Science.gov

Sample records for acid catalyzed condensation

  1. Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

    NASA Astrophysics Data System (ADS)

    Casale, Mia T.; Richman, Aviva R.; Elrod, Matthew J.; Garland, Rebecca M.; Beaver, Melinda R.; Tolbert, Margaret A.

    Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet-visible (UV-vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C 2-C 8). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.

  2. Kinetics of Acid-Catalyzed Aldol Condensation Reactions of Aliphatic Aldehydes

    NASA Astrophysics Data System (ADS)

    Elrod, M. J.; Casale, M. T.; Richman, A. R.; Beaver, M. R.; Garland, R. M.; Tolbert, M. A.

    2006-12-01

    While it is well established that organic compounds compose a large fraction of the atmospheric aerosol mass, the mechanisms through which organics are incorporated into atmospheric aerosols are not well understood. Acid-catalyzed reactions of compounds with carbonyl groups have recently been suggested as important pathways for transfer of volatile organics into acidic aerosols. In the present study, ultraviolet-visible (UV-Vis) spectroscopy was used to monitor the kinetics of formation of the products of the aldol condensation reaction of a range of aliphatic aldehydes (C2-C8) The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature.

  3. Synthesis of esters by immobilized-lipase-catalyzed condensation reaction of sugars and fatty acids in water-miscible organic solvent.

    PubMed

    Adachi, Shuji; Kobayashi, Takashi

    2005-02-01

    A lipase-catalyzed condensation reaction in an organic solvent is a promising means of synthesizing esters. Reaction equilibrium constant, which is usually defined on the basis of reactant concentration, is an important parameter for estimating equilibrium yield. It is shown that the constant is markedly, affected by some factors, such as the hydration of a sugar substrate and the interaction of a reactant with a solvent. To reasonably design the reaction system or determine the reaction conditions, attention should be paid to these factors. From the viewpoint of kinetics, substrate selectivity for carboxylic acids also numerically correlates to the electrical and steric properties of these acids. Reactor systems for continuously producing esters through an immobilized-lipase-catalyzed condensation reaction are developed. PMID:16233762

  4. Amine catalyzed condensation of tetraethylorthosilicate

    NASA Technical Reports Server (NTRS)

    Jones, S.

    2001-01-01

    The catalysis of the condensation of hydrolyzed metal alkoxides by amines has been mentioned in the literature, but there has been no systematic study of their influence on the rate of the condensation reaction of the alkoxide and the microstructure of the resultant gel.

  5. Studies of manufacturing controlled-release graphene acid and catalyzing synthesis of chalcone with Claisen-Schmidt condensation reaction

    NASA Astrophysics Data System (ADS)

    Li, Jihui; Feng, Jia; Li, Mei; Wang, Qiaolian; Su, Yumin; Jia, Zhixin

    2013-07-01

    In the paper, graphene acid (GA) was manufactured, using flake graphite as raw material, and the acidity and the structure of GA were characterized as well as. Then, chalcone was synthesized in the presence of GA, using acetophenone and benzaldehyde as the reactant. The results showed that the acidity of GA was for pH = 1.12 in aqueous solution, and it was structured by the graphene sheets with the spaces between the graphene sheet and the graphene sheet and sulfuric acid (H2SO4) and acetic acid (CH3CO2H) inside the spaces. At the same time, the results also exhibited that the chalcone yield was able to reach 60.36% when GA dosage was 5 g, and the chalcone yields could attain apart 60.36, 52.05 and 31.16% when 5 g of GA was used thrice. This shows that GA is not only a high-performance catalyst, but also a controlled-release catalyst.

  6. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

    PubMed

    Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel

    2015-01-01

    We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups. PMID:26111185

  7. The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation

    NASA Astrophysics Data System (ADS)

    Yu, Xiaofang; Yu, Xiaobo; Wu, Shujie; Liu, Bo; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-02-01

    Acid-base bifunctional heterogeneous catalysts containing carboxylic and amine groups, which were immobilized at defined distance from one another on the mesoporous solid were synthesized by immobilizing lysine onto carboxyl-SBA-15. The obtained materials were characterized by X-ray diffraction (XRD), N 2 adsorption, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron micrographs (SEM), transmission electron micrographs (TEM), elemental analysis, and back titration. Proximal-C-A-SBA-15 with a proximal acid-base distance was more active than maximum-C-A-SBA-15 with a maximum acid-base distance in aldol condensation reaction between acetone and various aldehydes. It appears that the distance between acidic site and basic site immobilized on mesoporous solid should be an essential factor for catalysis optimization.

  8. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis.

    PubMed

    Lin, Shuangjun; Van Lanen, Steven G; Shen, Ben

    2009-03-17

    Nonribosomal peptide synthetases (NRPSs) catalyze the biosynthesis of many biologically active peptides and typically are modular, with each extension module minimally consisting of a condensation, an adenylation, and a peptidyl carrier protein domain responsible for incorporation of an amino acid into the growing peptide chain. C-1027 is a chromoprotein antitumor antibiotic whose enediyne chromophore consists of an enediyne core, a deoxy aminosugar, a benzoxazolinate, and a beta-amino acid moiety. Bioinformatics analysis suggested that the activation and incorporation of the beta-amino acid moiety into C-1027 follows an NRPS mechanism whereby biosynthetic intermediates are tethered to the peptidyl carrier protein SgcC2. Here, we report the biochemical characterization of SgcC5, an NRPS condensation enzyme that catalyzes ester bond formation between the SgcC2-tethered (S)-3-chloro-5-hydroxy-beta-tyrosine and (R)-1-phenyl-1,2-ethanediol, a mimic of the enediyne core. SgcC5 uses (S)-3-chloro-5-hydroxy-beta-tyrosyl-SgcC2 as the donor substrate and exhibits regiospecificity for the C-2 hydroxyl group of the enediyne core mimic as the acceptor substrate. Remarkably, SgcC5 is also capable of catalyzing amide bond formation, albeit with significantly reduced efficiency, between (S)-3-chloro-5-hydroxy-beta-tyrosyl-(S)-SgcC2 and (R)-2-amino-1-phenyl-1-ethanol, an alternative enediyne core mimic bearing an amine at its C-2 position. Thus, SgcC5 is capable of catalyzing both ester and amide bond formation, providing an evolutionary link between amide- and ester-forming condensation enzymes. PMID:19246381

  9. Optimizing the Acid Catalyzed Synthesis of Hyperbranched Poly(Glycerol-diacids) Oligomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oligomeric pre-polymers were synthesized by the acid-catalyzed condensation of glycerol with succinic acid, glutaric acid and azelaic acid in dimethylsulfoxide (DMSO) or dimethylformamide (DMF). The prepolymers were obtained, on average in 84% yield, and were characterized by proton NMR, MALDI-TOF ...

  10. The Lewis acid catalyzed synthesis of hyperbranched Oligo(glycerol-diacid)s in aprotic polar media

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Lewis-acid, titanium (IV) butoxide (15% (w/w; catalyst/reactants)), was used to catalyze the condensation of 0.05 mol glycerol with 0.10 mol of either succinic acid, glutaric acid, or azelaic acid to produce oligomers. The reactions were refluxed in dilute solutions of dimethylsulfoxide (DMSO) o...

  11. Mechanism of Boron-Catalyzed N-Alkylation of Amines with Carboxylic Acids.

    PubMed

    Zhang, Qi; Fu, Ming-Chen; Yu, Hai-Zhu; Fu, Yao

    2016-08-01

    Mechanistic study has been carried out on the B(C6F5)3-catalyzed amine alkylation with carboxylic acid. The reaction includes acid-amine condensation and amide reduction steps. In condensation step, the catalyst-free mechanism is found to be more favorable than the B(C6F5)3-catalyzed mechanism, because the automatic formation of the stable B(C6F5)3-amine complex deactivates the catalyst in the latter case. Meanwhile, the catalyst-free condensation is constituted by nucleophilic attack and the indirect H2O-elimination (with acid acting as proton shuttle) steps. After that, the amide reduction undergoes a Lewis acid (B(C6F5)3)-catalyzed mechanism rather than a Brønsted acid (B(C6F5)3-coordinated HCOOH)-catalyzed one. The B(C6F5)3)-catalyzed reduction includes twice silyl-hydride transfer steps, while the first silyl transfer is the rate-determining step of the overall alkylation catalytic cycle. The above condensation-reduction mechanism is supported by control experiments (on both temperature and substrates). Meanwhile, the predicted chemoselectivity is consistent with the predominant formation of the alkylation product (over disilyl acetal product). PMID:27441997

  12. Aldol Condensation of Volatile Carbonyl Compounds in Acidic Aerosols

    NASA Astrophysics Data System (ADS)

    Noziere, B.; Esteve, W.

    2003-12-01

    Reactions of volatile organic compounds in acidic aerosols have been shown recently to be potentially important for organic aerosol formation and growth. Aldol condensation, the acid-catalyzed polymerization of carbonyl compounds, is a likely candidate to enhance the flux of organic matter from the gas phase to the condensed phase in the atmosphere. Until now these reactions have only been characterized for conditions relevant to synthesis (high acidities and liquid phase systems) and remote from atmospheric ones. In this work, the uptake of gas-phase acetone and 2,4\\-pentanedione by sulfuric acid solutions has been measured at room temperature using a Rotated Wetted Wall Reactor coupled to a Mass Spectrometer. The aldol condensation rate constants for 2,4\\-pentanedione measured so far for sulfuric acid solutions between 96 and 70 % wt. display a variation with acidity in agreement with what predicted in the organic chemical literature. The values of these constants, however, are much lower than expected for this compound, and comparable to the ones of acetone. Experiments are underway to complete this study to lower acidities and understand the discrepancies with the predicted reactivity.

  13. Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

    NASA Astrophysics Data System (ADS)

    Garland, Rebecca M.; Elrod, Matthew J.; Kincaid, Kristi; Beaver, Melinda R.; Jimenez, Jose L.; Tolbert, Margaret A.

    While it is well established that organics compose a large fraction of the atmospheric aerosol mass, the mechanisms through which organics are incorporated into atmospheric aerosols are not well understood. Acid-catalyzed reactions of compounds with carbonyl groups have recently been suggested as important pathways for transfer of volatile organics into acidic aerosols. In the present study, we use the aerodyne aerosol mass spectrometer (AMS) to probe the uptake of gas-phase hexanal into ammonium sulfate and sulfuric acid aerosols. While both deliquesced and dry non-acidic ammonium sulfate aerosols showed no organic uptake, the acidic aerosols took up substantial amounts of organic material when exposed to hexanal vapor. Further, we used 1H-NMR, Fourier transform infrared (FTIR) spectroscopy and GC-MS to identify the products of the acid-catalyzed reaction of hexanal in acidic aerosols. Both aldol condensation and hemiacetal products were identified, with the dominant reaction products dependent upon the initial acid concentration of the aerosol. The aldol condensation product was formed only at initial concentrations of 75-96 wt% sulfuric acid in water. The hemiacetal was produced at all sulfuric acid concentrations studied, 30-96 wt% sulfuric acid in water. Aerosols up to 88.4 wt% organic/11.1 wt% H 2SO 4/0.5 wt% water were produced via these two dimerization reaction pathways. The UV-VIS spectrum of the isolated aldol condensation product, 2-butyl 2-octenal, extends into the visible region, suggesting these reactions may impact aerosol optical properties as well as aerosol composition. In contrast to previous suggestions, no polymerization of hexanal or its products was observed at any sulfuric acid concentration studied, from 30 to 96 wt% in water.

  14. Molecular Dynamics Simulations of Aldol Condensation Catalyzed by Alkylamine-Functionalized Crystalline Silica Surfaces.

    PubMed

    Kim, Ki Chul; Moschetta, Eric G; Jones, Christopher W; Jang, Seung Soon

    2016-06-22

    Molecular dynamics simulations are performed to investigate the cooperatively catalyzed aldol condensation between acetone and 4-nitrobenzaldehyde on alkylamine (or alkylenamine)-grafted silica surfaces, focusing on the mechanism of the catalytic activation of the acetone and 4-nitrobenzaldehyde by the acidic surface silanols followed by the nucleophilic attack of the basic amine functional group toward the activated reactant. From the analysis of the correlations between the catalytically active acid-base sites and reactants, it is concluded that the catalytic cooperativity of the acid-base pair can be affected by two factors: (1) the competition between the silanol and the amine (or enamine) to form a hydrogen bond with a reactant and (2) the flexibility of the alkylamine (or alkylenamine) backbone. Increasing the flexibility of the alkylamine facilitates the nucleophilic attack of the amine on the reactants. From the molecular dynamics simulations, it is found that C3 propylamine and C4 butylamine linkers exhibit the highest probability of reaction, which is consistent with the experimental observation that the activity of the aldol reaction on mesoporous silica depends on the length of alkylamine grafted on the silica surface. This simulation work serves as a pioneering study demonstrating how the molecular simulation approach can be successfully employed to investigate the cooperative catalytic activity of such bifunctional acid-base catalysts. PMID:27238580

  15. Amyloid Aggregates Arise from Amino Acid Condensations under Prebiotic Conditions.

    PubMed

    Greenwald, Jason; Friedmann, Michael P; Riek, Roland

    2016-09-12

    Current theories on the origin of life reveal significant gaps in our understanding of the mechanisms that allowed simple chemical precursors to coalesce into the complex polymers that are needed to sustain life. The volcanic gas carbonyl sulfide (COS) is known to catalyze the condensation of amino acids under aqueous conditions, but the reported di-, tri-, and tetra-peptides are too short to support a regular tertiary structure. Here, we demonstrate that alanine and valine, two of the proteinogenic amino acids believed to have been among the most abundant on a prebiotic earth, can polymerize into peptides and subsequently assemble into ordered amyloid fibers comprising a cross-β-sheet quaternary structure following COS-activated continuous polymerization of as little as 1 mm amino acid. Furthermore, this spontaneous assembly is not limited to pure amino acids, since mixtures of glycine, alanine, aspartate, and valine yield similar structures. PMID:27511635

  16. Acid-Catalyzed Isomerization of Carvone to Carvacrol

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Mattingly, Shawn P.

    2005-01-01

    The acid-catalyzed isomerization of carvone to carvacrol, first reported by Ritter and Ginsburg, is especially well suited with a permanent-magnet FT instrument. The acid-catalyzed isomerization of carvone to carvacrol produced a 61% yield after a three hour reflux with 30% aqueous sulfuric acid.

  17. MINIATURE ACID CONDENSATION SYSTEM: DESIGN AND OPERATION

    EPA Science Inventory

    An extractive source sampling system was designed and constructed. The sampling system measures gaseous sulfuric acid and sulfur dioxide in combustion emissions. The miniature acid condensation system (MACS) includes a high-temperature quartz probe and quartz-filter holder. Since...

  18. Enantioselective Multicomponent Condensation Reactions of Phenols, Aldehydes, and Boronates Catalyzed by Chiral Biphenols.

    PubMed

    Barbato, Keith S; Luan, Yi; Ramella, Daniele; Panek, James S; Schaus, Scott E

    2015-12-01

    Chiral diols and biphenols catalyze the multicomponent condensation reaction of phenols, aldehydes, and alkenyl or aryl boronates. The condensation products are formed in good yields and enantioselectivities. The reaction proceeds via an initial Friedel-Crafts alkylation of the aldehyde and phenol to yield an ortho-quinone methide that undergoes an enantioselective boronate addition. A cyclization pathway was discovered while exploring the scope of the reaction that provides access to chiral 2,4-diaryl chroman products, the core of which is a structural motif found in natural products. PMID:26576776

  19. Pd-catalyzed arylation of chlorotrifluoroethylene using arylboronic acids.

    PubMed

    Yamamoto, Tetsuya; Yamakawa, Tetsu

    2012-07-01

    The palladium-catalyzed cross-coupling of chlorotrifluoroethylene and arylboronic acids proceeds in the presence of a base and H(2)O to provide α,β,β-trifluorostyrene derivatives in satisfactory yields. PMID:22691065

  20. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    SciTech Connect

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  1. Silver-catalyzed protodecarboxylation of heteroaromatic carboxylic acids.

    PubMed

    Lu, Pengfei; Sanchez, Carolina; Cornella, Josep; Larrosa, Igor

    2009-12-17

    A simple and highly efficient protodecarboxylation procedure for a variety of heteroaromatic carboxylic acids catalyzed by Ag(2)CO(3) and AcOH in DMSO is described. This methodology can also perform the selective monoprotodecarboxylation of several aromatic dicarboxylic acids. PMID:19924891

  2. 40 CFR 721.2086 - Coco acid triamine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Coco acid triamine condensate... Specific Chemical Substances § 721.2086 Coco acid triamine condensate, polycarboxylic acid salts. (a... coco acid triamine condensate, poly-car-box-ylic acid salts. (PMN P-92-446) is subject to...

  3. 40 CFR 721.2086 - Coco acid triamine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Coco acid triamine condensate... Specific Chemical Substances § 721.2086 Coco acid triamine condensate, polycarboxylic acid salts. (a... coco acid triamine condensate, poly-car-box-ylic acid salts. (PMN P-92-446) is subject to...

  4. Iron-catalyzed vinylogous aldol condensation of Biginelli products and its application toward pyrido[4,3-d]pyrimidinones.

    PubMed

    Zhang, Lianqiang; Zhang, Zhiguo; Liu, Qingfeng; Liu, Tongxin; Zhang, Guisheng

    2014-03-01

    A novel iron-catalyzed vinylogous aldol condensation of Biginelli products with aryl aldehydes has been developed for the syntheses of potential bioactive (E)-6-arylvinyl-dihydropyrimidin-2(1H)-ones. These materials are valuable synthetic precursors to drug-like pyrido[4,3-d]pyrimidine derivatives. The amide group at the 5-position of the dihydropyrimidin-2(1H)-ones played an important role in the vinylogous aldol condensation reaction. PMID:24517724

  5. Palladium(III)-catalyzed fluorination of arylboronic acid derivatives.

    PubMed

    Mazzotti, Anthony R; Campbell, Michael G; Tang, Pingping; Murphy, Jennifer M; Ritter, Tobias

    2013-09-25

    A practical, palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is presented. The reaction is operationally simple and amenable to multigram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway, involving a Pd(III) intermediate that has been isolated and characterized. PMID:24040932

  6. Acid-catalyzed dehydrogenation of amine-boranes

    DOEpatents

    Stephens, Frances Helen; Baker, Ralph Thomas

    2010-01-12

    A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [R.sup.1R.sup.2B--NR.sup.3R.sup.4].sub.n product. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources.

  7. Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts

    SciTech Connect

    Kandel, Kapil; Althaus, Stacey M.; Peeraphatdit, Chorthip; Kobayashi, Takeshi; Trewyn, Brian G.; Pruski, Marek; Slowing, Igor I.

    2012-05-23

    In this study, we demonstrate how materials science can be combined with the established methods of organic chemistry to find mechanistic bottlenecks and redesign heterogeneous catalysts for improved performance. By using solid-state NMR, infrared spectroscopy, surface and kinetic analysis, we prove the existence of a substrate inhibition in the aldol condensation catalyzed by heterogeneous amines. We show that modifying the structure of the supported amines according to the proposed mechanism dramatically enhances the activity of the heterogeneous catalyst. We also provide evidence that the reaction benefits significantly from the surface chemistry of the silica support, which plays the role of a co-catalyst, giving activities up to two orders of magnitude larger than those of homogeneous amines. This study confirms that the optimization of a heterogeneous catalyst depends as much on obtaining organic mechanistic information as it does on controlling the structure of the support.

  8. Aerobic Copper-Catalyzed O-Methylation with Methylboronic Acid.

    PubMed

    Jacobson, Clare E; Martinez-Muñoz, Noelia; Gorin, David J

    2015-07-17

    The oxidative coupling of alkylboronic acids with oxygen nucleophiles offers a strategy for replacing toxic, electrophilic alkylating reagents. Although the Chan-Lam reaction has been widely applied in the arylation of heteroatom nucleophiles, O-alkylation with boronic acids is rare. We report a Cu-catalyzed nondecarboxylative methylation of carboxylic acids with methylboronic acid that proceeds in air with no additional oxidant. An isotope-labeling study supports an oxidative cross-coupling mechanism, in analogy to that proposed for Chan-Lam arylation. PMID:26111825

  9. Decomposition of peracetic acid catalyzed by vanadium complexes

    SciTech Connect

    Makarov, A.P.; Gekhman, A.E.; Moiseev, I.I.; Polotryuk, O.Y.

    1986-02-01

    This paper studies the decomposition of peracetic acid (AcOOH) in acetic acid (AcOH) catalyzed by vanadium complexes. It is shown that peractic acid in acetic acid solutions of ammonium anadate decomposes with the predominant formation of 0/sub 2/ and small amounts of CO/sub 2/, the yield of which increases with increasing temperature and peracetic acid concentration. Both reactions proceed without the formation of free radicals in amounts detectable by ESR spectroscopy. The rate of oxygen release under conditions in which the formation of CO/sub 2/ is insignificant obeys a kinetic equation indicating the intermediate formation of a complex between V/sup 5 +/ ions and peracetic acid and the slow conversion of this complex into the observed products.

  10. 40 CFR 721.2086 - Coco acid triamine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Coco acid triamine condensate, polycarboxylic acid salts. 721.2086 Section 721.2086 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2086 Coco acid triamine condensate, polycarboxylic acid salts....

  11. 40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Fatty acid amine condensate, polycarboxylic acid salts. 721.3620 Section 721.3620 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts....

  12. 40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid amine condensate, polycarboxylic acid salts. 721.3620 Section 721.3620 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts....

  13. 40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acid amine condensate, polycarboxylic acid salts. 721.3620 Section 721.3620 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts....

  14. 40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acid amine condensate, polycarboxylic acid salts. 721.3620 Section 721.3620 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts....

  15. 40 CFR 721.2086 - Coco acid triamine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Coco acid triamine condensate, polycarboxylic acid salts. 721.2086 Section 721.2086 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2086 Coco acid triamine condensate, polycarboxylic acid salts....

  16. 40 CFR 721.2086 - Coco acid triamine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Coco acid triamine condensate, polycarboxylic acid salts. 721.2086 Section 721.2086 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2086 Coco acid triamine condensate, polycarboxylic acid salts....

  17. 40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acid amine condensate, polycarboxylic acid salts. 721.3620 Section 721.3620 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts....

  18. 4-Dimenthylaminopyridine or Acid-Catalyzed Synthesis of Esters: A Comparison

    ERIC Educational Resources Information Center

    van den Berg, Annemieke W. C.; Hanefeld, Ulf

    2006-01-01

    A set of highly atom-economic experiments was developed to highlight the differences between acid- and base-catalyzed ester syntheses and to introduce the principles of atom economy. The hydrochloric acid-catalyzed formation of an ester was compared with the 4-dimethylaminopyradine-catalyzed ester synthesis.

  19. Synthesis of Rosin Acid Starch Catalyzed by Lipase

    PubMed Central

    Lin, Rihui; Li, He; Long, Han; Su, Jiating; Huang, Wenqin

    2014-01-01

    Rosin, an abundant raw material from pine trees, was used as a starting material directly for the synthesis of rosin acid starch. The esterification reaction was catalyzed by lipase (Novozym 435) under mild conditions. Based on single factor experimentation, the optimal esterification conditions were obtained as follows: rosin acid/anhydrous glucose unit in the molar ratio 2 : 1, reaction time 4 h at 45°C, and 15% of lipase dosage. The degree of substitution (DS) reaches 0.098. Product from esterification of cassava starch with rosin acid was confirmed by FTIR spectroscopy and iodine coloration analysis. Scanning electron microscopy and X-ray diffraction analysis showed that the morphology and crystallinity of the cassava starch were largely destroyed. Thermogravimetric analysis indicated that thermal stability of rosin acid starch decreased compared with native starch. PMID:24977156

  20. Solvent effects in acid-catalyzed biomass conversion reactions.

    PubMed

    Mellmer, Max A; Sener, Canan; Gallo, Jean Marcel R; Luterbacher, Jeremy S; Alonso, David Martin; Dumesic, James A

    2014-10-27

    Reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural. A solvent of particular importance is γ-valerolactone (GVL), which leads to significant increases in reaction rates compared to water in addition to increased product selectivity. GVL has similar effects on the kinetics for the dehydration of 1,2-propanediol to propanal and for the hydrolysis of cellobiose to glucose. Based on results obtained for homogeneous Brønsted acid catalysts that span a range of pKa values, we suggest that an aprotic organic solvent affects the reaction kinetics by changing the stabilization of the acidic proton relative to the protonated transition state. This same behavior is displayed by strong solid Brønsted acid catalysts, such as H-mordenite and H-beta. PMID:25214063

  1. 40 CFR 721.6200 - Fatty acid polyamine condensate, phosphoric acid ester salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Fatty acid polyamine condensate, phosphoric acid ester salts. 721.6200 Section 721.6200 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.6200 Fatty acid polyamine condensate, phosphoric...

  2. 40 CFR 721.6200 - Fatty acid polyamine condensate, phosphoric acid ester salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid polyamine condensate, phosphoric acid ester salts. 721.6200 Section 721.6200 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.6200 Fatty acid polyamine condensate, phosphoric...

  3. 40 CFR 721.6200 - Fatty acid polyamine condensate, phosphoric acid ester salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acid polyamine condensate, phosphoric acid ester salts. 721.6200 Section 721.6200 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.6200 Fatty acid polyamine condensate, phosphoric...

  4. 40 CFR 721.6200 - Fatty acid polyamine condensate, phosphoric acid ester salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acid polyamine condensate, phosphoric acid ester salts. 721.6200 Section 721.6200 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.6200 Fatty acid polyamine condensate, phosphoric...

  5. 40 CFR 721.6200 - Fatty acid polyamine condensate, phosphoric acid ester salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acid polyamine condensate, phosphoric acid ester salts. 721.6200 Section 721.6200 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.6200 Fatty acid polyamine condensate, phosphoric...

  6. Cooperative Catalysis: Calcium and Camphorsulfonic Acid Catalyzed Cycloisomerization of Diynols.

    PubMed

    Rauser, Marian; Schroeder, Sebastian; Niggemann, Meike

    2015-11-01

    The first transition metal-free cycloisomerization of easily accessible diynols is presented as a novel approach to bicyclic 2H-pyrans. As a one-step protocol, the reaction proceeds in a single reaction cascade by intertwining mechanistic fragments borrowed from transition metal-catalyzed Claisen rearrangment of vinyl ethers with our own work on allenyl/propargyl cation rearrangements and a 6π-oxo-electrocylization. It is enabled by a new cooperative catalytic system that combines a simple Ca(2+) catalyst with camphorsulfonic acid. PMID:26403228

  7. Deoxycholic acid transformations catalyzed by selected filamentous fungi.

    PubMed

    Kollerov, V V; Lobastova, T G; Monti, D; Deshcherevskaya, N O; Ferrandi, E E; Fronza, G; Riva, S; Donova, M V

    2016-03-01

    More than 100 filamentous fungi strains, mostly ascomycetes and zygomycetes from different phyla, were screened for the ability to convert deoxycholic acid (DCA) to valuable bile acid derivatives. Along with 11 molds which fully degraded DCA, several strains were revealed capable of producing cholic acid, ursocholic acid, 12-keto-lithocholic acid (12-keto-LCA), 3-keto-DCA, 15β-hydroxy-DCA and 15β-hydroxy-12-oxo-LCA as major products from DCA. The last metabolite was found to be a new compound. The ability to catalyze the introduction of a hydroxyl group at the 7(α/β)-positions of the DCA molecule was shown for 32 strains with the highest 7β-hydroxylase activity level for Fusarium merismoides VKM F-2310. Curvularia lunata VKM F-644 exhibited 12α-hydroxysteroid dehydrogenase activity and formed 12-keto-LCA from DCA. Acremonium rutilum VKM F-2853 and Neurospora crassa VKM F-875 produced 15β-hydroxy-DCA and 15β-hydroxy-12-oxo-LCA, respectively, as major products from DCA, as confirmed by MS and NMR analyses. For most of the positive strains, the described DCA-transforming activity was unreported to date. The presented results expand the knowledge on bile acid metabolism by filamentous fungi, and might be suitable for preparative-scale exploitation aimed at the production of marketed bile acids. PMID:26718089

  8. A Condensing Enzyme from the Seeds of Lesquerella fendleri That Specifically Elongates Hydroxy Fatty Acids1

    PubMed Central

    Moon, Hangsik; Smith, Mark A.; Kunst, Ljerka

    2001-01-01

    Lesquerella fendleri seed oil contains up to 60% hydroxy fatty acids, nearly all of which is the 20-carbon hydroxy fatty acid lesquerolic acid (d-14-hydroxyeicos-cis-11-enoic acid). Previous work suggested that lesquerolic acid in L. fendleri was formed by the elongation of the 18-carbon hydroxy fatty acid, ricinoleic acid. To identify a gene encoding the enzyme involved in hydroxy fatty acid elongation, an L. fendleri genomic DNA library was screened using the coding region of the Arabidopsis Fatty Acid Elongation1 gene as a probe. A gene, LfKCS3, with a high sequence similarity to known very long-chain fatty acid condensing enzymes, was isolated. LfKCS3 has a 2,062-bp open reading frame interrupted by two introns, which encodes a polypeptide of 496 amino acids. LfKCS3 transcripts accumulated only in the embryos of L. fendleri and first appeared in the early stages of development. Fusion of the LfKCS3 promoter to the uidA reporter gene and expression in transgenic Arabidopsis resulted in a high level of β-glucuronidase activity exclusively in developing embryos. Seeds of Arabidopsis plants transformed with LfKCS3 showed no change in their very long-chain fatty acid content. However, when these Arabidopsis plants were crossed with the transgenic plants expressing the castor oleate 12-hydroxylase, significant amounts of 20-carbon hydroxy fatty acids accumulated in the seed, indicating that the LfKCS3 condensing enzyme specifically catalyzes elongation of 18-carbon hydroxy fatty acids. PMID:11743108

  9. Acid-catalyzed Heterogeneous Reactions in SOA Formation

    NASA Astrophysics Data System (ADS)

    Ng, N.; Keywood, M.; Varutbangkul, V.; Gao, S.; Loewer, E.; Surratt, J.; Richard, F. C.; John, S. H.

    2003-12-01

    The importance of heterogeneous reactions in secondary organic aerosol (SOA) formation has recently excited a great deal of interest in the aerosol community. Jang and Kamens (2001) showed enhanced aerosol yield from aldehydes, which can be produced by atmospheric photochemical reactions, in the presence of acidic seed. They suggest that the carbonyl functional groups of the aldehydes further react in the aerosol phase via hydration, polymerization, and hemiacetal/acetal formation with alcohols at an accelerated rate in the presence of acid. Jang et al. (2003) demonstrated similar results using a flow reactor and Czoschke et al. (in press) qualitatively showed increased yields for isoprene and alpha-pinene ozonolysis in the presence of acidic seed. While these findings are intriguing and important, the conditions under which the experiments were carried out were atmospherically unrealistic. A series of SOA formation experiments have been carried out in the Caltech Indoor Chamber Facility, which is comprised of dual 28 m3 FEP Teflon chambers, with the flexibility to carry out both dark ozonolysis and photochemical OH oxidation reactions. Cycloheptene and alpha-pinene were oxidized in the presence of neutral seed under dry (<10% RH) and humid (50% RH) conditions and in the presence of acidic seed under humid (50% RH) conditions. The SOA yields for these experiments will be presented, and the extent of the influence of acid-catalyzed reactions on SOA yield will be discussed. Reference List 1. Cocker, D. R. III. and R. C. Flagan and J. H. Seinfeld, State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environmental Science and Technology, 35, 2594-2601, 2001. 2. Czoschke, N. M., M. Jang, and R. M. Kamens, Effect of acid seed on biogenic sceondary organic aerosol growth, Atmospheric Environment, In press. 3. Jang, M., S. Lee, and R. M. Kamens, Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor

  10. Hydrolysis of cellulose catalyzed by novel acidic ionic liquids.

    PubMed

    Zhuo, Kelei; Du, Quanzhou; Bai, Guangyue; Wang, Congyue; Chen, Yujuan; Wang, Jianji

    2015-01-22

    The conversion of cellulosic biomass directly into valuable chemicals becomes a hot subject. Six novel acidic ionic liquids (ILs) based on 2-phenyl-2-imidazoline were synthesized and characterized by UV-VIS, TGA, and NMR. The novel acidic ionic liquids were investigated as catalysts for the hydrolysis of cellulose in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The acidic ionic liquids with anions HSO4(-) and Cl(-) showed better catalytic performance for the hydrolysis of cellulose than those with H2PO4(-). The temperature and dosage of water affect significantly the yield of total reducing sugar (TRS). When the hydrolysis of cellulose was catalyzed by 1-propyl sulfonic acid-2-phenyl imidazoline hydrogensulfate (IL-1) and the dosage of water was 0.2g, the TRS yield was up to 85.1% within 60 min at 100°C. These new acidic ionic liquids catalysts are expected to have a wide application in the conversion of cellulose into valuable chemicals. PMID:25439867

  11. Condensation of acetol and acetic acid vapor with sprayed liquid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A cellulose-derived fraction of biomass pyrolysis vapor was simulated by evaporating acetol and acetic acid (AA) from flasks on a hot plate. The liquid in the flasks was infused with heated nitrogen. The vapor/nitrogen stream was superheated in a tube oven and condensed by contact with a cloud of ...

  12. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

    ERIC Educational Resources Information Center

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles

    2011-01-01

    This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

  13. Palladium-catalyzed synthesis of aromatic carboxylic acids with silacarboxylic acids.

    PubMed

    Friis, Stig D; Andersen, Thomas L; Skrydstrup, Troels

    2013-03-15

    Aryl iodides and bromides were easily converted to their corresponding aromatic carboxylic acids via a Pd-catalyzed carbonylation reaction using silacarboxylic acids as an in situ source of carbon monoxide. The reaction conditions were compatible with a wide range of functional groups, and with the aryl iodides, the carbonylation was complete within minutes. The method was adapted to the double and selective isotope labeling of tamibarotene. PMID:23441830

  14. Gold catalyzed double condensation reaction: Synthesis, antimicrobial and cytotoxicity of spirooxindole derivatives.

    PubMed

    Parthasarathy, K; Praveen, Chandrasekar; Jeyaveeran, J C; Prince, A A M

    2016-09-01

    Microwave assisted synthesis of spirooxindoles via tandem double condensation between isatins and 4-hydroxycoumarin under gold catalysis is reported. The reaction is practical to perform, since the products can be isolated by simple filtration without requiring tedious column chromatography. The scope of this chemistry is exemplified by preparing structurally diverse spirooxindoles (22 examples) in excellent yields. Antimicrobial evaluation of the synthesized compounds revealed that three compounds (3a, 3f and 3s) exhibited significant MIC values in comparison to the standard drugs. Molecular docking studies of these compounds with AmpC-β-lactamase receptor revealed that 3a exhibited minimum binding energy (-117.819kcal/mol) indicating its strong affinity towards amino acid residues via strong hydrogen bond interaction. All compounds were also evaluated for their in vitro cytotoxicity against COLO320 cancer cells. Biological assay and molecular docking studies demonstrated that 3g is the most active compound in terms of its low IC50 value (50.0μM) and least free energy of binding (-8.99kcal/mol) towards CHK1 receptor, respectively. PMID:27476145

  15. Reactive Transport Modeling of Acid Gas Generation and Condensation

    SciTech Connect

    G. Zhahg; N. Spycher; E. Sonnenthal; C. Steefel

    2005-01-25

    Pulvirenti et al. (2004) recently conducted a laboratory evaporation/condensation experiment on a synthetic solution of primarily calcium chloride. This solution represents one potential type of evaporated pore water at Yucca Mountain, Nevada, a site proposed for geologic storage of high-level nuclear waste. These authors reported that boiling this solution to near dryness (a concentration factor >75,000 relative to actual pore waters) leads to the generation of acid condensate (pH 4.5) presumably due to volatilization of HCl (and minor HF and/or HNO{sub 3}). To investigate the various processes taking place, including boiling, gas transport, and condensation, their experiment was simulated by modifying an existing multicomponent and multiphase reactive transport code (TOUGHREACT). This code was extended with a Pitzer ion-interaction model to deal with high ionic strength. The model of the experiment was set-up to capture the observed increase in boiling temperature (143 C at {approx}1 bar) resulting from high concentrations of dissolved salts (up to 8 m CaCl{sub 2}). The computed HCI fugacity ({approx} 10{sup -4} bars) generated by boiling under these conditions is not sufficient to lower the pH of the condensate (cooled to 80 and 25 C) down to observed values unless the H{sub 2}O mass fraction in gas is reduced below {approx}10%. This is because the condensate becomes progressively diluted by H{sub 2}O gas condensation. However, when the system is modeled to remove water vapor, the computed pH of instantaneous condensates decreases to {approx}1.7, consistent with the experiment (Figure 1). The results also show that the HCl fugacity increases, and calcite, gypsum, sylvite, halite, MgCl{sub 2}4H{sub 2}O and CaCl{sub 2} precipitate sequentially with increasing concentration factors.

  16. A preliminary investigation of acid-catalyzed polymerization reactions of shale oil distillates

    SciTech Connect

    Netzel, D.A.

    1991-04-01

    Sinor (1989) reported that a major specialty market may exist for shale oil as an asphalt blending material. Shale oil can be converted to an asphalt blending material by acid catalyzed condensation and polymerization reactions of the many molecular species comprising the composition of shale oil. To simplify the investigation, crude shale oil was separated by distillation into three distillates of different hydrocarbon and heteroaromatic compositions. These distillates were then treated with two different types of acids to determine the effect of acid type on the end products. Three western shale oil distillates, a naphtha, a middle distillate, and an atmospheric gas oil, were reacted with anhydrous AlCl{sub 3} and 85% H{sub 2}SO{sub 4} under low-severity conditions. At relatively low temperatures, little change in the hydrocarbon composition was noted for the AlCl{sub 3} reactions. AlCl{sub 3}{center dot} (a polymerized product and/or complex) was formed. However, it is assumed that the sludge was mainly the result of heteroaromatic-AlCl{sub 3} reactions.

  17. A preliminary investigation of acid-catalyzed polymerization reactions of shale oil distillates

    SciTech Connect

    Netzel, D.A.

    1991-04-01

    Sinor (1989) reported that a major specialty market may exist for shale oil as an asphalt blending material. Shale oil can be converted to an asphalt blending material by acid catalyzed condensation and polymerization reactions of the many molecular species comprising the composition of shale oil. To simplify the investigation, crude shale oil was separated by distillation into three distillates of different hydrocarbon and heteroaromatic compositions. These distillates were then treated with two different types of acids to determine the effect of acid type on the end products. Three western shale oil distillates, a naphtha, a middle distillate, and an atmospheric gas oil, were reacted with anhydrous AlCl{sub 3} and 85% H{sub 2}SO{sub 4} under low-severity conditions. At relatively low temperatures, little change in the hydrocarbon composition was noted for the AlCl{sub 3} reactions. AlCl{sub 3}{center_dot} (a polymerized product and/or complex) was formed. However, it is assumed that the sludge was mainly the result of heteroaromatic-AlCl{sub 3} reactions.

  18. Glucosamine condensation catalyzed by 1-ethyl-3-methylimidazolium acetate: mechanistic insight from NMR spectroscopy.

    PubMed

    Jia, Lingyu; Pedersen, Christian Marcus; Qiao, Yan; Deng, Tiansheng; Zuo, Pingping; Ge, Wenzhi; Qin, Zhangfeng; Hou, Xianglin; Wang, Yingxiong

    2015-09-21

    The basic ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) could efficiently catalyze the conversion of 2-amino-2-deoxy-d-glucose (GlcNH2) into deoxyfructosazine (DOF) and fructosazine (FZ). Mechanistic investigation by NMR studies disclosed that [C2C1Im][OAc], exhibiting strong hydrogen bonding basicity, could coordinate with the hydroxyl and amino groups of GlcNH2via the promotion of hydrogen bonding in bifunctional activation of substrates and further catalyzing product formation, based on which a plausible reaction pathway involved in this homogeneous base-catalyzed reaction was proposed. Hydrogen bonding as an activation force, therefore, is responsible for the remarkable selectivity and rate enhancement observed. PMID:26278065

  19. Lipase-catalyzed fractionation of conjugated linoleic acid isomers.

    PubMed

    Haas, M J; Kramer, J K; McNeill, G; Scott, K; Foglia, T A; Sehat, N; Fritsche, J; Mossoba, M M; Yurawecz, M P

    1999-09-01

    -18:2 could be obtained in the unreacted free fatty acid fraction. These lipase-catalyzed reactions provide a means for the preparative-scale production of high-purity cis-9,trans-11-18:2, and a corresponding CLA fraction depleted of this isomer. PMID:10574663

  20. Integrated Production of Xylonic Acid and Bioethanol from Acid-Catalyzed Steam-Exploded Corn Stover.

    PubMed

    Zhu, Junjun; Rong, Yayun; Yang, Jinlong; Zhou, Xin; Xu, Yong; Zhang, Lingling; Chen, Jiahui; Yong, Qiang; Yu, Shiyuan

    2015-07-01

    High-efficiency xylose utilization is one of the restrictive factors of bioethanol industrialization. However, xylonic acid (XA) as a new bio-based platform chemical can be produced by oxidation of xylose with microbial. So, an applicable technology of XA bioconversion was integrated into the process of bioethanol production. After corn stover was pretreated with acid-catalyzed steam-explosion, solid and liquid fractions were obtained. The liquid fraction, also named as acid-catalyzed steam-exploded corn stover (ASC) prehydrolyzate (mainly containing xylose), was catalyzed with Gluconobacter oxydans NL71 to prepare XA. After 72 h of bioconversion of concentrated ASC prehydrolyzate (containing 55.0 g/L of xylose), the XA concentration reached a peak value of 54.97 g/L, the sugar utilization ratio and XA yield were 94.08 and 95.45 %, respectively. The solid fraction was hydrolyzed to produce glucose with cellulase and then fermented with Saccharomyces cerevisiae NL22 to produce ethanol. After 18 h of fermentation of concentrated enzymatic hydrolyzate (containing 86.22 g/L of glucose), the ethanol concentration reached its highest value of 41.48 g/L, the sugar utilization ratio and ethanol yield were 98.72 and 95.25 %, respectively. The mass balance showed that 1 t ethanol and 1.3 t XA were produced from 7.8 t oven dry corn stover. PMID:25947618

  1. Dicarboxylic acid anhydride condensation with compounds containing active methylene groups. 4: Some 4-nitrophthalic anhydride condensation reactions

    NASA Technical Reports Server (NTRS)

    Oskaja, V.; Rotberg, J.

    1985-01-01

    By 4-nitrophthalic anhydride condensation with acetoacetate in acetic anhydride and triethylamine solution with subsequent breakdown of the intermediate condensation product, 5-nitroindanedione-1,3 was obtained. A 4-nitrophthalic anhydride with acetic anhydride, according to reaction conditions, may yield two products: in the presence of potassium acetate and at high temperatures 4-(or 5-)-nitro-2-acetylbenzoic acid is formed: in the presence of triethylamine and at room temperature 5-( or 6-)-nitrophthalic acetic acid is isolated. A 4-nitrophthalic anhydride and malonic acid in pyridine solution according to temperature yield either 5-( or 6-)-nitrophthalic acetic acid or 4-(or 5-)-nitro-2-acetylbenzoic acid.

  2. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  3. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  4. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., polyamine condensate. 721.6220 Section 721.6220 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  5. Synthesis of dibenzoxepine lactams via a Cu-catalyzed one-pot etherification/aldol condensation cascade reaction: application toward the total synthesis of aristoyagonine.

    PubMed

    Lim, Hye Sun; Choi, Young Lok; Heo, Jung-Nyoung

    2013-09-20

    A general synthesis of dibenzoxepine lactams has been developed using a one-pot Cu-catalyzed etherification/aldol condensation cascade reaction. The reaction of 4-hydroxyisoindolin-1-one with a wide range of 2-bromobenzaldehydes in the presence of a copper catalyst provided various aristoyagonine derivatives in good yields. PMID:24000941

  6. Gallium(III)- and calcium(II)-catalyzed Meyer-Schuster rearrangements followed by intramolecular aldol condensation or endo-Michael addition.

    PubMed

    Presset, M; Michelet, B; Guillot, R; Bour, C; Bezzenine-Lafollée, S; Gandon, V

    2015-03-28

    The first gallium- and calcium-catalyzed Meyer-Schuster rearrangements are described. Under substrate control, the incipient conjugated ketones can be trapped intramolecularly by β-keto esters or amides to yield cyclic products after aldol condensation or endo-Michael addition. An interesting additive effect that promotes the latter tandem process with calcium has been found. PMID:25503868

  7. Laser-catalyzed spin-exchange process in a Bose-Einstein condensate

    SciTech Connect

    Jing, H.; Jiang, Y.; Zhang Weiping; Meystre, P.

    2010-03-15

    We show theoretically that it is possible to optically control collective spin-exchange processes in spinor Bose condensates through virtual photoassociation. The interplay between optically induced spin exchange and spin-dependent collisions provides a flexible tool for the control of atomic spin dynamics, including enhanced or inhibited quantum spin oscillations, the optically induced ferromagnetic-to-antiferromagnetic transition, and coherent matter-wave spin conversion.

  8. Direct ortho-arylation of ortho-substituted benzoic acids: overriding Pd-catalyzed protodecarboxylation.

    PubMed

    Arroniz, Carlos; Ironmonger, Alan; Rassias, Gerry; Larrosa, Igor

    2013-02-15

    ortho-Arylation of ortho-substituted benzoic acids is a challenging process due to the tendency of the reaction products toward Pd-catalyzed protodecarboxylation. A simple method for preventing decarboxylation in sterically hindered benzoic acids is reported. The method described represents a reliable and broadly applicable entry to 2-aryl-6-substituted benzoic acids. PMID:23373630

  9. Steady-state kinetics and inhibition studies of the aldol condensation reaction catalyzed by bovine liver and Escherichia coli 2-keto-4-hydroxyglutarate aldolase.

    PubMed

    Grady, S R; Wang, J K; Dekker, E E

    1981-04-28

    Two sensitive assays, one which fluorometrically measures only the L isomer of 2-keto-4-hydroxyglutarate after decarboxylation to L-malate and the other which spectrophotometrically determines both enantiomers by reductive amination with glutamate dehydrogenase, are described. By use of these assays, the steady-state kinetics of the aldol condensation of pyruvate with glyoxylate, as catalyzed by 2-keto-4-hydroxyglutarate aldolase from either bovine liver or Escherichia coli, were studied as was the inhibition of this reaction by glyoxylate and other anions. For the E. coli aldolase, double-reciprocal plots are linear except at high (above 5 mM) glyoxylate concentrations; apparent Km values increase with increasing concentrations of the fixed substrate. The data are consistent with an ordered reaction sequence. Inhibition by halides follows the lyotropic or Hofmeister series. Esters are not good inhibitors; mono-, di-, and tricarboxylic acids are increasingly inhibitory. Of the substrate analogues tested, hydroxypyruvate is the most potent inhibitor. Inhibition studies with citrate, acetaldehyde, and glyoxylate (all competitive inhibitors) suggest there are two domains at the active site-the Schiff base forming lysyl residue which interacts with carbonyl analogues (like acetaldehyde) and a center of positive charge which binds anions (like citrate). In contrast to the bacterial enzyme, liver 2-keto-4-hydroxyglutarate aldolase is inhibited in a competitive manner by much lower concentrations (0.1 mM or even lower) of glyoxylate. Many salts and some carboxylic acids activate the liver enzyme. Similarly, substrate analogues like 2-ketobutyrate and fluoropyruvate are mild activators; no effect is seen with acetaldehyde. Besides glyoxylate, only glyoxal, 2-ketoglutarate, and hydroxypyruvate inhibit the aldol condensation reaction. A uniform value of 1 is found for the number of inhibitor molecules bound per active site of either liver or E. coli 2-keto-4-hydroxyglutarate

  10. Enzyme-Catalyzed Asymmetric Domino Thia-Michael/Aldol Condensation Using Pepsin.

    PubMed

    Xiang, Yang; Song, Jian; Zhang, Yong; Yang, Da-Cheng; Guan, Zhi; He, Yan-Hong

    2016-07-15

    The novel catalytic promiscuity of pepsin from porcine gastric mucosa for the asymmetric catalysis of the domino thia-Michael/aldol condensation reaction in MeCN and buffer was discovered for the first time. Broad substrate specificity was tested, and a series of corresponding products were obtained with enantioselectivities of up to 84% ee. This specific catalysis was demonstrated by using recombinant pepsin and control experiments with denatured and inhibited pepsin. The reaction was also shown to occur in the active site by site-directed mutagenesis (the Asp32Ala mutant of pepsin), and a possible mechanism was proposed. PMID:27348476

  11. Rapid and Efficient Functionalized Ionic Liquid-Catalyzed Aldol Condensation Reactions Associated with Microwave Irradiation

    PubMed Central

    Wang, Chang; Liu, Jing; Leng, Wenguang; Gao, Yanan

    2014-01-01

    Five quaternary ammonium ionic liquid (IL) and two tetrabutylphosphonium ILs were prepared and characterized. An environmentally benign and convenient functionalized ionic liquid catalytic system was thus explored in the aldol condensation reactions of aromatic aldehydes with acetone. The aldol reactions proceeded more efficiently through microwave-assisted heating than through conventional thermal heating. The yield of products obtained under microwave heating for 30 min was approximately 90%, and the ILs can be recovered and reused at least five times without apparent loss of activity. In addition, this catalytic system can be successfully extended to the Henry reactions. PMID:24445262

  12. Selective and recyclable depolymerization of cellulose to levulinic acid catalyzed by acidic ionic liquid.

    PubMed

    Ren, Huifang; Girisuta, Buana; Zhou, Yonggui; Liu, Li

    2015-03-01

    Cellulose depolymerization to levulinic acid (LA) was catalyzed by acidic ionic liquids (ILs) selectively and recyclably under hydrothermal conditions. The effects of reaction temperature, time, water amount and cellulose intake were investigated. Dilution effect becomes more pronounced at lower cellulose intake, dramatically improving the yield of LA to 86.1%. A kinetic model has been developed based on experimental data, whereby a good fit was obtained and kinetic parameters were derived. The relationships between IL structure, polymeric structure and depolymerization efficiency were established, shedding light on the in-depth catalytic mechanism of IL, inclusive of acidity and hydrogen bonding ability. The LA product can be readily separated through extraction by methyl isobutyl ketone (MIBK) and IL can be reused over five cycles without loss of activity. This environmentally friendly methodology can be applied to selective production of LA from versatile biomass feedstocks, including cellulose and derivatives, glucose, fructose and HMF. PMID:25498672

  13. Template properties of oligocytidylates formed in the montmorillonite catalyzed condensation of ImpC. [Abstract only

    NASA Technical Reports Server (NTRS)

    Ferris, James P.; Ertem, Goezen

    1994-01-01

    In an attempt to investigate the prebiotic formation of phosphodiester bond in RNA, we have studied the self condensation of 5'-phosphorimidazolide of adenosine (ImpA), in aqueous solutions containing 0.2 M sodium chloride and 0.075 M magnesium chloride at pH 8 using clay minerals as catalyst. In the presence of certain montmorillonites, oligomers containing up to ten monomer units in their chain were formed, while in control experiments, where no catalyst was added, the major product was 5',5'-diadenosine diphosphate, A(sup 5')ppA. In reactions carried out with ImpA: A(sup 5')ppA mixtures at 9:1 mole ratio, oligomers of the type A(sup 5')p(pA)(sub n) and (A(sup 5')p)(sub n)A(sup 5')ppA(pA)(sub n) formed at the expense of (pA)(sub n) type oligomers. Addition of A(sup 5')ppA to the reaction mixture increased the regiospecifity of 3',5'-link formation from 67% to 79%. The condensation of the 5'-phosphorimidazolide of cytidine, ImpC, was also carried out in the presence and absence of A(sup 5')ppA under the same conditions and oligomers containing up to twelve monomer units were obtained.

  14. Fast Knoevenagel Condensations Catalyzed by an Artificial Schiff-Base-Forming Enzyme.

    PubMed

    Garrabou, Xavier; Wicky, Basile I M; Hilvert, Donald

    2016-06-01

    The simple catalytic motifs utilized by enzymes created by computational design and directed evolution constitute a potentially valuable source of chemical promiscuity. Here we show that the artificial retro-aldolase RA95.5-8 is able to use a reactive lysine in a hydrophobic pocket to accelerate promiscuous Knoevenagel condensations of electron-rich aldehydes and activated methylene donors. Optimization of this activity by directed evolution afforded an efficient enzyme variant with a catalytic proficiency of 5 × 10(11) M(-1) and a >10(8)-fold catalytic advantage over simple primary and secondary amines. Divergent evolution of de novo enzymes in this way could be a promising strategy for creating tailored biocatalysts for many synthetically useful reactions. PMID:27196438

  15. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aryl sulfonate of a fatty acid mixture... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  16. 40 CFR 721.6220 - Aryl sulfonate of a fatty acid mixture, polyamine condensate.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aryl sulfonate of a fatty acid mixture... Specific Chemical Substances § 721.6220 Aryl sulfonate of a fatty acid mixture, polyamine condensate. (a... generically as an aryl sulfonate of a fatty acid mixture, polyamine condensate (PMN P-91-584) is subject...

  17. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol,...

  18. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol,...

  19. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol,...

  20. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol,...

  1. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. 721.3800 Section 721.3800... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol,...

  2. Benzoic acid 2-hydroxylase, a soluble oxygenase from tobacco, catalyzes salicylic acid biosynthesis

    SciTech Connect

    Leon, J.; Shulaev, V.; Yalpani, N.

    1995-10-24

    Benzoic acid 2-hydroxylase (BA2H) catalyzes the biosynthesis of salicylic acid from benzoic acid. The enzyme has been partially purified and characterized as a soluble protein of 160 kDa. High-efficiency in vivo labeling of salicyclic acid with {sup 18}O{sub 2} suggested that BA2H is an oxygenase that specifically hydroxylates the ortho position of benzoic acid. The enzyme was strongly induced by either tobacco mosaic virus inoculation of benzoic acid infiltration of tobacco leaves and it was inhibited by CO and other inhibitors of cytochrome P450 hydroxylases. The BA2H activity was immunodepleted by antibodies raised against SU2, a soluble cytochrome P450 from Streptomyces griseolus. The anti-SU2 antibodies immunoprecipitated a radiolabeled polypeptide of around 160 kDa from the soluble protein extracts of L-[{sup 35}S]-methionine-fed tobacco leaves. Purified BA2H showed CO-difference spectra with a maximum at 457 nm. These data suggest that BA2H belongs to a novel class of soluble, high molecular weight cytochrome P450 enzymes. 21 refs., 6 figs., 1 tab.

  3. KI-catalyzed α-acyloxylation of acetone with carboxylic acids.

    PubMed

    Wu, Ya-Dong; Huang, Bei; Zhang, Yue-Xin; Wang, Xiao-Xu; Dai, Jian-Jun; Xu, Jun; Xu, Hua-Jian

    2016-07-01

    The KI-catalyzed reaction of acetone with aromatic carboxylic acids is achieved, leading to α-acyloxycarbonyl compounds in good to excellent yields under mild reaction conditions. The present method exhibits good functional-group compatibility. Notably, this reaction system is even suitable for cinnamic acid, 3-phenylpropiolic acid and 4-phenylbutanoic acid. A kinetic isotope effect (KIE) study indicates that C-H cleavage of the acetone is the rate-limiting step in the catalytic cycle. PMID:27251323

  4. Formation of Linear Polyenes in Thermal Dehydration of Polyvinyl Alcohol, Catalyzed by Phosphotungstic Acid

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.

    2015-01-01

    In order to obtain linear polyenes in polyvinyl alcohol films via acid-catalyzed thermal dehydration of the polyvinyl alcohol, we used phosphotungstic acid as the catalyst: a safe and heat-stable solid chemical compound. We established that phosphotungstic acid, introduced as solid nanoparticles into polyvinyl alcohol films, is a more effective dehydration catalyst than hydrochloric acid, since in contrast to HCl it does not evaporate from the film during heat treatment.

  5. The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

  6. Catalyzed ring-opening polymerization of epoxidized soybean oil by hydrated and anhydrous fluoroantimonic acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by the super acid, fluroantimonic acid hexahydrate (HSbF6-6H2O), and the anhydrous form (HSbF6) in ethyl acetate was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (SA-RPESO and SAA-...

  7. Palladium(II)/Brønsted Acid-Catalyzed Enantioselective Oxidative Carbocyclization-Borylation of Enallenes.

    PubMed

    Jiang, Tuo; Bartholomeyzik, Teresa; Mazuela, Javier; Willersinn, Jochen; Bäckvall, Jan-E

    2015-05-11

    An enantioselective oxidative carbocyclization-borylation of enallenes that is catalyzed by palladium(II) and a Brønsted acid was developed. Biphenol-type chiral phosphoric acids were superior co-catalysts for inducing the enantioselective cyclization. A number of chiral borylated carbocycles were synthesized in high enantiomeric excess. PMID:25808996

  8. Palladium(II)/Brønsted Acid-Catalyzed Enantioselective Oxidative Carbocyclization–Borylation of Enallenes**

    PubMed Central

    Jiang, Tuo; Bartholomeyzik, Teresa; Mazuela, Javier; Willersinn, Jochen; Bäckvall, Jan-E

    2015-01-01

    An enantioselective oxidative carbocyclization–borylation of enallenes that is catalyzed by palladium(II) and a Brønsted acid was developed. Biphenol-type chiral phosphoric acids were superior co-catalysts for inducing the enantioselective cyclization. A number of chiral borylated carbocycles were synthesized in high enantiomeric excess. PMID:25808996

  9. Characterization of fatty amides produced by lipase-catalyzed amidation of multihydroxylated fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Novel multi-hydroxylated primary fatty amides produced by direct amidation of 7,10-dihydroxy-8(E)-octadecenoic acid (DOD) and 7,10,12-trihydroxy-8(E)-octadecenoic acid (TOD) were characterized by GC-MS and NMR. The amidation reactions were catalyzed by immobilized Pseudozyma (Candida) antarctica li...

  10. Studies on the self-catalyzed Knoevenagel condensation, characterization, DPPH radical scavenging activity, cytotoxicity, and molecular properties of 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones using single crystal XRD and DFT techniques

    NASA Astrophysics Data System (ADS)

    Suresh Kumar, G. S.; Antony Muthu Prabhu, A.; Bhuvanesh, N.

    2014-10-01

    We have studied the self-catalyzed Knoevenagel condensation, spectral characterization, DPPH radical scavenging activity, cytotoxicity, and molecular properties of 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones using single crystal XRD and DFT techniques. In the absence of any catalyst, a series of novel 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones were synthesized using Meldrum’s acid and formylphenoxyaliphatic acid(s) in water. These molecules are arranged in the dimer form through intermolecular H-bonding in the single crystal XRD structure. Compounds have better DPPH radical scavenging activity and cytotoxicity against A431 cancer cell line. The optimized molecular structure, natural bond orbital analysis, electrostatic potential map, HOMO-LUMO energies, molecular properties, and atomic charges of these molecules have been studied by performing DFT/B3LYP/3-21G(*) level of theory in gas phase.

