41 GPa to about 68 GPa.

  20. Synthesis and characterization of the dimercury(I)-linked compound [PPn]4[(Re7C(CO)21Hg)2]. Oxidative cleavage of the mercury-mercury bond leading to carbidoheptarhenate complexes of mercury(II), including [PPN][Re7C(CO)21Hg(S=C(NME2)2)].

    PubMed

    Wright, C A; Brand, U; Shapley, J R

    2001-09-10

    The reaction of [PPN](3)[Re(7)C(CO)(21)] with Hg(2)(NO(3))(2).2H(2)O in dichloromethane formed the complex [PPN](4)[(Re(7)C(CO)(21)Hg)(2)] ([PPN](4)[1]), isolated in 60% yield. Analogous salts of [1](4-) with [PPh(4)](+) and [NEt(4)](+) were also prepared. The crystal structure of [PPN](4)[1] showed that two carbidoheptarhenate cores are linked by a dimercury(I) unit (d(Hg-Hg) = 2.610(4) A), with each individual mercury atom face-bridging. Oxidative cleavage of the Hg-Hg bond in [1](4-) was effected by 4-bromophenyl disulfide to form [Re(7)C(CO)(21)HgSC(6)H(4)Br](2-) ([4](2-)), by I(2) to form [Re(7)C(CO)(21)HgI](2-) ([5](2-)), and by Br(2) to form [Re(7)C(CO)(21)HgBr](2-) ([6](2-)). Oxidation of [1](4-) by ferrocenium ion (2 equiv) in the presence of tetramethylthiourea resulted in the derivative [Re(7)C(CO)(21)HgSC(NMe(2))(2)](-) ([7](-)). The molecular structure of [PPN][7] was determined by X-ray crystallography. This is the first example of a carbidoheptarhenate-mercury complex with a neutral ligand on mercury, and ligand exchange was demonstrated by displacement with triethylphosphine. Complex [7](-) can also be prepared by protonating [Re(7)C(CO)(21)HgO(2)CCH(3)](2-) in the presence of tetramethylthiourea. Cyclic voltammetry data to calibrate and compare the redox properties of compounds [1](4-) and [7](-) have been measured.

  1. Efficient nickel mediated carbon-carbon bond cleavage of organonitriles.

    PubMed

    Schaub, Thomas; Döring, Christian; Radius, Udo

    2007-05-28

    The reactions of the nickel complex [Ni(2)(iPr(2)Im)4(COD)] 1 with organonitriles smoothly and irreversibly proceed via intermediates with eta(2)-coordinated organonitrile ligands such as [Ni(iPr(2)Im)2(eta(2)-(CN)-PhCN)] 2 and [Ni(iPr(2)Im)2(eta(2)-(CN)-pTolCN)] 4 to yield aryl cyanide complexes of the type trans-[Ni(iPr(2)Im)2(CN)(Ar)] (Ar = Ph 3, pTol 5, 4-CF(3)C(6)H(4) 6, 2,4-(OMe)2C(6)H(3) 7, 2-C(4)H(3)O 8, 2-C(5)H(4)N 9). The compounds 3, 7, 9 and have been structurally characterized. For the conversion of 2 to 3 a free activation enthalpy DeltaG++(328 K) of 103.47 +/- 0.79 kJ mol(-1) was calculated from time dependent NMR spectroscopy. The analogous reaction of arylnitriles with electron releasing substituents or heteroaromatic organonitriles is significantly faster compared to the reaction with benzonitrile or toluonitrile. The reactions of 1 with acetonitrile or trimethylsilyl cyanide afforded [Ni(iPr(2)Im)2(CN)(Me)] 10 and structurally characterized [Ni(iPr(2)Im)2(CN)(SiMe(3))] 11. The usage of an organonitrile with a longer alkyl chain, adiponitrile, yielded [Ni(iPr(2)Im)2(eta(2)-(CN)-NCC(4)H(8)CN)] 12 as well as the C-CN activation product [Ni(iPr(2)Im)2(CN)(C(4)H(8)CN)]13 in thermal and photochemical reactions, although this pathway seems to be significantly interfered with by decomposition pathways under the formation of the dicyanide complex [Ni(iPr(2)Im)(2)(CN)(2)] 14.

  2. Nonenzymatic oxidative cleavage of peptide bonds in apoprotein B-100.

    PubMed

    Fong, L G; Parthasarathy, S; Witztum, J L; Steinberg, D

    1987-12-01

    Incubation of low density lipoprotein (LDL) with endothelial cells converts it to a form that is avidly degraded by macrophages via the acetyl LDL receptor. This modification has previously been shown to be accompanied by extensive breakdown of the major LDL protein (apoB-100) to smaller peptides. ApoB-100 is known to undergo partial degradation during isolation and purification which is commonly attributed to proteolytic enzymes derived from plasma or to contaminant bacteria. In the present studies addition of any of ten different inhibitors of proteolytic enzymes failed to inhibit the endothelial cell-induced degradation of LDL apoB-100 or its subsequent enhanced rate of degradation by macrophages (termed biological modification). Conversely, deliberate digestion of LDL with any of five well-characterized proteolytic enzymes degraded apoB-100 extensively but did not cause biological modification. The disappearance of intact apoB-100 during incubation with endothelial cells paralleled the formation of thiobarbituric acid (TBA)-reactive substances and the breakdown could be completely prevented by the addition of antioxidants or metal chelators. Finally, the incubation of LDL with a free radical-generating system (dihydroxyfumaric acid and Fe3+-ADP) in the absence of cells resulted in the breakdown of apoB-100. These results suggest that the breakdown of apoB-100 during oxidative modification of LDL, whether cell-induced or catalyzed by transition metals, is not mediated by proteolytic enzymes but rather is linked to oxidative attack on the polypeptide chain, either directly or secondary to peroxidation of closely associated LDL lipids.

  3. Serine-selective aerobic cleavage of peptides and a protein using a water-soluble copper-organoradical conjugate.

    PubMed

    Seki, Yohei; Tanabe, Kana; Sasaki, Daisuke; Sohma, Youhei; Oisaki, Kounosuke; Kanai, Motomu

    2014-06-16

    The site-specific cleavage of peptide bonds is an important chemical modification of biologically relevant macromolecules. The reaction is not only used for routine structural determination of peptides, but is also a potential artificial modulator of protein function. Realizing the substrate scope beyond the conventional chemical or enzymatic cleavage of peptide bonds is, however, a formidable challenge. Here we report a serine-selective peptide-cleavage protocol that proceeds at room temperature and near neutral pH value, through mild aerobic oxidation promoted by a water-soluble copper-organoradical conjugate. The method is applicable to the site-selective cleavage of polypeptides that possess various functional groups. Peptides comprising D-amino acids or sensitive disulfide pairs are competent substrates. The system is extendable to the site-selective cleavage of a native protein, ubiquitin, which comprises more than 70 amino acid residues.

  4. Two-dimensional B-C-O alloys: a promising class of 2D materials for electronic devices.

    PubMed

    Zhou, Si; Zhao, Jijun

    2016-04-28

    Graphene, a superior 2D material with high carrier mobility, has limited application in electronic devices due to zero band gap. In this regard, boron and nitrogen atoms have been integrated into the graphene lattice to fabricate 2D semiconducting heterostructures. It is an intriguing question whether oxygen can, as a replacement of nitrogen, enter the sp2 honeycomb lattice and form stable B-C-O monolayer structures. Here we explore the atomic structures, energetic and thermodynamic stability, and electronic properties of various 2D B-C-O alloys using first-principles calculations. Our results show that oxygen can be stably incorporated into the graphene lattice by bonding with boron. The B and O species favor forming alternate patterns into the chain- or ring-like structures embedded in the pristine graphene regions. These B-C-O hybrid sheets can be either metals or semiconductors depending on the B : O ratio. The semiconducting (B2O)nCm and (B6O3)nCm phases exist under the B- and O-rich conditions, and possess a tunable band gap of 1.0-3.8 eV and high carrier mobility, retaining ∼1000 cm2 V(-1) s(-1) even for half coverage of B and O atoms. These B-C-O alloys form a new class of 2D materials that are promising candidates for high-speed electronic devices.

  5. Characterization of Ta-B-C nanostructured hard coatings

    NASA Astrophysics Data System (ADS)

    Buršík, J.; Buršíková, V.; Souček, P.; Zábranský, L.; Vašina, P.

    2017-02-01

    Microstructure and mechanical properties of Ta-B-C nanocrystalline layers prepared by magnetron sputtering were studied. DC magnetron sputtering was used to prepare thin layers on rotated substrates. Various deposition parameters were tested. Microstructure of layers was studied by means of scanning and transmission electron microscopy on thin lamellar cross sections prepared using a focussed ion beam. Both undisturbed layers and the volume under relatively large indentation prints (load of 1 N) were observed. The microstructure observations were correlated with mechanical properties characterized by means of nanoindentation experiments in both the static and the dynamic loading regime. Elastic modulus, indentation hardness and fracture resistance of prepared nanostructured coatings were evaluated and discussed.

  6. Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex.

    PubMed

    Shima, Takanori; Hu, Shaowei; Luo, Gen; Kang, Xiaohui; Luo, Yi; Hou, Zhaomin

    2013-06-28

    Both the Haber-Bosch and biological ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong N≡N triple bond and forming an N-H bond. This has spurred investigations of the reactivity of molecular multimetallic hydrides with dinitrogen. We report here the reaction of a trinuclear titanium polyhydride complex with dinitrogen, which induces dinitrogen cleavage and partial hydrogenation at ambient temperature and pressure. By (1)H and (15)N nuclear magnetic resonance, x-ray crystallographic, and computational studies of some key reaction steps and products, we have determined that the dinitrogen (N2) reduction proceeds sequentially through scission of a N2 molecule bonded to three Ti atoms in a μ-η(1):η(2):η(2)-end-on-side-on fashion to give a μ2-N/μ3-N dinitrido species, followed by intramolecular hydrogen migration from Ti to the μ2-N nitrido unit.

  7. Kinetic analysis of the cleavage of natural and synthetic substrates by the Serratia nuclease.

    PubMed

    Friedhoff, P; Meiss, G; Kolmes, B; Pieper, U; Gimadutdinow, O; Urbanke, C; Pingoud, A

    1996-10-15

    The extracellular nuclease from Serratia marcescens is a non-specific endonuclease that hydrolyzes double-stranded and single-stranded DNA and RNA with high specific activity. Steady-state and presteady-state kinetic cleavage experiments were performed with natural and synthetic DNA and RNA substrates to understand the mechanism of action of the Serratia nuclease. Most of the natural substrates are cleaved with similar Kcat and K(m) values, the Kcat/K(m) ratios being comparable to that of staphylococcal nuclease. Substrates with extreme structural features, like poly(dA).poly(dT) or poly(dG).poly(dC), are cleaved by the Serratia nuclease with a 50 times higher or 10 times lower K(m), respectively, as salmon testis DNA. Neither with natural DNA or RNA nor synthetic oligodeoxynucleotide substrates did we observe substrate inhibition for the Serratia nuclease as reported recently. Experiments with short oligodeoxynucleotides confirmed previous results that for moderately good cleavage activity the substrate should contain at least five phosphate residues. Shorter substrates are still cleaved by the Serratia nuclease, albeit at a rate reduced by a factor of more than 100. Cleavage experiments with oligodeoxynucleotides substituted by a single phosphorothioate group showed that the negative charge of the pro-Rp-oxygen of the phosphate group 3' adjacent to the scissile phosphodiester bond is essential for cleavage, as only the Rp-phosphorothioate supports cleavage at the 5' adjacent phosphodiester bond. Furthermore, the modified bond itself is only cleaved in the Rp-diastereomer, albeit 1000 times more slowly than the corresponding unmodified phosphodiester bond, which offers the possibility to determine the stereochemical outcome of cleavage. Pre-steady-state cleavage experiments demonstrate that it is not dissociation of products but association of enzyme and substrate or the cleavage of the phosphodiester bond that is the rate-limiting step of the reaction. Finally

  8. Production of charmed tetraquarks from B c and B decays

    NASA Astrophysics Data System (ADS)

    He, Xiao-Gang; Wang, Wei; Zhu, Rui-Lin

    2017-01-01

    Hadronic states composed of multi-quark flavors may exist in reality since they are not prohibited by quantum chromodynamics (QCD). Compact four-quark systems of a color singlet are classified as tetraquarks. To understand the properties of these states, more theoretical and experimental efforts are needed. In this work, we study charmed tetraquarks with three light flavors using flavor SU(3) symmetry. States with three different light quarks must be in a \\bar{{6}} or a {{15}} multiplet. We investigate the production of charmed tetraquarks X c in B\\to {X}c({\\overline{X}}c)P and {B}c\\to {X}cP decays. Whether the states with three light quarks belong to \\bar{{6}} or {{15}} can be determined by studying various tetraquark B and B c decays. We demonstrate that the decay amplitudes for these decays can be parametrized by a few irreducible SU(3) invariant amplitudes. We then derive relations for decay widths and charge-parity-violating rate difference, which can be examined experimentally. Although no experimental measurements are available yet, they might be accessed at the ongoing and forthcoming experiments such as LHCb and Belle-II. Measurements of these observables can not only provide useful information for the study of exotics spectroscopy but also provide valuable information towards a better understanding of some non-perturbative aspects of QCD.

  9. Machine Learning Energies of 2 Million Elpasolite (A B C2D6) Crystals

    NASA Astrophysics Data System (ADS)

    Faber, Felix A.; Lindmaa, Alexander; von Lilienfeld, O. Anatole; Armiento, Rickard

    2016-09-01

    Elpasolite is the predominant quaternary crystal structure (AlNaK2F6 prototype) reported in the Inorganic Crystal Structure Database. We develop a machine learning model to calculate density functional theory quality formation energies of all ˜2 ×106 pristine A B C2D6 elpasolite crystals that can be made up from main-group elements (up to bismuth). Our model's accuracy can be improved systematically, reaching a mean absolute error of 0.1 eV /atom for a training set consisting of 10 ×103 crystals. Important bonding trends are revealed: fluoride is best suited to fit the coordination of the D site, which lowers the formation energy whereas the opposite is found for carbon. The bonding contribution of the elements A and B is very small on average. Low formation energies result from A and B being late elements from group II, C being a late (group I) element, and D being fluoride. Out of 2 ×106 crystals, 90 unique structures are predicted to be on the convex hull—among which is NFAl2Ca6, with a peculiar stoichiometry and a negative atomic oxidation state for Al.

  10. Bent Bonds and Multiple Bonds.

    ERIC Educational Resources Information Center

    Robinson, Edward A.; Gillespie, Ronald J.

    1980-01-01

    Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

  11. Surface chain cleavage behavior of PBIA fiber induced by direct fluorination

    NASA Astrophysics Data System (ADS)

    Cheng, Zheng; Wu, Peng; Li, Baoyin; Chen, Teng; Liu, Yang; Ren, Mengmeng; Wang, Zaoming; Lai, Wenchuan; Wang, Xu; Liu, Xiangyang

    2016-10-01

    The surface chain cleavage behavior of PBIA fiber induced by direct fluorination was reported based on the analysis of physical and chemical changes on the fiber surface. The chain cleavage product was obtained to evaluate the chemical reaction during the fluorination process, and its impact on composites performance was also involved. DSC, FTIR spectra, UV-vis absorption spectra and H1NMR were utilized to analyze the chemical structure and composition of the chain cleavage product. The results show gaseous fluorine is most likely to attack the benzimidazole and amide bond in PBIA unit, which was also demonstrated by molecular simulation. Owing to the polar groups contained in chain cleavage products, the wettability of epoxy resin to fiber has been improved, leading to an 11.5% increase of adhesive strength of fiber-epoxy composite.

  12. Specificity of hammerhead ribozyme cleavage.

    PubMed Central

    Hertel, K J; Herschlag, D; Uhlenbeck, O C

    1996-01-01

    To be effective in gene inactivation, the hammerhead ribozyme must cleave a complementary RNA target without deleterious effects from cleaving non-target RNAs that contain mismatches and shorter stretches of complementarity. The specificity of hammerhead cleavage was evaluated using HH16, a well-characterized ribozyme designed to cleave a target of 17 residues. Under standard reaction conditions, HH16 is unable to discriminate between its full-length substrate and 3'-truncated substrates, even when six fewer base pairs are formed between HH16 and the substrate. This striking lack of specificity arises because all the substrates bind to the ribozyme with sufficient affinity so that cleavage occurs before their affinity differences are manifested. In contrast, HH16 does exhibit high specificity towards certain 3'-truncated versions of altered substrates that either also contain a single base mismatch or are shortened at the 5' end. In addition, the specificity of HH16 is improved in the presence of p7 nucleocapsid protein from human immunodeficiency virus (HIV)-1, which accelerates the association and dissociation of RNA helices. These results support the view that the hammerhead has an intrinsic ability to discriminate against incorrect bases, but emphasizes that the high specificity is only observed in a certain range of helix lengths. Images PMID:8670879

  13. Oxidative cleavage with hydrogen peroxide: preparation of polycarboxylic acids from cyclic olefins.

    PubMed

    Fujitani, Kango; Mizutani, Toshihiro; Oida, Tatsuo; Kawase, Tokuzo

    2009-01-01

    Oxidative cleavage of carbon-carbon double bonds of cyclic olefins with hydrogen peroxide in the presence of heteropolyacids has been investigated as a clean and environmentally friendly preparation of polycarboxylic acids. In the presence of 12-tungstophospholic acid (H(3)PW(12)O(40)), adipic acid was obtained in 95% yield from cyclohexene in lipophilic phase and hydrogen peroxide in aqueous phase. In addition, 1,2,3,4-butanetetracarboxylic acid was also obtained in 87% yield from 1,2,3,6-tetrahydrophtharic acid anhydride, while endic acid anhydride did not afford corresponding 2,3,6-cyclopentanetetracarboxylic acid but only lactone compound was obtained. In this oxidation process, oxidative cleavage of carbon-carbon double bonds would proceed as the sequential reactions in which the rate determining step is oxidative cleavage of vicinal-diol compounds.

  14. 31 CFR 315.91 - Additional requirements; bond of indemnity.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Miscellaneous...

  15. Unusual nickel-mediated C-S cleavage of alkyl and aryl sulfoxides.

    PubMed

    Schaub, Thomas; Backes, Marc; Radius, Udo

    2007-05-28

    The first examples of transition metal mediated C-S cleavage of sulfoxides containing sp2- and sp3-hybridized carbon bonds attached to the sulfur atom and the first example of a structurally characterized complex featuring an oxygen-bound sulfinyl ligand are presented.

  16. Determinants of chymotrypsin C cleavage specificity in the calcium binding loop of human cationic trypsinogen

    PubMed Central

    Szabó, András; Sahin-Tóth, Miklós

    2013-01-01

    SUMMARY The pancreatic serine protease chymotrypsin C (CTRC) cleaves the Leu81-Glu82 peptide bond in the calcium binding loop of human cationic trypsinogen and thereby promotes its degradation. This serves as a protective mechanism against ectopic trypsinogen activation in the pancreas. In the present study we demonstrate that cleavage of the Leu81-Glu82 peptide bond by CTRC is highly specific and other human pancreatic chymotrypsins (CTRB1, CTRB2, CTRL1) and elastases (ELA2A, ELA3A, ELA3B) do not catalyze this reaction. To elucidate the mechanistic basis for CTRC specificity, we surveyed the primary (P1) cleavage preference of these pancreatic proteases on peptide substrates. We found that CTRC cleaved after a P1 Leu with at least 10-fold higher catalytic efficiency than other enzymes tested. To assess extended subsite interactions, we introduced Ala-mutations into human cationic trypsinogen at the P3, P1' P3' and P4' amino-acid positions, where P1-P1' corresponds to Leu81-Glu82. Interestingly, CTRC mediated cleavage was stimulated 3-fold by mutation E82A and unaffected by mutations E79A and N84A, but all three mutations compromised specificity and resulted in increased cleavage by ELA2A. Mutation E85A decreased CTRC cleavage by 2-fold. Remarkably, other chymotrypsins and elastases did not cleave human cationic trypsinogen even with the L81F or L81A mutations, which introduced favorable P1 residues for these enzymes. We conclude that specific cleavage of the Leu81-Glu82 peptide bond in human cationic trypsinogen by CTRC is primarily determined by its distinctively high activity on leucyl peptide bonds, whereas the P1' Glu82, P3' Asn84 and P4' Glu85 residues serve as additional specificity determinants. PMID:23035638

  17. Organic Monolayers by B(C6F5)3-Catalyzed Siloxanation of Oxidized Silicon Surfaces

    PubMed Central

    2017-01-01

    Inspired by the homogeneous catalyst tris(pentafluorophenyl) borane [B(C6F5)3], which acts as a promotor of Si–H bond activation, we developed and studied a method of modifying silicon oxide surfaces using hydrosilanes with B(C6F5)3 as the catalyst. This dedihydrosiloxanation reaction yields complete surface coverage within 10 min at room temperature. Organic monolayers derived from hydrosilanes with varying carbon chain lengths (C8–C18) were prepared on oxidized Si(111) surfaces, and the thermal and hydrolytic stabilities of the obtained monolayers were investigated in acidic (pH 3) medium, basic (pH 11) medium, phosphate-buffered saline (PBS), and deionized water (neutral conditions) for up to 30 days. DFT calculations were carried out to gain insight into the mechanism, and the computational results support a mechanism involving silane activation with B(C6F5)3. This catalyzed reaction path proceeds through a low-barrier-height transition state compared to the noncatalyzed reaction path. PMID:28230381

  18. Crispene A, B, C and D, Four New Clerodane Type Furanoid Diterpenes from Tinospora crispa (L.)

    PubMed Central

    Hossen, Farhad; Ahasan, Rubaida; Haque, Mohammad Rashedul; Begum, Bilkis; Hasan, Choudhury Mahmood

    2016-01-01

    Background: Tinospora crispa (L.) is used to alleviate the symptoms of diabetes mellitus in folk medicine. It is also used for hypertension and to treat malaria, remedy for diarrhea, and as vermifuge. Materials and Methods: Stems of T. crispa were collected, sun dried for several days followed by oven dried for 24 h at a considerably low temperature and then ground into coarse powder. The powdered stems were soaked in methanol at room temperature for 14 days with occasional shaking. The extract was collected by filtration, and the solvent was evaporated under reduced pressure in a rotary evaporator to obtain a solid residue which was then subjected to fractionation using the modified Kupchan partitioning method into n-hexane, CCl4, CHCl3 and aqueous soluble fractions. The n-hexane soluble fraction was chromatographed over sephadex (LH-20) and the column was eluted with n-hexane: CH2Cl2:MeOH (2:5:1) followed by CH2Cl2:MeOH (9:1) and MeOH (100%) in order to increase the polarities. The column fractions were then concentrated and subjected to thin layer chromatography screening and the fractions with a satisfactory resolution of compounds were rechromatographed over silica gel to isolate the pure compounds. Results: Four new furanoid diterpenes of clerodane types, Crispene A, B, C, and D (1–4), including one known furanoid diterpene glucoside, borapetoside E (5), were isolated from the stems of T. crispa. The structures of these compounds were elucidated by means of extensive spectroscopic analysis and by comparison of their spectral data with closely related compounds. Conclusion: We have reported four new furanoid diterpenes of clerodane types, including one known furanoid diterpene glucoside. This is the first report of any clerodane diterpene having olefinic bond between C-6 and C-7. SUMMARY Crispene A, B, C, and D, four new furanoid diterpenes of clerodane types from Tinospora crispaCrispene C, an unusual furanoid diterpene with olifinic bond between C-6 and C

  19. Microstructure and cleavage in lath martensitic steels.

    PubMed

    Morris, John W; Kinney, Chris; Pytlewski, Ken; Adachi, Y

    2013-02-01

    In this paper we discuss the microstructure of lath martensitic steels and the mechanisms by which it controls cleavage fracture. The specific experimental example is a 9Ni (9 wt% Ni) steel annealed to have a large prior austenite grain size, then examined and tested in the as-quenched condition to produce a relatively coarse lath martensite. The microstructure is shown to approximate the recently identified 'classic' lath martensite structure: prior austenite grains are divided into packets, packets are subdivided into blocks, and blocks contain interleaved laths whose variants are the two Kurjumov-Sachs relations that share the same Bain axis of the transformation. When the steel is fractured in brittle cleavage, the laths in the block share {100} cleavage planes and cleave as a unit. However, cleavage cracks deflect or blunt at the boundaries between blocks with different Bain axes. It follows that, as predicted, the block size governs the effective grain size for cleavage.

  20. Microstructure and cleavage in lath martensitic steels

    NASA Astrophysics Data System (ADS)

    Morris, John W., Jr.; Kinney, Chris; Pytlewski, Ken; Adachi, Y.

    2013-02-01

    In this paper we discuss the microstructure of lath martensitic steels and the mechanisms by which it controls cleavage fracture. The specific experimental example is a 9Ni (9 wt% Ni) steel annealed to have a large prior austenite grain size, then examined and tested in the as-quenched condition to produce a relatively coarse lath martensite. The microstructure is shown to approximate the recently identified ‘classic’ lath martensite structure: prior austenite grains are divided into packets, packets are subdivided into blocks, and blocks contain interleaved laths whose variants are the two Kurjumov-Sachs relations that share the same Bain axis of the transformation. When the steel is fractured in brittle cleavage, the laths in the block share {100} cleavage planes and cleave as a unit. However, cleavage cracks deflect or blunt at the boundaries between blocks with different Bain axes. It follows that, as predicted, the block size governs the effective grain size for cleavage.

  1. 31 CFR 315.30 - Series E bonds and savings notes.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 31 Money and Finance: Treasury 2 2014-07-01 2014-07-01 false Series E bonds and savings notes. 315.... SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.30 Series E bonds and savings notes. Series E bonds and savings notes are discount securities. The accrued...

  2. Pistol ribozyme adopts a pseudoknot fold facilitating site-specific in-line cleavage

    PubMed Central

    Ren, Aiming; Vušurović, Nikola; Gebetsberger, Jennifer; Gao, Pu; Juen, Michael; Kreutz, Christoph; Micura, Ronald; Patel, Dinshaw J.

    2016-01-01

    The field of small self-cleaving nucleolytic ribozymes has been invigorated by the recent discovery of the twister, twister-sister, pistol and hatchet ribozymes. We report on the crystal structure of the env25 pistol ribozyme, which adopts a compact tertiary architecture stabilized by an embedded pseudoknot fold. The G-U cleavage site adopts a splayed-apart conformation with in-line alignment of the modeled 2′-O of G for attack on the adjacent to-be-cleaved P-O5′ bond. Highly conserved residues G40 (N1 position) and A32 (N3 and 2′-OH positions) are aligned to act as general base and general acid respectively to accelerate cleavage chemistry, with their roles confirmed from cleavage assays on mutants, and an increased pKa of 4.7 for A32. Our structure of the pistol ribozyme defines how the overall and local topologies dictate the in-line alignment at the G-U cleavage site, with cleavage assays on mutants identifying key residues participating in acid-base catalyzed cleavage chemistry. PMID:27398999

  3. Thiaphosphiranes and Their Complexes: Systematic Study on Ring Strain and Ring Cleavage Reactions.

    PubMed

    Espinosa Ferao, Arturo; Streubel, Rainer

    2016-10-03

    A computational study on energies and geometries of a representative set of thiaphosphirane derivatives 1a-e and their W(CO)5 (W) and BH3 (B) complexes is reported. A particular focus was put on ring-opening reactions of κP- (2) and κS-complex isomers (3). Concerning the ring strain energy, a general trend was observed for compounds 1a,d, 2Wa,d, and 2Ba,d: (i) substituted rings are less strained than the parent compounds, and (ii) κP-complexation with a W(CO)5 group (2Wa,d) significantly increases the ring strain (5.63 and 4.38 kcal/mol) which is exceeded in the case of κP-BH3 complexation (2Ba,d) (7.14 and 7.22 kcal/mol). To unveil the thermal endocyclic bond weakness, a variety of bond strength related descriptors such as bond distance, relaxed force constants k(0), Bader's quantitative theory of atoms-in-molecules parameters such as the electron density ρ(r) and its Laplacian at bond critical points, and several bond order quantities (Wiberg bond index, Mayer bond order, and Löwdin bond order) were calculated. Heterolytic ring-opening reactions were investigated, revealing some general trends: (i) the strongest donor substituent at carbon significantly lowers relative energies for both the P-C and C-S bond cleavage products as well as the corresponding transition states, (ii) κP-complexes are more stable than the corresponding κS-complexes, for cyclic and acyclic species, and (iii) P-to-S haptotropic shifts in P-C bond cleavage products are disfavored processes, whereas it is more favored for C-S bond cleavage products. Other rearrangement products, being within energetic reach, were located on the potential energy surface. Two deserve particular mention as one stems from a combined H2 elimination and C-S bond cleavage of 2Bb and the other represents a first case of peribicyclic reaction leading to 7B'.

  4. On the mechanism of RNA phosphodiester backbone cleavage in the absence of solvent

    PubMed Central

    Riml, Christian; Glasner, Heidelinde; Rodgers, M. T.; Micura, Ronald; Breuker, Kathrin

    2015-01-01

    Ribonucleic acid (RNA) modifications play an important role in the regulation of gene expression and the development of RNA-based therapeutics, but their identification, localization and relative quantitation by conventional biochemical methods can be quite challenging. As a promising alternative, mass spectrometry (MS) based approaches that involve RNA dissociation in ‘top-down’ strategies are currently being developed. For this purpose, it is essential to understand the dissociation mechanisms of unmodified and posttranscriptionally or synthetically modified RNA. Here, we have studied the effect of select nucleobase, ribose and backbone modifications on phosphodiester bond cleavage in collisionally activated dissociation (CAD) of positively and negatively charged RNA. We found that CAD of RNA is a stepwise reaction that is facilitated by, but does not require, the presence of positive charge. Preferred backbone cleavage next to adenosine and guanosine in CAD of (M+nH)n+ and (M−nH)n− ions, respectively, is based on hydrogen bonding between nucleobase and phosphodiester moieties. Moreover, CAD of RNA involves an intermediate that is sufficiently stable to survive extension of the RNA structure and intramolecular proton redistribution according to simple Coulombic repulsion prior to backbone cleavage into c and y ions from phosphodiester bond cleavage. PMID:25904631

  5. Cleavage plane determination in amphibian eggs.

    PubMed

    Sawai, T; Yomota, A

    1990-01-01

    In the present study using eggs of Cynops pyrrhogaster and Xenopus laevis, we examined (1) structural changes in the cytoplasm before the appearance of the cleavage furrow using a cytochemical method, (2) the time of cleavage plane determination depending on the mitotic apparatus (MA), by changing the shape of the eggs, and (3) the time of arrival of the "cleavage stimulus" at the cortex, by injecting colchicine solution or removing cytoplasm. Results were as follows: (1) In amphibian eggs the diastema was formed after development of the MA, appearing between the two asters after the MA had begun to degenerate. (2) The cleavage plane was preliminarily determined by the MA in the meta- to anaphase of karyokinesis. At this time, however, the egg cortex had not yet received the "cleavage stimulus" indispensable for furrow formation. (3) The egg cortex was really prepared to establish the furrow just after the edge of the diastema arrived at the cortex, when the MA had already degenerated. These results imply that the cleavage plane of the amphibian eggs is determined in two steps: the first, depending on the MA, is the determination of the direction of the growth of the diastema, and the second is the arrival of the "cleavage stimulus" at the cortex in association with the diastema.

  6. Hydrolytic cleavage of DNA-model substrates promoted by polyoxovanadates.

    PubMed

    Steens, Nele; Ramadan, Ahmed M; Absillis, Gregory; Parac-Vogt, Tatjana N

    2010-01-14

    Hydrolysis of 4-nitrophenyl phosphate (NPP) and bis-4-nitrophenyl phosphate (BNPP), two commonly used DNA model substrates, was examined in vanadate solutions by means of (1)H, (31)P and (51)V NMR spectroscopy. The hydrolysis of the phosphoester bond in NPP at 50 degrees C and pH 5.0 proceeds with a rate constant of 1.74 x 10(-5) s(-1). The cleavage of the phosphoester bond in BNPP at 70 degrees C and pH 5.0 proceeds with a rate constant of 3.32 x 10(-6) s(-1), representing an acceleration of four orders of magnitude compared to the uncatalyzed cleavage. Inorganic phosphate and nitrophenol (NP) were the only products of hydrolysis. The NMR spectra did not show evidence of any paramagnetic species, excluding the possibility of V(V) reduction to V(IV), indicating that the cleavage of the phosphoester bond is purely hydrolytic. The pH dependence of k(obs) revealed that the hydrolysis proceeds fastest in solutions of pH 5.5. Comparison of the rate profile with the concentration profile of polyoxovanadates shows a striking overlap of the k(obs) profile with the concentration of decavanadate (V(10)). Kinetic experiments at 37 degrees C using a fixed amount of NPP and increasing amounts of V(10) permitted the calculation of catalytic (k(c) = 5.67 x 10(-6) s(-1)) and formation constants for the NPP-V(10) complex (K(f) = 71.53 M(-1)). Variable temperature (31)P NMR spectra of a reaction mixture revealed broadening and shifting of the (31)P resonance upon addition of increasing amounts of decavanadate and upon increasing temperature, implying the dynamic exchange process between free and bound NPP at higher temperatures. The origin of the hydrolytic activity of V(10) is most likely due its high lability and its dissociation into smaller fragments which may allow the attachment of NPP and BNPP into the polyoxovanadate framework.

  7. Cleavage at Arg-1689 influences heavy chain cleavages during thrombin-catalyzed activation of factor VIII.

    PubMed

    Newell, Jennifer L; Fay, Philip J

    2009-04-24

    The procofactor, factor VIII, is activated by thrombin or factor Xa-catalyzed cleavage at three P1 residues: Arg-372, Arg-740, and Arg-1689. The catalytic efficiency for thrombin cleavage at Arg-740 is greater than at either Arg-1689 or Arg-372 and influences reaction rates at these sites. Because cleavage at Arg-372 appears rate-limiting and dependent upon initial cleavage at Arg-740, we investigated whether cleavage at Arg-1689 influences catalysis at this step. Recombinant B-domainless factor VIII mutants, R1689H and R1689Q were prepared and stably expressed to slow and eliminate cleavage, respectively. Specific activity values for the His and Gln mutations were approximately 50 and approximately 10%, respectively, that of wild type. Thrombin activation of the R1689H variant showed an approximately 340-fold reduction in the rate of Arg-1689 cleavage, whereas the R1689Q variant was resistant to thrombin cleavage at this site. Examination of heavy chain cleavages showed approximately 4- and 11-fold reductions in A2 subunit generation and approximately 3- and 7-fold reductions in A1 subunit generation for the R1689H and R1689Q mutants, respectively. These results suggest a linkage between light chain cleavage and cleavages in heavy chain. Results obtained evaluating proteolysis of the factor VIII mutants by factor Xa revealed modest rate reductions (<5-fold) in generating A2 and A1 subunits and in cleaving light chain at Arg-1721 from either variant, suggesting little dependence upon prior cleavage at residue 1689 as compared with thrombin. Overall, these results are consistent with a competition between heavy and light chains for thrombin exosite binding and subsequent proteolysis with binding of the former chain preferred.

  8. Catalytic CO2 activation assisted by rhenium hydride/B(C6F5)3 frustrated Lewis pairs--metal hydrides functioning as FLP bases.