  11. A Lewis Acid Catalyzed Annulation to 2,1-Benzisoxazoles

    PubMed Central

    2015-01-01

    We report here a new, atom economical annulation to 2,1-benzisoxazole scaffolds via the BF3·Et2O-catalyzed reaction of glyoxylate esters and nitrosoarenes. The developed method represents a convergent route to this compound class from previously unexplored inputs and provides a range of 2,1-benzisoxazoles in moderate to high yields under convenient conditions. Along with exploration of substrate scope, initial mechanistic investigation through 18O labeling and the synthesis of a reaction intermediate provides evidence for an unusual umpolung addition of glyoxylates to nitrosobenzenes with high O-selectivity, followed by a new type of Friedel–Crafts cyclization. PMID:25157596

  12. Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions.

    PubMed

    Hausoul, Peter J C; Negahdar, Leila; Schute, Kai; Palkovits, Regina

    2015-10-12

    The aqueous Ru/C-catalyzed hydrogenolysis of biomass-based polyols such as erythritol, xylitol, sorbitol, and cellobitol is studied under neutral and acidic conditions. For the first time, the complete product spectrum of C2 C6 polyols is identified and, based on a thorough analysis of the reaction mixtures, a comprehensive reaction mechanism is proposed, which consists of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions. The data reveal that the Ru-catalyzed deoxygenation reaction is highly selective for the cleavage of terminal hydroxyl groups. Changing from neutral to acidic conditions suppresses decarbonylation, consequently increasing the selectivity towards deoxygenation. PMID:26448526

  13. Pd(II)-Catalyzed Asymmetric Addition of Arylboronic Acids to Isatin-Derived Ketimines.

    PubMed

    He, Qun; Wu, Liang; Kou, Xuezhen; Butt, Nicholas; Yang, Guoqiang; Zhang, Wanbin

    2016-01-15

    A Pd(II)/Pyrox-catalyzed enantioselecitve addition of arylboronic acids to 3-ketimino oxindoles was developed, providing chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields and with good enantioselectivities. A variety of functionalized 3-ketimino oxindoles can be used, and the method tolerates some variation in arylboronic acid scope. This asymmetric arylation provides an alternative efficient catalytic method for the preparation of chiral 3-aryl-3-amino-2-oxindoles, which also represents the first example of a Pd(II)-catalyzed addition of arylborons to exocyclic ketimines. PMID:26720106

  14. A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

    PubMed

    Qi, Xinxin; Li, Chong-Liang; Wu, Xiao-Feng

    2016-04-18

    Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. PMID:26934464

  15. Stenotrophomonas maltophilia OleC-Catalyzed ATP-Dependent Formation of Long-Chain Z-Olefins from 2-Alkyl-3-hydroxyalkanoic Acids.

    PubMed

    Kancharla, Papireddy; Bonnett, Shilah A; Reynolds, Kevin A

    2016-08-01

    The bacterial pathway of olefin biosynthesis starts with OleA catalyzed "head-to-head" condensation of two CoA-activated long-chain fatty acids to generate (R)-2-alkyl-3-ketoalkanoic acids. A subsequent OleD-catalyzed reduction generates (2R,3S)-2-alkyl-3-hydroxyalkanoic acids. We now show that the final step in the pathway is an OleC-catalyzed ATP-dependent decarboxylative dehydration to form the corresponding Z olefins. Higher kcat /Km values were seen for substrates with longer alkyl chains. All four stereoisomers of 2-hexyl-3-hydroxydecanoic acid were shown to be substrates, and GC-MS and NMR analyses confirmed that the product in each case was (Z)-pentadec-7-ene. LC-MS analysis supported the formation of AMP adduct as an intermediate. The enzymatic and stereochemical course of olefin biosynthesis from long-chain fatty acids by OleA, OleD and OleC is now established. PMID:27238740

  16. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    ERIC Educational Resources Information Center

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

    2011-01-01

    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  17. Dietary phenolic acids and ascorbic acid: Influence on acid-catalyzed nitrosative chemistry in the presence and absence of lipids.

    PubMed

    Combet, Emilie; El Mesmari, Aziza; Preston, Tom; Crozier, Alan; McColl, Kenneth E L

    2010-03-15

    Acid-catalyzed nitrosation and production of potentially carcinogenic nitrosative species is focused at the gastroesophageal junction, where salivary nitrite, derived from dietary nitrate, encounters the gastric juice. Ascorbic acid provides protection by converting nitrosative species to nitric oxide (NO). However, NO may diffuse into adjacent lipid, where it reacts with O(2) to re-form nitrosative species and N-nitrosocompounds (NOC). In this way, ascorbic acid promotes acid nitrosation. Using a novel benchtop model representing the gastroesophageal junction, this study aimed to clarify the action of a range of water-soluble antioxidants on the nitrosative mechanisms in the presence or absence of lipids. Caffeic, ferulic, gallic, or chlorogenic and ascorbic acids were added individually to simulated gastric juice containing secondary amines, with or without lipid. NO and O(2) levels were monitored by electrochemical detection. NOC were measured in both aqueous and lipid phases by gas chromatography-tandem mass spectrometry. In the absence of lipids, all antioxidants tested inhibited nitrosation, ranging from 35.9 + or - 7.4% with gallic acid to 93 + or - 0.6% with ferulic acid. In the presence of lipids, the impact of each antioxidant on nitrosation was inversely correlated with the levels of NO they generated (R(2) = 0.95, p<0.01): gallic, chlorogenic, and ascorbic acid promoted nitrosation, whereas ferulic and caffeic acids markedly inhibited nitrosation. PMID:20026204

  18. Iridium-catalyzed enantioselective hydrogenation of unsaturated heterocyclic acids.

    PubMed

    Song, Song; Zhu, Shou-Fei; Pu, Liu-Yang; Zhou, Qi-Lin

    2013-06-01

    Spiral binding: A highly enantioselective hydrogenation of unsaturated heterocyclic acids has been developed by using chiral iridium/spirophosphino oxazoline catalysts (see scheme; BArF(-) =tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Boc=tert-butoxycarbonyl). This reaction provided an efficient method for the preparation of optically active heterocyclic acids with excellent enantioselectivities. PMID:23610004

  19. Iron-Catalyzed Acylation of Polyfunctionalized Aryl- and Benzylzinc Halides with Acid Chlorides.

    PubMed

    Benischke, Andreas D; Leroux, Marcel; Knoll, Irina; Knochel, Paul

    2016-08-01

    FeCl2 (5 mol %) catalyzes a smooth and convenient acylation of functionalized arylzinc halides at 50 °C (2-4 h) and benzylic zinc chlorides at 25 °C (0.5-4 h) with a variety of acid chlorides leading to polyfunctionalized diaryl and aryl heteroaryl ketones. PMID:27457108

  20. Palladium-Catalyzed Construction of Amidines from Arylboronic Acids under Oxidative Conditions.

    PubMed

    Zhu, Fengxiang; Li, Yahui; Wang, Zechao; Orru, Romano V A; Maes, Bert U W; Wu, Xiao-Feng

    2016-06-01

    A valuable palladium-catalyzed three-component coupling reaction for the synthesis of amidines has been developed. Using arylboronic acids, isocyanides, and anilines as the reactants under oxidative conditions, various amidines were isolated in good yields with good functional group tolerances. PMID:27061735

  1. Chiral phosphoric acid catalyzed asymmetric addition of naphthols to para-quinone methides.

    PubMed

    Wong, Yuk Fai; Wang, Zhaobin; Sun, Jianwei

    2016-06-28

    An asymmetric addition of naphthols to in situ generated para-quinone methides catalyzed by a chiral phosphoric acid is described. A range of useful triarylmethanes can be generated from stable general para-hydroxybenzyl alcohols with good efficiency and enantioselectivity. PMID:26932597

  2. One-Pot Synthesis of Arylketones from Aromatic Acids via Palladium-Catalyzed Suzuki Coupling.

    PubMed

    Wu, Hongxiang; Xu, Baiping; Li, Yue; Hong, Fengying; Zhu, Dezhao; Jian, Junsheng; Pu, Xiaoer; Zeng, Zhuo

    2016-04-01

    A palladium-catalyzed one-pot procedure for the synthesis of aryl ketones has been developed. Triazine esters when coupled with aryl boronic acids provided aryl ketones in moderate to excellent yields (up to 95%) in the presence of 1 mol % Pd(PPh3)2Cl2 for 30 min. PMID:26949103

  3. Transformation of cellulose and its derived carbohydrates into formic and lactic acids catalyzed by vanadyl cations.

    PubMed

    Tang, Zhenchen; Deng, Weiping; Wang, Yanliang; Zhu, Enze; Wan, Xiaoyue; Zhang, Qinghong; Wang, Ye

    2014-06-01

    The transformation of cellulose or cellulose-derived carbohydrates into platform chemicals is the key to establish biomass-based sustainable chemical processes. The systems able to catalyze the conversion of cellulose into key chemicals in water without the consumption of hydrogen are limited. We report that simple vanadyl (VO(2+)) cations catalyze the conversions of cellulose and its monomer, glucose, into lactic acid and formic acid in water. We have discovered an interesting shift of the major product from formic acid to lactic acid on switching the reaction atmosphere from oxygen to nitrogen. Our studies suggest that VO(2+) catalyzes the isomerization of glucose to fructose, the retro-aldol fragmentation of fructose to two trioses, and the isomerization of trioses, which leads to the formation of lactic acid under anaerobic conditions. The oxidative cleavage of C-C bonds in the intermediates caused by the redox conversion of VO2(+)/VO(2+) under aerobic conditions results in formic acid and CO2. We demonstrate that the addition of an alcohol suppresses the formation of CO2 and enhances the formic acid yield significantly to 70-75 %. PMID:24798653

  4. Syntheses of hydroxamic acid-containing bicyclic β-lactams via palladium-catalyzed oxidative amidation of alkenes.

    PubMed

    Jobbins, Maria O; Miller, Marvin J

    2014-02-21

    Palladium-catalyzed oxidative amidation has been used to synthesize hydroxamic acid-containing bicyclic β-lactam cores. Oxidative cleavage of the pendant alkene provides access to the carboxylic acid in one step. PMID:24483144

  5. Telomerization of amino acids with butadiene, catalyzed by palladium complexes

    SciTech Connect

    Dzhemilev, U.M.; Fakhretdinov, R.N.; Telin, A.G.

    1987-01-10

    The telomerization of ..cap alpha..-, ..beta..-, ..gamma..-, and epsilon-amino acids having various structures with butadiene under the influence of the three-component palladium catalyst Pd(acac)/sub 2/-PPh/sub 3/-AlEt/sub 3/ was investigated in DMSO-toluene solution. The ..cap alpha..- and epsilon-aliphatic and also the ..cap alpha..-, ..beta..-, and ..gamma..-aromatic amino acids react with butadiene, giving the products from octadienylation at the amino group exclusively. Under the conditions of telomerization aliphatic ..beta..-amino acids are cleaved with the formation of unsaturated tertiary amines. In the case of aliphatic ..gamma..-amino acids it is possible to obtain telomers alkylated at the carbonyl group.

  6. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    PubMed Central

    Hemric, Brett N

    2016-01-01

    Summary This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates. PMID:26877805

  7. Copper-assisted palladium(II)-catalyzed direct arylation of cyclic enaminones with arylboronic acids.

    PubMed

    Kim, Yong Wook; Niphakis, Micah J; Georg, Gunda I

    2012-11-01

    Described herein is a palladium(II)-catalyzed direct arylation of cyclic enaminones with arylboronic acids. The versatility of this method is that both electron-rich and electron-poor boronic acids can be coupled in high yields. A mixture of two Cu(II) additives was crucial for efficient cross-coupling. The role of each Cu(II) reagent appears to be distinct and complementary serving to assist catalyst reoxidation and transmetalation through a putative arylcopper intermediate. PMID:23088256

  8. Lewis Acid Catalyzed Selective Reactions of Donor-Acceptor Cyclopropanes with 2-Naphthols.

    PubMed

    Kaicharla, Trinadh; Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G; Biju, Akkattu T

    2016-08-16

    Lewis acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with 2-naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)3 as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene-fused cyclopentanes. Interestingly, engaging Sc(OTf)3 as the Lewis acid, a Friedel-Crafts-type addition of 2-naphthols to cyclopropanes takes place, thus affording functionalized 2-naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields. PMID:27391792

  9. Triflic Acid-Catalyzed Enynes Cyclization: A New Strategy beyond Electrophilic π-Activation.

    PubMed

    Yu, Zhunzhun; Liu, Lu; Zhang, Junliang

    2016-06-13

    The cyclization of enynes, catalyzed by a transition metal, represents a powerful tool to construct an array of cyclic compounds through electrophilic π-activation. In this paper, we disclose a new and efficient strategy for enynes cyclization catalyzed by triflic acid. The salient features of this transformation includes a broad substrate scope, metal free synthesis, open flask and mild conditions, good yields, ease of operation, low catalyst loading, and easy scale-up to gram scale. A preliminary mechanism study demonstrated that the activation model of the reaction was σ-activation, which is different from the transition-metal-catalyzed enynes cyclization. Our strategy affords a complementary method to the traditional strategies, which use transition-metal catalysts. PMID:27124814

  10. Choline Chloride Catalyzed Amidation of Fatty Acid Ester to Monoethanolamide: A Green Approach.

    PubMed

    Patil, Pramod; Pratap, Amit

    2016-01-01

    Choline chloride catalyzed efficient method for amidation of fatty acid methyl ester to monoethanolamide respectively. This is a solvent free, ecofriendly, 100% chemo selective and economically viable path for alkanolamide synthesis. The Kinetics of amidation of methyl ester were studied and found to be first order with respect to the concentration of ethanolamine. The activation energy (Ea) for the amidation of lauric acid methyl ester catalyzed by choline chloride was found to be 50.20 KJ mol(-1). The 98% conversion of lauric acid monoethanolamide was obtained at 110°C in 1 h with 6% weight of catalyst and 1:1.5 molar ratio of methyl ester to ethanolamine under nitrogen atmosphere. PMID:26666271

  11. Inorganic acid-catalyzed tautomerization of vinyl alcohol to acetaldehyde

    NASA Astrophysics Data System (ADS)

    Karton, Amir

    2014-01-01

    The vinyl alcohol-acetaldehyde tautomerization reaction has recently received considerable attention as a potential route for the formation of organic acids in the troposphere (Andrews et al., 2012 [7]). We examine the catalytic effect of inorganic acids in the troposphere (e.g. HNO3, H2SO4 and HClO4) on the vinyl alcohol-acetaldehyde tautomerization reaction, by means high-level thermochemical procedures. We show that H2SO4 and HClO4 catalysts lead to near-zero reaction barrier heights for the vinyl alcohol → acetaldehyde reaction, and to low reaction barrier heights in the reverse direction (ΔH298‡=40.6 and 39.5 kJ mol, respectively).

  12. Palladium-Catalyzed α-Arylation of Aryl Acetic Acid Derivatives via Dienolate Intermediates with Aryl Chlorides and Bromides

    PubMed Central

    2016-01-01

    To date, examples of α-arylation of carboxylic acids remain scarce. Using a deprotonative cross-coupling process (DCCP), a method for palladium-catalyzed γ-arylation of aryl acetic acids with aryl halides has been developed. This protocol is applicable to a wide range of aryl bromides and chlorides. A procedure for the palladium-catalyzed α-arylation of styryl acetic acids is also described. PMID:25582024

  13. Acid-Catalyzed Reaction of Epoxides on Atmospheric Nanoparticles

    NASA Astrophysics Data System (ADS)

    Xu, W.; Gomez-Hernandez, M.; Lal, V.; Qiu, C.; Khalizov, A. F.; Wang, L.; Zhang, R.

    2013-12-01

    Aerosol plays an important role in affecting the earth climate and harming human health. Atmospheric aerosols can be formed from either primary emissions or gas-to-particle conversion process. Numerous studies, including both experimental and theoretical, have been carried out to elucidate the mechanism of gas-to-particle conversion process (a.k.a. nucleation) and the later growth stage of newly formed nanoparticles. However, a complete list of species involving in the nucleation and growth processes of nanoparticles is still poorly understood. The growth of newly formed sulfuric acid - water nanoparticles has been suggested to involve several potential organic vapors, such as amines, glyoxal, 2-4 hexadienal, and epoxides. In the present study, new formed sulfuric acid -water nanoparticles were size selected by a differential mobility analyzer and exposed to epoxide vapors. The size-change after exposure was detected using the second differential mobility analyzer. The size-enlarged particles were then collected by an electrostatic precipitator, thermal vaporized, and analyzed by an ion drift chemical ionization mass spectrometer. Our results show that the sizes of nanoparticles are increased considerably and the magnitude of the increment in size is size-dependent. Mass spectrometry analysis of the nanoparticles after exposure demonstrates that low volatile organosulfate and oligomers are formed in nanoparticles upon their exposure to epoxide vapors.

  14. Enantioselective Rh(I)-Catalyzed Addition of Arylboronic Acids to Cyclic Ketimines.

    PubMed

    Kong, Jongrock; McLaughlin, Mark; Belyk, Kevin; Mondschein, Ryan

    2015-11-20

    A method for the enantioselective synthesis of chiral α-tertiary amines via Rh-catalyzed 1,2-addition of arylboronic acids to cyclic ketimines is described. The products are efficiently accessed in good yields and excellent enantioselectivities using a commercially available chiral ligand. The reaction scope includes vinyl, aryl, and heteroarylboronic acids with yields ranging from 40% to 99% and enantiomeric excesses from 88% to 99%. Conversion of an addition product into an α,α-diaryl-substituted amino acid is also demonstrated. PMID:26542775

  15. Nickel-Catalyzed Cross-Coupling of Redox-Active Esters with Boronic Acids.

    PubMed

    Wang, Jie; Qin, Tian; Chen, Tie-Gen; Wimmer, Laurin; Edwards, Jacob T; Cornella, Josep; Vokits, Benjamin; Shaw, Scott A; Baran, Phil S

    2016-08-01

    A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross-coupling between alkyl-carboxylic acids and boronic acids is described. This Ni-catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox-active ester derivatives, specifically N-hydroxy-tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2 ⋅6 H2 O-$9.5 mol(-1) , Et3 N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption. PMID:27380912

  16. Tunable and Diastereoselective Brønsted Acid Catalyzed Synthesis of β-Enaminones.

    PubMed

    Kang, Ye-Won; Cho, Yu Jin; Han, Seung Jin; Jang, Hye-Young

    2016-01-15

    The Brønsted acid catalyzed Meyer-Schuster reaction of hemiaminals was studied for the stereoselective synthesis of β-enaminones. Hemiaminals were formed from propargyl aldehydes (or the oxidation of propargyl alcohols) and amines in the presence of Brønsted acids. A critical step to control the stereochemistry of the products is the protonation of the corresponding allenol intermediate, which is dictated by the Brønsted acid used, the steric effect of the amine, and the electronic effect of the propargyl aldehyde. PMID:26741050

  17. Lipase-catalyzed acidolysis of menhaden oil with conjugated linoleic acid: effect of water content.

    PubMed

    Torres, Carlos F; Hill, Charles G

    2002-06-01

    The effect of the water content on the lipase-catalyzed (Candida rugosa) interesterification (acidolysis) of menhaden oil with conjugated linoleic acid was studied for amounts of added water ranging from 0-4% (w/w). The rate of the acidolysis reaction increased with increasing water content, but the corresponding percentage of n-3 fatty acids liberated also increased. The implications of water content for minimization of the release of n-3 fatty acid residues while maximizing incorporation of CLA are discussed. PMID:12115120

  18. Asymmetric, Three-Component, One-Pot Synthesis of Spiropyrazolones and 2,5-Chromenediones from Aldol Condensation/NHC-Catalyzed Annulation Reactions.

    PubMed

    Wang, Lei; Li, Sun; Chauhan, Pankaj; Hack, Daniel; Philipps, Arne R; Puttreddy, Rakesh; Rissanen, Kari; Raabe, Gerhard; Enders, Dieter

    2016-04-01

    A novel one-pot, three-component diastereo- and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β-unsaturated pyrazolones, which react with a second equivalent of enal through an N-heterocyclic carbene (NHC)-catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3-diketones, 2,5-chromenediones are available through [2+4] annulation. PMID:26864437

  19. Seeking the Limits of Low-Temperature Nuclear Fusion: Sticking in Muon-Catalyzed Fusion, and Piezonuclear Fusion in Deuterium/condensed Matter Systems

    NASA Astrophysics Data System (ADS)

    Taylor, Stuart F.

    Studies seeking an upper limit of two types of low temperature nuclear fusion is presented. The upper limit for muon catalyzed fusion is generally considered to be the number of fusions per muon obtainable. The limiting factor has been found to be how often the muon remains bound to the alpha produced by the fusion, known as the "sticking fraction." Experiments directly measuring the sticking and determining the sticking using high tritium fractions are presented. In deuterium/condensed matter systems the question is nearly whether nuclear fusion proceeds at all. Experiments where neutrons around deuterided titanium and palladium are measured are presented.

  20. Organosolv liquefaction of sugarcane bagasse catalyzed by acidic ionic liquids.

    PubMed

    Chen, Zhengjian; Long, Jinxing

    2016-08-01

    An efficient and eco-friendly process is proposed for sugarcane bagasse liquefaction under mild condition using IL catalyst and environmental friendly solvent of ethanol/H2O. The relationship between IL acidic strength and its catalytic performance is investigated. The effects of reaction condition parameters such as catalyst dosage, temperature, time and solvent are also intensively studied. The results show that ethanol/H2O has a significant promotion effect on the simultaneous liquefaction of sugarcane bagasse carbohydrate and lignin. 97.5% of the bagasse can be liquefied with 66.46% of volatile product yield at 200°C for 30min. Furthermore, the IL catalyst shows good recyclability where no significant loss of the catalytic activity is exhibited even after five runs. PMID:27115746

  1. Acetyl xylan esterase of Aspergillus ficcum catalyzed the synthesis of peracetic acid from ethyl acetate and hydrogen peroxide.

    PubMed

    Park, Seung-Moon

    2011-11-01

    Recombinant acetyl xylan esterase (rAXE) of Aspergillus ficcum catalyzed the synthesis of peracetic acid (PAA) from ethyl acetate and hydrogen peroxide. Ten micrograms of rAXE catalyzed the synthesis of 1.34 mM of PAA, which can be used for the pretreatment of cellulosic biomass in situ. PMID:21824816

  2. Keto-Enol Tautomerizations Catalyzed by Water and Carboxylic Acids

    NASA Astrophysics Data System (ADS)

    da Silva, G.

    2009-12-01

    The ability of weakly-bound complexes to influence the kinetics of gas phase reactions, particularly in atmospheric chemistry, has long been speculated. This study uses quantum chemistry and statistical reaction rate theory to identify that bound water molecules can significantly reduce barriers to intramolecular hydrogen shift reactions, via a double-hydrogen-shift mechanism. The bound water molecule directly participates in the hydrogen shift reaction, exchanging a H atom with its counterpart. For the vinyl alcohol to acetaldehyde keto-enol tautomerization this mechanism cuts the reaction barrier approximately in half, reducing it by over 30 kcal mol-1. In contrast, while a non-participatory ‘bystander’ water molecule also reduces the hydrogen shift barrier, it is only by around 3 kcal/mol. When a carboxylic acid replaces water in the double-hydrogen-shift mechanism the barrier to keto-enol tautomerization is decimated, reduced to less than 6 kcal/mol (around 15 kcal/mol in the reverse direction). This results from reduced strain in the hydrogen shift transition state, and achieves enol lifetimes in the troposphere that become short on relevant timescales. Rapid enol to ketone isomerizations are currently required to explain the oxidation products of isoprene. The wider significance of rapid hydrogen shift reactions in atmospherically relevant molecules and radicals is also explored.

  3. Chiral phosphoric acid catalyzed enantioselective synthesis of β-amino-α,α-difluoro carbonyl compounds.

    PubMed

    Kashikura, Wataru; Mori, Keiji; Akiyama, Takahiko

    2011-04-01

    A biphenol-based chiral phosphoric acid bearing a 9-anthryl group at each of the 3,3'-positions catalyzed the asymmetric Mannich-type reaction of N-Boc imine with difluoroenol silyl ethers in the presence of MS3A in THF to afford β-amino-α,α-difluoroketones in good yields and with excellent enantioselectivities. Optically pure 3,3-difluoroazetidin-2-one was readily synthesized from the Mannich-adduct. PMID:21391557

  4. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    PubMed

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. PMID:26150397

  5. One site is enough: a theoretical investigation of iron-catalyzed dehydrogenation of formic Acid.

    PubMed

    Sánchez-de-Armas, Rocío; Xue, Liqin; Ahlquist, Mårten S G

    2013-09-01

    Dehydrogenation of HCO2H: The reaction mechanism for the dehydrogenation of formic acid catalyzed by a highly active and selective iron complex has been studied by DFT. The most favorable pathway shows the hydride in Fe-H complexes acting as a spectator ligand throughout the catalytic cycle. This result opens up the Fe complex for modification in order to achieve more efficient and selective catalysts. PMID:23907850

  6. Synthesis and Preliminary Biological Study of Bisindolylmethanes Accessed by an Acid-Catalyzed Hydroarylation of Vinylindoles

    PubMed Central

    Pathak, Tejas P.; Osiak, Jaroslaw G.; Vaden, Rachel M.; Welm, Bryan E.; Sigman, Matthew S.

    2012-01-01

    An acid-catalyzed hydroarylation reaction of vinyl indoles is reported, which tolerates a wide range of heterocycles as the exogenous nucleophile such as indoles, pyrroles, and indolizines. The method rapidly accesses the biologically relevant bisindolylmethane scaffold in good to excellent yields. Evaluation of the biological activity of several synthesized analogues reveals cytotoxic activity against and selectivity for the MCF-7 breast cancer cell line. PMID:22778488

  7. [Lipase-catalyzed production of biodiesel from high acid value waste oil with ultrasonic assistant].

    PubMed

    Wang, Jian-Xun; Huang, Qing-De; Huang, Feng-Hong; Wang, Jiang-Wei; Huang, Qin-Jie

    2007-11-01

    Biodiesel fuel produced with the enzyme-catalyzed esterification and transesterification of high acid value waste oil through ultrasonic assistant was explored. Propyl oleate, biodiesel, converted from high acid value waste oil and 1-proponal catalyzed with immobilized lipases from Candida antarctica and Aspergillus oryzae in conditions of ultrasonic assistant. Commercial immobilized lipase Novozym 435 from C. antarctica was used as biocatalyst catalyzing high acid value waste oil and 1-proponal esterification and transesterification to propyl oleate under the ultrasonic assistant conditions and different conditions such as lipases amounts, initiatory molar ratio of propanol to oil, frequency of ultrasonic and power of ultrasonic were investigated and optimized. It is revealed that the enzymatic activity of Novozym435 is enhanced and, in particular, enzyme-catalyzed transesterification activity is enhanced obviously under the ultrasonic assistant conditions. Low frequency and mild energy ultrasonic is a key factor for enhancing enzymatic activity, emulsifying oil-propanol system and accelerating the speed of produce diffusing in the system. Under the optimal ultrasonic assistant reaction conditions, such as Novozym435 amounts 8% by oil quantity, initiatory molar ratio of propanol to oil 3:1, frequency of ultrasonic 28 KHz, power of ultrasonic 100 W and temperature of water batch 40-45 degrees C, the conversion ratio to propyl oleate reached to 94.86% in 50 mins in comparison with the highest conversion ratio to propyl oleate 84.43% under the conventional mechanical agitation conditions. Furthermore, it is demonstrated that various short chain linear and branched alcohols (C1-C5) show high conversion ratio to fatty acid alkyl esters (biodiesel) under the optimal ultrasonic assistant reaction conditions. On the other hand, ultrasonic energy is propitious to reduce the adsorption of product propyl oleate, by-product glycerol and other emplastics in system on the

  8. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    PubMed Central

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-01

    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

  9. Sulfuric, hydrochloric, and nitric acid-catalyzed triacetone triperoxide (TATP) reaction mixtures: an aging study.

    PubMed

    Fitzgerald, Mark; Bilusich, Daniel

    2011-09-01

    The organic peroxide explosive triacetone triperoxide (TATP) is regularly encountered by law enforcement agents in various stages of its production. This study utilizes solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to examine sulfuric acid-, hydrochloric acid-, and nitric acid-catalyzed TATP syntheses during the initial 24 h of these reactions at low temperatures (5-9°C). Additionally, aging of the reaction mixtures was examined at both low and ambient temperatures (19-21°C) for a further 9 days. For each experiment, TATP could be readily identified in the headspace above the reaction mixture 1 h subsequent to the combination of reagents; at 24 h, TATP and diacetone diperoxide (DADP) were prominent. TATP degraded more rapidly than DADP. Additionally, chlorinated acetones chloroacetone and 1,1,-dichloroacetone were identified in the headspace above the hydrochloric acid-catalyzed TATP reaction mixture. These were not present when the catalyst was sulfuric acid or nitric acid. PMID:21595692

  10. Solid acid-catalyzed depolymerization of barley straw driven by ball milling.

    PubMed

    Schneider, Laura; Haverinen, Jasmiina; Jaakkola, Mari; Lassi, Ulla

    2016-04-01

    This study describes a time and energy saving, solvent-free procedure for the conversion of lignocellulosic barley straw into reducing sugars by mechanocatalytical pretreatment. The catalytic conversion efficiency of several solid acids was tested which revealed oxalic acid dihydrate as a potential catalyst with high conversion rate. Samples were mechanically treated by ball milling and subsequently hydrolyzed at different temperatures. The parameters of the mechanical treatment were optimized in order to obtain sufficient amount of total reducing sugar (TRS) which was determined following the DNS assay. Additionally, capillary electrophoresis (CE) and Fourier transform infrared spectrometry (FT-IR) were carried out. Under optimal conditions TRS 42% was released using oxalic acid dihydrate as a catalyst. This study revealed that the acid strength plays an important role in the depolymerization of barley straw and in addition, showed, that the oxalic acid-catalyzed reaction generates low level of the degradation product 5-hydroxymethylfurfural (HMF). PMID:26859328

  11. Copper-catalyzed intermolecular trifluoromethylarylation of alkenes: mutual activation of arylboronic acid and CF3+ reagent.

    PubMed

    Wang, Fei; Wang, Dinghai; Mu, Xin; Chen, Pinhong; Liu, Guosheng

    2014-07-23

    A novel copper-catalyzed intermolecular trifluoromethylarylation of alkenes is developed using less active ether-type Togni's reagent under mild reaction conditions. Various alkenes and diverse arylboronic acids are compatible with these conditions. Preliminary mechanistic studies reveal that a mutual activation process between arylboronic acid and CF3(+) reagent is essential. In addition, the reaction might involve a rate-determining transmetalation, and the final aryl C-C bond is derived from reductive elimination of the aryl(alkyl)Cu(III) intermediate. PMID:24983408

  12. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water.

    PubMed

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun

    2009-01-01

    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated. PMID:25084408

  13. Asymmetric epoxidation of allylic alcohols catalyzed by vanadium-binaphthylbishydroxamic Acid complex.

    PubMed

    Noji, Masahiro; Kobayashi, Toshihiro; Uechi, Yuria; Kikuchi, Asami; Kondo, Hisako; Sugiyama, Shigeo; Ishii, Keitaro

    2015-03-20

    A vanadium-binaphthylbishydroxamic acid (BBHA) complex-catalyzed asymmetric epoxidation of allylic alcohols is described. The optically active binaphthyl-based ligands BBHA 2a and 2b were synthesized from (S)-1,1'-binaphthyl-2,2'-dicarboxylic acid and N-substituted-O-trimethylsilyl (TMS)-protected hydroxylamines via a one-pot, three-step procedure. The epoxidations of 2,3,3-trisubstituted allylic alcohols using the vanadium complex of 2a were easily performed in toluene with a TBHP water solution to afford (2R)-epoxy alcohols in good to excellent enantioselectivities. PMID:25714329

  14. A General Access to Propargylic Ethers through Brønsted Acid Catalyzed Alkynylation of Acetals and Ketals with Trifluoroborates .

    PubMed

    Baxter, Matthew; Bolshan, Yuri

    2015-09-21

    A general Brønsted acid catalyzed methodology for the alkynylation of acetals and ketals with alkynyltrifluoroborate salts has been developed. The reaction proceeds rapidly to afford valuable synthetic building block propargylic ethers in good to excellent yields. Unlike Lewis acid catalyzed transformations of trifluoroborates, this approach does not proceed via unstable organodifluoroborane intermediate. As a result, the developed methodology features excellent functional group tolerance and good atom economy. PMID:26248543

  15. Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid, aluminum chloride, and hydrochloric acid

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.; Malyi, A. B.

    2016-07-01

    Formation of linear polyenes-(CH=CH)n-via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10-12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.

  16. Mechanical and microstructural properties of two-step acid-base catalyzed silica gels

    SciTech Connect

    Meyers, D.E.; Kirkbir, F.; Murata, H.; Chaudhuri, S.R.; Sarkar, A.

    1994-12-31

    The mechanical and microstructural properties of two-step acid-base catalyzed silica gels were examined as functions of aging time, catalyst concentration, and hydrolysis time. Cylindrical gels were prepared using Si(OC{sub 2}H{sub 5}){sub 4}, C{sub 2}H{sub 5}OH, and H{sub 2}O, with HCl followed by NH{sub 3} as catalysts. Mechanical properties were obtained from three-point bend tests, and the microstructures of dried gels were analyzed using nitrogen adsorption/desorption techniques. Gel strength initially increased with aging time at 70 C, then leveled off after about one week. When the sol was hydrolyzed for less than two hours, there were significant differences in the properties of gels catalyzed with relative molar amounts of 0.0001 and 0.0002 HCl. However, as the hydrolysis time was increased, the gels all had similar properties, independent of the amount of HCl. The amount of NH{sub 3} influenced gelation time and to a lesser extent, the strength, but had no observable effect on pore size. The two-step catalysis procedure produced gels with strength and pore size combinations intermediate to those of either single acid or base-catalyzed gels.

  17. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

    PubMed Central

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-01-01

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

  18. Regioselective Enzymatic β-Carboxylation of para-Hydroxy- styrene Derivatives Catalyzed by Phenolic Acid Decarboxylases

    PubMed Central

    Wuensch, Christiane; Pavkov-Keller, Tea; Steinkellner, Georg; Gross, Johannes; Fuchs, Michael; Hromic, Altijana; Lyskowski, Andrzej; Fauland, Kerstin; Gruber, Karl; Glueck, Silvia M; Faber, Kurt

    2015-01-01

    We report on a ‘green’ method for the utilization of carbon dioxide as C1 unit for the regioselective synthesis of (E)-cinnamic acids via regioselective enzymatic carboxylation of para-hydroxystyrenes. Phenolic acid decarboxylases from bacterial sources catalyzed the β-carboxylation of para-hydroxystyrene derivatives with excellent regio- and (E/Z)-stereoselectivity by exclusively acting at the β-carbon atom of the C=C side chain to furnish the corresponding (E)-cinnamic acid derivatives in up to 40% conversion at the expense of bicarbonate as carbon dioxide source. Studies on the substrate scope of this strategy are presented and a catalytic mechanism is proposed based on molecular modelling studies supported by mutagenesis of amino acid residues in the active site. PMID:26190963

  19. 21 CFR 573.500 - Condensed, extracted glutamic acid fermentation product.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED... fermentation product. Condensed, extracted glutamic acid fermentation product may be safely used in animal feed... glutamic acid. (b) It is used or intended for use as follows: (1) In poultry feed as a source of protein...

  20. 21 CFR 573.500 - Condensed, extracted glutamic acid fermentation product.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED... fermentation product. Condensed, extracted glutamic acid fermentation product may be safely used in animal feed... glutamic acid. (b) It is used or intended for use as follows: (1) In poultry feed as a source of protein...

  1. 21 CFR 573.500 - Condensed, extracted glutamic acid fermentation product.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED... fermentation product. Condensed, extracted glutamic acid fermentation product may be safely used in animal feed... glutamic acid. (b) It is used or intended for use as follows: (1) In poultry feed as a source of protein...

  2. 21 CFR 573.500 - Condensed, extracted glutamic acid fermentation product.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED... fermentation product. Condensed, extracted glutamic acid fermentation product may be safely used in animal feed... glutamic acid. (b) It is used or intended for use as follows: (1) In poultry feed as a source of protein...

  3. Synthesis of 2-monoacylglycerols and structured triacylglycerols rich in polyunsaturated fatty acids by enzyme catalyzed reactions.

    PubMed

    Rodríguez, Alicia; Esteban, Luis; Martín, Lorena; Jiménez, María José; Hita, Estrella; Castillo, Beatriz; González, Pedro A; Robles, Alfonso

    2012-08-10

    This paper studies the synthesis of structured triacylglycerols (STAGs) by a four-step process: (i) obtaining 2-monoacylglycerols (2-MAGs) by alcoholysis of cod liver oil with several alcohols, catalyzed by lipases Novozym 435, from Candida antartica and DF, from Rhizopus oryzae, (ii) purification of 2-MAGs, (iii) formation of STAGs by esterification of 2-MAGs with caprylic acid catalyzed by lipase DF, from R. oryzae, and (iv) purification of these STAGs. For the alcoholysis of cod liver oil, absolute ethanol, ethanol 96% (v/v) and 1-butanol were compared; the conditions with ethanol 96% were then optimized and 2-MAG yields of around 54-57% were attained using Novozym 435. In these 2-MAGs, DHA accounted for 24-31% of total fatty acids. In the operational conditions this lipase maintained a stable level of activity over at least 11 uses. These results were compared with those obtained with lipase DF, which deactivated after only three uses. The alcoholysis of cod liver oil and ethanol 96% catalyzed by Novozym 435 was scaled up by multiplying the reactant amounts 100-fold and maintaining the intensity of treatment constant (IOT=3g lipase h/g oil). In these conditions, the 2-MAG yield attained was about 67%; these 2-MAGs contained 36.6% DHA. The synthesized 2-MAGs were separated and purified from the alcoholysis reaction products by solvent extraction using solvents of low toxicity (ethanol and hexane); 2-MAG recovery yield and purity of the target product were approximately 96.4% and 83.9%, respectively. These 2-MAGs were transformed to STAGs using the optimal conditions obtained in a previous work. After synthesis and purification, 93% pure STAGs were obtained, containing 38% DHA at sn-2 position and 60% caprylic acid (CA) at sn-1,3 positions (of total fatty acids at these positions), i.e. the major TAG is the STAG with the structure CA-DHA-CA. PMID:22759534

  4. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    NASA Technical Reports Server (NTRS)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  5. Immune-responsive gene 1 protein links metabolism to immunity by catalyzing itaconic acid production.

    PubMed

    Michelucci, Alessandro; Cordes, Thekla; Ghelfi, Jenny; Pailot, Arnaud; Reiling, Norbert; Goldmann, Oliver; Binz, Tina; Wegner, André; Tallam, Aravind; Rausell, Antonio; Buttini, Manuel; Linster, Carole L; Medina, Eva; Balling, Rudi; Hiller, Karsten

    2013-05-01

    Immunoresponsive gene 1 (Irg1) is highly expressed in mammalian macrophages during inflammation, but its biological function has not yet been elucidated. Here, we identify Irg1 as the gene coding for an enzyme producing itaconic acid (also known as methylenesuccinic acid) through the decarboxylation of cis-aconitate, a tricarboxylic acid cycle intermediate. Using a gain-and-loss-of-function approach in both mouse and human immune cells, we found Irg1 expression levels correlating with the amounts of itaconic acid, a metabolite previously proposed to have an antimicrobial effect. We purified IRG1 protein and identified its cis-aconitate decarboxylating activity in an enzymatic assay. Itaconic acid is an organic compound that inhibits isocitrate lyase, the key enzyme of the glyoxylate shunt, a pathway essential for bacterial growth under specific conditions. Here we show that itaconic acid inhibits the growth of bacteria expressing isocitrate lyase, such as Salmonella enterica and Mycobacterium tuberculosis. Furthermore, Irg1 gene silencing in macrophages resulted in significantly decreased intracellular itaconic acid levels as well as significantly reduced antimicrobial activity during bacterial infections. Taken together, our results demonstrate that IRG1 links cellular metabolism with immune defense by catalyzing itaconic acid production. PMID:23610393

  6. Immune-responsive gene 1 protein links metabolism to immunity by catalyzing itaconic acid production

    PubMed Central

    Michelucci, Alessandro; Cordes, Thekla; Ghelfi, Jenny; Pailot, Arnaud; Reiling, Norbert; Goldmann, Oliver; Binz, Tina; Wegner, André; Tallam, Aravind; Rausell, Antonio; Buttini, Manuel; Linster, Carole L.; Medina, Eva; Balling, Rudi; Hiller, Karsten

    2013-01-01

    Immunoresponsive gene 1 (Irg1) is highly expressed in mammalian macrophages during inflammation, but its biological function has not yet been elucidated. Here, we identify Irg1 as the gene coding for an enzyme producing itaconic acid (also known as methylenesuccinic acid) through the decarboxylation of cis-aconitate, a tricarboxylic acid cycle intermediate. Using a gain-and-loss-of-function approach in both mouse and human immune cells, we found Irg1 expression levels correlating with the amounts of itaconic acid, a metabolite previously proposed to have an antimicrobial effect. We purified IRG1 protein and identified its cis-aconitate decarboxylating activity in an enzymatic assay. Itaconic acid is an organic compound that inhibits isocitrate lyase, the key enzyme of the glyoxylate shunt, a pathway essential for bacterial growth under specific conditions. Here we show that itaconic acid inhibits the growth of bacteria expressing isocitrate lyase, such as Salmonella enterica and Mycobacterium tuberculosis. Furthermore, Irg1 gene silencing in macrophages resulted in significantly decreased intracellular itaconic acid levels as well as significantly reduced antimicrobial activity during bacterial infections. Taken together, our results demonstrate that IRG1 links cellular metabolism with immune defense by catalyzing itaconic acid production. PMID:23610393

  7. Salicylic acid-induced superoxide generation catalyzed by plant peroxidase in hydrogen peroxide-independent manner

    PubMed Central

    Kimura, Makoto; Kawano, Tomonori

    2015-01-01

    It has been reported that salicylic acid (SA) induces both immediate spike and long lasting phases of oxidative burst represented by the generation of reactive oxygen species (ROS) such as superoxide anion radical (O2•−). In general, in the earlier phase of oxidative burst, apoplastic peroxidase are likely involved and in the late phase of the oxidative burst, NADPH oxidase is likely involved. Key signaling events connecting the 2 phases of oxidative burst are calcium channel activation and protein phosphorylation events. To date, the known earliest signaling event in response to exogenously added SA is the cell wall peroxidase-catalyzed generation of O2•− in a hydrogen peroxide (H2O2)-dependent manner. However, this model is incomplete since the source of the initially required H2O2 could not be explained. Based on the recently proposed role for H2O2-independent mechanism for ROS production catalyzed by plant peroxidases (Kimura et al., 2014, Frontiers in Plant Science), we hereby propose a novel model for plant peroxidase-catalyzed oxidative burst fueled by SA. PMID:26633563

  8. Acid-catalyzed Furfuryl Alcohol Polymerization: Characterizations of Molecular Structure and Thermodynamic Properties

    SciTech Connect

    Kim, Taejin; Assary, Rajeev A.; Marshall, Christopher L.; Gosztola, David J.; Curtiss, Larry A.; Stair, Peter C.

    2011-07-22

    The liquid-phase polymerization of furfuryl alcohol catalyzed by sulfuric acid catalysts and the identities of molecular intermediates were investigated by using Raman spectroscopy and density functional theory calculation. At room temperature, with an acid catalyst, a vigorous furfuryl alcohol polymerization reaction was observed, whereas even at a high water concentration, furfuryl alcohol was very stable in the absence of an acid catalyst. Theoretical studies were carried out to investigate the thermodynamics of protonation of furfuryl alcohol, initiation of polymerization, and formation of conjugated dienes and diketonic species by using the B3LYP level of theory. A strong aliphatic C=C band observed in the calculated and measured Raman spectra provided crucial evidence to understand the polymerization reaction mechanism. It is confirmed that the formation of a conjugated diene structure rather than a diketone structure is involved in the furfuryl alcohol polymerization reaction.

  9. Acid-catalyzed furfurly alcohol polymerization : characterizations of molecular structure and thermodynamic properties.

    SciTech Connect

    Kim, T.; Assary, R. S.; Marshall, C. L.; Gosztola, D. J.; Curtiss, L. A.; Stair, P. C.

    2011-01-01

    The liquid-phase polymerization of furfuryl alcohol catalyzed by sulfuric acid catalysts and the identities of molecular intermediates were investigated by using Raman spectroscopy and density functional theory calculation. At room temperature, with an acid catalyst, a vigorous furfuryl alcohol polymerization reaction was observed, whereas even at a high water concentration, furfuryl alcohol was very stable in the absence of an acid catalyst. Theoretical studies were carried out to investigate the thermodynamics of protonation of furfuryl alcohol, initiation of polymerization, and formation of conjugated dienes and diketonic species by using the B3LYP level of theory. A strong aliphatic C=C band observed in the calculated and measured Raman spectra provided crucial evidence to understand the polymerization reaction mechanism. It is confirmed that the formation of a conjugated diene structure rather than a diketone structure is involved in the furfuryl alcohol polymerization reaction.

  10. Pitfalls in protein quantitation using acid-catalyzed O18 labeling: hydrolysis-driven deamidation

    PubMed Central

    Wang, Shunhai; Bobst, Cedric E.; Kaltashov, Igor A.

    2011-01-01

    Proteolysis combined with O18 labeling emerged recently as a powerful tool for quantitation of proteins for which suitable internal standards cannot be produced using molecular biology methods. Several recent reports suggested that acid-catalyzed O18 labeling may be superior to the commonly accepted enzymatic protocol, as it may allow more significant spacing between the isotopic clusters of labeled and unlabeled peptides, thereby eliminating signal interference and enhancing the quality of quantitation. However, careful examination of this procedure reveals that the results of protein quantitation assisted by acid-catalyzed O18 labeling are highly peptide-dependent. The inconsistency was found to be caused by deamidation of Asn, Gln and carbamidomethylated Cys residues during prolonged exposure of the proteolytic fragments to the acidic environment of the labeling reaction, which translates into a loss in signal for theses peptides. Taking deamidation into account leads to a significant improvement in the consistency of quantitation across a range of different proteolytic fragments. PMID:21819098

  11. Iron-Catalyzed Diastereoselective Synthesis of Unnatural Chiral Amino Acid Derivatives.

    PubMed

    Zhang, Hao; Li, Haifang; Yang, Haijun; Fu, Hua

    2016-07-15

    An iron-catalyzed diastereoselective synthesis of unnatural chiral (S)-α-amino acids with γ-quaternary carbon centers has been developed. The protocol uses inexpensive iron salt as the catalyst, readily available 2-phthaloyl acrylamide and alkenes as the starting materials, and phenylsilane as the reductant, and the reactions were performed well in mixed solvent of 1,2-dichloroethane and ethylene glycol at room temperature. The method shows some advantages including simple and wide substrates, mild conditions, high diastereoselectivity, and easy workup procedures. PMID:27367820

  12. Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

    PubMed

    Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

    2015-12-01

    A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. PMID:26344422

  13. Negative resists for electron-beam lithography utilizing acid-catalyzed intramolecular dehydration of phenylcarbinol

    NASA Astrophysics Data System (ADS)

    Migitaka, Sonoko; Uchino, Shou-ichi; Ueno, Takumi; Yamamoto, Jiro; Kojima, Kyoko; Hashimoto, Michiaki; Shiraishi, Hiroshi

    1996-06-01

    Acid-catalyzed intramolecular dehydration of phenylcarbinol is used to design highly sensitive negative resists for electron beam lithography. Of the phenylcarbinol resists evaluated in this study, the resist composed of 1,3-bis(alpha-hydroxyisopropyl)benzene (Diol-1), m/p-cresol novolak resin, and diphenyliodonium triflate (DIT) shows the best lithographic performance in terms of sensitivity and resolution. Fine 0.25-micrometer line-and-space patterns were formed by using the resist containing Diol-1 with a dose of 3.6 (mu) C/cm2 in conjunction with a 50 kV electron beam exposure system.

  14. Palladium(II)-Catalyzed Tandem Synthesis of Acenes Using Carboxylic Acids as Traceless Directing Groups.

    PubMed

    Kim, Kiho; Vasu, Dhananjayan; Im, Honggu; Hong, Sungwoo

    2016-07-18

    A straightforward synthetic strategy for generating useful anthracene derivatives was developed involving palladium(II)-catalyzed tandem transformation with carboxylic acids as traceless directing groups. Carboxyl-directed C-H alkenylation, carboxyl-directed secondary C-H activation and rollover, intramolecular C-C bond formation, and decarboxylative aromatization are proposed as the key steps in the tandem reaction pathway. This novel synthetic route utilizes a broad range of substrates and provides a convenient synthetic tool that allows access to acenes. PMID:27244536

  15. Synthesis of phytuberin. 4-endo-tet acid-catalyzed cyclization of alpha-hydroxy epoxides.

    PubMed

    Prangé, Thierry; Rodríguez, María S; Suárez, Ernesto

    2003-05-30

    The total synthesis of phytuberin, a phytoalexin of the Solanum genus, from (-)-alpha-santonin is reported. The key steps include (a) reductive cleavage of the C-O bond of the gamma-lactone with concomitant protection of the C1 double bond, (b) Sharpless stereocontrolled hydroxy-assisted epoxidation of allylic alcohol 6 and simultaneous deprotection of the C1 double bond, (c) a rare 4-endo-tet acid-catalyzed cyclization of an alpha-hydroxy epoxide, and (d) an unprecedented 4-exo selenocyclization of a homoallylic alcohol. PMID:12762747

  16. Rh(III)-catalyzed dehydrogenative alkylation of (hetero)arenes with allylic alcohols, allowing aldol condensation to indenes.

    PubMed

    Shi, Zhuangzhi; Boultadakis-Arapinis, Mélissa; Glorius, Frank

    2013-07-25

    Efficient Rh(III)-catalyzed C-H activation of different classes of (hetero)arenes such as 2-phenylpyridine, indoles, aryl ketones and acetanilide and their dehydrogenative cross-coupling with allylic alcohols are described. Several important skeletons such as β-aryl aldehydes and ketones, 2-acetylindenes, 3,4-dihydro-1H-quinolin-2-one and quinoline could be produced using this protocol. PMID:23765402

  17. Hydroxyapatite catalyzed aldol condensation: Synthesis, spectral linearity, antimicrobial and insect antifeedant activities of some 2,5-dimethyl-3-furyl chalcones

    NASA Astrophysics Data System (ADS)

    Subramanian, M.; Vanangamudi, G.; Thirunarayanan, G.

    2013-06-01

    A series of 2,5-dimethyl-3-furyl chalcones [2E-1-(2,5-dimethyl-3-furyl)-3-(substituted phenyl)-2-propen-1-ones] have been synthesized by Hydrotalcite catalyzed aldol condensation between 3-acetyl-2,5-dimethylfuron and substituted benzaldehydes. Yields of chalcones are more than 80%. These chalcones were characterized by their physical constants and spectral data. The group frequencies of infrared ν(cm-1) of CO s-cis and s-trans, CH in-plane and out of plane, CHdbnd CH out of plane, lbond2 Cdbnd Crbond2 out of plane modes, NMR chemical shifts δ(ppm) of Hα, Hβ, CO, Cα and Cβ of these chalcones were correlated with Hammett substituent constants, F and R parameters using single and multi-regression analyses. From the results of statistical analyses, the effects of substituents on the group frequencies are explained. Antibacterial, antifungal and insect antifeedant activities of these chalcones have been studied.

  18. Production of Chiral (R)-3-Hydroxyoctanoic Acid Monomers, Catalyzed by Pseudomonas fluorescens GK13 Poly(3-Hydroxyoctanoic Acid) Depolymerase▿

    PubMed Central

    Gangoiti, Joana; Santos, Marta; Llama, María J.; Serra, Juan L.

    2010-01-01

    The extracellular medium-chain-length polyhydroxyalkanoate (MCL-PHA) depolymerase of Pseudomonas fluorescens GK13 catalyzes the hydrolysis of poly(3-hydroxyoctanoic acid) [P(3HO)]. Based on the strong tendency of the enzyme to interact with hydrophobic materials, a low-cost method which allows the rapid and easy purification and immobilization of the enzyme has been developed. Thus, the extracellular P(3HO) depolymerase present in the culture broth of cells of P. fluorescens GK13 grown on mineral medium supplemented with P(3HO) as the sole carbon and energy source has been tightly adsorbed onto a commercially available polypropylene support (Accurel MP-1000) with high yield and specificity. The activity of the pure enzyme was enhanced by the presence of detergents and organic solvents, and it was retained after treatment with an SDS-denaturing cocktail under both reducing and nonreducing conditions. The time course of the P(3HO) hydrolysis catalyzed by the soluble and immobilized enzyme has been assessed, and the resulting products have been identified. After 24 h of hydrolysis, the dimeric ester of 3-HO [(R)-3-HO-HO] was obtained as the main product of the soluble enzyme. However, the immobilized enzyme catalyzes almost the complete hydrolysis of P(3HO) polymer to (R)-3-HO monomers under the same conditions. PMID:20400568

  19. 7-deoxyloganetic acid synthase catalyzes a key 3 step oxidation to form 7-deoxyloganetic acid in Catharanthus roseus iridoid biosynthesis.

    PubMed

    Salim, Vonny; Wiens, Brent; Masada-Atsumi, Sayaka; Yu, Fang; De Luca, Vincenzo

    2014-05-01

    Iridoids are key intermediates required for the biosynthesis of monoterpenoid indole alkaloids (MIAs), as well as quinoline alkaloids. Although most iridoid biosynthetic genes have been identified, one remaining three step oxidation required to form the carboxyl group of 7-deoxyloganetic acid has yet to be characterized. Here, it is reported that virus-induced gene silencing of 7-deoxyloganetic acid synthase (7DLS, CYP76A26) in Catharanthus roseus greatly decreased levels of secologanin and the major MIAs, catharanthine and vindoline in silenced leaves. Functional expression of this gene in Saccharomyces cerevisiae confirmed its function as an authentic 7DLS that catalyzes the 3 step oxidation of iridodial-nepetalactol to form 7-deoxyloganetic acid. The identification of CYP76A26 removes a key bottleneck for expression of iridoid and related MIA pathways in various biological backgrounds. PMID:24594312

  20. Acid-catalyzed reactions of a disecondary aromatic diol with alkanols

    SciTech Connect

    Zaitsev, B.A.; Dantsig, L.L.

    1986-07-10

    On heating a disecondary aromatic diol with an alkanol in an aromatic solvent in the presence of an acid catalyst, condensation telomerization takes place with the formation of oligomeric ethers, alcoholysis of which and condensation of hydroxylated intermediate products gives dialkyl ethers of the diol, followed by cleavage of these ethers to give vinyl- and divinylaromatic compounds, and cationic polyaddition of these monomers to give straight-chain unsaturated oligomers, giving mixtures of vinylaromatic compounds and unsaturated straight-chain oligomers. The rate of cleavage of dialkoxy-derivatives of the aromatic diol decreases as the reaction progresses as a result of the increasing concentration of the liberated alkanol, which modifies the activity of the catalyst.

  1. Metal ion-humic acid nanoparticle interactions: role of both complexation and condensation mechanisms.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-07-21

    Purely Donnan type models for electrostatic binding by humic acid (HA) nanoparticles are shown to be physically incomplete. To describe the extent of ion binding by HA, such models need to invoke parameters that are not consistent with experimental observations. These disparate parameters include anomalously high Donnan potentials, as well as intrinsic affinity constants for electrostatically associating ions such as Ca(2+). In contrast, the recently introduced counterion condensation - Donnan model (CCD) provides a physicochemically realistic description of the electrostatic contribution to metal ion binding by humic acid nanoparticles. The extent of Ca(2+)-HA association can be adequately described solely in terms of electrostatics only, including counterion condensation in the intraparticulate double layer in addition to Donnan partitioning in the remainder of the particle body. The binding of Cd(ii), Pb, (ii) and Cu(ii) by HA also involves inner-sphere complex formation leading to intraparticulate metal species distributions with major proportions of condensed and complexed ions. PMID:27327433

  2. Evaluation of bicinchoninic acid as a ligand for copper(I)-catalyzed azide-alkyne bioconjugations.

    PubMed

    Christen, Erik H; Gübeli, Raphael J; Kaufmann, Beate; Merkel, Lars; Schoenmakers, Ronald; Budisa, Nediljko; Fussenegger, Martin; Weber, Wilfried; Wiltschi, Birgit

    2012-09-01

    The Cu(I)-catalyzed cycloaddition of terminal azides and alkynes (click chemistry) represents a highly specific reaction for the functionalization of biomolecules with chemical moieties such as dyes or polymer matrices. In this study we evaluate the use of bicinchoninic acid (BCA) as a ligand for Cu(I) under physiological reaction conditions. We demonstrate that the BCA-Cu(I)-complex represents an efficient catalyst for the conjugation of fluorophores or biotin to alkyne- or azide-functionalized proteins resulting in increased or at least equal reaction yields compared to commonly used catalysts like Cu(I) in complex with TBTA (tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine) or BPAA (bathophenanthroline disulfonic acid). The stabilization of Cu(I) with BCA represents a new strategy for achieving highly efficient bioconjugation reactions under physiological conditions in many application fields. PMID:22821135

  3. Mechanism of silver- and copper-catalyzed decarboxylation reactions of aryl carboxylic acids.

    PubMed

    Xue, Liqin; Su, Weiping; Lin, Zhenyang

    2011-11-28

    Silver- and copper-catalyzed decarboxylation reactions of aryl carboxylic acids were investigated with the aid of density functional theory calculations. The reaction mechanism starts with a carboxylate complex of silver or copper. Decarboxylation occurs via ejecting CO(2) from the carboxylate complex followed by protodemetallation with an aryl carboxylic acid molecule to regenerate the starting complex. Our results indicated that the primary factor to affect the overall reaction barriers is the ortho steric destabilization effect on the starting carboxylate complexes for most cases. Certain ortho substituents that are capable of coordinating with the catalyst metal center without causing significant ring strain stabilize the decarboxylation transition states and reduce the overall reaction barriers. However, the coordination effect is found to be the secondary factor when compared with the ortho effect. PMID:21979246

  4. 21 CFR 573.500 - Condensed, extracted glutamic acid fermentation product.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Condensed, extracted glutamic acid fermentation product. 573.500 Section 573.500 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food...

  5. Lewis acid-catalyzed intramolecular condensation of ynol ether-acetals. Synthesis of alkoxycycloalkene carboxylates

    PubMed Central

    Tran, Vincent

    2012-01-01

    Treatment of ynol ether-tethered dialkyl acetals with catalytic quantities of scandium triflate in CH3CN gives rise to five-, six-, and seven-membered alkoxycycloalkene carboxylates in good to excellent yields. Trisubstituted and tetrasubsituted carbocyclic and heterocyclic alkenes may be formed by this method, and the products obtained may serve as useful intermediates for natural product synthesis. PMID:23170869

  6. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery.

    PubMed

    Miao, Guohou; Chen, Xiaofeng; Dong, Hua; Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing

    2013-10-01

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. (29)Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. PMID:23910338

  7. Selective heterogeneous acid catalyzed esterification of N-terminal sulfyhdryl fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Our interest in thiol fatty acids lies in their antioxidative, free radical scavenging, and metal ion scavenging capabilities as applied to cosmeceutical and skin care formulations. The retail market is filled with products containing the disulfide-containing free fatty acid, lipoic acid. These pr...

  8. Purification and characterization of cannabidiolic-acid synthase from Cannabis sativa L.. Biochemical analysis of a novel enzyme that catalyzes the oxidocyclization of cannabigerolic acid to cannabidiolic acid.

    PubMed

    Taura, F; Morimoto, S; Shoyama, Y

    1996-07-19

    We identified a unique enzyme that catalyzes the oxidocyclization of cannabigerolic acid to cannabidiolic acid (CBDA) in Cannabis sativa L. (CBDA strain). The enzyme, named CBDA synthase, was purified to apparent homogeneity by a four-step procedure: ammonium sulfate precipitation followed by chromatography on DEAE-cellulose, phenyl-Sepharose CL-4B, and hydroxylapatite. The active enzyme consists of a single polypeptide with a molecular mass of 74 kDa and a pI of 6.1. The NH2-terminal amino acid sequence of CBDA synthase is similar to that of Delta1-tetrahydrocannabinolic-acid synthase. CBDA synthase does not require coenzymes, molecular oxygen, hydrogen peroxide, and metal ion cofactors for the oxidocyclization reaction. These results indicate that CBDA synthase is neither an oxygenase nor a peroxidase and that the enzymatic cyclization does not proceed via oxygenated intermediates. CBDA synthase catalyzes the formation of CBDA from cannabinerolic acid as well as cannabigerolic acid, although the kcat for the former (0.03 s-1) is lower than that for the latter (0.19 s-1). Therefore, we conclude that CBDA is predominantly biosynthesized from cannabigerolic acid rather than cannabinerolic acid. PMID:8663284

  9. Multi-shell model of ion-induced nucleic acid condensation

    NASA Astrophysics Data System (ADS)

    Tolokh, Igor S.; Drozdetski, Aleksander V.; Pollack, Lois; Baker, Nathan A.; Onufriev, Alexey V.

    2016-04-01

    We present a semi-quantitative model of condensation of short nucleic acid (NA) duplexes induced by trivalent cobalt(iii) hexammine (CoHex) ions. The model is based on partitioning of bound counterion distribution around single NA duplex into "external" and "internal" ion binding shells distinguished by the proximity to duplex helical axis. In the aggregated phase the shells overlap, which leads to significantly increased attraction of CoHex ions in these overlaps with the neighboring duplexes. The duplex aggregation free energy is decomposed into attractive and repulsive components in such a way that they can be represented by simple analytical expressions with parameters derived from molecular dynamic simulations and numerical solutions of Poisson equation. The attractive term depends on the fractions of bound ions in the overlapping shells and affinity of CoHex to the "external" shell of nearly neutralized duplex. The repulsive components of the free energy are duplex configurational entropy loss upon the aggregation and the electrostatic repulsion of the duplexes that remains after neutralization by bound CoHex ions. The estimates of the aggregation free energy are consistent with the experimental range of NA duplex condensation propensities, including the unusually poor condensation of RNA structures and subtle sequence effects upon DNA condensation. The model predicts that, in contrast to DNA, RNA duplexes may condense into tighter packed aggregates with a higher degree of duplex neutralization. An appreciable CoHex mediated RNA-RNA attraction requires closer inter-duplex separation to engage CoHex ions (bound mostly in the "internal" shell of RNA) into short-range attractive interactions. The model also predicts that longer NA fragments will condense more readily than shorter ones. The ability of this model to explain experimentally observed trends in NA condensation lends support to proposed NA condensation picture based on the multivalent "ion binding

  10. Laboratory studies of the formation of polar stratospheric clouds: Nitric acid condensation on thin sulfuric acid films

    NASA Astrophysics Data System (ADS)

    Iraci, Laura T.; Middlebrook, Ann M.; Tolbert, Margaret A.

    1995-10-01

    Thin sulfuric acid films were exposed to 5 × 10-8 - 8 × 10-7 torr HNO3 and 2 - 3 × 10-4 torr H2O and cooled to temperatures near the ice frost point. Fourier transform infrared (FTIR) spectroscopy was used to probe the condensed-phase species during isothermal experiments, and gas pressures were monitored with mass spectrometry. Supercooled liquid sulfuric acid films exposed to HNO3 (6 ≤ SNAT ≤ 114) showed indications of HNO3 uptake to form ternary solutions of approximately 4 wt % HNO3, 38 wt % H2SO4, and 59 wt % H2O, followed by crystallization of nitric acid trihydrate (NAT). NAT crystallization did not initiate significant crystallization of the supercooled H2SO4, but the H2SO4 often crystallized to sulfuric acid tetrahydrate (SAT) upon warming. In contrast, when crystalline SAT films were exposed to HNO3 and water, NAT did not condense within several hours, even at HNO3 saturation ratios of 30 or higher. Calculations of the contact parameter from experimental data indicate that m <0.76 for NAT on SAT. Our film studies suggest that crystalline polar stratospheric cloud (PSC) growth is most easily accomplished when stratospheric sulfate aerosols (SSAs) remain liquid, absorb HNO3, and produce crystalline nitric acid trihydrate via heterogeneous nucleation. If SSAs crystallize to SAT at some point during the winter, nitric acid condensation is hindered, and PSC formation could become more difficult.

  11. Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 19: Condensation of phthalic and substituted phthalic anhydrides with benzoylacetic ester

    NASA Technical Reports Server (NTRS)

    Rotberg, Y. T.; Oshkaya, V. P.

    1985-01-01

    Phthalylbenzoylacetic ester and its nitro and halogen derivatives were prepared through condensation of phthalic anhydride, nitrophthalic anhydride, and phthalic halide anhydride with benzoylacetic ester in a solution of acetic anhydride and triethylamine. The condensation of hemipinic acid anhydride proceeds similarly, but under more drastic conditions. Derivatives of indan-1,3-dione are also formed, with a small yield, in the reaction of nitrophthalic anhydrides with benzoylacetic ester in the presence of increased quantities of triethylamine.

  12. Oxidation of benzene with hydrogen peroxide catalyzed with ferrocene in the presence of pyrazine carboxylic acid

    NASA Astrophysics Data System (ADS)

    Shul'pina, L. S.; Durova, E. L.; Kozlov, Yu. N.; Kudinov, A. R.; Strelkova, T. V.; Shul'pin, G. B.

    2013-12-01

    It is found that ferrocene in the presence of small amounts of pyrazine carboxylic acid (PCA) effectively catalyzes the oxidation of benzene to phenol with hydrogen peroxide. Two main differences upon the oxidation of two different substrates, i.e., cyclohexane and benzene, with the same H2O2-ferrocene-PCA catalytic system are revealed: the rates of benzene oxidation and hydrogen peroxide decomposition are several times lower than the rate of cyclohexane oxidation at close concentrations of both substrates, and the rate constant ratios for the reactions of oxidizing particles with benzene and acetonitrile are significantly lower than would be expected for reactions involving free hydroxyl radicals. The overall rate of hydrogen peroxide decomposition, including both the catalase and oxidase routes, is lower in the presence of benzene than in the presence of cyclohexane. It is suggested on the grounds of these data that a catalytically active particle different from the one generated in the absence of benzene is formed in the presence of benzene. This particle catalyzes hydrogen peroxide decomposition less efficiently than the initial complex and generates a dissimilar oxidizing particle that exhibits higher selectivity. It is shown that reactivity of the system at higher concentrations of benzene differs from that of an initial system not containing an aromatic component with the capability of π-coordination with metal ions.

  13. Electrochemical impedance spectroscopy sensor for ascorbic acid based on copper(I) catalyzed click chemistry.

    PubMed

    Qiu, Suyan; Gao, Sen; Liu, Qida; Lin, Zhenyu; Qiu, Bin; Chen, Guonan

    2011-07-15

    Copper(I) species can be acquired from the reduction of copper(II) by ascorbic acid (AA) in situ, and which in turn quantitative catalyze the azides and alkynes cycloaddition reaction. In this study, propargyl-functionalized ferrocene (propargyl-functionalized Fc) has been modified on the electrode through reacting with azide terminal modified Au electrode via copper(I) catalyzed azides and alkynes cycloaddition (CuAAC) reaction. The electrochemical impedance spectroscopy (EIS) measurement has been applied to test the electron transfer resistance of the Au electrode before and after click reaction. The changes of the fractional surface coverage (θ) with different AA concentrations are characterized. It is found that the θ value has a linear response to the logarithm of AA concentration in the range of 5.0 pmol/L to 1.0 nmol/L with the detection limits of 2.6 pmol/L. The sensor shows a good stability and selectivity. And it has been successfully applied to the AA detection in the real samples (urine) with satisfactory results. PMID:21596552

  14. beta-Lactamase-catalyzed hydrolysis of acyclic depsipeptides and acyl transfer to specific amino acid acceptors.

    PubMed Central

    Pratt, R F; Govardhan, C P

    1984-01-01

    beta-Lactamases from all three classes, A, B, and C, catalyze the hydrolysis of specific acyclic depsipeptide (PhCH2CONHCR1R2CO2CHR3CO2H) analogs of acyl-D-alanyl-D-alanine peptides. The depsipeptides investigated, which are chemically as reactive toward nucleophiles as penicillins, are in general poor substrates, although differences between the classes of beta-lactamases have been observed: the order of effectiveness seems to be C greater than B greater than A. Certain class A and C beta-lactamases also catalyze phenylacetylglycyl transfer between phenylacetylglycyl depsipeptides and specific amino acid acceptors, a type of reaction hitherto identified more closely with D-alanyl-D-alanine transpeptidases than with beta-lactamases. Preliminary indications of an acyl-enzyme intermediate in these reactions have been obtained. These results support the suggestion [Tipper, D.J. and Strominger, J.L. (1965) Proc. Natl. Acad. Sci. USA 54, 1133-1141] that beta-lactamases are evolutionary descendants of bacterial cell wall D-alanyl-D-alanine transpeptidases. PMID:6424114

  15. Membrane protein complexes catalyze both 4- and 3-hydroxylation of cinnamic acid derivatives in monolignol biosynthesis.

    PubMed

    Chen, Hsi-Chuan; Li, Quanzi; Shuford, Christopher M; Liu, Jie; Muddiman, David C; Sederoff, Ronald R; Chiang, Vincent L

    2011-12-27

    The hydroxylation of 4- and 3-ring carbons of cinnamic acid derivatives during monolignol biosynthesis are key steps that determine the structure and properties of lignin. Individual enzymes have been thought to catalyze these reactions. In stem differentiating xylem (SDX) of Populus trichocarpa, two cinnamic acid 4-hydroxylases (PtrC4H1 and PtrC4H2) and a p-coumaroyl ester 3-hydroxylase (PtrC3H3) are the enzymes involved in these reactions. Here we present evidence that these hydroxylases interact, forming heterodimeric (PtrC4H1/C4H2, PtrC4H1/C3H3, and PtrC4H2/C3H3) and heterotrimeric (PtrC4H1/C4H2/C3H3) membrane protein complexes. Enzyme kinetics using yeast recombinant proteins demonstrated that the enzymatic efficiency (V(max)/k(m)) for any of the complexes is 70-6,500 times greater than that of the individual proteins. The highest increase in efficiency was found for the PtrC4H1/C4H2/C3H3-mediated p-coumaroyl ester 3-hydroxylation. Affinity purification-quantitative mass spectrometry, bimolecular fluorescence complementation, chemical cross-linking, and reciprocal coimmunoprecipitation provide further evidence for these multiprotein complexes. The activities of the recombinant and SDX plant proteins demonstrate two protein-complex-mediated 3-hydroxylation paths in monolignol biosynthesis in P. trichocarpa SDX; one converts p-coumaric acid to caffeic acid and the other converts p-coumaroyl shikimic acid to caffeoyl shikimic acid. Cinnamic acid 4-hydroxylation is also mediated by the same protein complexes. These results provide direct evidence for functional involvement of membrane protein complexes in monolignol biosynthesis. PMID:22160716

  16. Formation of cloud condensation nuclei by oxidative processing: Unsaturated fatty acids

    NASA Astrophysics Data System (ADS)

    Broekhuizen, Keith E.; Thornberry, Troy; Kumar, P. Pradeep; Abbatt, Jonathan P. D.

    2004-12-01

    The ability of submicron oleic acid and linoleic acid particles, or condensation nuclei (CN), to act as cloud condensation nuclei (CCN) has been investigated using a tandem differential mobility analyzer (TDMA) coupled to a flow tube reactor and a thermal gradient diffusion chamber (TGDC). The size change and CCN properties of pure oleic acid, mixed oleic acid/methanol, and pure linoleic acid particles have been investigated as a function of exposure to ozone. Pure oleic and linoleic acid particles were CCN inactive for all particle diameters (≤300 nm) and supersaturations (≤1%) studied. The mixed oleic acid/methanol particles, however, had a critical activation diameter of 188 nm for an experimental water supersaturation of 0.6%. Under low ozone exposures (<1 × 10-4 atm s), both the oleic acid and linoleic acid particles decreased in size. In particular, oleic acid particles lost 25% of their initial volume, consistent with the loss of nonanal, a volatile reaction product. However, no increase in CCN activity was observed at these exposures. Under conditions of much higher ozone exposure, e.g., 0.42 atm s, the pure oleic acid particles became CCN active, with a critical activation diameter of 161 nm at 0.6% supersaturation. CCN activity for the linoleic acid particles was never observed, even under these high ozone exposures not typically observed in the atmosphere. By contrast, the mixed oleic acid/methanol particles showed enhanced activation under atmospherically relevant ozone exposures (<1 × 10-4 atm s). These results suggest that the products of the ozone plus unsaturated fatty acid reaction do promote the CCN activity of the particles; however, the degree of activity is dependent on both the level of ozone exposure and the chemical nature of the particle. These results are the first to demonstrate that the CCN properties of pure organic aerosols can be modified through oxidative processing.

  17. Lipase-catalyzed synthesis of fatty acid amide (erucamide) using fatty acid and urea.

    PubMed

    Awasthi, Neeraj Praphulla; Singh, R P

    2007-01-01

    Ammonolysis of fatty acids to the corresponding fatty acid amides is efficiently catalysed by Candida antartica lipase (Novozym 435). In the present paper lipase-catalysed synthesis of erucamide by ammonolysis of erucic acid and urea in organic solvent medium was studied and optimal conditions for fatty amides synthesis were established. In this process erucic acid gave 88.74 % pure erucamide after 48 hour and 250 rpm at 60 degrees C with 1:4 molar ratio of erucic acid and urea, the organic solvent media is 50 ml tert-butyl alcohol (2-methyl-2-propanol). This process for synthesis is economical as we used urea in place of ammonia or other amidation reactant at atmospheric pressure. The amount of catalyst used is 3 %. PMID:17898456

  18. Mechanisms and energetics for acid catalyzed β-D-glucose conversion to 5-hydroxymethylfurfurl.

    PubMed

    Qian, Xianghong

    2011-10-27

    Car-Parrinello based ab initio molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations were carried out to investigate the mechanism and energetics for acid-catalyzed β-d-glucose conversion to 5-hydroxymethylfurfurl (HMF) in water. HMF is a critical intermediate for biomass conversion to biofuels. It was found that protonation of the C2-OH on glucose, the breakage of the C2-O2 bond, and the formation of the C2-O5 bond is the critical rate-limiting step for the direct glucose conversion to HMF without converting to fructose first, contrary to the wide-spread assumption in literature that fructose is the main intermediate for glucose conversion to HMF. The calculated reaction barrier of 30-35 kcal/mol appears to be solvent-induced and is in excellent agreement with experimental observations. PMID:21916465

  19. Efficient acid-catalyzed (18) F/(19) F fluoride exchange of BODIPY dyes.

    PubMed

    Keliher, Edmund J; Klubnick, Jenna A; Reiner, Thomas; Mazitschek, Ralph; Weissleder, Ralph

    2014-07-01

    Fluorine-containing fluorochromes are important validation agents for positron emission tomography imaging compounds, as they can be readily validated in cells by fluorescence imaging. In particular, the (18) F-labeled BODIPY-FL fluorophore has emerged as an important platform, but little is known about alternative (18) F-labeling strategies or labeling on red-shifted fluorophores. In this study we explore acid-catalyzed (18) F/(19) F exchange on a range of commercially available N-hydroxysuccinimidyl ester and maleimide BODIPY fluorophores. We show this method to be a simple and efficient (18) F-labeling strategy for a diverse span of fluorescent compounds, including a BODIPY-modified PARP-1 inhibitor, and amine- and thiol-reactive BODIPY fluorophores. PMID:24596307

  20. Cinchona Urea-Catalyzed Asymmetric Sulfa-Michael Reactions: The Brønsted Acid-Hydrogen Bonding Model.

    PubMed

    Grayson, Matthew N; Houk, K N

    2016-07-27

    The cinchona alkaloid-derived urea-catalyzed asymmetric conjugate addition of aromatic thiols to cycloalkenones was studied using density functional theory (DFT). Deprotonation of the thiol gives a protonated amine that activates the electrophile by Brønsted acid catalysis, while the urea group binds the nucleophilic thiolate by hydrogen bonding. These results demonstrate the generality of the Brønsted acid-hydrogen bonding transition state (TS) model for cinchona alkaloid catalysis that we recently showed to be favored over Wynberg's widely accepted ion pair-hydrogen bonding model and represent the first detailed mechanistic study of a cinchona urea-catalyzed reaction. The conformation of the catalyst methoxy group has a strong effect on the TS, an effect overlooked in previous mechanistic studies of reactions catalyzed by cinchona alkaloids. PMID:27396591

  1. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    SciTech Connect

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2013-01-01

    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of

  2. A Practical Guide for Predicting the Stereochemistry of Bifunctional Phosphoric Acid Catalyzed Reactions of Imines.

    PubMed

    Reid, Jolene P; Simón, Luis; Goodman, Jonathan M

    2016-05-17

    Chiral phosphoric acids have become powerful catalysts for the stereocontrolled synthesis of a diverse array of organic compounds. Since the initial report, the development of phosphoric acids as catalysts has been rapid, demonstrating the tremendous generality of this catalyst system and advancing the use of phosphoric acids to catalyze a broad range of asymmetric transformations ranging from Mannich reactions to hydrogenations through complementary modes of activation. These powerful applications have been developed without a clear mechanistic understanding of the reasons for the high level of stereocontrol. This Account describes investigations into the mechanism of the phosphoric acid catalyzed addition of nucleophiles to imines, focusing on binaphthol-based systems. In many cases, the hydroxyl phosphoric acid can form a hydrogen bond to the imine while the P═O interacts with the nucleophile. The single catalyst, therefore, activates both the electrophile and the nucleophile, while holding both in the chiral pocket created by the binaphthol and constrained by substituents at the 3 and 3' positions. Detailed geometric and energetic information about the transition states can be gained from calculations using ONIOM methods that combine the advantages of DFT with some of the speed of force fields. These high-level calculations give a quantitative account of the selectivity in many cases, but require substantial computational resources. A simple qualitative model is a useful complement to this complex quantitative model. We summarize our calculations into a working model that can readily be sketched by hand and used to work out the likely sense of selectivity for each reaction. The steric demands of the different parts of the reactants determine how they fit into the chiral cavity and which of the competing pathways is favored. The preferred pathway can be found by considering the size of the substituents on the nitrogen and carbon atoms of the imine electrophile

  3. Nitric acid catalyzed hydrolysis of SO3 in the formation of sulfuric acid: A theoretical study

    NASA Astrophysics Data System (ADS)

    Long, Bo; Chang, Chun-Ran; Long, Zheng-Wen; Wang, Yi-Bo; Tan, Xing-Feng; Zhang, Wei-Jun

    2013-08-01

    The gas-phase hydrolysis of SO3 in the presence of one water molecule, two water molecules, and nitric acid is investigated utilizing high level quantum chemical methods and transition state theory. The calculated results demonstrate that nitric acid exerts a strong catalytic role in the hydrolysis of SO3 because the activated barrier of hydrolysis of SO3 with the assistance of nitric acid is reduced to about 3.7 kcal/mol, which is about 20 kcal/mol lower than that of the SO3 reaction with water relative to the respective pre-reactive complex.

  4. Lewis Acid Catalyzed Regiospecific Cross-Dehydrative Coupling Reaction of 2-Furylcarbinols with β-Keto Amides or 4-Hydroxycoumarins: A Route to Furyl Enols.

    PubMed

    Miao, Maozhong; Luo, Yi; Li, Hongli; Xu, Xin; Chen, Zhengkai; Xu, Jianfeng; Ren, Hongjun

    2016-06-17

    Lewis acid catalyzed directly dehydrative carbon-carbon bond formation reaction of 2-furylcarbinols with β-keto amides provides a straightforward method for regioselective synthesis of (Z)-furyl enols. Moreover, this Lewis acid catalyzed cross-coupling reaction can be extended to an interesting heterocyclic version featuring a functionalized 3-furyl-4-hydroxycoumarin synthesis. PMID:27224045

  5. Acid-catalyzed conversion of xylose, xylan and straw into furfural by microwave-assisted reaction.

    PubMed

    Yemiş, Oktay; Mazza, Giuseppe

    2011-08-01

    Furfural is a biomass derived-chemical that can be used to replace petrochemicals. In this study, the acid-catalyzed conversion of xylose and xylan to furfural by microwave-assisted reaction was investigated at selected ranges of temperature (140-190°C), time (1-30 min), substrate concentration (1:5-1:200 solid:liquid ratio), and pH (2-0.13). We found that a temperature of 180°C, a solid:liquid ratio of 1:200, a residence time of 20 min, and a pH of 1.12 gave the best furfural yields. The effect of different Brønsted acids on the conversion efficiency of xylose and xylan was also evaluated, with hydrochloric acid being found to be the most effective catalyst. The microwave-assisted process provides highly efficient conversion: furfural yields obtained from wheat straw, triticale straw, and flax shives were 48.4%, 45.7%, and 72.1%, respectively. PMID:21620690

  6. Selective Nickel- and Manganese-Catalyzed Decarboxylative Cross Coupling of Some α,β-Unsaturated Carboxylic Acids with Cyclic Ethers

    PubMed Central

    Zhang, Jia-Xiang; Wang, Yan-Jing; Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Xing, Ya-Lan; Li, Yi-He; Wen, Jia-Long

    2014-01-01

    A nickel- and manganese-catalyzed decarboxylative cross coupling of α, β-unsaturated carboxylic acids with cyclic ethers such as tetrahydrofuran and 1, 4-dioxane was developed. Oxyalkylation was achieved when nickel acetate was used as catalyst, while manganese acetate promoted the reaction of alkenylation. PMID:25502282

  7. Efficient Synthesis of 3,3'-Mixed Bisindoles via Lewis Acid Catalyzed Reaction of Spiro-epoxyoxindoles and Indoles.

    PubMed

    Hajra, Saumen; Maity, Subrata; Maity, Ramkrishna

    2015-07-17

    An efficient strategy for the synthesis of 3-(3-indolyl)-oxindole-3-methanol has been developed to achieve a Lewis acid catalyzed, highly regioselective ring opening of spiro-epoxyoxindoles with indoles. The method is used for the gram-scale formal total synthesis of (±)-gliocladin C. PMID:26158390

  8. Two-step one-pot synthesis of benzoannulated spiroacetals by Suzuki-Miyaura coupling/acid-catalyzed spiroacetalization.

    PubMed

    Butkevich, Alexey N; Corbu, Andrei; Meerpoel, Lieven; Stansfield, Ian; Angibaud, Patrick; Bonnet, Pascal; Cossy, Janine

    2012-10-01

    Substituted benzoannulated spiroacetals were prepared from (2-haloaryl)alkyl alcohols and dihydropyranyl or dihydrofuranyl pinacol boronates using a Suzuki-Miyaura coupling followed by an acid-catalyzed spirocyclization. Application of the reaction to a glycal boronate provides an approach to annulated spiroacetals in enantiopure form. PMID:22998767

  9. Lipase-catalyzed process in an anhydrous medium with enzyme reutilization to produce biodiesel with low acid value.

    PubMed

    Azócar, Laura; Ciudad, Gustavo; Heipieper, Hermann J; Muñoz, Robinson; Navia, Rodrigo

    2011-12-01

    One major problem in the lipase-catalyzed production of biodiesel or fatty acid methyl esters (FAME) is the high acidity of the product, mainly caused by water presence, which produces parallel hydrolysis and esterification reactions instead of transesterification to FAME. Therefore, the use of reaction medium in absence of water (anhydrous medium) was investigated in a lipase-catalyzed process to improve FAME yield and final product quality. FAME production catalyzed by Novozym 435 was carried out using waste frying oil (WFO) as raw material, methanol as acyl acceptor, and 3Å molecular sieves to extract the water. The anhydrous conditions allowed the esterification of free fatty acids (FFA) from feedstock at the initial reaction time. However, after the initial esterification process, water absence avoided the consecutives reactions of hydrolysis and esterification, producing FAME mainly by transesterification. Using this anhydrous medium, a decreasing in both the acid value and the diglycerides content in the product were observed, simultaneously improving FAME yield. Enzyme reuse in the anhydrous medium was also studied. The use of the moderate polar solvent tert-butanol as a co-solvent led to a stable catalysis using Novozym 435 even after 17 successive cycles of FAME production under anhydrous conditions. These results indicate that a lipase-catalyzed process in an anhydrous medium coupled with enzyme reuse would be suitable for biodiesel production, promoting the use of oils of different origin as raw materials. PMID:21889401

  10. Persistent Water-Nitric Acid Condensate with Saturation Water Vapor Pressure Greater than That of Hexagonal Ice.

    PubMed

    Gao, Ru-Shan; Gierczak, Tomasz; Thornberry, Troy D; Rollins, Andrew W; Burkholder, James B; Telg, Hagen; Voigt, Christiane; Peter, Thomas; Fahey, David W

    2016-03-10

    A laboratory chilled mirror hygrometer (CMH), exposed to an airstream containing water vapor (H2O) and nitric acid (HNO3), has been used to demonstrate the existence of a persistent water-nitric acid condensate that has a saturation H2O vapor pressure greater than that of hexagonal ice (Ih). The condensate was routinely formed on the mirror by removing HNO3 from the airstream following the formation of an initial condensate on the mirror that resembled nitric acid trihydrate (NAT). Typical conditions for the formation of the persistent condensate were a H2O mixing ratio greater than 18 ppm, pressure of 128 hPa, and mirror temperature between 202 and 216 K. In steady-state operation, a CMH maintains a condensate of constant optical diffusivity on a mirror through control of only the mirror temperature. Maintaining the persistent condensate on the mirror required that the mirror temperature be below the H2O saturation temperature with respect to Ih by as much as 3 K, corresponding to up to 63% H2O supersaturation with respect to Ih. The condensate was observed to persist in steady state for up to 16 h. Compositional analysis of the condensate confirmed the co-condensation of H2O and HNO3 and thereby strongly supports the conclusion that the Ih supersaturation is due to residual HNO3 in the condensate. Although the exact structure or stoichiometry of the condensate could not be determined, other known stable phases of HNO3 and H2O are excluded as possible condensates. This persistent condensate, if it also forms in the upper tropical troposphere, might explain some of the high Ih supersaturations in cirrus and contrails that have been reported in the tropical tropopause region. PMID:26447682

  11. Potential of phosphoric acid-catalyzed pretreatment and subsequent enzymatic hydrolysis for biosugar production from Gracilaria verrucosa.

    PubMed

    Kwon, Oh-Min; Kim, Sung-Koo; Jeong, Gwi-Taek

    2016-07-01

    This study combined phosphoric acid-catalyzed pretreatment and enzymatic hydrolysis to produce biosugars from Gracilaria verrucosa as a potential renewable resource for bioenergy applications. We optimized phosphoric acid-catalyzed pretreatment conditions to 1:10 solid-to-liquid ratio, 1.5 % phosphoric acid, 140 °C, and 60 min reaction time, producing a 32.52 ± 0.06 % total reducing sugar (TRS) yield. By subsequent enzymatic hydrolysis, a 68.61 ± 0.90 % TRS yield was achieved. These results demonstrate the potential of phosphoric acid to produce biosugars for biofuel and biochemical production applications. PMID:27003825

  12. Copper Catalyzed Sodium Tetraphenylborate, Triphenylborane, Diphenylborinic Acid and Phenylboronic Acid Decomposition Kinetic Studies in Aqueous Alkaline Solutions

    SciTech Connect

    Crawford, C.L.

    1999-03-15

    This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 degrees C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB {tilde} 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB {tilde} 2PB < 1PB {tilde} NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8 percent decomposition over {tilde} 500 h) towards thermal hydrolysis in 1.5 M NaOH when contained in carbon-steel vessels sealed under air at ambient temperature (23 - 25 degrees C) with no added copper. Measurable (> 10-7 Mh-1) thermal hydrolysis of the phenylborate species occurs at 55 to 70 degrees C in alkaline (0.6-2.3 M OH-, 2-4.7 M Na+) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 degrees C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.

  13. Tandem hydrogenation and condensation of fluorinated α,β-unsaturated ketones with primary amines, catalyzed by nickel.

    PubMed

    Castellanos-Blanco, Nahury; Flores-Alamo, Marcos; García, Juventino J

    2015-09-21

    A simple homogeneous catalytic system based on nickel phosphine complexes has been developed for the transfer hydrogenation and condensation of α,β-unsaturated ketones to yield saturated ones and saturated imines using primary amines as hydrogen donors. Thus, a wide range of fluorinated 1,5-diaryl-1,4-pentadiene-3-ones were allowed to react with substituted benzylamines in the presence of [(dippe)Ni(μ-H)]2 (dippe = 1,2-bis-(diisopropylphosphino)-ethane) using ethanol as a solvent at 180 °C to give the corresponding saturated carbonyl compounds; here hydrogenation of the C[double bond, length as m-dash]C bond was preferred over the C[double bond, length as m-dash]O bond. Under the same reaction conditions but using an excess of benzylamine, a tandem process is then favoured, starting also with the reduction of the C[double bond, length as m-dash]C bond followed by a nucleophilic addition of the primary amine to yield valuable saturated imines with good to excellent yields (62%-91%). PMID:26250992

  14. Palladium-catalyzed decarboxylative annulation of 2-arylbenzoic acids with [60]fullerene via C-H bond activation.

    PubMed

    Zhou, Dian-Bing; Wang, Guan-Wu

    2015-03-01

    A convenient and highly efficient palladium-catalyzed decarboxylative annulation of 2-arylbenzoic acids with [60]fullerene has been exploited to synthesize the novel and scarce [60]fullerene-fused dihydrophenanthrenes. The use of Lewis acid ZnCl2 is crucial for the success of the present formal [4 + 2] annulation reaction. Plausible reaction pathways leading to the observed products have been proposed, and the electrochemistry of the fullerene products has also been investigated. PMID:25700187

  15. Synthesis of imides via palladium-catalyzed decarboxylative amidation of α-oxocarboxylic acids with secondary amides.

    PubMed

    Xu, Ning; Liu, Jie; Li, Dengke; Wang, Lei

    2016-05-18

    An efficient synthesis of imides has been developed through a Pd-catalyzed decarboxylative amidation of α-oxocarboxylic acids with secondary amides. The reactions of N-substituted N-heteroarene-2-carboxamides with 2-oxo-2-arylacetic acids proceeded smoothly to generate the corresponding products in good yields in the presence of Pd(OAc)2 and K2S2O8. PMID:27143171

  16. Palladium-Catalyzed Room-Temperature Acylative Suzuki Coupling of High-Order Aryl Borons with Carboxylic Acids.

    PubMed

    Si, Shufen; Wang, Chen; Zhang, Nan; Zou, Gang

    2016-05-20

    This note describes a dimethyl dicarbonate-assisted, Pd(OAc)2/PPh3-catalyzed acylative Suzuki coupling of carboxylic acids with diarylborinic acids or tetraarylboronates for practical and efficient synthesis of sterically undemanding aryl ketones at room temperature. More than just cost-effective alternatives to aryl boronic acids, diarylborinic acids and tetraarylboronates displayed higher reactivity in the acylative Suzuki coupling. A variety of alkyl aryl ketones, including those bearing a hydroxy, bromo, or carbonyl group, could be readily obtained in modest to excellent yields. PMID:27100118

  17. Immobilized phospholipase A1-catalyzed modification of phosphatidylcholine with n-3 polyunsaturated fatty acid.

    PubMed

    Zhao, TingTing; No, Da Som; Kim, Byung Hee; Garcia, Hugo S; Kim, Yangha; Kim, In-Hwan

    2014-08-15

    n-3 Polyunsaturated fatty acids (n-3 PUFA)-enriched phosphatidylcholine (PC) was successfully produced with fatty acid from fish oil and PC from soybean by immobilized phospholipase A1-catalyzed acidolysis. Detailed studies of immobilization were carried out, and Lewatit VP OC 1600 was selected as a carrier for preparation of immobilized phospholipase A1, which was used for modification of PC by acidolysis. For acidolysis of PC with n-3 PUFA, the effects of several parameters, namely, water content, temperature, and enzyme loading on the reaction time course were investigated to determine optimum conditions. The optimum water content, temperature, and enzyme loading were 1.0%, 55 °C, and 20%, respectively. The highest incorporation (57.4 mol%) of n-3 PUFA into PC was obtained at 24h and the yield of PC was 16.7 mol%. The yield of PC increased significantly by application of vacuum, even though a slight decrease of n-3 PUFA incorporation was observed. PMID:24679762

  18. Dual Lewis Acid/Lewis Base Catalyzed Acylcyanation of Aldehydes: A Mechanistic Study.

    PubMed

    Laurell Nash, Anna; Hertzberg, Robin; Wen, Ye-Qian; Dahlgren, Björn; Brinck, Tore; Moberg, Christina

    2016-03-01

    A mechanistic investigation, which included a Hammett correlation analysis, evaluation of the effect of variation of catalyst composition, and low-temperature NMR spectroscopy studies, of the Lewis acid-Lewis base catalyzed addition of acetyl cyanide to prochiral aldehydes provides support for a reaction route that involves Lewis base activation of the acyl cyanide with formation of a potent acylating agent and cyanide ion. The cyanide ion adds to the carbonyl group of the Lewis acid activated aldehyde. O-Acylation by the acylated Lewis base to form the final cyanohydrin ester occurs prior to decomplexation from titanium. For less reactive aldehydes, the addition of cyanide is the rate-determining step, whereas, for more reactive, electron-deficient aldehydes, cyanide addition is rapid and reversible and is followed by rate-limiting acylation. The resting state of the catalyst lies outside the catalytic cycle and is believed to be a monomeric titanium complex with two alcoholate ligands, which only slowly converts into the product. PMID:26592522

  19. Origins of stereoselectivities in chiral phosphoric acid catalyzed allylborations and propargylations of aldehydes.

    PubMed

    Wang, Hao; Jain, Pankaj; Antilla, Jon C; Houk, K N

    2013-02-01

    The chiral BINOL-phosphoric acid catalyzed allylboration and propargylation reactions are studied with density functional theory (B3LYP and B3LYP-D3). Two different models were recently proposed for these reactions by Goodman and our group, respectively. In Goodman's model for allylborations, the catalyst interacts with the boronate pseudoaxial oxygen. By contrast, our model for propargylations predicts that the catalyst interacts with the boronate pseudoequatorial oxygen. In both models, the phosphoric acid stabilizes the transition state by forming a strong hydrogen bond with the oxygen of the boronate and is oriented by a formyl hydrogen bond (Goodman model) and by other electrostatic attractions in our model. Both of these models have now been reinvestigated for both allylborations and propargylations. For the most effective catalyst for these reactions, the lowest energy transition state corresponds to Goodman's axial model, while the best transition state leading to the minor enantiomer involves the equatorial model. The high enantioselectivity observed with only the bulkiest catalyst arises from the steric interactions between the substrates and the bulky groups on the catalyst, and the resulting necessity for distortion of the catalyst in the disfavored transition state. PMID:23298338

  20. Hetropolyacid-Catalyzed Oxidation of Glycerol into Lactic Acid under Mild Base-Free Conditions.

    PubMed

    Tao, Meilin; Yi, Xiaohu; Delidovich, Irina; Palkovits, Regina; Shi, Junyou; Wang, Xiaohong

    2015-12-21

    Lactic acid (LA) is a versatile platform molecule owing to the opportunity to transform this compound into useful chemicals and materials. Therefore, efficient production of LA based on inexpensive renewable feedstocks is of utmost importance for insuring its market availability. Herein, we report the efficient conversion of glycerol into LA catalyzed by heteropolyacids (HPAs) under mild base-free conditions. The catalytic performance of molecular HPAs appears to correlate with their redox potential and Brønsted acidity. Namely, H3 PMo(12)O(40) (HPMo) exhibits the best selectivity towards LA (90 %) with 88 % conversion of glycerol. Loading of HPMo onto a carbon support (HPMo/C) further improves LA productivity resulting in 94 % selectivity at 98 % conversion under optimized reaction conditions. The reaction takes place through the formation of dihydroxyacetone/glyceraldehyde and pyruvaldehyde as intermediates. No leaching of HPMo was observed under the applied reaction conditions and HPMo/C could be recycled 5 times without significant loss of activity. PMID:26611678

  1. Origins of Stereoselectivities in Chiral Phosphoric Acid-Catalyzed Allylborations and Propargylations of Aldehydes

    PubMed Central

    Wang, Hao; Jain, Pankaj; Antilla, Jon C.; Houk, K. N.

    2013-01-01

    The chiral BINOL-phosphoric acid catalyzed allylboration and propargylation reactions are studied with density functional theory (B3LYP and B3LYP-D3). Two different models were recently proposed for these reactions by Goodman and our group, respectively. In Goodman's model for allylborations, the catalyst interacts with the boronate pseudo-axial oxygen. By contrast, our model for propargylations predicts that the catalyst interacts with the boronate pseudo-equatorial oxygen. In both models, the phosphoric acid stabilizes the transition state by forming a strong hydrogen bond with the oxygen of the boronate, and is oriented by a formyl hydrogen bond (Goodman model), and by other electrostatic attractions in our model. Both of these models have now been reinvestigated for both allylborations and propargylations. For the most effective catalyst for these reactions, the lowest energy transition state corresponds to Goodman's axial model, while the best transition state leading to minor enantiomer involves the equatorial model. The high enantioselectivity observed with only the bulkiest catalyst arises from the steric interactions between the substrates and the bulky groups on the catalyst, and the resulting necessity for distortion of the catalyst in the disfavored transition state. PMID:23298338

  2. Computational Mechanistic Studies of Acid-Catalyzed Lignin Model Dimers for Lignin Depolymerization

    SciTech Connect

    Kim, S.; Sturgeon, M. R.; Chmely, S. C.; Paton, R. S.; Beckham, G. T.

    2013-01-01

    Lignin is a heterogeneous alkyl-aromatic polymer that constitutes up to 30% of plant cell walls, and is used for water transport, structure, and defense. The highly irregular and heterogeneous structure of lignin presents a major obstacle in the development of strategies for its deconstruction and upgrading. Here we present mechanistic studies of the acid-catalyzed cleavage of lignin aryl-ether linkages, combining both experimental studies and quantum chemical calculations. Quantum mechanical calculations provide a detailed interpretation of reaction mechanisms including possible intermediates and transition states. Solvent effects on the hydrolysis reactions were incorporated through the use of a conductor-like polarizable continuum model (CPCM) and with cluster models including explicit water molecules in the first solvation shell. Reaction pathways were computed for four lignin model dimers including 2-phenoxy-phenylethanol (PPE), 1-(para-hydroxyphenyl)-2-phenoxy-ethanol (HPPE), 2-phenoxy-phenyl-1,3-propanediol (PPPD), and 1-(para-hydroxyphenyl)-2-phenoxy-1,3-propanediol (HPPPD). Lignin model dimers with a para-hydroxyphenyl ether (HPPE and HPPPD) show substantial differences in reactivity relative to the phenyl ether compound (PPE and PPPD) which have been clarified theoretically and experimentally. The significance of these results for acid deconstruction of lignin in plant cell walls will be discussed.

  3. Cooperative Effects Between Arginine and Glutamic Acid in the Amino Acid-Catalyzed Aldol Reaction.

    PubMed

    Valero, Guillem; Moyano, Albert

    2016-08-01

    Catalysis of the aldol reaction between cyclohexanone and 4-nitrobenzaldehyde by mixtures of L-Arg and of L-Glu in wet dimethyl sulfoxide (DMSO) takes place with higher enantioselectivity (up to a 7-fold enhancement in the anti-aldol for the 1:1 mixture) than that observed when either L-Glu or L-Arg alone are used as the catalysts. These results can be explained by the formation of a catalytically active hydrogen-bonded complex between both amino acids, and demonstrate the possibility of positive cooperative effects in catalysis by two different α-amino acids. Chirality 28:599-605, 2016. © 2016 Wiley Periodicals, Inc. PMID:27362554

  4. Heat transfer, erosion and acid condensation characteristics for novel H-type finned oval tube

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Zhao, X.; Tang, G.

    2015-09-01

    Low efficiency of heat transfer, acid corrosion and erosion of economizers affect the economy and security in coal-fired power plants significantly. The H-type finned oval tube is proposed to alleviate these problems. Based on the H-type finned oval tube, we investigated three novel types of fins, including bleeding dimples, longitudinal vortex generators (LVGs), and compound dimple-LVG. We considered the three aspects together, and obtained the heat transfer, acid condensation rate and erosion loss. The results show that the tube bank with the new structured fins can improve the performance on the three aspects, and the compound dimple-LVG performs the highest comprehensive effect.

  5. The formation and self-assembly of long prebiotic oligomers produced by the condensation of unactivated amino acids on oxide surfaces.

    PubMed

    Martra, Gianmario; Deiana, Chiara; Sakhno, Yuriy; Barberis, Ilvis; Fabbiani, Marco; Pazzi, Marco; Vincenti, Marco

    2014-04-25

    In situ IR and mass spectrometry evidence for the catalytic formation on SiO2 and TiO2 surfaces of glycine oligomers (poly-Gly) up to 16 units long by successive feeding with monomers from the vapor phase is presented. Parallel experiments carried out on hydroxyapatite resulted in the unreactive adsorption of Gly, thus indicating that the oligomerization was specifically catalyzed by the surfaces of SiO2 and TiO2 . Furthermore, the poly-Gly moved on the surface when contacted with H2 O vapor and formed self-assembled aggregates containing both helical and β-sheet-like structural motifs. These results indicate that polypeptides formed by the condensation of amino acids adsorbed on a mineral surface can evolve into structured supramolecular assemblies. PMID:24616011

  6. Activation Energies for an Enzyme-Catalyzed and Acid-Catalyzed Hydrolysis: An Introductory Interdisciplinary Experiment for Chemists and Biochemists.

    ERIC Educational Resources Information Center

    Adams, K. R.; Meyers, M. B.

    1985-01-01

    Background information, procedures used, and typical results obtained are provided for an experiment in which students determine and compare the Arrhenius activation energies (Ea) for the hydrolysis of salicin. This reaction is subject to catalysis both by acid and by the enzyme emulsin (beta-d-glucoside glycohydrolase). (JN)

  7. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    PubMed

    Ranney, April P; Ziemann, Paul J

    2016-04-28

    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be <8 × 10(-4), at least a factor of 10(4) less than that for HNO3 in water. The results indicate that HNO3 was only weakly dissociated in the SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed. PMID:27043733

  8. Polymers from amino acids: development of dual ester-urethane melt condensation approach and mechanistic aspects.

    PubMed

    Anantharaj, S; Jayakannan, M

    2012-08-13

    A new dual ester-urethane melt condensation methodology for biological monomers-amino acids was developed to synthesize new classes of thermoplastic polymers under eco-friendly and solvent-free polymerization approach. Naturally abundant L-amino acids were converted into dual functional ester-urethane monomers by tailor-made synthetic approach. Direct polycondensation of these amino acid monomers with commercial diols under melt condition produced high molecular weight poly(ester-urethane)s. The occurrence of the dual ester-urethane process and the structure of the new poly(ester-urethane)s were confirmed by (1)H and (13)C NMR. The new dual ester-urethane condensation approach was demonstrated for variety of amino acids: glycine, β-alanine, L-alanine, L-leucine, L-valine, and L-phenylalanine. MALDI-TOF-MS end group analysis confirmed that the amino acid monomers were thermally stable under the melt polymerization condition. The mechanism of melt process and the kinetics of the polycondensation were studied by model reactions and it was found that the amino acid monomer was very special in the sense that their ester and urethane functionality could be selectively reacted by polymerization temperature or catalyst. The new polymers were self-organized as β-sheet in aqueous or organic solvents and their thermal properties such as glass transition temperature and crystallinity could be readily varied using different l-amino acid monomers or diols in the feed. Thus, the current investigation opens up new platform of research activates for making thermally stable and renewable engineering thermoplastics from natural resource amino acids. PMID:22713137

  9. Condensed-Phase Nitric Acid in a Tropical Subvisible Cirrus Cloud

    NASA Technical Reports Server (NTRS)

    Popp, P. J.; Marcy, T. P.; Watts, O. A.; Gao, R. S.; Fahey, D. W.; Weinstock, E. M.; Smith, J. B.; Herman, R. L.; Tropy, R. F.; Webster, C. r.; Christensen, L. E.; Baumgardner, D. G.; Voigt, C.; Kaercher, B.; Wilson, J. C.; Mahoney, M. J.; Jensen, E. J.; Bui, T. P.

    2007-01-01

    In situ observations in a tropical subvisible cirrus cloud during the Costa Rica Aura Validation Experiment on 2 February 2006 show the presence of condensed-phase nitric acid. The cloud was observed near the tropopause at altitudes of 16.3-17.7 km in an extremely cold (183-191 K) and dry 5 ppm H2O) air mass. Relative humidities with respect to ice ranged from 150-250% throughout most of the cloud. Optical particle measurements indicate the presence of ice crystals as large as 90 microns in diameter. Condensed RN031H20 molar ratios observed in the cloud particles were 1-2 orders of magnitude greater than ratios observed previously in cirrus clouds at similar RN03 partial pressures. Nitric acid trihydrate saturation ratios were 10 or greater during much of the cloud encounter, indicating that RN03 may be present in the cloud particles as a stable condensate and not simply physically adsorbed on or trapped in the particles.

  10. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    PubMed

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias

    2015-04-20

    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. PMID:25728921

  11. Multi-shell model of ion-induced nucleic acid condensation.

    PubMed

    Tolokh, Igor S; Drozdetski, Aleksander V; Pollack, Lois; Baker, Nathan A; Onufriev, Alexey V

    2016-04-21

    We present a semi-quantitative model of condensation of short nucleic acid (NA) duplexes induced by trivalent cobalt(iii) hexammine (CoHex) ions. The model is based on partitioning of bound counterion distribution around single NA duplex into "external" and "internal" ion binding shells distinguished by the proximity to duplex helical axis. In the aggregated phase the shells overlap, which leads to significantly increased attraction of CoHex ions in these overlaps with the neighboring duplexes. The duplex aggregationfree energy is decomposed into attractive and repulsive components in such a way that they can be represented by simple analytical expressions with parameters derived from molecular dynamic simulations and numerical solutions of Poisson equation. The attractive term depends on the fractions of bound ions in the overlapping shells and affinity of CoHex to the "external" shell of nearly neutralized duplex. The repulsive components of the free energy are duplex configurational entropy loss upon the aggregation and the electrostatic repulsion of the duplexes that remains after neutralization by bound CoHex ions. The estimates of the aggregationfree energy are consistent with the experimental range of NA duplex condensation propensities, including the unusually poor condensation of RNA structures and subtle sequence effects upon DNAcondensation. The model predicts that, in contrast to DNA, RNA duplexes may condense into tighter packed aggregates with a higher degree of duplex neutralization. An appreciable CoHex mediated RNA-RNA attraction requires closer inter-duplex separation to engage CoHex ions (bound mostly in the "internal" shell of RNA) into short-range attractive interactions. The model also predicts that longer NA fragments will condense more readily than shorter ones. The ability of this model to explain experimentally observed trends in NAcondensation lends support to proposed NAcondensation picture based on the multivalent "ion binding shells

  12. 3-Ketoacyl-acyl carrier protein synthase III from spinach (Spinacia oleracea) is not similar to other condensing enzymes of fatty acid synthase.

    PubMed Central

    Tai, H; Jaworski, J G

    1993-01-01

    A cDNA clone encoding spinach (Spinacia oleracea) 3-ketoacyl-acyl carrier protein synthase III (KAS III), which catalyzes the initial condensing reaction in fatty acid biosynthesis, was isolated. Based on the amino acid sequence of tryptic digests of purified spinach KAS III, degenerate polymerase chain reaction (PCR) primers were designed and used to amplify a 612-bp fragment from first-strand cDNA of spinach leaf RNA. A root cDNA library was probed with the PCR fragment, and a 1920-bp clone was isolated. Its deduced amino acid sequence matched the sequences of the tryptic digests obtained from the purified KAS III. Northern analysis confirmed that it was expressed in both leaf and root. The clone contained a 1218-bp open reading frame coding for 405 amino acids. The identity of the clone was confirmed by expression in Escherichia coli BL 21 as a glutathione S-transferase fusion protein. The deduced amino acid sequence was 48 and 45% identical with the putative KAS III of Porphyra umbilicalis and KAS III of E. coli, respectively. It also had a strong local homology to the plant chalcone synthases but had little homology with other KAS isoforms from plants, bacteria, or animals. PMID:8290632

  13. Structural basis for the recognition of mycolic acid precursors by KasA, a condensing enzyme and drug target from Mycobacterium tuberculosis.

    PubMed

    Schiebel, Johannes; Kapilashrami, Kanishk; Fekete, Agnes; Bommineni, Gopal R; Schaefer, Christin M; Mueller, Martin J; Tonge, Peter J; Kisker, Caroline

    2013-11-22

    The survival of Mycobacterium tuberculosis depends on mycolic acids, very long α-alkyl-β-hydroxy fatty acids comprising 60-90 carbon atoms. However, despite considerable efforts, little is known about how enzymes involved in mycolic acid biosynthesis recognize and bind their hydrophobic fatty acyl substrates. The condensing enzyme KasA is pivotal for the synthesis of very long (C38-42) fatty acids, the precursors of mycolic acids. To probe the mechanism of substrate and inhibitor recognition by KasA, we determined the structure of this protein in complex with a mycobacterial phospholipid and with several thiolactomycin derivatives that were designed as substrate analogs. Our structures provide consecutive snapshots along the reaction coordinate for the enzyme-catalyzed reaction and support an induced fit mechanism in which a wide cavity is established through the concerted opening of three gatekeeping residues and several α-helices. The stepwise characterization of the binding process provides mechanistic insights into the induced fit recognition in this system and serves as an excellent foundation for the development of high affinity KasA inhibitors. PMID:24108128

  14. Structural Basis for the Recognition of Mycolic Acid Precursors by KasA, a Condensing Enzyme and Drug Target from Mycobacterium Tuberculosis *

    PubMed Central

    Schiebel, Johannes; Kapilashrami, Kanishk; Fekete, Agnes; Bommineni, Gopal R.; Schaefer, Christin M.; Mueller, Martin J.; Tonge, Peter J.; Kisker, Caroline

    2013-01-01

    The survival of Mycobacterium tuberculosis depends on mycolic acids, very long α-alkyl-β-hydroxy fatty acids comprising 60–90 carbon atoms. However, despite considerable efforts, little is known about how enzymes involved in mycolic acid biosynthesis recognize and bind their hydrophobic fatty acyl substrates. The condensing enzyme KasA is pivotal for the synthesis of very long (C38–42) fatty acids, the precursors of mycolic acids. To probe the mechanism of substrate and inhibitor recognition by KasA, we determined the structure of this protein in complex with a mycobacterial phospholipid and with several thiolactomycin derivatives that were designed as substrate analogs. Our structures provide consecutive snapshots along the reaction coordinate for the enzyme-catalyzed reaction and support an induced fit mechanism in which a wide cavity is established through the concerted opening of three gatekeeping residues and several α-helices. The stepwise characterization of the binding process provides mechanistic insights into the induced fit recognition in this system and serves as an excellent foundation for the development of high affinity KasA inhibitors. PMID:24108128

  15. Condensational growth and trace species scavenging in stratospheric sulfuric acid/water aerosol droplets

    NASA Technical Reports Server (NTRS)

    Tompson, Robert V., Jr.

    1991-01-01

    Stratospheric aerosols play a significant role in the environment. The composition of aerosols is believed to be a liquid solution of sulfuric acid and water with numerous trace species. Of these trace species, ozone in particular was recognized as being very important in its role of shielding the environment from harmful ultraviolet radiation. Also among the trace species are HCl and ClONO2, the so called chlorine reservoir species and various oxides of nitrogen. The quantity of stratospheric aerosol and its particle size distribution determines, to a large degree, the chemistry present in the stratosphere. Aerosols experience 3 types of growth: nucleation, condensation, and coagulation. The application of condensation investigations to the specific problem of stratospheric aerosols is discussed.

  16. Enantioselective Synthesis of 1,2-Dihydronaphthalene-1-carbaldehydes by Addition of Boronates to Isochromene Acetals Catalyzed by Tartaric Acid

    PubMed Central

    Luan, Yi; Barbato, Keith S.; Moquist, Philip N.; Kodama, Tomohiro; Schaus, Scott E.

    2015-01-01

    Tartaric acid is an ideal asymmetric catalyst as it is abundant, cheap, and environmentally friendly. (+)-Tartaric acid was found to catalyze a novel enantioselective [4 + 2] cycloaddition of isochromene acetals and vinylboronates. A variety of substituted isochromene acetals were tolerated, furnishing the desired dihydronaphthalenes and dihydrobenzofluorene products in good yields. High enantiomeric ratios (up to 98.5:1.5) and excellent diastereoselectivities (all >99:1) were observed employing 10 mol % of (+)-tartaric acid as the catalyst, in combination with 5 mol % of Ho(OTf)3. PMID:25715172

  17. Cu-Catalyzed Consecutive Hydroxylation and Aerobic Oxidative Cycloetherification under Microwave Conditions: Entry to 2-Arylbenzofuran-3-carboxylic Acids.

    PubMed

    Xu, Tianlong; Zhang, Ensheng; Wang, Dejian; Wang, Yan; Zou, Yong

    2015-05-01

    A convenient one-pot synthesis of 2-arylbenzofuran-3-carboxylic acids from (E)-2-(2-bromophenyl)-3-phenylacrylic acids via Cu-catalyzed consecutive hydroxylation and aerobic oxidative cycloetherification under microwave conditions has been developed. This protocol employed the reagent combination of Cu(OAc)2, 1,10-phen, and KOH in DMSO/H2O (1:1), all of which are cost-effective, readily available, and easily removable from the reaction mixture. Utilizing this synthetic protocol, various 2-arylbenzofuran-3-carboxylic acids as well as the natural product moracin M have been synthesized in satisfactory yields under mild conditions. PMID:25836742

  18. NAD(+)-independent aldehyde oxidase catalyzes cofactor balanced 3-hydroxypropionic acid production in Klebsiella pneumoniae.

    PubMed

    Li, Ying; Liu, Luo; Tian, Pingfang

    2014-11-01

    The limiting step for biosynthesis of 3-hydroxypropionic acid (3-HP) in Klebsiella pneumoniae is the conversion of 3-hydroxypropionaldehyde (3-HPA) to 3-HP. This reaction is catalyzed by aldehyde dehydrogenase (ALDH) with NAD(+) as a cofactor. Although NAD(+)-dependent ALDH overexpression facilitates 3-HP biosynthesis, ALDH activity decreases and 3-HP stops accumulation when NAD(+) is exhausted. Here, we show that an NAD(+)-independent aldehyde oxidase (AOX) from Pseudomonas sp. AIU 362 holds promise for cofactor-balanced 3-HP production in K. pneumoniae. The AOX coding gene, alod, was heterologously expressed in E. coli and K. pneumoniae, and their respective crude cell extracts showed 38.1 U/mg and 16.6 U/mg activities toward propionaldehyde. The recombinant K. pneumoniae expressing alod showed 13.7 U/mg activity toward 3-HPA; K m and V max were 6.7 mM and 42 μM/min/mg, respectively. In shake-flask cultures, the recombinant K. pneumoniae strain produced 0.89 g 3-HP/l, twice that of the control. Moreover, it produced 3 g 3-HP/l during 24 h fed-batch cultivation in a 5 l bioreactor. The results indicate that AOX can efficiently convert 3-HPA into 3-HP. PMID:24980850

  19. Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Zahn, Dirk

    2004-05-01

    The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C⋯O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate.

  20. PNPCB heterocycles via thermal and Lewis acid catalyzed trans-hydroborations.

    PubMed

    Fan, Louie; Stephan, Douglas W

    2016-05-31

    The compounds iPr2P(BH3)N3, tBu2PC[triple bond, length as m-dash]CR (R = Ph , tBu , Cy ) and Ph2PC[triple bond, length as m-dash]CR (R = Ph , tBu , Cy ) were reacted to give the products tBu2P(C[triple bond, length as m-dash]CR)NP(BH3)iPr2 (R = Ph , tBu , Cy ) and Ph2P(C[triple bond, length as m-dash]CR)NP(BH3)iPr2 (R = Ph , tBu , Cy ). Subsequent thermally induced or Lewis acid catalyzed intramolecular hydroboration of and afforded the PNPCB heterocyclic compounds Ph2P(C[double bond, length as m-dash]CHPh)NP(BH2)iPr2 and tBu2P(C[double bond, length as m-dash]CHPh)NP(BH2)iPr2, respectively. Compounds and were crystallographically characterized and the mechanisms and implications for the synthesis of inorganic heterocycles are considered. PMID:27177164

  1. Highly Sensitive Determination of Ethylenediaminetetraacetic Acid Using a Permanganate Chemiluminescence System Catalyzed by Gold Nanoparticles.

    PubMed

    Abolhasani, Jafar; Hassanzadeh, Javad; Ghorbani-Kalhor, Ebrahim

    2015-01-01

    A sensitive and selective chemiluminescence method was developed to determine ethylenediaminetetraacetic acid (EDTA) in water samples. It was observed that gold nanoparticles (AuNPs) catalyzed chemiluminescence (CL) reactions of permanganate-aldehydes which underwent an enhancement effect in the presence of iron(III) ions (Fe(3+)). This effect is more remarkable in the presence of EDTA, and a highly intensive CL emission is created in proportion to the EDTA concentration. These observations form the basis of the method for the high sensitive determination of EDTA in the 0.83 - 167 nmol L(-1) concentration range, with a detection limit of 0.25 nmol L(-1). The relative standard deviations for five repeated measurements of 5, 40 and 140 nmol L(-1) EDTA were 1.14, 2.48 and 0.65%, respectively. The method has good selectivity toward EDTA, and there are no interferences from other ions. The offered method has good precision, and was satisfactorily used for the sensitive determination of EDTA in water samples. PMID:26256596

  2. Ammonium nitrate evaporation and nitric acid condensation in DMT CCN counters

    NASA Astrophysics Data System (ADS)

    Romakkaniemi, S.; Jaatinen, A.; Laaksonen, A.; Nenes, A.; Raatikainen, T.