    PubMed

    Jiang, Yanfeng; Blacque, Olivier; Fox, Thomas; Berke, Heinz

    2013-05-22

    Reaction of 1 with B(C6F5)3 under 1 bar of CO2 led to the instantaneous formation of the frustrated Lewis pair (FLP)-type species [ReHBr(NO)(PR3)2(η(2)-O═C═O-B(C6F5)3)] (2, R = iPr a, Cy b) possessing two cis-phosphines and O(CO2)-coordinated B(C6F5)3 groups as verified by NMR spectroscopy and supported by DFT calculations. The attachment of B(C6F5)3 in 2a,b establishes cooperative CO2 activation via the Re-H/B(C6F5)3 Lewis pair, with the Re-H bond playing the role of a Lewis base. The Re(I) η(1)-formato dimer [{Re(μ-Br)(NO)(η(1)-OCH═O-B(C6F5)3)(PiPr3)2}2] (3a) was generated from 2a and represents the first example of a stable rhenium complex bearing two cis-aligned, sterically bulky PiPr3 ligands. Reaction of 3a with H2 cleaved the μ-Br bridges, producing the stable and fully characterized formato dihydrogen complex [ReBrH2(NO)(η(1)-OCH═O-B(C6F5)3)(PiPr3)2] (4a) bearing trans-phosphines. Stoichiometric CO2 reduction of 4a with Et3SiH led to heterolytic splitting of H2 along with formation of bis(triethylsilyl)acetal ((Et3SiO)2CH2, 7). Catalytic reduction of CO2 with Et3SiH was also accomplished with the catalysts 1a,b/B(C6F5)3, 3a, and 4a, showing turnover frequencies (TOFs) between 4 and 9 h(-1). The stoichiometric reaction of 4a with the sterically hindered base 2,2,6,6-tetramethylpiperidine (TMP) furnished H2 ligand deprotonation. Hydrogenations of CO2 using 1a,b/B(C6F5)3, 3a, and 4a as catalysts gave in the presence of TMP TOFs of up to 7.5 h(-1), producing [TMPH][formate] (11). The influence of various bases (R2NH, R = iPr, Cy, SiMe3, 2,4,6-tri-tert-butylpyridine, NEt3, PtBu3) was studied in greater detail, pointing to two crucial factors of the CO2 hydrogenations: the steric bulk and the basicity of the base.

  9. Proteolytic Cleavage Driven by Glycosylation*

    PubMed Central

    Kötzler, Miriam P.; Withers, Stephen G.

    2016-01-01

    Proteolytic processing of human host cell factor 1 (HCF-1) to its mature form was recently shown, unexpectedly, to occur in a UDP-GlcNAc-dependent fashion within the transferase active site of O-GlcNAc-transferase (OGT) (Lazarus, M. B., Jiang, J., Kapuria, V., Bhuiyan, T., Janetzko, J., Zandberg, W. F., Vocadlo, D. J., Herr, W., and Walker, S. (2013) Science 342, 1235–1239). An interesting mechanism involving formation and then intramolecular rearrangement of a covalent glycosyl ester adduct of the HCF-1 polypeptide was proposed to account for this unprecedented proteolytic activity. However, the key intermediate remained hypothetical. Here, using a model enzyme system for which the formation of a glycosyl ester within the enzyme active site has been shown unequivocally, we show that ester formation can indeed lead to proteolysis of the adjacent peptide bond, thereby providing substantive support for the mechanism of HCF-1 processing proposed. PMID:26515062

  10. Sticker Bonding.

    ERIC Educational Resources Information Center

    Frazier, Laura Corbin

    2000-01-01

    Introduces a science activity on the bonding of chemical compounds. Assigns students the role of either a cation or anion and asks them to write the ions they may bond with. Assesses students' understanding of charge, bonding, and other concepts. (YDS)

  11. Undirected, Homogeneous C–H Bond Functionalization: Challenges and Opportunities

    PubMed Central

    2016-01-01

    The functionalization of C–H bonds has created new approaches to preparing organic molecules by enabling new strategic “disconnections” during the planning of a synthetic route. Such functionalizations also have created the ability to derivatize complex molecules by modifying one or more of the many C–H bonds. For these reasons, researchers are developing new types of functionalization reactions of C–H bonds and new applications of these processes. These C–H bond functionalization reactions can be divided into two general classes: those directed by coordination to an existing functional group prior to the cleavage of the C–H bond (directed) and those occurring without coordination prior to cleavage of the C–H bond (undirected). The undirected functionalizations of C–H bonds are much less common and more challenging to develop than the directed reactions. This outlook will focus on undirected C–H bond functionalization, as well as related reactions that occur by a noncovalent association of the catalyst prior to C–H bond cleavage. The inherent challenges of conducting undirected functionalizations of C–H bonds and the methods for undirected functionalization that are being developed will be presented, along with the factors that govern selectivity in these reactions. Finally, this outlook discusses future directions for research on undirected C–H functionalization, with an emphasis on the limitations that must be overcome if this type of methodology is to become widely used in academia and in industry. PMID:27294201

  12. Iron-dependent oxidative inactivation with affinity cleavage of pyruvate kinase.

    PubMed

    Murakami, Keiko; Tsubouchi, Ryoko; Fukayama, Minoru; Qiao, Shanlou; Yoshino, Masataka

    2009-07-01

    Treatment of rabbit muscle pyruvate kinase with iron/ascorbate caused an inactivation with the cleavage of peptide bond. The inactivation or fragmentation of the enzyme was prevented by addition of Mg2+, catalase, and mannitol, but ADP and PEP the substrates did not show any effect. Protective effect of catalase and mannitol suggests that hydroxyl radical produced through the ferrous ion-dependent reduction of oxygen is responsible for the inactivation/fragmentation of the enzyme. SDS-PAGE and TOF-MS analysis confirmed five pairs of fragments, which were determined to result from the cleavage of the Lys114-Gly115, Glu117-Ile118, Asp177-Gly178, Gly207-Val208, and Phe243-Ile244 bonds of the enzyme by amino-terminal sequencing analysis. Protection of the enzyme by Mg2+ implies the identical binding sites of Fe2+ and Mg2+, but the cleavage sites were discriminated from the cofactor Mg2+-binding sites. Considering amino acid residues interacting with metal ions and tertiary structure, Fe2+ ion may bind to Asp177 neighboring to Gly207 and Glu117 neighboring to Lys114 and Phe243, causing the peptide cleavage by hydroxyl radical. Iron-dependent oxidative inactivation/fragmentation of pyruvate kinase can explain the decreased glycolytic flux under aerobic conditions. Intracellular free Mg2+ concentrations are responsible for the control of cellular respiration and glycolysis.

  13. [([superscript t]Bu[subscript 2]PCH[subscript 2]SiMe[subscript 2])[subscript 2]N]Rh[superscript I]? Rapidly Reversible H-C(sp[superscript 3]) and H−C(sp[superscript 2]) Bond Cleavage by Rhodium(I)

    SciTech Connect

    Verat, Alexander Y.; Pink, Maren; Fan, Hongjun; Tomaszewski, John; Caulton, Kenneth G.

    2008-10-03

    The product of the reaction of (tBu{sub 2}PCH{sub 2}SiMe{sub 2}){sub 2}N{sup -} (MgCl{sup +} salt) with [RhCl(cyclooctene){sub 2}]{sub 2} is a Rh{sup III} complex where one {sup t}Bu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 x 4 C-H bonds of the four {sup t}Bu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at {approx}10{sup 3} s{sup -1} at 25 C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms {eta}{sup 2}-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H){sub 2}.

  14. Catalysts of DNA Strand Cleavage at Apurinic/Apyrimidinic Sites

    PubMed Central

    Minko, Irina G.; Jacobs, Aaron C.; de Leon, Arnie R.; Gruppi, Francesca; Donley, Nathan; Harris, Thomas M.; Rizzo, Carmelo J.; McCullough, Amanda K.; Lloyd, R. Stephen

    2016-01-01

    Apurinic/apyrimidinic (AP) sites are constantly formed in cellular DNA due to instability of the glycosidic bond, particularly at purines and various oxidized, alkylated, or otherwise damaged nucleobases. AP sites are also generated by DNA glycosylases that initiate DNA base excision repair. These lesions represent a significant block to DNA replication and are extremely mutagenic. Some DNA glycosylases possess AP lyase activities that nick the DNA strand at the deoxyribose moiety via a β- or β,δ-elimination reaction. Various amines can incise AP sites via a similar mechanism, but this non-enzymatic cleavage typically requires high reagent concentrations. Herein, we describe a new class of small molecules that function at low micromolar concentrations as both β- and β,δ-elimination catalysts at AP sites. Structure-activity relationships have established several characteristics that appear to be necessary for the formation of an iminium ion intermediate that self-catalyzes the elimination at the deoxyribose ring. PMID:27363485

  15. Phase composition and tribomechanical properties of Ti-B-C nanocomposite coatings prepared by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Sánchez-López, J. C.; Abad, M. D.; Justo, A.; Gago, R.; Endrino, J. L.; García-Luis, A.; Brizuela, M.

    2012-09-01

    Protective nanocomposite coatings based on hard ceramic phases (TiC, TiB2) combined with amorphous carbon (a-C) are of interest because of their adequate balance between mechanical and tribological performances. In this work, Ti-B-C nanocomposite coatings were prepared by co-sputtering of graphite and TiB2 targets. Varying the discharge power ratio applied to the graphite and TiB2 targets from 0 to 2, the a-C content in the coatings could be tuned from 0 to 60%, as observed by means of Raman and x-ray photoelectron spectroscopy (XPS). The microstructural characterization demonstrated a progressive decrease in crystallinity from an initial nanocrystalline (nc) TiB2-like structure to a distorted TiBxCy ternary compound with increasing C concentration. X-ray absorption near-edge structure measurements on the B K-edge helped to determine a hexagonal arrangement around the B atoms in the ternary TiBxCy phase. A fitting analysis of the C 1s XPS peak allowed us to evaluate the relative amount of a-C and TiBxCy components. A drastic change in hardness (from 52 to 13 GPa) and friction coefficient values (from 0.8 to 0.2) is noticed when moving from nc-TiB2 to TiBC/a-C nanocomposites. The fraction of a-C necessary to decrease the friction below 0.2 was found to be 45%. Raman observation of the wear tracks determined the presence of disordered sp2-bonded carbon phase associated with the diminution of the friction level.

  16. Sequence-specific cleavage of dsRNA by Mini-III RNase.

    PubMed

    Głów, Dawid; Pianka, Dariusz; Sulej, Agata A; Kozłowski, Łukasz P; Czarnecka, Justyna; Chojnowski, Grzegorz; Skowronek, Krzysztof J; Bujnicki, Janusz M

    2015-03-11

    Ribonucleases (RNases) play a critical role in RNA processing and degradation by hydrolyzing phosphodiester bonds (exo- or endonucleolytically). Many RNases that cut RNA internally exhibit substrate specificity, but their target sites are usually limited to one or a few specific nucleotides in single-stranded RNA and often in a context of a particular three-dimensional structure of the substrate. Thus far, no RNase counterparts of restriction enzymes have been identified which could cleave double-stranded RNA (dsRNA) in a sequence-specific manner. Here, we present evidence for a sequence-dependent cleavage of long dsRNA by RNase Mini-III from Bacillus subtilis (BsMiniIII). Analysis of the sites cleaved by this enzyme in limited digest of bacteriophage Φ6 dsRNA led to the identification of a consensus target sequence. We defined nucleotide residues within the preferred cleavage site that affected the efficiency of the cleavage and were essential for the discrimination of cleavable versus non-cleavable dsRNA sequences. We have also determined that the loop α5b-α6, a distinctive structural element in Mini-III RNases, is crucial for the specific cleavage, but not for dsRNA binding. Our results suggest that BsMiniIII may serve as a prototype of a sequence-specific dsRNase that could possibly be used for targeted cleavage of dsRNA.

  17. Targeting allosteric disulphide bonds in cancer.

    PubMed

    Hogg, Philip J

    2013-06-01

    Protein action in nature is generally controlled by the amount of protein produced and by chemical modification of the protein, and both are often perturbed in cancer. The amino acid side chains and the peptide and disulphide bonds that bind the polypeptide backbone can be post-translationally modified. Post-translational cleavage or the formation of disulphide bonds are now being identified in cancer-related proteins and it is timely to consider how these allosteric bonds could be targeted for new therapies.

  18. Does Cleavage Work at Work? Men, but Not Women, Falsely Believe Cleavage Sells a Weak Product

    ERIC Educational Resources Information Center

    Glick, Peter; Chrislock, Karyna; Petersik, Korinne; Vijay, Madhuri; Turek, Aleksandra

    2008-01-01

    We examined whether men, but not women, would be distracted by a female sales representative's exposed cleavage, leading to greater perceived efficacy for a weak, but not for a strong product. A community sample of 88 men and 97 women viewed a video of a female pharmaceutical sales representative who (a) had exposed cleavage or dressed modestly…

  19. Evidence for the exclusive decay B(c)+- --> J/psi pi+- and measurement of the mass of the B(c)+- meson.

    PubMed

    Abulencia, A; Acosta, D; Adelman, J; Affolder, T; Akimoto, T; Albrow, M G; Ambrose, D; Amerio, S; Amidei, D; Anastassov, A; Anikeev, K; Annovi, A; Antos, J; Aoki, M; Apollinari, G; Arguin, J-F; Arisawa, T; Artikov, A; Ashmanskas, W; Attal, A; Azfar, F; Azzi-Bacchetta, P; Azzurri, P; Bacchetta, N; Bachocou, H; Badgett, W; Barbaro-Galtieri, A; Barnes, V E; Barnett, B A; Baroiant, S; Bartsch, V; Bauer, G; Bedeschi, F; Behari, S; Belforte, S; Bellettini, G; Bellinger, J; Belloni, A; Ben-Haim, E; Benjamin, D; Beretvas, A; Beringer, J; Berry, T; Bhatti, A; Binkley, M; Bisello, D; Bishai, M; Blair, R E; Blocker, C; Bloom, K; Blumenfeld, B; Bocci, A; Bodek, A; Boisvert, V; Bolla, G; Bolshov, A; Bortoletto, D; Boudreau, J; Bourov, S; Boveia, A; Brau, B; Bromberg, C; Brubaker, E; Budagov, J; Budd, H S; Budd, S; Burkett, K; Busetto, G; Bussey, P; Byrum, K L; Cabrera, S; Campanelli, M; Campbell, M; Canelli, F; Canepa, A; Carlsmith, D; Carosi, R; Carron, S; Casarsa, M; Castro, A; Catastini, P; Cauz, D; Cavalli-Sforza, M; Cerri, A; Cerrito, L; Chang, S H; Chapman, J; Chen, Y C; Chertok, M; Chiarelli, G; Chlachidze, G; Chlebana, F; Cho, I; Cho, K; Chokheli, D; Chou, J P; Chu, P H; Chuang, S H; Chung, K; Chung, W H; Chung, Y S; Cijliak, M; Ciobanu, C I; Ciocci, M A; Clark, A; Clark, D; Coca, M; Connolly, A; Convery, M; Conway, J; Cooper, B; Copic, K; Cordelli, M; Cortiana, G; Cranshaw, J; Cruz, A; Cuevas, J; Culbertson, R; Cyr, D; Da Ronco, S; D'Auria, S; D'Onofrio, M; Dagenhart, D; de Barbaro, P; De Cecco, S; Deisher, A; De Lentdecker, G; Dell'Orso, M; Demers, S; Demortier, L; Deng, J; Deninno, M; De Pedis, D; Derwent, P F; Devlin, T; Dionisi, C; Dittmann, J R; DiTuro, P; Dörr, C; Dominguez, A; Donati, S; Donega, M; Dong, P; Donini, J; Dorigo, T; Dube, S; Ebina, K; Efron, J; Ehlers, J; Erbacher, R; Errede, D; Errede, S; Eusebi, R; Fang, H C; Farrington, S; Fedorko, I; Fedorko, W T; Feild, R G; Feindt, M; Fernandez, J P; Field, R; Flanagan, G; Flores-Castillo, L R; Foland, A; Forrester, S; Foster, G W; Franklin, M; Freeman, J C; Fujii, Y; Furic, I; Gajjar, A; Gallinaro, M; Galyardt, J; Garcia, J E; Garcia Sciveres, M; Garfinkel, A F; Gay, C; Gerberich, H; Gerchtein, E; Gerdes, D; Giagu, S; Giannetti, P; Gibson, A; Gibson, K; Ginsburg, C; Giolo, K; Giordani, M; Giunta, M; Giurgiu, G; Glagolev, V; Glenzinski, D; Gold, M; Goldschmidt, N; Goldstein, J; Gomez, G; Gomez-Ceballos, G; Goncharov, M; González, O; Gorelov, I; Goshaw, A T; Gotra, Y; Goulianos, K; Gresele, A; Griffiths, M; Grinstein, S; Grosso-Pilcher, C; Grundler, U; Guimaraes da Costa, J; Haber, C; Hahn, S R; Hahn, K; Halkiadakis, E; Hamilton, A; Han, B-Y; Handler, R; Happacher, F; Hara, K; Hare, M; Harper, S; Harr, R F; Harris, R M; Hatakeyama, K; Hauser, J; Hays, C; Hayward, H; Heijboer, A; Heinemann, B; Heinrich, J; Hennecke, M; Herndon, M; Heuser, J; Hidas, D; Hill, C S; Hirschbuehl, D; Hocker, A; Holloway, A; Hou, S; Houlden, M; Hsu, S-C; Huffman, B T; Hughes, R E; Huston, J; Ikado, K; Incandela, J; Introzzi, G; Iori, M; Ishizawa, Y; Ivanov, A; Iyutin, B; James, E; Jang, D; Jayatilaka, B; Jeans, D; Jensen, H; Jeon, E J; Jones, M; Joo, K K; Jun, S Y; Junk, T R; Kamon, T; Kang, J; Karagoz-Unel, M; Karchin, P E; Kato, Y; Kemp, Y; Kephart, R; Kerzel, U; Khotilovich, V; Kilminster, B; Kim, D H; Kim, H S; Kim, J E; Kim, M J; Kim, M S; Kim, S B; Kim, S H; Kim, Y K; Kirby, M; Kirsch, L; Klimenko, S; Klute, M; Knuteson, B; Ko, B R; Kobayashi, H; Kondo, K; Kong, D J; Konigsberg, J; Kordas, K; Korytov, A; Kotwal, A V; Kovalev, A; Kraus, J; Kravchenko, I; Kreps, M; Kreymer, A; Kroll, J; Krumnack, N; Kruse, M; Krutelyov, V; Kuhlmann, S E; Kusakabe, Y; Kwang, S; Laasanen, A T; Lai, S; Lami, S; Lammel, S; Lancaster, M; Lander, R L; Lannon, K; Lath, A; Latino, G; Lazzizzera, I; Lecci, C; LeCompte, T; Lee, J; Lee, J; Lee, S W; Lefèvre, R; Leonardo, N; Leone, S; Levy, S; Lewis, J D; Li, K; Lin, C; Lin, C S; Lindgren, M; Lipeles, E; Liss, T M; Lister, A; Litvintsev, D O; Liu, T; Liu, Y; Lockyer, N S; Loginov, A; Loreti, M; Loverre, P; Lu, R-S; Lucchesi, D; Lujan, P; Lukens, P; Lungu, G; Lyons, L; Lys, J; Lysak, R; Lytken, E; Mack, P; MacQueen, D; Madrak, R; Maeshima, K; Maksimovic, P; Manca, G; Margaroli, F; Marginean, R; Marino, C; Martin, A; Martin, M; Martin, V; Martínez, M; Maruyama, T; Matsunaga, H; Mattson, M E; Mazini, R; Mazzanti, P; McFarland, K S; McGivern, D; McIntyre, P; McNamara, P; McNulty, R; Mehta, A; Menzemer, S; Menzione, A; Merkel, P; Mesropian, C; Messina, A; von der Mey, M; Miao, T; Miladinovic, N; Miles, J; Miller, R; Miller, J S; Mills, C; Milnik, M; Miquel, R; Miscetti, S; Mitselmakher, G; Miyamoto, A; Moggi, N; Mohr, B; Moore, R; Morello, M; Movilla Fernandez, P; Mülmenstädt, J; Mukherjee, A; Mulhearn, M; Muller, Th; Mumford, R; Murat, P; Nachtman, J; Nahn, S; Nakano, I; Napier, A; Naumov, D; Necula, V; Neu, C; Neubauer, M S; Nicolas, L; Nielsen, J; Nigmanov, T; Nodulman, L; Norniella, O; Ogawa, T; Oh, S H; Oh, Y D; Okusawa, T; Oldeman, R; Orava, R; Osterberg, K; Pagliarone, C; Palencia, E; Paoletti, R; Papadimitriou, V; Papikonomou, A; Paramonov, A A; Parks, B; Pashapour, S; Patrick, J; Pauletta, G; Paulini, M; Paus, C; Pellett, D E; Penzo, A; Phillips, T J; Piacentino, G; Piedra, J; Pitts, K; Plager, C; Pondrom, L; Pope, G; Portell, X; Poukhov, O; Pounder, N; Prakoshyn, F; Pronko, A; Proudfoot, J; Ptohos, F; Punzi, G; Pursley, J; Rademacker, J; Rahaman, A; Rakitin, A; Rappoccio, S; Ratnikov, F; Reisert, B; Rekovic, V; van Remortel, N; Renton, P; Rescigno, M; Richter, S; Rimondi, F; Rinnert, K; Ristori, L; Robertson, W J; Robson, A; Rodrigo, T; Rogers, E; Rolli, S; Roser, R; Rossi, M; Rossin, R; Rott, C; Ruiz, A; Russ, J; Rusu, V; Ryan, D; Saarikko, H; Sabik, S; Safonov, A; Sakumoto, W K; Salamanna, G; Salto, O; Saltzberg, D; Sanchez, C; Santi, L; Sarkar, S; Sato, K; Savard, P; Savoy-Navarro, A; Scheidle, T; Schlabach, P; Schmidt, E E; Schmidt, M P; Schmitt, M; Schwarz, T; Scodellaro, L; Scott, A L; Scribano, A; Scuri, F; Sedov, A; Seidel, S; Seiya, Y; Semenov, A; Semeria, F; Sexton-Kennedy, L; Sfiligoi, I; Shapiro, M D; Shears, T; Shepard, P F; Sherman, D; Shimojima, M; Shochet, M; Shon, Y; Shreyber, I; Sidoti, A; Sill, A; Sinervo, P; Sisakyan, A; Sjolin, J; Skiba, A; Slaughter, A J; Sliwa, K; Smirnov, D; Smith, J R; Snider, F D; Snihur, R; Soderberg, M; Soha, A; Somalwar, S; Sorin, V; Spalding, J; Spezziga, M; Spinella, F; Squillacioti, P; Stanitzki, M; Staveris-Polykalas, A; St Denis, R; Stelzer, B; Stelzer-Chilton, O; Stentz, D; Strologas, J; Stuart, D; Suh, J S; Sukhanov, A; Sumorok, K; Sun, H; Suzuki, T; Taffard, A; Tafirout, R; Takashima, R; Takeuchi, Y; Takikawa, K; Tanaka, M; Tanaka, R; Tecchio, M; Teng, P K; Terashi, K; Tether, S; Thom, J; Thompson, A S; Thomson, E; Tipton, P; Tiwari, V; Tkaczyk, S; Toback, D; Tollefson, K; Tomura, T; Tonelli, D; Tönnesmann, M; Torre, S; Torretta, D; Tourneur, S; Trischuk, W; Tsuchiya, R; Tsuno, S; Turini, N; Ukegawa, F; Unverhau, T; Uozumi, S; Usynin, D; Vacavant, L; Vaiciulis, A; Vallecorsa, S; Varganov, A; Vataga, E; Velev, G; Veramendi, G; Veszpremi, V; Vickey, T; Vidal, R; Vila, I; Vilar, R; Vollrath, I; Volobouev, I; Würthwein, F; Wagner, P; Wagner, R G; Wagner, R L; Wagner, W; Wallny, R; Walter, T; Wan, Z; Wang, M J; Wang, S M; Warburton, A; Ward, B; Waschke, S; Waters, D; Watts, T; Weber, M; Wester, W C; Whitehouse, B; Whiteson, D; Wicklund, A B; Wicklund, E; Williams, H H; Wilson, P; Winer, B L; Wittich, P; Wolbers, S; Wolfe, C; Worm, S; Wright, T; Wu, X; Wynne, S M; Yagil, A; Yamamoto, K; Yamaoka, J; Yamashita, Y; Yang, C; Yang, U K; Yao, W M; Yeh, G P; Yi, K; Yoh, J; Yorita, K; Yoshida, T; Yu, I; Yu, S S; Yun, J C; Zanello, L; Zanetti, A; Zaw, I; Zetti, F; Zhang, X; Zhou, J; Zucchelli, S

    2006-03-03

    We report the first evidence for a fully reconstructed decay mode of the B(c)+- meson in the channel B(c)+- --> J/psi pi+-, with J/psi --> mu+ mu-. The analysis is based on an integrated luminosity of 360 pb(-1) in pp collisions at 1.96 TeV center of mass energy collected by the Collider Detector at Fermilab. We observe 14.6 +/- 4.6 signal events with a background of 7.1 +/- 0.9 events, and a fit to the J/psi pi+-mass spectrum yields a B(c)+- mass of 6285.7 +/- 5.3(stat) +/- 1.2(syst) MeV/c2. The probability of a peak of this magnitude occurring by random fluctuation in the search region is estimated as 0.012%.

  20. Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO)10(bmf) clusters and HOs3(CO)8( -C6H4)[ -PhPCC(Ph2P)CH(OMe)OC(O)

    SciTech Connect

    Kandala, Srikanth; Yang, Li; Campana, Charles F.; Nesterov, Vladimir; Richmond, Michael G.

    2010-07-01

    The labile cluster 1,2-Os3(CO)10(MeCN)2 (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os3(CO)10(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358 383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os3(CO)10(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os3(CO)10(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs3(CO)9(C29H23O3P2) (3a c). Thermolysis of HOs3(CO)9(C29H23O3P2) (3a c) in refluxing toluene leads to P C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)8( -C6H4)( -C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os3(CO)10(diphosphine) derivatives prepared by our groups.

  1. Structural basis of cohesin cleavage by separase

    PubMed Central

    Lin, Zhonghui; Luo, Xuelian; Yu, Hongtao

    2016-01-01

    Accurate chromosome segregation requires timely dissolution of chromosome cohesion after chromosomes are properly attached to the mitotic spindle. Separase is absolutely essential for cohesion dissolution in organisms from yeast to man1,2. It cleaves the kleisin subunit of cohesin and opens the cohesin ring to allow chromosome segregation. Cohesin cleavage is spatiotemporally controlled by separase-associated regulatory proteins, including the inhibitory chaperone securin3–6, and by phosphorylation of both the enzyme and substrates7–12. Dysregulation of this process causes chromosome missegregation and aneuploidy, contributing to cancer and birth defects. Despite its essential functions, atomic structures of separase have not been determined. Here, we report crystal structures of the separase protease domain from Chaetomium thermophilum, alone or covalently bound to unphosphorylated and phosphorylated inhibitory peptides derived from a cohesin cleavage site. These structures reveal how separase recognizes cohesin and how cohesin phosphorylation by polo-like kinase 1 (Plk1) enhances cleavage. Consistent with a previous cellular study13, mutating two securin residues in a conserved motif that partially matches the separase cleavage consensus converts securin from a separase inhibitor to a substrate. Our study establishes atomic mechanisms of substrate cleavage by separase and suggests competitive inhibition by securin. PMID:27027290

  2. Study of the B+c → J/ΨD+s and B+c → J/ΨD*s+ decays with the ATLAS detector

    DOE PAGES

    Aad, G.; Abbott, B.; Abdallah, J.; ...

    2016-01-05

    The decays B+c → J/ΨD+s and B+c → J/ΨD*s+ are studied with the ATLAS detector at the LHC using a dataset corresponding to integrated luminosities of 4.9 and 20.6 fb–1 of pp collisions collected at centre-of-mass energies √s = 7 TeV and 8 TeV, respectively. Furthermore, signal candidates are identified through J/ψ → μ+μ- and D(*)+s → Φπ+(γ/π0) decays.

  3. Nanomechanical cleavage of molybdenum disulphide atomic layers.

    PubMed

    Tang, Dai-Ming; Kvashnin, Dmitry G; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M; Yakobson, Boris I; Sorokin, Pavel B; Lou, Jun; Golberg, Dmitri

    2014-04-03

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  4. Nanomechanical cleavage of molybdenum disulphide atomic layers

    NASA Astrophysics Data System (ADS)

    Tang, Dai-Ming; Kvashnin, Dmitry G.; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M.; Yakobson, Boris I.; Sorokin, Pavel B.; Lou, Jun; Golberg, Dmitri

    2014-04-01

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  5. Cleavage fracture in bainitic and martensitic microstructures

    SciTech Connect

    Zhang, X.Z.; Knott, J.F.

    1999-09-29

    This paper addresses the mechanisms of cleavage fracture in the pressure-vessel steel A533B. Microstructures of single bainite microstructures exhibit a higher propensity for brittle cleavage fracture than do those of auto-tempered martensites. The K{sub 1c} values of mixed microstructures are determined by the statistical distribution of the two phases and the range of the values is bounded by limits set by those for the single-phase microstructures. The results are explained in terms of the RKR model, which involves a local cleavage stress {sigma}*{sub F} and a distance ahead of the macrocrack tip, X, as two critical parameters. It is found that the carbides or carbide colonies act as critical microcrack nuclei, and hence play a key role in determining the fracture toughness, although packet boundaries in bainite may give rise to pop-in arrests in displacement-controlled tests.

  6. Limited caspase cleavage of human BAP31.

    PubMed

    Määttä, J; Hallikas, O; Welti, S; Hildén, P; Schröder, J; Kuismanen, E

    2000-11-10

    Human BAP31 was cleaved at both of its two identical caspase cleavage sites in two previously reported models of apoptosis. We show here that only the most carboxy-terminal site is cleaved during apoptosis induced in HeLa cells by tunicamycin, tumor necrosis factor and cycloheximide, or staurosporine. Similar results were obtained in HL-60 cells using Fas/APO-1 antibodies, or cycloheximide. This limited cleavage, which is inhibited by several caspase inhibitors, removes eight amino acids from human BAP31 including the KKXX coat protein I binding motif. Ectopic expression of the resulting cleavage product induces redistribution of mannosidase II from the Golgi and prevents endoplasmic reticulum to Golgi transport of virus glycoproteins.

  7. Understanding regioselective cleavage in peptide hydrolysis by a palladium(II) aqua complex: a theoretical point of view.

    PubMed

    Yeguas, Violeta; Campomanes, Pablo; López, Ramón; Díaz, Natalia; Suárez, Dimas

    2010-07-01

    Hydrolytic cleavage of the oligopeptides Ace-Ala-Lys-Tyr-Gly approximately Gly-Met-Ala-Ala-Arg-Ala and Ace-Lys-Gly-Gly-Ala-Gly approximately Pro-Met-Ala-Ala-Arg-Gly by [Pd(H(2)O)(4)](2+) was theoretically investigated by using molecular dynamics simulations and quantum mechanical calculations. The Pd anchorage to the peptide sequence is crucial to provoke the cleavage of the second bond upstream from the anchored methionine. For both cases, the most favorable reaction mechanism is a three-step route. The first step coincides with the experimental suggestion found for the Gly approximately Pro-Met sequence on a cleavage caused by an external attack of a water molecule to a complex in trans conformation of the scissile Gly approximately Gly and Gly approximately Pro peptide bonds. However, our results uncover the important role played by the presence of a Pd-coordinated water molecule, which simultaneously interacts with the carbonyl oxygen atom of the Gly amino acid in the Gly approximately Gly and Gly approximately Pro bonds. In accordance with experimental facts, the rise of the hydrolysis reaction rate when the Pro amino acid is located in the scissile peptide bond was also corroborated. The findings obtained at a molecular level from the present computations not only are relevant to rationalize the previously reported experiments but also could be of importance in designing new Pd(II) complexes for the regioselective cleavage of peptides and proteins.

  8. First observation of the decay B(c)+ → J/ψπ(+) π- π+.

    PubMed

    Aaij, R; Abellan Beteta, C; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves, A A; Amato, S; Amhis, Y; Anderson, J; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Bachmann, S; Back, J J; Balagura, V; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bates, A; Bauer, C; Bauer, Th; Bay, A; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Benayoun, M; Bencivenni, G; Benson, S; Benton, J; Bernet, R; Bettler, M-O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blanks, C; Blouw, J; Blusk, S; Bobrov, A; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Büchler-Germann, A; Burducea, I; Bursche, A; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carson, L; Carvalho Akiba, K; Casse, G; Cattaneo, M; Cauet, Ch; Charles, M; Charpentier, Ph; Chiapolini, N; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Corti, G; Couturier, B; Cowan, G A; Currie, R; D'Ambrosio, C; David, P; David, P N Y; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Paula, L; De Simone, P; Decamp, D; Deckenhoff, M; Degaudenzi, H; Del Buono, L; Deplano, C; Derkach, D; Deschamps, O; Dettori, F; Dickens, J; Dijkstra, H; Diniz Batista, P; Domingo Bonal, F; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Dzhelyadin, R; Dziurda, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisele, F; Eisenhardt, S; Ekelhof, R; Eklund, L; Elsasser, Ch; Elsby, D; Esperante Pereira, D; Falabella, A; Färber, C; Fardell, G; Farinelli, C; Farry, S; Fave, V; Fernandez Albor, V; Ferro-Luzzi, M; Filippov, S; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furcas, S; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garnier, J-C; Garofoli, J; Garra Tico, J; Garrido, L; Gascon, D; Gaspar, C; Gauld, R; Gauvin, N; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hampson, T; Hansmann-Menzemer, S; Harji, R; Harnew, N; Harrison, J; Harrison, P F; Hartmann, T; He, J; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Hicks, E; Holubyev, K; Hopchev, P; Hulsbergen, W; Hunt, P; Huse, T; Huston, R S; Hutchcroft, D; Hynds, D; Iakovenko, V; Ilten, P; Imong, J; Jacobsson, R; Jaeger, A; Jahjah Hussein, M; Jans, E; Jansen, F; Jaton, P; Jean-Marie, B; Jing, F; John, M; Johnson, D; Jones, C R; Jost, B; Kaballo, M; Kandybei, S; Karacson, M; Karbach, T M; Keaveney, J; Kenyon, I R; Kerzel, U; Ketel, T; Keune, A; Khanji, B; Kim, Y M; Knecht, M; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kruzelecki, K; Kucharczyk, M; Kudryavtsev, V; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J-P; Lefèvre, R; Leflat, A; Lefrançois, J; Leroy, O; Lesiak, T; Li, L; Li Gioi, L; Lieng, M; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; von Loeben, J; Lopes, J H; Lopez Asamar, E; Lopez-March, N; Lu, H; Luisier, J; Mac Raighne, A; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Magnin, J; Malde, S; Mamunur, R M D; Manca, G; Mancinelli, G; Mangiafave, N; Marconi, U; Märki, R; Marks, J; Martellotti, G; Martens, A; Martin, L; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Massafferri, A; Mathe, Z; Matteuzzi, C; Matveev, M; Maurice, E; Maynard, B; Mazurov, A; McGregor, G; McNulty, R; Meissner, M; Merk, M; Merkel, J; Miglioranzi, S; Milanes, D A; Minard, M-N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Mylroie-Smith, J; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neufeld, N; Nguyen, A D; Nguyen-Mau, C; Nicol, M; Niess, V; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Pal, B K; Palacios, J; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Paterson, S K; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perego, D L; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pessina, G; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pie Valls, B; Pietrzyk, B; Pilař, T; Pinci, D; Plackett, R; Playfer, S; Plo Casasus, M; Polok, G; Poluektov, A; Polycarpo, E; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pugatch, V; Puig Navarro, A; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Raven, G; Redford, S; Reid, M M; Dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Roa Romero, D A; Robbe, P; Rodrigues, E; Rodrigues, F; Rodriguez Perez, P; Rogers, G J; Roiser, S; Romanovsky, V; Rosello, M; Rouvinet, J; Ruf, T; Ruiz, H; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salzmann, C; Sannino, M; Santacesaria, R; Santamarina Rios, C; Santinelli, R; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Savrina, D; Schaack, P; Schiller, M; Schindler, H; Schleich, S; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M-H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Skwarnicki, T; Smith, N A; Smith, E; Sobczak, K; Soler, F J P; Solomin, A; Soomro, F; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Swientek, S; Szczekowski, M; Szczypka, P; Szumlak, T; T'jampens, S; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tsaregorodtsev, A; Tuning, N; Ubeda Garcia, M; Ukleja, A; Uwer, U; Vagnoni, V; Valenti, G; Vazquez Gomez, R; Vazquez Regueiro, P; Vecchi, S; Velthuis, J J; Veltri, M; Viaud, B; Videau, I; Vieira, D; Vilasis-Cardona, X; Visniakov, J; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voss, H; Waldi, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wishahi, J; Witek, M; Witzeling, W; Wotton, S A; Wyllie, K; Xie, Y; Xing, F; Xing, Z; Yang, Z; Young, R; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhong, L; Zvyagin, A

    2012-06-22

    The decay B(c)(+) → J/ψπ(+) π(-) π(+) is observed for the first time, using 0.8 fb(-1) of pp collisions at sqrt[s] = 7 TeV collected by the LHCb experiment. The ratio of branching fractions B(B(c)(+) → J/ψπ(+) π(-) π(+))/B(B(c)(+)→J/ψπ^{+}) is measured to be 2.41 ± 0.30 ± 0.33, where the first uncertainty is statistical and the second is systematic. The result is in agreement with theoretical predictions.

  9. Degradation of diphenyl ether in Sphingobium phenoxybenzoativorans SC_3 is initiated by a novel ring-cleavage dioxygenase.

    PubMed

    Cai, Shu; Chen, Li-Wei; Ai, Yu-Chun; Qiu, Ji-Guo; Wang, Cheng-Hong; Shi, Chao; He, Jian; Cai, Tian-Ming

    2017-03-10

    Sphingobium phenoxybenzoativorans SC_3 degrades and utilizes diphenyl ether (DE) and 2-carboxy DE as its sole carbon and energy source. In this study, we report the degradation of DE and 2-carboxy DE initiated by a novel ring-cleavage angular dioxygenase (Dpe) in the strain. Dpe functions at the angular carbon and its adjacent carbon (C1a, C2) of a benzene ring in DE (or the 2-carboxy benzene ring in 2-carboxy DE) and cleaves the C1a-C2 bond (decarboxylation is simultaneously happened for 2-carboxy DE), yielding 2,4-hexadienal phenyl ester, which is subsequently hydrolyzed to muconic acid semialdehyde and phenol. Dpe is a type IV Rieske non-heme iron oxygenase (RHO) and consists of three components: a hetero-oligomer oxygenase, a [2Fe-2S]-type ferredoxin and a GR (glutathione reductase)-type reductase. Genetic analyses revealed that dpeA1A2 plays an essential role in degradation and utilization of DE and 2-carboxy DE in S. phenoxybenzoativorans SC_3. Enzymatic study showed that transformation of one molecule of DE needs two molecules of oxygen and two molecules of NADH, supporting the assumption that the cleavage of DE catalyzed by Dpe is a continuous two-step dioxygenation process: DE is dioxygenated at C1a, C2 to form an hemiacetal-like intermediates, which is further dioxygenated resulting the cleavage of the C1a-C2 bond to form one molecule of 2,4-hexadienal phenyl ester and two molecules of H2O. This study extends our knowledge of the mode and mechanism of ring-cleavage of aromatic compounds.IMPORTANCE Benzene ring-cleavage, catalyzed by dioxygenase, is the key and speed limiting step in the aerobic degradation of aromatic compounds. Previously reported ring-cleavage of DEs, the benzene ring needs to be firstly dihydroxylated at lateral position, and subsequently dehydrogenated and opened through extradiol cleavage. This process requires three enzymes (two dioxygenases and one dehydrogenase). In this study, we identified a novel angular dioxygenase (Dpe) in S

  10. Better Efforts Could Help Rid the U.S. of Hepatitis B, C: Report

    MedlinePlus

    ... Better Efforts Could Help Rid the U.S. of Hepatitis B, C: Report Plus, 90,000 fewer deaths ... Improved prevention, screening and treatment could help eliminate hepatitis B and C as serious public health problems ...

  11. The production of X(3940) and X(4160) in B c decays

    NASA Astrophysics Data System (ADS)

    Wang, Zhi-Hui; Zhang, Yi; Wang, Tian-hong; Jiang, Yue; Wang, Guo-Li

    2016-10-01

    Considering X(3940) and X(4160) as {η }c(3S) and {η }c(4S), we study the production of X(3940) and X(4160) in exclusive weak decays of the B c meson by the improved Bethe-Salpeter (BS) method. Using the relativistic BS equation and the Mandelstam formalism, we calculate the corresponding decay form factors. The predictions of the corresponding branching ratios are: {{Br}}({B}c+\\to X(3940){e}+{ν }e)=1.0× {10}-4 and {{Br}}({B}c+\\to X(4160) {e}+{ν }e)=2.4× {10}-5. This will provide a new way to observe X(3940) and X(4160) in the future, as well as to improve the knowledge of B c meson decay.

  12. Variations in geomagnetic intensity and temperature in the second Millennium B.C. in Spain

    NASA Astrophysics Data System (ADS)

    Nachasova, I. E.; Burakov, K. S.

    2012-05-01

    The Bronze ceramics of the Baeza archeological monument in Spain is studied by archaeomagnetic methods. In the 19th and 18th centuries B.C, the intensity of the geomagnetic field varied from 40 to 60 mkT. The variations are smooth; they attained their maximum in the 16th to 15th centuries B.C. The obtained data on the variations in the geomagnetic intensity perfectly agree with the results of previous investigations for the ceramics from the Bronze Age multilayered archeological monuments Azuer and Ubeda. The temperature in the region of the Baeza monument is estimated in the interval from the 18th to the 13th centuries B.C. It experiences wave-like variation, ranging from ˜15 to 23°C and attains its maximum in the 16th century B.C.

  13. B-C Bond in Diamond Single Crystal Synthesized with h-BN Additive at High Pressure and High Temperature

    NASA Astrophysics Data System (ADS)

    Yong, Li; Zhen-Xiang, Zhou; Xue-Mao, Guan; Shang-Sheng, Li; Ying, Wang; Xiao-Peng, Jia; Hong-An, Ma

    2016-02-01

    Not Available Supported by the National Natural Science Foundation of China under Grant No 51172089, the Natural Science Foundation of Guizhou Province Education Department under Grant No KY[2013]183, and the Natural Science Foundation of Guizhou Province Science and Technology Agency under Grant Nos LH[2015]7232 and LH[2015]7228.

  14. 31 CFR 315.38 - Payment during lifetime of owner of beneficiary bond.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES General Provisions...

  15. 31 CFR 315.27 - Application for relief-nonreceipt of bond.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Relief for Loss,...

  16. Observation of the decay B(c)(+) → B(s)(0)π+.

    PubMed

    Aaij, R; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves, A A; Amato, S; Amerio, S; Amhis, Y; Anderlini, L; Anderson, J; Andreassen, R; Andrews, J E; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Baalouch, M; Bachmann, S; Back, J J; Baesso, C; Balagura, V; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bauer, Th; Bay, A; Beddow, J; Bedeschi, F; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Bencivenni, G; Benson, S; Benton, J; Berezhnoy, A; Bernet, R; Bettler, M-O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blouw, J; Blusk, S; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bowen, E; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Bursche, A; Busetto, G; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Campora Perez, D; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carranza-Mejia, H; Carson, L; Carvalho Akiba, K; Casse, G; Cassina, L; Castillo Garcia, L; Cattaneo, M; Cauet, Ch; Cenci, R; Charles, M; Charpentier, Ph; Chen, P; Cheung, S-F; Chiapolini, N; Chrzaszcz, M; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Cogneras, E; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Coquereau, S; Corti, G; Couturier, B; Cowan, G A; Craik, D C; Cunliffe, S; Currie, R; D'Ambrosio, C; David, P; David, P N Y; Davis, A; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Paula, L; De Silva, W; De Simone, P; Decamp, D; Deckenhoff, M; Del Buono, L; Déléage, N; Derkach, D; Deschamps, O; Dettori, F; Di Canto, A; Dijkstra, H; Dogaru, M; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Durante, P; Dzhelyadin, R; Dziurda, A; Dzyuba, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisenhardt, S; Eitschberger, U; Ekelhof, R; Eklund, L; El Rifai, I; Elsasser, Ch; Falabella, A; Färber, C; Farinelli, C; Farry, S; Ferguson, D; Fernandez Albor, V; Ferreira Rodrigues, F; Ferro-Luzzi, M; Filippov, S; Fiore, M; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furfaro, E; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garofoli, J; Garosi, P; Garra Tico, J; Garrido, L; Gaspar, C; Gauld, R; Gersabeck, E; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Giubega, L; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gorbounov, P; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Griffith, P; Grünberg, O; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hall, S; Hamilton, B; Hampson, T; Hansmann-Menzemer, S; Harnew, N; Harnew, S T; Harrison, J; Hartmann, T; He, J; Head, T; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Heß, M; Hicheur, A; Hicks, E; Hill, D; Hoballah, M; Hombach, C; Hulsbergen, W; Hunt, P; Huse, T; Hussain, N; Hutchcroft, D; Hynds, D; Iakovenko, V; Idzik, M; Ilten, P; Jacobsson, R; Jaeger, A; Jans, E; Jaton, P; Jawahery, A; Jing, F; John, M; Johnson, D; Jones, C R; Joram, C; Jost, B; Kaballo, M; Kandybei, S; Kanso, W; Karacson, M; Karbach, T M; Kenyon, I R; Ketel, T; Khanji, B; Kochebina, O; Komarov, I; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kucharczyk, M; Kudryavtsev, V; Kurek, K; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J-P; Lefèvre, R; Leflat, A; Lefrançois, J; Leo, S; Leroy, O; Lesiak, T; Leverington, B; Li, Y; Li Gioi, L; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; Lohn, S; Longstaff, I; Lopes, J H; Lopez-March, N; Lu, H; Lucchesi, D; Luisier, J; Luo, H; Lupton, O; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Malde, S; Manca, G; Mancinelli, G; Maratas, J; Marconi, U; Marino, P; Märki, R; Marks, J; Martellotti, G; Martens, A; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Martins Tostes, D; Martynov, A; Massafferri, A; Matev, R; Mathe, Z; Matteuzzi, C; Maurice, E; Mazurov, A; McCarthy, J; McNab, A; McNulty, R; McSkelly, B; Meadows, B; Meier, F; Meissner, M; Merk, M; Milanes, D A; Minard, M-N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Mordà, A; Morello, M J; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neubert, S; Neufeld, N; Nguyen, A D; Nguyen, T D; Nguyen-Mau, C; Nicol, M; Niess, V; Niet, R; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Oyanguren, A; Pal, B K; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pearce, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pescatore, L; Pesen, E; Pessina, G; Petridis, K; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pietrzyk, B; Pilař, T; Pinci, D; Playfer, S; Plo Casasus, M; Polci, F; Polok, G; Poluektov, A; Polycarpo, E; Popov, A; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pritchard, A; Prouve, C; Pugatch, V; Puig Navarro, A; Punzi, G; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Rauschmayr, N; Raven, G; Redford, S; Reid, M M; Dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Rives Molina, V; Roa Romero, D A; Robbe, P; Roberts, D A; Rodrigues, A B; Rodrigues, E; Rodriguez Perez, P; Roiser, S; Romanovsky, V; Romero Vidal, A; Rouvinet, J; Ruf, T; Ruffini, F; Ruiz, H; Ruiz Valls, P; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salustino Guimaraes, V; Sanmartin Sedes, B; Santacesaria, R; Santamarina Rios, C; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Savrina, D; Schiller, M; Schindler, H; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M-H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Sirendi, M; Skidmore, N; Skwarnicki, T; Smith, N A; Smith, E; Smith, E; Smith, J; Smith, M; Sokoloff, M D; Soler, F J P; Soomro, F; Souza, D; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stevenson, S; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Sun, L; Sutcliffe, W; Swientek, S; Syropoulos, V; Szczekowski, M; Szczypka, P; Szilard, D; Szumlak, T; T'jampens, S; Teklishyn, M; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Tonelli, D; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tresch, M; Tsaregorodtsev, A; Tsopelas, P; Tuning, N; Ubeda Garcia, M; Ukleja, A; Ustyuzhanin, A; Uwer, U; Vagnoni, V; Valenti, G; Vallier, A; Vazquez Gomez, R; Vazquez Regueiro, P; Vázquez Sierra, C; Vecchi, S; Velthuis, J J; Veltri, M; Veneziano, G; Vesterinen, M; Viaud, B; Vieira, D; Vilasis-Cardona, X; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voß, C; Voss, H; de Vries, J A; Waldi, R; Wallace, C; Wallace, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wicht, J; Wiechczynski, J; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wimberley, J; Wishahi, J; Wislicki, W; Witek, M; Wotton, S A; Wright, S; Wu, S; Wyllie, K; Xie, Y; Xing, Z; Yang, Z; Yuan, X; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhokhov, A; Zhong, L; Zvyagin, A

    2013-11-01

    The result of a search for the decay B(c)(+) → B(s)(0) π+ is presented, using the B(s)(0) → D(s)(-)π+ and B(s)(0) → J/ψ Ø channels. The analysis is based on a data sample of pp collisions collected with the LHCb detector, corresponding to an integrated luminosity of 1 fb(-1) taken at a center-of-mass energy of 7 TeV, and 2 fb(-1) taken at 8 TeV. The decay B(c)(+) → B(s)(0)π+ is observed with significance in excess of 5 standard deviations independently in both decay channels. The measured product of the ratio of cross sections and branching fraction is [σ(B(c)(+))/σ(B(s)(0))] × B(B(c)(+)→ B(s)(0)π+) = [2.37 ± 0.31 (stat)± 0.11 (syst)(-0.13)(+0.17)(τ(B)(c)(+)))] × 10(-3), in the pseudorapidity range 2<η(B)<5, where the first uncertainty is statistical, the second is systematic, and the third is due to the uncertainty on the B(c)(+) lifetime. This is the first observation of a B meson decaying to another B meson via the weak interaction.

  17. Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster.

    PubMed

    Kang, Xiaohui; Luo, Gen; Luo, Lun; Hu, Shaowei; Luo, Yi; Hou, Zhaomin

    2016-09-14

    Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

  18. Enhancing the specificity of the enterokinase cleavage reaction to promote efficient cleavage of a fusion tag.

    PubMed

    Shahravan, S Hesam; Qu, Xuanlu; Chan, I-San; Shin, Jumi A

    2008-06-01

    In our work with designed minimalist proteins based on the bZIP motif, we have found our His-tagged proteins to be prone to inclusion body formation and aggregation; we suspect this problem is largely due to the His tag, known to promote aggregation. Using AhR6-C/EBP, a hybrid of the AhR basic region and C/EBP leucine zipper, as representative of our bZIP-like protein family, we attempted removal of the His tag with enterokinase (EK) but obtained the desired cleavage product in very small yield. EK is known for proteolysis at noncanonical sites, and most cleavage occurred at unintended sites. We manipulated experimental conditions to improve specificity of proteolysis and analyzed the cleavage products; no effect was observed after changing pH, temperature, or the amount of EK. We then suspected the accessibility of the EK site was impeded due to protein aggregation. We found that the easily implemented strategy of addition of urea (1-4 M) greatly improved EK cleavage specificity at the canonical site and reduced adventitious cleavage. We believe that this enhancement in specificity is due to a more "open" protein structure, in which the now accessible canonical target can compete effectively with adventitious cleavage sites of related sequence.

  19. Measurement of the ratio of branching fractions B({B}c+to J/{ψK}+)/B({B}c+to J/{ψπ}+)

    NASA Astrophysics Data System (ADS)

    Aaij, R.; Adeva, B.; Adinolfi, M.; Ajaltouni, Z.; Akar, S.; Albrecht, J.; Alessio, F.; Alexander, M.; Ali, S.; Alkhazov, G.; Alvarez Cartelle, P.; Alves, A. A.; Amato, S.; Amerio, S.; Amhis, Y.; An, L.; Anderlini, L.; Andreassi, G.; Andreotti, M.; Andrews, J. E.; Appleby, R. B.; Aquines Gutierrez, O.; Archilli, F.; d'Argent, P.; Arnau Romeu, J.; Artamonov, A.; Artuso, M.; Aslanides, E.; Auriemma, G.; Baalouch, M.; Babuschkin, I.; Bachmann, S.; Back, J. J.; Badalov, A.; Baesso, C.; Baldini, W.; Barlow, R. J.; Barschel, C.; Barsuk, S.; Barter, W.; Batozskaya, V.; Batsukh, B.; Battista, V.; Bay, A.; Beaucourt, L.; Beddow, J.; Bedeschi, F.; Bediaga, I.; Bel, L. J.; Bellee, V.; Belloli, N.; Belous, K.; Belyaev, I.; Ben-Haim, E.; Bencivenni, G.; Benson, S.; Benton, J.; Berezhnoy, A.; Bernet, R.; Bertolin, A.; Betti, F.; Bettler, M.-O.; van Beuzekom, M.; Bezshyiko, I.; Bifani, S.; Billoir, P.; Bird, T.; Birnkraut, A.; Bitadze, A.; Bizzeti, A.; Blake, T.; Blanc, F.; Blouw, J.; Blusk, S.; Bocci, V.; Boettcher, T.; Bondar, A.; Bondar, N.; Bonivento, W.; Borgheresi, A.; Borghi, S.; Borisyak, M.; Borsato, M.; Bossu, F.; Boubdir, M.; Bowcock, T. J. V.; Bowen, E.; Bozzi, C.; Braun, S.; Britsch, M.; Britton, T.; Brodzicka, J.; Buchanan, E.; Burr, C.; Bursche, A.; Buytaert, J.; Cadeddu, S.; Calabrese, R.; Calvi, M.; Calvo Gomez, M.; Campana, P.; Campora Perez, D.; Capriotti, L.; Carbone, A.; Carboni, G.; Cardinale, R.; Cardini, A.; Carniti, P.; Carson, L.; Carvalho Akiba, K.; Casse, G.; Cassina, L.; Castillo Garcia, L.; Cattaneo, M.; Cauet, Ch.; Cavallero, G.; Cenci, R.; Charles, M.; Charpentier, Ph.; Chatzikonstantinidis, G.; Chefdeville, M.; Chen, S.; Cheung, S.-F.; Chobanova, V.; Chrzaszcz, M.; Cid Vidal, X.; Ciezarek, G.; Clarke, P. E. L.; Clemencic, M.; Cliff, H. V.; Closier, J.; Coco, V.; Cogan, J.; Cogneras, E.; Cogoni, V.; Cojocariu, L.; Collazuol, G.; Collins, P.; Comerma-Montells, A.; Contu, A.; Cook, A.; Coquereau, S.; Corti, G.; Corvo, M.; Costa Sobral, C. M.; Couturier, B.; Cowan, G. A.; Craik, D. C.; Crocombe, A.; Cruz Torres, M.; Cunliffe, S.; Currie, R.; D'Ambrosio, C.; Dall'Occo, E.; Dalseno, J.; David, P. N. Y.; Davis, A.; De Aguiar Francisco, O.; De Bruyn, K.; De Capua, S.; De Cian, M.; De Miranda, J. M.; De Paula, L.; De Serio, M.; De Simone, P.; Dean, C.-T.; Decamp, D.; Deckenhoff, M.; Del Buono, L.; Demmer, M.; Derkach, D.; Deschamps, O.; Dettori, F.; Dey, B.; Di Canto, A.; Dijkstra, H.; Dordei, F.; Dorigo, M.; Dosil Suárez, A.; Dovbnya, A.; Dreimanis, K.; Dufour, L.; Dujany, G.; Dungs, K.; Durante, P.; Dzhelyadin, R.; Dziurda, A.; Dzyuba, A.; Déléage, N.; Easo, S.; Egede, U.; Egorychev, V.; Eidelman, S.; Eisenhardt, S.; Eitschberger, U.; Ekelhof, R.; Eklund, L.; Elsasser, Ch.; Ely, S.; Esen, S.; Evans, H. M.; Evans, T.; Falabella, A.; Farley, N.; Farry, S.; Fay, R.; Fazzini, D.; Ferguson, D.; Fernandez Albor, V.; Ferrari, F.; Ferreira Rodrigues, F.; Ferro-Luzzi, M.; Filippov, S.; Fini, R. A.; Fiore, M.; Fiorini, M.; Firlej, M.; Fitzpatrick, C.; Fiutowski, T.; Fleuret, F.; Fohl, K.; Fontana, M.; Fontanelli, F.; Forshaw, D. C.; Forty, R.; Franco Lima, V.; Frank, M.; Frei, C.; Fu, J.; Furfaro, E.; Färber, C.; Gallas Torreira, A.; Galli, D.; Gallorini, S.; Gambetta, S.; Gandelman, M.; Gandini, P.; Gao, Y.; García Pardiñas, J.; Garra Tico, J.; Garrido, L.; Garsed, P. J.; Gascon, D.; Gaspar, C.; Gavardi, L.; Gazzoni, G.; Gerick, D.; Gersabeck, E.; Gersabeck, M.; Gershon, T.; Ghez, Ph.; Gianì, S.; Gibson, V.; Girard, O. G.; Giubega, L.; Gizdov, K.; Gligorov, V. V.; Golubkov, D.; Golutvin, A.; Gomes, A.; Gorelov, I. V.; Gotti, C.; Grabalosa Gándara, M.; Graciani Diaz, R.; Granado Cardoso, L. A.; Graugés, E.; Graverini, E.; Graziani, G.; Grecu, A.; Griffith, P.; Grillo, L.; Gruberg Cazon, B. R.; Grünberg, O.; Gushchin, E.; Guz, Yu.; Gys, T.; Göbel, C.; Hadavizadeh, T.; Hadjivasiliou, C.; Haefeli, G.; Haen, C.; Haines, S. C.; Hall, S.; Hamilton, B.; Han, X.; Hansmann-Menzemer, S.; Harnew, N.; Harnew, S. T.; Harrison, J.; Hatch, M.; He, J.; Head, T.; Heister, A.; Hennessy, K.; Henrard, P.; Henry, L.; Hernando Morata, J. A.; van Herwijnen, E.; Heß, M.; Hicheur, A.; Hill, D.; Hombach, C.; Hulsbergen, W.; Humair, T.; Hushchyn, M.; Hussain, N.; Hutchcroft, D.; Idzik, M.; Ilten, P.; Jacobsson, R.; Jaeger, A.; Jalocha, J.; Jans, E.; Jawahery, A.; John, M.; Johnson, D.; Jones, C. R.; Joram, C.; Jost, B.; Jurik, N.; Kandybei, S.; Kanso, W.; Karacson, M.; Kariuki, J. M.; Karodia, S.; Kecke, M.; Kelsey, M.; Kenyon, I. R.; Kenzie, M.; Ketel, T.; Khairullin, E.; Khanji, B.; Khurewathanakul, C.; Kirn, T.; Klaver, S.; Klimaszewski, K.; Koliiev, S.; Kolpin, M.; Komarov, I.; Koopman, R. F.; Koppenburg, P.; Kozachuk, A.; Kozeiha, M.; Kravchuk, L.; Kreplin, K.; Kreps, M.; Krokovny, P.; Kruse, F.; Krzemien, W.; Kucewicz, W.; Kucharczyk, M.; Kudryavtsev, V.; Kuonen, A. K.; Kurek, K.; Kvaratskheliya, T.; Lacarrere, D.; Lafferty, G.; Lai, A.; Lambert, D.; Lanfranchi, G.; Langenbruch, C.; Langhans, B.; Latham, T.; Lazzeroni, C.; Le Gac, R.; van Leerdam, J.; Lees, J.-P.; Leflat, A.; Lefrançois, J.; Lefèvre, R.; Lemaitre, F.; Lemos Cid, E.; Leroy, O.; Lesiak, T.; Leverington, B.; Li, Y.; Likhomanenko, T.; Lindner, R.; Linn, C.; Lionetto, F.; Liu, B.; Liu, X.; Loh, D.; Longstaff, I.; Lopes, J. H.; Lucchesi, D.; Lucio Martinez, M.; Luo, H.; Lupato, A.; Luppi, E.; Lupton, O.; Lusiani, A.; Lyu, X.; Machefert, F.; Maciuc, F.; Maev, O.; Maguire, K.; Malde, S.; Malinin, A.; Maltsev, T.; Manca, G.; Mancinelli, G.; Manning, P.; Maratas, J.; Marchand, J. F.; Marconi, U.; Marin Benito, C.; Marino, P.; Marks, J.; Martellotti, G.; Martin, M.; Martinelli, M.; Martinez Santos, D.; Martinez Vidal, F.; Martins Tostes, D.; Massacrier, L. M.; Massafferri, A.; Matev, R.; Mathad, A.; Mathe, Z.; Matteuzzi, C.; Mauri, A.; Maurin, B.; Mazurov, A.; McCann, M.; McCarthy, J.; McNab, A.; McNulty, R.; Meadows, B.; Meier, F.; Meissner, M.; Melnychuk, D.; Merk, M.; Merli, A.; Michielin, E.; Milanes, D. A.; Minard, M.-N.; Mitzel, D. S.; Molina Rodriguez, J.; Monroy, I. A.; Monteil, S.; Morandin, M.; Morawski, P.; Mordà, A.; Morello, M. J.; Moron, J.; Morris, A. B.; Mountain, R.; Muheim, F.; Mulder, M.; Mussini, M.; Müller, D.; Müller, J.; Müller, K.; Müller, V.; Naik, P.; Nakada, T.; Nandakumar, R.; Nandi, A.; Nasteva, I.; Needham, M.; Neri, N.; Neubert, S.; Neufeld, N.; Neuner, M.; Nguyen, A. D.; Nguyen-Mau, C.; Nieswand, S.; Niet, R.; Nikitin, N.; Nikodem, T.; Novoselov, A.; O'Hanlon, D. P.; Oblakowska-Mucha, A.; Obraztsov, V.; Ogilvy, S.; Oldeman, R.; Onderwater, C. J. G.; Otalora Goicochea, J. M.; Otto, A.; Owen, P.; Oyanguren, A.; Pais, P. R.; Palano, A.; Palombo, F.; Palutan, M.; Panman, J.; Papanestis, A.; Pappagallo, M.; Pappalardo, L. L.; Pappenheimer, C.; Parker, W.; Parkes, C.; Passaleva, G.; Pastore, A.; Patel, G. D.; Patel, M.; Patrignani, C.; Pearce, A.; Pellegrino, A.; Penso, G.; Pepe Altarelli, M.; Perazzini, S.; Perret, P.; Pescatore, L.; Petridis, K.; Petrolini, A.; Petrov, A.; Petruzzo, M.; Picatoste Olloqui, E.; Pietrzyk, B.; Pikies, M.; Pinci, D.; Pistone, A.; Piucci, A.; Playfer, S.; Plo Casasus, M.; Poikela, T.; Polci, F.; Poluektov, A.; Polyakov, I.; Polycarpo, E.; Pomery, G. J.; Popov, A.; Popov, D.; Popovici, B.; Potterat, C.; Price, E.; Price, J. D.; Prisciandaro, J.; Pritchard, A.; Prouve, C.; Pugatch, V.; Puig Navarro, A.; Punzi, G.; Qian, W.; Quagliani, R.; Rachwal, B.; Rademacker, J. H.; Rama, M.; Ramos Pernas, M.; Rangel, M. S.; Raniuk, I.; Raven, G.; Redi, F.; Reichert, S.; dos Reis, A. C.; Remon Alepuz, C.; Renaudin, V.; Ricciardi, S.; Richards, S.; Rihl, M.; Rinnert, K.; Rives Molina, V.; Robbe, P.; Rodrigues, A. B.; Rodrigues, E.; Rodriguez Lopez, J. A.; Rodriguez Perez, P.; Rogozhnikov, A.; Roiser, S.; Romanovskiy, V.; Romero Vidal, A.; Ronayne, J. W.; Rotondo, M.; Rudolph, M. S.; Ruf, T.; Ruiz Valls, P.; Saborido Silva, J. J.; Sadykhov, E.; Sagidova, N.; Saitta, B.; Salustino Guimaraes, V.; Sanchez Mayordomo, C.; Sanmartin Sedes, B.; Santacesaria, R.; Santamarina Rios, C.; Santimaria, M.; Santovetti, E.; Sarti, A.; Satriano, C.; Satta, A.; Saunders, D. M.; Savrina, D.; Schael, S.; Schellenberg, M.; Schiller, M.; Schindler, H.; Schlupp, M.; Schmelling, M.; Schmelzer, T.; Schmidt, B.; Schneider, O.; Schopper, A.; Schubert, K.; Schubiger, M.; Schune, M.-H.; Schwemmer, R.; Sciascia, B.; Sciubba, A.; Semennikov, A.; Sergi, A.; Serra, N.; Serrano, J.; Sestini, L.; Seyfert, P.; Shapkin, M.; Shapoval, I.; Shcheglov, Y.; Shears, T.; Shekhtman, L.; Shevchenko, V.; Shires, A.; Siddi, B. G.; Silva Coutinho, R.; Silva de Oliveira, L.; Simi, G.; Simone, S.; Sirendi, M.; Skidmore, N.; Skwarnicki, T.; Smith, E.; Smith, I. T.; Smith, J.; Smith, M.; Snoek, H.; Sokoloff, M. D.; Soler, F. J. P.; Souza, D.; Souza De Paula, B.; Spaan, B.; Spradlin, P.; Sridharan, S.; Stagni, F.; Stahl, M.; Stahl, S.; Stefko, P.; Stefkova, S.; Steinkamp, O.; Stemmle, S.; Stenyakin, O.; Stevenson, S.; Stoica, S.; Stone, S.; Storaci, B.; Stracka, S.; Straticiuc, M.; Straumann, U.; Sun, L.; Sutcliffe, W.; Swientek, K.; Syropoulos, V.; Szczekowski, M.; Szumlak, T.; T'Jampens, S.; Tayduganov, A.; Tekampe, T.; Tellarini, G.; Teubert, F.; Thomas, C.; Thomas, E.; van Tilburg, J.; Tisserand, V.; Tobin, M.; Tolk, S.; Tomassetti, L.; Tonelli, D.; Topp-Joergensen, S.; Toriello, F.; Tournefier, E.; Tourneur, S.; Trabelsi, K.; Traill, M.; Tran, M. T.; Tresch, M.; Trisovic, A.; Tsaregorodtsev, A.; Tsopelas, P.; Tully, A.; Tuning, N.; Ukleja, A.; Ustyuzhanin, A.; Uwer, U.; Vacca, C.; Vagnoni, V.; Valat, S.; Valenti, G.; Vallier, A.; Vazquez Gomez, R.; Vazquez Regueiro, P.; Vecchi, S.; van Veghel, M.; Velthuis, J. J.; Veltri, M.; Veneziano, G.; Venkateswaran, A.; Vernet, M.; Vesterinen, M.; Viaud, B.; Vieira, D.; Vieites Diaz, M.; Vilasis-Cardona, X.; Volkov, V.; Vollhardt, A.; Voneki, B.; Voong, D.; Vorobyev, A.; Vorobyev, V.; Voß, C.; de Vries, J. A.; Vázquez Sierra, C.; Waldi, R.; Wallace, C.; Wallace, R.; Walsh, J.; Wang, J.; Ward, D. R.; Wark, H. M.; Watson, N. K.; Websdale, D.; Weiden, A.; Whitehead, M.; Wicht, J.; Wilkinson, G.; Wilkinson, M.; Williams, M.; Williams, M. P.; Williams, M.; Williams, T.; Wilson, F. F.; Wimberley, J.; Wishahi, J.; Wislicki, W.; Witek, M.; Wormser, G.; Wotton, S. A.; Wraight, K.; Wright, S.; Wyllie, K.; Xie, Y.; Xing, Z.; Xu, Z.; Yang, Z.; Yin, H.; Yu, J.; Yuan, X.; Yushchenko, O.; Zangoli, M.; Zarebski, K. A.; Zavertyaev, M.; Zhang, L.; Zhang, Y.; Zhang, Y.; Zhelezov, A.; Zheng, Y.; Zhokhov, A.; Zhu, X.; Zhukov, V.; Zucchelli, S.

    2016-09-01

    The ratio of branching fractions {R}_{K/π}≡ B({B}c+to J/{ψK}+)/B({B}c+to J/{ψπ}+) is measured with pp collision data collected by the LHCb experiment at centre-of-mass energies of 7 TeV and 8 TeV, corresponding to an integrated luminosity of 3 fb-1. It is found to be R K/π = 0.079 ± 0.007 ± 0.003, where the first uncertainty is statistical and the second is systematic. This measurement is consistent with the previous LHCb result, while the uncertainties are significantly reduced. [Figure not available: see fulltext.

  20. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    SciTech Connect

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  1. Application of immobilized bovine enterokinase in repetitive fusion protein cleavage for the production of mucin 1.

    PubMed

    Kubitzki, Tina; Minör, Daniel; Mackfeld, Ursula; Oldiges, Marco; Noll, Thomas; Lütz, Stephan

    2009-11-01

    Bovine enterokinase is a serine protease that catalyzes the hydrolysis of peptide bonds and plays a key role in mammalian metabolism. Because of its high specificity towards the amino acid sequence (Asp)(4)-Lys, enterokinase is a potential tool for the cleavage of fusion proteins, which are gaining more importance in biopharmaceutical production. A candidate for adaptive cancer immunotherapy is mucin 1, which is produced recombinantly as a fusion protein in CHO cells. Here, we present the first repetitive application of immobilized enterokinase for the cleavage of the mucin fusion protein. The immobilization enables a facile biocatalytic process due to simplified separation of the biocatalyst and the target protein. Immobilized enterokinase was applied in a maximum of 18 repetitive reactions. The enzyme utilization (total turnover number) was increased significantly 419-fold compared to unbound enzyme by both immobilization and optimization of process conditions. Slight enzyme inactivation throughout the reaction cycles was observed, but was compensated by adjusting the process time accordingly. Thus, complete fusion protein cleavage was achieved. Furthermore, we obtained isolated mucin 1 with a purity of more than 90% by applying a simple and efficient purification process. The presented results demonstrate enterokinase to be an attractive tool for fusion protein cleavage.

  2. Short RNA duplexes guide sequence-dependent cleavage by human Dicer.

    PubMed

    Bergeron, Lucien; Perreault, Jean-Pierre; Abou Elela, Sherif

    2010-12-01

    Dicer is a member of the double-stranded (ds) RNA-specific ribonuclease III (RNase III) family that is required for RNA processing and degradation. Like most members of the RNase III family, Dicer possesses a dsRNA binding domain and cleaves long RNA duplexes in vitro. In this study, Dicer substrate selectivity was examined using bipartite substrates. These experiments revealed that an RNA helix possessing a 2-nucleotide (nt) 3'-overhang may bind and direct sequence-specific Dicer-mediated cleavage in trans at a fixed distance from the 3'-end overhang. Chemical modifications of the substrate indicate that the presence of the ribose 2'-hydroxyl group is not required for Dicer binding, but some located near the scissile bonds are needed for RNA cleavage. This suggests a flexible mechanism for substrate selectivity that recognizes the overall shape of an RNA helix. Examination of the structure of natural pre-microRNAs (pre-miRNAs) suggests that they may form bipartite substrates with complementary mRNA sequences, and thus induce seed-independent Dicer cleavage. Indeed, in vitro, natural pre-miRNA directed sequence-specific Dicer-mediated cleavage in trans by supporting the formation of a substrate mimic.

  3. Blocking aggrecanase cleavage in the aggrecan interglobular domain abrogates cartilage erosion and promotes cartilage repair

    PubMed Central

    Little, Christopher B.; Meeker, Clare T.; Golub, Suzanne B.; Lawlor, Kate E.; Farmer, Pamela J.; Smith, Susan M.; Fosang, Amanda J.