    2014-05-01

    The effect of inorganic semivolatile aerosol compounds on the cloud condensation nucleus (CCN) activity of aerosol particles was studied by using a computational model for a DMT-CCN counter, a cloud parcel model for condensation kinetics and experiments to quantify the modelled results. Concentrations of water vapour and semivolatiles as well as aerosol trajectories in the CCN column were calculated by a computational fluid dynamics model. These trajectories and vapour concentrations were then used as an input for the cloud parcel model to simulate mass transfer kinetics of water and semivolatiles between aerosol particles and the gas phase. Two different questions were studied: (1) how big a fraction of semivolatiles is evaporated from particles after entering but before particle activation in the DMT-CCN counter? (2) How much can the CCN activity be increased due to condensation of semivolatiles prior to the maximum water supersaturation in the case of high semivolatile concentration in the gas phase? Both experimental and modelling results show that the evaporation of ammonia and nitric acid from ammonium nitrate particles causes a 10 to 15 nm decrease to the critical particle size in supersaturations between 0.1% and 0.7%. On the other hand, the modelling results also show that condensation of nitric acid or similar vapour can increase the CCN activity of nonvolatile aerosol particles, but a very high gas phase concentration (as compared to typical ambient conditions) would be needed. Overall, it is more likely that the CCN activity of semivolatile aerosol is underestimated than overestimated in the measurements conducted in ambient conditions.

  3. The cytosolic carboxypeptidases CCP2 and CCP3 catalyze posttranslational removal of acidic amino acids

    PubMed Central

    Tort, Olivia; Tanco, Sebastián; Rocha, Cecilia; Bièche, Ivan; Seixas, Cecilia; Bosc, Christophe; Andrieux, Annie; Moutin, Marie-Jo; Avilés, Francesc Xavier; Lorenzo, Julia; Janke, Carsten

    2014-01-01

    The posttranslational modification of carboxy-terminal tails of tubulin plays an important role in the regulation of the microtubule cytoskeleton. Enzymes responsible for deglutamylating tubulin have been discovered within a novel family of mammalian cytosolic carboxypeptidases. The discovery of these enzymes also revealed the existence of a range of other substrates that are enzymatically deglutamylated. Only four of six mammalian cytosolic carboxypeptidases had been enzymatically characterized. Here we complete the functional characterization of this protein family by demonstrating that CCP2 and CCP3 are deglutamylases, with CCP3 being able to hydrolyze aspartic acids with similar efficiency. Deaspartylation is a novel posttranslational modification that could, in conjunction with deglutamylation, broaden the range of potential substrates that undergo carboxy-terminal processing. In addition, we show that CCP2 and CCP3 are highly regulated proteins confined to ciliated tissues. The characterization of two novel enzymes for carboxy-terminal protein modification provides novel insights into the broadness of this barely studied process. PMID:25103237

  4. A heteromeric membrane-bound prenyltransferase complex from hop catalyzes three sequential aromatic prenylations in the bitter acid pathway.

    PubMed

    Li, Haoxun; Ban, Zhaonan; Qin, Hao; Ma, Liya; King, Andrew J; Wang, Guodong

    2015-03-01

    Bitter acids (α and β types) account for more than 30% of the fresh weight of hop (Humulus lupulus) glandular trichomes and are well known for their contribution to the bitter taste of beer. These multiprenylated chemicals also show diverse biological activities, some of which have potential benefits to human health. The bitter acid biosynthetic pathway has been investigated extensively, and the genes for the early steps of bitter acid synthesis have been cloned and functionally characterized. However, little is known about the enzyme(s) that catalyze three sequential prenylation steps in the β-bitter acid pathway. Here, we employed a yeast (Saccharomyces cerevisiae) system for the functional identification of aromatic prenyltransferase (PT) genes. Two PT genes (HlPT1L and HlPT2) obtained from a hop trichome-specific complementary DNA library were functionally characterized using this yeast system. Coexpression of codon-optimized PT1L and PT2 in yeast, together with upstream genes, led to the production of bitter acids, but no bitter acids were detected when either of the PT genes was expressed by itself. Stepwise mutation of the aspartate-rich motifs in PT1L and PT2 further revealed the prenylation sequence of these two enzymes in β-bitter acid biosynthesis: PT1L catalyzed only the first prenylation step, and PT2 catalyzed the two subsequent prenylation steps. A metabolon formed through interactions between PT1L and PT2 was demonstrated using a yeast two-hybrid system, reciprocal coimmunoprecipitation, and in vitro biochemical assays. These results provide direct evidence of the involvement of a functional metabolon of membrane-bound prenyltransferases in bitter acid biosynthesis in hop. PMID:25564559

  5. The fatty acid desaturase 2 (FADS2) gene product catalyzes Δ4 desaturation to yield n-3 docosahexaenoic acid and n-6 docosapentaenoic acid in human cells

    PubMed Central

    Park, Hui Gyu; Park, Woo Jung; Kothapalli, Kumar S. D.; Brenna, J. Thomas

    2015-01-01

    Docosahexaenoic acid (DHA) is a Δ4-desaturated C22 fatty acid and the limiting highly unsaturated fatty acid (HUFA) in neural tissue. The biosynthesis of Δ4-desaturated docosanoid fatty acids 22:6n-3 and 22:5n-6 are believed to proceed via a circuitous biochemical pathway requiring repeated use of a fatty acid desaturase 2 (FADS2) protein to perform Δ6 desaturation on C24 fatty acids in the endoplasmic reticulum followed by 1 round of β-oxidation in the peroxisomes. We demonstrate here that the FADS2 gene product can directly Δ4-desaturate 22:5n-3→22:6n-3 (DHA) and 22:4n-6→22:5n-6. Human MCF-7 cells lacking functional FADS2-mediated Δ6-desaturase were stably transformed with FADS2, FADS1, or empty vector. When incubated with 22:5n-3 or 22:4n-6, FADS2 stable cells produce 22:6n-3 or 22:5n-6, respectively. Similarly, FADS2 stable cells when incubated with d5-18:3n-3 show synthesis of d5-22:6n-3 with no labeling of 24:5n-3 or 24:6n-3 at 24 h. Further, both C24 fatty acids are shown to be products of the respective C22 fatty acids via elongation. Our results demonstrate that the FADS2 classical transcript mediates direct Δ4 desaturation to yield 22:6n-3 and 22:5n-6 in human cells, as has been widely shown previously for desaturation by fish and many other organisms.—Park, H. G., Park, W. J., Kothapalli, K. S. D., Brenna, J. T. The fatty acid desaturase 2 (FADS2) gene product catalyzes Δ4 desaturation to yield n-3 docosahexaenoic acid and n-6 docosapentaenoic acid in human cells. PMID:26065859

  6. Protease- and Acid-catalyzed Labeling Workflows Employing 18O-enriched Water

    PubMed Central

    Klingler, Diana; Hardt, Markus

    2013-01-01

    steps and reaction intermediates in complex proteolytic pathway reactions. Furthermore, the PALeO-reaction allows us to identify proteolytic enzymes such as the serine protease trypsin that is capable to rebind its cleavage products and catalyze the incorporation of a second 18O-atom. Such "double-labeling" enzymes can be used for postdigestion 18O-labeling, in which peptides are exclusively labeled by the carboxyl oxygen exchange reaction. Our third strategy extends labeling employing 18O-enriched water beyond enzymes and uses acidic pH conditions to introduce 18O-stable isotope signatures into peptides. PMID:23462971

  7. Silylium ion-catalyzed challenging Diels-Alder reactions: the danger of hidden proton catalysis with strong Lewis acids.

    PubMed

    Schmidt, Ruth K; Müther, Kristine; Mück-Lichtenfeld, Christian; Grimme, Stefan; Oestreich, Martin

    2012-03-01

    The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Brønsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)(3)P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Brønsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the

  8. FTIR and {sup 31}P-NMR spectroscopic analyses of surface species in phosphate-catalyzed lactic acid conversion

    SciTech Connect

    Gunter, G.C.; Tam, M.S.; Miller, D.J.

    1996-11-01

    The surface species present on silica/alumina-supported sodium phosphates, active catalysts for the conversion of lactic acid to acrylic acid and 2,3-pentanedione, are examined by pre- and postreaction MAS {sup 31}P-NMR and FTIR spectroscopies. Species present following lactic acid conversion are identified by transmission FTIR of phosphates supported on silicon disks (as a model catalyst system) and verified by {sup 31}P-NMR and diffuse reflectance IR spectroscopy of actual catalysts used in reaction. Monosodium phosphate (NaH{sub 2}PO{sub 4}) condenses to a mixture of sodium polyphosphate (NaPO{sub 3}){sub n} and sodium trimetaphosphate (Na{sub 3}P{sub 3}O{sub 9}), which exhibit little catalytic activity for converting lactic acid to desired products. Disodium phosphate (Na{sub 2}HPO{sub 4}) condenses to tetrasodium pyrophosphate (Na{sub 4}P{sub 2}O{sub 7}), and proton transfer from lactic acid to pyrophosphate results in the formation of sodium lactate. Trisodium phosphate (Na{sub 3}PO{sub 4}) accepts a proton from lactic acid to form sodium lactate and disodium phosphate, which condenses to pyrophosphate. The presence of pyrophosphate and sodium lactate on supported disodium and trisodium phosphates explains their similar catalytic properties; the larger quantity of sodium lactate present on trisodium phosphate leads to higher conversions at lower temperatures. 40 refs., 14 figs., 2 tabs.

  9. Probing the "additive effect" in the proline and proline hydroxamic acid catalyzed asymmetric addition of nitroalkanes to cyclic enones.

    PubMed

    Hanessian, Stephen; Govindan, Subramaniyan; Warrier, Jayakumar S

    2005-11-01

    The effect of chirality and steric bulk of 2,5-disubstituted piperazines as additives in the conjugate addition of 2-nitropropane to cyclohexenone, catalyzed by l-proline, was investigated. Neither chirality nor steric bulk affects the enantioselectivity of addition, which gives 86-93% ee in the presence of achiral and chiral nonracemic 2,5-disubstituted piperazines. Proline hydroxamic acid is shown for the first time to be an effective organocatalyst in the same Michael reaction. PMID:16189834

  10. Kinetics and mechanism of the acid-catalyzed hydrolysis of a hypermodified nucleoside wyosine and its 5'-monophosphate.

    PubMed Central

    Golankiewicz, B; Zielonacka-Lis, E; Folkman, W

    1985-01-01

    The rates of acid-catalyzed hydrolysis of a hypermodified nucleoside, wyosine and its 5'-monophosphate were determined at various pH, temperature and buffer concentrations. The results show that despite distinct differences in structure and the glycosyl bond stability, the hydrolysis of wyosine proceeds via cleavage of the C-N bond by A-1 mechanism, analogously to simple nucleosides. Unlike majority of other monophosphates studied so far, wyosine 5'-monophosphate is not more stable than respective nucleoside. PMID:4000960

  11. Effect of metal ions in a heated nitric acid solution on the corrosion behavior of a titanium-5% tantalum alloy in the hot nitric acid condensate

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Takeuchi, M.; Nakajima, Y.; Hirano, H.; Uchiyama, G.; Nojima, Y.; Fujine, S.; Matsumoto, S.

    2013-01-01

    For evaluating the application of titanium and its alloys as components of equipment for storing nitric acid condensate in spent nuclear fuel reprocessing plants, the corrosion behavior of titanium-5% tantalum alloy (Ti-5Ta) in a continuously renewed hot nitric acid condensate, and particularly the effect of metal ions in the heated nitric acid solution, was investigated. Corrosion experiments in an apparatus designed to renew the condensate at regular intervals showed that the corrosion rate of Ti-5Ta in the condensate increased linearly with the nitric acid concentration. The surface morphology of Ti-5Ta coupons after the corrosion experiments indicated uniform corrosion under any condition. The oxide film on the coupons had nearly constant thickness, and it was composed of mainly lower Ti oxides, such as TiO and Ti2O3, regardless of the nitric acid concentration in the condensate. The experimental results also showed that the addition of metal ions into the heated nitric acid solution increased the nitric acid concentration in the condensate, which resulted in a higher corrosion rate of Ti-5Ta. The corrosion rate increased noticeably as the valence of the metal ion increased and its ionic radius decreased. This effect of metal ions in the heated nitric acid solution on the corrosion rate of Ti-5Ta in the condensate was evaluated quantitatively based on the Gibbs free energy of hydration of the metal ions, and the calculated corrosion rates of Ti-5Ta in the condensate were found to be in good agreement with the experimental values.

  12. A Simple and Efficient Synthesis of an Acid-labile Polyphosphoramidate by Organobase-catalyzed Ring-Opening Polymerization and Transformation to Polyphosphoester Ionomers by Acid Treatment

    PubMed Central

    Zhang, Shiyi; Wang, Hai; Shen, Yuefei; Zhang, Fuwu; Seetho, Kellie; Zou, Jiong; Taylor, John-Stephen A.; Dove, Andrew P.; Wooley, Karen L.

    2013-01-01

    The direct synthesis of an acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an overall two-step preparation of polyphosphodiester ionomers (PPEI) by acid-assisted cleavage of the phosphoramidate bonds along the backbone of the polyphosphoramidate were developed in this study. The ultrafast organobase-catalyzed ring-opening polymerization of a cyclic phospholane methoxyethyl amidate monomer initiated by benzyl alcohol allowed for the preparation of well-defined polyphosphoramidates (PPA) with predictable molecular weights, narrow molecular weight distributions (PDI<1.10), and well-defined chain ends. Cleavage of the acid-labile phosphoramidate bonds on the polyphosphoramidate repeat units was evaluated under acidic conditions over a pH range of 1–5, and the complete hydrolysis produced polyphosphodiesters. The thermal properties of the resulting polyphosphoester ionomer acid and polyphosphoester ionomer sodium salt exhibited significant thermal stability. The parent PPA and both forms of the PPEIs showed low cytotoxicities toward HeLa cells and RAW 264.7 mouse macrophage cells. The synthetic methodology developed here has enriched the family of water-soluble polymers prepared by rapid and convenient organobase-catalyzed ring-opening polymerizations and straightforward chemical medication reactions, which are designed to be hydrolytically degradable and have promise for numerous biomedical and other applications. PMID:23997276

  13. Synthesis of Aryl Sulfonamides via Palladium-Catalyzed Chlorosulfonylation of Arylboronic Acids

    PubMed Central

    DeBergh, J. Robb; Niljianskul, Nootaree; Buchwald, Stephen L.

    2013-01-01

    A palladium-catalyzed method for the preparation of sulfonamides is described. The process exhibits significant functional group tolerance and allows for the preparation of a number of arylsulfonyl chlorides and sulfonamides under mild conditions. PMID:23837740

  14. Phosphorus-carbon bond formation by lewis Acid catalyzed/mediated addition of silylphosphines.

    PubMed

    Hayashi, Minoru; Matsuura, Yutaka; Nishimura, Yasunobu; Yamasaki, Toshikazu; Imai, Yoshito; Watanabe, Yutaka

    2007-09-28

    Triethylaluminum-catalyzed/mediated addition of a silylphosphine to aldehydes and epoxides is described. Organophosphines containing a silyloxy group at the alpha- or beta-position on the alkyl substituent are successfully prepared in good yields. PMID:17784776

  15. Manganese(II) catalyzes the bicarbonate-dependent oxidation of amino acids by hydrogen peroxide and the amino acid-facilitated dismutation of hydrogen peroxide.

    PubMed

    Berlett, B S; Chock, P B; Yim, M B; Stadtman, E R

    1990-01-01

    In bicarbonate/CO2 buffer, Mn(II) and Fe(II) catalyze the oxidation of amino acids by H2O2 and the dismutation of H2O2. As the Mn(II)/Fe(II) ratio is increased, the yield of carbonyl compounds per mole of leucine oxidized is essentially constant, but the ratio of alpha-ketoisocaproate to isovaleraldehyde formed increases, and the fraction of H2O2 converted to O2 increases. In the absence of Fe(II), the rate of Mn(II)-catalyzed leucine oxidation is directly proportional to the H2O2, Mn(II), and amino acid concentrations and is proportional to the square of the HCO3- concentration. The rate of Mn(II)-catalyzed O2 production in the presence of 50 mM alanine or leucine is about 4-fold the rate observed in the absence of amino acids and accounts for about half of the H2O2 consumed; the other half of the H2O2 is consumed in the oxidation of the amino acids. In contrast, O2 production is increased nearly 18-fold by the presence of alpha-methylalanine and accounts for about 90% of the H2O2 consumed. The data are consistent with the view that H2O2 decomposition is an inner sphere (cage-like) process catalyzed by a Mn coordination complex of the composition Mn(II), amino acid, (HCO3-)2. Oxidation of the amino acid in this complex most likely proceeds by a free radical mechanism involving hydrogen abstraction from the alpha-carbon as a critical step. The results demonstrate that at physiological concentrations of HCO3- and CO2, Mn(II) is able to facilitate Fenton-type reactions. PMID:2296594

  16. Tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization between vinyl ether boronates and vinyl halides: a concise approach to polysubstituted furans.

    PubMed

    Butkevich, Alexey N; Meerpoel, Lieven; Stansfield, Ian; Angibaud, Patrick; Corbu, Andrei; Cossy, Janine

    2013-08-01

    Polysubstituted 2-(ω-hydroxyalkyl)furans were prepared by tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization starting from appropriately substituted 3-haloallylic alcohols and dihydrofuran-, dihydropyran- or glycal-derived pinacol boronates. PMID:23855589

  17. Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species

    NASA Astrophysics Data System (ADS)

    Pradeep Kumar, P.; Broekhuizen, K.; Abbatt, J. P. D.

    2003-05-01

    The ability of sub-micron-sized organic acid particles to act as cloud condensation nuclei (CCN) has been examined at room temperature using a newly constructed continuous-flow, thermal-gradient diffusion chamber (TGDC). The organic acids studied were: oxalic, malonic, glutaric, oleic and stearic. The CCN properties of the highly soluble acids - oxalic, malonic and glutaric - match very closely Köhler theory predictions which assume full dissolution of the dry particle and a surface tension of the growing droplet equal to that of water. In particular, for supersaturations between 0.3 and 0.6, agreement between the dry particle diameter which gives 50% activation and that calculated from Köhler theory is to within 3nm on average. In the course of the experiments, considerable instability of glutaric acid particles was observed as a function of time and there is evidence that they fragment to some degree to smaller particles. Stearic acid and oleic acid, which are both highly insoluble in water, did not activate at supersaturations of 0.6% with dry diameters up to 140nm. Finally, to validate the performance of the TGDC, we present results for the activation of ammonium sulfate particles that demonstrate good agreement with Köhler theory if solution non-ideality is considered. Our findings support earlier studies in the literature that showed highly soluble organics to be CCN active but insoluble species to be largely inactive.

  18. Acid-catalyzed conversion of mono- and poly-sugars into platform chemicals: effects of molecular structure of sugar substrate.

    PubMed

    Hu, Xun; Wu, Liping; Wang, Yi; Song, Yao; Mourant, Daniel; Gunawan, Richard; Gholizadeh, Mortaza; Li, Chun-Zhu

    2013-04-01

    Hydrolysis/pyrolysis of lignocellulosic biomass always produces a mixture of sugars with distinct structures as intermediates or products. This study tried to elucidate the effects of molecular structure of sugars on their acid-catalyzed conversions in ethanol/water. Location of carbonyl group in sugars (fructose versus glucose) and steric configuration of hydroxyl groups (glucose versus galactose) significantly affected yields of levulinic acid/ester (fructose>glucose>galactose). The dehydration of fructose to 5-(hydroxymethyl)furfural produces much less soluble polymer than that from glucose and galactose, which results in high yields of levulinic acid/ester from fructose. Anhydrate sugar such as levoglucosan tends to undergo the undesirable decomposition to form less levulinic acid/ester. Catalytic behaviors of the poly-sugars (sucrose, maltose, raffinose, β-cyclodextrins) were determined much by their basic units. However, their big molecular sizes create the steric hindrance that significantly affects their followed conversion over solid acid catalyst. PMID:23454803

  19. Acid-Catalyzed Conversion of Furfuryl Alcohol to Ethyl Levulinate in Liquid Ethanol

    PubMed Central

    González Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James; Curtiss, Larry A.

    2014-01-01

    Reaction pathways for the acid-catalyzed conversion of furfuryl alcohol (FAL) to ethyl levulinate (EL) in ethanol were investigated using liquid chromatography-mass spectrometry (LC-MS), 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, and ab initio high-level quantum chemical (G4MP2) calculations. Our combined studies show that the production of EL at high yields from FAL is not accompanied by stoichiometric production of diethyl either (DEE), indicating that ethoxymethyl furan (EMF) is not an intermediate in the major reaction pathway. Several intermediates were observed using an LC-MS system, and three of these intermediates were isolated and subjected to reaction conditions. The structures of two intermediates were elucidated using 1D and 2D NMR techniques. One of these intermediates is EMF, which forms EL and DEE in a secondary reaction pathway. The second intermediate identified is 4,5,5-triethoxypentan-2-one, which is analogous to one of the intermediates observed in the conversion of FAL to LA in water (i.e. 4,5,5-trihydroxypentan-2-one). Furthermore, conversion of this intermediate to EL again involves the formation of DEE, indicating that it is also part of a secondary pathway. The primary pathway for production of EL involves solvent-assisted transfer of a water molecule from the partially detached protonated hydroxyl group of FAL to a ring carbon, followed by intra-molecular hydrogen shift, where the apparent reaction barrier for the hydrogen shift is relatively smaller in ethanol (21.1 kcal/mol) than that in water (26.6 kcal/mol). PMID:25035710

  20. Evidence for 13-carbon enrichment in oxalic acid via iron catalyzed photolysis in aqueous phase

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2012-02-01

    To investigate the effect of photochemical aging on the stable carbon isotopic ratio (δ13C) of oxalic acid (OxA), a dominant organic species in atmospheric aerosols, we conducted a laboratory photolysis of OxA under H2O2-Fe3+(Fe2+)-UV system in aqueous phase and measured δ13C of remaining OxA. Our results showed that a significant photolysis of OxA occurred with OH radical but the isotopic fractionation of OxA was insignificant. In contrast, in the presence of Fe3+ (Fe2+), we found a significant enrichment of 13C in remaining OxA. We also found that kinetic isotope effect (KIE) of OxA largely depends on photochemical age (irradiation time) and concentration ratios of OxA to iron; 3.20 ± 0.49‰ (2.18 ± 1.18‰) and 21.62 ± 5.41‰ in 90 min and 180 min irradiation, in which OxA and Fe3+ (Fe2+) ratios were 50:1 and 200:1, respectively. The enrichment of 13C in remaining OxA was more significant during the photolysis catalyzed by Fe3+ (7‰) than by Fe2+ (3‰) in 90 min irradiation when OxA and iron ratios are the same (50:1). This study provides a laboratory evidence for the isotopic enrichment of 13C in OxA with photochemical aging. This approach is useful for better interpretation of atmospheric isotopic measurements in terms of the extent of atmospheric processing of aerosols.

  1. Do stable nitroxide radicals catalyze or inhibit the degradation of hyaluronic acid?

    PubMed

    Lurie, Ziva; Offer, Tal; Russo, Angelo; Samuni, Amram; Nitzan, Dorrit

    2003-07-15

    Reactive oxygen-derived species and particularly OH radicals can degrade hyaluronic acid (HA), resulting in a loss of viscosity and a subsequent decrease in its effectiveness as a joint-lubricating agent. The production of OH in the vicinity of HA can be catalyzed by bound redox-active metals, which participate in the Haber-Weiss reaction. Damage to HA can also occur as a result of hypochlorite formed by myeloperoxidase (MPO). The protective reagents commonly used to inhibit oxidative stress-induced degradation of HA include antioxidative enzymes, such as SOD and catalase, chelators that coordinate metal ions rendering them redox-inactive, and scavengers of radicals, such as OH, as well as nonradical reactive species. In recent years, stable cyclic nitroxides have also been widely used as effective antioxidants. In many cases, nitroxide antioxidants operate catalytically and mediate their protective effect through an exchange between their oxidized and reduced forms. It was anticipated, therefore, that nitroxides would protect HA from oxidative degradation as well. On the other hand, nitroxides serve as catalysts in many oxidation reactions of alcohols, sugars and polysaccharides, including hyalouronan. Such opposite effects of nitroxides on oxidative degradation are particularly intriguing and the aim of the present study was to examine their effect on HA when subjected to diverse forms of oxidative stress. The results indicate that nitroxides protect HA from OH radicals generated enzymatically or radiolytically. The protective effect is attributable neither to the scavenging of OH nor to the oxidation of reduced metal, but to the reaction of nitroxides with secondary carbohydrate radicals-most likely peroxyl radicals. PMID:12853073

  2. Cp*Rh(iii)-catalyzed electrophilic amination of arylboronic acids with azo compounds for synthesis of arylhydrazides.

    PubMed

    Lau, Yan-Fung; Chan, Chun-Ming; Zhou, Zhongyuan; Yu, Wing-Yiu

    2016-07-12

    A [Cp*Rh(iii)]-catalyzed electrophilic amination of arylboronic acids with diethyl azodicarboxylate (DEAD) was developed, and arylhydrazides were produced in excellent yields and selectivity. The analogous amination with the arylazocarboxylates afforded the corresponding N,N-diarylhydrazides. The electrophilic amination of arylboronic acids with azocarboxylates proceeds readily under mild conditions with excellent functional group tolerance. Up to 99% yields were obtained. Preliminary mechanistic studies revealed that prior formation of an arylrhodium(iii) intermediate for the azo coupling reaction can be ruled out. PMID:27339710

  3. Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides.

    PubMed

    Kiyokawa, Kensuke; Kojima, Takumi; Hishikawa, Yusuke; Minakata, Satoshi

    2015-10-26

    The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing substituents at the α- and β-positions. In the reaction, N-iodo-N-chloroamides, generated by the reaction of a chloramine salt with I2 , function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives. PMID:26493878

  4. Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation.

    PubMed

    Deeming, Alex S; Russell, Claire J; Willis, Michael C

    2016-01-11

    A redox-neutral palladium(II)-catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high-yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C- or N-based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one-pot, two-step process. PMID:26596861

  5. Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 1: Condensation of phthalic anhydride with acetoacetic and malonic ester

    NASA Technical Reports Server (NTRS)

    Oshkaya, V. P.; Vanag, G. Y.

    1985-01-01

    Phthalic anhydride was condensed with acetoacetic ester in acetic anhydride and triethylamine solution, and when phthalyl chloride was reacted with sodium acetoacetic ester compounds were formed of the phthalide and indandione series: phthalylacetoacetic ester and a derivative of indan-1,3-dione which after boiling with hydrochloric acid yielded indan-1,3-dione. Phthalylmalonic ester was obtained from phthalic anhydride and malonic ester in the presence of triethylamine.

  6. Isoreticular two-dimensional covalent organic frameworks synthesized by on-surface condensation of diboronic acids.

    PubMed

    Dienstmaier, Jürgen F; Medina, Dana D; Dogru, Mirjam; Knochel, Paul; Bein, Thomas; Heckl, Wolfgang M; Lackinger, Markus

    2012-08-28

    On-surface self-condensation of 1,4-benzenediboronic acid was previously shown to yield extended surface-supported, long-range-ordered two-dimensional covalent organic frameworks (2D COFs). The most important prerequisite for obtaining high structural quality is that the polycondensation (dehydration) reaction is carried out under slightly reversible reaction conditions, i.e., in the presence of water. Only then can the subtle balance between kinetic and thermodynamic control of the polycondensation be favorably influenced, and defects that are unavoidable during growth can be corrected. In the present study we extend the previously developed straightforward preparation protocol to a variety of para-diboronic acid building blocks with the aim to tune lattice parameters and pore sizes of 2D COFs. Scanning tunneling microscopy is employed for structural characterization of the covalent networks and of noncovalently self-assembled structures that form on the surface prior to the thermally activated polycondensation reaction. PMID:22775491

  7. Production of high-oleic acid tallow fractions using lipase-catalyzed directed interesterification, using both batch and continuous processing.

    PubMed

    MacKenzie; Stevenson

    2000-08-01

    Immobilized lipases were used to catalyze batch-directed interesterification of tallow, resulting in oleins containing significantly higher levels of unsaturated fatty acids than obtained by fractionation without lipase. After 14 days, a reaction catalyzed by 2% Novozym 435 yielded 57% olein unsaturation, compared with 45% in a no-enzyme control. Free fatty acid levels increased to 2-3% during reactions. Incubation of the enzyme in multiple batches of melted fat caused a gradual loss of interesterification activity, apparently due to progressive dehydration. The activity could be restored by addition of water to the reaction medium. Immobilized lipase was also used to catalyze directed interesterification in a continuous flow reactor. Melted tallow was circulated through a packed bed enzyme reactor and a separate crystallization vessel. The temperatures of the two parts of the apparatus were controlled separately to allow crystallization to occur separately from interesterification. Operation of the reactor with conventionally dry, prefractionated tallow allowed the formation of an olein consisting of up to 60% unsaturated fatty acids. The greatest changes in olein fatty acid composition were achieved when the fractionation temperature was kept constant at a value that promoted selective crystallization of trisaturated triglycerides that were continuously produced by enzymic interesterification. The enzyme could be reused without apparent loss of activity, and its activity was apparently enhanced by preincubation in melted tallow for up to several days. Control of both the water activity of the enzyme and tallow feedstock and of the absorption of atmospheric water vapor were required to maintain enzyme activity, during multiple reuse and minimize free fatty acid formation. This method may form the basis for a process to produce highly mono-unsaturated tallow fractions for use in food applications (e.g. frying) where a "healthy" low saturated fat product is required

  8. Rhodium(I)-catalyzed regiospecific dimerization of aromatic acids: two direct C-H bond activations in water.

    PubMed

    Gong, Hang; Zeng, Huiying; Zhou, Feng; Li, Chao-Jun

    2015-05-01

    2,2'-Diaryl acids are key building blocks for some of the most important and high-performance polymers such as polyesters and polyamides (imides), as well as structural motifs of MOFs (metal-organic frameworks) and biological compounds. In this study, a direct, regiospecific and practical dimerization of simple aromatic acids to generate 2,2'-diaryl acids has been discovered, which proceeds through two rhodium-catalyzed C-H activations in water. This reaction can be easily scaled up to gram level by using only 0.4-0.6 mol % of the rhodium catalyst. As a proof-of-concept, the natural product ellagic acid was synthesized in two steps by this method. PMID:25765625

  9. A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins.

    PubMed

    Dee, Sean J; Bell, Alexis T

    2011-08-22

    An investigation was carried out into the hydrolysis of cellulose dissolved in 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) catalyzed by mineral acids. Glucose, cellobiose, and 5-hydroxymethylfurfural (5-HMF) were observed as the primary reaction products. The initial rate of glucose formation was determined to be of first order in the concentrations of dissolved glucan and protons and of zero order in the concentration of water. The absence of a dependence on water concentration suggests that cleavage of the β-1,4-glycosidic linkages near chain ends is irreversible. The apparent activation energy for glucose formation is 96 kJ mol(-1). The absence of oligosaccharides longer than cellobiose suggests that cleavage of interior glycosidic bonds is reversible due to the slow diffusional separation of cleaved chains in the highly viscous glucan/ionic liquid solution. Progressive addition of water during the course of glucan hydrolysis inhibited the rate of glucose dehydration to 5-HMF and the formation of humins. The inhibition of glucose dehydration is attributed to stronger interaction of protons with water than the 2-OH atom of the pyranose ring of glucose, the critical step in the proposed mechanism for the formation of 5-HMF. The reduction in humin formation associated with water addition is ascribed to the lowered concentration of 5-HMF, since the formation of humins is suggested to proceed through the condensation polymerization of 5-HMF with glucose. PMID:21809450

  10. Nitric acid in polar stratospheric clouds - Similar temperature of nitric acid condensation and cloud formation

    NASA Technical Reports Server (NTRS)

    Pueschel, Rudolf F.; Snetsinger, Kenneth G.; Hamill, Patrick; Goodman, Jindra K.; Mccormick, M. Patrick

    1990-01-01

    As shown independently by two different techniques, nitric acid aerosols and polar stratospheric clouds (PSCs) both form below similar threshold temperatures. This supports the idea that the PSC particles involved in chlorine activation and ozone depletion in the winter polar stratosphere are composed of nitric acid. One technique used to show this is the inertial impaction of nitric acid aerosols using an Er-2 aircraft; the other method is remote sensing of PSCs by the Stratospheric Aerosol Measurement (SAM II) satellite borne optical sensor. Both procedures were in operation during the Arctic Airborne Stratospheric Expedition in 1989, and the Airborne Antarctic Ozone Experiment in 1987. Analysis of Arctic particles gathered in situ indicates the presence of nitric acid below a 'first appearance' temperature Tfa = 202 K. This is the same highest temperature at which PSCs are seen by the SAM II satellite. In comparison, a 'first appearance' temperature Tfa = 198 K as found for the Antarctic samples.

  11. A {sup 13}C NMR study of the condensation chemistry of acetone and acetaldehyde adsorbed at the Bronsted acid sites in H-ZSM-5

    SciTech Connect

    Biaglow, A.I.; Sepa, J.; Gorte, R.J.

    1995-02-01

    Several bimolecular, acid-catalyzed condensation reactions of acetone and acetaldehyde have been examined in H-ZSM-5, along with the adsorption complexes formed by the products, using {sup 13}C NMR. For acetone, the hydrogen-bonded adsorption complex is stable at room temperature and coverages below one molecule per Broensted acid site. Reaction to mesityl oxide occurs only at higher coverages or temperatures, which are necessary to induce site exchange. The adsorption complex exhibits reaction chemistry analogous to that observed in solution phase, forming adsorption complexes of chloroacetone upon exposure to Cl{sub 2} and of imines upon exposure to NH{sub 3} or dimethylamine. The reactions of acetaldehyde to crotonaldehyde and imines are similar, although they occur at a faster rate due to the higher mobility of this molecule. The adsorption complexes formed by acetone, acetaldehyde, and their condensation products can all be described as rigid, hydrogen-bonded complexes at low coverages. Complexes formed from imines and enamines exhibit isotropic chemical shifts nearly identical to those observed in magic acids, indicating that proton transfer is nearly complete for these molecules. The extent of proton transfer for the remaining molecules varies with the proton affinity of the molecule, ranging from close to complete proton transfer for mesityl oxide and crotonaldehyde to almost complete absence of proton transfer for the chloroacetones. The differences and similarities between these reactions in the zeolite and in solution phase are discussed, along with the implications for understanding the primary processes responsible for these reactions in zeolites. 34 refs., 16 figs., 1 tab.

  12. Optimization of the enzyme-catalyzed synthesis of amino acid-based surfactants from palm oil fractions.

    PubMed

    Soo, Ee Lin; Salleh, Abu Bakar; Basri, Mahiran; Zaliha Raja Abdul Rahman, Raja Noor; Kamaruddin, Kamarulzaman

    2003-01-01

    The feasibility of using palm oil fractions as cheap and abundant sources of raw material for the synthesis of amino acid surfactants was investigated. Of a number of enzymes screened, the best results were obtained with the immobilized enzyme, Lipozyme. The effects of temperature, solvent, incubation period, fatty substrate/amino acid molar ratio, enzyme amount, and water removal on the reactions were analyzed and compared to those on reactions with free fatty acids and pure triglycerides as fatty substrates. All reactions were most efficient when carried out at high temperatures (70-80 degrees C) in hexane as a solvent. However, while reactions with free fatty acids proceeded better when a slight excess of the free fatty acids over the amino acids was used, reactions with triglycerides and palm oil fractions were best performed at equimolar ratios. Also, the addition of molecular sieves slightly enhanced reactions with free fatty acids but adversely affected reactions with triglycerides and palm oil fractions. Although reactions with palm oil fractions took longer (6 d) to reach equilibrium compared to reactions with free fatty acids (4 d) and pure triglycerides (4 d), better yields were obtained. Such lipase-catalyzed transacylation of palm oil fractions with amino acids is potentially useful in the production of mixed medium- to long-chain surfactants for specific applications. PMID:16233420

  13. Core acid treatment influence on well reservoir properties in Kazan oil-gas condensate field

    NASA Astrophysics Data System (ADS)

    Janishevskii, A.; Ezhova, A.

    2015-11-01

    The research involves investigation of the influence of hydrochloric acid (HCI-12%) and mud acid (mixture: HCl - 10% and HF - 3%) treatment on the Upper-Jurassic reservoir properties in Kazan oil-gas condensate field wells. The sample collection included three lots of core cylinders from one and the same depth (all in all 42). Two lots of core cylinders were distributed as following: first lot - reservoir properties were determined, and, then thin sections were cut off from cylinder faces; second lot- core cylinders were exposed to hydrochloric acid treatment, then, after flushing the reservoir properties were determined, and thin sections were prepared. Based on the quantitative petrographic rock analysis, involvin 42 thin sections, the following factors were determined: granulometric mineral composition, cement content, intergranular contacts and pore space structure. According to the comparative analysis of initial samples, the following was determined: content decrease of feldspar, clay and mica fragments, mica, clay and carbonate cement; increase of pore spaces while in the investigated samples- on exposure of rocks to acids effective porosity and permeability value range is ambiguous.

  14. Peptide synthesis catalyzed by an antibody containing a binding site for variable amino acids.

    PubMed

    Hirschmann, R; Smith, A B; Taylor, C M; Benkovic, P A; Taylor, S D; Yager, K M; Sprengeler, P A; Benkovic, S J

    1994-07-01

    Monoclonal antibodies, induced with a phosphonate diester hapten, catalyzed the coupling of p-nitrophenyl esters of N-acetyl valine, leucine, and phenylalanine with tryptophan amide to form the corresponding dipeptides. All possible stereoisomeric combinations of the ester and amide substrates were coupled at comparable rates. The antibodies did not catalyze the hydrolysis of the dipeptide product nor hydrolysis or racemization of the activated esters. The yields of the dipeptides ranged from 44 to 94 percent. The antibodies were capable of multiple turnovers at rates that exceeded the rate of spontaneous ester hydrolysis. This achievement suggests routes toward creating a small number of antibody catalysts for polypeptide syntheses. PMID:8023141

  15. Acid-catalyzed isomerization of rhenium alkyne complexes to rhenium allene complexes via 1-metallacyclopropene intermediates

    SciTech Connect

    Casey, C.P.; Brady, J.T.

    1998-10-12

    The alkyne complexes C{sub 5}Me{sub 5}(CO){sub 2}Re({eta}{sup 2}-MeC{triple_bond}CMe) (1) and C{sub 5}H{sub 5}(CO){sub 2}Re({eta}{sup 2}-MeC{triple_bond}CMe) (6) underwent acid-catalyzed isomerization by way of 1-metallacyclopropene intermediates to form the allene complexes C{sub 5}Me{sub 5}(CO){sub 2}Re({eta}{sup 2}-2,3-MeHC{double_bond}C{double_bond}CH{sub 2}) (5) and C{sub 5}H{sub 5}(CO){sub 2}Re({eta}{sup 2}-2,3-MeHC{double_bond}C{double_bond}CH{sub 2}) (7). Stoichiometric reaction of 1 with CF{sub 3}CO{sub 2}H initially produced the kinetic addition product C{sub 5}Me{sub 5}(CO){sub 2}Re[{eta}{sup 2}-(Z)-MeHC{double_bond}CMeO{sub 2}CCF{sub 3}] (8-Z), which slowly isomerized to the thermodynamically more stable E isomer 8-E. The reaction of 6 with CF{sub 3}CO{sub 2}H at {minus}73 C produced only C{sub 5}H{sub 5}(CO){sub 2}Re[{eta}{sup 2}-(E)-MeHC{double_bond}CMeO{sub 2}CCF{sub 3}] (9-E), which isomerized at -60 C to a 80:20 equilibrium mixture of 9-E and 9-Z. Treatment of 9-E and 9-Z with base led to formation of allene complex 7. The rate of this elimination was independent of base concentration. Labeling studies showed that the 1-metallacyclopropene intermediate C{sub 5}H{sub 5}(CO){sub 2}({eta}{sup 2}-CMeCHMe){sup +}CF{sub 3}CO{sub 2}{sup {minus}} (12-CF{sub 3}CO{sub 2}) undergoes a number of important reactions which include, in order of decreasing relative rates: (1) addition of trifluoroacetate to give enol trifluoroacetate complexes, (2) deprotonation to give complexed allenes, (3) degenerate 1,2-hydride migrations, (4) hydride migrations to give {eta}{sup 3}-allyl complexes, and (5) deprotonation to give complexed alkynes.

  16. Adsorption and condensation of amino acids and nucleotides with soluble mineral salts

    NASA Technical Reports Server (NTRS)

    Orenberg, J.; Lahav, N.

    1986-01-01

    The directed synthesis of biopolymers in an abiotic environment is presumably a cyclic sequence of steps which may be realized in a fluctuating environment such as a prebiotic pond undergoing wetting-drying cycles. Soluble mineral salts have been proposed as an essential component of this fluctuating environment. The following sequence may be considered as a most primitive mechanism of information transfer in a fluctuating environment: (1) adsorption of a biomolecule onto a soluable mineral salt surface to act as an adsorbed template; (2) specific adsorption of biomonomers onto the adsorbed template; (3) condensation of the adsorbed biomonomers; and (4) desorption of the elongated oligomer. In this investigation, the salts selected for study were CaSO4.2H2O(gypsum), SrSO4, and several other metal sulfates and chlorides. Adsorption of the monomeric species, gly, 5'AMP 5'GMP, and 5'CMP was investigated. The adsorbed template biopolymers used were Poly-A, Poly-G, Poly-C, and Poly-U. The results of studies involving these experimental participants, the first two steps of the proposed primitive information transfer mechanism, and condensation of amino acids to form oligomers in a fluctuating environment are to be reported.

  17. Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

    PubMed Central

    Mei, Xuefeng; August, Adam T.; Wolf, Christian

    2008-01-01

    A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99%. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti- and unprecedented trans-syn-dimeric structures. PMID:16388629

  18. Nitric acid in polar stratospheric clouds: Similar temperature of nitric acid condensation and cloud formation

    SciTech Connect

    Pueschel, R.F.; Snetsinger, K.G. ); Hamill, P.; Goodman, J.K. ); McCormick, M.P. )

    1990-03-01

    As shown independently by two different techniques, nitric acid aerosols and polar stratospheric clouds both form below similar threshold temperatures. This supports the idea that the polar stratospheric cloud (PSC) particles involved in chlorine activation and ozone depletion in the winter polar stratosphere are composed of nitric acid. One technique used to show this is inertial impaction of nitric acid aerosols using an ER-2 aircraft; the other method is remote sensing of PSCs by the Stratospheric Aerosol Measurement (SAM II) satellite borne optical sensor. Both procedures were in operation during the Arctic Airborne Stratospheric Expedition in 1989, and the Airborne Antarctic Ozone Experiment in 1987. Analysis of Arctic particles gathered in situ indicates the presence of nitric acid below a first appearance temperature T{sub fa} = 202 K. This is the same highest temperature at which PSCs are seen by the SAM II satellite. In comparison, a first appearance temperature T{sub fa} = 198 K was found for the Antarctic samples.

  19. Lewis Acid Catalyzed Ring-opening Polymerization of Epoxidized Soybean Oil in Liquid Carbon Dioxide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by boron trifluoride diethyl etherate (BF3•OEt2), in liquid carbon dioxide, was conducted in an effort to develop useful biobased biodegradable polymers. The resulting polymers (RPESO) were characterized by FTIR spectroscopy, diff...

  20. Pd-catalyzed divergent trifluoroethylation and arylation of arylboronic acids by aryl(2,2,2-trifluoroethyl)iodonium triflates.

    PubMed

    Yang, Jing; Han, Qiu-Yan; Zhao, Cheng-Long; Dong, Tao; Hou, Zhi-Yuan; Qin, Hua-Li; Zhang, Cheng-Pan

    2016-08-10

    Highly electrophilic aryl(2,2,2-trifluoroethyl)iodonium triflates have been used for the first time as trifluoroethyl and aryl transfer reagents in Pd-catalyzed functionalization of arylboronic acids. Electron-rich arylboronic acids reacted with aryl(2,2,2-trifluoroethyl)iodonium triflates (2a-b) in CH3CN in the presence of Pd2(dba)3 and K3PO4 at room temperature to provide trifluoroethyl arenes in up to 82% yield, while the reactions of both electron-rich and -poor arylboronic acids with 2a-b in DMF in the presence of Pd[P(t-Bu)3]2 and Cs2CO3 at 40 °C afforded arylation products in up to 99% yield. This tunable protocol allows access to trifluoroethyl arenes or biaryls in good to excellent yields under mild conditions and without the addition of extra ligands. PMID:27384263

  1. Hyaluronic acid-based hydrogels crosslinked by copper-catalyzed azide-alkyne cycloaddition with tailorable mechanical properties.

    PubMed

    Piluso, Susanna; Hiebl, Bernhard; Gorb, Stanislav N; Kovalev, Alexander; Lendlein, Andreas; Neffe, Axel T

    2011-02-01

    Biopolymers of the extracellular matrix are attractive starting materials for providing degradable and biocompatible biomaterials. In this study, hyaluronic acid-based hydrogels with tunable mechanical properties were prepared by the use of copper- catalyzed azide-alkyne cycloaddition (known as "click chemistry"). Alkyne-functionalized hyaluronic acid was crosslinked with linkers having two terminal azide functionalities, varying crosslinker density as well as the lengths and rigidity of the linker molecules. By variation of the crosslinker density and crosslinker type, hydrogels with elastic moduli in the range of 0.5-4 kPa were prepared. The washed materials contained a maximum of 6.8 mg copper per kg dry weight and the eluate of the gel crosslinked with diazidostilbene did not show toxic effects on L929 cells. The hyaluronic acid-based hydrogels have potential as biomaterials for cell culture or soft tissue regeneration applications. PMID:21374560

  2. Palladium-Catalyzed Oxidative Sulfenylation of Indoles and Related Electron-Rich Heteroarenes with Aryl Boronic Acids and Elemental Sulfur.

    PubMed

    Li, Jianxiao; Li, Chunsheng; Yang, Shaorong; An, Yanni; Wu, Wanqing; Jiang, Huanfeng

    2016-09-01

    An efficient and convenient palladium-catalyzed C-H bond oxidative sulfenylation of indoles and related electron-rich heteroarenes with aryl boronic acids and elemental sulfur has been described. This procedure provides a useful and direct approach for the assembly of a wide range of structurally diverse 3-sulfenylheteroarenes with moderate to excellent yields from simple and readily available starting materials. Moreover, this synthetic protocol is suitable for N-protected and unprotected indoles. Notably, the construction of two C-S bonds in one step was also achieved in this transformation. PMID:27500941

  3. Mechanism of Pd-Catalyzed Decarbonylation of Biomass-Derived Hydrocinnamic Acid to Styrene following Activation as an Anhydride.

    PubMed

    Ortuño, Manuel A; Dereli, Büşra; Cramer, Christopher J

    2016-05-01

    All elementary steps in the mechanism of Pd-catalyzed decarbonylation of hydrocinnamic acid through formation of a mixed anhydride species have been characterized through electronic structure calculations. Oxidative addition of the mixed anhydride to a singly or doubly ligated Pd is followed by decarbonylation, alkene formation, and catalyst regeneration. Metal-assisted deprotonation of the alkyl-Pd species by a coordinated carboxylate is predicted to be the rate-determining step; theory suggests that bulkier phosphine ligands (e.g., P(o-Tol)3) reduce the free energy of activation substantially, while variation of the auxiliary anhydride has little influence on efficiency. PMID:27077600

  4. Influence of organic acids on oscillations and waves in the ferroin-catalyzed Belousov-Zhabotinsky reaction

    NASA Astrophysics Data System (ADS)

    Krüger, Frank; Nagy-Ungvárai, Zsuzsanna; Müller, Stefan C.

    Experiments of the influence of mesoxalic and tartronic acid on the oscillatory behavior and on the spiral tip motion in a ferroin-catalyzed Belousov-Zhabotinsky (BZ) solution are reported. The oscillations were observed in batch and CSTR systems, and for the investigations of the spiral tip motion an open gel reactor was used. A characteristic shoulder in the oscillations is associated with an additional Br - production phase. The chemical parameters for a transition from a hypocycloidal to a circular tip trajectory are found. The findings are compared with the temporal and spatial dynamic behavior, occurring during the ageing process of the solution.

  5. Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids.

    PubMed

    McCammant, Matthew S; Shigeta, Takashi; Sigman, Matthew S

    2016-04-15

    A Pd-catalyzed 1,3-difunctionalization of terminal alkenes using 1,1-disubstituted alkenyl nonaflates and arylboronic acid coupling partners is reported. This transformation affords allylic arene products that are difficult to selectively access using traditional Heck cross-coupling methodologies. The evaluation of seldom employed 1,1-disubstituted alkenyl nonaflate coupling partners led to the elucidation of subtle mechanistic features of π-allyl stabilized Pd-intermediates. Good stereo- and regioselectivity for the formation of 1,3-addition products can be accessed through a minimization of steric interactions that emanate from alkenyl nonaflate substitution. PMID:27019228

  6. Palladium-Catalyzed Defluorinative Coupling of 1-Aryl-2,2-Difluoroalkenes and Boronic Acids: Stereoselective Synthesis of Monofluorostilbenes.

    PubMed

    Thornbury, Richard T; Toste, F Dean

    2016-09-12

    The palladium-catalyzed defluorinative coupling of 1-aryl-2,2-difluoroalkenes with boronic acids is described. Broad functional-group tolerance arises from a redox-neutral process by a palladium(II) active species which is proposed to undergo a β-fluoride elimination to afford the products. The monofluorostilbene products were formed with excellent diastereoselectivity (≥50:1) in all cases, and it is critical, as traditional chromatographic techniques often fail to separate monofluoroalkene isomers. As a demonstration of this method's unique combination of reactivity and functional-group tolerance, a Gleevec® analogue, using a monofluorostilbene as an amide isostere, was synthesized. PMID:27511868

  7. Brönsted Acid-Catalyzed One-Pot Synthesis of Indoles from o-Aminobenzyl Alcohols and Furans

    PubMed Central

    Kuznetsov, Alexey; Makarov, Anton; Rubtsov, Alexandr E.; Butin, Alexander V.; Gevorgyan, Vladimir

    2013-01-01

    Brönsted acid-catalyzed one-pot synthesis of indoles from o-aminobenzyl alcohols and furans has been developed. This method operates via the in situ formation of aminobenzylfuran, followed by its recyclization into the indole core. The method proved to be efficient for substrates possessing different functional groups, including -OMe, -CO2Cy, and -Br. The resulting indoles can easily be transformed into diverse scaffolds, including 2,3- and 1,2-fused indoles, and indole possessing an α,β-unsaturated ketone moiety at the C-2 position. PMID:24255969

  8. Vapor-phase esterification of acetic acid with ethanol catalyzed by a macroporous sulfonated styrene-divinylbenzene (20%) resin

    SciTech Connect

    Gimenez, J.; Costa, J.; Cervera, S.

    1987-02-01

    The kinetics of the vapor-phase (85-120/sup 0/C) esterification of acetic acid with ethyl alcohol, at atmospheric pressure, catalyzed by a macroporous sulfonated styrene-divinylbenzene (DVB;20%) resin, has been studied. A simple first-order model (r = kp/sub 1/) fits experimental kinetic data properly for a constant reactants ratio. Discussion by means of L-H-H-W models shows that the rate-controlling step is the surface reaction with a single-site mechanism. The apparent activation energy is 4000 cal/mol.

  9. Direct Access to α,α-Difluoroacylated Arenes by Palladium-Catalyzed Carbonylation of (Hetero)Aryl Boronic Acid Derivatives.

    PubMed

    Andersen, Thomas L; Frederiksen, Mette W; Domino, Katrine; Skrydstrup, Troels

    2016-08-22

    A palladium-catalyzed carbonylative coupling of (hetero)aryl boronates or boronic acid salts with carbon monoxide and α-bromo-α,α-difluoroamides and bromo-α,α-difluoroesters is described herein. The method is useful for the synthesis of a diverse selection of (hetero)aryl α,α-difluoro-β-ketoamides and α,α-difluoro-β-ketoesters, which are useful building blocks for the generation of functionalized difluoroacylated and difluoroalkyl arenes. The method could be further extended to a one-pot protocol for the formation of difluoroacetophenones. PMID:27346239

  10. Delayed production of sulfuric acid condensation nuclei in the polar stratosphere from El Chichon volcanic vapors

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.; Gringel, W.

    1985-01-01

    It is pointed out that measurements of the vertical profiles of atmospheric condensation nuclei (CN) have been conducted since 1973. Studies with a new instrument revealed that the CN concentration undergoes a remarkable annual variation in the 30-km region characterized by a large increase in the late winter/early spring period with a subsequent decay during the remainder of the year. The event particles are observed to be volatile at 150 C, suggesting a sulfuric acid-water composition similar to that found in the normal 20 km aerosol layer. The development of about 10 to the 7th metric tons of sulfuric acid aerosol following the injection of sulfurous gases by El Chichon in April 1982, prompted Hofmann and Rosen (1983) to predict a very large CN event for 1983. The present investigation is concerned with the actual observation of the predicted event. Attention is given to the observation of a very large increase of what appear to be small sulfuric acid droplets at 30-km altitude in January 1983 over Laramie, WY, in January 1983.

  11. {beta}-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    SciTech Connect

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F.

    1995-03-24

    {beta}-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 {degrees}C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6-{sup 2}H{sub 2}]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 {plus_minus} 0.01. These values support the B{sub AC}2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other {beta}-lactams. The measured {beta}-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 {plus_minus} 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A{sub AC}1 mechanism with an intermediate acylium ion. If this were so, the calculated {beta}-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 {plus_minus} 0.01. This suggests an early A{sub AC}1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A{sub AC}1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 {plus_minus} 0.00 in 1 M HCl and 0.22 {plus_minus} 0.01 in 33.3 wt % H{sub 2}SO{sub 4}. 1 fig., 3 tabs.

  12. Conjugated linoleic acid increases in milk from cows fed condensed corn distillers solubles and fish oil.

    PubMed

    Bharathan, M; Schingoethe, D J; Hippen, A R; Kalscheur, K F; Gibson, M L; Karges, K

    2008-07-01

    Twelve lactating Holstein cows were randomly assigned to 1 of 4 experimental diets in a replicated 4 x 4 Latin square design with 4-wk periods to ascertain the lactational response to feeding fish oil (FO), condensed corn distillers solubles (CDS) as a source of extra linoleic acid, or both. Diets contained either no FO or 0.5% FO and either no CDS or 10% CDS in a 2 x 2 factorial arrangement of treatments. Diets were fed as total mixed rations for ad libitum consumption. The forage to concentrate ratio was 55:45 on a dry matter basis for all diets and the diets contained 16.2% crude protein. The ether extract concentrations were 2.86, 3.22, 4.77, and 5.02% for control, FO, CDS, and FOCDS diets, respectively. Inclusion of FO or CDS or both had no effect on dry matter intake, feed efficiency, body weight, and body condition scores compared with diets without FO and CDS, respectively. Yields of milk (33.3 kg/d), energy-corrected milk, protein, lactose, and milk urea N were similar for all diets. Feeding FO and CDS decreased milk fat percentages (3.85, 3.39, 3.33, and 3.12%) and yields compared with diets without FO and CDS. Proportions of trans-11 C18:1 (vaccenic acid), cis-9 trans-11 conjugated linoleic acid (CLA; 0.52, 0.90, 1.11, and 1.52 g/100 g of fatty acids), and trans-10 cis-12 CLA (0.07, 0.14, 0.13, and 0.16 g/100 g of fatty acids) in milk fat were increased by FO and CDS. No interactions were observed between FO and CDS on cis-9 trans-11 CLA although vaccenic acid tended to be higher with the interaction. The addition of CDS to diets increased trans-10 C18:1. Greater ratios of vaccenic acid to cis-9 trans-11 CLA in plasma than in milk fat indicate tissue synthesis of cis-9 trans-11 CLA in the mammary gland from vaccenic acid in cows fed FO or CDS. Feeding fish oil at 0.5% of diet dry matter with a C18:2 n-6 rich source such as CDS increased the milk CLA content but decreased milk fat percentages. PMID:18565937

  13. Characterization of a Cross-Linked Protein-Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

    SciTech Connect

    Silakov, Alexey; Grove, Tyler L.; Radle, Matthew I.; Bauerle, Matthew R.; Green, Michael T.; Rosenzweig, Amy C.; Boal, Amie K.; Booker, Squire J.

    2014-08-14

    RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process

  14. Characterization of a Cross-Linked Protein–Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

    PubMed Central

    2015-01-01

    RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process. PMID:24806349

  15. Lewis Acid Catalyzed Friedel-Crafts Alkylation of Alkenes with Trifluoropyruvates.

    PubMed

    Xiang, Bin; Xu, Teng-Fei; Wu, Liang; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-05-01

    A Friedel-Crafts alkylation reaction of styrenes with trifluoropyruvates has been developed, which delivered allylic alcohols in excellent yields (up to 98%) using the Ni(ClO4)2·6H2O/bipyridine complex as a catalyst. The asymmetric reaction was catalyzed by the chiral Cu(OTf)2/bisoxazoline complex to afford the corresponding chiral allylic alcohols bearing trifluoromethylated quaternary stereogenic centers in moderate enantioselectivities (up to 75% ee). PMID:27028539

  16. Ring-opening polymerization of epoxidized soybean oil catalyzed by the superacid, Fluroantimonic acid hexahydrate (HSbF6-6H2O)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by the super acid, fluroantimonic acid hexahydrate (HSbF6-6H2O), in ethyl acetate was conducted. The resulting polymers, SA-RPESO, were characterized using infrared spectroscopy, differential scanning calorimetry, thermogravimetri...

  17. Crystal Structures of Xanthomonas campestris OleA Reveal Features That Promote Head-to-Head Condensation of Two Long-Chain Fatty Acids

    SciTech Connect

    Goblirsch, Brandon R.; Frias, Janice A.; Wackett, Lawrence P.; Wilmot, Carrie M.