    2007-01-01

    Aggrecan loss from cartilage in arthritis is mediated by aggrecanases. Aggrecanases cleave aggrecan preferentially in the chondroitin sulfate–2 (CS-2) domain and secondarily at the E373↓374A bond in the interglobular domain (IGD). However, IGD cleavage may be more deleterious for cartilage biomechanics because it releases the entire CS-containing portion of aggrecan. Recent studies identifying aggrecanase-2 (ADAMTS-5) as the predominant aggrecanase in mouse cartilage have not distinguished aggrecanolysis in the IGD from aggrecanolysis in the CS-2 domain. We generated aggrecan knockin mice with a mutation that rendered only the IGD resistant to aggrecanases in order to assess the contribution of this specific cleavage to cartilage pathology. The knockin mice were viable and fertile. Aggrecanase cleavage in the aggrecan IGD was not detected in knockin mouse cartilage in situ nor following digestion with ADAMTS-5 or treatment of cartilage explant cultures with IL-1α. Blocking cleavage in the IGD not only diminished aggrecan loss and cartilage erosion in surgically induced osteoarthritis and a model of inflammatory arthritis, but appeared to stimulate cartilage repair following acute inflammation. We conclude that blocking aggrecanolysis in the aggrecan IGD alone protects against cartilage erosion and may potentiate cartilage repair. PMID:17510707

  4. Enantioselective cleavage of supercoiled plasmid DNA catalyzed by chiral macrocyclic lanthanide(III) complexes.

    PubMed

    Krężel, Artur; Lisowski, Jerzy

    2012-02-01

    The enantiomers of the Sm (III), Eu (III) and Yb (III) complexes [LnL(NO(3))(2)](NO(3)) of a chiral hexaazamacrocycle were tested as catalysts for the hydrolytic cleavage of supercoiled plasmid DNA. The catalytic activity was remarkably enantioselective; while the [LnL(SSSS)(NO(3))(2)](NO(3)) enantiomers promoted the cleavage of plasmid pBR322 from the supercoiled form (SC) to the nicked form (NC), the [LnL(RRRR)(NO(3))(2)](NO(3)) enantiomers were inactive. Kinetics of plasmid DNA hydrolysis was also investigated by agarose electrophoresis and it indicated typical single-exponential cleavage reaction. The hydrolytic mechanism of DNA cleavage was confirmed by the successful ligation of hydrolysis product by T4 ligase. The NMR study of the solutions of the complexes in various buffers indicated that the complexes exist as monomeric cationic complexes [LnL(H(2)O)(3)](3+) in slightly acidic solutions and as dimeric cationic complexes [Ln(2)L(2)(μ-OH)(2)(H(2)O)(2)](4+) in slightly basic 8mM solutions, with the latter form being a possible catalyst for hydrolysis of phosphodiester bonds.

  5. Cleavage Specificity Analysis of Six Type II Transmembrane Serine Proteases (TTSPs) Using PICS with Proteome-Derived Peptide Libraries

    PubMed Central

    Béliveau, François; Leduc, Richard; Overall, Christopher M.

    2014-01-01

    Background Type II transmembrane serine proteases (TTSPs) are a family of cell membrane tethered serine proteases with unclear roles as their cleavage site specificities and substrate degradomes have not been fully elucidated. Indeed just 52 cleavage sites are annotated in MEROPS, the database of proteases, their substrates and inhibitors. Methodology/Principal Finding To profile the active site specificities of the TTSPs, we applied Proteomic Identification of protease Cleavage Sites (PICS). Human proteome-derived database searchable peptide libraries were assayed with six human TTSPs (matriptase, matriptase-2, matriptase-3, HAT, DESC and hepsin) to simultaneously determine sequence preferences on the N-terminal non-prime (P) and C-terminal prime (P’) sides of the scissile bond. Prime-side cleavage products were isolated following biotinylation and identified by tandem mass spectrometry. The corresponding non-prime side sequences were derived from human proteome databases using bioinformatics. Sequencing of 2,405 individual cleaved peptides allowed for the development of the family consensus protease cleavage site specificity revealing a strong specificity for arginine in the P1 position and surprisingly a lysine in P1′ position. TTSP cleavage between R↓K was confirmed using synthetic peptides. By parsing through known substrates and known structures of TTSP catalytic domains, and by modeling the remainder, structural explanations for this strong specificity were derived. Conclusions Degradomics analysis of 2,405 cleavage sites revealed a similar and characteristic TTSP family specificity at the P1 and P1′ positions for arginine and lysine in unfolded peptides. The prime side is important for cleavage specificity, thus making these proteases unusual within the tryptic-enzyme class that generally has overriding non-prime side specificity. PMID:25211023

  6. Copper-dependent inhibition and oxidative inactivation with affinity cleavage of yeast glutathione reductase.

    PubMed

    Murakami, Keiko; Tsubouchi, Ryoko; Fukayama, Minoru; Yoshino, Masataka

    2014-06-01

    Effects of copper on the activity and oxidative inactivation of yeast glutathione reductase were analyzed. Glutathione reductase from yeast was inhibited by cupric ion and more potently by cuprous ion. Copper ion inhibited the enzyme noncompetitively with respect to the substrate GSSG and NADPH. The Ki values of the enzyme for Cu(2+) and Cu(+) ion were determined to be 1 and 0.35 μM, respectively. Copper-dependent inactivation of glutathione reductase was also analyzed. Hydrogen peroxide and copper/ascorbate also caused an inactivation with the cleavage of peptide bond of the enzyme. The inactivation/fragmentation of the enzyme was prevented by addition of catalase, suggesting that hydroxyl radical produced through the cuprous ion-dependent reduction of oxygen is responsible for the inactivation/fragmentation of the enzyme. SDS-PAGE and TOF-MS analysis confirmed eight fragments, which were further determined to result from the cleavage of the Met17-Ser18, Asn20-Thr21, Glu251-Gly252, Ser420-Pro421, Pro421-Thr422 bonds of the enzyme by amino-terminal sequencing analysis. Based on the kinetic analysis and no protective effect of the substrates, GSSG and NADPH on the copper-mediated inactivation/fragmentation of the enzyme, copper binds to the sites apart from the substrate-sites, causing the peptide cleavage by hydroxyl radical. Copper-dependent oxidative inactivation/fragmentation of glutathione reductase can explain the prooxidant properties of copper under the in vivo conditions.

  7. Reaction between radicals and N-alkoxyamines As coordinated cleavage with fragmentation

    NASA Astrophysics Data System (ADS)

    Denisov, E. T.; Shestakov, A. F.

    2015-08-01

    Quantum chemical calculations of the enthalpy and activation energy of two reactions with MeO{2/⊙} attacking the CH- and CH2-groups of 2,2,6,6-tetramethylpiperidineoxy-2'-butane are performed. It is shown that the cleavage of hydrogen atoms is accompanied by coordinated breaking of N-O-bonds in the former case and C-O-bonds in the latter. Based on the obtained results, a new scheme is proposed for the cyclic mechanism behind the cleavage of chains on nitroxyl radicals in oxidizing hydrocarbons and polymers that agrees with experimental data. At the center of this cyclic mechanism lies the fast exothermic reaction between peroxyl radicals and N-alkoxyamine with the cleavage of H atoms and the coordinated fragmentation of molecules. Using the model of intersecting parabolas, an algorithm for calculating the enthalpies, activation energies, and rate constants of these reactions with the participation of alkyl, alkoxy, aminyl, peroxyl, phenoxyl, thiyl, and hydroxyl radicals is proposed.

  8. Unexpected Trypsin Cleavage at Ubiquitinated Lysines

    PubMed Central

    2015-01-01

    Unexpected tryptic cleavage has been characterized at modified K48 residues in polyubiquitins. In particular, the tryptic products of all seven of the lysine-linked dimers of ubiquitin and of three trimers—linear Ub–48Ub–48Ub, linear Ub–63Ub–63Ub, and the branched trimer [Ub]2–6,48Ub—have been analyzed. In addition to the peptide products expected under commonly used tryptic conditions, we observe that peptides are formed with an unexpected ε-glycinylglycinyl-Lys carboxyl terminus when the site of linkage is Lys48. Trypsin from three different commercial sources exhibited this aberration. Initial cleavage at R74 is proposed in a distal ubiquitin to produce a glycinylglycinyl-lysine residue which is bound by trypsin. PMID:26182167

  9. 31 CFR 315.30 - Series E bonds and savings notes.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 31 Money and Finance:Treasury 2 2013-07-01 2013-07-01 false Series E bonds and savings notes. 315... BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.30 Series E bonds and savings notes. Series E bonds and savings notes are discount securities. The accrued interest...

  10. 31 CFR 315.30 - Series E bonds and savings notes.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false Series E bonds and savings notes. 315... BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.30 Series E bonds and savings notes. Series E bonds and savings notes are discount securities. The accrued interest...

  11. 31 CFR 315.30 - Series E bonds and savings notes.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 31 Money and Finance:Treasury 2 2012-07-01 2012-07-01 false Series E bonds and savings notes. 315... BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.30 Series E bonds and savings notes. Series E bonds and savings notes are discount securities. The accrued interest...

  12. On the Relative Merits of Non-Orthogonal and Orthogonal Valence Bond Methods Illustrated on the Hydrogen Molecule

    ERIC Educational Resources Information Center

    Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul

    2008-01-01

    Valence bond (VB) is one of the cornerstone theories of quantum chemistry. Even if in practical applications the molecular orbital (MO) approach has obtained more attention, some basic chemical concepts (such as the nature of the chemical bond and the failure of the single determinant-based MO methods in describing the bond cleavage) are normally…

  13. Chronology for the Aegean Late Bronze Age 1700-1400 B.C.

    PubMed

    Manning, Sturt W; Ramsey, Christopher Bronk; Kutschera, Walter; Higham, Thomas; Kromer, Bernd; Steier, Peter; Wild, Eva M

    2006-04-28

    Radiocarbon (carbon-14) data from the Aegean Bronze Age 1700-1400 B.C. show that the Santorini (Thera) eruption must have occurred in the late 17th century B.C. By using carbon-14 dates from the surrounding region, cultural phases, and Bayesian statistical analysis, we established a chronology for the initial Aegean Late Bronze Age cultural phases (Late Minoan IA, IB, and II). This chronology contrasts with conventional archaeological dates and cultural synthesis: stretching out the Late Minoan IA, IB, and II phases by approximately 100 years and requiring reassessment of standard interpretations of associations between the Egyptian and Near Eastern historical dates and phases and those in the Aegean and Cyprus in the mid-second millennium B.C.

  14. Carotenoid Cleavage Oxygenases from Microbes and Photosynthetic Organisms: Features and Functions

    PubMed Central

    Ahrazem, Oussama; Gómez-Gómez, Lourdes; Rodrigo, María J.; Avalos, Javier; Limón, María Carmen

    2016-01-01

    Apocarotenoids are carotenoid-derived compounds widespread in all major taxonomic groups, where they play important roles in different physiological processes. In addition, apocarotenoids include compounds with high economic value in food and cosmetics industries. Apocarotenoid biosynthesis starts with the action of carotenoid cleavage dioxygenases (CCDs), a family of non-heme iron enzymes that catalyze the oxidative cleavage of carbon–carbon double bonds in carotenoid backbones through a similar molecular mechanism, generating aldehyde or ketone groups in the cleaving ends. From the identification of the first CCD enzyme in plants, an increasing number of CCDs have been identified in many other species, including microorganisms, proving to be a ubiquitously distributed and evolutionarily conserved enzymatic family. This review focuses on CCDs from plants, algae, fungi, and bacteria, describing recent progress in their functions and regulatory mechanisms in relation to the different roles played by the apocarotenoids in these organisms. PMID:27792173

  15. Carotenoid Cleavage Oxygenases from Microbes and Photosynthetic Organisms: Features and Functions.

    PubMed

    Ahrazem, Oussama; Gómez-Gómez, Lourdes; Rodrigo, María J; Avalos, Javier; Limón, María Carmen

    2016-10-26

    Apocarotenoids are carotenoid-derived compounds widespread in all major taxonomic groups, where they play important roles in different physiological processes. In addition, apocarotenoids include compounds with high economic value in food and cosmetics industries. Apocarotenoid biosynthesis starts with the action of carotenoid cleavage dioxygenases (CCDs), a family of non-heme iron enzymes that catalyze the oxidative cleavage of carbon-carbon double bonds in carotenoid backbones through a similar molecular mechanism, generating aldehyde or ketone groups in the cleaving ends. From the identification of the first CCD enzyme in plants, an increasing number of CCDs have been identified in many other species, including microorganisms, proving to be a ubiquitously distributed and evolutionarily conserved enzymatic family. This review focuses on CCDs from plants, algae, fungi, and bacteria, describing recent progress in their functions and regulatory mechanisms in relation to the different roles played by the apocarotenoids in these organisms.

  16. General access to taiwaniaquinoids based on a hypothetical abietane C7-C8 cleavage biogenetic pathway.

    PubMed

    Tapia, Rubén; Guardia, Juan J; Alvarez, Esteban; Haidöur, Ali; Ramos, Jose M; Alvarez-Manzaneda, Ramón; Chahboun, Rachid; Alvarez-Manzaneda, Enrique

    2012-01-06

    A new strategy for synthesizing taiwaniaquinoids, a group of terpenoids with an unusual rearranged 5(6→7) or 6-nor-5(6→7)abeo-abietane skeleton, which exhibit promising biological activities, is reported. The procedure, based on the cleavage of the C7-C8 double bond of abietane diterpenes, is the only one yet reported for synthesizing C(20) taiwaniaquinoids bearing a carbon function on the cyclopentane B ring; it is also applicable to the synthesis of the wide variety of existing taiwaniaquinoids. Utilizing this, (-)-taiwaniaquinone A, F, G, and H, (-)-taiwaniaquinol B, and (-)-dichroanone have been synthesized from (+)-abietic acid. The versatility of this strategy allows us to propose the abietane C7-C8 cleavage as a possible biosynthetic pathway to this type of rearranged diterpenes; this proposal seems to be supported by phytochemical evidence.

  17. Bulk superhard B-C-N nanocomposite compact and method for preparing thereof

    DOEpatents

    Zhao, Yusheng; He, Duanwei

    2004-07-06

    Bulk, superhard, B-C-N nanocomposite compact and method for preparing thereof. The bulk, superhard, nanocomposite compact is a well-sintered compact and includes nanocrystalline grains of at least one high-pressure phase of B-C-N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compact has a Vicker's hardness of about 41-68 GPa. It is prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture, and sintering the encapsulated ball-milled mixture at a pressure of about 5-25 GPa and at a temperature of about 1000-2500 K.

  18. Syntheses and properties of B-C-N and BN nanostructures.

    PubMed

    Ma, Renzhi; Golberg, Dmitri; Bando, Yoshio; Sasaki, Takayoshi

    2004-10-15

    The current status of research on boron-carbon-nitrogen (B-C-N) and boron nitride (BN) nanotubes is presented. The latest achievements in syntheses, analyses and property measurements of these nanoscale tubular architectures are reviewed. The characteristic features of B-C-N and BN nanotubes, compared with conventional C nanotubes, are paid special attention. In particular, the latest breakthroughs in the chemical vapour deposition synthesis of BN nanotubes and an insight into their unique structures are highlighted. A wide range of potential applications is also envisaged, based on the recent progress, which includes pioneering results in BN nanocable fabrication, gas adsorption, electron transport and field emission measurements.

  19. A New Solution to the Matrix Equation X−AX¯B=C

    PubMed Central

    2014-01-01

    We investigate the matrix equation X−AX¯B=C. For convenience, the matrix equation X−AX¯B=C is named as Kalman-Yakubovich-conjugate matrix equation. The explicit solution is constructed when the above matrix equation has unique solution. And this solution is stated as a polynomial of coefficient matrices of the matrix equation. Moreover, the explicit solution is also expressed by the symmetric operator matrix, controllability matrix, and observability matrix. The proposed approach does not require the coefficient matrices to be in arbitrary canonical form. At the end of this paper, the numerical example is shown to illustrate the effectiveness of the proposed method. PMID:25133243

  20. Yankee bonds

    SciTech Connect

    Delaney, P. )

    1993-10-01

    Yankee and Euromarket bonds may soon find their way into the financing of power projects in Latin America. For developers seeking long-term commitments under build, own, operate, and transfer (BOOT) power projects in Latin America, the benefits are substantial.

  1. Intein-Promoted Cyclization of Aspartic Acid Flanking the Intein Leads to Atypical N-Terminal Cleavage.

    PubMed

    Minteer, Christopher J; Siegart, Nicolle M; Colelli, Kathryn M; Liu, Xinyue; Linhardt, Robert J; Wang, Chunyu; Gomez, Alvin V; Reitter, Julie N; Mills, Kenneth V

    2017-02-28

    Protein splicing is a post-translational reaction facilitated by an intein, or intervening protein, which involves the removal of the intein and the ligation of the flanking polypeptides, or exteins. A DNA polymerase II intein from Pyrococcus abyssi (Pab PolII intein) can promote protein splicing in vitro on incubation at high temperature. Mutation of active site residues Cys1, Gln185, and Cys+1 to Ala results in an inactive intein precursor, which cannot promote the steps of splicing, including cleavage of the peptide bond linking the N-extein and intein (N-terminal cleavage). Surprisingly, coupling the inactivating mutations to a change of the residue at the C-terminus of the N-extein (N-1 residue) from the native Asn to Asp reactivates N-terminal cleavage at pH 5. Similar "aspartic acid effects" have been observed in other proteins and peptides but usually only occur at lower pH values. In this case, however, the unusual N-terminal cleavage is abolished by mutations to catalytic active site residues and unfolding of the intein, indicating that this cleavage effect is mediated by the intein active site and the intein fold. We show via mass spectrometry that the reaction proceeds through cyclization of Asp resulting in anhydride formation coupled to peptide bond cleavage. Our results add to the richness of the understanding of the mechanism of protein splicing and provide insight into the stability of proteins at moderately low pH. The results also explain, and may help practitioners avoid, a side reaction that may complicate intein applications in biotechnology.

  2. 47 CFR 52.12 - North American Numbering Plan Administrator and B&C Agent.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... B&C Agent. 52.12 Section 52.12 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED... Agent will conduct their respective operations with oversight from the Federal Communications Commission (the “Commission”) and with recommendations from the North American Numbering Council (“NANC”)....

  3. Presenting Computer Literacy for the B.C. Generation at the Smithsonian Institution.

    ERIC Educational Resources Information Center

    Martin, C. Dianne; Heller, Rachelle S.

    1984-01-01

    Though computer literacy has become a key educational issue of the 1980s, little attention has been paid to adults over the age of 25 who received their formal education Before Computers (B.C.). One-day seminars (developed at the request of the Smithsonian Institution) designed to satisfy this need are described. (JN)

  4. Instructional Media Production for Early Childhood Education: A. B. C. Jig-Saw Puzzle, a Model

    ERIC Educational Resources Information Center

    Yusuf, Mudashiru Olalere; Olanrewaju, Olatayo Solomon; Soetan, Aderonke K.

    2015-01-01

    In this paper, a. b. c. jig-saw puzzle was produced for early childhood education using local materials. This study was a production based type of research, to serve as a supplemental or total learning resource. Its production followed four phases of development referred to as information, design, production and evaluation. The storyboard cards,…

  5. The Comet Of 44 B.C. and Caesar's Funeral Games

    NASA Astrophysics Data System (ADS)

    Ramsey, John T.; Licht, A. Lewis

    1997-05-01

    Using insights from physics and classics, this book explores the social and cultural implications of the spectacular, daylight comet that was observed in 44 B.C. during the games that the future emperor Augustus gave in honor of the late Julius Caesar.

  6. Spatiotemporal analysis of RhoA/B/C activation in primary human endothelial cells

    PubMed Central

    Reinhard, Nathalie R.; van Helden, Suzanne F.; Anthony, Eloise C.; Yin, Taofei; Wu, Yi I.; Goedhart, Joachim; Gadella, Theodorus W. J.; Hordijk, Peter L.

    2016-01-01

    Endothelial cells line the vasculature and are important for the regulation of blood pressure, vascular permeability, clotting and transendothelial migration of leukocytes and tumor cells. A group of proteins that that control the endothelial barrier function are the RhoGTPases. This study focuses on three homologous (>88%) RhoGTPases: RhoA, RhoB, RhoC of which RhoB and RhoC have been poorly characterized. Using a RhoGTPase mRNA expression analysis we identified RhoC as the highest expressed in primary human endothelial cells. Based on an existing RhoA FRET sensor we developed new RhoB/C FRET sensors to characterize their spatiotemporal activation properties. We found all these RhoGTPase sensors to respond to physiologically relevant agonists (e.g. Thrombin), reaching transient, localized FRET ratio changes up to 200%. These RhoA/B/C FRET sensors show localized GEF and GAP activity and reveal spatial activation differences between RhoA/C and RhoB. Finally, we used these sensors to monitor GEF-specific differential activation of RhoA/B/C. In summary, this study adds high-contrast RhoB/C FRET sensors to the currently available FRET sensor toolkit and uncover new insights in endothelial and RhoGTPase cell biology. This allows us to study activation and signaling by these closely related RhoGTPases with high spatiotemporal resolution in primary human cells. PMID:27147504

  7. 24 CFR 964.18 - HA role in activities under subparts B & C.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 24 Housing and Urban Development 4 2011-04-01 2011-04-01 false HA role in activities under subparts B & C. 964.18 Section 964.18 Housing and Urban Development REGULATIONS RELATING TO HOUSING AND... opportunities for skills training for public housing residents. To the extent possible, the training...

  8. 24 CFR 964.18 - HA role in activities under subparts B & C.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 24 Housing and Urban Development 4 2014-04-01 2014-04-01 false HA role in activities under subparts B & C. 964.18 Section 964.18 Housing and Urban Development REGULATIONS RELATING TO HOUSING AND... opportunities for skills training for public housing residents. To the extent possible, the training...

  9. 48 CFR 1827.303 - Contract clauses. (NASA supplements paragraphs (a), (b), (c) and (d))

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true Contract clauses. (NASA supplements paragraphs (a), (b), (c) and (d)) 1827.303 Section 1827.303 Federal Acquisition Regulations System....303(d)(1) (i) through (iv) is met, the contracting officer shall consult with the...

  10. Ancient Skeletal Evidence for Leprosy in India (2000 B.C.)

    PubMed Central

    Robbins, Gwen; Tripathy, V. Mushrif; Misra, V. N.; Mohanty, R. K.; Shinde, V. S.; Gray, Kelsey M.; Schug, Malcolm D.

    2009-01-01

    Background Leprosy is a chronic infectious disease caused by Mycobacterium leprae that affects almost 250,000 people worldwide. The timing of first infection, geographic origin, and pattern of transmission of the disease are still under investigation. Comparative genomics research has suggested M. leprae evolved either in East Africa or South Asia during the Late Pleistocene before spreading to Europe and the rest of the World. The earliest widely accepted evidence for leprosy is in Asian texts dated to 600 B.C. Methodology/Principal Findings We report an analysis of pathological conditions in skeletal remains from the second millennium B.C. in India. A middle aged adult male skeleton demonstrates pathological changes in the rhinomaxillary region, degenerative joint disease, infectious involvement of the tibia (periostitis), and injury to the peripheral skeleton. The presence and patterning of lesions was subject to a process of differential diagnosis for leprosy including treponemal disease, leishmaniasis, tuberculosis, osteomyelitis, and non-specific infection. Conclusions/Significance Results indicate that lepromatous leprosy was present in India by 2000 B.C. This evidence represents the oldest documented skeletal evidence for the disease. Our results indicate that Vedic burial traditions in cases of leprosy were present in northwest India prior to the first millennium B.C. Our results also support translations of early Vedic scriptures as the first textual reference to leprosy. The presence of leprosy in skeletal material dated to the post-urban phase of the Indus Age suggests that if M. leprae evolved in Africa, the disease migrated to India before the Late Holocene, possibly during the third millennium B.C. at a time when there was substantial interaction among the Indus Civilization, Mesopotamia, and Egypt. This evidence should be impetus to look for additional skeletal and molecular evidence of leprosy in India and Africa to confirm the African origin of

  11. In-line alignment and Mg2+ coordination at the cleavage site of the env22 twister ribozyme

    PubMed Central

    Ren, Aiming; Košutić, Marija; Rajashankar, Kanagalaghatta R.; Frener, Marina; Santner, Tobias; Westhof, Eric; Micura, Ronald; Patel, Dinshaw J.

    2015-01-01

    Small self-cleaving nucleolytic ribozymes contain catalytic domains that accelerate site-specific cleavage/ligation of phosphodiester backbones. We report on the 2.9-Å crystal structure of the env22 twister ribozyme, which adopts a compact tertiary fold stabilized by co-helical stacking, double-pseudoknot formation and long-range pairing interactions. The U-A cleavage site adopts a splayed-apart conformation with the modeled 2′-O of U positioned for in-line attack on the adjacent to-be-cleaved P-O5′ bond. Both an invariant guanosine and a Mg2+ are directly coordinated to the non-bridging phosphate oxygens at the U-A cleavage step, with the former positioned to contribute to catalysis and the latter to structural integrity. The impact of key mutations on cleavage activity identified an invariant guanosine that contributes to catalysis. Our structure of the in-line aligned env22 twister ribozyme is compared with two recently-reported twister ribozymes structures, which adopt similar global folds, but differ in conformational features around the cleavage site. PMID:25410397

  12. Diffusion bonding

    DOEpatents

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  13. Activity dependent CAM cleavage and neurotransmission

    PubMed Central

    Conant, Katherine; Allen, Megan; Lim, Seung T.

    2015-01-01

    Spatially localized proteolysis represents an elegant means by which neuronal activity dependent changes in synaptic structure, and thus experience dependent learning and memory, can be achieved. In vitro and in vivo studies suggest that matrix metalloproteinase and adamalysin activity is concentrated at the cell surface, and emerging evidence suggests that increased peri-synaptic expression, release and/or activation of these proteinases occurs with enhanced excitatory neurotransmission. Synaptically expressed cell adhesion molecules (CAMs) could therefore represent important targets for neuronal activity-dependent proteolysis. Several CAM subtypes are expressed at the synapse, and their cleavage can influence the efficacy of synaptic transmission through a variety of non-mutually exclusive mechanisms. In the following review, we discuss mechanisms that regulate neuronal activity-dependent synaptic CAM shedding, including those that may be calcium dependent. We also highlight CAM targets of activity-dependent proteolysis including neuroligin and intercellular adhesion molecule-5 (ICAM-5). We include discussion focused on potential consequences of synaptic CAM shedding, with an emphasis on interactions between soluble CAM cleavage products and specific pre- and post-synaptic receptors. PMID:26321910

  14. Autocatalytic cyclization of an excised intervening sequence RNA is a cleavage-ligation reaction.

    PubMed

    Zaug, A J; Grabowski, P J; Cech, T R

    The intervening sequence (IVS) of the Tetrahymena ribosomal RNA precursor is excised as a linear RNA molecule which subsequently cyclizes itself in a protein-independent reaction. Cyclization involves cleavage of the linear IVS RNA 15 nucleotides from its 5' end and formation of a phosphodiester bond between the new 5' phosphate and the original 3'-hydroxyl terminus of the IVS. This recombination mechanism is analogous to that by which splicing of the precursor RNA is achieved. The circular molecules appear to have no direct function in RNA splicing, and we propose the cyclization serves to prevent unwanted RNA from driving the splicing reactions backwards.

  15. Mechanochemistry: one bond at a time.

    PubMed

    Liang, Jian; Fernández, Julio M

    2009-07-28

    Single-molecule force-clamp spectroscopy offers a novel platform for mechanically denaturing proteins by applying a constant force to a polyprotein. A powerful emerging application of the technique is that, by introducing a disulfide bond in each protein module, the chemical kinetics of disulfide bond cleavage under different stretching forces can be probed at the single-bond level. Even at forces much lower than that which can rupture the chemical bond, the breaking of the S-S bond at the presence of various chemical reducing agents is significantly accelerated. Our previous work demonstrated that the rate of thiol/disulfide exchange reaction is force-dependent and well-described by an Arrhenius term of the form r = A(exp((FΔx(r) - E(a))/k(B)T)[nucleophile]). From Arrhenius fits to the force dependency of the reduction rate, we measured the bond elongation parameter, Δx(r), along the reaction coordinate to the transition state of the S(N)2 reaction cleaved by different nucleophiles and enzymes, never before observed by any other technique. For S-S cleavage by various reducing agents, obtaining the Δx(r) value can help depicting the energy landscapes and elucidating the mechanisms of the reactions at the single-molecule level. Small nucleophiles, such as 1,4-dl-dithiothreitol (DTT), tris(2-carboxyethyl)phosphine (TCEP), and l-cysteine, react with the S-S bond with monotonically increasing rates under the applied force, while thioredoxin enzymes exhibit both stretching-favored and -resistant reaction-rate regimes. These measurements demonstrate the power of the single-molecule force-clamp spectroscopy approach in providing unprecedented access to chemical reactions.

  16. 31 CFR 315.26 - Application for relief-after receipt of bond.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Relief for Loss, Theft... of a mutilated bond should be submitted to the Bureau. (d) Execution of claims application....

  17. First-Principles Calculations of the Ideal Cleavage Energy of Bulk Niobium(111)/ α-Alumina(0001) Interfaces

    NASA Astrophysics Data System (ADS)

    Batirev, I. G.; Alavi, A.; Finnis, M. W.; Deutsch, T.

    1999-02-01

    We report ab initio calculations of the work of adhesion for O- and Al-terminated Nb(111)/ α-alumina(0001) interfaces. Strong ionic bonds formed by Nb4 d --> O2 p electron donation account for the high adhesive strength of O-terminated interfaces. However, cleavage preferentially occurs between metal atoms at both O- and Al-terminated interfaces, and their adhesion has both covalent and ionic character.

  18. [On the Features of Embryonic Cleavage in Diverse Fish Species].

    PubMed

    Desnitskiy, A G

    2015-01-01

    Literature on the earliest steps of fish embryogenesis (including a number of "non-model" species) has been considered. The main attention has been paid to the loss of cleavage division synchrony and the first latitudinal cleavage furrow. In teleostean embryos, the features of their meroblastic cleavage are not rigidly associated with egg size. The midblastula transition (in a form clearly enough) occurs in some chondrostean and teleostean fishes, but it has not been detected in the representatives of sarcopterygian and chondrichthyan fishes.

  19. Early cleavage in Phoronis muelleri (Phoronida) displays spiral features.

    PubMed

    Pennerstorfer, Markus; Scholtz, Gerhard

    2012-01-01

    The view that early cleavage in Phoronida follows a radial pattern is widely accepted. However, data supporting this characterization are ambiguous. Studies have been repeatedly reporting variation between individual embryos, and the occurrence of embryos exhibiting oblique divisions or nonradial cell arrangements. Such embryos were often considered to represent variation within radial cleavage, or artificial appearances. Cleavage in Phoronis muelleri was previously characterized as "derived radial," but also oblique spindles and cell elongations, and shifted cell arrangements were observed. We studied the early cleavage in P. muelleri applying 4D microscopy, fluorescent staining, and confocal laser scanning microscopy. To deal with the problem of variation we provide statistical evaluations of our data. These show that oblique divisions do not represent variational abnormalities. In fact, they reveal that most cells divide obliquely from the third cleavage onwards. What is more, in almost all cells the axis of the third cleavage is inclined dextrally. The fourth cleavage is even stronger sinistrally pronounced. Subsequently, the pattern of alternating cleavage orientation is largely restricted to animal and vegetal blastomeres. As a result of the obliqueness of divisions, four cells encircle the poles in most embryos. Cross furrows are occasionally present. We found no indications for radial cleavage in P. muelleri. In contrast, the observed cleavage displays several characters consistent with the pattern of spiral cleavage. A close relation of phoronid and spiralian cleavage is also suggested by molecular phylogenies, allying both groups in the Lophotrochozoa. We suggest our findings to represent morphological support for this lophotrochozoan/spiralian affinity of Phoronida.

  20. Evidence for New Madrid earthquakes in A.D. 300 and 2350 B.C

    USGS Publications Warehouse

    Tuttle, M.P.; Schweig, E. S.; Campbell, J.; Thomas, P.M.; Sims, J.D.; Lafferty, R. H.

    2005-01-01

    Six episodes of earthquake-induced liquefaction are associated with soil horizons containing artifacts of the Late Archaic (3000-500 B.C.) and Early to Middle Woodland (500 B.C.-A.D. 400) cultural periods at the Burkett archaeological site in the northern part of the New Madrid seismic zone, where little information about prehistoric earthquakes has been available. Radiocarbon dating of organic material and analysis of artifacts are used to estimate the ages of the liquefaction features and times of the causative earthquakes. The most recent episode of liquefaction occurred after A.D. 1670, produced small sand dikes, and is probably related to the 1895 Charleston, Missouri earthquake. The preceding episode struck the area in A.D. 300 ?? 200 years and generated a sand blow that contains Late Woodland artifacts and buries an Early to Middle Woodland cultural horizon. Four older episodes of liquefaction occurred in 2350 B.C. ?? 200 years and may have been produced by a sequence of closely timed earthquakes. The four earlier episodes produced graben structures, sand dikes, and associated sand blows on which a cultural mound was constructed. The Burkett liquefaction features that formed about 2350 B.C. and A.D. 300 are relatively large and similar in age to other liquefaction features in northeastern Arkansas and southeastern Missouri, respectively. If the prehistoric features at the Burkett site and those of similar age elsewhere in the region are the result of the same earthquakes, then this suggests that they were similar in size to the three largest (M 7-8) 1811-1812 New Madrid earthquakes. A New Madrid-type earthquake in A.D. 300 ?? 200 years would support an average recurrence time of 500 years. Although this study extends the earthquake chronology back to 2500 B.C., it is uncertain that the record of New Madrid events is complete for the period between 2350 B.C. and A.D. 300. As demonstrated by this study, information about other prehistoric earthquakes may be

  1. Pi Bond Orders and Bond Lengths

    ERIC Educational Resources Information Center

    Herndon, William C.; Parkanyi, Cyril

    1976-01-01

    Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

  2. Structural Basis for Accelerated Cleavage of Bovine Pancreatic Trypsin Inhibitor (BPTI) by Human Mesotrypsin

    SciTech Connect

    Salameh,M.; Soares, A.; Hockla, A.; Radisky, E.

    2008-01-01

    Human mesotrypsin is an isoform of trypsin that displays unusual resistance to polypeptide trypsin inhibitors and has been observed to cleave several such inhibitors as substrates. Whereas substitution of arginine for the highly conserved glycine 193 in the trypsin active site has been implicated as a critical factor in the inhibitor resistance of mesotrypsin, how this substitution leads to accelerated inhibitor cleavage is not clear. Bovine pancreatic trypsin inhibitor (BPTI) forms an extremely stable and cleavage-resistant complex with trypsin, and thus provides a rigorous challenge of mesotrypsin catalytic activity toward polypeptide inhibitors. Here, we report kinetic constants for mesotrypsin and the highly homologous (but inhibitor sensitive) human cationic trypsin, describing inhibition by, and cleavage of BPTI, as well as crystal structures of the mesotrypsin-BPTI and human cationic trypsin-BPTI complexes. We find that mesotrypsin cleaves BPTI with a rate constant accelerated 350-fold over that of human cationic trypsin and 150,000-fold over that of bovine trypsin. From the crystal structures, we see that small conformational adjustments limited to several side chains enable mesotrypsin-BPTI complex formation, surmounting the predicted steric clash introduced by Arg-193. Our results show that the mesotrypsin-BPTI interface favors catalysis through (a) electrostatic repulsion between the closely spaced mesotrypsin Arg-193 and BPTI Arg-17, and (b) elimination of two hydrogen bonds between the enzyme and the amine leaving group portion of BPTI. Our model predicts that these deleterious interactions accelerate leaving group dissociation and deacylation.

  3. Study of semileptonic {\\rm{\\Upsilon }}({nS}) \\rightarrow {B}_{c}{\\ell }{\\bar{\

    NASA Astrophysics Data System (ADS)

    Chang, Qin; Zhu, Jie; Wang, Xiao-Lin; Sun, Jun-Feng; Yang, Yue-Ling

    2017-01-01

    In this paper, the tree-dominated and CKM-favored {{\\Upsilon }}({nS})\\to {B}c{\\ell }{\\bar{ν }}{\\ell } (n=1,2,3) decays are studied within the Standard Model. The theoretical predictions and some discussions for the observables including the branching fractions, the ratios {R}{{\\Upsilon }({nS})}, the lepton spin asymmetries and the forward-backward asymmetries are presented. Numerically, the {{\\Upsilon }}({nS})\\to {B}c{\\ell }{\\bar{ν }}{\\ell } decays have relatively large branching fractions of the order { O }({10}-10{--}{10}-9). In addition, the feasibility of measuring these decay modes at the current heavy-flavor experiments (LHCb, CMS and Belle-II) are discussed.