    2012-10-25

    OleA is a thiolase superfamily enzyme that has been shown to catalyze the condensation of two long-chain fatty acyl-coenzyme A (CoA) substrates. The enzyme is part of a larger gene cluster responsible for generating long-chain olefin products, a potential biofuel precursor. In thiolase superfamily enzymes, catalysis is achieved via a ping-pong mechanism. The first substrate forms a covalent intermediate with an active site cysteine that is followed by reaction with the second substrate. For OleA, this conjugation proceeds by a nondecarboxylative Claisen condensation. The OleA from Xanthomonas campestris has been crystallized and its structure determined, along with inhibitor-bound and xenon-derivatized structures, to improve our understanding of substrate positioning in the context of enzyme turnover. OleA is the first characterized thiolase superfamily member that has two long-chain alkyl substrates that need to be bound simultaneously and therefore uniquely requires an additional alkyl binding channel. The location of the fatty acid biosynthesis inhibitor, cerulenin, that possesses an alkyl chain length in the range of known OleA substrates, in conjunction with a single xenon binding site, leads to the putative assignment of this novel alkyl binding channel. Structural overlays between the OleA homologues, 3-hydroxy-3-methylglutaryl-CoA (HMG-CoA) synthase and the fatty acid biosynthesis enzyme FabH, allow assignment of the two remaining channels: one for the thioester-containing pantetheinate arm and the second for the alkyl group of one substrate. A short {beta}-hairpin region is ordered in only one of the crystal forms, and that may suggest open and closed states relevant for substrate binding. Cys143 is the conserved catalytic cysteine within the superfamily, and the site of alkylation by cerulenin. The alkylated structure suggests that a glutamic acid residue (Glu117{beta}) likely promotes Claisen condensation by acting as the catalytic base. Unexpectedly

  18. Crystal Structures of Xanthomonas campestris OleA Reveal Features That Promote Head-to-Head Condensation of Two Long-Chain Fatty Acids

    SciTech Connect

    Goblirsch, BR; Frias, JA; Wackett, LP; Wilmot, CM

    2012-05-22

    OleA is a thiolase superfamily enzyme that has been shown to catalyze the condensation of two long-chain fatty acylcoenzyme A (CoA) substrates. The enzyme is part of a larger gene cluster responsible for generating long-chain olefin products, a potential biofuel precursor. In thiolase superfamily enzymes, catalysis is achieved via a ping-pong mechanism. The first substrate forms a covalent intermediate with an active site cysteine that is followed by reaction with the second substrate. For OleA, this conjugation proceeds by a nondecarboxylative Claisen condensation. The OleA from Xanthomonas campestris has been crystallized and its structure determined, along with inhibitor-bound and xenon-derivatized structures, to improve our understanding of substrate positioning in the context of enzyme turnover. OleA is the first characterized thiolase superfamily member that has two long-chain alkyl substrates that need to be bound simultaneously and therefore uniquely requires an additional alkyl binding channel. The location of the fatty acid biosynthesis inhibitor, cerulenin, that possesses an alkyl chain length in the range of known OleA substrates, in conjunction with a single xenon binding site, leads to the putative assignment of this novel alkyl binding channel. Structural overlays between the OleA homologues, 3-hydroxy-3-methylglutaryl-CoA (HMG-CoA) synthase and the fatty acid biosynthesis enzyme FabH, allow assignment of the two remaining channels: one for the thioester-containing pantetheinate arm and the second for the alkyl group of one substrate. A short beta-hairpin region is ordered in only one of the crystal forms, and that may suggest open and closed states relevant for substrate binding. Cys143 is the conserved catalytic cysteine within the superfamily, and the site of alkylation by cerulenin. The alkylated structure suggests that a glutamic acid residue (Glu117 beta) likely promotes Claisen condensation by acting as the catalytic base. Unexpectedly, Glu117

  19. Spectroscopic Investigation of the Species Involved in the Rhodium-Catalyzed Oxidative Carbonylation of Toluene to Toluic Acid

    SciTech Connect

    Zakzeski, Joseph; Burton, Sarah D.; Behn, Andrew; Head-Gordon, Martin P.; Bell, Alexis T.

    2009-11-14

    A spectroscopic investigation of complexes used to catalyze the oxidative carbonylation of toluene to para-toluic acid was conducted. Rhodium complexes were analyzed by 103Rh and 13C NMR, UV-visible spectroscopy, and infrared spectroscopy. In the presence of vanadium and oxygen, the resting state of the Rh catalyst was found to exist as a Rh(III) complex with carbonyl and trifluoroacetate ligands, consistent with the structure Rh(CO)2(TFA)3. The complex exhibited a carbonyl peak with an unusual degree of shielding, which resulted in the appearance of the carbonyl peak at an unprecedented upfield position in the 13C NMR spectrum. This shielding was caused by interaction of the carbonyl group with the trifluoroacetate ligand. In the absence of oxygen, the Rh(III) complex reduced to Rh(I), and the reduced form exhibited properties resembling the catalyst precursor. Structures and spectroscopic properties calculated using Density Functional Theory were in good agreement with experimental results. The vanadium co-catalyst was similarly characterized by 51V NMR and UV-visible spectroscopy. The oxidized species corresponded to [(VO2)(TFA)]2, whereas the reduced species corresponded (VO)(TFA)2. The spectroscopic results obtained in this study confirm the identity of the species that have been proposed to be involved in the Rh-catalyzed oxidative carbonylation of toluene to toluic acid.

  20. Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Mori, Keiji; Itakura, Tsubasa; Akiyama, Takahiko

    2016-09-12

    Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o-tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method. PMID:27491630

  1. Synthesis of diverse β-quaternary ketones via palladium-catalyzed asymmetric conjugate addition of arylboronic acids to cyclic enones

    PubMed Central

    Holder, Jeffrey C.; Goodman, Emmett D.; Kikushima, Kotaro; Gatti, Michele; Marziale, Alexander N.; Stoltz, Brian M.

    2014-01-01

    The development and optimization of a palladium-catalyzed asymmetric conjugate addition of arylboronic acids to cyclic enone conjugate acceptors is described. These reactions employ air-stable and readily-available reagents in an operationally simple and robust transformation that yields β-quaternary ketones in high yields and enantioselectivities. Notably, the reaction itself is highly tolerant of atmospheric oxygen and moisture and therefore does not require the use of dry or deoxygenated solvents, specially purified reagents, or an inert atmosphere. The ring size and β-substituent of the enone are highly variable, and a wide variety of β-quaternary ketones can be synthesized. More recently, the use of NH4PF6 has further expanded the substrate scope to include heteroatom-containing arylboronic acids and β-acyl enone substrates. PMID:26461082

  2. Ternary copper complexes and manganese (III) tetrakis(4-benzoic acid) porphyrin catalyze peroxynitrite-dependent nitration of aromatics.

    PubMed

    Ferrer-Sueta, G; Ruiz-Ramírez, L; Radi, R

    1997-12-01

    Peroxynitrite is a powerful oxidant formed in biological systems from the reaction of nitrogen monoxide and superoxide and is capable of nitrating phenols at neutral pH and ambient temperature. This peroxynitrite-mediated nitration is catalyzed by a number of Lewis acids, including CO2 and transition-metal ion complexes. Here we studied the effect of ternary copper-(II) complexes constituted by a 1,10-phenanthroline and an amino acid as ligands. All the complexes studied accelerate both the decomposition of peroxynitrite and its nitration of 4-hydroxyphenylacetic acid at pH > 7. The rate of these reactions depends on the copper complex concentration in a hyperbolic plus linear manner. The yield of nitrated products increases up to 2.6-fold with respect to proton-catalyzed nitration and has a dependency on the concentration of copper complexes which follows the same function as observed for the rate constants. The manganese porphyrin complex, Mn(III)tetrakis(4-benzoic acid)porphyrin [Mn(tbap)], also promoted peroxynitrite-mediated nitration with an even higher yield (4-fold increase) than the ternary copper complexes. At pH = 7.5 +/- 0.2 the catalytic behavior of the copper complexes can be linearly correlated with the pKa of the phenanthroline present as a ligand, implying that a peroxynitrite anion is coordinated to the copper ion prior to the nitration reaction. These observations may prove valuable to understand the biological effects of these transition-metal complexes (i.e., copper and manganese) that can mimic superoxide dismutase activity and, in the case of the ternary copper complexes, show antineoplastic activity. PMID:9437523

  3. Zeolite-Catalyzed Isomerization of Oleic Acid to Branched-Chain Isomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Branched-chain saturated fatty acids have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids and have better low-temperature properties than linear saturated fatty acids. Previous studies in converting unsaturated fatty acids to br...

  4. Lipase-catalyzed ethanolysis of milk fat with a focus on short-chain fatty acid selectivity.

    PubMed

    Lubary, Marta; ter Horst, Joop H; Hofland, Gerard W; Jansens, Peter J

    2009-01-14

    Mixtures of fatty acid ethyl esters were produced by lipase-catalyzed ethanolysis of milk fat triglycerides. Three commercial immobilized lipases (Lipozyme TL, Lipozyme RM, and Novozym 435) were tested in different reaction conditions with the aim of maximizing the conversion of the short-chain fatty acid fraction of milk fat to flavor ethyl esters. The influence of the reactants molar ratio was investigated, as well as three different reaction media, that is, hexane, CO(2)-expanded liquid (GXL), and the solvent-free mixture. Novozym 435 showed the highest activity in all conditions. This lipase also exhibited selectivity for short-chain fatty acids, which, at short reaction times, resulted in a product mixture richer in short-chain fatty acids than the original milk fat. The highest selectivities were obtained in hexane and in CO(2)-expanded liquid fat, at low ethanol to fat ratios. Using dense CO(2) as the reaction cosolvent is attractive because it results in the largest short-chain fatty acid enrichment in the product mixture, while leaving no residues in the product. PMID:19072544

  5. Increase of Oleic Acid Content in Phosphatidylcholine through Lipase-catalyzed Interesterification: Optimization by Response Surface Methodology.

    PubMed

    Yang, Guolong; Yang, Lihui

    2015-01-01

    In order to obtain phosphatidylcholine (PC) with higher amount of oleic acid, the interesterification between soybean PC and Camellia oleifera oil (COO) rich in oleic acid catalyzed by lipase was studied in hexane. For this aim three commercially available immobilized lipases (Novozym 435, Lipozyme TLIM and Lipozyme RMIM) were assayed and Novozym 435 was finally selected for further optimization. The effects of the factors, such as PC concentration, substrate ratio, water amount, lipase dosage and temperature, on the oleic acid content in PC and PC recovery during the interesterification were investigated. The conditions of the interesterification were optimized using response surface methodology. The optimum conditions were as follows: lipase dosage 13 % (based on the mass of PC and COO), reaction temperature 55°C, water amount 5% (based on the mass of PC), reaction time 8 h, PC concentration 0.3g/mL (PC/hexane), PC-to-COO ratio 1:3 (acyl groups in PC/acyl groups in COO, mol/mol). Under these conditions, oleic acid content and PC recovery were 40.8 ± 0.5% and 69.0 ± 2.8%, respectively. Analysis of variance (ANOVA) showed that the regression models were adequate for predicting the interesterifiction. The orders of reaction variables affecting on oleic acid content and PC recovery were water amount > reaction time > lipase dosage > reaction temperature, and water amount > reaction temperature > lipase dosage > reaction time, respectively. PMID:25891113

  6. Silver(I)-Catalyzed Iodination of Arenes: Tuning the Lewis Acidity of N-Iodosuccinimide Activation.

    PubMed

    Racys, Daugirdas T; Sharif, Salaheddin A I; Pimlott, Sally L; Sutherland, Andrew

    2016-02-01

    A mild and rapid method for the iodination of arenes that utilizes silver(I) triflimide as a catalyst for activation of N-iodosuccinimide has been developed. The transformation was found to be general for a wide range of anisole, aniline, acetanilide, and phenol derivatives and allowed the late-stage iodination of biologically active compounds such as PIMBA, a SPECT imaging agent of breast cancer, and (-)-IBZM, a dopamine D2 receptor antagonist. The method was also modified for the radioiodination of arenes using a one-pot procedure involving the in situ generation of [(125)I]-N-iodosuccinimide followed by the silver(I)-catalyzed iodination. PMID:26795534

  7. Consecutive condensation, C-N and N-N bond formations: a copper- catalyzed one-pot three-component synthesis of 2H-indazole.

    PubMed

    Kumar, Manian Rajesh; Park, Ahbyeol; Park, Namjin; Lee, Sunwoo

    2011-07-01

    2H-Indazoles are synthesized using copper-catalyzed, one-pot, three-component reactions of 2-bromobenzaldehydes, primary amines, and sodium azide. A copper catalyst plays the key role in the formation of C-N and N-N bonds. This method has a broad substrate scope with a high tolerance for a variety of functional groups. PMID:21644532

  8. Breath condensate hydrogen peroxide correlates with both airway cytology and epithelial lining fluid ascorbic acid concentration in the horse.

    PubMed

    Deaton, Christopher M; Marlin, David J; Smith, Nicola C; Smith, Ken C; Newton, Richard J; Gower, Susan M; Cade, Susan M; Roberts, Colin A; Harris, Pat A; Schroter, Robert C; Kelly, Frank J

    2004-02-01

    The relationship between hydrogen peroxide (H2O2) concentration in expired breath condensate (EBC) and cytology of the respiratory tract obtained from tracheal wash (TW) or bronchoalveolar lavage (BAL), and epithelial lining fluid (ELF) antioxidant status is unknown. To examine this we analysed the concentration of H2O2 in breath condensate from healthy horses and horses affected by recurrent airway obstruction (RAO), a condition considered to be an animal model of human asthma. The degree of airway inflammation was determined by assessing TW inflammation as mucus, cell density and neutrophil scores, and by BAL cytology. ELF antioxidant status was determined by measurement of ascorbic acid, dehydroascorbate, reduced and oxidised glutathione, uric acid and alpha-tocopherol concentrations. RAO-affected horses with marked airway inflammation had significantly higher concentrations of breath condensate H2O2 than control horses and RAO-affected horses in the absence of inflammation (2.0 +/- 0.5 micromol/l. 0.4 +/- 0.2 micromol/l and 0.9 +/- 0.2 micromol/l H2O2, respectively; p < 0.0001). The concentration of breath condensate H2O2 was related inversely to the concentration of ascorbic acid in ELF (r = -0.80; p < 0.0001) and correlated positively with TW inflammation score (r = 0.76, p < 0.0001) and BAL neutrophil count (r = 0.80, p < 0.0001). We conclude that the concentration of H2O2 in breath condensate influences the ELF ascorbic acid concentration and provides a non-invasive diagnostic indicator of the severity of neutrophilic airway inflammation. PMID:15104214

  9. Pd-Catalyzed Coupling of γ-C(sp(3))-H Bonds of Oxalyl Amide-Protected Amino Acids with Heteroaryl and Aryl Iodides.

    PubMed

    Han, Jian; Zheng, Yongxiang; Wang, Chao; Zhu, Yan; Huang, Zhi-Bin; Shi, Da-Qing; Zeng, Runsheng; Zhao, Yingsheng

    2016-07-01

    Pd-catalyzed regioselective coupling of γ-C(sp(3))-H bonds of oxalyl amide-protected amino acids with heteroaryl and aryl iodides is reported. A wide variety of iodides are tolerated, giving the corresponding products in moderate to good yields. Various oxalyl amide-protected amino acids were compatible in this C-H transformation, thus representing a practical method for constructing non-natural amino acid derivatives. PMID:27286881

  10. Total Synthesis of cis-Clavicipitic Acid from Asparagine via Ir-Catalyzed C-H bond Activation as a Key Step.

    PubMed

    Tahara, Yu-ki; Ito, Mamoru; Kanyiva, Kyalo Stephen; Shibata, Takanori

    2015-08-01

    4-Substituted tryptophan derivatives and the total synthesis of cis-clavicipitic acid were achieved in reactions in which Ir-catalyzed C-H bond activation was a key step. The starting material for these reactions is asparagine, which is a cheap natural amino acid. The reductive amination step from the 4-substituted tryptophan derivative gave cis-clavicipitic acid with perfect diastereoselectivity. PMID:26178075

  11. UGT74D1 catalyzes the glucosylation of 2-oxindole-3-acetic acid in the auxin metabolic pathway in Arabidopsis.

    PubMed

    Tanaka, Keita; Hayashi, Ken-ichiro; Natsume, Masahiro; Kamiya, Yuji; Sakakibara, Hitoshi; Kawaide, Hiroshi; Kasahara, Hiroyuki

    2014-01-01

    IAA is a naturally occurring auxin that plays a crucial role in the regulation of plant growth and development. The endogenous concentration of IAA is spatiotemporally regulated by biosynthesis, transport and its inactivation in plants. Previous studies have shown that the metabolism of IAA to 2-oxindole-3-acetic acid (OxIAA) and OxIAA-glucoside (OxIAA-Glc) may play an important role in IAA homeostasis, but the genes involved in this metabolic pathway are still unknown. In this study, we show that UGT74D1 catalyzes the glucosylation of OxIAA in Arabidopsis. By screening yeasts transformed with Arabidopsis UDP-glycosyltransferase (UGT) genes, we found that OxIAA-Glc accumulates in the culture media of yeasts expressing UGT74D1 in the presence of OxIAA. Further, we showed that UGT74D1 expressed in Escherichia coli converts OxIAA to OxIAA-Glc. The endogenous concentration of OxIAA-Glc decreased by 85% while that of OxIAA increased 2.5-fold in ugt74d1-deficient mutants, indicating the major role of UGT74D1 in OxIAA metabolism. Moreover, the induction of UGT74D1 markedly increased the level of OxIAA-Glc and loss of root gravitropism. These results indicate that UGT74D1 catalyzes a committed step in the OxIAA-dependent IAA metabolic pathway in Arabidopsis. PMID:24285754

  12. Determination of DNA adducts by combining acid-catalyzed hydrolysis and chromatographic analysis of the carcinogen-modified nucleobases.

    PubMed

    Leung, Elvis M K; Deng, Kailin; Wong, Tin-Yan; Chan, Wan

    2016-01-01

    The commonly used method of analyzing carcinogen-induced DNA adducts involves the hydrolysis of carcinogen-modified DNA samples by using a mixture of enzymes, followed by (32)P-postlabeling or liquid chromatography (LC)-based analyses of carcinogen-modified mononucleotides/nucleosides. In the present study, we report the development and application of a new approach to DNA adduct analysis by combining the H(+)/heat-catalyzed release of carcinogen-modified nucleobases and the use of LC-based methods to analyze DNA adducts. Results showed that heating the carcinogen-modified DNA samples at 70 °C for an extended period of 4 to 6 h in the presence of 0.05% HCl can efficiently induce DNA depurination, releasing the intact carcinogen-modified nucleobases for LC analyses. After optimizing the hydrolysis conditions, DNA samples with C8- and N (2) -modified 2'-deoxyguanosine, as well as N (6) -modified 2'-deoxyadenosine, were synthesized by reacting DNA with 1-nitropyrene, acetaldehyde, and aristolochic acids, respectively. These samples were then hydrolyzed, and the released nucleobase adducts were analyzed using LC-based analytical methods. Analysis results demonstrated a dose-dependent release of target DNA adducts from carcinogen-modified DNA samples, indicating that the developed H(+)/heat-catalyzed hydrolysis method was quantitative. Comparative studies with enzymatic digestion method on carcinogen-modified DNA samples revealed that the two hydrolysis methods did not yield systematically different results. PMID:26581621

  13. Modeling suberization with peroxidase-catalyzed polymerization of hydroxycinnamic acids: cross-coupling and dimerization reactions.

    PubMed

    Arrieta-Baez, Daniel; Stark, Ruth E

    2006-04-01

    An anionic potato peroxidase (EC 1.11.1.7, APP) thought to be involved in suberization after wounding was isolated from slices of Solanum tuberosum in order to elucidate the first steps of dehydrogenative polymerization between pairs of different hydroxycinnamic acids (FA, CafA, CA and SA) present in wound-healing plant tissues. Use of a commercial horseradish peroxidase (HRP)-H2O2 catalytic system gave the identical major products in these coupling reactions, providing sufficient quantities for purification and structural elucidation. Using an equimolar mixture of pairs of hydroxycinnamic acid suberin precursors, only caffeic acid is coupled to ferulic acid and sinapic acid in separate cross-coupling reactions. For the other systems, HRP and APP reacted as follows: (1) preferentially with ferulic acid in a reaction mixture that contained p-coumaric and ferulic acids; (2) with sinapic acid in a mixture of p-coumaric and sinapic acids; (3) with sinapic acid in a mixture of ferulic and sinapic acids; (4) with caffeic acid in a reaction mixture of p-coumaric and caffeic acids. The resulting products, isolated and identified by NMR and MS analysis, had predominantly beta-beta-gamma-lactone and beta-5 benzofuran molecular frameworks. Five cross-coupling products are described for the first time, whereas the beta-O-4 dehydrodimers identified from the caffeic acid and sinapic acid cross-coupling reaction are known materials that are highly abundant in plants. These reactivity trends lead to testable hypotheses regarding the molecular architecture of intractable suberin protective plant materials, complementing prior analysis of monomeric constituents by GC-MS and polymer functional group identification from solid-state NMR, respectively. PMID:16524605

  14. An Expeditious Synthesis of Sialic Acid Derivatives by Copper(I)-Catalyzed Stereodivergent Propargylation of Unprotected Aldoses

    PubMed Central

    2016-01-01

    We developed a copper(I)-catalyzed stereodivergent anomeric propargylation of unprotected aldoses as a facile synthetic pathway to a broad variety of sialic acid derivatives. The soft allenylcopper(I) species, catalytically generated from stable allenylboronic acid pinacolate (2), is unusually inert to protonolysis by the multiple hydroxy groups of the substrates and thereby functions as a carbon nucleophile. The key additive B(OMe)3 facilitated ring-opening of the nonelectrophilic cyclic hemiacetal forms of aldoses to the reactive aldehyde forms. The chirality of the catalyst, and not the internal stereogenic centers of substrates, predominantly controlled the stereochemistry of the propargylation step; i.e., the diastereoselectivity was switched simply by changing the catalyst chirality. This is the first nonenzyme catalyst-controlled stereodivergent C–C bond elongation at the anomeric center of unprotected aldoses, which contain multiple protic functional groups and stereogenic centers. The propargylation products can be expeditiously transformed into naturally occurring and synthetic sialic acid derivatives in a simple three-step sequence. This synthetic method, which requires no protecting groups, can be performed on a gram-scale and thus offers general and practical access to various sialic acid derivatives from unprotected aldoses. PMID:27163022

  15. Influence of fatty acid on lipase-catalyzed synthesis of ascorbyl esters and their free radical scavenging capacity.

    PubMed

    Stojanović, Marija; Carević, Milica; Mihailović, Mladen; Veličković, Dušan; Dimitrijević, Aleksandra; Milosavić, Nenad; Bezbradica, Dejan

    2015-01-01

    Fatty acid (FA) ascorbyl esters are recently emerging food, cosmetic, and pharmaceutical additives, which can be prepared in an eco-friendly way by using lipases as catalysts. Because they are amphiphilic molecules, which possess high free radical scavenging capacity, they can be applied as liposoluble antioxidants as well as emulsifiers and biosurfactants. In this study, the influence of a wide range of acyl donors on ester yield in lipase-catalyzed synthesis and ester antioxidant activity was examined. Among saturated acyl donors, higher yields and antioxidant activities of esters were achieved when short-chain FAs were used. Oleic acid gave the highest yield overall and its ester exhibited a high antioxidant activity. Optimization of experimental factors showed that the highest conversion (60.5%) in acetone was achieved with 5 g L(-1) of lipase, 50 mM of vitamin C, 10-fold molar excess of oleic acid, and 0.7 mL L(-1) of initial water. Obtained results showed that even short- and medium-chain ascorbyl esters could be synthesized with high yields and retained (or even exceeded) free radical scavenging capacity of l-ascorbic acid, indicating prospects of broadening their application in emulsions and liposomes. PMID:25224149

  16. An Expeditious Synthesis of Sialic Acid Derivatives by Copper(I)-Catalyzed Stereodivergent Propargylation of Unprotected Aldoses.

    PubMed

    Wei, Xiao-Feng; Shimizu, Yohei; Kanai, Motomu

    2016-01-27

    We developed a copper(I)-catalyzed stereodivergent anomeric propargylation of unprotected aldoses as a facile synthetic pathway to a broad variety of sialic acid derivatives. The soft allenylcopper(I) species, catalytically generated from stable allenylboronic acid pinacolate (2), is unusually inert to protonolysis by the multiple hydroxy groups of the substrates and thereby functions as a carbon nucleophile. The key additive B(OMe)3 facilitated ring-opening of the nonelectrophilic cyclic hemiacetal forms of aldoses to the reactive aldehyde forms. The chirality of the catalyst, and not the internal stereogenic centers of substrates, predominantly controlled the stereochemistry of the propargylation step; i.e., the diastereoselectivity was switched simply by changing the catalyst chirality. This is the first nonenzyme catalyst-controlled stereodivergent C-C bond elongation at the anomeric center of unprotected aldoses, which contain multiple protic functional groups and stereogenic centers. The propargylation products can be expeditiously transformed into naturally occurring and synthetic sialic acid derivatives in a simple three-step sequence. This synthetic method, which requires no protecting groups, can be performed on a gram-scale and thus offers general and practical access to various sialic acid derivatives from unprotected aldoses. PMID:27163022

  17. The Acid Hydrolysis Mechanism of Acetals Catalyzed by a Supramolecular Assembly in Basic Solution

    SciTech Connect

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-09-24

    A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate limiting step of the reaction revealed a negative entropy of activation ({Delta}S{double_dagger} = -9 cal mol{sup -1}K{sup -1}) and an inverse solvent isotope effect (k(H{sub 2}O)/k(D{sub 2}O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate diethoxymethane.

  18. Acetylation of bacterial cellulose catalyzed by citric acid: Use of reaction conditions for tailoring the esterification extent.

    PubMed

    Ávila Ramírez, Jhon Alejandro; Gómez Hoyos, Catalina; Arroyo, Silvana; Cerrutti, Patricia; Foresti, María Laura

    2016-11-20

    Bacterial cellulose (BC) nanoribbons were partially acetylated by a simple direct solvent-free route catalyzed by citric acid. The assay of reaction conditions within chosen intervals (i.e. esterification time (0.5-7h), catalyst content (0.08-1.01mmol/mmol AGU), and temperature (90-140°C)), illustrated the flexibility of the methodology proposed, with reaction variables which can be conveniently manipulated to acetylate BC to the required degree of substitution (DS) within the 0.20-0.73 interval. Within this DS interval, characterization results indicated a surface-only process in which acetylated bacterial cellulose with tunable DS, preserved fibrous structure and increased hydrophobicity could be easily obtained. The feasibility of reusing the catalyst/excess acylant in view of potential scale-up was also illustrated. PMID:27561540

  19. Depolymerization of crystalline cellulose catalyzed by acidic ionic liquids grafted onto sponge-like nanoporous polymers.

    PubMed

    Liu, Fujian; Kamat, Ranjan K; Noshadi, Iman; Peck, Daniel; Parnas, Richard S; Zheng, Anmin; Qi, Chenze; Lin, Yao

    2013-10-01

    The acidic ionic liquid (IL) functionalized polymer (PDVB-SO3H-[C3vim][SO3CF3]) possesses abundant nanoporous structures, strong acid strength and unique capability for deconstruction of crystalline cellulose into sugars in ILs. The polymer shows much improved catalytic activities in comparison with mineral acids, homogeneous acidic ionic liquids and the acidic resins such as Amberlyst 15. The enhanced catalytic activity found in the polymer is attributed to synergistic effects between the strongly acidic group and the ILs grafted onto the polymer, which by itself is capable of breaking down the crystalline structures of cellulose. This study may help develop cost-effective and green routes for conversion of biomass to fuels. PMID:23958800

  20. Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution.

    PubMed

    Cui, Lei; Chen, He; Liu, Chao; Li, Chaozhong

    2016-05-01

    Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 as the catalyst, the reactions of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in satisfactory yields under mild conditions. This site-specific allylation method is applicable to all primary, secondary, and tertiary alkyl acids and exhibits wide functional group compatibility. PMID:27065060

  1. Palladium-catalyzed cross-coupling of sterically demanding boronic acids with α-bromocarbonyl compounds.

    PubMed

    Zimmermann, Bettina; Dzik, Wojciech I; Himmler, Thomas; Goossen, Lukas J

    2011-10-01

    A catalyst system generated in situ from Pd(dba)(2) and tri(o-tolyl)phosphine mediates the coupling of arylboronic acids with alkyl α-bromoacetates under formation of arylacetic acid esters at unprecedented low loadings. The new protocol, which involves potassium fluoride as the base and catalytic amounts of benzyltriethylammonium bromide as a phase transfer catalyst, is uniquely effective for the synthesis of sterically demanding arylacetic acid derivatives. PMID:21863787

  2. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    SciTech Connect

    Zhang, Jinyu; Zhou, Guowei Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} and a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.

  3. Acceleration of Enantioselective Cycloadditions Catalyzed by Second-Generation Chiral Oxazaborolidinium Triflimidates by Biscoordinating Lewis Acids.

    PubMed

    Thirupathi, Barla; Breitler, Simon; Mahender Reddy, Karla; Corey, E J

    2016-08-31

    The activation of second-generation fluorinated oxazaborolidines by the strong acid triflimide (Tf2NH) in CH2Cl2 solution leads to highly active chiral Lewis acids that are very effective catalysts for (4 + 2) cycloaddition. We report herein that this catalytic activity can be further enhanced by the use of Tf2NH in combination with the biscoordinating Lewis acid TiCl4 or SnCl4 as a coactivator. The effective increase in acidity of an exceedingly strong protic acid is greater for biscoordinating TiCl4 and SnCl4 than for monocoordinating salts, even the strong Lewis acids AlBr3 and BBr3 in CH2Cl2 or CH2Cl2/toluene. The increase in the effective acidity of Tf2NH can be understood in terms of a stabilized cyclic anionic complex of Tf2N(-) and TiCl4, which implies a broader utility than that described here. The utility of Tf2NH-TiCl4 activation of fluorinated oxazaborolidines is documented by examples including the first enantioselective (4 + 2) cycloaddition to α,β-unsaturated acid chlorides. PMID:27530433

  4. Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Zhenfa; Docherty, Kenneth S.; Zhang, Haofei; Budisulistiorini, Sri Hapsari; Rubitschun, Caitlin L.; Shaw, Stephanie L.; Knipping, Eladio M.; Edgerton, Eric S.; Kleindienst, Tadeusz E.; Gold, Avram; Surratt, Jason D.

    2011-01-01

    Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NOx conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (> 99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7–6.4% for β-IEPOX and 3.4–5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C5-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NOx, isoprene-dominated regions influenced by the presence of acidic aerosols. PMID:22103348

  5. C8-Selective Acylation of Quinoline N-Oxides with α-Oxocarboxylic Acids via Palladium-Catalyzed Regioselective C-H Bond Activation.

    PubMed

    Chen, Xiaopei; Cui, Xiuling; Wu, Yangjie

    2016-08-01

    A facile and efficient protocol for palladium-catalyzed C8-selective acylation of quinoline N-oxides with α-oxocarboxylic acids has been developed. In this approach, N-oxide was utilized as a stepping stone for the remote C-H functionalization. The reactions proceeded efficiently under mild reaction conditions with excellent regioselectivity and broad functional group tolerance. PMID:27441527

  6. Formation of C(sp(3))-C(sp(3)) Bonds by Palladium Catalyzed Cross-Coupling of α-Diazoketones and Allylboronic Acids.

    PubMed

    Belhomme, Marie-Charlotte; Wang, Dong; Szabó, Kálmán J

    2016-05-20

    Palladium catalyzed cross-coupling of allylboronic acids with α-diazoketones was studied. The reaction selectively affords the linear allylic product. The reaction proceeds with formation of a new C(sp(3))-C(sp(3)) bond. The reaction was performed without an external oxidant, likely without the Pd-catalyst undergoing redox reactions. PMID:27166509

  7. A Convenient Palladium-Catalyzed Carbonylative Synthesis of Benzofuran-2(3 H)-ones with Formic Acid as the CO Source.

    PubMed

    Qi, Xinxin; Li, Hao-Peng; Wu, Xiao-Feng

    2016-09-01

    A general and convenient palladium-catalyzed carbonylation procedure for the synthesis of benzofuran-2(3 H)-ones from phenols and aldehydes has been developed. With formic acid as the CO source, a variety of benzofuran-2(3 H)-ones were obtained in moderate to good yields. PMID:27539230

  8. 3-Component synthesis of α-substituted sulfonamides via Brønsted acid-catalyzed C(sp(3))-H bond functionalization of 2-alkylazaarenes.

    PubMed

    Beisel, T; Kirchner, J; Kaehler, T; Knauer, J; Soltani, Y; Manolikakes, G

    2016-06-28

    A Brønsted acid-catalyzed addition of 2-alkylazaarenes to in situ generated N-sulfonylimines through selective C(sp(3))-H bond functionalization has been developed. This protocol provides an atom- and step-economic approach to α-substituted sulfonamides. PMID:26868020

  9. Biodiesel production from high acid value waste frying oil catalyzed by superacid heteropolyacid.

    PubMed

    Cao, Fenghua; Chen, Yang; Zhai, Fengying; Li, Jing; Wang, Jianghua; Wang, Xiaohong; Wang, Shengtian; Zhu, Weimin

    2008-09-01

    Transesterification of waste cooking oil with high acid value and high water contents using heteropolyacid H3PW12O40 x 6H2O (PW12) as catalyst was investigated. The hexahydrate form of PW(12) was found to be the most promising catalyst which exhibited highest ester yield 87% for transesterification of waste cooking oil and ester yield 97% for esterification of long-chain palmitic acid, respectively. The PW12 acid catalyst shows higher activity under the optimized reaction conditions compared with conventional homogeneous catalyst sulfuric acid, and can easily be separated from the products by distillation of the excess methanol and can be reused more times. The most important feature of this catalyst is that the catalytic activity is not affected by the content of free fatty acids (FFAs) and the content of water in the waste cooking oil and the transesterification can occur at a lower temperature (65 degrees C), a lower methanol oil ratio (70:1) and be finished within a shorter time. The results illustrate that PW12 acid is an excellent water-tolerant and environmentally benign acid catalyst for production of biodiesel from waste cooking oil. PMID:18646228

  10. Preparation of biodiesel from rice bran fatty acids catalyzed by heterogeneous cesium-exchanged 12-tungstophosphoric acids.

    PubMed

    Srilatha, K; Sree, Rekha; Prabhavathi Devi, B L A; Sai Prasad, P S; Prasad, R B N; Lingaiah, N

    2012-07-01

    Biodiesel synthesis from rice bran fatty acids (RBFA) was carried out using cesium exchanged 12-tungstophosphoric acid (TPA) catalysts. The physico-chemical properties of the catalysts were derived from X-ray diffraction (XRD), Fourier transform infrared (FTIR), temperature programmed desorption (TPD) of NH(3) and scanning electron microscopy (SEM). The characterization techniques revealed that the Keggin structure of TPA remained intact as Cs replaced protons. The partial exchange of Cs for protons resulted in an increase in acidity and the catalysts with one Cs(+) (Cs(1)H(2)PW(12)O(40)) showed highest acidity. Under optimized conditions about 92% conversion of RBFA was obtained. The catalyst was reused for five times and retained of its original activity. Pseudo-first order model was applied to correlate the experimental kinetic data. Modified tungstophosphoric acids are efficient solid acid catalysts for the synthesis of biodiesel from the oils containing high FFA. PMID:22609655

  11. Mycolic acid biosynthesis and enzymic characterization of the beta-ketoacyl-ACP synthase A-condensing enzyme from Mycobacterium tuberculosis.

    PubMed

    Kremer, Laurent; Dover, Lynn G; Carrère, Séverine; Nampoothiri, K Madhavan; Lesjean, Sarah; Brown, Alistair K; Brennan, Patrick J; Minnikin, David E; Locht, Camille; Besra, Gurdyal S

    2002-06-01

    Mycolic acids consist of long-chain alpha-alkyl-beta-hydroxy fatty acids that are produced by successive rounds of elongation catalysed by a type II fatty acid synthase (FAS-II). A key feature in the elongation process is the condensation of a two-carbon unit from malonyl-acyl-carrier protein (ACP) to a growing acyl-ACP chain catalysed by a beta-ketoacyl-ACP synthase (Kas). In the present study, we provide evidence that kasA from Mycobacterium tuberculosis encodes an enzyme that elongates in vivo the meromycolate chain, in both Mycobacterium smegmatis and Mycobacterium chelonae. We demonstrate that KasA belongs to the FAS-II system, which utilizes primarily palmitoyl-ACP rather than short-chain acyl-ACP primers. Furthermore, in an in vitro condensing assay using purified recombinant KasA, palmitoyl-AcpM and malonyl-AcpM, KasA was found to express Kas activity. Also, mutated KasA proteins, with mutation of Cys(171), His(311), Lys(340) and His(345) to Ala abrogated the condensation activity of KasA in vitro completely. Finally, purified KasA was highly sensitive to cerulenin, a well-known inhibitor of Kas, which may lead to the development of novel anti-mycobacterial drugs targeting KasA. PMID:12023885

  12. Stereospecificity of reactions catalyzed by bacterial D-amino acid transaminase.

    PubMed

    Martínez del Pozo, A; Merola, M; Ueno, H; Manning, J M; Tanizawa, K; Nishimura, K; Soda, K; Ringe, D

    1989-10-25

    The spectral shift from 420 to 338 nm when pure bacterial D-amino acid transaminase binds D-amino acid substrates is also exhibited in part by high concentrations of L-amino acids (L-alanine and L-glutamate) but not by simple dicarboxylic acids or monoamines. Slow processing of L-alanine to D-alanine was observed both by coupled enzymatic assays using D-amino acid oxidase and by high pressure liquid chromatography analysis employing an optically active chromophore (Marfey's reagent). When the acceptor for L-alanine was alpha-ketoglutarate, D-glutamate was also formed. This minor activity of the transaminase involved both homologous (L-alanine and D-alanine) and heterologous (L-alanine and D-glutamate) substrate pairs and was a function of the nature of the keto acid acceptor. In the presence of alpha-ketoisovalerate, DL-alanine was almost completely processed to D-valine; within the limits of the assay no L-valine was detected. With alpha-ketoisocaproate, 90% of the DL-alanine was converted to D-leucine. In the mechanism of this transaminase reaction, there may be more stereoselective constraints for the protonation of the quinonoid intermediate during the second half-reaction of the transamination reaction, i.e. the donation of the amino group from the pyridoxamine 5'-phosphate coenzyme to a second keto acid acceptor, than during removal of the alpha proton in the initial steps of the reaction pathway. Thus, with this D-amino acid transaminase, the discrete steps of transamination ensure fidelity of the stereospecificity of reaction pathway. PMID:2808352

  13. Nickel-Catalyzed Hiyama-type Decarboxylative Coupling of Propiolic Acids and Organosilanes.

    PubMed

    Edwin Raja, Gabriel Charles; Irudayanathan, Francis Mariaraj; Kim, Han-Sung; Kim, Jimin; Lee, Sunwoo

    2016-06-17

    A Ni catalytic system was developed for the decarboxylative coupling reaction of alkynyl carboxylic acids with organosilanes. Ni(acac)2 and 1,10-phenanthroline showed the best result in the presence of CsF and CuF2 at 120 °C. This system tolerated the presence of alkyl, alkoxy, halogen, nitro, cyano, ketone, and ester functional groups. Moreover, the reaction with but-2-ynedioic acid and organosilane afforded the corresponding symmetrical diarylalkynes. PMID:27188502

  14. Correction: Acid-catalyzed carboxylic acid esterification and ester hydrolysis mechanism: acylium ion as a sharing active intermediate via a spontaneous trimolecular reaction based on density functional theory calculation and supported by electrospray ionization-mass spectrometry.

    PubMed

    Shi, Hongchang; Wang, Yilei; Hua, Ruimao

    2015-12-28

    Correction for 'Acid-catalyzed carboxylic acid esterification and ester hydrolysis mechanism: acylium ion as a sharing active intermediate via a spontaneous trimolecular reaction based on density functional theory calculation and supported by electrospray ionization-mass spectrometry' by Hongchang Shi et al., Phys. Chem. Chem. Phys., 2015, DOI: 10.1039/c5cp02914g. PMID:26583937

  15. Regiospecific O-methylation of naphthoic acids catalyzed by NcsB1, an O-methyltransferase involved in the biosynthesis of the enediyne antitumor antibiotic neocarzinostatin.

    PubMed

    Luo, Yinggang; Lin, Shuangjun; Zhang, Jian; Cooke, Heather A; Bruner, Steven D; Shen, Ben

    2008-05-23

    Neocarzinostatin, a clinical anticancer drug, is the archetypal member of the chromoprotein family of enediyne antitumor antibiotics that are composed of a nonprotein chromophore and an apoprotein. The neocarzinostatin chromophore consists of a nine-membered enediyne core, a deoxyaminosugar, and a naphthoic acid moiety. We have previously cloned and sequenced the neocarzinostatin biosynthetic gene cluster and proposed that the biosynthesis of the naphthoic acid moiety and its incorporation into the neocarzinostatin chromophore are catalyzed by five enzymes NcsB, NcsB1, NcsB2, NcsB3, and NcsB4. Here we report the biochemical characterization of NcsB1, unveiling that: (i) NcsB1 is an S-adenosyl-L-methionine-dependent O-methyltransferase; (ii) NcsB1 catalyzes regiospecific methylation at the 7-hydroxy group of its native substrate, 2,7-dihydroxy-5-methyl-1-naphthoic acid; (iii) NcsB1 also recognizes other dihydroxynaphthoic acids as substrates and catalyzes regiospecific O-methylation; and (iv) the carboxylate and its ortho-hydroxy groups of the substrate appear to be crucial for NcsB1 substrate recognition and binding, and O-methylation takes place only at the free hydroxy group of these dihydroxynaphthoic acids. These findings establish that NcsB1 catalyzes the third step in the biosynthesis of the naphthoic acid moiety of the neocarzinostatin chromophore and further support the early proposal for the biosynthesis of the naphthoic acid and its incorporation into the neocarzinostatin chromophore with free naphthoic acids serving as intermediates. NcsB1 represents another opportunity that can now be exploited to produce novel neocarzinostatin analogs by engineering neocarzinostatin biosynthesis or applying directed biosynthesis strategies. PMID:18387946

  16. How Acid-Catalyzed Decarboxylation of 2,4-Dimethoxybenzoic Acid Avoids Formation of Protonated CO2.

    PubMed

    Howe, Graeme W; Vandersteen, Adelle A; Kluger, Ronald

    2016-06-22

    The decarboxylation of 2,4-dimethoxybenzoic acid (1) is accelerated in acidic solutions. The rate of reaction depends upon solution acidity in a manner that is consistent with the formation of the conjugate acid of 1 (RCO2H2(+)), with its higher energy ring-protonated tautomer allowing the requisite C-C bond cleavage. However, this would produce the conjugate acid of CO2, a species that would be too energetic to form. Considerations of mechanisms that fit the observed rate law were supplemented with DFT calculations. Those results indicate that the lowest energy pathway from the ring-protonated reactive intermediate involves early proton transfer from the carboxyl group to water along with C-C bond cleavage, producing 1,3-dimethoxybenzene and CO2 directly. PMID:27241436

  17. Novel Dextranase Catalyzing Cycloisomaltooligosaccharide Formation and Identification of Catalytic Amino Acids and Their Functions Using Chemical Rescue Approach*

    PubMed Central

    Kim, Young-Min; Kiso, Yoshiaki; Muraki, Tomoe; Kang, Min-Sun; Nakai, Hiroyuki; Saburi, Wataru; Lang, Weeranuch; Kang, Hee-Kwon; Okuyama, Masayuki; Mori, Haruhide; Suzuki, Ryuichiro; Funane, Kazumi; Suzuki, Nobuhiro; Momma, Mitsuru; Fujimoto, Zui; Oguma, Tetsuya; Kobayashi, Mikihiko; Kim, Doman; Kimura, Atsuo

    2012-01-01

    A novel endodextranase from Paenibacillus sp. (Paenibacillus sp. dextranase; PsDex) was found to mainly produce isomaltotetraose and small amounts of cycloisomaltooligosaccharides (CIs) with a degree of polymerization of 7–14 from dextran. The 1,696-amino acid sequence belonging to the glycosyl hydrolase family 66 (GH-66) has a long insertion (632 residues; Thr451–Val1082), a portion of which shares identity (35% at Ala39–Ser1304 of PsDex) with Pro32–Ala755 of CI glucanotransferase (CITase), a GH-66 enzyme that catalyzes the formation of CIs from dextran. This homologous sequence (Val837–Met932 for PsDex and Tyr404–Tyr492 for CITase), similar to carbohydrate-binding module 35, was not found in other endodextranases (Dexs) devoid of CITase activity. These results support the classification of GH-66 enzymes into three types: (i) Dex showing only dextranolytic activity, (ii) Dex catalyzing hydrolysis with low cyclization activity, and (iii) CITase showing CI-forming activity with low dextranolytic activity. The fact that a C-terminal truncated enzyme (having Ala39–Ser1304) has 50% wild-type PsDex activity indicates that the C-terminal 392 residues are not involved in hydrolysis. GH-66 enzymes possess four conserved acidic residues (Asp189, Asp340, Glu412, and Asp1254 of PsDex) of catalytic candidates. Their amide mutants decreased activity (11,500 to 140,000 times), and D1254N had 36% activity. A chemical rescue approach was applied to D189A, D340G, and E412Q using α-isomaltotetraosyl fluoride with NaN3. D340G or E412Q formed a β- or α-isomaltotetraosyl azide, respectively, strongly indicating Asp340 and Glu412 as a nucleophile and acid/base catalyst, respectively. Interestingly, D189A synthesized small sized dextran from α-isomaltotetraosyl fluoride in the presence of NaN3. PMID:22461618

  18. An experimental and computational assessment of acid-catalyzed azide-nitrile cycloadditions.

    PubMed

    Cantillo, David; Gutmann, Bernhard; Kappe, C Oliver

    2012-12-01

    The mechanism of the azide-nitrile cycloaddition mediated by different Brønsted and Lewis acids has been addressed through DFT calculations. In all cases activation of the nitrile substrate by the Brønsted or Lewis acid catalyst was found to be responsible for the rate enhancement. According to DFT calculations the cycloaddition proceeds in a stepwise fashion involving the initial formation of an open-chain imidoyl azide intermediate. Kinetic experiments performed using N-methyl-2-pyrrolidone as solvent and sodium azide as azide source demonstrate that all evaluated Brønsted acids have the same efficiency toward cycloaddition with benzonitrile, suggesting that hydrazoic acid is the actual dominant catalytic species in these tetrazole syntheses. Lewis acids such as Zn or Al salts perform in a similar manner, activating the nitrile moiety and leading to an open-chain intermediate that subsequently cyclizes to produce the tetrazole nucleus. The most efficient catalyst evaluated was 5-azido-1-methyl-3,4-dihydro-2H-pyrrolium azide, which can readily be generated in situ from aluminum chloride, sodium azide in N-methyl-2-pyrrolidone. The efficiency of this catalyst has been examined by preparation of a series of 5-substituted-1H-tetrazoles. The desired tetrazole structures were obtained in high yields within 3-10 min employing controlled microwave heating. PMID:23126486

  19. Acid-catalyzed liquefaction of bagasse in the presence of polyhydric alcohol.

    PubMed

    Zhang, Hairong; Luo, Jun; Li, Yingying; Guo, Haijun; Xiong, Lian; Chen, Xinde

    2013-08-01

    Bagasse was subjected to a liquefaction process with polyethylene glycol/glycerol using sulfuric acid as catalyst. The effects of various liquefaction conditions, such as reaction time, liquefaction temperature, catalyst content, and liquid ratio (liquefaction solvents/bagasse), on the liquefied residue (LR) content and hydroxyl and acid numbers of liquefied products were investigated. The preferred liquefaction condition of bagasse was determined through orthogonal experiments. The results showed that the catalyst content and reaction time have a greater influence than liquid ratio and liquefaction temperature on the percentage of LR. The hydroxyl and acid numbers of the liquefied products were influenced by many factors, including liquefaction temperature, reaction time, acid content, and liquid ratio. The hydroxyl number of liquefied products decreased as the liquefaction reaction progressed, but the acid number of liquefied products increased. Based on the obtained data, the kinetics for liquefaction was modeled using the first-order reaction rate law and the apparent activation energy for the liquefaction of bagasse was estimated to be 38.30 kJ mol(-1). PMID:23740473

  20. Regulation of fatty acid sup 18 O exchange catalyzed by pancreatic carboxylester lipase. 1. Mechanism and kinetic properties

    SciTech Connect

    Muderhwa, J.M.; Schmid, P.C.; Brockman, H.L. )

    1992-01-14

    The exchange of {sup 18}O between H{sub 2}O and long-chain free fatty acids is catalyzed by pancreatic carboxylester lipase. For palmitic, oleic, and arachidonic acid in aqueous suspension and for 13,16-cis,cis-docosadienoic acid (DA) in monomolecular films, carboxyl oxygens were completely exchanged with water oxygens of the bulk aqueous phase. With enzyme at either substrate or catalytic concentrations in the argon-buffer interface, the exchange of DA oxygens obeyed a random sequential mechanism, i.e., {sup 18}O, {sup 18}O-DA {rightleftharpoons} {sup 18}O, {sup 16}O-DA {rightleftharpoons} {sup 16}O, {sup 16}O-DA. This indicates that the dissociation of the enzyme{center dot}DA complex is much faster than the rate-limiting step in the overall exchange reaction. Kinetic analysis of {sup 18}O exchange showed a first-order dependence on surface enzyme and DA concentrations, i.e., the reaction was limited by the acylation rate. The values of k{sub cat}/K{sub m}, 0.118 cm{sup 2} pmol{sup {minus}1} s{sup {minus}1}, for the exchange reaction was comparable to that for methyl oleate hydrolysis and 5-fold higher than that for cholesteryl oleate hydrolysis in monolayers. Thus, fatty acids are good substrates' for carboxylester lipase. With substrate levels of carboxylester lipase in the interfacial phase, the acylation rate constant k{sub cat}/K{sub m} was 200-fold lower than that obtained with catalytic levels of enzyme. This suggests a possible restriction of substrate diffusion in the protein-covered substrate monolayer.

  1. Synthesis of ascorbyl oleate by transesterification of olive oil with ascorbic acid in polar organic media catalyzed by immobilized lipases.

    PubMed

    Moreno-Perez, Sonia; Filice, Marco; Guisan, Jose M; Fernandez-Lorente, Gloria

    2013-09-01

    The reaction of transesterification between oils (e.g., olive oil) and ascorbic acid in polar anhydrous media (e.g., tert-amyl alcohol) catalyzed by immobilized lipases for the preparation of natural liposoluble antioxidants (e.g., ascorbyl oleate) was studied. Three commercial lipases were tested: Candida antarctica B lipase (CALB), Thermomyces lanuginosus lipase (TLL) and Rhizomucor miehei lipase (RML). Each lipase was immobilized by three different protocols: hydrophobic adsorption, anionic exchange and multipoint covalent attachment. The highest synthetic yields were obtained with CALB adsorbed on hydrophobic supports (e.g., the commercial derivative Novozym 435). The rates and yields of the synthesis of ascorbyl oleate were higher when using the solvent dried with molecular sieves, at high temperatures (e.g. 45°C) and with a small excess of oil (2 mol of oil per mol of ascorbic acid). The coating of CALB derivatives with polyethyleneimine (PEI) improved its catalytic behavior and allowed the achievement of yields of up to 80% of ascorbyl oleate in less than 24h. CALB adsorbed on a hydrophobic support and coated with PEI was 2-fold more stable than a non-coated derivative and one hundred-fold more stable than the best TLL derivative. The best CALB derivative exhibited a half-life of 3 days at 75°C in fully anhydrous media, and this derivative maintained full activity after 28 days at 45°C in dried tert-amyl alcohol. PMID:23891831

  2. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    SciTech Connect

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  3. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand. PMID:25196789

  4. Inhibitory activity of thermal copolymers of amino acids for the metal-catalyzed hydrolysis of an RNA dinucleotide

    NASA Astrophysics Data System (ADS)

    Kawamura, Kunio; Nagahama, Minoru; Yao, Toshio

    2006-01-01

    It is well known that the hydrolysis of RNA is substantially catalyzed by several metal ions. Although this fact poses a problem for the RNA world hypothesis, there may have been unknown pathways for the protection of RNA molecules against the hydrolytic degradation under the primitive earth conditions. Thus, we have investigated whether or not thermal copolymers of amino acids (TCAA) inhibit the catalytic activity of metal ions for the RNA hydrolyses; TCAA is a suitable model material for prebiotic protein-like molecules since TCAA involving peptide bonding is readily prepared by heating amino acid mixtures under prebiotic conditions. The activities of metal ions that Fe(III) and Co(II) enhance somewhat the 3',5'-cytidylylguanosine (CpG) hydrolysis and Ce(III) and Eu(III) accelerate greatly the CpG hydrolysis were notably reduced by TCAA. This fact indicates that protein-like molecules would have played important roles for the accumulation of RNA under the primitive earth conditions.

  5. Lipase catalyzed synthesis of neutral glycerides rich in micronutrients from rice bran oil fatty acid distillate.

    PubMed

    Nandi, Sumit; Gangopadhyay, Sarbani; Ghosh, Santinath

    2008-01-01

    Neutral glycerides with micronutrients like sterols, tocopherols and squalene may be prepared from cheap raw material like rice bran oil fatty acid distillate (RBO FAD). RBO FAD is an important byproduct of vegetable oil refining industries in the physical refining process. Glycerides like triacylglycerols (TAG), diacylglycerols (DAG) and monoacylglycerols (MAG) containing significant amounts of unsaponifiable matter like sterols, tocopherols and hydrocarbons (mainly squalene) may certainly be considered as novel functional food ingredients. Fatty acids present in RBO FAD were esterified with glycerol of varying amount (1:0.33, 1:0.5, 1:1 and 1:1.5 of FAD : glycerol ratio) for 8 h using non-specific enzyme NS 40013 (Candida antartica). After esterification the product mixture containing mono, di- and triglycerides was purified by molecular distillation to remove excess free fatty acids and also other volatile undesirable components. The purified product containing sterols, tocopherols and squalene can be utilized in various food formulations. PMID:18838832

  6. Chiral Phosphoric Acid Catalyzed Asymmetric Ugi Reaction by Dynamic Kinetic Resolution of the Primary Multicomponent Adduct.

    PubMed

    Zhang, Yun; Ao, Yu-Fei; Huang, Zhi-Tang; Wang, De-Xian; Wang, Mei-Xiang; Zhu, Jieping

    2016-04-18

    Reaction of isonitriles with 3-(arylamino)isobenzofuran-1(3H)-ones in the presence of a catalytic amount of an octahydro (R)-binol-derived chiral phosphoric acid afforded 3-oxo-2-arylisoindoline-1-carboxamides in high yields with good to high enantioselectivities. An enantioselective Ugi four-center three-component reaction of 2-formylbenzoic acids, anilines, and isonitriles was subsequently developed for the synthesis of the same heterocycle. Mechanistic studies indicate that the enantioselectivity results from the dynamic kinetic resolution of the primary Ugi adduct, rather than from the C-C bond-forming process. The resulting heterocycle products are of significant medicinal importance. PMID:26997306

  7. Kinetics of the acid-catalyzed hydration of allene and propyne

    SciTech Connect

    Cramer, P.; Tidwell, T.T.

    1981-06-19

    The kinetics of the conversion of allene and propyne to acetone in aqueous sulfuric acid have been measured. The solvent isotope effects k/sub H/sup +//k/sub D/sup +// and the dependence of the rates on acidity are consistent with the Ad/sub E/2 mechanism of rate-limiting protonation at the terminal carbons leading to the intermediate 2-propenyl cation CH/sub 3/C/sup +/H=CH/sub 2/ in each case, followed by hydration to the enol and isomerization to acetone. This route is strongly favored by published theoretical studies. (2 tables)

  8. Chiral Pyridoxal-Catalyzed Asymmetric Biomimetic Transamination of α-Keto Acids.

    PubMed

    Shi, Limin; Tao, Chuangan; Yang, Qin; Liu, Yong Ethan; Chen, Jing; Chen, Jianfeng; Tian, Jiaxin; Liu, Feng; Li, Bo; Du, Yongling; Zhao, Baoguo

    2015-12-01

    A series of chiral pyridoxals 8 and 9 have been developed from commercially available pyridoxine and (S)-α,α-diarylprolinols. The pyridoxals exhibited good catalytic activity in an asymmetric transamination of α-keto acids with 2,2-diphenylglycine (7f) as the amine source to give various α-amino acids in 29-85% yields with 53-80% ee's. The current asymmetric transamination has successfully mimicked a complete biological transamination process characterized by two half-transaminations, a small chiral pyridoxal molecule acting as the catalyst, and enantioselective control. PMID:26580893

  9. Hydrolysis of ketene catalyzed by formic acid: modification of reaction mechanism, energetics, and kinetics with organic acid catalysis.

    PubMed

    Louie, Matthew K; Francisco, Joseph S; Verdicchio, Marco; Klippenstein, Stephen J; Sinha, Amitabha

    2015-05-14

    The hydrolysis of ketene (H2C═C═O) to form acetic acid involving two water molecules and also separately in the presence of one to two water molecules and formic acid (FA) was investigated. Our results show that, while the currently accepted indirect mechanism, involving addition of water across the carbonyl C═O bond of ketene to form an ene-diol followed by tautomerization of the ene-diol to form acetic acid, is the preferred pathway when water alone is present, with formic acid as catalyst, addition of water across the ketene C═C double bond to directly produce acetic acid becomes the kinetically favored pathway for temperatures below 400 K. We find not only that the overall barrier for ketene hydrolysis involving one water molecule and formic acid (H2C2O + H2O + FA) is significantly lower than that involving two water molecules (H2C2O + 2H2O) but also that FA is able to reduce the barrier height for the direct path, involving addition of water across the C═C double bond, so that it is essentially identical with (6.4 kcal/mol) that for the indirect ene-diol formation path involving addition of water across the C═O bond. For the case of ketene hydrolysis involving two water molecules and formic acid (H2C2O + 2H2O + FA), the barrier for the direct addition of water across the C═C double bond is reduced even further and is 2.5 kcal/mol lower relative to the ene-diol path involving addition of water across the C═O bond. In fact, the hydrolysis barrier for the H2C2O + 2H2O + FA reaction through the direct path is sufficiently low (2.5 kcal/mol) for it to be an energetically accessible pathway for acetic acid formation under atmospheric conditions. Given the structural similarity between acetic and formic acid, our results also have potential implications for aqueous-phase chemistry. Thus, in an aqueous environment, even in the absence of formic acid, though the initial mechanism for ketene hydrolysis is expected to involve addition of water across the

  10. Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed g-Valerolactone Production

    DOE PAGESBeta

    Villa, Alberto; Schiavoni, Marco; Chan-Thaw, Carine E.; Fulvio, Pasquale F; Mayes, Richard T; Dai, Sheng; More, Karren Leslie; Veith, Gabriel M; Prati, Laura

    2015-01-01

    The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1% Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of Scontaining groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70 8C and 7 bar H2) the catalyst shows high selectivity to g-valerolactonemore » (GVL; >95%) and high stability on recycling. However, under more severe conditions (200 8C and pH2=40 bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid.« less

  11. Iron/Brønsted Acid Catalyzed Asymmetric Hydrogenation: Mechanism and Selectivity-Determining Interactions.

    PubMed

    Hopmann, Kathrin H

    2015-07-01

    Hydrogenation catalysts involving abundant base metals such as cobalt or iron are promising alternatives to precious metal systems. Despite rapid progress in this field, base metal catalysts do not yet achieve the activity and selectivity levels of their precious metal counterparts. Rational improvement of base metal complexes is facilitated by detailed knowledge about their mechanisms and selectivity-determining factors. The mechanism for asymmetric imine hydrogenation with Knölker's iron complex in the presence of chiral phosphoric acids is here investigated computationally at the DFT-D level of theory, with models of up to 160 atoms. The resting state of the system is found to be an adduct between the iron complex and the deprotonated acid. Rate-limiting H2 splitting is followed by a stepwise hydrogenation mechanism, in which the phosphoric acid acts as the proton donor. C-H⋅⋅⋅O interactions between the phosphoric acid and the substrate are involved in the stereocontrol at the final hydride transfer step. Computed enantiomeric ratios show excellent agreement with experimental values, indicating that DFT-D is able to correctly capture the selectivity-determining interactions of this system. PMID:26039958

  12. POLYSTYRENE SULFONIC ACID CATALYZED GREENER SYNTHESIS OF HYDRAZONES IN AQUEOUS MEDIUM USING MICROWAVES

    EPA Science Inventory

    An environmentally benign aqueous protocol for the synthesis of cyclic, bi-cyclic, and heterocyclic hydrazones using polystyrene sulfonic acid (PSSA) as a catalyst has been developed; the simple reaction proceeds efficiently in water in the absence of any organic solvent under mi...