  4. Construction of the Tricyclic A-B-C Core of the Veratrum Alkaloids

    PubMed Central

    Taber, Douglass F.; Berry, James F.

    2014-01-01

    Organocatalyzed enantioselective allylation of 2-iodocyclohexenone followed by methylation and oxy-Cope rearrangement delivered enantiomerically-enriched 2-methyl 3-allyl cyclohexanone, that engaged in acid-catalyzed Robinson annulation to give the bicyclic enone. Subsequent elaboration of the pendant allyl group into an α-diazo β-keto ester set the stage for Rh-mediated cyclization to deliver the tricyclic A-B-C core of the Veratrum alkaloids. PMID:23859604

  5. PROCESS WATER BUILDING, TRA605. SECTIONS B, C AND D SHOW ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    PROCESS WATER BUILDING, TRA-605. SECTIONS B, C AND D SHOW RELATIONSHIP BETWEEN FLASH EVAPORATORS (ABOVE) AND SEAL AND SUMP TANKS (BELOW). BASEMENT FLOOR IS BELOW GRADE; FIRST FLOOR, ABOVE GRADE. SHIELDING TOLERANCES. BLAW-KNOX 3150-5-7, 8/1950. INL INDEX NO. 531-605-00-098-100012, REV. 2. - Idaho National Engineering Laboratory, Test Reactor Area, Materials & Engineering Test Reactors, Scoville, Butte County, ID

  6. Brittle to ductile transition in cleavage fracture

    SciTech Connect

    Argon, A.S.; Berg, Q.

    1992-09-30

    The problem of interpretation of fracture transition from brittle to ductile or vice versa is the subject of study. An instrumented tapered double cantilever beam (TDCB) has been developed as a definitive tool in the study of the intrinsic mechanism in single crystalline samples. In this experiment, the crack velocity is directly proportional to actuator velocity. In experiments performed on TDCB shaped Si single crystals, oriented for cleavage on either [l brace]111[r brace] or [l brace]110[r brace] planes, a number of troubling features of jerky carck extension were encountered. Evidence suggests that nucleation of dislocation loops from crack tip is easier than moving these dislocations away from crack tip. 14 refs, 1 fig.

  7. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.

    2014-01-01

    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  8. Lifetime of B_{c}^{-} Mesons Constrains Explanations for Anomalies in B→D^{(*)}τν.

    PubMed

    Alonso, Rodrigo; Grinstein, Benjamín; Martin Camalich, Jorge

    2017-02-24

    We investigate a new constraint on new-physics interpretations of the anomalies observed in B→D^{(*)}τν decays making use of the lifetime of the B_{c}^{-} meson. A constraint is obtained by demanding that the rate for B_{c}^{-}→τ^{-}ν[over ¯] does not exceed the fraction of the total width that is allowed by the calculation of the lifetime in the standard model. This leads to a very strong bound on new-physics scenarios involving scalar operators since they lift the slight, but not negligible, chiral suppression of the B_{c}^{-}→τ^{-}ν[over ¯] amplitude in the standard model. The new constraint renders a scalar interpretation of the enhancement measured in R_{D^{*}} implausible, including explanations implementing extra Higgs doublets or certain classes of leptoquarks. We also discuss the complementarity of R_{D^{(*)}} and a measurement of the longitudinal polarization of the τ in the B→D^{*}τν decay in light of our findings.

  9. On the study of the mechanical properties of Mo-B-C coatings

    NASA Astrophysics Data System (ADS)

    Zábranský, Lukáš; Buršíková, Vilma; Souček, Pavel; Vašina, Petr; Buršík, Jiří

    2016-08-01

    Mo2BC thin films show a favourable combination of high stiffness, hardness and elastic modulus together with moderate ductility. In this study we focused on the comparison of mechanical properties of Mo-B-C thin films with different structures (nanocrystalline or amorphous). The thin films were deposited on steel, hard metal and silicon substrates using DC magnetron sputtering. The mechanical properties of Mo-B-C films were studied using indentation techniques under both quasistatic and dynamic conditions using a wide range of loads from 50 μN up to 1 N. The results showed that even amorphous Mo-B-C thin films had high hardness of 19.5 ± 0.5 GPa and elastic modulus of 276 ± 5 GPa. Their hardness is comparable with the common amorphous diamond-like carbon coatings. Moreover, their fracture toughness is significantly higher. The results of mechanical tests were correlated with microstructure observations carried out using scanning and transmission electron microscopy. The images of the deformed area under the residual indentation imprints showed no cracking even after high loads or after indentation with sharp cube corner indenter. Contribution to the topical issue "6th Central European Symposium on Plasma Chemistry (CESPC-6)", edited by Nicolas Gherardi, Ester Marotta and Cristina Paradisi

  10. Cleavage of nicotinamide adenine dinucleotide by the ribosome-inactivating protein from Momordica charantia.

    PubMed

    Vinkovic, M; Dunn, G; Wood, G E; Husain, J; Wood, S P; Gill, R

    2015-09-01

    The interaction of momordin, a type 1 ribosome-inactivating protein from Momordica charantia, with NADP(+) and NADPH has been investigated by X-ray diffraction analysis of complexes generated by co-crystallization and crystal soaking. It is known that the proteins of this family readily cleave the adenine-ribose bond of adenosine and related nucleotides in the crystal, leaving the product, adenine, bound to the enzyme active site. Surprisingly, the nicotinamide-ribose bond of oxidized NADP(+) is cleaved, leaving nicotinamide bound in the active site in the same position but in a slightly different orientation to that of the five-membered ring of adenine. No binding or cleavage of NADPH was observed at pH 7.4 in these experiments. These observations are in accord with current views of the enzyme mechanism and may contribute to ongoing searches for effective inhibitors.

  11. Bonded Lubricants

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Another spinoff to the food processing industry involves a dry lubricant developed by General Magnaplate Corp. of Linden, N.J. Used in such spacecraft as Apollo, Skylab and Viking, the lubricant is a coating bonded to metal surfaces providing permanent lubrication and corrosion resistance. The coating lengthens equipment life and permits machinery to be operated at greater speed, thus increasing productivity and reducing costs. Bonded lubricants are used in scores of commercia1 applications. They have proved particularly valuable to food processing firms because, while increasing production efficiency, they also help meet the stringent USDA sanitation codes for food-handling equipment. For example, a cookie manufacturer plagued production interruptions because sticky batter was clogging the cookie molds had the brass molds coated to solve the problem. Similarly, a pasta producer faced USDA action on a sanitation violation because dough was clinging to an automatic ravioli-forming machine; use of the anti-stick coating on the steel forming plates solved the dual problem of sanitation deficiency and production line downtime.

  12. The Oxygenase CAO-1 of Neurospora crassa Is a Resveratrol Cleavage Enzyme

    PubMed Central

    Díaz-Sánchez, Violeta; F. Estrada, Alejandro; Limón, M. Carmen; Al-Babili, Salim

    2013-01-01

    The genome of the ascomycete Neurospora crassa encodes CAO-1 and CAO-2, two members of the carotenoid cleavage oxygenase family that target double bonds in different substrates. Previous studies demonstrated the role of CAO-2 in cleaving the C40 carotene torulene, a key step in the synthesis of the C35 apocarotenoid pigment neurosporaxanthin. In this work, we investigated the activity of CAO-1, assuming that it may provide retinal, the chromophore of the NOP-1 rhodopsin, by cleaving β-carotene. For this purpose, we tested CAO-1 activity with carotenoid substrates that were, however, not converted. In contrast and consistent with its sequence similarity to family members that act on stilbenes, CAO-1 cleaved the interphenyl Cα-Cβ double bond of resveratrol and its derivative piceatannol. CAO-1 did not convert five other similar stilbenes, indicating a requirement for a minimal number of unmodified hydroxyl groups in the stilbene background. Confirming its biological function in converting stilbenes, adding resveratrol led to a pronounced increase in cao-1 mRNA levels, while light, a key regulator of carotenoid metabolism, did not alter them. Targeted Δcao-1 mutants were not impaired by the presence of resveratrol, a phytoalexin active against different fungi, which did not significantly affect the growth and development of wild-type Neurospora. However, under partial sorbose toxicity, the Δcao-1 colonies exhibited faster radial growth than control strains in the presence of resveratrol, suggesting a moderate toxic effect of resveratrol cleavage products. PMID:23893079

  13. Alkali Metal Control over N–N Cleavage in Iron Complexes

    PubMed Central

    2015-01-01

    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber–Bosch process, there is still ambiguity about the number of Fe atoms involved during the N–N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe–N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N–N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N–N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2. PMID:25412468

  14. A novel carotenoid cleavage activity involved in the biosynthesis of Citrus fruit-specific apocarotenoid pigments

    PubMed Central

    Rodrigo, María J.; Alquézar, Berta; Al-Babili, Salim

    2013-01-01

    Citrus is the first tree crop in terms of fruit production. The colour of Citrus fruit is one of the main quality attributes, caused by the accumulation of carotenoids and their derivative C30 apocarotenoids, mainly β-citraurin (3-hydroxy-β-apo-8′-carotenal), which provide an attractive orange-reddish tint to the peel of oranges and mandarins. Though carotenoid biosynthesis and its regulation have been extensively studied in Citrus fruits, little is known about the formation of C30 apocarotenoids. The aim of this study was to the identify carotenoid cleavage enzyme(s) [CCD(s)] involved in the peel-specific C30 apocarotenoids. In silico data mining revealed a new family of five CCD4-type genes in Citrus. One gene of this family, CCD4b1, was expressed in reproductive and vegetative tissues of different Citrus species in a pattern correlating with the accumulation of C30 apocarotenoids. Moreover, developmental processes and treatments which alter Citrus fruit peel pigmentation led to changes of β-citraurin content and CCD4b1 transcript levels. These results point to the involvement of CCD4b1 in β-citraurin formation and indicate that the accumulation of this compound is determined by the availability of the presumed precursors zeaxanthin and β-cryptoxanthin. Functional analysis of CCD4b1 by in vitro assays unequivocally demonstrated the asymmetric cleavage activity at the 7′,8′ double bond in zeaxanthin and β-cryptoxanthin, confirming its role in C30 apocarotenoid biosynthesis. Thus, a novel plant carotenoid cleavage activity targeting the 7′,8′ double bond of cyclic C40 carotenoids has been identified. These results suggest that the presented enzyme is responsible for the biosynthesis of C30 apocarotenoids in Citrus which are key pigments in fruit coloration. PMID:24006419

  15. A novel carotenoid cleavage activity involved in the biosynthesis of Citrus fruit-specific apocarotenoid pigments.

    PubMed

    Rodrigo, María J; Alquézar, Berta; Alós, Enriqueta; Medina, Víctor; Carmona, Lourdes; Bruno, Mark; Al-Babili, Salim; Zacarías, Lorenzo

    2013-11-01

    Citrus is the first tree crop in terms of fruit production. The colour of Citrus fruit is one of the main quality attributes, caused by the accumulation of carotenoids and their derivative C30 apocarotenoids, mainly β-citraurin (3-hydroxy-β-apo-8'-carotenal), which provide an attractive orange-reddish tint to the peel of oranges and Mandarins. Though carotenoid biosynthesis and its regulation have been extensively studied in Citrus fruits, little is known about the formation of C30 apocarotenoids. The aim of this study was to the identify carotenoid cleavage enzyme(s) [CCD(s)] involved in the peel-specific C30 apocarotenoids. In silico data mining revealed a new family of five CCD4-type genes in Citrus. One gene of this family, CCD4b1, was expressed in reproductive and vegetative tissues of different Citrus species in a pattern correlating with the accumulation of C30 apocarotenoids. Moreover, developmental processes and treatments which alter Citrus fruit peel pigmentation led to changes of β-citraurin content and CCD4b1 transcript levels. These results point to the involvement of CCD4b1 in β-citraurin formation and indicate that the accumulation of this compound is determined by the availability of the presumed precursors zeaxanthin and β-cryptoxanthin. Functional analysis of CCD4b1 by in vitro assays unequivocally demonstrated the asymmetric cleavage activity at the 7',8' double bond in zeaxanthin and β-cryptoxanthin, confirming its role in C30 apocarotenoid biosynthesis. Thus, a novel plant carotenoid cleavage activity targeting the 7',8' double bond of cyclic C40 carotenoids has been identified. These results suggest that the presented enzyme is responsible for the biosynthesis of C30 apocarotenoids in Citrus which are key pigments in fruit coloration.

  16. DNAzyme hybridization, cleavage, degradation, and sensing in undiluted human blood serum.

    PubMed

    Zhou, Wenhu; Chen, Qingyun; Huang, Po-Jung Jimmy; Ding, Jinsong; Liu, Juewen

    2015-04-07

    RNA-cleaving DNAzymes provide a unique platform for developing biosensors. However, a majority of the work has been performed in clean buffer solutions, while the activity of some important DNAzymes in biological sample matrices is still under debate. Two RNA-cleaving DNAzymes (17E and 10-23) are the most widely used. In this work, we carefully studied a few key aspects of the 17E DNAzyme in human blood serum, including hybridization, cleavage activity, and degradation kinetics. Since direct fluorescence monitoring is difficult due to the opacity of serum, denaturing and nondenaturing gel electrophoresis were combined for studying the interaction between serum proteins and DNAzymes. The 17E DNAzyme retains its activity in 90% human blood serum with a cleavage rate of 0.04 min(-1), which is similar to that in the PBS buffer (0.06 min(-1)) with a similar ionic strength. The activity in serum can be accelerated to 0.3 min(-1) with an additional 10 mM Ca(2+). As compared to 17E, the 10-23 DNAzyme produces negligible cleavage in serum. Degradation of both the substrate and the DNAzyme strand is very slow in serum, especially at room temperature. Degradation occurs mainly at the fluorophore label (linked to DNA via an amide bond) instead of the DNA phosphodiester bonds. Serum proteins can bind more tightly to the 17E DNAzyme complex than to the single-stranded substrate or enzyme. The 17E DNAzyme hybridizes extremely fast in serum. With this understanding, the detection of DNA using the 17E DNAzyme is demonstrated in serum.

  17. Zymogen activation confers thermodynamic stability on a key peptide bond and protects human cationic trypsin from degradation.

    PubMed

    Szabó, András; Radisky, Evette S; Sahin-Tóth, Miklós

    2014-02-21

    Human cationic trypsinogen, precursor of the digestive enzyme trypsin, can be rapidly degraded to protect the pancreas when pathological conditions threaten, while trypsin itself is impressively resistant to degradation. For either form, degradation is controlled by two necessary initial proteolytic events: cleavage of the Leu81-Glu82 peptide bond by chymotrypsin C (CTRC) and cleavage of the Arg122-Val123 peptide bond by trypsin. Here we demonstrate that the Leu81-Glu82 peptide bond of human cationic trypsin, but not trypsinogen, is thermodynamically stable, such that cleavage by CTRC leads to an equilibrium mixture containing 10% cleaved and 90% uncleaved trypsin. When cleaved trypsin was incubated with CTRC, the Leu81-Glu82 peptide bond was re-synthesized to establish the same equilibrium. The thermodynamic stability of the scissile peptide bond was not dependent on CTRC or Leu-81, as re-synthesis was also accomplished by other proteases acting on mutated cationic trypsin. The Leu81-Glu82 peptide bond is located within a calcium binding loop, and thermodynamic stability of the bond was strictly dependent on calcium and on the calcium-coordinated residue Glu-85. Trypsinolytic cleavage of the Arg122-Val123 site was also delayed in trypsin relative to trypsinogen in a calcium-dependent manner, but for this bond cleavage was modulated by kinetic rather than thermodynamic control. Our results reveal that the trypsinogen to trypsin conformational switch modulates cleavage susceptibility of nick sites by altering both the thermodynamics and kinetics of cleavage to protect human cationic trypsin from premature degradation.

  18. 48 CFR 1827.409 - Solicitation provisions and contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e...

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e), (i), and (k)) 1827.409 Section 1827... provisions and contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e), (i), and (k)) (a) The..., Rights in Data—Special Works by adding paragraph (f) as set forth in 1852.227-17. (k)(i) The...

  19. 48 CFR 1827.302 - Policy. (NASA supplements paragraphs (a), (b), (c), (d), (e), (f), (g), and (i)).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... paragraphs (a), (b), (c), (d), (e), (f), (g), and (i)). 1827.302 Section 1827.302 Federal Acquisition... paragraphs (a), (b), (c), (d), (e), (f), (g), and (i)). (a) Introduction. (i) NASA policy with respect to any.... (c) Government license. For each subject invention made in the performance of work under a...

  20. 48 CFR 1827.409 - Solicitation provisions and contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e...

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... and contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e), (i), and (k)) 1827.409... Solicitation provisions and contract clauses. (NASA supplements paragraph (a), (b), (c), (d), (e), (i), and (k.... (k)(i) The contracting officer shall add paragraph (e) as set forth in 1852.227-19(a) to the...

  1. 46 CFR 153.486 - Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. (a) If NLS... 46 Shipping 5 2014-10-01 2014-10-01 false Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. 153.486 Section 153.486 Shipping COAST GUARD, DEPARTMENT OF...

  2. 46 CFR 153.486 - Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. (a) If NLS... 46 Shipping 5 2012-10-01 2012-10-01 false Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. 153.486 Section 153.486 Shipping COAST GUARD, DEPARTMENT OF...

  3. 46 CFR 153.486 - Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. (a) If NLS... 46 Shipping 5 2013-10-01 2013-10-01 false Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. 153.486 Section 153.486 Shipping COAST GUARD, DEPARTMENT OF...

  4. 46 CFR 153.486 - Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. (a) If NLS... 46 Shipping 5 2011-10-01 2011-10-01 false Design and equipment for removing NLS residue by ventilation: Categories A, B, C, and D. 153.486 Section 153.486 Shipping COAST GUARD, DEPARTMENT OF...

  5. 26 CFR 1.674(d)-2 - Limitations on exceptions in section 674 (b), (c), and (d).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 26 Internal Revenue 8 2010-04-01 2010-04-01 false Limitations on exceptions in section 674 (b), (c), and (d). 1.674(d)-2 Section 1.674(d)-2 Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE... § 1.674(d)-2 Limitations on exceptions in section 674 (b), (c), and (d). (a) Power to remove...

  6. 26 CFR 1.674(d)-2 - Limitations on exceptions in section 674 (b), (c), and (d).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 26 Internal Revenue 8 2011-04-01 2011-04-01 false Limitations on exceptions in section 674 (b), (c), and (d). 1.674(d)-2 Section 1.674(d)-2 Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE... Substantial Owners § 1.674(d)-2 Limitations on exceptions in section 674 (b), (c), and (d). (a) Power...

  7. Site specificity of DSP-PP cleavage by BMP1.

    PubMed

    Yang, Robert T; Lim, Glendale L; Yee, Colin T; Fuller, Robert S; Ritchie, Helena H

    2014-08-01

    Bone morphogenic protein 1 (BMP1), a metalloproteinase, is known to cleave a wide variety of extracellular matrix proteins, suggesting that a consensus substrate cleavage amino acid sequence might exist. However, while such a consensus sequence has been proposed based on P4 to P4' (i.e. the four amino acids flanking either side of the BMP1 cleavage site; P4P3P2P1|P1'P2'P3'P4') sequence homologies between two BMP1 substrates, dentin matrix protein 1 and dentin sialoprotein phosphophoryn (DSP-PP) (i.e. xMQx|DDP), no direct testing has so far been attempted. Using an Sf9 cell expression system, we have been able to produce large amounts of uncleaved DSP-PP. Point mutations introduced into this recombinant DSP-PP were then tested for their effects on DSP-PP cleavage by either Sf9 endogenous tolloid-related protein 1 (TLR-1) or by its human homolog, BMP1. Here, we have measured DSP-PP cleavage efficiencies after modifications based on P4-P4' sequence comparisons with dentin matrix protein 1, as well as for prolysyl oxidase and chordin, two other BMP1 substrates. Our results demonstrate that any mutations within or outside of the DSP-PP P4 to P4' cleavage site can block, impair or accelerate DSP-PP cleavage, and suggest that its BMP1 cleavage site is highly conserved in order to regulate its cleavage efficiency, possibly with additional assistance from its conserved exosites. Thus, BMP1 cleavage cannot be based on a consensus substrate cleavage site.

  8. Oxidative addition of methane and benzene C--H bonds to rhodium center: A DFT study

    NASA Astrophysics Data System (ADS)

    Bi, Siwei; Zhang, Zhenwei; Zhu, Shufen

    2006-11-01

    A density functional theory study on mechanisms of the oxidative addition of methane and benzene C-H bonds to the rhodium center containing Cp and PMe 3 ligands has been performed. Our calculated results confirm that the C-H bond cleavage from a sigma complex to a hydride alkyl complex is the rate-determining step. Compared with the case of methane C-H bond, the oxidative addition of benzene C-H bond is more favorable kinetically and thermodynamically. Stronger backdonation from metal center to the σ ∗ antibonding orbital of benzene C-H bond is responsible for the observations.

  9. Distinct oxidative cleavage and modification of bovine [Cu- Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule.

    PubMed

    Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L; Rao, V Ashutosh

    2016-05-01

    We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5Å from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction.

  10. Amide-directed photoredox-catalysed C-C bond formation at unactivated sp(3) C-H bonds.

    PubMed

    Chu, John C K; Rovis, Tomislav

    2016-11-10

    Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp(3) C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

  11. Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds

    NASA Astrophysics Data System (ADS)

    Chu, John C. K.; Rovis, Tomislav

    2016-11-01

    Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp3 C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

  12. Characterisation by molecular hybridization of RNA fragments isolated from ancient (1400 B.C.) seeds.

    PubMed

    Rollo, F

    1985-12-01

    The analysis of cress seeds from Thebes dated approximately 1400 years B.C. showed that fragments of RNA up to 10 bases in length were still present in the ancient seeds. After having been made radioactive at the 5'OH terminus, the RNA fragments were used as probes in a spot hybridization experiment. They were shown to hybridize to cress DNA and, to a lesser extent, to that of phylogenetically distant species. When fixed onto nitrocellulose and probed with different cloned genes, the RNA fragments were shown to originate from breakage of the 25 and 18s cytoplasmic rRNA.

  13. New Synthetic Strategies for Structured Silicones Using B(C6F5)3

    NASA Astrophysics Data System (ADS)

    Brook, Michael A.; Grande, John B.; Ganachaud, François

    The dehydrocarbonative condensation of alkoxysilanes + hydrosilanes in the presence of the Lewis acid catalyst B(C6F5)3 (R3SiOR' + HSiR3 '' → R3SiOSiR3 '' + R ' H) - described throughout this review as the Piers-Rubinsztajn reaction - provides a new, mild strategy for the controlled synthesis of silicones. In this review we examine the mechanistic parameters that control the reaction, and outline the types of accessible small molecules, linear, branched, and cross-linked materials (resins and elastomers) that can be prepared using this and related reactions.

  14. Walter Miles, Pop Warner, B. C. Graves, and the psychology of football.

    PubMed

    Baugh, Frank G; Benjamin, Ludy T

    2006-01-01

    In 1926-1927, a graduate student, B. C. Graves, working with Stanford University psychologist Walter Miles and legendary football coach Pop Warner, conducted an investigation of variations in signal calling as they affected the charging times of football players. The study was one of two that involved Miles and the ingenious multiple chronograph that he had invented to time the reactions of seven players simultaneously. These studies represented a brief digression in the career of Miles, who certainly was no sport psychologist. They tell of an interesting collaboration between scientist and coaches that produced one of the richest studies in sport psychology in the first half of the twentieth century.

  15. Identification of the diamond-like B-C phase by confocal Raman spectroscopy.

    PubMed

    Zinin, P V; Kudryashov, I; Konishi, N; Ming, L C; Solozhenko, V L; Sharma, S K

    2005-08-01

    The new diamond-like B-C phase was obtained from the graphite-like BC phase in a laser-heated diamond anvil cell at high temperature 2230+/-140 K and high pressure 45 GPa. Raman spectra of the new phase measured at ambient conditions revealed a peak at 1315 cm(-1), which was attributed to longitudinal-optical (LO) mode. The X-Y Raman mapping was used to investigate spatial distribution of the diamond-like phases and was shown to be a powerful tool in studying the sp(2)-to-sp(3) phase transformations occurring in the diamond cell under high temperature and high pressure.

  16. 3-Keto-5-aminohexanoate Cleavage Enzyme

    PubMed Central

    Bellinzoni, Marco; Bastard, Karine; Perret, Alain; Zaparucha, Anne; Perchat, Nadia; Vergne, Carine; Wagner, Tristan; de Melo-Minardi, Raquel C.; Artiguenave, François; Cohen, Georges N.; Weissenbach, Jean; Salanoubat, Marcel; Alzari, Pedro M.

    2011-01-01

    The exponential increase in genome sequencing output has led to the accumulation of thousands of predicted genes lacking a proper functional annotation. Among this mass of hypothetical proteins, enzymes catalyzing new reactions or using novel ways to catalyze already known reactions might still wait to be identified. Here, we provide a structural and biochemical characterization of the 3-keto-5-aminohexanoate cleavage enzyme (Kce), an enzymatic activity long known as being involved in the anaerobic fermentation of lysine but whose catalytic mechanism has remained elusive so far. Although the enzyme shows the ubiquitous triose phosphate isomerase (TIM) barrel fold and a Zn2+ cation reminiscent of metal-dependent class II aldolases, our results based on a combination of x-ray snapshots and molecular modeling point to an unprecedented mechanism that proceeds through deprotonation of the 3-keto-5-aminohexanoate substrate, nucleophilic addition onto an incoming acetyl-CoA, intramolecular transfer of the CoA moiety, and final retro-Claisen reaction leading to acetoacetate and 3-aminobutyryl-CoA. This model also accounts for earlier observations showing the origin of carbon atoms in the products, as well as the absence of detection of any covalent acyl-enzyme intermediate. Kce is the first representative of a large family of prokaryotic hypothetical proteins, currently annotated as the “domain of unknown function” DUF849. PMID:21632536

  17. Lesion Recognition and Cleavage by Endonuclease V

    PubMed Central

    Lin, Jun; Gao, Honghai; Schallhorn, Kathryn A.; Harris, Rebecca M.; Cao, Weiguo; Ke, Pu Chun

    2008-01-01

    Endonuclease V (endo V) recognizes and cleaves deoxyinosine in deaminated DNA. These enzymatic activities are precursors of DNA repair and are fueled by metal ions such as Ca2+ and Mg2+, with the former being associated with protein binding and the latter with DNA cleavage. Using the technique of fluorescence resonance energy transfer (FRET) we determined the single-molecule kinetics of endo V in a catalytic cycle using a substrate of deoxyinosine-containing single-stranded DNA (ssDNA). The ssDNA was labeled with TAMRA, a fluorescence donor, while the endo V was labeled with Cy5, a fluorescence acceptor. The time lapses of FRET, resulting from the sequential association, recognition, and dissociation of the deoxyinosine by the endo V, were determined at 5.9 s, 14.5 s, and 9.1 s, respectively, in the presence of Mg2+. In contrast, the process of deoxyinosine recognition appeared little affected by the metal type. The prolonged association and dissociation events in the presence of the Ca2+-Mg2+ combination, as compared to that of Mg2+ alone, support the hypothesis that endo V has two metal binding sites to regulate its enzymatic activities. PMID:17521169

  18. Measurement of the cleavage energy of graphite

    PubMed Central

    Wang, Wen; Dai, Shuyang; Li, Xide; Yang, Jiarui; Srolovitz, David J.; Zheng, Quanshui

    2015-01-01

    The basal plane cleavage energy (CE) of graphite is a key material parameter for understanding many of the unusual properties of graphite, graphene and carbon nanotubes. Nonetheless, a wide range of values for the CE has been reported and no consensus has yet emerged. Here we report the first direct, accurate experimental measurement of the CE of graphite using a novel method based on the self-retraction phenomenon in graphite. The measured value, 0.37±0.01 J m−2 for the incommensurate state of bicrystal graphite, is nearly invariant with respect to temperature (22 °C≤T≤198 °C) and bicrystal twist angle, and insensitive to impurities from the atmosphere. The CE for the ideal ABAB graphite stacking, 0.39±0.02 J m−2, is calculated based on a combination of the measured CE and a theoretical calculation. These experimental measurements are also ideal for use in evaluating the efficacy of competing theoretical approaches. PMID:26314373

  19. Peptidase specificity from the substrate cleavage collection in the MEROPS database and a tool to measure cleavage site conservation

    PubMed Central

    Rawlings, Neil D.

    2016-01-01

    One peptidase can usually be distinguished from another biochemically by its action on proteins, peptides and synthetic substrates. Since 1996, the MEROPS database (http://merops.sanger.ac.uk) has accumulated a collection of cleavages in substrates that now amounts to 66,615 cleavages. The total number of peptidases for which at least one cleavage is known is 1700 out of a total of 2457 different peptidases. This paper describes how the cleavages are obtained from the scientific literature, how they are annotated and how cleavages in peptides and proteins are cross-referenced to entries in the UniProt protein sequence database. The specificity profiles of 556 peptidases are shown for which ten or more substrate cleavages are known. However, it has been proposed that at least 40 cleavages in disparate proteins are required for specificity analysis to be meaningful, and only 163 peptidases (6.6%) fulfil this criterion. Also described are the various displays shown on the website to aid with the understanding of peptidase specificity, which are derived from the substrate cleavage collection. These displays include a logo, distribution matrix, and tables to summarize which amino acids or groups of amino acids are acceptable (or not acceptable) in each substrate binding pocket. For each protein substrate, there is a display to show how it is processed and degraded. Also described are tools on the website to help with the assessment of the physiological relevance of cleavages in a substrate. These tools rely on the hypothesis that a cleavage site that is conserved in orthologues is likely to be physiologically relevant, and alignments of substrate protein sequences are made utilizing the UniRef50 database, in which in each entry sequences are 50% or more identical. Conservation in this case means substitutions are permitted only if the amino acid is known to occupy the same substrate binding pocket from at least one other substrate cleaved by the same peptidase. PMID

  20. Follow-on cable coupling lightning test. Volume 2: Appendixes A, B, C, and D

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The following information from the follow-on cable coupling lightning test of the Space Shuttle Booster is presented: (1) resistance measurements (cover-to-cover and cover-to-floor plate); (2) resistance measurements (external bond strap-to-case); (3) resistance measurements (internal bond strap-to-case) and; (4) follow-on cable coupling lightning test data plots. The bulk of the document comprises the follow-on cable coupling lightning test data plots.

  1. Familial Alzheimer’s mutations within APPTM increase Aβ42 production by enhancing accessibility of ɛ-cleavage site

    NASA Astrophysics Data System (ADS)

    Chen, Wen; Gamache, Eric; Rosenman, David J.; Xie, Jian; Lopez, Maria M.; Li, Yue-Ming; Wang, Chunyu

    2014-01-01

    The high Aβ42/Aβ40 production ratio is a hallmark of familial Alzheimer’s disease, which can be caused by mutations in the amyloid precursor protein (APP). The C-terminus of Aβ is generated by γ-secretase cleavage within the transmembrane domain of APP (APPTM), a process that is primed by an initial ɛ-cleavage at either T48 or L49, resulting in subsequent production of Aβ42 or Aβ40, respectively. Here we solve the dimer structures of wild-type APPTM (AAPTM WT) and mutant APPTM (FAD mutants V44M) with solution NMR. The right-handed APPTM helical dimer is mediated by GXXXA motif. From the NMR structural and dynamic data, we show that the V44M and V44A mutations can selectively expose the T48 site by weakening helical hydrogen bonds and increasing hydrogen-deuterium exchange rate (kex). We propose a structural model in which FAD mutations (V44M and V44A) can open the T48 site γ-secretase for the initial ɛ-cleavage, and consequently shift cleavage preference towards Aβ42.

  2. Quantification of DNA cleavage specificity in Hi-C experiments.

    PubMed

    Meluzzi, Dario; Arya, Gaurav

    2016-01-08

    Hi-C experiments produce large numbers of DNA sequence read pairs that are typically analyzed to deduce genomewide interactions between arbitrary loci. A key step in these experiments is the cleavage of cross-linked chromatin with a restriction endonuclease. Although this cleavage should happen specifically at the enzyme's recognition sequence, an unknown proportion of cleavage events may involve other sequences, owing to the enzyme's star activity or to random DNA breakage. A quantitative estimation of these non-specific cleavages may enable simulating realistic Hi-C read pairs for validation of downstream analyses, monitoring the reproducibility of experimental conditions and investigating biophysical properties that correlate with DNA cleavage patterns. Here we describe a computational method for analyzing Hi-C read pairs to estimate the fractions of cleavages at different possible targets. The method relies on expressing an observed local target distribution downstream of aligned reads as a linear combination of known conditional local target distributions. We validated this method using Hi-C read pairs obtained by computer simulation. Application of the method to experimental Hi-C datasets from murine cells revealed interesting similarities and differences in patterns of cleavage across the various experiments considered.

  3. The VHSE-based prediction of proteasomal cleavage sites.

    PubMed

    Xie, Jiangan; Xu, Zhiling; Zhou, Shangbo; Pan, Xianchao; Cai, Shaoxi; Yang, Li; Mei, Hu

    2013-01-01

    Prediction of proteasomal cleavage sites has been a focus of computational biology. Up to date, the predictive methods are mostly based on nonlinear classifiers and variables with little physicochemical meanings. In this paper, the physicochemical properties of 14 residues both upstream and downstream of a cleavage site are characterized by VHSE (principal component score vector of hydrophobic, steric, and electronic properties) descriptors. Then, the resulting VHSE descriptors are employed to construct prediction models by support vector machine (SVM). For both in vivo and in vitro datasets, the performance of VHSE-based method is comparatively better than that of the well-known PAProC, MAPPP, and NetChop methods. The results reveal that the hydrophobic property of 10 residues both upstream and downstream of the cleavage site is a dominant factor affecting in vivo and in vitro cleavage specificities, followed by residue's electronic and steric properties. Furthermore, the difference in hydrophobic potential between residues flanking the cleavage site is proposed to favor substrate cleavages. Overall, the interpretable VHSE-based method provides a preferable way to predict proteasomal cleavage sites.

  4. Use of Cleavage as an Aid in the Optical Determination of Minerals.

    ERIC Educational Resources Information Center

    Ehlers, Ernest G.

    1980-01-01

    Described is the use of cleavage as an aid to microscopic determination of unknown minerals by immersion methods. Cleavages are examined in relation to fragment shapes, types of extinction, and cleavage-optical relationships. (Author/DS)

  5. Determination of the Proteolytic Cleavage Sites of the Amyloid Precursor-Like Protein 2 by the Proteases ADAM10, BACE1 and γ-Secretase

    PubMed Central

    Hogl, Sebastian; Kuhn, Peer-Hendrik; Colombo, Alessio; Lichtenthaler, Stefan F.

    2011-01-01

    Regulated intramembrane proteolysis of the amyloid precursor protein (APP) by the protease activities α-, β- and γ-secretase controls the generation of the neurotoxic amyloid β peptide. APLP2, the amyloid precursor-like protein 2, is a homolog of APP, which shows functional overlap with APP, but lacks an amyloid β domain. Compared to APP, less is known about the proteolytic processing of APLP2, in particular in neurons, and the cleavage sites have not yet been determined. APLP2 is cleaved by the β-secretase BACE1 and additionally by an α-secretase activity. The two metalloproteases ADAM10 and ADAM17 have been suggested as candidate APLP2 α-secretases in cell lines. Here, we used RNA interference and found that ADAM10, but not ADAM17, is required for the constitutive α-secretase cleavage of APLP2 in HEK293 and SH-SY5Y cells. Likewise, in primary murine neurons knock-down of ADAM10 suppressed APLP2 α-secretase cleavage. Using mass spectrometry we determined the proteolytic cleavage sites in the APLP2 sequence. ADAM10 was found to cleave APLP2 after arginine 670, whereas BACE1 cleaves after leucine 659. Both cleavage sites are located in close proximity to the membrane. γ-secretase cleavage was found to occur at different peptide bonds between alanine 694 and valine 700, which is close to the N-terminus of the predicted APLP2 transmembrane domain. Determination of the APLP2 cleavage sites enables functional studies of the different APLP2 ectodomain fragments and the production of cleavage-site specific antibodies for APLP2, which may be used for biomarker development. PMID:21695060

  6. B/C mixing and vibrational relaxation in XeF

    NASA Astrophysics Data System (ADS)

    Lorents, D. C.

    From several runs, time-dependent profiles (resolution, approximately 1 ns) are accumulated of the B and C state fluorescence in Ne, Ar, N2, and SF6 at pressures ranging from zero to several thousand torr as well as in the mixtures Ar/Xe and N2/Xe. It is noted that over the same time period Brashears and Setser (1980) completed pressure-dependent spectral intensity measurements in the same gases over a similar pressure range using steady-state photodissociation of XeF2 with uv lamps. On the basis of the integrated spectral profiles of the uv and visible intensities, they determined the relative B and C state fluorescent yields as a function of gas density. With the two-state model, they also obtained a set of B/C mixing and quenching rate constants for various additives, assuming a pure B state initial population and reasonable values for the radiative lifetimes. It is noted that the rate constants derived by these two different techniques are not completely consistent. These two data sets - the integrated and time-dependent intensity measurement over a wide pressure range - constitute a comprehensive data set from which a consistent detailed model of the kinetic behavior of the B/C states of XeF is thought to be possible.

  7. Early (300−100 B.C.) temple precinct in the Valley of Oaxaca, Mexico

    PubMed Central

    Redmond, Elsa M.; Spencer, Charles S.

    2013-01-01

    Archaeological investigations during the past two decades in Mexico’s Valley of Oaxaca have documented the appearance of key public buildings, such as the royal palace and multiroom temple, associated with the rise of an archaic state at ca. 300−100 B.C. A fuller picture is now emerging from the site of El Palenque, where recent excavations have defined a temple precinct on the east side of the site’s plaza. This precinct exhibits characteristics similar to those of the temple precincts of later Mesoamerican states described by Colonial period sources. The excavation data document a walled enclosure containing three multiroom temples, two special residences identified as priests’ residences, and an array of ritual features and activity areas. The temple precinct’s components are interpreted as comprising a hierarchy of temples staffed by a specialized priesthood. A series of radiocarbon dates indicate that the precinct’s differentiated components were all in use during the 300−100 B.C. period of archaic state emergence. The El Palenque temple precinct is the earliest temple precinct excavated thus far in the Valley of Oaxaca. PMID:23610387

  8. Early (300-100 B.C.) temple precinct in the Valley of Oaxaca, Mexico.

    PubMed

    Redmond, Elsa M; Spencer, Charles S

    2013-05-07

    Archaeological investigations during the past two decades in Mexico's Valley of Oaxaca have documented the appearance of key public buildings, such as the royal palace and multiroom temple, associated with the rise of an archaic state at ca. 300-100 B.C. A fuller picture is now emerging from the site of El Palenque, where recent excavations have defined a temple precinct on the east side of the site's plaza. This precinct exhibits characteristics similar to those of the temple precincts of later Mesoamerican states described by Colonial period sources. The excavation data document a walled enclosure containing three multiroom temples, two special residences identified as priests' residences, and an array of ritual features and activity areas. The temple precinct's components are interpreted as comprising a hierarchy of temples staffed by a specialized priesthood. A series of radiocarbon dates indicate that the precinct's differentiated components were all in use during the 300-100 B.C. period of archaic state emergence. The El Palenque temple precinct is the earliest temple precinct excavated thus far in the Valley of Oaxaca.

  9. Comparison of Sterol Biomarkers for Sewage with other Measures in Victoria Harbour, B.C., Canada

    NASA Astrophysics Data System (ADS)

    Mudge, S. M.; Lintern, D. Gwyn

    1999-01-01

    A lipid biomarker survey was conducted in Victoria Harbour, Canada, to compare the distribution of sewage-derived organic matter with existing results from bacterial studies. Previous surveys [Miller (1993) Report prepared by Capital Regional District Engineering Department, Victoria, B.C. Canada and Miller et al. (1995) Report prepared by CRD Environmental Services Group and Aquatic Science Consultants Ltd., B.C., Canada] of sewage contamination in the harbour were based principally on infrequent faecal coliform counts. The use of lipid biomarkers to determine time-averaged concentrations of sewage components in sediments may be a more appropriate method for defining areas where sewage is causing environmental or human health risks. 5β-Coprostanol was measured together with other sterols, fatty acids and fatty alcohols. Generally, sewage contamination shown by these lipid biomarkers was coincident with high faecal coliform counts from previous studies. However, this survey suggests, contrary to faecal coliform counts, that Portage Inlet was a region where sewage had accumulated in the sediments, possibly due to nearby overflow facilities or tidal pumping. Although the bacterial counts were low, sewage-derived organic matter was accumulating in the slack areas. In sediments of the Gorge and West Bay there were low faecal biomarker concentrations; this was probably due to the strong tidal currents which do not allow faecal matter to settle in sediments. Faecal coliform counts, however, indicated poor water quality in these same regions but this probably reflects fresh discharges passing through this area without leading to settlement.

  10. Specific oxidative cleavage of carotenoids by VP14 of maize

    SciTech Connect

    Schwartz, S.H.; Zeevaart, J.A.D.; Gage, D.A.; Tan, Bao Cai

    1997-06-20

    The plant growth regulator abscisic acid (ABA) is formed by the oxidative cleavage of an epoxy-carotenoid. The synthesis of other apocarotenoids, such as vitamin A in animals, may occur by a similar mechanism. In ABA biosynthesis, oxidative cleavage is the first committed reaction and is believed to be the key regulatory step. A new ABA-deficient mutant of maize has been identified and the corresponding gene, Vp14, has been cloned. The recombinant VP14 protein catalyzes the cleavage of 9-cis-epoxy-carotenoids to form C{sub 25} apo-aldehydes and xanthoxin, a precursor of ABA in higher plants.

  11. Detection of nucleic acid sequences by invader-directed cleavage

    DOEpatents

    Brow, Mary Ann D.; Hall, Jeff Steven Grotelueschen; Lyamichev, Victor; Olive, David Michael; Prudent, James Robert

    1999-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The 5' nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof. The present invention further relates to methods and devices for the separation of nucleic acid molecules based by charge.

  12. Rubber oxygenase and latex clearing protein cleave rubber to different products and use different cleavage mechanisms.

    PubMed

    Birke, Jakob; Jendrossek, Dieter

    2014-08-01

    Two types of enzyme for oxidative cleavage of poly(cis-1,4-isoprene) are known. One is rubber oxygenase (RoxA) that is secreted by Xanthomonas sp. strain 35Y and a few other Gram-negative rubber-degrading bacteria during growth on polyisoprene. RoxA was studied in the past, and the recently solved structure showed a structural relationship to bacterial cytochrome c peroxidases (J. Seidel et al., Proc. Natl. Acad. Sci. U. S. A. 110:13833-13838, 2013, http://dx.doi.org/10.1073/pnas.1305560110). The other enzyme is latex-clearing protein (Lcp) that is secreted by rubber-degrading actinomycetes, but Lcp has not yet been purified. Here, we expressed Lcp of Streptomyces sp. strain K30 in a ΔroxA background of Xanthomonas sp. strain 35Y and purified native (untagged) Lcp. The specific activities of Lcp and RoxA were 0.70 and 0.48 U/mg, respectively. Lcp differed from RoxA in the absence of heme groups and other characteristics. Notably, Lcp degraded polyisoprene via endo-type cleavage to tetra-C20 and higher oligo-isoprenoids with aldehyde and keto end groups, whereas RoxA used an exo-type cleavage mechanism to give the main end product 12-oxo-4,8-dimethyltrideca-4,8-diene-1-al (ODTD). RoxA was able to cleave isolated Lcp-derived oligo-isoprenoid molecules to ODTD. Inhibitor studies, spectroscopic investigations and metal analysis gave no indication for the presence of iron, other metals, or cofactors in Lcp. Our results suggest that Lcp could be a member of the growing group of cofactor-independent oxygenases and differs in the cleavage mechanism from heme-dependent RoxA. In conclusion, RoxA and Lcp represent two different answers to the same biochemical problem, the cleavage of polyisoprene, a polymer that has carbon-carbon double bonds as the only functional groups for enzymatic attack.

  13. Chemical Bonds II

    ERIC Educational Resources Information Center

    Sanderson, R. T.

    1972-01-01

    The continuation of a paper discussing chemical bonding from a bond energy viewpoint, with a number of examples of single and multiple bonds. (Part I appeared in volume 1 number 3, pages 16-23, February 1972.) (AL)

  14. A glucuronoyl esterase from Acremonium alcalophilum cleaves native lignin-carbohydrate ester bonds.

    PubMed

    Arnling Bååth, Jenny; Giummarella, Nicola; Klaubauf, Sylvia; Lawoko, Martin; Olsson, Lisbeth

    2016-08-01

    The Glucuronoyl esterases (GE) have been proposed to target lignin-carbohydrate (LC) ester bonds between lignin moieties and glucuronic acid side groups of xylan, but to date, no direct observations of enzymatic cleavage on native LC ester bonds have been demonstrated. In the present investigation, LCC fractions from spruce and birch were treated with a recombinantly produced GE originating from Acremonium alcalophilum (AaGE1). A combination of size exclusion chromatography and (31) P NMR analyses of phosphitylated LCC samples, before and after AaGE1 treatment provided the first evidence for cleavage of the LC ester linkages existing in wood.

  15. What Determines Bond Costs. Municipal Bonds Series.

    ERIC Educational Resources Information Center

    Young, Douglas; And Others

    Public officials in small towns who participate infrequently in the bond market need information about bond financing. This publication, one in a series of booklets published by the Western Rural Development Center using research gathered between 1967-77, discusses factors influencing the marketability and cost of bond financing for towns and…

  16. Spontaneous Si-C bond cleavage in (Triphos(Si))-nickel complexes.

    PubMed

    Petuker, Anette; Mebs, Stefan; Schuth, Nils; Gerschel, Philipp; Reback, Matthew L; Mallick, Bert; van Gastel, Maurice; Haumann, Michael; Apfel, Ulf-Peter

    2017-01-17

    Herein, we report on the versatile reactions of CH3C(CH2PPh2)3 as well as CH3Si(CH2PPh2)3 derived Ni-complexes. While Ni[CH3C(CH2PPh2)3] complexes reveal high stability, the Ni[CH3Si(CH2PPh2)3] analogs show rapid decomposition at room temperature and afford the unprecedented pseudo-tetrahedral phosphino methanide complex 5. We provide a detailed electronic structure of 5 from X-ray absorption and emission spectroscopy data analysis in combination with DFT calculations, as well as from comparison with structurally related complexes. A mechanistic study for the formation of complex 5 by reaction with BF4(-) is presented, based on a comparison of experimental data with quantum chemical calculations. We also show a simple route towards isolable Ni(i)-complexes on the gram scale.

  17. Electrochemical Reduction of Trivalent Organophosphorus Compounds: Mechanism and Products from Phosphorus-Heteroatom Bond Cleavage.

    DTIC Science & Technology

    1986-08-19

    nitrate in acetonitrile separated from the catholyte by a microporous Vycor frit. In a typical experiment the anolyte solution consisted of 200 ml of dry...grams (0.004 moles) of chlorodiphenylphosphine. The anolyte and catholyte solutions were circulated from separate flasks by ECO Model 920 Teflon Pumps

  18. Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources.

    PubMed

    Galangau, Olivier; Delbaere, Stéphanie; Ratel-Ramond, Nicolas; Rapenne, Gwénaël; Li, Ruiji; Calupitan, Jan Patrick Dela Cruz; Nakashima, Takuya; Kawai, Tsuyoshi

    2016-11-18

    In this paper, we present a novel concept for "smarter" photolabile organic compounds combining not one but two caged functions. As proof of principle, this diarylethene-based compound possesses two inhibited chemical groups (OMe and OAc) and its efficient release in different solvents is reported. In low- to medium-polarity media, both MeOH and AcOH are released, with a slight preferential uncaging of AcOH except in 1,4-dioxane, where MeOH is preferentially released. In contrast, DMSO or DMF render AcOH release strongly dominating. DFT calculations of the corresponding photoreactive conformations not only afford strong support to the observed release of MeOH and AcOH but also qualitatively explain the preferential release of acid in terms of dispersive noncovalent interactions. Finally, mechanistic aspects are discussed on the bases of the spectroscopic observations and of the TD-DFT calculations.

  19. Nitrososynthase triggered oxidative carbon-carbon bond cleavage in baumycin biosynthesis

    PubMed Central

    Al-Mestarihi, Ahmad; Romo, Anthony; Liu, Hung-wen; Bachmann, Brian O.

    2013-01-01

    Baumycins are coproduced with clinically important anticancer secondary metabolites daunorubicin and doxorubicin, which are glycosylated anthracyclines isolated from Streptomyces peucetius. The distinguishing feature of baumycins is the presence of an unusual acetal moiety appended to daunosamine, which is hydrolyzed during acidic extraction of daunorubicin from fermentation broth. The structure of the baumycin acetal suggests that it is likely derived from an unknown C-3” methyl deoxysugar cleaved between the C-3” and C-4” positions. This is supported by analysis of the baumycin/daunorubicin biosynthetic gene cluster (dox), which also encodes putative proteins consistent with production of an anthracycline dissacharide containing a branched sugar. Notably, the dnmZ gene in the dox gene cluster possesses high translated sequence similarity to nitrososynthases, which are flavin-dependent amine monooxygenases involved in the four electron oxidation of aminosugars to nitrososugars. Herein we demonstrate that DnmZ is an amino sugar nitrososynthase initiating the conversion of thymidine-5’-diphosphate-l-epi-vancosamine to a ring opened product via a previously uncharacterized retro oxime-aldol reaction. PMID:23885759

  20. Nitrogen dioxide reaction with proteins: Evidence for peptide bond cleavage at lysine residues

    SciTech Connect

    Hood, D.B.

    1991-01-01

    Nitrogen dioxide (NO{sub 2}), an air pollutant produced by burning fossil fuels and a component of cigarette smoke, is thought to contribute to the pathogenesis of pulmonary diseases, such as emphysema. To gain information on the mechanism by which NO{sub 2} damages the lung, in vitro exposures of {alpha}{sub 1}-proteinase inhibitor ({alpha}{sub 1}-PI), elastin, bovine serum albumin (BSA), human serum albumin (HSA) and synthetic poly-L-lysine were performed. A genetic deficiency of {alpha}{sup 1}-PI predisposes humans to emphysema and NO{sub 2} has been hypothesized to damage {alpha}{sub 1}-PI, which would leave proteases such as human neutrophil elastase, (HNE) free to attack lung structural proteins. The ability of {alpha}{sub 1}-PI to inhibit HNE declined with exposure to 50% of the control value at molar ratios of NO{sub 2}:{alpha}{sub 1}-PI of 400:1 and greater. Exposure of {alpha}{sub 1}-PI to NO{sub 2} resulted in a 50% lose of immunoreactivity with either monoclonal or polyclonal antibodies in an enzyme-linked immunosorbent assay at molar ratios of NO{sub 2}:{alpha}{sub 1}-PI of essentially 100:1 and greater. The mechanisms of these effects were investigated via ultraviolet-visible spectroscopy and amino acid analysis. The remaining target molecules were labeled by reductive methylation of amino groups with {sup 3}H-HCHO prior to treatment with NO{sub 2} in aqueous solutions at physiological pH. Time course exposure of 5 mg {sup 3}H-insoluble bovine ligamentum nuchae elastin suspensions with up to 120 {mu}moles of NO{sub 2} resulted in 90% solubilization of the label. Amino acid analysis of the soluble and insoluble fractions from these exposures confirmed that 80% of the {sup 3}H-dimethyllysine residues were in the soluble fraction.

  1. Catalysis and co-catalysis of bond cleavages in coal and coal analogs

    SciTech Connect

    Miller, B.

    1993-01-01

    In a continuation of our studies on the efficacy of aromatic amines as catalysts for transfer hydrogenolysis reaction, we studied 2- anilinoethanol as a possible catalyst. This molecule proved to be almost as effective as 2-aminophenol for hydrogenolysis of di-2- naphthyl either in a five hour reaction period.

  2. Detection of nucleic acids by multiple sequential invasive cleavages

    SciTech Connect

    Hall, Jeff G; Lyamichev, Victor I; Mast, Andrea L; Brow, Mary Ann D

    2012-10-16

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof. The present invention further relates to methods and devices for the separation of nucleic acid molecules based on charge. The present invention also provides methods for the detection of non-target cleavage products via the formation of a complete and activated protein binding region. The invention further provides sensitive and specific methods for the detection of human cytomegalovirus nucleic acid in a sample.

  3. Detection of nucleic acids by multiple sequential invasive cleavages 02

    DOEpatents

    Hall, Jeff G.; Lyamichev, Victor I.; Mast, Andrea L.; Brow, Mary Ann D.

    2002-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof. The present invention further relates to methods and devices for the separation of nucleic acid molecules based on charge. The present invention also provides methods for the detection of non-target cleavage products via the formation of a complete and activated protein binding region. The invention further provides sensitive and specific methods for the detection of human cytomegalovirus nucleic acid in a sample.

  4. Detection of nucleic acids by multiple sequential invasive cleavages

    DOEpatents

    Hall, Jeff G.; Lyamichev, Victor I.; Mast, Andrea L.; Brow, Mary Ann D.

    1999-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof. The present invention further relates to methods and devices for the separation of nucleic acid molecules based on charge. The present invention also provides methods for the detection of non-target cleavage products via the formation of a complete and activated protein binding region. The invention further provides sensitive and specific methods for the detection of human cytomegalovirus nucleic acid in a sample.

  5. [Expression and immunity of multi-HIV B'/C subype genes in replicating DNA vaccines].

    PubMed

    Gao, Ying-ying; Deng, Yao; Qi, Xiang-rong; Zhang, Xiang-min; Meng, Xin; Wang, Hui-juan; Tan, Wen-jie; Ruan, Li

    2010-05-01

    To understand the effect of various gene structures of HIV B'/C subtype on the gene expression and immunity in DNA vaccine, replicating DNA vector pSCK2 was used to construct seven DNA vaccines carrying one or more of HIV B'/C subtype genes: gagpol, gp160 and rtn (rev, tat and nef fusion gene). Immunofluorescence staining indicated that Gag, Gp160, Rev, Tat and Nef could be expressed from the seven DNA vaccines. Stronger expression was observed with the gene in single-gene expression plasmid or with the gene located at upper-IRES in double- or multi-gene expression plasmid. ELISA test showed that Gag induced higher antibody response, but the antibody titers stimulated by Gp160, Pol, or RTN were very low. Both Gag single-gene expression plasmid and Gag-RTN double-gene expression plasmid separately inoculating induced stronger antibody response against Gag than Gag-Gp160 double-gene expression plasmid and Gagpol-Gp160-RTN multi-gene expression plasmid or combined inoculation of Gag and Gp160 single-gene expression plasmids did. ELISPOT detection showed that all the seven DNA vaccines could stimulate cellular immune response against Gag, Pol, Gp160, Tat, and Nef, respectively. Gagpol or Gp160 single-gene expression plasmid separately inoculating stimulated the strongest cellular immune response. Tat and Nef expressed in all the plasmids induced similar immune response. These results indicated that HIV B'/C subtype genes gagpol, gp160 and rtn could be efficiently expressed in the replicating DNA vaccine vector, single-gene expression plasmid had the higher gene expression level and induced stronger immune response; combined immunization of Gagpol and Gp160 had dramatically lower immunity than Gagpol or Gp160 separated immunization did. Immunity of RTN had no difference between combined and separated immunizations. Therefore, in case of immunization with DNA vaccines containing different HIV genes, it is necessary to optimize the combined immunization procedure

  6. Mechanisms for ribotoxin-induced ribosomal RNA cleavage

    SciTech Connect

    He, Kaiyu; Zhou, Hui-Ren; Pestka, James J.

    2012-11-15

    The Type B trichothecene deoxynivalenol (DON), a ribotoxic mycotoxin known to contaminate cereal-based foods, induces ribosomal RNA (rRNA) cleavage in the macrophage via p38-directed activation of caspases. Here we employed the RAW 264.7 murine macrophage model to test the hypothesis that this rRNA cleavage pathway is similarly induced by other ribotoxins. Capillary electrophoresis confirmed that the antibiotic anisomycin (≥ 25 ng/ml), the macrocylic trichothecene satratoxin G (SG) (≥ 10 ng/ml) and ribosome-inactivating protein ricin (≥ 300 ng/ml) induced 18s and 28s rRNA fragmentation patterns identical to that observed for DON. Also, as found for DON, inhibition of p38, double-stranded RNA-activated kinase (PKR) and hematopoietic cell kinase (Hck) suppressed MAPK anisomycin-induced rRNA cleavage, while, in contrast, their inhibition did not affect SG- and ricin-induced rRNA fragmentation. The p53 inhibitor pifithrin-μ and pan caspase inhibitor Z-VAD-FMK suppressed rRNA cleavage induced by anisomycin, SG and ricin, indicating that these ribotoxins shared with DON a conserved downstream pathway. Activation of caspases 8, 9 and 3 concurrently with apoptosis further suggested that rRNA cleavage occurred in parallel with both extrinsic and intrinsic pathways of programmed cell death. When specific inhibitors of cathepsins L and B (lysosomal cysteine cathepsins active at cytosolic neutral pH) were tested, only the former impaired anisomycin-, SG-, ricin- and DON-induced rRNA cleavage. Taken together, the data suggest that (1) all four ribotoxins induced p53-dependent rRNA cleavage via activation of cathepsin L and caspase 3, and (2) activation of p53 by DON and anisomycin involved p38 whereas SG and ricin activated p53 by an alternative mechanism. Highlights: ► Deoxynivalenol (DON) anisomycin, satratoxin G (SG) and ricin are ribotoxins. ► Ribotoxins induce 18s and 28s rRNA cleavage in the RAW 264.7 macrophage model. ► Ribotoxins induce rRNA cleavage via

  7. A statistical model for cleavage fracture of low alloy steel

    SciTech Connect

    Chen, J.H.; Wang, G.Z.; Wang, H.J.

    1996-10-01

    A new statistical model for cleavage fracture of the low alloy steel is proposed. This model is based on a recently suggested physical model and takes account of the effect of the preceding loading processes. This statistical model satisfactorily describes the failure probability distribution of 42 precracked specimens fractured at various loads at a test temperature of {minus}100 C. The micromechanisms of cleavage fracture of low alloy steel are also further discussed.

  8. A facile and chemoselective conjugate reduction using polymethylhydrosiloxane (PMHS) and catalytic B(C6F5)3.

    PubMed

    Chandrasekhar, Srivari; Chandrashekar, Gudise; Reddy, Marepally Srinivasa; Srihari, Pabbaraja

    2006-05-07

    A highly chemoselective conjugate reduction of electron-deficient Michael acceptors, including alpha,beta-unsaturated ketones, carboxylic esters, nitriles and nitro compounds with PMHS in the presence of catalytic B(C6F5)3 is described.

  9. Synthesis of new Diamond-like B-C Phases under High Pressure and Temperatures

    SciTech Connect

    Ming, L. C.; Zinin, P. V.; Sharma, S. K.

    2014-04-22

    A cubic BC3 (c-BC3) phase was synthesized by direct transformation from graphitic phases at a pressure of 39 GPa and temperature of 2200 K in a laser-heated diamond anvil cell (DAC). A combination of x-ray diffraction (XRD), electron diffraction (ED), transmission electron microscopy (TEM) imaging, and electron energy loss spectroscopy (EELS) measurements lead us to conclude that the obtained phase is hetero-nano-diamond, c-BC3. The EELS measurements show that the atoms inside the cubic structure are bonded by sp3 bonds.

  10. Some new members of MAX family including light-elements: Nanolayered Hf2XY (X= Al, Si, P and Y=B, C, N)

    NASA Astrophysics Data System (ADS)

    Aydin, Sezgin; Tatar, Aynur; Ciftci, Yasemin Oztekin

    2016-03-01

    The structural, electronic, mechanical and dynamical properties of new members of MAX family (Hf2XY, X=Al, Si, P and Y= B, C, N compounds) with Cr2AlC-type structure have been investigated by first-principles density functional plane-wave pseudopotential calculations within generalized gradient approximation. From calculated cohesive energies, all compounds are energetically stable. And, from calculated elastic constants and phonon dispersion curves, it is shown that all compounds are mechanically stable, while the boron including ones are dynamically unstable except for Hf2PB. At the same time, related mechanical properties such as bulk and shear moduli are calculated. For further mechanical characterization, hardnesses of the compounds are determined theoretically. It is observed from electronic structure calculations including band structure and partial density of states, all stable compounds are metallic. Additionally, bonding nature of the compounds are analyzed by using 3D and 2D electron density maps, Mulliken atomic charges and bond overlap populations.

  11. Distinct OGT-Binding Sites Promote HCF-1 Cleavage

    PubMed Central

    Bhuiyan, Tanja; Waridel, Patrice; Kapuria, Vaibhav; Zoete, Vincent; Herr, Winship

    2015-01-01

    Human HCF-1 (also referred to as HCFC-1) is a transcriptional co-regulator that undergoes a complex maturation process involving extensive O-GlcNAcylation and site-specific proteolysis. HCF-1 proteolysis results in two active, noncovalently associated HCF-1N and HCF-1C subunits that regulate distinct phases of the cell-division cycle. HCF-1 O-GlcNAcylation and site-specific proteolysis are both catalyzed by O-GlcNAc transferase (OGT), which thus displays an unusual dual enzymatic activity. OGT cleaves HCF-1 at six highly conserved 26 amino acid repeat sequences called HCF-1PRO repeats. Here we characterize the substrate requirements for OGT cleavage of HCF-1. We show that the HCF-1PRO-repeat cleavage signal possesses particular OGT-binding properties. The glutamate residue at the cleavage site that is intimately involved in the cleavage reaction specifically inhibits association with OGT and its bound cofactor UDP-GlcNAc. Further, we identify a novel OGT-binding sequence nearby the first HCF-1PRO-repeat cleavage signal that enhances cleavage. These results demonstrate that distinct OGT-binding sites in HCF-1 promote proteolysis, and provide novel insights into the mechanism of this unusual protease activity. PMID:26305326

  12. Refractory and Hard Materials in the Ti-Si-B-C-N System - Phase Equilibria, Phase Reactions and Thermal Stabilities

    DTIC Science & Technology

    2004-12-01

    1 REFRACTORY AND HARD MATERIALS IN THE Ti-Si-B-C-N SYSTEM – PHASE EQUILIBRIA , PHASE REACTIONS AND THERMAL STABILITIES Hans Jürgen Seifert...the underlying phase equilibria and reactions have to be known in detail. The main goal of this work was to study the thermal stability with...respect to the phase equilibria and the phase reactions of ceramics and refractory and hard materials in the Ti-Si-B-C-N system by means of CALPHAD

  13. Determination of the method of construction of 1650 B.C. wall paintings.

    PubMed

    Papaodysseus, Constantin; Fragoulis, Dimitrios K; Panagopoulos, Mihalis; Panagopoulos, Thanasis; Rousopoulos, Panayiotis; Exarhos, Mihalis; Skembris, Angelos

    2006-09-01

    In this paper, a methodology of general applicability is presented for answering the question if an artist used a number of archetypes to draw a painting or if he drew it freehand. In fact, the contour line parts of the drawn objects that potentially correspond to archetypes are initially spotted. Subsequently, the exact form of these archetypes and their appearance throughout the painting is determined. The method has been applied to celebrated Thera Late Bronze Age wall paintings with full success. It has been demonstrated that the artist or group of artists has used seven geometrical archetypes and seven corresponding well-constructed stencils (four hyperbolae, two ellipses, and one Archimedes' spiral) to draw the wall painting "Gathering of Crocus" in 1650 B.C. This method of drawing seems to be unique in the history of arts and of great importance for archaeology, and the history of mathematics and sciences, as well.

  14. Publications on fish parasites and diseases, 330 B.C.-A.D

    USGS Publications Warehouse

    McGregor, E.A.

    1963-01-01

    These references were collected in 1924, but until now this collection has been available only in manuscript form. Because of the current increased interest in this field, this bibliography is being issued to make it more generally accessible. They include the earliest known references to fish parasites (330 B.C.) as well as a nearly complete collection up to 1924. In some instances only one or two works of a more prolific researcher are cited, therefore it is recommended that the student use the Index-Catalogue of Medical and Veterinary Zoology (U. S. Department of Agriculture) freely. For more current work consult the following, of which Dogiel et al.(1958), Hoffman and Sindermann (1962), Schaperclaus (1954), and Snieszko et aL(in press) have extensive bibliographies:

  15. Branching fractions of B(c) decays involving J/ψ and X(3872)

    NASA Astrophysics Data System (ADS)

    Hsiao, Y. K.; Geng, Chao-Qiang

    2017-01-01

    We study two-body B(c) → Mc(π,K) and semileptonic decays with , where is regarded as the tetraquark state cc¯uū(dd¯). With the decay constant determined from the data, we predict that , , and . With the form factors in QCD models, we calculate that and (4.7 ± 2.0) × 10-6, and and (1.35 ± 0.18) × 10-3, respectively, and extract the ratio of the fragmentation fractions to be fc/fu = (6.4 ± 1.9) × 10-3. Supported in part by National Center for Theoretical Sciences, National Science Council (NSC-101-2112-M-007-006-MY3), MoST (MoST-104-2112-M-007-003-MY3) National Science Foundation of China (11675030)

  16. Publications on fish parasites and diseases, 330 B.C.-A.D. 1923

    USGS Publications Warehouse

    McGregor, E.A.

    1963-01-01

    These references were collected in 1924, but until now this collection has been available only in manuscript:fbrm. Because of the current increased interest in this field, this bibliography is being issued to make it more generally accessible. They include the earliest known references to fish parasites (330 B. C.) as well as a nearly complete collection up to 1924. In some instances only one or two works of a more prolific re"searcher are cited, therefore it is recommended that the student use the Index-Catalogue of Medical and Veterinary Zoology (U. S. Department of Agriculture) freely. For more current work consult the following, of which Dogiel et al.(1958), Hoffman and Sindermann (1962), Scha'perclaus (1954), and Snieszko et aL(in press) have extensive bibliographies

  17. Physical properties of layered homologous RE-B-C(N) compounds

    NASA Astrophysics Data System (ADS)

    Mori, Takao; Zhang, Fuxiang; Leithe-Jasper, Andreas

    2004-02-01

    Physical properties of a series of homologous RE-B-C(N) B 12 cluster compounds REB 17CN, REB 22C 2N, and RE B28.5C4 (RE= Er, Ho) were investigated. The structures of the compounds are layer-like along the c-axis, with rare earth and B 6 octahedral layers separated by B 12 icosahedral and C-B-C chain layers whose number increases successively from two B 12 layers for the REB 17CN compound to four for the REB 28.5C 4 compound. The rare earth atoms are configured in two triangular flat layers which are stacked on top of one another in AB stacking where the nearest-neighbor rare earth directions are the three atoms forming a triangle in the adjacent layer. The series of homologous compounds exhibit a spin glass transition with Tf shifting in correspondence with variations of the basal plane lattice constants, consistent with the magnetic interaction being effective in the basal planes. The isothermal remanent magnetization shows a stretched exponential decay I m(t)∝ exp[-Ct -(1-n)] . Exponents determined for the different homologous compounds were scaled as a function of Tr= T/ Tf and found to follow the empirical dependency determined for typical spin glasses. It is indicated that a mixture of disorder originating from the partial occupancy of the rare earth sites and frustration of interactions due to the unique configuration is responsible for the manifestation of spin glass transitions in these homologous systems.

  18. Metal-organic frameworks with phosphotungstate incorporated for hydrolytic cleavage of a DNA-model phosphodiester.

    PubMed

    Han, Qiuxia; Zhang, Lejie; He, Cheng; Niu, Jiangyang; Duan, Chunying

    2012-05-07

    Five phosphotungstate-incorporated metal-organic frameworks {[Eu(4)(dpdo)(9)(H(2)O)(16)PW(12)O(40)]}(PW(12)O(40))(2)·(dpdo)(3)·Cl(3) (1); {ZnNa(2)(μ-OH)(dpdo)(4)(H(2)O)(4)[PW(12)O(40)]}·3H(2)O (2); {Zn(3)(dpdo)(7)}[PW(12)O(40)](2)·3H(2)O (3); and [Ln(2)H(μ-O)(2)(dpdo)(4)(H(2)O)(2)][PW(12)O(40)]·3H(2)O (Ln = Ho for 4 and Yb for 5) (dpdo = 4,4'-bipyridine-N,N'-dioxide) have been synthesized through a one-step hydrothermal reaction and characterized by elemental analyses, infrared (IR) spectroscopy, photoluminescence, and single-crystal X-ray diffraction (XRD). The structural analyses indicate that 1-5 display diversity structure from one-dimensional (1D) to three-dimensional (3D) series of hybrids. Kinetic experiments for the hydrolytic cleavage of DNA-model phosphodiester BNPP (bis(p-nitrophenyl)phosphate) were followed spectrophotometrically for the absorbance increase at 400 nm in EPPS (4-(2-hydroxyethyl)piperazine-1-propane sulfonic acid) buffer solution, because of the formation of p-nitrophenoxide with 1-5 under conditions of pH 4.0 and 50 °C. Ultraviolet (UV) spectroscopy indicate that the cleavage of the phosphodiester bond proceeds with the pseudo-first-order rate constant in the range of 10(-7)-10(-6) s(-1), giving an inorganic phosphate and p-nitrophenol as the final products of hydrolysis. The results demonstrate that 1-5 have good catalytic activity and reusability for hydrolytic cleavage of BNPP.

  19. Targeted expression, purification, and cleavage of fusion proteins from inclusion bodies in Escherichia coli.

    PubMed

    Hwang, Peter M; Pan, Jonathan S; Sykes, Brian D

    2014-01-21

    Today, proteins are typically overexpressed using solubility-enhancing fusion tags that allow for affinity chromatographic purification and subsequent removal by site-specific protease cleavage. In this review, we present an alternative approach to protein production using fusion partners specifically designed to accumulate in insoluble inclusion bodies. The strategy is appropriate for the mass production of short peptides, intrinsically disordered proteins, and proteins that can be efficiently refolded in vitro. There are many fusion protein systems now available for insoluble expression: TrpLE, ketosteroid isomerase, PurF, and PagP, for example. The ideal fusion partner is effective at directing a wide variety of target proteins into inclusion bodies, accumulates in large quantities in a highly pure form, and is readily solubilized and purified in commonly used denaturants. Fusion partner removal under denaturing conditions is biochemically challenging, requiring harsh conditions (e.g., cyanogen bromide in 70% formic acid) that can result in unwanted protein modifications. Recent advances in metal ion-catalyzed peptide bond cleavage allow for more mild conditions, and some methods involving nickel or palladium will likely soon appear in more biological applications.

  20. Copper- and Vanadium-Catalyzed Oxidative Cleavage of Lignin using Dioxygen.

    PubMed

    Mottweiler, Jakob; Puche, Marta; Räuber, Christoph; Schmidt, Thomas; Concepción, Patricia; Corma, Avelino; Bolm, Carsten

    2015-06-22

    Transition-metal-containing hydrotalcites (HTc) and V(acac)3 /Cu(NO3 )2 ⋅3 H2 O (acac=acetylacetonate) mixtures were tested for their catalytic activity in the cleavage of the lignin model compound erythro-1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-l,3-propanediol (1) with molecular oxygen as oxidant. Both catalytic systems displayed high activity and good selectivity and afforded veratric acid as the main product. The catalyst behavior was studied by EPR spectroscopy, XRD, and Raman spectroscopy. After the catalysts were established for the model system, lignin depolymerization studies were performed with various organsolv and kraft lignin sources. The oxidative depolymerization and lignin bond cleavage were monitored by gel permeation chromatography (GPC), MALDI MS, and 2D-NMR (HSQC). Irrespective of the lignin pretreatment, both HTc-Cu-V and V(acac)3 /Cu(NO3 )2 ⋅3 H2 O were able to cleave the β-O-4 linkages and the resinol structures to form dimeric and trimeric products.