  13. ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. II. ACID AND GENERAL BASE CATALYZED HYDROLYSIS

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

  14. Lewis base additives improve the zeolite ferrierite-catalyzed synthesis of isostearic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Isostearic acid (IA) is of interest for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for IA production through isomerization of fatty aci...

  15. Chiral Brønsted Acid Catalyzed Enantioselective Phosphonylation of Allylamine via Oxidative Dehydrogenation Coupling.

    PubMed

    Cheng, Ming-Xing; Ma, Ran-Song; Yang, Qiang; Yang, Shang-Dong

    2016-07-01

    A new strategy for the synthesis of chiral α-amino phosphonates by enantioselective C-H phosphonylation of allylamine with phosphite in the presence of a chiral Brønsted acid catalyst has been developed. This protocol successfully integrates direct C-H oxidation with asymmetric phosphonylation and exhibits high enantioselectivity. PMID:27331612

  16. Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed g-Valerolactone Production

    SciTech Connect

    Villa, Alberto; Schiavoni, Marco; Chan-Thaw, Carine E.; Fulvio, Pasquale F; Mayes, Richard T; Dai, Sheng; More, Karren Leslie; Veith, Gabriel M; Prati, Laura

    2015-01-01

    The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1% Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of Scontaining groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70 8C and 7 bar H2) the catalyst shows high selectivity to g-valerolactone (GVL; >95%) and high stability on recycling. However, under more severe conditions (200 8C and pH2=40 bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid.

  17. Acid-functionalized mesoporous carbon: an efficient support for ruthenium-catalyzed γ-valerolactone production.

    PubMed

    Villa, Alberto; Schiavoni, Marco; Chan-Thaw, Carine E; Fulvio, Pasquale F; Mayes, Richard T; Dai, Sheng; More, Karren L; Veith, Gabriel M; Prati, Laura

    2015-08-10

    The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1 % Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of S-containing groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70 °C and 7 bar H2 ) the catalyst shows high selectivity to γ-valerolactone (GVL; >95 %) and high stability on recycling. However, under more severe conditions (200 °C and p H 2=40 bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid. PMID:26089180

  18. Ca(OH)2-Catalyzed Condensation of Aldehydes with Methyl ketones in Dilute Aqueous Ethanol: A Comprehensive Access to α,β-Unsaturated Ketones

    NASA Astrophysics Data System (ADS)

    Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing

    2016-07-01

    Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5–10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its 1H NMR spectrum.

  19. Ca(OH)2-Catalyzed Condensation of Aldehydes with Methyl ketones in Dilute Aqueous Ethanol: A Comprehensive Access to α,β-Unsaturated Ketones

    PubMed Central

    Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing

    2016-01-01

    Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5–10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its 1H NMR spectrum. PMID:27443482

  20. Ca(OH)2-Catalyzed Condensation of Aldehydes with Methyl ketones in Dilute Aqueous Ethanol: A Comprehensive Access to α,β-Unsaturated Ketones.

    PubMed

    Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing

    2016-01-01

    Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5-10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its (1)H NMR spectrum. PMID:27443482

  1. Imidase catalyzing desymmetric imide hydrolysis forming optically active 3-substituted glutaric acid monoamides for the synthesis of gamma-aminobutyric acid (GABA) analogs.

    PubMed

    Nojiri, Masutoshi; Hibi, Makoto; Shizawa, Hiroaki; Horinouchi, Nobuyuki; Yasohara, Yoshihiko; Takahashi, Satomi; Ogawa, Jun

    2015-12-01

    The recent use of optically active 3-substituted gamma-aminobutyric acid (GABA) analogs in human therapeutics has identified a need for an efficient, stereoselective method of their synthesis. Here, bacterial strains were screened for enzymes capable of stereospecific hydrolysis of 3-substituted glutarimides to generate (R)-3-substituted glutaric acid monoamides. The bacteria Alcaligenes faecalis NBRC13111 and Burkholderia phytofirmans DSM17436 were discovered to hydrolyze 3-(4-chlorophenyl) glutarimide (CGI) to (R)-3-(4-chlorophenyl) glutaric acid monoamide (CGM) with 98.1% enantiomeric excess (e.e.) and 97.5% e.e., respectively. B. phytofirmans DSM17436 could also hydrolyze 3-isobutyl glutarimide (IBI) to produce (R)-3-isobutyl glutaric acid monoamide (IBM) with 94.9% e.e. BpIH, an imidase, was purified from B. phytofirmans DSM17436 and found to generate (R)-CGM from CGI with specific activity of 0.95 U/mg. The amino acid sequence of BpIH had a 75% sequence identity to that of allantoinase from A. faecalis NBRC13111 (AfIH). The purified recombinant BpIH and AfIH catalyzed (R)-selective hydrolysis of CGI and IBI. In addition, a preliminary investigation of the enzymatic properties of BpIH and AfIH revealed that both enzymes were stable in the range of pH 6-10, with an optimal pH of 9.0, stable at temperatures below 40 °C, and were not metalloproteins. These results indicate that the use of this class of hydrolase to generate optically active 3-substituted glutaric acid monoamide could simplify the production of specific chiral GABA analogs for drug therapeutics. PMID:26205522

  2. Direct amidation of carboxylic acids catalyzed by ortho-iodo arylboronic acids: catalyst optimization, scope, and preliminary mechanistic study supporting a peculiar halogen acceleration effect.

    PubMed

    Gernigon, Nicolas; Al-Zoubi, Raed M; Hall, Dennis G

    2012-10-01

    The importance of amides as a component of biomolecules and synthetic products motivates the development of catalytic, direct amidation methods employing free carboxylic acids and amines that circumvent the need for stoichiometric activation or coupling reagents. ortho-Iodophenylboronic acid 4a has recently been shown to catalyze direct amidation reactions at room temperature in the presence of 4A molecular sieves as dehydrating agent. Herein, the arene core of ortho-iodoarylboronic acid catalysts has been optimized with regards to the electronic effects of ring substitution. Contrary to the expectation, it was found that electron-donating substituents are preferable, in particular, an alkoxy substituent positioned para to the iodide. The optimal new catalyst, 5-methoxy-2-iodophenylboronic acid (MIBA, 4f), was demonstrated to be kinetically more active than the parent des-methoxy catalyst 4a, providing higher yields of amide products in shorter reaction times under mild conditions at ambient temperature. Catalyst 4f is recyclable and promotes the formation of amides from aliphatic carboxylic acids and amines, and from heteroaromatic carboxylic acids and other functionalized substrates containing moieties like a free phenol, indole and pyridine. Mechanistic studies demonstrated the essential role of molecular sieves in this complex amidation process. The effect of substrate stoichiometry, concentration, and measurement of the catalyst order led to a possible catalytic cycle based on the presumed formation of an acylborate intermediate. The need for an electronically enriched ortho-iodo substituent in catalyst 4f supports a recent theoretical study (Marcelli, T. Angew. Chem. Int. Ed.2010, 49, 6840-6843) with a purported role for the iodide as a hydrogen-bond acceptor in the orthoaminal transition state. PMID:23013456

  3. Kinetics of cytochrome P450 2E1-catalyzed oxidation of ethanol to acetic acid via acetaldehyde.

    PubMed

    Bell-Parikh, L C; Guengerich, F P

    1999-08-20

    The P450 2E1-catalyzed oxidation of ethanol to acetaldehyde is characterized by a kinetic deuterium isotope effect that increases K(m) with no effect on k(cat), and rate-limiting product release has been proposed to account for the lack of an isotope effect on k(cat) (Bell, L. C., and Guengerich, F. P. (1997) J. Biol. Chem. 272, 29643-29651). Acetaldehyde is also a substrate for P450 2E1 oxidation to acetic acid, and k(cat)/K(m) for this reaction is at least 1 order of magnitude greater than that for ethanol oxidation to acetaldehyde. Acetic acid accounts for 90% of the products generated from ethanol in a 10-min reaction, and the contribution of this second oxidation has been overlooked in many previous studies. The noncompetitive intermolecular kinetic hydrogen isotope effects on acetaldehyde oxidation to acetic acid ((H)(k(cat)/K(m))/(D)(k(cat)/K(m)) = 4.5, and (D)k(cat) = 1.5) are comparable with the isotope effects typically observed for ethanol oxidation to acetaldehyde, and k(cat) is similar for both reactions, suggesting a possible common catalytic mechanism. Rapid quench kinetic experiments indicate that acetic acid is formed rapidly from added acetaldehyde (approximately 450 min(-1)) with burst kinetics. Pulse-chase experiments reveal that, at a subsaturating concentration of ethanol, approximately 90% of the acetaldehyde intermediate is directly converted to acetic acid without dissociation from the enzyme active site. Competition experiments suggest that P450 2E1 binds acetic acid and acetaldehyde with relatively high K(d) values, which preclude simple tight binding as an explanation for rate-limiting product release. The existence of a rate-determining step between product formation and release is postulated. Also proposed is a conformational change in P450 2E1 occurring during the course of oxidation and the discrimination of P450 2E1 between acetaldehyde and its hydrated form, the gem-diol. This multistep P450 reaction is characterized by kinetic

  4. Acid-catalyzed hydrolysis of BMS-582664: degradation product identification and mechanism elucidation.

    PubMed

    Zhao, Fang; Derbin, George; Miller, Scott; Badawy, Sherif; Hussain, Munir

    2012-09-01

    BMS-582664 is an investigational drug intended for cancer treatment through oral administration. The preformulation studies revealed two unexpected degradation products under acidic conditions by reversed-phase high-performance liquid chromatography with ultraviolet detection. Additional liquid chromatography-mass spectrometry results suggested that these were cleavage (hydrolysis) products of a diaryl ether. To further understand the degradation mechanism, the reaction was carried out in (18) O-labeled water. The (18) O was found to be incorporated in only one of the two hydrolysis products. The results suggest that the corresponding α carbon in the heterocycle was unusually eletrophilic in acidic conditions probably because of the protonation of the neighboring nitrogen. This led to the selective attack by water and the consequent hydrolysis products. The study provides a new example of hydrolytic degradation of pharmaceutical compounds, and the reaction center is an aromatic heterocyclic carbon with an aryloxy substitution. PMID:22189636

  5. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions.

    PubMed

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu

    2015-06-10

    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst. PMID:26011419

  6. Homogeneous Catalyzed Reactions of Levulinic Acid: To γ-Valerolactone and Beyond.

    PubMed

    Omoruyi, Uwaila; Page, Samuel; Hallett, Jason; Miller, Philip W

    2016-08-23

    Platform chemicals derived from lignocellulosic plant biomass are viewed as a sustainable replacement for crude oil-based feedstocks. Levulinic acid (LA) is one such biomass-derived chemical that has been widely studied for further catalytic transformation to γ-valerolactone (GVL), an important 'green' fuel additive, solvent, and fine chemical intermediate. Although the transformation of LA to GVL can be achieved using heterogeneous catalysis, homogeneous catalytic systems that operate under milder reactions, give higher selectivities and can be recycled continuously are attracting considerable attention. A range of new homogeneous catalysts have now been demonstrated to efficiently convert LA to GVL and to transform LA directly to other value-added chemicals such as 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF). This Minireview covers recent advances in the area of homogeneous catalysis for the conversion of levulinic acid and levulinic ester derivatives to GVL and chemicals beyond GVL. PMID:27464831

  7. Continuous lipase-catalyzed esterification of soybean fatty acids under ultrasound irradiation.

    PubMed

    Trentin, Claudia M; Scherer, Robison P; Dalla Rosa, C; Treichel, H; Oliveira, D; Oliveira, J Vladimir

    2014-05-01

    This work investigates the continuous production of alkyl esters from soybean fatty acid (FA) charges using immobilized Novozym 435 as catalyst. The experiments were performed in a packed-bed bioreactor evaluating the effects of FA charge to alcohol (methanol and ethanol) molar ratio, from 1:1 to 1:6, substrate flow rate in the range of 0.5-2.5 mL/min and output irradiation power up to 154 W, at fixed temperature of 65 °C, on the reaction conversion. Results showed that almost complete conversions to fatty acids ethyl esters were achieved at mild ultrasonic power (61.6 W), FA to ethanol molar ratio of 1:6, operating temperature (65 °C) and remained nearly constant for long-term reactions without negligible enzyme activity losses. PMID:24078183

  8. Lewis Acid Catalyzed Synthesis of α-Trifluoromethyl Esters and Lactones by Electrophilic Trifluoromethylation.

    PubMed

    Katayev, Dmitry; Matoušek, Václav; Koller, Raffael; Togni, Antonio

    2015-12-01

    An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of secondary, tertiary, and quaternary α-trifluoromethyl esters and lactones in high yield (up to 98%). PMID:26588788

  9. Comparative study of abiogenesis of cysteine and other amino acids catalyzed by various metal ions.

    PubMed

    Bahadur, K; Sen, P

    1975-01-01

    The present work pertains to the study of the influence of nickel, cobalt, thorium, vanadium, molybdate, ferrous ions on the formation of cysteine which is synthesized abiogenically together with other amino acids in sterilized aqueous mixtures of ammonium thiocyanate, formaldehyde, potassium dihydrogen phosphate, calcium acetate, and biological minerals after irradiating by artificial light. The effect of these catalysts on cysteine formation was of the order: Fe++ greater than Mo++ greater than Th++++ greater than V++ greater than Co++ greater than Ni. PMID:1189468

  10. Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

    PubMed

    Bandar, Jeffrey S; Ascic, Erhad; Buchwald, Stephen L

    2016-05-11

    A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance. PMID:27121395

  11. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave.

    PubMed

    Su, Tong-Chao; Fang, Zhen; Zhang, Fan; Luo, Jia; Li, Xing-Kang

    2015-01-01

    In this study, magnetic carbonaceous acids were synthesized by pyrolysis of the homogeneous mixtures of glucose and magnetic Fe3O4 nanoparticles, and subsequent sulfonation. The synthesis conditions were optimized to obtain a catalyst with both high acid density (0.75 mmol g(-1)) and strong magnetism [magnetic saturation, Ms = 19.5 Am(2) kg(-1)]. The screened catalyst (C-SO3H/Fe3O4) was used to hydrolyze ball-milled cellulose in a microwave reactor with total reducing sugar (TRS) yield of 25.3% under the best conditions at 190 °C for 3.5 h. It was cycled for at least seven times with high catalyst recovery rate (92.8%), acid density (0.63 mmol g(-1)) and magnetism (Ms = 12.9 Am(2) kg(-1)), as well as high TRS yield (20.1%) from the hydrolysis of ball-milled cellulose. The catalyst was further successfully tested for the hydrolysis of tropical biomass with high TRS and glucose yields of 79.8% and 58.3% for bagasse, 47.2% and 35.6% for Jatropha hulls, as well as 54.4% and 35.8% for Plukenetia hulls. PMID:26648414

  12. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave

    NASA Astrophysics Data System (ADS)

    Su, Tong-Chao; Fang, Zhen; Zhang, Fan; Luo, Jia; Li, Xing-Kang

    2015-12-01

    In this study, magnetic carbonaceous acids were synthesized by pyrolysis of the homogeneous mixtures of glucose and magnetic Fe3O4 nanoparticles, and subsequent sulfonation. The synthesis conditions were optimized to obtain a catalyst with both high acid density (0.75 mmol g-1) and strong magnetism [magnetic saturation, Ms = 19.5 Am2 kg-1]. The screened catalyst (C-SO3H/Fe3O4) was used to hydrolyze ball-milled cellulose in a microwave reactor with total reducing sugar (TRS) yield of 25.3% under the best conditions at 190 °C for 3.5 h. It was cycled for at least seven times with high catalyst recovery rate (92.8%), acid density (0.63 mmol g-1) and magnetism (Ms = 12.9 Am2 kg-1), as well as high TRS yield (20.1%) from the hydrolysis of ball-milled cellulose. The catalyst was further successfully tested for the hydrolysis of tropical biomass with high TRS and glucose yields of 79.8% and 58.3% for bagasse, 47.2% and 35.6% for Jatropha hulls, as well as 54.4% and 35.8% for Plukenetia hulls.

  13. Phosphatidylcholine enrichment with medium chain fatty acids by immobilized phospholipase A(1) -catalyzed acidolysis.

    PubMed

    Ochoa, Angélica A; Hernández-Becerra, Josafat A; Cavazos-Garduño, Adriana; García, Hugo S; Vernon-Carter, Eduardo J

    2013-01-01

    Phospholipids are a biologically and industrially important class of compounds whose physical properties can be improved for diverse applications by substitution of medium-chain fatty acids for their native fatty acid chains. In this study, phosphatidylcholine (PC) was enriched with medium-chain fatty acids (MCFAs) by acidolysis with phospholipase A(1) (PLA(1) ) immobilized on Duolite A568. Response surface methodology was employed to evaluate the effects of the molar ratio of substrates (PC to free MCFAs), enzyme loading, and reaction temperature on the incorporation of free MCFAs into PC and on PC recovery. Enzyme loading and molar ratio of substrates contributed positively, but temperature negatively, to the incorporation of free MCFAs into PC. Increases in enzyme loading and the molar ratio of PC to free MCFAs led to increased incorporation of the latter into the former, but increased temperature had the opposite effect. By contrast, an increase in enzyme loading led to decreased PC recovery. Increased temperature had also a negative effect on PC recovery. Optimal conditions for maximum incorporation and PC recovery were molar ratio of PC to free MCFAs of 1:16, enzyme loading of 16%, and 50°C. Under these conditions, the incorporation of free MCFAs was 41% and the PC recovery was 53%. PMID:23074091

  14. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave

    PubMed Central

    Su, Tong-Chao; Fang, Zhen; Zhang, Fan; Luo, Jia; Li, Xing-Kang

    2015-01-01

    In this study, magnetic carbonaceous acids were synthesized by pyrolysis of the homogeneous mixtures of glucose and magnetic Fe3O4 nanoparticles, and subsequent sulfonation. The synthesis conditions were optimized to obtain a catalyst with both high acid density (0.75 mmol g−1) and strong magnetism [magnetic saturation, Ms = 19.5 Am2 kg−1]. The screened catalyst (C-SO3H/Fe3O4) was used to hydrolyze ball-milled cellulose in a microwave reactor with total reducing sugar (TRS) yield of 25.3% under the best conditions at 190 °C for 3.5 h. It was cycled for at least seven times with high catalyst recovery rate (92.8%), acid density (0.63 mmol g−1) and magnetism (Ms = 12.9 Am2 kg−1), as well as high TRS yield (20.1%) from the hydrolysis of ball-milled cellulose. The catalyst was further successfully tested for the hydrolysis of tropical biomass with high TRS and glucose yields of 79.8% and 58.3% for bagasse, 47.2% and 35.6% for Jatropha hulls, as well as 54.4% and 35.8% for Plukenetia hulls. PMID:26648414

  15. Ruthenium-Catalyzed Oxidative Homocoupling of Arylboronic Acids in Water: Ligand Tuned Reactivity and Mechanistic Study.

    PubMed

    Tyagi, Deepika; Binnani, Chinky; Rai, Rohit K; Dwivedi, Ambikesh D; Gupta, Kavita; Li, Pei-Zhou; Zhao, Yanli; Singh, Sanjay K

    2016-06-20

    Molecular catalysts based on water-soluble arene-Ru(II) complexes ([Ru]-1-[Ru]-5) containing aniline (L1), 2-methylaniline (L2), 2,6-dimethylaniline (L3), 4-methylaniline (L4), and 4-chloroaniline (L5) were designed for the homocoupling of arylboronic acids in water. These complexes were fully characterized by (1)H, (13)C NMR, mass spectrometry, and elemental analyses. Structural geometry for two of the representative arene-Ru(II) complexes [Ru]-3 and [Ru]-4 was established by single-crystal X-ray diffraction studies. Our studies showed that the selectivity toward biaryls products is influenced by the position and the electronic behavior of various substituents of aniline ligand coordinated to ruthenium. Extensive investigations using (1)H NMR, (19)F NMR, and mass spectral studies provided insights into the mechanistic pathway of homocoupling of arylboronic acids, where the identification of important organometallic intermediates, such as σ-aryl/di(σ-aryl) coordinated arene-Ru(II) species, suggested that the reaction proceeds through the formation of crucial di(σ-aryl)-Ru intermediates by the interaction of arylboronic acid with Ru-catalyst to yield biaryl products. PMID:27276384

  16. Schiff base structured acid-base cooperative dual sites in an ionic solid catalyst lead to efficient heterogeneous knoevenagel condensations.

    PubMed

    Zhang, Mingjue; Zhao, Pingping; Leng, Yan; Chen, Guojian; Wang, Jun; Huang, Jun

    2012-10-01

    An acid-base bifunctional ionic solid catalyst [PySaIm](3)PW was synthesized by the anion exchange of the ionic-liquid (IL) precursor 1-(2-salicylaldimine)pyridinium bromide ([PySaIm]Br) with the Keggin-structured sodium phosphotungstate (Na(3) PW). The catalyst was characterized by FTIR, UV/Vis, XRD, SEM, Brunauer-Emmett-Teller (BET) theory, thermogravimetric analysis, (1)H NMR spectroscopy, ESI-MS, elemental analysis, and melting points. Together with various counterparts, [PySaIm](3)PW was evaluated in Knoevenagel condensation under solvent and solvent-free conditions. The Schiff base structure attached to the IL cation of [PySaIm](3)PW involves acidic salicyl hydroxyl and basic imine, and provides a controlled nearby position for the acid-base dual sites. The high melting and insoluble properties of [PySaIm](3)PW are relative to the large volume and high valence of PW anions, as well as the intermolecular hydrogen-bonding networks among inorganic anions and IL cations. The ionic solid catalyst [PySaIm](3)PW leads to heterogeneous Knoevenagel condensations. In solvent-free condensation of benzaldehyde with ethyl cyanoacetate, it exhibits a conversion of 95.8 % and a selectivity of 100 %; the conversion is even much higher than that (78.2 %) with ethanol as a solvent. The solid catalyst has a convenient recoverability with only a slight decrease in conversion following subsequent recyclings. Furthermore, the new catalyst is highly applicable to many substrates of aromatic aldehydes with activated methylene compounds. On the basis of the characterization and reaction results, a unique acid-base cooperative mechanism within a Schiff base structure is proposed and discussed, which thoroughly explains not only the highly efficient catalytic performance of [PySaIm](3)PW, but also the lower activities of various control catalysts. PMID:22907828

  17. Upcycling potato peel waste - Data of the pre-screening of the acid-catalyzed liquefaction.

    PubMed

    Ventura, Patrícia; Bordado, João Carlos Moura; Mateus, Maria Margarida; Galhano Dos Santos, Rui

    2016-06-01

    Herein, the data acquired regarding the preliminary and exploratory experiments conducted with potato peel as a biomass source for the direct thermochemical liquefaction is disclosed. The procedure was carried out in a 2-ethylhexanol/DEG solvent mixture at 160 °C in the presence of p-Toluenesulfonic acid. The adopted procedure afforded a bio-oil in high yield (up to 93%) after only 30 min. For longer reaction times, higher amounts of solid residues were obtained leading, consequently, to lower yields. PMID:27182538

  18. Molecular cytogenetics by polymerase catalyzed amplification or in situ labelling of specific nucleic acid sequences

    SciTech Connect

    Bolund, L.; Brandt, C.; Hindkjaer, J.; Koch, J.; Koelvraa, S.; Pedersen, S. )

    1993-01-01

    The Polymerase Chain Reaction (PCR) can be performed on isolated cells or chromosomes and the product can be analyzed by DNA technology or by FISH to test metaphases. The authors have good experiences analyzing aberrant chromosomes by FACS sorting, PCR with degenerated primers and painting of test metaphases with the PCR product. They also utilize polymerases for PRimed IN Situ labelling (PRINS) of specific nucleic acid sequences. In PRINS oligonucleotides are hybridized to their target sequences and labeled nucleotides are incorporated at the site of hybridization with the oligonucleotide as primer. PRINS may eventually allow the study of individual genes, gene expression and even somatic mutations (in mRNA) in single cells.

  19. Synergistic Acid-Catalyzed Synthesis of N-Aryl-Substituted Azacycles from Anilines and Cyclic Ethers.

    PubMed

    Zhang, Zhenbei; Miao, Chengxia; Xia, Chungu; Sun, Wei

    2016-04-01

    A metal-free and efficient approach to N-aryl-substituted azacycles from arylamines and cyclic ethers is described. In this synthesis, the synergistic effect between Lewis and Brønsted acids is crucial to the ring-opening of cyclic ethers and the subsequent cyclization. The use of B(C6F5)3 enabled the formation of frustrated Lewis pairs (FLPs) from the reactants, and the resulting FLPs allowed ready access to the N-arylazacycles in moderate to good yields via further cyclization. Water is the sole waste resulting from the reaction, thereby making it an environmentally benign process. PMID:26962879

  20. The Mycobacterium tuberculosis FAS-II condensing enzymes: their role in mycolic acid biosynthesis, acid-fastness, pathogenesis and in future drug development.

    PubMed

    Bhatt, Apoorva; Molle, Virginie; Besra, Gurdyal S; Jacobs, William R; Kremer, Laurent

    2007-06-01

    Mycolic acids are very long-chain fatty acids representing essential components of the mycobacterial cell wall. Considering their importance, characterization of key enzymes participating in mycolic acid biosynthesis not only allows an understanding of their role in the physiology of mycobacteria, but also might lead to the identification of new drug targets. Mycolates are synthesized by at least two discrete elongation systems, the type I and type II fatty acid synthases (FAS-I and FAS-II respectively). Among the FAS-II components, the condensing enzymes that catalyse the formation of carbon-carbon bonds have received considerable interest. Four condensases participate in initiation (mtFabH), elongation (KasA and KasB) and termination (Pks13) steps, leading to full-length mycolates. We present the recent biochemical and structural data for these important enzymes. Special emphasis is given to their role in growth, intracellular survival, biofilm formation, as well as in the physiopathology of tuberculosis. Recent studies demonstrated that phosphorylation of these enzymes by mycobacterial kinases affects their activities. We propose here a model in which kinases that sense environmental changes can phosphorylate the condensing enzymes, thus representing a novel mechanism of regulating mycolic acid biosynthesis. Finally, we discuss the attractiveness of these enzymes as valid targets for future antituberculosis drug development. PMID:17555433

  1. Mechanism of alkane dehydrogenation catalyzed by acidic zeolites: Ab initio transition path sampling

    NASA Astrophysics Data System (ADS)

    Bučko, Tomáš; Benco, Lubomir; Dubay, Orest; Dellago, Christoph; Hafner, Jürgen

    2009-12-01

    The dehydrogenation of propane over acidic chabazite has been studied using ab initio density-functional simulations in combination with static transition-state searches and dynamic transition path sampling (TPS) methods at elevated temperatures. The acidic zeolite has been modeled both using a small cluster and a large periodic model consisting of two unit cells, the TPS simulations allow to account for the effect of temperature and entropy. In agreement with experimental observations we find propene as the dominant reaction product and that the barrier for the dehydrogenation of a methyl group is higher than that for a methylene group. However, whereas all studies based on small cluster models (including the present one) conclude that the reaction proceeds via the formation of an alkoxy intermediate, our TPS studies based on a large periodic model lead to the conclusion that propene formation occurs via the formation of various forms of propyl cations stabilized by entropy, while the formation of an alkoxy species is a relatively rare event. It was observed only in 15% of the reactive trajectories for methyl dehydrogenation and even in only 8% of the methylene dehydrogenation reactions. Our studies demonstrate the importance of entropic effects and the need to account for the structure and flexibility of the zeolitic framework by using large periodic models.

  2. Brønsted Acid-Catalyzed Transfer Hydrogenation of Imines and Alkenes Using Cyclohexa-1,4-dienes as Dihydrogen Surrogates.

    PubMed

    Chatterjee, Indranil; Oestreich, Martin

    2016-05-20

    Cyclohexa-1,4-dienes are introduced to Brønsted acid-catalyzed transfer hydrogenation as an alternative to the widely used Hantzsch dihydropyridines. While these hydrocarbon-based dihydrogen surrogates do offer little advantage over established protocols in imine reduction as well as reductive amination, their use enables the previously unprecedented transfer hydrogenation of structurally and electronically unbiased 1,1-di- and trisubstituted alkenes. The mild procedure requires 5.0 mol % of Tf2NH, but the less acidic sulfonic acids TfOH and TsOH work equally well. PMID:27181437

  3. Self-catalyzed syntheses, structural characterization, DPPH radical scavenging-, cytotoxicity-, and DFT studies of phenoxyaliphatic acids of 1,8-dioxo-octahydroxanthene derivatives

    NASA Astrophysics Data System (ADS)

    Suresh Kumar, G. S.; Antony Muthu Prabhu, A.; Seethalashmi, P. G.; Bhuvanesh, N.; Kumaresan, S.

    2014-02-01

    One-pot, in-water syntheses of phenoxyaliphatic acids of 1,8-dioxo-octahydroxanthene derived from dimedone and formylphenoxyaliphatic acids are reported. Geometries of compounds 2b, 2c, and 5a have been examined crystallographically. The synthesized compounds showed better DPPH radical scavenging activity and cytotoxicity against A431 cancer cell line. The molecular properties of all synthesized xanthenes have been investigated using single crystal XRD and DFT method. Self-catalyzed Bronsted-Lowry acid catalytic behavior was also investigated by both experimental and theoretical methods.

  4. Kinetics and mechanism of the heterogeneous catalyzed oxidative decolorization of Acid-Blue 92 using bimetallic metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    El-sharkawy, Rehab G.; El-din, Ahmed S. Badr; Etaiw, Safaa El-din H.

    2011-09-01

    The kinetics study of the oxidative decolorization of Acid-Blue 92 has been investigated by hydrogen peroxide catalyzed with bimetallic metal-organic frameworks. The used metal-organic frameworks (MOF) are [Ph 3SnCu(CN) 2·L] where L = pyrazine (pyz) 1, methylpyrazine (mepyz) 2, 4,4'-bipyridine (bpy) 3, trans-1,2-bis(4-pyridyl)ethene (tbpe) 4 or 1,2-bis(4-pyridyl)ethane (bpe) 5. The reaction was followed by conventional UV-Vis spectrophotometer at λmax = 571 nm. The reaction exhibited first-order kinetics with respect to [dye] and [H 2O 2]. The reactivity of the catalysts depends on the type of the medium and thereafter decreases in strong alkaline media. Addition of NaCl enhances the reaction rate. Also, the irradiation of the reaction with UV-light enhanced the rate of AB-92 mineralization by about 86.9%. The reaction was entropy-controlled as confirmed by the isokinetic relationship. A reaction mechanism was proposed with the formation of free radicals as an oxidant.

  5. Enantioselective acylation of β-phenylalanine acid and its derivatives catalyzed by penicillin G acylase from Alcaligenes faecalis.

    PubMed

    Li, Dengchao; Ji, Lilian; Wang, Xinfeng; Wei, Dongzhi

    2013-01-01

    This study developed a simple, efficient method for producing racemic β-phenylalanine acid (BPA) and its derivatives via the enantioselective acylation catalyzed by the penicillin G acylase from Alcaligenes faecalis (Af-PGA). When the reaction was run at 25°C and pH 10 in an aqueous medium containing phenylacetamide and BPA in a molar ratio of 2:1, 8 U/mL enzyme and 0.1 M BPA, the maximum BPA conversion efficiency at 40 min only reached 36.1%, which, however, increased to 42.9% as the pH value and the molar ratio of phenylacetamide to BPA were elevated to 11 and 3:1, respectively. Under the relatively optimum reaction conditions, the maximum conversion efficiencies of BPA derivatives all reached about 50% in a relatively short reaction time (45-90 min). The enantiomeric excess value of product (ee(p)) and enantiomeric excess value of substrate (ee(s)) were all above 98% and 95%, respectively. These results suggest that the method established in this study is practical, effective, and environmentally benign and may be applied to industrial production of enantiomerically pure BPA and its derivatives. PMID:23302108

  6. Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

    PubMed Central

    Gulzar, Naeem; Klussmann, Martin

    2014-01-01

    The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Brønsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown. PMID:24998636

  7. No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Peltier, R. E.; Sullivan, A. P.; Weber, R. J.; Wollny, A. G.; Holloway, J. S.; Brock, C. A.; de Gouw, J. A.; Atlas, E. L.

    2007-03-01

    Aircraft-based measurements of the water-soluble fraction of fine PM organic carbon (WSOC) and inorganic salt composition in the Atlanta, GA region were conducted in the summer of 2004. Five notable plumes of SO2, apparently from coal-fired power plants, were intercepted, and had NH4 +/SO4 2- molar ratios ranging from approximately 0.8 to 1.4 compared to molar ratios near 2 outside of the plumes. Sulfate aerosol concentrations increased from a regional background of 5-8 μg m-3 to as high as 19.5 μg m-3 within these plumes. No increase in WSOC concentrations was observed in plumes compared to out-of-plumes within a WSOC measurement uncertainty of 8%. These measurements suggest that secondary organic aerosol formation via heterogeneous acid-catalyzed reactions within power plant plumes are not likely a significant contributor to the ambient aerosol mass loading in Atlanta and the surrounding region. Because this region is rich in both biogenic and anthropogenic volatile organic carbon (VOC), the results may be widely applicable.

  8. Mechanistic studies of highly enantio- and diastereoselective aza-Petasis-Ferrier rearrangement catalyzed by chiral phosphoric acid.

    PubMed

    Terada, Masahiro; Komuro, Takazumi; Toda, Yasunori; Korenaga, Toshinobu

    2014-05-14

    The precise mechanism of the highly anti- and enantioselective aza-Petasis-Ferrier (APF) rearrangement of hemiaminal vinyl ethers catalyzed by a chiral phosphoric acid was investigated by undertaking experimental and theoretical studies. The APF rearrangement is characterized by the following unique mechanistic features: (i) efficient optical kinetic resolution of the starting racemic hemiaminal vinyl ether, (ii) enantioconvergent process from racemic hemiaminal vinyl ethers to optically active β-amino aldehyde products, and (iii) anomalous temperature effects on the enantioselectivity (enantioselectivity increases as reaction temperature increases). The following experiments were conducted to elucidate the unique mechanistic features as well as to uncover the overall scheme of the present rearrangement: (A) X-ray crystallographic analysis of the recovered hemiaminal vinyl ether to determine its absolute configuration, (B) rearrangements of enantiomerically pure hemiaminal vinyl ethers to validate the stereochemical relationship between the hemiaminal vinyl ethers and β-amino aldehydes, (C) theoretical studies on the transition states of the C-O bond cleavage and C-C bond formation steps to gain an insight into the optical kinetic resolution of the hemiaminal vinyl ether and the origin of the stereoselectivity, as well as to elucidate the overall scheme of the present rearrangement, and (D) crossover experiments of two hemiaminal vinyl ethers having different vinyl ether and aliphatic substituents to comprehend the mechanism of the anomalous temperature effect and the enantioconvergent process. The results of experiments and theoretical studies fully support the proposed mechanism of the present anti- and enantioselective APF rearrangement. PMID:24746095

  9. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    NASA Astrophysics Data System (ADS)

    Zhang, Jinyu; Zhou, Guowei; Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d100), and cell parameter (a0) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d100 and a0 continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%.

  10. Site-Specific Radiofluorination of Biomolecules with 8-[(18)F]-Fluorooctanoic Acid Catalyzed by Lipoic Acid Ligase.

    PubMed

    Drake, Christopher R; Sevillano, Natalia; Truillet, Charles; Craik, Charles S; VanBrocklin, Henry F; Evans, Michael J

    2016-06-17

    New methodologies for site-specifically radiolabeling proteins with (18)F are required to generate high quality radiotracers for preclinical and clinical applications with positron emission tomography. Herein, we report an approach by which we use lipoic acid ligase (LplA) to conjugate [(18)F]-fluorooctanoic acid to an antibody fragment bearing the peptide substrate of LplA. The mild conditions of the reaction preserve antibody immunoreactivity, and the efficiency of LplA allows for >90% yield even with very small amounts of peptidic precursor (1-10 nmol). These features are advantageous compared to the current gold standard in the field. Moreover, the methodology introduces a new application for an important tool in chemical biology. PMID:27008570

  11. Iridium-Catalyzed ortho-Arylation of Benzoic Acids with Arenediazonium Salts.

    PubMed

    Huang, Liangbin; Hackenberger, Dagmar; Gooßen, Lukas J

    2015-10-19

    In the presence of catalytic [{IrCp*Cl2 }2 ] and Ag2 CO3 , Li2 CO3 as the base, and acetone as the solvent, benzoic acids react with arenediazonium salts to give the corresponding diaryl-2-carboxylates under mild conditions. This C-H arylation process is generally applicable to diversely substituted substrates, ranging from extremely electron-rich to electron-poor derivatives. The carboxylate directing group is widely available and can be removed tracelessly or employed for further derivatization. Orthogonality to halide-based cross-couplings is achieved by the use of diazonium salts, which can be coupled even in the presence of iodo substituents. PMID:26465654

  12. Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile.

    PubMed

    Yu, Lei; Zhang, Qi; Li, Shu-Shuang; Huang, Jun; Liu, Yong-Mei; He, He-Yong; Cao, Yong

    2015-09-21

    Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. PMID:26224033

  13. Metal-Free Ammonia-Borane Dehydrogenation Catalyzed by a Bis(borane) Lewis Acid.

    PubMed

    Lu, Zhenpin; Schweighauser, Luca; Hausmann, Heike; Wegner, Hermann A

    2015-12-14

    The storage of energy in a safe and environmentally benign way is one of the main challenges of today's society. Ammonia-borane (AB=NH3 BH3 ) has been proposed as a possible candidate for the chemical storage of hydrogen. However, the efficient release of hydrogen is still an active field of research. Herein, we present a metal-free bis(borane) Lewis acid catalyst that promotes the evolution of up to 2.5 equivalents of H2 per AB molecule. The catalyst can be reused multiple times without loss of activity. The moderate temperature of 60 °C allows for controlling the supply of H2 on demand simply by heating and cooling. Mechanistic studies give preliminary insights into the kinetics and mechanism of the catalytic reaction. PMID:26537288

  14. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

    DOE PAGESBeta

    Liberman-Martin, Allegra L.; Bergman, Robert G.; Tilley, T. Don

    2015-04-16

    Bis(perfluorocatecholato)silane Si(cat(F)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat(F)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BAr(F)4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

  15. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

    SciTech Connect

    Liberman-Martin, Allegra L.; Bergman, Robert G.; Tilley, T. Don

    2015-04-16

    Bis(perfluorocatecholato)silane Si(cat(F)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat(F)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BAr(F)4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

  16. A Heteromeric Membrane-Bound Prenyltransferase Complex from Hop Catalyzes Three Sequential Aromatic Prenylations in the Bitter Acid Pathway1[OPEN

    PubMed Central

    Li, Haoxun; Ban, Zhaonan; Qin, Hao; Ma, Liya; King, Andrew J.

    2015-01-01

    Bitter acids (α and β types) account for more than 30% of the fresh weight of hop (Humulus lupulus) glandular trichomes and are well known for their contribution to the bitter taste of beer. These multiprenylated chemicals also show diverse biological activities, some of which have potential benefits to human health. The bitter acid biosynthetic pathway has been investigated extensively, and the genes for the early steps of bitter acid synthesis have been cloned and functionally characterized. However, little is known about the enzyme(s) that catalyze three sequential prenylation steps in the β-bitter acid pathway. Here, we employed a yeast (Saccharomyces cerevisiae) system for the functional identification of aromatic prenyltransferase (PT) genes. Two PT genes (HlPT1L and HlPT2) obtained from a hop trichome-specific complementary DNA library were functionally characterized using this yeast system. Coexpression of codon-optimized PT1L and PT2 in yeast, together with upstream genes, led to the production of bitter acids, but no bitter acids were detected when either of the PT genes was expressed by itself. Stepwise mutation of the aspartate-rich motifs in PT1L and PT2 further revealed the prenylation sequence of these two enzymes in β-bitter acid biosynthesis: PT1L catalyzed only the first prenylation step, and PT2 catalyzed the two subsequent prenylation steps. A metabolon formed through interactions between PT1L and PT2 was demonstrated using a yeast two-hybrid system, reciprocal coimmunoprecipitation, and in vitro biochemical assays. These results provide direct evidence of the involvement of a functional metabolon of membrane-bound prenyltransferases in bitter acid biosynthesis in hop. PMID:25564559

  17. Sulfamic Acid-Catalyzed Lead Perovskite Formation for Solar Cell Fabrication on Glass or Plastic Substrates.

    PubMed

    Guo, Yunlong; Sato, Wataru; Shoyama, Kazutaka; Nakamura, Eiichi

    2016-04-27

    Lead perovskite materials such as methylammonium triiodoplumbate(II) (CH3NH3PbI3, PV) are promising materials for printable solar cell (SC) applications. The preparation of PV involves a series of energetically costly cleavages of the μ-iodo bridges via conversion of a mixture of PbI2 (PI) and methylammonium iodide (CH3NH3I, MAI) in N,N-dimethylformamide (DMF) into a precursor solution containing a polymeric strip of a plumbate(II) dimer [(MA(+))2(PbI3(-))2·(DMF)2]m, which then produces a perovskite film with loss of DMF upon spin-coating and heating of the substrate. We report here that the PI-to-PV conversion and the PV crystal growth to micrometer size can be accelerated by a small amount of zwitterionic sulfamic acid (NH3SO3, SA) and that sulfamic acid facilitates electron transfer to a neighboring electron-accepting layer in an SC device. As a result, an SC device on indium tin oxide (ITO)/glass made of a 320 nm thick PV film using 0.7 wt % SA showed a higher short-circuit current, open-circuit voltage, and fill factor and hence a 22.5% higher power conversion efficiency of 16.02% compared with the device made without SA. The power conversion efficiency value was reproducible (±0.3% for 25 devices), and the device showed very small hysteresis. The device without any encapsulation showed a respectable longevity on a shelf under nitrogen under ambient light. A flexible device similarly fabricated on ITO/poly(ethylene naphthalate) showed an efficiency of 12.4%. PMID:27054265

  18. Interstellar condensed (icy) amino acids and precursors: theoretical absorption and circular dichroism under UV and soft X-ray irradiation

    NASA Astrophysics Data System (ADS)

    Da Pieve, F.; Avendaño-Franco, G.; De Proft, F.; Geerlings, P.

    2014-05-01

    The photophysics of interstellar ices and condensed molecules adsorbed on grains is of primary importance for studies on the origin of the specific handedness of complex organic molecules delivered to the early Earth and of the homochirality of the building blocks of life. Here, we present quantum mechanical calculations based on time-dependent density functional theory for the absorption and circular dichroism (CD) of isovaline and its chiral precursor 5-ethyl-5-methylhydantoin, both observed in meteoritic findings. The systems are considered in their geometrical conformation as extracted from a full solid (icy) matrix, as a shortcut to understand the behaviour of molecules with fixed orientation, and/or taking into account the full solid matrix. In the context of a possible `condensation-warming plus hydrolysis-recondensation' process, we obtain that: (i) for low-energy excitations, the `condensed' precursor has a stronger CD with respect to the amino acid, suggesting that the handedness of the latter could be biased by asymmetric photolysis of the precursor in cold environments; (ii) enantiomeric excess could in principle be induced more efficiently in both systems for excitation at higher energies (VUV). X-ray absorption near-edge spectroscopy and related CD results could serve as support for future experiments on ionization channels.

  19. A method for the determination of the hepatic enzyme activity catalyzing bile acid acyl glucuronide formation by high-performance liquid chromatography with pulsed amperometric detection.

    PubMed

    Ikegawa, S; Oohashi, J; Murao, N; Goto, J

    2000-05-01

    A method for the determination of the activity of hepatic glucuronyltransferase catalyzing formation of bile acid 24-glucuronides using high-performance liquid chromatography (HPLC) with pulsed amperometric detection (PAD) has been developed. Bile acid 24-glucuronides were simultaneously separated on a semimicrobore column, Capcell Pak C18UG120, using 20 mM ammonium phosphate (pH 6.0)-acetonitrile (27:10 and 16:10) as the mobile phase in the stepwise gradient elution mode. A 1 M potassium hydroxide solution for the hydrolysis of the 24-glucuronides, which liberates the corresponding bile acids and glucuronic acid, was mixed with the mobile phase in a post-column mode, and the resulting eluant was heated at 90 degrees C, the 24-glucuronides being monitored using a pulsed amperometric detector; the limit of detection was 10 ng. The proposed method was applied to the determination of the hepatic enzyme activity catalyzing bile acid 24-glucuronide formation and the result exhibited the efficient 24-glucuronide formation of the monohydroxylated bile acid, lithocholic acid. PMID:10850616

  20. Unique Reactivity Patterns Catalyzed by Internal Lewis Acid Assisted Hydrogen Bond Donors

    NASA Astrophysics Data System (ADS)

    Auvil, Tyler Jay

    The advancement of hydrogen bond donor (HBD) organocatalysis has been inhibited by a number of challenges. Conventional HBDs suffer from high catalyst loadings and operate in only limited types of reactions, typically the activation of 1,2- and 1,4-acceptors for nucleophilic attack. One strategy to address the shortcomings of HBD catalysis is to design innovative catalysts with improved reactivity. To this end, boronate ureas have been developed as a new family of enhanced HBD catalysts that enable useful new reactivity patterns. Boronate ureas are easily-accessible, small organic molecules that benefit from improved catalytic abilities plausibly due to internal coordination of the urea carbonyl to a strategically placed Lewis acid. Optimization of the boronate urea scaffold has revealed their enhanced catalytic activity, enabling new directions in HBD catalysis. The discovery of boronate ureas has allowed for the unveiling of new HBD activation modes, providing unique reactivity patterns that are inaccessible with conventional HBD catalysts. Among these reactivity patterns is the activation of strained nitrocyclopropane carboxylates for nucleophilic ring-opening reactions, which affords a swift route to access gamma-amino-alpha-nitroester building blocks. The ring-opening method was highlighted by its utilization in the total synthesis of a CB-1 receptor inverse agonist, which was recently patented by Eli Lilly. Additionally, boronate ureas can elicit carbene-like reactivity from alpha-diazocarbonyl compounds, allowing for organocatalytic heteroatom-hydrogen insertions reactions, the first of their kind. The boronate urea activation of alpha-nitrodiazoesters has permitted the development of an unsymmetric double alpha-arylation process, affording a synthetically challenging motif in a single flask. The alpha-arylation reaction proceeds through a conceptually novel organocatalytic transient N--H insertion process, employing anilines as carbene activators. The use

  1. Progressive deconstruction of Arundo donax Linn. to fermentable sugars by acid catalyzed ionic liquid pretreatment.

    PubMed

    You, Ting-Ting; Zhang, Li-Ming; Xu, Feng

    2016-01-01

    Acid enhanced ionic liquid (IL) 1-n-butyl-3-methylimidazolium chloride ([C4 mim]Cl) pretreatment has shown great potential for boosting the yield of sugars from biomass cost-effectively and environmental-friendly. Pretreatment with shorter processing time will promote the commercial viability. In this work, pretreatment of reduced Amberlyst catalysis time of 34 min was demonstrated to be the most effective among time-varying pretreatments, evidenced by partial removal of hemicellulose and cellulose crystal transformation of Arundo donax Linn. A higher fermentable sugar concentration of 10.42 g/L (2% substrate) was obtained after 72 h of saccharification than the others. Total processing time to reach 92% glucose yield was cut down to approximately 26 h. Progressive deconstruction of crop cell wall was occurred with increased catalysis time by gradual releasing of H3O(+) of Amberlyst. However, vast lignin re-deposited polymers on fibers could hinder further enzymatic hydrolysis. These discoveries provide new insights into a more economic pretreatment for bioethanol production. PMID:26363822

  2. Hyaluronic Acid Hydrogels Formed in Situ by Transglutaminase-Catalyzed Reaction.

    PubMed

    Ranga, Adrian; Lutolf, Matthias P; Hilborn, Jöns; Ossipov, Dmitri A

    2016-05-01

    Enzymatically cross-linked hydrogels can be formed in situ and permit highly versatile and selective tethering of bioactive molecules, thereby allowing for a wealth of applications in cell biology and tissue engineering. While a number of studies have reported the bioconjugation of extracellular matrix (ECM) proteins and peptides into such matrices, the site-specific incorporation of biologically highly relevant polysaccharides such as hyaluronic acid (HA) has thus far not been reported, limiting our ability to reconstruct this key feature of the in vivo ECM. Here we demonstrate a novel strategy for transglutaminase-mediated covalent linking of HA moieties to a synthetic poly(ethylene glycol) (PEG) macromer resulting in the formation of hybrid HA-PEG hydrogels. We characterize the ensuing matrix properties and demonstrate how these cytocompatible gels can serve to modulate the cellular phenotype of human mammary cancer epithelial cells as well as mouse myoblasts. The use of HA as a novel building block in the increasingly varied library of synthetic PEG-based artificial ECMs should have applications as a structural as well as a signaling component and offers significant potential as an injectable matrix for regenerative medicine. PMID:27014785

  3. Acid-Catalyzed Algal Biomass Pretreatment for Integrated Lipid and Carbohydrate-Based Biofuels Production

    SciTech Connect

    Laurens, L. M. L.; Nagle, N.; Davis, R.; Sweeney, N.; Van Wychen, S.; Lowell, A.; Pienkos, P. T.

    2014-11-12

    One of the major challenges associated with algal biofuels production in a biorefinery-type setting is improving biomass utilization in its entirety, increasing the process energetic yields and providing economically viable and scalable co-product concepts. We demonstrate the effectiveness of a novel, integrated technology based on moderate temperatures and low pH to convert the carbohydrates in wet algal biomass to soluble sugars for fermentation, while making lipids more accessible for downstream extraction and leaving a protein-enriched fraction behind. We studied the effect of harvest timing on the conversion yields, using two algal strains; Chlorella and Scenedesmus, generating biomass with distinctive compositional ratios of protein, carbohydrate, and lipids. We found that the late harvest Scenedesmus biomass had the maximum theoretical biofuel potential at 143 gasoline gallon equivalent (GGE) combined fuel yield per dry ton biomass, followed by late harvest Chlorella at 128 GGE per ton. Our experimental data show a clear difference between the two strains, as Scenedesmus was more successfully converted in this process with a demonstrated 97 GGE per ton. Our measurements indicated a release of >90% of the available glucose in the hydrolysate liquors and an extraction and recovery of up to 97% of the fatty acids from wet biomass. Techno-economic analysis for the combined product yields indicates that this process exhibits the potential to improve per-gallon fuel costs by up to 33% compared to a lipids-only process for one strain, Scenedesmus, grown to the mid-point harvest condition.

  4. Lewis acid-catalyzed in situ transesterification/esterification of microalgae in supercritical ethanol.

    PubMed

    Jin, Binbin; Duan, Peigao; Xu, Yuping; Wang, Bing; Wang, Feng; Zhang, Lei

    2014-06-01

    The activities of several Lewis acid catalysts such SnCl2, FeCl3, ZnCl2, AlCl3, and NbCl5 for the in situ transesterification/esterification of lipid contained within a microalga (Chlorella pyrenoidosa) in ethanol at 350°C were examined to identify the most suitable catalyst in term of crude biodiesel (CBD) yield. Of those catalysts tested, ZnCl2 showed the highest performance toward the CBD production. Using ZnCl2 as catalyst, effects of reaction temperature (200-370 °C), time (0-120 min), ethanol to microalga ratio (EtOH:MA) (5/5-40/5), catalyst loading (0-30 wt.%), and algae moisture (0-80 wt.%) on the yields of product fractions and the properties of CBD were studied. The presence of ZnCl2 not only promoted the production of CBD but also showed activities toward the deoxygenation and denitrogenation of CBD. The moisture content in the starting material is the most influential factor affecting the yield and properties of CBD. PMID:24768889

  5. An N-Heterocyclic Carbene-Catalyzed Oxidative γ-Aminoalkylation of Saturated Carboxylic Acids through in Situ Activation Strategy: Access to δ-Lactam.

    PubMed

    Que, Yonglei; Xie, Yuanwei; Li, Tuanjie; Yu, Chenxia; Tu, Shujiang; Yao, Changsheng

    2015-12-18

    An N-Heterocyclic Carbene (NHC)-catalyzed oxidative formal [4 + 2] annulation of acylhydrazones with saturated carboxylic acids bearing γ-H to assemble δ-lactams featuring a chiral carbon stereogenic center was developed through an in situ activation strategy. The ready availability of the starting materials, excellent enantioselectivity, facile assembly, high yields, and potential biological significance of the final products make this protocol an attractive alternative for the construction of the pyridinone scaffold. PMID:26646554

  6. Chiral Phosphorus-Olefin Ligands for the Rh(I) -Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins.

    PubMed

    Chen, Qian; Li, Liang; Zhou, Guangli; Ma, Xiaoli; Zhang, Lu; Guo, Fang; Luo, Yi; Xia, Wujiong

    2016-05-20

    New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; this reaction provides the desired products in excellent yields and high enantioselectivities. The origin of observed stereoselectivity has been investigated by density functional theory (DFT) calculations. PMID:27017447

  7. Synthesis of theanine from glutamic acid gamma-methyl ester and ethylamine catalyzed by Escherichia coli having gamma-glutamyltranspeptidase activity.

    PubMed

    Zhang, Fei; Zheng, Qing-Zhong; Jiao, Qing-Cai; Liu, Jun-Zhong; Zhao, Gen-Hai

    2010-08-01

    Glutamic acid gamma-methyl ester (GAME) was used as substrate for theanine synthesis catalyzed by Escherichia coli cells possessing gamma-glutamyltranspeptidase activity. The yield was about 1.2-fold higher than with glutamine as substrate. The reaction was optimal at pH 10 and 45 degrees C, and the optimal substrate ratio of GAME to ethylamine was 1:10 (mol/mol). With GAME at 100 mmol, 95 mmol theanine was obtained after 8 h. PMID:20383735

  8. Nickel-Catalyzed Cross Couplings of Benzylic Ammonium Salts and Boronic Acids: Stereospecific Formation of Diarylethanes via C–N Bond Activation

    PubMed Central

    Maity, Prantik; Shacklady-McAtee, Danielle M.; Yap, Glenn P. A.; Sirianni, Eric R.; Watson, Mary P.

    2014-01-01

    We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes from readily available chiral benzylic amines. PMID:23268734

  9. Acid-Catalyzed Algal Biomass Pretreatment for Integrated Lipid and Carbohydrate-Based Biofuels Production

    DOE PAGESBeta

    Laurens, L. M. L.; Nagle, N.; Davis, R.; Sweeney, N.; Van Wychen, S.; Lowell, A.; Pienkos, P. T.

    2014-11-12

    One of the major challenges associated with algal biofuels production in a biorefinery-type setting is improving biomass utilization in its entirety, increasing the process energetic yields and providing economically viable and scalable co-product concepts. We demonstrate the effectiveness of a novel, integrated technology based on moderate temperatures and low pH to convert the carbohydrates in wet algal biomass to soluble sugars for fermentation, while making lipids more accessible for downstream extraction and leaving a protein-enriched fraction behind. We studied the effect of harvest timing on the conversion yields, using two algal strains; Chlorella and Scenedesmus, generating biomass with distinctive compositionalmore » ratios of protein, carbohydrate, and lipids. We found that the late harvest Scenedesmus biomass had the maximum theoretical biofuel potential at 143 gasoline gallon equivalent (GGE) combined fuel yield per dry ton biomass, followed by late harvest Chlorella at 128 GGE per ton. Our experimental data show a clear difference between the two strains, as Scenedesmus was more successfully converted in this process with a demonstrated 97 GGE per ton. Our measurements indicated a release of >90% of the available glucose in the hydrolysate liquors and an extraction and recovery of up to 97% of the fatty acids from wet biomass. Techno-economic analysis for the combined product yields indicates that this process exhibits the potential to improve per-gallon fuel costs by up to 33% compared to a lipids-only process for one strain, Scenedesmus, grown to the mid-point harvest condition.« less

  10. Strain-level bacterial identification by CeO2-catalyzed MALDI-TOF MS fatty acid analysis and comparison to commercial protein-based methods

    PubMed Central

    Cox, C. R.; Jensen, K. R.; Saichek, N. R.; Voorhees, K. J.

    2015-01-01

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has emerged as a rapid approach for clinical bacterial identification. However, current protein-based commercial bacterial ID methods fall short when differentiating closely related species/strains. To address this shortcoming, we employed CeO2-catalyzed fragmentation of lipids to produce fatty acids using the energy inherent to the MALDI laser as a novel alternative to protein profiling. Fatty acid profiles collected from Enterobacteriaceae, Acinetobacter, and Listeria using CeO2-catalyzed metal oxide laser ionization (MOLI MS), processed by principal component analysis, and validated by leave–one-out cross-validation (CV), showed 100% correct classification at the species level and 98% at the strain level. In comparison, protein profile data from the same bacteria yielded 32%, 54% and 67% mean species-level accuracy using two MALDI-TOF MS platforms, respectively. In addition, several pathogens were misidentified by protein profiling as non-pathogens and vice versa. These results suggest novel CeO2-catalyzed lipid fragmentation readily produced (i) taxonomically tractable fatty acid profiles by MOLI MS, (ii) highly accurate bacterial classification and (iii) consistent strain-level ID for bacteria that were routinely misidentified by protein-based methods. PMID:26190224

  11. Molecular mechanism of acid-catalyzed hydrolysis of peptide bonds using a model compound.

    PubMed

    Pan, Bin; Ricci, Margaret S; Trout, Bernhardt L

    2010-04-01

    The stability of peptide bonds is a critical aspect of biological chemistry and therapeutic protein applications. Recent studies found elevated nonenzymatic hydrolysis in the hinge region of antibody molecules, but no mechanism was identified. As a first step in providing a mechanistic interpretation, this computational study examines the rate-determining step of the hydrolytic reaction of a peptide bond under acidic pH by a path sampling technique using a model compound N-MAA. Most previous computational studies did not include explicit water molecules, whose effects are significant in solution chemistry, nor did they provide a dynamic picture for the reaction process in aqueous conditions. Because no single trajectory can be used to describe the reaction dynamics due to fluctuations at finite temperatures, a variant version of the transition path sampling technique, the aimless shooting algorithm, was used to sample dynamic trajectories and to generate an ensemble of transition trajectories according to their statistical weights in the trajectory space. Each trajectory was computed as the time evolution of the molecular system using the Car-Parrinello molecular dynamics technique. The likelihood maximization procedure and its modification were used in extracting dynamically relevant degrees of freedom in the system, and approximations of the reaction coordinate were compared. Its low log-likelihood score and poor p(B) histogram indicate that the C-O distance previously assumed as the reaction coordinate for the rate-determining step is inadequate in describing the dynamics of the reaction. More than one order parameter in a candidate set including millions of geometric quantities was required to produce a convergent reaction coordinate model; its involvement of many degrees of freedom suggests that this hydrolytic reaction step is very complex. In addition to affecting atoms directly involved in bond-making and -breaking processes, the water network also has

  12. Utilization of Condensed Distillers Solubles as Nutrient Supplement for Production of Nisin and Lactic Acid from Whey

    NASA Astrophysics Data System (ADS)

    Liu, Chuanbin; Hu, Bo; Chen, Shulin; Glass, Richard W.

    The major challenge associated with the rapid growth of the ethanol industry is the usage of the coproducts, i.e., condensed distillers solubles (CDS) and distillers dried grains, which are currently sold as animal feed supplements. As the growth of the livestock industries remains flat, alternative usage of these coproducts is urgently needed. CDS is obtained after the removal of ethanol by distillation from the yeast fermentation of a grain or a grain mixture by condensing the thin stillage fraction to semisolid. In this work, CDS was first characterized and yeast biomass was proven to be the major component of CDS. CDS contained 7.50% crude protein but with only 42% of that protein being water soluble. Then, CDS was applied as a nutrient supplement for simultaneous production of nisin and lactic acid by Lactococcus lactis subsp. lactis (ATCC 11454). Although CDS was able to support bacteria growth and nisin production, a strong inhibition was observed when CDS was overdosed. This may be caused by the existence of the major ethanol fermentation byproducts, especially lactate and acetate, in CDS. In the final step, the CDS based medium composition for nisin and lactic acid production was optimized using response surface methodology.

  13. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    SciTech Connect

    Gonzalez Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James A.; Curtiss, Larry A.

    2012-02-14

    The conversion of furfuryl alcohol (FAL) to levulinic acid over Amberlyst TM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5- trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  14. Light-absorbing aldol condensation products in acidic aerosols: Spectra, kinetics, and contribution to the absorption index

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; Esteve, William

    The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190-1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300-500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96-75 wt% H 2SO 4 solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of -(70±15) kJ mol -1 in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H 2SO 4 and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10 -4, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.

  15. How Do Perfluorinated Alkanoic Acids Elicit Cytochrome P450 to Catalyze Methane Hydroxylation? An MD and QM/MM Study

    PubMed Central

    Li, Chunsen; Shaik, Sason

    2013-01-01

    Recent experimental studies show that usage of perfluoro decanoic acid (PFDA), as a dummy substrate, can elicit P450BM3 to perform hydroxylation of small alkanes, such as methane (ref. 17) and propane (ref. 17 and ref. 18). To comprehend the mechanism whereby PFDA operates to potentiate P450BM3 to catalyze the hydroxylation of small alkanes, we used molecular dynamics (MD) and hybrid quantum mechanical / molecular mechanical (QM/MM) calculations. The MD results show that without the PFDA, methane escapes the active site, while the presence of PFDA can potentially induce a productive Cpd I-Methane juxtaposition for rapid oxidation. Nevertheless, when only a single methane molecule is present near the PFDA, it still escapes the pocket within less than a nanosecond. However, when three methane molecules are present in the pocket, they alternate quasi-periodically such that at all times (within 10 ns), a molecule of methane is always present in the proximity of Cpd I in a reactive conformation. Our results further demonstrate that the PFDA does not exert any electrostatic catalysis, whether the PFDA is in the protonated or deprotonated forms. Taken together, we conclude that methane hydroxylation requires, in addition to PFDA, a high partial pressure of methane that will cause a high methane concentration in the active site. Further study of ethane and propane hydroxylations demonstrates that higher alkane concentration is helpful for all the three small alkanes. Thus for the smallest alkane, methane, at least three molecules are necessary whereas for the larger ethane, two molecules are needed to force one ethane to be closer to Cpd I. Finally, for propane a second molecule is helpful but not absolutely necessary; for this molecule the PFDA may well be sufficient to keep propane close to Cpd I for efficient oxidation. We therefore propose that high alkane pressure should assist small alkane hydroxylation by P450 in a manner inversely proportional to the size of the

  16. Palladium(II)‐Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox‐Neutral, Phosphine‐Free Transformation

    PubMed Central

    Deeming, Alex S.; Russell, Claire J.

    2015-01-01

    Abstract A redox‐neutral palladium(II)‐catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high‐yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C‐ or N‐based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one‐pot, two‐step process. PMID:26596861

  17. Divergent reactivity in palladium-catalyzed annulation with diarylamines and α,β-unsaturated acids: direct access to substituted 2-quinolinones and indoles.

    PubMed

    Kancherla, Rajesh; Naveen, Togati; Maiti, Debabrata

    2015-06-01

    A palladium-catalyzed CH activation strategy has been successfully employed for exclusive synthesis of a variety of 3-substituted indoles. A [3+3] annulation for synthesizing substituted 2-quinolinones was recently developed by reaction of α,β-unsaturated carboxylic acids with diarylamines under acidic conditions. In the present work, an analogous [3+2] annulation is achieved from the same set of starting materials under basic conditions to generate 1,3-disubstituted indoles exclusively. Mechanistic studies revealed an ortho-palladation-π-coordination-β-migratory insertion-β-hydride elimination reaction sequence to be operative under the reaction conditions. PMID:25941155

  18. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.

    PubMed

    Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M

    2014-09-01

    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. PMID:25045161

  19. IAA-synthase, an enzyme complex from Arabidopsis thaliana catalyzing the formation of indole-3-acetic acid from (S)-tryptophan.

    PubMed

    Müller, A; Weiler, E W

    2000-08-01

    An enzyme complex was isolated from Arabidopsis thaliana that catalyzes the entire pathway of biosynthesis of the major plant growth hormone, indole-3-acetic acid (IAA), from (S)-tryptophan. The 160-180 kDa, soluble complex catalyzes a strictly O2-dependent reaction which requires no further added factors and is stereospecific for the substrate (S)-tryptophan (app. Km = 120 microM). H2(18)O labeling proved that both oxygen atoms of IAA were delivered via H2O. This, as well as immunological evidence for the presence of a nitrilase-like protein in the complex, suggests the reaction to proceed via the intermediate indole-3-acetonitrile. IAA-synthase forms a tight metabolite channel committed to IAA production and occurs in shoots, roots and cell cultures of A. thaliana. PMID:11030425

  20. The formation of acid rain in the atmosphere, adjacent to the TTP with the joint-condensing of sulfur dioxide and water vapor

    NASA Astrophysics Data System (ADS)

    Gvozdyakov, D. V.; Gubin, V. E.; Matveeva, A. A.

    2014-08-01

    Presents the results of mathematical simulation of the condensation process of sulphur dioxide and water vapor on the condensation nuclei surface under the action of natural factors. Numerical investigations were carried out for the summer at a moderate speed of the wind. The influence of the parameter of condensation on the speed of the process of sulfuric acid drops formation in the air space was analyzed. Time ranges, sufficient for the formation of the acid rain sedimentation in the atmosphere, adjacent to the areas of thermal power station work were established. It is shown that the speed of air masses movement effects on the process of acid anthropogenic admixtures dispersion in the atmosphere. Approbation of the obtained results was carried out by checking the difference scheme conservative and solution of test problems.

  1. Origin of saline, neutral-pH, reduced epithermal waters by reaction of acidic magmatic gas condensates with wall rock

    SciTech Connect

    Reed, M.H. . Dept. of Geological Sciences)

    1993-04-01

    Fluid inclusions in quartz and sphalerite of epithermal veins containing galena, sphalerite and chalcopyrite with silver sulfides and electrum commonly have salinities of 2 to 10 weight percent NaCl equivalent. Examples include Bohemia, OR, Comstock, NV, and Creede, CO. Salinities in such base metal-rich systems are apparently greater than those in gold-adularia, base metal-poor systems such as Sleeper, NV, Republic, WA, and Hishikare, Kyushu. Saline epithermal fluids are commonly assumed to have been derived from saline magmatic brines, from local host formations, as has been suggested for Creede, or from evaporative concentration (boiling) of more dilute meteoric ground water. Another possibility, which may be the most common origin, is reaction of wall rocks with magmatic gas condensates rich in HCl and sulfuric acid. A mixture of one part Augustine Volcanic gas condensate in 10 parts cold ground water has a pH of 0.7 and the dominant cation is H[sup +] by a factor of 10[sup 4]. Calculated reaction of this condensate mixture with andesite at 300 C to a water/rock ratio (w/r) of 4.6 yields an NaCl-dominated fluid with a total salinity of 2.1 wt %. and pH 3.7. Further reaction, to w/r 0.14 yields a fluid salinity of 2.6 wt % and pH of 5.7; this fluid is in equilibrium with a propylitic alteration assemblage. Aqueous sulfide accumulates during the rock reaction as sulfate is reduced to sulfide when ferrous iron is oxidized to ferric iron. Sulfide concentration in the latter fluid is 32 ppm, far exceeding sulfate concentration. In the overall reaction, hydrogen ion is exchanged for base cations (including base metals) and sulfate is reduced to sulfide.

  2. Additional Nucleophile-Free FeCl3-Catalyzed Green Deprotection of 2,4-Dimethoxyphenylmethyl-Protected Alcohols and Carboxylic Acids.

    PubMed

    Sawama, Yoshinari; Masuda, Masahiro; Honda, Akie; Yokoyama, Hiroki; Park, Kwihwan; Yasukawa, Naoki; Monguchi, Yasunari; Sajiki, Hironao

    2016-01-01

    The deprotection of the methoxyphenylmethyl (MPM) ether and ester derivatives can be generally achieved by the combinatorial use of a catalytic Lewis acid and stoichiometric nucleophile. The deprotections of 2,4-dimethoxyphenylmethyl (DMPM)-protected alcohols and carboxylic acids were found to be effectively catalyzed by iron(III) chloride without any additional nucleophile to form the deprotected mother alcohols and carboxylic acids in excellent yields. Since the present deprotection proceeds via the self-assembling mechanism of the 2,4-DMPM protective group itself to give the hardly-soluble resorcinarene derivative as a precipitate, the rigorous purification process by silica-gel column chromatography was unnecessary and the sufficiently-pure alcohols and carboxylic acids were easily obtained in satisfactory yields after simple filtration. PMID:27373632

  3. Effect of benzoic acid on the removal of 1,2-dichloroethane by a siderite-catalyzed hydrogen peroxide and persulfate system.

    PubMed

    Li, Shengpin; Li, Mengjiao; Luo, Ximing; Huang, Guoxin; Liu, Fei; Chen, Honghan

    2016-01-01

    Benzoic acid can affect the iron-oxide mineral dissolution and react with hydroxyl radical. This study investigated its effect on 1,2-dichloroethane removal process by siderite-catalyzed hydrogen peroxide and persulfate. The variation of benzoic acid concentrations can affect pH value and soluble iron concentrations; when benzoic acid varied from 0 to 0.5 mmol/L, pH increased while Fe(2+) and Fe(3+) concentrations decreased, resulting in 1,2-dichloroethane removal efficiency which decreased from 91.2 to 5.0%. However, when benzoic acid varied from 0.5 to 10 mmol/L, pH decreased while Fe(2+) and Fe(3+) concentrations increased, resulting in 1,2-dichloroethane removal efficiency which increased from 5.0 to 83.4%. PMID:26308917

  4. Aldol Condensation Products and Polyacetals in Organic Films Formed from Reactions of Propanal in Sulfuric Acid at Upper Troposphere/Lower Stratosphere (UT/LS) Aerosol Acidities

    NASA Astrophysics Data System (ADS)

    Bui, J. V. H.; Perez-Montano, S.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.; Van Wyngarden, A. L.

    2015-12-01

    Aerosols in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt. %) which is highly reflective towards UV and visible radiation. However, airborne measurements have shown that these particles may also contain a significant amount of organic material. Experiments combining organics (propanal, glyoxal and/or methylglyoxal) with sulfuric acid at concentrations typical of UT/LS aerosols produced highly colored surface films (and solutions) that have the potential to impact chemical, optical and/or cloud-forming properties of aerosols. In order to assess the potential for such films to impact aerosol chemistry or climate properties, experiments were performed to identify the chemical processes responsible for film formation. Surface films were analyzed via Attenuated Total Reflectance-FTIR and Nuclear Magnetic Resonance spectroscopies and are shown to consist primarily of aldol condensation products and cyclic and linear polyacetals, the latter of which are likely responsible for separation from the aqueous phase.

  5. One-pot SSA-catalyzed β-elimination: An efficient and inexpensive protocol for easy access to the glycal of sialic acid

    PubMed Central

    Paragas, Erickson M.; Monreal, I. Abrrey; Vasil, Chris M.; Saludes, Jonel P.

    2014-01-01

    Neu5Ac2en1Me per-OAc, the fully protected glycal of sialic acid, is a key intermediate in the discovery of therapeutics and diagnostics, including anti-influenza drugs and proteolysis resistant peptidomimetic foldamers. The synthesis of this sialic acid derivative, however, still relies on standard sugar chemistry that utilizes multi-step methodologies. Herein we report a facile and highly efficient microwave-assisted preparation of Neu5Ac1Me using silica sulfuric acid (SSA) as solid-supported acid catalyst that is one- to two-orders of magnitude faster than standard procedures. We also describe the microwave-assisted and SSA-catalyzed one-pot, rapid, solvent free reaction that combines both peracetylation and β-elimination reactions in one step to generate the glycal from Neu5Ac1Me. We coined the term One-pot SSA-catalyzed Technology for β-Elimination Protocol (OneSTEP) to describe this least laborious, most efficient, and practical preparation to date of Neu5Ac2en1Me per-OAc in terms of yield, time, reagent cost, and waste generation. PMID:25497336

  6. Discrimination of ionic pollutants except condensation nuclei of acid fog using an ultrasonic humidifier.

    PubMed

    Yoshimura, Keiji; Kikuchi, Ryoei; Kimoto, Takashi; Ozeki, Toru; Imano, Kazuhiko; Kajikawa, Masahiro; Ogawa, Nobuaki

    2006-06-01

    Fog droplets in the atmosphere are first produced by the activation of cloud condensation nuclei (CCN), which are originally some ionic compound. Subsequently, the nuclei grow by vapor diffusion. Fog droplets are polluted through the activation process and successive diffusion growth and residence (post activation). We cannot distinguish the effects of the two pollution processes of natural fog water samples. We found that fog droplets can be produced artificially without CCN using an ultrasonic humidifier. Because the artificial fog droplets are not polluted by CCN, the movement of the fog droplets in natural air will take up some pollutants in the air. Consequently, the two pollution processes of fog (the activation of CCN and the post activation process) can be discriminated using data from field experiments. This sampling analytical method is extremely important for further research regarding fog, clouds and environmental chemistry. PMID:16772683

  7. Mechanistic aspects of the rhodium-catalyzed enantioselective transfer hydrogenation of [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source

    SciTech Connect

    Leitner, W. Universitaet Regensburg ); Brown, J.M. ); Brunner, H. )

    1993-01-13

    The mechanism of the rhodium-catalyzed enantioselective transfer hydrogenation of methylenebutanedioic acid (itaconic acid) (1) and related [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source is investigated. Kinetic studies using [sup 1]H NMR spectroscopy are presented. Formic acid decomposition is shown to be the rate-limiting step with 1 as the substrate, while hydrogen transfer turns out to be rate determining in the case of (E)-(phenylmethylene)butanedioic acid ((E)-phenylitaconic acid) (3). Furthermore, extensive use is made of deuterium labeling and the analysis of part-deuterated products by [sup 1]H and [sup 13]C[l brace][sup 1]H,[sup 2]H[r brace] NMR spectroscopy. Taken together, these results indicate that the mechanism of rhodium-catalyzed transfer hydrogenation with formic acid/triethylamine as the hydrogen source most likely involves decarboxylation of a transient formate species to form hydridic complexes of rhodium, in which the Rh-H entity has a long lifetime relative to hydrogen transfer to the substrate. 40 refs., 5 figs., 1 tab.

  8. Expedient synthesis of tetrahydroquinoline-3-spirohydantoin derivatives via the Lewis acid-catalyzed tert-amino effect reaction.

    PubMed

    Briones, John F; Basarab, Gregory S

    2016-06-30

    Magnesium triflate was found to effectively catalyze the tert-amino effect reaction (T-reaction) involving ethyl 3-(2-(dialkylamino)-phenyl)-2-nitroacrylates leading to tetrahydroquinoline nitroester derivatives. These compounds can be readily transformed to the corresponding valuable spirohydantoin derivatives. PMID:27314439

  9. Enantioselective [4 + 2]-Annulation of Oxadienes and Allenones Catalyzed by an Amino Acid Derived Phosphine: Synthesis of Functionalized Dihydropyrans.

    PubMed

    Ni, Huanzhen; Yao, Weijun; Waheed, Abdul; Ullah, Nisar; Lu, Yixin

    2016-05-01

    An enantioselective [4 + 2]-annulation process between cyano-activated oxadienes and allenones is developed. An l-valine-derived phosphine was efficient in catalyzing the reaction, and a wide range of highly functionalized dihydropyrans were prepared in high yields and with excellent enantioselectivities. PMID:27091405

  10. Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

    PubMed Central

    Surasani, Rajendra; Rao, A V Dhanunjaya; Chandrasekhar, K B

    2012-01-01

    Summary Simple and efficient procedures for palladium-catalyzed cross-coupling reactions of N-substituted 4-bromo-7-azaindole (1H-pyrrole[2,3-b]pyridine), with amides, amines, amino acid esters and phenols through C–N and C–O bond formation have been developed. The C–N cross-coupling reaction of amides, amines and amino acid esters takes place rapidly by using the combination of Xantphos, Cs2CO3, dioxane and palladium catalyst precursors Pd(OAc)2/Pd2(dba)3. The combination of Pd(OAc)2, Xantphos, K2CO3 and dioxane was found to be crucial for the C–O cross-coupling reaction. This is the first report on coupling of amides, amino acid esters and phenols with N-protected 4-bromo-7-azaindole derivatives. PMID:23209536

  11. Following solid-acid-catalyzed reactions by MAS NMR spectroscopy in liquid phase--zeolite-catalyzed conversion of cyclohexanol in water.

    PubMed

    Vjunov, Aleksei; Hu, Mary Y; Feng, Ju; Camaioni, Donald M; Mei, Donghai; Hu, Jian Z; Zhao, Chen; Lercher, Johannes A

    2014-01-01

    A microautoclave magic angle spinning NMR rotor is developed enabling in situ monitoring of solid-liquid-gas reactions at high temperatures and pressures. It is used in a kinetic and mechanistic study of the reactions of cyclohexanol on zeolite HBEA in 130 °C water. The (13) C spectra show that dehydration of 1-(13) C-cyclohexanol occurs with significant migration of the hydroxy group in cyclohexanol and the double bond in cyclohexene with respect to the (13) C label. A simplified kinetic model shows the E1-type elimination fully accounts for the initial rates of 1-(13) C-cyclohexanol disappearance and the appearance of the differently labeled products, thus suggesting that the cyclohexyl cation undergoes a 1,2-hydride shift competitive with rehydration and deprotonation. Concurrent with the dehydration, trace amounts of dicyclohexyl ether are observed, and in approaching equilibrium, a secondary product, cyclohexyl-1-cyclohexene is formed. Compared to phosphoric acid, HBEA is shown to be a more active catalyst exhibiting a dehydration rate that is 100-fold faster per proton. PMID:24282024

  12. N-Acyl Amino Acid Ligands for Ruthenium(II)-Catalyzed meta-C-H tert-Alkylation with Removable Auxiliaries.

    PubMed

    Li, Jie; Warratz, Svenja; Zell, Daniel; De Sarkar, Suman; Ishikawa, Eloisa Eriko; Ackermann, Lutz

    2015-11-01

    Acylated amino acid ligands enabled ruthenium(II)-catalyzed C-H functionalizations with excellent levels of meta-selectivity. The outstanding catalytic activity of the ruthenium(II) complexes derived from monoprotected amino acids (MPAA) set the stage for the first ruthenium-catalyzed meta-functionalizations with removable directing groups. Thereby, meta-alkylated anilines could be accessed, which are difficult to prepare by other means of direct aniline functionalizations. The robust nature of the versatile ruthenium(II)-MPAA was reflected by challenging remote C-H transformations with tertiary alkyl halides on aniline derivatives as well as on pyridyl-, pyrimidyl-, and pyrazolyl-substituted arenes. Detailed mechanistic studies provided strong support for an initial reversible C-H ruthenation, followed by a SET-type C-Hal activation through homolytic bond cleavage. Kinetic analyses confirmed this hypothesis through an unusual second-order dependence of the reaction rate on the ruthenium catalyst concentration. Overall, this report highlights the exceptional catalytic activity of ruthenium complexes derived from acylated amino acids, which should prove instrumental for C-H activation chemistry beyond remote functionalization. PMID:26418891

  13. Pd-Catalyzed Regioselective Alkoxycarbonylation of 1-Alkenes Using a Lewis Acid [SnCl2 or Ti(O(i)Pr)4] and a Phosphine.

    PubMed

    Amézquita-Valencia, Manuel; Achonduh, George; Alper, Howard

    2015-06-19

    The phosphine ligand mediated palladium catalyzed alkoxycarbonylation of alkenes was investigated with the objective of attaining good linear selectivity for the ester. The effect of various parameters such as solvents, additives, palladium precursors, CO pressures, and alkenes of various structural complexities were examined. The results revealed the importance of using a Lewis acid such as SnCl2 or Ti(O(i)Pr)4 in combination with a monodentate ligand such CYTOP 292 or P(p-anisyl)3 to enhance the regioselectivity for the linear isomers in the range of 70-96%. PMID:26005796

  14. Copper-catalyzed α-amination of phosphonates and phosphine oxides: a direct approach to α-amino phosphonic acids and derivatives.

    PubMed

    McDonald, Stacey L; Wang, Qiu

    2014-02-10

    A direct approach to important α-amino phosphonic acids and its derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of CN bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope. PMID:24474326

  15. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    PubMed

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-01

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps. PMID:26575242

  16. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    PubMed

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-01

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling. PMID:27439145

  17. Palladium-catalyzed β-C(sp(3))-H arylation of phthaloyl alanine with hindered aryl iodides: synthesis of complex β-aryl α-amino acids.

    PubMed

    Zhang, Xuekai; He, Gang; Chen, Gong

    2016-06-28

    An efficient protocol for palladium-catalyzed β-C(sp(3))-H arylation of aliphatic carboxamides equipped with a 2-(2-pyridyl) ethylamine (PE) auxiliary was developed. The PE auxiliary is uniquely effective at facilitating the arylation of primary C(sp(3))-H bonds with sterically hindered aryl iodides. A variety of aryl iodides bearing alkoxyl, carbonyl, nitro and halogen groups on the ortho position can react with the PE-coupled phthaloyl alanine substrate in moderate to excellent yield. These reactions offer a useful solution for preparing complex β-aryl α-amino acid products from readily accessible starting materials. PMID:26781005

  18. Copper-catalyzed asymmetric synthesis of tertiary α-hydroxy phosphonic acid derivatives with in situ generated nitrosocarbonyl compounds as the oxygen source.

    PubMed

    Maji, Biplab; Yamamoto, Hisashi

    2014-12-22

    α-Hydroxy phosphonic acids and their derivatives are highly bioactive structural motifs. It is now reported that these compounds can be accessed through the copper-catalyzed direct α-oxidation of β-ketophosphonates using in situ generated nitrosocarbonyl compounds as an electrophilic oxygen source. These reactions proceeded in high yields (up to 95 %) and enantioselectivities (up to >99 % ee) for both cyclic as well as acyclic substrates. This method was also applied for the synthesis of α,β-dihydroxy phosphonates and β-amino-α-hydroxy phosphonates. PMID:25348199

  19. Synthesis of beta-lactones by the regioselective, cobalt and Lewis acid catalyzed carbonylation of simple and functionalized epoxides.

    PubMed

    Lee, J T; Thomas, P J; Alper, H

    2001-08-10

    The PPNCo(CO)(4) and BF(3) x Et(2)O catalyzed carbonylation of simple and functionalized epoxides in DME gives the corresponding beta-lactones regioselectively in good to high yields. The carbonylation occurred selectively at the unsubstituted C-O bond of the epoxide ring, and this reaction tolerates various functional groups such as alkenyl, halide, hydroxy, and alkyl ether. PMID:11485465

  20. Synthetic applications of Pd(II)-catalyzed C-H carboxylation and mechanistic insights: expedient routes to anthranilic acids, oxazolinones, and quinazolinones.

    PubMed

    Giri, Ramesh; Lam, Jonathan K; Yu, Jin-Quan

    2010-01-20

    A Pd(II)-catalyzed reaction protocol for the carboxylation of ortho-C-H bonds in anilides to form N-acyl anthranilic acids has been developed. This reaction procedure provides a novel and efficient strategy for the rapid assembly of biologically and pharmaceutically significant molecules, such as benzoxazinones and quinazolinones, from simple anilides without installing and removing an external directing group. The reaction conditions are also amenable to the carboxylation of N-phenyl pyrrolidinones. A monomeric palladacycle containing p-toluenesulfonate as an anionic ligand has been characterized by X-ray crystallography, and the crucial role of p-toluenesulfonic acid in the activation of C-H bonds in the presence of carbon monoxide is discussed. Identification of two key intermediates, a mixed anhydride and benzoxazinone formed by reductive elimination from organometallic Ar(CO)Pd(II)-OTs species, provides mechanistic evidence for a dual-reaction pathway. PMID:20000840

  1. Aromatization of hydrocarbons by oxidative dehydrogenation catalyzed by the mixed addenda heteropoly acid H sub 5 PMo sub 10 V sub 2 O sub 40

    SciTech Connect

    Neumann, R. ); Lissle, M. )

    1989-09-15

    The mixed addenda heteropoly acid H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} dissolved in 1,2-dichloroethane with tetraglyme, forming the (tetraglyme){sub 3}-H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} complex, catalyzes the aromatization of cyclic dienes at moderate temperatures in the presence of molecular oxygen. Dehydrogenations of exocyclic dienes such as limonene show that dehydrogenation is preceded by isomerization to their endocyclic isomers. Aromatization takes place by successive one-electron transfers and proton abstractions from the organic substrate to the heteropoly acid the latter being reoxidized by dioxygen coupled with the formation of water.

  2. Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization.

    PubMed

    Lewis, Jennifer D; Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-08-17

    Hf-, Sn-, and Zr-Beta zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. PMID:26138135

  3. Short communication: assessment of the potential of cinnamaldehyde, condensed tannins, and saponins to modify milk fatty acid composition of dairy cows.

    PubMed

    Benchaar, C; Chouinard, P Y

    2009-07-01

    This study was conducted to determine whether feeding cinnamaldehyde (main component of cinnamon bark essential oil; Cinnamon cassia), condensed tannins from quebracho trees (Schinopsis balansae), or saponins from Yucca schidigera altered the milk fatty acid profile of dairy cows. For this purpose, 4 lactating cows were used in 4 x 4 Latin square design (28-d period) and fed a total mixed ration containing no additive (control), or supplemented with cinnamaldehyde (1 g/d; CIN), quebracho condensed tannin extract (150 g/d; 70% of tannins; QCT), or Yucca schidigera saponin extract (60 g/d; 10% of saponins; YSE). Results revealed no effects of feeding CIN or QCT on milk fatty acid profile. Supplementation with YSE resulted in some modifications of milk fatty acid profile as suggested by the reduced proportions of C6:0 (2.71 vs. 2.95%), C8:0 (1.66 vs. 1.89%), and trans-11 C18:1 (0.92 vs. 1.01%). Results show low potential of cinnamaldehyde, condensed tannins, and saponins to alter ruminal biohydrogenation process and modify the fatty acid profile of milk fat at the feeding rates used in this study. Further investigations are needed to determine the factors that limit the effects of these secondary metabolites on ruminal microbial populations involved in the biohydrogenation processes of unsaturated fatty acids. PMID:19528616

  4. Difference analysis of the enzymatic hydrolysis performance of acid-catalyzed steam-exploded corn stover before and after washing with water.

    PubMed

    Zhu, Junjun; Shi, Linli; Zhang, Lingling; Xu, Yong; Yong, Qiang; Ouyang, Jia; Yu, Shiyuan

    2016-10-01

    The difference in the enzymatic hydrolysis yield of acid-catalyzed steam-exploded corn stover (ASC) before and after washing with water reached approximately 15 % under the same conditions. The reasons for the difference in the yield between ASC and washed ASC (wASC) were determined through the analysis of the composition of ASC prehydrolyzate and sugar concentration of enzymatic hydrolyzate. Salts produced by neutralization (CaSO4, Na2SO4, K2SO4, and (NH4)2SO4), sugars (polysaccharides, oligosaccharides, and monosaccharides), sugar-degradation products (weak acids and furans), and lignin-degradation products (ethyl acetate extracts and nine main lignin-degradation products) were back-added to wASC. Results showed that these products, except furans, exerted negative effect on enzymatic hydrolysis. According to the characteristics of acid-catalyzed steam explosion pretreatment, the five sugar-degradation products' mixture and salts [Na2SO4, (NH4)2SO4] showed minimal negative inhibition effect on enzymatic hydrolysis. By contrast, furans demonstrated a promotion effect. Moreover, soluble sugars, such as 13 g/L xylose (decreased by 6.38 %), 5 g/L cellobiose (5.36 %), 10 g/L glucose (3.67 %), as well as lignin-degradation products, and ethyl acetate extracts (4.87 %), exhibited evident inhibition effect on enzymatic hydrolysis. Therefore, removal of soluble sugars and lignin-degradation products could effectively promote the enzymatic hydrolysis performance. PMID:27277746

  5. 5-Methylisoxazole-3-carboxamide-Directed Palladium-Catalyzed γ-C(sp(3))-H Acetoxylation and Application to the Synthesis of γ-Mercapto Amino Acids for Native Chemical Ligation.

    PubMed

    Pasunooti, Kalyan Kumar; Yang, Renliang; Banerjee, Biplab; Yap, Terence; Liu, Chuan-Fa

    2016-06-01

    Palladium-catalyzed acetoxylation of the primary γ-C(sp(3))-H bonds in the amino acids Val, Thr, and Ile was achieved using a newly discovered 5-methylisoxazole-3-carboxamide directing group. The γ-acetoxylated α-amino acid derivatives could be easily converted to γ-mercapto amino acids, which are useful for native chemical ligation (NCL). The first application of NCL at isoleucine in the semisynthesis of a Xenopus histone H3 protein was also demonstrated. PMID:27218276

  6. Lipase-catalyzed synthesis of structured phenolic lipids in solvent-free system using flaxseed oil and selected phenolic acids as substrates.

    PubMed

    Sorour, Noha; Karboune, Salwa; Saint-Louis, Richard; Kermasha, Selim

    2012-04-15

    Structured phenolic lipids (PLs) were obtained by lipase-catalyzed transesterification of flaxseed oil, in a solvent-free system (SFS), with selected phenolic acids, including hydroxylated and/or methoxylated derivatives of cinnamic, phenyl acetic and benzoic acids. A bioconversion yield of 65% was obtained for the transesterification of flaxseed oil with 3,4-dihydroxyphenyl acetic acid (DHPA). However, the effect of the chemical structure of phenolic acids on the transesterification of flaxseed oil in SFS was of less magnitude as compared to that in organic solvent system (OSS). Using DHPA, the APCI-MS analysis confirmed the synthesis of monolinolenyl, dilinolenyl, linoleyl linolenyl and oleyl linolenyl dihydroxyphenyl acetates as phenolic lipids. A significant increase in the enzymatic activity from 200 to 270 nmol of PLs/g solid enzyme/min was obtained upon the addition of the non-ionic surfactant Span 65. However, upon the addition of the anionic surfactant, sodium bis-2-ethylhexyl sulfosuccinate (AOT), and the cationic one, hexadecyltrimethylammonium bromide (CTAB), the enzymatic activity was decreased slightly from 200 to 192 and 190 nmol of PLs/g solid enzyme/min, respectively. The results also showed that the increase in DHPA concentration from 20 to 60 mM resulted in a significant increase in the volumetric productivity (P(V)) from 1.61 to 4.74 mg PLs per mL reaction mixture per day. PMID:22329891

  7. Triflic Acid-Catalyzed Cycloisomerization Reactions of Donor-Acceptor Cyclopropanes: Access to Alkyl 5-Arylfuran-2-carboxylates.

    PubMed

    Zhu, Yuequan; Xu, Panpan; Gong, Yuefa

    2016-06-01

    A direct synthetic strategy starting from alkyl 1-alkoxy-2-aroylcyclopropanecarboxylates was developed for the construction of alkyl 5-arylfuran-2-carboxylates. These donor-acceptor cyclopropanes smoothly undergo a simple ring-opening reaction or/and cycloisomerization reaction in the presence of acid at room temperature, which greatly depends on the properties of the acid used in the experiment. Alkyl 5-arylfuran-2-carboxylates were afforded in high yields in triflic acid, whereas alkyl 2,5-dioxo-5-phenylpentanoate became the major product in other protic acids and Lewis acids. PMID:27156857

  8. Ion condensation behavior and dynamics of water molecules surrounding the sodium poly(methacrylic acid) chain in water: a molecular dynamics study.

    PubMed

    Chung, Yung-Ting; Huang, Ching-I

    2012-03-28

    All-atom molecular dynamics simulations are used to study the condensation behavior of monovalent (Na(+)) and multivalent (Ca(2+)) salt counterions associated with the co-ions (Cl(-)) surrounding the charged poly(methacrylic acid) (PMAA) chain in water. The study is extended to the influences on chain conformation, local arrangement, and dynamics of water in the highly diluted aqueous solutions. We find that even when the salt ions are monovalent, they attract more than one charged monomer and act as a bridging agent within the chain, as the multivalent salt ions. In principle, the salt ions bridge between not only the "non-adjacent" but also the "adjacent" charged monomers, leading to a more coil-like and a locally stretched conformation, respectively. With an increase in the salt concentration, the amount of coiled-type condensed ions increase and reach a maximum when the chain conformation becomes the most collapsed; whereas, the stretched-type shows an opposite trend. Our results show that the attractive interactions through the condensed salt ions between the non-adjacent monomers are responsible for the conformational collapse. When the salt concentration increases high enough, a significant increase for the stretched-type condensed ions makes an expansion effect on the chain. These stretched-type salt ions, followed by the adsorption of the co-ions and water molecules, tend to form a multilayer organization outside surrounding the PMAA chain. Thus, the expansion degree of the chain conformation is greatly limited. When only the monovalent Na(+) ions are present in the solutions, water molecules are primarily adsorbed into either the condensed Na(+) ions or the COO(-) groups. These adsorbed water molecules form hydrogen bonds with each other and enhance the local bridging behavior associated with the Na(+) condensation on the resultant chain conformation. With an increase in the amount of multivalent Ca(2+) salt ions, more water molecules are bonded directly

  9. Evidence for the inhibition of the terminal step of ruminal alpha-linolenic acid biohydrogenation by condensed tannins.

    PubMed

    Khiaosa-Ard, R; Bryner, S F; Scheeder, M R L; Wettstein, H-R; Leiber, F; Kreuzer, M; Soliva, C R

    2009-01-01

    Effects of condensed tannins (CT), either via extract or plant-bound, and saponin extract on ruminal biohydrogenation of alpha-linolenic acid (ALA) were investigated in vitro. Grass-clover hay served as basal diet (control). The control hay was supplemented with extracts contributing either CT from Acacia mearnsii [7.9% of dietary dry matter (DM)] or saponins from Yucca schidigera (1.1% of DM). The fourth treatment consisted of dried sainfoin (Onobrychis viciifolia), a CT-containing forage legume, in an amount also providing 7.9% CT in dietary DM. All diets were supplemented with linseed oil at a level contributing 60% of total dietary ALA in all treatments. Diets were incubated for 10 d (n = 4) in the rumen simulation technique system, using the last 5 d for statistical evaluation. Fatty acids were analyzed in feed, feed residues, incubation fluid, and its effluent. Data were subjected to ANOVA considering diet and experimental run as main effects. Both CT treatments reduced ruminal fiber and crude protein degradation, and lowered incubation fluid ammonia concentration. Only the CT extract suppressed methane formation and shifted microbial populations toward bacteria at cost of protozoa. The saponin extract remained without clear effects on fermentation characteristics except for increased protozoal counts. The extent of ALA biohydrogenation was 20% less with the CT plant, but this probably resulted from reduced organic matter degradability rather than from an inhibition of biohydrogenation. After incubation analysis of incubation fluid effluent and feed residues showed a considerable proportion of the 3 biohydrogenation intermediates, cis-9, trans-11, cis-15 C18:3, trans-11, cis-15 C18:2, and trans-11 C18:1, which did not occur in the initial feeds. Only the CT-extract diet led to a different profile in the effluent compared with the control diet with trans-11 C18:1 being considerably increased at cost of C18:0. This could have been achieved by suppressing

  10. Synthesis of ethers by GaBr3 -catalyzed reduction of carboxylic acid esters and lactones by siloxanes.

    PubMed

    Biermann, Ursula; Metzger, Jürgen O

    2014-02-01

    Ethers were synthesized by reduction of the respective esters catalyzed by gallium bromide (GaBr3 ) and using siloxanes, preferentially 1,1,3,3-tetramethyldisiloxane, as reductant. Methyl oleate, triglycerides, that is, tributyrine and glyceryl triundec-10-enoate as well as γ- and δ-lactones were converted into the respective ethers in high to moderate yields. γ-Lactones were reduced with high selectivity in the presence of a methyl ester functionality. The reduction has been carried out at room temperature or moderately elevated temperature of up to 60 °C using stoichiometric amounts of the reductant and 0.005-0.01 equiv of GaBr3 as catalyst per ester functionality without any solvent added. After a reaction time of 1-4 h the conversion of the substrate was 100 %. The product was separated from polymeric siloxanes formed as coupled product by simple distillation. PMID:24488681

  11. Hybrid Quantum Mechanics/Molecular Mechanics-Based Molecular Dynamics Simulation of Acid-Catalyzed Dehydration of Polyols in Liquid Water

    SciTech Connect

    Caratzoulas, Stavros; Courtney, Timothy; Vlachos, Dionisios G.

    2011-01-01

    We use the conversion of protonated glycerol to acrolein for a case study of the mechanism of acid-catalyzed dehydration of polyols in aqueous environments. We employ hybrid Quamtum Mechanics/Molecular Mechanics Molecular Dynamics (QM/MM MD) simulations with biased sampling and perform free energy calculations for the elementary steps of the reaction. We investigate the effects of solvent dynamics and in particular the role of quantum mechanical water in the dehydration mechanism. We present results supporting a mechanism that proceeds via water-mediated proton transfers and thus through an enol intermediate. We find that the first dehydration may take place by two, low-energy pathways requiring, respectively, 20.9 and 18.8 kcal/mol of activation free energy. The second dehydration requires 19.9 kcal/mol of activation free energy while for the overall reaction we compute a free energy change of -8 kcal/mol.

  12. Bispalladacycle-catalyzed Brønsted acid/base-promoted asymmetric tandem azlactone formation-Michael addition.

    PubMed

    Weber, Manuel; Jautze, Sascha; Frey, Wolfgang; Peters, René

    2010-09-01

    Cooperative activation by a soft bimetallic catalyst, a hard Brønsted acid, and a hard Brønsted base has allowed the formation of highly enantioenriched, diastereomerically pure masked alpha-amino acids with adjacent quaternary and tertiary stereocenters in a single reaction starting from racemic N-benzoylated amino acids. The products can, for example, be used to prepare bicyclic dipeptides. PMID:20715774

  13. Pyruvate decarboxylase catalyzes decarboxylation of branched-chain 2-oxo acids but is not essential for fusel alcohol production by Saccharomyces cerevisiae.

    PubMed

    ter Schure, E G; Flikweert, M T; van Dijken, J P; Pronk, J T; Verrips, C T

    1998-04-01

    The fusel alcohols 3-methyl-1-butanol, 2-methyl-1-butanol, and 2-methyl-propanol are important flavor compounds in yeast-derived food products and beverages. The formation of these compounds from branched-chain amino acids is generally assumed to occur via the Ehrlich pathway, which involves the concerted action of a branched-chain transaminase, a decarboxylase, and an alcohol dehydrogenase. Partially purified preparations of pyruvate decarboxylase (EC 4.1.1.1) have been reported to catalyze the decarboxylation of the branched-chain 2-oxo acids formed upon transamination of leucine, isoleucine, and valine. Indeed, in a coupled enzymatic assay with horse liver alcohol dehydrogenase, cell extracts of a wild-type Saccharomyces cerevisiae strain exhibited significant decarboxylation rates with these branched-chain 2-oxo acids. Decarboxylation of branched-chain 2-oxo acids was not detectable in cell extracts of an isogenic strain in which all three PDC genes had been disrupted. Experiments with cell extracts from S. cerevisiae mutants expressing a single PDC gene demonstrated that both PDC1- and PDC5-encoded isoenzymes can decarboxylate branched-chain 2-oxo acids. To investigate whether pyruvate decarboxylase is essential for fusel alcohol production by whole cells, wild-type S. cerevisiae and an isogenic pyruvate decarboxylase-negative strain were grown on ethanol with a mixture of leucine, isoleucine, and valine as the nitrogen source. Surprisingly, the three corresponding fusel alcohols were produced in both strains. This result proves that decarboxylation of branched-chain 2-oxo acids via pyruvate decarboxylase is not an essential step in fusel alcohol production. PMID:9546164

  14. Assay, purification, and characterization of cobaltochelatase, a unique complex enzyme catalyzing cobalt insertion in hydrogenobyrinic acid a,c-diamide during coenzyme B12 biosynthesis in Pseudomonas denitrificans.

    PubMed Central

    Debussche, L; Couder, M; Thibaut, D; Cameron, B; Crouzet, J; Blanche, F

    1992-01-01

    Hydrogenobyrinic acid a,c-diamide was shown to be the substrate of cobaltochelatase, an enzyme that catalyzes cobalt insertion in the corrin ring during the biosynthesis of coenzyme B12 in Pseudomonas denitrificans. Cobaltochelatase was demonstrated to be a complex enzyme composed of two different components of M(r) 140,000 and 450,000, which were purified to homogeneity. The 140,000-M(r) component was shown to be coded by cobN, whereas the 450,000-M(r) component was composed of two polypeptides specified by cobS and cobT. Each component was inactive by itself, but cobaltochelatase activity was reconstituted upon mixing CobN and CobST. The reaction was ATP dependent, and the Km values for hydrogenobyrinic acid a,c-diamide, Co2+, and ATP were 0.085 +/- 0.015, 4.2 +/- 0.2, and 220 +/- 36 microM, respectively. Spectroscopic data revealed that the reaction product was cob(II)yrinic acid a,c-diamide, and experiments with a coupled-enzyme incubation system containing both cobaltochelatase and cob(II)yrinic acid a,c-diamide reductase (F. Blanche, L. Maton, L. Debussche, and D. Thibaut, J. Bacteriol. 174:7452-7454, 1992) confirmed this result. This report not only provides the first evidence that hydrogenobyrinic acid and its a,c-diamide derivative are indeed precursors of adenosylcobalamin but also demonstrates that precorrin-6x, precorrin-6y, and precorrin-8x, three established precursors of hydrogenobyrinic acid (D. Thibaut, M. Couder, A. Famechon, L. Debussche, B. Cameron, J. Crouzet, and F. Blanche, J. Bacteriol. 174:1043-1049, 1992), are also on the pathway to cobalamin. Images PMID:1429466

  15. NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7.

    PubMed

    Peng, Yanrong; Fu, Dongmei; Liu, Renhua; Zhang, Feifang; Liang, Xinmiao

    2008-03-01

    A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS). PMID:18177919

  16. Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

    PubMed

    Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

    2010-05-17

    Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

  17. Conversion of nicotinic acid to trigonelline is catalyzed by N-methyltransferase belonged to motif B′ methyltransferase family in Coffea arabica

    SciTech Connect

    Mizuno, Kouichi; Matsuzaki, Masahiro; Kanazawa, Shiho; Tokiwano, Tetsuo; Yoshizawa, Yuko; Kato, Misako

    2014-10-03

    Graphical abstract: Trigonelline synthase catalyzes the conversion of nicotinic acid to trigonelline. We isolated and characterized trigonelline synthase gene(s) from Coffea arabica. - Highlights: • Trigonelline is a major compound in coffee been same as caffeine is. • We isolated and characterized trigonelline synthase gene. • Coffee trigonelline synthases are highly homologous with coffee caffeine synthases. • This study contributes the fully understanding of pyridine alkaloid metabolism. - Abstract: Trigonelline (N-methylnicotinate), a member of the pyridine alkaloids, accumulates in coffee beans along with caffeine. The biosynthetic pathway of trigonelline is not fully elucidated. While it is quite likely that the production of trigonelline from nicotinate is catalyzed by N-methyltransferase, as is caffeine synthase (CS), the enzyme(s) and gene(s) involved in N-methylation have not yet been characterized. It should be noted that, similar to caffeine, trigonelline accumulation is initiated during the development of coffee fruits. Interestingly, the expression profiles for two genes homologous to caffeine synthases were similar to the accumulation profile of trigonelline. We presumed that these two CS-homologous genes encoded trigonelline synthases. These genes were then expressed in Escherichiacoli, and the resulting recombinant enzymes that were obtained were characterized. Consequently, using the N-methyltransferase assay with S-adenosyl[methyl-{sup 14}C]methionine, it was confirmed that these recombinant enzymes catalyzed the conversion of nicotinate to trigonelline, coffee trigonelline synthases (termed CTgS1 and CTgS2) were highly identical (over 95% identity) to each other. The sequence homology between the CTgSs and coffee CCS1 was 82%. The pH-dependent activity curve of CTgS1 and CTgS2 revealed optimum activity at pH 7.5. Nicotinate was the specific methyl acceptor for CTgSs, and no activity was detected with any other nicotinate derivatives, or

  18. MASS SPECTROMETRIC IDENTIFICATION OF AN AZOBENZENE DERIVATIVE PRODUCED BY SMECTITE-CATALYZED CONVERSION OF 3-AMINO-4-HYDROXPHENYLARSONIC ACID

    EPA Science Inventory

    We report here the first evidence of a possible mechanism for the formation of an azobenzene arsonic acid compound in the environment The compound was formed when 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) was added to aqueous suspensions of smectite clay The 3-amino-HPAA...

  19. The acid-catalyzed decompostion of phenacylcobalamin: evidence for the formation of an enol-Co(III) pi-complex intermediate.

    PubMed

    Brown, K L; Chu, M M; Ingraham, L L

    1976-04-01

    Phenacylcobalamin has been synthesized and characterized by thin-layer chromatography and uv-visible spectroscopy, as well as identification of the cobalt-containing and organic products of its cleavage in acid and base and by aerobic photolysis. The major organic product from all three cleavage reactions is acetophenone and the cobalt-containing product is aquacobalamin (or hydroxocobalamin, its conjugate base). In aqueous acidic solution (pH 0 to 7.3, ionic strength 1.0 M, and 25.0 degrees C), the kinetics of the formation of aquacobalamin are biphasic representing the linear sum of two exponential terms. The pH dependence of the first-order rate constant of both phases shows a first-order dependence on proton concentration but with an inflection point ot pH 3.55 for the faster phase and at pH 4.03 for the slower phase. This behavior is interpreted in terms of the specific acid catalyzed formation of an intermediate from both "base on" and "base off" phenacylcobalamin with different second-order rate constants for each form, followed by an intermediate decompotion step with a similar formal mechanism. The nature of the intermediate is discussed and it is concluded to be a pi-complex between cob(III)alamin and the enol of acetophenone. PMID:4086

  20. DFT Study of Solvent Effects in Acid-Catalyzed Diels-Alder Cycloadditions of 2,5-Dimethylfuran and Maleic Anhydride.

    PubMed

    Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J

    2015-09-24

    Density functional theory electronic structure calculations were used to explore the mechanism for the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride (MA). Reaction paths are reported for uncatalyzed and Lewis and Brønsted acid-catalyzed reactions in vacuum and in a broad range of solvents. The calculations show that, while the uncatalyzed Diels-Alder reaction is thermally feasible in vacuum, a Lewis acid (modeled as Na(+)) lowers the activation barrier by interacting with the dienophile (MA) and decreasing the HOMO-LUMO gap of the reactants. A Brønsted acid (modeled as a proton) can bind to a carbonyl oxygen in MA, changing the reaction mechanism from concerted to stepwise and eliminating the activation barrier. Solvation effects were studied with the SMD model. Electrostatic effects play the largest role in determining the solvation energy of the transition state, which tracks the net dipole moment at the transition state. For the uncatalyzed reaction, the dipole moment is largely determined by charge transfer between the reactants, but in the reactions with ionic catalysts, there is no simple relationship between solvation of the transition state and charge transfer between the reactants. Nonelectrostatic contributions to solvation of the reactants and transition state also make significant contributions to the activation energy. PMID:26331220

  1. Synthesis and characterization of poly(lactic acid)/ montmorillonite nanocomposites by in situ polycondensation catalyzed by non-metal-based compound.

    PubMed

    Kaewprapan, Kulwadee; Phattanarudee, Siriwan

    2012-01-01

    Poly(lactic acid)/montmorillonite nanocomposites were prepared by using non-toxic catalysts, i.e., phthalic acid and succinimide, via in situ polycondensation in presence of silicate. Concentrations of catalysts and clay were varied in a range of 0-3% wt and 0-0.5% wt, respectively. The reaction condition was controlled at 180 degrees C for 24 hr under a reduced pressure. Viscosity average molecular weight of the synthesized polymers and nanocomposites were characterized and compared using an Ubbelohde viscometer. Pattern of silicate distribution in the composites was investigated by X-ray diffraction to correlate with thermal properties evaluated by differential scanning calorimetry and thermogravimetric analysis. The results showed that the addition of catalysts at 2% wt gave the highest product yield (55-60%). The presence of silicate affected on molecular weight reduction, and the diffracted patterns suggested an intercalated structure. With a small amount of added filler, a significant improvement in thermal property and crystallinity of the resultant composites was obtained compared to those of the catalyzed polymers, in which the composites with succinimide exhibited overall better thermal stability and higher crystallinity than the ones prepared with phthalic acid. PMID:22524057

  2. Enzymatic α-glucuronylation of maltooligosaccharides using α-glucuronic acid 1-phosphate as glycosyl donor catalyzed by a thermostable phosphorylase from Aquifex aeolicus VF5.

    PubMed

    Umegatani, Yuta; Izawa, Hironori; Nawaji, Mutsuki; Yamamoto, Kazuya; Kubo, Akiko; Yanase, Michiyo; Takaha, Takeshi; Kadokawa, Jun-ichi

    2012-03-01

    This paper describes thermostable phosphorylase-catalyzed α-glucuronylation of maltooligosaccharides for the direct synthesis of anionic oligosaccharides having a glucuronic acid residue at the non-reducing end. When the reaction of α-glucuronic acid 1-phosphate (GlcA-1-P) as a glycosyl donor and maltotriose as a glycosyl acceptor was performed in the presence of thermostable phosphorylase from Aquifex aeolicus VF5, high performance anion exchange chromatography analysis of the reaction mixture suggested the production of a glucuronylated tetrasaccharide, whose structure was also confirmed by the MALDI-TOF MS measurement of the crude products. Furthermore, treatment of the crude products with glucoamylase supported that the α-glucuronic acid unit was positioned at the non-reducing end of the tetrasaccharide and (1)H NMR analysis suggested that it was bound in an α-(1→4)-linkage. When the α-glucuronylation of maltotetraose using GlcA-1-P was conducted, α-glucuronylated oligosaccharides with various degrees of polymerization were produced. On the other hand, the α-glucuronylation of maltotetraose using GlcA-1-P in the presence of potato phosphorylase did not occur at all, indicating no recognition of GlcA-1-P by potato phosphorylase. PMID:22265379

  3. N-Heterocyclic carbene-catalyzed [4 + 2] cyclization of α,β-unsaturated carboxylic acids bearing γ-H with isatins: an enantioselective synthesis of spirocyclic oxindole-dihydropyranones.

    PubMed

    Zhu, Ling; Yu, Chenxia; Li, Tuanjie; Wang, Yuhong; Lu, Yinan; Wang, Wenjing; Yao, Changsheng

    2016-01-28

    An NHC-catalyzed asymmetric [4 + 2] annulation of isatins and α,β-unsaturated carboxylic acids bearing γ-H gave spirocyclic oxindole-dihydropyranones successfully via an in situ activation strategy. This protocol featured easy availability of raw materials, good yields and excellent enantioselectivities (up to 99% ee). PMID:26690686

  4. The influence of the form of condensation nucleus on the formation and propagation of acid precipitation near operating TPS

    NASA Astrophysics Data System (ADS)

    Gvozdyakov, D. V.; Gubin, V. E.

    2015-01-01

    The results of numerical studies of condensation on the surface of the air component of atmospheric condensation nuclei of various shapes. Mathematical modeling performed at ambient temperatures typical of summer and winter seasons. It is found that the trajectory of motion of particles of various shapes differ significantly. Numerical studies were carried out at atmospheric parameters corresponding airspace adjacent to the areas of the TPP. Testing results obtained audited conservative difference scheme.

  5. Stepwise esterification of phytosterols with conjugated linoleic acid catalyzed by Candida rugosa lipase in solvent-free medium.

    PubMed

    Torres, Carlos F; Torrelo, Guzman; Vazquez, Luis; Señorans, F Javier; Reglero, Guillermo

    2008-12-01

    We conducted a near quantitative esterification of phytosterols from soybean oil deodorizer distillate with conjugated linoleic acid. We used a 1:1 molar ratio of sterols to conjugated linoleic acid. For that matter, stepwise addition of sterols was investigated. Total sterols were divided into several portions and added sequentially to the reaction mixture. Using this methodology, purities of up to 80% steryl esters were obtained that consumed more than 90% of the total conjugated linoleic acid. In addition, the effects of temperature, amount, and stability of lipase were also evaluated. PMID:19134551

  6. Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

    USGS Publications Warehouse

    Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.

    2003-01-01

    The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

  7. Chiral Phosphoric Acid Catalyzed [3 + 2] Cycloaddition and Tandem Oxidative [3 + 2] Cycloaddition: Asymmetric Synthesis of Substituted 3-Aminodihydrobenzofurans.

    PubMed

    Gelis, Coralie; Bekkaye, Mathieu; Lebée, Clément; Blanchard, Florent; Masson, Géraldine

    2016-07-15

    Asymmetric [3 + 2] cycloaddition of quinones with ene- and thioene-carbamates was achieved by chiral phosphoric acid catalysis, providing the corresponding 3-amino-2,3-dihydrobenzofurans in excellent yields with moderate to good diastereoselectivities and excellent enantioselectivities. An asymmetric tandem oxidative cycloaddition protocol starting from hydroquinones was also accomplished with phenyliodine(III) diacetate and a chiral phosphoric acid in the same reaction vessel. PMID:27352020

  8. Highly regio- and diastereoselective synthesis of CF3-substituted lactones via photoredox-catalyzed carbolactonization of alkenoic acids.

    PubMed

    Yasu, Yusuke; Arai, Yusuke; Tomita, Ren; Koike, Takashi; Akita, Munetaka

    2014-02-01

    Trifluoromethylative lactonization of both terminal and internal alkenoic acids by photoredox catalysis has been developed. The use of a Ru photocatalyst and Umemoto's reagent as a CF3 source is key in the present carbolactonization. This is the first example of a highly endo- and diastereoselective synthesis of CF3-substituted five-, six-, and seven-membered ring lactones from internal alkenoic acids. PMID:24422891

  9. Electrolyte vapor condenser

    DOEpatents

    Sederquist, Richard A.; Szydlowski, Donald F.; Sawyer, Richard D.

    1983-01-01

    A system is disclosed for removing electrolyte from a fuel cell gas stream. The gas stream containing electrolyte vapor is supercooled utilizing conventional heat exchangers and the thus supercooled gas stream is passed over high surface area passive condensers. The condensed electrolyte is then drained from the condenser and the remainder of the gas stream passed on. The system is particularly useful for electrolytes such as phosphoric acid and molten carbonate, but can be used for other electrolyte cells and simple vapor separation as well.

  10. Electrolyte vapor condenser

    DOEpatents

    Sederquist, R.A.; Szydlowski, D.F.; Sawyer, R.D.

    1983-02-08

    A system is disclosed for removing electrolyte from a fuel cell gas stream. The gas stream containing electrolyte vapor is supercooled utilizing conventional heat exchangers and the thus supercooled gas stream is passed over high surface area passive condensers. The condensed electrolyte is then drained from the condenser and the remainder of the gas stream passed on. The system is particularly useful for electrolytes such as phosphoric acid and molten carbonate, but can be used for other electrolyte cells and simple vapor separation as well. 3 figs.

  11. Imino-Oxy Acetic Acid Dealkylation as Evidence for an Inner-Sphere Alcohol Intermediate in the Reaction Catalyzed by Peptidylglycine α-Hydroxylating Monooxygenase (PHM)

    PubMed Central

    McIntyre, Neil R.; Lowe, Edward W.; Merkler, David J.

    2009-01-01

    Peptidylglycine α-hydroxylating monooxygenase (PHM, EC 1.14.17.3) catalyzes the stereospecific hydroxylation of a glycyl α-carbon in a reaction that requires O2 and ascorbate. Subsequent dealkylation of the α-hydroxyglycine by another enzyme, peptidylamidoglycolate lyase (PAL. EC 4.3.2.5), yields a bioactive amide and glyoxylate. PHM is a non-coupled, type II dicopper monooxygenase which activates O2 at only a single copper atom, CuM. In this study, the PHM mechanism was probed using a non-natural substrate, benzaldehyde imino-oxy acetic acid (BIAA). PHM catalyzes the O-oxidative dealkylation of BIAA to benzaldoxime and glyoxylate with no involvement of PAL. The minimal kinetic mechanism for BIAA was shown to be steady-state ordered using primary deuterium kinetic isotope effects. The D(V/K)APPARENT, BIAA decreased from 14.7 ± 1.0 as [O2] → 0 to 1.0 ± 0.2 as [O2] → ∞ suggesting the dissociation rate constant from the PHM·BIAA complex decreases as [O2] increases; thereby, reducing the steady-state concentration of [PHM]free. BIAA was further used to differentiate between potential oxidative Cu/O species using a QM/MM reaction coordinate simulation to determine which species could yield product O-dealkylation that matched our experimental data. The results of this study provided compelling evidence for the presence of a covalently linked CuII-alkoxide intermediate with a quartet spin state responsible BIAA oxidation. PMID:19569683

  12. Free radical derivatives formed from cyclooxygenase-catalyzed dihomo-γ-linolenic acid peroxidation can attenuate colon cancer cell growth and enhance 5-fluorouracil׳s cytotoxicity

    PubMed Central

    Xu, Yi; Qi, Jin; Yang, Xiaoyu; Wu, Erxi; Qian, Steven Y.