  1. Phosphodiester hydrolysis and specific DNA binding and cleavage promoted by guanidinium-functionalized zinc complexes.

    PubMed

    He, Juan; Sun, Jing; Mao, Zong-Wan; Ji, Liang-Nian; Sun, Hongzhe

    2009-05-01

    Two new Zn(II) complexes containing guanidinium groups, [Zn(L(1))Cl(2)](ClO(4))(2).H(2)O.CH(3)OH (1) and [Zn(L(2))Cl(2)](ClO(4))(2).0.5H(2)O (2), were synthesized and characterized (L(1)=5,5'-di[1-(guanidyl)methyl]-2,2'-bipyridyl bication and L(2)=6,6'-di[1-(guanidyl)methyl]-2,2'-bipyridyl bication). Both complexes are able to catalyze bis(p-nitrophenyl) phosphate (BNPP) hydrolysis efficiently. Obtained kinetic data reveal that both 1 and 2 show nearly 300- and 600-fold rate enhancement of BNPP hydrolysis, respectively, compared to their simple analogue without the guanidinium groups [Zn(bpy)Cl(2)] (bpy=2,2'-bipyridy) (3). Enhanced acceleration for cleavage of BNPP could be attributed to cooperative interaction between the Zn(II) ion and the guanidinium groups by electrostatic interaction and H-bonding. Studies on inhibition of sequence-specific endonucleases (DraI and SmaI) by complexes show that 1 and 2 are able to recognize nucleotide sequence, -TTT;AAA-, and highly effectively cleave the plasmid DNA in the presence of hydrogen peroxide, while 3 has no specific binding to the DNA target sequences and only shows low DNA cleavage activity.

  2. Catalysis of poliovirus VP0 maturation cleavage is not mediated by serine 10 of VP2.

    PubMed Central

    Harber, J J; Bradley, J; Anderson, C W; Wimmer, E

    1991-01-01

    The maturation of the poliovirus capsid occurs as the result of a single unexplained proteolytic event during which 58 to 59 copies of the 60 VP0 capsid protein precursors are cleaved. An autocatalytic mechanism for cleavage of VP0 to VP4 and VP2 was proposed by Arnold et al. (E. Arnold, M. Luo, G. Vriend, M. G. Rossman, A. C. Palmenberg, G. D. Parks, M. J. Nicklin, and E. Wimmer, Proc. Natl. Acad. Sci. USA 84:21-25, 1987) in which serine 10 of VP2 is activated by virion RNA to catalyze VP4-VP2 processing. The hypothesis rests on the observation that a hydrogen bond was observed between serine 10 of VP2 (S2010) and the carboxyl terminus of VP4 in three mature picornaviral atomic structures: rhinovirus 14, mengovirus, and poliovirus type 1 (Mahoney). We constructed mutant viruses with cysteine (S2010C) or alanine (S2010A) replacing serine 10 of VP2; these exhibited normal proteolytic processing of VP0. While our results do not exclude an autocatalytic mechanism for the maturation cleavage, they do eliminate the conserved S2010 residue as the catalytic amino acid. Images PMID:1845893

  3. Using Multiple Bonding Strategies.

    PubMed

    Larson, Thomas D

    2015-01-01

    There are many ways to bond to tooth structure, some micro-mechanical some chemical, some a combination. Different dentin bonding materials have different bonding strengths to differently prepared surfaces, and because of differences in their nature, different areas of tooth structure present peculiar bonding challenges. This paper will review a variety of material types, elucidating their particular bonding strengths and commenting on improved bonding strategies to increase durability, strength, and favorable pulpal response. In this discussion, resin dentin bonding systems, glass ionomers, Gluma, resin cements, and newer combined products will br reviewed.

  4. Size effects and strain localization in atomic-scale cleavage modeling.

    PubMed

    Elsner, B A M; Müller, S

    2015-09-04

    In this work, we study the adhesion and decohesion of Cu(1 0 0) surfaces using density functional theory (DFT) calculations. An upper stress to surface decohesion is obtained via the universal binding energy relation (UBER), but the model is limited to rigid separation of bulk-terminated surfaces. When structural relaxations are included, an unphysical size effect arises if decohesion is considered to occur as soon as the strain energy equals the energy of the newly formed surfaces. We employ the nudged elastic band (NEB) method to show that this size effect is opposed by a size-dependency of the energy barriers involved in the transition. Further, we find that the transition occurs via a localization of bond strain in the vicinity of the cleavage plane, which resembles the strain localization at the tip of a sharp crack that is predicted by linear elastic fracture mechanics.

  5. Identification of an imino group indispensable for cleavage by a small ribozyme.

    PubMed

    Spitale, Robert C; Volpini, Rosaria; Heller, Moriah G; Krucinska, Jolanta; Cristalli, Gloria; Wedekind, Joseph E

    2009-05-06

    The hairpin ribozyme is a small, noncoding RNA (ncRNA) that catalyzes a site-specific phosphodiester bond cleavage reaction. Prior biochemical and structural analyses pinpointed the amidine moiety of base Ade38 as a key functional group in catalysis, but base changes designed to probe function resulted in localized misfolding of the active site. To define the requirements for chemical activity using a conservative modification, we synthesized and incorporated N1-deazaadenosine into the full-length ribozyme construct. This single-atom variant severely impairs activity, although the active-site fold remains intact in the accompanying crystal structures. The results demonstrate the essentiality of the imino moiety as well as the importance of its interaction with the substrate in the precatalytic and transition-state conformations. This work demonstrates the efficacy of single-atom approaches in the analysis of ncRNA structure-function relationships.

  6. Kinetic isotope effects for RNA cleavage by 2'-O- transphosphorylation: Nucleophilic activation by specific base

    PubMed Central

    Harris, Michael E; Dai, Qing; Gu, Hong; Kellerman, Dan; Piccirilli, Joseph A; Anderson, Vernon E

    2010-01-01

    To better understand the interactions between catalysts and transition states during RNA strand cleavage, primary 18O kinetic isotope effects and solvent D2O isotope effects were measured to probe the mechanism of base-catalyzed 2'-O-transphosphorylation of the RNA dinucleotide 5'-UpG-3'. The observed 18O KIEs for the nucleophilic 2'-O and in the 5'-O leaving group at pH 14 are both large relative to reactions of phosphodiesters with good leaving groups, indicating that the reaction catalyzed by hydroxide has a transition state (TS) with advanced phosphorus-oxygen bond fission to the leaving group (18kLG = 1.034 ± 0.004) and phosphorous-nucleophile bond formation (18kNUC = 0.984 ± 0.004). A breakpoint in the pH dependence of the 2'-O-transphosphorylation rate to a pH independent phase above pH 13 has been attributed to the pKa of the 2'-OH nucleophile. A smaller nucleophile KIE is observed at pH 12 (18kNUC = 0.995 ± 0.004) that is interpreted as the combined effect of the equilibrium isotope effect (~1.02) on deprotonation of the 2′-hydroxyl nucleophile and the intrinsic KIE on the nucleophilic addition step (ca. 0.981). An alternative mechanism in which the hydroxide ion acts as a general base is considered unlikely given the lack of a solvent deuterium isotope effect above the breakpoint in the pH versus rate profile. These results represent the first direct analysis of the transition state for RNA strand cleavage. The primary 18O KIE results and the lack of a kinetic solvent deuterium isotope effect together provide strong evidence for a late transition state and 2'-O nucleophile activation by specific base catalysis. PMID:20669950

  7. Selective cleavage of protonated penetratin and its substitutes under low-energy collision-induced dissociation condition.

    PubMed

    Peng, Juan; Zu, Lily; Fang, Weihai; Huang, Lingyun; Wang, Yaru; He, Dacheng

    2010-06-01

    An understanding of the dissociation of penetratin is important for improving its metabolic stability and cargo-delivery efficiency. In this study, we describe the selective cleavage of the K15-K16 amide bond of penetratin under the low-energy collision-induced dissociation condition in mass spectrometry. A variety of penetratin substitutes have been studied in which key basic amino acids have been substituted within the sequence. The calculated structure indicates that an alpha-helix structure prevents the fragmentation of the central peptide domain and the side chain of lysine is involved in the proton translocation process.

  8. Symmetrical P4 cleavage at cobalt: characterization of intermediates on the way from P4 to coordinated P2 units.

    PubMed

    Dürr, Simon; Ertler, Daniel; Radius, Udo

    2012-03-19

    Degradation of white phosphorus (P(4)) in the coordination sphere of transition metals is commonly divided into two major pathways depending on the P(x) ligands obtained. Consecutive metal-assisted P-P bond cleavage of four bonds of the P(4) tetrahedron leads to complexes featuring two P(2) ligands (symmetric cleavage) or one P(3) and one P(1) ligand (asymmetric cleavage). A systematic investigation of the degradation of white phosphorus P(4) to coordinated μ,η(2:2)-bridging diphosphorus ligands in the coordination sphere of cobalt is presented herein as well as isolation of each of the decisive intermediates on the reaction pathway. The olefin complex [Cp*Co((i)Pr(2)Im)(η(2)-C(2)H(4))], 1 (Cp* = η(5)-C(5)Me(5), (i)Pr(2)Im = 1,3-di-isopropylimidazolin-2-ylidene), reacts with P(4) to give [Cp*Co((i)Pr(2)Im)(η(2)-P(4))], 2, the insertion product of [Cp*Co((i)Pr(2)Im)] into one of the P-P bonds. Addition of a further equivalent of the Co(I) complex [Cp*Co((i)Pr(2)Im)(η(2)-C(2)H(4))], 1, induces cleavage of a second P-P bond to yield the dinuclear complex [{Cp*Co((i)Pr(2)Im)}(2)(μ,η(2:2)-P(4))], 3, in which a kinked cyclo-P(4)(4-) ligand bridges two cobalt atoms. Consecutive dissociation of the N-heterocyclic carbene with concomitant rearrangement of the cyclo-P(4) ligand and P-P dissociation leads to complexes [Cp*Co(μ,η(4:2)-P(4))Co((i)Pr(2)Im)Cp*], 4, featuring a P(4) chain, and [{Cp*Co(μ,η(2:2)-P(2))}(2)], 5, in which two isolated P(2)(2-) ligands bridge two [Cp*Co] fragments. Each of these reactions is quantitative if performed on an NMR scale, and each compound can be isolated in high yields and large quantities.

  9. Solar photochemical oxidation of alcohols using catalytic hydroquinone and copper nanoparticles under oxygen: oxidative cleavage of lignin models.

    PubMed

    Mitchell, Lorna J; Moody, Christopher J

    2014-11-21

    Alcohols are converted into to their corresponding carbonyl compounds using catalytic amounts of 1,4-hydroquinone with a copper nanoparticle electron transfer mediator with oxygen as the terminal oxidant in acetone as solvent under visible light irradiation. These conditions employing biorenewable hydroquinone as reagent were developed from initial experiments using stoichiometric amounts of 1,4-benzoquinone as oxidant. A range of benzylic and aliphatic primary and secondary alcohols are oxidized, affording the corresponding aldehydes or ketones in moderate to excellent yields. The methodology is also applicable to the oxidative degradation of lignin model compounds that undergo C-C bond cleavage to give simple aromatic compounds.

  10. Separating electrophilicity and Lewis acidity: the synthesis, characterization, and electrochemistry of the electron deficient tris(aryl)boranes B(C6F5)(3-n)(C6Cl5)n (n = 1-3).

    PubMed

    Ashley, Andrew E; Herrington, Thomas J; Wildgoose, Gregory G; Zaher, Hasna; Thompson, Amber L; Rees, Nicholas H; Krämer, Tobias; O'Hare, Dermot

    2011-09-21

    A new family of electron-deficient tris(aryl)boranes, B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 1-3), has been synthesized, permitting an investigation into the steric and electronic effects resulting from the gradual replacement of C(6)F(5) with C(6)Cl(5) ligands. B(C(6)F(5))(2)(C(6)Cl(5)) (3) is accessed via C(6)Cl(5)BBr(2), itself prepared from donor-free Zn(C(6)Cl(5))(2) and BBr(3). Reaction of C(6)Cl(5)Li with BCl(3) in a Et(2)O/hexane slurry selectively produced B(C(6)Cl(5))(2)Cl, which undergoes B-Cl exchange with CuC(6)F(5) to afford B(C(6)F(5))(C(6)Cl(5))(2) (5). While 3 forms a complex with H(2)O, which can be rapidly removed under vacuum or in the presence of molecular sieves, B(C(6)Cl(5))(3) (6) is completely stable to refluxing toluene/H(2)O for several days. Compounds 3, 5, and 6 have been structurally characterized using single crystal X-ray diffraction and represent the first structure determinations for compounds featuring B-C(6)Cl(5) bonds; each exhibits a trigonal planar geometry about B, despite having different ligand sets. The spectroscopic characterization using (11)B, (19)F, and (13)C NMR indicates that the boron center becomes more electron-deficient as n increases. Optimized structures of B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) using density functional theory (B3LYP/TZVP) are all fully consistent with the experimental structural data. Computed (11)B shielding constants also replicate the experimental trend almost quantitatively, and the computed natural charges on the boron center increase in the order n = 0 (0.81) < n = 1 (0.89) < n = 2 (1.02) < n = 3 (1.16), supporting the hypothesis that electrophilicity increases concomitantly with substitution of C(6)F(5) for C(6)Cl(5). The direct solution cyclic voltammetry of B(C(6)F(5))(3) has been obtained for the first time and electrochemical measurements upon the entire series B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) corroborate the spectroscopic data, revealing C(6)Cl(5) to be a more electron

  11. Cleavage of Signal Regulatory Protein α (SIRPα) Enhances Inflammatory Signaling.

    PubMed

    Londino, James D; Gulick, Dexter; Isenberg, Jeffrey S; Mallampalli, Rama K

    2015-12-25

    Signal regulatory protein α (SIRPα) is a membrane glycoprotein immunoreceptor abundant in cells of monocyte lineage. SIRPα ligation by a broadly expressed transmembrane protein, CD47, results in phosphorylation of the cytoplasmic immunoreceptor tyrosine-based inhibitory motifs, resulting in the inhibition of NF-κB signaling in macrophages. Here we observed that proteolysis of SIRPα during inflammation is regulated by a disintegrin and metalloproteinase domain-containing protein 10 (ADAM10), resulting in the generation of a membrane-associated cleavage fragment in both THP-1 monocytes and human lung epithelia. We mapped a charge-dependent putative cleavage site near the membrane-proximal domain necessary for ADAM10-mediated cleavage. In addition, a secondary proteolytic cleavage within the membrane-associated SIRPα fragment by γ-secretase was identified. Ectopic expression of a SIRPα mutant plasmid encoding a proteolytically resistant form in HeLa cells inhibited activation of the NF-κB pathway and suppressed STAT1 phosphorylation in response to TNFα to a greater extent than expression of wild-type SIRPα. Conversely, overexpression of plasmids encoding the proteolytically cleaved SIRPα fragments in cells resulted in enhanced STAT-1 and NF-κB pathway activation. Thus, the data suggest that combinatorial actions of ADAM10 and γ-secretase on SIRPα cleavage promote inflammatory signaling.

  12. Cleavage Entropy as Quantitative Measure of Protease Specificity

    PubMed Central

    Fuchs, Julian E.; von Grafenstein, Susanne; Huber, Roland G.; Margreiter, Michael A.; Spitzer, Gudrun M.; Wallnoefer, Hannes G.; Liedl, Klaus R.

    2013-01-01

    A purely information theory-guided approach to quantitatively characterize protease specificity is established. We calculate an entropy value for each protease subpocket based on sequences of cleaved substrates extracted from the MEROPS database. We compare our results with known subpocket specificity profiles for individual proteases and protease groups (e.g. serine proteases, metallo proteases) and reflect them quantitatively. Summation of subpocket-wise cleavage entropy contributions yields a measure for overall protease substrate specificity. This total cleavage entropy allows ranking of different proteases with respect to their specificity, separating unspecific digestive enzymes showing high total cleavage entropy from specific proteases involved in signaling cascades. The development of a quantitative cleavage entropy score allows an unbiased comparison of subpocket-wise and overall protease specificity. Thus, it enables assessment of relative importance of physicochemical and structural descriptors in protease recognition. We present an exemplary application of cleavage entropy in tracing substrate specificity in protease evolution. This highlights the wide range of substrate promiscuity within homologue proteases and hence the heavy impact of a limited number of mutations on individual substrate specificity. PMID:23637583

  13. Binding and cleavage of nucleic acids by the "hairpin" ribozyme.

    PubMed

    Chowrira, B M; Burke, J M

    1991-09-03

    The "hairpin" ribozyme derived from the minus strand of tobacco ringspot virus satellite RNA [(-)sTRSV] efficiently catalyzes sequence-specific RNA hydrolysis in trans (Feldstein et al., 1989; Hampel & Triz, 1989; Haseloff & Gerlach, 1989). The ribozyme does not cleave DNA. An RNA substrate analogue containing a single deoxyribonucleotide residue 5' to the cleavage site (A-1) binds to the ribozyme efficiently but cannot be cleaved. A DNA substrate analogue with a ribonucleotide at A-1 is cleaved; thus A-1 provides the only 2'-OH required for cleavage. These results support cleavage via a transphosphorylation mechanism initiated by attack of the 2'-OH of A-1 on the scissile phosphodiester. The ribozyme discriminates between DNA and RNA in both binding and cleavage. Results indicate that the 2'-OH of A-1 functions in complex stabilization as well as cleavage. The ribozyme efficiently cleaves a phosphorothioate diester linkage, suggesting that the pro-Rp oxygen at the scissile phosphodiester does not coordinate Mg2+.

  14. Cleavage of Signal Regulatory Protein α (SIRPα) Enhances Inflammatory Signaling*

    PubMed Central

    Londino, James D.; Gulick, Dexter; Isenberg, Jeffrey S.; Mallampalli, Rama K.

    2015-01-01

    Signal regulatory protein α (SIRPα) is a membrane glycoprotein immunoreceptor abundant in cells of monocyte lineage. SIRPα ligation by a broadly expressed transmembrane protein, CD47, results in phosphorylation of the cytoplasmic immunoreceptor tyrosine-based inhibitory motifs, resulting in the inhibition of NF-κB signaling in macrophages. Here we observed that proteolysis of SIRPα during inflammation is regulated by a disintegrin and metalloproteinase domain-containing protein 10 (ADAM10), resulting in the generation of a membrane-associated cleavage fragment in both THP-1 monocytes and human lung epithelia. We mapped a charge-dependent putative cleavage site near the membrane-proximal domain necessary for ADAM10-mediated cleavage. In addition, a secondary proteolytic cleavage within the membrane-associated SIRPα fragment by γ-secretase was identified. Ectopic expression of a SIRPα mutant plasmid encoding a proteolytically resistant form in HeLa cells inhibited activation of the NF-κB pathway and suppressed STAT1 phosphorylation in response to TNFα to a greater extent than expression of wild-type SIRPα. Conversely, overexpression of plasmids encoding the proteolytically cleaved SIRPα fragments in cells resulted in enhanced STAT-1 and NF-κB pathway activation. Thus, the data suggest that combinatorial actions of ADAM10 and γ-secretase on SIRPα cleavage promote inflammatory signaling. PMID:26534964

  15. Cleavage entropy as quantitative measure of protease specificity.

    PubMed

    Fuchs, Julian E; von Grafenstein, Susanne; Huber, Roland G; Margreiter, Michael A; Spitzer, Gudrun M; Wallnoefer, Hannes G; Liedl, Klaus R

    2013-04-01

    A purely information theory-guided approach to quantitatively characterize protease specificity is established. We calculate an entropy value for each protease subpocket based on sequences of cleaved substrates extracted from the MEROPS database. We compare our results with known subpocket specificity profiles for individual proteases and protease groups (e.g. serine proteases, metallo proteases) and reflect them quantitatively. Summation of subpocket-wise cleavage entropy contributions yields a measure for overall protease substrate specificity. This total cleavage entropy allows ranking of different proteases with respect to their specificity, separating unspecific digestive enzymes showing high total cleavage entropy from specific proteases involved in signaling cascades. The development of a quantitative cleavage entropy score allows an unbiased comparison of subpocket-wise and overall protease specificity. Thus, it enables assessment of relative importance of physicochemical and structural descriptors in protease recognition. We present an exemplary application of cleavage entropy in tracing substrate specificity in protease evolution. This highlights the wide range of substrate promiscuity within homologue proteases and hence the heavy impact of a limited number of mutations on individual substrate specificity.

  16. Tris(3-hydroxypropyl)phosphine (THPP): A mild, air-stable reagent for the rapid, reductive cleavage of small-molecule disulfides.

    PubMed

    McNulty, James; Krishnamoorthy, Venkatesan; Amoroso, Dino; Moser, Michael

    2015-10-01

    Tris(3-hydroxypropyl)phosphine (THPP) is demonstrated to be a versatile, water-soluble and air-stable reducing agent, allowing for the rapid, irreversible reductive cleavage of disulfide bonds in both aqueous and buffered aqueous-organic media. The reagent shows exceptional stability at biological pH under which condition it permits the rapid reduction of a wide range of differentially functionalized small-molecule disulfides.

  17. Leather material found on a 6th B.C. Chinese bronze sword: a technical study.

    PubMed

    Luo, Wugan; Si, Yi; Wang, Hongmin; Qin, Ying; Huang, Fengchun; Wang, Changsui

    2011-09-01

    During July to November, 2006, an important archaeological excavation was conducted in Yun country, Hubei province, southern China. Chinese archaeologists found some remnant of leather materials, covered with red pigments, on a 6th century B.C. Chinese bronze sword. To understand the technology/ies that may have been utilized for manufacturing the leathers, a combined of Raman spectroscopy, FT-IR and XRF was thus applied to the remnant of leather materials. Raman analyses showed that red pigment on the leather was cinnabar (HgS). FT-IR and XRF analyses indicated that the content of some elements, such as Ca (existing as CaCO3) and Fe (existing as Fe2O3), were much higher than those in the surrounding grave soil. The results inferred an application of lime depilation and retting, and the Fe-Al compound salt as tanning agent. And it was furthermore implicated that the Fe-Al salt tanning technique had been developed in the middle and late Spring and Autumn Period of China.

  18. Polycomb Group Targeting through Different Binding Partners of RING1B C-Terminal Domain

    PubMed Central

    Wang, Renjing; Taylor, Alexander B.; Leal, Belinda Z.; Chadwell, Linda V.; Ilangovan, Udayar; Robinson, Angela K.; Schirf, Virgil; Hart, P. John; Lafer, Eileen M.; Demeler, Borries; Hinck, Andrew P.; McEwen, Donald G.; Kim, Chongwoo A.

    2015-01-01

    SUMMARY RING1B, a Polycomb Group (PcG) protein, binds methylated chromatin through its association with another PcG protein called Polycomb (Pc). However, RING1B can associate with nonmethylated chromatin suggesting an alternate mechanism for RING1B interaction with chromatin. Here, we demonstrate that two proteins with little sequence identity between them, the Pc cbox domain and RYBP, bind the same surface on the C-terminal domain of RING1B (C-RING1B). Pc cbox and RYBP each fold into a nearly identical, intermolecular beta sheet with C-RING1B and a loop structure which are completely different in the two proteins. Both the beta sheet and loop are required for stable binding and transcription repression. Further, a mutation engineered to disrupt binding on the Drosophila dRING1 protein prevents chromatin association and PcG function in vivo. These results suggest that PcG targeting to different chromatin locations relies, in part, on binding partners of C-RING1B that are diverse in sequence and structure. PMID:20696397

  19. Polyketide-nonribosomal peptide epothilone antitumor agents: the EpoA, B, C subunits.

    PubMed

    Walsh, Christopher T; O'Connor, Sarah E; Schneider, Tanya L

    2003-08-01

    The epothilones are a family of macrolactone natural products from the myxobacterial species Sorangium cellulosum. Similar to taxol, they are of current clinical interest as anticancer agents. Sequence analysis of the epothilone gene cluster allowed the identification of polyketide synthase and nonribosomal peptide synthetase modules involved in catalyzing epothilone biosynthesis. Given this information, it has been possible to test the predicted functions of several modules to date. EpoA ACP, EpoB, and EpoC have been overproduced in Escherichia coli, allowing in vitro reconstitution of the EpoA/B/C interface and production of the expected epothilone precursor. Further experiments probed the tolerance of EpoB and EpoC for unnatural substrates. These studies of the first three modules of the epothilone biosynthetic cluster suggest that combinatorial biosynthesis may lead to the production of a variety of epothilone analogs that incorporate diversity into the heterocycle starter unit. Additional efforts with the remaining modules, coupled with increased understanding of the macrocyclizing thioesterase domain, may lead to the production of epothilone variants with improved clinical properties.

  20. Final environmental impact statement, Washington Water Power/B.C. Hydro Transmission Interconnection Project

    SciTech Connect

    Not Available

    1992-10-01

    Washington Water Power (WWP) proposes to construct and operate an electric transmission line that would connect with the electrical system of the British Columbia Hydro and Power Authority (B.C. Hydro). The project would be composed of a double-circuit, 230-kilovolt (kV) transmission line from WWP`s existing Beacon Substation located northeast of Spokane, Washington to the international border located northwest of Metaline Falls, Washington. The original Presidential permit application and associated proposed route presented in the draft environmental impact statement (DEIS) have been modified to terminate at the Beacon Substation, instead of WWP`s initially proposed termination point at the planned Marshall Substation located southwest of Spokane. A supplemental draft EIS was prepared and submitted for review to not only examine the new proposed 5.6 miles of route, but to also compare the new Proposed Route to the other alternatives previously analyzed in the DEIS. This final EIS (FEIS) assesses the environmental effects of the proposed transmission line through construction, operation, maintenance, and abandonment activities and addresses the impacts associated with the Proposed Action, Eastern Alternative, Western Alternative, Northern Crossover Alternative, Southern Crossover Alternative, and No Action Alternative. The FEIS also contains the comments received and the responses to these comments submitted on the DEIS and Supplemental DEIS.

  1. Carbon Inhomogeneity and Superconducting Properties of Mg(B,C)2

    NASA Astrophysics Data System (ADS)

    Cooley, L. D.; Zambano, A. J.; Moodenbaugh, A. R.; Klie, R. F.

    2006-03-01

    Mg and B4C mixtures (molecular ratio of [1:2]) were reacted in a single step in stainless steel from 850 C to 1300 C to produce nominal MgB1.8C0.2 as estimated from unit cell volumes. Reactions from 850 to 1100 C produced an inhomogeneous superconducting phase despite the initial atomic B4C compound, suggesting that carbon segregation is an important part of these reactions. For reactions above 1100 C, the critical temperature Tc increased from 18 to 28 K as the strain (as estimated from x-ray diffraction peak broadening) decreased at nominally constant carbon content, suggesting that structural order is also important. These changes will be discussed with regard to the formation and coarsening of amorphous and crystalline impurity phases observed by electron microscopy, which affect electron scattering and connectivity. Since only scattering affects the upper critical field, whereas both scattering and connectivity affect the transport properties, optimization of these reactions is crucial to understanding the potential for Mg(B,C)2 as a high-field superconductor.

  2. Drought frequency in central California since 101 B.C. recordered in giant sequoia tree rings

    SciTech Connect

    Hughes, M.K.; Brown, P.M.

    1992-01-01

    Well replicated tree-ring width index chronologies have been developed for giant sequoia at three sites in the Sierra Nevada, California. Extreme low-growth events in these chronologies correspond with regional drought events in the twentieth century in the San Joaquin drainage, in which the giant sequoia sites are located. This relationship is based upon comparison of tree-ring indices with August Palmer Drought Severity Indices for California Climate Division 5. Ring-width indices in the lowest decile from each site were compared. The frequency of low-growth events which occurred at all three sites in the same year is reconstructed from 101 B.C. to A.D. 1988. The inferred frequency of severe drought events changes through time, sometimes suddenly. The period from roughly 1850 to 1950 had one of the lowest frequencies of drought of any one hundred year period in the 2089 year record. The twentieth century so far has had a below-average frequency of extreme droughts. 26 refs., 6 figs., 1 tab.

  3. THRESHOLD STUDIES ON TNT, COMPOSITION B, C-4, AND ANFO EXPLOSIVES USING THE STEVEN IMPACT TEST

    SciTech Connect

    Vandersall, K S; Switzer, L L; Garcia, F

    2006-06-20

    Steven Impact Tests were performed at low velocity on the explosives TNT (trinitrotolulene), Composition B (63% RDX, 36% TNT, and 1% wax by weight), C-4 (91% RDX, 5.3% Di (2-ethylhexyl) sebacate, 2.1% Polyisobutylene, and 1.6% motor oil by weight) and ANFO (94% ammonium Nitrate with 6% Fuel Oil) in attempts to obtain a threshold for reaction. A 76 mm helium driven gas gun was used to accelerate the Steven Test projectiles up to approximately 200 m/s in attempts to react (ignite) the explosive samples. Blast overpressure gauges, acoustic microphones, standard video and high-speed photography were used to characterize the level of any high explosive reaction violence. No bulk reactions were observed in the TNT, Composition B, C-4 or ANFO explosive samples impacted up to velocities in the range of 190-200 m/s. This work will outline the experimental details and discuss the lack of reaction when compared to the reaction thresholds of other common explosives. These results will also be compared to that of the Susan Test and reaction thresholds observed in the common small-scale safety tests such as the drop hammer and friction tests in hopes of drawing a correlation.

  4. Processing of Oak Ridge B&C pond sludge surrogate in the transportable vitrification system

    SciTech Connect

    Zamecnik, J.R.; Young, S.R.; Peeler, D.K.; Smith, M.E.

    1997-04-16

    The Transportable Vitrification System (TVS) developed at the Savannah River Site is designed to process low-level and mixed radioactive wastes into a stable glass product. The TVS consists of a feed preparation and delivery system, a joule-heated melter, and an offgas treatment system. Surrogate Oak Ridge Reservation (ORR) B&C pond sludge was treated in a demonstration of the TVS system at Clemson University and at ORR. After initial tests with soda-lime-silica (SLS) feed, three melter volumes of glass were produced from the surrogate feed. A forthcoming report will describe glass characterization; and melter feeding, operation, and glass pouring. Melter operations described will include slurry characterization and feeding, factors affecting feed melt rates, glass pouring and pour rate constraints, and melter operating temperatures. Residence time modeling of the melter will also be discussed. Characterization of glass; including composition, predicted liquidity and viscosity, Toxic Characteristic Leaching Procedure (TCLP), and devitrification will be covered. Devitrification was a concern in glass container tests and was found to be mostly dependent on the cooling rate. Crucible tests indicated that melter shutdown with glass containing Fe and Li was also a devitrification concern, so the melter was flushed with SLS glass before cooldown.

  5. Leather material found on a 6th B.C. Chinese bronze sword: A technical study

    NASA Astrophysics Data System (ADS)

    Luo, Wugan; Si, Yi; Wang, Hongmin; Qin, Ying; Huang, Fengchun; Wang, Changsui

    2011-09-01

    During July to November, 2006, an important archaeological excavation was conducted in Yun country, Hubei province, southern China. Chinese archaeologists found some remnant of leather materials, covered with red pigments, on a 6th century B.C. Chinese bronze sword. To understand the technology/ies that may have been utilized for manufacturing the leathers, a combined of Raman spectroscopy, FT-IR and XRF was thus applied to the remnant of leather materials. Raman analyses showed that red pigment on the leather was cinnabar (HgS). FT-IR and XRF analyses indicated that the content of some elements, such as Ca (existing as CaCO 3) and Fe (existing as Fe 2O 3), were much higher than those in the surrounding grave soil. The results inferred an application of lime depilation and retting, and the Fe-Al compound salt as tanning agent. And it was furthermore implicated that the Fe-Al salt tanning technique had been developed in the middle and late Spring and Autumn Period of China.

  6. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  7. Experimental verification of cleavage characteristic stress vs grain size

    SciTech Connect

    Lei, W. . Dept. of Mechanical Engineering); Li, D.; Yao, M. . School of Materials Science and Engineering)

    1994-07-01

    Instead of the accepted cleavage fracture stress [sigma][sub f] proposed by Knott et al, a new parameter S[sub co], named as ''cleavage characteristic stress,'' has been recently recommended to characterize the microscopic resistance to cleavage fracture. To give a definition, S[sub co] is the fracture stress at the brittle/ductile transition temperature of steels in plain tension, below which the yield strength approximately equals the true fracture stress combined with an abrupt curtailment of ductility. By considering a single-grain microcrack arrested at a boundary, Huang and Yao set up an expression of S[sub co] as a function of grain size. The present work was arranged to provide an experimental verification of S[sub co] vs grain size.

  8. Accurate in vitro cleavage by RNase III of phosphorothioate-substituted RNA processing signals in bacteriophage T7 early mRNA.

    PubMed Central

    Nicholson, A W; Niebling, K R; McOsker, P L; Robertson, H D

    1988-01-01

    To test the ability of an RNA processing enzyme to cleave chemically-modified RNA substrates, RNA transcripts containing RNase III cleavage sites were enzymatically synthesized in vitro to contain specific phosphorothioate diester internucleotide linkages. One transcript (R1.1 RNA) was generated using phage T7 RNA polymerase and a cloned segment of phage T7 DNA containing the R1.1 RNase III processing site. The second transcript was the phage T7 polycistronic early mRNA precursor, which was synthesized using E. coli RNA polymerase and T7 genomic DNA. The RNA transcripts contained phosphorothioate diester groups at positions including the scissile bonds. The modified RNAs were stable to incubation in Mg2+-containing buffer, and were specifically cleaved by RNase III. RNA oligonucleotide sequence analysis showed that the modified R1.1 RNA processing site was the same as the canonical site and contained a phosphorothioate bond. Furthermore, RNase III cleaved the phosphorothioate internucleotide bond with 5' polarity. RNase III cleavage of phosphorothioate substituted T7 polycistronic early mRNA precursor produced the same gel electrophoretic pattern as that obtained with the control transcript. Thus, RNase III cleavage specificity is not altered by phosphorothioate internucleotide linkages. Images PMID:3279395

  9. Facile electrochemical detection of botulinum neurotoxin type E using a two-step proteolytic cleavage.

    PubMed

    Park, Seonhwa; Shin, Yu Mi; Song, Ji-Joon; Yang, Haesik

    2015-10-15

    Facile electrochemical methods for measuring protease concentration or protease activity are essential for point-of-care testing of toxic proteases. However, electrochemical detection of proteases, such as botulinum neurotoxin type E (BoNT/E), that cleave a peptide bond between two specific amino acid residues is challenging. This study reports a facile and sensitive electrochemical method for BoNT/E detection. The method is based on a two-step proteolytic cleavage using a target BoNT/E light chain (BoNT/E-LC) and an externally supplemented exopeptidase, L-leucine-aminopeptidase (LAP). BoNT/E-LC cleaves a peptide bond between arginine and isoleucine in IDTQNRQIDRI-4-amino-1-naphthol (oligopeptide-AN) to generate isoleucine-AN. Subsequently, LAP cleaves a bond between isoleucine and AN to liberate a free electroactive AN species. The liberated AN participates in electrochemical-chemical-chemical (ECC) redox cycling involving Ru(NH3)6(3+), AN, and a reducing agent, which allows a high signal amplification. Electrochemical detection is carried out without surface modification of indium-tin oxide electrodes. We show that dithiothreitol is beneficial for enhancing the enzymatic activity of BoNT/E-LC and also for achieving a fast ECC redox cycling. An incubation temperature of 37°C and the use of phosphate buffered saline (PBS) buffer resulted in optimal signal-to-background ratios for efficient BoNT/E detection. BoNT/E-LC could be detected at concentrations of approximately 2.0 pg/mL, 0.2, and 3 ng/mL after 4h, 2h, and 15 min incubation in PBS buffer, respectively, and approximately 0.3 ng/mL after 2-h incubation in bottled water. The method developed could be applied in fast, sensitive, and selective detection of any protease that cleaves a peptide bond between two specific amino acid residues.