    2014-01-01

    Dihomo-γ-linolenic acid (DGLA) and its downstream fatty acid arachidonic acid (AA) are both nutritionally important ω–6 polyunsaturated fatty acids (ω–6s). Evidence shows that, via COX-mediated peroxidation, DGLA and its metabolites (1-series prostaglandins) are associated with anti-tumor activity, while AA and its metabolites (2-series prostaglandins) could be tightly implicated in various cancer diseases. However, it still remains a mystery why DGLA and AA possess contrasting bioactivities. Our previous studies showed that DGLA could go through an exclusive C-8 oxygenation pathway during COX-catalyzed lipid peroxidation in addition to a C-15 oxygenation pathway shared by both DGLA and AA, and that the exclusive C-8 oxygenation could lead to the production of distinct DGLA׳s free radical derivatives that may be correlated with DGLA׳s anti-proliferation activity. In the present work, we further investigate the anti-cancer effect of DGLA׳s free radical derivatives and their associated molecular mechanisms. Our study shows that the exclusive DGLA׳s free radical derivatives from C-8 oxygenation lead to cell growth inhibition, cell cycle arrest and apoptosis in the human colon cancer cell line HCA-7 colony 29, probably by up-regulating the cancer suppressor p53 and the cell cycle inhibitor p27. In addition, these exclusive radical derivatives were also able to enhance the efficacy of 5-Fluorouracil (5-FU), a widely used chemo-drug for colon cancer. For the first time, we show how DGLA׳s radical pathway and metabolites are associated with DGLA׳s anti-cancer activities and able to sensitize colon cancer cells to chemo-drugs such as 5-FU. Our findings could be used to guide future development of a combined chemotherapy and dietary care strategy for colon cancer treatment. PMID:25114837

  13. Evolution of Diterpene Metabolism: Sitka Spruce CYP720B4 Catalyzes Multiple Oxidations in Resin Acid Biosynthesis of Conifer Defense against Insects1[C][W][OA

    PubMed Central

    Hamberger, Björn; Ohnishi, Toshiyuki; Hamberger, Britta; Séguin, Armand; Bohlmann, Jörg

    2011-01-01

    Diterpene resin acids (DRAs) are specialized (secondary) metabolites of the oleoresin defense of conifers produced by diterpene synthases and cytochrome P450s of the CYP720B family. The evolution of DRA metabolism shares common origins with the biosynthesis of ent-kaurenoic acid, which is highly conserved in general (primary) metabolism of gibberellin biosynthesis. Transcriptome mining in species of spruce (Picea) and pine (Pinus) revealed CYP720Bs of four distinct clades. We cloned a comprehensive set of 12 different Sitka spruce (Picea sitchensis) CYP720Bs as full-length cDNAs. Spatial expression profiles, methyl jasmonate induction, and transcript enrichment in terpenoid-producing resin ducts suggested a role of CYP720B4 in DRA biosynthesis. CYP720B4 was characterized as a multisubstrate, multifunctional enzyme by the formation of oxygenated diterpenoids in metabolically engineered yeast, yeast in vivo transformation of diterpene substrates, in vitro assays with CYP720B4 protein produced in Escherichia coli, and alteration of DRA profiles in RNA interference-suppressed spruce seedlings. CYP720B4 was active with 24 different diterpenoid substrates, catalyzing consecutive C-18 oxidations in the biosynthesis of an array of diterpene alcohols, aldehydes, and acids. CYP720B4 was most active in the formation of dehydroabietic acid, a compound associated with insect resistance of Sitka spruce. We identified patterns of convergent evolution of CYP720B4 in DRA metabolism and ent-kaurene oxidase CYP701 in gibberellin metabolism and revealed differences in the evolution of specialized and general diterpene metabolism in a gymnosperm. The genomic and functional characterization of the gymnosperm CYP720B family highlights that the evolution of specialized metabolism involves substantial diversification relative to conserved, general metabolism. PMID:21994349

  14. Evidence for a transient peroxynitro acid in the reaction catalyzed by nitronate monooxygenase with propionate 3-nitronate.

    PubMed

    Smitherman, Crystal; Gadda, Giovanni

    2013-04-16

    Nitronate monooxygenase is a flavin-dependent enzyme that catalyzes the denitrification of propionate 3-nitronate (P3N) and other alkyl nitronates. The enzyme was previously known as 2-nitropropane dioxygenase, until its reclassification in 2010 by the IUBMB. Physiologically, the monooxygenase from fungi protects the organism from the environmental occurrence of P3N, which shuts down the Krebs cycle by inactivating succinate dehydrogenase and fumarase. The inhibition of these enzymes yields severe neurological disorders or death. Here, we have used for the first time steady-state and rapid kinetics, viscosity and pH effects, and time-resolved absorbance spectroscopy of the enzyme in turnover with P3N and the substrate analogue ethyl nitronate (EN) to elucidate the mechanism of the reaction. A transient increase in absorbance at ∼300 nm, never reported before, was seen during steady-state turnover of the enzyme with P3N and oxygen, with no concomitant changes between 400 and 600 nm. The transient species was not detected when oxygen was absent. Anaerobic reduction of the enzyme with P3N yielded anionic flavosemiquinone and was fast (e.g., ≥1900 s(-1)). Steady-state kinetics demonstrated that oxygen reacts before the release of the product of P3N oxidation from the enzyme. No pH effects were seen with P3N on kcat/Km, kcat/Koxygen, and kcat; in contrast, with EN, the kcat/Km and kcat decreased with increasing pH defining two plateaus and a pKa ∼ 8.0. Solvent viscosity at the pH optima suggested product release as being partially controlling the overall rate of turnover with the physiological substrate and its analogue. A mechanism that satisfies the kinetic results is proposed. PMID:23530838

  15. 4-O-methylation of glucuronic acid in Arabidopsis glucuronoxylan is catalyzed by a domain of unknown function family 579 protein

    PubMed Central

    Urbanowicz, Breeanna R.; Peña, Maria J.; Ratnaparkhe, Supriya; Avci, Utku; Backe, Jason; Steet, Heather F.; Foston, Marcus; Li, Hongjia; O’Neill, Malcolm A.; Ragauskas, Arthur J.; Darvill, Alan G.; Wyman, Charles; Gilbert, Harry J.; York, William S.

    2012-01-01

    The hemicellulose 4-O-methyl glucuronoxylan is one of the principle components present in the secondary cell walls of eudicotyledonous plants. However, the biochemical mechanisms leading to the formation of this polysaccharide and the effects of modulating its structure on the physical properties of the cell wall are poorly understood. We have identified and functionally characterized an Arabidopsis glucuronoxylan methyltransferase (GXMT) that catalyzes 4-O-methylation of the glucuronic acid substituents of this polysaccharide. AtGXMT1, which was previously classified as a domain of unknown function (DUF) 579 protein, specifically transfers the methyl group from S-adenosyl-l-methionine to O-4 of α-d-glucopyranosyluronic acid residues that are linked to O-2 of the xylan backbone. Biochemical characterization of the recombinant enzyme indicates that GXMT1 is localized in the Golgi apparatus and requires Co2+ for optimal activity in vitro. Plants lacking GXMT1 synthesize glucuronoxylan in which the degree of 4-O-methylation is reduced by 75%. This result is correlated to a change in lignin monomer composition and an increase in glucuronoxylan release during hydrothermal treatment of secondary cell walls. We propose that the DUF579 proteins constitute a previously undescribed family of cation-dependent, polysaccharide-specific O-methyl-transferases. This knowledge provides new opportunities to selectively manipulate polysaccharide O-methylation and extends the portfolio of structural targets that can be modified either alone or in combination to modulate biopolymer interactions in the plant cell wall. PMID:22893684

  16. Acidic Condensation of BODIPYs with Aldehydes: A Quick and Versatile Route to Alkenyl-BODIPYs and C(sp(3) )-Connected DYEmers.

    PubMed

    Ahrens, Johannes; Cordes, Birte; Wicht, Richard; Wolfram, Benedikt; Bröring, Martin

    2016-07-18

    The condensation of aldehydes with BODIPY (boron dipyrrin) luminophores was investigated. Formaldehyde can be used to connect two BODIPYs at each of the three pyrrolic C positions (α-, β-, and β'-positions) in a quick and highly selective manner, yielding new DYEmers (di- and oligomeric BODIPY derivatives) with varied photophysical properties. Benzaldehydes form DYEmers only at the β- and the β'-positions. For aliphatic aldehydes the DYEmer formation competes with the elimination of water from a proposed alcohol intermediate, leading to the formation of α- and β-alkenyl-BODIPYs. 2-Phenylacetaldehyde and similar precursors exclusively yield elimination products. These acid-mediated transformations are valuable alternatives to the well-established, base-promoted Knoevenagel condensation protocol that is typically employed in the preparation of BODIPYs with near infrared (NIR)-shifted absorptions. PMID:27140934

  17. Common Inorganic Salts Catalyze the Transformations of Organic Compounds in Atmospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Noziere, B.; Dziedzic, P.; Cordova, A.

    2008-12-01

    This presentation reports the discovery that inorganic salts that are ubiquitous in atmospheric aerosols are efficient catalysts for the transformations of organic compounds in these aerosols, by reactions such as aldol condensation or acetal formation.1 For some of these salts, these catalytic properties were not even known in chemistry.2 Kinetic and product studies of these reactions will be presented for carbonyl compounds such as acetaldehyde, acetone, and glyoxal,1,3 and compared with previously known catalysts such as the recently discovered amino acids.4,5 These studies show that these salts make the reactions as fast in typical tropospheric aerosols as in concentrated sulfuric acid. These reactions produce secondary "fulvic" compounds that absorb light in the near UV and visible and would affect the optical properties of aerosols.1,5 They would also account for the depletion of glyoxal recently reported in Mexico city.3 Thus, while acid catalysis is several orders of magnitudes too slow to be significant in tropospheric aerosols, this work identifies new processes that should be ubiquitous in these aerosols and important for atmospheric chemistry. Refs. 1Noziere, B., Dziedzic, P., Cordova, A., Common inorganic ions catalyze chemical reactions of organic compounds in atmospheric aerosols, Submitted, 2008. 2 Noziere, B., Cordova, A., A novel catalyst for aldol condensation reaction, patent pending 02/10/2007. 3Noziere, B., Dziedzic, P., Cordova, A., Products and kinetics of the liquid-phase reaction of glyoxal catalyzed by inorganic ions, Submitted to J. Phys. Chem. A, 2008. 4Noziere, B., and Cordova, A., A Kinetic and Mechanistic Study of the Amino Acid-Catalyzed Aldol Condensation of Acetaldehyde in Aqueous and Salt Solutions, J. Phys. Chem. A, 112, 2827, 2008. 5Noziere, B., Dziedzic, P., and Cordova, A., The Formation of Secondary Light-Absorbing "fulvic-like" Oligomers: A Common Process in Aqueous and Ionic Atmospheric Particles?, Geophys. Res. Lett., 34

  18. Lewis acid catalyzed ring-opening polymerization of natural epoxy oil (Euphorbia oil) in carbon dioxide media

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In an attempt to build up useful application of plant oil based polymers, natural epoxy oil (euphorbia oil-EuO) was polymerized in liquid carbon dioxide in the presence of Lewis acid catalyst [Boron trifluoride diethyl etherate (BF3•OEt2)]. The resulting polymers (RPEuO) were characterized by FTIR ...

  19. Pd-Catalyzed, Cu(I)-Mediated Cross-Couplings of Bisarylthiocyclobutenediones with Boronic Acids and Organostannanes

    PubMed Central

    Aguilar-Aguilar, Angélica; Liebeskind, Lanny S.; Peña-Cabrera, Eduardo

    2009-01-01

    Bisarylthiocyclobutenedione 7 reacted smoothly with a variety of both organostannanes and (hetero)aryl boronic acids in the presence of a catalytic amount of Pd and a stoichiometric amount of CuTC, to produce symmetrical disubstituted cyclobutenediones in yields that range from 37 to 94% (18 examples). PMID:17892299

  20. Copper-Catalyzed Carboxylation of Alkenylzirconocenes with Carbon Dioxide Leading to α,β-Unsaturated Carboxylic Acids.

    PubMed

    Wang, Sheng; Shao, Peng; Chen, Chao; Xi, Chanjuan

    2015-10-16

    A variety of alkenylzirconocenes were efficiently carboxylated by CO2 utilizing the (IMes)CuCl catalyst yielding the corresponding α,β-unsaturated carboxylic acids in good yields. This reaction could be carried out in a one-pot operation via sequential carbozirconation of alkynes and carboxylation using CO2 as starting materials under room temperature. PMID:26406296

  1. Lipase-catalyzed production of a bioactive fatty amide derivative of 7,10-dihydroxy-8(E)-octadecenoic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fatty amides are of considerable interest due to their wide ranging industrial applications in detergents, shampoo, cosmetics and surfactant formulations. They are produced commercially from fatty acids by reacting with anhydrous ammonia at approximately 200 deg C and 345-690 KPa pressure. We inve...

  2. Lipase-catalyzed interesterification of soybean oil with an omega-3 polyunsaturated fatty acid concentrate prepared from sardine oil.

    PubMed

    Akimoto, Masamichi; Izawa, Maki; Hoshino, Kazumi; Abe, Ken-Ichi; Takahashi, Hiromi

    2003-02-01

    To reduce the content of linoleoyl moiety in soybean oil, soybean oil that contains 53.0% linoleoyl moiety as molar acyl moiety composition was interesterified with an omega-3 polyunsaturated fatty acid (PUFA) concentrate (24.0 mol% eicosapentaenoic acid [EPA], 40.4 mol% docosahexaenoic acid [DHA]) prepared from sardine oil, using an immobilized sn-1,3-specific lipase from Rhizomucor miehei (Lipozyme IM). The reaction was carried out in a batch reactor at 37 degrees C under the following conditions: 500 micromol of soybean oil, molar ratio of omega-3 PUFA concentrate to soybean oil = 1.0-6.0,5.0 mL of heptane, and 30 batch interesterification units of enzyme. After the reaction time of 72 h, modified soybean oil, which contains 34.9% linoleoyl, 10.1% eicosapentaenoyl, and 14.2% docosahexaenoyl moieties, was produced at the molar reactant ratio of 6.0. In this oil, the total omega-3 acyl moiety composition reached 34.1%; the molar ratio of omega-3 to omega-6 acyl moieties was enhanced by five times compared with soybean oil. Compared with palmitic acid, DHA was kinetically six times less reactive, although the EPA was by 16% more reactive. PMID:12603099

  3. Acid-catalyzed carboxylic acid esterification and ester hydrolysis mechanism: acylium ion as a sharing active intermediate via a spontaneous trimolecular reaction based on density functional theory calculation and supported by electrospray ionization-mass spectrometry.

    PubMed

    Shi, Hongchang; Wang, Yilei; Hua, Ruimao

    2015-11-11

    By DFT calculation, we found that acid-catalyzed carboxylic acid esterification and ester hydrolysis are brief two-step reactions. First, the carboxylic acid hydroxyl-oxygen or ester alkyl-oxygen is protonated, which generates a highly active acylium ion. The protonation requires an activation energy (Ea) of 4-10 kcal mol(-1), and is the rate-controlling step of the esterification or hydrolysis. Sequentially, the acylium ion spontaneously reacts with two alcohol or two water molecules to form a neutral product molecule; this is a trimolecular reaction. The acylium ion is the highly active intermediate shared by esterification and hydrolysis. ESI-MS data for several typical carboxylic acids confirmed that their acylium ions are easily generated. For 2,4,6-trialkylbenzoic acid and its ester, the two unsubstituted carbons in the benzene ring are very easily protonated, and we have thus revealed the root of the success of Newman's method. Based on these results, the popular esterification and hydrolysis mechanism in organic chemistry textbooks is incorrect. PMID:26445892

  4. Polyene Formation Catalyzed by Phosphotungstic Acid and Aluminum Chloride in Thin Films of Poly(Vinyl Alcohol)

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.; Maly, A. B.

    2016-01-01

    Formation of linear polyenes -(CH=CH) n - during thermal dehydration of thin layers (9-20 μm) of poly(vinyl alcohol) containing phosphotungstic-acid and aluminum-chloride catalysts was investigated. It was found that the concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid increased smoothly with increasing annealing time although the kinetics of the dehydration were independent of the film thickness. The polyene ( n ≥ 8) formation rate in films containing aluminum chloride dropped quickly with decreasing film thickness and increasing annealing time. As a result, long-chain polyenes practically did not form regardless of the annealing time for a film thickness of 11 μm.

  5. Production of 5-hydroxymethylfurfural from corn stalk catalyzed by corn stalk-derived carbonaceous solid acid catalyst.

    PubMed

    Yan, Lulu; Liu, Nian; Wang, Yu; Machida, Hiroshi; Qi, Xinhua

    2014-12-01

    A carbonaceous solid acid was prepared by hydrothermal carbonization of corn stalk followed by sulfonation and was characterized by FT-IR, XRD, SEM and elemental analysis techniques. The as-prepared corn stalk-derived carbonaceous solid acid catalyst contained SO3H, COOH, and phenolic OH groups, and was used for the one-step conversion of intact corn stalk to 5-hydroxymethylfurfural (5-HMF) in the ionic liquid 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]), where a 5-HMF yield of 44.1% was achieved at 150 °C in 30 min reaction time. The catalytic system was applicable to initial corn stalk concentration of up to ca. 10 wt.% for the production of 5-HMF. The synthesized catalyst and the developed process of using corn stalk-derived carbon catalyst for corn stalk conversion provide a green and efficient strategy for crude biomass utilization. PMID:25444888

  6. The development of copper-catalyzed aerobic oxidative coupling of H-tetrazoles with boronic acids and an insight into the reaction mechanism.

    PubMed

    Liu, Chao-You; Li, Yu; Ding, Jin-Ying; Dong, De-Wen; Han, Fu-She

    2014-02-17

    The development of a highly efficient and practical protocol for the direct C-N coupling of H-tetrazole and boronic acid was presented. A careful and patient optimization of a variety of reaction parameters revealed that this conventionally challenge reaction could indeed proceed efficiently in a very simple system, that is, just by stirring the tetrazoles and boronic acids under oxygen in the presence of different Cu(I) or Cu(II) salts with only 5 mol % loading in DMSO at 100 °C. Most significantly, the reaction could proceed very smoothly in a regiospecific manner to afford the 2,5-disubstituted tetrazoles in high to excellent yields. A mechanistic study revealed that both tetrazole and DMSO are crucial for the generation of catalytically active copper species in the reaction process in addition to their role as reactant and solvent, respectively. It is demonstrated that in the reaction cycle, the Cu(I) catalyst could be oxidized to Cu(II) by oxygen to form a [CuT2D] complex (T = tetrazole anion; D = DMSO) through an oxidative copper amination reaction. The Cu(II) complex thus formed was confirmed to be the real catalytically active copper species. Namely, the Cu(II) complex disproportionates to aryl Cu(III) and Cu(I) in the presence of boronic acid. Facile elimination of the Cu(III) species delivers the C-N-coupled product. The results presented herein not only provide a reliable and efficient protocol for the synthesis of 2,5-disubstituted tetrazoles, but most importantly, the mechanistic results would have broad implications for the de novo design and development of new methods for Cu-catalyzed coupling reactions. PMID:24449340

  7. Palladium(0)-Catalyzed Allylation of Highly Acidic and Nonnucleophilic Anilines. The Origin of Stereochemical Scrambling When Using Allylic Carbonates.

    PubMed

    Moreno-Mañas, Marcial; Morral, Lurdes; Pleixats, Roser

    1998-09-01

    Acidic anilines such as diphenylamine, phenothiazine, and nitroanilines are efficiently allylated under palladium catalysis using allyl carbonates as allylating reagents. A stereochemical study of the reactions of ethyl cis-5-methyl-2-cyclohexenylcarbonate with 4-nitro- and 2,4-dinitroaniline was performed. Bidentate phosphines as stabilizing ligands gave clean retention of configuration whereas triphenylphosphine permitted cis-trans isomerization of the allylic carbonate, the allylation reactions occurring under Curtin-Hammet preequilibrium conditions. PMID:11672246

  8. Decarboxylative Palladium(II)-Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

    PubMed Central

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-01-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2CCF3)2], 6-methyl-2,2′-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h−1 by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min−1. PMID:23983102

  9. Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Brønsted Acid.

    PubMed

    Terada, Masahiro; Ota, Yusuke; Li, Feng; Toda, Yasunori; Kondoh, Azusa

    2016-08-31

    Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp(2)-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp(3)-hybridized carbon atom. In particular, substitution at the chiral sp(3)-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid. PMID:27490239

  10. Decarboxylative palladium(II)-catalyzed synthesis of aryl amidines from aryl carboxylic acids: development and mechanistic investigation.

    PubMed

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-10-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2 CCF3 )2 ], 6-methyl-2,2'-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h(-1) by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min(-1) . PMID:23983102

  11. CONDENSATION CAN

    DOEpatents

    Booth, E.T. Jr.; Pontius, R.B.; Jacobsohn, B.A.; Slade, C.B.

    1962-03-01

    An apparatus is designed for condensing a vapor to a solid at relatively low back pressures. The apparatus comprises a closed condensing chamber, a vapor inlet tube extending to the central region of the chamber, a co-axial tubular shield surrounding the inlet tube, means for heating the inlet tube at a point outside the condensing chamber, and means for refrigeratirg the said chamber. (AEC)

  12. Impact of zeolite aging in hot liquid water on activity for acid-catalyzed dehydration of alcohols

    SciTech Connect

    Vjunov, Aleksei; Derewinski, Miroslaw A.; Fulton, John L.; Camaioni, Donald M.; Lercher, Johannes A.

    2015-08-19

    The catalytic performance of zeolite in aqueous medium depends on a multitude of factors, such as the concentration and distribution of active sites and framework integrity. Al K–edge extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations are used to determine the distribution of tetrahedral Al sites both qualitatively and quantitatively for both parent and 48 h 160 ºC water treated HBEA catalysts. There is no evidence of Al coordination modification after aging in water. The distribution and concentration of Al T–sites, active centers for the dehydration of cyclohexanol, do not markedly impact the catalytic performance in water, because the Brønsted acidic protons are present in the form of hydrated hydronium ions and thus have very similar acid properties. The results suggest that all Brønsted acid sites are equally active in aqueous medium. The decrease of zeolite catalytic performance after water treatment is attributed to the reduced concentration of Brønsted acid sites. Increasing the stability of pore walls and decreasing the rate of Si–O–Si group hydrolysis may result in improved apparent zeolite catalytic performance in aqueous medium. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland), J. Z. Hu and S. D. Burton (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MD acknowledges support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. HIM imaging and NMR experiments were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE Office of Science, Office of Biological

  13. Upcycling potato peel waste – Data of the pre-screening of the acid-catalyzed liquefaction

    PubMed Central

    Ventura, Patrícia; Bordado, João Carlos Moura; Mateus, Maria Margarida; Galhano dos Santos, Rui

    2016-01-01

    Herein, the data acquired regarding the preliminary and exploratory experiments conducted with potato peel as a biomass source for the direct thermochemical liquefaction is disclosed. The procedure was carried out in a 2-ethylhexanol/DEG solvent mixture at 160 °C in the presence of p-Toluenesulfonic acid. The adopted procedure afforded a bio-oil in high yield (up to 93%) after only 30 min. For longer reaction times, higher amounts of solid residues were obtained leading, consequently, to lower yields. PMID:27182538

  14. Characterization of the linoleic acid Δ9 hydratase catalyzing the first step of polyunsaturated fatty acid saturation metabolism in Lactobacillus plantarum AKU 1009a.

    PubMed

    Takeuchi, Michiki; Kishino, Shigenobu; Hirata, Akiko; Park, Si-Bum; Kitamura, Nahoko; Ogawa, Jun

    2015-06-01

    Linoleic acid Δ9 hydratase, which is involved in linoleic acid saturation metabolism of Lactobacillus plantarum AKU 1009a, was cloned, expressed as a his-tagged recombinant enzyme, purified with an affinity column, and characterized. The enzyme required FAD as a cofactor and its activity was enhanced by NADH. The maximal activities for the hydration of linoleic acid and for the dehydration of 10-hydroxy-cis-12-octadecenoic acid (HYA) were observed at 37 °C in buffer at pH 5.5 containing 0.5 M NaCl. Free C16 and C18 fatty acids with cis-9 double bonds and 10-hydroxy fatty acids served as substrates for the hydration and dehydration reactions, respectively. The apparent Km value for linoleic acid was estimated to be 92 μM, with a kcat of 2.6∙10(-2) s(-1) and a Hill factor of 3.3. The apparent Km value for HYA was estimated to be 98 μM, with a kcat of 1.2∙10(-3) s(-1). PMID:25476761

  15. Lactic Acid Production from Pretreated Hydrolysates of Corn Stover by a Newly Developed Bacillus coagulans Strain.

    PubMed

    Jiang, Ting; Qiao, Hui; Zheng, Zhaojuan; Chu, Qiulu; Li, Xin; Yong, Qiang; Ouyang, Jia

    2016-01-01

    An inhibitor-tolerance strain, Bacillus coagulans GKN316, was developed through atmospheric and room temperature plasma (ARTP) mutation and evolution experiment in condensed dilute-acid hydrolysate (CDH) of corn stover. The fermentabilities of other hydrolysates with B. coagulans GKN316 and the parental strain B. coagulans NL01 were assessed. When using condensed acid-catalyzed steam-exploded hydrolysate (CASEH), condensed acid-catalyzed liquid hot water hydrolysate (CALH) and condensed acid-catalyzed sulfite hydrolysate (CASH) as substrates, the concentration of lactic acid reached 45.39, 16.83, and 18.71 g/L by B. coagulans GKN316, respectively. But for B. coagulans NL01, only CASEH could be directly fermented to produce 15.47 g/L lactic acid. The individual inhibitory effect of furfural, 5-hydroxymethylfurfural (HMF), vanillin, syringaldehyde and p-hydroxybenzaldehyde (pHBal) on xylose utilization by B. coagulans GKN316 was also studied. The strain B. coagulans GKN316 could effectively convert these toxic inhibitors to the less toxic corresponding alcohols in situ. These results suggested that B. coagulans GKN316 was well suited to production of lactic acid from undetoxified lignocellulosic hydrolysates. PMID:26863012

  16. Lactic Acid Production from Pretreated Hydrolysates of Corn Stover by a Newly Developed Bacillus coagulans Strain

    PubMed Central

    Jiang, Ting; Qiao, Hui; Zheng, Zhaojuan; Chu, Qiulu; Li, Xin; Yong, Qiang; Ouyang, Jia

    2016-01-01

    An inhibitor-tolerance strain, Bacillus coagulans GKN316, was developed through atmospheric and room temperature plasma (ARTP) mutation and evolution experiment in condensed dilute-acid hydrolysate (CDH) of corn stover. The fermentabilities of other hydrolysates with B. coagulans GKN316 and the parental strain B. coagulans NL01 were assessed. When using condensed acid-catalyzed steam-exploded hydrolysate (CASEH), condensed acid-catalyzed liquid hot water hydrolysate (CALH) and condensed acid-catalyzed sulfite hydrolysate (CASH) as substrates, the concentration of lactic acid reached 45.39, 16.83, and 18.71 g/L by B. coagulans GKN316, respectively. But for B. coagulans NL01, only CASEH could be directly fermented to produce 15.47 g/L lactic acid. The individual inhibitory effect of furfural, 5-hydroxymethylfurfural (HMF), vanillin, syringaldehyde and p-hydroxybenzaldehyde (pHBal) on xylose utilization by B. coagulans GKN316 was also studied. The strain B. coagulans GKN316 could effectively convert these toxic inhibitors to the less toxic corresponding alcohols in situ. These results suggested that B. coagulans GKN316 was well suited to production of lactic acid from undetoxified lignocellulosic hydrolysates. PMID:26863012

  17. Iodine-Catalyzed Polysaccharide Esterification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A review is provided of the recent reports to use iodine-catalyzed esterification reaction to produce esters from polysaccharides. The process entails reaction of the polysaccharide with an acid anhydride in the presence of a catalytic level of iodine, and in the absence of additional solvents. T...

  18. Lipase-catalyzed acidolysis of tripalmitin with capric acid in organic solvent medium: Analysis of the effect of experimental conditions through factorial design and analysis of multiple responses.

    PubMed

    Foresti, María Laura; Ferreira, María Luján

    2010-05-01

    The acidolysis of tripalmitin with capric acid catalyzed by an immobilized form of a 1,3-positionally selective lipase (Rhizomucor miehei) showed to be effective for the synthesis of structured lipids of the MLL and MLM type. The effects that reaction parameters such as substrate molar ratio (N), biocatalyst load (E), and reaction temperature (T) have on selected responses variables (i.e. total conversion of tripalmitin, selectivity and yield of the desired structured lipid, hydrolysis yield, and acyl migration importance), were evaluated by use of an experimental factorial design of three factors and three levels with two central points and with a confidence level of 95%. The range of each parameter was selected as follows: N=3-9, E=5-15wt%, T=50-70°C. The statistical analysis of results was addressed by use of both simple linear models and more complicated quadratic models using specific commercial software. The results obtained showed that a proper selection of reaction conditions is needed in order to maximize not only the yield of the desired structured lipid, but also to minimize the generation of hydrolysis and acyl migration by-products. PMID:25919616

  19. No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia - article no. L06801

    SciTech Connect

    Peltier, R.E.; Sullivan, A.P.; Weber, R.J.; Wollny, A.G.; Holloway, J.S.; Brock, C.A.; de Gouw, J.A.; Atlas, E.L.

    2007-03-15

    Aircraft-based measurements of the water-soluble fraction of fine PM organic carbon (WSOC) and inorganic salt composition in the Atlanta, GA region were conducted in the summer of 2004. Five notable plumes of SO{sub 2}, apparently from coal-fired power plants, were intercepted, and had NH{sub 4}{sup +}/SO4{sup 2-} molar ratios ranging from approximately 0.8 to 1.4 compared to molar ratios near 2 outside of the plumes. Sulfate aerosol concentrations increased from a regional background of 5 - 8 {mu} g m{sup -3} to as high as 19.5 {mu} g m{sup -3} within these plumes. No increase in WSOC concentrations was observed in plumes compared to out-of-plumes within a WSOC measurement uncertainty of 8%. These measurements suggest that secondary organic aerosol formation via heterogeneous acid-catalyzed reactions within power plant plumes are not likely a significant contributor to the ambient aerosol mass loading in Atlanta and the surrounding region. Because this region is rich in both biogenic and anthropogenic volatile organic carbon (VOC), the results may be widely applicable.

  20. Identification of a potential general acid/base in the reversible phosphoryl transfer reactions catalyzed by tyrosine recombinases: Flp H305

    PubMed Central

    Whiteson, Katrine L.; Chen, Yu; Chopra, Neeraj; Raymond, Amy C.; Rice, Phoebe A.

    2007-01-01

    Summary Flp provides a unique opportunity to apply the tools of chemical biology to phosphoryl transfer reactions. Flp and other tyrosine recombinases catalyze site-specific DNA rearrangements via a phosphotyrosine intermediate, similar to the mechanism of type Ib topoisomerases [1]. Unlike most related enzymes, Flp’s nucleophilic tyrosine derives from a different protomer than the remainder of its active site [2, 3]. Because the tyrosine can be supplied exogenously, non-natural synthetic analogs can be used. Here we examine the catalytic role of Flp’s conserved H305. DNA cleavage was studied using a peptide containing either tyrosine (pKa≅10), or 3-fluoro-tyrosine (pKa≅8.4). Religation was studied using DNA substrates with 3’-phospho-cresol (pKa≅10) or 3’-para-nitro-phenol (pKa≅7.1) mimicking the covalent protein-DNA intermediate. In both cases, the tyrosine analog with the lower pKa specifically restored the activity of an H305 mutant. These results provide the first experimental evidence that this conserved histidine functions as a general acid/base catalyst in tyrosine recombinases. PMID:17317566

  1. Efficient dehydration of 6-gingerol to 6-shogaol catalyzed by an acidic ionic liquid under ultrasound irradiation.

    PubMed

    Kou, Xingran; Li, Xingze; Rahman, Md Ramim Tanver; Yan, Minming; Huang, Huanhuan; Wang, Hongxin; Su, Yihai

    2017-01-15

    6-Gingerol and 6-shogaol are the main bioactive compounds in ginger. Although 6-shogaol has more and better bioactivities than its precursor 6-gingerol, the low content of 6-shogaol in ginger restricts its bioactive effects in functional foods. The traditional preparation methods of 6-shogaol are defective because of the environmental hazards and low efficiency of the processes. In this study, an efficient, easy and eco-friendly dehydration conversion of 6-gingerol to 6-shogaol is presented using an acidic ionic liquid 1-butyl-3-methylimidazolium hydrosulfate ([Bmim]HSO4) under ultrasound irradiation. The key parameters, including reaction temperature, reaction time, mass ratio of catalyst to substrate and ultrasonic power in each reaction process, were investigated. The yield of 6-shogaol reached as high as 97.16% under optimized condition. The catalyst could be separated from the reaction mixture and reused five times with only a slight loss of activity. PMID:27542467

  2. Studies of reaction variables for lipase-catalyzed production of alpha-linolenic acid enriched structured lipid and oxidative stability with antioxidants.

    PubMed

    Mitra, Kanika; Shin, Jung-Ah; Lee, Jeung-Hee; Kim, Seong-Ai; Hong, Soon-Taek; Sung, Chang-Keun; Xue, Cheng Lian; Lee, Ki-Teak

    2012-01-01

    Alpha-linolenic acid (ALA) enriched structured lipid (SL) was produced by lipase-catalyzed interesterification from perilla oil (PO) and corn oil (CO). The effects of different reaction conditions (substrate molar ratio [PO/CO 1:1 to 1:3], reaction time [0 to 24 h], and reaction temperature [55 to 65 °C]) were studied. Lipozyme RM IM from Rhizomucor miehei was used as biocatalyst. We obtained 32.39% of ALA in SL obtained under the optimized conditions (molar ratio-1:1 [PO:CO], temperature-60 °C, reaction time-15 h). In SL, the major triacylglycerol (TAG) species (linolenoyl-linolenoyl-linolenoyl glycerol [LnLnLn], linolenoyl-linolenoyl-linoleoyl glycerol [LnLnL]) mainly from PO and linoleoyl-linoleoyl-oleoyl glycerol (LLO), linoleoyl-oleoyl-oleoyl glycerol (LOO), palmitoyl-linoleoyl-oleoyl glycerol (PLO) from CO decreased while linolenoyl-linolenoyl-oleoyl glycerol (LnLnO) (18.41%), trilinolein (LLL) (9.06%), LLO (16.66%), palmitoyl-linoleoyl-linoleoyl glycerol (PLL) (9.69%) were increased compared to that of physical blend. Total tocopherol content (28.01 mg/100 g), saponification value (SV) (192.2), and iodine value (IV) (161.9) were obtained. Furthermore, oxidative stability of the SL was also investigated by addition of 3 different antioxidants (each 200 ppm of rosemary extract [SL-ROS], BHT [SL-BHT], catechin [SL-CAT]) was added into SL and stored in 60 °C oven for 30 d. 2-Thiobabituric acid-reactive substances (TBARS) value was 0.16 mg/kg in SL-CAT and 0.18 mg/kg in SL-ROS as compared with 0.22 mg/kg in control (SL) after oxidation. The lowest peroxide value (POV, 200.9 meq/kg) and longest induction time (29.88 h) was also observed in SL-CAT. PMID:22122200

  3. Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing.

    PubMed

    Huang, Yi; Wang, Wen; Li, Zou; Qin, Xiaoli; Bu, Lijuan; Tang, Zhiyong; Fu, Yingchun; Ma, Ming; Xie, Qingji; Yao, Shouzhuo; Hu, Jiming

    2013-06-15

    We report here on a facile enzymatic polymerization protocol to prepare enzyme-poly(thiophene-3-boronic acid) (PTBA) polymeric biocomposites (PBCs) for high-performance mono-/bi-enzyme amperometric biosensing. Horseradish peroxidase (HRP)-catalyzed polymerization of thiophene-3-boronic acid (TBA) monomer was conducted in aqueous solution containing HRP (or plus glucose oxidase (GOx)) by either directly added or GOx-glucose generated oxidant H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting the dialysis-isolated PBCs on Au-plated Au electrode (Auplate/Au), followed by coating with an outer-layer chitosan (CS) film. The boronic acid residues are capable of covalent bonding with enzyme at the glycosyl sites (boronic acid-diols interaction), which should less affect the enzymatic activity as compared with the common cases of covalent bonding at the peptide chains, and UV-vis spectrophotometric tests confirmed that the encapsulated HRP almost possesses its pristine enzymatic specific activity. The enzyme electrodes were studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry in the presence of Fe(CN)6(4-) mediator. The CS/HRP-PTBA/Auplate/Au electrode responded linearly to H2O2 concentration from 1 to 300 μM with a sensitivity of 390 μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1 μM. The bienzyme CS/GOx-HRP-PTBA(H2O2)/Auplate/Au electrode responded linearly to glucose concentration from 5 μM to 0.83 mM with a sensitivity of 75.1 μA mM(-1)cm(-2) and a LOD of 1 μM, and it is found here that the use of Fe(CN)6(4-) that can only efficiently mediate HRP favorably avoids the "unusual amperometric responses" observed when other mediators that can efficiently turn over both HRP and GOx are used. PMID:23391705

  4. Production of L-malic acid with fixation of HCO3(-) by malic enzyme-catalyzed reaction based on regeneration of coenzyme on electrode modified by layer-by-layer self-assembly method.

    PubMed

    Zheng, Haitao; Ohno, Yoko; Nakamori, Toshihiko; Suye, Shin-Ichiro

    2009-01-01

    Malic enzyme prepared and purified from Brevundimonas diminuta IFO13182 catalyzed the decarboxylation reaction of malate to pyruvate and CO2 using NAD+ as the coenzyme, and the reverse reaction was used in the present study for L-malic acid production with fixation of HCO3(-) as a model compound for carbon source. The L-malic acid production was based on electrochemical regeneration of NADH on a carbon plate electrode modified by layer-by-layer adsorption of polymer-bound mediator (Alginic acid bound viologen derivative, Alg-V), polymer-bound coenzyme (Alginic acid bound NAD+, Alg-NAD+), and lipoamide dehydrogenase (LipDH). Electrochemical reduction of immobilized NAD+ catalyzed by LipDH in a multilayer film was achieved, and the L-malic acid production with HCO3(-) fixation system with layer-by-layer immobilization of Alg-V/LipDH/Alg-NAD+/malic enzyme multilayer film on the electrode gave an L-malic acid production of nearly 11.9 mmol and an HCO3(-) fixation rate of nearly 47.4% in a buffer containing only KHCO3 and pyruvic acid potassium salt, using a cation exchange membrane. The total turnover number of NADH within 48 h was about 19,000, which suggests that efficient NADH regeneration and fast electron transfer were achieved within the multilayer film, and that the modified electrode is a potential method for the fixation of HCO3(-) without addition of free coenzyme. PMID:19147103

  5. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    PubMed

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin

    2016-07-20

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed. PMID:27310182

  6. Sulfate radical-induced degradation of Acid Orange 7 by a new magnetic composite catalyzed peroxymonosulfate oxidation process.

    PubMed

    Chen, Dan; Ma, Xiaolong; Zhou, Jizhi; Chen, Xi; Qian, Guangren

    2014-08-30

    We synthesized a novel magnetic composite, Fe3O4/Cu(Ni)Cr-LDH, as a heterogeneous catalyst for the degradation of organic dyes in the solution using sulfate radical-based advanced oxidation processes. The physicochemical properties of the composite synthesized via two-step microwave hydrothermal method were characterized by several techniques, such as X-ray diffraction (XRD), inductively coupled plasma (ICP), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The degradation tests were performed at 25°C with Acid Orange 7 (AO7) initial concentration of 25mg/L and AO7/peroxymonosulfate (PMS) molar ratio of 1:10, which showed that the complete degradation by Fe3O4/Cu1.5Ni0.5Cr-LDH could be achieved and the mineralization rate could reach 46%. PMS was activated by Cu (II) and Fe (II/III) of Fe3O4/Cu(Ni)Cr-LDH to generate sulfate radicals (SO4(-)). Subsequently, the organic functional groups of AO7 molecules were destroyed by sulfate radicals (SO4(-)), inducing the degradation of AO7. Moreover, the catalytic behavior of the catalysts could be reused five times. Therefore, our work suggested that the Fe3O4/Cu(Ni)Cr-LDH composite could be applied widely for the treatment of organic dyes in wastewater. PMID:25103453

  7. Catalyzed ester synthesis using Candida rugosa lipase entrapped by poly(N-isopropylacrylamide-co-itaconic acid) hydrogel.

    PubMed

    Milašinović, Nikola; Jakovetić, Sonja; Knežević-Jugović, Zorica; Milosavljević, Nedeljko; Lučić, Marija; Filipović, Jovanka; Kalagasidis Krušić, Melina

    2014-01-01

    This study reports the synthesis of polymeric matrices based on N-isopropylacrylamide and itaconic acid and its application for immobilization of lipase from Candida rugosa. The lipase was immobilized by entrapment method. Free and immobilized lipase activities, pH and temperature optima, and storage stability were investigated. The optimum temperature for free and entrapped lipase was found to be 40 and 45 °C, while the optimum pH was observed at pH 7 and 8, respectively. Both hydrolytic activity in an aqueous medium and esterolytic activity in an organic medium have been evaluated. Maximum reaction rate (V max) and Michaelis-Menten constants (K m ) were also determined for immobilized lipase. Storage stability of lipase was increased as a result of immobilization process. Furthermore, the operational stability and reusability of the immobilized lipase in esterification reaction have been studied, and it was observed that after 10 cycles, the residual activity for entrapped lipase was as high as 50%, implying that the developed hydrogel and immobilized system could provide a promising solution for the flavor ester synthesis at the industrial scale. PMID:24701136

  8. Catalyzed Ester Synthesis Using Candida rugosa Lipase Entrapped by Poly(N-isopropylacrylamide-co-itaconic Acid) Hydrogel

    PubMed Central

    Milašinović, Nikola; Jakovetić, Sonja; Knežević-Jugović, Zorica; Milosavljević, Nedeljko; Lučić, Marija; Filipović, Jovanka; Kalagasidis Krušić, Melina

    2014-01-01

    This study reports the synthesis of polymeric matrices based on N-isopropylacrylamide and itaconic acid and its application for immobilization of lipase from Candida rugosa. The lipase was immobilized by entrapment method. Free and immobilized lipase activities, pH and temperature optima, and storage stability were investigated. The optimum temperature for free and entrapped lipase was found to be 40 and 45°C, while the optimum pH was observed at pH 7 and 8, respectively. Both hydrolytic activity in an aqueous medium and esterolytic activity in an organic medium have been evaluated. Maximum reaction rate (Vmax) and Michaelis-Menten constants (Km) were also determined for immobilized lipase. Storage stability of lipase was increased as a result of immobilization process. Furthermore, the operational stability and reusability of the immobilized lipase in esterification reaction have been studied, and it was observed that after 10 cycles, the residual activity for entrapped lipase was as high as 50%, implying that the developed hydrogel and immobilized system could provide a promising solution for the flavor ester synthesis at the industrial scale. PMID:24701136

  9. A kinetic study on the Novozyme 435-catalyzed esterification of free fatty acids with octanol to produce octyl esters.

    PubMed

    Chowdhury, Avisha; Mitra, Debarati

    2015-01-01

    Octyl esters can serve as an important class of biolubricant components replacing their mineral oil counterparts. The purpose of the current work was to investigate the enzymatic esterification reaction of free fatty acids (FFA, from waste cooking oil) with octanol in a solvent-free system using a commercial lipase Novozyme 435. It was found that the esterificaton reaction followed the Ping-pong bi-bi kinetics with no inhibition by substrates or products within the studied concentration range. The maximum reaction rate was estimated to be 0.041 mol L(-1) g(-1) h(-1) . Additionally, the stability of Novozyme 435 in the current reaction system was studied by determining its activity and final conversion of FFA to esters after 12 successive utilizations. Novozyme 435 exhibited almost 100% enzyme activity up to 7 cycles of reaction and gradually decreased (by 5%) thereafter. The kinetic parameters evaluated from the study shall assist in the design of reactors for large-scale production of octyl esters from a cheap biomass source. The enzyme reusability data can further facilitate mass production by curtailing the cost of expensive enzyme consumption. PMID:26334440

  10. Metal- and Oxidant-Free Synthesis of Quinazolinones from β-Ketoesters with o-Aminobenzamides via Phosphorous Acid-Catalyzed Cyclocondensation and Selective C-C Bond Cleavage.

    PubMed

    Li, Zhongwen; Dong, Jianyu; Chen, Xiuling; Li, Qiang; Zhou, Yongbo; Yin, Shuang-Feng

    2015-10-01

    A general and efficient phosphorous acid-catalyzed cyclocondensation of β-ketoesters with o-aminobenzamides via selective C-C bond cleavage leading to quinazolinones is developed. This reaction proceeds smoothly under metal- and oxidant-free conditions, giving both 2-alkyl- and 2-aryl-substituted quinazolinones in excellent yields. This strategy can also be applied to the synthesis of other N-heterocycles, such as benzimidazoles and benzothiazoles. PMID:26339716

  11. Copper catalyzed N-arylation of amidines with aryl boronic acids and one-pot synthesis of benzimidazoles by a Chan-Lam-Evans N-arylation and C-H activation/C-N bond forming process.

    PubMed

    Li, Jihui; Bénard, Sébastien; Neuville, Luc; Zhu, Jieping

    2012-12-01

    Mono-N-arylation of benzamidines 1 with aryl boronic acids 2 was effectively achieved in the presence of a catalytic amount of Cu(OAc)(2) and NaOPiv under mild aerobic conditions. Combining this step with an intramolecular direct C-H bond functionalization, catalyzed by the same catalytic system but under oxygen at 120 °C, afforded benzimidazoles 3 in good to excellent yields. PMID:23151245

  12. Selective dimerization of arylalkynes to (E)-1,4-diaryl enynes catalyzed by the [Ru(p-cymene)Cl(2)](2)/acetic acid system under phosphine-free conditions.

    PubMed

    Bassetti, Mauro; Pasquini, Chiara; Raneri, Antonino; Rosato, Deborah

    2007-06-01

    The commercially available di-mu-chlorobis[(p-cymene)chlororuthenium(II)] complex catalyzes the dimerization of aromatic alkynes in acetic acid at room temperature to form the corresponding (E)-1,4-diarylbut-1-ene-3-yne derivatives, with high stereoselectivity. The procedure does not require the use of additives and can be carried out in the presence of water or aprotic cosolvents, under homogeneous conditions. PMID:17497925

  13. Visual detection of trace copper ions based on copper-catalyzed reaction of ascorbic acid with oxygen

    NASA Astrophysics Data System (ADS)

    Hou, Xin Yan; Chen, Shu; Shun, Lian Ju; Zhao, Yi Ni; Zhang, Zhi Wu; Long, Yun Fei; Zhu, Li

    2015-10-01

    A visual detection method for trace Cu2+ in aqueous solutions using triangular silver nanoplates (abbreviated as TAgNPs) as the probe was developed. The method is based on that TAgNPs could be corroded in sodium thiosulfate (Na2S2O3) solutions. The absorption spectrum of TAgNPs solution changed when it is corroded by Na2S2O3. The reaction of oxygen with ascorbic acid (Vc) in the presence of a low concentration of Cu2+ generates hydrogen peroxide that reacts with Na2S2O3, which leads the concentration of Na2S2O3 in the solution to be decreased. Therefore, the reaction between TAgNPs and the reacted mixture of Na2S2O3/Vc/Cu2+ was prevented efficiently. When the Na2S2O3 concentration and reaction time are constant, the decrease in the concentration of Na2S2O3 is directly proportional to the Cu2+ concentration. Thus, morphology, color, and maximum absorption wavelength of TAgNPs changed with the change of Cu2+ concentration. The changed maximum absorption wavelength of TAgNPs (Δλ) is proportional to Cu2+ concentration in the range from 7.5 × 10-9 to 5.0 × 10-7 M with a correlation coefficient of r = 0.9956. Moreover, color change of TAgNP solution was observed clearly over a Cu2+ concentration range from 7.5 × 10-8 to 5.0 × 10-7 M. This method has been used to detect the Cu2+ content of a human hair sample, and the result is in agreement with that obtained by the atomic absorption spectroscopy (AAS) method.

  14. The role of hydroxyl group acidity on the activity of silica-supported secondary amines for the self-condensation of n-butanal.

    PubMed

    Shylesh, Sankaranarayanapillai; Hanna, David; Gomes, Joseph; Canlas, Christian G; Head-Gordon, Martin; Bell, Alexis T

    2015-02-01

    The catalytic activity of secondary amines supported on mesoporous silica for the self-condensation of n-butanal to 2-ethylhexenal can be altered significantly by controlling the Brønsted acidity of M--OH species present on the surface of the support. In this study, M--OH (M=Sn, Zr, Ti, and Al) groups were doped onto the surface of SBA-15, a mesoporous silica, prior to grafting secondary propyl amine groups on to the support surface. The catalytic activity was found to depend critically on the synthesis procedure, the nature and amount of metal species introduced and the spatial separation between the acidic sites and amine groups. DFT analysis of the reaction pathway indicates that, for weak Brønsted acid groups, such as Si--OH, the rate-limiting step is C--C bond formation, whereas for stronger Brønsted acid groups, such as Ti and Al, hydrolysis of iminium species produced upon C--C bond formation is the rate-limiting step. Theoretical analysis shows further that the apparent activation energy decreases with increasing Brønsted acidity of the M--OH groups, consistent with experimental observation. PMID:25314616

  15. MAM3 catalyzes the formation of all aliphatic glucosinolate chain lengths in Arabidopsis.

    PubMed

    Textor, Susanne; de Kraker, Jan-Willem; Hause, Bettina; Gershenzon, Jonathan; Tokuhisa, James G

    2007-05-01

    Chain elongated, methionine (Met)-derived glucosinolates are a major class of secondary metabolites in Arabidopsis (Arabidopsis thaliana). The key enzymatic step in determining the length of the chain is the condensation of acetyl-coenzyme A with a series of omega-methylthio-2-oxoalkanoic acids, catalyzed by methylthioalkylmalate (MAM) synthases. The existence of two MAM synthases has been previously reported in the Arabidopsis ecotype Columbia: MAM1 and MAM3 (formerly known as MAM-L). Here, we describe the biochemical properties of the MAM3 enzyme, which is able to catalyze all six condensation reactions of Met chain elongation that occur in Arabidopsis. Underlining its broad substrate specificity, MAM3 also accepts a range of non-Met-derived 2-oxoacids, e.g. converting pyruvate to citramalate and 2-oxoisovalerate to isopropylmalate, a step in leucine biosynthesis. To investigate its role in vivo, we identified plant lines with mutations in MAM3 that resulted in a complete lack or greatly reduced levels of long-chain glucosinolates. This phenotype could be complemented by reintroduction of a MAM3 expression construct. Analysis of MAM3 mutants demonstrated that MAM3 catalyzes the formation of all glucosinolate chain lengths in vivo as well as in vitro, making this enzyme the major generator of glucosinolate chain length diversity in the plant. The localization of MAM3 in the chloroplast suggests that this organelle is the site of Met chain elongation. PMID:17369439

  16. CYP3A Specifically Catalyzes 1β-Hydroxylation of Deoxycholic Acid: Characterization and Enzymatic Synthesis of a Potential Novel Urinary Biomarker for CYP3A Activity.

    PubMed

    Hayes, Martin A; Li, Xue-Qing; Grönberg, Gunnar; Diczfalusy, Ulf; Andersson, Tommy B

    2016-09-01

    The endogenous bile acid metabolite 1β-hydroxy-deoxycholic acid (1β-OH-DCA) excreted in human urine may be used as a sensitive CYP3A biomarker in drug development reflecting in vivo CYP3A activity. An efficient and stereospecific enzymatic synthesis of 1β-OH-DCA was developed using a Bacillus megaterium (BM3) cytochrome P450 (P450) mutant, and its structure was confirmed by nuclear magnetic resonance (NMR) spectroscopy. A [(2)H4]-labeled analog of 1β-OH-DCA was also prepared. The major hydroxylated metabolite of deoxycholic acid (DCA) in human liver microsomal incubations was identified as 1β-OH-DCA by comparison with the synthesized reference analyzed by UPLC-HRMS. Its formation was strongly inhibited by CYP3A inhibitor ketoconazole. Screening of 21 recombinant human cytochrome P450 (P450) enzymes showed that, with the exception of extrahepatic CYP46A1, the most abundant liver P450 subfamily CYP3A, including CYP3A4, 3A5, and 3A7, specifically catalyzed 1β-OH-DCA formation. This indicated that 1β-hydroxylation of DCA may be a useful marker reaction for CYP3A activity in vitro. The metabolic pathways of DCA and 1β-OH-DCA in human hepatocytes were predominantly via glycine and, to a lesser extent, via taurine and sulfate conjugation. The potential utility of 1β-hydroxylation of DCA as a urinary CYP3A biomarker was illustrated by comparing the ratio of 1β-OH-DCA:DCA in a pooled spot urine sample from six healthy control subjects to a sample from one patient treated with carbamazepine, a potent CYP3A inducer; 1β-OH-DCA:DCA was considerably higher in the patient versus controls (ratio 2.8 vs. 0.4). Our results highlight the potential of 1β-OH-DCA as a urinary biomarker in clinical CYP3A DDI studies. PMID:27402728

  17. Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

    PubMed Central

    Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

    2015-01-01

    Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

  18. Syntheses and Transformations of α-Amino Acids via Palladium-Catalyzed Auxiliary-Directed sp(3) C-H Functionalization.

    PubMed

    He, Gang; Wang, Bo; Nack, William A; Chen, Gong

    2016-04-19

    α-Amino acids (αAA) are one of the most useful chiral building blocks for synthesis. There are numerous general strategies that have commonly been used for αAA synthesis, many of which employ de novo synthesis focused on enantioselective bond construction around the Cα center and others that consider conversion of existing αAA precursors carrying suitable functional groups on side chains (e.g., serine and aspartic acid). Despite significant advances in synthetic methodology, the efficient synthesis of enantiopure αAAs carrying complex side chains, as seen in numerous peptide natural products, remains challenging. Complementary to these "conventional" strategies, a strategy based on the selective functionalization of side chain C-H bonds, particularly sp(3) hybridized C-H bonds, of various readily available αAA precursors may provide a more straightforward and broadly applicable means for the synthesis and transformation of αAAs. However, many hurdles related to the low reactivity of C(sp(3))-H bonds and the difficulty of controlling selectivity must be overcome to realize the potential of C-H functionalization chemistry in this synthetic application. Over the past few years, we have carried out a systematic investigation of palladium-catalyzed bidentate auxiliary-directed C-H functionalization reactions for αAA substrates. Our strategies utilize two different types of amide-linked auxiliary groups, attached at the N or C terminus of αAA substrates, to exert complementary regio- and stereocontrol on C-H functionalization reactions through palladacycle intermediates. A variety of αAA precursors can undergo multiple modes of C(sp(3))-H functionalization, including arylation, alkenylation, alkynylation, alkylation, alkoxylation, and intramolecular aminations, at the β, γ, and even δ positions to form new αAA products with diverse structures. In addition to transforming αAAs at previously unreachable positions, these palladium-catalyzed C

  19. An alternative reaction for heme degradation catalyzed by the Escherichia coli O157:H7 ChuS protein: Release of hematinic acid, tripyrrole and Fe(III).

    PubMed

    Ouellet, Yannick H; Ndiaye, Cheikh Tidiane; Gagné, Stéphane M; Sebilo, Anne; Suits, Michael D L; Jubinville, Éric; Jia, Zongchao; Ivancich, Anabella; Couture, Manon

    2016-01-01

    As part of the machinery to acquire, internalize and utilize heme as a source of iron from the host, some bacteria possess a canonical heme oxygenase, where heme plays the dual role of substrate and cofactor, the later catalyzing the cleavage of the heme moiety using O2 and electrons, and resulting in biliverdin, carbon monoxide and ferrous non-heme iron. We have previously reported that the Escherichia coli O157:H7 ChuS protein, which is not homologous to heme oxygenases, can bind and degrade heme in a reaction that releases carbon monoxide. Here, we have pursued a detailed characterization of such heme degradation reaction using stopped-flow UV-visible absorption spectrometry, the characterization of the intermediate species formed in such reaction by EPR spectroscopy and the identification of reaction products by NMR spectroscopy and Mass spectrometry. We show that hydrogen peroxide (in molar equivalent) is the key player in the degradation reaction, at variance to canonical heme oxygenases. While the initial intermediates of the reaction of ChuS with hydrogen peroxide (a ferrous keto π neutral radical and ferric verdoheme, both identified by EPR spectroscopy) are in common with heme oxygenases, a further and unprecedented reaction step, involving the cleavage of the porphyrin ring at adjacent meso-carbons, results in the release of hematinic acid (a monopyrrole moiety identified by NMR spectroscopy), a tripyrrole product (identified by Mass spectrometry) and non-heme iron in the ferric oxidation state (identified by EPR spectroscopy). Overall, the unprecedented reaction of E. coli O157:H7 ChuS provides evidence for a novel heme degradation activity in a Gram-negative bacterium. PMID:26598215

  20. Horseradish peroxidase-catalyzed polymerization of L-DOPA for mono-/bi-enzyme immobilization and amperometric biosensing of H2O2 and uric acid.

    PubMed

    Dai, Mengzhen; Huang, Ting; Chao, Long; Xie, Qingji; Tan, Yueming; Chen, Chao; Meng, Wenhua

    2016-03-01

    Horseradish peroxidase (HRP)-catalyzed polymerization of L-DOPA (vs. dopamine) in the presence of H2O2 (and uricase (UOx)) was exploited to immobilize mono-/bi-enzymes for hydroquinone-mediated amperometric biosensing of H2O2 and uric acid (UA). The relevant polymeric biocomposites (PBCs) were prepared in phosphate buffer solution containing HRP and L-DOPA (or plus UOx) after adding H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting some of the PBCs on Au-plated Au (Au(plate)/Au) electrodes, followed by coating with an outer-layer chitosan (CS) film for each. UV-vis spectrophotometry, scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy were used for film characterization and/or process monitoring. The HRP immobilized by enzyme catalysis well preserved its bioactivity, as confirmed by UV-vis spectrophotometry. Under optimized conditions, the monoenzyme CS/HRP-poly(L-DOPA) (PD)/Au(plate)/Au electrode potentiostated at -0.1V responded linearly to H2O2 concentration from 0.001 to 1.25mM with a sensitivity of 700μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1μM, and the bienzyme CS/UOx-HRP-PD/Au(plate)/Au electrode at -0.1V responded linearly to UA concentration from 0.001 to 0.4mM with a sensitivity of 349μA mM(-1)cm(-2) and a LOD of 0.1μM. The mono-/bi-enzyme biosensors based on biosynthesized PD performed better than many reported analogues and those based on similarly biosynthesized polydopamine. PMID:26717822