  10. The mechanism of human tyrosyl-DNA phosphodiesterase 1 in the cleavage of AP site and its synthetic analogs.

    PubMed

    Lebedeva, Natalia A; Rechkunova, Nadejda I; Ishchenko, Alexander A; Saparbaev, Murat; Lavrik, Olga I

    2013-12-01

    The mechanism of hydrolysis of the apurinic/apyrimidinic (AP) site and its synthetic analogs by using tyrosyl-DNA phosphodiesterase 1 (Tdp1) was analyzed. Tdp1 catalyzes the cleavage of AP site and the synthetic analog of the AP site, 3-hydroxy-2(hydroxymethyl)-tetrahydrofuran (THF), in DNA by hydrolysis of the phosphodiester bond between the substituent and 5' adjacent phosphate. The product of Tdp1 cleavage in the case of the AP site is unstable and is hydrolyzed with the formation of 3'- and 5'-margin phosphates. The following repair demands the ordered action of polynucleotide kinase phosphorylase, with XRCC1, DNA polymerase β, and DNA ligase. In the case of THF, Tdp1 generates break with the 5'-THF and the 3'-phosphate termini. Tdp1 is also able to effectively cleave non-nucleotide insertions in DNA, decanediol and diethyleneglycol moieties by the same mechanism as in the case of THF cleavage. The efficiency of Tdp1 catalyzed hydrolysis of AP-site analog correlates with the DNA helix distortion induced by the substituent. The following repair of 5'-THF and other AP-site analogs can be processed by the long-patch base excision repair pathway.

  11. Cleavage of HPV-16 E6/E7 mRNA mediated by modified 10-23 deoxyribozymes.

    PubMed

    Reyes-Gutiérrez, Pablo; Alvarez-Salas, Luis M

    2009-09-01

    Deoxyribozymes (DXZs) are small oligodeoxynucleotides capable of mediating phosphodiester bond cleavage of a target RNA in a sequence-specific manner. These molecules are a new generation of artificial catalytic nucleic acids currently used to silence many disease-related genes. The present study describes a DXZ (Dz1023-434) directed against the polycistronic mRNA from the E6 and E7 genes of human papillomavirus type 16 (HPV-16), the main etiological agent of cervical cancer. Dz1023-434 showed efficient cleavage against a bona fide antisense window at nt 410-445 within HPV-16 E6/E7 mRNA even in low [Mg(2+)] conditions. Using a genetic analysis as guidance, we introduced diverse chemical modifications within Dz1023-434 catalytic core to produce a stable locked nucleic acid (LNA)-modified DXZ (Dz434-LNA) with significant cleavage activity of full E6/E7 transcripts. Cell culture testing of Dz434-LNA produced a sharp decrement of E6/E7 mRNA levels in HPV-16-positive cells resulting in decreased proliferation and considerable cell death in a specific and dose-dependent manner. No significant effects were observed with inactive or scrambled control DXZs nor from using HPV-negative cells, suggesting catalysis-dependent effect and high specificity. The biological effects of Dz434-LNA suggest a potential use for the treatment of cervical cancer.

  12. Abnormal early cleavage events predict early embryo demise: sperm oxidative stress and early abnormal cleavage.

    PubMed

    Burruel, Victoria; Klooster, Katie; Barker, Christopher M; Pera, Renee Reijo; Meyers, Stuart

    2014-10-13

    Human embryos resulting from abnormal early cleavage can result in aneuploidy and failure to develop normally to the blastocyst stage. The nature of paternal influence on early embryo development has not been directly demonstrated although many studies have suggested effects from spermatozoal chromatin packaging, DNA damage, centriolar and mitotic spindle integrity, and plasma membrane integrity. The goal of this study was to determine whether early developmental events were affected by oxidative damage to the fertilizing sperm. Survival analysis was used to compare patterns of blastocyst formation based on P2 duration. Kaplan-Meier survival curves demonstrate that relatively few embryos with short (<1 hr) P2 times reached blastocysts, and the two curves diverged beginning on day 4, with nearly all of the embryos with longer P2 times reaching blastocysts by day 6 (p < .01). We determined that duration of the 2nd to 3rd mitoses were sensitive periods in the presence of spermatozoal oxidative stress. Embryos that displayed either too long or too short cytokineses demonstrated an increased failure to reach blastocyst stage and therefore survive for further development. Although paternal-derived gene expression occurs later in development, this study suggests a specific role in early mitosis that is highly influenced by paternal factors.

  13. Historic volcanism, European dry fogs, and greenland Acid precipitation, 1500 B.C. To a.d. 1500.

    PubMed

    Stothers, R B; Rampino, M R

    1983-10-28

    Historic dry fogs in Europe, acid precipitation in Greenland, and major explosive volcanic eruptions correlate well with each other between 1500 B.C. and A.D. 1500. European (Mediterranean and Icelandic) volcanic eruptions appear to be the source of at least five of the nine largest acidity signals found in Greenland ice for this period. Between 152 B.C. and A.D. 43, eruptions of sulfur-rich Mount Etna probably supplied about 15 percent of the smaller acidity signals.

  14. Frustrated Lewis pair-like reactions of nucleophilic palladium carbenes with B(C6F5)3.

    PubMed

    Cui, Peng; Comanescu, Cezar C; Iluc, Vlad M

    2015-04-11

    The reactions of two nucleophilic palladium carbene complexes with the strong Lewis acid B(C6F5)3 afforded two zwitterionic products. One of them features a remote nucleophilic attack at the para-carbon of the supporting ligand, while the other indicates C-F activation of B(C6F5)3. Both behaviours are reminiscent of the reactivity of frustrated Lewis pairs due to the steric inaccessibility of the nucleophilic carbon center, but are unprecedented for transition metal carbene complexes. Furthermore, when those reactions are carried out in the presence of H2, products resulting from H2 splitting are observed.

  15. A photo Lewis acid generator (PhLAG): controlled photorelease of B(C6F5)3.

    PubMed

    Khalimon, Andrey Y; Piers, Warren E; Blackwell, James M; Michalak, David J; Parvez, Masood

    2012-06-13

    A molecule that releases the strong organometallic Lewis acid B(C(6)F(5))(3) upon irradiation with 254 nm light has been developed. This photo Lewis acid generator (PhLAG) now enables the photocontrolled initiation of several reactions catalyzed by this important Lewis acid. Herein is described the synthesis of the triphenylsulfonium salt of a carbamato borate based on a carbazole function, its establishment as a PhLAG, and the application of the photorelease of B(C(6)F(5))(3) to the fabrication of thin films of a polysiloxane material.

  16. Photo Lewis acid generators: photorelease of B(C6F5)3 and applications to catalysis.

    PubMed

    Khalimon, Andrey Y; Shaw, Bryan K; Marwitz, Adam J V; Piers, Warren E; Blackwell, James M; Parvez, Masood

    2015-11-07

    A series of molecules capable of releasing of the strong organometallic Lewis acid B(C6F5)3 upon exposure to 254 nm light have been developed. These photo Lewis acid generators (PhLAGs) can now serve as photoinitiators for several important B(C6F5)3-catalyzed reactions. Herein is described the synthesis of the triphenylsulfonium and diphenyliodonium salts of carbamato- and hydridoborates, their establishment as PhLAGs, and studies aimed at defining the mechanism of borane release. Factors affecting these photolytic reactions and the application of this concept to photoinduced hydrosilylation reactions and construction of siloxane scaffolds are also discussed.

  17. 31 CFR 315.30 - Series E bonds and savings notes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Interest § 315.30 Series E...

  18. Planning a distribution automation pilot project at B.C. Hydro

    SciTech Connect

    Benedictson, E.; Dwyer, A.; Herejk, I.

    1994-12-31

    In 1989, a small team of engineers and managers from B.C. Hydro`s Customer Services Group made an exploratory partnership trip to a DA product supplier. While the partnership initiative failed, it served to raise corporate awareness of the need for a comprehensive DA approach. Shortly thereafter, the Window 2000 Project name were formulated. From the inception of the Window 2000 Project, it was clear that the team faced a major strategy challenge, due to recent corporate history. The corporation had just completed a major generation and transmission system expansion program, and enjoyed a considerable energy and capacity surplus, coupled with increased debt load. Concurrently, a select segment of the corporation was developing what was to become the internationally successful Power Smart energy conservation initiative. The team developed a communication plan based on several key principles. Presentations were made to various stakeholders including Customer Services and Corporate Management committees. Permission to proceed with the Window 2000 project was obtained in 1990. A multi-disciplined team of employees representing Customer Services, Power Smart, Production, System Planning, and Stations Engineering was assembled. Leadership was provided by a full-time project leader, and by a senior management steering committee. In addition, the project leader assembled an informal group of advisors for the purpose of defining alternative approaches, generating new information, and testing of ideas. The team members were encouraged to avoid concentrating on corporate or personal turf issues, and the team environment was maintained free of {open_quotes}politics{close_quotes}. This fostered cooperation and objectivity in idea generation and evaluation. The team was given an open mandate to define and to recommend DA functions for implementation.

  19. Epidemiological update of hepatitis B, C and delta in Latin America.

    PubMed

    Alvarado-Mora, Mónica V; Pinho, João R Rebello

    2013-01-01

    Viral hepatitis B, C and delta still remain a serious problem in Latin America. Data from the 1980s indicated that HBV and HDV infection are the main causes of chronic hepatitis. However, the spread of HBV infection could be controlled through the implementation of immunization programmes. Different countries from Mexico to Argentina display marked differences in terms of HBV genotype distribution. HBV genotype F has been identified as the most frequent in most Latin America countries, except for Mexico and Brazil, where genotypes H and A are the most frequent, respectively. In Latin America, the overall prevalence of HCV antibody is estimated to be 1.5%. Latin American countries have been very proactive in screening their blood supplies, thus minimizing risk of HCV transmission through transfusion. The number of diagnosed and treated patients is still low, thereby increasing the burden of complications such as liver cirrhosis or hepatocellular carcinoma. The most prevalent HCV genotype is 1, which is the genotype with the greatest worldwide spread, but it is a different genotype from other regions like Africa and Asia. HDV is present worldwide but its distribution pattern is not uniform. HDV was recently detected in novel geographic regions, reinforcing that it is a very serious health threat in under-developed countries. The main prevalence areas are the Mediterranean basin, the Middle East, central and northern Asia, western and central Africa, the Amazonian basin (Brazil, Peru, Venezuela and Colombia) and the Pacific islands. Novel strategies to increase HBV immunization in the Latin American population are needed to warrant thorough coverage in the rural areas.

  20. Infection with hepatitis A, B, C, and delta viruses among patients with acute hepatitis in Mongolia.

    PubMed

    Tsatsralt-Od, Bira; Takahashi, Masaharu; Endo, Kazunori; Buyankhuu, Osorjin; Baatarkhuu, Oidov; Nishizawa, Tsutomu; Okamoto, Hiroaki

    2006-05-01

    One hundred ten consecutive patients (60 males and 50 females; age, mean +/- standard deviation [SD], 22.6 +/- 6.4 years; range 16-48 years) who were clinically diagnosed with sporadic acute hepatitis between December 2004 and January 2005 in Ulaanbaatar, Mongolia, were studied. IgM antibodies to hepatitis A virus were detected in 18 patients (16.4%), IgM antibodies to hepatitis B core (anti-HBc IgM) in 38 patients (34.5%) including two patients with concurrent hepatitis delta virus (HDV) infection, and hepatitis C virus RNA in nine patients (8.2%). There were 30 hepatitis B virus (HBV) carriers who had detectable hepatitis B surface antigen and antibodies to HDV but were negative for anti-HBc IgM, suggesting that they acquired type D acute hepatitis due to superinfection of HDV on a background of chronic HBV infection. None had IgM antibodies to hepatitis E virus (HEV). Consequently, 16.4, 32.7, 6.4, 1.8, and 27.3% of the patients were diagnosed as having acute hepatitis of type A, B, C, type B + D (HBV/HDV coinfection), and type D (superinfection of HDV), respectively. The cause of hepatitis was not known in the remaining 17 patients (15.5%). All 18 HAV isolates were genotyped as IA, all 9 HCV isolates were genotyped as 1b, and all 32 HDV isolates were classified into genotype I. The distribution of HBV genotypes among the 67 HBV isolates was A (1.5%, n = 1) and D (98.5%, n = 66). The present study indicates that de novo infections of HAV, HBV, HCV, and HDV are prevalent among young adults in Mongolia.

  1. AFOSR Wafer Bonding

    DTIC Science & Technology

    2009-07-31

    cleanliness (foreign particles) and surface morphology (roughness). Two silicon wafers, when properly cleaned, can easily bond at room temperature because of...4 Figure IV data for nSi-nGaN bond. Structure is similar to that shown in Figure Difficulties and Knowledge Added Surface Morphology and...Particles One of the most important features of materials in determining whether they will bond is the quality of the bonding surfaces , in both

  2. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  3. Evolution of development in the sea star genus Patiriella: clade-specific alterations in cleavage.

    PubMed

    Cerra, Anna; Byrne, Maria

    2004-01-01

    Examination of early development in five species of the Patiriella sea star species complex indicates that the ancestral-type radial holoblastic cleavage (Type I) is characteristic of P. regularis and P. exigua, whereas cleavage in species from the calcar clade followed multiple alternatives (Types II-IV) from holoblastic to meroblastic. Considering that invariant radial cleavage is thought to play a role in embryonic axis formation in echinoderms, we documented the details of blastomere formation in Patiriella sp. and followed development of the embryos. In Type II cleavage, the first and second cleavage planes appeared simultaneously at one pole of the embryo, dividing it directly into four equally sized blastomeres. In Type III cleavage, the first and second cleavage planes appeared simultaneously, followed promptly by the third cleavage plane, dividing the embryo directly into eight equally sized blastomeres. In Type IV cleavage, numerous furrows appeared simultaneously at one end of the embryo, dividing it into 32-40 equally sized blastomeres. Confocal sections revealed that embryos with cleavage Types II-IV were initially syncytial. The timing of karyokinesis in embryos with Types II and III cleavage was similar to that seen in clutch mates with Type I cleavage. Karyokinesis in embryos with Type IV cleavage, however, differed in timing compared with Type I clutch mates. Alteration in cleavage was not associated with polarized distribution of maternally provided nutrients. For each cleavage type, development was normal to the competent larval stage. Although variable blastomere configuration in the calcar clade may be linked to possession of a lecithotrophic development, other Patiriella species with this mode of development have typical cleavage. The presence of variable cleavage in all calcar clade species indicates that phylogenetic history has played a role in the distribution of this embryonic trait in Patiriella. The plasticity in early cleavage in these

  4. Reaction coordinate analysis for beta-diketone cleavage by the non-heme Fe2+-dependent dioxygenase Dke1.

    PubMed

    Straganz, Grit D; Nidetzky, Bernd

    2005-09-07

    Acetylacetone dioxygenase from Acinetobacter johnsonii (Dke1) utilizes a non-heme Fe2+ cofactor to promote dioxygen-dependent conversion of 2,4-pentanedione (PD) into methylglyoxal and acetate. An oxidative carbon-carbon bond cleavage by Dke1 is triggered from a C-3 peroxidate intermediate that performs an intramolecular nucleophilic attack on the adjacent carbonyl group. But how does Dke1 bring about the initial reduction of dioxygen? To answer this question, we report here a reaction coordinate analysis for the part of the Dke1 catalytic cycle that involves O2 chemistry. A weak visible absorption band (epsilon approximately 0.2 mM(-1) cm(-1)) that is characteristic of an enzyme-bound Fe2+-beta-keto-enolate complex served as spectroscopic probe of substrate binding and internal catalytic steps. Transient and steady-state kinetic studies reveal that O2-dependent conversion of the chromogenic binary complex is rate-limiting for the overall reaction. Linear free-energy relationship analysis, in which apparent turnover numbers (k(app) cat) for enzymatic bond cleavage of a series of substituted beta-dicarbonyl substrates were correlated with calculated energies for the highest occupied molecular orbitals of the corresponding beta-keto-enolate structures, demonstrates unambiguously that k(app) cat is governed by the electron-donating ability of the substrate. The case of 2'-hydroxyacetophenone (2'HAP), a completely inactive beta-dicarbonyl analogue that has the enol double bond delocalized into the aromatic ring, indicates that dioxygen reduction and C-O bond formation cannot be decoupled and therefore take place in one single kinetic step.

  5. Acrylic mechanical bond tests

    SciTech Connect

    Wouters, J.M.; Doe, P.J.

    1991-02-01

    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  6. Rapid adhesive bonding concepts

    NASA Technical Reports Server (NTRS)

    Stein, B. A.; Tyeryar, J. R.; Hodges, W. T.

    1984-01-01

    Adhesive bonding in the aerospace industry typically utilizes autoclaves or presses which have considerable thermal mass. As a consequence, the rates of heatup and cooldown of the bonded parts are limited and the total time and cost of the bonding process is often relatively high. Many of the adhesives themselves do not inherently require long processing times. Bonding could be performed rapidly if the heat was concentrated in the bond lines or at least in the adherends. Rapid adhesive bonding concepts were developed to utilize induction heating techniques to provide heat directly to the bond line and/or adherends without heating the entire structure, supports, and fixtures of a bonding assembly. Bonding times for specimens are cut by a factor of 10 to 100 compared to standard press bonding. The development of rapid adhesive bonding for lap shear specimens (per ASTM D1003 and D3163), for aerospace panel bonding, and for field repair needs of metallic and advanced fiber reinforced polymeric matrix composite structures are reviewed.

  7. Bonding aluminum beam leads

    NASA Technical Reports Server (NTRS)

    Burkett, F. S.

    1978-01-01

    Report makes it relatively easy for hybrid-circuit manufacturers to convert integrated circuit chips with aluminum bead leads. Report covers: techniques for handling tiny chips; proper geometries for ultrasonic bonding tips; best combinations of pressure, pulse time, and ultrasonic energy for bonding; and best thickness for metal films to which beam leads are bonded.

  8. Characterization of disulfide bonds by planned digestion and tandem mass spectrometry.

    PubMed

    Na, Seungjin; Paek, Eunok; Choi, Jong-Soon; Kim, Duwoon; Lee, Seung Jae; Kwon, Joseph

    2015-04-01

    The identification of disulfide bonds provides critical information regarding the structure and function of a protein and is a key aspect in understanding signaling cascades in biological systems. Recent proteomic approaches using digestion enzymes have facilitated the characterization of disulfide-bonds and/or oxidized products from cysteine residues, although these methods have limitations in the application of MS/MS. For example, protein digestion to obtain the native form of disulfide bonds results in short lengths of amino acids, which can cause ambiguous MS/MS analysis due to false positive identifications. In this study we propose a new approach, termed planned digestion, to obtain sufficient amino acid lengths after cleavage for proteomic approaches. Application of the DBond software to planned digestion of specific proteins accurately identified disulfide-linked peptides. RNase A was used as a model protein in this study because the disulfide bonds of this protein have been well characterized. Application of this approach to peptides digested with Asp-N/C (chemical digestion) and trypsin under acid hydrolysis conditions identified the four native disulfide bonds of RNase A. Missed cleavages introduced by trypsin treatment for only 3 hours generated sufficient lengths of amino acids for identification of the disulfide bonds. Analysis using MS/MS successfully showed additional fragmentation patterns that are cleavage products of S-S and C-S bonds of disulfide-linkage peptides. These fragmentation patterns generate thioaldehydes, persulfide, and dehydroalanine. This approach of planned digestion with missed cleavages using the DBond algorithm could be applied to other proteins to determine their disulfide linkage and the oxidation patterns of cysteine residues.

  9. Binding of factor VIII to von willebrand factor is enabled by cleavage of the von Willebrand factor propeptide and enhanced by formation of disulfide-linked multimers.

    PubMed

    Bendetowicz, A V; Morris, J A; Wise, R J; Gilbert, G E; Kaufman, R J

    1998-07-15

    von Willebrand factor (vWF) is a multimeric adhesive glycoprotein with one factor VIII binding site/subunit. Prior reports suggest that posttranslational modifications of vWF, including formation of N-terminal intersubunit disulfide bonds and subsequent cleavage of the propeptide, influence availability and/or affinity of factor VIII binding sites. We found that deletion of the vWF propeptide produced a dimeric vWF molecule lacking N-terminal intersubunit disulfide bonds. This molecule bound fluorescein-labeled factor VIII with sixfold lower affinity than multimeric vWF in an equilibrium flow cytometry assay (approximate KDs, 5 nmol/L v 0.9 nmol/L). Coexpression of propeptide-deleted vWF with the vWF propeptide in trans yielded multimeric vWF that displayed increased affinity for factor VIII. Insertion of an alanine residue at the N-terminus of the mature vWF subunit destroyed binding to factor VIII, indicating that the native mature N-terminus is required for factor VIII binding. The requirement for vWF propeptide cleavage was shown by (1) a point mutation of the vWF propeptide cleavage site yielding pro-vWF that was defective in factor VIII binding and (2) correlation between efficiency of intracellular propeptide cleavage and factor VIII binding. Furthermore, in a cell-free system, addition of the propeptide-cleaving enzyme PACE/furin enabled factor VIII binding in parallel with propeptide cleavage. Our results indicate that high-affinity factor VIII binding sites are located on N-terminal disulfide-linked vWF subunits from which the propeptide has been cleaved.

  10. The Mycobacterium tuberculosis ORF Rv0654 encodes a carotenoid oxygenase mediating central and excentric cleavage of conventional and aromatic carotenoids.

    PubMed

    Scherzinger, Daniel; Scheffer, Erdmann; Bär, Cornelia; Ernst, Hansgeorg; Al-Babili, Salim

    2010-11-01

    Mycobacterium tuberculosis, the causative agent of tuberculosis, is assumed to lack carotenoids, which are widespread pigments fulfilling important functions as radical scavengers and as a source of apocarotenoids. In mammals, the synthesis of apocarotenoids, including retinoic acid, is initiated by the β-carotene cleavage oxygenases I and II catalyzing either a central or an excentric cleavage of β-carotene, respectively. The M. tuberculosis ORF Rv0654 codes for a putative carotenoid oxygenase conserved in other mycobacteria. In the present study, we investigated the corresponding enzyme, here named M. tuberculosis carotenoid cleavage oxygenase (MtCCO). Using heterologously expressed and purified protein, we show that MtCCO converts several carotenoids and apocarotenoids in vitro. Moreover, the identification of the products suggests that, in contrast to other carotenoid oxygenases, MtCCO cleaves the central C15-C15' and an excentric double bond at the C13-C14 position, leading to retinal (C(20)), β-apo-14'-carotenal (C(22)) and β-apo-13-carotenone (C(18)) from β-carotene, as well as the corresponding hydroxylated products from zeaxanthin and lutein. Moreover, the enzyme cleaves also 3,3'-dihydroxy-isorenieratene representing aromatic carotenoids synthesized by other mycobacteria. Quantification of the products from different substrates indicates that the preference for each of the cleavage positions is determined by the hydroxylation and the nature of the ionone ring. The data obtained in the present study reveal MtCCO to be a novel carotenoid oxygenase and indicate that M. tuberculosis may utilize carotenoids from host cells and interfere with their retinoid metabolism.

  11. Modeling Radial Holoblastic Cleavage: A Laboratory Activity for Developmental Biology.

    ERIC Educational Resources Information Center

    Ellis, Linda K.

    2000-01-01

    Introduces a laboratory activity designed for an undergraduate developmental biology course. Uses Play-Doh (plastic modeling clay) to build a multicellular embryo in order to provide a 3-D demonstration of cleavage. Includes notes for the instructor and student directions. (YDS)

  12. Cleavage sites within the poliovirus capsid protein precursors

    SciTech Connect

    Larsen, G.R.; Anderson, C.W.; Dorner, A.J.; Semler, B.L.; Wimmer, E.

    1982-01-01

    Partial amino-terminal sequence analysis was performed on radiolabeled poliovirus capsid proteins VP1, VP2, and VP3. A computer-assisted comparison of the amino acid sequences obtained with that predicted by the nucleotide sequence of the poliovirus genome allows assignment of the amino terminus of each capsid protein to a unique position within the virus polyprotein. Sequence analysis of trypsin-digested VP4, which has a blocked amino terminus, demonstrates that VP4 is encoded at or very near to the amino terminus of the polyprotein. The gene order of the capsid proteins is VP4-VP2-VP3-VP1. Cleavage of VP0 to VP4 and VP2 is shown to occur between asparagine and serine, whereas the cleavages that separate VP2/VP3 and VP3/VP1 occur between glutamine and glycine residues. This finding supports the hypothesis that the cleavage of VP0, which occurs during virion morphogenesis, is distinct from the cleavages that separate functional regions of the polyprotein.

  13. A review of statistical methods for prediction of proteolytic cleavage.

    PubMed

    duVerle, David A; Mamitsuka, Hiroshi

    2012-05-01

    A fundamental component of systems biology, proteolytic cleavage is involved in nearly all aspects of cellular activities: from gene regulation to cell lifecycle regulation. Current sequencing technologies have made it possible to compile large amount of cleavage data and brought greater understanding of the underlying protein interactions. However, the practical impossibility to exhaustively retrieve substrate sequences through experimentation alone has long highlighted the need for efficient computational prediction methods. Such methods must be able to quickly mark substrate candidates and putative cleavage sites for further analysis. Available methods and expected reliability depend heavily on the type and complexity of proteolytic action, as well as the availability of well-labelled experimental data sets: factors varying greatly across enzyme families. For this review, we chose to give a quick overview of the general issues and challenges in cleavage prediction methods followed by a more in-depth presentation of major techniques and implementations, with a focus on two particular families of cysteine proteases: caspases and calpains. Through their respective differences in proteolytic specificity (high for caspases, broader for calpains) and data availability (much lower for calpains), we aimed to illustrate the strengths and limitations of techniques ranging from position-based matrices and decision trees to more flexible machine-learning methods such as hidden Markov models and Support Vector Machines. In addition to a technical overview for each family of algorithms, we tried to provide elements of evaluation and performance comparison across methods.

  14. Mitochondria Localize to the Cleavage Furrow in Mammalian Cytokinesis

    PubMed Central

    Lawrence, Elizabeth J.; Mandato, Craig A.

    2013-01-01

    Mitochondria are dynamic organelles with multiple cellular functions, including ATP production, calcium buffering, and lipid biosynthesis. Several studies have shown that mitochondrial positioning is regulated by the cytoskeleton during cell division in several eukaryotic systems. However, the distribution of mitochondria during mammalian cytokinesis and whether the distribution is regulated by the cytoskeleton has not been examined. Using live spinning disk confocal microscopy and quantitative analysis of mitochondrial fluorescence intensity, we demonstrate that mitochondria are recruited to the cleavage furrow during cytokinesis in HeLa cells. After anaphase onset, the mitochondria are recruited towards the site of cleavage furrow formation, where they remain enriched as the furrow ingresses and until cytokinesis completion. Furthermore, we show that recruitment of mitochondria to the furrow occurs in multiple mammalian cells lines as well as in monopolar, bipolar, and multipolar divisions, suggesting that the mechanism of recruitment is conserved and robust. Using inhibitors of cytoskeleton dynamics, we show that the microtubule cytoskeleton, but not actin, is required to transport mitochondria to the cleavage furrow. Thus, mitochondria are specifically recruited to the cleavage furrow in a microtubule-dependent manner during mammalian cytokinesis. Two possible reasons for this could be to localize mitochondrial function to the furrow to facilitate cytokinesis and / or ensure accurate mitochondrial inheritance. PMID:23991162

  15. Stimulation of cleavage of membrane proteins by calmodulin inhibitors.

    PubMed Central

    Díaz-Rodríguez, E; Esparís-Ogando, A; Montero, J C; Yuste, L; Pandiella, A

    2000-01-01

    The ectodomain of several membrane-bound proteins can be shed by proteolytic cleavage. The activity of the proteases involved in shedding is highly regulated by several intracellular second messenger pathways, such as protein kinase C (PKC) and intracellular Ca(2+). Recently, the shedding of the adhesion molecule L-selectin has been shown to be regulated by the interaction of calmodulin (CaM) with the cytosolic tail of L-selectin. Prevention of CaM-L-selectin interaction by CaM inhibitors or mutation of a CaM binding site in L-selectin induced L-selectin ectodomain shedding. Whether this action of CaM inhibitors also affects other membrane-bound proteins is not known. In the present paper we show that CaM inhibitors also stimulate the cleavage of several other transmembrane proteins, such as the membrane-bound growth factor precursors pro-transforming growth factor-alpha and pro-neuregulin-alpha2c, the receptor tyrosine kinase, TrkA, and the beta-amyloid precursor protein. Cleavage induced by CaM inhibitors was a rapid event, and resulted from the activation of a mechanism that was independent of PKC or intracellular Ca(2+) increases, but was highly sensitive to hydroxamic acid-based metalloprotease inhibitors. Mutational analysis of the intracellular domain of the TrkA receptor indicated that CaM inhibitors may stimulate membrane-protein ectodomain cleavage by mechanisms independent of CaM-substrate interaction. PMID:10677354

  16. Mitochondria localize to the cleavage furrow in mammalian cytokinesis.

    PubMed

    Lawrence, Elizabeth J; Mandato, Craig A

    2013-01-01

    Mitochondria are dynamic organelles with multiple cellular functions, including ATP production, calcium buffering, and lipid biosynthesis. Several studies have shown that mitochondrial positioning is regulated by the cytoskeleton during cell division in several eukaryotic systems. However, the distribution of mitochondria during mammalian cytokinesis and whether the distribution is regulated by the cytoskeleton has not been examined. Using live spinning disk confocal microscopy and quantitative analysis of mitochondrial fluorescence intensity, we demonstrate that mitochondria are recruited to the cleavage furrow during cytokinesis in HeLa cells. After anaphase onset, the mitochondria are recruited towards the site of cleavage furrow formation, where they remain enriched as the furrow ingresses and until cytokinesis completion. Furthermore, we show that recruitment of mitochondria to the furrow occurs in multiple mammalian cells lines as well as in monopolar, bipolar, and multipolar divisions, suggesting that the mechanism of recruitment is conserved and robust. Using inhibitors of cytoskeleton dynamics, we show that the microtubule cytoskeleton, but not actin, is required to transport mitochondria to the cleavage furrow. Thus, mitochondria are specifically recruited to the cleavage furrow in a microtubule-dependent manner during mammalian cytokinesis. Two possible reasons for this could be to localize mitochondrial function to the furrow to facilitate cytokinesis and / or ensure accurate mitochondrial inheritance.

  17. Emergent mechanistic diversity of enzyme-catalysed beta-diketone cleavage.

    PubMed

    Grogan, Gideon

    2005-06-15

    The enzymatic cleavage of C-C bonds in beta-diketones is, comparatively, a little studied biochemical process, but one that has important relevance to human metabolism, bioremediation and preparative biocatalysis. In recent studies, four types of enzymes have come to light that cleave C-C bonds in the beta-diketone functionality using different chemical mechanisms. OPH [oxidized poly(vinyl alcohol) hydrolase from Pseudomonas sp. strain VM15C], which cleaves nonane-4,6-dione to butyrate and pentan-2-one is a serine-triad hydrolase. Dke1 (diketone-cleaving enzyme from Acinetobacter johnsonii) is a dioxygenase, cleaving acetylacetone to methylglyoxal and acetate. Fumarylacetoacetate hydrolase cleaves fumarylacetoacetate to fumarate and acetoacetate using a water molecule, activated by a catalytic His/Asp dyad, aided by a calcium ion that both chelates the enol acid form of the substrate and indirectly positions the water for nucleophilic attack at a carbonyl group. 6-oxocamphor hydrolase cleaves nonenolizable cyclic beta-diketones and is a homologue of the crotonase superfamily, employing a catalytic His/Asp dyad to activate a water molecule for nucleophilic attack at a carbonyl group on one prochiral face of the diketone substrate, effecting desymmetrizations of symmetrical substrates.

  18. Production of dicarboxylic acids from novel unsaturated fatty acids by laccase-catalyzed oxidative cleavage.

    PubMed

    Takeuchi, Michiki; Kishino, Shigenobu; Park, Si-Bum; Kitamura, Nahoko; Watanabe, Hiroko; Saika, Azusa; Hibi, Makoto; Yokozeki, Kenzo; Ogawa, Jun

    2016-06-27

    The establishment of renewable biofuel and chemical production is desirable because of global warming and the exhaustion of petroleum reserves. Sebacic acid (decanedioic acid), the material of 6,10-nylon, is produced from ricinoleic acid, a carbon-neutral material, but the process is not eco-friendly because of its energy requirements. Laccase-catalyzing oxidative cleavage of fatty acid was applied to the production of dicarboxylic acids using hydroxy and oxo fatty acids involved in the saturation metabolism of unsaturated fatty acids in Lactobacillus plantarum as substrates. Hydroxy or oxo fatty acids with a functional group near the carbon-carbon double bond were cleaved at the carbon-carbon double bond, hydroxy group, or carbonyl group by laccase and transformed into dicarboxylic acids. After 8 h, 0.58 mM of sebacic acid was produced from 1.6 mM of 10-oxo-cis-12,cis-15-octadecadienoic acid (αKetoA) with a conversion rate of 35% (mol/mol). This laccase-catalyzed enzymatic process is a promising method to produce dicarboxylic acids from biomass-derived fatty acids.

  19. BIOLOGICAL ACTIVITY OF THE CLEAVAGE PRODUCT OF HUMAN IMMUNOGLOBULIN G WITH CYANOGEN BROMIDE

    PubMed Central

    Lahav, Mira; Arnon, Ruth; Sela, Michael

    1967-01-01

    Treatment of human IgG with cyanogen bromide in 0.05 M HCl under specified conditions resulted in the cleavage of about half of its methionyl peptide bonds. A major fragment of about 5S was isolated from the reaction mixture by gel filtration in quantitative yield. The CNBr fragment reacted fully with goat antiserum against human light chain, but its reaction with anti-heavy chain was markedly decreased. The treatment with CNBr caused a drastic decrease in the following biological activities of IgG: complement fixing, skin binding, reaction with antiglobulin factors, and reaction with specific anti-Gm(12) serum. On the other hand, the reaction with serum of anti-Gm(1) or anti-Gm(4) specificity was not impaired and antibody activity, namely antistreptolysin and isohemagglutinin, was retained after the treatment with CNBr. It is concluded that the CNBr cleaves preferentially the methionyl bonds in the Fc portion of IgG, and that the major fragment obtained, denoted F(ab'')2, has still the combining properties of a divalent antibody. The possible therapeutic uses of F(ab'')2 are discussed. PMID:4164692

  20. Gleevec shifts APP processing from a β-cleavage to a nonamyloidogenic cleavage

    PubMed Central

    Netzer, William J.; Bettayeb, Karima; Sinha, Subhash C.; Flajolet, Marc; Bustos, Victor

    2017-01-01

    Neurotoxic amyloid-β peptides (Aβ) are major drivers of Alzheimer’s disease (AD) and are formed by sequential cleavage of the amyloid precursor protein (APP) by β-secretase (BACE) and γ-secretase. Our previous study showed that the anticancer drug Gleevec lowers Aβ levels through indirect inhibition of γ-secretase activity. Here we report that Gleevec also achieves its Aβ-lowering effects through an additional cellular mechanism. It renders APP less susceptible to proteolysis by BACE without inhibiting BACE enzymatic activity or the processing of other BACE substrates. This effect closely mimics the phenotype of APP A673T, a recently discovered mutation that protects carriers against AD and age-related cognitive decline. In addition, Gleevec induces formation of a specific set of APP C-terminal fragments, also observed in cells expressing the APP protective mutation and in cells exposed to a conventional BACE inhibitor. These Gleevec phenotypes require an intracellular acidic pH and are independent of tyrosine kinase inhibition, given that a related compound lacking tyrosine kinase inhibitory activity, DV2-103, exerts similar effects on APP metabolism. In addition, DV2-103 accumulates at high concentrations in the rodent brain, where it rapidly lowers Aβ levels. This study suggests that long-term treatment with drugs that indirectly modulate BACE processing of APP but spare other BACE substrates and achieve therapeutic concentrations in the brain might be effective in preventing or delaying the onset of AD and could be safer than nonselective BACE inhibitor drugs. PMID:28115709